Catalyst for fischer tropsch synthesis and method of its preparation

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

 

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 elevated pressures. 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. Overheating 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].

There are 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. forming the stationary is th layer, is placed inside the tube, separating the gas space with the catalyst and the liquid phase (water), due to the heat which the heat. In this case a large role in the dissipation plays thermal conductivity of the solid catalyst.

Known cobalt catalyst for Fischer-Tropsch synthesis [patent application U.S. 2003/139286 A1 (2003)]. The catalyst is a cobalt deposited on a coated carbon oxide media (Al2About3, SiO2the aluminosilicate, TiO2, MgO). The media containing the carbon, prepared as described in European patent EP 0681868 A1 (1995). The carbon content is from 0.1 g to 100 g of the carrier to 40 g 100 g media. The catalyst is prepared jointly by impregnation with solutions of salts of cobalt and metal - promoter in slurry - reactor with subsequent drying in a rotary evaporator under vacuum and calcination in air flow 6 h at 250°C. thereafter, the catalyst was partially restored in a stream of hydrogen for 2 h at 230°C. Then spend the next joint impregnated with drying and roasting. The use of such media can improve the stability of the catalyst in a three-phase reactor. The disadvantage of this catalyst is the complexity of preparation.

Known catalyst for Fischer-Tropsch synthesis [international patent application WO 86/01499 A1], not only at the store cobalt, or iron, supported on a carrier, which is carbon with a specific surface area of not less than 100 m2/, the ratio of the total specific surface area determined by BET, specific surface, the primary surface shall not exceed 4:1, and the ratio of the specific surface, the primary surface to a specific surface side of the plane should be at least 10:1. The catalyst also contains a promoter - platinum (0.2 to 10 wt.%). The catalyst is prepared by impregnation of a carbon powder (0.5-1.0 mm) with aqueous solutions of metal salts. Pre-carbon from organic materials (coconut charcoal, peat, coal, carbidization polymers) is treated at temperatures from 300 to 3300°consistently in an inert, oxidizing and again inert atmosphere. The synthesis is carried out at 150-300°S, 0.1-5 MPa, and the ratio of H2/CO - 1/1-3/1. The disadvantages of such a catalyst must be attributed to the low selectivity of the products5+.

Known catalyst for synthesis of hydrocarbons from synthesis gas [Russian patent SU 1819158 A3 (1990)]. The catalyst contains iron as the active component, copper, silicon and potassium, and activated by steam or mineral acid coal (2-20 wt.%). However 50-100% of coal particles have a size of 0.1-100 μm. The catalyst was prepared by the dissolution of iron and copper in nitric acid, heating the resulting solution to Kip the tion, add to the boiling solution of alkaline solution or soda ash, bringing the resulting suspension to a pH of 7-8, Department of potassium liquid glass, followed by nitric acid treatment, the sludge separation of the catalyst mass, drying, forming, extrusion, additional drying and grinding. The Fischer-Tropsch synthesis is carried out in a reactor with a fixed catalyst bed at a pressure of 20-30 bar and a temperature of about 220 to 320°C. the Yield of the hydrocarbon wax is 40-55% in terms of hydrocarbon, C2and C2+. The disadvantages of this catalyst is its low productivity and selectivity for the target products, and sophisticated way of cooking.

The closest one is cobalt catalyst for synthesis of hydrocarbons From5-C25from CO and H2based on activated carbon (content of 20-90 wt.%), derived from the bark of almond, coconut, palm wood or coal (U.S. patent No. 6720283 (2004)). The carrier is characterized by a surface area of 200-2000 m2/g pore volume of 0.3-2 ml/g and a pore diameter of from 4 to 1000 Å. The catalyst is prepared by impregnation of powder medium (20-40 mesh) solutions of nitrates of Co, Zr, or CE in vacuum (80 kPa) with subsequent drying at room temperature for several days, drying at 80-90°With whom for 8 h at 110-120° C for 10 h Recovery can be performed during 1-50 h at 100-700°With the current H2. Synthesis is carried out under conditions: 120-350°C, 0.5 To 10 MPa, N2/CO=1-3. As a result, when the conversion FROM 54-86% of the hydrocarbon, C5-C25are formed with selectivity 67-83%. The main disadvantages of this catalyst is its low selectivity for the target product and the complexity of the preparation of media for the preparation of the catalyst (long drying).

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 the VIII group of the Periodic system of Mendeleev and the media containing oxide component, and carbon fiber.

The active component may comprise 5-40% by weight of the catalyst.

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

Optionally, the catalyst can containing the ü promoters, which can be used metal Zirconia or metal VII or 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.

Carbon fiber can be used in the form of lengths of not more than 3 mm and a diameter of not more than 20 μm, preferably a diameter of not more than 10 μm and a length of 2 mm.

In the particular case of carbon fiber can be characterized by a specific surface area not higher than 800 m2/year

In particular, if the content of carbon fiber is 1-25% by weight of the catalyst.

The technical result is also achieved by the fact that upon receipt of the catalyst for Fischer-Tropsch synthesis, 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 an oxide component, carbon fiber 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 the carbon fiber may comprise 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 pore-forming component.

Would the giving of the active component can be formed impregnation of the 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, carbon fiber, 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.% cobalt, 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 productivity and selectivity of the target product and a low selectivity by-product is methane.

At the first stage of preparation of the catalyst prepared media. For this mix of carbon fiber, oxide component carrier, boehmite and a pore-forming component with 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 inert gas at 110-550°for 6-20 hours. Active component (to the viola) is applied by impregnation in several stages from a solution of salts of cobalt 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 inert gas 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 and H2carried 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. The synthesis gas may contain up to 25% vol. of nitrogen.

Example 1.

A sample of catalyst comprising 30%/(Al2O3+25% HC) is 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 the mixture is added 3.5 g of powder HC 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 souchelnytskyi. 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 nitrogen, raising the temperature from 110 to 550°With a speed of 3-4°/min. At a temperature of 550°can withstand 5 o'clock the extrudate is cooled in a stream of nitrogen, is unloaded 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. 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 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.

The rolled sample is atora composition 30%/(Al 2O3+14% HC) is 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 the mixture is added 2 g of a powder of carbon fiber 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 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 nitrogen, raising the temperature from 110 to 550°With a speed of 3-4°/min. At a temperature of 550°can withstand 5 o'clock the extrudate is cooled in a stream of nitrogen, is unloaded 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%/(Al2O3+7% HC) is 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 the mixture was added 1 g of powder of carbon fiber and dateline mix 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: 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 nitrogen, raising the temperature from 110 to 550°With a speed of 3-4°/min. At a temperature of 550°With stand 4 hours, the catalyst is cooled in a stream of nitrogen, is unloaded 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%/(Al2O3+1% HC) is 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 the mixture is added 0.15 g of carbon fibers 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° - 2 hours is Izuchenie extrudates loaded into a quartz flow reactor and calcined in a stream of nitrogen, raising the temperature from 110 to 550°With a speed of 3-4°/min. At a temperature of 550°With stand 4 hours, the catalyst is cooled in a stream of nitrogen, is unloaded 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%/(Al2O3+25% HC) is 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% HC) is 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 a stream of nitrogen at a temperature of 400°C for 1 h

2 impregnation. Like the first.

3 popitka,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 in a stream of nitrogen 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 3. 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% to 0.5% Re/(Al2O3+14% HC) is prepared by the following method.

The media is prepared as in example 2.

Cobalt and rhenium is applied, as in example 4.

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

Example 8.

A sample of catalyst comprising 30% To 0.5% Pt/Al2O3+14% HC) is prepared by the following method.

The media is prepared as in example 2.

Cobalt and platinum applied as in example 4.

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% HC) is 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% In the) is 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% Co/(TiO2+14% HC) is 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 the mixture is added 2 g of carbon fibers 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 nitrogen, raising the temperature from 110 to 550°With a speed of 3-4°/min. At a temperature of 550°With stand 4 hours, the catalyst is cooled in a stream of nitrogen, is unloaded 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% HC) is prepared by the following method.

The media is prepared as in example 2.

is elesa 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 a stream of nitrogen at a temperature of 450°C for 1 h

2 impregnation. 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% HC) is 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 1H.

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, the sample of catalyst was 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% to 0.5% Re/(Al2O3+14% HC) is prepared by the following method.

The media is prepared as in example 2.

Cobalt and rhenium is applied, as in example 4.

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% Co/Al2O3prepared 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 a homogeneous mA the son. To a mixture of 1.2 g of methyl cellulose and mix thoroughly until smooth. Then to the mixture is added 8 g of a 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 nitrogen, raising the temperature from 110 to 550°With a speed of 3-4°/min. At a temperature of 550°can withstand 5 o'clock the extrudate is cooled in a stream of nitrogen, is unloaded 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-paraffins With11+], wt.%
1689839285
27578710281
37888510276
46012788570
56211808775
67788510087
78578811090
88998611088
98078610085
10858859885
11759819286
127012758078
135511808590
14509859092
155432 636259

Industrial applicability

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

1. The catalyst for Fischer-Tropsch synthesis, containing as an active component, a metal of the VIII group of the Periodic system of Mendeleev and the media containing oxide component, and carbon fiber.

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 the promoters, which are 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 carbon fiber contained in the form of lengths of not more than 3 mm and a diameter of not more than 20 μm.

7. The catalyst according to claim 6, characterized in that the segments of the carbon fibers are in the form of cylinders.

8. The catalyst according to claim 1, characterized in that the carbon fiber characterizes the I specific surface area not higher than 800 m 2/year

9. The catalyst according to claim 1, characterized in that the content of carbon fiber is 1-25% by weight of the catalyst.

10. 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 an oxide component, a binder, a plasticizer, and carbon fiber.

11. The method according to claim 10, characterized in that the oxide component contains alumina and/or silica and/or titanium oxide and/or zirconium oxide.

12. The method according to claim 10, characterized in that the content of carbon fiber is 1-25% by weight of the catalyst.

13. The method according to claim 10, characterized in that the binder used boehmite in the amount of 5-15% by weight of the catalyst.

14. The method according to claim 10, wherein the paste further comprises a pore-forming component.

15. The method according to claim 10, 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.

16. The method according to claim 10, characterized in that it further carry out the impregnation of the support with a solution of salts of the promoters, which is used for the metal is zirconium or metals VII-VIII groups of the Periodic system of Mendeleev's and/or their oxides.

17. The method according to item 16, 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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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: petrochemical processes.

SUBSTANCE: synthesis gas is subjected to conversion to produce liquid hydrocarbons in sequentially connected reactors containing catalytic slurry of at least one solid catalyst in a liquid phase. Reactors are triphase bubble column-type reactors provided with virtually full stirring characterized by liquid Peclet number below 8, gas Peclet number below 0.2, and diameter larger than 6 m. Last reactor at least partially receives at least part of at least one of the gas fractions collected at the outlet of at least one of other reactors. At least one reactor is supplied with stream of catalytic slurry coming directly out of another reactor, and at least one stream of catalytic slurry coming out of reactor is at least partially separated so as to receive liquid product substantially free of catalyst and catalyst-rich catalytic slurry, which is then recycled.

EFFECT: improved process technology.

10 cl, 8 dwg, 7 ex

FIELD: organic synthesis catalysts.

SUBSTANCE: invention provides fischer-tropsch process catalyst comprising at least one metal suitably absorbing carbon monoxide and at least one promoter, said metal and said promoter being dispersed on a substrate to form catalytic particle having BET surface area between 100 and 250 m2/g so that size of metal oxide crystallites ranges from 40 to 200 while said metal and said promoter are different compound and said particle has predominantly smooth and uniform morphology of surface. substrate is characterized by particle size between 60 and 150 μm, surface area 90 to 210 m2/g, pore volume 0.35 to 0.50 mL/g, and pore diameter 8 to 20 nm. Described are also catalyst and a method of preparing catalyst including cobalt dispersed onto substrate to form catalyst particle.

EFFECT: increased surface of catalyst, improved uniformity in distribution of metal, and reduced size of metal crystallites.

33 cl, 9 dwg, 1 tbl, 10 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: petrochemical processes and catalysts.

SUBSTANCE: invention relates to the area of production of olefin hydrocarbons via catalytic dehydrogenation of corresponding C3-C5-paraffin hydrocarbons and can be applied in chemical and petrochemical industries. C3-C5-Paraffin hydrocarbon dehydrogenation catalyst is described containing chromium oxide, alkaline metal oxide, transition metals, and carrier, said carrier being nanostructured oxygen-containing aluminum compound of general formula: Al2O3-x(OH)x*nH2O, wherein x=0-0.28 and n=0.03-1.8, consisting of nanostructured primary particles 2-5 nm in size and characterized by disordered/imperfect layered structure similar to byerlyte structure. Method of preparing this catalyst as well as process of dehydrogenating C3-C5-paraffin hydrocarbons into olefins are also described, the latter being conducted in fluidized bed of described catalyst, which is recycled within the circuit: dehydrogenation reactor - regeneration reactor.

EFFECT: increased mechanical strength at high catalytic activity and stability.

20 cl, 1 dwg, 2 tbl, 10 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to catalysts and process of steam conversion of hydrocarbons to produce synthesis gas. Proposed catalyst for steam conversion of hydrocarbons contains nickel oxide (4.0-9.2%) and magnesium oxide (4.0-6.5%) supported by porous metallic nickel (balancing amount). Carrier has specific surface area 0.10-0.20 m2/g, total pore volume 0.07-0.12 cm3/g, predominant pore radius 1-30 μm, and porosity at least 40%. Described are also catalyst preparation method and generation of synthesis gas via steam conversion of hydrocarbons.

EFFECT: increased heat conductivity of catalyst resulting in stable activity in synthesis gas generation process.

8 cl, 1 tbl, 5 ex

FIELD: alternative fuels.

SUBSTANCE: invention relates to autothermal conversion of hydrocarbon fuel to produce synthesis gas, which can be used in chemical production, for burning at catalytic heat plants, and in hydrogen power engineering. Proposed catalyst contains, as active components, cobalt oxide, manganese oxide, and barium oxide, and, as carrier, refractory reinforced metalporous carrier. Catalyst is prepared by impregnation of carrier with barium and manganese salt solution at Ba/Mn =5:4 followed by drying, calcination, impregnation with cobalt salt solution, drying, and calcination. Invention further describes generation of synthesis gas via autothermal conversion of hydrocarbon fuel performed utilizing above-described catalyst.

EFFECT: enabled catalyst exhibiting high heat conductivity, high activity in production of synthesis gas, and resistance to coking and deactivation with sulfur compounds present in diesel fuel and gasoline.

6 cl, 1 tbl, 3 ex

FIELD: petrochemical processes and catalysts.

SUBSTANCE: invention provides isodewaxing catalyst for petroleum fractions containing supported platinum and modifiers wherein supporting carrier is fine powdered high-purity alumina mixed with zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40 at following proportions of components, wt %: platinum 0.15-0.60, alumina 58.61-89.43, zeolite 5-40, tungsten oxide (modifier) 1-4, and indium oxide (modifier) 0.24-0.97. Preparation of catalyst comprises preparing carrier using method of competitive impregnation from common solution of platinum-hydrochloric, acetic, and hydrochloric acids followed by drying and calcinations, wherein carrier is prepared by gelation of fine powdered high-purity alumina with the aid of 3-15% nitric acid solution followed by consecutive addition of silicotungstenic acid solution and indium chloride solution, and then zeolite ZSM 5 in H form having SiO2/Al2O3 molar ratio 25-80 or with zeolite BETA in H form having SiO2/Al2O3 molar ratio 25-40.

EFFECT: increased yield of isoparaffin hydrocarbons.

7 cl, 2 tbl, 7 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

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