RU2610526C2 - Catalyst for fischer-tropsch process in compact version and production method thereof (versions) - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to petrochemistry, gas chemistry, coal chemistry and concerns Fischer-Tropsch synthesis in a compact version, which requires synthesis of hydrocarbons in high-efficiency modes at a rate of more than 1,000 kg/m³ _cat⋅h. Catalyst is characterised by that it has specific surface area in tempered state of 50–92 m²/g and after recovery specific surface area of metal cobalt 10.3–25.5 m²/g, average size of particles of metal cobalt 5.0–18.5 nm and particle dispersity 5.4–20.0 % and containing 41–50 wt% of cobalt from weight of calcined catalyst and a support with specific surface area 86–423 m²/g and pore volume of support of 0.20–1.07 cm³/g, selected from: zirconium oxide or aluminium oxide, modified by applying zirconium oxide, or silicon oxide, modified by applying zirconium oxide, or zirconium oxide, modified by depositing aluminium oxide, or silicon oxide modified by application of aluminium oxide, wherein amount of modifying is oxide is 10–40 wt% of weight of support. Method of producing catalyst according to first version comprises multiple impregnation of support with aqueous solution of cobalt precursor with subsequent drying and calcining, or co-precipitation of cobalt carbonate from basic solution in presence of support, drying and calcination – according to second version.

EFFECT: higher selectivity of catalyst with respect to formation of hydrocarbons C₅₊ of not less than 60 % with CO conversion of not less than 70 % and maximum output of catalyst for high-molecular hydrocarbons is not less than 1,000 kg/m³ _cat⋅h.

5 cl, 1 tbl, 16 ex

Description

The invention relates to petrochemistry, gas chemistry, coal chemistry and relates to Fischer-Tropsch synthesis, in particular a catalyst and a method for producing a catalyst for the synthesis of hydrocarbons according to the Fischer-Tropsch method when carrying out the process in a compact form, requiring the synthesis of hydrocarbons in high-performance modes with a bulk flow rate of not less than 10000 h ^-1 with a capacity of more than 1000 kg / m ³ _cat ⋅ h.

Along with large-tonnage projects for the production of synthetic hydrocarbons from alternative sources of raw materials in Qatar, South Africa, Nigeria, which are associated with the world's largest natural gas fields, many companies are implementing compact mobile technologies for processing natural gas into liquid fuel. The main advantage of such technologies is the possibility of their use in small and remote deposits of hydrocarbon resources, including deep-sea offshore fields. In particular, such technologies are focused on the processing of associated petroleum gas, a significant proportion of which is burned at the fields. Less than 10% of the world's natural gas fields are capable of supplying large-tonnage refineries for the production of synthetic oil with a capacity of 10,000 barrels / day or more. At the same time, the creation of production facilities with a capacity of about 2000 barrels per day may be economically feasible for 40% of the world's natural gas fields.

Associated petroleum gas, shale gas and gases generated by gasification of waste and biomass may also be involved as raw materials in the implementation of compact technologies for processing hydrocarbon gases.

To ensure compact size and reduce capital costs when creating mobile plants for the processing of hydrocarbon gases into synthetic oil, the technology should provide high performance per unit volume of the reactor. This, in turn, requires the use of catalysts capable of stably operating in high-performance conditions with a bulk feed rate of 10,000 h ^-1 or more and high selectivity for the formation of high molecular weight hydrocarbons.

A known catalyst for the implementation of the Fischer-Tropsch process in a compact form, dispersed in a microfiber matrix, described in patent application US 2013216445 A1, 08/22/2013 and patent application of international patent office WO 2013126341 A1, 08/29/2013 by Ceramatec Inc., developing a modular Fischer-Tropsch synthesis technology. Particles of microfiber material in which a nanoscale metal catalyst is dispersed are used as the basis for the catalyst. The catalyst may contain nickel, cobalt, lanthanum, iron or alloys (FeCuK, CoRu). A carrier (alumina or silicon oxide) and promoters (Mn, La) can be used. The particle size of the catalyst is from 10 μm to 1 mm in a microfiber matrix or 0.5 mm to 5 mm in the form of conventional extrudates. The temperature of the reagents at the inlet is 225.2 ° C, in the catalyst layer 230-232 ° C, below the catalyst layer 226.6 ° C. The temperature of the coolant is 215 ° C, an average of 15 ° C lower than in the catalyst bed. Productivity is 750 kg _{C5 +} / m ³ _cat ⋅h.

The disadvantage of this catalyst is its low productivity, which does not allow to efficiently process synthesis gas as a result of the Fischer-Tropsch process when it is implemented in a compact version.

A known method of producing a catalyst for the implementation of the Fischer-Tropsch process in a compact form, described in WO 2008104793 A3, 12/04/2008 of Oxford catalysts Ltd., in which the active metal is in the form of carbide. The catalyst includes a support and cobalt carbide. The cobalt content is 10-50 mass%, preferably about 30 mass%. The promoters are selected from the series: Pd, Pt, Rh, Ru, Ir, Au, Ag and Os, preferably Ru. The content of promoters is about 0.2 mass%. Other metals such as Zn, Cu, Mn, Mo, W and others in an amount of about 3% can be added as modifiers. A catalyst preparation method involves impregnating a support with a solution of an active metal precursor and a polar organic compound, where the solution contains a small amount of water or does not contain water, drying and calcining at atmospheric pressure and 500 ° C in an oxygen-free atmosphere or with a small oxygen content to form metal carbides. The described catalysts in the Fischer-Tropsch synthesis at 220 ° C, 17.5 atm, a space velocity of 2000 h ^-1 and a ratio of H ₂ / CO = 2 make it possible to achieve a CO conversion of 50-84% and a high molecular weight hydrocarbon productivity of 160-280 kg / m ³ _cat ⋅h

The disadvantage of this method of producing catalysts for the Fischer-Tropsch process for the compact implementation of the process is their low productivity and the presence of cobalt in the composition of the carbide catalyst, which under conditions of high-performance hydrocarbon synthesis will lead to increased methane formation and low selectivity of the synthesis gas processing into high molecular weight hydrocarbons.

A known method of producing a catalyst for the implementation of the Fischer-Tropsch process in a compact embodiment, comprising a carrier and cobalt deposited on a carrier described in WO 2012107718 A3, 01/03/2013 and 2013114098 A1, 08.08.2013. The modified carrier is prepared by treating the carrier with a solution containing a titanium compound and a carboxylic acid, followed by drying at a temperature of 100-130 ° C and calcining at a temperature of 200-350 ° C. Application of the active component is carried out by repeatedly impregnating the modified carrier with a solution containing the active metal precursor and carboxylic acid, followed by drying and calcination. The carrier can be selected from the group: solid oxides, carbon, zeolites, boron nitride or silicon carbide. Suitable solid oxides are alumina, silicon, titanium, zirconium and zinc. The content of titanium oxide is 11-30 mass%. As the active metal, cobalt is used. As the promoter, Pd, Pt, Rh, Ru, Re, Ir, Au, Ag, Os with a content of from 0.01 to 30 mass%, preferably 0.2 mass%, are used. In addition, various modifiers Zr, Ti, V, Cr, Mn, Ni, Cu and others can be used in an amount of about 3 mass%.

The disadvantage of this method of producing a catalyst is the strong interaction of titanium oxide with the active component cobalt, leading to the formation of refractory compounds and a decrease in the activity of the catalyst, which will make impossible long-term stable operation in the high-performance mode of the catalyst obtained in this way.

Also known is a method of producing a catalyst for the implementation of the Fischer-Tropsch process in a compact embodiment by the coprecipitation method described by EA 014214 B1, 10.29.2010. The proposed catalyst obtained by the coprecipitation method is suitable for the implementation of the Fischer-Tropsch process at volumetric speeds of the synthesis gas in the range of 1000-25000 h ^-1 , i.e. under the conditions of the implementation of the Fischer-Tropsch process in a compact form, and contains 5-40 wt.% cobalt and the carrier is aluminum oxide, including 1-5 wt.% lithium by weight of the carrier. The tests of the catalyst were carried out in a fixed-bed reactor with an inner diameter of 4 mm when the catalyst was diluted with silicon carbide at a CO conversion of about 50%.

The disadvantage of this catalyst is the poor thermal stability of the catalyst, as evidenced by the need for dilution of the catalyst with silicon carbide and the Fischer-Tropsch process with CO conversion of about 50%, while for the effective conversion of synthesis gas to synthetic hydrocarbons, the CO conversion should be at least 70% . A disadvantage of this catalyst is the use of lithium-modified alumina as a carrier, since lithium increases methane formation, especially in high-performance conditions and at high CO conversion, and alumina forms non-reducible compounds with cobalt under conditions of high-performance Fischer-Tropsch synthesis.

The closest technical solution to this invention when obtaining a catalyst for the implementation of the Fischer-Tropsch process in a compact embodiment, the impregnation method is the catalyst and the method described in patent US 7217741 B2, 05.15.2007 from company Compact GTL. To carry out the Fischer-Tropsch synthesis process in a compact version, a catalyst of the following composition is used: the catalyst support is γ-alumina stabilized with lanthanum, the cobalt content is 9-29% by weight of the catalyst, ruthenium, platinum or gadolinium oxide are used as a promoter in the Co ratio / promoter from 10000/1 to 10/1. The Fischer-Tropsch synthesis reaction is carried out at a temperature of 250-280 ° C, a pressure of 2.5 MPa when the synthesis gas is converted in two stages and the degree of conversion per passage is not more than 65%.

The disadvantage of this catalyst is the low content of the active component, which makes long-term stable operation of the catalyst in a high-performance mode difficult, the low conversion of raw materials in one pass and the high temperatures necessary to achieve such a level of conversion at which a high proportion of methane and light hydrocarbons in the synthesis products is likely , which will not allow to efficiently process synthesis gas into synthetic hydrocarbons during the implementation of the Fischer-Tropsch process in a compact version when using the proposed catalyst.

The closest technical solution to this invention when obtaining a catalyst for the implementation of the Fischer-Tropsch process in a compact embodiment, the coprecipitation method is the catalyst described in WO 2001087480, 11/22/2001. The Fischer-Tropsch synthesis catalyst has a cobalt content of 40-85 mass% and a specific surface area of metallic cobalt after reduction of more than 25 m ² / g. The catalyst is obtained by coprecipitation of cobalt carbonate from a basic solution having a pH in the range of 7-12, containing ammonia, ammonium carbonate, cobalt carbonate and water, and a carrier in a mass ratio of carrier: cobalt of 0.15-0.5 when the mixture is heated to a temperature of 60- 110 ° C for a period of time until the solution becomes clear. Then the solid was filtered off, washed and dried in air at a temperature of 120 ° C and, if necessary, calcined in air. It is proposed to use aluminum oxide as a carrier of such a catalyst.

The disadvantage of such a catalyst is the use of alumina as a catalyst carrier, since it is known that alumina, when reacted with cobalt at the temperatures of the Fischer-Tropsch process, as well as during calcination and activation of the catalyst, forms non-reducible compounds, for example, cobalt aluminates, which leads to the exclusion parts of cobalt from the active state and rapid deactivation of alumina-cobalt catalysts under the conditions of high-performance Fischer-Tropsch synthesis, suggesting significant Tel'nykh exotherm causes local overheating of the catalyst surface, and high water vapor partial pressure that intensifies the formation of inactive cobalt compounds.

These disadvantages suggest the impossibility of using the catalyst obtained by coprecipitation in accordance with patent WO 2001087480, 11/22/2001, in the implementation of the Fischer-Tropsch process in a compact form.

The technical task of the claimed group of inventions is to develop a catalyst suitable for the implementation of the Fischer-Tropsch process in a compact version, and a method for producing such a catalyst (options). The implementation of the claimed group of inventions eliminates these disadvantages of the known catalysts and methods for their preparation.

The technical result from the implementation of the claimed group of inventions is to achieve the selectivity of the proposed catalyst with respect to the formation of C ₅₊ hydrocarbons of at least 62% with CO conversion of at least 70% and a maximum catalyst productivity for high molecular weight hydrocarbons of at least 1000 kg / m ³ _cat ⋅ h.

The activity, performance, and selectivity of cobalt-containing catalysts in the Fischer-Tropsch synthesis, as well as the stability of their operation, is influenced by the particle size of the cobalt metal, the phase composition of the catalyst, the nature and structural characteristics of the support, and the introduction of promoters. The selection of the optimal combination of these parameters and the preparation conditions of the catalysts allows us to implement a sufficient number of active centers for the synthesis of high molecular weight hydrocarbons to achieve effective and stable operation of the catalysts in high-performance modes.

The high-performance catalysts for the implementation of the Fischer-Tropsch synthesis in a compact form should have a high density of active centers, providing a high specific reaction rate, as well as the ability to maintain high activity for a long time. To create such catalysts, a high cobalt content is necessary with its high dispersion on the surface of the support and optimal interaction with the support, depending on the chemical nature of the latter. The high specific surface area of metallic cobalt after reduction (S _Co0 > 10 m ² / g) provides high catalyst activity, while the high dispersion of metallic cobalt particles (D _Co > 5%) improves the stability of the catalysts and increases the selectivity for the formation of high molecular weight hydrocarbons . When the particle size of metallic cobalt (d _Co ) is less than 4 nm, which corresponds to a dispersion of more than 25%, an increase in the cobalt-carrier interaction is characteristic, which leads to a decrease in the activity of the catalyst and its rapid deactivation.

The use of oxides with a high acidity of the surface, such as alumina, also leads to an increase in the interaction of the active component with the carrier. As a result of the interaction of cobalt and alumina compounds during the synthesis of the catalyst, its activation and the production of synthetic hydrocarbons in its presence, irreplaceable inactive compounds are formed that reduce the content of cobalt available for the formation of active centers, which can lead to irreversible catalyst deactivation. Therefore, in order to exclude the possibility of the formation of a significant amount of such inactive cobalt-containing compounds in a high-performance catalyst for the implementation of the Fischer-Tropsch synthesis in a compact version, it is preferable to use oxides that do not form non-reducible cobalt-containing compounds, such as, for example, silicon oxide and zirconium oxide, or modified alumina zirconium oxide or silicon to reduce the acidity of the surface.

Surface modification of non-dispersive supports, for example, silicon oxide, can increase the dispersion of the active component in a catalyst based on such a support.

The technical result from the implementation of the claimed group of inventions is achieved in that the catalyst for the implementation of the Fischer-Tropsch process in a compact form has a specific surface area in the calcined state of 50-92 m ² / g of catalyst and after recovery, the specific surface area of metallic cobalt is 10.3-25, 5 m ² / g of catalyst, the average particle size of metallic cobalt is 5.0-18.5 nm and the particle size dispersion is 5.4-20.0%, contains 41-50 mass% of cobalt by weight of the calcined catalyst and a carrier having a specific surface area it is 86-423 m ² / g and the pore volume of the carrier is 0.20-1.07 cm ^{3 /} g selected from the group: zirconium oxide or alumina modified by applying zirconium oxide, or silicon oxide modified by applying zirconium oxide, or oxide zirconium, modified by applying alumina, or silicon oxide, modified by applying alumina, while the amount of modifying oxide is from 10 to 40 mass% of the mass of the carrier, the rest.

According to the first embodiment, the method of producing a catalyst for the implementation of the Fischer-Tropsch process in a compact form consists in repeatedly impregnating a carrier selected from the group: zirconium oxide or alumina modified by applying zirconium oxide, or silicon oxide modified by applying zirconium oxide, or zirconia modified by applying alumina, or silica, modified by applying alumina, while the amount of modifying oxide is from 10 to 40 mass% of the weight of the nose ator, aqueous cobalt precursor - cobalt nitrate. Each stage of impregnation is carried out with stirring for 0.2-3 h of the support or catalyst precursor in an excess volume of a solution of cobalt nitrate in water compared to the pore volume of the support, followed by filtration of the excess solution, drying of the catalyst precursor at 80-150 ° C for 8 -16 hours and its calcination at 270-500 ° C for 2-24 hours after each stage of application of the active component. The amount of impregnation is determined by the achievement of the cobalt content in the catalyst in the range of 41-50% by weight of the calcined catalyst.

The method involves the additional introduction of a promoter selected from the group: rhenium, ruthenium in an amount of 0.5-2.0 mass%, which helps to increase the dispersion of metallic cobalt on the surface of the reduced catalyst, carried out by joint impregnation at each stage of impregnation.

According to the second variant, a method for producing a catalyst for the implementation of the Fischer-Tropsch process in a compact version, providing for the co-precipitation of a cobalt precursor - cobalt carbonate from a basic solution containing ammonia, ammonium carbonate, cobalt carbonate and water, co-heating the mixture with stirring until the color of the solution disappears, separating the precursor by filtration , drying and calcining, use a carrier selected from the group: zirconium oxide or alumina, modified by applying zirconium oxide, or silicon oxide, mod itsirovanny applying zirconium oxide, or zirconia modified by applying alumina or silica modified alumina application, the amount of modifying oxide is from 10 to 40 wt% of the weight of the carrier.

These distinguishing features are significant.

The preparation of the catalyst by the described methods makes it possible to use it for the implementation of the Fischer-Tropsch process in a compact form. The selectivity of the proposed catalyst in relation to the formation of C ₅₊ hydrocarbons is at least 62% with a CO conversion of at least 70%. The maximum productivity of the catalyst for high molecular weight hydrocarbons is at least 1000 kg / m ³ _cat ⋅ h.

The preparation according to this invention of a catalyst for the implementation of the Fischer-Tropsch process in a compact form is carried out by preliminary obtaining the carrier, followed by the introduction of active components into its composition. The main component of the carrier selected from the group: alumina, zirconia, silicon oxide, can be obtained by any method known in science and technology, for example, by calcining a precursor of the main component of the carrier, which are mainly inorganic compounds, in particular nitrates, oxonitrates, hydroxides and oxohydroxides, or by synthesis of a carrier with an ordered structure, for example, as a result of hydrothermal synthesis of mesoporous silicates.

Alumina and silica are modified by applying zirconia to their surface, and zirconia and silica are modified by applying alumina to their surface by any method known in the art, for example, by impregnation.

The catalyst obtained by the methods described above has a cobalt content in the calcined catalyst of 41-50 mass%, specific surface area after calcination of 50-92 m ² / g of catalyst, and after reduction of the catalyst in a stream of hydrogen with a space velocity of 3000 h ^-1 for 1 h at at a temperature of 400 ° C has a specific surface area of cobalt metal of 10.3-25.5 m ² / g of catalyst, an average particle size of cobalt metal of 5.0-18.5 nm and a particle size of 5.4-20.0%.

The content of cobalt and rhenium or ruthenium, if any, can be determined by any known method, for example, by the method of inductively coupled plasma — atomic electron spectroscopy.

Before carrying out the Fischer-Tropsch process in a compact form, the catalyst is activated.

The study of the catalysts in the Fischer-Tropsch synthesis in its compact form was carried out by passing synthesis gas through a fixed catalyst bed. The efficiency of the catalyst was evaluated by the residual content of carbon monoxide in the composition of the exhaust gases, selectivity for the formation of hydrocarbons With ₅₊ and performance for high molecular weight hydrocarbons with 1 m ^{3 of} catalyst per hour.

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

, где

where

- масса монооксида углерода в 1 м³ входящего в реактор газа;

- the mass of carbon monoxide in 1 m ³ entering the reactor gas;

- масса монооксида углерода в 1 м³ выходящего из реактора газа.

- the mass of carbon monoxide in 1 m ³ leaving the reactor gas.

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

, где

where

m _{C / C5 +} is the mass of carbon contained in liquid hydrocarbons resulting from the synthesis of gas entering the reactor from 1 m ³ ;

m _{C / COin} - mass of carbon contained in carbon monoxide in 1 m ^{3 of} gas entering the reactor;

m _{C / COout} - the mass of carbon contained in carbon monoxide in 1 m ³ leaving the reactor gas.

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

, где

where

m _{c5 +} is the mass of high molecular weight hydrocarbons resulting from the synthesis of 1 m ^{3 of the} synthesis gas entering the reactor;

Q _ν is the volumetric feed rate of the synthesis gas, h ^-1 .

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, by gas or gas-liquid chromatography.

The method is implemented in accordance with the following examples.

Example A is an example of comparison and illustrates the implementation of the method of producing a catalyst by impregnation in accordance with the analogue reproduced to illustrate the advantages of the claimed method using available materials.

Example B is an example of comparison and illustrates the implementation of a method for producing a catalyst by coprecipitation in accordance with an analog reproduced to illustrate the advantages of the claimed method using available materials.

Examples 1-16 show the implementation of the method according to this invention.

Example A

The composition catalyst (29% Co + 1% Ru + 69.3% γ-Al ₂ O ₃ + 0.7% La ₂ O ₃ ) was obtained using a support prepared by impregnating γ-Al ₂ O _{3 with an} aqueous solution of lanthanum hexahydrate nitrate followed by calcination at a temperature of 500 ° C for 4 h, has a specific surface area of 163 m ² / g and a pore volume of 0.48 cm ^{3 /} g. The resulting support was impregnated in two stages: in the first, 15 wt% Co was added from an aqueous solution cobalt hexahydrate nitrate, followed by drying at a temperature of 120 ° C for 12 hours and calcining at a temperature of 500 ° C for 4 hours, in the second stage local impregnated carrier 14 wt% Co and 1 wt% Ru from the aqueous solution of cobalt nitrate hexahydrate and ruthenium chloride hydrate, followed by drying at 120 ° C for 12 hours and calcination at 500 ° C for 4 hours.

The maximum performance in the presence of this catalyst under the conditions stated in patent US 7217741 B2, 05/15/2007, was achieved at 239 ° C and a space velocity of 10,000 h ^-1 .

Example B

The catalyst composition, mass%: (46.0Co + 54.0Al ₂ O ₃ ) is obtained by coprecipitation of cobalt carbonate from an aqueous solution of ammonium hydroxide and ammonium carbonate, containing, mass%: 13.0NH ₃ , 8.0 (NH ₄ ) ₂ CO ₃ , 9.0 cobalt carbonate and water - the rest, pH = 8.7, on alumina with a ratio of Al ₂ O ₃ / Co = 0.2. In the process of coprecipitation, the solution is heated with stirring to a temperature of 80 ° C, maintained for a period of time until the solution becomes transparent. The solid is then filtered off, washed and dried in air at 120 ° C and calcined in air at 400 ° C for 6 hours. The alumina used as a support for this catalyst is obtained by calcining aluminum hydroxide at a temperature of 500 ° C for 4 hours, has a specific surface area of 189 m ² / g and a pore volume of 0.45 cm ^{3 /} g.

Maximum productivity in the presence of this catalyst under the conditions stated in WO2001087480 was achieved at 220 ° C. and a space velocity of 11,000 h ⁻¹ .

Example 1

The composition catalyst, mass%: (48.0Co + 52.0ZrO ₂ ) is obtained by coprecipitation of cobalt carbonate from an aqueous solution of ammonium hydroxide and ammonium carbonate, containing, mass%: 10.0NH ₃ , 3.0 (NH ₄ ) ₂ CO ₃ , 8.0 cobalt carbonate, water - the rest, pH = 10.0 per zirconium oxide at a ratio of ZrO ₂ / Co = 0.4. In the process of coprecipitation, the solution is heated with stirring to a temperature of 85 ° C, maintained until the color disappears, filtered off, dried at 110 ° C for 12 hours and calcined at 450 ° C for 3 hours.

Zirconium oxide used as a carrier of this catalyst is obtained by calcining zirconium oxonitrate at a temperature of 400 ° C for 4 hours, has a specific surface area of 86 m ² / g and a pore volume of 0.2 cm ³ / g.

Maximum productivity in the presence of this catalyst was achieved at 246 ° C and a space velocity of 14,000 h ^-1 .

Example 2

The composition catalyst, mass%: (42.0Co + 23.2Al ₂ O ₃ + 34.8SBA-15) is obtained by coprecipitation of cobalt carbonate from an aqueous solution of ammonium hydroxide and ammonium carbonate, containing, mass%: 18.0NH ₃ , 3.0 (NH ₄ ) ₂ CO ₃ , 5.0 cobalt carbonate, water - the rest, pH = 10.5, on a carrier (40% Al ₂ O ₃ + 60% SBA-15) with a carrier / Co ratio of 0.3. In the process of coprecipitation, the solution is heated with stirring to a temperature of 95 ° C, kept until the color disappears, filtered off, dried at a temperature of 120 ° C for 8 hours and calcined at a temperature of 400 ° C for 2 hours.

The support of this catalyst is obtained by impregnating SBA-15 mesoporous silicate with an aqueous solution of aluminum nitrate, followed by calcination at 550 ° C for 5 hours, has a specific surface area of 107 m ² / g and a pore volume of 0.21 cm ³ / g.

Maximum productivity in the presence of this catalyst was achieved at a temperature of 241 ° C and a space velocity of 11000 h ^-1 .

Example 3

The catalyst composition, wt.%: (41.0Co + 5.9ZrO ₂ + 53.1Al ₂ O ₃ ) is obtained by coprecipitation of cobalt carbonate from an aqueous solution of ammonium hydroxide and ammonium carbonate, containing, wt.%: 15.0NH ₃ , 4.0 ( NH ₄ ) ₂ CO ₃ , 4.0 cobalt carbonate, water - the rest, pH = 11.0, on the carrier at a ratio of (10% ZrO ₂ + 90% Al ₂ O ₃ ) / Co = 0.3. In the process of coprecipitation, the solution is heated with stirring to a temperature of 98 ° C, kept until the color disappears, filtered off, dried at 105 ° C for 16 hours and calcined at a temperature of 250 ° C for 24 hours.

The support of this catalyst is obtained by impregnating alumina with an aqueous solution of zirconium oxonitrate, followed by calcining at a temperature of 500 ° C for 10 hours, has a specific surface area of 126 m ² / g and a pore volume of 0.52 cm ³ / g.

Maximum productivity in the presence of this catalyst was achieved at 241 ° C and a space velocity of 10,000 h ^-1 .

Example 4

The catalyst composition, mass%: (47.0Co + 10.6Al ₂ O ₃ + 42,4ZrO ₂ ) is obtained by coprecipitation of cobalt carbonate from an aqueous solution of ammonium hydroxide and ammonium carbonate, containing, mass%: 13.0NH ₃ , 7.0 ( NH ₄ ) ₂ CO ₃ , 8.0 cobalt carbonate, water - the rest, pH = 10.2, on the carrier at a ratio of (20% Al ₂ O ₃ + 80% ZrO ₂ ) / Co = 0.5. In the process of coprecipitation, the solution is heated with stirring to a temperature of 90 ° C, kept until the color disappears, filtered off, dried at 115 ° C for 13 hours and calcined at a temperature of 500 ° C for 7 hours

A support of this catalyst is obtained by coprecipitation of aluminum nitrate with an aqueous solution of ammonium hydroxide on zirconia, followed by calcination at 550 ° C for 5 hours, has a specific surface area of 113 m ² / g and a pore volume of 0.29 cm ³ / g.

The maximum performance in the presence of this catalyst was achieved at a temperature of 249 ° C and a space velocity of 13000 h ^-1 .

Example 5

The composition catalyst, wt%: (46.0Co + 13.5ZrO ₂ + 40.5SiO ₂ ) is obtained by coprecipitation of cobalt carbonate from an aqueous solution of ammonium hydroxide and ammonium carbonate, containing, wt%: 13.0NH ₃ , 5.0 (NH ₄ ) ₂ CO ₃ , 6.0 cobalt carbonate, water - the rest, pH = 10.5, on the carrier at a ratio of (25% ZrO ₂ + 75% SiO ₂ ) / Co = 0.35. In the process of coprecipitation, the solution is heated with stirring to a temperature of 94 ° C, maintained until the color disappears, filtered off, dried at 115 ° C for 14 hours and calcined at a temperature of 280 ° C for 20 hours.

The support of this catalyst is obtained by impregnating silicon oxide with an aqueous solution of zirconium oxonitrate, followed by calcining at a temperature of 450 ° C for 12 hours, has a specific surface area of 126 m ² / g and a pore volume of 0.52 cm ³ / g.

Maximum productivity in the presence of this catalyst was achieved at 241 ° C and a space velocity of 10,000 h ^-1 .

Example 6

The composition catalyst, mass%: (50.0Co + 10.0Al ₂ O ₃ + 40,0SBA-15) was obtained by triple impregnation of the support (20 mass% Al ₂ O ₃ +80 mass% SBA-15) with an aqueous solution of cobalt nitrate. After each stage of impregnation, drying is carried out at a temperature of 140 ° C for 10 hours and calcination at a temperature of 450 ° C for 3 hours

The support of this catalyst is obtained by impregnating SBA-15 mesoporous silicate with an aqueous solution of aluminum nitrate, followed by calcination at 550 ° C for 5 hours, has a specific surface area of 399 m ² / g and a pore volume of 0.49 cm ³ / g.

The maximum performance in the presence of this catalyst was achieved at a temperature of 250 ° C and a space velocity of 12000 h ^-1 .

Example 7

The composition catalyst, mass%: (50.0Co + 13.5ZrO ₂ + 36.5SBA-15) is obtained by triple impregnation of the support (27 mass% ZrO ₂ +73 mass% SBA-15) with an aqueous solution of cobalt nitrate. After each stage of impregnation, drying is carried out at a temperature of 95 ° C for 12 hours and calcination at a temperature of 500 ° C for 4 hours.

The support of this catalyst is obtained by impregnating SBA-15 mesoporous silicate with an aqueous solution of zirconium oxonitrate, followed by calcining at a temperature of 500 ° C for 10 hours, has a specific surface area of 185 m ² / g and a pore volume of 0.25 cm ³ / g.

The maximum performance in the presence of this catalyst was achieved at a temperature of 246 ° C and a space velocity of 12000 h ^-1 .

Example 8

The catalyst composition, mass%: (44.0Co + 56.0ZrO ₂ ) is obtained by four-fold impregnation of zirconium oxide with an aqueous solution of cobalt nitrate. After each stage of impregnation, drying is carried out at a temperature of 110 ° C for 12 hours and annealing at a temperature of 270 ° C for 24 hours.

The carrier of this catalyst is zirconium oxide obtained from an aqueous solution of ZrO (NO ₃ ) ₂ ⋅ 2H ₂ O when it is coprecipitated with ammonium hydroxide in the presence of P123 copolymer in a molar ratio of P123 / Zr = 0.03 at a temperature of 88 ° C for 24 hours with constant stirring followed by drying at 110 ° C for 24 hours and calcining at 500 ° C for 4 hours, has a specific surface area of 104 m ² / g and a pore volume of 0.21 cm ³ / g

The maximum performance in the presence of this catalyst was achieved at a temperature of 250 ° C and a space velocity of 16,000 h ^-1 .

Example 9

The composition catalyst, mass%: (41.0Co + 5.9Al ₂ O ₃ + 53.1MSM-41) is obtained by triple impregnation of the support (10 mass% Al ₂ O ₃ +90 mass% MSM-41) with an aqueous solution of cobalt nitrate. After each stage of impregnation, drying is carried out at a temperature of 130 ° C for 9 hours and calcination at a temperature of 300 ° C for 18 hours.

The support of this catalyst is obtained by impregnating the mesoporous silicate MCM-41 with an aqueous solution of aluminum nitrate, followed by calcination at 550 ° C for 5 hours, has a specific surface area of 423 m ² / g and a pore volume of 0.95 cm ³ / g.

Maximum productivity in the presence of this catalyst was achieved at 246 ° C and a space velocity of 11000 h ^-1 .

Example 10

The catalyst composition, mass%: (46.0Co + 10.8Al ₂ O ₃ + 43,2ZrO ₂ ) is obtained by triple impregnation of the support (20 mass% Al ₂ O ₃ +80 mass% ZrO ₂ ) with an aqueous solution of cobalt nitrate. After each stage of impregnation, drying is carried out at a temperature of 115 ° C for 10 hours and annealing at a temperature of 300 ° C for 21 hours.

The support of this catalyst is obtained by coprecipitation of aluminum nitrate with an aqueous solution of ammonium hydroxide in the presence of zirconium oxide, followed by calcination at 550 ° C for 5 hours, has a specific surface area of 112 m ² / g and a pore volume of 0.24 cm ³ / g.

Maximum productivity in the presence of this catalyst was achieved at 243 ° C and a space velocity of 11000 h ^-1 .

Example 11

The catalyst composition, mass%: (49.0Co + 51.0ZrO ₂ ) is obtained by four-fold impregnation of zirconium oxide with an aqueous solution of cobalt nitrate. After each stage of impregnation, drying is carried out at a temperature of 140 ° C for 10 hours and calcination at a temperature of 400 ° C for 3 hours.

Zirconium oxide used as a carrier of this catalyst is obtained by calcining zirconium oxonitrate at a temperature of 400 ° C for 4 hours, has a specific surface area of 86 m ² / g and a pore volume of 0.2 cm ³ / g.

The maximum performance in the presence of this catalyst was achieved at a temperature of 250 ° C and a space velocity of 18,000 h ^-1 .

Example 12

The composition catalyst, mass%: (47.0Co + 5.3ZrO ₂ + 47.7Al ₂ O ₃ ) was obtained by triple impregnation of the support — 10 mass% ZrO ₂ / Al ₂ O _{3 with an} aqueous solution of cobalt nitrate. After each stage of impregnation, drying is carried out at a temperature of 80 ° C for 16 hours and calcination at a temperature of 500 ° C for 2 hours.

The support of this catalyst is obtained by impregnating mesoporous alumina with an aqueous solution of zirconium oxonitrate, followed by calcining at a temperature of 500 ° C for 10 hours, has a specific surface area of 372 m ² / g and a pore volume of 1.07 cm ³ / g.

The maximum performance in the presence of this catalyst was achieved at a temperature of 250 ° C and a space velocity of 12000 h ^-1 .

Example 13

The composition catalyst, mass%: (50.0Co + 20.0Al ₂ O ₃ + 30.0MSM-41) is obtained by triple impregnation of the support (40 mass% Al ₂ O ₃ +60 mass% MSM-41) with an aqueous solution of cobalt nitrate. After each stage of impregnation, drying is carried out at a temperature of 115 ° C for 14 hours, calcination at a temperature of 350 ° C for 12 hours

The support of this catalyst is prepared by impregnating the mesoporous silicate MCM-41 with an aqueous solution of aluminum nitrate, followed by calcination at 550 ° C for 5 hours, has a specific surface area of 255 m ² / g and a pore volume of 0.67 cm ³ / g.

The maximum performance in the presence of this catalyst was achieved at a temperature of 250 ° C and a space velocity of 14,000 h ^-1 .

Example 14

The composition catalyst, mass%: (50.0Co + 15.0Al ₂ O ₃ + 35,0ZrO ₂ ) is obtained by triple impregnation of the support (30 mass% Al ₂ O ₃ +70 mass% ZrO ₂ ) with an aqueous solution of cobalt nitrate. After each stage of impregnation, drying is carried out at a temperature of 110 ° C for 10 hours and calcination at a temperature of 350 ° C for 8 hours.

The support of this catalyst is obtained by impregnation of zirconium oxide with an aqueous solution of aluminum nitrate, followed by calcination at a temperature of 500 ° C for 10 hours, has a specific surface area of 117 m ² / g and a pore volume of 0.22 cm ³ / g.

The maximum performance in the presence of this catalyst was achieved at a temperature of 247 ° C and a space velocity of 10,000 h ^-1 .

Example 15

The catalyst composition, mass%: (49.0Co + 2.0Re + 51.0ZrO ₂ ) is obtained by four-fold impregnation of zirconium oxide with an aqueous solution of cobalt nitrate and ammonium perrenate. After each stage of impregnation, drying is carried out at a temperature of 150 ° C for 9 hours and annealing at a temperature of 300 ° C for 22 hours

Zirconium oxide used as a carrier of this catalyst is obtained by calcining zirconium oxonitrate at a temperature of 400 ° C for 4 hours, has a specific surface area of 86 m ² / g and a pore volume of 0.2 cm ³ / g.

The maximum performance in the presence of this catalyst was achieved at a temperature of 246 ° C and a space velocity of 17,000 h ^-1 .

Example 16

The catalyst composition, mass: (50.0Co + 0.5Ru + 20.0Al ₂ O ₃ + 30SBA-15) is obtained by triple impregnation of the carrier (40 mass% Al ₂ O ₃ +60 mass% SBA-15) with an aqueous solution of cobalt nitrate and ruthenium chloride. After each stage of impregnation, drying is carried out at a temperature of 90 ° C for 14 hours and calcination at a temperature of 500 ° C for 5 hours.

The support of this catalyst is obtained by impregnating SBA-15 mesoporous silicate with an aqueous solution of aluminum nitrate, followed by calcining at a temperature of 500 ° C for 10 hours, has a specific surface area of 107 m ² / g and a pore volume of 0.21 cm ³ / g.

The maximum performance in the presence of this catalyst was achieved at a temperature of 250 ° C and a space velocity of 14,000 h ^-1 .

The table shows the performance of the Fischer-Tropsch synthesis in a compact version, in the presence of catalysts prepared in accordance with examples of comparison A and B and examples of the implementation of the invention 1-16, for maximum performance mode set for each example.

The catalysts prepared in accordance with the comparative examples have a low efficiency in the synthesis of hydrocarbons according to the Fischer-Tropsch method in its compact form, which is characterized by low selectivity in relation to the formation of high molecular weight hydrocarbons equal to 38-52%, and the maximum catalyst productivity equal to 523-754 kg / m ³ _cat ⋅h. The catalyst and methods for its preparation of this invention provide high efficiency in the synthesis of high molecular weight hydrocarbons during the Fischer-Tropsch process in a compact version with a selectivity (S _{C5 +} ,%) with respect to the formation of C ₅₊ hydrocarbons of at least 62% during the conversion of CO (K _CO ,%) more than 70% and maximum catalyst productivity for high molecular weight hydrocarbons (P _{C5 +} , kg / m ³ _cat ⋅ h) of at least 1000 kg / m ³ _cat ⋅ h.

The catalysts obtained in accordance with the described method are more efficient for the implementation of the Fischer-Tropsch process in a compact form compared to catalysts known in the art.

Claims (5)

1. The catalyst for the implementation of the Fischer-Tropsch process in a compact form, having a specific surface area in the calcined state of 50-92 m ² / g of catalyst and after recovery, the specific surface area of metallic cobalt is 10.3-25.5 m ² / g of catalyst, average the particle size of cobalt metal is 5.0-18.5 nm and the particle size dispersion is 5.4-20.0% and containing 41-50 wt.% cobalt by weight of the calcined catalyst and a carrier having a specific surface area of 86-423 m ² / g and a pore volume of the carrier of 0.20-1.07 cm ³ / g, selected from the group: zirconium oxide silt and alumina modified by applying zirconia, or silica modified by applying zirconia, or zirconia modified by applying alumina, or silicon oxide, modified by applying alumina, wherein the amount of modifying oxide is from 10 to 40% by weight carrier mass. 2. The catalyst according to claim 1, characterized in that it further comprises a promoter selected from the group: rhenium, ruthenium, in an amount of from 0.5 to 2.0 wt.%. 3. A method of producing a catalyst for the implementation of the Fischer-Tropsch process in a compact embodiment according to claim 1, which consists in repeatedly impregnating a support selected from the group: zirconium oxide or alumina modified by applying zirconium oxide, or silicon oxide modified by applying zirconium oxide or zirconia modified by applying alumina or silica modified by applying alumina, wherein the amount of modifying oxide is from 10 to 40 mass% about the mass of the carrier, until the content of 41-50 wt.% cobalt of the mass of the calcined catalyst is reached, with an aqueous solution of the cobalt precursor cobalt nitrate, followed by drying at a temperature of 80-150 ° C for 9-16 hours and annealing at a temperature of 270-500 ° C within 2-24 hours after each stage of impregnation. 4. The method according to p. 3, characterized in that it additionally contribute a promoter selected from the group: rhenium, ruthenium, in an amount of from 0.5 to 2.0 wt.% Co-impregnation at each stage of impregnation. 5. A method of producing a catalyst for the implementation of the Fischer-Tropsch process in a compact form according to claim 1, which provides for the coprecipitation of a cobalt precursor — cobalt carbonate from a basic solution containing ammonia, ammonium carbonate, cobalt carbonate and water, heating the mixture with stirring until the color of the solution disappears, separation of the precursor by filtration, drying and calcination, characterized in that they use a carrier selected from the group: zirconium oxide or alumina modified by applying zirconium oxide, or cream oxide modified by applying zirconium oxide, or zirconium oxide modified by applying alumina, or silicon oxide modified by applying alumina, wherein the amount of modifying oxide is from 10 to 40% by weight of the carrier.