Method of obtaining alkane and aromatic hydrocarbons
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
The invention relates to the field of heterogeneous catalytic transformations of organic compounds, namely the catalytic transformation of renewable raw materials - products of the fermentation of biomass (ethanol, fusel oil) and their mixtures with vegetable oil in alkane-aromatic fraction C3-C11+that can be used to obtain components of fuels.
Currently, attention is being paid to the processing of biomass into energy products, including fuel components and important petrochemical products.
Ethanol, the production of which has now 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-oil origin energy sources and including hydrocarbon components of fuels and a wide range of solvents [Varfolomeev S. D., Moiseev I. I., Myasoedov B. F. // Bulletin of the Russian Academy of Sciences, 2009, vol. 79, No. 7, pp. 595-607].
The main method of ethanol production is the enzymatic fermentation of organic produce, as by-products formed ether-aldehyde fraction and up to 20 wt.% fusel oils, consisting mainly of propanol, butanol and isoamyl alcohol [Impurities of ethyl alcohol and their removal by distillation (review) / �.F. The dry valley, L. I. Prikhodko // Izvestiya vuzov. Food technology, 1983. No. 5. - S. 23-28].
The literature describes methods of conversion of vegetable oils in aliphatic-aromatic hydrocarbon fraction in the presence of zeolite catalysts [W. Charusiri, W. Yongchareon, T. Vitidsant, Korean J. Chem. Eng., 2006, 23, 349; A. G. Dedov, A. S. Loktev, L. H. Conasev, M. N. Kartashev, V. S. 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 metanoobrazovanie and low stability of the catalysts to coxworthy and, as a consequence, a rapid loss of activity.
A method of producing a liquid fuel hydrocarbons catalytic conversion of vegetable oils in the presence of catalysts - high-silica zeolites ZSM-5 and ZSM-12 [US Pat. 4300009; Chem. Abstrs., 1981, 10, 150109]. As raw materials use corn, peanut, castor, tall oil and jojoba oil, which, unlike the rest belonging to the triglycerides of fatty acids, is an ester of fatty acid and higher Monohydric alcohols. When using the catalyst HZSM-5 (zeolite ZSM-5 in the hydrogen form), 400°C, feed rate Casteau�new oil 2.5 g/g of catalyst per hour and a further supply of hydrogen 5 ml/min the resulting fuel hydrocarbons with the release of 78%, including benzene-toluene-xylene fraction (mixture of benzene, toluene, ethylbenzene and xylenes) with a yield of 48%, aromatic hydrocarbons (C9-C13with the release of 25%. When using other oils the yield of liquid fuel hydrocarbons and catalytic performance were significantly worse.
The disadvantage of this method is the low productivity of the catalyst.
A method of producing a fuel hydrocarbons containing predominantly compounds of the aromatic series, the conversion of rapeseed oil in the presence of HZSM-5 zeolite with a ratio of SiO2/Al2O3=48, with catalyst loading of 1 g, a temperature of 370±5°C, feed rate of rapeseed oil W=3 g/g cat-RA / hour [Y. S. Prasad, N. N. Bakhshi, Appl. Catal., 1985, 18, 71]. The yield of aromatic hydrocarbons reaches 44%, including benzene-toluene-xylene fraction of 39%. The performance 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 in aromatic hydrocarbons.
A method of producing aromatic hydrocarbons C6-C10high temperature contacting hydrocarbons and/or oxygen-containing compounds with a catalyst comprising a zeolite with structure of ZSM-5 or ZSM-11, modified elements or compounds� elements I, II, IV, V, VI, VII and VIII groups in an amount of 0.05-5.0 wt.%, at a temperature 280-460°C. the Contacting of the feedstock with the catalyst can be carried out in the presence of hydrogen gas [RU 2163624, 2001].
However, when using as starting raw materials of vegetable oils containing triglycerides of acids, carrying out the process in the interval of temperatures above leads to a rather low yield of the target products at extremely low productivity of the catalyst on the sum of hydrocarbons (g/g of catalyst per hour). In addition, the obtained aromatic hydrocarbons contaminated with by-products - liquid non-aromatic compounds, which when contacting temperature below 470°C consist mainly of a mixture of fatty acids of complex composition. Said mixture of fatty acids, on the one hand, prevents the selective allocation of aromatic hydrocarbons is non-recyclable waste, which leads to serious environmental problems and, consequently, a lower vostrebovatelnosti known method in the processing of vegetable oils.
A method of producing aromatic hydrocarbons by high temperature contacting vegetable oils containing triglycerides of acids, with a catalyst comprising vysokokremnistykh�y zeolite, having structure similar to ZSM-5, and the promoter oxide or mixtures of oxides of transition metals selected from oxides of zinc, chromium, iron, at a temperature in the catalyst bed 470-630°C. the Process is carried out in the presence of hydrogen. The hydrogen used in the feed rate of 50-200 ml/g (100-150 ml/g) catalyst in a min. Hydrogen fed to the reactor in which it reaches the catalyst, and perform heating of the catalyst to a predetermined temperature, after which the supply to the reactor oils of plant origin with a speed of 2-7 g/g catalyst / hour [EN 2470004, C07C 15/02, C07C 4/06, C10G 3/00, B01J 29/40, 20.12.2012].
The disadvantages of this method include high temperature process and the need for the use of hydrogen.
The closest to the claimed invention (the prototype) is a method for producing alkane and aromatic hydrocarbons, whereby the product of processing of biomass - ethanol and/or obtained from diethyl ether under an inert atmosphere (Ar) is passed through a layer of pre-reduced catalyst constituting the zeolite CVM containing 0.4-1 wt.% Pd and 0.5-1 wt.% Zn at a temperature of 350-400°C and the volumetric feed rate of ethanol and/or diethyl ether of 0.4-0.8 h-1[Khadzhiev S. N., Kolesnichenko N. In., Tsodikov M. V., Gekhman A. E., Jonas, D. A., Chudakov, M. V., Chistyakov V. A., Moiseev I. I. Method of getting� alkane and aromatic fractions / Patent of Russia 2466976. Publ. 20.11.2012].
However, to achieve high yield of the target products in the method according to the prior art requires the prior selection of pure, not contaminated with fusel oils, ethanol from waste biomass or its transformation into diethyl ether. It does not solve the problem of disposal of waste is separated from the ethanol trudnoreshaemyh fusel oils.
At present the problem of full utilization of fusel oil is not resolved, and are mostly destroyed by burial or incineration in furnaces in the composition of the oil. The most efficient is the allocation of them isoamyl alcohol by fractional distillation, but in this case, to 52% wt. components of fusel oil finds use as commercial products and will pollute the environment [see B. Laskin, M., Malin, S. A., Korostelev S. A. the Problem of utilization of fusel oils - the main waste alcohol production, the ways of their rational processing. Sat. scientific papers of the conference "Modern trends in theoretical and applied research '2011", vol. 28, pp. 26-29. Chemistry. - Odessa: Black Sea Coast, 2011].
The object of the invention is the creation of a one-step method for producing alkane and aromatic hydrocarbons from the products of fermentation of biomass and their mixtures with oils of plant origin, which allows to obtain C�left products with high yield in significantly improved performance and stability of the catalyst and devoid of the disadvantages of the prototype. This ensures effective utilization of fusel oil, or products of fermentation of biomass containing fusel oil.
To solve this problem a method of producing alkane and aromatic hydrocarbons from waste biomass for the hydrocarbon components of the fuel, including the transmission of products of processing biomass through a layer of pre-reduced catalyst based on zeolite a digital computer, containing Pd and Zn, in an inert atmosphere at an elevated temperature, with the aim of expanding the raw material base for the hydrocarbon components of fuels and the use of hydrogen produced in the reaction zone during the reaction of aromatization of alcohols fermentation mixture or fusel oil characterized by the fact that as the catalyst, Pd-Zn/CVM/A12O3the catalyst of the General formula 0.6 wt.% Pd-1 wt.% Zn/Al2O3/CVM, and the products of processing biomass containing a mixture of organic products of fermentation (fermentation mixture) or fusel oil, is passed through the catalyst bed at a temperature of 280-500°C and a space velocity of 0.3-6 h-1.
Products of processing of biomass can be a mixture of organic products of fermentation, when the volumetric throughput rate through the catalyst bed 0,3-4,8 h-1and pace�the atur 330-420°C.
Products of processing of biomass can consist of 25-75 vol.% a mixture of fermentation products and vegetable oil - the rest, at a space velocity of passing them through a bed of catalyst of 0.6-6 h-1.
Products of processing of biomass can consist of 25 to 100 vol.% fusel oil and about 0-75. % of vegetable oil, when the volumetric throughput rate through the catalyst bed of 0.6-6 h-1and a temperature of 330-500°C.
Use vegetable oil, selected from: sunflower oil, rapeseed oil, peanut oil, corn oil, castor oil, oil produced by special cultures of algae.
Us in the development of this method found that the reductive dehydration of a number of alcohols, diethyl ether and acetone in the presence of a catalyst of Pd-Zn/CVM/Al2O3resulting in the formation of alkane and aromatic fractions, proceeds with 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 co-processing is based on the consumption of hydrogen produced in situ in the process of formation of aromatic hydrocarbons from the products of fermentation, recovery deoxygenation vegetable oil.
The complexity of the joint transformation products of fermentation and vegetable oil is that the products f�mentali become in contact with regenerated catalyst in an inert environment; the leakage reduction of deoxygenation vegetable oil needs a high pressure of hydrogen.
When using the proposed method achieved the following technical results:
- increase the yield of desired products;
- ensuring high purity of the target products;
- significant performance improvements catalyst on the amount of target products;
- reduction of methane production very;
- the expansion of raw materials base for the hydrocarbon components of the fuel;
education is easily detachable side recyclable products while reducing their output;
- simplifying technology;
- the process is carried out without added molecular hydrogen, because of the reaction system can produce enough hydrogen to experimental data showed substrates and stability of the catalyst to coxworthy;
- effective utilization of raw materials containing fusel oil;
- achieving an optimal balance of alkanes and aromatic compounds in the resulting fractions.
Synthesis of alkane and aromatic fractions is carried out in a flow reactor with recirculation of gaseous products with a stationary layer of catalyst, which is used as Pd-Zn/CVM/Al2O3the catalyst of the General formula 0.6 wt.% Pd-1 wt.% Zn/Al2/sub> O3/CVM with a ratio Si/Al=30, obtained as described in patent RU 2248341 C1, SS 1/20, B01J 29/44, publ. 20.03.2005, pre-reduced with hydrogen at 450°C for 10 hours. As raw materials use:
1. raw 1: vegetable oil, e.g., sunflower oil, rapeseed oil, peanut oil, corn oil, castor oil, oil produced by special cultures of algae;
2. 2 raw material: fermentation mixture comprising 80% ethanol and 20% of fusel oil, simulating organic products fermentation of plant raw materials, such as corn, potatoes, sugar beet, wheat and rye;
3. raw 3: fusel oil, representing a mixture model of alcohol: 20% propyl, 5% isopropanol, 20% isobutyl, 5% n-butyl, 50% isoamyl.
The 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 was lowered to desired to obtain alkane and aromatic fractions, create pressure 0.5 MPa (Ar) and the supply source of the fermentation of mixtures of fusel oils or their mixtures with vegetable oils on the catalyst, the amount of which in the reactor is 20 cm3with a space velocity of 0.3-6
Liquid products after the reactor is collected in a cooled receiver (1st on the go has a temperature of 0°C, 2nd - 15°C), the gaseous products were collected in a Gasometer and analyze their composition by gas chromatography.
The gaseous products are light With1-C5hydrocarbons (methane, ethane, ethylene, propane, propylene, butanes, butenes, Pentanes, pentene), hydrogen, carbon monoxide and carbon dioxide. Qualitative and quantitative composition of gaseous products is determined by gas chromatography, the method of absolute calibration.
The composition of liquid products is determined by the methods of gas-liquid chromatography and gas chromatography-mass spectrometry.
The presence of residual mono - and polyglycerol fatty acids and free acids in the reaction products was carried out by IR-spectroscopy.
The following examples illustrate the invention, but in no way limit it.
In examples 1-5 are the results of the enzymatic conversion of a mixture comprising 80% ethanol and 20% of fusel oil, at a temperature of 330°C, a pressure of argon (Ar) Of 0.5 MPa and different volumetric flow rates of the starting materials- 0,3; 0,6; 1,2; 2,4; 4,8 respectively.
As can be seen from table 1, for all values of flow rate is achieved comprehensive transformation �of komponentov fermentation mixture, while space velocity in the range of 1.2 to 2.4 h-1is best, because when complete conversion of the feedstock is achieved the highest yield of the target products - hydrocarbons consisting of alkanes With3-C6and aromatics With6-C11that are components of gasoline and kerosene fractions of motor fuels.
The increase in volumetric feed rate of the starting materials to 4.8 h-1significantly reduces the yield of the target product at the expense of a proportional increase in the yield of oxygenates (oxygen-containing compounds, representing, mainly, ethers convertible alcohols). The decrease in the volumetric feed rate of the starting materials from 1.2 to 0.3 h-1leads to lower yield of the desired hydrocarbon fraction and an increased yield of light hydrocarbons With1-C2.
In examples 6-9, the results are given of the transformation of the fermentation mixture comprising 80% ethanol and 20% of fusel oils at different temperatures 280; 300; 420; 500 respectively, and 330°C in example 2 to yield hydrocarbon products. The results of these experiments are shown in tables 1 and 2.
From the experimental results it follows that the temperature of 330°C is optimal for the transformation products of fermentation. When this temperature is reached the highest output and�Kang-aromatic hydrocarbons. Reduce temperature to 300°C dramatically increases (~ 10 times the yield of ethylene and olefins With3-C6the yield of alkanes falls to 1%, the yield of aromatic hydrocarbons is reduced from 30 to 15 wt. %. Further lowering of the temperature leads to an increased yield of olefins and to reduce the yield of alkane and aromatic fractions. Increasing the temperature to 420°C leads to a twofold decrease in the yield of alkanes With3-C6and an equivalent increase in the amount of methane and ethane in the reaction products. Further increasing the temperature to 500°C reduces the yield of alkanes With3-C6to 0.76 wt.% and aromatics until 23,25 wt.% proportionally increasing the yield of methane and ethane to John 19: 26 and 15,91 wt.% respectively.
Thus, a direct catalytic treatment of the fermentation mixture consisting of 80% ethanol and 20% of fusel oil at a temperature of 330°C and a space velocity of 1.2 h-1allows to get of 60.5 wt.% valuable hydrocarbon fuels based on the weight of the missed material.
As can be seen from tables 1 and 2, in the process of formation of aromatic hydrocarbons in the reaction zone is allocated to 0.11 wt%. hydrogen. This allows for the organization of joint transformation products of fermentation and recovery deoxygenation vegetable oil. Effective deoxygenate oil flows at a higher temperature of 420°C under without�Chi in the reaction zone of molecular hydrogen.
|The influence of space velocity on the conversion of the fermentation mixture comprising 80% ethanol and 20% of fusel oils (raw materials 2) at a temperature of 330°C, a pressure of argon of 0.5 MPa|
|The product yield (wt.%)|
|No. example||The volumetric feed rate of the raw material W, h-1||Conversion of the original substances, %||H2||Water||CO+CO2||CH4||C2H6||C2H4||Alkanes (C3-C6||Oxygenates||Olefins C3-C6||Aromatics C6-C11|
|5||4,8||0,01||20,02||0,69||0,06||levels lower than the 5.37||7,14||5,92||40||4,08||16,71|
|The effect of temperature on the enzymatic conversion of a mixture comprising 80% ethanol and 20% of fusel oil (raw material 2), at a space velocity of the filing of the original substances 1.2 h-1and a pressure of 0.5 MPa|
|The yield of products (wt.%)|
|No. example||T, °C||Conversion of the original substances, %||H2||Water||CO+CO2||CH4||C2H6||C2H4||Alkanes (C3-C6||Oxygenates||Olefins C3-C6||Aromatics C6-C11|
|7||300||100||0,01||20,23||of 3.98||0,06||3||13,47||of 0.87||7.23 percent||35,78||to 15.37|
|9||500||100||0,11||40,02||John 19: 26||15,91||0||0,76||0||0||23,25|
In examples 10-12 are conducting a joint transformation of the fermentation mixture comprising 80% ethanol and 20% of fusel oil, together with various amounts of added vegetable oils (examples 10-11 - rapeseed oil, representing the triglycerides of the following fatty acids: stearic (4,79 wt.%), oleic (93,313 wt.%), londonboy (1,795 wt.%), erucic (is 0.102 wt.%); example 12 - sunflower oil, representing the triglycerides of the following fatty acids: palmitic (6,3 wt.%), stearic (3.7 wt.%), oleic (88,3 wt.%), linoleic (0.5 wt.%), londonboy (0.9 wt.%), erucic (0.3 wt.%) 75, 50 and 25%. respectively. The results of the transformations in examples are shown in table 3.
As seen from table 3, the addition of vegetable oil to the products of fermentation is directly proportional to increases the total yield of hydrocarbons (C3-C11. However, the composition of the hydrocarbon products is changing compared with the results of the conversions are only some products of fermentation: decreases the yield of alkanes increases the yield of aromatic hydrocarbons and olefins. From table 3 can bookmark�chit, what is the optimal mixture to which was added 25%. vegetable oil, because during the processing of this mixture, the yield of alkanes the most high, and the yield of olefins is the lowest.
In examples 13-17 examine the effect of temperature on the joint transformation of the fermentation mixture comprising 80% ethanol and 20% of fusel oil containing 25 vol.% Vegetable oil (example 13 - rapeseed oil, representing the triglycerides of the following fatty acids: stearic (4,79 wt.%), oleic (93,313 wt.%), londonboy (1,795 wt.%), erucic (is 0.102 wt.%), example 14 - microalgae oil nannocloropsis salina, representing the triglycerides of the following fatty acids: lauric 5.5 wt.%, palmitic and 37.5 wt.%, palmitoleic of 23.3 wt.%, stearic 1.3 wt.%, oleic of 13.4 wt.%, londonboy of 18.7 wt.%, erucic 0.4 wt.%; examples 15-17 - oil microalgae phaeodactylum triocrnutum representing the triglycerides of the following fatty acids: myristic 4.5 wt.%, palmitic and 25.8 wt.%, palmitoleic and 37.5 wt.%, stearic 1.3 wt.%, oleic of 15.2 wt.%, londonboy of 14.7 wt.%. The results of the transformations of the examples 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 significantly reduces the yield of the desired hydrocarbon fractions. At higher� temperature increases the output of dead-end products of C 1and C2due to the cracking of hydrocarbon products.
|The results of the joint transformation products of the fermentation mixture comprising 80% ethanol and 20% of fusel oil (raw material 2) with vegetable oil (raw material 1) at a pressure of 0.5 MPa (Ar), T=420°C, W=1,2 h-1|
|No. example||The raw material content, % vol.||conversion of the original substances, %||The product yield (wt.%)|
|the products of fermentation (80% ethanol+20% fusel oil)||vegetable oil||water||CO+CO2||CH4||C2H6||C2H4||alkanes (C3-C6||olefins C3-C6||aromatics C6-C11|
|10||75||25||100||30,88||1,5||0,13||1,49||of 0.87||10,49||of 6.46||48,63|
|The temperature dependence of the joint conversion of 75%. the fermentation mixture comprising 80% ethanol and 20% of fusel oil (raw material 2) with 25%. vegetable oil (raw material 1) at a pressure of 0.5 MPa (Ar), W=1,2 h-1|
|The product yield (wt.%)|
|No. example||T, °C||conversion of the original substances, %||water||CO+CO2||CH4||C2H6||C2H4||alkanes (C3-C6||oxygenates||olefins C3-C6||aromatics C6-C11|
|15||420||100||30,88||1,05||0,13||1,49||of 0.87||10,49||0||of 6.46||48,63|
|16||450||100||27,99||2,89||at 6.92||2,05||1,42||3,51||0||to 2.94||52,28|
In examples 18-21 investigated the effect of space velocity on the yield of hydrocarbon products joint transformation mixture consisting of 75%. the fermentation mixture comprising 80% ethanol and 20% from fusel oil and 25%. vegetable oils (examples 18, 19 - rapeseed oil�, representing the triglycerides of the following fatty acids: stearic (4,79 wt.%), oleic (93,313 wt.%), londonboy (1,795 wt.%), erucic (is 0.102 wt.%); examples 20, 21 - mustard oil, representing the triglycerides of the following fatty acids: linoleic to 31.7 wt.%, oleic of 44.5 wt.% erucic of 12.8 wt.%, behenic 2.2 wt.%, Aksenova, to 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 table 5, at a space velocity of 0.6 h-1observed maximum value of the output of alkanes (C3-C6. With increasing flow rate decreases the yield of aliphatic hydrocarbons (alkanes and olefins C3-C6) and proportionally increases the yield of aromatic hydrocarbons, reaching a maximum value 57,81% wt. at a volumetric feed rate of the substrate 4,8 h-1. The decrease in the yield of alkanes and olefins is due to the mechanism of transformation of organic products in various classes of hydrocarbons. Previously it was shown that the formation of alkanes with greatest probability occurs as a result of oligomerization olefins, which are intermediate products formed during the dehydration of alcohols. Formation of aromatic hydrocarbons, mainly occurs as a result of the so-called mechanism of "hydrocarbon pool" [M. Stocker, Microporous Mesoporous Mater. 1999, 29, 3-8; Jeffery L. White, Methanol-to-hydrocarbon chemistry: The carbon pool (r)evolution, Catal. Sci. Technol., 2011, 1, 1630-1635], in which hydrocarbon fragments organic products craterous and subjected to condensation in the pores of the zeolite catalyst. As it was established, the growth of hydrocarbon chains in the presence of a catalytic system Pd-Zn/CVM/Al2O3occurs with a slower speed in comparison with the processes of dehydrocyclization and flavoring. As a result, it can be assumed that when the dummy contact time dominated by the reaction of aromatization, rather than the growth of the aliphatic chain hydrocarbons.
|The influence of the volumetric feed rate of the joint process of conversion of 75%. the fermentation mixture comprising 80% ethanol and 20% of fusel oil (raw material 2) with 25%. vegetable oil (raw material 1) at a pressure of 0.5 MPa (Ar), T=420°C|
|The product yield (wt.%)|
|No. example||the volumetric feed rate of raw materials, h-1||conversion of the original substances, %||water||CO+CO||CH4||C2H6||C2H4||alkanes V3-C6||oxygenates||olefins C3-C6||aromatics C6-C11|
|19||1,2||100||30,88||1,05||0,13||1,49||of 0.87||10,49||0||of 6.46||48,63|
|21||4,8||100||26,06||of 0.87||0,07||0,49||1,48||4,12||of 5.32||a 3.78||57,81|
Conduct joint transformation of vegetable oils (examples 23, 24 - rapeseed oil, representing the triglycerides of the following fatty acids: stearic (4,79 wt.%), oleic (93,313 wt.%), londonboy (1,795 wt.%), erucic (is 0.102 wt.%), examples 25, 26 - corn oil representing 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 acid and 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-1and different ratio of substrates. The results are shown in table 6.
From the table it follows that the net fusel oil (20% propyl, 5% isopropanol, 20% isobutyl, 5% n-butyl, 50% isoamyl) without ethanol efficiently converted into alkane-aromatic fraction of hydrocarbons (C3-C11with the release of up to 67 wt%. The addition of fusel oil vegetable oil proportionally reduces the yield of alkanes and increase the yield of olefins, C3-C6and aromatic hydrocarbons, the maximum total output which is achieved on the raw mix composition of 25 vol.% fusel oil and 75%. of vegetable oil.
The maximum number of alkane hydrocarbons is produced from a raw material mixture consisting of 25 vol.% vegetable oil and 75%. fusel oil.
Thus, these results show that the joint transformation effectively implemented in the absence of ethanol, resulting in leakage of conjugated reactions cross-condensation of the hydrocarbon skeleton of alcohols and recovery of deoxyguanosine. It may also be noted that the proposed method can effectively obtain the hydrocarbon components of the fuel, also with the exclusion of ethanol� of organic compound fermentation products (from raw materials 3).
1. A method of producing alkane and aromatic hydrocarbons from waste biomass for the hydrocarbon components of the fuel, including the transmission of products of processing biomass through a layer of pre-reduced catalyst based on zeolite a digital computer, containing Pd and Zn, in an inert atmosphere at an elevated temperature, characterized in that as the catalyst, Pd-Zn/CVM/Al2O3the catalyst of the General formula 0.6 wt.% Pd-1 wt.% Zn/A12O3/CVM, and the products of processing biomass containing a mixture of organic fermentation products or fusel oil, is passed through the catalyst bed at a temperature of 280-500°C and a space velocity of 0.3-6 h-1.
2. A method according to claim 1, characterized in that the products of biomass processing are a mixture of organic fermentation products in the volumetric throughput rate through the catalyst bed 0,3-4,8 h-1and a temperature of 330-420°C.
3. A method according to claim 1, characterized in that the products of processing of biomass consist of 25-75 vol.% a mixture of fermentation products and vegetable oil - the rest, at a space velocity of passing them through a bed of catalyst of 0.6-6 h-1.
4. A method according to claim 1, characterized in that the products of processing of biomass consist of 25 to 100 vol.% fusel oil and about 0-75% of vegetable oil, when the volumetric throughput rate through the catalyst bed of 0.6-6 h-1and a temperature of 330-500°C.
5. A method according to any one of claims. 3 and 4, characterized in that the vegetable oil is selected from: sunflower oil, rapeseed oil, peanut oil, corn oil, castor oil, oil produced by special cultures of algae.
SUBSTANCE: described is catalyst for single-stage manufacturing of components for jet and Diesel fuels from oil and fat raw material, containing platinum or palladium, fixed on the surface of porous carrier, represented by borate-containing aluminium oxide, with the following component ratio, wt %: Pt or Pd 0,10-0.50; B2O3 5-25; Al2O3 - the remaining part. Catalyst can be prepared by granulation of mixture of aluminium oxide hydrate of pseudoboehmite structure with orthoboric acid with the following drying of granules at 120°C and annealing at 550-700°C for 16 h. Granules are soaked with solutions of hexachloroplatinic acid or palladium chloride, subjected to drying at 120°C and annealing at 500°C. Method of single-stage manufacturing of components for jet and Diesel fuels with improved low-temperature properties from oil and fat raw material in presence of claimed catalyst includes passing mixture of hydrogen and oil and fat raw material through immobile layer of catalyst at temperature 380°C, pressure 4.0 MPa, mass rate of raw material supply 1 h-1 and with volume ratio hydrogen:raw material, equal 1300.
EFFECT: increased efficiency of single-stage manufacturing of components for jet and Diesel fuels with improved low-temperature properties from oil and fat raw material due to simplification of catalyst composition, method of its preparation and reduction of catalyst cost.
3 cl, 4 tbl, 4 ex
SUBSTANCE: invention relates to methods of producing pyrolysis oil. A method of producing biomass-derived pyrolysis oil (38) with low metal content includes steps of: filtering a biomass-derived pyrolysis oil (12) with a high-throughput filter unit (20) having throughput of 10 l/m2/h or higher to form biomass-derived pyrolysis oil (22) with low content of solid substances; filtering the biomass-derived pyrolysis oil (22) with low content of solid substances with a fine filter (28) having a pore diameter of 50 mcm or less to form biomass-derived pyrolysis oil (30) with very low content of solid substances; and contacting the biomass-derived pyrolysis oil (30) with very low content of solid substances with an ion-exchange resin to remove metal ions and form biomass-derived pyrolysis oil (38) with low metal content. A version of the method is also disclosed.
EFFECT: total metal content is reduced to concentration of 100 ppm or less.
10 cl, 1 dwg
SUBSTANCE: method includes producing synthesis gas, converting the synthesis gas into methanol, producing a concentrate of aromatic hydrocarbons and water from the methanol in the presence of a catalyst, separating the water, blowing off hydrocarbon residues from the water, separating the formed concentrate of aromatic hydrocarbons and a hydrogen-containing gas, which is at least partially used when producing synthesis gas, to change the ratio H2:CO=1.8-2.3:1 therein. The production of aromatic hydrocarbons from methanol in the presence of a catalyst is carried out in two series-connected aromatic hydrocarbon synthesis reactors - a first low-temperature isothermic aromatic and aliphatic hydrocarbon synthesis reactor and a second high-temperature adiabatic reactor for synthesis of aromatic and aliphatic hydrocarbons from the aliphatic hydrocarbons formed in the first reactor and subsequent stabilisation in a unit for stabilising the concentrate of aromatic hydrocarbons. At least part of the hydrogen-containing gas is fed into a synthesis gas production unit and used to obtain synthesis gas using an autothermal reforming technique with a pre-reforming or non-catalytic partial oxidation unit using oxygen or oxygen-air mixtures as the oxidising agent to change the ratio according to the relationship (m.f.H2-m.f.CO2)/(m.f.CO+m.f.CO2)≥2, where m.f. is the molar fraction of a component in synthesis gas. The invention also relates to an apparatus.
EFFECT: high efficiency of producing concentrates of aromatic hydrocarbons.
12 cl, 2 dwg, 1 ex
FIELD: oil and gas industry.
SUBSTANCE: invention relates to a method for obtaining hydrocarbon products, which involves the following stages: (a) provision of synthesis gas containing hydrogen, carbon monoxide and carbon dioxide; (b) reaction of conversion of synthesis gas to an oxygenate mixture containing methanol and dimethyl ester, in presence of one or more catalysts, which simultaneously catalyse the reaction of conversion of hydrogen and carbon monoxide to oxygenates, at pressure of at least 4 MPa; (c) extraction from stage (b) of an oxygenate mixture containing quantities of methanol, dimethyl ester, carbon dioxide and water together with non-reacted synthesis gas, introduction of the whole amount of the oxygenate mixture without any additional treatment to a stage of catalytic conversion of oxygenates (d); (d) reaction of oxygenate mixture in presence of a catalyst, which is active in conversion of oxygenates to higher hydrocarbons; (e) extraction of the outlet flow from stage (d) and separation of the outlet flow into tail gas containing carbon dioxide occurring from synthesis gas and carbon dioxide formed at stage (b), liquid hydrocarbon phase containing the higher hydrocarbons obtained at stage (d) and liquid water phase where the pressure used at stages (c)-(e) is mainly the same as that used at stage (b); besides, some part of tail gas obtained at stage (e) is recirculated to stage (d), and the rest part of tail gas is discharged.
EFFECT: this method is a method in which there is no recirculation of non-reacted synthesis gas to a synthesis stage of oxygenates and without any cooling of a conversion reaction of dimethyl ester to higher hydrocarbons.
6 cl, 2 ex, 1 tbl, 2 dwg
SUBSTANCE: claimed invention relates to liquid fuel compositions. Invention deals with liquid fuel composition, containing, at least, one fuel component and from 0.1%(vil.) to 99.5% (vol.) of fraction of distillation of component, which contains, at least, one C4+ compound, derived from water-soluble oxygenated hydrocarbon. Method includes supply of water and water-soluble oxygenated hydrocarbon, including C1+O1+ hydrocarbon, in water liquid phase and/or vapour phase; supply of H2; carrying out catalytic reaction in liquid and/or vapour phase between oxygenated hydrocarbon and H2 in presence of deoxygenation catalyst at temperature of deoxygenation and pressure of deoxygenation to obtain oxygenate, which contains C1+O1-3 hydrocarbon in reaction flow; and carrying put catalytic reaction in liquid and/or vapour phase for oxygenate in presence of condensation catalyst at temperature of condensation and pressure of condensation to obtain C4+ compound, where C4+ compound includes representative, selected from the group, consisting of C4+ alcohol, C4+ ketone, C4+ alkane, C4+ alkene, C5+ cycloalkane, C5+ cycloalkene, aryl, condensed aryl and their mixture. Invention also relates to petrol composition, Diesel fuel composition, kerosene composition and methods of obtaining thereof.
EFFECT: improved characteristics of fuel composition, containing component, obtained from biomass.
9 cl, 19 dwg, 14 tbl, 59 ex
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
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.
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
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
SUBSTANCE: invention relates to method of isomerisation of raw material flow, containing one or more C4-C6 paraffins, which includes: A) contact of raw material flow with isomerisation catalyst in reaction zone of isomerisation under isomerisation conditions in order to obtain flow, discharged from isomerisation zone; B) passing part of flow, discharged from isomerisation zone, into stabiliser zone, and withdrawal of stabilised upper flow, containing one or more C5-hydrocarbons, lower flow, which contains 85 wt % of one or more C6+ hydrocarbons, and raw material flow of stripping column, containing 10 wt % of one or more C5+ hydrocarbons; C) passing raw material flow of stripping column into stripping zone and separation of raw material flow of stripping zone into upper flow of stripping column, containing 5 wt % of one or more C4-hydrocarbons, and lower flow of stripping column, containing 90 wt % of one or more C5+ hydrocarbons; and (D) supply of part of lower flow of stripping column into zone of isopentane withdrawal, which contains column for isopentane withdrawal, and supply of lower flow from column for isopentane withdrawal into reaction zone of isomeration.
EFFECT: method requires less engineering support.
10 cl, 6 tbl, 2 dwg
SUBSTANCE: invention relates to a method for isomerisation of C5-C6 hydrocarbons with supply of circulating hydrogen, which includes loading hydrogen and feedstock containing C5-C6 hydrocarbons into an isomerisation zone, products of which are fed into a separator, removing a product stream containing C4 or heavier hydrocarbons from below the separator into a fractionation unit consisting of at least one fractionation column, and removing from the top of the separator a gas stream consisting of hydrogen and light hydrocarbons, which is subjected to recirculation using a recirculating compressor for combining with the feedstock, into which an additional amount of hydrogen is fed if necessary. The method includes purification of the circulating hydrogen stream from C5 and C6 hydrocarbons, which are the end products of the isomerisation process, to a value not greater than presence thereof in the feedstock, and also from components which boil at a temperature higher than the boiling point of isopentane. The fractionation unit consists of a stabiliser, a first and a second fractionation column. The present invention also relates to an apparatus for carrying out said method.
EFFECT: use of the present method enables to obtain an isomerisation product having a high octane number.
16 cl, 2 tbl, 6 dwg
SUBSTANCE: invention relates to method of removal of spent regenerating agent from regenerated drying device in system for isomerisation of flow of hydrocarbons, rich in C4 hydrocarbons and/or rich in at least one of C5 and C6 hydrocarbons. Claimed method includes: a) application of at least one valve and at least one of regulating valve and restricting hole for extrusion of spent regenerating agent from newly regenerated drying device in form of ascending flow to low-pressure device until pressure in newly regenerated drying device reaches value from 14 kPag to 69 kPag (2-10 pounds per sq. inch), with spent regenerating agent being selected from the group, consisting of isomerised C4 hydrocarbon product, isomerised C5-C6 hydrocarbon product, and gas; b) extrusion of spent regenerating agent from at least part of cross-over pipeline, located between said newly regenerated drying device and second drying device, with application of at least one valve and at least one of said regulating valve and said restricting hole; and c) functioning of both said newly regenerated drying device and said second drying device in successive mode for a time interval. Invention also relates to device.
EFFECT: application of claimed invention makes it possible to reduce degree of impact produced by gas drying device on reservoirs located downstream of flow.
10 cl, 1 ex, 4 dwg
SUBSTANCE: method includes: A) bringing flow of raw material in reaction zone of isomerisation with catalyst of isomerisation under conditions of isomerisation, in order to obtain flow, which flows out of isomerisation zone, B) into zone of stabiliser and extraction of stabilised upper flow, which contains one or more C5- hydrocarbons, lower flow, which contains at least 85 wt % of one or more C6+ hydrocarbons, and side fraction, which contains at least 85 wt % of one or more C5+ hydrocarbons. Then C) passing at least part of side fraction in evaporating zone; and D) supply of lower flow of evaporating column, which contains at least 90 wt % of one or more C5+ hydrocarbons, into zone of separating C5 and passing of flow from zone of separation of hydrocarbons C5 in reaction zone of isomerisation.
EFFECT: method demands lower engineering provision for recirculation of C5 stream.
10 cl, 5 tbl, 1 dwg
SUBSTANCE: method includes chemical conversion of isoprene in a bioisoprene composition to non-isoprene compounds by: (a) heating the bioisoprene composition or subjecting said composition to catalytic conditions suitable for isoprene dimerisation to produce an isoprene dimer and then catalytically hydrogenating the isoprene dimer to form a saturated C10 fuel component; or (b) (i) partially hydrogenating the bioisoprene composition to produce an isoamylene, (ii) dimerising the isoamylene with a mono-olefin selected from a group consisting of isoamylene, propylene and isobutene to form a double compound and (iii) completely hydrogenating the double compound to produce a fuel component. The bioisoprene composition is produced by a genetically engineered cell culture, suitable microorganisms, plant or animals. The invention also relates to a system for producing fuel and a fuel composition.
EFFECT: fuel contains fewer impurities inherent to fuel obtained using petro-isoprene.
28 cl, 21 tbl, 32 ex, 173 dwg
SUBSTANCE: invention relates to a method of producing base oil which involves bringing C10+ hydrocarbon material into contact with a catalyst and hydrogen in isomerisation conditions to obtain base oil. The catalyst contains a molecular sieve, having the topology of a MTT structure and crystallite diameter from 200 to 400 Å in the longest direction, at least one metal selected from a group consisting of Ca, Cr, Mg, La, Na, Pr, Sr, K and Nd, and at least one group VIII metal. The invention also relates to versions of a method for deparaffination of hydrocarbon material, using a similar catalyst.
EFFECT: use of the present invention enables to obtain a product with improved viscosity index at lower flow temperatures.
30 cl, 6 ex, 3 tbl, 11 dwg
SUBSTANCE: invention relates to method of realisation of Fischer-Tropsch synthesis on conversion of H2 and CO-containing reaction mixture into product, containing at least one aliphatic hydrocarbon, which has at least 5 carbon atoms. Method includes first running reaction mixture through micro-channel reactor, which contain contacting Fischer-Tropsch catalyst, which contains Co, applied on carrier, in amount at least 25 wt %. After that, heat transfer from working micro-channels to heat exchanger is carried out, after which obtained product is discharged from micro-channel reactor with ensuring volume rate of flow of reaction mixture and product through working micro-channels at least 1000 h-1 and as a result obtained are at least 0.5 grams of aliphatic hydrocarbon, having at least 5 carbon atoms, per gram of catalyst per hour, with methane selectivity in product lower than approximately 25%.
EFFECT: application of claimed method will make it possible to obtain high levels of CO conversion and high levels of desired product selectivity.
79 cl, 4 ex, 18 dwg
SUBSTANCE: invention relates to a method of processing hydrocarbon compounds containing at least one nitrile (nitrogen-containing) functional group. The method is characterised by that it involves processing said compounds at a hydrodenitrogenation step by reaction with hydrogen at absolute hydrogen pressure ranging from 0.1 to 10 MPa, at temperature ranging from 200°C to 500°C and in the presence of a hydrodenitrogenation catalyst, wherein nitrile compounds are selected from a group comprising methylglutaronitrile, ethylsuccinonitrile, 2-pentenenitrile, 2-methyl-2-butenenitrile or mixtures thereof, as well as ortho-TDA isomers.
EFFECT: use of the present method enables to remove nitrogen from hydrocarbon-containing wastes.
9 cl, 6 ex, 5 tbl
SUBSTANCE: present invention relates to a method of separating at least one straight C4-C20 hydrocarbon from a fluid mixture containing said straight hydrocarbon and at least one branched isomer thereof. The method involves a step of bringing the fluid mixture into contact with an adsorbent which contains a porous organometallic skeletal material containing at least one at least bidentate organic compound, having a coordination bond with at least one metal ion for adsorption of the straight hydrocarbon, where the at least one at least bidentate organic compound is a monocyclic, bicyclic or polycyclic ring system and is unsubstituted or has one or more substitutes, independently selected from a group consisting of a halogen atom, C1-6-alkyl, phenyl, NH2, NH(C1-6-alkyl), N(C1-6-alkyl)2, OH, O-phenyl and OC1-6-alkyl, where the substitutes C1-6-alkyl and phenyl are unsubstituted or have one or more substitutes, independently selected from a group consisting of a halogen atom, NH2, NH(C1-6-alkyl), N(C1-6-alkyl)2, OH, O-phenyl and OC1-6-alkyl, wherein the ring system of the at least one at least bidentate organic compound is a substituted imidazole, and where said at least one metal ion is an ion of a metal selected from a group consisting of Zn, Cu, Co, Ni, Fe and Mn. The invention also relates to use of said porous organometallic skeletal material in the method of separating straight hydrocarbons from branched isomers thereof.
EFFECT: present invention provides an alternative, easily to make absorbent.
9 cl, 4 ex, 3 dwg
SUBSTANCE: invention relates to the method for selective production of hydrocarbons suitable for use as diesel fuel, consisting in decarbonylation / decarboxylation of a mixture of carbonic acids C8-C24 (saturated and non-saturated) in a dissolvent in hydrogen atmosphere in presence of a heterogeneous catalyst representing palladium on aluminium oxide at the temperature of 200-400°C and pressure of 0.1-5 MPa. The method is characterised by the fact that a granulated catalyst is used, in which palladium is distributed in the surface layer of the carried with penetration depth of 0.1-0.6 mm and palladium content in the catalyst making 0.25-5 wt %.
EFFECT: invention provides an efficient industrial method for selective production of hydrocarbons from renewable sources using highly efficient catalysts of fatty acids deoxygenation to saturated hydrocarbons suitable for use as components of diesel fuel.
2 cl, 8 ex, 1 tbl
SUBSTANCE: invention relates to a method of producing aromatic compounds from a hydrocarbon feed stream. The method includes steps of: directing the hydrocarbon feed stream into a separation apparatus to obtain a light process stream having low concentration of endothermic hydrocarbon components, and a heavy process stream having a higher concentration of endothermic components; directing the light process stream into a first reforming apparatus, having a first operating temperature higher than 540°C, to obtain an output stream from the first reforming apparatus; directing the heavy process stream into a second reforming apparatus, having a second operating temperature lower than 540°C, to obtain an output stream from the second reforming apparatus; and directing the output stream from the first reforming apparatus and the output stream from the second reforming apparatus into an apparatus for separating aromatic hydrocarbons to obtain a stream of the purified product - aromatic hydrocarbons and an aromatic hydrocarbon-impoverished raffinate stream; wherein the first reforming apparatus and the second reforming apparatus contain the same catalyst.
EFFECT: use of the present method increases output of aromatic hydrocarbons.
8 cl, 5 dwg, 2 tbl