Process of producing hydrocarbons from carbon oxides and hydrogen

FIELD: alternate fuel production and catalysts.

SUBSTANCE: synthesis gas containing H2, CO, and CO2 is brought into contact, in first reaction zone, with bifunctional catalyst consisting of (i) metal oxide component containing 65-70% ZnO, 29-34%, Cr2O3, and up to 1% W2O5 and (ii) acid component comprised of zeolite ZSM-5 or ZSM-11, beta-type zeolite or crystalline silica-alumino-phosphate having structure SAPO-5 at silica-to-alumina molar ratio no higher than 200, whereas, in second reaction zone, multifunctional acid catalyst is used containing zeolite ZSM-5 or ZSM-11 and having silica-to-alumina molar ratio no higher than 200.

EFFECT: increased selectivity with regard to C5+-hydrocarbons and increased yield of C5+-hydrocarbons based on synthesis gas supplied.

7 cl, 2 tbl, 15 ex

 

The invention relates to organic chemistry, namely, a process for the production of hydrocarbons and, in particular, to obtain5+hydrocarbons by catalytic conversion of a mixture WITH N2and CO2(hereinafter referred to as synthesis gas). The resulting liquid hydrocarbon fraction can be used as motor fuels with a low content of benzene.

A method of obtaining5+hydrocarbons from the gas containing H2and, by contacting the gas at a temperature of 220-400°C, a pressure of 10-100 ATM, space velocity initial synthesis gas 100-5000 h-1and a molar ratio of N2/WITH equal 1-3, with a catalyst containing a mixture of iron catalyst for Fischer-Tropsch synthesis in oxidized or reduced form, promoted by oxides of aluminum, silicon, alkaline or alkaline-earth metals, and acid component (patent No. 2204546 RF, CL C 07 C 1/04, 2003 [1]). According to this method, the produced liquid hydrocarbon mixtures have high content of ISO-paraffins and olefins, and a moderate (no more than 35% wt.) the content of aromatic hydrocarbons.

There is also known a method of one-step conversion of synthesis gas having a molar ratio of H2/CO>1,9 in hydrocarbons boiling in the range of gasoline and diesel fractions, mixed trifunctional is utilizatori, consisting of a catalyst for Fischer-Tropsch synthesis (iron promoted with oxides of aluminium, silicon, alkaline and alkaline-earth metal or cobalt), catalyst for conversion of methanol to hydrocarbons (zeolite ZSM-5 or silicalite with the content of SiO2>99%) and the methanol synthesis catalyst (based on the oxides of copper and zinc) (patent No. 5344849 U.S. CL C 07 C 1/04, 1994 [2]). The use of this catalyst are given in [2] conditions (pressure 7-70 MPa, temperature of 200-400° (C) allows from synthesis gas having a molar ratio of N2/≫1,9, to obtain a hydrocarbon mixture boiling in the range of gasoline and diesel fractions consisting mainly of paraffinic and olefinic hydrocarbons and containing aromatic hydrocarbons within 9-20 wt.%.

Major General shortcomings of the methods [1] and [2] are high olefin content (up to 16 wt.%. [2] and more [1]) and n-paraffins (18-24% wt. [2] and more [1])5+hydrocarbons with a relatively low content of aromatic hydrocarbons (up to 20% wt. [2] and not more than 35 wt.%. [1]). In both methods the target products are low-octane gasoline (up to 90% wt. in C5+with PTS 66-77 THEM [2] and up to 80-82 THEM [1] and diesel fraction hydrocarbons (10% wt. [2] and higher [1]), which after additional stage hydrogenation of olefins can be used the Ana as vysokotsenovoj diesel fuel.

A method of obtaining hydrocarbon gasoline fractions from the gas containing H2and CO2or H2, CO2and, by contacting the gas at a temperature of 320-440°C, a pressure of 40-100 ATM and the volume ratio of N2/(CO+CO2), is 1-3 with a catalyst containing zeolite ZSM-5 or ZSM-11 and metal oxide component comprising the oxides of zinc, copper and/or chromium (patent No. 2089533 RF, CL C 07 C 1/12, 10 G 2/00, 1997 [3]). According to this method, the target products of the transformation mixture of N2, CO2(and in some examples are liquid gasoline fraction hydrocarbons with high (40 to 84 wt.%) the content of aromatic hydrocarbons. The main disadvantages of the method [3] are low outputs (40-120 g/nm3synthesis gas) and the performance of the process on gasoline fraction (20-125 g/l cat-RA/h), as well as additional consumption of expensive hydrogen recovery CO2up WITH.

Closest to the invention is a method for hydrocarbon gasoline fractions from synthesis gas containing H2, CO and CO2and having the volume ratio of N2/(CO+CO2), is equal to 1-3, by contacting the gas at a temperature of 320-440°C, a pressure of 40 to 100 atmospheres with a catalyst containing zeolite ZSM-5 and the metal oxide component (patent No. 2175960 RF, CL C 07 C 1/04, 2001, [4]). In this way use is circulatio gas stream after reactor volume ratio of the number of circulating gas to the raw synthesis gas, 0.1-1000, and the process is carried out at a volumetric feed rate of the original synthesis gas 200-5000 h-1, volume relations in the original syngas CO/CO2more than 4 and N2/CO211. According to this method, the liquid products of the conversion of synthesis gas are gasoline fraction (5-C10hydrocarbons) and water containing methanol from 1 to 10% wt.

In this way [4] there are disadvantages:

1) relatively low content of aromatic hydrocarbons in the C5+hydrocarbons not exceeding 30 wt.%, that makes it difficult to obtain commercial gasoline with more than 90 04;

2) high residual methanol content in water from 1 to 10% wt.

In the present invention in comparison with the closest analogue [4] the observed increase in selectivity for aromatic hydrocarbons (up to 45-50% wt. and more) and the reduction of methanol in water to a concentration of less than 1% wt.

Closest to the proposed by its technical essence is a method of producing motor fuels by catalytic conversion of a mixture of N2and WITH or mixture of CO, and CO2at elevated temperatures and pressure in two stages (patent No. 2143417 RF, CL C 07 C 1/04, 1999 [5]). According to the selected prototype in the first stage, the feedstock is in contact with a catalyst comprising zeolite ZSM-5 and metal oxide component containing (the AC.%) CuO - 38-64, ZnO - 24-34, Cr2O3- 0-22, Al2About3- 6-9, mixed in a mass ratio of 20-50/80-50, the gas flow after the first stage reactor without separation is directed to the second stage, where upon contact with a catalyst comprising zeolite ZSM-5 and metal oxide component containing (wt.%) ZnO - 65-70, Cr2O3- 29-34, W2O3- 1, mixed in a ratio of 30-99/70-1, is the conversion of dimethyl ether and components of synthesis gas into gasoline fraction, gaseous hydrocarbons and water fraction.

The main disadvantage of the presented prototype is a low selectivity for C5+hydrocarbons (63-74% wt.) and low output With5+hydrocarbons filed on synthesis gas (114-137 g/nm3).

The present invention is to increase the selectivity With5+hydrocarbons and an increase in the output of C5+hydrocarbons filed on synthesis gas.

The problem is solved in that in a method of producing hydrocarbon gasoline fractions from synthesis gas containing From co and CO2through the consistent shielding gas in at least two reaction zones at elevated temperatures and pressures with a bifunctional catalyst in the first reaction zone consisting of acid and metal oxide components, use a metal oxide component, aderrasi metal oxide composition, wt.%: ZnO - 65-70, Cr2About3- 29-34, W2O5- no more than 1 and as the acid component of the bifunctional zeolite catalyst is used with the structure of ZSM-5 or ZSM-11, zeolite type beta or crystalline silicoaluminate with the structure of SAPO-5, and the second reaction zone use monofunctional acidic catalyst containing a zeolite with structure of ZSM-5 or ZSM-11.

The problem is solved also by the fact that the acid component of the bifunctional catalyst has a molar ratio of SiO2/Al2O3not more than 200.

The problem is solved also by the fact that the zeolite monofunctional acid catalyst has a molar ratio of SiO2/Al2O3not more than 200.

The task is solved in that the contacting of the gas in the first reaction zone is carried out at a pressure of 40-100 MPa and a temperature of 340-420°C.

The task is solved in that the contacting of the gas in the second reaction zone is conducted at a pressure of 40-100 MPa and a temperature of 320-460°C.

The problem is solved also by the fact that the process is carried out at a volumetric feed rate of the original synthesis gas 200-5000 h-1and volume relationships in the original synthesis gas H2/(CO+CO2)=1-3, WITH/CO2>2 and H2/CO2>6.

The problem is solved also by the fact that the process is carried out at the circulation gas flow to volume ratio of the number of cirkuliruyusiy gas to the raw synthesis gas, equal 1-1000.

Distinctive features of the invention are:

1) in the first reaction zone using metal oxide component of a bifunctional catalyst containing, wt.%: ZnO - 65-70, Cr2O3- 29-34, W2O5- not more than 1;

2) as the acid component of the bifunctional zeolite catalyst is used with the structure of ZSM-5 or ZSM-11, zeolite type beta or crystalline silicoaluminate with the structure of SAPO-5 having a molar ratio of SiO2/Al2O3not more than 200;

3) in the second reaction zone is used monofunctional acidic catalyst containing a zeolite with structure of ZSM-5 or ZSM-11 having a molar ratio of SiO2/Al2O3not more than 200;

4) contacting the gas in the first reaction zone is carried out at a pressure of 40-100 MPa and a temperature of 340-420°C;

5) contacting the gas in the second reaction zone is conducted at a pressure of 40-100 MPa and a temperature of 320-460°C;

6) the process is carried out at a volumetric feed rate of the original synthesis gas 200-5000 h-1dimensional relationship of H2/(CO+CO2), is equal to 1-3, WITH/CO2>2 and H2/CO2>6;

7) the process is carried out at the circulation gas flow to volume ratio of the number of circulating gas to the raw synthesis gas, equal 1-1000.

The choice of catalyst for the conversion of synthesis gas in coal is hydrogen products based on in the temperature range 340-420°With the combination of metal oxide catalyst for methanol synthesis and acid component allows you to take thermodynamic limit of the reaction of methanol synthesis by reaction of formation of aromatic hydrocarbons and ISO-paraffins. Therefore, in the present invention to obtain a gasoline fraction hydrocarbons used bifunctional catalysts which included oxides of Zn, Cr and W, converting the synthesis gas to methanol at temperatures 340-420°and as the acid component of the bifunctional catalysts applied vysokoglinozemistyj zeolites with structure of ZSM-5 or ZSM-11, zeolite type beta or crystalline silicoaluminate with the structure of SAPO-5.

In the long run there is a gradual sakakawea acid component of a bifunctional catalyst, followed by reduction of selectivity for aromatic hydrocarbons and increasing content of methanol in the reaction products. Reducing aromatics in the gasoline fraction hydrocarbons below a certain minimum limit may lead to the deterioration of the anti-knock properties of commercial gasoline. The increase in the concentration of methanol in the reaction products creates additional problems for his removal from the formed during the synthesis of water, and also leads to uvelicheniya original synthesis gas. In the present invention to stabilize the process indicators used for shielding gas in the second reaction zone monofunctional acid catalyst, to prevent "leakage" of methanol and save selectivity for aromatic hydrocarbons at a level sufficient to maintain a high octane number of the resulting gasoline.

The choice of conditions for the synthesis of gasoline from a gas containing H2, CO and CO2due to the following factors. High blood pressure is necessary for deeper conversion of synthesis gas. Lower limit of temperature range of operation of a bifunctional catalyst (340° (C) determined by the minimum activity of the catalyst, the excess of the upper temperature limit (420° (C) reduces the service life of metal oxide component of the bifunctional catalyst. The contacting of the gas with monofunctional acidic catalyst in the second reaction zone, depending on the value of the "breakthrough of methanol, and duration of acid catalyst is carried out at a temperature of from 320 to 460°C. the Volumetric feed rate of the original synthesis gas is determined by the activity used bifunctional catalyst at a fixed pressure and temperature. The ratio between H2and FROM,and between CO and CO 2is determined by the stoichiometry of chemical reactions synthesis of hydrocarbons. Based on theoretical assumptions experiments were conducted under conditions sufficiently close to the stoichiometric ratio between "C", "O" and "H" and therefore favorable for the synthesis of methanol and its conversion into hydrocarbons With5-C10. We have shown previously [3]that at high concentrations of CO2in the synthesis gas (above 10% vol.) decreases the yield of gasoline fraction hydrocarbons and performance of a bifunctional catalyst. Therefore, the proposed method was introduced lower limits of CO2in the synthesis gas in a volumetric relations/CO2>2 and H2/CO2>6.

An important role in achieving high selectivity and productivity of the process With5+hydrocarbons belongs circulation of the gas stream after separation of liquid products. First, the continuous removal of water and liquid hydrocarbons from the gas contacting largely suppresses the reaction of the formation of low carbon dioxide and decreases the rate of reactions of cracking C5+of hydrocarbons. Secondly, the high linear velocity of the circulating gas stream in combination with a constant entrainment of excess heat from the area of catalysis positively affect the temperature distribution in R is the actor, improve the processes of heat transfer and mass transfer. The circulation gas flow to volume ratio of the number of circulating gas to the raw synthesis gas (a ratio of circulation) may be equal to from 1 to 1000, but it is better to have the value of the ratio of circulation within 5-400.

Example 1 (the prototype). The synthesis gas composition (vol.%): H2- 68, 29, and CO2- 3 arrives at the installation with a bulk velocity of 2300 h-1(based on the total volume of catalysts 1 and stage 2), is mixed with the circulating gas before entry into the reactor for the synthesis of dimethyl ether (DME), and the resulting gas mixture in contact with a catalyst comprising zeolite ZSM-5 and metal oxide component containing (wt.%) CuO - 62, ZnO - 30, Al2O3- 8, mixed in a mass ratio of 35/65, at a temperature of 300°and a pressure of 80 ATM. In the reactor oxides of carbon and hydrogen are converted into DME with selectivity greater than 90%. The gas flow after synthesis reactor DME without distinguishing the products are sent to the second stage, where upon contact with a catalyst comprising zeolite ZSM-5 and metal oxide component containing (wt.%) ZnO - 67, Cr2O3- 32, W2O5- 1, mixed in a mass ratio of 30/70, at a temperature of 400°and a pressure of 80 bar is the conversion of dimethyl ether, carbon oxides and hydrogen in gasoline fra is tion, gaseous hydrocarbons and water fraction (more than 98 wt.% H2O). Conversion of DME more than 99%; the total transformation of the components of synthesis gas ("input - output" of the installation) is not less than 90%. The gas stream after the second stage reactor is cooled and separated in the separator liquid products are condensed hydrocarbons, water and methanol from the gas phase. Liquid products are consistently separated into a gasoline fraction, methanol water and hydrocarbons With3-C4. To prevent accumulation of light hydrocarbons part of the gas stream after the separator is continuously withdrawn from circulation circuit, and the main gas stream is mixed with the synthesis gas and supplied to the synthesis reactor DME. Conditions and the main results of experience are shown in table 1.

Industrial applicability of the invention is illustrated by examples 2-15.

Example 2. The synthesis gas is fed to the installation with a bulk velocity 820 h-1(based on the total volume of catalysts), is mixed with the circulating gas before entry into the reactor for the synthesis of hydrocarbons and the resulting gas mixture is in contact in the 1st reaction zone with a bifunctional catalyst comprising zeolite ZSM-5 and metal oxide component at a temperature of 400°and a pressure of 80 ATM. The gas stream after contact with bifunctional katal the congestion without releasing products direct to the 2nd reaction zone, where in contact with monofunctional catalyst containing zeolite ZSM-5 at a temperature of 400°and a pressure of 80 bar is an additional conversion of hydrocarbons, methanol and dimethyl ether with the formation of high-octane gasoline (5+)1-C4hydrocarbons and water. The gas stream after contact is cooled and separated in the separator liquid products from gas phase. Liquid products are consistently separated into a gasoline fraction, methanol water and dissolved them in CO2and hydrocarbons With3-C4. To prevent accumulation of methane and light hydrocarbons part of the gas stream after the separator is continuously withdrawn from circulation circuit, and the main gas stream is mixed with the original synthesis gas and is fed into the reactor for the synthesis of hydrocarbons. Volume ratio of the components in the original syngas conditions and the main results of experience are shown in table 1. Molar relationship SiO2/Al2About3in the acid component of the bifunctional catalyst and zeolite monofunctional catalyst are presented in table 2.

Examples 3-10. Analogous to example 2. Volume ratio of the components in the original syngas conditions and the main results of the experiments are shown in table 1.

Example 11. Analogous to example 2. Different those who, as a bifunctional catalyst using a composition consisting of zeolite ZSM-11 and metal oxide component. Volume ratio of the components in the original syngas conditions and the main results of experience are shown in table 1.

Example 12. Analogous to example 2. Characterized in that, as the monofunctional catalyst is used, the zeolite ZSM-11. Volume ratio of the components in the original syngas conditions and the main results of experience are shown in table 1.

Example 13. Analogous to example 2. Distinguished by the fact that as a bifunctional catalyst using a composition consisting of a-type zeolite beta and a metal oxide component. Volume ratio of the components in the original syngas conditions and the main results of experience are shown in table 1.

Examples 14-15. Analogous to example 2. Distinguished by the fact that as a bifunctional catalyst using a composition consisting of crystalline silicoaluminate with the structure of SAPO-5 and metal oxide component. Volume ratio of the components in the original syngas conditions and the main results of the experiments are shown in table 1.

As seen in the table 1 results, the proposed method allows to obtain C5+the hydrocarbon content of 2-60 wt.%. aromatics and has advantages compared with prototype:

1) selectivity education5+hydrocarbons above the average of 10-11%;

2) exit C5+hydrocarbons in the calculation of the original synthesis gas is 1.1-1.2 times higher.

td align="left"> Content. Benzene in C5+, % wt.
Table 1.

Comparison of parameters and indicators of the processes of transformation of synthesis gas for the prototype and the claimed method
Conditions of experience and key indicators12345
the placeholderthe inventive method
Cat-R 1-th reaction zoneCu-Zn-(Cr)-Al+ZSM-5Zn-Cr+ZSM-5Zn-Cr+ZSM-5Zn-Cr+ZSM-5Zn-Cr+ZSM-5
Cat-R in the 2nd reaction zoneZn-Cr+ZSM-5ZSM-5ZSM-5ZSM-5ZSM-5
The multiplicity circulation1001208060
Pressure, ATM8080808080
The temperature in the 1st reaction zone, °300400380380 400
The temperature in the 2nd reaction zone, °400400380400420
About. speed Ref. synthesis gas (per Σ cat.), h-12300820440740650
H2/(CO+CO2)2,11,82,02,12,1
H2/CO222,759,195,4225,78,6
CO/CO2the 9.730,846,4106,73,1
Conversion, % wt.94 (CO+CO2)92>999590
Conversion of CO2, % wt.---83
Select the terrain along With5+, % wt.73,981,482,180,579,6
Exit C5+submitted SG, g/nm3137160165155139
The content of AU in C5+, % wt.59,151,341,546,7
0,20,30,30,3
The content of CH2HE+DME in water, % wt.less than 2tracestracestracestraces

Content. CH2HE+DME in water, % wt.
Table 1. (continued)
Conditions of experience and key indicatorsEXAMPLES
678910
Cat-R 1-th reaction zoneZn-Cr+ZSM-5Zn-Cr+ZSM-5Zn-Cr+ZSM-5Zn-Cr+ZSM-5Zn-Cr+ZSM-5
Cat-R in the 2nd reaction zoneZSM-5ZSM-5ZSM-5ZSM-5ZSM-5
The multiplicity circulation150150150150300
Pressure, ATM10080606080
The temperature in the 1st reaction zone,°420400360420400
The temperature in the 2nd reaction zone,°42042038 440420
About. speed Ref. synthesis gas (per Σ cat.), h-123001600570780790
H2/(CO+CO2)1,91,91,91,92,2
H2/CO2,66066066066010,5
CO/CO23393393393393,7
Conversion, % wt.9695879090
Conversion of CO2, % wt.----81
Select the terrain on C5+, % wt.82,381,880,178,5of 83.4
Exit C5+submitted SG, g/nm3166147130134132
The content of AU in C5+, % wt.of 45.747,134,255,143,6
Content. benzene in C5+, % wt.0,40,30,20,50,4
tracestracestracestracestraces

Table 1. (continued)
Conditions of experience and key indicatorsEXAMPLES
1112131415
Cat-R 1-th reaction zoneZn-Cr+ZSM-11Zn-Cr+ZSM-5Zn-Cr+BetaZn-Cr+SAPO-5Zn-Cr+SAPO-5
Cat-R in the 2nd reaction zoneZSM-5ZSM-11ZSM-5ZSM-5ZSM-5
The multiplicity circulation150150400400400
Pressure, ATM4060808080
The temperature in the 1st reaction zone, °360340400420400
The temperature in the 2nd reaction zone, °:360340420460440
About. speed Ref. synthesis gas (per Σ cat.), h-1 930870120020001500
H2/(CO+CO2)1,91,92.02.02.0
H2/CO2660660>1000>1000>1000
CO/CO2339339>500>500>500
Conversion, % wt.8989848680
Conversion of CO2, % wt.-----
Select the terrain along With5+, % wt.70,370,968.775.371.9
Exit C5+submitted SG, g/nm312012297130126
The content of AU in C5+, % wt.20,618,226.545.644.2
Content. benzene in C5+, % wt.0,10,10.10.80.7
The content of CH2HE+DME in water, % wt.tracestracesMark the less than 1less than 1

Table 2.

Molar relationship SiO2/Al2O3used zeolites and crystalline silicoaluminate
The acid componentThe molar ratio of SiO2/Al2O3
examples 2-5examples 6-10example 11example 12Example 13examples 14-15
bifunctional catalyst7027522775<1
monofunctional catalyst707070527070

1. The method of obtaining hydrocarbon gasoline fractions from synthesis gas containing H2, Co and CO2through the consistent shielding gas in at least two reaction zones at elevated temperatures and pressures with a bifunctional catalyst in the first reaction zone consisting of acid and metal oxide components, characterized in that the metal oxide component of the bifunctional catalyst contains a metal oxide composition, wt.%: ZnO - 65-70; Cr2O 3- 29-34; W2O5- no more than 1, and as the acid component of the bifunctional zeolite catalyst is used with the structure of ZSM-5 or ZSM-11, zeolite type beta or crystalline silicoaluminate with the structure of SAPO-5, and the second reaction zone use monofunctional acidic catalyst containing a zeolite with structure of ZSM-5 or ZSM-11.

2. The method according to claim 1, characterized in that the acid component of the bifunctional catalyst has a molar ratio of SiO2/Al2O3not more than 200.

3. The method according to claim 1, characterized in that the zeolite monofunctional acid catalyst has a molar ratio of SiO2/Al2O3not more than 200.

4. The method according to claim 1, characterized in that the contacting of the gas in the first reaction zone is carried out at a pressure of 40-100 MPa and a temperature of 340-420°C.

5. The method according to claim 1, characterized in that the contacting of the gas in the second reaction zone is conducted at a pressure of 40-100 MPa and a temperature of 320-460°C.

6. The method according to claim 1, characterized in that the process is carried out at a volumetric feed rate of the original synthesis gas 200-5000 h-1and volume relationships in the original synthesis gas H2/(CO+CO2)=1-3, WITH/CO2>2 and H2/CO2>6.

7. The method according to claim 1, characterized in that the process is carried out at the circulation gas flow to volume ratio of Koli is esta circulating gas to the raw synthesis gas, equal 1-1000.



 

Same patents:

FIELD: engineering of Fischer-Tropsch catalysts, technology for producing these and method for producing hydrocarbons using said catalyst.

SUBSTANCE: catalyst includes cobalt in amount ranging from 5 to 20 percents of mass of whole catalyst on argil substrate. Aforementioned substrate has specific surface area ranging from 5 to 50 m2/g. Catalyst is produced by thermal processing of argil particles at temperature ranging from 700 to 1300°C during period of time from 1 to 15 hours and by saturating thermally processed particles with cobalt. Method for producing hydrocarbon is realized accordingly to Fischer-Tropsch method in presence of proposed catalyst.

EFFECT: possible achievement of high selectivity relatively to C5+ at low values of diffusion resistance inside particles.

3 cl, 9 ex, 9 dwg

FIELD: organic chemistry.

SUBSTANCE: claimed method includes a) reaction of carbon monoxide and hydrogen in presence of effective amount of Fischer-Tropsch catalyst; b) separation of at least one hydrocarbon cut containing 95 % of C15+-hydrocarbons from obtained hydrocarbon mixture; c) contacting separated cut with hydrogen in presence of effective amount of hydration catalyst under hydration conditions; d) treatment of hydrated hydrocarbon cut by medium thermal cracking; and e) separation of mixture, including linear C5+-olefins from obtained cracking-product. Method for production of linear alcohols by oxidative synthesis of abovementioned olefins also is disclosed.

EFFECT: improved method for production of linear olefins.

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FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to methods for preparing catalyst precursors and group VIII metal-based catalysts on carrier, and to a process of producing hydrocarbons from synthesis gas using catalyst of invention. Preparation of precursor of group VIII metal-based catalyst comprises: (i) imposing mechanical energy to mixture containing refractory oxide, combining catalyst precursor with water to form paste comprising at least 60 wt % of solids, wherein ratio of size of particles present in system in the end of stage (i) to that in the beginning of stage (i) ranges from 0.02 to 0.5; (ii) mixing above prepared paste with water to form suspension containing no more than 55% solids; (iii) formation and drying of suspension from stage (ii); and (iv) calcination. Described are also method of preparing group VIII metal-based catalyst using catalyst precursor involving reduction reaction and process for production of hydrocarbons by bringing carbon monoxide into contact with hydrogen are elevated temperature and pressure in presence of above-prepared catalyst.

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12 cl, 1 tbl, 3 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to synthesis of C5-C100-hydrocarbons from CO and H2, which catalyst contains carrier based on alumina prepared from gibbsite-structure aluminum hydroxide and cobalt in concentration of 15 to 50%. Carrier is prepared by mixing dry cobalt compound with dry gibbsite-structure aluminum hydroxide at cobalt-to aluminum molar ratio between 1:1 and 1:30, followed by calcination, impregnation (in two or more steps) with aqueous cobalt salt solution, and heat treatment. Invention also discloses process of producing C5-C100-hydrocarbons using above catalyst.

EFFECT: increased selectivity of catalyst regarding production of high-molecular hydrocarbons at reduced yield of methane.

7 cl, 1 tbl, 10 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention provides Fischer-Tropsch catalyst, which consists essentially of cobalt oxide deposited on inert carrier essentially composed of alumina, said cobalt oxide being consisted essentially of crystals with average particle size between 20 and 80 Å. Catalyst preparation procedure comprises following stages: (i) preparing alumina-supported intermediate compound having general formula I: [Co2+1-xAl+3x(OH)2]x+[An-x/n]·mH2O (I), wherein x ranges from 0.2 to 0.4, preferably from 0.25 to 0.35; A represents anion; x/n number of anions required to neutralize positive charge; and m ranges from 0 to 6 and preferably is equal to 4; (ii) calcining intermediate compound I to form crystalline cobalt oxide. Invention also described a Fischer-Tropsch process for production of paraffin hydrocarbons in presence of above-defined catalyst.

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16 cl, 12 tbl, 2 ex

FIELD: petroleum chemistry, chemical technology.

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2 cl, 6 dwg, 2 ex

FIELD: petrochemical process catalysts.

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10 cl, 1 tbl, 3 ex

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8 cl, 2 tbl, 19 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: in order to increase CO-into-hydrocarbons conversion, invention provides alumina-supported catalyst containing 10-20% active Co component (calculated as CoO), 0.1-1.0% promoter F, and 0.3-1.0% platinum group metal or first transition series metal promoters or mixtures thereof.

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2 tbl, 8 ex

FIELD: petroleum chemistry, organic chemistry, chemical technology.

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7 cl, 1 tbl, 2 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation catalyst containing oxides selected from oxides of aluminum, silicon, phosphorus, nickel, cobalt, molybdenum, and tungsten involves mixing starting components, namely oxide sources, molding, drying, and calcination, or mixing a part of these components and then adding components selected from molybdenum tungsten, nickel, and cobalt oxides, after which an organic compound selected from organic bases or alcohol is added to mixture, which is allowed to stand for 20-35 h at 85-100°C. Further, resulting solid phase is mixed with pseudoboehmite pretreated with nitric acid to form hydrocarbon conversion catalyst that can also be used as catalyst carrier in the same process.

EFFECT: ensured high hydrocarbon conversion at low hydrogen pressure.

5 cl, 2 dwg, 4 tbl, 3 ex

The invention relates to the production of catalysts for selective reduction of NOx

The invention relates to chemistry

FIELD: petrochemical process catalysts.

SUBSTANCE: non-oxidative conversion of methane becomes more efficient owing to increased yield of desired product obtained on Mo-containing zeolite catalyst prepared by modifying zeolite with molybdenum in solid phase. In particular, molybdenum in the form of nano-size powder (obtained according to electric explosion technique in argon atmosphere) is mixed with ZSM-type zeolite and mixture is then calcined resulting in catalyst with molybdenum level 0.5 to 6.0%.

EFFECT: increased catalyst activity in methane-to-aromatic hydrocarbons conversion process.

1 tbl, 7 ex

The invention relates to the refining and petrochemical industries, in particular to methods of producing catalysts for the conversion of aliphatic hydrocarbons2-C12in high-octane gasoline and/or aromatic hydrocarbons

The invention relates to the refining and petrochemical industries, in particular to methods of producing catalysts for the conversion of aliphatic hydrocarbons WITH2-C12in high-octane gasoline and/or aromatic hydrocarbons

The invention relates to the refining and petrochemical industries and is dedicated to the creation of the catalysts used in the processing of aliphatic hydrocarbons in the concentrate of aromatic hydrocarbons or high-octane component of gasoline
The invention relates to the synthesis of the catalysts used, in particular, for the conversion of hydrocarbons into high-level components of motor fuels, aromatic hydrocarbons
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