Method of producing cobalt catalyst

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts. Described are methods of producing a cobalt Fischer-Tropsch synthesis catalyst, which involve preparation of a granular support from starting material - oxides of group III and IV metals, mixing the latter with modifying additives, followed by calcining, saturation with cobalt compounds, followed by calcining and activation of the catalyst in a current of a hydrogen-containing gas during Fischer-Tropsch synthesis.

EFFECT: low power consumption of the Fischer-Tropsch synthesis process.

2 cl, 11 tbl, 18 ex

 

The invention relates to petrochemistry, gas chemistry, coal chemistry and relates to the Fischer-Tropsch synthesis, in particular the preparation technology of the cobalt catalyst for Fischer-Tropsch synthesis.

Known method of preparing a cobalt catalyst for Fischer-Tropsch synthesis based on zeolites, in which the cobalt is introduced a two-step impregnation of soluble compounds of cobalt with successive drying after each stage at temperatures between 200 and 600°C. the Catalyst was activated in a stream of hydrogen at 450°C (U.S. Patent 7,723,252).

The disadvantage of this technology is the high activation temperature of the catalyst, requiring the use of expensive construction materials for the reaction apparatus.

A method of obtaining a catalyst in which the catalyst is exposed to a gas containing carbon monoxide and not more than 30 vol.% hydrogen, at temperatures of 200-350°C and atmospheric pressure (U.S. Patent No. 5,585,316).

The disadvantage of this method is used as the activating agent gas, which is different in composition from the process gases used in the synthesis of hydrocarbons by the method of Fischer-Tropsch process, which requires the creation of separate units of their mixing and separate lines for the supply of these gases to the reactor.

The closest technical solution to this invention javljaetsja obtain a cobalt catalyst for Fischer-Tropsch synthesis, as the carrier which is aluminum oxide or other basic oxides, modified by impregnation of organic compounds of metals of group IVB (zirocnia, hafnium, titanium). The active ingredient in them is made by impregnation of the support with solutions of organic compounds of active metals or mineral salts or CARBONYLS of cobalt, iron or ruthenium. The last stage of preparation of the catalyst to synthesis in this patent indicates its pre-activation in the reactor with a fixed bed in the presence of synthesis gas at a pressure of from 0.7 to 1.4 MPa and a stepwise raising the temperature from 220 to 270°C (U.S. Patent No. 4,681,867).

The disadvantage of this method is the need for a separate stage of activation of the catalyst synthesis gas.

The purpose of this invention is the reduction of energy consumption in the production of synthetic hydrocarbons in the presence of a catalyst due to its activation of synthesis gas or hydrogen containing gas at temperatures not exceeding 250°C.

The technical result that can achieve the goal is to reduce the temperature activation of the cobalt catalyst for Fischer-Tropsch synthesis.

The technical result is achieved in that the granular carrier is prepared by calcination of raw materials at a temperature of from 400 to 800°C for 1 to 20 hours is in, which is then pulverized to a particle size not exceeding 0.5 mm and before granulation is mixed with a modifier of compounds of transition metals of group III of the Periodic table of Mendeleev, and after granulation carrier calcined at a temperature of from 400 to 800°C, while the activation of the catalyst is carried out directly in the process of the Fischer-Tropsch synthesis when heated catalyst, which is carried out in several stages, step by raising the temperature, and at the first stage the temperature is raised at a rate of 0.5-2°C/min up to 180-200°C and maintained at this temperature until reaching a stable performance for the conversion of carbon monoxide and selectivity on liquid hydrocarbons and methane, while the indicators are considered to be stable if the relative difference in their values up to 10 Rel.%, and then the raise the temperature of 8-12°C at the rate of 0.1-2°C/min until a temperature of not more than 250°C. the raw material for the carrier is chosen from the group of aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, cerium oxide, a mixed oxide, amorphous or crystalline aluminosilicates. The modifier is chosen from the group of compounds of transition metals of group III of the Periodic table DI Mendeleev: Al2O3La2O3, Y2O3CeO2and injected into the carrier in an amount of from 1 to 20 wt.%. The number connect the deposits of cobalt, applied to the media, in terms of metallic cobalt is from 10 to 30 wt.% by weight of the finished catalyst. As the hydrogen-containing gas, a mixture of hydrogen and carbon monoxide with a molar ratio of 1.9 to 2.2. The gas pressure in the activation process is 1.5-2.5 MPa, and the volumetric rate of gas during activation support within 500-1500 h-1.

The technical result according to the second variant of the method is achieved in that the granular carrier is prepared by calcination of raw materials at a temperature of from 400 to 800°C for 1 to 20 hours, which is then pulverized to a particle size not exceeding 0.5 mm and before granulation is mixed with a modifier of compounds of transition metals of groups III and IV of the Periodic table DI Mendeleev, and after granulation carrier calcined at a temperature of from 400 to 800°C, while the activation of the catalyst is carried out at the hydrogen content in the gas is not less than 10 vol.% and a temperature of 240-250°C for 16-48 hours in the synthesis reactor Fischer-Tropsch fixed bed catalyst by heating the catalyst by passing a hydrogen-containing gas over the catalyst precursor at atmospheric pressure, the rate of temperature rise to the final value maintained within the range of 0.5 to 2.0 deg/min

The feedstock for the media selected from the group of aluminum, silicon, titanium, zirconium, cerium, either amorphous or crystalline silicates or mixtures thereof.

Modifier selected from the group of compounds of transition metals of groups III and IV of the Periodic table DI Mendeleev: Al2O3La2O3, Y2O3CeO2, ZrO2. The promoter chosen from the group of metals VII and VIII groups of the Periodic table DI Mendeleev: Pt, Pd, Re, Ru.

A number of compounds of cobalt, deposited on the carrier, in terms of metallic cobalt is from 10 to 30 wt.%, when this promoter is introduced into the catalyst in an amount of from 0.1 to 1.5 wt.%, and the volumetric rate of gas during activation support within 500-3000 h-1.

These distinctive features significant.

The preparation of the catalyst according to the described technology allows you to activate it at low temperatures, as well as directly in the process of the Fischer-Tropsch synthesis, which leads to lower capital costs and metal production.

The preparation of the catalyst according to this invention is carried out preliminary preparation of a carrier, followed by the introduction in his composition of the active component. First, the precursor of the primary component carrier, which are predominantly inorganic salts, in particular the nitrates of the metals of groups III and IV of the Periodic TA is Litsa DI Mendeleev, preferably of aluminum, silicon, titanium, zirconium, either amorphous or crystalline silicates or mixtures thereof, calcined at temperatures of 400-800°C for 1-20 hours. Then the calcined material is crushed to a fraction with a particle size up to 0.5 mm Before granulating powdered material mixed with a modifier selected from the group of compounds of transition metals of groups III and IV of the Periodic table DI Mendeleev: Al2O3La2O3, Y2O3CeO2, ZrO2. Powdered media granularit by extrusion into cylindrical pellets. Granules carrier calcined at temperatures of 400-800°C. the Modifier in the calculation of 1-20 wt.% in the calcined carrier is introduced into the composition at the stage of preparation of granules media, or by impregnation of the support with an aqueous solution of precursor modifier, prior to the introduction of the active component, with subsequent calcination of the carrier at temperatures of 400-800°C.

The application of active component is in the amount of 10-30 wt.% the finished catalyst in one or several stages, which usually does not exceed three, by impregnation of the support or catalyst precursor in an aqueous solution of cobalt salts, for example, setevogo of cobalt nitrate, followed by calcination after each stage making active componentry temperatures from 270 to 500°C for 1-4 hours.

The introduction of promoters is carried out by a separate impregnation stage, or joint impregnated with an active component, an oxide promoters preferably in the first impregnation stage, or before the first stage of introduction of the active component. For metal promoters preferably at the last stage of introduction of the active component with joint impregnation, either as a separate stage after the introduction of the active component. In the case of single-stage impregnation of the catalyst or its precursor precursor promoter after its submission annealing is carried out at temperatures of from 270 to 500°C for 1-4 hours.

The activation is carried out at a temperature in the range from 180 to 250°C in the presence of hydrogen or synthesis gas. The catalyst placed in the reactor Fischer-Tropsch synthesis with a fixed layer, is heated in a stream of hydrogen or a mixture of carbon monoxide and hydrogen (synthesis gas) is selected to process the volumetric rate of gas to the initial temperature, typically in the range of 240-250°C to activate pure hydrogen or a mixture of inert gas and 180-200°C to activate the synthesis gas. Then, in the case of use as a gas activation mixture of carbon monoxide and hydrogen, the temperature of the speed rises to a final value of 250°C with a step of 8-12°C. the Rate of temperature increase up to the initial value with which is 0.5 to 2 deg/min, lift speed between the speed of the temperature regime is 0.1-2 deg/min Duration-keeping at the temperature at each step for catalyst-activated synthesis gas, is determined by the stabilization of the values of CO conversion and selectivity for liquid hydrocarbons and methane at a given temperature. The activation procedure when using pure hydrogen or mixtures thereof with inert gas continuously 16-48 hours.

The calculation of the CO conversion is carried out according to the following formula:

KCO=mCOinx-mCOinsxmCOinx100%where

mCOinxmass of carbon monoxide in 1 m3included in the reactor gas

mCOinsxmass of carbon monoxide in 1 m3coming out of the reactor gas.

Determination of selectivity in liquid the hydrocarbons is carried out according to the following formula:

SC5+=mC/C5+mC/COinx-mC/COinsx100%where

mC/C5+is the mass of carbon contained in the liquid hydrocarbons from the synthesis of 1 m3the incoming gas into the reactor;

mC/Attitudeis the mass of carbon contained in the carbon monoxide in 1 m3the incoming gas into the reactor;

mC/Ingis the mass of carbon contained in the carbon monoxide in 1 m3coming out of the reactor gas.

Determination of the selectivity to methane is carried out according to the following formula:

SCH4=mC/CH4mC/COinx-mC/COinsx100%where

mC/CH4- the mass of the carbon in the methane produced in the synthesis of 1 m3included in the reactor gas.

The calculation of the yield of liquid hydrocarbons according to the following formula:

BC5+=mC5+1000Vinx.n.y.where

mC5+- weight liquid hydrocarbons resulting from the Fischer-Tropsch synthesis over time τ;

Vinx.n.y.- volume passing through the layer of catalyst synthesis gas, m3.

The determination of initial and formed substances in the exhaust from the reactor Fischer-Tropsch synthesis gases can be carried out by any known method, for example, by means of gas-liquid chromatography.

The activation process according to the present invention can be performed using one of two options.

Option 1

Freshly prepared catalyst loaded into the reactor Fischer-Tropsch synthesis, served in a reactor a mixture of carbon monoxide and hydrogen with a ratio of 1.9 to 2.2 for volumetric speed 500-3000 h-1and set the operating pressure in the reactor of 1.5-2.5 MPa. Then the catalyst is heated to the initial temperature of the tours in the range of 180-200°C with a heating rate of 0.5-2 deg/min and kept at this temperature until reaching a stable performance for the conversion of carbon monoxide and selectivity for liquid hydrocarbons and methane. The indicators are considered to be stable if the difference in their values up to 10 Rel.%. The temperature was then raised at 8-12°C at the rate of 0.1 to 2 deg/min and so on until a temperature of not more than 250°C.

Option 2

Freshly prepared catalyst is crushed to a fraction of 0.1-0.2 mm, is loaded into the reactor Fischer-Tropsch synthesis, served in a reactor a mixture of hydrogen and inert gas (argon, nitrogen or helium) with a hydrogen content of not less than 10 vol.% or pure hydrogen at a flow rate 1000-3000 h-1and a pressure of from 0.05 to 2.0 MPa. Then the catalyst is heated to an initial temperature in the range of 240-250°C with a heating rate of 0.5-2 deg/min and maintain the catalyst under these conditions within 16-48 hours.

After activation, the reactor is cooled in a stream of hydrogen or hydrogen-containing gas to a temperature less than 160°C and replace the flow of the activating agent on the flow of the mixture of carbon monoxide and hydrogen at a flow rate of 1000 h-1and establish a working reactor pressure of 2.0 MPa. Then the catalyst is heated to the chosen temperature synthesis of 210-230°C.

The efficiency of the catalyst was evaluated by the residual content of carbon monoxide in the composition of the exhaust gases and content in the products of the synthesis of hydrocarbons with the number of carbon atoms is not less than 5 in the synthesis of liquid hydrocarbons in the Fischer-Tropsch synthesis about what Oskanian synthesis gas with a ratio of hydrogen to carbon monoxide from 1.9:1 to 2.2:1 through the fixed catalyst bed, a volume of 2.5 ml, loaded in a tubular reactor with a diameter of 13 mm, with a bulk velocity 500-1500 h-1in the temperature range of 180 to 250°C. under a pressure of 1.5-2.5 MPa. Method implemented in accordance with these examples.

Example 1 (example of comparison)

In this example, is considered one of the most common in industry catalyst for Fischer-Tropsch synthesis 10%Co/γ-Al2O3(cobalt catalyst containing 10% of the mass. cobalt deposited on γ-alumina) and commonly used way it is activated at a temperature of 450°C.

The precursor of the carrier of γ-Al2O3- boehmite (AlO(OH)), annealed at a temperature of 450°C for 4 hours. The resulting powder was pulverized to a fraction of not more than 0.2 mm Crushed media granularit into cylindrical pellets with a diameter of 2 mm, which is subjected to calcination at 500°C.

The application of active component carried out in one stage impregnation with an aqueous solution setevogo nitrate of cobalt in an amount of 10 wt.% and calcining the catalyst precursor at a temperature of 400°C for 1 hour. The catalyst was activated at 450°C in a stream of hydrogen with a bulk velocity of 3000 h-1within 1 hour at a pressure of 0.1 MPa.

Examples of preparation of the catalyst activation for option 1.

Example 1-1

Catalyst 10%Co/(90%Al2O3+10%CeO2contains 10% to the of Balto by weight of catalyst and 90% of the media.

The precursor of the carrier of γ-Al2O3- boehmite (AlO(OH)), annealed at a temperature of 450°C for 4 hours. The resulting powder was pulverized to a fraction of not more than 0.2 mm Crushed carrier is mixed with the modifier - cerium oxide CeO2in the amount of 10 wt.% from mass media and granulated into cylindrical pellets with a diameter of 2 mm, which is subjected to calcination at 400°C.

The application of active component carried out in one stage impregnation with an aqueous solution setevogo nitrate of cobalt in an amount of 10 wt.% and calcining the catalyst precursor at a temperature of 400°C for 1 hour.

Freshly prepared catalyst loaded into the reactor Fischer-Tropsch synthesis, served in a reactor a mixture of carbon monoxide and hydrogen with a molar ratio of 1.9 at flow rate of 800 h-1and establish a working reactor pressure of 2.0 MPa. Then the catalyst is heated to an initial temperature of 190°C with a heating rate of 1.0 ° /min, followed by activation of the catalyst is conducted according to the following time-temperature program:

Temperature, °CTime, h
1906
2006
2106
2206
2306
2406
25012

The rate of temperature rise between steps of 0.5 deg/min

Example 1-2

Catalyst 10%Co/(88%ZrO2+12%La2O3contains 10% cobalt by weight of catalyst and 90% of the media.

The precursor medium ZrO2- dowolny nitrate Zirconia ZrO(NO3)2·2H2O calcined at 400°C for 8 hours. The resulting powder was pulverized to a fraction of 0.1 mm, Crushed carrier is mixed with the modifier oxide lanthanum La2O3in the amount of 12 wt.% from mass media and granulated into cylindrical pellets with a diameter of 2 mm, which are subjected to calcination at 550°C. the Deposition of the active component is carried out in one stage impregnation with an aqueous solution setevogo nitrate of cobalt in an amount of 10 wt.% and calcining the catalyst precursor at a temperature of 350°C for 1.5 hours.

The catalyst loaded into the reactor Fischer-Tropsch synthesis, served in a reactor a mixture of carbon monoxide and hydrogen with a molar ratio of 1.95 at flow rate of 900 h-1and establish the working pressure in the reactor of 2.1 MPa. Then the catalyst is heated to an initial temperature of 180°C with a heating rate of 0.5 deg/min, followed by activation of the catalyst is conducted according to the following time-temperature program:

Temperature, °CTime, h
1806
1906
2006
2106
2206
23012
24012
25018

The rate of temperature rise between steps of 0.1°C/min

Example 1-3

The catalyst was 20%Co/(99%ZrO2+1%Y2O3contains 20% cobalt by weight of catalyst and 80% of the media.

The precursor medium ZrO2- dowolny nitrate Zirconia ZrO(NO3)2·2H2O calcined at a temperature of 450°C for 10 hours. The resulting powder was pulverized to a fraction of 0.05 mm Crushed carrier is mixed with the modifier - yttrium oxide in an amount of 1 wt.% from mass media and granular the t in cylindrical pellets with a diameter of 2 mm, which is subjected to calcination at 600°C for 11 hours.

The application of active component is carried out in two stages impregnation with an aqueous solution setevogo nitrate of cobalt in the amount of 20 wt.% and calcining the catalyst precursor at a temperature of 380°C for 2.5 hours.

The catalyst loaded into the reactor Fischer-Tropsch synthesis, served in a reactor a mixture of carbon monoxide and hydrogen with a ratio of 1.99 at flow rate of 1500 h-1and set operating pressure in the reactor was 1.5 MPa. Then the catalyst is heated to an initial temperature of 200°C with heating rate of 2.0 ° /min, followed by activation of the catalyst is conducted according to the following time-temperature program:

Temperature, °CTime, h
2006
2106
22016
23018
24018
25018

The rate of temperature rise between steps of 0.3 deg/min

Example 1-4

The catalyst 30%C+50%ZrO 2+20%γ-Al2O3contains 30% cobalt by weight of catalyst, 50% of zirconium oxide and 20% of aluminum oxide and activated by the method 1 of the present invention.

The precursor medium ZrO2- dowolny nitrate Zirconia ZrO(NO3)2·2H2O calcined at 500°C for 12 hours. The resulting powder was pulverized to a fraction of less than 0.15 mm Crushed carrier is mixed with a modifier, aluminum oxide Al2O3in the amount of 20 wt.% from the mass of catalyst and hestevognen nitrate of cobalt, corresponding to 30 wt.% cobalt on the finished catalyst. The resulting mass is granulated into cylindrical pellets with a diameter of 2 mm, which are subjected to calcination at 400°C for 12 hours.

The catalyst loaded into the reactor Fischer-Tropsch synthesis, served in a reactor a mixture of carbon monoxide and hydrogen with a ratio of 2.0 at the flow rate of 1200 h-1and set the operating pressure in the reactor to 1.8 MPa. Then the catalyst is heated to an initial temperature of 200°C with heating rate of 1.5 ° /min, followed by activation of the catalyst is conducted according to the following time-temperature program:

Temperature, °CTime, h
2006
2106
2206
2306
2406
2506

The rate of temperature rise between treads - 1.0 deg/min

Example 1-5

Catalyst 12%Co/(82%TiO2+18%γ-Al2O3contains 12% cobalt by weight of catalyst and 88% of the medium and is activated according to the method 1 of the present invention.

The precursor medium TiO2- exonetric titanium TiO(NO3)2calcined at 800°C for 9 hours. The resulting powder was pulverized to a fraction of less than 0.25 mm Crushed carrier is mixed with a modifier, aluminum oxide γ-Al2O3in the amount of 18 wt.% from mass media and granulated into cylindrical pellets with a diameter of 2 mm, which are subjected to calcination at 650°C for 7 hours.

The application of active component is in the amount of 12 wt.% one-stage impregnation with an aqueous solution setevogo of cobalt nitrate and calcining the catalyst precursor at 500°C for 1 hour.

Freshly prepared catalyst loaded into the reactor Fischer-Tropsch synthesis, served in the reactor mixture is of carbon monoxide and hydrogen with a ratio of 2.1 for the flow rate 500 h -1and establish a working reactor pressure of 2 MPa. Then the catalyst is heated to an initial temperature of 200°C with heating rate of 2 deg/min, followed by activation of the catalyst is conducted according to the following time-temperature program:

Temperature, °CTime, h
2006
2106
2216
2306
24014
24818

The rate of temperature rise between steps is 1.5 deg/min

Example 1-6

The catalyst 17%Co/(40%ZrO2+40%SiO2+20%γ-Al2O3contains 17% cobalt by weight of catalyst and 83% of the media.

The precursor medium ZrO2- dowolny nitrate Zirconia ZrO(NO3)2·2H2O calcined at a temperature of 540°C for 1 hour. The resulting powder was pulverized to a fraction of 0.3 mm Precursor media SiO2- spherical silica gel is crushed to a fraction of 0.3 mm Powders SiO2and ZrO2first mix, and then add to the recip is authorized mixture modifier - aluminum oxide γ-Al2O3in the amount of 20 wt.% from the mass media, and granularit into cylindrical pellets with a diameter of 2 mm, which are subjected to calcination at 800°C for 20 hours.

The application of active component is in the amount of 17 wt.% the two stages of impregnation with an aqueous solution setevogo of cobalt nitrate and calcining the catalyst precursor at a temperature of 290°C for 2.5 hours.

Freshly prepared catalyst loaded into the reactor Fischer-Tropsch synthesis, served in a reactor a mixture of carbon monoxide and hydrogen with a ratio of 2.2 for flow rate 1000 h-1and establish a working reactor pressure of 2 MPa. Then the catalyst is heated to an initial temperature of 200°C with heating rate of 1 deg/min, followed by activation of the catalyst is conducted according to the following time-temperature program:

Temperature, °CTime, h
2006
2106
2206
23012
24018
24918

The rate of temperature rise between steps - 2.0 deg/min

Example 1-7

The catalyst was 20%Co/(94%γ-Al2O3+6%ZrO2contains 20% cobalt by weight of catalyst and 80% of the media.

The precursor of the carrier of γ-Al2O3- oxohydroxide aluminum AlO(OH), annealed at a temperature of 480°C for 20 hours. The resulting powder was ground to particles less than 0.4 mm and modify it to 6 wt.% zirconium oxide obtained from the two-water of exonerate zirconium, granularit into cylindrical pellets with a diameter of 2 mm, which are subjected to calcination at 500°C for 1 hour.

The application of active component is in the amount of 20 wt.% the two stages of impregnation with an aqueous solution setevogo of cobalt nitrate and calcining the catalyst precursor at 500°C for 1 hour.

Freshly prepared catalyst loaded into the reactor Fischer-Tropsch synthesis, served in a reactor a mixture of carbon monoxide and hydrogen with a ratio of 1.92 at flow rate of 1000 h-1and set the operating pressure in the reactor of 2.5 MPa. Then the catalyst is heated to an initial temperature of 200°C with heating rate of 1.5 ° /min, followed by activation of the catalyst is conducted according to the following time-temperature program:

Temperature, °CTime, h
2006
2106
2206
2306
24012
25018

The rate of temperature rise between steps of 0.5 deg/min

Example 1-8

The catalyst was 20%Co/(95%γ-Al2O3+5%ZrO2is different from the catalyst in example 7 so that modification of aluminum oxide is an oxide of zirconium in an amount of 5 wt.% from mass media obtained from 70%aqueous solution of n-propylated zirconium n-propanol, followed by granulating and calcining in a stream of air at 420°C for 3.5 hours.

Freshly prepared catalyst loaded into the reactor Fischer-Tropsch synthesis, served in a reactor a mixture of carbon monoxide and hydrogen with a ratio of 1.97 at flow rate of 1000 h-1and establish a working reactor pressure of 2 MPa. Then the catalyst is heated to an initial temperature of 200°C with heating rate of 1.2 deg/min, followed by activation of the catalyst is conducted according to the following temperature-time prog is the Amma:

Temperature, °CTime, h
2006
2106
2206
23012
24112
25018

The rate of temperature rise between steps - 1.2 deg/min

Example 1-9

The catalyst was 20%Co/(90%CeO2+10%ZrO2contains 20% cobalt by weight and 80% of the media.

Precursor media CeO2- Ce(NO3)3·6H2O (shestibalny nitrate of cerium(III)), annealed at a temperature of 450°C for 16 hours. The resulting powder was ground to particles less than 0.45 mm, mixed with a modifier - zirconium oxide ZrO2in the amount of 10 wt.% from mass media and granulated into cylindrical pellets with a diameter of 2 mm, which are subjected to calcination at 500°C for 13 hours.

The application of active component is carried out in the amount of 20 wt.% the two stages of impregnation with an aqueous solution setevogo Nitra is and cobalt and calcining the catalyst precursor at a temperature of 270°C for 1 hour.

Freshly prepared catalyst loaded into the reactor Fischer-Tropsch synthesis, served in a reactor a mixture of carbon monoxide and hydrogen with a ratio of 2.05, at flow rate of 1200 h-1and set the operating pressure in the reactor of 2.5 MPa. Then the catalyst is heated to an initial temperature of 200°C with heating rate of 1.0 ° /min, followed by activation of the catalyst is conducted according to the following time-temperature program:

Temperature, °CTime, h
2006
2096
21812
23012
24112
25018

The rate of temperature rise between steps - 1.5 deg/min

Table 1 shows the performance of the Fischer-Tropsch synthesis, carried out in the presence of catalysts, activated in accordance with option 1 of this method.

Table 1
Example Conversion, %Selectivity for CH4, %The selectivity for C5+, %Output, g C5+/m3synthesis gas
174285081
1-171275781
1-276265687
1-374324970
1-469285473
1-568285273
1-660354246
1-772 285275
1-880285281
1-973265282

With option 2 the activation of the catalyst is realized in accordance with the following examples.

Example 2 (example of comparison)

In this example, the catalyst for Fischer-Tropsch synthesis 30%Co/Al2O3(cobalt catalyst containing 30% of the mass. cobalt supported on alumina) and commonly used way it is activated at a temperature of 450°C.

Precursor carrier Al2O3- boehmite (AlO(OH)), annealed at a temperature of 450°C for 4 hours. The resulting powder to grind to a fraction of less than 0.2 mm Crushed granulated media in cylindrical pellets with a diameter of 2 mm, which are subjected to calcination at 500°C. the Deposition of the active component is in the amount of 30 wt.% three stages of impregnation with an aqueous solution setevogo of cobalt nitrate and calcining the catalyst precursor at a temperature of 270°C for 2 hours after each impregnation stage. The catalyst activates pri°C in a stream of hydrogen with a bulk velocity of 3000 h -1within 1 hour at a pressure of 0.1 MPa. The rate of temperature rise to the final value was 2.0 deg/min Determination of the activity and selectivity of the catalyst of example and comparison catalysts of the other samples is carried out at flow rate of synthesis gas (ratio of H2:CO=2), equal to 1000 h-1at a temperature of 210-230°C.

The catalysts activated by option 2.

Example 2-1

The catalyst 30%Co+0,1%Pd/(99%Al2O3+1%La2O3contains 30% cobalt and 0.1%Pd by weight of catalyst and 69.9 per cent of the media.

Precursor carrier Al2O3- oxohydroxide aluminum AlO(OH) calcined at 800°C for 16 hours. The resulting powder was pulverized to a fraction of 0.02 mm and mixed with a modifier in the amount of 1% lanthanum oxide and granularit into cylindrical pellets with a diameter of 2 mm, which is subjected to calcination at 750°C for 1 hour.

The application of active component is carried out in the amount of 30 wt.% three stages of impregnation with an aqueous solution setevogo of cobalt nitrate and calcining the catalyst precursor at a temperature of 270°C for 2 hours after each impregnation stage. Palladium is introduced into the catalyst joint impregnation with cobalt in the third stage of introduction of the active component from the corresponding amount of ammonium chloride solution, Pallady the (II) (PdCl 2).

The catalyst was activated at 240°C in a stream of hydrogen with a bulk velocity of 3000 h-1within 24 hours at a pressure of 0.12 MPa. The rate of temperature rise to the final value was 2.0 deg/min

Example 2-2

The catalyst 30%Co+0.5%of Re/(98.5%of Al2O3+1.5%of La2O3contains 30% cobalt by weight of the catalyst, 0.5% rhenium and 69.5 wt.% media.

Precursor carrier Al2O3- oxohydroxide aluminum AlO(OH), annealed at a temperature of 580°C for 2 hours. The resulting powder was pulverized to a fraction of 0.45 mm and mixed with a modifier in the amount of 1.5% of lanthanum oxide and granularit into cylindrical pellets with a diameter of 2 mm, which is subjected to calcination at 750°C for 7 hours.

The application of active component is in the amount of 30 wt.% three stages of impregnation with an aqueous solution setevogo of cobalt nitrate and calcining the catalyst precursor at a temperature of 285°C for 3 hours after each impregnation stage. Rhenium is deposited with joint impregnation of the catalyst precursor with a corresponding amount of ammonium perrhenate dissolved in water together with hestevognen nitrate of cobalt, in the third stage of introduction of the active component.

The catalyst was activated at 245°C in a stream of hydrogen with a bulk velocity of 1500 h-1for 27 hours at a pressure of 0.11 MPa. Soon the industry growth temperature to the final value was 1.2 deg/min

Example 2-3

The catalyst was 20%Co+0,2%Ru/(80%Hβ+20%Al2O3contains 20% cobalt and 0.2% ruthenium by weight of catalyst and 79.8 wt.% media.

The precursor medium - zeolite Hβ module 40 (Zeolyst) calcined at 400°C for 1 hour. The resulting powder was pulverized to a fraction of 0.1 mm and mixed with the modifier in the amount of 20% of oxide of Al, then granularit into cylindrical pellets with a diameter of 2 mm, which is subjected to calcination at 500°C for 9 hours.

The application of active component is in the amount of 20 wt.% the two stages of impregnation with an aqueous solution setevogo of cobalt nitrate and calcining the catalyst precursor at a temperature of 270°C for 4 hours after each impregnation stage. Ruthenium is deposited with joint impregnation of the catalyst precursor with a corresponding amount of hydrated ruthenium chloride (RuCl3·H2O)dissolved in water together with hestevognen nitrate of cobalt, in the third stage of introduction of the active component.

The catalyst was activated at 249°C in a stream of a mixture of argon and hydrogen content of the last 10 vol.% with a bulk velocity of 2800 h-1for 32 hours at a pressure of 0.1 MPa. The rate of temperature rise to the final value was 0.5 deg/min

Example 2-4

The catalyst was 20%Co+1.5%of Ru/(91%ZrO2+9%γ-Al2O3contains 20% cobalt is and and 1.5% ruthenium by weight of catalyst and 78.5% of the media.

The precursor medium ZrO2- dowolny nitrate Zirconia ZrO(NO3)2·2H2O calcined at a temperature of 60°C for 14 hours. The resulting powder was pulverized to a fraction of less than 0.25 mm Crushed carrier is mixed with a modifier, aluminum oxide γ-Al2O3in the amount of 9% by weight of the carrier and granularit into cylindrical pellets with a diameter of 2 mm, which is subjected to annealing at 770°C for 20 hours.

The application of active component is in the amount of 20 wt.% the two stages of impregnation with an aqueous solution setevogo of cobalt nitrate and calcining the catalyst precursor at a temperature of 290°C for 3.5 hours. Ruthenium is deposited with joint impregnation of the catalyst precursor with a corresponding amount of hydrated ruthenium chloride (RuCl3·H2O)dissolved in water together with hestevognen nitrate of cobalt, in the third stage of introduction of the active component.

The catalyst was activated at 243°C in a stream of a mixture of argon and hydrogen with a hydrogen content of 50 vol.% with a bulk velocity of 2600 h-1for 16 hours at a pressure of 0.1 MPa. The rate of temperature rise to the final value was 0.8 deg/min

Example 2-5

The catalyst was 20%Co+0,3%Re/(90%ZrO2+10%CeO2contains 20% cobalt by weight of catalyst, 0.3 wt.% rhenium and 79,7 wt.% media.

PR is the cursor media ZrO 2- dowolny nitrate Zirconia ZrO(NO3)2·2H2O calcined at 400°C for 6 hours. The resulting powder was ground to particles less than 0,35 mm Crushed carrier is mixed with the modifier oxide Ce in the amount of 10% by weight of the carrier and granulated into cylindrical pellets with a diameter of 2 mm, which are subjected to calcination at 800°C.

The application of active component is in the amount of 20 wt.% the two stages of impregnation with an aqueous solution setevogo of cobalt nitrate and calcining the catalyst precursor at 500°C for 1 hour after each impregnation stage. Rhenium is deposited with joint impregnation of the catalyst precursor with a corresponding amount of ammonium perrhenate dissolved in water together with hestevognen nitrate of cobalt, in the second stage of introduction of the active component.

The catalyst was activated at 246°C in a stream of a mixture of nitrogen and hydrogen at a content of 80 vol.% with a bulk velocity of 1000 h-1within 24 hours at a pressure of 0.1 MPa. The rate of temperature rise to the final value amounted to 1.4 deg/min

Example 2-6

The catalyst was 20%Co+0.5%of Re/(90%ZrO2+10%Y2O3contains 20% cobalt, 0.5 wt.% rhenium and of 79.5 wt.% media.

The precursor medium ZrO2- dowolny nitrate Zirconia ZrO(NO3)2·2H2O use liveout at a temperature of 420°C for 4 hours. The resulting powder was ground to particles less than 0.5 mm Crushed carrier is mixed with a modifier oxide Y in the amount of 10% by weight of the carrier and granularit into cylindrical pellets with a diameter of 2 mm, which is subjected to calcination at 400°C for 3.5 hours.

The application of active component is carried out in the amount of 20 wt.% the two stages of impregnation with an aqueous solution setevogo of cobalt nitrate and calcining the catalyst precursor at a temperature of 400°C for 1 hour after each impregnation stage. Rhenium is deposited with joint impregnation of the catalyst precursor with a corresponding amount of ammonium perrhenate dissolved in water together with hestevognen nitrate of cobalt, in the second stage of introduction of the active component.

The catalyst was activated at 244°C in a stream of a mixture of helium and hydrogen at a hydrogen content of about 90.% with a bulk velocity of 2200 h-1within 48 hours at a pressure of 0.1 MPa. The rate of temperature rise to the final value was 0.5 deg/min

Example 2-7

The catalyst was 20%Co+0,7%Pt(90%ZrO2+10%γ-Al2O3contains 20% cobalt by weight of catalyst, 0.7 wt.% platinum and to 79.3 wt.% media.

The precursor medium ZrO2- dowolny nitrate Zirconia ZrO(NO3)2·2H2O calcined at a temperature of 480°C for 7 hours. The resulting powder was pulverized to F. the shares is less than 0.4 mm. Chopped mixed media with modifier - alumina γ-Al2O3in the amount of 10% by weight of the carrier and granularit into cylindrical pellets with a diameter of 2 mm, which is subjected to annealing at 790°C for 11 hours.

The application of active component is in the amount of 20 wt.% the two stages of impregnation with an aqueous solution setevogo of cobalt nitrate and calcining the catalyst precursor at a temperature of 280°C for 1.5 hours after each impregnation stage. Platinum is made with joint impregnation of the precursor catalyst corresponding H2PtCl6·6H2O, dissolved in water together with hestevognen nitrate of cobalt, in the second stage of introduction of the active component.

The catalyst was activated at 249°C in a stream of hydrogen with a bulk velocity of 1200 h-1for 20 hours at a pressure of 0.1 MPa. The rate of temperature rise to the final value was 0.8 deg/min

Example 2-8

Catalyst 10%Co+1%Pd/(90%ZrO2-SO4+10%γ-Al2O3contains 20% cobalt by weight of the catalyst, and 1.0 wt.% palladium and 79% of the medium and is activated according to the method 2 of the present invention.

The precursor medium ZrO2- dowolny nitrate Zirconia ZrO(NO3)2·2H2O calcined at a temperature of 600°C for 20 hours. The resulting powder was pulverized to a fraction of men who e 0,25 mm. Chopped mixed media with modifier - alumina γ-Al2O3in the amount of 10% by weight of the carrier and granulated into cylindrical pellets with a diameter of 2 mm, which is subjected to annealing at 770°C. Next, the carrier is modified by sulfation of zirconium oxide by impregnation of 20%sulfuric acid, followed by calcination at 600°C for 2 hours.

The application of active component is in an amount of 10 wt.% one-stage impregnation with an aqueous solution setevogo of cobalt nitrate and calcining the catalyst precursor at a temperature of 270°C for 2 hours. Palladium is introduced into the catalyst joint impregnation with cobalt in the first stage of introduction of the active component from the corresponding amount of ammonia solution of palladium (II) chloride (PdCl2).

The catalyst was activated at 250°C in a stream of hydrogen with a bulk velocity of 3000 h-1within 24 hours at a pressure of 0.1 MPa. The rate of temperature rise to the final value was 1.5 deg/min

Table 2 shows the performance of the Fischer-Tropsch synthesis, carried out in the presence of catalysts, activated by option 2.

81
Table 2
ExampleTo nverse WITH, %Selectivity for CH4, %The selectivity for C5+, %Output, g C5+/m3synthesis gas
230207141
2-141147760
2-253118277
2-336128154
2-428108447
2-553236665
2-634157651
2-7341252
2-834207045

Obtained in this method the catalyst is highly effective for the Fischer-Tropsch synthesis and provides a high catalytic activity and selectivity for the target product.

1. A method of obtaining a cobalt catalyst comprising preparing a granular media from the source of raw materials - oxides of the metals of groups III and IV of the Periodic table DI Mendeleev, mixing the latter with modifying additives, followed by calcination, impregnation compounds cobalt and calcining and activating the catalyst in a stream of hydrogen containing gas, characterized in that the granular carrier is prepared by calcination of raw materials selected from the group of: aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, cerium oxide, mixtures of the listed oxides, amorphous or crystalline silicates at a temperature of from 400 to 800°C for from 1 to 20 h, which is then pulverized to a particle size not exceeding 0.5 mm and before granulation is mixed with a modifier selected from the group of Al2O3La2O3, Y2O3CeO2which is introduced into the carrier in an amount of from 1 is about 20 wt.% from mass media and calcined at a temperature of from 400 to 800°C, after granulation, the carrier is impregnated with compounds of cobalt in the range from 10 to 30 wt.% by weight of catalyst based on cobalt metal and calcined at a temperature of from 270 to 500°C, while the activation of the catalyst is carried out directly in the process of the Fischer-Tropsch synthesis when heated catalyst, which is carried out in several stages, step by raising the temperature, and at the first stage the temperature is raised at a rate of 0.5-2°C/min up to 180-200°C and maintained at this temperature until reaching a stable performance for the conversion of carbon monoxide and selectivity for liquid hydrocarbons and methane, while the indicators are considered to be stable if the relative difference of their values to 10 Rel.%and then the raise the temperature of 8-12°C at the rate of 0.1-2°C/min until a temperature of not more than 250°C, and the pressure of the gas in the activation process is 1.5-2.5 MPa, and the volumetric rate of gas during activation support within 500-1500 h-1.

2. A method of obtaining a cobalt catalyst comprising preparing a granular media from the source of raw materials - oxides of the metals of groups III and IV of the Periodic table DI Mendeleev, mixing the latter with modifying additives, followed by calcination, impregnation compounds of cobalt and promoters and calcining the activation of the catalyst in a stream of hydrogen containing gas, characterized in that the granular carrier is prepared by calcination of raw materials selected from the group of: aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, amorphous or crystalline silicates at a temperature of from 400 to 800°C for 1 to 20 h, which is then pulverized to a particle size not exceeding 0.5 mm and before granulation is mixed with a modifier in an amount of from 1 to 20 wt.% from mass media, selected from the group of Al2O3La2O3, Y2O3SEO2, ZrO2, and calcined at a temperature of from 400 to 800°C. after pelleting the carrier is impregnated with compounds of cobalt, the amount of which in terms of metallic cobalt is from 10 to 30 wt.% by weight of the catalyst, and the promoter is introduced into the catalyst in an amount of from 0.1 to 1.5 wt.% by weight of the catalyst, which choose a metal from the group of Pt, Pd, Re, Ru, then the granules are calcined at a temperature of from 270 to 500°C, while the activation of the catalyst is carried out at the hydrogen content in the gas is not less than 10 vol.% and a temperature of 240-250°C for 16-48 h in the synthesis reactor Fischer-Tropsch fixed bed catalyst by heating the catalyst by passing a hydrogen-containing gas over the catalyst precursor at atmospheric pressure, and the rate of temperature rise to the final value of p is derivat in the range of 0.5-2.0°C/min, and the volumetric rate of gas during activation support within 1000-3000 h-1.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: method of producing a Fischer-Tropsch synthesis catalyst, involving calcining material: nitrate, oxonitrate, hydroxide or oxohydroxide of aluminium, zirconium, silicon or titanium, at temperature of 400-800°C, grinding particles to size of not more than 0.5 mm, granulating, calcining the granules at temperature of 400-800°C, saturating with a solution of cobalt compounds in amount of 20-30 wt % and promoters selected from: Re, Ru, followed by calcination at temperature of 270-450°C, grinding the granules to particle size of not more than 0.5 mm, mixing with a zeolite selected from: ZSM-5, Y, β, content of which ranges from 30 to 70% of the mass of the ready catalyst, granulating the obtained mixture together with boehmite, the mass of which ranges from 10 to 20% of the mass of the mixture, and calcining at temperature of 400-600°C, ion exchange of the granules with soluble compounds of palladium or Fe, Co, Ni, with content thereof of 0.5-8.0% of the mass of the ready catalyst, in a suspension of granules and a solution of said metal compounds at temperature of 60-80°C for 1-3 hours, drying the suspension at temperature of 80-150°C and calcining the residue at temperature of 300-500°C, activating the catalyst with hydrogen at 250-500°C in a fixed bed Fischer-Tropsch synthesis reactor while passing hydrogen with volume rate of 3000 h-1 at atmospheric pressure.

EFFECT: low cost of the catalyst, high stability of the catalyst.

1 tbl, 48 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts of obtaining aliphatic hydrocarbons from carbon oxide and hydrogen and their application. Catalyst for obtaining aliphatic hydrocarbons from carbon oxide and hydrogen, which contains nano-size catalytically active particles of metal cobalt or iron, is described, and it is obtained by pyrolysis of macromolecules of polyacrylonitrile (PAN) in presence of iron and cobalt salts in inert atmosphere under influence of IR-irradiation at temperature 300-700°C after preliminary annealing in air. Method of obtaining aliphatic hydrocarbons from carbon oxide and hydrogen at increased temperature and pressure in presence of upper described catalyst is described.

EFFECT: simplification of catalyst obtaining and reduction of process cost.

5 cl, 2 dwg, 1 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a catalyst suitable for use in catalysis of a Fischer-Tropsch reaction. Described is a catalyst which contains cobalt metal deposited on zinc oxide and zirconium (IV) oxide in amount ranging from 0.5 to 2.5 wt % with respect to the metal, per mass of the calcined catalyst, wherein the volume-average particle size of the catalyst ranges from 2 mcm to less than 75 mcm. Described is use of the catalyst in a Fischer-Tropsch method or when hydrogenating functional groups and a Fischer-Tropsch method.

EFFECT: improved mechanical stability of the catalyst with balance between catalyst activity properties and separation thereof from the reaction mixture by filtering.

16 cl, 1 tbl, 6 ex

FIELD: chemistry.

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

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts for producing aliphatic hydrocarbons. Described is a catalyst for producing aliphatic hydrocarbons from carbon monoxide and hydrogen, which contains iron nanoparticles and formed in situ directly in the reaction zone during heat treatment of catalyst components in a hydrogen or carbon monoxide stream in molten paraffin, characterised by that the iron nanoparticles are promoted with copper, with the following ratio of components, wt %: Cu - 5-25; Fe - the balance. Described is a method of producing aliphatic hydrocarbons from carbon monoxide and hydrogen in the presence of said catalyst.

EFFECT: low content of alkenes.

4 cl, 1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to versions of a method of conducting a Fischer-Tropsch process for producing liquid hydrocarbons mainly containing diesel fuel or a diesel mixture to obtain a liquid hydrocarbon product containing less than 10 wt % wax (>C23) and more than 65% of the (C9-C23) diesel fraction. One of the versions of the method includes the following steps: carrying out operations at pressure below 200 pounds per square inch (absolute); and using a cobalt catalyst having a Fischer-Tropsch support with cobalt metal crystallites on it, wherein the cobalt metal crystallites have average diameter greater than 16 nm.

EFFECT: invention is used to obtain a diesel fraction without further processing of the product.

38 cl, 8 tbl, 12 ex, 11 dwg

FIELD: power engineering.

SUBSTANCE: in a solar concentrator they carry out separately simultaneous stepwise heating of water steam and its mixture with a methane-containing gas, which is then sent to a reaction of steam catalytic conversion of the methane-containing gas into a sectioned catalytic reactor, installed outside the solar concentrator, the flow rate of water steam and its mixture with the methane-containing gas is reduced as the solar energy flow is reducing.

EFFECT: using this method makes it possible to reduce thermal costs for the process of energy resources generation and also to efficiently supply various energy resources under conditions of unavailability of methane sources, and also in the period of solar energy flow reduction at night time and when cloudiness increases.

8 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for selective synthesis of high-quality gasoline fractions from synthesis gas and a method for production thereof. Described is a highly selective catalyst for producing high-quality gasoline fractions from synthesis gas, which consists of cobalt, a promoter and a molecular sieve, wherein the weight content of cobalt is 1-30%, the weight content of the promoter is 0.01-5%, and the remaining part is a molecular sieve, with respect to the weight of the catalyst, wherein the molecular sieve is one or more molecular sieves selected from molecular sieves Beta, ZSM-5, MOR, Y and MCM-22, wherein acidity of the molecular sieve is expressed through the amount of adsorbed NH3, and the adsorption capacity of the molecular sieve ranges from 0.16 to 0.50 mmol NH3/g; the molecular sieve has a microporous-mesoporous structure, wherein the micropores have diameter of 0.4-0.9 nm, and the mesopores have diameter of 2-30 nm, the specific surface area of the molecular sieve is 100-900 m2/g and the volume of micropores and mesopores is 0.1-0.6 cm3/g, respectively. Described is a method of producing a highly selective catalyst used for synthesis of high-quality gasoline fractions from synthesis gas by Fischer-Tropsch synthesis, involving the following steps: (1) preparing a weighed portion of a cobalt salt according to content of components given above, mixing with a solvent which is deionised water, alcohol or a ketone, to obtain a solution which contains a cobalt salt with concentration of 0.5-20 wt %; (2) preparing a weighed portion of a promoter according to content of components established above, adding to the prepared solution a cobalt salt and stirring for 0.5-3 hours; (3) preparing a weighed portion of a molecular sieve according to content of components established above, adding the molecular sieve to the prepared solution of cobalt salt, stirring for 0.1-15 hours and holding for 0.1-24 hours; (4) evaporating the suspension at temperature of 40-100°C and drying the obtained solid substance under a vacuum at temperature of 30-100°C for 1-24 hours; (5) calcining the dried substance on air at temperature of 300-550°C for 2-10 hours; (6) moulding the calcined powder as a catalyst precursor; (7) reducing the catalyst precursor in a hydrogen atmosphere or a mixture of hydrogen and an inert gas at temperature of 300-550°C for 1-10 hours.

EFFECT: described is a highly selective catalyst for producing high-quality gasoline fractions from synthesis gas.

13 cl, 17 tbl, 16 ex

FIELD: chemistry.

SUBSTANCE: invention relates to Fischer-Tropsch synthesis catalysts. Described is a method of producing a precursor of a cobalt-containing Fischer-Tropsch synthesis catalyst, which involves adding a polyfunctional carboxylic acid of general formula HOOC-C*R1C*R2~COOH(1) where, C* in each of the groups C*R1 and C*R2 is a sp2-hybridised carbon atom and R1 and R2 are identical or different and each is selected from a group consisting of hydrogen and alkyl which contains not more than six carbon atoms, into and/or onto catalyst support particles, with the ratio of the amount of the polyfunctional carboxylic acid and the size of the surface of the support in the range of 0.3-10 mcmol of carboxylic acid/m2 of the surface of the support; while adding carboxylic acid into and/or onto the catalyst support particles or after, simultaneously adding a cobalt compound into and/or onto the catalyst support particles and calcining the saturated support to form a precursor of a cobalt-containing Fischer-Tropsch synthesis catalyst.

EFFECT: described is a method of producing a Fischer-Tropsch synthesis catalyst which involves reduction of a catalyst precursor obtained using the described method; described is a method of producing hydrocarbons, which involves bringing into contact synthesis gas which contains hydrogen (H2) and carbon monoxide (CO), at high temperature of 80°C-250°C and high pressure of 10-40 bar with a Fischer-Tropsch synthesis catalyst obtained using said method, and a Fischer-Tropsch reaction between hydrogen and carbon monoxide.

17 cl; 2 dwg; 4 tbl; 7 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of separating liquid phase by-products of Fischer-Tropsch synthesis, which involves the following steps: a) feeding the liquid phase by-products into a standard fractionation column (1) in its middle part with output of a portion of the stream I, having a boiling point range from 50 to 120°C, as a side cut to obtain light components having boiling point below 50°C from the top of the column, and heavy components, having boiling point higher than 120°C from the bottom of the column; b) feeding the stream I into a column (2) for separating acetic acid in its middle part to obtain a stream of aqueous solution II, containing alcohols and ketones, having boiling point range from 50 to 100°C from the top of the column, and a stream III of aqueous solution of acetic acid from the bottom of the column; and c) feeding the stream II into a column (3) for separating ethanol in its middle part to obtain a stream IV of a mixture of methanol and acetone from the top of the column and a stream V of aqueous solution of ethanol and n-propanol from the bottom of the column (see dwg 3).

EFFECT: high efficiency of the process.

9 cl, 4 dwg, 30 tbl, 30 ex

FIELD: chemistry.

SUBSTANCE: method of producing a Fischer-Tropsch synthesis catalyst, involving calcining material: nitrate, oxonitrate, hydroxide or oxohydroxide of aluminium, zirconium, silicon or titanium, at temperature of 400-800°C, grinding particles to size of not more than 0.5 mm, granulating, calcining the granules at temperature of 400-800°C, saturating with a solution of cobalt compounds in amount of 20-30 wt % and promoters selected from: Re, Ru, followed by calcination at temperature of 270-450°C, grinding the granules to particle size of not more than 0.5 mm, mixing with a zeolite selected from: ZSM-5, Y, β, content of which ranges from 30 to 70% of the mass of the ready catalyst, granulating the obtained mixture together with boehmite, the mass of which ranges from 10 to 20% of the mass of the mixture, and calcining at temperature of 400-600°C, ion exchange of the granules with soluble compounds of palladium or Fe, Co, Ni, with content thereof of 0.5-8.0% of the mass of the ready catalyst, in a suspension of granules and a solution of said metal compounds at temperature of 60-80°C for 1-3 hours, drying the suspension at temperature of 80-150°C and calcining the residue at temperature of 300-500°C, activating the catalyst with hydrogen at 250-500°C in a fixed bed Fischer-Tropsch synthesis reactor while passing hydrogen with volume rate of 3000 h-1 at atmospheric pressure.

EFFECT: low cost of the catalyst, high stability of the catalyst.

1 tbl, 48 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing an aqueous suspension of a noble metal colloid and use thereof. Described is a method of producing an aqueous suspension of a noble metal colloid which involves reducing a noble metal salt in an aqueous solution using a functionalised water-soluble quaternary ammonium salt in the absence of organic solvents to form elementary nanoparticles, wherein functionalisation of the water-soluble quaternary ammonium salt involves the presence of at least one reducing group such as -CH2OH or cyclohexenyl, preferably in combination with at least one bulky group selected from C6+ alkyl, cycloalkyl, aralkyl, alkaryl or aryl. Described is a method of producing a noble metal catalyst on a substrate, which involves bringing the described suspension into contact with a substrate material and separating the catalyst with the noble metal. Described is a method of producing 3-hexenol, which involves reducing 3-hexyn-1-ol in the presence of a colloid suspension obtained using the method described above. Described is a method of producing 3-hexenol, which involves reducing 3-hexyn-1-ol in the presence of a catalyst obtained using said method.

EFFECT: obtaining an aqueous colloid suspension of a noble metal.

19 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to Fischer-Tropsch synthesis catalysts. Described is a method of producing a precursor of a cobalt-containing Fischer-Tropsch synthesis catalyst, which involves adding a polyfunctional carboxylic acid of general formula HOOC-C*R1C*R2~COOH(1) where, C* in each of the groups C*R1 and C*R2 is a sp2-hybridised carbon atom and R1 and R2 are identical or different and each is selected from a group consisting of hydrogen and alkyl which contains not more than six carbon atoms, into and/or onto catalyst support particles, with the ratio of the amount of the polyfunctional carboxylic acid and the size of the surface of the support in the range of 0.3-10 mcmol of carboxylic acid/m2 of the surface of the support; while adding carboxylic acid into and/or onto the catalyst support particles or after, simultaneously adding a cobalt compound into and/or onto the catalyst support particles and calcining the saturated support to form a precursor of a cobalt-containing Fischer-Tropsch synthesis catalyst.

EFFECT: described is a method of producing a Fischer-Tropsch synthesis catalyst which involves reduction of a catalyst precursor obtained using the described method; described is a method of producing hydrocarbons, which involves bringing into contact synthesis gas which contains hydrogen (H2) and carbon monoxide (CO), at high temperature of 80°C-250°C and high pressure of 10-40 bar with a Fischer-Tropsch synthesis catalyst obtained using said method, and a Fischer-Tropsch reaction between hydrogen and carbon monoxide.

17 cl; 2 dwg; 4 tbl; 7 ex

FIELD: process engineering.

SUBSTANCE: invention relates to catalysts of hydrogen and oxygen recombination. Proposed method consists in impregnating catalyst porous base with solution of compound of catalytically active metal and liquid chemical reducing agent. After drying of said base, it is calcined to reduction of catalytically active metal. It differs from known processes in that aforesaid chemical reducing agent represents hydroxyethylated monoalkyl phenol with the number of bonded moles of ethylene oxide varying from one to ten, or the mix of oxyethylated mono- and dialkylphenols. Note here that said reducing agent is added directly to solution of compound of catalytically active metal.

EFFECT: simplified and accelerated production, higher catalyst properties, reduced losses.

7 cl, 2 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to chemistry of organosilicon compounds, namely to elaboration of efficient sulphur-containing catalyst, applied for direct synthesis of triethoxysilane from metallurgical silicon and ethyl alcohol, as well as to method of obtaining said catalyst. Described is catalyst of direct synthesis of triethoxysilane based on copper chloride (1), representing ultrafine copper powders (1), whose spherical aggregates have diameter from 600 nm to 3 mcm and consist of globules with diameter to 200 nm, which, in their turn, represent nanoparticles of copper chloride (1) with size to 20 nm. Also described is method of obtaining described above catalyst by reductive thermolysis of chelate copper complex, obtained in situ from copper chloride dehydrate (11) in polyol medium.

EFFECT: obtaining target product with selectivity above 80%.

2 cl, 11 ex, 4 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to heterogeneous catalysis, particularly a method of producing a catalyst for ortho-para conversion of protium. Described is a method of producing a catalyst for ortho-para conversion of protium, involving obtaining metal nanoparticles in a reverse micellar solution, consisting of a metal salt solution, a surfactant in form of sodium bis(2-ethylhexyl)sulphosuccinate, and a nonpolar solvent, isooctane, followed by deposition on a support, wherein reduction of the metal salt takes place upon reaction with quercetin; the support used is SiO2 and the metal salt used is RhCl3 or RuOHCl3 and reverse micellar solutions of rhodium or ruthenium are prepared with molar ratio of the aqueous metal salt solution to the surfactant ranging from 1:1 to 10:1; a water-alcohol solution is then added in amount of 5-50 wt %, a quercetin solution is added in amount of 0.5-5 wt % and ammonia solution is added in amount of 10-30 wt %.

EFFECT: obtaining a catalyst with high activity and capable of operating in the temperature range of 77-110 K.

2 cl, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a catalyst for protium-deuterium isotopic exchange. Described is a method of producing a catalyst for protium-deuterium isotopic exchange, involving obtaining metal nanoparticles in a reverse micellar solution consisting of a metal salt solution, a surfactant which is sodium bis(2-ethylhexyl)sulphosuccinate, and a nonpolar solvent, isooctane, followed by deposition on a support, wherein reduction of the metal salt takes place upon reaction with quercetin; the support used is Sibunit and the metal salt used is RhCl3 or RuOHCl3 and reverse micellar solutions of rhodium or ruthenium are prepared with molar ratio of the aqueous metal salt solution to the surfactant ranging from 1:1 to 10:1; a water-alcohol solution is then added in amount of 5-50 wt %, a quercetin solution is added in amount of 0.5-5 wt % and ammonia solution is added in amount of 10-30 wt %.

EFFECT: catalyst for protium-deuterium isotopic exchange, having high catalytic activity, is obtained.

2 cl, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a catalyst for protium-deuterium isotopic exchange. Described is a method of producing a catalyst for protium-deuterium isotopic exchange, involving obtaining metal nanoparticles in a reverse micellar solution consisting of a metal salt solution, a surfactant which is sodium bis(2-ethylhexyl)sulphosuccinate, and a nonpolar solvent, isooctane, followed by deposition on a support, wherein reduction of the metal salt takes place upon reaction with quercetin; the support used is SiO2 and the metal salt used is RhCl3 or RuOHCl3 and reverse micellar solutions of rhodium or ruthenium are prepared with molar ratio of the aqueous metal salt solution to the surfactant ranging from 1:1 to 10:1; a water-alcohol solution is then added in amount of 5-50 wt %, a quercetin solution is added in amount of 0.5-5 wt % and ammonia solution is added in amount of 10-30 wt %.

EFFECT: catalyst for protium-deuterium isotopic exchange, having high catalytic activity, is obtained.

2 cl, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to heterogeneous catalysis, particularly a method of producing a catalyst for ortho-para conversion of protium. Described is a method of producing a catalyst for ortho-para conversion of protium, involving obtaining metal nanoparticles in a reverse micellar solution, consisting of a metal salt solution, a surfactant in form of sodium bis(2-ethylhexyl)sulphosuccinate, a nonpolar solvent, isooctane, followed by deposition on an Al2O3 support, wherein reduction of the metal salt takes place upon reaction with quercetin; the metal salt used is RhCl3 or RuOHCl3 and reverse micellar solutions of rhodium or ruthenium are prepared with molar ratio of the aqueous metal salt solution to the surfactant ranging from 1:1 to 10:1; a water-alcohol solution is then added in amount of 5-50 wt %, a quercetin solution is added in amount of 0.5-5 wt % and ammonia solution is added in amount of 10-30 wt %.

EFFECT: obtaining a catalyst with high activity and meant for operation in the temperature range of 77-110 K.

2 cl, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to heterogeneous catalysis, particularly a method of producing a catalyst for ortho-para conversion of protium. Described is a method of producing a catalyst for ortho-para conversion of protium, involving obtaining metal nanoparticles in a reverse micellar solution, consisting of a metal salt solution, a surfactant in form of sodium bis(2-ethylhexyl)sulphosuccinate, and a nonpolar solvent, isooctane, followed by deposition on a support, wherein reduction of the metal salt takes place upon reaction with quercetin; the support used is Sibunit and the metal salt used is RhCl3 or RuOHCl3 and reverse micellar solutions of rhodium or ruthenium are prepared with molar ratio of the aqueous metal salt solution to the surfactant ranging from 1:1 to 10:1; a water-alcohol solution is then added in amount of 5-50 wt %, a quercetin solution is added in amount of 0.5-5 wt % and ammonia solution is added in amount of 10-30 wt %.

EFFECT: obtaining a catalyst with high activity and capable of operating in the temperature range of 77-110 K.

2 cl, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: method of producing a Fischer-Tropsch synthesis catalyst, involving calcining material: nitrate, oxonitrate, hydroxide or oxohydroxide of aluminium, zirconium, silicon or titanium, at temperature of 400-800°C, grinding particles to size of not more than 0.5 mm, granulating, calcining the granules at temperature of 400-800°C, saturating with a solution of cobalt compounds in amount of 20-30 wt % and promoters selected from: Re, Ru, followed by calcination at temperature of 270-450°C, grinding the granules to particle size of not more than 0.5 mm, mixing with a zeolite selected from: ZSM-5, Y, β, content of which ranges from 30 to 70% of the mass of the ready catalyst, granulating the obtained mixture together with boehmite, the mass of which ranges from 10 to 20% of the mass of the mixture, and calcining at temperature of 400-600°C, ion exchange of the granules with soluble compounds of palladium or Fe, Co, Ni, with content thereof of 0.5-8.0% of the mass of the ready catalyst, in a suspension of granules and a solution of said metal compounds at temperature of 60-80°C for 1-3 hours, drying the suspension at temperature of 80-150°C and calcining the residue at temperature of 300-500°C, activating the catalyst with hydrogen at 250-500°C in a fixed bed Fischer-Tropsch synthesis reactor while passing hydrogen with volume rate of 3000 h-1 at atmospheric pressure.

EFFECT: low cost of the catalyst, high stability of the catalyst.

1 tbl, 48 ex

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