Liquid fuel compositions based on catalytically deoxygenated and condensed ogygenated carbohydrates

FIELD: chemistry.

SUBSTANCE: claimed invention relates to liquid fuel compositions. Invention deals with liquid fuel composition, containing, at least, one fuel component and from 0.1%(vil.) to 99.5% (vol.) of fraction of distillation of component, which contains, at least, one C4+ compound, derived from water-soluble oxygenated hydrocarbon. Method includes supply of water and water-soluble oxygenated hydrocarbon, including C1+O1+ hydrocarbon, in water liquid phase and/or vapour phase; supply of H2; carrying out catalytic reaction in liquid and/or vapour phase between oxygenated hydrocarbon and H2 in presence of deoxygenation catalyst at temperature of deoxygenation and pressure of deoxygenation to obtain oxygenate, which contains C1+O1-3 hydrocarbon in reaction flow; and carrying put catalytic reaction in liquid and/or vapour phase for oxygenate in presence of condensation catalyst at temperature of condensation and pressure of condensation to obtain C4+ compound, where C4+ compound includes representative, selected from the group, consisting of C4+ alcohol, C4+ ketone, C4+ alkane, C4+ alkene, C5+ cycloalkane, C5+ cycloalkene, aryl, condensed aryl and their mixture. Invention also relates to petrol composition, Diesel fuel composition, kerosene composition and methods of obtaining thereof.

EFFECT: improved characteristics of fuel composition, containing component, obtained from biomass.

9 cl, 19 dwg, 14 tbl, 59 ex

 

The technical field to which the invention relates.

The present invention relates to liquid fuel compositions containing the component produced from water-soluble oxygenating hydrocarbon.

The level of technology

The development of new technologies for producing energy from resources other than fossil fuels, has been paid great attention. A resource that shows prospects as an alternative to fossil fuel is a biomass. In contrast to fossil fuels, biomass is renewable.

One type of biomass is a biomass of plant origin. Biomass of plant origin is the most abundant source of carbohydrate in the world because of lignocellulosic materials forming the membrane of cells in higher plants. Membrane of plant cells are divided into two sections - primary cell membrane and secondary membrane of cells. Primary sheath cells provides a structure for growing cells and is formed from three main polysaccharides (cellulose, pectin and hemicellulose) and one group of glycoproteins. The secondary sheath cells, which is formed after the growth of cells, also contains polysaccharides and hardened due to the polymeric lignin covalently crosslinked with hemicellulose is. Hemicellulose and pectin are usually found in abundance, but cellulose is a predominant polysaccharide and the most abundant source of carbohydrates.

Most vehicles, whether it be ships, trains, planes or automobiles, require the use of a high power generated by the internal combustion engine and/or jet engines. These engines require the use of cleaner-burning fuels, which generally have a liquid form or, to a lesser extent, are compressed gases. Liquid fuels are more suitable for transportation because of their high specific energy and their ability to be pumped by the pump, which makes handling them easier.

Currently, biomass is the only renewable alternative for liquid fuels vehicles. Unfortunately, the development progress in the development of new technologies for the production of liquid biofuels has been slow, particularly for liquid fuel products that meet modern infrastructure. Despite the possibility of obtaining resources from biomass, a wide range of fuels, such as ethanol, methanol, biodiesel, diesel fuel, Fischer-Tropsch kerosene and gas fuel such as hydrogen is methane, these fuels may require the use of new technologies of distribution and/or combustion technologies that are appropriate to their characteristics. Getting these fuels also tends to be expensive.

Ethanol, for example, receive as a result of the conversion of carbohydrate biomass into sugar, which is then converted into ethanol by fermentation method. Ethanol is the most widely used biofuel today, with modern production 4.3 billion gallons (16,3 billion DM3in the year calculated on the starch culture, such as corn. However, ethanol characteristic of very significant drawbacks with respect to its heat of combustion of the fuel in comparison with the magnitude of the energy required for its production. The ethanol obtained by fermentation, contains large quantities of water, usually in the presence of only approximately 5 percent of ethanol per volume of the aqueous/alcoholic fermentation. Removal of this water is vysokoenergichnym and often requires the use as a heat source of natural gas. Ethanol is also characterized by lower energy content compared to gasoline, which means the need to use more fuel to pass identical distances. This is Nol is very corrosive with respect to the fuel systems and cannot be transported in pipelines. As a result, the ethanol is transported between cities in the trucks, which increases to him the total cost and energy consumption. Taking into account the full energy used in agricultural machinery and equipment, cultivation, planting, fertilizers, pesticides, herbicides, fungicides, petroleum-based, irrigation, harvesting, transportation to processing plants, fermentation, distillation, drying, transportation fuel base and pumps in petrol stations, and smaller supplying energy to birds ethanol fuel, the resulting added and delivered to consumers the value of supplying energy to birds is very small.

Biodiesel represents another potential source of energy. Biodiesel can be obtained from vegetable oils, animal fats, waste vegetable oils, oils from microalgae or recycled restaurant greases, and it is obtained by the method in which oil is produced from organic matter, combined with alcohol (ethanol or methanol) in the presence of a catalyst to obtain ethyl or methyl ether complex. Produced from biomass ethyl or methyl esters can then be mixed with conventional diesel fuel or used as pure fuels is (100% bio diesel). Biodiesel fuel is also expensive to manufacture and creates various problems in its use and burning. For example, in order to avoid gelation at low temperatures may require special techniques.

Biomass can also be gasified to produce synthesis gas formed primarily of hydrogen and carbon monoxide, also called synthetic gas or synthesis gas. The synthesis gas produced today are used directly to generate heat and electric energy, but from the synthesis gas can be produced by several types of biofuels. From the synthesis gas can be extracted hydrogen, or first can be catalytically converted into methanol. Gas can also be passed through a biological reactor for ethanol production or use of the catalyst for the Fischer-Tropsch turned into a liquid stream, with properties similar to diesel fuel that is called diesel Fischer-Tropsch process. However, these methods tend to be expensive.

There is a need in the compositions of liquid fuels, which contain a component which can be produced from biomass, and which is capable of being used in modern infrastructure, namely, in the same distribution system and at the same DV is the circulation without any need for special modifications. Also, there is a need in the compositions of liquid fuels, which contain a component which can be produced from biomass, and which do not depend on microorganisms, enzymes or other expensive and delicate production methods.

Summary of invention

The present invention provides a composition of liquid fuel containing fraction distillation component containing at least one4+connection is made from water-soluble oxygenating hydrocarbon, obtained by the method comprising;

water supply and water soluble oxygenating hydrocarbon, including C1+O1+the hydrocarbon in an aqueous liquid phase and/or vapor phase;

the supply of N2;

carrying out catalytic reactions in liquid and/or vapor phase between oxygendemanding hydrocarbon and NC in the presence of a catalyst of deoxyguanosine at a temperature of deoxyadenosine and pressure deoxyadenosine to obtain oxygenate containing in the reaction stream C1+O1-3hydrocarbon; and

carrying out catalytic reactions in liquid and/or vapor phase the oxygenate in the presence of a condensation catalyst at a condensation temperature and condensation pressure to obtain C4+connection

where C4+the connection includes a representative of the El, selected from the group consisting of C4+alcohol,4+ketone,4+alkane, With4+alkene, C5+cycloalkane,5+cycloalkene, aryl, condensed aryl and mixtures thereof;

where the composition is a liquid fuel selected from:

the composition of the gas, characterized by an initial boiling point in the range from 15°C to 70°C. (IP123), a temperature of the end of the boil, equal at most 230°C. (IP123), the value of the research octane number of each in the range from 85 to 110 (ASTM D2699) and value motor octane number of MOC in the range from 75 to 100 (ASTM d 2700);

the composition of diesel fuel, characterized by an initial boiling point in the range from 130°C to 230°C. (IP123), a temperature of the end of the boil, equal at most 410°C. (IP123), and cetane number in the range from 35 to 120 (ASTM R); and

the composition of kerosene, characterized by an initial boiling point in the range from 80 to 150°C., the temperature of the end of the boil in the range from 200 to 320°C and viscosity at 20°C in the range from 0.8 to 10 mm2/s (ASTM D445).

The present invention also provides a composition of gasoline containing component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, characterized by the temperature of the end of the boil in the range from 150 to 220°C., a density at 15°C in diapazonom 700 to 890 kg/m 3, a sulfur content equal to at most 5 mg/kg, the level of oxygen equal to, at most, a 3.5% (mass.), the value of each in the range from 80 to 110 and is MUCH in the range from 70 to 100 where the above-mentioned composition of gasoline is characterized by an initial boiling point in the range from 15°C to 70°C. (IP123), a temperature of the end of the boil, equal at most 220°C. (IP123), a is each in the range from 85 to 110 (ASTM D2699) and is MUCH in the range from 75 to 100 (ASTM D2700).

The present invention also provides a composition of diesel fuel containing component containing at least one4+connection is made from water-soluble oxygenating hydrocarbon, and is characterized by T in the range from 220 to 380°C, a flash point in the range from 30 to 70°C density at 15°C in the range from 700 to 900 kg/m3, a sulfur content equal to at most 5 mg/kg, the level of oxygen content equal to at most 10% (mass.), and a viscosity at 40°C in the range from 0.5 to 6 cSt, where said composition is a diesel fuel characterized by an initial boiling point in the range from 130°C to 230°C. (IP123), a temperature of the end of the boil, equal at most 410°C. (IP123), and cetane number in the range from 35 to 120 (ASTM D613).

The present invention also provides a composition of kerosene containing comp the element, containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, and characterized by an initial boiling point in the range from 120 to 215°C, the temperature of the end of the boil in the range from 220 to 320°C., a density at 15°C in the range of from 700 to 890 kg/m3, a sulfur content equal to, at most, 0,1% (mass.), levels of total aromatics, equal to, at most, 30% (vol.), the freezing temperature of - 40°C or less, a maximum height of mecoptera flame, equal at least 18 mm, a viscosity at 20°C in the range from 1 to 10 cSt and specific energy content in the range from 40 to 47 MJ/kg, where the above-mentioned composition of the kerosene is characterized by an initial boiling point in the range from 80 to 150°C., the temperature of the end of the boil in the range from 200 to 320°C and viscosity at 20°C in the range from 0.8 to 10 mm2/s (ASTM D445).

The present invention also provides a method of obtaining the composition of the liquid fuel corresponding to the present invention, comprising mixing:

(a) fraction distillation component containing at least one4+connection is made from water-soluble oxygenating hydrocarbon, obtained by the method, including:

water supply and water soluble oxygenating hydrocarbon, the soda is containing C 1+About1+the hydrocarbon in an aqueous liquid phase and/or vapor phase;

the supply of H2;

carrying out catalytic reactions in liquid and/or vapor phase between oxygendemanding hydrocarbon and H2in the presence of a catalyst of deoxyguanosine at a temperature of deoxyadenosine and pressure deoxyadenosine to obtain oxygenate containing in the reaction stream With1+O1-3hydrocarbon; and

carrying out catalytic reactions in liquid and/or vapor phase the oxygenate in the presence of a condensation catalyst at a condensation temperature and condensation pressure to obtain4+connection

where C4+the connection includes a representative selected from the group consisting of C4+alcohol,4+ketone,4+alkane, With4+alkene, With5+cycloalkane,5+cycloalkene, aryl, condensed aryl and mixtures thereof, and (b) at least one fuel component.

Brief description of drawings

Figure 1 is a block diagram illustrating various ways to get associated with the present invention.

Figure 2 illustrates a potential chemical pathways that make possible the conversion of carbohydrates, such as sugar, deoxyadenosine hydrocarbons.

Figure 3 is an illustration of various reaction pathways included deoxyadenosine sorbitol to obtain oxygenates and hydrogen reforming of the aqueous phase (RVF).

Figure 4 is an illustration of thermodynamic equilibrium along the reaction path for the conversion of acetone to 2-methylpentan at 100°C and 400°C.

Figure 5 is a graph illustrating the equilibrium constants associated with the intermediate reaction products and a total transformation in the case of the reaction between 2 moles of acetone and 3 moles of hydrogen to produce 1 mole of 2-methylpentane and 2 moles of water.

Figure 6 is a block diagram illustrating a reactor system configured for delivering on recycling of hydrogen, oxygenates and oxygenated hydrocarbons.

Figure 7 is a block diagram illustrating a reactor system configured to provide air or oil as the element temperature control.

Figure 8 is a block diagram illustrating a reactor system for the present invention.

Figure 9 is a block diagram illustrating a reactor system that uses two reactors.

Figure 10 is a block diagram illustrating a reactor system that uses two lines of raw materials.

Figure 11 is an illustration of a reactor suitable for use in implementing the present invention in practice.

Figure 12 represents the way the second schedule, illustrating the distribution of carbon atoms for monooxygenation derived from glycerin.

Figure 13 is a graph illustrating the axial temperature profile of the reactor when it is used to obtain the compounds of the feedstock in the form of oxygenated hydrocarbons.

Figure 14 is a graph illustrating the time dependency of the percentage of carbon atoms of the raw materials, published in the form of oxygenates after transformation flow oxygenate feedstock in C5+connection.

Figure 15 is a graph illustrating the time dependency of the percentage of carbon atoms of raw materials coming in the form of a5+hydrocarbons after the conversion of the oxygenate stream of raw materials.

Figure 16 is a graph illustrating the time dependency of the percentage of carbon atoms of raw materials coming in the form of a5+aromatic hydrocarbons after the conversion of the oxygenate stream of raw materials.

Figure 17 is a graph showing the cumulative mass percentage of paraffin and aromatic compounds produced after transformation of flow of the feedstock in the form of sucrose and xylose.

Figure 18 is a graph illustrating the calorific value With hydrocarbons produced after production of gasoline from sorbitol, as a percentage of the calorific value of the feedstock.

Figure 19 is a graph illustrating the percentage of carbon atoms extracted in the form of aromatic hydrocarbons after receiving gasoline from sorbitol, demonstrated in the percentage of carbon atoms present in the feedstock. Detailed description of the invention

The composition of the liquid fuel of the present invention contain a component that contains at least one4+connection is made from water-soluble oxygenating hydrocarbon. Preferably the water-soluble oxygenated hydrocarbon is produced from biomass.

Typically, the method of producing a component containing at least one4+connection is made from water-soluble oxygenating hydrocarbon, leads to the production of hydrocarbons, ketones and alcohols produced from biomass of oxygenated hydrocarbons such as sugars, polyalcohols, xylytol, cellulosic polymers, lignocelluloses, hemicelluloses, sugars and the like.

Component made of a water-soluble oxygenating hydrocarbon, contains4+alkanes,4+alkenes, With5+cycloalkanes, C5+cycloalkene, aryl is, condensed arily,4+alcohols4+ketones and mixtures thereof (collectively referred to in this document as "C4+connections"). With4+hydrocarbons usually contain from 4 to 30 carbon atoms and may represent alkanes or alkenes with a branched or straight-chain or unsubstituted, monosubstituted or polyamidine the aromatics (Areli) or cycloalkanes. With4+alcohols and C4+ketones can be cyclic, branched or straight chain and contain from 4 to 30 carbon atoms.

Light fractions, first of all, With4-C9can be separated for use in gasoline. The average fractions, such as C7-C14can be separated as kerosene, for example, for use in jet fuel, while the heavy fraction, that is, C12-C24can be separated for use in diesel fuel. Most of the heavy fraction can be used as lubricants or subjected to cracking for additional fractions of gasoline and/or diesel fuel. With4+compounds produced from water-soluble oxygenated hydrocarbons, may also find use as industrial chemicals, such as xylene, regardless of whether it is an intermediate or final product.

The method receiving the ia component, made from water-soluble oxygenating hydrocarbon

A common way of producing a component made of a water-soluble oxygenating hydrocarbon, illustrated in figure 1. The solution of the initial raw material containing water-soluble oxygenated hydrocarbon containing one or more carbon atoms, is introduced into reaction with hydrogen on the catalyst deoxyadenosine to get oxygenates, and after that the oxygenate is introduced into the reaction in the condensation catalyst under conditions of temperature and pressure effective to undergo the condensation reaction, which results in4+connections. Hydrogen may have its origin from any source, but preferably it is produced from biomass in place or in parallel when using a reformer in the aqueous phase. Hydrogen and oxygendemand hydrocarbons can also be supplemented sent to recycling the hydrogen and oxygendemanding hydrocarbons produced in the way. Oxygenated hydrocarbon can be a monosaccharide, disaccharide, polysaccharide, cellulose, hemicellulose, lignin, sugars, sugar alcohols or other polyhydric alcohols, or may be produced by hydrogenation of sugar, furfural, carboxylic acid, ketone or furan or hydrogenolysis of sugars, sugar alcohols polysaccharide, of monosaccharide, disaccharide or a polyhydric alcohol.

One unique aspect of the method of producing a component made of a water-soluble oxygenating hydrocarbon in the present invention, is that C4+connections are manufactured from components of biomass catalytic methods rather than methods using microorganisms, enzymes, high temperature gasification or interesterification. The method of producing a component made of a water-soluble oxygenating hydrocarbon in the present invention, may also lead to the production of hydrogen in place, thus avoiding payments on external sources of hydrogen, such as hydrogen, obtained by steam reforming of natural gas or electrolysis or thermolysis of water. The method of producing a component made of a water-soluble oxygenating hydrocarbon in the present invention, also leads to a water, which can be sent for recycling and used in ways that are located along the process stream before, or returned to the environment. The method of producing a component made of a water-soluble oxygenating hydrocarbon in the present invention, can also lead to a non-condensed gazoobraznymi in order to obtain a source of heat in the reactor system or external methods.

Carbohydrates on Earth are the most widespread naturally occurring organic compounds. The carbohydrates produced during photosynthesis - the process by which energy from the sun into chemical energy by combining carbon dioxide with water to form carbohydrates and oxygen:

Sunlight = sunlight.

The energy of sunlight due to this process is stored in plants in the form of chemical energy in the form of carbohydrates. Carbohydrates, particularly when in the form of Sugars, are vysokoreaktsionnye-able compounds that are easily oxidized living substance, which leads to the production of energy, carbon dioxide and water. In proceedings of the plants of these carbohydrates are stored in the form or Sugars, or starches, or polymeric cellulose and/or hemicellulose.

The presence of oxygen in the molecular structure of carbohydrates contributes to the reactivity of Sugars in biological systems. Technology ethanol fermentation uses this vysokoreaktsionnye-able nature, providing ethanol at ambient temperatures. Fermentation technology, essentially defunctionalized vysokoreaktsionnye-able sugar to obtain a partially oxidized hydrocarbon - this is Nola. However, ethanol characteristic of very significant drawbacks with respect to its heat of combustion, as it was stressed above.

Figure 2 demonstrates the potential chemical pathways that allow carbohydrates, such as sugar, to turn in deoxyadenosine hydrocarbons. Water-soluble carbohydrates are known to react with hydrogen on the catalyst (catalysts) with the formation of polyols as a result of either hydrogenation or hydrogenolysis. Historically, the hydrogen received from the outside, that is, from natural gas or by other means, but in accordance with the present invention it can now be obtained in place or in parallel by reforming in the aqueous phase to the polyhydric alcohol.

Reforming in the aqueous phase (RVF) for a polyhydric alcohol proceeds through the formation of aldehyde (as demonstrated on figure 2), where the aldehyde reacts with water on the catalyst with the formation of hydrogen, carbon dioxide and smaller polyhydric alcohol. Polyhydric alcohol can further react with hydrogen on the catalyst during the sequence of reactions deoxyadenosine with the formation of either alcohol or ketone or aldehyde substances that can undergo the condensation reaction with the formation contains more atoms angle of the ode or compounds with a straight chain, or compounds with branched chain or cyclic compounds. The condensation reaction can be either catalyzed by acid or base catalyzed, or catalyzed by both acid and base. The resulting compound may be a hydrocarbon or hydrocarbons containing oxygen, the oxygen can be removed by reaction with hydrogen on the catalyst. The resulting condensed products include C4+alcohols, C4+ketones, C4+alkanes,4+alkenes, C5+cycloalkanes, C5+cycloalkene, arily, condensed arily and mixtures thereof. Mixtures can be fractionated and mixed to obtain the proper mixtures of molecules that are typically found in gasoline, kerosene (such as jet fuel or diesel fuel.

Defunctionalization starts as a result of the reaction between glucose and hydrogen or by the reaction of hydrogenation or hydrogenolysis reactions for the conversion of cyclic molecules of sugar in its corresponding linear alcohol, sorbitol or lower polyhydric alcohols, such as, inter alia, glycerol, propylene glycol, ethylene glycol, xylitol. As mentioned above, the hydrogen can come from any source, but preferably are hydrogen generated by m the STU" in the reformer in the aqueous phase, or excess hydrogen is sent to recycling of the reactor system.

During the reforming process in the aqueous phase of carbohydrate before splitting ties With With or With-O is first subjected to dehydration with the formation of adsorbed intermediates. Subsequent splitting ties With-leads to the formation of CO and H2and then reacts with water to form CO; and H2the reaction of the conversion of water gas. Various ways and methods of RVF are described in U.S. patent No. 6699457; 6964757 and 6964758; and patent application U.S. No. 11234727 (all of which the authors are Cortright et al., and the title is a "Low-Temperature Hydrogen Production from Oxygenated Hydrocarbons"); and U.S. patent No. 6953873 (whose authors are Cortright et al., and the title is a "Low Temperature Hydrocarbon Production from Oxygenated Hydrocarbons"); and the publication WO 2007/075476 A2 (whose authors are Cortright et al., and the title is a "Catalyst and Methods for Reforming Oxygenated Compounds"), all of which are incorporated by reference herein. The terms "reforming in the aqueous phase" and "RVF" in General must be given for reforming of oxygenated hydrocarbons and water to form hydrogen and carbon dioxide, regardless of the passage of reactions in the gas phase or in the condensed liquid phase. The term "H2RVF" shall mean adored, obtained according to the method of RVF.

The resulting oxygenated hydrocarbon, namely, sorbitol or glycerol, propylene glycol, xylitol, and the like, are additionally subjected to defunctionalization the reactions deoxyadenosine to get oxygenates, such as alcohols, ketones, aldehydes, furans, diols, triola, hydroxycarbonate acid and carboxylic acid and intended for use in subsequent condensation reactions. Figure 3 illustrates the different ways of reactions involved in deoxyadenosine sorbitol to obtain oxygenates and hydrogen RVF. As you can imagine in the General case, without limitation to any particular theory, the reaction of deoxyadenosine include a combination of various different reaction pathways, including without limitation: reactions hydrodeoxygenation, serial dehydration-hydrogenation, hydrogenolysis, hydrogenation and dehydration, which may lead to the removal of oxygen from oxygenating hydrocarbons with the formation of hydrocarbon molecules, opisyvayuschaya General formula C1+O1-3.

The resulting oxygenates turn in4+compounds by condensation. As you can imagine, without limitation to any particular theory, the reaction of the acid condensation in common with what you learn consist of a sequence of stages, including: (a) dehydration of oxygenates to form olefins; (b) oligomerization of olefins; (C) reaction of cracking; (d) cyclization of larger olefins with the formation of aromatics; (e) isomerization of paraffin; and (f) reaction with the transfer of a hydrogen atom with the formation of paraffins. As you can imagine the reaction of the primary condensation in the General case consists of a sequence of stages, including: (1) aldorino condensation with the formation of β-hydroxyketone or β-hydroxyaldehyde; (2) dehydration of β-hydroxyketone or β-hydroxyaldehyde with the formation of conjugated northward; (3) hydrogenation of the conjugated northward with the formation of ketone or aldehyde, which may participate in subsequent condensation reactions or transformations in alcohol or hydrocarbon; and (4) hydrogenation of CARBONYLS with the formation of alcohols, or Vice versa. As you can imagine the reaction of acid-base condensation generally include any of the preceding stages acidic and/or basic reactions.

In certain embodiments of the implementation of the condensation reaction proceed at typical temperatures and pressures condensation. However, in various embodiments, the implementation of more favourable may also be carrying out condensation reactions under conditions of temperature and/or pressure, which are elevated in comparison with t the m what takes place in the typical ways condensation. In General, the reactions of condensation at elevated conditions resulting in the receipt of unfavorable thermodynamics, which limits the degree of transformation in the condensation products. As shown by the present invention, carrying out the reaction using catalysts condensation and opissyvayusya lower temperatures and pressures eliminates these limitations and suddenly promotiom direct conversion of the condensation products to hydrocarbons, ketones and alcohols. Transformation, in turn, leads to the removal of the condensation products from the reaction mixture, thereby, eliminates restrictions on thermodynamics of the system, making possible the completion of additional condensation reactions. Elevated conditions of temperature and/or pressure also prevent excessive conversion of oxygenates directly to their corresponding hydrocarbons. The method is also characterized and additional benefit in ensuring the passage of reactions condensation reactions deoxyadenosine and reactions RVF in the same reactor and under steady-state equilibrium.

For any given reaction indicator of the ease of passage of the direct reaction is the change in free energy. The more negative will be to change off the ne energy the more favorable will be the reaction. In the reaction, associated with a large negative change in free energy, in the General case are favorable and have the potential for demonstrating high degrees of conversion in the reaction products. On the contrary, reactions associated with positive changes in free energy are not preferred and by their very nature are limited in regard to the extent to which reactants are transformed into products. By way of illustration, figure 4 shows the change of free energy associated with the stages along the reaction path for the conversion of acetone and hydrogen in the C6hydrocarbon (2-methylpentane) and water at 100°C and 400°C. the Known levels of free energy for a stable intermediate compounds produced during a given path, shown as a solid line. The first stage of the reaction path is aldorino condensation of two molecules of acetone with the formation of one molecule diacetone alcohol. Reaction at a lower temperature (100°C) is characterized by the change in free energy is 53 kJ/mol and is thermodynamically favorable, while the reaction at higher temperature (400°C) is less favorable due to the change in free energy of 10 kJ/mol. Have in mind that the maximum grade is converting pure acetone in datetoday alcohol for this stage decreases with increasing temperature (from more than 99% of theoretical maximum degree of conversion at 100°C and atmospheric pressure to only 15% at 400°C and atmospheric pressure). In line with this, the limit of thermodynamic equilibrium generates an absolute limit to the amount diacetone alcohol, which can be obtained under specified conditions and in the absence of other reactions. This is further illustrated in figure 5, which represents the equilibrium constants associated with the intermediate reaction products and a total transformation in the case of the reaction between 2 moles of acetone and 3 moles of hydrogen to produce 1 mole of 2-methylpentane and 2 moles of water. As you can see, the equilibrium constant for the conversion of acetone in datetoday alcohol by increasing the temperature decreases.

The present invention circumvents this problem by the direct transformation of the product of condensation in the connection, which provides more favorable reaction medium. In the above case, the result of the removal diacetone alcohol from the reaction mixture by the reaction of dehydration, which forms mesityloxide, you may receive an additional amount diacetone alcohol. In particular, combination in the form of a stage of condensation and dehydration to obtain mesityloxide and water from acetone results in n is much more favorable reaction medium. As illustrated in figure 5, the degree of conversion of acetone in mesityloxide and the water is somewhat more favorable at higher temperatures.

The total pressure of the reaction system also has a beneficial effect on the maximum theoretical degree to which the reagent can form the product. Considering the above example the condensation reaction, the degree of conversion of acetone in datetoday alcohol is limited to the value of 15% at 400°C and atmospheric pressure for feedstock in the form of pure acetone. As a result of increasing pressure system to a pressure of 600 lb/in2(wt.) (4140 kPa (psig) the equilibrium degree of conversion is shifted so that at the same temperature could be achieved, the degree of transformation that goes up to 76%. In the case of reactions, demonstrating the resulting decrease in the number of moles of product in comparison with the number of moles of reagent, increasing the pressure of the system (while keeping all other conditions constant) will lead to an increase in the equilibrium degree of conversion in the product. For the total conversion of ketones to hydrocarbons usually occurs resulting decrease in the number of moles of product in comparison with the number of moles of reactant, thus, a higher pressure reactions which will lead to a higher equilibrium potential degrees of transformation.

The method of producing a component made of a water-soluble oxygenating hydrocarbon in the present invention, achieves a balance with the above thermodynamic constraints as a result of operation when using condensation catalysts and conditions for temperature and pressure, to compensate for any reduction in production of the condensation products increase the degree of conversion into other products, for processes located along the process stream further. The kinetics of the total system is also more favorable, so that products can be obtained continuously and with more desirable speed. In regard to the scale of production, after startup of the reactor system can be controlled by the method, and the reaction could proceed at a stationary equilibrium.

Oxygenates With4+connections are made from oxygenates. In accordance with the usage in this document in respect of the method of producing a component made of a water-soluble oxygenating hydrocarbons, oxygenates in the General case, denote hydrocarbon compounds containing 1 or more carbon atoms and from 1 to 3 oxygen atoms, (herein denoted as C1+O1-3hydrocarbons, such as alcohols, ket is Bered, aldehydes, furans, hydroxycarbonate acid, carboxylic acids, diols and trioli. Preferably the oxygenate blends contain from 1 to 6 carbon atoms or from 2 to 6 carbon atoms or 3 to 6 carbon atoms. The alcohols may include, without limitation, primary, secondary, linear, branched or cyclic C1+alcohols, such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, butanol, pentanol, Cyclopentanol, hexanol, cyclohexanol, 2-methylcyclopentanone, heptanol, octanol, nonanol, decanol, undecanol, dodecanol and their isomers. The ketones may include, without limitation, hydroxyketone, cyclic ketones, diketones, acetone, propanone, 2-oxopropanal, butanone, butane-2,3-dione, 3-hydroxybutyl-2-it, pentanone, Cyclopentanone, pentane-2,3-dione, pentane-2,4-dione, hexane, cyclohexanone, 2-methylcyclopentanone, heptanone, octanone, nonanone, decane, undecane, dodecane, methylglyoxal, butandiol, pentandiol, diclohexal and their isomers. The aldehydes may include, without limitation, hydroxyaldehyde, acetaldehyde, Propionaldehyde, Butyraldehyde, pentanal, hexanal, heptanal, octanal, nonal, decanal, undecanal, dodecanal and their isomers. Carboxylic acids can include, without limitation formic acid, acetic acid, propionic acid, butane acid, pentanesulfonate, hexanoic acid, heptane acid, their isomers and derivatives, including gidroksilirovanii derivatives, such as 2-hydroxybutanoic acid and lactic acid. Diols may include without limitation ethylene glycol, propylene glycol, 1,3-propandiol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanol, dodecanol and their isomers. Triodes can include without limitation, glycerol, 1,1,1-Tris(hydroxymethyl)ethane(trimethyllead), trimethylolpropane, hexanetriol and their isomers. Furans, furfural include, without limitation, furan, tetrahydrofuran, dihydrofuran, 2-furanmethanol, 2-methyltetrahydrofuran, 2.5-dimethyltetrahydrofuran, 2-methylfuran, 2-utilityserver, 2-ethyl furan, hydroxymethylfurfural, 3-hydroxymitragynine, tetrahydro-3-furanol, 2.5-dimethylfuran, 5-hydroxymethyl-2(5H)-furanone, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydropyrazolo acid, dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydrofurfuryl alcohol, 1-(2-furyl)stanol, hydroxymethylfurfural and their isomers.

The oxygenates may have its origin from any source, but preferably they are produced from biomass. In accordance with the usage in this document, the term "biomass" refers without limitation to the organic materials produced by plants, such as whether the Thiey the roots, seeds and stalks) and end products of metabolism in microbes and animals. Common sources of biomass include: (1) agricultural wastes such as corn stalks, straw, peel and seeds, remnants of the sugar cane, bagasse, nutshell and manure from cattle, poultry and pigs; (2) wood materials, such as wood or bark, sawdust, wood residues sawnwood and factory scrap; (3) municipal waste such as paper waste and yard waste; and (4) plants for energy use, such as poplar, willow, switchgrass, alfalfa, Prairie Falcon, corn, soybeans and the like. This term also refers to the main structural elements of the above-mentioned sources, namely, inter alia, sugars, lignin, cellulose polymers, hemicellulose and starch.

Oxygenates from biomass can be obtained by any known method. Such methods include, without limitation, fermentation technology that uses enzymes and micro-organisms, the reaction of the Fischer-Tropsch process to obtain2-10alpha-alcohols and technology of pyrolysis to obtain alcohols from petroleum. In one embodiment, oxygenates the benefits of using technology catalytic reforming, such as technology BioForming™, developed the th company Virent Energy Systems, Inc. (Madison, Wisconsin). Oxygendemand hydrocarbons

In one embodiment, the oxygenates are produced by the method of catalytic reforming of oxygenated hydrocarbons. Oxygendemand hydrocarbons can be any water-soluble oxygendemanding hydrocarbon containing one or more carbon atoms and at least one oxygen atom (herein denoted as C1+O1+hydrocarbons). Preferably oxygenated hydrocarbon contains from 2 to 12 carbon atoms (C1-12O1-11and hydrocarbon), and more preferably from 2 to 6 carbon atoms (C1-6O1-6hydrocarbon). Oxygenated hydrocarbon can also be characterized quantitatively by the ratio of oxygen to carbon in the range from 0.5:1 to 1.5:1, including ratios 0,75:1,0, 1,0:1,0, 1,25:1,0, 1,5:1,0 and other intermediate ratio. In one example, the oxygenated hydrocarbon is characterized by the quantitative ratio of oxygen to carbon of 1:1. Non-limiting examples of preferred water-soluble oxygenated hydrocarbons include monosaccharides, disaccharides, polysaccharides, sugars, polyalcohols, xylytol, validity, ethanediol, atention, acetic acid, propanol, propandiol, propionic acid, glycerol, glyceraldehyde, dihydroxyacetone, lactic acid is one pyruvic acid, malonic acid, butanediol, butane acid, aldosterone, tartaric acid, aldopentose, hexoses, katoteros, cetainty, ketohexose, validity, hemicellulose, cellulose derivatives, lignocellulosic derivatives, starches, polyols and the like. Preferably, the oxygenated hydrocarbon comprises sugars, polyalcohols, xylytol, sugars and other polyols. More preferably, the oxygenated hydrocarbon is a sugar, such as glucose, fructose, sucrose, maltose, lactose, mannose or xylose, or sugar alcohols, such as Arabic, aritra, glycerol, isomalt, lactic, ▫ maltitol, mannitol, sorbitol, xylitol, ribitol or glycol.

Oxygendemand hydrocarbons must also identify and include alcohols produced by hydrogenation or hydrogenolysis of any representatives of the above. In certain embodiments of the preferred implementation may be the transformation of the original oxygenating hydrocarbon in another form oxygenating hydrocarbon, which may be easier converted into the desired oxygenates (e.g., primary, secondary, tertiary or polyhydric alcohols). For example, some sugar can turn into oxygenates as effectively as their respective derivatives, sugar alcohols the century What is desired, therefore may be the transformation of the source material, such as sugar, furfural, carboxylic acid, ketone, or furan, its corresponding alcohol derivative, such as by hydrogenation, or molecules of lower alcohols, for example, by hydrogenolysis.

As for the hydrogenation of Sugars, furfurals, carboxylic acids, ketones and furans to obtain the corresponding alcohol form, known various methods, including those that are described by the authors: W. S. Kwak et al. (publication WO 2006/093364 A1 and WO 2005/021475A1) - enable obtaining derivatives of Sugars alditol of monosaccharides in the hydrogenation over ruthenium catalyst; and Elliot et al. (U.S. patent No. 6253797 and 6570043) - description of use do not contain Nickel and rhenium ruthenium catalyst on the carrier, more than 75%, consisting of rutile titanium dioxide, for the conversion of Sugars into polyalcohols, xylytol, all of which are incorporated by reference herein. Other suitable ruthenium catalysts are described by the authors Arndt et al. in published patent application U.S. 2006/0009661 (filed December 3, 2003), and Arena in U.S. patent No. 4380679 (filed April 12, 1982), 4380680 (filed may 21, 1982), 4503274 (filed August 8, 1983), 4382150 (filed January 19, 1982) and 4487980 (filed April 29, 1983), all of which through the links included in this document.The catalytic hydrogenation in General includes Cu, Re, Ni, Fe, Co, Ru, Pd, Rh, Pt, Os, Ir and their alloys, or a combination, either individually or jointly with promoters, such as W, Mo, Au, Ag, Cr, Zn, Mn, Sn, b, P, Bi, and alloys or combinations. The hydrogenation catalyst may also include any one of the carriers, in addition opissyvayusya below and depending on the desired functionality of the catalyst. Other effective materials hydrogenation catalysts include or supported on a carrier, Nickel, or ruthenium-modified rhenium. In the General case, the hydrogenation reaction is carried out at a temperature of hydrogenation in the range from approximately 80°C to 250°C and pressures of hydrogenation in the range from about 100 lb/in2(wt.) (689 kPa (psig) up to 2000 lb/in2(wt.) (13800 kPa (psig). The hydrogen used in the reaction may include N2received in place, external H2N2sent for recycling, or a combination of both.

The hydrogenation catalyst may also include supported on a carrier, the catalyst based on a metal from group VIII and a metal sponge material such as sponge Nickel catalyst. A well-known class of materials that are effective for various hydrogenation reactions, activated form of sponge Nickel catalysts (e.g., Raney Nickel). One type of sponge Nickel catalyst is a catalyst which type A, available in the company Activated Metals and Chemicals, Inc., Sevierville, Tennessee. Catalyst type A is promoted molybdenum catalyst, typically containing about 1.5% molybdenum and 85% Nickel. The use of sponge Nickel catalyst together with the feedstock containing xylose and dextrose, is described by the authors M. L. Cunningham et al. in the publication US 6,498,248, filed September 9, 1999 and by reference incorporated herein. The use of a catalyst based on Raney Nickel together with hydrolyzed corn starch is also described in the publication US 4,694,113 filed June 4, 1986 and by reference incorporated herein.

Obtain a suitable hydrogenation catalysts based on Raney Nickel is described by the authors A. Yoshino et al. in published patent application U.S. 2004/0143024, filed November 7, 2003 and by reference incorporated herein. The catalyst based on Raney Nickel can be obtained by processing the alloy is approximately equal to the mass amounts of Nickel and aluminium aqueous alkaline solution, for example containing about 25% (mass.) of sodium hydroxide. Aluminium under the action of aqueous alkaline solution to selectively dissolved, leaving particles, having a sponge-like structure and is mainly formed of Nickel, not the main amount of aluminum. In the initial alloy may also be included promoter metals, such as molybdenum or chromium, in an amount such that sponge Nickel catalyst would remain approximately 1-2% (mass.).

In yet another embodiment, the hydrogenation catalyst produced by impregnating a suitable material carrier solution nitrosylated ruthenium (III), nitrosylated ruthenium (III) or ruthenium chloride (III) in water to obtain a solid substance, which is then dried for 13 hours at 120°C in a rotating ball furnace (residual water content is less than 1% (mass.)). Then the solid substance recover at atmospheric pressure in a stream of hydrogen at 300°C (without annealing) or 400°C (annealing) for 4 hours in a rotating ball furnace. After cooling and make the inertness of nitrogen, the catalyst can then be passivated in the by-passing over it 5% (vol.) oxygen in nitrogen over a period of time with a duration of 120 minutes.

In yet another embodiment, the hydrogenation reaction carried out using a catalyst comprising a Nickel-rhenium catalyst or Nickel catalyst modified with tungsten. One example of a suitable hydrogenation catalyst is a composition of Nickel-re is avago catalyst, deposited on a carbon carrier, vpisivaushiesya authors Werpy et al. in the publication US 7,038,094, filed September 30, 2003 and incorporated by reference in this document.

In other embodiments, the implementation of desirable may also be a transformation of the original oxygenating hydrocarbon, such as sugar, sugar alcohols or other polyhydric alcohol, a smaller molecule that can easily be converted into the desired oxygenates, as hydrogenolysis. These smaller molecules can include primary, secondary, tertiary or polyhydric alcohols containing fewer carbon atoms than the original oxygenated hydrocarbon. As for such reactions, hydrogenolysis, known in their various ways, including those that describe: the authors Werpy et al. in U.S. patent No. 6479713 (filed October 23, 2001), 6677385 (filed August 6, 2002), 66841085 (filed October 23, 2001) and 7083094 (filed September 30, 2003), all of which are incorporated by reference in this document and describe the hydrogenolysis containing 5 to 6 carbon atoms Sugars and polyalcohols, xylytol to obtain propylene glycol, ethylene glycol and glycerol using registertimer polymetallic catalyst. Other systems include those that are described by the author Arena in U.S. patent No. 4401823 (filed may 18, 1981), therefore, the priority for the use of carbon pyropolymer catalyst, containing transition metals (such as chromium, molybdenum, tungsten, rhenium, manganese, copper, cadmium) or metals from group VIII such as iron, cobalt, Nickel, platinum, palladium, rhodium, ruthenium, iridium and osmium), to obtain alcohols, acids, ketones and ethers of polyhydroxylated compounds, such as sugars and polyalcohols, xylytol, and in U.S. patent No. 4496780 (filed June 22, 1983) related to the use of the catalyst system, containing a noble metal from group VIII on a solid carrier together with the oxide of the alkali earth metal, to produce glycerol, ethylene glycol and 1,2-propane diol from carbohydrates, with each of them by reference is incorporated herein. Another system includes the one that is described by the authors Dubeck et al. in U.S. patent No. 4476331 (filed September 6, 1983) related to the use of modified ruthenium sulfide catalyst to obtain ethylene glycol and propylene glycol from larger polyhydric alcohols, such as sorbitol, and also by reference incorporated herein.Other systems include those described in the publication Saxena et al., "Effect of Catalyst Constituents on (Ni, Mo and Cu)/Kieselguhr-Catalyzed Sucrose Hydrogenolysis", Ind. Eng. Chem. Res. 44, 1466-1473 (2005), describing the use of Ni, W and Cu on kieselguhr carrier and by reference incorporated herein.

In one embodiment, the hydrogenolysis catalyst comprises Cr, Mo, W, Re, Mn, Cu, Cd, Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir or Os and their alloys, or a combination, either individually or jointly with promoters, such as Au, Ag, Cr, Zn, Mn, Sn, Bi, In, and their alloys, or a combination. Other effective materials of catalysts in the hydrogenolysis may include the above-mentioned metals, combined with the oxide of the alkali earth metal or adhering to a catalytically active carrier such as diatomaceous earth, or any one of the carriers, in addition opissyvayusya below.

Technological conditions for carrying out the hydrogenolysis reaction will vary depending on the type of feedstock and the desired products. In the General case, the hydrogenolysis reaction is carried out at a temperature equal to at least 110°C. or in the range from 110°C to 300°C or 170°C. to 240°C. the Reaction should be carried out in basic conditions, preferably at pH values in the range of from about 8 to about 13, or when the pH value in the range from about 10 to about 12. The reaction should also be carried out at pressures in the range of from about 10 lb/in2(wt.) (for 68.9 kPa (psig) up to 2400 lbs/inch2(wt.) (16500 kPa (psig) or from about 250 lb/in2(wt.) (1720 kPa (psig) up to 2000 lb/in2(wt.) (13800 kPa (wt.) or from about 700 lb/in 2(wt.) (4830 kPa (psig) up to 1600 lb/in2(wt.) (11000 kPa (psig).

The hydrogen used in the reaction may include Hz obtained in place, external H2N2sent for recycling, or a combination of both.

Getting oxygenates

Oxygenates are synthesized by carrying out reaction between aqueous solution of raw materials containing water and water soluble oxygendemand hydrocarbons, and hydrogen on the catalytic material to obtain the desired oxygenates. Preferably the hydrogen is produced in place when using a reformer in the aqueous phase (H2received "on the spot", or H2RVF), or it is a combination of N2RVF, external H2or H2sent to recycling, or just external H2or H2sent to recycling. The term "external H2"refers to hydrogen, which does not have its origin a solution of raw materials, but which is added in the reactor system from an external source. The term "H2sent to recycling" refers to the unspent hydrogen, which in its origin is the solution of raw materials, and which is collected and then sent back for recycling in the reactor system for later use. External N2and H2sent to recycling, also may be collectively or individually called "additional H 2". In the more General case of H2can be added to Supplement the hydrogen RVF or for substitution include stage hydrogen RVF or to increase the pressure of the reaction system or to increase the molar ratio between hydrogen and carbon and/or oxygen in order to improve the yield in the form of certain types of reaction products, such as ketones and alcohols.

In ways, using H2RVF, oxygenates receive as a result of carrying out catalytic reactions for a portion of the aqueous feedstock containing water and water soluble oxygendemand hydrocarbons, in the presence of a catalyst RVF when the temperature of the reformer and the pressure of the reformer to obtain H2RVF and catalytic reaction between the H2RVF (and H2sent to recycling, and/or external H2and part of the solution of the feedstock in the presence of a catalyst of deoxyguanosine at a temperature of deoxyadenosine and pressure deoxyadenosine to obtain the desired oxygenates. In systems that use as a source of hydrogen (H2sent to recycling or external H2, oxygenates just get in the catalytic reaction between the H2sent to recycling, and/or external H2and the solution of the feedstock in the presence the AI catalyst deoxyguanosine at temperatures and pressures deoxyadenosine. In each of the above cases, the oxygenates may also include oxygenate sent to recycling, (C1+O1-3the hydrocarbons are sent to recycling). Unless other specified, then any discussion of catalysts RVF and catalysts deoxyadenosine will represent non-limiting examples of suitable catalytic materials.

The catalyst deoxyadenosine is preferably a heterogeneous catalyst comprising one or more materials capable of catalyzing the passage of the reaction between hydrogen and oxygendemanding hydrocarbon in order to remove one or more oxygen atoms from oxygenating hydrocarbon to obtain alcohols, ketones, aldehydes, furans, carboxylic acids, hydroxycarbonic acids, diodes and triolo. In General, the materials will adhere to the media, and may include without limitation, Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, and their alloys and combinations. Catalyst deoxyadenosine may include data elements individually or in combination with one or more representatives from Mn, Cr, Mo, W, V, Nb, TA, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, and combinations thereof. In one embodiment, the catalyst deoxyadenosine includes Pt, Ru, si, Re, Co, Fe, Ni, W or Mo. In yet another embodiment, the catalyst dioxygenyl the cation comprises Fe or Re and, at least one transition metal selected from Ir, Ni, Pd, P, Rh and Ru. In yet another embodiment, the catalyst comprises Fe, Re and at least Cu or one transition metal from group VIIIB. The carrier may be any one of the carriers, in addition opissyvayusya below, including a nitride, carbon, silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, vanadium oxide, cerium dioxide, zinc oxide, chromium oxide, boron nitride, heteroalicyclic, kieselguhr, hydroxyapatite, and mixtures thereof. Catalyst deoxyadenosine can also be atomically identical to the catalyst RVF or condensation catalyst.

The catalyst deoxyadenosine can also be bifunctional catalyst. For example, acidic media (e.g. media, characterized by low isoelectric points) capable of catalyzing the passage of the dehydration reactions of oxygenated compounds with subsequent passage of hydrogenation reactions on the active sites of metal catalysts in the presence of N2that again leads to carbon atoms that are not bound to atoms of oxygen. Bifunctional path dehydration/hydrogenation spends H2and leads to the subsequent formation of various polyols, diols, ketones, aldehydes, alcohols and cyclic ethers, such as f is wound and Pirani. Examples of catalysts include wallpaperjohnny Zirconia, Titania-Zirconia, sulfated Zirconia, acidic alumina, silica-alumina, zeolites and heteropolyanions media. Heteroalicyclic are a class of solid-phase acids, examples of which are substances such as H3+xPMo12-xVxO40H4SiW12O40H6PW12O40and H6P2W18O62. Heteroalicyclic represent a solid acid having a well-defined local structure, the most common of which is the structure of Keggin on tungsten basis.

The load of the first element (i.e., si, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, alloys thereof and combinations) is in the range from 0.25% (wt.) up to 25% (mass.) on the carbon with the inclusion of intermediate mass percentages in increments of 0.10°/o and 0.05%, such as 1,00%, 1,10%, 1,15%, 2,00%, 2,50%, 5,00%, 10,00%, 12,50%, 15,00% and 20.00%. The preferred quantitative atomic ratio for the second element (i.e., Mn, Cr, Mo, W, V, Nb, TA, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, and combinations thereof) is in the range from 0.25: 1 to 10: 1, including any intermediate ratio is such as to 0.50, and 1.00, of 2.50 to 5.00 and 7.50 to 1. In the case of harassment of the catalyst to the carrier the combination of rolled atora and media will include from 0.25% (wt.) up to 10% (mass.) the primary element.

Upon receipt of oxygenates oxygenated hydrocarbons combine with water to obtain an aqueous solution of the feedstock having a concentration effective to promote formation of the desired reaction products. The ratio between water and carbon per mole preferably is in the range from about 0.5:1 to about 100: 1, including ratios, such as 1:1,2:1,3:1,4:1,5:1,6:1,7:1,8:1,9:1,10:1,15:1,25:1,50:1,75:1,100:1 and any intermediate ratio. The solution of the feedstock can also be characterized as a solution comprising at least a 1.0 mass percent (% (mass.)) of the total solution as oxygenating hydrocarbon. For example, the solution may include one or more oxygenated hydrocarbons, while the total concentration of oxygenated hydrocarbons in the solution is at least about 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% (mass.) and more, when the inclusion of any intermediate percentage and depending on the used of oxygenated hydrocarbons. In one embodiment, the solution of the feedstock includes at least approximately 10%, 20%, 30%, 40%, 50% or 60% (mass.) sugar, such as glucose, fructose, sucrose or xylose, or sugar alcohols such as sorbitol, mannitol, glycerol or xylitol. Also includes the share of the public ratio between water and carbon and percentages are outside the above ranges. Preferably the carrying component of the solution of the original material is water. In some embodiments, the implementation of the solution raw material consists essentially of water, one or more oxygenated hydrocarbons, and optionally one or more modifiers of raw materials, opissyvayusya in this document, such as hydroxides of alkali metals or salts of alkaline or alkaline earth metals or acids. The solution of the feedstock may also include sent for recycling oxygendemand hydrocarbons sent to recycling of the reactor system. The solution of the feedstock may also contain negligible amounts of hydrogen, preferably less than about 1.5 mol of hydrogen to one mole of the starting material. In preferred embodiments, the implementation of hydrogen in the solution of the initial raw material is not added.

The solution of the feedstock is introduced into reaction with hydrogen in the presence of a catalyst of deoxyadenosine under conditions of temperature and pressure deoxyadenosine and mass hourly flow rate, effective to obtain the desired oxygenates. Specific derived oxygenates will depend on various factors, including the solution of raw materials, reaction temperature, pressure, reaction, concentration of water, the concentration of water is an ode, the reactivity of the catalyst and the solution flow rate of the feedstock, because it affects the volumetric rate (mass/volume of reagent per unit of catalyst per unit time), the gas hourly space velocity (GCOS) and mass hourly space velocity (MCOS). For example, the increase over time of consumption, thereby reducing the impact on the feedstock, catalysts will reduce the degree of completion of the reactions that can occur, thus, will lead to increased output for higher diodes and triolo decreasing outputs for ketones and alcohols.

The temperature and pressure deoxyadenosine preferably chosen ensures keeping at least part of the feedstock in the state of liquid phase at the inlet hole of the reactor. However, it is recognized that the conditions of temperature and pressure can also be selected for a more favorable deliver the desired products in the vapor phase. In the General case, the reaction should be conducted in technological terms, when thermodynamics of the proposed reaction is favorable. For example, the minimum pressure required to bear part of the feedstock in the state of liquid phase is likely to vary depending on the reaction temperature. With increasing temperature the R-keeping of raw materials in the state of liquid phase in General, if you desire require a higher pressure. Suitable operating conditions are also pressure greater than that which will be required for the keeping of raw materials in the state of liquid phase (i.e., vapor phase).

In liquid reactions in the condensed phase the pressure in the reactor must be sufficient to withstand reagents in the state of the condensed liquid phase at the inlet hole of the reactor. For liquid-phase reactions, the reaction temperature may be in the range of approximately 80°C to 300°C and pressure of the reaction is from about 72 lb/in2(wt.) (496 kPa (psig) up to 1300 lb/in2(wt.) (8960 kPa (psig). In one embodiment, the reaction temperature is in the range from about 120°C to 300°C or from about 200°to 280°C., or from about 220°C to 260°C and pressure of the reaction is preferably in the range from approximately 72 to 1200 lb/in2(wt.) (from 496 to 8270 kPa (psig) or from about 145 to 1200 lb/in2(wt.) (from 1000 to 8270 kPa (psig) or from about 200 to 725 lb/in2(wt.) (from 1380 to 5000 kPa (psig) or from about 365 to 700 lb/in2(wt.) (from 2520 to 4830 kPa (psig) or approximately 600 to 650 lbs/inch (wt.) (from 4140 to 4480 kPa (psig).

In the case of vapor-phase reactions, the reaction must be conducted at a temperature at which the vapor pressure oxigenio the spent hydrocarbon is at least about 0.1 ATM (and preferably much more), and thermodynamics of the reaction is favorable. This temperature will vary depending on the particular used oxygenating hydrocarbon compounds, but in General for vapor-phase reactions is in the range from about 100°C. to 600°C. Preferably the reaction temperature is in the range from about 120°to about 300°C. or from about 200°to about 280°C. or from about 220°C. to about 260°C.

In yet another embodiment, the temperature deoxyadenosine is in the range from about 100°C to 400°C or from about 120°C to 300°C or from about 200°C to 280°C and pressure of the reaction is preferably in the range from approximately 72 to 1300 lb/in2(wt.) (496 8,960 kPa (psig) or from about 72 up to 1200 lbs/inch (wt.) (from 496 to 8270 kPa (psig) or from about 200 to 725 lb/in2(wt.) (from 1380 to 5000 kPa (psig) or from about 365 to 700 lb/in2(wt.) (from 2520 to 4830 kPa (psig).

The method using the condensed liquid phase can also be realized using a modifier that increases the activity and/or stability of the catalyst. Is preferred that the water and the oxygenated hydrocarbon has entered into reaction with a suitable pH value in the range from approximately 1.0 to approximately 10.0, including intermediate pH values in increments of 0.1 and 0.05, and more preferably at a pH value in the range of approximately 4.0 to approximately 10.0. In the General case modifier to the solution of the initial raw material is added in amounts ranging from about 0.1% to about 10% (mass.) in comparison with the total mass of the system used catalyst, although in the present invention are included and the number outside this range.

In the General case, the reaction must be performed under conditions in which the residence time of the solution of raw materials on the catalyst will be appropriate to obtain the desired products. For example, the value MCOS for the reaction may be at least about 0.1 gram oxygenating hydrocarbon per gram of catalyst per hour, and more preferably is MCOS is in the range of approximately from 0.1 to 40.0 g/g-h, including the value MCOS approximately 0,25, 0,5, 0,75, 1,0, 1,0, 1,1, 1,2, 1,3, 1,4, 1,5, 1,6, 1,7, 1,8, 1,9, 2,0, 2,1, 2,2, 2,3, 2,4, 2,5, 2,6, 2,7, 2,8, 2,9, 3,0, 3,1, 3,2, 3,3, 3,4, 3,5, 3,6, 3,7, 3,8, 3,9, 4,0, 4,1, 4,2, 4,3, 4,4, 4,5, 4,6, 4,7, 4,8, 4,9, 5,0, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40 g/g-HR.

The hydrogen used in the reaction of deoxyadenosine, preferably represents H2received in place, but may also be an external and H2or H2sent is on recycling. In the presence of external H2its amount is preferably served sparingly. Most preferably the number of external H2served in amounts that provide less than one hydrogen atom, one oxygen atom in all of oxygenated hydrocarbons in the stream of the feedstock prior to introduction into contact with the catalyst deoxyadenosine. For example, the molar ratio between the external H2and total soluble oxygendemanding hydrocarbons in the solution of the feedstock preferably choose providing that no more than one hydrogen atom, one oxygen atom in oxygeneration hydrocarbon. The molar ratio between oxygendemanding hydrocarbons in the feedstock and external H2introduced in the feedstock, is also preferably is not greater than 1:1, or more preferably goes up to 2:1,3:1,5:1,10:1,20:1 and more (including 4:1,6:1,7:1,8:1,9:1,11:1,12:1,13:1,14:1,15:1,16:1,17:1,18:1 and 19:1). The amount (moles) external H2introduced in the feedstock, is 0-100%, 0-95%, 0-90%, 0-85%, 0-80%, 0-75%, 0-70%, 0-65%, 0-60%, 0-55%, 0-50%, 0-45%, 0-40%, 0-35%, 0-30%, 0-25%, 0-20%, 0-15%, 0-10%, 0-5%, 0-2% or 0-1% of the total number of moles oxygenating hydrocarbons (hydrocarbons) in the feedstock, including all intermediate intervals. In the case of the introduction of a solution of raw materials or any of the th part in the reaction with hydrogen RVF and external Hz molar ratio between hydrogen RVF and external H 2will be at least, 1:20,1:15,1:10,1:5,1:3,1:2,1:1,2:1,3:1,5:1,10:1,15:1,20:1 and intermediate ratios (including 4:1,6:1,7:1,8:1,9:1,11:1,12:1,13:1,14:1,15:1,16:1,17:1,18;1 and 19:1 and the facing ratio). Preferably, the oxygenated hydrocarbon is introduced into the reaction with H2in the presence of a minor effective amount of external H2.

The number of added external H2(or more H2) can be calculated considering the concentration of oxygenated hydrocarbons in the solution of the feedstock. Preferably the amount of added external H2is to provide a molar ratio between the oxygen atoms of oxygenated hydrocarbons and hydrogen atoms (i.e., 2 atoms of oxygen in one molecule of gaseous H2), less than or equal to 1.0. For example, in the case of raw materials in the form of an aqueous solution of glycerin (3 atoms of oxygen), the number of extra added to the feedstock, preferably is not more than about 1.5 mol H2on one mol of glycerol (C3H8About3), and preferably not more than about 1.25, and 1.0 to 0.75, and 0.50 or 0.25. In General, the amount of added H2is smaller than the number that corresponds with a ratio of 0.75, and more preferably not Bo isim, than the number that corresponds with multiplicity 0,67, 0,50, 0,33, 0,30, 0,25, 0,20, 0,15, 0,10, 0,05, 0,01 the total number of H2(H2RVF and external H2), which would provide for quantitative atomic ratio between the atoms of oxygen and hydrogen is 1:1.

The number of H2RVF in the reactor can be identified or detected by any suitable method. The number of H2RVF can be determined from the composition of the product stream, depending on the composition of the flow of raw materials, compositions (compositions) of the catalyst and reaction conditions, regardless of the actual mechanism of the reaction observed in the flow of the feedstock. The number of H2RVF can be calculated based on the catalyst, reaction conditions (e.g., flow, temperature, pressure and the like) and the content of the feedstock and reaction products. For example, the feedstock can be introduced into contact with the catalyst RVF (e.g., platinum) to obtain H2RVF in place and the first stream of reaction products in the absence of catalyst deoxyadenosine. The feedstock can also be put into contact with a catalyst RVF and catalyst deoxyguanosine for receiving the second flow of the reaction products. As a result of comparison of the compositions of the first flow cont the mswb reactions and the second stream of reaction products at comparable reaction conditions it is possible to identify the presence of H 2RVF and calculate the amount of H2RVF, for Example, increasing the number of oxygenated compounds, characterized by high degrees of hydrogenation, the reaction product in comparison with the components of the feedstock may indicate the presence of H2RVF.

Production of hydrogen "on-site"

One advantage of the method of producing a component made of a water-soluble oxygenating hydrocarbon, in the present invention is that it provides the collection and use of H2received "on the spot". H2RVF is produced from the feedstock at reforming conditions in the aqueous phase when using the reforming catalyst in the aqueous phase (catalyst RVF). Catalyst RVF is preferably a heterogeneous catalyst capable of catalyzing the completion of the reaction water and oxygenated hydrocarbons with the formation of H2in opissyvayusya following conditions. In one embodiment, the catalyst RVF includes a carrier and at least one metal from group VIIIB, Fe, Ru, Os, Ir, Co, Rh, Pt, Pd, Ni, and their alloys and combinations. The catalyst RVF may also include at least one additional material from metals of group VIIIB, group VIIB, group VIB, group VB, group IVB, group IV, group IB, group IVA or group VA, such as Cu, B, Mn, Re, Cr, o, Bi, W, V, Nb, TA, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, their alloys and combinations. The preferred metal of group VIIB includes Re, Mn, or combinations thereof. The preferred metal of group VIB includes Cr, Mo, W or a combination of both. Preferred metals of group VIIIB include Pt, Rh, Ru, Pd, Ni or a combination of both. The media may include any one of opissyvayusya below catalysts carriers depending on the desired activity of the catalyst system.

The catalyst RVF can also be atomically identical to the catalyst deoxyadenosine or condensation catalyst. For example, the catalyst RVF and deoxyadenosine may include Pt, fused or mixed with Ni, Ru, Cu, Fe, Rh, Re, their alloys and combinations. The catalyst RVF and catalyst deoxyadenosine may also include Ru, fused or mixed with Ge, Bi, In, Ni, Sn, Cu, Fe, Rh, Pt, and their alloys and combinations. The catalyst RVF may also include Ni, fused or mixed with Sn, Ge, Bi, In, Cu, Re, Ru, Fe, and their alloys and combinations.

The preferred utilization of primary metal from group VIIIB is in the range from 0.25% (wt.) up to 25% (mass.) on the carbon with the inclusion of intermediate mass percentages in increments of 0.10% and 0.05%, such as 1,00%, 1,10%, 1,15%, 2,00%, 2,50%, 5,00%, 10,00%, 12,50%, 15,00% and 20.00%. The preferred quantitative atomic ratio of the second material is located the range from 0.25 to 1 to 10 to 1, including intermediate ratio is such as to 0.50, and 1.00, of 2.50 to 5.00 and 7.50 to 1.

Receiving one preferred composition of the catalyst is additionally achieved by adding oxides of elements of group IIIB and the respective rare earth oxides. In this case, the preferred components will be an oxide or lanthanum, or cerium. The preferred quantitative atomic ratio between the compounds of elements of group IIIB and the primary metal from group VIIIB is in the range from 0.25 to 1 to 10 to 1, including an intermediate ratio is such as to 0.50, and 1.00, of 2.50 to 5.00 and 7.50 to 1.

Another preferred catalyst composition is one which contains platinum and rhenium. The preferred quantitative atomic ratio of Pt and Re is in the range from 0.25 to 1 to 10 to 1, including an intermediate ratio is such as to 0.50, 1.00, it is 2.50, 5.00 and 7,00 to 1. The preferred loading level Pt is in the range from 0.25% (wt.) to 5.0% (wt.) when enabled, the intermediate mass percentages in increments of 0.10% and 0.05%. is such as 0,35%, 0,45%, 0,75%, 1,10%, 1,15%, 2,00%, 2,50%, 3,0% and 4.0%.

Preferably the catalyst RVF and catalyst deoxyguanosine have the same atomic composition. The catalysts can also have different compositions. In this case, the preferred number of the national atomic ratio of the catalyst RVF and catalyst deoxyadenosine is in the range from 5:1 to 1:5, for example, but not limited to, 4,5:1,4,0:1,3,5:1,3,0:1,2,5:1,2,0:1,1,5:1,1:1,1:1,5,1:2,0,1:2,5,1:3,0,1:3,5,1:4,0,1:4,5 and any intermediate values.

Like reactions deoxyadenosine conditions for temperature and pressure are preferably chosen ensures keeping at least part of the feedstock in the state of liquid phase at the inlet hole of the reactor. Conditions for temperature and pressure of the reformer can also be selected that provide a better obtain the desired products in the vapor phase. In General, the reaction RVF should be carried out at a temperature at which thermodynamics is favorable. For example, the minimum pressure required to bear part of the feedstock in the state of liquid phase will vary depending on the reaction temperature. With increasing temperature for keeping the original raw material in the state of liquid phase in the General case will require higher pressure. A suitable operating pressure is any pressure in excess of the pressure which is necessary for keeping the original raw material in the state of liquid phase (i.e., vapor phase). In the case of vapor-phase reactions, the reaction must be conducted at a temperature of the reformer when the vapor pressure oxygenating hydrocarbon compounds is, at least, will bring the flax 0.1 ATM (and preferably much more) and thermodynamics of the reaction is favorable. The temperature will vary depending on the particular used oxygenating hydrocarbon compounds, but generally is in the range from about 100°C to 450°C or from about 100°C to 300°C, for reactions in the vapor phase. In the case of liquid-phase reactions, the reaction temperature may be in the range of approximately 80°C to 400°C and pressure of the reaction is from about 72 lbs/inch (wt.) (496 kPa (psig) up to 1300 lb/in2(wt.) (8960 kPa (psig).

In one embodiment, the reaction temperature is in the range from about 100°C to 400°C or from about 120°C to 300°C or from about 200°to 280°C. or from about 150°C. to 270°C. the Pressure of the reaction is preferably in the range from approximately 72 to 1300 lb/in2(wt.) (496 8,960 kPa (psig) or from about 72 to 1200 lb/in2(wt.) (from 496 to 8270 kPa (psig) or from about 145 to 1200 lb/in2(wt.) (from 1000 to 8270 kPa (psig) or from about 200 to 725 lb/in2(wt.) (from 1380 to 5000 kPa (psig) or from about 365 to 700 lb/in2(wt.) (from 2520 to 4830 kPa (psig) or approximately 600 to 650 lb/in2(wt.) (from 4140 to 4480 kPa (psig).

The method using the condensed liquid phase so the e can be realized using the modifier, which increases the activity and/or stability of the catalyst RVF. Is preferred that the water and the oxygenated hydrocarbon has entered into reaction with a suitable pH value in the range from approximately 1.0 to 10.0 or when the pH value in the range from about 4.0 to 10,0, including intermediate values of pH in increments of 0.1 and 0.05. In the General case modifier to the solution of the initial raw material is added in amounts ranging from about 0.1% to about 10% (mass.) in comparison with the total mass of the system used catalyst, although in the present invention are included and the number outside this range.

To optimize the fraction of hydrogen in the reaction products in the solution of raw materials can also be added and salts of alkaline or alkaline earth metals. Examples of suitable water soluble salts include one or more representatives selected from the group consisting of hydroxide, salts of carbonic acid, nitric acid or chlorine-hydrogen acid of the alkali or alkaline earth metal. For example, add (basic) salts of alkali metals to obtain a pH in the range from about pH 4.0 to about pH 10,0 can improve the selectivity of the reforming reactions in hydrogen.

Adding acidic compounds also can supply the IC receiving in opissyvayusya following hydrogenation reactions increased selectivity for the desired reaction products. Water-soluble salt is preferred to choose from the group consisting of salts of nitric acid, phosphoric acid, sulfuric acid, chloride-hydrogen acid and mixtures thereof. In the case of acidic modifier is preferred to exist in sufficient quantity to reduce the pH of the stream water of the raw materials to values in the range from about pH 1.0 to about pH 4.0. The decrease in the pH value of the flow of raw materials in this way can increase the proportion of oxygenates in the final reaction products.

In the General case, the reaction should be conducted under conditions in which the residence time of the solution of raw materials for the catalyst RVF will be adequate to get the number of hydrogen RVF, sufficient for the reaction with the second part of the solution of raw materials for the catalyst deoxyadenosine and obtain the desired oxygenates. For example, the value MCOS for the reaction may be at least about 0.1 gram oxygenating hydrocarbon per gram of catalyst RVF, and preferably is in the range from approximately 1.0 to 40.0 grams oxygenating hydrocarbon per gram of catalyst RVF, and more preferably approximately from 0.5 to 8.0 grams oxygenating hydrocarbon per gram of catalyst RVF. what is as for the increase in scale of production, after starting the reactor system RVF should be controlled by the way, so the reaction will proceed at a stationary equilibrium.

Stage condensing

The resulting oxygenates turned into C4+compounds by condensation. As you can imagine, without limitation to any particular theory, the reaction of the acid condensation in the General case consists of a sequence of stages, including (a) dehydration of oxygenates to form olefins; (b) oligomerization of olefins; (C) reaction of cracking; (d) cyclization of larger olefins with the formation of aromatics; (e) isomerization of paraffin; and (f) reaction with the transfer of a hydrogen atom with the formation of paraffins. As you can imagine the reaction of the primary condensation in the General case consists of a sequence of stages, including: (1) aldorino condensation with the formation of β-hydroxyketone or β-hydroxyaldehyde; (2) dehydration of β-hydroxyketone or β-hydroxyaldehyde with the formation of conjugated northward; (3) hydrogenation of the conjugated northward with the formation of ketone or aldehyde, which may participate in subsequent condensation reactions or transformations in alcohol or hydrocarbon; and (4) hydrogenation of CARBONYLS with the formation of alcohols, or Vice versa. How can PR is staviti, reactions acid-base condensation generally include any of the preceding stages acidic and/or basic reactions.

Getting4+compounds takes place by condensation of oxygenates in the presence of a condensation catalyst. The condensation catalyst in the General case will be the catalyst that can form more long-chain connection in the connection of two oxygen-containing substances through a new bond of carbon-carbon and converting the resulting compounds in the hydrocarbon, alcohol or ketone, such as an acid catalyst, basic catalyst or a multifunctional catalyst containing both acidic and basic functionality. The condensation catalyst may include, without limitation, the carbides, nitrides, zirconium dioxide, aluminum oxide, silicon dioxide, silicates, phosphates, zeolites, oxides of titanium, oxides of zinc, oxides of vanadium, oxides of lanthanum, oxides of yttrium, oxides of scandium, magnesium oxides, oxides of cerium, oxides of barium, oxides of calcium, hydroxides, heteroalicyclic, inorganic acid, the acid-modified resin, basically-modified resins, and combinations thereof. The condensation catalyst may include the above-mentioned compounds individually or in combination with a modifier, such as CE, La, Y, Sc, P, b, Bi, Li, Na, K, Rb, Cs, Mg, Ca, r, Ba, and combinations thereof. The condensation catalyst for the functionality of the metal may include a metal, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, and alloys and combinations. The condensation catalyst may also be atomically identical to the catalyst RVF and/or catalyst deoxyadenosine.

The condensation catalyst may be self-supporting (i.e., the catalyst does not require the use of another material, performing the functions of media) or may require a separate carrier, suitable for suspension of the catalyst in a stream of reagent. One particularly advantageous media is a dioxide of silicon, in particular silicon dioxide, characterized by a large specific surface area (greater than 100 square meters per gram) and obtained according to the method of the Sol-gel synthesis, deposition method or pyrogenic method. In other variants of implementation, in particular in the case of the condensation catalyst in powder form, the catalyst may include a binder to facilitate making the catalyst of the desired form of the catalyst. Applicable methods include obtaining extrusion, pelleting, chipping in oil or other known methods. To obtain a molded material can also be blended with each other and extradiol the us zinc oxide, the aluminum oxide and peptization. After drying the material is calcined at a temperature adequate to obtain a catalytically active phase, which usually requires the use of temperatures higher than 450°C. Other carriers catalyst may include those which are described in more detail below.

Acid catalysts

The reaction of the acid condensation carried out using acid catalysts. Acid catalysts can include, without limitation, the aluminosilicates (zeolites), silicoaluminate (SAPO), aluminum phosphate (ALPO), amorphous silica-alumina, Zirconia, sulfated Zirconia, wallpaperjohnny Zirconia, tungsten carbide, molybdenum carbide, titanium dioxide, acidic alumina, phosphated alumina, phosphated silica, sulfated types of carbon, phosphated varieties of carbon, acid resins, heteroalicyclic, inorganic acids, and combinations thereof. In one embodiment, the catalyst may also include a modifier, such as CE, Y, Sc, La, P, b, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and combinations thereof. The catalyst for the functionality of the metal can also be modified by adding a metal, such as Cu, Ag, AU, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, and alloys and is combinatii, and/or sulfides and oxides of Ti, Zr, V, Nb, TA, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, Cd, P, and combinations thereof. Particularly suitable for use as a promoter for the present method was also recognized as gallium. The acid catalyst may be homogeneous, self-supporting or adhering to any one of the carriers, in addition opissyvayusya below, including media containing carbon, silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, vanadium oxide, cerium dioxide, nitride, boron nitride, heteroalicyclic, their alloys and mixtures.

Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y and lanthanides can also be as a result of currency introduced in the zeolite to obtain a zeolite catalyst having activity. The term "zeolite" in accordance with the usage in this document refers not only to the microporous crystalline aluminosilicate, but also to a microporous crystalline metal-containing aluminosilicate structures, such as haloaluminate and hallucinati. The functionality of the metal may be formed of metals such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, and alloys and combinations.

Examples of suitable zeolite catalysts include ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-48. Zeolite ZSM-5 and normal receive are described in U.S. patent No. 3702886; Re. 29,948 (vysokoglinozemistyj ZM-5); 4100262 and 4139600, all of which are incorporated by reference herein. Zeolite ZSM-11 and normal receive are described in U.S. patent No. 3709979, which by reference is incorporated herein. Zeolite ZSM-12 and a conventional receive are described in U.S. patent No. 3832449, by reference incorporated herein. Zeolite ZSM-23 and the normal receive are described in U.S. patent No. 4076842, by reference incorporated herein. Zeolite ZSM-35 and normal receive are described in U.S. patent No. 4016245, by reference incorporated herein. Another receipt ZSM-35 is described in U.S. patent No. 4107195, the description of which by reference is incorporated herein.ZSM-48 and normal receive are described in U.S. patent No. 4375573, by reference incorporated herein. Other examples of the zeolite catalysts are described in U.S. patent 5019663 and U.S. patent 7022888, also through links included in this document.

In accordance with the description in U.S. patent 7022888 acid catalyst may be bifunctional pentesilea zeolite catalyst comprising at least one metallic element from the group of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, and alloys and combinations and modifier from the group of Ga, In, Zn, Fe, Mo, Au, Ag, Y, Sc, Ni, P, The lanthanides and the of combinaci. The zeolite preferably contains a strong acid and a dehydrating centers and can be used in conjunction with streams of reagents containing oxygenated hydrocarbon, at a temperature less than 500°C. Bifunctional pentesilea zeolite may have a crystal structure of ZSM-5, ZSM-8 or ZSM-11, consisting of a large number of 5-membered oxygen rings, that is, pentesilea rings. The zeolite having the structure of ZSM-5, is a particularly preferred catalyst. Bifunctional pentesilea the zeolite catalyst is preferably a zeolite of type ZSM-5 modified with the use of Ga and/or In, such as H-ZSM-5, impregnated using Ga and/or In H-ZSM-5 containing Ga and/or In entered in the result of the exchange, N-gallosilikata having the structure of ZSM-5, and H-haloaluminate having the structure of ZSM-5. Bifunctional pentesilea zeolite ZSM-5 can contain tetrahedral aluminum and/or gallium, located in the zeolite framework or lattice, and octahedral gallium or indium. Octahedral centers are preferably not present in the zeolite framework, but are present in the zeolite channels in close proximity to the zeolite proton acid centers, which are ascribed to the presence of the zeolite tetrahedrite the CSOs of aluminum and gallium. Tetrahedral or frame Al and/or Ga, seems to be responsible for the acid function of the zeolite, and the octahedral or scarcely Ga and/or In, seems to be responsible for dehydrating function of the zeolite.

In one embodiment, the condensation catalyst may be an N-haloaluminate bifunctional pintasilgo zeolite ZSM-5, characterized by the molar ratio of frame (tetrahedral Si/Al and Si/Ga of approximately 10-100 and 15-150, respectively, and levels of Nekrassova (octahedral) Ga, equal to approximately 0.5 to 5.0% (wt.). In the case of data pentesilea N-haloaluminate zeolites as catalyst for the condensation density of strong acid sites can be adjusted when using a molar ratio of frame Al/Si: how big is the ratio of Al/Si, the greater the density of strong acid sites. Highly dispersed substance Nekrassova gallium oxide can be obtained by davallianae zeolite using pre-processing when using H2and water vapor. Preferred is a zeolite containing a strong acid sites with a high density and highly dispersed substance Nekrassova gallium oxide in close vicinity of the zeolite acidic center. The optional catalyst can contain any binder, such as a material of aluminum oxide, silicon dioxide or clay. The catalyst may be used in the form of granules, extrudates, and particles of various shapes and sizes.

Acid catalysts can include one or more zeolite structures, including klickpedale structure of silica-alumina. Zeolites are crystalline microporous materials with well-defined porous structure. Zeolites contain active centers, usually the acid sites, which can be obtained in the zeolite framework. The strength and concentration of active centers can be tuned to specific applications. Examples of zeolites suitable for the condensation of secondary alcohols and alkanes may contain silicates, optionally modified with cations, such as in the case of Ga, In, Zn, Mo and mixtures of such cations, as described, for example, in U.S. patent No. 3702886, which by reference is incorporated herein. As recognized state of the art, the specific structure of the zeolite or zeolites can be modified to obtain a mixture of products of other quantities of various hydrocarbon compounds. Depending on the structure of the zeolite catalyst, the mixture of products may contain different to what icesta aromatic and cyclic hydrocarbons.

Alternatively, if the implementation in practice of the present invention could be used solid acid catalysts, such as aluminum oxide, modified phosphates, chloride, silicon dioxide and other acidic oxides. Furthermore, the acidity can provide either sulfated Zirconia, or wallpaperjohnny Zirconia. When the promotion condensation of oxygenates to obtain C5+hydrocarbons and/or C5+monooxygenation also suitable are catalysts based on Re and Pt/Re. Re is sufficiently acidic for promotion of acid-catalyzed condensation. Acidity can also be increased in activated carbon by adding or sulfates, or phosphates.

The main catalysts

The reaction of the primary condensation carried out using a basic catalyst. The basic catalyst includes, at least, Li, Na, K, Cs, B, Rb, Mg, CA, Sr, Si, Ba, Al, Zn, CE, La, Y, Sc, Y, Zr, Ti, hydrotalcite, zinc aluminate, phosphate, processed base aluminosilicate zeolite, a basic resin, basically nitride, their alloys, or a combination. The basic catalyst may also include oxides of Ti, Zr, V, Nb, TA, Mo, Cr, W, Mn, Re, Al, Ga, In, Co, Ni, Si, Cu, Zn, Sn, Cd, Mg, P, Fe, and combinations thereof. In one embodiment, the condensation catalyst more the tion includes metal, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, and alloys and combinations. Preferred materials of elements from groups IA include Li, Na, K, Cs and Rb. The preferred materials of the elements of the group include Mg, CA, Sr and Ba. The preferred materials of the elements from the group of PV include Zn and Cd. Preferred materials of elements from groups IIIB include Y and La. Basic resins include resins which demonstrate the presence of the basic functionality, such as Amberlyst. The basic catalyst may be self-supporting or adhering to any one of the carriers, in addition opissyvayusya below, including media containing carbon, silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, vanadium oxide, cerium dioxide, nitride, boron nitride, heteroalicyclic, their alloys and mixtures.

The basic catalyst may also include zeolites and other microporous media, which contain compounds of elements of group IA, such as Li, Na, K, Cs and Rb. Preferably the material of the element from group IA is present in a quantity greater than that required to neutralize the acidic nature of the media. These materials can be used in any combination and in combination with aluminum oxide or silicon dioxide. The function of the metal can also be formed in the addition of metals from groups who VIIIB or si, Ga, In, Zn or Sn.

In one embodiment, the condensation catalyst is produced from a combination of MgO and Al2O3to obtain material hydrotalcite. Another preferred material contains ZnO and Al2O3in the form of aluminium spinel. Another preferred material is a combination of ZnO, Al2O3and CuO. Each of these materials may also include additional function metal formed by the metal of group VIIIB, such as Pd or Pt. In one embodiment, the basic catalyst is a metal oxide containing Cu, Ni, Zn, V, Zr or mixtures thereof. In yet another embodiment, the basic catalyst is a metal of zinc aluminate, including Pt, Pd, Cu, Ni or mixtures thereof.

The preferred loading level of the primary metal is in the range from 0.10% (mass.) up to 25% (mass.) when enabled, the intermediate mass percentages in increments of 0.10% and 0.05%, such as 1,00%, 1,10%, 1,15%, 2,00%, 2,50%, 5,00%, 10,00%, 12,50%, 15,00% and 20.00%. The preferred quantitative atomic ratio of the second metal in the presence thereof is in the range from 0.25 to 1 to 10 to 1, including an intermediate ratio is such as to 0.50, and 1.00, of 2.50 to 5.00 and 7.50 to 1.

Acid-base catalysts

The reaction of the acid-base condensation is performed during use of the implement multifunctional catalyst, containing both acidic and basic functionality. Acid-base catalyst may include hydrotalcite, zinc aluminate, phosphate, Li, Na, K, Cs, B, Rb, Mg, Si, Ca, Sr, Ba, Al, Ce, La, Sc, Y, Zr, Ti, Zn, Cr, and combinations thereof. In additional embodiments, the implementation of the acid-base catalyst may also include one or more oxides of elements from the group of Ti, Zr, V, Nb, TA, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, Cd, P, and combinations thereof. Acid-base catalyst may also include the functionality of metal formed using cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys thereof or combinations. In one embodiment, the catalyst further includes Zn, Cd, or phosphate. In one embodiment, the condensation catalyst is a metal oxide containing Pd, Pt, cu or Ni, and still more preferably an aluminate or a metal oxide of zirconium containing Mg and si, Pt, Pd or Ni. Acid-base catalyst may also include hydroxyapatite (HAP) in combination with any one or more of the aforementioned metals. Acid-base catalyst may be self-supporting or adhering to any one of the carriers, in addition opissyvayusya below, including media containing carbon, silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, vanadium oxide, dioxide, CERI is, nitride, boron nitride, heteroalicyclic, their alloys and mixtures.

The condensation catalyst may also include zeolites and other microporous media, which contain compounds of elements of group IA, such as Li, Na, K, Cs and Rb. Preferably the material of the element from group IA is present in a quantity less than that required to neutralize the acidic nature of the media. The function of the metal can also be formed in the result of adding the metals of group VIIIB or si, Ga, In, Zn or Sn.

In one embodiment, the condensation catalyst is produced from a combination of MgO and Al2O3to obtain material hydrotalcite. Another preferred material contains a combination of MgO and ZrO2or a combination of ZnO and Al2O3. Each of these materials may also include additional function metal formed by copper or a metal from group VIIIB, such as Ni, Pd, Pt or a combination of the above components.

In case of inclusion of a metal of group IIB, VIB, VIIB, VIIIB, IIA or IVA, the load of metal will be in the range from 0.10% (mass.) up to 10% (mass.) when enabled, the intermediate mass percentages in increments of 0.10% and 0.05%, will be such as 1,00%, 1,10%, 1,15%, 2,00%, 2,50%, 5,00% and 7.50%, and the like. In case of inclusion of the second metal preferred quantitative atomic balance of the group for the second metal will be in the range from 0.25 to 1 to 5 to 1, including interim ratios will be such as to 0.50, and 1.00, and 5,00 2,50 1.

The condensation reaction

Concrete obtained With4+connections will depend on various factors, including without limitation the type of oxygenates in the flow of reagents, temperatures, condensation, condensing pressure, the reactivity of the catalyst and the flow rate of the reagents, as it affects the volumetric rate, is GCOS and is MCOS. Preferably the flow of reagents is introduced into contact with the catalyst condensation when the value MCOS, which is appropriate for obtaining the desired hydrocarbon products. Is MCOS is preferably at least about 0.1 gram of oxygenate in the stream of reactants per hour, more preferably is MCOS is in the range of approximately from 0.1 to 40.0 g/g-h, including the value MCOS approximately 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35 g/g-h, and intermediate increments.

In General, the condensation reaction should be carried out at a temperature at which thermodynamics of the proposed reaction is favorable. In the case of liquid reactions in the condensed phase the pressure in the reactor should be sufficient to absorb at least part of the reagents in the state of the condensed liquid is a phase in the inlet hole of the reactor. In the case of vapor-phase reactions, the reaction must be conducted at a temperature at which the vapor pressure of oxygenates is at least about 0.1 ATM (and preferably much more), and thermodynamics of the reaction is favorable. The condensing temperature will vary depending on the particular used oxygenate, but generally is in the range from about 80°C to 500°C for the reactions taking place in the vapor phase, and more preferably from about 125°C. to 450°C. In the case of liquid-phase reactions condensing temperature may be in the range of approximately 80°C to 500°C and the condensing pressure is from about 0 lb/in2(wt.) (0 kPa (psig) up to 1200 lb/in2(wt.) (8270 kPa (psig). Preferably, the condensing temperature is in the range from about 125°to 300°C., or from about 125°C to 250°C, or from about 250°C to 425°C. the Pressure of the reaction is preferably at least about 0.1 ATM or is in the range from approximately 0 to 1200 lb/in2(wt.) (from 0 to 8270 kPa (psig) or from about 0 to 1000 lb/in2(wt.) (from 0 to 6890 kPa (psig) or from about 0 to 700 lb/in2(wt.) (from 0 to 4830 kPa (psig).

The variation of the above, and other factors in common with what you learn as a result will lead to modification of specific composition and outputs 4+connections. For example, the variation of temperature and/or pressure of the reactor system or specific formulations of the catalyst may result in the receipt With4+alcohols and/or ketones instead of C4+of hydrocarbons. With4+the hydrocarbon product may also contain a wide range of olefins and alkanes of various sizes (usually branched alkanes). Depending on the used catalyst condensation of the hydrocarbon product may also include aromatic and cyclic hydrocarbon compounds. With4+the hydrocarbon product may also have undesirable high levels of olefins, which can lead to the formation or the formation of deposits in internal combustion engines, or other undesirable hydrocarbon products. In this case, the hydrocarbon molecules may not necessarily be subjected to hydrogenation to restore ketones to alcohols and hydrocarbons, while alcohols and unsaturated hydrocarbon can be recovered in alkanes, which thus leads to the formation of more desirable hydrocarbon product, characterized by low levels of olefins, aromatics or alcohols.

Stage post-processing in General will be the reaction of hiderow the tion, which removes the remaining carbonyl group or a hydroxyl group. In this case, can be used any one of the aforementioned hydrogenation catalysts. Such catalysts can include any one or more of the following metals: Cu, Ni, Fe, Co, Ru, Pd, Rh, Pt, Ir, Os, their alloys, or a combination, individually or jointly with promoters, such as Au, Ag, Cr, Zn, Mn, Sn, Cu, Bi and their alloys, can be used with different levels of loading in the range from approximately 0.01 to approximately 20% (mass.) on the aforementioned media.

In the General case, a post-processing step is carried out at temperatures post-processing in the range of about from 80°C to 250°C and pressures of post-processing in the range of from about 100 lb/in2(689 kPa (psig) up to 2000 lb/in2(wt.) (13800 kPa (psig). Stage post-processing can be carried out in the vapor phase or the liquid phase and, when necessary, can use the H2received in place, external H2H2sent to recycling, or combinations thereof.

On the composition and outputs4+compounds and the activity and stability of catalyst condensation effects can have and also other factors such as the concentration of water or junk oxygenates. In this case, the method may include the study of the dehydration, which removes part of the water before condensation or separation unit to remove unwanted oxygenates. For example, separation system, such as a phase separator, extractor, cleaner or distillation column, can be set at the stage of condensation to remove part of the water from the stream reagents containing oxygenates. Separation system can also be installed and to remove specific oxygenates that will provide desirable flow of products containing hydrocarbons, characterized by a certain range of number of carbon atoms, or use as final products or in other systems or methods.

C4+connection

The practice of the method of producing a component made of a water-soluble oxygenating hydrocarbon in the present invention, the results With4+alkanes, C4+alkenes, C5+cycloalkanes, C5+cycloalkenes, arrow, condensed arrow,4+alcohols, C4+ketones and mixtures thereof. C4+alkanes and C4+alkenes contain from 4 to 30 carbon atoms (C4-30alkanes and C4-30 alkenes) and can be alkanes or alkenes with a branched or straight chain. C4+alkanes and C4+alkenes can also include fractions of C4-9C7-14C12-24is Lukanov and alkenes, accordingly, With4-9fraction refers to gasoline, C7-14fraction refers to kerosene (e.g., jet fuel), and12-24fraction refers to diesel fuel and other industrial applications. Examples of the various C4+alkanes and C4+alkenes include, without limitation butane, butane, pentane, Panten, 2-methylbutane, hexane, hexane, 2-methylpentane, 3-methylpentane, 2,2-Dimethylbutane, 2,3-Dimethylbutane, heptane, hapten, octane, octene, 2,2,4-trimethylpentane, 2,3-dimethylhexane, 2,3,4-trimethylpentane, 2,3-dimethylpentane, Nanan, none, Dean, mission, undecane, undecen, dodecan, dodecan, tridecan, tridecen, tetradecane, tetradecene, pentadecane, pentadecane, hexadecane, hexadecan, septillion, reptilian, octillion, ochildren, nonillion, noeldechen, alcosan, achozen, Unakitan, Unakitan, dakotan, Thaksin, triacetin, triacetin, tetracosane, tetracosane and their isomers.

With5+cycloalkanes and C5+cycloalkene contain from 5 to 30 carbon atoms and may be unsubstituted, monosubstituted or polyamideimide. In the case of monosubstituted and preparation of polysubstituted compounds substituted group may include branched C3+alkyl, C1+alkyl straight chain, branched C3+alkylen,1+alkylen straight chain, C2+alkylen straight chain, phenyl or their combination is. In one embodiment, at least one of the substituted groups include branched C3-12alkyl, C1-12alkyl straight chain, branched C3-12alkylene, C1-12alkylen straight chain, C2-12alkylen straight chain, phenyl or a combination of both. In yet another embodiment, at least one of the substituted groups include branched C3-4alkyl, C1-4alkyl straight chain, branched C3-4alkylene, C1-4alkylen straight chain, C2-4alkylen straight chain, phenyl or a combination of both. Examples of desirable C5+cycloalkanes and C5+cycloalkenes include, without limitation, cyclopentane, cyclopentene, cyclohexane, cyclohexene, methylcyclopentene, methylcyclopentene, ethylcyclopentane, ethylcyclopentane, ethylcyclohexane, ethylcyclohexane and their isomers.

In General, arily will consist of an aromatic hydrocarbon or unsubstituted (phenyl), or monosubstituted or polyamidine form. In the case of monosubstituted and preparation of polysubstituted compounds substituted group may include branched C3+alkyl, C1+alkyl straight chain, branched C3+alkylene, C2+alkylen straight chain, phenyl or a combination of both. In one embodiment, at least one of the substituted groups include branched With 3-12alkyl, C1-12alkyl straight chain, branched C3-12alkylen,2-12alkylen straight chain, phenyl or a combination of both. In yet another embodiment, at least one of the substituted groups include branched C3-4alkyl, C1-4alkyl straight chain, branched C3-4alkylene, C2-4alkylen straight chain, phenyl or a combination of both. Examples of different arrow include without limitation, benzene, toluene, xylene (xylene, ethylbenzene, para-xylene, meta-xylene, ortho-xylene, With9the aromatics.

Condensed arily in General will consist of bicyclic and polycyclic aromatic hydrocarbons or unsubstituted, or monosubstituted or polyamidine form. In the case of monosubstituted and preparation of polysubstituted compounds substituted groups may include branched C3+alkyl, C1+alkyl straight chain, branched C3+alkylen,2+alkylen straight chain, phenyl or a combination of both. In yet another embodiment, at least one of the substituted groups include branched C3-4alkyl, C1-4alkyl straight chain, branched C3-4alkylene, C2-4alkylen straight chain, phenyl or a combination of both. Examples of various condensed allow include, without limitation naphthalene, antrac is h, tetrahydronaphthalen and decahydronaphthalene, indan, inden and their isomers.

With4+the alcohols may also be cyclic, branched or straight chain and contain from 4 to 30 carbon atoms. In General, a4+alcohol can be a connection, vpisivaushiesya the formula, R1-OH, where R1is a representative selected from the group consisting of branched C4+of alkyl, C4+the alkyl straight chain, branched C4+alkylene, C4+alkylene straight chain, substituted C5+cycloalkane, unsubstituted C5+cycloalkane, substituted C5+cycloalkene, unsubstituted C5+cycloalkene, aryl, phenyl, and combinations thereof. Examples of desirable4+alcohols include, without limitation butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, reptilianos, octillery, nordkanal, eicosanol, onakosano, daikatana, triacontanol, tetracosane and their isomers.

With4+ketones can also be cyclic, branched or straight chain and contain from 4 to 30 carbon atoms. In General, a4+the ketone can be a compound, vpisivaushiesya formula

where R3and R4independently are representative, abiramam from the group consisting of branched C3+of alkyl, C1+the alkyl straight chain, branched C3+alkylene,2+alkylene straight chain, substituted C5+cycloalkane, unsubstituted With5+cycloalkane, substituted C5+cycloalkene, unsubstituted C5+cycloalkene, aryl, phenyl, and combinations thereof. Examples of desirable C4+ketones include, without limitation butanone, pentanone, hexanone, heptanone, octanone, nonanone, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptaldehyde, octaldehyde, noeldechen, eicosane, onakosano, joacasino, tricosane, tetracosane and their isomers.

Light fractions of the above, mainly With4-C9can be separated for use in gasoline. The average fractions, such as C7-C14can be separated for use in kerosene (e.g., jet fuel), while the heavy fraction, that is, With12-C14can be separated for use in diesel fuel. Most of the heavy fraction can be used as lubricants or subjected to cracking for additional fractions of gasoline and/or diesel fuel.

Media catalyst

In the above-mentioned various embodiments, the implementation of the system of the catalyst include a carrier suitable for the suspension of the catalyst in the solution of the feedstock. The media should be one that provides a stable platform for the selected catalyst and the conditions of the reactions. The carrier may take any form which is stable under the selected reaction conditions from the point of view of the execution of the function at the desired levels and is particularly stable in aqueous solutions of the feedstock. Such media include, without limitation carbon, silica, silica-alumina, aluminum oxide, zirconium dioxide, titanium dioxide, cerium dioxide, vanadium oxide, a nitride, boron nitride, heteroalicyclic, hydroxyapatite, zinc oxide, chromium oxide and mixtures thereof. Can also be used and nanoporous media, such as zeolites, carbon nanotubes or carbon fullerene.

One particularly preferred catalyst carrier is a carbon, in particular carbon carriers, characterized by a relatively large specific surface areas (greater than 100 square meters per gram). These kinds of include carbon activated carbon (granulated, powdered or pelletized), fabric, felts or fibers of activated carbon, carbon nanotubes or naoroji, carbon fullerene, carbon honeycomb structure, characterized by a large specific area is poverhnosti, carbon foams (reticulated carbon foam and carbon blocks. Carbon can be obtained as a result of either chemical or steam activation peat, wood, lignite, coal, coconut shell, olive pits and carbon petroleum-based. Another preferred carrier is a granular activated carbon obtained from coconut. In one embodiment, the catalyst RVF and deoxygenation consists of Pt on carbon, while Pt advanced alloys or mixed with Ni, Ru, Cu, Fe, Rh, Re, their alloys and combinations.

Another preferred carrier of the catalyst is a zirconium dioxide. The Zirconia can be obtained by precipitation of zirconium hydroxide of zirconium salts, when carrying out processing by Sol-gel method or any other method. Zirconium dioxide is preferably present in crystalline form, obtained by calcination of the material of the precursor at temperatures higher than 400°C, and may include both tetragonal and monoclinic crystalline phase. To improve structural or catalytic properties of Zirconia can be added modifier. Such modifiers include, without limitation sulfate, tungstate, phosphate, shall ICSID titanium, silicon dioxide and oxides of metals from groups IIIB, particularly CE, La or Y. In one embodiment, the catalyst RVF and deoxyadenosine consists of Pt on a modified silica-Zirconia mainly in the tetragonal phase, while Pt advanced alloys or mixed with Ni, Ru, Cu, Fe, Rh, Re, their alloys and combinations.

Another preferred catalyst carrier is titanium dioxide. Titanium dioxide can be obtained by deposition of titanium salts, when carrying out processing by Sol-gel method or any other method. Titanium dioxide is preferably present in crystalline form and may include both anatase and rutile crystalline phase. To improve structural or catalytic properties of titanium dioxide may be added to the modifier. Such modifiers include, without limitation sulfate, silicon dioxide and oxides of metals from groups IIIB, particularly CE, La, or Y. In one embodiment, the catalyst RVF and receive oxygenate consists of EN on the titanium dioxide mainly in the rutile phase, while EN advanced alloys or mixed with Ge, Bi, In, Ni, Sn, Cu, Fe, Re, Rh, Pt, and their alloys and combinations.

Another preferred catalyst carrier is an oxide cream the Oia. Silicon dioxide may not necessarily be combined with the alumina to produce material of silicon dioxide-aluminum oxide. In one embodiment, the catalyst RVF is a Pt at the silicon dioxide-aluminum oxide or silicon dioxide, while Pt advanced alloys or mixed with Ni, Ru, Cu, Fe, Rh, Re, their alloys and combinations. In yet another embodiment, the catalyst RVF is a Ni on silica-alumina or silica, with advanced Nickel alloys or mixed with Sn, Ge, Bi, Bu, Cu, Re, Ru, Fe, and their alloys and combinations.

The media can also be subjected to processing or modification to improve its properties. For example, the carrier may be subjected to processing as a result of surface modification, modification of surface fragments, such as hydrogen and hydroxyl. Superficial group of hydrogen and hydroxyl can lead to local variations of pH values, which affect the catalytic efficiency. The media can also be modified, for example, in the processing sulfates, phosphates, wolframate, silanes, lanthanide compounds of alkali metals or alkaline earth compounds metals. In the case of carbon carriers may be carbon p is durgnat pre-treatment with water vapor, oxygen (from the air), inorganic acids or hydrogen peroxide to obtain a larger number of surface oxygen centers. The preferred pre-treatment would be to use either oxygen or hydrogen peroxide. Subjected to preliminary processing of carbon can also be modified by adding oxides of elements of group IVB and group VB. It is preferable to use oxides of Ti, V, Zr, and mixtures thereof.

System catalysts, either individually or in mixture with each other, can be obtained using conventional methods known to experts in the relevant field of technology. Such methods include methods of achieving initial humidity, evaporative impregnation, chemical vapour deposition, protravnogo priming, magnetron sputtering, and the like. The method selected for the manufacture of the catalyst is not particularly critical time to implement the functions of the invention with the proviso that different catalysts will lead to different results depending on factors such as the total specific surface area, porosity, and the like.

Additional materials

To improve the passage of the reaction or to promote its passage to obtained what I desired reaction products to a solution of raw materials at various stages of the method can be added for additional materials and compositions ("supplements"). Additives may include without limitation, acids, salts and additional amounts of hydrogen or feedstock. For passing appropriate reactions such additives can be added directly to the flow of the feedstock prior to its introduction into contact with the corresponding catalyst or in conjunction with this introduction to the contact or directly in the reaction layer.

In one embodiment, the additive may further include a solution of raw materials to supply additional oxygenated hydrocarbons upon receipt of oxygenates. The feedstock can include any one or more of the above oxygenated hydrocarbons, including any one or more representatives from polyalcohols, xylytol, glucose, polyols, glycerin or sugars. For example, the additional material may include glycerin. In this embodiment, the crude glycerin is used to initiate the reaction and hydrogen in order to avoid contamination of the catalyst deoxyadenosine pollutants from crude glycerol. Then to increase the amount of oxygenated hydrocarbons that are available for processing, to a solution of raw materials add purified glycerol prior to the introduction of the initial solution of the feedstock into contact with a catalyst dioxygenase the project or simultaneously with the introduction. Presumably depending on the characteristics of the catalyst RVF and catalyst deoxyadenosine reverse can be used for crude glycerol which performs the function of the additive.

In yet another embodiment, the additive may further include oxygenates for the condensation reaction. Oxygenates can include any one or more of the above oxygenates. For example, the additional material may include propyl alcohol. In this embodiment, propyl alcohol can be obtained in a parallel system of glycerin feedstock, and then combined with oxygenates obtained by processing sorbitol feedstock to form a flow of the reagents, the most effective to obtain a product containing a combination of C6-12of hydrocarbons.

In yet another embodiment, the additional material may include sent to recycling oxygenates and/or oxygendemand hydrocarbons, unreacted completely during retrieval method. Oxygenates and oxygendemand hydrocarbons can include any one or more of the above oxygenates and oxygenated hydrocarbons.

In yet another additional embodiment, the additional material may include acid and with whom and, added in the way. Adding acidic compounds can lead to increased selectivity for the desired oxygenates and, ultimately, With4+the compounds. Water-soluble acids can include, without limitation, salts of nitric acid, phosphoric acid, sulfuric acid, chloride-hydrogen acid and mixtures thereof. In the case of an optional acid modifier preferred to be his presence in sufficient quantity to reduce the pH of the stream water of the raw materials to values in the range from about pH 1.0 to about pH 4.0. The decrease in the pH value of the flow of raw materials at the time of receipt of oxygenates in this way can increase the proportion of diols, polyols, ketones or alcohols for the subsequent condensation.

Reactor system

Reaction vpisivaushiesya herein can be conducted in any suitable reactor designs, including in flow reactors, continuous, periodic, properities or multiboot reactors without limitation in respect of construction, size, geometry, cost, and the like. The reactor system can also use the system with fluidized catalytic layer system with pressure maintenance and regeneration of the layer system with a fixed is at the forefront, system with a movable layer, or a combination of the above options. Preferably the present invention is put into practice using a flow system continuous operation at a stationary equilibrium.

In a flow system continuous reactor system includes at least a layer of the reforming unit, adapted to receive an aqueous solution of the feedstock and hydrogen, the layer deoxyadenosine adapted to receive oxygenates from hydrogen and part of the solution of the initial raw material and the layer of condensation to obtain a4+compounds of oxygenates. Layer reforming configure for introducing an aqueous solution of the feedstock in the vapor phase or the liquid phase in contact with the catalyst RVF and hydrogen in the flow of reagents. Layer deoxyadenosine configure to receive the flow of reagents when introduced into contact with the catalyst deoxyadenosine and obtain the desired oxygenates. A layer of condensation configured to receive a flow of Regents when introduced into contact with the condensation catalyst and obtain desirable With4+connections. In the case of systems that do not include a step for hydrogen RVF may be removed layer reforming. In the case of systems that do not include a step for hydrogen or oxygenate can be removed layers of reforming and deok is generowania. Because the catalyst RVF, catalyst deoxyadenosine and the condensation catalyst may also be atomically identical, the catalysts can exist in the same layer. In the case of systems involving phase hydrogenation or hydrogenolysis, before layer deoxyinosine and/or reforming may be included additional reaction layer. In the case of systems, including a post-processing step, after the layer of condensation may be included additional reaction layer to implement the method post-processing.

In systems that produce both hydrogen and oxygenates, a layer of condensation can be placed in the tank the same reactor together with a layer of reforming or capacity of the second reactor communicating with a capacity of the first reactor, comprising a layer of reforming. A layer of condensation can be in the capacity of one and the same reactor together with a layer of reforming or deoxyadenosine or in the capacity of the individual reactor communicating with a tank reactor, comprising a layer of deoxyadenosine. Each tank reactor preferably includes a discharge outlet adapted to remove the product stream from the reactor vessel. In systems containing phase hydrogenation stage or hydrogenolysis, the layer of the reaction of hydrogenation or hydrogenolysis can be succinctly is ti the same reactor together with a layer of reforming or deoxyadenosine or in the capacity of the individual reactor, communicating with the capacity of the reactor, including the reforming layer and/or layer deoxyadenosine. In the case of systems, including a post-processing step, the reaction layer post-processing can be in the capacity of one and the same reactor together with a layer of condensation or in the capacity of the individual reactor communicating with a tank reactor, comprising a layer of condensation.

The reactor system may also include an additional outlet to ensure the removal of parts of the flow of reagents for the purpose of additional incentives or direction of passage of the reaction to produce the desired reaction products and to ensure the collection and shipment to recycling the by-products of the reaction for use in other parts of the system. The reactor system may also include additional inlet openings to allow the introduction of additional materials for the purpose of providing additional incentives or direction of passage of the reaction to produce the desired reaction products and delivering on the recycling side reaction products for use in the method of reforming. For example, the system may be designed so that the catalyst RVF would result in excessive hydrogen, with part of the excess hydrogen is removed and re-enter in the method according to the course of the process stream for further additions reaction of oxygenates on the catalyst condensation or post-processing of the condensation product with the aim of obtaining the desired C 4+connections. Alternatively, the system may be designed so that the catalyst RVF would result in excessive hydrogen, with part of the excess hydrogen is removed and used in other ways during the process stream before, such as ways of pre-processing of the feedstock and the reaction of hydrogenation or hydrogenolysis.

The reactor system may also include elements that provide separation of the flow of reagents for the various components, which can find application in various reaction schemes, or simple promotion of the completion of the desired reactions. For example, separation system, such as a phase separator, extractor, cleaner or distillation column, can be set at the stage of condensation for removal of water from the flow of reagents to stimulate the completion of the condensation reaction to create favorable conditions for producing hydrocarbons. Separation system can also be installed and to remove specific oxygenates and providing the flow of desirable products containing hydrocarbons, characterized by a certain range of number of carbon atoms, or use as final products or in other systems or methods.

In one vari is NTE the implementation of the reaction system configure so to set the direction of flow of an aqueous solution of raw materials to ensure maximum interaction with H2received "on the spot". The reactor can be designed in such a way that the flow of reagents flowed least horizontally, vertically or diagonally with respect to the gravitational plane for maximizing system efficiency. In systems where the flow of the reactants flows vertically or diagonally with respect to the gravitational plane, the flow may proceed either against the direction of action of gravity (system with upward flow or the direction of action of the gravity system (downdraft) or option, combined from both. In one preferred embodiment, the capacity of the reactor RVF and/or deoxyinosine design in the form of a system with upward flow, while the capacity of the condensation reactor design in the form of downdraft. In this embodiment, the solution of the initial raw material is first injected into contact with the reforming layer containing the catalyst RVF, for the formation of H2received "on the spot". Due to this configuration of the reactor H2RVF then under certain conditions will be able to seep through the second reaction layer containing the catalyst deoxy the mapping, with a speed greater than or equal to the speed of solution of the raw materials, for for maximizing the interaction between the solution of the feedstock and H2and the catalyst for deoxyadenosine. The resulting flow of reagents after that submit for processing in the condensation reactor configuration downdraft.

In case of presence of a catalyst RVF and catalyst deoxyguanosine in one chamber, the catalyst RVF and catalyst deoxyguanosine can be placed in a configuration with laying in a pile to ensure the introduction of the solution of the feedstock in the first contact with the catalyst RVF, and then with the catalyst deoxyadenosine or series of catalysts deoxyadenosine depending on the desired reaction products. The reaction catalyst layers for RVF and catalyst or catalysts deoxyadenosine can also be placed side by side with each other depending on the specific use flow mechanism. In any case, the solution of the feedstock can be introduced into a reaction chamber through one or more inlet holes, and then routed through the catalysts for processing. In yet another embodiment, the solution of the initial raw material is directed through the catalyst RVF to obtain H2RVF, and thereafter as H2RVF, and the remaining solution of the feedstock is directed through the catalyst or catalysts deoxyadenosine to obtain the desired oxygenates. In a parallel configuration, the solution of raw materials can be divided for directing the first part of the solution of the feedstock to the reforming layer where to get the H2RVF, and the second part - layer deoxyadenosine where to get the desired oxygenates using H2RVF obtained in place. Alternatively, the reactor can be configured for adapting to using two separate solutions of the starting materials, the first solution of the feedstock is sent to the capacity of the reactor RVF, and the second solution of the feedstock is sent to the capacity of the reactor deoxyadenosine. In one sequential reactor configuration can be designed in such a way that the solution of raw materials flowed through the tank reactor RVF in the capacity of the reactor deoxyadenosine. In the variants of implementation, using a combined catalyst RVF/deoxyguanosine, obtaining H2RVF and oxygenates occurs at the same time. In any of these systems due to receipt of H2RVF in place when using the pumping mechanism creates pressure, which also directs the solution of the feedstock through the reactor chamber.

Figure 6 is a process flow illustrating one potential reactor system suitable for use in the project in the implementation in practice of the method of producing a component, made from water-soluble oxygenating hydrocarbon in the present invention. The flow of the feedstock in the form of oxygenated hydrocarbons 1 (containing or not containing water) is mixed with a stream sent to recycling water and sent to recycling oxygenates in position 2, to obtain an aqueous solution of raw materials 3. The solution of the initial raw material 3 is then subjected to hydrogenation at a preliminary processing stage 4 for the solution of the initial raw material 5, which is easier turns in the desired oxygenates. H2for stage hydrogenation can be performed from an external source 22 or represent hydrogen, sent to recycling of the system, as illustrated below for stages 13-21. The solution of the initial raw material 5 is introduced into the reaction vessel of the reactor 8, which contains the catalyst RVF and catalyst deoxyadenosine, to obtain the product stream 7 containing water, H2, carbon dioxide, hydrocarbons and oxygenates. After that the water in the product stream 7 is removed at the position 8 to obtain the product stream 10 containing oxygenates, hydrogen, carbon dioxide and hydrocarbons. Then the water from the stage of dehydration 8 sent for recycling in positions 9 and 15 for mixing with the flow of oxygenated hydrocarbons in position 2. After that, the product stream 10 confused is scout through capacity reactor 11, which includes a condensation catalyst, to obtain the product stream 12 containing C4+compounds, water, H2and carbon dioxide. Then the product stream 12 perepuskat through a three-phase separator 13 for separating non-condensable gases 16 (i.e., hydrogen, carbon dioxide, methane, ethane and propane) from the hydrocarbon products stream 14 containing C4+connections and water 15. Water 15 from the separator can be either sent for recycling or removed from the system. Non-condensable gas stream 16 can be erepoxen through separation installation 17 to receive the stream of purified N219 and the flow of raffinate 18, containing carbon dioxide, methane, ethane, propane and some hydrogen. After that, the purified H219 may be either removed from the system at position 20 or erepoxen through the compressor departure recycling 21 to receive the stream of hydrogen sent to recycling, 23.

In another preferred reactor system is illustrated in figure 7, are invited to the first reactor system for the conversion of the desired solution of the feedstock in C4+connection. The solution of raw materials stored in the tank 1, and then perepuskat on the supply line 2 into the loading pump 3. Boot pump 3 increases the pressure of the solution of the feedstock to the desired pressure, the tion reaction, for example, 600 lb/in2(wt.) (4140 kPa (psig), and then unloads the solution along the line 4 in the electric pre-heater 5, which heats the feedstock to the desired temperature at the inlet opening. After this heated solution 6 perepuskat in the technological part of the reactor, having essentially the configuration of the "pipe-in-pipe pipe 7 pipe 8). Depending on the pressure of the reactor and temperatures that are several degrees, the flow of the reactants flowing through the pipe reactor 7, in the General case will always be maintained essentially in a state of liquid phase, but may evaporate due to the heat of condensation from a remote part 7b, so that the main part of the product, leaving the edge of the reactor outlet line 15, would have the form of steam.

Degree and area of the degrees of the pipe reactor 7 include (combined) catalyst RVF/deoxyadenosine and the condensation catalyst, each of which fill the sequential catalytic layers (i.e., one on top of another). In this example, the pipe reactor 7 contains the catalyst RVF/deoxyguanosine clusters of part 7a of the pipe reactor 7 and the condensation catalyst in a remote part 7b. The catalyst system below is based on having a small sphere made of stainless steel, is placed on the Frit of nerzaveushsei. Sphere of stainless steel are also placed on top of the layer of catalyst. To facilitate the separation of spent catalyst when sent to the recycling or regeneration of the catalyst layers separated by means of a porous material, such as glass wool. The reactor can also be physically divided into separate tubes with channels connecting pipes to ensure continuity of flow. This arrangement can provide better regulation of heat transfer, making it possible to optimize the temperature in accordance with the requirements for reactions at several stages of the reactor.

The reaction RVF is usually endothermic, while the condensation reaction is usually vysokotekhnologicheskoi. Preferably the reactor system makes use of the heat generated in the condensation reaction, for conducting heat in the reactions of RVF and deoxyadenosine. One advantage of carrying out both of these reactions together with each other is the direct transfer of heat from the exothermic reaction of condensation to the endothermic reforming reactions/deoxyguanosine.

The process tube 7 is preferably made of a thermally conductive material configured to transfer heat from a remote part 7b to close part 7a. In addition, technology is a mini pipe can be warmed with hot oil or hot air, flowing through the annular space between the process tube 7 and the outer tube 8. Hot air can be obtained by heating the ambient air of the blower 10 electric heater 12 and sent to the reactor through line 13. Can also be used and the hot oil, which is obtained when using the heater and pump (not shown) and sent to the reactor through line 13. Configuration flow for this system is such that the hot air (or oil) in the pipe 8 proceeded least in countercurrent with respect to the process fluid in the pipe 7. In line with this, the pipe reactor 7 is preferably warmer bottom than at the top.

Alternatively, process pipe 7 can be divided into two separate pipes or areas to facilitate optimization of the reaction conditions separately for reactions RVF and deoxyguanosine and for the condensation reaction. For example, data can be simplified separation of spent catalyst for regeneration. On two-zone of the second stage in a vertical reactor heat generated by condensation in the lower zone may be moved as a result of convection in the upper zone for use in the reforming reaction. The second zone can also be configured with the purpose of obtaining a continuous or stepwise gradient for mixed catalysts reforming and condensation, with a greater number of the reforming catalyst is on the top edge, and a greater amount of condensation catalyst is located on the bottom edge.

The exhaust flow 15 from the pipe reactor 7 includes gaseous products such as hydrogen, co and CO2), as well as water and organic liquid products. The exhaust stream is cooled to the ambient temperature when using a water-cooled tube in tube condenser 16. After that, the exhaust stream 17 from the condenser 16 is directed to a three-phase separator for phase separation of products: non-condensable gas 18 (upper phase), the organic liquid phase of lower density 19 (middle phase) and the aqueous liquid phase of higher density 20 (the lower phase). System pressure support in the controlled keeping the flow of non-condensable gas through line 21. The liquid level support in the controlled-keeping current components of the aqueous phase in line 23. After that, the organic liquid phase is removed from the top of the aqueous phase in line 22.

The aqueous phase is 20 taken along the line 23. If the content in the aqueous phase of 20 significant amounts of residual oxygenates (i.e., products of incomplete reforming) the aqueous phase 20 can be sent back through the line 23 to the source of raw materials 6, where it is used as a feedstock that is sent back to the reactor. Thus, extract the level of carbon content and calorific value of intermediate methods.

The average phase 19 contains C5+connection. Typically, this phase contains hydrocarbons and monooxygenase range mainly from C4to C30. Light fractions, mainly With4-C9can be separated for use in gasoline. The middle fraction, that is, C7-C14can be separated for use as kerosene (e.g., jet fuel). Heavy fractions, that is, C12-C24can be separated for use in diesel fuel. Most of the heavy fraction can be used as lubricants or subjected to cracking for additional fractions of gasoline and/or diesel fuel.

Vapor phase 18 contains hydrogen and other reaction products RVF, such as gaseous carbon monoxide, carbon dioxide, methane, ethane, propane, butane, pentane and/or hexane. Part of the gas blown from the system through line 22 to prevent accumulation in the system of light hydrocarbons and CO2. Gases can also be used as a source of fuel to generate heat for the reactor system. In regard to the scale of production, after startup of the reactor system can be controlled by the method, and is eacli proceeded in a stationary equilibrium.

Component containing at least one C4+connection

Component containing at least one4+the connection is produced from the water-soluble hydrocarbon according to the aforementioned method, before using it in the liquid fuel compositions of the present invention preferably separated into various fractions by distillation to any known method. Preferably component containing at least one C4+the connection produced by the aforementioned method, divided into more than one fraction distillation, where at least one of the fractions of the distillation is light, medium or heavy fraction, opisyvayuschaya herein below.

As described above, the light fractions, mainly C4-C9can be separated for use in gasoline. Medium fractions, for example, With7-C14can be separated for use as kerosene, for example, for use in jet fuel. Heavy fractions, for example, C12-C24can be separated for use in diesel fuel. Most of the heavy fraction can be used as lubricants or may be subjected to cracking for more factions, intended for use in the fractions of gasoline, kerosene and/or diesel the fuel.

Since the component containing at least one4+connection is made from water-soluble oxygenating hydrocarbon, usually produced from biomass, the age of the component or its fraction is less than 100 years, preferably less than 40, more preferably less than 20 years, according to the calculation of the concentration of carbon-14 in the component. Light fractions

Light fractions of the component containing at least one4+ the connection is made from water-soluble oxygenating hydrocarbon, preferably have one or more of the following properties (from LF-i to LF-vi):

(LF-i) the temperature of the end of the boil in the range from 150 to 220°C., more preferably in the range from 160 to 210°C;

(LF-ii) density at 15°C in the range of from 700 to 890 kg/m3more preferably in the range from 720 to 800 kg/m3;

(LF-iii) the sulfur content equal to at most 5 mg/kg, more preferably at most 1 mg/kg;

(LF-iv) oxygen levels equal to, at most, a 3.5% (mass.), more preferably at most 3.0 percent (mass.), usually, most of 2.7% (mass.);

(LF-v) is each in the range from 80 to 110, more preferably in the range of from 90 to 100;

(LF-vi) is MUCH in the range from 70 to 100, more preferably in the range from 80 to 90.

Usually light fractions of the component, containing at least one4+connection is made from water-soluble oxygenating hydrocarbon, have properties that correspond to each of the properties in detail opissyvayusya in the above positions from LF-i to LF-vi, more often each of the preferred values for each property in detail opissyvayusya in the above positions from LF-i to LF-vi.

Medium fractions

The average fraction of the component containing at least one4+connection is made from water-soluble oxygenating hydrocarbon, preferably have one or more of the following properties (MF-i to MF-vix):

(MF-i) initial boiling point in the range from 120 to 215°C., more preferably in the range of from 130 to 205°C;

(MF-ii) the temperature of the end of the boil in the range from 220 to 320°C., more preferably in the range from 230 to 320°C;

(MF-iii) density at 15°C in the range of from 700 to 890 kg/m, more preferably in the range from 730 to 840 kg/m3;

(MF-iv) sulfur level equal to, at most, 0,1% (mass.), more preferably at most 0.01 percent (mass.);

(MF-v) the total content of aromatics, equal to, at most, 30% (vol.), more preferably, at most, 25% (vol.), even more preferably, at most, 20% (vol.), most preferably, the thing is great, 15% (vol.);

(MF-vi) freezing point equal to 40°C. or less, more preferably, at least 47°C. or less;

(MF-vii) maximum height mecoptera flame, equal at least 18 mm, more preferably at least 19 mm, even more preferably at least 25 mm;

(MF-viii) viscosity at - 20°C in the range from 1 to 10 cSt, more preferably in the range of from 2 to 8 cSt;

(MF-vix), the specific energy content in the range from 40 to 47 MJ/kg, more preferably in the range from 42 to 46 MJ/kg

Usually the average fraction of the component containing at least one4+connection is made from water-soluble oxygenating hydrocarbon, have properties that correspond to each of the properties in detail opissyvayusya in the above positions from MF-i to MF-vix, more often each of the preferred values for each property in detail opissyvayusya in the above positions from MF-i to MF-vix.

Heavy fractions

The heavy fractions of the component containing at least one C4+the connection is made from water-soluble oxygenating hydrocarbon, preferably have one or more of the following properties (from HF-i to HF-vi):

(HF-i) is T in the range from 220 to 380°C., more preferably in the range of from 260 to 360°C;

(HF-ii) paced the fever outbreaks in the range from 30 to 70°C, more preferably in the range from 33 to 60°C;

(HF-iii) density at 15°C in the range from 700 to 900 kg/m3more preferably in the range of from 750 to 850 kg/m3;

(HF-iv) sulfur content equal to at most 5 mg/kg, more preferably at most 1 mg/kg;

(HF-v) oxygen levels equal to, at most, 10% (mass.), more preferably at most 8% (mass.);

(HF-vi) viscosity at 40°C in the range from 0.5 to 6 cSt, more preferably in the range from 1 to 5 cSt.

Usually the heavy fractions of the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, have properties that correspond to each of the properties in detail opissyvayusya in the above positions from HF-i to HP-vi, more often each of the preferred values for each property in detail opissyvayusya in the above positions from HF-i to HF-vi.

Composition of liquid fuels

The amount of component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon and is present in the composition of the liquid fuel of the present invention is at least 0.1 percent (by vol.) in the calculation of the total volume of the composition of the liquid fuel. More preferably the number to the component made from water-soluble oxygenating hydrocarbon and is present in the composition of the liquid fuel of the present invention, optionally corresponds to one or more of the following parameters (i) to (XX):

(i) at least a 0.5% (vol.)

(ii) at least 1% (vol.)

(in) at least a 1.5% (vol.)

(iv) at least 2% (vol.)

(V) at least a 2.5% (vol.)

(vi) at least 3% (vol.)

(vii) at least 3,5% (vol.)

(viii) at least 4% (vol.)

(ix) at least 4,5% (vol.)

(X) at least 5% (vol.)

(xi) most of 99.5% (vol.)

(xii) at most, 99% (vol.)

(xiii) at most 98% (vol.)

(xiv) at most 97% (vol.)

(XV) at most 96% (vol.)

(xvi) at most 95% (vol.)

(xvii) the most, 90% (vol.)

(xviii) at most 85% (vol.)

(xix) at most, 80% (vol.)

(XX) at most 75% (vol.)

Typically, the amount of component containing at least one4+connection is made from water-soluble oxygenating hydrocarbon and is present in the composition of the liquid fuel of the present invention, corresponds to one parameter selected from the above items (i) to (x), and one parameter selected from the above positions from (xi) to (XX).

Usually in the case of the gasoline compositions of the present invention, the quantity is the creation of the component, containing at least one4+connection is made from water-soluble oxygenating hydrocarbon and is present in the composition of gasoline, will be in the range from 0.1 to 60% (vol.), from 0.5 to 55% (vol.) or from 1 to 50% (vol.).

Usually in the case of diesel fuel compositions of the present invention, the amount of component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon and is present in the composition of diesel fuel would be in the range of from 0.1 to 60% (vol.), from 0.5 to 55% (vol.) or from 1 to 50% (vol.).

Usually in the case of the compositions of kerosene of the present invention, the amount of component containing at least one4+connection is made from water-soluble oxygenating hydrocarbon and is present in the composition of kerosene will be in the range from 0.1 to 90% (vol.), from 0.5 to 85% (vol.) or from 1 to 80% (vol.), as in the range from 0.1 to 60% (vol.), from 0.5 to 55% (vol.) or from 1 to 50% (vol.).

The composition of the liquid fuel of the present invention is usually chosen from the composition of gasoline, kerosene or diesel fuel.

In the case of the composition of liquid fuel in the form of a composition of the gasoline composition of gasoline will be characterized by an initial boiling point in the range of the t 15°C to 70°C. (IP123), the temperature of the end of the boil, equal at most 230°C. (IP123), a is each in the range from 85 to 110 (ASTM D2699) and is MUCH in the range from 75 to 100 (ASTM D2700).

In the case of the composition of liquid fuel in the form of a composition of the kerosene composition of kerosene will be characterized by an initial boiling point in the range from 110 to 150°C., the temperature of the end of the boil in the range from 200 to 320°C and viscosity at 20°C in the range from 0.8 to 10 mm2/s (ASTM D445).

In the case of the composition of liquid fuel in the form of a composition of the diesel fuel composition of diesel fuel will be characterized by an initial boiling point in the range from 130°C to 230°C. (IP123), a temperature of the end of the boil, equal at most 410°C. (IP123), and cetane number in the range from 35 to 120 (ASTM D613).

Preferably the composition of the liquid fuel of the present invention further comprises one or more fuel additives.

The composition of gasoline

The composition of gasoline corresponding to the present invention usually contains a mixture of hydrocarbons boiling in the range from 15 to 230°C, more frequently in the range from 25 to 230°C (EN-ISO 3405). The initial boiling point of the gasoline compositions of the present invention is in the range from 15 to 70°C. (IP123), preferably in the range of from 20 to 60°C., more preferably in the range of from 25 to 50°C. the temperature of the end of the pile, the Oia compositions of gasoline, of the present invention is at most 230°C., preferably at most 220°C., more preferably at most 210°C. the Optimum ranges and distillation curves usually vary according to climate and season of the year.

In addition to the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, the hydrocarbon composition of gasoline can be produced by any method known state of the art, usually hydrocarbons can be produced by any known method from straight-run gasoline, synthetically derived aromatic hydrocarbon mixtures, hydrocarbons subjected to thermal or catalytic cracking of petroleum fractions subjected to hydrocracking, hydrocarbons, is subjected to catalytic reforming, or mixtures thereof.

Research octane number (IOC) of the gasoline compositions of the present invention is in the range from 85 to 110 (ASTM D2699). Preferably the value of each composition of the gasoline will be at least 90, for example, be in the range of from 90 to 110, more preferably be at least 91, for example, be in the range from 91 to 105, even more preferably to make, at m is re, 92, for example, be in the range from 92 to 103, more preferably be at least 93, for example, be in the range of from 93 to 102, and most preferably be at least 94, for example, be in the range from 94 to 100.

Motor octane number (MOC) of the gasoline compositions of the present invention is in the range from 75 to 100 (ASTM D2699). Preferably is MOC composition of the gasoline will be at least 80, for example, be in the range of from 80 to 100, more preferably be at least 81, for example, be in the range of from 81 to 95, more preferably be at least 82, for example, be in the range of from 82 to 93, more preferably be at least 83, for example, be in the range of from 83 to 92, and most preferably be at least 84, for example, to be in the range of 84 to 90.

Typically, the compositions of gasoline contain a mixture of components selected from one or more of the following groups: saturated hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons and oxygendemand hydrocarbons. Typically, the composition of the gasoline may contain a mixture of saturated hydrocarbons, olefinic hydrocarbons, aromatic hydrocarbons, and optionally oxygen avannah hydrocarbons.

Usually the content of olefinic hydrocarbons in the composition of gasoline is in the range from 0 to 40% (vol.) in the calculation of the amount of gasoline (ASTM D1319); preferably, the content of olefinic hydrocarbons in the composition of gasoline is in the range from 0 to 30% (vol.) in the calculation of the amount of the composition of gasoline, more preferably a content of olefinic hydrocarbons in the composition of gasoline is in the range from 0 to 20% (vol.) in the calculation of the amount of the composition of gasoline.

Typically, the content of aromatic hydrocarbons in the composition of gasoline is in the range from 0 to 70% (vol.) in the calculation of the amount of gasoline (ASTM D1319), for example, the content of aromatic hydrocarbons in the composition of gasoline is in the range from 10 to 60% (vol.) in the calculation of the amount of the composition of gasoline; preferably, the content of aromatic hydrocarbons in the composition of gasoline is in the range from 0 to 50% (vol.) in the calculation of the amount of the composition of gasoline, for example, the content of aromatic hydrocarbons in the composition of gasoline is in the range from 10 to 50% (vol.) in the calculation of the amount of the composition of gasoline.

The levels of benzene in the composition of gasoline is at most 10% (vol.), more preferably, at most 5% (by vol.), in particular, at most, 1% (vol.), in calculating n is the number of compositions of gasoline.

The composition of the gasoline is preferably characterized by a low or ultra-low sulfur level, for example, equal to, at most, 1000 hours/million (mass.) (mass parts per million parts), preferably not more than 500 hours/million (mass.), more preferably not more than 100, even more preferably not greater than 50, and most preferably not more than 10 hours/million (mass.).

The composition of gasoline is also preferably characterized by a low total lead levels, such as at most 0.005 g/l, most preferably is free of lead - contains no added lead compounds (i.e., is neosvoennoy).

In the case of content in the composition of gasoline oxygenated hydrocarbons, at least a portion deoxygenating hydrocarbons will replace oxygendemand hydrocarbons. The level of oxygen content in gasoline can reach up to 30% (mass.) (EN 1601) based on the weight of the composition of gasoline. For example, the level of oxygen content in gasoline can reach up to 25% (mass.), preferably up to 10% (mass.). Typically, the concentration of oxygenates will meet the minimum concentration selected from any one of 0, 0,2, 0,4, 0,6, 0,8, 1,0 and 1.2% (mass.), and the maximum concentration selected from any one of 5, 4,5, 4,0, 3,5, 3,0 � 2,7 mass percent.

Examples of oxygenated hydrocarbons, non-oxygenated hydrocarbons that may be present in the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, which may be included in gasoline, include alcohols, ethers, esters, ketones, aldehydes, carboxylic acids and their derivatives, and oxygen-containing heterocyclic compounds. Preferably oxygendemand hydrocarbons that can be included in the gasoline, which are selected from alcohols (such as methanol, ethanol, propanol, isopropanol, butanol, tert-butanol and isobutyl alcohol), ethers (preferably ethers containing 5 or more carbon atoms per molecule, for example, methyl tert-butyl ether) and esters (preferably ethers containing 5 or more carbon atoms per molecule); one particularly preferred oxygenated hydrocarbon is an ethanol.

In the case of the presence in the composition of gasoline oxygenated hydrocarbons, the amount of oxygenated hydrocarbons in the composition of gasoline can vary over a wide range. For example, in countries such as Brazil and the USA, currently commercially available gasolines containing a major proportion of oxygenated ug is evagorou, for example, E85, and gasoline containing a minor proportion of oxygenated hydrocarbons, for example, E10 and E5. Therefore, the amount of oxygenated hydrocarbons present in the composition of the gas, preferably selected from one of the following quantities: up to 85% (by vol.); up to 65% (by vol.); up to 30% (vol.); up to 20% (by vol.); up to 15% (vol.); and up to 10% (by vol.), depending on the desired final formulation of gasoline. Typically, the composition of the gasoline may contain at least 0.5, 1.0, or 2.0 percent (vol.)oxygenated hydrocarbons.

Examples of suitable compositions include gasoline gasoline, which are characterized by a content of olefinic hydrocarbons in the range from 0 to 20% (vol.) (ASTM D1319), the level of oxygen content in the range from 0 to 5% (mass.) (EN 1601), and polynuclear aromatic hydrocarbons in the range from 0 to 50% (vol.) (ASTM D1319) and levels of benzene equal to, at most, 1% (vol.).

Although it is not critical to the present invention, but the composition of the gasoline of the present invention typically can optionally include one or more fuel additives. The concentration and nature of the fuel additives (additives) that can be included in the composition of the gasoline of the present invention, are not critical. Non-limiting examples of suitable types of fuel additives to the e can be included in the composition of the gasoline of the present invention, include antioxidants, corrosion inhibitors, detergents, additives to prevent turbidity fuel anti-knock additives, decontamination officers metals, compounds that protect from increased wear of the valve seat, colouring agents, friction modifiers, liquid carriers, diluents and markers. Examples of suitable such additives in General are described in U.S. patent No. 5855629.

Usually the fuel additives can be mixed with one or more diluents or liquid media to obtain a concentrate of additives, then the additive concentrate may be blended with the composition of the gasoline of the present invention.

The concentration of the active substances) of any additives present in the composition of the gasoline of the present invention, preferably comes down to 1% (mass.), more preferably is in the range from 5 to 1000 hours/million (mass.), in an advantageous embodiment in the range from 75 to 300 hours/million (mass.), such as from 95 to 150 hours/million (mass.).

Alternatively, the composition of the gasoline of the present invention can be an aviation gasoline. In the case of the composition of the gasoline in the form of aviation gasoline, depending on the grade aviation gasoline motor octane lean mixture will comprise at least 80 (ASTM D2700) and motor octane number-enriched mixture b the children to be at least 87 (ASTM D 909), or motor octane lean a mixture will be at least 99,5 (ASTM D2700), and the grade of gasoline will be at least 130 (ASTM D 909). In addition, in the case of the composition of the gasoline in the form of aviation gasoline Reid vapor pressure at 37.8°C will be in the range from 38,0 49.0 kPa (ASTM D323), the temperature of the end of the boil will be at most 170°C (ASTM D 86), and the amount of tetraethyl lead will be most of 0.85 g Pb/l, the Composition of the oil fuel

The composition of the gasoline fuel of the present invention find application in aircraft engines, such as jet engines or aviation diesel engines, but also in any other suitable power source or ignition.

In addition to the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, the composition of kerosene fuel can contain a mixture of two or more different fuel components and/or include additives introduced, as described below.

Composition kerosene fuel will typically have a boiling point in the range from 80 to 320°C., preferably in the range of from 110 to 320°C., more preferably in the range from 130 to 300°C, depending on the brand and the COI is whether. Usually they will have a density in the range from 775 to 845 kg/m3preferably from 780 to 830 kg/m3at 15°C (e.g., ASTM D4502 or IP 365). Usually they will be characterized by an initial boiling point in the range from 80 to 150°C., preferably in the range of from 110 to 150°C., and the temperature of the end of the boil in the range from 200 to 320°C. Their kinematic viscosity at - 20°C (ASTM D445) is typically in the range from 0.8 to 10 mm2/sec, preferably from 1.2 to 8.0 mm2/s.

In the case of the composition of the oil fuel may be desirable content of the fuel produced by the method of Fischer-Tropsch, if the composition of the gasoline fuel, indeed, will contain the fuel produced by the method of Fischer-Tropsch, usually it will contain 5% (vol.) or more, preferably 10% (vol.) or more or more preferably 25% (vol.) and more fuel is produced according to the method of Fischer-Tropsch.

The fuel produced by the method of Fischer-Tropsch must be suitable for use as kerosene fuel. Therefore, its components (or most of them, for example, 95% (mass.) and more) should have a boiling point in the above range, that is from 110 to 320°C., preferably from 130 to 300°C. In a suitable case, it will be characterized by the distillation temperature to 90% (vol./about.) (T90) in the range of about 180 to 250°C. preferably 180 to 230°C.

The term "manufactured by the method of Fischer-Tropsch" implies that the fuel is a product of synthesis according to the method of condensation of the Fischer-Tropsch or is it derived. The reaction of the Fischer-Tropsch process converts carbon monoxide and hydrogen into longer chain, usually paraffinic, hydrocarbons:

n(CO+2H2)=(-CH2-)n+nH2O+heat

in the presence of an appropriate catalyst and typically at elevated temperatures (for example, in the range from 125 to 300°C., preferably from 175 to 250°C) and/or pressures (e.g., in the range from 500 to 10000 kPa, preferably from 1200 to 5000 kPa). If desired, can be used for quantitative ratio of hydrogen:carbon monoxide is other than 2:1.

Themselves monoxide and hydrogen can be produced from organic or inorganic, natural or synthetic sources, usually either from natural gas or from organically produced methane.

Kerosene product can be obtained directly as a result of this reaction, or indirectly, for example, in the fractionation product of the Fischer-Tropsch synthesis or subjected to hydrobromide product of the Fischer-Tropsch synthesis. Hydrobromide may include hydrocracking to regulate boiling range (see, nab is emer, publication GB-B-2077289 and EP-A-0147873) and/or hydroisomerization, which can improve characteristics of ludoteques basic fuel increased proportion of branched paraffins. In the publication EP-A-0583836 describes the two-stage method of hydrobromide by which the product of the Fischer-Tropsch synthesis is first subjected to hydroconversion in conditions such that it is essentially not subject to any isomerization or hydrocracking (this leads to hydrogenation of olefins and oxygen-containing components) and after that at least part of the resulting product is subjected to hydroconversion under conditions such that the hydrocracking and isomerization proceeded to obtain essentially paraffinic hydrocarbon fuel. Desirable kerosene fraction (fraction) can then be selected, for example, by distillation.

To modify the properties of the condensation products of the Fischer-Tropsch process can be used in other processing after synthesis, such as polymerization, alkylation, distillation, cracking-decarboxylation, isomerization and hydroreforming, as described, for example, in the publication US-A-4125566 and US-A-4478955.

Typical catalysts for the synthesis of paraffin hydrocarbons by the method of Fischer-Tropsch contain as catalytically active component, a metal of the group VIII of the periodic table, in particular, ruthenium, iron, cobalt or Nickel. Suitable such catalysts are described, for example, in the publication EP-A-0583836 (pages 3 and 4).

One example of the method based on the method of Fischer-Tropsch is a way SMDS (synthesis of middle distillate from the Shell), vpisivaushiesya in the publication "The Shell Middle Distillate Synthesis Process", van der Burgt et al. (paper delivered at the 5thSynfuels Worldwide Symposium, Washington DC, November 1985; see also the publication from November 1989 with the same title from Shell International Petroleum Company Ltd., London, UK). This method (also sometimes called " technology "conversion of gas-to-liquid" or "YLL" from Shell™) results in products sredneminimalnogo range in the conversion of synthesis gas produced from natural gas (mainly methane), heavy long-chain hydrocarbon (paraffin) wax, which can then be subjected to hydroconversion and fractionation to produce liquid transport fuels such as kerosene composition of the fuel. One version of the method SMDS using a reactor with a fixed bed stage catalytic conversion, is currently used in Bintulu, Malaysia, and its products were mixed with the oils, produced from the crude oil in commercially available automotive fuels.

Gasoil and kerosene, the floor is obtained according to the method of the SDMS are, commercially available in the company Royal Dutch/Shell Group of Companies.

In an appropriate case, in accordance with the present invention kerosene fuel produced by the method of Fischer-Tropsch will consist of at least 90% (mass.), preferably, at least 95% (mass.), more preferably, at least 98% (mass.), even more preferably, at least 99% (mass.), most preferably, at least 99,8% (mass.), paraffin components typically normal paraffins and isoparaffins. The mass ratio between normal paraffins and ISO preferably will be within the ranges shown above. The actual value for this ratio will be determined partly by way of hydroconversion used to produce kerosene from the product of the Fischer-Tropsch synthesis. Also there might be some cyclic paraffins.

Thanks to the method of Fischer-Tropsch kerosene produced by the method of Fischer-Tropsch, characterized essentially by the absence of sulfur and nitrogen or undetectable levels of their content. Compounds containing these heteroatoms, tend to perform the function of poisons for catalysts for Fischer-Tropsch, and therefore they are removed from the feedstock in the form of synthesis gas. In addition, usually implemented method does not or almost does not lead to the floor of the structure of aromatic components. The content of aromatics in kerosene Fischer-Tropsch process as defined in accordance with ASTM D4629 will usually be less than 5% (mass.), preferably less than 2% (mass.), more preferably less than 1% (mass.), and most preferably less than 0.2% (mass.).

Kerosene produced according to the method of Fischer-Tropsch process, which can be used in the compositions of the gasoline fuel of the present invention, will typically be characterized by a density in the range from 730 to 770 kg/m3at 15°C kinematic viscosity in the range from 1.2 to 6, preferably from 2 to 5, more preferably from 2 to 3.5 mm2/s at 20°C; and a sulfur content equal to 20 hours/million (mass.) (mass parts per million parts) or less, preferably 5 hours/million (mass.) or less.

Preferably it is a product obtained by carrying out the condensation reaction of methane according to the method of Fischer-Tropsch using quantitative ratio of hydrogen/carbon monoxide, less than 2.5, preferably less than about 1.75, more preferably in the range from 0.4 to 1.5, and in the ideal case when using a cobalt containing catalyst. In an appropriate case, it will be obtained from the subjected to hydrocracking product of the Fischer-Tropsch synthesis (for example, as described in public is of GB-B-2077289 and/or EP-A-0147873) or more preferably the product of the two-way hydroconversion, such as the one described in the publication EP-A-0583836 (see above). In the latter case, the preferred features of the process of hydroconversion can be those which are described on pages 4 to 6 and the examples in the publication EP-A-0583836.

The composition of the gasoline fuel of the present invention preferably contains not more than 3000 hours/million (mass.) sulfur, more preferably not more than 2000 hours/million (mass.), or not more than 1000 hours/million (mass.), or not more than 500 hours/million (mass.), of sulfur.

In the composition of the gasoline fuel or its components it is possible to introduce additives (composition containing additives) or not to introduce additives (composition, free from additives). In the case of the introduction of additives, for example, at the refinery or at a later stage distribution of fuel, the composition will contain a minor amount of one or more additives selected from, for example, additives for removing static charges (for example, STADIS™ 450 (from Octel)), antioxidants (for example, substituted (tertiary butyl)phenol), additives, decontaminating metals (for example, N,N'-disalicylidene-1,2-propandiamine), anti-icing fuel additives (for example, dietilaminoetilovogo ether), additives in the form of a corrosion inhibitor/lubricity improver (for example, APOLLO™ PRI 19 (Apollo), DCI 4A (from Octel), NALCO™ 5403 (from Naico)) or additives, which improve the heat resistance (e.g., ARA 101™ (Shell)), which is approved by the international civil and/or military specifications for jet fuel.

Unless other specified, then the concentration of the active substances) of each such additional component in the composition of the gasoline fuel containing additives introduced, will be at the levels required or permitted in the international technical requirements for jet fuel.

In the above statement of the amount (concentration, % vol., hours/million (mass.), % (mass.)) components treated with an active substance, that is, with the exception of volatile solvents/materials diluents, if only there were no other in the corresponding description.

The composition of the gasoline fuel of the present invention is particularly applicable in the case of use or intention of use of the composition of the gasoline fuel in a jet engine.

The composition of diesel fuel

The composition of diesel fuel corresponding to the present invention usually contains a mixture of hydrocarbons boiling in the range from 130 to 410°C, more frequently in the range from 150 to 400°C. the initial boiling point of diesel fuel compositions, suitable for the actual operation of the present invention, is in the range from 130 to 230°C. (IP123), preferably in the range of from 140 to 220°C., more preferably in the range of from 150 to 210°C. the temperature of the end of boiling compositions of diesel fuel, corresponding to the present invention, is at most 410°C., preferably, at most, 405°C, more preferably at most 400°C.

In addition to the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, the composition of diesel fuel may contain a mixture of two or more different components of diesel fuel, and/or it can be entered additives, as described below.

Such compositions diesel fuel will contain one or more base fuels, which typically may contain liquid hydrocarbon credability oil (gasoil), for example, gas oils produced from oil. Such fuel will typically have a boiling point within the aforementioned range, depending on grade and use. Usually they will be characterized by a density in the range from 750 to 1000 kg/m3preferably from 780 to 860 kg/m3at 15°C (e.g., ASTM D4502 or IP 365) and cetane number (ASTM D613) in the range from 35 to 120, more preferably from 40 to 85. Usually they will be characterised temperature is dependent on the initial boiling point is in the aforementioned range and the temperature of the end of the boil, equal at most 410°C., preferably, at most, 405°C, more preferably at most 400°C., most preferably in the range from 290 to 400°C. Their kinematic viscosity at 40°C (ASTM D445) in an appropriate case, it may be in the range from 1.2 to 4.5 mm2/s.

One example of the gas oil produced from oil, represents a basic fuel Swedish Class 1, which will be characterized by a density in the range from 800 to 820 kg/m3at 15°C (SS-EN ISO 3675, SS-EN ISO 12185), value T equal to 320°C and less, (SS-EN ISO 3405) and kinematic viscosity at 40°C (SS-EN ISO 3104) in the range from 1.4 to 4.0 mm2/s as identified in accordance with Swedish national specification EC1.

Optional diesel fuel can form or diesel fuel may be fuel-based remineralise oils, such as biofuels (other than the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon or fuel produced by the method of Fischer-Tropsch. These fuels Fischer-Tropsch process can be, for example, produced from natural gas, NGL, crude oil or shale oil, residue oil refining or oil shale, coal or biomass.

The amount of fuel produced by the method of the Fischer-Tropsch and used in the composition of diesel fuel of the present invention, may be in the range from 0% to the rest of the composition of diesel fuel (i.e., part of the composition of diesel fuel, which is not a component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon), preferably from 5% to the rest of the composition of diesel fuel, more preferably from 5% to 75% (vol.) from the composition of diesel fuel. In the case of this composition of diesel fuel may be desirable content of 10% (vol.) or more, more preferably 20% (vol.) and more, still more preferably 30% (vol.) and more fuel is produced according to the method of Fischer-Tropsch. In the case of such diesel fuels particularly preferred is a content of from 30 to 75% (vol.), and, in particular 30 to 70% (vol.), fuel produced by the method of Fischer-Tropsch. Carrying component of diesel fuel formed by the component that contains at least one4+connection is made from water-soluble oxygenating hydrocarbon, and optionally one or more other components of diesel fuel.

This component of the fuel produced by the method of Fischer-Tropsch, is any fraction in the range sredneminimalnogo fuel, which can be isolated from (not necessarily subjected to Otago the hydrocracking) of the product of the Fischer-Tropsch synthesis. Typical faction will boil within the boiling range of naphtha, kerosene or gas oil. Preferably use the product of Fischer-Tropsch boiling in the boiling range of kerosene or gas oil, because these products are easier to work with, for example, in a residential area. Such products in a suitable case will contain a number, greater than 90% (mass.), the fraction which boils in the range from 160 to 400°C., preferably to about 370°C. Examples of kerosene and gas oil produced by the method of Fischer-Tropsch, are described in the publications EP-A-0583836, WO-A-97/14768, WO-A-97/14769, WO-A-00/11116, WO-A-00/11117, WO-A-01/83406, WO-A-01/83648, WO-A-01/83 647, WO-A-01/8 3641, WO-A-00/20535, WO-A-00/20534, EP-A-1101813, US-A-5766274, US-A-5378348, US-A-5888376 and US-A-6204426.

The product of the Fischer-Tropsch process in a suitable case will contain more than 80% (mass.), but in a more appropriate case more than 95% (mass.), isoparaffins and normal paraf ins and less than 1% (mass.) aromatic, this carrying component is a naphthenic compounds. The level of sulfur and nitrogen is very low and usually less than the detection limits of these compounds. For this reason, the level of sulfur in the composition of diesel fuel containing the product of the Fischer-Tropsch process can be very low.

The composition of diesel fuel preferably contains not more than 5000 hours/million (mass.) sulfur, more preferably no more than what, than 500 hours/million (mass.), or not more than 350 hours/million (mass.), or not more than 150 hours/million, (mass.), or not more than 100 hours/million (mass.), or not more than 70 hours/million (mass.), or not more than 50 hours/million (mass.), or not more than 30 hours/million (mass.), or not more than 20 hours/million (mass.), or most preferably not more than 15 hours/million (mass.), of sulfur.

Diesel fuel typically also includes one or more fuel additives.

In the fuel based on diesel fuel it is possible to introduce additives (composition containing additives) or not to introduce additives (composition, free from additives). In the case of the introduction of additives, for example, at an oil company, it will contain minor amounts of one or more additives selected from, for example, additives for removing static charges, additives, reducing resistance to flow in pipes, additives that reduce hydraulic losses (for example, copolymers of ethylene/vinyl acetate or copolymers of acrylate/maleic anhydride), additives that improve lubricity, antioxidants and additives that protect from precipitation of wax.

Known and commercially available additives to diesel fuels, including detergents. Such additives can be added to diesel fuel at levels expected to reduce, eliminate or sameline the accumulation of deposits in the engine.

Examples of detergents that are suitable for use in additives for diesel fuel with the purposes of the present invention include polymethylsiloxane suktinimida or suktinimida polyamines, for example, polyisobutenylsuccinic or polyisobutenylsuccinic, aliphatic amines, Mannich bases or amines and a polyolefin (e.g., polyisobutylene-) -maleic anhydrides. Operations dispersant additives are described, for example, in the publication GB-A-960493, EP-A-0147240, EP-A-0482253, EP-A-0613938, EP-A-0557516 and WO-A-98/42808. Particularly preferred are polymethylsiloxane suktinimida, such as polyisobutenylsuccinic.

The mixture of additives to diesel fuel may contain other components in addition to the scrubbing insertion tool. Examples are the lubricity improvers; additives to prevent clouding of the fuel, for example, alkoxysilane phenol-formaldehyde polymers; protivopolozhnostei (for example, polysiloxane, modified simple polyester); additives to improve ignition, (cetane improvers) (e.g., 2-ethylhexanate (AGN), cyclohexylmethyl, di-tert-butylperoxide and those compounds which are described in the publication US-A-4208190 in the fragment from column 2, line 27 to column 3, the timing 21); anti-corrosion additives (for example, propane-12-diology complex polyether tetrapropylene acids or esters, derived from a polyhydric alcohol and a derivative of succinic acid, with a derivative of succinic acid has at least on one of its alpha-carbon atoms unsubstituted or substituted aliphatic hydrocarbon group containing from 20 to 500 carbon atoms, for example, pentaerythrityl complex fluids polyisobutylene succinic acid); corrosion inhibitors; odorants; anti-wear additives; anti-oxidants (for example, phenol derivatives, such as 2,6-di-tert-butylphenol, or phenylendiamine, such as N,N'-di-sec-butyl-p-phenylenediamine); the decontamination officers metals; combustion improvers; additives, removing static electricity; improvers of ludoteques; and additives that protect from precipitation of wax.

The mixture of additives to diesel fuel may contain a lubricity improver, especially in the case of small sulfur level (for example, 500 hours/million (mass.) and less) in the composition of diesel fuel. The composition of diesel fuel containing typed additives, lubricity improver usually present with a concentration of less than 1000 hours/million (mass.), preferably in the range from 50 to 1000 hours/million (mass.), more preferably from 70 to 1000 hours/million (mass.). Suitable commercially available lubricity improvers include p is ishiki on the basis of ester and acid. Other lubricity improvers are described in the patent literature, in particular, in connection with their use in diesel fuel, low sulfur content, for example:

- article Danping Wei and H. A. Spikes, "The Lubricity of Diesel Fuels", Wear, III (1986)217-235;

publication WO-A-95/33805 - improvers of ludoteques to improve lubricity of low-sulfur fuels;

publication WO-A-94/17160 - specific esters derived from carboxylic acid and alcohol, where the acid contains from 2 to 50 carbon atoms, and the alcohol contains 1 or more carbon atoms, in particular, glycerylmonostearate and diisobutylaluminum, as fuel additives to reduce wear in the injection system of the diesel engine;

publication US-A-5490864 - specific dithiophosphinate divertimenti based esters as anti-wear additives that increase lubricity to low-sulfur diesel fuels; and

publication WO-A-98/01515 - specific alkylaromatic compounds having at least one carboxyl group attached to aromatic nuclei, to impart antiwear action that increases lubricity, particularly in low-sulfur diesel fuels.

In the case of the composition of diesel fuel is preferred may also be soberanianational, more preferably in combination with an anti-corrosion additive and/or a corrosion inhibitor and/or an additive that improves lubricity.

Unless other specified, then the concentration of the active substances) of each component of the additives in the composition of diesel fuel containing additives introduced, preferably will reach up to 10000 hours/million (mass.), more preferably be in the range of from 0.1 to 1000 hours/million (mass.), in the best case, from 0.1 to 300 hours/million (mass.), such as from 0.1 to 150 hours/million (mass.).

The concentration of the active substances) of any additives to prevent clouding of the fuel in the composition of diesel fuel preferably will be in the range from 0.1 to 20 hours/million (mass.), more preferably from 1 to 15 hours/million (mass.), even more preferably from 1 to 10 hours/million (mass.), in the best case, from 1 to 5 hours/million (mass.). Concentration (active substance) present any additives which improve the ignition, preferably will be 2600 hours/million (mass.) or less, more preferably 2000 hours/million (mass.) and less opportunity to be in the range from 300 to 1500 hours/million (mass.). The concentration of the active substances) of any detergent additive in the composition of diesel fuel preferably will be in the range from 5 to 1500 hours/million (mass), more preferably from 10 to hours/million (mass.), most preferably from 20 to 500 hours/million (mass.).

In the case of the composition of diesel fuel, for example, a mixture of fuel additives will typically contain detergent additives, optionally together with other aforementioned components and diluent that is compatible with diesel fuel, which may be a mineral oil, a solvent, such as those sold by Shell companies under the trade mark "SHELLSOL", a polar solvent, such as esters and, in particular, an alcohol, for example, hexanol, 2-ethylhexanol, decanol, isotridecanol and mixtures of alcohols, such as those sold by Shell companies under the trade mark "LINEVOL", especially alcohol LINEVOL 79, which is a mixture With7-9primary alcohols, or a mixture With12-14alcohols which are commercially available.

The total content of additives in the composition of diesel fuel in an appropriate case, it may be in the range from 0 to 10000 hours/million (mass.), and preferably to be less than 5000 hours/million (mass.).

In the above statement of the amount (concentration, % vol., hours/million (mass.), % (mass.)) components refer to the active substance, that is, with the exception of volatile solvents/materials thinners.

The method of obtaining the composition of liquid fuels

The composition of the liquid fuel this is part II of the invention is produced by mixing:

(a) component produced from water-soluble oxygenating hydrocarbon, and

(b) at least one fuel component.

The term "component fuel" refers to a component used to obtain the composition of the liquid fuel, or the composition of the liquid fuel as such, which does not represent a component produced from water-soluble oxygenating hydrocarbon. Examples of propellants include components of fuels that are currently used in the production of gasoline, kerosene and/or diesel fuel, such as flows of products produced from crude oil, flows of products produced by the method of Fischer-Tropsch, oxygenates and biofuel components.

Usually threads of products produced from crude oil, are the streams of products derived from oil refining company and also referred to herein threads refineries. Non-limiting examples of such flows refineries include:

- C4s"(low-boiling fraction, usually containing more than 80% (vol.) paraffin and olefin With4connections).

- Light straight-run fractions (fractions PL) or naphtha (low-boiling fraction With4-C7hydrocarbons (temperature end of the boil, lower than p is blithedale 140°C). These hydrocarbons are mainly paraffins and low octane. The flow is characterized by a low content of aromatics and a certain level of content of naphthenes).

- Isomeric (low-boiling fraction (temperature end boiling point less than about 110°C), resulting from the isomerization of C5and C6paraffins in the faction PL/ligroin to obtain isomers with higher octane number).

- Lightweight, untreated () or heavy platformate (or a light crude (BUT) or heavy reformed) (fraction resulting from catalytic reforming of naphtha, subjected hydrobromide, to receive the stream of high-octane, high content of aromatics and low content of olefins).

- Alkylate (including aviation alkylate) (fraction resulting from the alkylation of isobutane C4and3the olefins to obtain high-octane paraffins from branched chain).

Light or heavy catalytic cracking gasoline (VCC or TBCC) (fraction resulting from the processing of heavier threads in the catalytic cracking fluidized-bed catalyst for more lung ug is evagorou, including olefins).

- Straight-run kerosene (fraction characterized by a high content of paraffin hydrocarbons and usually by distillation temperature in the range from approximately 150°C +/-10°C. to about 260°C +/- approximately 20°C).

- Sweet kerosene oil (straight-run kerosene, which was subjected to processing for reducing levels of mercaptan, as well as reducing levels of total acid).

- Kerosene, subjected hydrobromide or Hydrotreating (straight-run kerosene, subjected soft hydroperiod, which is characterized by low levels of mercaptan, sulfur, olefins, acids, and metals).

- Kerosene subjected to rigid hydroperiod, (such as kerosene, deep hydrogenation, kerosene, subjected to hydrogenation desulfurization, kerosene, subjected to hydrocracking, (straight-run kerosene, which was subjected to more rigid hydroperiod than kerosene, subjected hydrobromide that usually leads to low levels of sulfur and nitrogen)).

- Straight-run distillates, boiling in the boiling range of diesel fuel.

- Gas oil is subjected to hydrocracking, (AGO).

Light oils from plants for coking subjected to cracking and hydrobromide.

- Gas oil is subjected to catalytic is cracking, (GED).

The oils subjected to thermal or steam cracking.

Oxygenates and components biofuels represent any such component that is suitable for use in compositions of liquid fuels, such as those described above in this document.

The method of obtaining the composition of gasoline

To obtain the composition of the gasoline of the present invention the aforementioned component produced from water-soluble oxygenating hydrocarbon, in particular, a light fraction of a component produced from water-soluble oxygenating hydrocarbon, unite, at least one component of the fuel.

The typical components of a fuel that can be mixed with a component produced from water-soluble oxygenating hydrocarbon, to obtain the composition of gasoline corresponding to the present invention, include:

- Composition of gasoline as such;

Streams refineries, such as C4s, fraction SQUARE, isomerate, light platformate, platformate BUT heavy platformate, alkylate, LBCC and TBCC;

- Oxygenates, such as alcohols and ethers. The preferred oxygenate components include methanol, ethanol, propanol, butanol, methyl(tertiary butyl) ether (MTBE) and ethyl(tertiary butyl) ether(ETBE); and

Components of biofuels, such as those described above in this document.

The term "composition of gasoline" in the case of its use in relation to a component of a fuel refers to a composition defined in the above section on the composition of gasoline.

Usually the composition of the gasoline of the present invention is produced by means of mixing:

(a) light fraction aforementioned component produced from water-soluble oxygenating hydrocarbon, and

(b) at least one fuel component selected from the stream refineries.

Preferably the composition of the gasoline of the present invention is produced by means of mixing:

(a) light fraction produced from water-soluble oxygenating hydrocarbon, as described above, and

(b) at least one fuel component selected from threads refineries in the form of C4s, fractions SQUARE, isomerate, light platformate, platformate BUT heavy platformate, alkylate, LBCC and TBCC; and optional oxygenate selected from ethanol, MTBE and ETBE.

More preferably the composition of the gasoline of the present invention is produced by means of mixing:

(a) light fraction aforementioned component produced from p is starimage in water oxygenating hydrocarbon, and

(b) at least one fuel component selected from threads refineries in the form of C4s, fractions SQUARE, heavy platformate, alkylate and LBCC; and optionally ethanol.

Depending on the amount of light fraction component produced from water-soluble oxygenating hydrocarbon, is used, the amount of used fuel components will vary to obtain the composition of gasoline with desirable properties.

For example, the composition of the gasoline of the present invention can be obtained by mixing:

(a) at least 0.1 percent (by vol.), in the calculation of the total volume of the fuel composition, light fraction aforementioned component produced from water-soluble oxygenating hydrocarbon, and

(b) at least one fuel component selected from threads refineries, in the following amounts: from 1 to 15% (vol.) C4sfrom 3 to 25% (vol.) fractions SQUARE, from 0 to 50% (vol.) heavy platformate, from 5 to 20% (vol.) alkylate and from 10 to 35% (vol.) VCC, based on the total number of the fuel composition; and optionally up to 85% ethanol, based on the amount of the total fuel composition.

Upon receipt of the gasoline compositions of the present invention, gellately the output may be a decline in the relative quantity of any fractions of DPS and/or heavy platformate in the composition of gasoline, relevant to the present invention, when increasing amounts of light fraction aforementioned component produced from water-soluble oxygenating hydrocarbon. Therefore, the composition of the gasoline of the present invention can be obtained by replacing at least part of any PL fractions and/or heavy platformate used in the production of gasoline, a light fraction of the aforementioned component produced from water-soluble oxygenating hydrocarbon.

Alternatively, the composition of the gasoline of the present invention is produced by means of mixing:

(a) light fraction aforementioned component produced from water-soluble oxygenating hydrocarbon, and

(b) the composition of gasoline.

If the resulting composition of gasoline is aviation gasoline, upon receipt of such aviation gasoline corresponding to the present invention, no oxygenates are not used.

The method of obtaining the composition of kerosene

To obtain the composition of kerosene present invention the aforementioned component produced from water-soluble oxygenating hydrocarbon, in particular, the average fraction of a component produced from water-soluble oxygenating hydrocarbon, unite, Myung is our least one component of the fuel.

The typical components of a fuel that can be mixed with a component produced from water-soluble oxygenating hydrocarbon, to obtain the composition of kerosene corresponding to the present invention, include threads refineries, such as straight-run kerosene, sweet kerosene, kerosene, subjected hydrobromide or Hydrotreating, and kerosene, subjected to rigid hydroperiod.

Usually the composition of kerosene present invention is produced by means of mixing:

(a) average fraction of the aforementioned component produced from water-soluble oxygenating hydrocarbon, and

(b) at least one fuel component selected from threads refineries in the form of straight-run kerosene, sweet kerosene, kerosene, subjected hydrobromide or Hydrotreating, and kerosene, subjected to rigid hydroperiod.

The method of obtaining the composition of diesel fuel

To obtain the composition of diesel fuel of the present invention the aforementioned component produced from water-soluble oxygenating hydrocarbon, in particular, the heavy fraction of a component produced from water-soluble oxygenating hydrocarbon, beginat, at least one component of the fuel.

The typical components of a fuel that can be mixed with a component produced from water-soluble oxygenating hydrocarbon, to obtain the composition of diesel fuel corresponding to the present invention, include:

The composition of diesel fuel as such;

Streams refineries, such as straight-run distillates, boiling in the boiling range of diesel fuel, gasoil, subjected to hydrocracking, (AGO), light oils from plants for coking subjected to cracking and hydrobromide, the oil is subjected to catalytic cracking, (GED), gasoil, subjected to a heat and steam cracking;

Components of biofuels, such as those described herein above.

The term "composition of diesel fuel" in the case of its use in relation to the fuel component is meant a composition defined in the above section on the composition of diesel fuel.

Usually the composition of diesel fuel of the present invention is produced by means of mixing:

(a) the heavy fractions of the aforementioned component produced from water-soluble oxygenating hydrocarbon, and

(b) at least one fuel component, Ibraimova from the stream refineries.

Preferably the composition of diesel fuel of the present invention is produced by means of mixing:

(a) the heavy fractions of the aforementioned component produced from water-soluble oxygenating hydrocarbon, and

(b) at least one fuel component, ubiraeva flows from refineries in the form of straight-run distillates, boiling in the boiling range of diesel fuel, gas oil, is subjected to hydrocracking, (AGO), light oils from plants for coking subjected to cracking and hydrobromide, gas oil, is subjected to catalytic cracking, (GED), gas oil, subjected to a heat and steam cracking; and optional component of biofuels.

The present invention additionally provides a method of operating an internal combustion engine, jet engine, or a steam boiler, where the method comprises introducing into the combustion chamber of the engine or steam boiler composition of the liquid fuel corresponding to the present invention.

The present invention will be further understood after reading the following further examples.

Examples

Examples of reactor systems

Example 1

Figure 8 shows a flowsheet illustrating one reactor system suitable for use when implemented and in practice of the present invention. The reservoir for the source of the raw material 1 performs a function of reservoir storage solutions feedstock. The solution of the initial raw material is brought from the reservoir to the source of the raw material 1 in the supply pump 3 through the supply line 2, after that it perepuskat on the discharge line 4 in the pre-heater 5. Pre-heater 5 may be a heat exchanger, heated by the heater with the heating resistor, or any other heat exchanger, the known state of the art. Thereafter, the preheated feedstock perepuskat on line 6, and in some cases combine with hydrogen 7 before introduction into the reactor 9 through line 8. One illustration of the potential of the reactor 9 is presented in figure 11 and more fully described in the example below, 4.

The temperature of the walls of the reactor 9 is maintained with the use of heaters blocks 10A, 10b, 10C and 10d, in this case, the heater with the heating resistor. After exiting the reactor 9, the reaction products do in-line outlet of the reactor 11 and is cooled to a temperature close to ambient temperature, in the refrigerator products of the reactor 12, which in result leads to the production of potentially three-phase product stream. From refrigerators products of the reactor 12, the reaction products pass through line 13 to the control valve the pressure is Oia 14, which is optionally used to control the pressure at the outlet of the reactor.

After the valve 14 products on line 15 enter the phase separator 16, where they're segregated into three separate phases: (1) non-condensable gas components 17, containing mainly hydrogen, carbon dioxide, methane, ethane and propane; (2) an organic liquid fraction 18, containing both hydrocarbons and3-30alcohols, ketones and carboxylic acids; and (3) the aqueous layer 19 containing mainly water and soluble in water oxygendemand compounds such as ethanol, isopropanol, acetone, propanol and acetic acid. Non-condensable gas fraction 17 can be directed along the line of the gaseous products of 20 in the reducing valve pressure 21. Pressure separator 16 is maintained with the use of the valve reducing the pressure 21. In an alternative mode of operation of the separator 16 can be maintained at a pressure approximately the same as the pressure at the outlet of the reactor, resulting in the discovery or exclusion of the valve. 14. In an alternative mode of operation then the pressure at the outlet of the reactor is controlled by the action of the valve reducing the pressure 21. The flow rate and the gas composition was measured after leaving the system through line 22.

Organic liquid fraction 18 leaves the separator p is line 23 before entering the valve shutter organics 24. The level of the organic phase in the separator is controlled in the control valve 24. The flow and composition of the organic fraction is determined after leaving the organic fraction of the system on line 25. Water liquid fraction 19 leaves the separator through line 26 before entering the valve shutter bottom sludge separator 27. The level of the aqueous phase in the separator is controlled in the control valve 27.

The flow and composition of the water fraction can be determined after leaving the water fraction of the system through line 28. In one alternative mode of operation as the organic liquid fraction 18 and water liquid fraction 19 leave the system through the valve shutter bottom sludge separator 27 and line 28, before the split in the decanter for measuring the composition and costs of the individual phases.

In all cases, alternative modes of operation do not affect the investigated catalytic methods. Alternative modes of operation may be used as recognized reasonable steps to optimal control method depending on the relative costs of gas phase 17, the organic liquid phase 18 and the aqueous phase 19.

Prior to initiating the flow of the feedstock in the reactor, unless other specified, the catalysts were recovered in stream flow, bodoro is and at 400°C, regardless of the restore is complete before loading the catalyst into the reactor.

Example 2

Figure 9 shows a flowsheet illustrating another reactor system suitable for use in the practice of the present invention. This configuration of the reactor comprises two separate reactor availability operation of both reactors with a serial connection or operation of only the first reactor. In addition, this configuration makes possible the elimination of the catalyst in the second reactor out of operation and the regeneration of his "place". After regeneration, the second reactor can be returned to operation without affecting the operation of the first reactor.

The reactor is similar to the reactor of example 1 with the exception that the reaction products from the refrigerator of the reaction products 12 could be directed to the second reactor through line 14 or directed to bypass the second reactor by-pass in the result of by-passing the line 44. In the case of the second reactor, the flow will be from the line 14 to the pressure regulating valve 15. The pressure regulating valve 15 may be used to control the pressure at the outlet of the first reactor. From the valve pressure regulation 15, the flow goes to stoparea valve to the inlet of the second reactor 17 and line 18. From line 18 to p the current flows in the line 19 and the pre-heater of the second reactor 20. In the illustrated embodiment, the pre-heater 20 is a heat exchanger, heated by the heater with the heating resistor.

Thereafter, the preheated feedstock perepuskat on line 19 to the second reactor 22, which is more fully described in example 4. The wall temperature of the reactor 22 is maintained with the use of block heaters 23a, 23b, 23C and 24d - in this case, the heater with the heating resistor. After leaving the reactor, the reaction products do in-line outlet of the second reactor 24, and then cooled in the refrigerator product of the second reactor 25. From refrigerators product of the second reactor 26 process stream can be directed along lines 26 and 27 to stoparea the valve outlet of the second reactor 28, line 29, then 30, and then into the separator products 31.

In the case of desirability operation of the second reactor valve 17 and the valve 28 will open, while the bypass valve of the second reactor 45 is closed to prevent bypass flow of the second reactor by-pass. In the case of the desirability of operating only the first reactor or in the case of regeneration of the second reactor valve 17 and the valve 28 will be closed, while the valve 45 will be opened.In the case of traversal of the second reactor to bypass productpage reactor flows directly from line 13 to line 44, through the bypass valve 45, line 46 and then into the line 30. In any case, regardless of whether the second reactor to exploit or bypass the bypass, the flow will be from the line 30 to the separator products.

In the phase separator 31, the reaction products separated into a gaseous fraction 32, the organic fraction 33 and the aqueous fraction 34, as described above in example 1. The gaseous fraction 32 is directed along the line of the gaseous products of 35 to the reducing valve pressure 36. Pressure separator 31 is maintained with the use of the valve reducing the pressure 36. In the case of operation of the second reactor 22 through the action of the valve reducing the pressure 36 will control the pressure at the outlet of the second reactor 22. In the case of traversal of the second reactor 22 to pass through the pressure reducing pressure 36 will control the pressure at the outlet of the first reactor 9.

The flow rate and the gas composition is measured when leaving the system through line 37. Organic liquid fraction 33 leaves the separator through line 38 before entering the valve shutter organics 39. The level of the organic phase in the separator is controlled in the control valve 39. The flow and composition of the organic fraction is determined after leaving the organic fraction of the system through line 40. Water liquid fraction 34 Sep'a leaves the ATOR on line 41 before entering the valve shutter bottom sludge separator 42. The level of the aqueous phase in the separator is controlled in the control valve 42. The flow and composition of the water fraction is determined after leaving the water fraction of the system through line 43. In one alternative mode of operation as the organic liquid fraction 33 and water liquid fraction 34 leave the system through the valve shutter bottom sludge separator 42 and line 43 before separation in the decanter for measuring the composition and costs of the individual phases. In all cases, alternative modes of operation do not affect the investigated catalytic methods. Alternative modes of operation are used as recognized reasonable steps to optimal control method depending on the relative costs of gas phase 35, organic liquid phase 33 and the aqueous phase 34.

Example 3

Figure 10 shows a process flowchart illustrating a reactor system with two feed pumps, suitable for use in the practice of the present invention. System with two feed pumps will be used, if desired, the mixture of the components of the feedstock will not exist in a single liquid phase. For example, two of the feed pump will be used if desirable feedstock in the form of a mixture of 50% (wt.) 2-pentanol and 50% (mass.) water is one the La delivery 2-pentanol, and the other for water delivery. Such a system can also be used for mixing raw materials, produced from two separate sources, such as the primary feedstock and oxygenfree hydrocarbon feedstock produced from the waste stream of the reactor system.

The first tank of raw materials 1 performs the function of a tank for the first solution of the feedstock, while the second tank to the source of raw materials 40 performs the function of the tank for the second solution of the feedstock. First the raw materials are delivered from the first tank to the source of the raw material 1 to the first supply pump 3 to the supply line of the first source of raw material 2. The first feedstock is then perepuskat on the discharge line of the first supply pump 4 to the supply line of the United feedstock 44. The second feedstock is delivered from the second tank to the source of raw material 40 in the second supply pump 42 through the supply line of the second feedstock 41. The second feedstock is then perepuskat along the line of discharge of the second feed pump 43 in the supply line combined feedstock 44. From the supply line combined feedstock 44 United feedstock perepuskat in the pre-heater 5. All other items are those that were shown in example with the exception what the aqueous phase 19 can be sent to a recycling tank for feedstock 40 for further processing or use in other ways.

Example 4

Figure 11 shows a schematic illustration of one type of reactor that can be used in the reactor systems described in examples 1, 2 and 3. The tube reactor 1 is formed of 316 stainless steel in the presence of either an internal diameter of 8.5 mm, or the inner diameter of 21.2 mm, depending on the experiment. Include line inlet 2 to ensure that the reactor feedstock or intermediate product, such as oxygenates. Include line outlet 3 for removal of the product from the reactor. A latching function in place of the layers of the medium pre-heating and catalyst takes the Frit inlet 4 formed of stainless steel. Wednesday pre-heating 5, consisting of granules of stainless steel, performs the function areas provide heat transfer from the walls of the reactor to ensure that the feedstock with the receipt of the catalyst 7 would be desirable temperature. To prevent mixing of materials between the environment pre-heating 5 and the catalyst 7 can be placed stainless steel mesh. Katal is jam 7 in its position may be based on the second Frit stainless steel 8.

In some cases, to provide a measurement of the temperature in the catalyst 7 and the preheating zone 5 can be a channel for input thermocouple 9. Controlled by keeping the temperature in the inlet hole of the reactor is carried out through the use of an external pre-heater before the introduction of the feedstock into the reactor through line 2, and may be held for more regulation in the control of heat transfer that takes place in the environment of pre-heating. In some cases, to achieve the desired temperature profile environment pre-heating is not required. Controlled keeping the wall temperature of the reactor is achieved by the use of external heaters in contact with the outer wall of the reactor. For controlled curing temperature of the wall of the reactor, if desired, can be used independently controlled zone heating.

Example 5 - Methods of analysis

The flows of products from opissyvayusya following examples were analyzed as follows. The organic liquid phase was collected and analyzed using a gas chromatograph or mass spectrometric detection or flame ionization detection. Separation of components was achieved when using the years of columns, containing bound 100% dimethylpolysiloxane stationary phase. The relative concentrations of the individual components were evaluated in the integration of peaks and dividing them by the sum of peak areas for the entire chromatogram. Compounds identified in the mapping result with a standard retention times and/or matching of mass spectra with compiled database of mass spectra. The compositions of the gas phase was determined by the method of gas chromatography using thermal conductivity detector and a flame ionization or mass spectrometric detectors for other components of the gas phase. The aqueous fraction was analyzed by the method of gas chromatography with and without using derivatization of organic components fractions using a flame ionization detector. The yields of products represent the number of carbon atoms present in each fraction of the product. Mass hourly space velocity (MCOS) was defined as the mass of the feedstock introduced into the system per unit mass of catalyst per hour and was calculated based on the mass oxygenating hydrocarbon feedstock with the exception of water present in the feedstock.

Getting oxygenates

Example 6 a catalyst for the hydrogenation

The catalyst of hiderow the deposits received in the result of adding the aqueous solution of dissolved nitrosylated ruthenium to carbon catalyst carrier (UU Carbon, Calgon, with particle sizes restricted to those that are retained on a sieve of 120 mesh after passing through a sieve of 60 mesh) to obtain the target level of 2.5% ruthenium. Water was added in excess pore volume, and evaporated in vacuum up to get a free flowing catalyst. Thereafter, the catalyst was dried overnight at 100°C in a vacuum drying Cabinet.

Example 7 a Catalyst RVF/deoxyadenosine

The combined catalyst RVF and deoxyadenosine received as a result of dissolution hexachloroplatinic acid and rhenium acid in water, and then add the mixture to the catalyst carrier in the form of monoclinic Zirconia (NorPro Saint-Gobain, Product code SZ31164, with particle sizes restricted to those that are retained on a sieve of 60 mesh after passing through the sieve 18 mesh) using the methods of achieving the initial moisture content to obtain the target level of the load plate 1.8% load, rhenium of 6.3% on the catalyst after subsequent decomposition of metal-containing precursors. The product was dried overnight in a vacuum drying Cabinet and then was progulivali in the stream of flowing air at 400°C.

Example 8 Transformation of sucrose into oxygenates

System catalysts referred to in the examples 6 and 7 examined for the conversion of sucrose in PR the intermediate product, containing oxygenates, when using the reactor system described in example 1. The study was performed using a tubular reactor made of stainless steel with an inner diameter of 21.2 mm, shown in example 4, and the analysis as described in example 5.

The reactor was loaded 31 grams of catalyst for the hydrogenation of example 6 and 76 grams of catalyst RVF from example 7, the hydrogenation catalyst was placed over the catalyst RVF when they are separated by a stainless steel mesh. Before the introduction of the feedstock into the reactor with the feedstock combined external hydrogen. Heaters, external to the reactor and shown on figure 8 in the positions 10A, 10b, 10C, 10d, kept at the following temperatures of the walls of the reactor: 10A - 125°C, 10b - 200°C, 10 ° C - 265°C 10d - 265°C, which in result led to obtaining temperatures of the layers of the reactor of approximately ~110-150°C for hydrogenation and 150-265°C for catalyst RVF/deoxyguanosine. These ranges indicate the approximate temperature of the wall of the reactor to the inlet hole and the outlet of each catalyst layer, respectively. The results of the experiment after 39 hours of operation shown in table 1. Is MCOS calculated from the mass of catalyst RVF/deoxyguanosine. VMT is the total monooxygenase include alcohols, ketones, tetrahydrofuran and cyclic monooxygenase. Cyclic monooxygenase include compounds in which the ring consists of oxygen, such as Cyclopentanone and cyclohexanone. The proportion of carbon atoms of raw materials contained in the unknown components of the aqueous phase, was determined as the difference between the number of carbon atoms due to the known measured components, and the total number of carbon atoms of the organic matter.

Example 9 a Catalyst RVF/deoxyadenosine

The catalyst was obtained as described in example 7 except for using catalyst carrier in the form of tetragonal Zirconia (NorPro Saint-Gobain, Product code SZ61152) with particle sizes restricted to those that are retained on a sieve of 60 mesh after passing through the sieve 18 mesh.

Example 10 a Catalyst RVF/deoxyadenosine

Hexachloroplatinum acid and rhenium acid, dissolved in water, was added to the catalyst carrier in the form of monoclinic Zirconia (NorPro Saint-Gobain, Product code SZ31164, with particle sizes restricted to those that are retained on a sieve of 60 mesh after passing through the sieve 18 mesh) using the methods of achieving the initial moisture content to obtain the target loading level of platinum 1.9% and load rhenium 1.8 percent on the catalyst after the placenta is subsequent decomposition of metal-containing precursors. The product was dried overnight in a vacuum drying Cabinet and then was progulivali in the stream of flowing air at 400°C.

Example 11 a Catalyst RVF/deoxyadenosine

The catalyst was obtained as described in example 7 except for using media in the form of activated carbon functionalized with hydrogen peroxide. First received media due to the slow addition of activated carbon (Calgon carbon UU, 60×120 mesh) to 30% increase hydrogen peroxide solution, then the mixture was left to stand over night. The aqueous phase decantation and carbon three times washed with deionized water, and then dried under vacuum at 100°C. Then the medium was added to the solution hexachloroplatinic acid and rhenium acid in water using the methods of achieving the initial moisture content to obtain the target loading level of platinum 1.8% load, rhenium 6.3% after subsequent decomposition of metal-containing precursors. The product was dried overnight in a vacuum drying Cabinet at 100°C.

Example 12 Conversion of sorbitol and glycerine

System catalysts referred to in example 9, example 10 and example 11, examined for the conversion of sorbitol or glycerol in an intermediate product containing oxygenates, when using the configuration Rea the Torah, described in example 1, and the analysis as described in example 5. The study was performed using a tubular reactor made of stainless steel with an inner diameter of 8.5 mm, shown in example 4. In all cases, the pressure of the reactor was kept equal to 625 lb/in2(wt.) (4310 kPa (psig). Temperature at the inlet hole and the outlet of the reactor shown in table 2, is intentionally kept at the use of heaters external to the reactor and shown on figure 8 in the positions 10A, 10b, 10C, 10d. The results of these experiments are shown in table 2.

Table 2 demonstrates the impact of the composition of the catalyst, the feedstock composition and operating conditions on the performance of turning. Figure 12 shows the distribution of the number of carbon atoms for monooxygenation obtained in the experiment D experiment that is the Main difference between these two experiments was to reaction temperature. In the case of experiment D was dominated by monooxygenase containing three or less carbon atoms, while in the case of the experiment E a significant proportion of monooxygenation contained four or more carbon atoms, testified to the passage of condensation reactions in the same Rea the operating zone, as in the case of hydrogen and reactions deoxyadenosine. Is MCOS receive based on the weight of catalyst RVF/deoxyguanosine. The result obtained hydrogen is the hydrogen that is present on the outlet in the form of H2that does not include the hydrogen produced and consumed in place. Total monooxygenase include alcohols, ketones, tetrahydrofuran and cyclic monooxygenase. Cyclic monooxygenase include compounds in which the ring consists of oxygen, such as Cyclopentanone and cyclohexanone. The proportion of carbon atoms of raw materials contained in the unknown components in the aqueous phase, was determined as the difference between the number of carbon atoms due to the known measured components, and the total number of carbon atoms of the organic matter.

Condensation of oxygenates using basic catalysts

Example 13

The catalyst carrier in the form of zinc aluminate was obtained by mixing the powder of zinc oxide and powdered alumina (Dispal 18N4-80, Sasol North America, Houston, Texas) to achieve the target ratio of 1.0 mole of ZnO and 1 mol Al2O3. After that, the aluminum oxide was added to dilute nitric acid at levels of 1% (mass.) HNO3. Konsisten the July doughy mass of the mixture was adjusted by adding water to obtain adobeopremieroe doughy mass, which then was extrudible when using laboratory-scale extruder. The extrudates were dried overnight in vacuum at 100°C. after this addition was dried at 200°C for one hour in flowing air, and then subsequently was progulivali at 750°C for 4 hours in flowing air. The resulting material is then grinded and sieved. Removed the material that was retained on a sieve of 60 mesh after passing through the sieve 18 mesh.

Example 14

To the calcined material from example 13 was added hexachloroplatinum acid using the methods of impregnating before reaching the initial moisture content to obtain the target loading level of platinum and 1.0% (mass.). The catalyst was dried overnight in vacuum at 100°C and progulivali at 400°C in flowing air.

Example 15

To the calcined material from example 13 was added palladium nitrate using the methods of impregnating before reaching the initial moisture content to obtain the target level of palladium loading of 0.5% (mass.). The catalyst was dried overnight in vacuum at 100°C and progulivali at 400°C in flowing air.

Example 16

Catalyst copper-zinc aluminate was obtained by mixing zinc oxide, copper oxide (I) and powdered alumina (Dispal 18N4-80) when the target CEO is wearing between 0.11 mol CuO and 0.9 mol of ZnO with one hand and one mol of Al 2O3on the other hand. After that, the aluminum oxide was added to dilute nitric acid at levels of 1% (mass.) HNO3. The pasty consistency of the mixture was adjusted by adding water to obtain adobeopremieroe doughy mass, which then was extrudible when using laboratory-scale extruder. The extrudates were dried overnight in vacuum at 100°C. after this addition was dried at 200°C for one hour in flowing air, and then subsequently was progulivali at 750°C for 4 hours in flowing air. The resulting material is then grinded and sieved. Removed the material that was retained on a sieve of 60 mesh after passing through the sieve 18 mesh.

Example 17

The catalyst in the form of a silicon dioxide-aluminum oxide modified with cesium, was obtained by adding cesium carbonate dissolved in water, the catalyst carrier in the form of a silicon dioxide-aluminum oxide Siralox (Sasol North America, Houston, Texas). The target loading level of cesium was 25% (mass.) in calculating the final weight of the catalyst. This material was dried for 24 hours in vacuum at 100°C and progulivali at 500°C for 6 hours in flowing air. After the annealing was added platinum using the methods impregnava the Oia to achieve initial moisture content to obtain the final level of loading of platinum 1% (mass.). After impregnation the catalyst was dried and then was progulivali at 500°C for 6 hours in flowing air.

Example 18

Silicon dioxide modified with cerium, was obtained by adding a solution of nitrate of cerium silica gel (Davisil grade 636, WR Grace Company) to achieve the ultimate load, 25% (mass.) CeO2. Thereafter, the resulting material was dried at 120°C for six hours and additionally progulivali at 550°C for six hours in flowing air. To the calcined material was added palladium nitrate using the methods of impregnating before reaching the initial moisture content to obtain the target level of palladium loading of 0.5% (mass.). After this, the material was dried at 120°C for six hours and additionally progulivali at 550°C for six hours in flowing air.

Example 19

System catalysts referred to in examples 14-18, examined for condensation in the vapor phase of various oxygenates. Studies were performed using a tubular reactor made of stainless steel with the values of the inner diameter of 8.5 mm and 21.2 mm, described in example 4, and in the reactor systems, is illustrated in figures 8 and 10. In the smaller reactor was loaded from 15 to 18 milliliters of the catalyst and from 50 to 70 ml of the in catalyst were loaded in a larger reactor. In all cases, the catalyst prior to use restored at 400°C in flowing hydrogen.

The organic liquid phase was collected and analyzed as described in example 5. Table 3 shows the yields and composition of organic products depending on operating conditions, the composition of the feedstock and added metal component of the catalysts described in the above examples 14-18. More than 100% shows the outputs of the organic phase, arise due to experimental error in the measurement of costs or composition of the process stream. Unfused components are those components that do not require the formation of new relationships, the carbon-carbon to obtain from a given feedstock. For simplicity, all compounds containing five or less carbon atoms, are unfused components. Total condensation products are those compounds that contain six or more carbon atoms, which require the formation of new relationships, the carbon-carbon to obtain from a given feedstock.

As demonstrated by experiments F and G, the product selectivity can be affected by the choice of the hydrogenating function, for example, Pt or Pd. Paraffins are largely formed on the catalyst, containing the m 1% platinum, in comparison with what took place for the catalyst containing 0.5% of palladium. The latter favored the formation of monooxygenation, mainly ketones. Experiments H and I further acknowledge this concept. As shown in experiment H, when used as a feedstock of isopropyl alcohol with a high output can be obtained condensed monooxygenase components >97% organic product containing >90% of the total number of carbon atoms in the inlet hole of the reactor. By increasing the reaction temperature and the use of copper to stimulate the passage of the reactions of hydrogenation selectivity can be shifted to obtain a substantial yield of olefins (experiment I). As demonstrated by experiments J, K and L, for promotion condensation of oxygenates with subsequent hydrogenation of the products of the initial condensation can be used several other heterogeneous catalysts. As demonstrated by experiments K and L, with decreasing temperature from 300°C to 250°C, the condensation rate decreases, so that in the resulting organic phase, the degree of transformation in condensed products decreased from 81% (mass.) up to 18% (mass.).

Condensation of oxygenates p and the use of acid-base catalysts

Example 20

Hydrotalcite catalyst was obtained from commercially available hydrotalcites media (ESM-350, ASM Catalysts, Baton Rouge, LA) as a result of grinding material and by-passing it through graded sieves to achieve particle sizes larger than 60 mesh, and smaller than 18 mesh. Then the material was progulivali in a quartz tubular reactor at 450°C for 6 hours in flowing nitrogen.

Example 21

To hydrocelectomy the catalyst of example 20 was added platinum using the methods of impregnating before reaching the initial moisture content to obtain the final target load, platinum 1% (mass.). Platinochloride predecessor was hexachloroplatinum acid (H2PtCl6. Impregnated material was dried overnight in vacuum at 100°C and then was progulivali at 400°C for 2 hours in flowing air.

Example 22

To hydrocelectomy the catalyst of example 20 was added platinum and tin using the methods of impregnating before reaching the initial moisture content to obtain the final target load 1% (mass.) Pt and 0.2% (wt.) Sn. Platinochloride predecessor was hexachloroplatinum acid (H2PtCl6, while tin was made of tin chloride SnCl2·2H2O. Impregnated m is a material predetermined dried overnight in vacuum at 100°C, then I progulivali at 450°C for 8 hours in a flowing nitrogen.

Example 23

Containing 5% magnesium oxide catalyst deposited on a granular zirconium dioxide, obtained using the methods of impregnating before reaching the initial moisture content to obtain the final target level of 5% (mass.) Mg. Magnesium was added in the form of magnesium nitrate, and dried overnight in vacuum at 100°C and then was progulivali at 450°C for 8 hours in flowing air. To the calcined material was added an aqueous solution of palladium nitrate to obtain a target level of palladium loading of 0.5% (mass.) using the methods of impregnating before reaching the initial moisture content. The catalyst was dried a second time and was progulivali at 400°C for six hours in flowing air.

Example 24

The catalyst carrier in the form of zinc aluminate was obtained by mixing the powder of zinc oxide and powdered alumina (Dispal 18N4-80, Sasol North America, Houston, Texas) to achieve the target ratio of 0.85 mole of ZnO and 1 mol Al2O3. To the total solid matter was added to dilute nitric acid at levels of 1% (mass.) HNO3. Consistency pasty mass was adjusted by adding water to obtain adobeopremieroe testors the second mass, suitable for extrusion, and the mixture was extrudible when using laboratory-scale extruder. The extrudates were dried overnight in vacuum at 100°C and then was progulivali at 750°C for 8 hours in flowing air. After that he received the material with dimensions of 18 to 60 mesh. To the calcined material was added an aqueous solution of palladium nitrate to obtain a target level of palladium loading of 0.5% (mass.) using the methods of impregnating before reaching the initial moisture content. After this, the catalyst was dried a second time and was progulivali at 400°C for six hours in flowing air.

Example 25

System catalysts referred to in the examples 21-24, used when carrying out reactions of vapor condensation for different oxygenates. Studies were performed using a tubular reactor made of stainless steel with the values of the inner diameter of 8.5 mm and 21.2 mm, described in example 4, and reactor systems, is illustrated in examples 1 and 3. In the smaller reactor was loaded from 15 to 18 milliliters of the catalyst and from 50 to 70 ml of catalyst were loaded in a larger reactor. In all cases, the catalyst prior to use restored at 400°C in flowing hydrogen.

The organic liquid phase was collected and analyzed as described in the example 5. Table 4 shows the yields and composition of organic products depending on operating conditions, the composition of the feedstock and added metal-containing component for hydrotalcite catalysts described in the above examples 21 and 22. As shown by the data of experiments, mainly hydrocarbon product can be obtained from acetone and isopropyl alcohol in the absence of added metal hydrogenating component. In experiment m, the product of the organic phase contained mainly debatepedia methylsiloxane cyclohexene referred in table 4 to categories other6+of hydrocarbons. Add to this the platinum catalyst (experiment N) favored the formation of condensed monooxygenation products, mainly ketones and alcohols, and the formation of some paraffins resulting deoxyadenosine ketones and alcohols. The selectivity was further shifted in favor of condensed monooxygenation in the dilution platinum tin and holding operation at higher pressure (experiment). Experiments P, Q, R and S illustrate the effect of reaction temperature for the condensation of the mixed feedstock containing pentanol and pentane. Increasing the reaction temperature from 300°C to 375°C stanovi the axis obvious gradual change of the composition of the products at decrease of selectivity on the condensed monooxygenation and increase selectivity condensed paraffins with increasing temperature.

Table 5 shows the impact of the components of the starting materials and the reaction temperature on the yields and composition of organic products for the catalysts of examples 23 and 24. Experiments T and U maps the condensation of 2-petrona and 2-methyltetrahydrofuran. In General, the condensation of 2-pentanone proceeds faster than the condensation of 2-methyltetrahydrofuran. However, under these conditions, the condensation products grew approximately 30% of tetrahydrofuran. Experiments 10 and 11 demonstrate the effect of reaction temperature in the case of use of raw materials in the form of pure isopropyl alcohol. At 300°C (experiment V) is dominated by monooxygenase condensation products, while at 400°C (experiment W) a significant part of the products consisted of hydrocarbons. In comparison with other experiments listed in tables 4 and 5, the experiment W a remarkable fact that the organic product was characterized by increased content of olefins. Adding to the feedstock valerianic acid (experiment X) suppressed the total rate of condensation and shifted the selectivity from paraffins to other hydrocarbons, mainly substituted aryl compounds.

More than 100% shows the outputs of the organic phase, arise due to experimental error in the measurement of supplies on the species or the composition of the process stream. Unfused components are those components that do not require the formation of new relationships, the carbon-carbon to obtain from a given feedstock. For simplicity, all compounds containing five or less carbon atoms, are unfused components. Total condensation products are those compounds that contain six or more carbon atoms, which require the formation of new relationships, the carbon-carbon to obtain from a given feedstock.

The main condensation of oxygenates with subsequent deoxyadenosine

Example 26

The catalyst carrier in the form of zinc aluminate was obtained similarly as in example 13 except for reducing the amount of zinc oxide to obtain a target ratio of 0.85 mole of ZnO and 1 mol Al2O3.

Example 27

To the calcined material from example 26 was added hexachloroplatinum acid using the methods of impregnating before reaching the initial moisture content to obtain the target loading level of platinum and 1.0% (mass.). The catalyst was dried overnight in vacuum at 100°C and progulivali at 400°C in flowing air.

Example 28

System catalysts referred to in examples 27 and 15, were investigated on the subject vapor condensation various oxygenates and their subsequent transformation into hydrocarbons. Studies were performed using a tubular reactor made of stainless steel with inner diameter of 21.2 mm, described in example 4, and reactor systems, is illustrated in examples 2 and 3. In two separate reactor was loaded with approximately 100 ml of each catalyst. Two reactors were Packed so that the exhaust stream from the first reactor would take place in the second reactor. The first reactor contains a catalyst of example 15, and the second reactor containing the catalyst of example 27. The catalyst prior to use restored at 400°C in flowing hydrogen. In all cases, the hydrogen prior to introduction into the reactor together with the raw material.

The products were separated and analyzed as described in example 5. Table 6 shows the outputs and composition of organic products depending on operating conditions and the composition of the feedstock upon receipt of consecutive reactions. Unfused components are those components that do not require the formation of new relationships, the carbon-carbon to obtain from a given feedstock. For simplicity, all compounds containing five or less carbon atoms, are unfused components. Total condensation products are those compounds that contain six or more atmosukarto, which require the formation of new relationships, the carbon-carbon to obtain from a given feedstock.

As demonstrated by experiments AA, BB, CC and DD, in sequential reactions of condensation and deoxyadenosine to obtain a product containing mainly With6+alkanes can be used in a variety of oxygenates. The products were characterized by a content of a greater fraction of alkanes and low levels of oxygenated compounds in comparison with the results shown in table 3. This demonstrates that the use of catalysts, characterized by different functionalities (i.e., basic+hydrogenating catalyst in the first reactor with subsequent acid+basic+hydrogenation catalyst in the second reactor) may be more effective for obtaining hydrocarbons from oxygenated compounds in comparison with the use of a catalyst which contains only the basic and hydrogenating functionality. In the experiment of ITS organic product obtained from AA to DD, and sent for recycling through the reaction system. After this processing, the final product contained mainly alkanes with only trace quantities of oxygen-containing components. The thus obtained hydrocarbons would be valuable for COI is whether as liquid fuels, such as gasoline, diesel fuel and jet fuel.

Fractionation products

Example 29

The material of the experiment from example 28 was collected and subjected to a stage of distillation. Distillation was carried out at atmospheric pressure using a simple single-stage periodic laboratory distillation apparatus. 2,950 liters of liquid product was added to a heated round bottom flask, which was performed the function of the boiler at the beginning of the experiment. Top product are condensed and egregiously on separate samples based on the temperature of the vapor phase in equilibrium with the boiling liquid, in the analysis of fractions as described in example 5. The distribution of the number of carbon atoms for fractions of the products shown in table 7. All fractions contained mainly alkanes.

The fraction extracted with boiling point less than 150°C, contain alkanes mainly in C5-10the range and would be suitable for use as a gasoline blending component. Materials from a range of higher boiling points could potentially be suitable for introduction into distillate fuel, kerosene and diesel fuel.

Example 30

The distilled product boiling in the range of the 150°C to 250°C, analyzed for suitability as jet fuel in commercial service testing (Intertek Testing Services, Illinois) in accordance with test method ASTM D1655. The sample has been successfully tested by all necessary technical requirements with the exception of technical specifications for flash point and density. Probably, the specification for the flash point could be met through the use of improved distillation products, while low density could be attributed to high levels of alkanes in the sample.

Obtaining C5+ compounds from glycerol using a single catalytic system

Example 31

System bimetallic catalyst containing platinum and rhenium (5% (mass.) platinum in a molar ratio of Pt:Re 1:2.5), and supported on a carrier in the form of activated carbon (Calgon carbon UU, 60×120 mesh) was obtained when using techniques to achieve initial moisture content. Activated carbon was slowly added 30% increase hydrogen peroxide solution. When you are finished adding carbon and the mixture was left to stand over night. The aqueous phase decantation and carbon three times washed with deionized water, and then dried under vacuum at 100°C. With stirring dropwise to the carbon functionalized peroxy the om hydrogen, was applied an aqueous solution having a volume equal to the volume of the initial humidity for impregnorium carbon of 10.4 ml, containing a solution of uranyl hexachloroplatinate (IV) distorta (Alfa Aesar, 39,85% Pt) and rhenium acid (Alfa Aesar, 76,41% HReO4). The wetted carbon was dried at 100°C in vacuum.

Example 32

104,4 gram of catalyst based on Pt/Re, 1:2,5 loaded into a tube reactor with a length of 63.5 cm, described in example 4 and example 1 with the exception that the temperature profile is intentionally kept as a result of heat exchange with a stream of hot air created by the blower and heater as illustrated in figure 7. Before the introduction of the liquid raw material in the catalyst layer, the catalyst was recovered in flowing hydrogen at 350°C for two hours. 50% (mass.) glycerin (Colgate Palmolive USP Grade), containing approximately 20 hours/million sulfate in aqueous solution, from top to bottom was applied to the reactor after pre-heating to 182°C at a mass hourly flow rate of 0.97 grams of glycerol per gram of catalyst per hour. From the bottom up through the annular space at 409°C was served hot air. The axial temperature profile in the center of the catalyst layer was measured using a retractable thermocouple as shown in example 4 and illustrated in Figo is e 13. Pressure separator maintained equal to 600 lb/in2(wt.) (4140 kPa (psig). The exhaust stream from the reactor was cooled using condenser water cooled and separated in a phase separator. Products of the gas phase was analyzed using a gas chromatograph, which allows for the analysis of hydrogen, carbon dioxide, methane, ethane, propane, butane, pentane and hexane. The organic phase was collected, weighed and sent to Southwest Research Institute (San Antonio, Texas) for analysis of gasoline. The aqueous phase was collected and weighed, and then analyzed by using the methods as GCMS and GC-PID. In this system was a complete transformation of glycerol. The following table 8 shows the outputs of the hydrogen, and the outputs of the compounds of carbon-containing products.

Obtaining C5+ compounds from polyalcohols, xylytol

Example 33

Experiments were performed using aqueous solutions of oxygenated hydrocarbons (e.g., a mixture of 50% (wt.) glycerin/water or a mixture of 50% (wt.) sorbitol/water) introduced into the reactor system of example 1. The feedstock is optionally modified by adding K2SO4at various concentrations (1, 20 or 50 hours/million).

Example 34

In the tube reactor of stainless steel 8.5 mm, described asuza in example 4, downloaded together 10,61 gram of catalyst based on Pt/Re, 1:2,5. Before the introduction of the liquid raw material in the catalyst layer, the catalyst was recovered in flowing hydrogen at 350°C for two hours. The glycerin solution with a concentration of 50% (mass.), containing approximately 1 hour/million sulfate in aqueous solution, from top to bottom was applied to the reactor when the value MCOS 1.24 grams of glycerol per gram of catalyst per hour. Subsequent tests were carried out by adding 20 hours/million and 50 hours/million sulfate in the form of K2SO4. The heater block is intentionally kept at 260°C and pressure of the separator is kept equal to 600 lb/in2(wt.) (4140 kPa (psig).

The organic phase was collected from the separator, weighed and analyzed according to the method of GC-MS as described in example 5. The following table 9 shows the outputs of the hydrogen, and the outputs of the compounds of carbon-containing products with varying amounts of sulfate added to the system. In this system was a complete transformation of glycerol. As demonstrated by the table, the liquid organic phase were formed by adding sulfate in a quantity greater than 20 hours/million

Example 35

In the tube reactor of stainless steel 8.5 mm, described in example 4, and the reactor system, proillyustrirovannoe the example 1, downloaded together 10,61 gram of catalyst based on Pt/Re, 1:2,5. Before the introduction of the liquid raw material in the catalyst layer, the catalyst was recovered in flowing hydrogen at 350°C for two hours. The glycerin solution with a concentration of 50% (mass.), containing either 1 h/million, or 20 hours/million sulfate in water, from top to bottom was applied to the reactor when the value MCOS 1.24 grams of glycerol per gram of catalyst per hour. The heater blocks controlled so that the first 10.1 cm of the reactor was maintained at least 260°C., the second 10.1 cm of the reactor was maintained at least approximately 306°C, subsequent 10.1 cm of the reactor was maintained at least approximately 355°C, and the last 10.1 cm of the reactor was maintained at least 400°C. the Pressure of the separator is kept equal to 600 lb/in2(wt.) (4140 kPa (psig).

The exhaust stream from the reactor was cooled using a water cooled condenser, were separated in a phase separator, and then analyzed as described in example 5. In this system was a complete transformation of glycerol. The following table 10 shows the outputs of the hydrogen, and the outputs of the compounds of carbon-containing products.

Example 36

System bimetallic catalyst containing platinum and rhenium (5% (mass.) platinum when the molar sootnoshenie the Pt: Re I: 5) and supported on a carrier in the form of activated carbon (Calgon carbon UU, 60×120 mesh) was obtained using the methods of achieving the initial moisture content. Activated carbon was slowly added 30% increase hydrogen peroxide solution. When you are finished adding carbon and the mixture was left to stand over night. The aqueous phase decantation and carbon three times washed with deionized water, and then dried under vacuum at 100°C. With stirring dropwise to the carbon functionalized with hydrogen peroxide, was applied an aqueous solution having a volume equal to the volume of the initial humidity for impregnorium carbon, and containing a solution of uranyl hexachloroplatinate (IV) distorta (Alfa Aesar, 39,85% Pt) and rhenium acid (Alfa Aesar, 76,41% HReO4). The wetted carbon was then dried at 100°C in vacuum.

Example 37

11.97 gram of catalyst based on Pt/Re, 1:5, described in example 36, were loaded into a stainless steel tube with a diameter of 8.5 mm, described in example 4, and the reactor system illustrated in example 1. Before the introduction of the liquid raw material in the catalyst layer, the catalyst was recovered in flowing hydrogen at 350°C for two hours. The solution of sorbitol concentration 57,2% (mass.), containing 0 hours/million sulfate in aqueous solution, from top to bottom was applied to the reactor when the value MCOS 1.20 grams of sorbitol per gram of catalyst per hour. The unit's electric is whether units controlled thereby, to the first 10.1 cm of the reactor was maintained at least 260°C., the second 10.1 cm of the reactor was maintained at least about 260°C, subsequent 10.1 cm of the reactor was maintained at least approximately 360°C, and the last 10.1 cm of the reactor was maintained at least 410°C. the Pressure of the separator is kept equal to 600 lb/in2(wt.) (4140 kPa (psig). The exhaust stream from the reactor was cooled using a water cooled condenser and separated in a phase separator. Fraction of the product was analyzed as described in example 5. In addition to this, the organic phase is collected, separated and weighed for shipment of the sample to the Southwest Research Institute (San Antonio, Texas) for analysis of gasoline. In this system was a complete transformation of glycerol. The following table 11 shows the outputs of the hydrogen, and the outputs of the compounds of carbon-containing products.

The conversion of oxygenates in C5+ compounds, the use of acid compounds

Example 38

Received water from 1.0 molar solution of lanthanum nitrate was added to the extrudates H-mordenite (BASF 712A-5-2641-1) to obtain the target level of 3% (mass.) La on the catalyst after subsequent decomposition of the metal-containing precursor. A solution of La in a short time mixed with the catalyst, and then finishing off what has been soaking at 80°C for 6 hours. After that, excess fluid was removed, and the catalyst was washed with deionized water. Then the catalyst was dried in a vacuum drying Cabinet and progulivali in air at 550°C. thereafter, the catalyst was grinded and sieved to limit the size of those particles that were retained on a sieve of 60 mesh after passing through the sieve 18 mesh.

Example 39

The extrudates H-mordenite (BASF 712A-5-2641-1, with particle sizes restricted to those that are retained on a sieve of 60 mesh after passing through the sieve 18 mesh) was added deionized water until the media coverage excess water. After that, the wet carrier was added water 0,36-molar solution of Nickel nitrate to obtain the target level of 1% (mass.) Ni after decomposition of the metal-containing precursor. The catalyst within a short period of time was stirred and left to stand for 48 hours. Thereafter, the catalyst was dried in a vacuum drying Cabinet and progulivali in air at 400°C.

Example 40

Received water from 1.0 molar solution of europium chloride and was added to H-mordenite (BASF 712A-5-2641-1, with particle sizes restricted to those that are retained on a sieve of 60 mesh after passing through the sieve 18 mesh) to obtain the target level of 3% (mass.) Eu on the catalyst after subsequent decomposition of the metal-containing predestin is of IKI. Solution Eu within a short period of time mixed with the catalyst, and then sought soaking at 80°C for 6 hours. After that, excess fluid was removed, and the catalyst was washed with deionized water. Then the catalyst was dried in a vacuum drying Cabinet and progulivali in air at 550°C. thereafter, the catalyst was grinded and sieved to limit the size of those particles that were retained on a sieve of 60 mesh after passing through the sieve 18 mesh.

Example 41

Extrudates of zeolite H-beta (extrudates with a diameter of 1.6 mm) was grinded and sieved to limit the size of those particles that were retained on a sieve of 60 mesh after passing through the sieve 18 mesh. Was added an aqueous solution of gallium nitrate to achieve the initial moisture content to obtain the target load of 1.2% (mass.) Ga on the catalyst after the decomposition of the metal-containing precursor. Thereafter, the catalyst was dried in a vacuum drying Cabinet and progulivali in air at 400°C.

Example 42

Phosphoric acid was diluted in deionized water and added to the initial moisture content to the media SiO2/Al2O3Davicat (Grace Davis, with particle sizes restricted to those that are retained on a sieve of 60 mesh after passing through the sieve 18 mesh) to achieve target levels of 5% (mass.) phosphorus on the spacecraft is alistore. Thereafter, the catalyst was dried overnight in a vacuum drying Cabinet and then progulivali in the stream of flowing air at 500°C.

Example 43

An aqueous solution of Nickel nitrate was added to the preparation of zeolite ZSM-5, associated with aluminum oxide (SiO2:Al2O3, 30:1, with particle sizes restricted to those that are retained on a sieve of 60 mesh after passing through the sieve 18 mesh) using the methods of achieving the initial moisture content to obtain the target level of loading of Nickel and 1.0% (mass.). The product was dried overnight in a vacuum drying Cabinet and then was progulivali in the stream of flowing air at 400°C.

Example 44

An aqueous solution of gallium nitrate was added to the preparation of zeolite ZSM-5, associated with aluminum oxide (SiO2:Al2O3, 80:1, with particle sizes restricted to those that are retained on a sieve of 60 mesh after passing through the sieve 18 mesh) using the methods of achieving the initial moisture content to obtain the target load, gallium 1,2% (mass.). The product was dried overnight in a vacuum drying Cabinet and then was progulivali in the stream of flowing air at 400°C.

Example 45

System catalysts, obtained using the methods of examples 38 to 44, examined for vapor condensation various oxygenates in which the temperature in the range of 325°to 375°C and the total pressure in the range from 200 lb/in 2(wt.) (1380 kPa (psig) up to 625 lb/in2(wt.) (4310 kPa (psig) and the value MCOS in the range from 1.9 to 42.8. These studies used two reactors of various sizes; in a tubular reactor made of stainless steel with an inner diameter of 8.5 mm were loaded 15 and 18 milliliters of the catalyst or from 50 to 70 ml of catalyst were loaded into a tubular reactor made of stainless steel 21.2 mm (example 4). The technological chain of reactions represented that described in example 1 or example 3, depending on the feedstock, in the analysis, as described in example 5.

The operating conditions and the results of these experiments are shown in table 12. Where the compositions of the feedstock together give less than 100%, the carrying component represented water. As demonstrated by these results, the substrates that can be converted into a C5+hydrocarbons in a wide range of conditions that represent a wide range of oxygenates including alcohols and ketones, such as 3-carbon and 5-carbon. When these transformations are particularly suitable for use are the zeolites, as demonstrated in experiments, FF, GG, HH, II, JJ, LL and MM. As demonstrated by the experiments, FF, GG, HH, II and JJ, the main products of the conversion of alcohol on mordenite and beta zeolites are n the FL olefinic condensation. The catalyst in the form of impregnated phosphorus silicon oxide-aluminum oxide - experiment QC - showed a similar selectivity profile products. In contrast, catalysts based on ZSM-5 experiments to LL and MM - has led to significant fractions of aromatic and paraffinic components.

Obtaining C5+compounds from oxygenated hydrocarbons

Example 46

Followed the method of preparation of the catalyst, identical to the method of example 44 with the exception that the material is ZSM-5, associated with aluminum oxide, characterized by the quantitative ratio of SiO2:Al2O330:1.

Example 47

The catalyst obtained using the method of 46, examined for vapor condensation of a mixture of oxygenates at 375°C and 200 lb/in2(wt.) (1380 kPa (psig). In this study, 11.3 grams of catalyst were loaded into a tubular reactor made of stainless steel with an inner diameter of 8.5 mm, described in example 4. The technological chain of reactions represented that described in example 3. A mixture of oxygenates included in the calculation of the mass, 25% 2-pentanone, 20% 3-pentanone, 20% 2-pentanol, 10% isopropyl alcohol, 10% valerianic acid, 5% 2-methyltetrahydrofuran. This mixture was added using a single pump in Rea is Torno system of example 3, while the second pump was added water so that the total feedstock would contain 60% (mass.) water and 40% (mass.) mixed oxygenates.

The monitoring method was carried out during the period in 128 hours, samples were periodically removed from the system for analysis of process performance. Each analysis was carried out as described in example 5. Figure 15 shows the time dependence of the fraction of carbon atoms of the feedstock, which left the reactor system in the form of C5+connections. Figure 16 shows the time dependence of the fraction of carbon atoms of the feedstock, which left the reactor system in the form of aromatic hydrocarbon. Figure 14 shows the time dependence of the fraction of carbon atoms of the feedstock, which left the reactor system in the form of oxygenates.

As shown by figures 14, 15 and 16, the catalyst is able to operate for extended periods of time using the mixture of oxygenates, which includes a mixture of oxygenates including alcohols, ketones, acid and tetrahydrofuran. Over time production of C5+compounds remains relatively stable, while the number of aromatic hydrocarbons present in the product decreases, and about the Koc of oxygenated compounds increases (figure 14). As you can imagine, the deactivation of the catalyst is mainly due to the accumulation of carbon deposits that restrict access of reactants to the active centers.

Example 48

An aqueous solution hexachloroplatinic acid and rhenium acid was added to the carbon catalyst carrier (OLC-AW, Calgon, with particle sizes restricted to those that were retained on the sieve 50 mesh after passing through a sieve of 120 mesh) using the methods of achieving the initial moisture content to obtain the target loading level of platinum 1.8% load, rhenium of 6.3% on the catalyst after subsequent decomposition of metal-containing precursors. The product was dried overnight in a vacuum drying Cabinet and then restored in a stream of flowing hydrogen at 400°C. After recovery of the catalyst was stored under nitrogen atmosphere until ready for use.

Example 49

Followed the method of preparation of the catalyst, identical to the method of example 44 with the exception that the material is ZSM-5, associated with aluminum oxide, characterized by the quantitative ratio of SiO2:Al2O3150:1.

Example 50

Hexachloroplatinum acid and rhenium acid, dissolved in water, was added to the catalyst carrier in the form of monoclinic Zirconia (NorPro Saint obain, product code SZ31164, with particle sizes restricted to those that are retained on a sieve of 60 mesh after passing through the sieve 18 mesh) using the methods of achieving the initial moisture content to obtain the target loading level of platinum 1.8% load, rhenium of 6.3% on the catalyst after subsequent decomposition of metal-containing precursors. The product was dried overnight in a vacuum drying Cabinet and then was progulivali in the stream of flowing air at 400°C.

Example 51

Followed the same technique as used for the preparation of the catalyst of example 50, with the exception that the target load rhenium was 1.8%.

Example 52

Zeolite ZSM-5, characterized by the quantitative ratio of SiO2:Al2O380:1, (Zeolyst International, CBV 8014) was stirred with powdered ZnO and Al2O3when a molar ratio of 1:1 so that the combined ZnO and Al2O3(Dispal 18N4-80, Sasol North America, Houston, Texas) would be 30% (mass.) of total solids. To the United ZnO and Al2O3added diluted nitric acid at levels of 2% (mass.) HNO3. Consistency pasty mass was adjusted by adding water to obtain adobeopremieroe doughy mass suitable for extrusion, and the mixture which was xtraceroute when using laboratory-scale extruder. The extrudates were dried overnight in vacuum at 100°C and then was progulivali at 600°C in flowing air.

Example 53

The material from example 52 was added an aqueous solution of gallium nitrate with particle sizes restricted to those that are retained on a sieve of 60 mesh after passing through the sieve 18 mesh, using the methods of achieving the initial moisture content to obtain the target load, gallium 1,2% (mass.). The product was dried overnight in a vacuum drying Cabinet and then was progulivali in the stream of flowing hydrogen at 400°C.

Example 54

The material from example 52 was added an aqueous solution of Nickel nitrate with particle sizes restricted to those that are retained on a sieve of 60 mesh after passing through the sieve 18 mesh, using the methods of achieving the initial moisture content to obtain the target level of loading of Nickel and 1.0% (mass.). The product was dried overnight in a vacuum drying Cabinet and then was progulivali in the stream of flowing hydrogen at 400°C.

Example 55

System catalysts referred to in the examples 6, 46, 48, 49, 51, 53 and 54, examined for the conversion of glycerol, sorbitol, sucrose and xylose in the hydrocarbons when using the configuration of the reactor described in example 2. Studies were performed using two tubular reactors of n is stainless steel with an inner diameter of 21.2 mm, demonstrated in example 4, and the analysis as described in example 5. On top of the condensation catalyst, is placed in the second reactor was placed wallpaperjohnny Zirconia (NorPro Saint Gobain, product code SZ61143, with particle sizes restricted to those that are retained on a sieve of 60 mesh after passing through the sieve 18 mesh) to obtain the evaporation zone of the exhaust stream of the first reactor before it enters the catalyst condensation.

Table 13 shows the results of these studies. In the case of the experiment NN (38% sucrose+7% xylose) with the feedstock prior to its introduction into the reactor consisted of a stream of hydrogen at a target flow rate equal to 3 times the value of the number of moles of sucrose plus 1.5 times the value of the number of moles of xylose. Other experiments were performed without an external supply of hydrogen. Heaters, external to the reactor and shown on figure 9 in the positions 10A, 10b, 10C, 10d, 23a, 23b, 23C and 23d, used for maintaining the temperature of the wall of the reactor as indicated in table 13. The hydrocarbon products of these studies, vpisivaushiesya in table 13, were grouped in C4- fraction, which were mainly in the gas phase at a temperature and ambient pressure, and C5+fraction, which in General is suitable for inclusion in the LM is the cue fuel. As demonstrated by the results, a wide range of Sugars and polyhydric alcohols can easily be turned into C5+hydrocarbons in ways vpisivaushiesya in this document. The distribution of paraffins and aromatic compounds according to this example is shown in Fig.17.

Example 56

The method described in example 55 and in the example illustrated in the experiment QQ from table 13, implemented during the period, greater than 400 hours. After the initial period of operation, the degree of transformation in aromatic components and the release of hydrocarbons decreased, as illustrated in figures 18 and 19 in the form of cycle 1. In the figure 18 demonstrated the calorific value of Cf+hydrocarbons present at the outlet of the second reactor, in the form of a percentage of the calorific value of the feedstock. Figure 19 illustrates the number of carbon atoms present in the form of aromatic hydrocarbons at the outlet of the second reactor, in the form of a percentage of the number of carbon atoms present in the feedstock. After about 120 hours of operation of the second reactor is bypassed by the bypass, while the first reactor cont the l function. Then spent the oxidative regeneration of the catalyst in the second reactor. During regeneration initiated a flow of nitrogen and air, so that the target oxygen concentration in the inlet hole of the second reactor would be 1% (mol.). After that, the temperature of the blocks of the second reactor was increased to 500°C and a flow of nitrogen and oxygen continued until until carbon dioxide at the outlet of the second reactor was no longer detected. Then the oxygen concentration was increased to the target level of 5% (mol.). The flow of this stream continued until until carbon dioxide at the outlet of the second reactor was no longer detected. At the moment the flow of oxygen is stopped, while the flow of nitrogen was continued. After that, the temperature of the blocks of the second reactor was reduced to 400°C, while the composition of the gas flowing through the catalyst layer was changed to hydrogen. Then the temperature of the blocks of the second reactor, adjusting, brought to those shown for the experiment QQ in table 13. After this second reactor was returned to operation, taking aim at obtaining conditions shown for experiment QQ in table 13. Then the second reactor was subjected to several cyclo is exploitation and regeneration, the results for the time period of operation shown in figures 18 and 19. As demonstrated by these results, the regeneration of the catalyst condensation has resulted in the restoration of the activity, which is consistent with theory that the main cause of deterioration of the catalyst over time was the formation of deposits of carbonaceous materials. In addition, as demonstrated by the results, the condensation catalyst can be regenerated multiple times without significant loss of performance.

Obtaining compositions of gasoline

Example 57

The composition of the gasoline composition of gasoline KB) was obtained by mixing a base gasoline with 5% (vol.), in the calculation of the volume of the final composition of the gasoline product of the method described in example 55 and in the example illustrated in the experiment PP from table 13.

Used the base gasoline and the resulting composition of gasoline are detailed in table 14.

Example 58

The composition of the gasoline composition of gasoline W2) was obtained by mixing a base gasoline with 10% (vol.), in the calculation of the volume of the final composition of the gasoline product of the method described in example 55 and in the example illustrated in the experiment 00 table 13.

Ispolzuya the camping base gasoline and the resulting composition of gasoline are detailed in table 14.

As you can see from the information presented in the above table 14, the composition of gasoline containing products obtained by the method described in example 55, demonstrate characteristics of distillation, extremely similar to what occurs for the base gasoline, and in the best case are characterized by a large research octane number (IOC) in comparison with the base gasoline. As well as you can see from the information presented in the above table 14, the composition of gasoline containing products obtained by the method described in example 55, have lower Reid vapor pressure (panel) in comparison with what occurs for the base petrol that in the best case can be used to decrement the control of gasoline in order to meet the specific requirements of the composition of gasoline or alternatively, ensure you add more significant amounts of gasoline components, which add to the compositions of gasoline could be limited due to the volatility of such components.

Example 59

When used as a feedstock sorbitol and sucrose got two different compositions of the gas, and then they were analyzed to determine the concentration of carbon-14 (14C) in them apostal the Institute with the for gasoline, petroleum-based.

The first sample of the gasoline V-18510) was obtained from a 50% aqueous solution of sorbitol in water using a reactor system similar to that described in example 55 with the exception that the system includes a second reactor condensation in the configuration of the lead/lag. The catalyst RVF/deoxyguanosine was obtained as described in example 50, while the condensation catalyst was obtained as described in example 43. At different temperatures and under different conditions conducted several experiments using sorbitol feedstock. The reaction RVF/deoxyguanosine conducted in the same reactor temperature profile in the range from low to high temperature with the variation of temperature in the range from 110°C to 130°C at the inlet opening and in the range of 235°C to 250°C at the outlet. The condensation reaction was carried out in a twin system with the variation of temperature in the behavior of the reactor in the range of 345°C to 385°C and the trailing reactor in the range from 260°C to 385°C. conditions for the pressure varied in the range from 620 lb/in2(wt.) (4270 kPa (psig) up to 630 lbs/inch2(wt.) (4340 kPa (psig) for reactions RVF/deoxyguanosine and in the range of 95 lb/in2(wt.) (655 kPa (psig) up to 105 lb/in2(wt.) (24 kPa (psig) for condensation reactions. Is MCOS varied in the range of about 0.9 to 1.1 h-1 for catalyst RVF/deoxyguanosine.

A second sample of gasoline (V-18512) was obtained from the total sample of gasoline produced from sucrose using the reactor system illustrated in figure 6. Sucrose was applied at different temperatures, pressures and values MCOS a hydrogenation catalyst containing 2.5% ruthenium on carbon UU (Calgon, with particle sizes restricted to those that are retained on a sieve of 120 mesh after passing through a sieve of 60 mesh), and the catalyst RVF/deoxyadenosine and the condensation catalyst, the aforementioned for sorbitol feedstock. Conditions for hydrogenation reactions varied depending on a temperature in the range from 115°C to 140°C and pressures in the range from 620 lb/in2(wt.) (4270 kPa (psig) up to 680 lb/in2(wt.) (4690 kPa (psig). Conditions on the value MCOS, temperature and pressure for RVF/deoxyguanosine represented the same as described for sorbitol. The condensation reaction was carried out in the same reactor condensation in terms of value MCOS, temperature and pressure, are identical to those as described above for advanced reactor.

The flows of products from various experiments with sorbitol were combined into one sample (V-18510), and then was subjected to a stage of re is once so, as described in example 29. The flows of products from various experiments with sucrose were also combined in one sample (V-18512), and then was subjected to distillation as described in example 29. Fraction distillation, having a boiling point of less than 210°C., were combined for subsequent contact to the final compositions of fuel. A sample of each fraction was also collected for testing for the presence of 14C.

Test for the presence of carbon-14 was conducted in Beta Analytical Inc (Miami, Florida USA) using document ASTM-D6866 Test Methods for Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis". In addition to testing for the presence of 14C in the samples V-18510 and V-18152 also conducted and the determination of the level of content material derived from biological raw materials for two additional samples taken at various filling stations in Madison, Wisconsin. The first sample (V-RRGWE) was a common neventually gasoline identified as containing up to 10%, while the second sample (V-SVPNE) was a high-grade gasoline. The results of the study are listed in the following table 15.

No. sampleMethod document ASTM-D6866 The average percentage of material derived from biological raw materials
V-18510Method - In99%
V-18512Method - In99%
V-RRGWEMethod - In7%
V-SVPNEMethod - In2%

1. Composition of liquid fuel containing at least one component of the fuel and 0.1% (vol.) up to 99.5% (vol.) fraction distillation component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, obtained by the method, including:
water supply and water soluble oxygenating hydrocarbon containing C1+O1+the hydrocarbon in an aqueous liquid phase and/or vapor phase;
the supply of H2;
carrying out catalytic reactions in liquid and/or vapor phase between oxygendemanding hydrocarbon and H2in the presence of a catalyst of deoxyguanosine at a temperature of deoxyadenosine and pressure deoxyadenosine to obtain oxygenate containing in the reaction stream C1+O1-3hydrocarbon;
catalytic the reaction in the liquid and/or vapor phase the oxygenate in the presence of a condensation catalyst at a condensation temperature and condensation pressure to obtain C 4+connection, and
the Department specified fraction distillation;
where the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, has an age of less than 100 years, according to the calculation of the concentration of carbon-14 in the component; and
where C4+the connection includes a representative selected from the group consisting of C4+alcohol, C4+ketone, C4+alkane, C4+alkene, C5+cycloalkane, C5+cycloalkene, aryl, condensed aryl and mixtures thereof;
where the composition of the liquid fuel to choose from:
the composition of the gas, characterized by an initial boiling point in the range from 15°C to 70°C (IP123), a temperature of the end of the boil, equal at most 230°C, (IP123), the value of the research octane number (IOC) in the range from 85 to 110 (ASTM D2699) and value motor octane number (MOC) in the range from 75 to 100 (ASTM D2700);
the composition of diesel fuel, characterized by an initial boiling point in the range from 130°C to 230°C (IP123), a temperature of the end of the boil, equal at most 410°C, (IP123) and cetane number in the range from 35 to 120 (ASTM D613); and
the composition of kerosene, characterized by an initial boiling point in the range from 80 to 150°C, the temperature of the end of the boil in the range from 200 to 320°C and viscosity at - 20°C in the range from 0.8 to 0 mm 2/s (ASTM D445);
where the catalyst deoxyadenosine contains an element selected from the group consisting of Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, alloys thereof and combinations, and a carrier selected from the group consisting of a nitride, carbon, silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, vanadium oxide, cerium dioxide, zinc oxide, chromium oxide, boron nitride, heteropolyacids, kieselguhr, hydroxyapatite, and mixtures thereof;
where the condensation catalyst contains a compound selected from the group of carbides, nitrides, zirconium dioxide, aluminum oxide, silicon dioxide, silicates, phosphates, zeolites, oxides of titanium, oxides of zinc, oxides of vanadium, oxides of lanthanum, oxides of yttrium, oxides of scandium, magnesium oxides, oxides of cerium, oxides of barium, oxides of calcium, hydroxides, heteroalicyclic, inorganic acid, the acid-modified resin, basically-modified resins, and combinations thereof;
where the temperature of deoxyadenosine and pressure deoxyadenosine choose to support at least a portion of oxygenating hydrocarbon in the state of liquid phase at the inlet hole of the reactor; and
where the condensation temperature and condensation pressure is chosen so as to maintain at least part of the oxygenate in the state of liquid phase at the inlet hole of the reactor.

2. The composition of the liquid t is Pliva on p. 1, where the composition of the liquid fuel further comprises one or more fuel additives.

3. The composition of gasoline containing at least one component of the fuel and 0.1% (vol.) up to 99.5% (vol.) component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, and characterized by the temperature of the end of the boil in the range from 150 to 220°C density at 15°C in the range of from 700 to 890 kg/m3, a sulfur content equal to at most 5 mg/kg, the level of oxygen equal to, at most, a 3.5% (mass.), the value of each in the range from 80 to 110 and is MUCH in the range from 70 to 100 where the above-mentioned composition of gasoline is characterized by an initial boiling point in the range from 15°C to 70°C (IP123), a temperature of the end of the boil, equal at most 220°C, (IP123), a is each in the range from 85 to 110 (ASTM D2699) and is MUCH in the range from 75 to 100 (ASTM D2700); and where the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, has an age of less than 100 years, according to the calculation of the concentration of carbon-14 in the component.

4. The composition of diesel fuel containing at least one component of the fuel and 0.1% (vol.) up to 99.5% (vol.) component containing at least one C4+with the Association, made from water-soluble oxygenating hydrocarbon, and characterized by the value of the T95 in the range from 220 to 380°C, a flash point in the range from 30 to 70°C density at 15°C in the range from 700 to 900 kg/m3, a sulfur content equal to at most 5 mg/kg, the level of oxygen content equal to at most 10% (mass.), and a viscosity at 40°C in the range from 0.5 to 6 cSt, where said composition is a diesel fuel characterized by an initial boiling point in the range from 130°C to 230°C (IP123), a temperature of the end of the boil, equal at most 410°C, (IP123) and cetane number in the range from 35 to 120 (ASTM D613); and where the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, has an age of less than 100 years, according to the calculation of the concentration of carbon-14 in the component.

5. The composition of kerosene containing at least one component of the fuel and 0.1% (vol.) up to 99.5% (vol.) component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, and characterized by an initial boiling point in the range from 120 to 215°C, the temperature of the end of the boil in the range from 220 to 320°C density at 15°C in the range of from 700 to 890 kg/m3, a sulfur content equal to, the Bo is ishee, 0,1% (mass.), levels of total aromatics, equal to, at most, 30% (vol.), the freezing temperature of - 40°C or less, a maximum height of mecoptera flame, equal at least 18 mm, a viscosity at 20°C in the range from 1 to 10 cSt and specific energy content in the range from 40 to 47 MJ/kg, where the above-mentioned composition of the kerosene is characterized by an initial boiling point in the range from 80 to 150°C, the temperature of the end of the boil in the range from 200 to 320°C and viscosity at - 20°C in the range from 0.8 to 10 mm2/s (ASTM D445); and where the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, has an age of less than 100 years, according to the calculation of the concentration of carbon-14 in the component.

6. The method of obtaining the composition of liquid fuel under item 1, comprising mixing:
(a) from 0.1% (vol.) up to 99.5% (vol.) fraction distillation component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, obtained by the method, including:
water supply and water soluble oxygenating hydrocarbon containing C1+O1+the hydrocarbon in an aqueous liquid phase and/or vapor phase;
the supply of H2;
carrying out catalytic reactions in liquid and/or vapor phase between oxygen ofanim hydrocarbon and H 2in the presence of a catalyst of deoxyguanosine at a temperature of deoxyadenosine and pressure deoxyadenosine to obtain oxygenate containing in the reaction stream C1+O1-3hydrocarbon; and
carrying out catalytic reactions in liquid and/or vapor phase the oxygenate in the presence of a condensation catalyst at a condensation temperature and condensation pressure to obtain C4+connection
the Department specified fraction distillation;
where the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, has an age of less than 100 years, according to the calculation of the concentration of carbon-14 in the component;
where C4+the connection includes a representative selected from the group consisting of C4+alcohol, C4+ketone, C4+alkane, C4+alkene, C5+cycloalkane, C5+cycloalkene, aryl, condensed aryl and mixtures thereof;
where the catalyst deoxyadenosine contains an element selected from the group consisting of Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, alloys thereof and combinations, and a carrier selected from the group consisting of a nitride, carbon, silicon dioxide, aluminum oxide, zirconium dioxide, titanium dioxide, vanadium oxide, cerium dioxide, zinc oxide, chromium oxide, boron nitride, heteroalicyclic is, kieselguhr, hydroxyapatite and mixtures thereof;
where the condensation catalyst contains a compound selected from the group of carbides, nitrides, zirconium dioxide, aluminum oxide, silicon dioxide, silicates, phosphates, zeolites, oxides of titanium, oxides of zinc, oxides of vanadium, oxides of lanthanum, oxides of yttrium, oxides of scandium, magnesium oxides, oxides of cerium, oxides of barium, oxides of calcium, hydroxides, heterophilically, inorganic acid, the acid-modified resin, basically-modified resins, and combinations thereof;
where the temperature of deoxyadenosine and pressure deoxyadenosine choose to support at least a portion of oxygenating hydrocarbon in the state of liquid phase at the inlet hole of the reactor; and
where the condensation temperature and condensation pressure is chosen so as to maintain at least part of the oxygenate in the state of liquid phase at the inlet hole of the reactor; and
(b) at least one fuel component.

7. The method of obtaining the composition of gasoline under item 3, comprising mixing:
(a) from 0.1% (vol.) up to 99.5% (vol.) component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, and characterized by the temperature of the end of the boil in the range from 150 to 250°C density at 15°C in the range of from 700 to 890 kg/m3that is the level of sulfur content, equal to at most 5 mg/kg, the level of oxygen equal to, at most, a 3.5% (mass.), the value of each in the range from 80 to 110 and is MUCH in the range from 70 to 100, where the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, has an age of less than 100 years, according to the calculation of the concentration of carbon-14 in the component; and
(b) at least one fuel component.

8. The method of obtaining the composition of diesel fuel under item 4, comprising mixing:
(a) from 0.1% (vol.) up to 99.5% (vol.) component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, and characterized by the value of the T95 in the range from 220 to 380°C, a flash point in the range from 30 to 70°C density at 15°C in the range from 700 to 900 kg/m3, a sulfur content equal to at most 5 mg/kg, the level of oxygen content equal to at most 10% (mass.), and a viscosity at 40°C in the range from 0.5 to 6 cSt, where the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, has an age of less than 100 years, according to the calculation of the concentration of carbon-14 in the component; and
(b) at least one fuel component.

9. SP is a way to obtain the composition of kerosene by p. 5, comprising mixing:
(a) from 0.1% (vol.) up to 99.5% (vol.) component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, and characterized by an initial boiling point in the range from 120 to 215°C, the temperature of the end of the boil in the range from 220 to 340°C density at 15°C in the range of from 700 to 890 kg/m3, a sulfur content equal to, at most, 0,1% (mass.), levels of total aromatics, equal to, at most, 30% (vol.), the freezing temperature of - 40°C or less, a maximum height of mecoptera flame, equal at least 18 mm, a viscosity at 20°C in the range from 1 to 10 cSt and specific energy content in the range from 40 to 47 MJ/kg, where the component containing at least one C4+connection is made from water-soluble oxygenating hydrocarbon, has an age of less than 100 years, according to the calculation of the concentration of carbon-14 in the component; and
(b) at least one component of the fuel.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: as mineral component used is coal dust, and as oil sludge - flowing cake, containing 40-65 wt % of water, with the following component ratio, wt %: flowing cake 50-70; coal dust to 100.

EFFECT: obtaining fuel composition for boiler station, possessing high stability, low corrosion activity, low content of sulphur and low cost.

1 tbl, 7 ex

FIELD: oil and gas industry.

SUBSTANCE: invention describes a viscosity-reducing additive for heavy oil fractions - tar oils, which is represented by sodium carboxylate being the waste of the vegetable oil production added to heavy oil fractions - tar oils in the quantity of 20-50 wt %.

EFFECT: reducing viscosity of heavy oil fractions - tar oils at addition of sodium carboxylate to them and increasing stability of the received mix.

3 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: alumoplatinum catalyst with the platinum content of 0.6 wt % is used as a hydration catalyst. The hydration process is carried out under pressure to 4 MPa, temperature of 250-300°C, volume rate of the raw material supply of 0.5-1.0 h-1 and a ratio of hydrogen-containing gas/raw material to 1500 nm3/m3.

EFFECT: extension of the raw material resources for the production of scarce jet fuel for supersonic aircraft, simplification of the technological scheme of the process and an increased output of the target jet fuel.

3 cl, 2 ex

FIELD: chemistry.

SUBSTANCE: method includes chemical conversion of isoprene in a bioisoprene composition to non-isoprene compounds by: (a) heating the bioisoprene composition or subjecting said composition to catalytic conditions suitable for isoprene dimerisation to produce an isoprene dimer and then catalytically hydrogenating the isoprene dimer to form a saturated C10 fuel component; or (b) (i) partially hydrogenating the bioisoprene composition to produce an isoamylene, (ii) dimerising the isoamylene with a mono-olefin selected from a group consisting of isoamylene, propylene and isobutene to form a double compound and (iii) completely hydrogenating the double compound to produce a fuel component. The bioisoprene composition is produced by a genetically engineered cell culture, suitable microorganisms, plant or animals. The invention also relates to a system for producing fuel and a fuel composition.

EFFECT: fuel contains fewer impurities inherent to fuel obtained using petro-isoprene.

28 cl, 21 tbl, 32 ex, 173 dwg

FIELD: chemistry.

SUBSTANCE: composition of aircraft gasoline contains isomerizate, alkylbenzene and tetraethyllead. As isomerizate applied is isomerizate of a light benzene fraction, predominantly C5-C6, as alkylbenzene applied is alkylbenzene, obtained by alkylation with the application of a hydrogen fluoride catalyst of a hydrocarbon fraction C3-C4, which is the product of catalytic cracking of vacuum gasoil, with the following component ratio, wt %: isomerizate of the benzene light fraction 7-30; tetralead to 0.1; alkylbenzene to 100. The claimed composition of aircraft gasoline meets all requirements of aircraft gasoline by TR CU 013/2011 and by GOST 1012-72, as well as perspective world analogues, for example "Avgas 100 LL".

EFFECT: compliance with the specified requirements.

3 cl, 3 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of manufacturing waxy Diesel fuel by hydrogenating processing of crude oil in the presence of a catalysts at higher temperatures and pressure, and further rectification of hydrogenisate with the separation of light and heavy Diesel fractions, which are further mixed, where as crude oil used is a mixture of gasoil of direct distillation of crude oil and a gasoline fraction of delayed coking, in a ratio from 95:5 wt % to 70:30 wt %, which is successively subjected to hydropurification, catalytic hydrodeparaffinisation and additional hydropurification, with a volume of the catalysts from the entire charge constituting: of hydropurification 45-65 wt %, catalytic hydrodeparaffinisation - 20-35 wt %, additional hydropurification - 10-30 wt %.

EFFECT: method makes it possible to extend raw material resources for the production of deficit waxy Diesel for land transport, exploited under conditions of cold and Arctic climate, due to inclusion into the composition of wide gasoline fraction of delayed coking.

3 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining oxygenates which increase exploitation properties of fuels for internal combustion engines, in which the interaction of glycerol with acetone takes place on an acidic catalyst, with the process taking place on a heterogenic catalyst in one stage in the flow reactor with regulation of a reagent supply in a ratio glycerol:acetone (1):5-20) and support in the reactor of a temperature from 35°C to 55°C, volume rate 0.5-1.5 h-1 and atmospheric pressure, with obtaining solketal as the main product, and return of acetone that did not react into the reactor. Also described is a method of obtaining oxygenates which increase exploitation properties of fuels for the internal combustion engines, in which the interaction of glycerol with acetone takes place on an acidic catalyst, with additional application of tert-butanol in interaction of glycerol with acetone, and the process takes place on a heterogenic catalyst in one stage in the flow reactor with regulation of a reagent supply in a ratio glycerol:tert-butanol:acetone (1):(3-5):(5-20) and support in the reactor of a temperature from 35°C to 55°C, volume rate 0.5-1.5 h-1 and atmospheric pressure, with obtaining solketal and tert-butyl ether of solketal as the main products, and return of acetone and tert-butanol that did not react into the reactor.

EFFECT: creation of efficient methods of obtaining environmentally friendly highly active oxygenate additives to automobile and aviation fuels, high-cetane oxygenate additives to Diesel fuels, which do not contain glycerol, due to ensuring complete glycerol conversion in a one-stage process.

2 cl, 1 dwg, 4 tbl

FIELD: chemistry.

SUBSTANCE: method is carried out by converting bioethanol at a first step on a zeolite catalyst containing iron, at temperature of 300-350°C and volume rate of 2 h-1 on liquid starting ethanol, then at a second step by hydrogenating the obtained product of converting ethanol on an industrial 3% or 5% platinum-containing catalyst at temperature of 250-300°C for 1.5-3 hours in an autoclave with periodic supply of hydrogen, followed by distillation of the hydrogenation product and separating the end product, which boils off at temperature higher than 135°C, with density of not less than 790 kg/m3 at 20°C and containing naphthenic products.

EFFECT: method enables to obtain reactive biofuel for aircraft gas-turbine engines, which is more environmentally friendly compared to traditional fuels.

1 dwg, 2 tbl

FIELD: oil and gas industry.

SUBSTANCE: hydrofining method to obtain hydrocarbon compositions includes hydrofining of mixture that contains component (A) - gas oil in quantity from 20 up to 95 wt %; component (A1) - benzene in quantity from 1 up to 40 wt %; component (B) of biologic origin containing fatty acid esters, probably including freed fatty acids; quantity of biologic component is from 4 up to 60 wt %. Moreover all percent ratios are referred to total weight of all components. Hydrocarbon composition (C) has been also claimed; this composition can be used as propellant and/or fuel; it is obtained by hydrofining method; it has cetane number more than 50, density of 820-845 kg/m3, content of polyaromatic compositions less than 1 by wt % in regard to total weight of hydrocarbon compound and total content of polyaromatic compositions less than 20 be wt % in regard to total weight of the composition.

EFFECT: obtaining hydrocarbon composition with improved low-temperature properties.

39 cl, 4 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an aviation fuel composition with octane number of at least 91 and rich mixture grade of at least 115 which is based on motor petrol, which contains a mixture of C6-C8 isoparaffin hydrocarbons 15-40 wt %, a C8 hydrogenated fraction with residual benzene content (not more than 3 wt %) of up to 10 wt %, tetraethyl lead 0.15-0.35 wt % and petrol with research octane number of at least 92 of up to 100 wt %. Disclosed aviation fuel composition based on motor petrol meets all requirements for aviation fuel according to TP TC 013/2011, mainly octane number of at least 91 and rich mixture grade of at least 15.

EFFECT: meeting requirements.

2 cl, 2 tbl

FIELD: chemistry.

SUBSTANCE: method includes stage of contact of pyrolysis oil, produced from biomass, with first catalyst of oxygen removal in presence of hydrogen under first, preliminarily set conditions of hydropurification with formation of first effluent stream of pyrolysis oil with low oxygen content. First catalyst of oxygen removal contains neutral catalytic carrier, nickel, cobalt and molybdenum. First catalyst of oxygen removal contains nickel in quantity from 0.1 to 1.5 wt % in terms of oxide. Version of method is also claimed.

EFFECT: extension of assortment of oxygen removal methods.

10 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: method consists in successive application on carrier - amorphous aluminium oxide - by method of soaking with following drying and annealing of: water solution of thermally unstable salt of element, selected from the first group, including titanium, tin, zirconium, then water solution of thermally unstable salt of element, selected from the second group, including molybdenum, tungsten, and after that water solution of thermally unstable salt of element, selected from the third group, including cobalt, nickel. Obtained catalyst contains, wt %: oxide of element from the first group - 4.2-15.0, oxide of element from the second group - 12.4-14.2, oxide of element from the third group - 2.1-3.8, remaining part - aluminium oxide. After that, catalyst is activated first by soaking in hydrogen medium at temperature 450-500°C, pressure 5-8 MPa for 3-4 h, then sulfidation at temperature 250-300°C, pressure 5-8 MPa for 3-4 h. And sulfidation is carried out with mixture of hydrogen sulfide and hydrogen with concentration of hydrogen sulfide 10-15 vol%.

EFFECT: method makes it possible to obtain catalyst, which has increased isomerisation ability and preserves catalytic activity with respect to reaction of isomerisation for long time, which results in obtaining Diesel fuel, which has improved low-temperature properties.

4 ex

FIELD: chemistry.

SUBSTANCE: method of biodiesel production is realised by the re-etherification in mixing natural oil, alcohol and a catalyst and following separation of the target product. The method is characterised by the fact that at the first stage of the re-etherification iron sulphate (II) is applied as the catalyst, after which iron sulphate and precipitated glycerol are separated and the mixture of alcohol, oil and ethers of fatty acids are supplied to the second stage of the re-etherification, at which as the catalyst used is an enzyme - lipase, immobilised on the surface, after which glycerol and the enzyme catalyst are separated and the mixture of alcohol and biodiesel is directed to a stage of the target product separation.

EFFECT: method makes it possible to simplify the process of the re-etherification reaction and increase the completeness of the reaction process.

6 cl, 1 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to hydraulic treatment of hydrocarbon fuel. Proposed method comprises production of hydrocarbon stock to be processed including renewable organic substance with hydrogen flow and its feed to hydraulic treatment by bringing said hydrocarbon stock in contact with at least one stationary catalyst bed. Exit flow is fed into hot separator for extraction of top fraction from hot separator and of bottom fraction from separator bottom. Top fraction is fed to water steam conversion while exit flow is directed into cold separator for extraction of gaseous top fraction from cold separator as gas flow enriched with hydrogen to be directed to circulation. Gaseous top fraction is fed to hydrogen sulphide recuperation plant to extract a gaseous flow with decreased content of hydrogen sulphide and carbon dioxide to be fed back in the process.

EFFECT: production of hydrogen to allow decreasing the fresh hydrogen demand at hydraulic treatment stage.

9 cl, 2 dwg, 3 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: claimed invention relates to methods (processes) and systems for processing triglyceride-containing oils of biological origin with obtaining base oils and fuels for vehicles. Method of obtaining base oil and Diesel fuel includes the following stages: a) processing triglyceride-containing vegetable oil with realisation of oligomerisation and deoxygenation of components on the basis of unsaturated fatty acids, contained in it, with obtaining oligomerised mixture, with said processing including hydration and further removal of water; b) isomerisation of oligomerised mixture above isomerisation catalyst with obtaining isomerised mixture, and isomerised mixture contains base oil component and Diesel fuel component, and isomerised mixture contains, at least, 10 wt % of alkanes with number of carbon atoms 30 or higher, and c) distillation of isomerised mixture with obtaining base oil and Diesel fuel, where oligomerised mixture includes oligomer component, and said oligomer component includes, at least, 50 wt % of dimeric compounds.

EFFECT: processing of oils of biological origin into wide range of products with good level of properties.

11 cl, 4 dwg, 1 ex

FIELD: chemistry.

SUBSTANCE: present invention describes a method of producing hydrocarbon raw material for synthesis of biofuel from lignin. The method involves hydrotreatment of lignin-containing raw material to obtain raw material for biofuel. The lignin-containing raw material contains lignin which is separated from black liquor from a pulping method. The lignin is separated from black liquor from a pulping method by injecting carbon dioxide (CO2) gas. The lignin-containing raw material further contains still residues from an oil refining plant.

EFFECT: as a result of hydrotreatment of lignin contained in raw material for biofuel, oxygen content and average molecular weight of the latter decreases compared to lignin.

8 cl, 6 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to catalysis, particularly, to extraction of catalyst in conversion of oxygenates into olefins. Proposed method comprises the jobs that follow. Flow of the products of oxygenates conversion into olefins is bypassed into reaction shutdown tower. Bottom flow of said tower containing the catalyst is removed. Bottom flow of said tower is separated to obtain in fact clarified fluid and flow bearing the catalyst. Catalyst-bearing flow is bypassed into drying chamber and dried therein to obtain in fact dry catalyst by mixing it with dry heated gas whereat said gas is heated to 150°C to 250°C. Dried catalyst is bypassed into catalyst regenerator for the latter to be recovered.

EFFECT: catalyst extraction.

9 cl, 1 dwg

FIELD: oil and gas industry.

SUBSTANCE: hydrofining method to obtain hydrocarbon compositions includes hydrofining of mixture that contains component (A) - gas oil in quantity from 20 up to 95 wt %; component (A1) - benzene in quantity from 1 up to 40 wt %; component (B) of biologic origin containing fatty acid esters, probably including freed fatty acids; quantity of biologic component is from 4 up to 60 wt %. Moreover all percent ratios are referred to total weight of all components. Hydrocarbon composition (C) has been also claimed; this composition can be used as propellant and/or fuel; it is obtained by hydrofining method; it has cetane number more than 50, density of 820-845 kg/m3, content of polyaromatic compositions less than 1 by wt % in regard to total weight of hydrocarbon compound and total content of polyaromatic compositions less than 20 be wt % in regard to total weight of the composition.

EFFECT: obtaining hydrocarbon composition with improved low-temperature properties.

39 cl, 4 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: method of producing bio-oil fuel from lignocellulose material, the method comprising the following steps: (a) solvating hemicellulose from lignocellulose material using a solvent, (b) removing the solvated hemicellulose from the solid substance remaining after step (a); and (c) solvating lignin and cellulose from the solid substance remaining after step (a) using a solvent at reaction temperature of 180-350°C and reaction pressure of 8-26 MPa, where the step (c) of solvating lignin and cellulose yields bio-oil.

EFFECT: improving use of the energy-producing potential of lignin and cellulose.

28 cl, 13 tbl, 6 dwg, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a hydrodeoxygenation method and catalyst for producing high-quality diesel and petroleum fuel from material which contains oxygen-containing components obtained from renewable organic materials. The method of producing hydrocarbon fuel from renewable biological organic material comprises the following steps: a) forming starting material by combining hydrocarbon fossil fuel with a renewable organic material, where content of the of the renewable organic material is 1-35 vol. %; b) mixing the starting material from step (a) with a hydrogen-rich gas and feeding the combined stream to the hydrodeoxygenation step by contacting said combined stream with a hydrodeoxygenation catalyst, where the hydrodeoxygenation catalyst is a supported Mo catalyst, having Mo content of 0.1-20 wt %, wherein the support is selected from aluminium oxide, silicon dioxide, titanium dioxide and combinations thereof, and said support has a bimodal porous structure with pores having diameter greater than 50 nm, which make up at least 2 vol. % of the total pore volume.

EFFECT: reduced coking susceptibility due to low local partial pressure of hydrogen.

14 cl, 4 tbl, 4 ex

FIELD: petroleum chemistry.

SUBSTANCE: method involves preparing synthesis gas, catalytic conversion of synthesis gas in reactor for synthesis of dimethyl ether (DME) at enhanced temperature and pressure wherein synthesis gas is contacted with catalyst followed by cooling the gaseous mixture and its separation for liquid and gaseous phases. Dimethyl ether is isolated from the liquid phase that is fed into catalytic reactor for synthesis of gasoline and the gaseous phase containing unreacted components of synthesis gas is fed to repeated catalytic conversion into additional reactor for synthesis of DME being without the parent synthesis gas. Residue of gaseous phase containing components of synthesis gas not reacted to DME after repeated catalytic conversion in additional reactor for synthesis of DME are oxidized in reactor for synthesis of carbon dioxide. Then carbon dioxide is separated and mixed its with natural gas at increased temperature and pressure that results to preparing synthesis gas that is fed to the catalytic conversion into reactor for synthesis of DME. Invention provides increasing yield of gasoline fraction and decrease of carbon dioxide waste in atmosphere.

EFFECT: improved method of synthesis.

4 cl, 1 tbl, 1 dwg, 1 ex

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