Methods and catalysts for removal of oxygen from pyrolysis oil, produced from biomass

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

 

Statement of priority

In the present application claims priority to application U.S. No. 13/150,844, filed June 1, 2011, the contents of which are fully included in the invention by reference.

The technical field to which the invention relates.

The present invention relates primarily to methods and catalysts for biofuel production, and more specifically to methods and catalysts for the production of pyrolysis oil with low content of oxygen produced from biomass by catalytic deoxyadenosine pyrolysis oil produced from biomass.

The level of technology

Fast pyrolysis is a process in which raw materials - organic carbon biomass, such biomass as wood waste, agricultural residues, algae, and other rapidly heated to a temperature between 300°C and 900°C in the absence of air using a pyrolysis reactor. In these conditions form solid products, liquid products and gaseous products of pyrolysis. The condensing part (pair) gaseous pyrolysis products is condensed with the formation of pyrolysis oil produced from biomass. Pyrolysis oil produced from biomass, can be directly burned as fuel in some devices, boilers and furnaces, and also it can SL is possible to live a raw material in the catalytic production of fuels refineries. Potentially, the pyrolysis oil produced from biomass can replace about 60% of motor fuel and, thus, reduced dependence on conventional oil and reduced impact on the environment.

However, pyrolysis oil produced from biomass is a complex, significantly oxidized organic liquid having characteristics that currently limit its use as biofuel. For example, the pyrolysis oil produced from biomass has high acidity and low energy density, due largely oxidized hydrocarbons in the oil, which are secondary transformations during storage. The term “oxygenated hydrocarbon” as used in the invention refers to organic compounds that contain hydrogen, carbon and oxygen. These oxidized hydrocarbons in the pyrolysis oil produced from biomass, include carboxylic acids, phenols, Cresols, alcohols, aldehydes and other Traditional pyrolysis oil produced from biomass, containing 30 wt.% oxygen, which is specified oxidized hydrocarbons. For the conversion of pyrolysis oil produced from biomass, biofuels and chemicals require full or partial removal of oxygen from p is rolinho oil, produced from biomass. Specified the removal of oxygen may occur in two main routes, namely by removing water or CO2. Unfortunately, the removal of oxygen from the pyrolysis oil produced from biomass, leads to a rapid clogging or fouling of process catalyst in the Hydrotreating reactor, due to the formation of solids from the pyrolysis oil produced from biomass. Components of the pyrolysis oil block technological catalysts, which leads to clogging of the catalyst bed, to reduce the activity of the catalyst and creates traffic jams in the Hydrotreating reactor. It is assumed that this blockage is called acid-catalyzed polymerization of the various components of the pyrolysis oil produced from biomass, thus formed or vitreous brown polymer, or powdered charred brown substance, which limits the duration of the work and the manufacturability of the pyrolysis oil produced from biomass.

Therefore, it is desirable to develop methods and catalysts for the production of pyrolysis fuel with a low content of oxygen, produced from biomass. In addition, it is also desirable to obtain pyrolysis oil with low content of oxygen produced from biomass, without sakurazawagalatasaray, in the reactor, thus increasing the duration of the work and improves the manufacturability of the pyrolysis oil produced from biomass. Furthermore, other desirable features and characteristics of the present invention will become apparent from the following description of the invention and the accompanying claims, considered in conjunction with the drawing and specified level of technology.

Summary of invention

In the invention methods and catalysts for the removal of oxygen from the pyrolysis oil produced from biomass. In accordance with an example embodiment of the invention, a method of removing oxygen from the pyrolysis oil produced from biomass, includes a stage of contacting the pyrolysis oil produced from biomass with the first catalyst to remove oxygen in the presence of hydrogen, in the first pre-determined Hydrotreating conditions with the formation of the first discharge flow of the pyrolysis oil with a low content of oxygen, produced from biomass. The first catalyst for the removal of oxygen includes neutral catalytic carrier, Nickel, cobalt and molybdenum. The first catalyst for the removal of oxygen (deoxyadenosine) contains Nickel in an amount of from 0.1 to 1.5 wt.%, in terms of the oxide.

In accordance with another example of the wasp is estline, a method for removing oxygen from the pyrolysis oil produced from biomass. This method includes a stage of introduction of hydrogen and the flow of raw materials containing pyrolysis oil produced from biomass, in the first Hydrotreating reactor containing a first catalyst to remove oxygen. The first Hydrotreating reactor is operated in a first predetermined conditions of Hydrotreating to get flowing stream of the first pyrolysis oil with a low content of oxygen, produced from biomass. The first catalyst for the removal of oxygen contains neutral catalytic carrier, Nickel, cobalt and molybdenum. The first catalyst for the removal of oxygen contains Nickel in an amount of from 0.1 to 1.5 wt.%, in terms of the oxide, cobalt in an amount of from 2 to 4 wt.%. in terms of the oxide, molybdenum in an amount of from 10 to 20 wt.%, in terms of the oxide. Neutral catalyst carrier selected from the group consisting of media - titanium dioxide (TiO2), zirconium dioxide (ZrO2), niobium oxide (Nb2O5), theta-alumina, and combinations of these media.

In accordance with another example implementation, the developed catalyst to remove oxygen from the pyrolysis oil produced from biomass. This catalyst contains neutral catalytic carrier, Nickel, Cobh is lit and molybdenum. The amount of Nickel in terms of oxide is from 0.1 to 1.5 wt.%, the amount of cobalt in terms of oxide is from 2 to 4 wt.%, the quantity of molybdenum in terms of oxide is from 10 to 20 wt.%. Neutral catalyst carrier selected from the group consisting of titanium dioxide (TiO2), zirconium dioxide (ZrO2), niobium oxide (Nb2O5), theta-alumina, and combinations of these media.

Brief description of drawing

In further embodiments of the present invention will be described in conjunction with the following drawing, in which similar elements are denoted by the same numbers of positions, and:

in Fig.1 schematically depicts a device for removing oxygen from the pyrolysis oil produced from biomass, in accordance with an example embodiment of the invention.

Detailed description of the invention

The following detailed description in its essence is simply illustrative and is not intended to limit the invention or limit the use and application of the invention. Furthermore, there is no intention to limit the invention to any theory set forth in the prior art or in the following detailed description.

Different ways of implementation discussed in the description of the invention relate to methods and to whom talization to remove oxygen from pyrolysis oil, produced from biomass. Unlike the prior art, is described in the embodiments of the invention receive the pyrolysis oil with a low content of oxygen produced from biomass by contacting the pyrolysis oil produced from biomass with a catalyst in the removal of oxygen in the presence of hydrogen at a pre-determined conditions of Hydrotreating. The catalyst for the removal of oxygen contains neutral catalytic carrier, cobalt, molybdenum and a small amount of Nickel, which is posted on neutral catalytic media. The inventors have discovered that during neutral catalytic carrier is stable and resistant to dissolution in the pyrolysis oil produced from biomass, which typically has a high water content, and, therefore, provides a strong and durable carrier for the catalytically active metal is cobalt, molybdenum and Nickel. In addition, neutral catalytic media does not contribute to acid catalyzed polymerization of the various components of the pyrolysis oil produced from biomass, which in other circumstances cause plugging of the catalyst. Moreover, the inventors have found that the activity of the cobalt-molybdenum catalyst, which is relatively weakly turns out the t resistance to clogging, it is possible to selectively enhance by adding a small amount of Nickel to effectively remove oxygen from the pyrolysis oil produced from biomass, without increasing catalytic activity in the processes that lead to the clogging of the catalyst.

It should be recognized that, although the oil without oxygen, obtained in accordance with embodiments of the present invention, is usually referred to in the invention as pyrolysis oil with low content of oxygen produced from biomass”, this expression usually involves any of the obtained oil, which has a lower oxygen concentration compared to conventional pyrolysis oil produced from biomass. The expression “pyrolysis oil with low content of oxygen produced from biomass” includes oil without oxygen, pyrolysis oil produced from biomass, in which all oxidized hydrocarbons are converted into hydrocarbons (i.e., “petroleum product”). Preferably the pyrolysis oil with a low content of oxygen produced from biomass that contains oxygen in an amount of from 0 to 5 percent by weight (wt.%). Used in the description, the term “hydrocarbons” means organic compounds that predominantly contain only hydrogen and carbon, then oxygen is absent. ispolzuemyi in the description, the term “oxygenated hydrocarbon” means an organic compound, which contain hydrogen, carbon and oxygen. Examples of oxidized hydrocarbons in the pyrolysis oil produced from biomass include alcohols such as phenols and Cresols, carboxylic acids, alcohols, aldehydes and other

Please refer to Fig.1, which shows a schematic diagram of a device 10 for removing oxygen from the pyrolysis oil produced from biomass in accordance with an example embodiment of the invention. The flow of raw material 12, which contains the pyrolysis oil produced from biomass, and hydrogen-containing gas 13, enters the first Hydrotreating reactor 14. Pyrolysis oil produced from biomass, can be obtained, for example, by pyrolysis of biomass in a pyrolysis reactor. In fact, there may be used any type of biomass pyrolysis in order to obtain pyrolysis oil produced from biomass. Pyrolysis oil produced from biomass that can be extracted from biomass material such as wood, agricultural waste, nuts and seeds, seaweed, remnants of forestry, and the like. Pyrolysis oil produced from biomass, can be obtained using different variants of pyrolysis, such as fast pyrolysis, vacuum pyrolysis, catalytic pyrolysis and slow pyrolysis or carbonization and the like. The composition of the pyrolysis oil produced by the CSO from biomass, can vary considerably and depends on the characteristics of raw materials and process parameters. Examples of the pyrolysis oil produced from biomass, “raw” can contain from 1000 to 2000 m D. the amount of metals, from 20 to 33 wt.%. water, which may have a high acidity (e.g., total acid number (OKC)>150) and the solids content of from 0.1 wt.%. up to 5 wt.%. Pyrolysis oil produced from biomass can be processed (for example, “raw”). However, if necessary, the pyrolysis oil produced from biomass, can be selectively processed to reduce any or all of the above impurities to the desired level.

The first Hydrotreating reactor 14 contains a first catalyst to remove oxygen. In the exemplary embodiment, the first catalyst in the removal of oxygen contains neutral catalytic media. Used in the invention, the term “neutral catalytic carrier” means a carrier, for which the total degree of conversion of Heptene-1 is less than 15% in the reactor for testing catalysts in the following conditions: 0.25 g of solid material media (crushed sieved fraction 0.25-0,42 mm (40/60 mesh)) is loaded into a tubular reactor and heated in an upward flow of hydrogen (1 atmosphere) up to 550°C for 60 minutes. The reactor is cooled to 425°C, sorostitute hydrogen support equal to 1 standard liter per minute (nl/min), and hepten-1 enters the catalyst bed (by injection or saturation flow of hydrogen at a rate of ~of 0.085 g/min Degree of conversion of Heptene-1 is defined as 100*(1-X(hepten-1)), where X is the molar fraction of Heptene-1, the hydrocarbon products, which is determined using gas chromatographic analysis of the stream flowing from the reactor. Can be used different ways of gas chromatography analysis, which are known from the prior art, and instead of gas chromatography analysis, it is possible to use other analysis methods known from the prior art, with which it is possible to calculate the molar fraction of n-Heptene in the product. Preferably, the neutral catalyst carrier includes titanium dioxide (TiO2), zirconium dioxide (ZrO2), niobium oxide (Nb2O5), theta-alumina, or a combination of these media, and more preferably contains titanium dioxide (TiO2) or zirconium dioxide (ZrO2) as a carrier. Metal oxide carriers that do not contain aluminum oxide, can be mixed with one or more additional components to improve the physical stability and/or phase stability of metal oxide. Components that improve physical stability, include (but are not limited to specified) carbon, other metal oxides which are economical and clay, which are known from the prior art. Components that improve the phase stability include, but are not limited specified) metals, transition metals, non-metals, lanthanide metals and combinations thereof. The term “theta-alumina used in the invention refers to aluminum oxide, which is measured by x-ray diffraction crystallinity corresponding to the characteristics of the Standards of the joint Committee of powder diffraction (Joint Committee on Powder Diffraction Standards) room 23-1009.

The first catalyst for the removal of oxygen also contains metals, deposited on a neutral catalytic media. Metals are Nickel, cobalt and molybdenum. In the example implementation of the first catalyst in the removal of oxygen Nickel is present in an amount of from 0.1 to 1.5 wt.% in terms of the oxide, and preferably from 0.5 to 1.0 wt.%. The cobalt in the first catalyst in the removal of oxygen, in terms of oxide, is present in an amount of from 2 to 4 wt.% and preferably 3 wt.%. Molybdenum in the first catalyst in the removal of oxygen, in terms of oxide, is present in an amount of from 10 to 20 wt.% and preferably 15 wt.%. The expression “in terms of oxide” means that the metal calculated as the oxide of the metal. When metals are initially introduced into the catalytic composition of neutral media,they are more likely to be present in the form of metal oxide, and not in the metallic state. Therefore, if the invention uses the expression metal "in terms of oxide, this means that the catalyst contains x% of metal oxide. The actual amount of metal will be a little less, depending on the specific stoichiometry of the oxide. Oxide during removal of oxygen passing into the metallic form of the metal in a neutral catalytic media.

The first hydrotreater unit 14, for example, can be periodic reactor or a continuous flow reactor such as a tubular reactor with upward or downward flow with a fixed (or other) layer of the catalyst, the reactor with continuous stirring and the like. In addition, can be used in other reactors, known to specialists in this field of technology of catalytic Hydrotreating of the feedstock oil-based. In the embodiment, the first hydrotreater unit 14 is operated in a first predetermined Hydrotreating conditions including a temperature from 100°C to 400°C, a pressure of from 3200 to 12400 kPa (450 to 1800 pounds per square inch), the volumetric rate of fluid from 0.25 volume of the liquid raw material/volume of catalyst per hour (h-1) to 1.0 h-1and the supply rate of hydrogen containing gas to 1 barrel of processed oil component from 1000 to 12,000 standard cubic feet (179-2148 m3/m3 ).

Pyrolysis oil produced from biomass and is contained in the flow of raw material 12, is in contact with the first catalyst in the removal of oxygen in the first pre-established conditions of Hydrotreating in the presence of hydrogen with the formation of the first flowing stream 16 pyrolysis oil with low content of oxygen produced from biomass by turning at least part of the oxidized hydrocarbons in the pyrolysis oil produced from biomass into hydrocarbons. In particular, the hydrogen from the hydrogen-containing gas 13 removes oxygen from the pyrolysis oil produced from biomass in the form of water, thus, it is a flowing stream 16 pyrolysis oil with a low content of oxygen, produced from biomass. Of oil, which is contained in the output stream 16 pyrolysis oil with low content of oxygen produced from biomass, can be partially removed oxygen with some residual oxidized hydrocarbons or the oxygen can be removed almost completely, and almost all of the oxygenated hydrocarbons into hydrocarbons.

Stemming the flow 16 of the pyrolysis oil with a low content of oxygen, produced from biomass, derived from the first Hydrotreating reactor 14 and is held in the separation device 18 for removal of water 20 education vytekajushie what about the thread 22 of the pyrolysis oil with a low content of water and oxygen, produced from biomass. The resulting stream 22 pyrolysis oil with low content of water and oxygen produced from biomass can be removed from the device 10 through the pipeline 24 (for example, if oxygen is removed almost completely), or alternatively, at least part of the discharge flow 22 pyrolysis oil with low content of water and oxygen, produced from biomass, can be sent through the pipeline 26.

In the exemplary embodiment, at least part of the discharge flow 22 pyrolysis oil with low content of water and oxygen, produced from biomass, are sent via the pipe 26 and is supplied to the second Hydrotreating reactor 28. The resulting stream 22 pyrolysis oil with low content of water and oxygen, produced from biomass, in contact with the second catalyst to remove oxygen in the presence of additional quantities of hydrogen containing gas 30, the second predetermined condition in the second Hydrotreating Hydrotreating reactor 28 to turn any remnants of oxidized hydrocarbons in stemming the flow 22 in the hydrocarbons with the formation of the second discharge flow 32 of the pyrolysis oil with a low content of oxygen, produced from biomass. Preferably, the second discharge flow 32 pyrolysis oil with low ash the content of oxygen, produced from biomass, the oxygen is removed almost completely, that is, the oil does not contain oxygen. The second catalyst for the removal of oxygen can be a conventional Hydrotreating catalyst, such as Nickel and molybdenum on gamma-alumina or other media known from the prior art, or alternatively, may have a composition similar to the first catalyst in the removal of oxygen. Second, pre-installed Hydrotreating conditions include a temperature from 300°C to 350°C, pressure from 3550 to 12400 kPa (500 to 1800 pounds per square inch), the volumetric rate of fluid from 0.5 h-1up to 1.5 hour-1and the supply rate of hydrogen containing gas to 1 barrel of processed oil component from 400 to 12,000 standard cubic feet (71,6-1432 m3/m3). The second Hydrotreating reactor 28 may be such as a tubular reactor with a fixed bed reactor with stirring and the like.

The minimum total number of the hydrogen-containing gas 13 and/or the additional hydrogen containing gas 30, which is necessary for the transformation of almost all of oxidized hydrocarbons in the pyrolysis oil produced from biomass and is contained in the flow of raw materials 12, contains 1-2 equivalents of hydrogen containing gas to one equivalent of the non-aqueous oxygen. Non-aqueous oxygen in the pyrolysis oil, mined is from biomass, included in the composition of functional groups in the oxidized hydrocarbon oil. For example, one equivalent of an alcohol functional group and a ketone functional group requires 1 equivalent of hydrogen containing gas to remove oxygen, while one equivalent of a complex of essential functional groups requires 2 equivalents of hydrogen containing gas, and 1 equivalent of the functional group of carboxylic acid requires 1.5 equivalents of hydrogen containing gas. Therefore, for example, the higher the content of esters and carboxylic acids in the pyrolysis oil produced from biomass, the more hydrogen-containing gas necessary for the transformation of all oxidized hydrocarbon oil into hydrocarbons. The minimum number of hydrogen containing gas to substantially remove oxygen from the pyrolysis oil produced from biomass, is from one to three molar equivalents of a non-aqueous oxygen in the oil. The amount of non-aqueous oxygen equal to (A-B), where A denotes the total amount of oxygen in the pyrolysis oil produced from biomass, which is determined by the combustion method, which is well known from the prior art, and B means the total amount of oxygen in the water pyrolysis oil produced from biomass. To determine B, first determine the total water content in the feast of lissom oil, produced from biomass by the method of titration with Karl Fischer reagent (ASTM D1364), which is known to experts in this field of technology. Can also be used an excess of the hydrogen-containing gas 13 and/or 30.

The second effluent stream 32 pyrolysis oil with low content of oxygen produced from biomass can be removed from the device 10 through the pipeline 34. In at least one embodiment, at least part of the discharge flow 22 pyrolysis oil with low content of water and oxygen, produced from biomass, and/or at least part of the resulting second thread 32 of the pyrolysis oil with a low content of oxygen produced from biomass recycle in the device 10 by filing in the flow of raw material 12. In one example, at least a portion of the flowing stream 22 pyrolysis oil with low content of water and oxygen, produced from biomass, are sent via the pipe 38 and is introduced into the flow of raw material 12 at the entrance to the first hydrotreatment reactor 14. In another example, the second effluent stream 32 pyrolysis oil with low content of oxygen produced from biomass, are sent via the pipe 36 and is introduced into the flow of raw material 12 at the entrance to the first hydrotreatment reactor 14. Recycling at least part of the discharge flow 22 of the pyrolysis oil with a low content of water is oxygen, produced from biomass and/or the second discharge flow 32 of the pyrolysis oil with a low content of oxygen, produced from biomass, helps to regulate the temperature of the highly exothermic process of removal of oxygen in the first Hydrotreating reactor 14. The benefits of recycling at least part of any of these flowing streams 22 and/or 32 include (but are not limited to) increasing the solubility of hydrogen, reducing the exothermic effect by dilution of the reactive particles and the decrease in the rate of bimolecular reactions, which leads to clogging of the catalyst. The preferred ratio of recirculating discharge flow 22 pyrolysis oil with low content of water and oxygen produced from biomass and/or recirculating the second discharge flow 32 of the pyrolysis oil with a low content of oxygen, produced from biomass, is from 1.5:1 to 5:1.

Therefore, the described methods and catalysts for the removal of oxygen from the pyrolysis oil produced from biomass. Unlike the prior art, is described in the embodiments of the invention receive the pyrolysis oil with a low content of oxygen produced from biomass by contacting the pyrolysis oil produced from biomass with a catalyst UDA is possible oxygen in the presence of hydrogen at a pre-determined conditions of Hydrotreating. The catalyst for the removal of oxygen includes neutral catalytic carrier, cobalt, molybdenum and a small amount of Nickel, which is posted on neutral catalytic media. This neutral catalytic carrier is stable and resistant to dissolution in the pyrolysis oil produced from biomass, which typically has a high water content and, therefore, provides a strong and durable carrier for the catalytically active metal is cobalt, molybdenum and Nickel. In addition, neutral catalytic media does not contribute to acid catalyzed polymerization of the various components of the pyrolysis oil produced from biomass, which in other circumstances cause plugging of the catalyst. Moreover, the activity of the cobalt-molybdenum catalyst, which is relatively weakly resists clogging, can be selectively enhanced by addition of a small amount of Nickel to effectively remove oxygen from the pyrolysis oil produced from biomass, without increasing catalytic activity in the processes that lead to the clogging of the catalyst.

Although at least one example embodiment of the invention described in the foregoing detailed description, it should be recognized that there are a large number of vari the Nations. In addition, it should be recognized that the exemplary embodiment or embodiments represent only examples, and not intended to be any limitation of the scope, applicability or configuration of the invention in any way. Rather, the detailed description is to provide the specialists in this field of technology convenient action plan for the practical implementation of the invention, it is obvious that can be made various changes in the function and arrangement of elements described in the exemplary embodiment, without deviating from the scope of the invention set forth in appended claims and their legal equivalents.

1. Method of removing oxygen from the pyrolysis oil produced from biomass, which includes a stage:
contact pyrolysis oil produced from biomass, with the first catalyst to remove oxygen in the presence of hydrogen in the first pre-established conditions of Hydrotreating, with the formation of the first discharge flow (16) of the pyrolysis oil produced from biomass, with low oxygen content, where the first catalyst in the removal of oxygen contains neutral catalytic carrier, Nickel, cobalt and molybdenum, and where the first catalyst in the removal of oxygen contains Nickel in an amount of from 0.1 to 1.5 wt.%, in Peresecina oxide.

2. The method according to p. 1, where the stage of contacting includes contacting the pyrolysis oil produced from biomass, with the first catalyst in the removal of oxygen, which contains Nickel in an amount of from 0.5 to 1 wt.%, in terms of the oxide.

3. The method according to p. 1, where the stage of contacting includes contacting the pyrolysis oil produced from biomass, with the first catalyst in the removal of oxygen, which contains cobalt in an amount of from 2 to 4 wt.%, in terms of the oxide.

4. The method according to p. 1, where the stage of contacting includes contacting the pyrolysis oil produced from biomass, with the first catalyst in the removal of oxygen, which contains molybdenum in an amount of from 10 to 20 wt.%, in terms of the oxide.

5. The method according to p. 1, where the stage of contacting includes contacting the pyrolysis oil produced from biomass, with the first catalyst in the removal of oxygen, which contains a neutral catalyst carrier selected from the group consisting of titanium dioxide (TiO2), zirconium dioxide (ZrO2), niobium oxide (Nb2O5), theta-alumina, and combinations of these media.

6. The method according to p. 1 which includes the additional step:
removal of water from the first discharge flow (16) of the pyrolysis oil produced from biomass, with low oxygen content, on the education of the resulting stream (22) pyrolysis oil, made from biomass, with low content of water and oxygen.

7. The method according to p. 6, where the first catalyst to remove oxygen contained in the first hydrotreatment reactor (14), and the stage of contacting includes the introduction of a flow of the raw material (12), which contains the pyrolysis oil produced from biomass, in the first hydrotreatment reactor (14) and where the method further comprises the stage of:
combining at least part of the resulting stream (22) of the pyrolysis oil produced from biomass, with low content of water and oxygen with a flow of raw material (12) for insertion into the first hydrotreatment reactor (14).

8. The method according to p. 6, which additionally includes the stage:
contacting at least part of the resulting stream (22) of the pyrolysis oil produced from biomass, with low content of water and oxygen, with the second catalyst to remove oxygen in the presence of hydrogen at a second predetermined Hydrotreating conditions with the formation of the second discharge flow (32) of the pyrolysis oil produced from biomass, with low oxygen content.

9. The method according to p. 8, where the first catalyst to remove oxygen contained in the first hydrotreatment reactor (14), and the stage of contacting includes the introduction of a flow of the raw material (12) containing pyrolysis oil produced from biomass, in the first reactor of the guide is ochistki (14) and where the method further comprises the stage of:
combining at least part of the second discharge flow (32) of the pyrolysis oil produced from biomass, with low oxygen content, flow of raw material (12) for insertion into the first hydrotreatment reactor (14).

10. Method of removing oxygen from the pyrolysis oil produced from biomass, where the method includes a stage:
the introduction of hydrogen and the flow of raw material (12) containing pyrolysis oil produced from biomass, in the first hydrotreatment reactor (14), which contains a first catalyst to remove oxygen, which is operated in a first predetermined conditions of Hydrotreating, with the formation of the first discharge flow (16) of the pyrolysis oil produced from biomass, with low oxygen content, where the first catalyst in the removal of oxygen contains neutral catalytic carrier, Nickel, cobalt and molybdenum, and where the first catalyst in the removal of oxygen contains Nickel in an amount of from 0.1 to 1.5 wt.%, in terms of the oxide, cobalt in an amount of from 2 to 4 wt.%, in terms of the oxide, molybdenum in an amount of from 10 to 20 wt.%, in terms of the oxide, and neutral catalyst carrier selected from the group consisting of titanium dioxide (TiO2), zirconium dioxide (ZrO2), niobium oxide (Nb2O5), theta-alumina, and combinations of these media.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to a method of hydrofining hydrocarbon material to obtain products with low sulphur content. The invention relates to a hydrofining method which comprises converting hydrocarbon material with high sulphur content at 340-375°C, pressure of 3.5-6.0 MPa, mass flow rate of the material of 1.0-1.5 h-1, volume ratio hydrogen/material of 300-500 m3/m3 in the presence of a heterogeneous catalyst containing cobalt, nickel and molybdenum in the form of bimetallic complex compounds [Co(H2O)x(L)y]2[Mo4O11(C6H5O7)2] and [Ni(H2O)x(L)y]2[Mo4O11(C6H5O7)2], where L is a partially deprotonated form of citric acid C6H6O7; x=0 or 2; y=0 or 1; silicon in the form of amorphous aluminosilicate, aluminium in the form of γ-Al2O3 and amorphous aluminosilicate, wherein the components are in the following concentrations, wt %: in total [Co(H2O)x(L)y]2[Mo4O11(C6H5O7)2] and [Ni(H2O)x(L)y]2[Mo4O11(C6H5O7)2] - 24.5-39.0; including [Co(H2O)x(L)y]2[Mo4O11(C6H5O7)2] - 6.2-29.5; [Ni(H2O)x(L)y]2[Mo4O11(C6H5O7)2] - 6.2-29.5; amorphous aluminosilicate - 5.9-37.8; γ-Al2O3 - the balance, which corresponds to the following content in a catalyst calcined at 550°C, wt %: MoO3 - 14.0-.,0; in total CoO+NiO - 3.6-6.0; including CoO - 0.9-4.5; NiO - 0.9-4.5; amorphous aluminosilicate - 6.7-42.0; Al2O3 - the balance.

EFFECT: obtaining oil products with low residual content of sulphur when hydrofining hydrocarbon material in the presence of a catalyst containing bimetallic complexes of Mo, Co, Ni and amorphous aluminosilicate.

5 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: described is catalyst including into its composition cobalt, nickel, molybdenum, aluminium and silicon, with cobalt, nickel and molybdenum contained in form of bimetal complex compounds [Co(H2O)x(L)y]2[Mo4O11(C6H5O7)2] and [Ni(H2O)x(L)y]2[Mo4O11(C6H5O7)2], where L is partly deprotonated form of citric acid C6H6O7; x=0 or 2; y=0 or 1; silicon in form of amorphous alumosilicate, aluminium in form of γ-Al2O3 and amorphous alumosilicate. Components in catalyst are contained in the following concentrations, wt %: in total [Co(H2O)x(L)y]2[Mo4O11(C6H5O7)2] and [Ni(H2O)x(L)y]2[Mo4O11(C6H5O7)2] - 24.5-39.0; including [Co(H2O)x(L)y]2[Mo4O11(C6H5O7)2] - 6,2-29,5; [Co(H2O)x(L)y]2[Mo4O11(C6H5O7)2] - 6,2-29,5; amorphous alumosilicate- 5.9-37.8; γ-Al2O3 -the remaining part, which corresponds to content in annealed at 550°C catalyst, wt %: MoO3 - 14.0-24.0; in total CoO+NiO - 3.6-6.0; including CoO - 0.9-4.5; NiO - 0.9-4.5; amorphous alumosilicate- 6.7-42.0; Al2O3 - the remaining part.

EFFECT: obtaining catalyst, which has maximal activity activity in target reactions, taking place in the process of hydropurification of hydrocarbon raw material.

4 cl, 3 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: method of preparing catalyst for purification of hydrocarbon raw material includes into composition cobalt, nickel, molybdenum, aluminium and silicon. Two bimetal complex compounds [Co(H2O)x(L)y]2[Mo4O11(C6H5O7)2] and [Ni(H2O)x(L)y]2[Mo4O11(C6H5O7)2], where L is partly deprotonated form of citric acid C6H6O7; x=0 or 2; y=0 or 1, are simultaneously applied on carrier, containing aluminium oxide and amorphous alumosilicate. After that, catalyst is dried with obtaining catalyst, containing components in the following concentrations, wt %: in total [Co(H2O)x(L)y]2[Mo4O11(C6H5O7)2] and [Ni(H2O)x(L)y]2[Mo4O11(C6H5O7)2] - 24.5-39.0; including [Co(H2O)x(L)y]2[Mo4O11(C6H5O7)2] - 6.2-29.5; [Ni(H2O)x(L)y]2[Mo4O11(C6H5O7)2] - 6.2-29.5; amorphous alumosilicate - 5.9-37.8; γ-Al2O3 - the remaining part. It corresponds to content in annealed at 550°C catalyst, wt %: MoO3 - 14.0-24.0; in total CoO+NiO - 3.6-6.0; including CoO - 0.9-4.5; NiO - 0.9-4.5; amorphous alumosilicate- 6.7-42.0; Al2O3 - the remaining part.

EFFECT: method makes it possible to obtain catalyst, which has maximal activity in target reactions, taking place in the process of hydropurification of hydrocarbon raw material, and provides obtaining petroleum products with low content of sulphur.

7 cl, 1 tbl, 8 ex

FIELD: chemistry.

SUBSTANCE: catalyst of hydroprocessing is obtained by the fixation of molybdenum and at least one component, selected from metals of 8-10 groups of the Periodic table, on an inorganic carrier, which contains aluminium oxide, in which the content of residual carbon is in the interval from 0.15 wt % to 3.0 wt %, intensity of peak of a molybdenum-containing complex metal oxide relative to the intensity of the main peak is in the interval from 0.60 to 1.00 in the X-ray diffraction spectrum (X-Ray), and either the intensity of peak of Mo-S bond, derivative from the peak of residual sulphur, relative to the intensity of the main peak is in the interval from 0.10 to 0.60 on a radial distribution curve, obtained from a spectrum of long fine structure of X-ray absorption in the analysis of the fine structure of X-ray absorption, or a part of Mo-S is in the interval from 77% to 99% in the structure spectrum close to the edge of X-ray absorption (X-ray), obtained in the analysis of the fine structure of X-ray absorption. The invention also relates to a method of obtaining a petroleum product, in which hydroprocessing of petroleum fraction is performed with the application of the said regenerated catalyst of hydroprocessing.

EFFECT: catalyst has an increased activity, provides an effective performance of hyrdoprocessing of petroleum fractions and contributes to the reduction of quantity of discharged wastes.

4 cl, 4 dwg, 1 tbl, 4 ex

FIELD: oil-and-gas industry.

SUBSTANCE: invention relates to production of super low-sulphur diesel fractions by hydrorefining at higher temperatures and pressure at alumocobalt (or nickel) molybdenum catalysts. Said hydrorefining is conducted 360-400°C, at least 30 atm, weight hour space velocity not over 1h-1, hydrogen-to-stock ratio of at least 300 nm3/m3.Catalyst is obtained by adsorption of active components from low-percentage water solution of salts on the surface of aluminium oxide carriers in two steps with intermediate drying: MoO3, is obtained at first step, CoO(NiO)·MoO3 or CoO(NiO) is obtained at second step.

EFFECT: production of super low-sulphur diesel fractions.

2 cl, 2 dwg, 7 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: disclosed is a method of preparing a regenerated hydrofining catalyst by regenerating a spent hydrofining catalyst in a given temperature range, where the given temperature range is from T1 -30°C or higher to T2 +30°C or lower, said temperature range being defined by conducting differential thermal analysis of the spent hydrofining catalyst, converting differential heat in a temperature measurement range from 100°C or higher to 600°C or lower into an electromotive force difference, double differentiation of the converted value on temperature to obtain the least extremal value and a second least extremal value, and presenting temperature which corresponds to the extremal value at the side of lower temperatures as T1 and temperature corresponding to the extremal value at the side of higher temperatures as T2. The invention also discloses a method of producing a petroleum product using said catalyst and the regenerated catalyst itself.

EFFECT: method enables to obtain a regenerated hydrofining catalyst, having a constantly high activity, from a spent hydrofining catalyst.

7 cl, 5 dwg, 1 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention is intended for chemical industry and can be used in catalysts for hydrocracking, hydroconversion and hydrofining processes. To obtain a heteropoly compound consisting of a nickel salt of vacancy-keggin-type heteropolyanions containing tungsten, x+y/2 equivalents of barium hydroxide are added to heteropolytungstic acids. Ba2+ cations are then substituted with Ni2+ cations as a result of ion exchange on cation-exchange resins subjected to exchange with Ni2+ cations in advance. The obtained heteropoly compound has the formula Nix+y/2AW11-yO39-5/2y,zH2O, and in another version has the formula Nix+1AW9O34,zH2O, where A is selected from phosphorus, silicon and boron, y=0 or 2, x=3.5, if A denotes phosphorus, x=4, if A denotes silicon, x=4.5, and z is a number from 0 to 36. Nickel atoms are not substituted with tungsten atoms but are located in the counterion position in the structure of said compound.

EFFECT: invention provides a high ratio Ni/W and output of more than 80%.

11 cl, 2 dwg, 4 tbl, 4 ex

FIELD: process engineering.

SUBSTANCE: invention relates to activation of catalysts for diesel fuel hydrofining and can be used in oil processing and petrochemical industries. Activation of nickel-molybdenum-alumina catalysts comprises bringing the catalyst in contact with the solution of ferriphenyl siloxane in organic solvent at cavitation hydrodynamic processing in bubble-cavitation layer of inert gas inside cavitation flow reactor at oscillation intensity of 0.25-0.55 W/m2 and 15-45°C for 5-25 min. Then, catalyst is cured in organic solvent at a room temperature, solvent is stripped and catalyst if dried and heat-treated.

EFFECT: higher desulfurising activity.

2 cl, 4 ex, 7 tbl

FIELD: chemistry.

SUBSTANCE: invention relates o field of catalysis. Described is catalyst of hydrotreatment of oil fractions, in which as carrier, applied is mixture of aluminium oxide and boric phosphate of variable composition, formed at the stage of burning H3BO3 and H3PO4 carrier, with the following component content, wt %: phosphomolybdic heteropolycomplex, P-[(MoO3)12] - 14.3-27.5; cobalt oxide CoO - 3.2-8.5; aluminium oxide - 56.5-81.6; boric phosphate - 0.9-7.5. Method of obtaining claimed catalyst is described.

EFFECT: increase of hydrotreatment process efficiency.

2 cl, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis. Described is a catalyst for hydrofining diesel fractions, which contains molybdenum disulphide, cobalt, nickel or iron, pseudoboehmite γ-AlOOH, obtained from electroexplosive aluminium nitride, which contains as a modifying additive nanodiamonds with size of not more than 20 nm, with the following ratio of components, wt %: pseudoboehmite - 10, nanodiamonds - 20, cobalt, nickel or iron - 20-30, molybdenum disulphide - the balance.

EFFECT: high mechanical stability of the catalyst.

2 cl, 1 tbl, 5 ex

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: chemistry.

SUBSTANCE: present invention relates to methods and systems for processing triglyceride-containing, biologically-derived oils to obtain base oils and transportation fuels. The method comprises the following steps: a) processing a triglyceride-containing vegetable oil to effect oligomerisation of unsaturated fatty acid components contained therein so as to obtain an oligomerised mixture; b) isomerising the oligomerised mixture over an isomerisation catalyst to obtain an isomerised mixture, wherein the isomerised mixture comprises a base oil component and a diesel fuel component; c) removing water from the isomerised mixture to obtain a dry isomerised mixture, wherein the dry isomerised mixture comprises at least 10 wt % alkanes having 30 or more carbon atoms; d) separating the dry isomerised mixture into a lower boiling fraction from which diesel fuel is subsequently derived, and a higher boiling fraction; and e) subsequently further isomerising at least a portion of the higher boiling fraction to obtain a base oil. A system for producing base oil and diesel fuel is also disclosed.

EFFECT: providing multiple product streams of given quality.

15 cl, 4 dwg, 1 ex

FIELD: oil and gas industry.

SUBSTANCE: invention is related to petrochemical analysis, in particular to method for manufacturing of catalyst for liquidphase hydration of 2',4',4-trinitrobenzanilide (TNBA) with obtainment of aromatic polyamine compounds widely used as intermediate products in production of dyes, heat-resistant polymers, synthesis of high-strength fibres, etc. The method for manufacturing of catalyst for liquidphase hydration of 2',4',4-TNBA includes impregnation of the cellular structure polyurethane matrix with ceramic slurry containing more than 30 wt % of α-aluminium oxide with subsequent drying at temperature of 100-120°C, tempering at temperature of 1050-1070°C, subsequent impregnation of the obtained high-porous cellular carrier by alumina sol (γ-Al2O3), drying at temperature of 100-120°C, tempering at temperature of 550-600°C, subsequent impregnation by aqueous solution of cobalt and iron nitrates at atmospheric temperature, tempering at 350-400°C, and upon tempering application of carbon nanotubes manufactured by methane pyrolysis at temperature less than 800°C, up to 0.15-0.20 wt % of the weight of the carrier with γ-Al2O3, then treatment with palladium nitrate solution, drying at temperature less than 120°C and tempering at temperature of 430-450°C, recovery of the obtained palladium oxide at the carrier by molecular hydrogen in nitrogen till palladium metal is obtained at temperature of 50-55°C.

EFFECT: reduction of the reaction duration, increase in the reaction rate due to increase of the catalyst specific surface, TNBA load to the catalyst, output of the target product.

4 ex

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