WO2014031030A1

WO2014031030A1 - Method for producing a cobalt catalyst

Info

Publication number: WO2014031030A1
Application number: PCT/RU2013/000524
Authority: WO
Inventors: Олег Николаевич ПРОТАСОВ; Сергей Анатольевич АЛХИМОВ; Дмитрий Александрович ГРИГОРЬЕВ; Михаил Николаевич МИХАЙЛОВ
Original assignee: Общество с ограниченной ответственностью "Объединенный центр исследований и разработок"
Priority date: 2012-08-24
Filing date: 2013-06-20
Publication date: 2014-02-27
Also published as: RU2493914C1

Abstract

The invention relates to petroleum chemistry, gas chemistry and carbon chemistry and concerns Fischer-Tropsch synthesis, in particular, a method for producing and subsequently activating a cobalt catalyst from Fischer-Tropsch synthesis. The activation method consists in that the catalyst is contacted with a hydrogen-containing gas or with a mixture of carbon monoxide and hydrogen in a process of converting same into hydrocarbons at Fischer-Tropsch synthesis temperatures. The catalyst produced and activated in accordance with the method being described is no less effective than catalysts produced and activated by other methods known in the art.

Description

The method of producing cobalt catalyst

Technical field

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

State of the art

A known method of preparing a cobalt Fischer-Tropsch synthesis catalyst based on zeolites, into which cobalt is introduced by two-stage impregnation with soluble cobalt compounds with sequential drying after each stage at temperatures of 200-600 ° C. The catalyst is activated in a stream of hydrogen at 450 ° C (US Patent 7,723,252).

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

A known method of producing 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 (US Patent No. 5,585,316).

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

The closest technical solution to this invention is a method for producing a cobalt catalyst for Fischer-Tropsch synthesis, the carrier of which is alumina or other basic oxides modified by impregnation with organic compounds of Group IVB metals (zirconium, hafnium, titanium). The active component is introduced into them by impregnating the carrier with solutions of organic compounds of active metals or their mineral salts or carbonyls of cobalt, iron or ruthenium. The last stage of preparation of the catalyst for synthesis in this patent indicates its preliminary activation in a fixed-bed reactor in the presence of synthesis gas at a pressure of 0.7 to 1.4 MPa and a stepwise rise in temperature from 220 to 270 ° C (US Patent J42 4,681,867) .

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

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

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

The technical result is achieved by the fact that the granular carrier is prepared by calcining the feedstock at a temperature of from 400 to 800 ° C for 1 to 20 hours, which is then crushed to particle sizes not higher than 0.5 mm and mixed with transition modifier with a modifier before granulation metals of group III of the Periodic table Mendeleev, and after granulation, the support is calcined at a temperature of 400 to 800 ° С, while the activation of the catalyst is carried out directly in the Fischer-Tropsch synthesis by heating the catalyst, which is carried out in several stages, raising the temperature stepwise, and in the first stage, the temperature is raised at a speed 0.5-2 ° C / min to 180-200 ° C and maintained at this temperature until stable carbon monoxide conversion and selectivity for liquid hydrocarbons and methane are achieved, while the readings are taken from labile with a relative difference in their values up to 10 rel.%, and then the temperature is raised by 8-12 ° C at a speed of 0.1-2 ° C / min until a temperature of not more than 250 ° C is reached. The feedstock for the carrier is selected from the group: aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, cerium oxide, oxide mixtures, amorphous or crystalline aluminosilicates. The modifier is selected from the group of transition metal compounds of group III of the Periodic table D.I. Mendeleev: A1 ₂ 0 ₃ , La ₂ 0 ₃ , Y ₂ 0 ₃ , Ce0 ₂ and introduced into the carrier in an amount of from 1 to 20 wt.%. The amount of cobalt compound deposited on the carrier, in terms of cobalt metal is from 10 to 30 wt.% By weight of the finished catalyst. A mixture of hydrogen and carbon monoxide with a molar ratio of 1.9-2.2 is used as a hydrogen-containing gas. The gas pressure during the activation process is 1.5-2.5 MPa, and the gas volumetric velocity during the activation period is maintained within 500-1500 hours. ^"1

The technical result according to the second variant of the method is achieved by the fact that a granular carrier is prepared by calcining the feedstock at a temperature of from 400 to 800 ° C for 1 to 20 hours, which is then ground to particle sizes not exceeding 0.5 mm and before granulation are mixed with a modifier of transition metal compounds of groups III and IV of the Periodic Table D. I.

Mendeleev, and after granulation, the carrier is calcined at a temperature of from 400 to

800 ° C, while the activation of the catalyst is carried out at a hydrogen content in the gas of at least 10 vol.% And a temperature of 240-250 ° C for 16-48 hours in a Fischer-Tropsch synthesis reactor with a fixed catalyst bed by heating the catalyst while passing a hydrogen-containing gas above the catalyst precursor at atmospheric pressure, wherein the rate of temperature rise to a final value is maintained within 0.5-2.0 deg / min.

The feedstock for the carrier is selected from the group: aluminum, silicon, titanium, zirconium, cerium, or amorphous or crystalline aluminosilicates or mixtures thereof.

The modifier is selected from the group of transition metal compounds of groups III and IV of the Periodic table D.I. Mendeleev: A1 ₂ 0 ₃ , La ₂ 0 ₃ , Y ₂ 0 ₃ , Ce0 ₂ , Zr0 ₂ . The promoter is selected from the group of metals VII and VIII of the group of the Periodic table D.I. Mendeleev: Pt, Pd, Re, Ru.

The amount of cobalt compound deposited on the carrier, in terms of metallic cobalt, is from 10 to 30 wt.%, While the promoter is introduced into the catalyst in an amount of from 0.1 to 1.5 wt.%, And the gas volumetric rate during the activation period is maintained in the range of 500-3000 hours ^"1 .

These distinguishing features are 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 Fischer-Tropsch synthesis, which entails a reduction in capital costs and metal production.

The preparation of the catalyst according to this invention is carried out by preliminary preparation of the carrier, followed by the introduction of the active component in its composition. First, the precursor of the main component of the carrier, which is mainly salts of inorganic acids, in particular, nitrates of metals of groups III and IV of the Periodic table Mendeleev, preferably aluminum, silicon, titanium, zirconium, or amorphous or crystalline aluminosilicates or mixtures thereof, are calcined at temperatures of 400-800 ° C for 1 to 20 hours. Then, the calcined material is ground to a fraction with a particle size of up to 0.5 mm. Before granulation, the crushed material is mixed with a modifier that is selected from the group of transition metal compounds of groups III and IV of the Periodic Table D.I. Mendeleev: A1 ₂ 0 ₃ , La ₂ 0 ₃ , Y ₂ 0 ₃ , Ce0 ₂ , Zr0 ₂ . The crushed support is granulated by extrusion into cylindrical granules.

The carrier granules are calcined at temperatures of 400-800 ° C. Modifier based on

1-20 wt.% In a calcined carrier is introduced into its composition at the stage of preparation of carrier granules, or by impregnating the carrier with an aqueous solution of a modifier precursor preceding the introduction of the active component, followed by calcining the carrier at temperatures of 400-800 ° C.

Application of the active component is carried out in an amount of 10-30 wt.% On the finished catalyst in one or several stages, the number of which usually does not exceed three, by impregnating the support or catalyst precursor with an aqueous solution of cobalt salt, for example, cobalt hexahydrate, followed by calcination after each stage making the active component at temperatures of 270-500 ° C for 1-4 hours.

The introduction of promoters is carried out by a separate stage of impregnation, either by co-impregnation with the active component, for oxide promoters, preferably in the first stage of impregnation, or before the first stage of introducing the active component. For metal promoters, it is preferable at the last stage of introducing the active component by co-impregnation, or in a separate stage after introducing the active component. In the case of a separate stage of impregnation of the catalyst or its precursor with the precursor of the promoter, after its introduction, calcination is carried out at temperatures of 270-500 ° C for 1-4 hours.

The activation process 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 a fixed-bed Fischer-Tropsch synthesis reactor, is heated in a stream of hydrogen or a mixture of carbon monoxide and hydrogen (synthesis gas) with a gas volumetric velocity selected for the process to an initial temperature, usually in the range of 240-250 ° C, to activate clean hydrogen or its mixture with an inert gas and 180-200 ° C for activation by synthesis gas. Then, in the case of using a mixture of carbon monoxide and hydrogen as an activation gas, the temperature rises stepwise to a final value of 250 ° C in increments of 8-12 ° C. The rate of temperature rise to the initial value is 0.5-2 degrees / min, the rise rate between the steps of the temperature regime is 0.1-2 degrees / min. The duration of aging at a temperature at each stage, for a catalyst activated by 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 using pure hydrogen or its mixture with an inert gas continues continuously for 16-48 hours. The calculation of CO conversion is carried out according to the following formula:

- mass of carbon monoxide in 1 m ^{3 of the} gas entering the reactor t _with ^you ₍₎ - mass of carbon monoxide in 1 m ³ of the gas leaving the reactor

The determination of selectivity for liquid hydrocarbons is carried out according to the following formula:

s _{C5 +} = ta ± _100% ^

mC I СОвх ~ ^т С I СОвых тс / С5 + - mass of carbon contained in liquid hydrocarbons resulting from the synthesis of gas entering the reactor from 1 m ³ ; С1СОвх - mass of carbon contained in carbon monoxide in 1 m ^{3 of} gas entering the reactor;

t, s s / SOv is the mass of carbon contained in carbon monoxide in 1 m of gas leaving the reactor.

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

tС / СОвх ^t С1 СОвых tС1СНА - mass of carbon contained in methane formed as a result of synthesis of gas entering the reactor from 1 m ³ .

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

_ t _{£ 1 ±} LS

cs + ^~ _{H y} , where

in

t _{С5 +} - mass of liquid hydrocarbons formed as a result of Fischer-Tropsch synthesis over time τ;

V ^ ^y is the volume of synthesis gas passing through the catalyst bed, m ³ .

The determination of the content of the starting and forming substances in the gases leaving the Fischer-Tropsch synthesis reactor can be carried out by any known method, for example, gas-liquid chromatography. The best options for implementation and acquisition

The activation process according to the present invention is carried out in one of two ways.

Option 1

Freshly prepared catalyst is loaded into a Fischer-Tropsch synthesis reactor, a mixture of carbon monoxide and hydrogen with a ratio of 1.9-2.2 at a space velocity of 500-3000 h ^{"1 is} fed to the reactor, and the working pressure in the reactor is set at 1.5-2.5 MPa Then the catalyst is heated to an initial temperature in the range of 180-200 ° C with a heating rate of 0.5-2 deg./min and maintained at this temperature until stable carbon monoxide conversion and selectivity for liquid hydrocarbons and methane are achieved. at ra lichii in their values and 10 rel.%. The temperature was then raised to 8-12 ° C at a rate of 0.1-2 gradUmin and so on to achieve a temperature not exceeding 250 ° C.

Option 2

Freshly prepared catalyst is crushed to a fraction of 0.1-0.2 mm, loaded into a Fischer-Tropsch synthesis reactor, a mixture of hydrogen and inert gas (argon, nitrogen or helium) with a hydrogen content of at least 10 vol.% Or pure hydrogen at a space velocity of 1000-3000 h ^"1 and a pressure of 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 degUmin and the catalyst is kept under these conditions for 16-48 hours.

After activation, the reactor is cooled in a stream of hydrogen or hydrogen-containing gas to a temperature of less than 160 ° C and the flow of the activating agent is replaced by a stream of a mixture of carbon monoxide and hydrogen at a space velocity of 1000 h ^"1 and the working pressure in the reactor is set to 2.0 MPa. Then, the catalyst is heated to selected synthesis temperature of 210-230 ° C.

The efficiency of the catalyst is estimated by the residual content of carbon monoxide in the exhaust gas and the content in the products of the synthesis of hydrocarbons with a number of carbon atoms of at least 5 during the synthesis of liquid hydrocarbons in the Fischer-Tropsch synthesis by passing synthesis gas with a hydrogen to carbon monoxide ratio of 1, 9: 1 to 2.2: 1 through a fixed catalyst bed, 2.5 ml in volume, loaded into a tubular reactor with a diameter of 13 mm, with a space velocity of 500-1500 h ^"1 in the temperature range 180-250 ° C under a pressure of 1.5 -2.5 MPa.

Examples of carrying out the invention

The method is implemented in accordance with the specified examples. Example 1-A (comparison example)

This example examines one of the most common industrial catalyst for Fischer-Tropsch synthesis of 10% Co y-A1 ₂ O ₃ (a cobalt catalyst containing 10% by weight of cobalt supported on γ-alumina) and a commonly used method for its activation at temperature 450 ° C.

The precursor of the carrier γ-Α1 ₂ 0 ₃ - boehmite (AU (OH)) is calcined at a temperature of 450 ° C for 4 hours. The resulting powder is ground to a fraction of not more than 0.2 mm. The crushed support is granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 500 ° C.

The application of the active component is carried out in one stage of impregnation with an aqueous solution of cobalt hexahydrate nitrate in an amount of 10 wt.%, Followed by calcination of the catalyst precursor at a temperature of 400 ° C for 1 hour. The catalyst is activated at 450 ° C in a stream of hydrogen with a space velocity of 3000 h ^"1 for 1 hour at a pressure of 0.1 MPa.

Examples of obtaining a catalyst with activation according to option 1.

Example 1-1

The 10% Co / catalyst (90% Al ₂ O 3 + 10% CeO ₂ ) contains 10% cobalt by weight of the catalyst and 90% of the support.

The precursor of the carrier γ-Α1 ₂ 0 ₃ - boehmite (AU (OH)) is calcined at a temperature of 450 ° C for 4 hours. The resulting powder is ground to a fraction of not more than 0.2 mm. The crushed support is mixed with a modifier - cerium oxide Ce0 ₂ in the amount of 10 wt.% By weight of the support and is granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 400 ° C.

The application of the active component is carried out in one stage of impregnation with an aqueous solution of cobalt hexahydrate nitrate in an amount of 10 wt.%, Followed by calcination of the catalyst precursor at a temperature of 400 ° C for 1 hour.

Freshly prepared catalyst is loaded into a Fischer-Tropsch synthesis reactor, a mixture of carbon monoxide and hydrogen with a molar ratio of 1, 9 is supplied at a space velocity of 800 h ^"1 and the working pressure in the reactor is set to 2.0 MPa. Then, the catalyst is heated to an initial temperature of 190 ° C with a heating rate of 1, 0 deg./min, then the activation of the catalyst is carried out according to the following temperature-time program:

Temperature, ° С Time, h

190 6 200 6

210 6

220 6

230 6

240 6

250 12

The rate of temperature increase between steps is 0.5 deg / min.

Example 1-2

The 10% Co / catalyst (88% ZrO2 + 12% La ₂ O ₃ ) contains 10% cobalt by weight of the catalyst and 90% of the support.

The precursor of the carrier Zr0 ₂ - _two -water zirconyl nitrate ZrO (N0 ₃ ) ₂ -2H ₂ 0 calcined at a temperature of 400 ° C for 8 hours. The resulting powder is ground to a fraction of 0.1 mm. The crushed support is mixed with a modifier — La ₂ 0 ₃ lanthanum oxide in an amount of 12 wt.% By weight of the support and is granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 550 ° C. Application of the active component is carried out in one stage of impregnation with an aqueous solution of cobalt hexahydrate nitrate in an amount of 10 wt.%, Followed by calcination of the catalyst precursor at a temperature of 350 ° C for 1.5 hours.

The catalyst is loaded into the Fischer-Tropsch synthesis reactor, a mixture of carbon monoxide and hydrogen with a molar ratio of 1.95 at a space velocity of 900 h ^{"1 is} fed to the reactor and the working pressure in the reactor is set to 2.1 MPa. Then, the catalyst is heated to an initial temperature of 180 ° C. with a heating rate of 0.5 deg./min, then the activation of the catalyst is carried out according to the following temperature-time program:

Temperature, ° С Time, h

180 6

190 6

200 6

210 6

220 6

230 12

240 12

250 18

The rate of temperature increase between steps is 0.1 ° C / min. Example 1-3

The 20% Co / catalyst (99% ZrO2 + l% Y ₂ O3) contains 20% cobalt by weight of the catalyst and 80% of the support.

The carrier precursor Zr0 ₂ - _two -water zirconyl nitrate ZrO (N0 ₃ ) ₂ -2H ₂ 0 calcined at a temperature of 450 ° C for 10 hours. The resulting powder is ground to a fraction of 0.05 mm. The crushed carrier is mixed with a modifier - yttrium oxide in an amount of 1 wt.% By weight of the carrier and granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 600 ° C for 1 1 hours.

Application of the active component is carried out in two stages of impregnation with an aqueous solution of cobalt hexahydrate nitrate in an amount of 20 wt.%, Followed by calcination of the catalyst precursor at a temperature of 380 ° C for 2.5 hours.

The resulting catalyst was loaded into a Fischer-Tropsch synthesis reactor, a mixture of carbon monoxide and hydrogen with a ratio of 1.99 was supplied to the reactor at a space velocity of 1500 h ^"1 and the operating pressure in the reactor was set to 1.5 MPa. Then, the catalyst was heated to an initial temperature of 200 ° C. with a heating rate of 2.0 deg./min, then the activation of the catalyst is carried out according to the following temperature-time program:

Temperature, ° С Time, h

200 6

210 6

220 16

230 18

240 18

250 18

The rate of temperature increase between steps is 0.3 deg./min.

Example 1-4

The catalyst 30% Co + 50% ZrO ₂ + 20% y-Al ₂ O3 contains 30% cobalt by weight of the catalyst, 50% zirconium oxide and 20% alumina and is activated according to method 1 of the present invention.

The precursor of the carrier Zr0 ₂ - _two -water zirconyl nitrate ZrO (N0 ₃ ) ₂ -2H ₂ 0 calcined at a temperature of 500 ° C for 12 hours. The resulting powder is ground to a fraction of less than 0.15 mm. The ground carrier is mixed with a modifier — aluminum oxide A1 ₂ 0 ₃ in an amount of 20 wt.% By weight of the catalyst and cobalt hexahydrate nitrate, corresponding to 30 wt.% cobalt per finished catalyst. The resulting mass is granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 400 ° C for 12 hours.

The resulting catalyst is loaded into a Fischer-Tropsch synthesis reactor, a mixture of carbon monoxide and hydrogen with a ratio of 2.0 is supplied to the reactor at a volumetric rate of 1200 h ^"1 and the working pressure in the reactor is set to 1.8 MPa. Then, the catalyst is heated to an initial temperature of 200 ° C. with a heating rate of 1, 5 deg./min, then the activation of the catalyst is carried out according to the following temperature-time program:

Temperature, ° С Time, h

200 _

210 6

220 6

230 6

240 6

250 6

The rate of temperature increase between steps is 1.0 deg./min.

Example 1-5

The catalyst 12% Co / (82% Ti0 ₂ + 18% y-Al ₂ 0 ₃ ) contains 12% cobalt by weight of the catalyst and 88% of the support and is activated according to method 1 of the present invention.

The carrier precursor T ₂ - titanium oxonitrate TiO (N0 ₃ ) _{2 is} calcined at a temperature of 800 ° C for 9 hours. The resulting powder is ground to a fraction of less than 0.25 mm. The crushed support is mixed with a modifier - alumina γ-Α1 ₂ 0 ₃ in the amount of 18 wt.% By weight of the support and is granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 650 ° C for 7 hours.

Application of the active component is carried out in an amount of 12 wt.% At one stage of impregnation with an aqueous solution of cobalt hexahydrate nitrate, followed by calcination of the catalyst precursor at a temperature of 500 ° C for 1 hour.

Freshly prepared catalyst is loaded into the Fischer-Tropsch synthesis reactor, a mixture of carbon monoxide and hydrogen is supplied to the reactor with a ratio of 2.1 at a space velocity of 500 h ^"1 and the working pressure in the reactor is set to 2 MPa. Then, the catalyst is heated to an initial temperature of 200 ° C at a speed heating 2 deg./min, then the activation of the catalyst is carried out according to the following temperature-time program:

Temperature, ° С Time, h

200 6

210 6

221 6

230 6

240 14

248 18

The rate of temperature increase between steps is 1.5 deg./min.

Example 1-6

The catalyst 17% Co / (40% ZrO2 + 40% SiO ₂ + 20% Y-Al ₂ O ₃ ) contains 17% cobalt by weight of the catalyst and 83% of the support.

The precursor of the carrier Zr0 ₂ - _two -water zirconyl nitrate ZrO (N0 ₃ ) ₂ -2H ₂ 0 calcined at a temperature of 540 ° C for 1 hour. The resulting powder is ground to a fraction of 0.3 mm. The Si0 ₂ carrier precursor, spherical silica gel, is ground to a fraction of 0.3 mm. Powders Si0 ₂ and Zr0 ₂ is first stirred and then added to the resulting mixture, a modifier -. Alumina y-A1 ₂ 0z in an amount of 20% by weight of the carrier, and pelletized into cylindrical pellets of 2 mm diameter which are subjected to calcination at 800 ° C within 20 hours.

Application of the active component is carried out in an amount of 17 wt.% By two stages of impregnation with an aqueous solution of cobalt hexahydrate nitrate, followed by annealing of the catalyst precursor at a temperature of 290 ° C for 2.5 hours.

Freshly prepared catalyst is loaded into the Fischer-Tropsch synthesis reactor, a mixture of carbon monoxide and hydrogen with a ratio of 2.2 is supplied to the reactor at a space velocity of 1000 h ^"1 and the working pressure in the reactor is set to 2 MPa. Then, the catalyst is heated to an initial temperature of 200 ° C at a speed heating 1 deg./min, then the activation of the catalyst is carried out according to the following temperature-time program:

Temperature, ° С Time, h

G) 6

210 6

220 6

230 12 240 18

249 18

The rate of temperature increase between steps is 2.0 degrees. / min

Example 1-7

The 20% Co / catalyst (94% y-AI ₂ O3 + 6% ZrO ₂ ) contains 20% cobalt by weight of the catalyst and 80% of the support.

The precursor of the y-Al ₂ 0 ₃ support, aluminum oxyhydroxide АУ (ОН), is calcined at a temperature of 480 ° С for 20 hours. The resulting powder is ground to a fraction of less than 0.4 mm and its 6 wt.% Zirconium oxide obtained from zirconium dichloromethane is modified, granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 500 ° C for 1 hour.

Application of the active component is carried out in an amount of 20 wt.% By two stages of impregnation of an aqueous solution of cobalt hexahydrate nitrate, followed by annealing of the catalyst precursor at a temperature of 500 ° C for 1 hour.

Freshly prepared catalyst is loaded into a Fischer-Tropsch synthesis reactor, a mixture of carbon monoxide and hydrogen with a ratio of 1.92 is supplied to the reactor at a space velocity of 1000 h ^"1 and the operating pressure in the reactor is set to 2.5 MPa. Then, the catalyst is heated to an initial temperature of 200 ° C. with a heating rate of 1, 5 deg./min, then the activation of the catalyst is carried out according to the following temperature-time program:

Temperature, ° С Time, h

200 6

210 6

220 6

230 6

240 12

250 18

The rate of temperature increase between steps is 0.5 deg./min.

Example 1-8

The catalyst 20% Co / (95% y-Al ₂ O3 + 5% ZrO ₂ ) differs from the catalyst in Example 7 in that the alumina is modified with zirconia in an amount of 5 wt.% Of the weight of the support obtained from 70% a solution of n-propyl oxide of zirconium in n-propanol, followed by granulation and calcination in a stream of air at 420 ° C for 3.5 hours. Freshly prepared catalyst is loaded into the Fischer-Tropsch synthesis reactor, a mixture of carbon monoxide and hydrogen with a ratio of 1, 97 is supplied to the reactor at a space velocity of 1000 h ^"1 and the working pressure in the reactor is set to 2 MPa. Then, the catalyst is heated to an initial temperature of 200 ° C at a speed heating 1.2 deg./min, then the activation of the catalyst is carried out according to the following temperature-time program:

Temperature, ° С Time, h

200 6

210 6

220 6

230 12

241 12

250 18

The rate of temperature increase between steps is 1.2 deg./min.

Example 1-9

The 20% Co / (90% CeO ₂ + 10% ZrO ₂ ) catalyst contains 20% cobalt by weight and 80% support.

The carrier precursor Ce0 ₂ - Ce () h) s-6H ₂ 0 (cerium (III) six-water nitrate) is calcined at a temperature of 450 ° C for 16 hours. The resulting powder is crushed to a fraction of less than 0.45 mm, mixed with a modifier - zirconium oxide Zr0 ₂ in the amount of 10 wt.% By weight of the carrier and granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 500 ° C for 13 hours.

Application of the active component is carried out in an amount of 20 wt.% By two stages of impregnation with an aqueous solution of cobalt hexahydrate nitrate, followed by calcination of the catalyst precursor at a temperature of 270 ° C for 1 hour.

Freshly prepared catalyst is loaded into a Fischer-Tropsch synthesis reactor, a mixture of carbon monoxide and hydrogen with a ratio of 2.05 is supplied to the reactor at a space velocity of 1200 h ^"1 and the working pressure in the reactor is set to 2.5 MPa. Then, the catalyst is heated to an initial temperature of 200 ° C. with a heating rate of 1, 0 deg./min, then the activation of the catalyst is carried out according to the following temperature-time program:

Temperature, ° С Time, h

200 6 209 6

218 12

230 12

241 12

250 18

The rate of temperature increase between steps is 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

The method with option 2 activation of the catalyst is implemented in accordance with the following examples.

Example 2-A (comparison example)

This example describes a Fischer-Tropsch synthesis catalyst 30% Co / A1 ₂ O ₃

(cobalt catalyst containing 30% by weight of cobalt supported on alumina) and a commonly used method for its activation at 450 ° C.

The precursor of the carrier A1 ₂ 0z - boehmite (AU (OH)) is calcined at a temperature of 450 ° C for 4 hours. The resulting powder was ground to a fraction of less than 0.2 mm. The crushed support is granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 500 ° C. The application of the active component is carried out in an amount of 30 wt.% Three stages of impregnation with an aqueous solution cobalt hexahydrate nitrate followed by calcination of the catalyst precursor at a temperature of 270 ° C for 2 hours after each stage of impregnation. The catalyst is activated at 450 ° C. in a stream of hydrogen with a space velocity of 3000 h ^’1 for 1 hour at a pressure of 0.1 MPa. The temperature growth rate to the final value was 2.0 deg / min. Determination of the activity and selectivity of the catalyst of comparative example and catalysts other examples are carried out at a volumetric rate of synthesis gas

(ratio of H ₂ : CO = 2) equal to 1000 h ^"1 at a temperature of 210-230 ° C.

Catalysts activated according to option 2.

Example 2-1

The catalyst 30% Co + 0, l% Pd / (99% Al ₂ O3 + l% La ₂ O3) contains 30% cobalt and

0, l% Pd by weight of the catalyst and 69.9% of the carrier.

The precursor of the support Al ₂ 0 3 - aluminum oxohydroxide АУ (ОН) is calcined at a temperature of 800 ° C for 16 hours. The resulting powder is ground to a fraction

0.02 mm and mixed with a modifier in the amount of 1% lanthanum oxide and granulated into cylindrical granules with a diameter of 2 mm, which are subjected to calcination at 750 ° C for 1 hour.

Application of the active component is carried out in an amount of 30 wt.% By three stages of impregnation with an aqueous solution of cobalt hexahydrate nitrate, followed by annealing of the catalyst precursor at a temperature of 270 ° C for 2 hours after each stage of impregnation. Palladium is introduced into the catalyst by co-impregnation with cobalt in the third stage of introducing the active component from an appropriate amount of an ammonia solution of palladium (II) chloride (PdCl ₂ ).

The catalyst was activated at 240 ° C. in a stream of hydrogen with a space velocity of 3000 h ^{1 1} for 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% Re / (98.5% Al ₂ O ₃ + l, 5% La ₂ O ₃ ) contains 30% cobalt by weight of the catalyst, 0.5% rhenium and 69.5 wt.% carrier.

The precursor of the carrier Al ₂ 0 ₃ - aluminum oxohydroxide АУ (ОН) is calcined at a temperature of 580 ° C for 2 hours. The resulting powder is ground to a fraction of 0.45 mm and mixed with a modifier in an amount of 1.5% lanthanum oxide and granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 750 ° C for 7 hours. The active component is applied in an amount of 30 wt.% By three stages of impregnation with an aqueous solution of cobalt hexahydrate nitrate, followed by annealing of the catalyst precursor at a temperature of 285 ° C for 3 hours after each stage of impregnation. Rhenium is introduced by co-impregnating the catalyst precursor with an appropriate amount of ammonium perrenate dissolved in water together with cobalt hexahydrate nitrate in the third stage of introducing the active component.

The catalyst was activated at 245 ° C. in a stream of hydrogen with a space velocity of 1500 h ^{1 1} for 27 hours at a pressure of 0.1 1 MPa. The rate of temperature rise to the final value was 1.2 deg / min.

Example 2-3

The catalyst 20% Co + 0.2% Ru / (80% Hp + 20% Al ₂ O ₃ ) contains 20% cobalt and 0.2% ruthenium by weight of the catalyst and 79.8 wt.% Of the carrier.

The carrier precursor, zeolite Ηβ with module 40 (Zeolyst), is calcined at a temperature of 400 ° C for 1 hour. The resulting powder is ground to a fraction of 0.1 mm and mixed with a modifier in an amount of 20% Al oxide, then granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 500 ° C for 9 hours.

Application of the active component is carried out in an amount of 20 wt.% By two stages of impregnation with an aqueous solution of cobalt hexahydrate nitrate, followed by annealing of the catalyst precursor at a temperature of 270 ° C for 4 hours after each stage of impregnation. Ruthenium is introduced by co-impregnating the catalyst precursor with an appropriate amount of hydrated ruthenium chloride (RuCl ₃ -H ₂ 0), dissolved in water along with cobalt hexahydrate nitrate, in the third stage of introducing the active component.

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

Example 2-4

The catalyst 20% Co + 1, 5% Ru / (91% ZrO ₂ + 9% y-Al ₂ O ₃ ) contains 20% cobalt and 1, 5% ruthenium by weight of the catalyst and 78.5% of the support.

The precursor of the carrier Zr0 ₂ - _two -water zirconyl nitrate ZrO (N0 ₃ ) 2-2H ₂ 0 calcined at a temperature of 600 ° C for 14 hours. The resulting powder is ground to a fraction of less than 0.25 mm. The crushed carrier is mixed with a modifier — alumina γ-Α1 ₂ 0 ₃ in an amount of 9% by weight of the carrier and granulate into cylindrical granules with a diameter of 2 mm, which are subjected to calcination at 770 ° C for 20 hours.

Application of the active component is carried out in an amount of 20 wt.% By two stages of impregnation of an aqueous solution of cobalt hexahydrate nitrate, followed by annealing of the catalyst precursor at a temperature of 290 ° C for 3.5 hours.

Ruthenium is introduced by co-impregnating the catalyst precursor with an appropriate amount of hydrated ruthenium chloride (RuCl ₃ H ₂ 0) dissolved in water along with cobalt hexahydrate nitrate in the third stage of introducing 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 space velocity of 2600 h ^"1 for 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 20% Co + 0.3% Re / (90% ZrO ₂ + 10% CeO ₂ ) contains 20% cobalt by weight of the catalyst, 0.3 wt.% Rhenium and 79.7 wt.% Of the carrier.

The precursor of the carrier Zr0 ₂ - _two -water zirconyl nitrate ZrO (N0) ₂ -2H ₂ 0 calcined at a temperature of 400 ° C for 6 hours. The resulting powder is ground to a fraction of less than 0.35 mm. The crushed support is mixed with a modifier — Ce oxide in an amount of 10% by weight of the support — and granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 800 ° C.

Application of the active component is carried out in an amount of 20 wt.% By two stages of impregnation with an aqueous solution of cobalt hexahydrate nitrate, followed by annealing of the catalyst precursor at a temperature of 500 ° C for 1 hour after each stage of impregnation. Rhenium is introduced by co-impregnating the catalyst precursor with an appropriate amount of ammonium perrenate dissolved in water together with cobalt hexahydrate nitrate in the second stage of introducing the active component.

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

Example 2-6

The catalyst 20% Co + 0.5% Re / (90% ZrO ₂ + 10% Y ₂ O ₃ ) contains 20% cobalt, 0.5 wt.% Rhenium and 79.5 wt.% Carrier. The precursor of the carrier Zr0 ₂ - _two -water zirconyl nitrate ZrO (N0 ₃ ) ₂ -2H ₂ 0 calcined at a temperature of 420 ° C for 4 hours. The resulting powder is ground to a fraction of less than 0.5 mm. The ground carrier is mixed with a modifier — Y oxide in an amount of 10% by weight of the carrier — and granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 400 ° C. for 3.5 hours.

Application of the active component is carried out in an amount of 20 wt.% By two stages of impregnation with an aqueous solution of cobalt hexahydrate nitrate, followed by annealing of the catalyst precursor at a temperature of 400 ° C for 1 hour after each stage of impregnation. Rhenium is introduced by co-impregnating the catalyst precursor with an appropriate amount of ammonium perrenate dissolved in water together with cobalt hexahydrate nitrate in the second stage of introducing the active component.

The catalyst is activated at 244 ° C in a stream of a mixture of helium and hydrogen with a hydrogen content of 90 vol.% With a space velocity of 2200 h ^"1 for 48 hours at a pressure of 0.1 MPa. The temperature growth rate to the final value was 0.5 deg / min .

Example 2-7

The catalyst 20% Co + 0.7% Pt / (90% ZrO ₂ + 10% y-Al ₂ O ₃ ) contains 20% cobalt by weight of the catalyst, 0.7% by weight of platinum and 79.3% by weight of the support.

The carrier precursor Zr0 ₂ - _two -water zirconyl nitrate ΖιΌ (Νθ ₃ ) ₂ · 2Η ₂ 0 is calcined at a temperature of 480 ° C for 7 hours. The resulting powder is ground to a fraction of less than 0.4 mm. The crushed support is mixed with a modifier — alumina γ-Α1 ₂ 0 ₃ in an amount of 10% by weight of the support — and granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 790 ° C for 1 1 hours.

Application of the active component is carried out in an amount of 20 wt.% By two stages of impregnation with an aqueous solution of cobalt hexahydrate nitrate, followed by annealing of the catalyst precursor at a temperature of 280 ° C for 1, 5 hours after each stage of impregnation. Platinum is introduced by co-impregnating the catalyst precursor with the corresponding H2PtCl ₆ -6H ₂ 0 dissolved in water together with cobalt hexahydrate in the second stage of introducing the active component.

The catalyst was activated at 249 ° C in a stream of hydrogen with a space velocity of 1200 h ^"1 for 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

The catalyst 10% Co + l% Pd / (90% ZrO ₂ -SO ₄ + 10% Y-Al ₂ O ₃ ) contains 20% cobalt by weight of the catalyst, 1.0 wt.% Palladium and 79% of the support and is activated by the method 2 of the present invention.

The precursor of the carrier Zr0 ₂ - _two -water zirconyl nitrate ZrO (N0 ₃ ) ₂ -2H ₂ 0 calcined at a temperature of 600 ° C for 20 hours. The resulting powder is ground to a fraction of less than 0.25 mm. The crushed support is mixed with a modifier - alumina γ-Α1 ₂ 0 ₃ in an amount of 10% by weight of the support - and granulated into cylindrical granules with a diameter of 2 mm, which are calcined at 770 ° C. Next, the carrier is modified by sulfation of zirconium oxide by impregnation with 20% sulfuric acid, followed by calcination at 600 ° C for 2 hours.

Application of the active component is carried out in an amount of 10 wt.% By one stage of impregnation of an aqueous solution of cobalt hexahydrate nitrate, followed by annealing of the catalyst precursor at a temperature of 270 ° C for 2 hours. Palladium is introduced into the catalyst by co-impregnation with cobalt in the first stage of introducing the active component from an appropriate amount of an ammonia solution of palladium chloride (I) (PdCl ₂ ).

The catalyst was activated at 250 ° C. in a stream of hydrogen with a space velocity of 3000 h ^{1 1} for 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 in option 2.

table 2

Example Conversion Selectivity Selectivity Output, gC ₊ / m ³

СО,% by СН ₄ ,% by С ₅₊ ,% synthesis gas

2-A 30 20 71 41

2-1 41 14 77 60

2-2 53 & 82 77

2-3 36 12 81 54

2-4 28 10 84 47

2-5 53 23 66 65

2-6 34 15 76 51

2-7 34 12 81 52 2-8 34 20 70 45

Industrial application

The catalyst obtained by this method is highly efficient in the Fischer-Tropsch synthesis and provides high catalytic activity and selectivity for the target product.

Claims

Claim

1. A method of producing a cobalt catalyst, including the preparation of a granular carrier from the feedstock - metal oxides of groups III and IV of the Periodic table Mendeleev, mixing the latter with modifying additives, followed by calcination, impregnation with cobalt compounds, followed by calcination and activation of the catalyst in a stream of hydrogen-containing gas, characterized in that the granular support is prepared by calcining a feedstock selected from the group: aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, cerium oxide, mixtures of these oxides, amorphous or crystalline aluminosilicates at a temperature of from 400 to 800 ° C for 1 to 20 hours, which is then ground chayut to particle size not greater than 0.5 mm, and prior to granulation is mixed with a modifier selected from the group: Α1 ₂ 0 _3, La ₂ 0 _3, Υ ₂ 0 _3, Se0 _2, which is introduced into the carrier in an amount from 1 to 20 weight % by weight of the carrier and calcined at a temperature of from 400 to 800 ° C. After granulation, the carrier is impregnated with cobalt compounds in an amount of from 10 to 30 wt.% By weight of the catalyst in terms of metal cobalt and calcined at a temperature of from 270 to 500 ° C, while the activation of the catalyst is carried out directly in the Fischer-Tropsch synthesis by heating the catalyst, which is carried out in several stages, stepwise raising the temperature, and in the first stage, the temperature is raised at a speed of 0.5-2 C / min to 180-200 ° C and maintained at this temperature until stable temperatures are reached carbon monoxide inversions and selectivity for liquid hydrocarbons and methane, while the indicators are considered stable with a relative difference of their values to 10 rel.%, and then the temperature is raised by 8-12 ° C at a speed of 0.1-2 ° C / min temperature not more than 250 ° C, and the gas pressure during activation is 1.5-2.5 MPa, and the gas volumetric velocity during the activation period is maintained within 500-1500 h ¹ .

2. A method of producing a cobalt catalyst, including the preparation of a granular carrier from the feedstock - metal oxides of groups III and IV of the Periodic table Mendeleev, mixing the latter with modifying additives, followed by calcination, impregnation with cobalt and promoter compounds, followed by calcination and activation of the catalyst in a stream of hydrogen-containing gas, characterized in that the granular support is prepared by calcining the feedstock selected from the group: aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, amorphous or crystalline aluminosilicates, at a temperature of 400 to 800 ° C for 1 to 20 hours, which is then ground to a particle size of not higher than 0.5 mm and before granulation is mixed with a modifier in an amount of from 1 to 20 wt.% by weight of the carrier selected from the group: A1 ₂ 0 ₃ , La ₂ 0 ₃ , Y ₂ 0, Ce0 ₂ , Zr0 ₂ , and calcined at a temperature of from 400 to 800 ° FROM. After granulation, the support is impregnated with cobalt compounds, 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, as which metal is selected from the group: 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 a hydrogen content of at least 10 vol.% and a temperature of 240-250 ° C in for 16-48 hours in a Fischer-Tropsch synthesis reactor with a still fired catalyst layer by heating the catalyst by passing a hydrogen-containing gas over the catalyst precursor at atmospheric pressure wherein the temperature increase rate to the final value is maintained within

0.5-2.0 deg / min, and the gas volumetric velocity during the activation period is maintained within 1000-3000 hours ^"1 .