Catalyst for fischer-tropsch synthesis and method for its producing

FIELD: chemistry.

SUBSTANCE: catalyst for Fischer-Tropsch synthesis is described, with metal from group VIII of the periodic table as an active component and carrier containing the oxide constituent and scale shaped metallic aluminum. The method for preparation of catalyst for Fischer-Tropsch synthesis is also described which consists in application of the active component upon the carrier by use of pipette; the carrier is prepared from paste by extrusion, the extrudates are exposed to air, dehumidified and baked and the used paste contains the oxide constituent, scale shaped metallic aluminium, binding agent and plasticiser.

EFFECT: catalyst's activity and selectivity in regard to high molecular hydrocarbons are increased.

15 cl, 1 tbl, 15 ex

 

The technical field to which the invention relates.

The invention relates to petrochemistry, gas chemistry, coal chemistry and relates to a catalyst for Fischer-Tropsch synthesis and the method of obtaining the specified catalyst.

The level of technology

The Fischer-Tropsch synthesis proceeds in the presence of catalysts based on metals of group VIII of the Periodic table. The composition of the catalyst determines the composition of the products obtained.

the Fischer-Tropsch process is exothermic and proceeds at high pressure. To maintain a high activity and selectivity of catalysts in this reaction needs such optimization of its members, which would reduce the likelihood of overheating that adversely affect the selectivity of the catalyst for the education of target products, leading to the most prevalent reaction of direct hydrogenation of CO to methane and deactivation of the catalyst [B.Jager, R.Espinoza "Advances in low temperature Fischer-Tropcsh synthesis", Catal.Today, 1995, V.23 supported, p.17-28].

The well-known two main options to resolve the above problems. In one case the process is carried out in liquid-phase conditions. When this liquid phase plays the role of reaction and the heat conductive environment at the same time, and the catalyst in suspension distributed in the liquid phase. Another solid catalyst in the form of granules, rings, etc. that form natvig the first layer, is placed inside the tube, separating the gas space with the catalyst and the liquid phase (water), through which the heat. In this case a large role in the dissipation plays thermal conductivity of the solid catalyst.

Known catalyst for use in the reactor with a fixed bed for the conversion processes, in particular, for obtaining hydrocarbons from synthesis gas [international application WO 02/07872 A1 (2002)]. The catalyst is a catalytically active metal of group VIII deposited on the oxide carrier, which is covered with a metal core made of aluminum, iron, copper, titanium or mixtures thereof. The metal base has the shape of a grid, a honeycomb or sponge. The drawback of such catalysts, called "korotkovym", is the difficulty of their preparation.

In addition, when using Korotkevich catalysts, the concentration of the catalytically active component in the reaction volume is low, which reduces the efficiency of the process and increases the dimensions of the reactor.

Known catalyst for Fischer-Tropsch synthesis, which represents a ceramic or metal monolith structure with a system of channels, the walls of which are covered with oxide media (Al2O3, SiO2, TiO2or zeolite), the active component (Co, Fe, Ru, Ni, and combinations thereof) and the promoter (Re, Pt, Ir, Rh, Pd, Ru is their combination) [U.S. Patent US 6,211,255 B1]. The active metal and the promoter was applied on the oxide carrier by impregnation, dried at 95°C for 2 days and was progulivali in air at 300°C for 16 h, the catalyst was crushed, mixed with water and applied to a ceramic or metal monolith with a density of cells 400 cells/inch, was dried at 130°16 h and was progulivali in air at 400°2 o'clock the disadvantages of such a catalyst is necessary to include the complexity of preparation, significant dilution of the catalytically active component carrier and, as a consequence, the low activity in the synthesis (conversion WITH less than 30%). In addition, the process proceeds in the Taylor flow, making it difficult for heat and mass transfer.

Closest to the proposed invention the catalyst is a catalyst for the synthesis of aliphatic hydrocarbons from CO and H2based on cobalt [Patent RU 2256501 S1 (2005)], which contains as a carrier of a metal powder of aluminum, in addition, may include a promoter selected from the group of metal-oxide - ZrO2or La2About3or2O - or metal - Re or Ru, or Pd, or Pt, and has the following composition in wt.%:

Co10-50,
The promoter0,5-3,
Al50-90.

Rolled the ATOR is prepared by impregnation of aluminum powder with an aqueous solution of cobalt nitrate with subsequent drying in a water bath and calcination in a stream of air at 450° C for 1 h Treatment with hydrogen is carried out at a temperature of 400-600°C for 1-5 h at a feed rate of N2- 100-3000 h-1. The synthesis is carried out at atmospheric pressure and temperatures 160-230°from a mixture of the composition: H266-68 mol.% and WITH 32-34 mol.%. The disadvantage of this catalyst is not sufficiently high activity, selectivity and performance when operating in an industrial environment.

Also known preparation method of catalyst for obtaining hydrocarbons and/or oxygen-containing derivatives from synthesis gas, wherein the catalyst is prepared by mixing powders of the active, heat-conductive and a pore-forming components with the subsequent shaping of the catalyst to pelletizing or rolling [international application WO 2004/069407 A1 (2004)]. As an active ingredient using a metal of group VIII deposited on an oxide carrier. As the heat-conducting component is used metallic copper, zinc, aluminum, tin or their alloys. As a pore-forming component is used, the oxide, hydroxide, carbonate, hydroxycarbonate or salt of one or more metals that are included with thermally or catalytically active component. The ratio of the mass content of the pore-forming agent to the heat transfer does not exceed 4, and catalytically asset is wow to the amount of heat-conductive and a pore-forming agent not less than 0.25. The content of the active metal in the catalytically active agent is less than 2 wt.%. The body of catalyst shape of a cylinder or a perforated cylinder or plate or a perforated plate. thermal treatment is carried out in a stream of hydrogen containing gas at temperatures above 400°or in two stages: in a current of inert gas at temperatures above 400°and in a current of hydrogen containing gas at temperatures above 300°C. the Disadvantages of such a catalyst is the complexity of its preparation and the low activity in the synthesis (conversion FROM does not exceed 38%), and insufficient high selectivity for hydrocarbons with high molecular weight.

Disclosure of inventions

The problem solved by the claimed inventions is to create a highly efficient catalyst for Fischer-Tropsch synthesis and method of its production.

Unified technical result is to increase the activity and selectivity of the catalyst in respect of hydrocarbons with high molecular weight by increasing its thermal conductivity.

The technical result is achieved by the fact that the catalyst for Fischer-Tropsch synthesis contains as an active component, a metal of group VIII of the Periodic system of Mendeleev and the media containing oxide component and aluminum metal in the form of scales.

The oxide component may contain aluminum oxide and/or silicon oxide and/or titanium oxide and/or zirconium oxide.

As promoters can be used, the metal is zirconium or metals VII-VIII groups of the Periodic system of Mendeleev's and/or their oxides, the content of promoters is 0.1-5% by weight of the catalyst.

Flakes of aluminum metal have a thickness of not more than 5 μm, and the linear dimension along the surface from 0.02 mm in the shortest dimension up to 3 mm in the longest dimension (preferably, linear size is in the range of 0.02-0.1 mm).

In particular, if the content of metallic aluminum in the form of flakes is 1-25% by weight of the catalyst.

The technical result is also achieved by the fact that the method of producing catalyst for Fischer-Tropsch synthesis, is that the active component is applied by impregnation to the media, which is prepared from the paste by extrusion, the extrudates stand in the air, dried and calcined, and use the paste contains an oxide component, the metallic aluminum in the form of flakes and binder.

As the oxide component can be used with aluminum oxide and/or silicon oxide and/or titanium oxide and/or zirconium oxide.

The content of metallic aluminum in the form of flakes can be 1-25% by weight of the catalyst.

As a binder can be used boehmite in the amount of 5-15% by weight of the catalyst.

The paste may contain a plasticizer and/or a pore-forming component.

The formation of the carrier can be carried out by extrusion of the paste with subsequent heat treatment and grinding to a fraction of the required size.

The introduction of the active component carried out by impregnation of a formed carrier with a solution of salts of the respective metals to its content of 5-40% by weight of the catalyst.

In the media can be entered promoters by impregnation of the support with a solution of their salts content of 0.1-5% by weight of the catalyst.

The implementation of the invention

The method of preparation of the catalyst proposed in the present invention is the preparation of a paste containing oxide component, the metal powder of aluminum, dimethyl ether, binder - boehmite, water, plasticizer and pore-forming component, extrusion, drying and calcination, followed by successive stages of impregnation with a solution of salts of the metals to make 5-40 wt.% the active component, and optionally, 0.1 to 5% promoter with intermediate stages of drying and calcination.

It is established that the use of catalyst, corresponding to the invention, the Fischer-Tropsch synthesis leads to high user and selectivity of the target product and a low selectivity by-product - the methane.

At the first stage of preparation of the catalyst prepared media. For this mix of metallic aluminum in the form of flakes with dimethyl ether, oxide component carrier, boehmite and a pore-forming component dimethyl ether, distilled water, nitric acid and plasticizer to paste, ekstragiruyut, stand in the air for 8-15 h, dried in an oven at 60-110°and calcined in a stream of air or inert gas at 110-550° for 6-20 hours. The active ingredient is administered by impregnation in several stages from a solution of salts of metals of group VIII (nitrate, acetate, formate, acetylacetonate, etc.). At each stage, the sample is dried on a water bath and the resulting catalyst precursor is dried and/or calcined in a stream of air at a temperature of from 100 to 1000°C for 0.5 to 10 hours. If necessary, similarly injected metal or oxide promoter.

Before synthesis, the sample of catalyst is activated by reduction in hydrogen flow (volumetric rate of 100-5000 h-1) at a temperature of 300-600°C for 0.5 to 5 hours

The synthesis of hydrocarbons from CO:N2carried out in a tubular reactor with a fixed bed of the catalyst at pressures of 0.1-4 MPa and a temperature of 150-300°C. the Molar ratio of CO/H2in the synthesis gas is 1/1-3. C the MES-gas may contain up to 25% vol. of nitrogen.

Example 1.

A sample of catalyst comprising 30%/(Al2About3+25%Al) was prepared by the following method.

To 2 g of boehmite SB-1 add a mixture of 0.45 ml of HNO3(64%), 8 ml of distilled water and 0.6 g of the plasticizer triethylene glycol (TEG). Mix thoroughly until smooth. To a mixture of 1.2 g of pore-forming component of methylcellulose and mix thoroughly until smooth. To the mixture is added 3.5 g of a powder of aluminum metal in the form of flakes, soaked in 3.5 ml of dimethyl ether, and mix thoroughly until smooth. Next, to the mixture of 4.5 g of the powder of Al2About3thoroughly mix until smooth and place in an extruder with Villeroy 2.5 mm extrudates stand in the air for 10 h and placed in a drying Cabinet. The mode of drying in a drying Cabinet: 60°C - 2 h, 80°C - 2 h, 110°C - 2 tsp Dried extrudates loaded into a quartz flow reactor and calcined in a stream of air, raising the temperature from 110 to 450°With a speed of 3-4°/min. At a temperature of 450°With stand 4 hours extrudates are cooled in a stream of air discharged from the reactor and crushed to a fraction of a 2.5×2-3 mm.

Cobalt is applied from an aqueous solution of its nitrate in three successive impregnation.

1 impregnation. 7,05 g of cobalt nitrate dissolved in distilled water and added to 10 g of the obtained carrier. mesh placed in a porcelain Cup and dried on a water bath for 30-60 min, then calcined in air flow at a temperature of 400°C for 1 h

2 impregnation. Like the first.

3 impregnation. 7,05 g of cobalt nitrate dissolved in distilled water and added to the material obtained in stage 2. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min

Before synthesis, the sample of catalyst was activated in a stream of hydrogen (O.S 3000 h-1) at 450°C for 1 h Synthesis of hydrocarbons is carried out in a tubular reactor with a fixed bed of catalyst at a pressure of 2 MPa and a temperature of 160-240°using synthesis gas with a molar ratio of CO/H2=1/2 (O.S 1000 h-1).

Example 2.

A sample of catalyst comprising 30%/(Al2About3+14%Al) was prepared by the following method.

To 2 g of boehmite SB-1 add a mixture of 0.45 ml of HNO3(64%), 8 ml of distilled water and 0.6 g of the plasticizer triethylene glycol (TEG). Mix thoroughly until smooth. To a mixture of 1.2 g of pore-forming component of methylcellulose and mix thoroughly until smooth. To the mixture is added 2 g of a powder of aluminum metal in the form of flakes moistened with 2 ml of dimethyl ether, and mix thoroughly until smooth. Then to the mixture is added 6 g of a powder of Al2About3thoroughly mix until smooth and place in an extruder with fil is Roy 2.5 mm The extrudates stand in the air for 10 h and placed in a drying Cabinet. The mode of drying in a drying Cabinet: 60°C - 2 h, 80°C - 2 h, 110°C - 2 tsp Dried extrudates loaded into a quartz flow reactor and calcined in a stream of air, raising the temperature from 110 to 450°With a speed of 3-4°/min. At a temperature of 450°With stand 4 hours extrudates are cooled in a stream of air discharged from the reactor and crushed to a fraction of a 2.5×2-3 mm.

Cobalt is applied, as in example 1.

Activation of the catalyst and the synthesis was performed as in example 1.

Example 3.

A sample of catalyst comprising 30%/(Al2About3+7%Al) was prepared by the following method.

To 2 g of boehmite SB-1 add a mixture of 0.45 ml of HNO3(64%), 8 ml of distilled water and 0.6 g of the plasticizer triethylene glycol (TEG). Mix thoroughly until smooth. To a mixture of 1.2 g of pore-forming component of methylcellulose and mix thoroughly until smooth. To the mixture was added 1 g of powder of aluminum metal in the form of flakes, soaked in 1 ml of dimethyl ether, and mix thoroughly until smooth. Next, to the mixture of 7 g of the powder of Al2About3thoroughly mix until smooth and place in an extruder with Villeroy 2.5 mm extrudates stand in the air for 10 h and placed in a drying Cabinet. The mode of drying in a drying Cabinet is: 60° C - 2 h, 80°C - 2 h, 110°C - 2 tsp Dried extrudates loaded into a quartz flow reactor and calcined in a stream of air, raising the temperature from 110 to 450°With a speed of 3-4°C/min. At a temperature of 450°With stand 4 hours extrudates are cooled in a stream of air discharged from the reactor and crushed to a fraction of a 2.5×2-3 mm

Cobalt is applied, as in example 1.

Activation of the catalyst and the synthesis was performed as in example 1.

Example 4.

A sample of catalyst comprising 30%/(Al2About3+1%Al) was prepared by the following method.

To 2 g of boehmite SB-1 add a mixture of 0.45 ml NHO3(64%), 8 ml of distilled water and 0.6 g of the plasticizer triethylene glycol (TEG). Mix thoroughly until smooth. To a mixture of 1.2 g of pore-forming component of methylcellulose and mix thoroughly until smooth. To the mixture is added 0.15 g of a powder of aluminum metal in the form of flakes, soaked in 1 ml of dimethyl ether, and mix thoroughly until smooth. Next, to the mixture of 7.85 g of the powder of Al2About3thoroughly mix until smooth and place in an extruder with Villeroy 2.5 mm extrudates stand in the air for 10 h and placed in a drying Cabinet. The mode of drying in a drying Cabinet: 60°C - 2 h, 80°C - 2 h, 110°C - 2 tsp Dried extrudates loaded into a quartz flow reactor and so kaliwat in air flow, raising the temperature from 110 to 450°With a speed of 3-4°/min. At a temperature of 450°With stand 4 hours extrudates are cooled in a stream of air discharged from the reactor and crushed to a fraction of a 2.5×2-3 mm

Cobalt is applied, as in example 1.

Activation of the catalyst and the synthesis was performed as in example 1.

Example 5.

A sample of catalyst comprising 10%/(Al2About3+25%Al) was prepared by the following method.

The media is prepared as in example 1.

Cobalt is applied from an aqueous solution of its nitrate.

7,05 g of cobalt nitrate dissolved in distilled water and added to 10 g of the obtained carrier. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min

Activation of the catalyst and the synthesis was performed as in example 1.

Example 6.

A sample of catalyst comprising 30%Co-0.1%of Re/(Al2O3+14%Al) was prepared by the following method.

The media is prepared as in example 2.

Cobalt is applied from an aqueous solution of its nitrate, and rhenium - of perrhenate ammonium in four successive impregnation.

1 impregnation. 7,05 g of cobalt nitrate dissolved in distilled water and added to 10 g of the obtained carrier. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min, and then calcined in air flow at a temperature of 400°C for 1 h

2 impregnation. Like the first.

3 impregnation. ,015 g perrhenate ammonium dissolved in distilled water and added to the material, obtained in stage 2. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min, and then calcined at a temperature of 450°C for 1 h

4 impregnation. 7,05 g of cobalt nitrate dissolved in distilled water and added to the material obtained in stage 2. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min

Activation of the catalyst and the synthesis was performed as in example 1.

Example 7.

A sample of catalyst comprising 30%Co-0.5%of Re/(Al2O3+14%Al) was prepared by the following method.

The media is prepared as in example 2.

Cobalt is applied from an aqueous solution of its nitrate, and rhenium - of perrhenate ammonium in four successive impregnation.

1 impregnation. 7,05 g of cobalt nitrate dissolved in distilled water and added to 10 g of the obtained carrier. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min, and then calcined in air flow at a temperature of 400°C for 1 h

2 impregnation. Like the first.

3 impregnation. 0.07 g of perrhenate ammonium dissolved in distilled water and added to the material obtained in stage 2. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min, and then calcined at a temperature of 450°C for 1 h

4 impregnation 7,05 g of cobalt nitrate dissolved in distillirovannoi and add to the material, obtained in stage 2. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min

Activation of the catalyst and the synthesis was performed as in example 1.

Example 8.

A sample of catalyst comprising 30%Co and 0.5%Pt/Al2O3+14%Al) was prepared by the following method.

The media is prepared as in example 2.

Cobalt and platinum applied as in example 7.

Activation of the catalyst and the synthesis was performed as in example 1.

Example 9.

A sample of catalyst comprising 30%Co-5%ZrO2/(Al2O3+14%Al) was prepared by the following method.

The media is prepared as in example 2.

Cobalt and zirconium oxide is applied as in example 7.

Activation of the catalyst and the synthesis was performed as in example 1.

Example 10.

A sample of catalyst comprising 30%Co-3%Fe2About3/(Al2About3+14%Al) was prepared by the following method.

The media is prepared as in example 2.

Cobalt and iron oxide is applied as in example 7.

Activation of the catalyst and the synthesis was performed as in example 1.

Example 11.

A sample of catalyst comprising 30%/(TiO2+14%Al) was prepared by the following method.

To 2 g of boehmite SB-1 add a mixture of 0.45 ml of HNO3(64%), 8 ml of distilled water and 0.6 g of the plasticizer triethylene glycol (TEG). Mix thoroughly until smooth. To a mixture of 1.2 g of pore-forming component of methylcellulose and carefully paramesh is live until smooth. To the mixture is added 2 g of a powder of aluminum metal in the form of flakes moistened with 2 ml of dimethyl ether, and mix thoroughly until smooth. Next, to the mixture of 6 g of powder TiO2thoroughly mix until smooth and place in an extruder with Villeroy 2.5 mm extrudates stand in the air for 10 h and placed in a drying Cabinet. The mode of drying in a drying Cabinet: 60°C - 2 h, 80°C - 2 h, 110°C - 2 tsp Dried extrudates loaded into a quartz flow reactor and calcined in a stream of air, raising the temperature from 110 to 450°With a speed of 3-4°/min. At a temperature of 450°With stand 4 hours extrudates are cooled in a stream of air discharged from the reactor and crushed to a fraction of a 2.5×2-3 mm.

Cobalt is applied, as in example 1.

Activation of the catalyst and the synthesis was performed as in example 1.

Example 12.

A sample of catalyst comprising 30%Fe/(Al2O3+14%Al) was prepared by the following method.

The media is prepared as in example 2.

Iron is applied from an aqueous solution of its nitrate in three successive impregnation.

1 impregnation. 10,31 g of iron nitrate dissolved in distilled water and added to 10 g of the obtained carrier. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min, and then calcined in air flow at a temperature of 450°C for 1 h

2 impregnated the ka. Like the first.

3 impregnation. 10,31 g of iron nitrate dissolved in distilled water and added to the material obtained in stage 2. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min

Before synthesis, the sample of catalyst was activated in a stream of hydrogen (O.S 3000 h-1) at 450°C for 1 h Synthesis of hydrocarbons is carried out in a tubular reactor with a fixed bed of catalyst at a pressure of 2 MPa and a temperature of 160-240°using synthesis gas with a molar ratio of CO/H2=1/2 (O.S 1000 h-1).

Example 13.

A sample of catalyst comprising 30%Ru/Al2O3+14%Al) was prepared by the following method.

The media is prepared as in example 2.

Ruthenium is applied from an aqueous solution of its chloride in three successive impregnation.

1 impregnation. 2,94 g of ruthenium chloride dissolved in distilled water and added to 10 g of the obtained carrier. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min, and then calcined in a stream of nitrogen at a temperature of 450°C for 1 h

2 impregnation. Like the first.

3 impregnation. 2,94 g of ruthenium chloride dissolved in distilled water and added to the material obtained in stage 2. The mixture is placed in a porcelain Cup and dried on a water bath for 30-60 min

Before synthesis of a sample of the cat who lyst activated in a stream of hydrogen (O.S 3000 h-1) at 550°C for 1 h Synthesis of hydrocarbons is carried out in a tubular reactor with a fixed bed of catalyst at a pressure of 2 MPa and a temperature of 160-240°using synthesis gas with a molar ratio of CO/H2=1/2 (O.S 1000 h-1).

Example 14.

A sample of catalyst comprising 30%Co-0.5%of Re/(Al2O3+14%Al) was prepared by the following method.

The media is prepared as in example 2.

Cobalt and rhenium is applied, as in example 7.

Activation of the catalyst was performed as in example 1.

The synthesis of hydrocarbons is carried out in a tubular reactor with a fixed bed of catalyst at a pressure of 2 MPa and a temperature of 170-250°using synthesis gas with a molar ratio of CO/H2=1/2 (O.S 2000 h-1).

Example 15 (Comparison).

A sample of catalyst comprising 30%/(Al2About3) is prepared by the following method.

To 2 g of boehmite SB-1 add a mixture of 0.45 ml of HNO3(64%), 7 ml of distilled water and 0.6 g of the plasticizer triethylene glycol (TEG). Mix thoroughly until smooth. To a mixture of 1.2 g of pore-forming component of methylcellulose and mix thoroughly until smooth. Then to the mixture is added 8 g of a powder of Al2O3thoroughly mix until smooth and place in an extruder with Villeroy 2.5 mm extrudates stand in the air for 10 h and placed in a drying Cabinet is. The mode of drying in a drying Cabinet: 60°C - 2 h, 80°C - 2 h, 110°C - 2 tsp Dried extrudates loaded into a quartz flow reactor and calcined in a stream of air, raising the temperature from 110 to 450°With a speed of 3-4°/min. At a temperature of 450°With stand 4 hours extrudates are cooled in a stream of air discharged from the reactor and crushed to a fraction of a 2.5×2-3 mm.

Cobalt is applied, as in example 1.

Activation of the catalyst and the synthesis was performed as in example 1.

Table
The performance of the Fischer-Tropsch synthesis carried out using samples of the catalysts corresponding to the invention
ExampleConversion, %Selectivity for CH4, %The selectivity for C5+, %Performance, kgf5+/m3cat/h[N-paraffinic11+], wt.%
1658859393
27068810586
37378710686
4641275 8575
56010829183
67578810895
78169011296
88378911093
98078510080
108278410285
117510808977
127011757775
13509869590
14488859096
155432636259

Industrial applicability

The invention relates to petrochemistry, gas chemistry, coal chemistry and can be used for Fischer-Tropsch synthesis.

1. The catalyst for Fischer-Tropsch synthesis, the content is of ASI as an active component, a metal of group VIII of the Periodic system of Mendeleev and the media, containing oxide component and aluminum metal in the form of scales.

2. The catalyst according to claim 1, characterized in that the active component is 5-40% by weight of the catalyst.

3. The catalyst according to claim 1, characterized in that the oxide component contains alumina and/or silica and/or titanium oxide and/or zirconium oxide.

4. The catalyst according to claim 1, characterized in that it further comprises a promoter which used metal Zirconia or metal VII-VIII groups of the Periodic system of Mendeleev's and/or their oxides.

5. The catalyst according to claim 4, characterized in that the content of the promoters is 0.1-5% by weight of the catalyst.

6. The catalyst according to claim 1, characterized in that the flakes of aluminum metal have a thickness of not more than 5 μm, and the linear dimension along the surface from 0.02 mm in the shortest dimension up to 3 mm in the longest dimension.

7. The catalyst according to claim 1, characterized in that the content of metallic aluminum in the form of flakes is 1-25% by weight of the catalyst.

8. The method of producing catalyst for Fischer-Tropsch synthesis according to claim 1, consisting in that the active ingredient is applied by impregnation to the media, which is prepared from the paste by extrusion, the extrudates stand in the air, dried and calcined, and use the paste contains oxide comp is engaged, aluminum metal in the form of flakes, binder and plasticizer.

9. The method according to claim 8, characterized in that the oxide component used aluminum oxide and/or silicon oxide and/or titanium oxide and/or zirconium oxide.

10. The method according to claim 8, characterized in that the content of metallic aluminum in the form of flakes is 1-25% by weight of the catalyst.

11. The method according to claim 8, characterized in that the binder used boehmite in the amount of 5-15% by weight of the catalyst.

12. The method of claim 8, wherein the paste further comprises a pore-forming component.

13. The method according to claim 8, characterized in that the introduction of the active component carried out by impregnation of a formed carrier with a solution of salts of metals of group VIII to its content of 5-40% by weight of the catalyst.

14. The method according to claim 8, characterized in that it further carry out the impregnation of the support with a solution of salts of the promoters, which are metal Zirconia or metal VII-VIII groups of the Periodic system of Mendeleev's and/or their oxides.

15. The method according to 14, characterized in that the impregnation of the support with a solution of salts of the promoters is carried out until the content of the promoters of 0.1-5% by weight of the catalyst.



 

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59 cl, 1 dwg, 1 tbl, 7 ex

FIELD: chemical engineering.

SUBSTANCE: invention relates to chemical process and catalytic reactors suitable for carrying out the process. In particular, Fischer-Tropsch synthesis is described involving compact block of catalytic reactor (10) forming passages wherein gas-permeable catalyst structure (16) is present, said passages extending between manifolds (18). Synthesis is performed in at least two steps since reactor block provides at least two consecutive passages (14, 14a) for Fischer-Tropsch synthesis process interconnected through manifold wherein gas flow velocity in the first passages is high enough to limit conversion of carbon monoxide to 65%. Gases are cooled in manifold between two steps so as to condense water steam and then passes through the second passage at flow velocity high enough to limit conversion of the rest of carbon monoxide to 65%.

EFFECT: reduced partial pressure of water steam and suppressed oxidation of catalyst.

17 cl, 3 dwg

FIELD: disproportionation reaction catalysts.

SUBSTANCE: invention relates to Fischer-Tropsch catalyst containing cobalt and zinc, to a method for preparation thereof, and to Fischer-Tropsch process. Catalyst according to invention containing co-precipitated cobalt and zinc particles, which are characterized by volume-average size below 150 μm and particle size distribution wherein at least 90% of the catalyst particle volume is occupied by particles having size between 0.4 and 2.5 times that of the average particle size and wherein zinc/cobalt atomic ratio within a range of 40 to 0.1. Catalyst is prepared by introducing acid solution containing zinc and cobalt ions at summary concentration 0.1 to 5 mole/L and alkali solution to reactor containing aqueous medium wherein acid solution and alkali solution come into contact with each other in aqueous medium at pH 4-9 (deviating by at most 0.2 pH units) at stirring with a speed determined by supplied power between 1 and 300 kW/L aqueous medium and temperature from 15 to 75°C. Resulting cobalt and zinc-including precipitate separated from aqueous medium, dried, and further treated to produce desired catalyst. Employment of catalyst in Fischer-Tropsch process is likewise described.

EFFECT: enhanced strength and separation properties suitable for Fischer-Tropsch process.

13 cl, 2 dwg, 1 tbl, 5 ex

FIELD: production of pigments and catalysts based on titanium dioxide, in particular, process for treatment of titanium dioxide for removal of sulfur, in particular sulfates.

SUBSTANCE: method involves treating calcined titanium dioxide at elevated temperatures using aqueous solution containing one or more ammonium compounds; separating titanium dioxide from aqueous solution and drying titanium dioxide. Ammonium compounds preferably used in treatment process are ammonium acetate or ammonium chloride.

EFFECT: increased efficiency in cleaning of titanium dioxide from sulfur, in particular sulfates.

9 cl, 5 tbl, 5 ex

FIELD: petrochemical process catalyst.

SUBSTANCE: invention relates to a method of preparing catalyst for use in Fischer-Tropsch process and to catalyst obtained according present invention. Preparation of catalyst suitable for conversion at least one synthesis gas component comprises: providing aqueous solution of organic acid; adding iron metal to acid solution; passing oxidant through the solution until iron metal is consumed and iron-containing slurry formed; grinding resulting slurry to achieve average particle size less than about 2 μm; adding at least one promoter to ground iron-containing slurry to form product suspension, concentration of said promoter being such as to obtain said product suspension containing solid phase constituting from about 10 to about 40% of the weight of suspension, including said promoter; performing spray drying of suspension to obtain particles; and calcining these particles to obtain desired catalyst.

EFFECT: optimized catalyst preparation procedure.

23 cl, 2 dwg, 1 tbl, 12 ex

FIELD: alternate fuel production.

SUBSTANCE: invention relates to synthesis of hydrocarbons from CO and H2, in particular to catalysts and methods for preparation thereof in order to carrying out synthesis of hydrocarbons C5 and higher according to Fischer-Tropsch reaction. Method resides in that non-calcined zeolite ZSM-12 in tetraethylammonium-sodium form is subjected to decationation at pH 5-9, after which decationized zeolite (30-70 wt %) is mixed with alumina binder while simultaneously adding cobalt (7.5-11.5 wt %) as active component and modifier, in particular boron oxide (3-5 wt %). Proposed method allows catalyst preparation time to be significantly reduced owing to combining support preparation and deposition of active component and modifier in one stage with required catalytic characteristics preserved. In addition, method is environmentally safe because of lack of waste waters, which are commonly present when active components are deposited using impregnation, coprecipitation, and ion exchange techniques.

EFFECT: reduced catalyst preparation time and improved environmental condition.

1 tbl, 10 ex

FIELD: chemistry.

SUBSTANCE: method is intended for preparation of catalysts of different industrial redox processes, particularly, gas afterburning, hydrating of vegetable oils etc. The method of preparation of catalysts of redox processes is described which consists in application of the active component from precious metals upon the oxide carrier, and at that the active component is applied upon the activated carbon, the received material is mixed with the oxide carrier, the mixture is grinded till highly dispersed condition at 650-800°C.

EFFECT: method allows preparation of catalyst with exactly required concentration and homogenous composition while preparation time is reduced.

4 ex

FIELD: chemistry.

SUBSTANCE: thiophen and its homologues are used in chemical industry and pharmacology for synthesis of polyorganosiloxanes, herbicides, physiologically active substances and aroma materials. Two catalyst types for thiophen preparation from sulfur-containing substances and C4-hydrocarbons are described. First type catalysts contain magnesium chromate and/or cupric chromate, aluminium oxide and probably magnesium and/or potassium and/or lanthanum oxides; second type catalysts have general formula tMg1-nCunCr2O4-xMgO-yK2O-zLa2O3/Al2O3, where t =5-25 Wt%; n=0-1 Wt%; x = 0-3.2 Wt%; y = 0-2 Wt%; z =0-10 Wt%; Al2O3 - the rest. Process is carried out at volume rate 400-1800 hr-1 and temperature 400-600°C, organic disulphides were used as sulfur-containing substances.

EFFECT: high yield of thiophen.

7 cl, 39 ex, 4 tbl

FIELD: petroleum refining; catalytic chemistry.

SUBSTANCE: there is described a method of catalyser reception, containing high-heat treatment of hydrargillite not classified on fractions, and hydrargillite with a target fraction from 50 to 200 microns in the interval of temperatures from 200°C to 600°C, the subsequent hydrothermal processing at temperature from 120°C to 220°C and pressure 0.2-2 MPa at pH value equal to 2-7, drying of the carrying agent and impregnating by solutions of active reductants at pressure from 0.6 kPa to 101.5 kPa, glowing of the impregnated carrying agent at temperature from 600°C to 900°C.

EFFECT: efficiency upgrading of process; high mechanical strength of catalyser; high activity and selectivity of catalyser in reaction of a paraffin hydrocarbons dehydrogenating.

7 cl, 1 tbl, 19 ex

FIELD: chemistry; petrochemistry; gas chemistry.

SUBSTANCE: catalyst for Fischer Tropsch synthesis and its carrying agent are described. Said catalyst contains metal of VIII group of Periodic Table as active component; said carrying agent contains oxide component and carbon fiber. Method of aforesaid catalyst preparation is also described, it consists in infiltration of active component to carrying agent. The carrying agent is produced by extrusion of the paste and then extrudates are exposed on the air, dried and calcinated. The processed paste contains oxide component, binder, plastifier and carbon fiber.

EFFECT: increasing of catalyst selectivity.

17 cl, 1 tbl, 15 ex

FIELD: chemical engineering.

SUBSTANCE: catalytic micro-passage plates comprises foam metals, metallic felt, and metallic cotton including catalyzer powder introduced into the pores of the metallic base. The number of passages ranges from 2 to 120 per 1 cm of length and depends on the size of the pores in metal. The width of the passage and width of the wall between the passages should be at lest five times larger than the size of pores in the metal used. The method of making the catalytic micro-passage plates is presented.

EFFECT: enhanced quality of catalytic plates.

11 cl, 5 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to catalysts exhibiting activity in hydrogenation of vegetable oils and fats and suitable for use in food processing industry, perfumery, petrochemical and petroleum processing industries. Invention describes a method for preparing granulated catalysts intended for liquid-phase hydrogenation of vegetable oils and distilled fatty acids and representing metallic palladium deposited in amount 0.5-2.0 wt % on carbon carrier, fraction 0.5-6.0 mm, having specific surface area 100-450 m2/g and pore volume 0.2-0.6 cm3/g. Hydrogenation process is conducted on fixed catalyst bed at 140-210°C, hydrogen pressure 2 to 12 atm and consumption or raw material 100 to 1500 g/h per 1 kg catalyst.

EFFECT: increased hydrogenation rate in production of technical sorts of solidified fat and increased stability of catalysts.

4 cl, 1 dwg, 3 tbl, 20 ex

FIELD: hydrogen production processes.

SUBSTANCE: invention relates to catalysts for hydrolysis of hydride compounds to produce pure hydrogen for being supplied to power installations, including fuel cells. Invention provides catalyst for production of hydrogen from aqueous or water-alkali solutions of hydride compounds containing platinum group metal deposited on complex lithium-cobalt oxide and, additionally, modifying agent selected from series: titanium dioxide, carbon material, oxide of metal belonging to aluminum, magnesium, titanium, silicon, and vanadium subgroups. According to second variant, catalyst contains no platinum group metal. Described are also catalyst preparation method (variants) and hydrogen generation process, which is conducted at temperature no higher than 60°C both in continuous and in periodic mode. As hydrogen source, sodium borohydride, potassium borohydride, and ammine-borane can be used.

EFFECT: increased catalyst activity at environmental temperatures (from -20 to 60°C), prolonged time of stable operation of catalytic system, and reduced or suppressed platinum metals in composition of catalyst.

14 cl, 1 tbl, 20 ex

FIELD: catalytic gas treatment.

SUBSTANCE: invention proposes catalyst for treating hydrogen-rich gas mixtures to remove carbon monoxide via methanation of carbon monoxide, said catalyst containing nickel-cerium oxide system. Catalyst is prepared by reaction of nickel compounds with cerium compound. Methanation of carbon monoxide is conducted at temperature not below 20°C and pressure not below 0.1 atm in presence of above-indicated catalyst.

EFFECT: enhanced removal of carbon monoxide to level below 10 ppm.

8 cl, 5 tbl, 9 ex

FIELD: gas treatment catalysts.

SUBSTANCE: invention relates to a method for preparing catalyst and to catalyst supported by block ceramic and metallic carrier having honeycomb structure for treating internal combustion engine exhaust gases. Preparation of catalyst comprises preliminary calcination of inert honeycomb block carrier followed by simultaneously depositing at 550-800°C, on its surface, intermediate coating of modified alumina and active phase consisting of one or several platinum group metals from water-alcohol suspension including aluminum hydroxide (boehmite, AlOOH), cerium nitrate, and one or several inorganic salts of platinum group metals. Coated material is then dried and subjected to heat treatment and reduction. According to invention, aforesaid suspension contains boehmite and cerium nitrate at 1:2 ratio and further contains reducing disaccharide so that suspension has following composition, wt %: AlOOH 18-20, Ce(NO3)3·6H2O 36-40, one or several platinum group metal salts (e.g., H2PtCl6, PdCl3, or RhCl3 calculated as metals) 1.5-1.8, reducing disaccharide 5-6, and water/alcohol (between 5:1 and 10:1) the rest. Thus obtained catalyst for treating internal combustion engine exhaust gases is characterized by: specific surface area of coating 80-100 m2/g, Al2O3 content 2.5-6.5%, CeO2 content 2.5-6.5%, active phase (calculated for platinum group metals) 0.2-0.4%, and block carrier to 100%.

EFFECT: simplified technology due to reduced number of technological stages and shortened process time, and enabled preparation of high-activity catalyst.

6 cl, 1 tbl, 8 ex

Ruthenium catalysts // 2322293

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to novel ruthenium catalysts, method for preparation thereof, and to employment thereof for catalytic hydrogenation of mono- and oligosaccharides in production of corresponding sugar alcohols. Ruthenium hydrogenation catalyst contains ruthenium supported by amorphous silica-based carrier, content of ruthenium being 0.2 to 7% of the weight of carrier, while carrier contains at least 90% silica and less than 10% of crystalline silicon dioxide phases. Catalyst is prepared by single or multiple treatment of carrier material with halogen-free solution of low-molecular weight ruthenium compound and subsequent drying of treated material at temperature not lower than 200°C immediately followed by reduction of dried material with hydrogen at 100 to 350°C. Herein disclosed is also a process for liquid-phase production of sugar alcohols (excepting sorbitol) via catalytic hydrogenation of corresponding mono- and oligosaccharides in presence of proposed catalysts.

EFFECT: increased activity and selectivity of catalysts.

16 cl, 4 tbl, 7 ex

FIELD: chemistry; petrochemistry; gas chemistry.

SUBSTANCE: catalyst for Fischer Tropsch synthesis and its carrying agent are described. Said catalyst contains metal of VIII group of Periodic Table as active component; said carrying agent contains oxide component and carbon fiber. Method of aforesaid catalyst preparation is also described, it consists in infiltration of active component to carrying agent. The carrying agent is produced by extrusion of the paste and then extrudates are exposed on the air, dried and calcinated. The processed paste contains oxide component, binder, plastifier and carbon fiber.

EFFECT: increasing of catalyst selectivity.

17 cl, 1 tbl, 15 ex

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