Blending stock preparation of refined fuel for transport

FIELD: chemistry.

SUBSTANCE: invention is used in propellant production for transport, which has low impurity level of sulphur and/or azote. Hydrocarbon material in oxidation zone is engaged with immiscible phase which contains acetic acid, water and oxidising agent that contains hydric dioxide and hydrogen acid. After separation, hydrocarbon phase containing oxygenated impurities are delivered to infusion zone in which part of remaining oxygenated impurities are extracted with the help of acetic acid aqueous solution. Infusion flow is delivered to separation zone for acetic acid reduction and, optionally, for the second delivering into oxidation and infusion zones.

EFFECT: simplification of the method and degree increase of cleaning.

13 cl, 9 tbl, 6 dwg

 

The scope of the invention

The present invention in General relates to various kinds of fuel for transport produced from natural oil, and in particular to methods of producing components of the mix of clean fuels for transport, which are liquid at ambient conditions. More specifically, the present invention relates to the creation of the United way, which provides for the selective oxidation of distillate oil to oxidation of sulfur-containing organic compounds and/or nitrogen-containing organic compounds and includes the operation of extraction, due to which such containing sulfur and nitrogen compounds are removed from the distillate to obtain the components of the mix of clean fuels for transportation that is friendly to the environment.

Prerequisites to the creation of inventions

It is well known that internal combustion engines have revolutionized the transport after their invention in the last decades of the 19th century. Among others, Benz and Daimler invented and improved engines using electrical (spark) ignition fuels such as gasoline. Rudolf Diesel invented and built the engine, called by his name, which use compression for ignition topl the VA, that allows the use of cheap fossil fuels. The development of advanced diesel engines for use in transport flowed along with the improved compositions of diesel fuel. Modern, with enhanced performance in diesel engines require the use of more advanced fuel compositions, however, cost remains an important consideration.

Currently, the majority of fuels for transport produced from natural oil. In fact, oil is still the world's main source of hydrocarbons, used as fuel and petrochemical feedstock. Despite the fact that the composition of natural or crude oil varies substantially, all kinds of crude oil contain sulfur compounds, and most contain nitrogen compounds, and may contain oxygen, but the oxygen content in most types of crude oil is low. Typically, the concentration of sulfur in crude oil is approximately less than 8 percent, with most types of crude oil has a sulfur concentration in the range from approximately 0.5 to 1.5 percent. The nitrogen concentration is usually less than 0.2 percent, but sometimes can reach 1.6 percent.

Crude oil is rarely used in the form in which it is extracted from the well,but you can usually convert the refinery into a wide range of fuels and petrochemical feedstock. Usually different types of fuel for transport produced by processing and mixing distilled fractions obtained from crude oil and meet the specific technical requirements of the end customer. Since most currently available in a large number of crude oil has a high sulfur content, the distilled fraction is required obeserving to get the products that meet specifications and/or requirements limiting environmental pollution. Sulfur-containing organic compounds in the fuel are the major source of environmental pollution. During combustion, they are converted to sulfur oxides, which, in turn, is converted to the oxyacids of sulfur and also create harmful emissions.

Even in the new, with enhanced performance in diesel engines combustion of conventional fuels creates smoke exhaust. It is known that oxidized compounds and compounds containing few chemical bonds of carbon-carbon or no-containing, such as methanol and methyl ether, produce very little smoke exhaust and exhaust gases. However, the majority of these compounds has a high vapour pressure and/or almost insoluble in diesel fuel, and these compounds have low Flammability that shows their cetane number. Moreover, it should be borne in mind that other ways of improving diesel fuel by chemical hydrogenation to reduce the sulfur content and komatsudani, lead to a reduction in lubricity. Diesel fuel with low lubricating ability can cause excessive wear of the fuel injectors and other moving parts that come into contact with fuel under high pressure.

Distilled fraction, which is used as a fuel or as a component of a mixture of fuel for use in internal combustion engines with compression (diesel engines)are of middle distillates, which typically contain approximately 1 to 3 percent by weight of sulfur. Previously the typical technical requirements for diesel fuel was allowed a maximum of 0.5 percent by weight sulfur. In 1993, legislation in Europe and the United States have limited the sulfur content in diesel fuel by the amount of 0.3 weight percent. In 1996 in Europe and the United States, and in 1997 in Japan, the maximum sulfur content in diesel fuel was limited by the amount of 0.05 weight percent. We should expect the continuation of this global trend towards lower levels of sulfur.

The introduction of new requirements to the level of emissions in the U.S. and other countries has led to substantial interest in catalytic about what abode emissions. However, it should be borne in mind that the problems associated with the use of catalytic processing emissions for diesel engines, and in particular for heavy-duty diesel engines are significantly different from the problems arising from the use of internal combustion engines with spark ignition (gasoline engines), due to two factors. Firstly, the normal trautenau (three way catalyst (TWC) is ineffective at removing NOx emissions from diesel engines, and secondly, the need to control particle emissions from diesel engines is significantly more acute than for gasoline engines.

New technologies emission treatment designed to control emissions from diesel engines, and the levels of sulfur in the fuel affect the effectiveness of such technologies. Sulfur is a catalyst poison, which reduces the catalytic activity. Moreover, in the context of catalytic control of emissions from diesel high sulfur content in the fuel also creates a secondary problem of particle emissions caused by the catalytic oxidation of sulfur and the reaction of water with the formation of sulphate of fog. This mist is part of the emissions of particles.

Emissions engines with compression ignition differ from emissions engines with spark zagig is because of, what different ways are used to initiate combustion. Ignition compression requires the combustion of drops of fuel in a very lean mixture of fuel with air. The combustion process leaves small particles of carbon, which leads to a significantly higher level of emissions than gasoline engines. Due to poor mixture of CO and gaseous hydrocarbon emissions are significantly lower than in the case of gasoline engines. However, a significant amount of unburned hydrocarbons are absorbed by the carbon particles. These hydrocarbons are called SOF (soluble organic fraction). These diesel emissions can create health problems due to inhalation of these small particles of carbon containing toxic hydrocarbons, and their receipt deep into the lungs.

Despite the fact that the combustion temperatures can lead to lower levels of particles, this leads to increased NOx emissions due to the well-known Zeldovich mechanism. In this case, it is necessary to maintain the aggregate level of emissions of particles and NOx emissions in accordance with the requirements to limit emissions.

You can put that ultra low sulfur fuel will allow the use of catalytic processing of emissions from diesel engines and to control emissions. Probably necessary levels of sulfur the fuel below 15 ppm (parts per million), to obtain the levels of particle emissions below 0.01 g/bhp-hr (grams/ brake horsepower in HP - hour). These levels are in good agreement with the new systems catalysts for emission treatment, which allow to obtain NOx emissions of 0.5 g/bhp-hr. Moreover, it should be borne in mind that the NOx capture systems are extremely sensitive to sulfur content in the fuel, and you can put that to maintain the activity of such systems requires the sulfur levels below 10 ppm.

Given the tightening of requirements for the sulphur content in fuels for transport, is becoming an increasingly important problem of removal of sulfur from crude oil and products of its processing. While in Europe, USA and Japan, the maximum sulfur content in diesel fuel has recently been limited by the amount of 0.05 wt%, it can be expected that in the near future, this level may be lower than 0.05 weight percent.

The usual catalysts for hydrodesulphurization unit (HDS) can be used to remove most of the sulfur from distillate oil intended for mixing, to obtain a purified fuel for transportation, but they are not suitable for removal of sulfur compounds where the sulfur atom spatial blocked in with a few rings of aromatic sulfur compounds. This is especially true in that case is, when heteroatom sulfur blocked twice (for example, 4,6-dimethyldibenzothiophene). These blocked dibenzothiophene dominate at low levels of sulfur, such as, for example, from 50 to 100 ppm, and require compliance with strict technological conditions for desulfurization. The conventional catalysts for hydrodesulphurization unit at high temperatures can lead to loss of performance, to rapid coking of the catalyst and deterioration of product quality (e.g., its color). The use of high pressure requires high capital investment.

To ensure compliance with possible more stringent emission control requirements specified blocked sulfur compounds also must be removed from the distillate of raw materials and products. There is an urgent need for cost-effective removal of sulfur from distillate and other hydrocarbon products.

There are many ways to remove sulfur from distillate feedstock and products. One such known method involves the oxidation of the oil fractions containing at least a large amount of material boiling at a temperature higher than the highest boiling point of the hydrocarbon materials (oil fractions containing at least a large amount of material boiling at temperatures above 550°F), with subsequent processing effluent, with whom containing a series of oxidized compounds at elevated temperatures, in order to form hydrogen sulfide (500°F to 1350°F), and/or hydrobromide to reduce the sulfur content in the hydrocarbon material. (see, for example, U.S. patent No. 3847798 and U.S. patent No. 5288390). However, it turned out that such methods have only limited usefulness, since they allow only a very low degree of desulfurization. In addition, you may experience a significant loss of valuable products due to cracking and/or formation of coke during the practical implementation of these processes. Therefore, it is desirable to develop a method that provides a high degree of desulfurization and reduces cracking and/or the formation of coke.

There are various ways to oxygenlive to improve fuel consumption. For example, in U.S. patent No. 2521698 described partial oxidation of hydrocarbon fuels, improving the cetane number. This patent relates to the processing of the fuel, which has a relatively low content of aromatic rings and a high content of paraffin. In U.S. patent No. 2912313 described the increase in cetane number due to the additive peroxide and dialoogiline in the middle fraction of the distillate fuel. In U.S. patent No. 2472152 described method for improving the cetane number of middle distillate fractions by oxidation of a saturated cyclic hydrocarbon or naphthenic uglevodorov the s in such fractions, to get naphthenic peroxides. This patent indicates that the oxidation can be accelerated in the presence of a metal salt, soluble in oil, as an inhibitor, however, the process is usually carried out in the presence of inorganic bases. However, the resulting naphthenic peroxides are harmful initiators resin. So you have to add inhibitors resin, such as fooly, Cresols and crazylove acid, the oxidized material to reduce or prevent the formation of resin compounds which are toxic and carcinogenic.

In U.S. patent No. 4494961 described the increase in cetane number raw, not processed, highly aromatic medium distillate fractions having a low hydrogen content, by entering in contact (with oxygen) fraction at a temperature of from 50°With up to 350°and under mild oxidizing conditions in the presence of a catalyst, which is (i) permanganate alkaline earth metal, (ii) an oxide of a metal of group IB, IIB, IIIB, IVB, VB, VIB, VIIB or VIIIB of the periodic system of elements, or a mixture of (i) and (ii). In the application for the European patent 0252606 A2 also describes the increase in cetane number average fraction of distillate fuel, which can be hydrocodene due to enter into contact with oxygen or an oxidant, in the presence of catalytic metals, such as tin, antimony, lead, is ismot and transition metals of groups IB, IIB, VB, VIB, VIIB and VIIIB of the periodic system of elements, mainly in the form of soluble oil metal salt. In this application indicate that the catalyst selectively oxidizes benzyl carbon atoms in the fuel into ketones.

In U.S. patent No. 4723963 described the increase in cetane number due to the introduction of at least 3 weight percent of an oxidized aromatic compounds in the middle fraction of the distillate hydrocarbon fuel boiling in the temperature range from 160°With up to 400°C. In this patent indicate that oxidized alkylaromatic and/or oxidized hydroaromatics connection mainly oxidized to benzyl protons of carbon.

In U.S. patent No. 6087544 described processing distillate feedstock to obtain a distillate fuel with a sulfur level is lower than in the distillate feedstock. Such fuels are due to fractionation of the distillate feedstock stream to a light fraction, which contains only approximately 50 to 100 ppm sulfur, and heavy fraction. The light fraction is subjected to hydrobromide to remove mostly all existing sulfur. Sweet light fraction is then mixed with half of the heavy fraction to obtain a distillate fuel with low sulfur content; for example, 85 percent by weight of sweet light fraction and 15 percent by weight of untreated heavy is racchi reduce the level of sulfur from 663 ppm to 310 ppm. However, if you receive such a low level of sulfur-only about 85 percent of the distillate feedstock receive in the form of the product, i.e. distillate fuel with low sulphur.

In the application for U.S. patent No. 2002/0035306 A1 disclosed a multi-stage method of desulfurization of liquid petroleum fuels, which would also remove nitrogen-containing compounds and aromatic compounds. The method includes the following operations: extraction of thiophene; oxidation of thiophene; extraction of oxide and dioxide thiophene; removing the solvent of the raffinate and treatment; removing the solvent of the extract and purification of the solvent recycling.

In this way seek to remove 5-65% thiophene material and containing nitrogen compounds and parts of aromatic compounds in the feed stream earlier operations oxidation. While the presence of aromatic compounds in diesel fuel leads to the suppression of cetane, in this way it is necessary to provide the end use of aromatic compounds. In addition, the presence of an effective amount of aromatic compounds used to increase the density of the fuel (Btu/gal) and improve cold flow properties of diesel fuel. Therefore, careful consideration should be given to the extraction of excessive amounts of aromatic compounds.

What concerning the Xia operations oxidation, the oxidant is prepared on site or in advance. Operating modes include a molar ratio of N2O2it's in the range of approximately from 1:1 to 2.2:1; the content of acetic acid in the original material from approximately 5 to 45%solvent content in the source material is from 10 to 25% and the amount of the catalyst is approximately less than 5,000 ppm of sulfuric acid, and mostly less than 1,000 ppm. In the mentioned patent also proposed to use an acid catalyst in the operation of oxidation, but mainly sulfuric acid. The use of sulfuric acid as acid oxidation is problematic, since the presence of water corrosion occurs, and when a small amount of water may occur sulfonation of hydrocarbons.

In accordance with this patent, the goal of the surgery extraction of oxide and dioxide thiophene is removing more than 90% of the various compounds substituted benzo - and dibenzo oxides of thiophene and N-oxide, plus the fraction of aromatic compounds with extracting solvent that is an aqueous solution of acetic acid with one or more co-solvents.

In U.S. patent No. 6368495 B1 also describes a multi-stage method of removing teofanov and derived from their oil fractions. This method includes the placing in contact of the flow of hydrocarbons from what kaliteli, and then enter into contact effluent operations oxidation with solid catalyst decomposition (splitting), for the decomposition of the oxidized sulfur-containing compounds, resulting receive the heated fluid flow and volatile sulfur compound. In the mentioned patent describes the use of such oxidizing agents as alkyl hydroperoxides, peroxides, percarbonates acid and oxygen.

In the publication WO 02/18518 A1 disclosed a two-stage method of desulfurization in which use flowing stream hydroacoustics. The method involves a two-phase oxidation of distillate hydrogen peroxide on the basis of an aqueous solution of formic acid for conversion of thiophene sulfur in the corresponding sulfones. During the oxidation process, some sulfones extracted in the oxidizing solution. These sulfones are removed from the hydrocarbon phase by using the subsequent operations division. The hydrocarbon phase, which contains the remaining sulfones, and then subjected to the operation of the extraction liquid - liquid or operation of a solid absorption.

The use of formic acid in the operation of oxidation cannot be recommended. Formic acid is more expensive than acetic acid. In addition, formic acid is considered the "restoring" solvent, which can gidrirovanii some metals and loosen and the. There is therefore need for exotic alloys to work with formic acid. These expensive alloys must be used in sections of the extraction solvent and the tanks for storage. The use of formic acid also leads to the necessity of using high temperatures to separate the hydrocarbon phase from the phase of an aqueous solution of oxidizing agent, in order to prevent third precipitated solid phase. It can be assumed that this undesirable phase can be formed due to lipophilic properties of formic acid. Therefore, at lower temperatures formic acid could not support in the solution of some extracted sulfones.

In U.S. patent No. 6171478 B1 describes another complex multistage method of desulfurization. In particular, this method provides for the operation of the hydrodesulphurization unit, the operation of oxidation, decomposition and operation of separation, in which a portion of the oxidized sulfur compounds are separated from the stream of effluent operations of decomposition. The aqueous oxidizing solution, which is used in the operation of oxidation, mainly contains acetic acid and hydrogen peroxide. Any residual hydrogen peroxide in affluence operations oxidation decomposed by contact effluent with catalyst decomposition.

Splitting operation is carried out with the use of what Finance selective solvent for the extraction of the oxidized sulfur compounds. In accordance with this patent, the preferred selective solvents are acetonitrile, dimethylformamide and sulfolane.

Already proposed a number of solvents for the removal of oxidized sulfur compounds. For example, in U.S. patent No. 6160193 offered a wide range of solvents suitable for use in the extraction of sulfones. The preferred solvent is dimethyl sulfoxide (DMSO).

A study similar to the list of solvents used for the extraction of sulfur compounds contained in the publication Otsuki, S.; Nonaka, T.; Takashima, N.; Qian, W.; Ishihara, A.; Imai, T.; Kabe, T. "Oxidative Desulfurization of Light Gas Oil and Vacuum Gas Oil by Oxidation and Solvent Extraction" Energy &Fuels 2000, 14, 1232. This list includes:

N,N-dimethylformamide (DMF)

Methanol

Acetonitrile

Sulfolan

In U.S. patent No.6160193 argues that there is a relationship between the polarity of the solvent and the efficiency of the extraction solvent. All solvents listed in these patents and publications are not amenable to blending with diesel fuel. All of these solvents can be characterized as polar protonotaria or aprotic solvents.

There are many harmful effects associated with the use of these solvents. While DMSO and sulfolane are good solvents for various VI is s extraction, there is a huge risk that any traces of these solvents that remain in the product may drastically increase the concentration of sulfur in the product in the form of diesel fuel. For example, even traces of DMSO in the final product at a concentration of 37 ppmw can increase the concentration of sulfur in the finished diesel fuel to 15 ppmw. Similar adverse effects may be associated with the use of acetonitrile, triethanolamine and DMF, which contain nitrogen atoms. Trace levels of these solvents dramatically increase the concentration of nitrogen in the finished product.

The above solvents are not very selective for sulfur, as they also remove aromatic compounds, in particular of monoaromatic compounds, as these varieties are probably the most polar components of diesel fuel. At first glance, it seems useful enrichment of diesel fuel saturated compounds (paraffins) due to the removal of these aromatic compounds that can increase the cetane number of the fuel. However, the reverse side of this solution is that the size of the stream extracting solvent is increasing dramatically and will contain the monoaromatic compounds, some of which must be recovered. For example, in the above publication known for the, what a DMP allows you to extract the unoxidized dibenzothiophene, but also removes a significant portion of oil. Significant effort may be needed to extract the hydrocarbons, but without accompanying recovery of dibenzothiophene.

Another problem when using the above solvent is evaporating temperature. Higher boiling point complicate the separation of trace amounts of solvent from the finished product due to boiling. Boil in this case, you can get through the sharing of certain components of diesel fuel with a lower boiling point. For example, DMSO has a boiling point of 189°or 372°F, a DMF has a boiling point of 153°or 307°F. Initial boiling point of diesel fuel is usually below the boiling points of these two solvents.

Another problem is the toxicity. While DMSO technically is a solvent with low toxicity, it can be classified as "super-solvent, which can dissolve a variety of connections. Skin contact solution DMSO leads to rapid penetration under the skin of the solute, which is one of the characteristics of DMSO. DMF is a toxin to the liver and possibly carcinogenic substance.

DMF is not enough for those who mikeski stable for to produce its distillation at atmospheric pressure. At atmospheric pressure, taking into account the boiling point of DMF, is also the decomposition of obtaining carbon monoxide and dimethylamine (Perrin, D.D.; Armarego, W.L.F. Purification of Laboratory Chemicals, 3rd Edition, Pergamon Press, Oxford, 1988, page 157). So you want to make distillation in vacuum.

In the patent ′193 specified limitations associated with the use of methanol as methanol has almost the same density, and typical hydrocarbon fuel. On the basis of the elimination method methanol is a good solvent because of its properties boiling, since it does not have nitrogen or sulfur. However, a significant fraction of the total hydrocarbon will also be extracted in a layer of methanol. Methanol is also disadvantageous due to the fact that it cannot be quickly separated from the diesel fuel.

Considering the above it becomes clear that there is a need to create a less complex and more economical method of desulfurization of distillate or diesel fuel, which does not use toxic solvents, such as acetonitrile or DMF, supernaturali, such as DMSO, or difficult to separate solvents, such as DMF.

In accordance with the present invention offers a relatively simple way, in which some portion of the oxidized sulfur-containing and/or the nitrogen-containing organic compounds, contained in the hydrocarbon raw material, extracted simultaneously during technological operations oxidation and then share with surgery decanting or phase separation. This separation of phases leads to the reduction of sulfur species and nitrogen removed advanced downstream by using the extraction operation. Furthermore, the method in accordance with the present invention allows to use a single solvent, namely acetic acid, as in the operation of the oxidation and extraction operations; and as a result you can only use one of the regeneration tower for regeneration of acetic acid as the operation of the oxidation and extraction operations. In accordance with a specific variant of the present invention, to use a limited number of expensive oxidant in the operation of oxidation.

Summary of invention

Proposed method for the production of clean fuels for transportation or blending components for clean fuels for transport, in which components of the product contains a reduced amount of sulfur-containing and/or nitrogen organic impurities. More specifically, the method in accordance with the present invention envisions the contact of hydrocarbons, which comprises containing sulfur and/or azo is organic impurities, with not miscible phase, which includes the oxidant, hydrogen peroxide, acetic acid and water in the zone of oxidation, thereby containing sulfur and/or nitrogen organic impurities are oxidized and part of such oxidized impurities extracted in not miscible phase. After oxidation is not miscible phase, which contains a portion of the oxidized sulfur and/or nitrogen is shared by the gravity separation to obtain a first hydrocarbon stream having a reduced content of sulfur-containing compounds and/or nitrogen.

The first hydrocarbon stream is then passed into the zone of the extraction liquid-liquid, which is used as extracting solvent, which contains acetic acid and water, designed for the preferential extraction of any remaining oxidized sulfur and/or nitrogen from the first stream of hydrocarbon, resulting in a gain of the second hydrocarbon stream having a reduced content of oxidized sulfur-containing compounds and/or nitrogen. The stream extraction, which contains oxidized organic sulfur compounds and/or nitrogen together with not miscible phase, which contains oxidized organic sulfur compounds and/or nitrogen separated from the first stream of hydrocarbon, then send the zone of separation, what the oxidized sulfur and/or nitrogen are separated from the acetic acid and water, and can then be re-directed to the oxidation zone and in the zone of the extraction liquid-liquid.

Brief description of drawings

1 schematically shows a first variant of the method in accordance with the present invention.

Figure 2 shows a graph of the concentration of sulfur in affluence operations oxidation for variants with catalyzed by acid oxidation and is not catalyzed by acid oxidation in accordance with the present invention.

Figure 3 shows a graph of the concentration of sulfur in affluence operation extraction for variants with catalyzed by acid oxidation and is not catalyzed by acid oxidation in accordance with the present invention.

Figure 4 shows the difference between the concentrations of sulfur in affluence oxidation and affluence extraction with option catalyzed by acid oxidation in accordance with the present invention

Figure 5 shows the difference between the concentrations of sulfur in affluence oxidation and affluence extraction for the case of no is catalyzed by acid oxidation in accordance with the present invention.

Figure 6 shows the difference between the concentrations of nitrogen in effluent oxidation zone for variants with acid catalyzed okisleniem with not catalyzed by acid oxidation in accordance with the present invention.

Detailed description of the invention

Suitable feedstocks usually contain the most purified flows, consisting mainly of hydrocarbon compounds that are liquid at ambient conditions. Suitable hydrocarbon feedstocks typically have a density in degrees American petroleum Institute (API) in the range from approximately 10° API to 100° API, mainly, from approximately 20° API up to 80 or 100° API, and even better, it is estimated that between 30° API to 70° or 100° API, to get the best results. These streams include, but are not limited to, liquid naphtha catalytic processing, liquid naphtha or naphtha detainee processing (delayed process), light naphtha direct distillation, naphtha hydrocracking, naphtha Hydrotreating process, alkylation, isomerate, catalytic reformer product and aromatic derivatives such flows, such as benzene, toluene, xylene, and combinations thereof. The catalytic product of reforming and naphtha catalytic cracking can often be split into threads with shorter intervals boiling point, such as light and heavy catalytic naphtha and light and heavy catalytic reformer product that can be specifically adapted for use as raw material in accordance with the present invention. Suppose the equipment flows are light naphtha direct distillation, naphtha catalytic cracking unit containing light and heavy parts naphtha catalytic cracking, catalytic reformer product containing light and heavy catalytic reformer product, as well as derivatives of such flows distillation of hydrocarbons.

Suitable feedstocks usually contain streams of distillate oil boiling in the temperature range approximately from 50°425°With, mainly, from approximately 150°With up to 400°and even better, from approximately 175°With up to 375°C, at atmospheric pressure, for best results. These streams include, but are not limited to, light middle distillate direct distillation, heavy middle distillate direct distillation, liquid petroleum products light catalytic cycle of the process of catalytic cracking, coking crude distillate, the distillate hydrocracking and collectively, and individually hydrotreated variants of these threads. The preferred streams are collectively and individually hydrotreated variants of liquid petroleum products light catalytic cycle of the process of catalytic cracking, the flow of coke oven crude distillate or distillate hydrocracking.

Provided also that can be used alone or combined several of the above streams of distillate used for the I as raw material for the method in accordance with the present invention. In many cases, the quality of clean transport fuel or blending components fuel for transport produced from various alternative sources of raw materials can be compared. In these cases, parameters such as flow volume, the location of the nearest connection and short-term economic forecasts determine which stream to use.

In accordance with the first aspect of the present invention proposes a method of production of a purified fuel or blending components for clean fuels for transport from the hydrotreated distillate oil. This hydrotreated distillate produced by Hydrotreating material distillate oil boiling at a temperature of approximately from 50°425°With, by means of a process that involves entering into the reaction distillate oil with a hydrogen source in the state of hydrogenation in the presence of a hydrogenation catalyst to assist by hydrogenation removal of sulfur and/or nitrogen from the hydrotreated distillate oil; may fractionation hydrotreated distillate oil by distillation, to obtain at least one boiling at a low temperature component of a mixture consisting of poor gray, rich monoaromatic compounds fraction, boiling at high temperature cheese is e, consisting of rich gray, poor monoaromatic compounds faction. In accordance with the first embodiment of the method in accordance with the present invention, hydrotreated distillate or boiling at a low temperature component can be used as a suitable raw material for implementing the method in accordance with the present invention.

Typically, useful hydrogenation catalysts contain at least one reactive metal selected from the group comprising d-transition elements of the periodic system of elements, each of which is embedded in an inert medium, in the amount of approximately from 0.1 percent to 30 percent by weight of the total catalyst. Suitable chemically active metals include d-transition elements in the periodic table of elements with atomic number from 21 to 30, 39 to 48 and 72 to 78.

The process of catalytic hydrogenation can be carried out under relatively mild conditions, in a fixed, moving or fluidized in a fluidized bed of catalyst. Mostly use fixed layer or multiple fixed catalyst under such conditions that a relatively long period of time passes until the moment when you need the regeneration. The average temperature in the reaction zone may be part of the better approximately from 200° With up to 450°With, mainly, from approximately 250°With up to 400°and even better, from approximately 275°With up to 350°for best results, the pressure may be within the range of approximately from 6 to 160 atmospheres.

The most preferred pressure range in which the hydrogenation provides a very good removal of sulfur at the minimum pressure and minimum amount of hydrogen required for the process hydrodesulphurization unit, is the range from 20 to 60 atmospheres, and mostly from approximately 25 to 40 atmospheres.

The circulation rate of hydrogen usually lie in the range from approximately 500 SCF/BbI standard cubic feet per barrel) to 20,000 SCF/BbI, mostly from approximately 2,000 SCF/BbI to 15,000 SCF/BbI, and even better, it is estimated that between 3,000 to 13,000 SCF/BbI for best results. Pressure of the reaction and the speed of circulation of hydrogen below these ranges can result in higher rates of deactivation of the catalyst, which reduces the efficiency of desulfurization, removal of nitrogen and aromatic compounds. Excessively high pressure reactions increase the power consumption and the cost of equipment while providing a slight advantage.

The hydrogenation process typically proceeds at the time of the volumetric velocity of the fluid, component-oriented the part from 0.2 h -1to 10.0 h-1mostly from approximately 0.5 h-1up to 3.0 hours-1and even better, from approximately 1.0 hour-1to 2.0 h-1to get the best results. An excessively high flow rate lead to lower complete hydrogenation.

Typically, the hydrogenation process in accordance with the present invention begins with operation pre-heating of the fraction of distillate. The fraction of the distillate is heated in heat exchangers feedstock/effluent earlier the introduction into the furnace for final heating to the desired inlet temperature of the reaction zone. The fraction of the distillate can be put into contact with a stream of hydrogen before, during and/or after heating.

The flow of hydrogen may be pure hydrogen or a mixture of such solvents as hydrocarbons, carbon monoxide, carbon dioxide, nitrogen, water, sulfur compounds and the like, the Flow of hydrogen should contain at least about 50 percent by volume of hydrogen, mainly, at least about 65 percent by volume of hydrogen, and better yet at least about 75 percent by volume of hydrogen to obtain the best results. Hydrogen may be supplied from a plant for producing hydrogen from plants for catalytic reforming or other means of producing hydrogen.

As the reaction hidrogenesse which is usually exothermic, use interstage cooling using heat transfer devices installed between the reactor with a porous layer or between layers of catalyst in the same reactor vessel. At least part of the heat generated from the process of hydrogenation, can be profitably recovered for use in the hydrogenation process. When not using this option recovery, cooling can be carried out with the use of such means of cooling such as water or air, or through the use of a stream of hydrogen introduced directly into the reactor. Two-stage processes allow you to get reduced to ectothermy temperature in the reactor and to provide better control of the temperature of the hydrogenation reactor.

Effluent of the reaction zone is typically cooled and the flow effluent sent to a separator to remove hydrogen. Some portion of the recovered hydrogen can be directed back to the process, while the other part of the hydrogen may be sent to external systems, such as installation for hydrogen or system cleaner fuel. The rate of production of hydrogen is often controlled to maintain the minimum acceptable purity hydrogen and to remove the hydrogen sulfide. The recovered hydrogen is usually to squeeze, to complement the fresh hydrogen is introduced into p. ocess for further hydrogenation.

Additional reduction of heteroaromatic sulfides in the fraction of distillate oil by Hydrotreating requires a very strong catalytic hydrogenation of the stream in order to convert these compounds into hydrocarbons and hydrogen sulfide (H2S). Usually, the greater the share of any hydrocarbon, the harder it is to carry out the hydrogenation in the sulfide. Consequently, the residual organo-sulphur compounds that remain after hydrobromide, represent the most closely substituted sulfides.

When raw is a distillate fraction with a high boiling point, obtained by hydrogenation of the stream distillation stream distillation mainly contains material boiling at a temperature of approximately from 200°425°C. Mainly stream distillation mainly contains material boiling at a temperature of approximately from approximately 250°With up to 400°and even better, boiling approximately at a temperature of from 275°With up to 375°C.

Useful fraction of distillate hydrogenation in accordance with the present invention mainly contain any one, several, or all threads distillation, boiling in the temperature range approximately from 50°425°With, mainly, from approximately 150°With up to 400°and even better, orientirovochno from 175° With up to 375°C, at atmospheric pressure. The lighter hydrocarbon components in the product as distillate can usually be more profitable converted into gasoline, but the presence of these boiling at a lower temperature materials in the distillate fuel is often limited to technical requirements on the flash temperature of the distillate fuel. Heavier hydrocarbon components boiling at temperatures above 400°can usually be better treated as raw material for catalytic cracking and converted into gasoline. The presence of heavy hydrocarbon components in the distillate fuel is further limited to the technical requirements on the final boiling point of distillate fuels.

Fractions of distillate hydrogenation in accordance with the present invention can contain high and low sulphur distillates straight distillation of crude oil derived from high and low sulphur, coke distillates, petroleum products light and heavy catalytic cycle of catalytic cracking and products in the boiling range of the distillate obtained from the hydrocracking units and Hydrotreating. Usually, coke distillate and petroleum products light and heavy catalytic cycle are components of the raw materials with the highest content of aromatic the ski compounds, in the range up to 80 percent by weight. A large part of the aromatic compounds coke oven distillate and cyclic oil is a monoaromatic and diaromatics connection, while the smaller part is triaromatic connection. Distillates direct distillation, such as distillates direct distillation with high and low sulfur content, have a lower content of aromatic compounds, in the range up to 20 percent by weight of aromatic compounds. Typically, the aromatic content of the combined feedstock for hydrogenation is in the range from approximately 5 percent by weight to 80 percent by weight, predominantly, from approximately 10 percent by weight to 70 percent by weight, and even better, it is estimated that between 20 percent by weight to 60 percent by weight.

The sulfur concentration in the fractions of the distillate hydrogenation in accordance with the present invention is typically a function of the crude mixture components with high and low sulfur, tank hydrogenated oil refinery per barrel of crude oil and an alternating arrangement of the components of the raw distillate hydrogenation. Components of the raw distillate with a higher sulphur content are usually distillates straight distillation of crude oil derived from vysokonadezhnye sulfur, coke distillates and catalytic cycle oil from plants fluid catalytic cracking process raw materials with a relatively high sulfur content. These components of the raw distillate may contain up to 2 percent by weight of elemental sulfur, but usually contain from approximately 0.1% by weight to 0.9% by weight of sulfur.

The nitrogen content in the fractions of the distillate hydrogenation in accordance with the present invention also is typically a function of nitrogen content in crude oil capacity oil hydrogenation plant per barrel of crude oil and an alternating arrangement of the components of the raw distillate hydrogenation. Components of the raw distillate with a higher nitrogen content are usually coke distillate and petroleum catalytic cycle. These components of the raw distillate can have full concentration of nitrogen up to 2000 ppm (parts per million), but usually have a concentration of nitrogen of approximately from 5 ppm to 900 ppm.

Typically, the sulfur compounds in the oil fractions are relatively nonpolar, heteroaromatic sulfides, such as substituted benzothiophene and dibenzothiophene. At first glance, it may seem that heteroaromatic sulfur compounds can be selectively extracted based on kotoryj characteristics, characteristic only of these heteroaromatic compounds. Despite the fact that the sulfur atom in these compounds has two disjoint pairs of electrons, which allow us to refer them to the grounds of Lewis, this feature is still insufficient to extraction with the help of Lewis sites acids. In other words, the selective extraction of heteroaromatic compounds of sulfur to obtain low levels of sulfur requires a more significant differences polarities between sulphides and hydrocarbons.

By oxidation in the liquid phase in accordance with the present invention it is possible to selectively convert the sulphides in the more polar Lubawskie basic (alkaline) oxidized sulfur compounds, such as sulfoxidov and sulfones. Such a connection as dimethyl sulfide is a highly non-polar molecule, while after the oxidation of the molecule becomes highly polar. Thus, due to selective oxidation heteroaromatic sulfides, such as benzothiophen and dibenzothiophen available in the streams of the distillation, the methods in accordance with the present invention can selectively cause the characteristic of high polarity in these heteroaromatic compounds. When the polarity of these undesirable sulfur compounds increase with oxidation in fluid the phase in accordance with the present invention, they can be selectively extracted using acetic acid, which contains the solvent, while the main stream of the hydrocarbon remains unchanged (no impact).

Other compounds that are also disjoint pairs of electrons, include amines. Heteroaromatic amines can also be found in the same streams where these sulfides. Amines are more basic (alkaline)than the sulphides. An isolated pair of electrons works as the basis of Bronsted-Lowry (proton acceptor), as well as a Lewis base (electron donor). This pair of electrons of the atom makes it difficult oxidation similar to the oxidation of sulphides.

In accordance with the first aspect of the present invention proposes a method of production of a purified fuel or blending components for clean fuels for transport, which includes the following operations: the use of hydrocarbon raw material containing a mixture of hydrocarbons and sulfur-containing and nitrogen-containing organic compounds, and the mixture has a density in the range from approximately 10° API to 100° API; introduction to the contact of the feedstock with not miscible phase containing acetic acid, water and an oxidizing agent containing hydrogen peroxide in the liquid phase of the reaction is ionic the mixture in the zone of oxidation, under conditions suitable for oxidation of one or more sulfur-containing and/or nitrogen-containing organic compounds; separating at least part containing acetic acid is not miscible phase from the reaction mixture; and the selection of the first stream of hydrocarbon containing a mixture of organic compounds that contains less sulfur and/or less nitrogen than in raw materials for the oxidation in the reaction zone. The oxidation conditions include increasing temperature in the range of approximately from 25°, 250°and sufficient pressure to maintain the reaction mixture is mainly in the liquid phase. Mainly, the oxidation conditions include a temperature approximately less than 90°and approximately higher than 25°and even better, it is estimated higher than 50°and approximately less than 90°C.

From the publication of Lin, S.; Smith, .R.; Ichikawa, N.; Baba, T.; Itow, M. International Journal of Chemical Kinetics, 1991 Vol. 23, pp.971 to 987 known that temperature over 90°can lead to undesirable thermal decomposition of hydrogen peroxide, which leads to higher rates of consumption.

The first hydrocarbon stream is then introduced into contact with the solvent, which contains acetic acid, in the area of the extraction liquid-liquid to get the stream extraction, containing at least part of the oxidized who's containing sulfur and/or nitrogen-containing organic compounds, remaining in the first stream of hydrocarbon and the second hydrocarbon stream containing a reduced amount of oxidized sulfur-containing and/or nitrogen-containing organic compounds. The second hydrocarbon stream then may emit in the form of fuel for transport or mixing component for mixing a fuel for transport, or introduce into contact with water in the second zone of the extraction liquid-liquid, to remove any undesired amount of acetic acid present in the second stream of hydrocarbon. The third hydrocarbon stream suitable for use as a transport fuel or a component of the mix of fuels for transportation, which has reduced the number of acetic acid, sulfur, and nitrogen, and then emit from the second extraction zone.

Typically, for use in accordance with the present invention is not miscible phase, which is used in the operation of oxidation, is formed by mixing hydrogen peroxide, acetic acid and water.

The hydrogen peroxide is added in such quantities that the stoichiometric molar ratio of hydrogen peroxide to sulfur and nitrogen is in the range approximately from 1:1 to 3:1. This stoichiometry determined from the condition that the stoichiometric ratio of hydrogen peroxide to the sulfide and hydrogen peroxide to nitrogen is accordingly the result 2:1 and 1:1. While increasing the stoichiometric relations allows to achieve a very high reduction of sulfur content, such high ratio also significantly increase the variety of costs, since the hydrogen peroxide is expensive industrial chemical.

In accordance with another embodiment of the present invention, the immiscible phase containing a proton acid, which does not contain sulfur or nitrogen, predominantly in the range from approximately 0.5 wt.% up to 10 wt.% immiscible phase, and even better, from approximately 1 wt.% up to 3 wt.%. The presence of an acid catalyst improves the desulfurization taking place in the zone of oxidation. Preferred proton acid is phosphoric acid. The use of sulfur-containing or nitrogen-containing acids, such as sulfuric acid or nitric acid, in the implementation of the method in accordance with the present invention it is not recommended, because these acids have the potential to increase the content of sulfur and nitrogen in the finished fuel received in the form of a product or component mixing. Using proton acid helps to reduce the amount of hydrogen peroxide. In accordance with this embodiment of the present invention, hydrogen peroxide is used in a stoichiometric molar ratio of peroxide is odorata for sulphur and nitrogen, comprising approximately from 1:1 to 3:1, and even better, from approximately 1:1 to 2:1 when using a proton acid.

Not miscible phase is primarily an aqueous solution obtained by mixing water, acetic acid and hydrogen peroxide, in such quantities that the amount of acetic acid mainly lies in the range approximately from 80 wt.% up to 99 wt.%, and even better, from approximately 95 wt.% up to 99 wt.%, in terms of the total weight of the immiscible phase.

The reaction is carried out in a period of time sufficient to achieve the desired degree of desulfurization and nitrogen removal. Mainly, the residence time of the reactants in the oxidation zone is in the range approximately from 5 to 180 minutes.

Applicants believe that the oxidation reaction causes a rapid reaction of organic percolate with divalent sulfur atom through an agreed not radical mechanism, resulting in the oxygen atom is in fact transferred to the sulfur atom. As has been mentioned here before, in the presence of a larger number of percolate sulfoxide is optionally converted into a sulfon, presumably due to the same mechanism. Similarly, it can be expected that the nitrogen atom in Amina will be oxidized in the same manner using the compounds of hidrobicicleta.

Approved the e, the oxidation in accordance with the present invention in the liquid reaction mixture contains an operation through which an oxygen atom is transferred bivalent sulfur atom, should not be understood in the sense that the processes in accordance with the present invention in fact allows to process through this reaction mechanism.

In accordance with the present invention, the term "oxidation" is understood as the oxidation using any tool that can oxidize one or more of sulfur-containing organic compounds and/or nitrogen-containing organic compounds, for example, to oxidize the sulfur atom of sulfur-containing organic molecules in the sulfoxide and/or sulfon.

Due to the input contact of the feedstock with immiscible phase in accordance with the present invention closely substituted sulfides are oxidized to their corresponding sulfoxidov and sulfones with minor joint oxidation, if it's there, mononuclear aromatic compounds. The high selectivity of the oxidizing agents in combination with a small number of closely substituted sulfides in hydrotreated streams, allows the use of the present invention as a very effective means of deep desulfurization with minimal losses of the finished product. Product loss is usually correspond to the number who have oxidized closely substituted sulfides. As the number of closely substituted sulfides present in the hydrotreated crude oil is comparatively low, respectively, small and product loss. Further, during the two-phase operation of the oxidation portion of the oxidized sulfur and nitrogen compounds simultaneously extracted in the immiscible phase, which contains hydrogen peroxide, acetic acid and water.

The reaction in the zone of oxidation can be performed in mode single boot or in a continuous mode. Experts can easily understand how you can use a reactor with a stirrer for mode single boot or reactor with a stirrer ("CSTR") for continuous operation. In the CSTR-type reactor the residence time corresponds to an average residence time of the reactants in the reactor.

After the surgery oxidation of two immiscible phases are separated in a mixer-settler or similar unit decantation using gravity separation of the phases. Specifically, the organic phase, namely the first stream of hydrocarbon, mainly has a reduced sulfur content in the range from 10 to 70%, in terms of sulphur content in raw materials. The first stream of hydrocarbon, namely the lighter phase, and then pass into the zone of extraction liquid-liquid.

The extraction liquid-liquid can be carried out with the use the of the solvent, containing acetic acid and water. It was found that when the solvent contains less water, the removal efficiency of sulfur increases; however, this may lead to excessive extraction of the first stream of hydrocarbon. Mainly, in order to prevent excessive extraction, but still to carry out the extraction of the desired number of compounds containing sulfur and/or nitrogen, the solvent in accordance with the present invention should contain approximately from 70 to 92 wt.%, but mainly it is estimated that between 85 to 92 wt.% acetic acid, with the balance water. The solvent is mainly to extract the oxidized sulfur-containing and/or nitrogen compounds from the first stream of hydrocarbon, resulting receive the second stream of hydrocarbon, which contains less oxidized sulfur-containing and/or nitrogen organic compounds. The extraction liquid-liquid can be conducted in any manner known in the art, including using countercurrent extraction and extraction using a counter or concurrent (parallel) thread. The preferred temperature range is from 25 to 200°Since, while the preferred pressure range is from 0 to 300 psig. This second stream of hydrocarbon, which contains less h is m 50 ppm S or less, than 50 ppm N, and mostly less than 20 ppm S and less than 20 ppm N, can then be allocated in the form of fuel or a component of a mixture of fuel.

If the solvent remains in the product or in the second hydrocarbon stream, can then be carried out the second operation of extracting water liquid-liquid.

The second operation of extracting water provides an introduction to the contact of the second hydrocarbon stream with water in order to extract the desired amount of acetic acid remaining in the second hydrocarbon stream.

The third hydrocarbon stream, which has reduced the number of acetic acid, and then isolated in the form of fuel or a component of the mixture fuel. The preferred operating temperature for this second operation of the extraction liquid-liquid is in the range from 25 to 100°and the preferred pressure is in the range from 0 to 300 psig (pounds per square inch).

A significant advantage of the present invention is that the use of acetic acid in the oxidation zone and in the zone of extraction.

In accordance with the preferred option, this allows for practical implementation of the present invention to miss the two immiscible phases are separated after surgery oxidation and operation of the extraction liquid-liquid the awn solvent in the form of acetic acid, in General the separation unit, such as a distillation column, in which the acetic acid and any excess water is separated from higher boiling sulfur-containing and/or nitrogen organic compounds. The extracted acetic acid can then be re-directed to the oxidation zone and in the zone of the extraction liquid-liquid. More precisely, the part of the extracted acetic acid can then be directed back into the zone of oxidation or possibly a make-up tank. Hydrogen peroxide, water, and possibly proton acid is added previously re-direction (acetic acid) in the zone of oxidation, so that the work in the zone of oxidation proceeded in accordance with the present invention. In addition, another part of acetic acid can be re-directed in the first extraction liquid-liquid, and in accordance with the present invention the water content set previously re-direction (acetic acid) in the zone of oxidation.

For a better understanding of the present invention, a more detailed description with reference to the drawings of some of the options that were given as examples of the invention.

Detailed description figure 1

The first variant of the present invention is schematically shown in figure 1.

The original diesel fuel (1), the cat who PoE is containing sulfur and/or nitrogen organic impurities, pass in the oxidation zone of the reactor (2). The stream, which contains acetic acid, hydrogen peroxide and water, is introduced into the oxidation zone of the reactor through line (3). The reaction mixture is passed into separator/settling tank (5) through line (4). The separator (5) is used for separation of the first intermediate hydrocarbon stream having a reduced content of organic impurities containing sulfur and/or nitrogen. Pipe (7) is used to remove water immiscible phase acetic acid, which contains oxidized sulfur and/or nitrogen.

The first intermediate hydrocarbon stream is removed from the separator through pipe (6) and enter into contact with an aqueous solution of acetic acid in the zone (8) of the extraction liquid-liquid. Acetic acid flowing into the extractor, liquid-liquid pipeline (11), is used for the extraction of residual oxidized sulfur and/or nitrogen from the first intermediate hydrocarbon stream. The second intermediate hydrocarbon stream having a reduced amount of oxidized sulfur and/or nitrogen, is then removed from the extraction zone through a pipeline (9) and pass in the zone (12) washing with water, which removes any residual acetic acid, and give the product (in the form of a cleared diesel fuel. - Approx. translator) through line (13).

Tr is borrowed (10) is used for flow extraction zone extraction in column (14) recovery of the solvent, in which the oxidized sulfur and/or nitrogen separated from the aqueous solution of acetic acid. Pipe (7) is also used for passing a flow of an aqueous solution of acetic acid from the separator/clarifier in the column recovery of the solvent. Pipe (15) is used for transmission of recovered acetic acid in the oxidation zone and in the zone of the extraction liquid-liquid through the pipes (16) and (17) respectively. The pipe (19) is used for transmission of fresh hydrogen peroxide and water in the zone of oxidation, while the pipe (18) is used for transmission of fresh make-up acetic acid in the process.

EXAMPLE 1

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Table I
Physical properties of the original diesel fuel
Analysis
Carbon (wt.%)86.84
Hydrogen (wt.%)12.54
Oxygen (wt.%)0.15
Sulfur (ppm)345
Nitrogen (ppm)112
Density API32.50
Specific gravity0.8628
Heat of combustion (BTU/Ib)19424
The types of hydrocarbon (wt.%)
Saturated61.0
Monoaromatic33.7
Diaromatics5.1
Triaromatic0.2
D86 Distillation (%)°F
IBP (initial point339.3
5.0393.3
10.0412.5
20.0438.2
30.0461.7
40.0482.6
50.0501.2
60.0522.5
70.0544.6
80.0570.5
90.0608.9
95.0645.8
FBP final boiling point658.5

Several experiments with pay load were carried out to illustrate the method in accordance with the present invention. The original diesel fuel had the composition shown in Table I.

Download hydrogen peroxide, acetic acid, water and a source of diesel fuel was maintained constant in all these experiments. In the reactor, which is a flask with a round bottom, fitted top with a stirrer and a partial condenser having an inlet and release and the PTA, and heating the shell was loaded with 300 g of the original diesel fuel (345 ppm S, 112 ppm N), 300 g of glacial acetic acid and 1.01 g of 30% aqueous hydrogen peroxide solution and 25.5 g of distilled and deionized ("D&D) water. The reaction mixture was intensively stirred and started her heat. Nitrogen was applied through the inlet for blowing the surface of the mixture, to prevent the accumulation of oxygen at the expense of any decomposition of the peroxide. After reaching a specified temperature level of the reaction mixture is kept at this temperature under stirring for a specified reaction time. After a period the oxidation product in the form of diesel fuel was cooled and decantation, and a sample was taken for analysis of the content of S and N. a Layer of diesel fuel was then extracted three parts of 85% aqueous solution of acetic acid (2:1 diesel fuel/solvent). A layer of diesel fuel after these transactions extraction and then subjected to the three operations of extraction with water (weight ratio 1:1 diesel fuel/ water). Then the finished product in the form of diesel fuel were analyzed by the content of S and N.

The conditions of the reaction, the results of desulfurization, removal of nitrogen and material balance are shown in Tables II-V. the Results of desulfurization and nitrogen removal are shown separately on the Les oxidation and after extraction, that is, the first results of desulfurization and nitrogen removal following stages of oxidation, and the second shows the results after stage extraction liquid-liquid.

Table II.
Oxidation at 50°and within 60 minutes
Run1234567
The acid catalystnoFormic acidPhosphoric acid
Download acid catalyst (wt.%)0.001.02.55.01.02.55.0
The extraction of raw materials (%)
Sulfur after oxidation25.243.540.348.439.446.145.5
Sulfur after extraction24.646.745.251.641.248.450.1
Nitrogen after oxidation 53.656.357.158.052.750.048.2
Nitrogen after extraction76.878.678.678.675.975.076.8
Balance (%)
Diesel fuel after oxidation107.2105.7105.9105.8106.9105.8106.7
An aqueous solution SPLA82.786.181.882.278.382.283.8
after oxidation
1-I extraction108.7108.4107.3107.2109.1104.0106.8
85% of the SPLA

2-I extraction

85% of the SPLA
102.2102.2103.0 103.0102.0102.8102.6
3-I extraction117.0102.0101.0100.2100.2101.198.6
85% of the SPLA
1-I extraction water105.9106.3105.6104.5105.3105.6105.6
2-I extraction water100.199.4100.099.8100.0100.899.9
3-I extraction water100.3100.3100.6100.4100.899.7100.3
Diesel fuel85.183.693.483.882.684.683.3
after extraction

48.2td align="center"> 83.1
Table III.
Oxidation at 50°and within 120 minutes
Run891011121314
The acid catalystnoFormic acidPhosphoric acid
Download acid catalyst (wt.%)0.001.02.55.01.02.55.0
The extraction of raw materials (%)
Sulfur after oxidation29.642.346.152.838.641.255.4
Sulfur after extraction42.044.648.755.742.642.062.0
Nitrogen after oxidation25.956.357.155.453.652.7
Nitrogen after extraction59.876.878.677.776.876.872.3
Balance (%)
Diesel fuel after oxidation106.7106.2105.91053108.21052106.3
An aqueous solution SPLA73.782.281.074.681.481.580.3
after oxidation
1-I extraction108.7108.7109.3107.9105.0106.9105.7
85% of the SPLA
-I extraction 102.2103.0102.8102.4103.8102.0103.0
85% of the SPLA
3-I extraction101.6102.4102.4102.299.8101.6101.0
85% of the SPLA
1-I extraction water104.9105.1104.9105.4105.1105.1105.3
2-I extraction water100.397.3100.799.9100.3100.4100.5
3-I extraction water0.00100.7100.096.8100.0100.199.7
Diesel fuel afterNo83.184.085.484.384.7
extractiondata

after oxidation
Table IV.
Oxidation at 80°and within 60 minutes
Run15161718192021
The acid catalystNoFormic acidPhosphoric acid
Download acid catalyst (wt.%)0.001.02.55.01.02.55.0
The extraction of raw materials (%)
Sulfur after oxidation41.756.558.662.351.3 56.852.2
Sulfur after extraction42.063.862.966.467.566.471.3
Nitrogen after oxidation22.351.855.457.146.457.155.4
Nitrogen after extraction59.875.976.876.875.077.775.9
Balance (%)
Diesel fuel106.5105.4105.5104.3104.4105.3106.4
after oxidation
An aqueous solution SPLA74.462.177.278.573.877.177.62
1-I extraction111.1110.9110.3107.4107.9107.3107.1
85% of the SPLA
2-I extraction103.0102.8102.6102.2101.2102.8103.2
85% of the SPLA
3-I extraction102.2101.8102.0101.4100.8101.4101.2
85% of the SPLA
1-I extraction water104.9104.7105.1105.5105.5105.7
2-I extraction water99.699.9100.099.8100.199.7100.5
3-I extraction water100.8101.3100.399.9100.4100.2100.2
Diesel fuel after82.681.882.384.483.983.583.8
extraction

tr>
Table V.
Oxidation at 80°and within 120 minutes
Run22232425262728
The acid catalystNoFormic acidPhosphoric acid
Download acid catalyst (wt.%)0.001.02.55.01.02.55.0
The extraction of raw materials (%)
Sulfur after oxidation55.458.860.057.454.558.362.6
Sulfur after extraction64.464.666.462.970.467.573.3
Nitrogen after oxidation22.356.357.153.656.353.654.5
Nitrogen after extraction63.476.876.874.176.875.975.9
Balance (%)
Diesel fuel106.1104.4104.8103.2102.8104.2106.1
after oxidation
An aqueous solution SPLA70.270.189.662.967258.272.9
after oxidation
1-I extraction110.5107.7105.7106.1105.4107.3107.9
85% of the SPLA
2-I extraction103.2103.0102.6101.6102.0102.0103.2
85% of the SPLA
3-I extraction102.0101.2101.4102.8101.0102.4101.6
85% of the SPLA /td>
1-I extraction water105.0104.9105.1105.2105.4106.1104.8
2-I extraction water100.099.5101.099.5100.4100.4101.2
3-I extraction water100.3100.6100.3100.9100.399.499.6
Diesel fuel after83.184.685185.884.384.783.6
extraction

See tables data allow a direct comparison of desulfurization and nitrogen removal without the addition of acid and with the addition of formic acid and phosphoric acid in the oxidized zone at the identical in other respects the conditions. Table II provides information on the oxidation at the least harsh conditions (50°and 60 minutes). Even under these very mild conditions, the presence of even very low concentration of acid catalyst improves the process in accordance with the present the invention. For example, the addition of 5 wt.% phosphoric acid leads to increased desulphurization after extraction from 25% (run 1) to 50% (run 7).

In Table IV the data set of experiments similar to that shown in Table II, except that the temperature of oxidation was increased from 50°C to 80°C. the Levels of desulfurization under these conditions increased slightly. Adding an acid catalyst provides higher levels of nitrogen removal than in run 15, when not using an acid catalyst. However, in General the levels of nitrogen removal after 60 minutes at 80°were not much higher than in the experiments at 50°C.

Comparison of the data presented in Table II and Table IV clearly shows that the temperature increase leads to an improvement in desulfurization. Apparently, adding more than 1 wt.% acid catalyst gives only a slight improvement of the results at both temperatures. Both acid catalyst at 50°s and 80°give mostly the same results.

Comparison of the data presented in Table II and Table III, when the temperature was fixed at 50°C, while the reaction time was increased from 60 to 120 minutes, shows that the reaction time has no significant effect on the desulfurization at this temperature, except use the lower 5% of an acid catalyst, when observed higher levels of desulfurization. However, increasing the reaction time up to 120 minutes increased duration of treatment allows runs with oxidation without the use of an acid catalyst to obtain results similar to experiments catalyzed by acid.

Comparison of the data presented in Tables IV and V, when the temperature was fixed at 80°and duration of treatment were, respectively, 60 and 120 minutes, indicates that phosphoric acid provides the best results at 80°and 120 minutes. Formic acid does not give any improvement in this case higher temperatures and longer treatment duration. As before, if a shorter reaction time one weight percent of an acid catalyst allows to obtain optimal results.

Comparison of data disasteraware in Table II and Table IV, when temperatures were, respectively, 50 and 80°With treatment duration of 60 minutes, shows that the use of the catalyst is useful in comparison with the control experiment only at 80°C. When the temperature is 50°and treatment duration of 60 minutes, the catalyst has no effect.

Comparison of data disasteraware, are shown in Tables III and V, is when the treatment duration was 120 minutes, and temperature were, respectively, 50°s and 80°C, shows that a higher disasteraware is achieved at 80°and 120 minutes with the addition of one weight percent phosphoric acid. It seems that increasing the concentration of acid decreases disasteraware.

In each run, the mass balance shows that the layer of diesel fuel after oxidation invariably exceeds 100%. The swelling layer of diesel fuel caused probably by the absorption layer acetic acid. However, the loss of acetic acid in the layer of diesel fuel is not considered when calculating the total losses of acetic acid by oxidation. It can be assumed that the acetic acid and water are likely to be lost in the distillation by purging with nitrogen at the reaction temperature. Observed accumulation of colorless liquid downstream from the partial condenser. It can be assumed that this material most likely not contain acetic acid/water.

The first 85% of the SPLA balance extraction was the highest compared to the subsequent second and third ekstragirovannymi. It can be assumed that the higher the balance after the first extraction are due to reverse extraction of acetic acid and oxidation of the layer of diesel fuel. However, the reverse extraction is not wholly successful, as the first is strayaway D& D water gives the highest balance in experiments with extraction of water. High balance caused by the removal of acetic acid. Subsequent extraction with water leads to the mass balance, returning almost to 100%. In General, the balance of diesel fuel is good; on average Recuperat about 85% by weight of the original diesel fuel. The rest is diesel fuel, probably extracted by solvents and can be recovered using conventional means.

Example 2

The following Table VI comparison between run 28 run 29 conducted in accordance with Example 1, and run 29 was carried out at a higher temperature oxidation (100°With and without the use of an acid catalyst.

Table VI.
Comparison of unoptimized and optimized oxidation conditions
Run2928
CatalystNo5 wt.% H3PO4
The concentration of H2About2in diesel fuel1,4631,010
Temperature (°)10080
Time (min)120
S (ppm) after 127129
S (ppm) after9692
The desulfurization (%)7273

Due to the additive 5 wt.% phosphoric acid and lowering the temperature to 80°substantially (45%) to reduce the consumption of hydrogen peroxide and to ensure a constant level of desulfurization.

Example 3

In our example we have used the same source of diesel fuel, as in Example 1. Modes of operation during oxidation are shown in Table VII.

Table VII.
The modes in the study of optimization of hydrogen peroxide
The specified level
Proton acidPhosphoric acid
The acid concentration (wt.% in the download)1
Diesel fuel (g)300
Ice SPLA (g)300
D&D water (g)25,5
Temperature (°and °F)80,176
Time (min)120
Download 30% N2About2(g)Variable

The sequence of operations when the experiment corresponded to do is set out in Example 1. Studied molar ratio stoichiometric excess of hydrogen peroxide are in the range from 0 to 200%, or from 1,010 to 3,030 ppm of hydrogen peroxide in the original diesel fuel. To study the effect of acid catalyst were also conducted runs with the absence of an acid catalyst to carry out a direct comparison.

To study the effect of water concentration at the stage of extraction was also carried out the extraction of the same input stage extraction three different solvents in the form of an aqueous solution of acetic acid having a concentration of acetic acid 75, 85 and 95%. After' the extraction of aqueous solution of acetic acid layer of diesel fuel were extracted using three parts D&D of water.

In Table VIII the results of operations oxidation and operation of the extraction source of diesel fuel in the oxidation with phosphoric acid and without acid catalyst, using a high loading of hydrogen peroxide.

td align="center"> 6
Table VIII.
Results oxidative desulfurization in the function of acid catalysis and stoichiometry of hydrogen peroxide
Run1234578910
030080103091106094109097112100
Acid catalysisNoYesNoYesNoYesNoYesNoYes
H2O2/S+N1X1.5.XH2..5X3.0X
H2O2in diesel fuel (ppm)1.0101.5152.0202.5253.030
55.454.558.866.762.671.667.569.972.568.7
The extraction of raw materials
Sulfur after oxidation (stage 1)
Sulfur after extraction (stage 2)64.470.471.084.480.390.487.593.691.694.2
Nitrogen after oxidation (stage 1)22.356.356.358.053.662.558.965.265.269.6
Nitrogen after extraction (stage 2)63.476.878.680.453.681.380.483.082.185.7
106102105106105105105105105105
The material balance (%)
Diesel fuel
after oxidation
An aqueous solution SPLA70.26773.275.76579.270.777.18979.0
after oxidation
1-I EXT 85% of the SPLA111105108112111108107113107111
2-I EXT 85% of the SPLA103102103105102103103104103103
3-I EXT 85% of the SPLA102101102102 101102102101102103
1-I extraction water105105106106106106106104105106
2-I extraction water100100991003998.299.599.199.2100
3-I extraction water100.310010010299.110199.510199.899.4
The final balance83.184.385.180.083.884.284.181.284.481.3
diesel fuel

From the data of the run becomes clear when studying product after oxidation, the sulfur concentration is mainly the same in the oxidation of acid and without acid catalyst, under constant load peroxide. In each of the sets described what s there is a tendency to reduce the sulfur concentration by increasing the concentration of peroxide. However, analysis of sulfur does not allow to distinguish between oxidized and non-oxidized sulfur compounds dissolved in the layer of diesel fuel. Except for runs 1 and 2, the same can be said about the varieties of nitrogen after oxidation. Figure 2 shows a graph of the residual concentration of sulfur in diesel fuel after oxidation for a series with catalyst and without catalyst. There is a gap between the two curves, the upper curve refers to a series of runs without catalyst. With increasing load peroxide difference in the desulfurization between the series with an acid catalyst and without acid catalyst begins to decrease. In any case, effluent operations oxidation does not contain less than 95 ppm of sulfur.

After sequence extraction using 85% aqueous solution of acetic acid and D&D of water is observed a greater reduction in concentrations of sulfur and nitrogen. As a rule, the steeper the decrease in the concentration of sulfur is observed with increasing loading peroxide. Figure 3 shows a graph of the concentration of sulfur in affluence extraction operations.

As in figure 2, in this case also there is a gap between the series of runs with catalyst and without catalyst. Curve with acid catalyst figure 3 shows a sharper decrease in sulfur concentration, but the concentration of sulfur begins at the level of about 20 pm sulfur (reduction of sulphur content 94%) with the need for peroxide, 3 times the stoichiometric requirement. Therefore, if you have 3 times more content peroxide and in the absence of acid catalyst, the product contains 29 ppm sulfur, which represents a 92% reduction in sulfur content.

Figs.4 and 5 show the difference between the concentration of sulfur after the stage of oxidation and sulfur concentration after phase extraction, in series with an acid catalyst (figure 4) and in series without acid catalyst (figure 5). The difference between the concentration of sulfur after the stage of oxidation and sulfur concentration after phase extraction increases significantly with increasing load peroxide. The difference of the concentrations shown in the form of a curve, superimposed on the corresponding histogram.

Figure 4 and 5 shows that diesel fuel is still a good solvent for the oxidized sulfur compounds. Figure 4 shows that effluent operations oxidation, which contains 98 ppm sulfur, i.e. has the lowest level of sulfur, does not provide the lowest concentration of sulfur in affluence operation of extraction. Figure 6 shows the improvement in nitrogen removal by increasing the concentration of the peroxide catalyst and additives. If we consider the series with an acid catalyst and without catalyst, in the presence of an acid catalyst provides better removal of nitrogen.

When is EP 4

A large number of oxidation products obtained using only 1x hydrogen peroxide (1010 ppm of hydrogen peroxide in diesel fuel), was prepared in accordance with the method used in Example 1. The concentration of water in the extraction liquid-liquid varied. The incoming flow of operation of the extraction contained 135 ppm sulfur and 55 ppm of nitrogen.

Aliquot part (100 g) of this material was extracted portions 3 × 50 g 95, 85 and 75% aqueous solution of acetic acid. After these operations, the extraction was extracted fraction of diesel fuel portions 3 × 50 g distilled and deionization (D&D) water to remove residual acetic acid. The results are shown below in Table IX.

Table IX.
Variable water concentration in operations extraction of acetic acid for oxidative desulfurization of diesel fuel using 1 wt.% phosphoric acid and a stoichiometric hydrogen peroxide, 120 minutes, 80°
Run123
The results of the oxidation
Sulfur (ppm)135
Nitrogen (ppm) 55
An aqueous solution of acetic acid (wt.%)958575
The results of extraction of diesel fuel
Sulfur (ppm)92112116
Nitrogen (ppm)122629
The extraction of raw materials
Sulfur (%)73.367.566.4
Nitrogen (%)89.376.874.1
Mass balance (%)
SPLA-1*103111113
SPLA-2110103102
SPLA-3109102101
Water-1108105104
Water-299100101
Water-310398.498.7
The final balance of diesel fuel (%)71.583.784.4
*insufficient deposition of a layer of acetic acid

As the rights of the lo, 95% aqueous acetic acid to give the highest degree of desulfurization, however, higher concentrations of 85 and 75%. Damage from the use of 95% acetic acid is in excess extraction. The mass balances for the second and third extraction of 95% acetic acid is higher than the balance sheets of the second and third extraction 85 and 75% acetic acid. Higher mass balances can be explained by the excessive extraction of diesel fuel, resulting in swelling of the fraction of acetic acid. The first extraction of 95% acetic acid creates low for the first extraction of the balance sheet, which is caused by the deposition of a layer of acetic acid, so that more of acetic acid remains in the diesel fuel. Note that the second external balance and the balance of extraction are very high.

From Table IX it is also possible to understand that increasing the water concentration in the solvent reduces the level of sulfur removal, however, allows you to save more diesel fuel. In this way compromises (exchanges) are essential. Balances extraction water are the highest in the operations of extraction using 95% acetic acid. These results show a significant inverse extraction held in diesel fuel acetic acid.

1 Method of desulfurization of hydrocarbons, includes sulfur-containing organic impurities and/or nitrogen-containing organic impurities, the method includes the following operations: (a) introduction to the contact of the feedstock with immiscible phase containing acetic acid, water and an oxidizing agent containing hydrogen peroxide and a proton acid, which does not contain sulfur or nitrogen, in the zone of oxidation, under the conditions stipulated in the zone of oxidation, in order to oxidize sulfur-containing and/or nitrogen-containing organic compounds; (b) separating at least part not miscible phase, which contains oxidized containing sulfur and/or nitrogen-containing organic compounds, to the formation of the first hydrocarbon stream having a reduced content of oxidized sulfur-containing and/or nitrogen compounds; (c) introduction to contact at least part of the first stream of hydrocarbon solvent containing acetic acid and water, in the area of the extraction liquid-liquid, to obtain a flow of extraction that contains at least a portion of the oxidized sulfur-containing and/or nitrogen-containing organic compounds, and cleared the second hydrocarbon stream having a reduced amount of oxidized sulfur-containing organic compounds and/or nitrogen-containing organic compounds; and (d) the selection of the second hydrocarbon stream.

2. The way is about to claim 1, in which the proton acid is present in the amount of approximately from 0.5 to 10 wt.%.

3. The method according to claim 1, wherein the proton acid is a phosphoric acid, and phosphoric acid is present in amounts of from approximately 1 to 3 wt.%.

4. The method according to claim 1, wherein the stoichiometric ratio of hydrogen peroxide to sulfur plus nitrogen in the hydrocarbon feedstock is in the range approximately from 1:1 to 2:1.

5. The method according to claim 1, in which the oxidation zone has a temperature below approximately 90°C.

6. The method according to claim 1, in which the processing time is approximately from 1 to 180 minutes

7. The method according to claim 1, in which acetic acid, which is used in the zone of oxidation, is present in the amount of approximately from 80 to 99 wt.% in terms of the weight of the immiscible phase.

8. The method according to claim 1, wherein the solvent used in the area of the extraction liquid-liquid contains approximately from 70 to 92 wt.% acetic acid.

9. The method according to claim 1, wherein the second hydrocarbon stream is directed to the second area extraction liquid-liquid, in which the second stream of hydrocarbon is introduced into contact with the solvent containing the water to get cleaned third hydrocarbon stream and the extract stream of water containing acetic acid.

10. The method according to claim 1, in which at least part of the hydrocarbon is about raw material is the product of a process of Hydrotreating distillate oil, the Hydrotreating process involves the introduction into the reaction distillate oil with a hydrogen source in the state of hydrogenation in the presence of a hydrogenation catalyst to assist by hydrogenation removal of sulfur and/or nitrogen from distillate oil.

11. The method according to claim 1, in which the immiscible phase and the flow of the extract is injected into the separation zone, in which acetic acid is separated and recovered from the oxidized sulfur-containing organic compounds and/or nitrogen-containing compounds.

12. The method according to claim 1, in which the oxidizer further comprises phosphoric acid in the amount of approximately from 1 to 3 wt.%; the oxidation zone has a temperature below approximately 90°; acetic acid, which is used in the zone of oxidation, is present in the amount of approximately from 95 to 99 wt.% in terms of weight extracted immiscible phase; solvent used in the area of the extraction liquid-liquid, is approximately 85 to 92 wt.%; and the stoichiometric ratio of hydrogen peroxide to sulfur plus nitrogen is in the range approximately from 1:1 to 2:1.

13. The method according to item 12, in which at least part of the hydrocarbon feedstock is a product of the process of Hydrotreating distillate oil with a Hydrotreating process involves the introduction into the reaction distillate oil source is hydrogen able hydrogenation in the presence of a hydrogenation catalyst, to assist by hydrogenation removal of sulfur and/or nitrogen from distillate oil.



 

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