RU2549571C2 - Method of obtaining alkane and aromatic hydrocarbons - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to the catalytic conversion of a renewable raw material - products of the biomass fermentation (ethanol, fusel alcohols) and their mixtures with vegetable oil into an alkane-aromatic fraction C₃-C₁₁₊, which can be used for obtaining fuel components. The method of obtaining alkane and aromatic hydrocarbons from the products of the biomass processing for obtaining the hydrocarbon fuel components includes passing the products of the biomass processing through a layer of a preliminarily regenerated zeolite ZSM-based catalyst, containing Pd and Zn, in an inert atmosphere at an increased temperature. The method is characterised by the fact that as the catalyst used is the Pd-Zn/ZSM/Al₂O₃ catalyst of the general formula of 0.6 wt % Pd-1 Zn/Al₂O₃/ZSM, with the products of the biomass processing, which contain a mixture of organic fermentation products or fusel alcohols, being passed through the catalyst layer at a temperature of 280-500°C and volume rate of 0.3-6 h^-1.

EFFECT: extension of the raw material base and method for obtaining alkane and aromatic hydrocarbons.

5 cl, 6 tbl, 26 ex

Description

The invention relates to the field of heterogeneous catalytic conversions of organic compounds, namely to the catalytic conversion of renewable raw materials - biomass fermentation products (ethanol, fusel oils) and mixtures thereof with vegetable oil into an alkane-aromatic fraction C ₃ -C ₁₁₊ , which can be used to obtain fuel components.

Currently, increased attention is being paid to the processing of biomass into energy carriers, including into fuel components and important petrochemical products.

Ethanol, whose production to date has reached 70 billion liters / year and continues to grow [Demirbas, A. 2008. Biodiesel: A realistic fuel alternative for diesel engines. Springer, London], is considered as a promising raw material of non-oil origin for obtaining energy carriers, including hydrocarbon components of fuels and a wide range of solvents [Varfolomeev SD, Moiseev II, Myasoedov B.F. // Bulletin of the Russian Academy of Sciences, 2009, t. 79, No. 7, p.595-607].

The main method for the production of ethanol is the enzymatic fermentation of organic products, while an ester-aldehyde fraction and up to 20 wt.% Fusel oils, consisting mainly of propanol, butanol and isoamyl alcohol, are formed as by-products [Ethanol impurities and their removal during rectification (review) / V.F. Sukhodol, L.I. Prikhodko // University proceedings. Food Technology, 1983. No. 5. - S.23-28].

The literature describes methods for converting vegetable oils into aliphatic-aromatic fractions of hydrocarbons in the presence of zeolite-containing catalysts [W. Charusiri, W. Yongchareon, T. Vitidsant, Korean J. Chem. Eng., 2006, 23, 349; A.G. Dedov, A.S. Loktev, L.Kh. Kunashev, M.N. Kartasheva, B.C. Bogatyrev, I.I. Moiseev, Chem. technology, 2002, 8, 15; J.A. Botas, D.P. Serrano, A. Garcia, J. de Vicente, R. Ramos, Catalytic conversion of rapeseed oil into raw chemicals and fuels over Ni- and Mo-modified nanocrystalline ZSM-5 zeolite, Catalysis Today, Volume 195, Issue 1, 15 November 2012 , Pages 59-70].

The disadvantage of these methods is the need to use molecular hydrogen, high methane formation and low resistance of the catalysts to coke formation and, as a result, a rapid loss of activity.

A known method of producing liquid fuel hydrocarbons by catalytic conversion of vegetable oils in the presence of catalysts - high silica zeolites ZSM-5 and ZSM-12 [US Pat. 430,0009; Chem. Abstrs., 1981, 10, 150109]. The raw materials used are corn, peanut, castor, tall oil and jojoba oil, which, unlike the others related to triglycerides of fatty acids, is an ester of fatty acids and monohydric higher alcohols. When using the HZSM-5 catalyst (ZSM-5 zeolite in hydrogen form), a temperature of 400 ° C, a castor oil supply rate of 2.5 g / g catalyst per hour and an additional hydrogen supply of 5 ml / min, fuel hydrocarbons were obtained with a yield of 78%, including benzene-toluene-xylene fraction (mixture of benzene, toluene, ethylbenzene and xylenes) with a yield of 48%, aromatic hydrocarbons C ₉ -C ₁₃ with a yield of 25%. When using other oils, the yield of liquid fuel hydrocarbons and the performance of the catalyst were significantly worse.

The disadvantage of this method is the low productivity of the catalyst.

A known method of producing fuel hydrocarbons containing predominantly aromatic compounds by converting rapeseed oil in the presence of HZSM-5 zeolite with a ratio of SiO ₂ / Al ₂ O ₃ = 48 with a catalyst loading of 1 g, temperature 370 ± 5 ° C, rapeseed oil feed rate W = 3 g / g cut-per hour [YS Prasad, NN Bakhshi, Appl. Catal., 1985, 18, 71]. The yield of aromatic hydrocarbons reaches 44%, including a 39% benzene-toluene-xylene fraction. The productivity of the catalyst for aromatic hydrocarbons does not exceed 1.323 g / g of catalyst per hour.

The disadvantage of this method is the low productivity of the catalyst for aromatic hydrocarbons.

A known method of producing aromatic hydrocarbons C ₆ -C ₁₀ high-temperature contacting of hydrocarbon feedstocks and / or oxygen-containing compounds with a catalyst containing a zeolite with a structure of ZSM-5 or ZSM-11, modified by elements or compounds of elements I, II, IV, V, VI, VII and VIII groups in an amount of 0.05-5.0 wt.%, at a temperature of 280-460 ° C. The contacting of the feedstock with the catalyst can be carried out in the presence of a hydrogen-containing gas [RU 2163624, 2001].

However, when using vegetable oils containing acid triglycerides as a feedstock, carrying out the process in the range of the above temperatures leads to a rather low yield of the target products with extremely low catalyst productivity in terms of total hydrocarbons (g / g of catalyst per hour). In addition, aromatic hydrocarbons obtained in this process are contaminated with by-products - liquid non-aromatic compounds, which at a contact temperature below 470 ° C consist mainly of a mixture of complex fatty acids. The specified mixture of fatty acids, on the one hand, prevents the selective release of aromatic hydrocarbons, on the other hand, is an unused waste, which leads to serious environmental problems and, as a result, the underestimated demand of the known method in the processing of vegetable oils.

A known method for producing aromatic hydrocarbons by high temperature contacting vegetable oil containing acid triglycerides with a catalyst containing high silica zeolite having a structure similar to ZSM-5, and a promoter in the form of an oxide or mixtures of transition metal oxides selected from oxides of zinc, chromium, iron, temperature in the catalyst bed 470-630 ° C. The process is carried out in the presence of hydrogen. In this case, hydrogen is used at a feed rate of 50-200 ml / g (100-150 ml / g) of catalyst per minute. Hydrogen is fed into the reactor in which it reaches the catalyst, and the catalyst is heated to predetermined temperatures, after which vegetable oil is fed into the reactor at a rate of 2-7 g / g of catalyst per hour [RU 2470004, C07C 15/02, C07C 4 / 06, C10G 3/00, B01J 29/40, 12/20/2012].

The disadvantages of the method are the elevated temperature of the process and the need to use hydrogen.

Closest to the claimed invention (prototype) is a method for producing alkane and aromatic hydrocarbons, according to which the biomass processing product is ethanol and / or diethyl ether obtained from it in an inert gas atmosphere (Ar) is passed through a layer of a pre-reduced catalyst, which is a zeolite of a digital computer, containing 0.4-1 wt.% Pd and 0.5-1 wt.% Zn, at a temperature of 350-400 ° C and a space velocity of ethanol and / or diethyl ether of 0.4-0.8 h ^-1 [Khadzhiev S.N., Kolesnichenko N.V., Tsodikov M.V., Gekhman A.E., Ionin D.A., Chudakova M.V., Chistyakov A.V., Moiseev I.I. A method of obtaining an alkane-aromatic fraction / Russian Patent 2466976. Publ. 11/20/2012].

However, to achieve a high yield of the target products in the prototype method, preliminary isolation of pure, not contaminated with fusel oils, ethanol from biomass processing products or its conversion to diethyl ether is required. However, the problem of waste disposal is not solved - hard fusel oils separated from ethanol are not separated.

Currently, the problem of the complete utilization of fusel oils has not been resolved, and they are mainly destroyed by burial or burning in fireboxes as part of fuel oil. The most rational is the allocation of isoamyl alcohol from them by fractional distillation, but even in this case up to 52% wt. components of fusel oils cannot be used as marketable products and will pollute the environment [see Laskin B.M., Malin S.A. Korostelev S.A. The problem of recycling fusel oils - the main waste of alcohol production, the ways of their rational processing. Sat scientific papers of the conference "Modern Directions of Theoretical and Applied Research ′ 2011", v. 28, p. 26-29. Chemistry. - Odessa: Black Sea, 2011].

The objective of the invention is the creation of a one-stage method for producing alkane and aromatic hydrocarbons from biomass fermentation products and mixtures thereof with vegetable oils, which allows to obtain target products with high yield with significantly increased productivity and stability of the catalyst and devoid of the disadvantages of the prototype. This ensures the efficient disposal of fusel oils or biomass fermentation products containing fusel oils.

To solve this problem, a method for producing alkane and aromatic hydrocarbons from biomass processing products to produce hydrocarbon components of fuels, including passing the biomass processing products through a layer of pre-reduced catalyst based on a zeolite CVM containing Pd and Zn, in an inert atmosphere at elevated temperature, with the aim of expansion of the raw material base for the production of hydrocarbon components of fuels and the use of hydrogen released into the reaction zone during the reaction the aromatization of alcohols of the fermentation mixture or fusel oil, characterized in that the catalyst is Pd-Zn / CVM / A1 ₂ O _{3 a} catalyst of the general formula 0.6 wt.% Pd-1 wt.% Zn / Al ₂ O ₃ / CVM, and biomass processing products containing a mixture of organic fermentation products (fermentation mixture) or fusel oils are passed through a catalyst bed at a temperature of 280-500 ° C and a space velocity of 0.3-6 h ^-1 .

Biomass processing products may be a mixture of organic fermentation products, at a space velocity of their transmission through the catalyst bed of 0.3-4.8 h ^-1 and a temperature of 330-420 ° C.

Biomass processing products may consist of 25-75 vol.% A mixture of fermentation products and vegetable oil - the rest, at a space velocity of passing them through the catalyst bed of 0.6-6 h ^-1 .

Biomass processing products may consist of 25-100 vol.% Fusel oil and 0-75 vol. % of vegetable oil, at a space velocity of passing them through the catalyst bed of 0.6-6 h ^-1 and a temperature of 330-500 ° C.

Use vegetable oil selected from the range: sunflower oil, rapeseed oil, peanut oil, corn oil, castor oil, oils produced by special crops of algae.

When developing this method, we found that reductive dehydration of a number of alcohols, diethyl ether and acetone in the presence of a Pd-Zn / CVM / Al ₂ O ₃ catalyst, leading to the formation of an alkane-aromatic fraction, proceeds with the evolution of hydrogen, which is caused by the formation of a number of aromatic compounds . In this regard, the development of a new method of joint processing is based on the consumption of hydrogen released in situ during the formation of aromatic hydrocarbons from fermentation products, on the reductive deoxygenation of vegetable oil.

The complexity of the joint conversion of fermentation products and vegetable oil lies in the fact that the fermentation products are converted in contact with the reduced catalyst in an inert medium, and the reductive deoxygenation of vegetable oil requires an increased hydrogen pressure.

When using the proposed method, the following technical results are achieved:

- increase the yield of target products;

- ensuring high purity of the target products;

- a significant increase in catalyst productivity by the sum of the target products;

- reduction in methane formation;

- expansion of the raw material base for the production of hydrocarbon components of fuels;

- the formation of easily separated by-products disposed of while reducing their yield;

- simplification of technology;

- the process is carried out without additionally introduced molecular hydrogen, because a sufficient amount of hydrogen is generated by the reaction system for hydrogenolysis of the substrates and ensuring the stability of the catalyst to coke formation;

- effective disposal of raw materials containing fusel oils;

- achieving the optimal ratio of alkanes and aromatic compounds in the resulting fraction.

The synthesis of the alkane-aromatic fraction is carried out in a flow reactor with the recirculation of gaseous products with a stationary catalyst layer, which is used as a Pd-Zn / CVM / Al ₂ O ₃ catalyst of the General formula 0.6 wt.% Pd-1 wt.% Zn / Al ₂ O ₃ / computer with a ratio of Si / Al = 30, obtained as described in patent RU 2248341 C1, C07C 1/20, B01J 29/44, publ. 03/20/2005, previously reduced with hydrogen at 450 ° C for 10 hours. As raw materials use:

1. Raw materials 1: vegetable oil, for example, sunflower oil, rapeseed oil, peanut oil, corn oil, castor oil, oils produced by special crops of algae;

2. Raw materials 2: a fermentation mixture consisting of 80% ethanol and 20% fusel oils, simulating organic products of fermentation of plant materials, such as corn, potatoes, beets, wheat and rye;

3. Raw materials 3: fusel oils, which are a model mixture of alcohols: 20% propyl, 5% isopropyl, 20% isobutyl, 5% n-butyl, 50% isoamyl.

Heat treatment is carried out using a toroidal electric furnace, which is located outside the tubular reactor. The height of the toroidal furnace corresponds to the height of the reactor. Upon completion of the heat treatment of the catalyst, the temperature of the reactor is reduced to that required to obtain the alkane-aromatic fraction, a pressure of 0.5 MPa (Ar) is created and the feed of initial fermentation mixtures, fusel oils or their mixtures with vegetable oils to the catalyst, the amount of which in the reactor is 20 cm, is started. ³ , with a space velocity of 0.3-6 hour ^-1 in flow mode.

The liquid products after the reactor are collected in cooled receivers (the first one has a temperature of 0 ° C, the second one is 15 ° C), the gaseous products are collected in a gas tank and their composition is analyzed by gas chromatography.

Gaseous products are light C ₁ -C ₅ hydrocarbons (methane, ethane, ethylene, propane, propylene, butanes, butenes, pentanes, pentenes), hydrogen, carbon monoxide and dioxide. The qualitative and quantitative composition of gaseous products is determined by gas chromatography, the absolute calibration method.

The composition of liquid products is determined by gas-liquid chromatography and chromatography-mass spectrometry.

The presence of residual mono- and polyglycerides of fatty acids, as well as free acids in the reaction products was carried out by IR spectroscopy.

The following examples illustrate the invention, but in no way limit it.

Examples 1-5

Examples 1-5 show the results of the conversion of a fermentation mixture consisting of 80% ethanol and 20% fusel oils, at a temperature of 330 ° C, an argon pressure (Ar) of 0.5 MPa, and various volumetric feed rates of the starting materials — 0, 3; 0.6; 1,2; 2.4; 4.8 respectively.

As can be seen from the data in table 1, for all values of the volumetric rate, an exhaustive conversion of the components of the fermentation mixture is achieved, while the volumetric rate in the range of 1.2-2.4 h ^-1 is optimal, since with the exhaustive conversion of the feedstock the highest yield of the target products - hydrocarbons consisting of C ₃ -C ₆ alkanes and C ₆ -C ₁₁ aromatics, which are components of the gasoline and kerosene fractions of motor fuels.

An increase in the volumetric feed rate of the starting materials to 4.8 h ⁻¹ significantly reduces the yield of the target products due to the proportional increase in the yield of oxygenates (oxygen-containing compounds, which are mainly ethers of convertible alcohols). A decrease in the volumetric feed rate of the starting materials from 1.2 to 0.3 h ⁻¹ leads to a decrease in the yield of the target hydrocarbon fraction and an increase in the yield of light hydrocarbons C ₁ –C ₂ .

Examples 6-9

Examples 6-9 show the results of the conversion of a fermentation mixture consisting of 80% ethanol and 20% fusel oils for various temperatures of 280; 300; 420; 500, respectively, and 330 ° C according to example 2 for the yield of hydrocarbon products. The results of these experiments are shown in tables 1 and 2.

From the results of the experiments it follows that a temperature of 330 ° C is optimal for the conversion of fermentation products. At this temperature, the highest yield of alkane aromatic hydrocarbons is achieved. Lowering the temperature to 300 ° C sharply increases (~ 10 times) the yield of ethylene and C ₃ -C ₆ olefins, the yield of alkanes drops to 1%, the yield of aromatic hydrocarbons decreases from 30 to 15 wt. % A further decrease in temperature leads to an increase in the yield of olefins and a decrease in the yield of the alkane-aromatic fraction. An increase in temperature to 420 ° C leads to a twofold decrease in the yield of C ₃ -C ₆ alkanes and an equivalent increase in the amount of methane and ethane in the reaction products. A further increase in temperature to 500 ° C reduces the yield of C ₃ -C ₆ alkanes to 0.76 wt.% And aromatics to 23.25 wt.% Proportionally increasing the yield of methane and ethane to 19.26 and 15.91 wt.%, Respectively.

Thus, the direct catalytic processing of a fermentation mixture consisting of 80% ethanol and 20% fusel oils at a temperature of 330 ° C and a space velocity of 1.2 h ^-1 allows to obtain 60.5 wt.% Of valuable hydrocarbon fuels based on the weight of the passed raw materials.

As can be seen from tables 1 and 2, in the process of formation of aromatic hydrocarbons in the reaction zone up to 0.11% of the mass. hydrogen. This allows the organization of the joint conversion of fermentation products and reductive deoxygenation of vegetable oil. Effective deoxygenation of the oil proceeds at a higher temperature of 420 ° C without supplying molecular hydrogen to the reaction zone.

Table 1 The effect of space velocity on the conversion of a fermentation mixture consisting of 80% ethanol and 20% fusel oils (feedstock 2), at a temperature of 330 ° C, argon pressure of 0.5 MPa The yield of products (wt.%) Example No. Volumetric feed rate W, h ^-1 The conversion of starting materials,% H ₂ Water CO + CO ₂ CH ₄ C ₂ H ₆ C ₂ H ₄ Alkanes C ₃ -C ₆ Oxygenates Olefins C ₃ -C ₆ Aromatics C ₆ -C ₁₁ one 0.3 one hundred 0.08 32.56 6.11 3.45 8.32 2.02 6.39 0 0,03 41.04 2 0.6 one hundred 0.08 34.47 3.98 2.41 7.11 1.13 10.65 0 0.09 40.08 3 1,2 one hundred 0.05 37.12 2.18 0.11 5.72 0.23 23.45 0 0.54 30.6 four 2,4 one hundred 0,03 38.12 1.34 0.05 3.61 0.25 27.43 0 1.39 27.78 5 4.8 one hundred 0.01 20.02 0.69 0.06 5.37 7.14 5.92 40 4.08 16.71

table 2 The effect of temperature on the conversion of a fermentation mixture consisting of 80% ethanol and 20% fusel oils (feed 2), with a volumetric feed rate of the starting materials of 1.2 h ^-1 , pressure of 0.5 MPa The yield of products (wt.%) Example No. T, ° C The conversion of starting materials,% H ₂ Water CO + CO ₂ CH ₄ C ₂ H ₆ C ₂ H ₄ Alkanes C ₃ -C ₆ Oxygenates Olefins C ₃ -C ₆ Aromatics C ₆ -C ₁₁ 6 280 one hundred 0 14.65 0.89 0.05 1.22 19.87 1.23 5.67 48.34 8.08 7 300 one hundred 0.01 20,23 3.98 0.06 3 13.47 0.87 7.23 35.78 15.37 8 420 one hundred 0.08 38.12 1.34 5.43 12.34 0 12.91 0 0 29.78 9 500 one hundred 0.11 40.02 0.69 19.26 15.91 0 0.76 0 0 23.25

Examples 10-12

In examples 10-12, a joint conversion of a fermentation mixture consisting of 80% ethanol and 20% fusel oils is carried out together with various amounts of added vegetable oils (examples 10-11 are rapeseed oil, which is triglycerides of the following fatty acids: stearic ( 4.79 wt.%), Oleic (93.313 wt.%), Gondoin (1.795 wt.%), Eruca (0.102 wt.%); Example 12 - sunflower oil, which is the triglycerides of the following fatty acids: palmitic (6.3 wt.%), stearic (3.7 wt.%), oleic (88.3 wt.%), linoleic (0.5 wt.%), gondoi new (0.9 wt.%), eruca (0.3 wt.%) 75, 50 and 25% vol., respectively. The results of the transformations of the examples are shown in table 3.

As can be seen from table 3, the addition of vegetable oil to the fermentation products directly proportionally increases the total yield of C ₃ -C ₁₁ hydrocarbons. However, the composition of hydrocarbon products changes in comparison with the results of the conversion of only fermentation products: the yield of alkanes decreases, the yield of aromatic hydrocarbons and olefins increases. From the data of table 3 we can conclude that the optimal mixture is in which added 25% vol. vegetable oil, because when processing this mixture, the yield of alkanes is the highest, and the yield of olefins is the lowest.

Example 13-17

In examples 13-17, the effect of temperature on the joint conversion of a fermentation mixture consisting of 80% ethanol and 20% fusel oils containing 25% vol. Vegetable oil (example 13 is rapeseed oil, which is the triglycerides of the following fatty acids: stearic (4.79 wt.%), Oleic (93.313 wt.%), Gondoin (1.795 wt.%), Eruca (0.102 wt.%), example 14 - microalgae oil nannocloropsis salina, which is the triglycerides of the following fatty acids: lauric 5.5 wt.%, palmitic 37.5 wt.%, palmitoleic 23.3 wt.%, stearic 1.3 wt.%, oleic 13, 4 wt.%, Gondoin 18.7 wt.%, Eruca 0.4 wt.%; Examples 15-17 - microalgae oil phaeodactylum triocrnutum, which is the following fatty triglycerides acids: myristic 4.5 wt.%, palmitic 25.8 wt.%, palmitoleic 37.5 wt.%, stearic 1.3 wt.%, oleic 15.2 wt.%, gondoic 14.7 wt.% The results of the transformations of the examples are presented in table 4.

From the data presented in table 4 it follows that the temperature of 420 ° C is optimal. At a lower temperature, the yield of the target hydrocarbon fraction is significantly reduced. At higher temperatures, the yield of dead ends C ₁ and C ₂ increases due to cracking of hydrocarbon products.

Table 3 The results of the joint conversion of the products of a fermentation mixture consisting of 80% ethanol and 20% fusel oils (feed 2) with vegetable oil (feed 1) at a pressure of 0.5 MPa (Ar), T = 420 ° C, W = 1 , 2 h ^-1 Example No. Raw materials, content,% vol. conversion of starting materials,% The yield of products (wt.%) fermentation products (80% ethanol + 20% fusel oils) vegetable oil water CO + CO ₂ CH ₄ C ₂ H ₆ C ₂ H ₄ alkanes C ₃ -C ₆ olefins C ₃ -C ₆ aromatics C ₆ -C ₁₁ 10 75 25 one hundred 30.88 1.05 0.13 1.49 0.87 10.49 6.46 48.63 eleven fifty fifty one hundred 24.35 0.98 0.17 1.23 0.94 4.39 13.29 54.65 12 25 75 one hundred 15.21 0.68 0.15 0.87 1,02 0.19 23.56 58.32

Table 4 The temperature dependence of the joint transformation of 75% vol. a fermentation mixture consisting of 80% ethanol and 20% fusel oils (raw material 2) with 25% vol. vegetable oil (raw material 1) at a pressure of 0.5 MPa (Ar), W = 1.2 h ^-1 The yield of products (wt.%) Example No. T, ° C conversion of starting materials,% water CO + CO ₂ CH ₄ C ₂ H ₆ C ₂ H ₄ alkanes C ₃ -C ₆ oxygenates olefins C ₃ -C ₆ aromatics C ₆ -C ₁₁ 13 270 one hundred 10,2 0.37 0.05 0.45 0.47 12.38 39.98 11.23 24.87 fourteen 330 one hundred 30.19 0.59 0.04 1.41 1.17 11.75 2.29 9.45 43.11 fifteen 420 one hundred 30.88 1.05 0.13 1.49 0.87 10.49 0 6.46 48.63 16 450 one hundred 27,99 2.89 6.92 2.05 1.42 3,51 0 2.94 52.28 17 500 one hundred 25.14 5.74 12.59 2.11 1.31 0.46 0 0.11 52,54

Examples 18-21

In examples 18-21, the effect of space velocity on the yield of hydrocarbon products of the joint conversion of a mixture consisting of 75% vol. fermentation mixture consisting of 80% ethanol and 20% fusel oils and 25% vol. vegetable oil (examples 18, 19 - rapeseed oil, which is the triglycerides of the following fatty acids: stearic (4.79 wt.%), oleic (93.313 wt.%), gondoin (1.795 wt.%), eruca (0.102 wt.% ); examples 20, 21 - mustard oil, which is the triglycerides of the following fatty acids: linoleic 31.7 wt.%, oleic 44.5 wt.%, eruca 12.8 wt.%, behenic 2.2 wt.%, eicosen , 9.8 wt.%) At a temperature of 420 ° C and a pressure of 0.5 MPa (Ar). The results are presented in table.5.

As can be seen from the data in table 5, at a space velocity of 0.6 h ^{-1 the} maximum yield of C ₃ -C ₆ alkanes is observed. With an increase in the space velocity, the yield of aliphatic hydrocarbons (alkanes and C ₃ -C ₆ alkanes and olefins) decreases and the yield of aromatic hydrocarbons increases proportionally, reaching a maximum value of 57.81% wt. with a volumetric feed rate of 4.8 h ^-1 . The decrease in the yield of alkanes and olefins is explained by the mechanism of conversion of organic products into various classes of hydrocarbons. We have previously shown that the formation of alkanes is most likely to occur as a result of oligomerization of olefins, which are intermediate products formed during the dehydration of alcohols. The formation of aromatic hydrocarbons mainly occurs as a result of the so-called “hydrocarbon pool” mechanism [M. Stocker, Microporous Mesoporous Mater. 1999, 29, 3-48; Jeffery L. White, Methanol-to-hydrocarbon chemistry: The carbon pool (r) evolution, Catal. Sci. Technol., 2011, 1, 1630-1635], as a result of which the hydrocarbon fragments of organic products crack and undergo condensation in the pores of the zeolite-containing catalyst. It was found that the growth of the hydrocarbon chain in the presence of the Pd-Zn / CVM / Al ₂ O ₃ catalyst system proceeds at a slower rate compared to dehydrocyclization and aromatization processes. As a result of this, it can be assumed that when the fictitious contact time is reduced, the aromatization reaction predominates, and not the growth of the aliphatic chain of hydrocarbons.

Table 5 The influence of the volumetric feed rate on the process of joint conversion of 75% vol. a fermentation mixture consisting of 80% ethanol and 20% fusel oils (raw material 2) with 25% vol. vegetable oil (raw material 1) at a pressure of 0.5 MPa (Ar), T = 420 ° C The yield of products (wt.%) Example No. volumetric feed rate, h ^-1 conversion of starting materials,% water CO + CO ₂ CH ₄ C ₂ H ₆ C ₂ H ₄ alkanes V ₃ -C ₆ oxygenates olefins C ₃ -C ₆ aromatics C ₆ -C ₁₁ eighteen 0.6 one hundred 30.82 1,11 1,56 3.37 0.12 19.37 0 12.49 31.16 19 1,2 one hundred 30.88 1.05 0.13 1.49 0.87 10.49 0 6.46 48.63 twenty 2,4 one hundred 30,99 0.94 0.11 1.21 1.31 6.21 0 5.31 53.92 21 4.8 one hundred 26.06 0.87 0,07 0.49 1.48 4.12 5.32 3.78 57.81 22 6 one hundred 11.03 0.84 0.05 0.15 1.71 2.75 27.12 3.24 53.11

Examples 23-26

Conduct a joint conversion of vegetable oil (examples 23, 24 - rapeseed oil, which is the triglycerides of the following fatty acids: stearic (4.79 wt.%), Oleic (93.313 wt.%), Gondoin (1.795 wt.%), Eruca (0.102 wt.%), examples 25, 26 - corn oil, which is the triglycerides of the following fatty acids: oleic 42.2 wt.%, linoleic 48.2 wt.%, linolenic 1.3 wt.%, arachidonic 0.4 wt. %; stearic 2.5 wt.%, palmitic 3.4 wt.%) and fusel oil (20% propyl, 5% isopropyl, 20% isobutyl, 5% n-butyl, 50% isoamyl alcohols) under optimal conditions - a temperature of 350 ° C, a space velocity of 1.2 h ^-1 and a different ratio of substrates. The results of the experiments are presented in table 6.

From the table it follows that pure fusel oil (20% propyl, 5% isopropyl, 20% isobutyl, 5% n-butyl, 50% isoamyl) without ethanol is effectively converted into the alkane-aromatic fraction of C ₃ -C ₁₁ hydrocarbons with the yield reaching 67% wt. The addition of vegetable oil to fusel oil proportionally reduces the yield of alkanes and increases the yield of C ₃ -C ₆ olefins and aromatic hydrocarbons, the maximum total yield of which is achieved on a 25% vol. fusel oil and 75% vol. vegetable oil.

The maximum amount of alkane hydrocarbons is formed from a raw mixture consisting of 25% vol. vegetable oil and 75% vol. fusel oil.

Thus, these results show that the joint conversion is effectively realized in the absence of ethanol, as a result of the occurrence of conjugated cross-condensation reactions of the hydrocarbon backbone of alcohols and reductive deoxygenation. It can also be noted that the proposed method can effectively obtain hydrocarbon components of fuels, also with the exception of ethanol from the organic mixture of fermentation products (from raw materials 3).

Claims (5)

1. A method of producing alkane and aromatic hydrocarbons from products of biomass processing to obtain hydrocarbon components of fuels, including passing the products of biomass processing through a layer of pre-reduced catalyst based on a zeolite CVM containing Pd and Zn, in an inert atmosphere at elevated temperature, characterized in that used as catalyst Pd-Zn / DCM / Al ₂ O ₃ catalyst of the general formula 0.6 wt.% Pd-1 wt.% Zn / A1 ₂ O ₃ / DCM and biomass products containing a mixture of organic produk s fermentation or fusel oil is passed through the catalyst bed at a temperature of 280-500 ° C and a WHSV of 0.3-6 h ^-1. 2. The method according to p. 1, characterized in that the biomass processing products are a mixture of organic fermentation products with a space velocity of transmission through the catalyst bed of 0.3-4.8 h ^-1 and a temperature of 330-420 ° C. 3. The method according to p. 1, characterized in that the biomass processing products consist of 25-75 vol.% A mixture of fermentation products and vegetable oil - the rest, with a volumetric rate of transmission through the catalyst layer of 0.6-6 h ^-1 . 4. The method according to p. 1, characterized in that the biomass processing products consist of 25-100 vol.% Fusel oil and 0-75 vol.% Vegetable oil, with a space velocity of passing them through the catalyst layer of 0.6-6 hours ^{- 1} and a temperature of 330-500 ° C. 5. The method according to any one of paragraphs. 3 and 4, characterized in that the vegetable oil is selected from the series: sunflower oil, rapeseed oil, peanut oil, corn oil, castor oil, oils produced by special crops of algae.