Method of producing methanation process catalyst

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a methanation process catalyst, which includes impregnating a support based on active aluminium oxide in the form of granules in a solution containing nickel nitrate, followed by drying at temperature of 100°C-120°C and calcining the impregnated support at temperature of 450°C-500°C, wherein a modification additive - an organic acid with concentration of 0.5-20.0 wt % - is added to the nickel nitrate solution, and the finished catalyst contains NiO monocrystallites with mean sampling size in the range of 2-3 nm, with concentration of NiO of 12.0-25.0 wt % and γ-Al2O3 - the balance.

EFFECT: high reliability and activity, low cost and faster implementation of the method.

3 cl, 1 tbl, 13 ex

 

The invention relates to a process for the preparation of catalysts based on Nickel. This catalyst can be used in the chemical industry for fine purification of hydrogen-containing gas mixtures of oxides of carbon by hydrogenation to methane (metyrosine).

Currently, there is a method of preparation of the catalyst for purification of hydrogen-containing gases monoxide and carbon dioxide by mixing the basic Nickel carbonate with active alumina or a mixture of aluminum oxide and calcium aluminate, adding to the mixture an aqueous solution of ammonia, followed by drying, calcination, the mixture of graphite and pelletizing [Catalysis in industry, No. 5, 2012, p.50, tab. No. 6, 7]. This technology has allowed to reduce the temperature of the recovery of more than 100°C in comparison with the previously developed catalysts series NIAP-07 (HKM). The disadvantages of this method include a high content of the active component NiO (33±3) wt.% in the resulting catalyst, and the necessity of molding pellets pelletizing. As a result, compaction catalyst mass and a decrease in total porosity, which reduces the activity of the catalyst.

A known method of preparation of Nickel catalysts by impregnation of the carrier with a solution containing compounds of Nickel in the de emmakate Nickel or ammonium carbonate complex of Nickel, further heat treatment, grinding, sealing and pelletizing [Copyright certificate №272283, 6 MCI B01J 23/755, 1970].

The disadvantages of this method include forming pellets pelletizing. In the tabletting process in the generated pressure is compaction tableting material, and in the resulting tablet catalyst is formed of a porous structure characterized by a low value of total porosity and significant predominance of micropores, which reduces the activity of the catalyst. In addition, the catalyst obtained by this method has a high bulk density and considerable variability in the strength of individual tablets. The disadvantage of the catalyst obtained by this method is the low thermal stability.

The closest in technical essence and the achieved result of the present invention is a method of producing a catalyst for the process of mahanirvana, including the impregnation of the carrier on the basis of active aluminum oxide in the form of granules in a solution containing Nickel nitrate with a concentration of 200 g/l, followed by drying at a temperature of 100°C.-120°C. and calcination at a temperature of 450°C-500°C, the impregnated carrier. Then carry out the impregnation of ammonium carbonate solution with a concentration of ammonia - 100-120 g/l, COsub> 2- 90-100 g/l, dried at a temperature of 100°C-120°C and calcined at a temperature of 450°C-500°C. the Finished catalyst contains 15-30 wt.% Nickel oxide [Patent RU 2472587, 6 IPC B01J 37/00, 37/02, 21/04, 23/755, SS 1/04, C9/04].

The disadvantages of this method are: low activity of the obtained catalyst, low reliability, high cost and long duration time period of the implementation of this method due to the need for impregnation of ammonium-carbonate solution, drying, calcination impregnated media.

The technical problem to be solved by the present invention is directed, is to create a method of producing catalyst mahanirvana high-availability and activity, allowing you to reduce costs and to shorten the time period of the method.

To solve this problem is proposed this method of producing a catalyst for the process of mahanirvana, including the impregnation of the carrier on the basis of active aluminum oxide in the form of granules in a solution containing Nickel nitrate, followed by drying at a temperature of 100°C.-120°C. and calcination at a temperature of 450°C-500°C, the impregnated carrier. When the impregnation of the support in a solution of Nickel nitrate introduce the modifying additive is an organic acid with a concentration of 0.5 to 20.0 wt.%. The finished catalyst content is t monocrystalline NiO with srednevyborgskoe size, lying in the range of 2-3 nm, with a concentration of NiO 12,0-to 25.0 wt.% and γ-Al2O3- the rest. As an organic acid using acetic or oxalic acid. Apply granules media in the form of balls or cylinders with a diameter and a height lying in the range of 1.5-6.0 mm, annealed at a temperature of 500°C-700°C.

The main distinguishing features of the proposed method consist in the fact that in a solution of Nickel nitrate introduce the modifying additive is an organic acid with a concentration of 0.5 to 20.0 wt.%, and the finished catalyst contains monocrystalline NiO with srednevyborgskoe size lying in the range of 2-3 nm, with a concentration of NiO 12,0-to 25.0 wt.% and γ-Al2O3- the rest.

Additional distinguishing features of the proposed method lies in the fact that as an organic acid using acetic or oxalic acid. Apply granules media in the form of balls or cylinders with a diameter and a height lying in the range of 1.5-6.0 mm, annealed at a temperature of 500°C-700°C.

The present invention meets the condition of patentability "novelty", as in the prior art failed to find technical solutions, the essential features which would coincide with all the features available in the independent claims of the present invention. The invention meets the condition of the Pat the capacity of "inventive step", because the prior art does not describe technological solutions, the hallmarks of which are aimed at the solution of the technical problem on which the present invention is directed. The invention meets the condition of patentability "industrial applicability"because to date, the invention was implemented in a pilot plant (example 9).

The present invention is confirmed by the following examples, with each example 2-9 shows all the process parameters, which are stated in claims 1 to 4 claims, while table 1 lists only those parameters that are reflected in the first paragraph of the claims. In addition, table 1 shows which of the organic acids - acetic, or oxalic acid is used.

Example 1 (prototype). Active aluminum oxide in the amount of 100 g in the form of balls with a diameter of 3-6 mm, annealed at 700°C for 4 hours. After cooling, the granules of the active alumina impregnated with 200 ml of an aqueous solution of Nickel nitrate with a concentration in terms of NiO 200 g/l, which is prepared by dissolving 158,9 g of Nickel nitrate setevogo in 121 ml of distilled water. Next, the impregnated carrier is dried at 110°C for 2 hours and calcined at a temperature of 450°C for 4 hours. Spend 3 cycles of impregnation-prokalivanie is. Then after cooling, the granules impregnated with 200 ml of an ammonium carbonate solution with a concentration of ammonia - 100 g/l290 g/l, dried at 100°C for 2 hours and calcined at a temperature of 470°C for 4 hours. Get the catalyst composition of NiO - a 30.7 wt.%, else - γ-AL2O3with srednevyborgskoe size nanocrystallites NiO, is 5.0 to nanometers.

Example 2. Active aluminum oxide in the amount of 100 g in the form of balls with a diameter of 1.5 mm, annealed at 500°C for 4 hours. After cooling, the granules of the active alumina impregnated in an aqueous solution of Nickel nitrate with the addition of acetic acid with the concentration of Nickel nitrate in terms of NiO 150 g/l and the concentration of acetic acid 10.0 wt.%, which is prepared by dissolving 119,1 g of Nickel nitrate setevogo of 120.5 ml of distilled water with the addition of 20 ml of acetic acid with the concentration of 99.5 wt.%. Next, the impregnated carrier is dried at 100°C for 2 hours and calcined at a temperature of 450°C for 4 hours. Spend 3 cycles of impregnation-calcination. Get the catalyst composition of NiO is 22.2 wt.%, else - γ-Al2O3with srednevyborgskoe size nanocrystallites NiO, equal to 2.7 to nanometers.

Example 3. Active aluminum oxide in the amount of 100 g in the form of cylinders with a diameter of 3.0 mm and a height of 3.0 mm, annealed at a temperature of 700°is within 4 hours. After cooling, the granules of active aluminum oxide is impregnated with an aqueous solution of Nickel nitrate with the addition of acetic acid with the concentration of Nickel nitrate in terms of NiO 250 g/l and the concentration of acetic acid 10.0 wt.%, which is prepared by dissolving 198,5 g of Nickel nitrate setevogo in 81 ml of distilled water with the addition of 20 ml of acetic acid with the concentration of 99.5 wt.%. Next, the impregnated carrier is dried at 100°C for 2 hours and calcined at 500°C for 4 hours. Spend 2 cycles of impregnation-calcination. Get the catalyst composition of NiO - to 25.0 wt.%, else - γ-Al2O3with srednevyborgskoe size nanocrystallites NiO equal to 2.5 nanometers.

Example 4. Active aluminum oxide in an amount of 200 g in the form of balls with a diameter of 6.0 mm, annealed at a temperature of 600°C for 4 hours. After cooling, the granules of active aluminum oxide is impregnated with an aqueous solution of Nickel nitrate with the addition of acetic acid with the concentration of Nickel nitrate in terms of NiO 150 g/l and the concentration of acetic acid 20.0 wt.%, which is prepared by dissolving 238,2 g of Nickel nitrate setevogo and 201 ml of distilled water with the addition of 80 ml of acetic acid with the concentration of 99.5 wt.%. Next, the impregnated carrier is dried at 120°C for 2 hours and calcined at a temperature of 470°C for 4 hours. Spend 2 cycle the impregnation-calcination. Get the catalyst composition of NiO is 20.1 wt.%, else - γ-Al2O3with srednevyborgskoe size monocrystalline NiO equal to 2.0 nanometers.

Example 5. Active aluminum oxide in the amount of 100 g in the form of cylinders with a diameter of 1.5 mm and a height of 6.0 mm, annealed at 500°C for 4 hours. After cooling, the granules of active aluminum oxide is impregnated with an aqueous solution of Nickel nitrate with the addition of acetic acid with the concentration of Nickel nitrate in terms of NiO 200 g/l and the concentration of acetic acid, and 0.5 wt.%, which is prepared by dissolving 158,8 g of Nickel nitrate setevogo in 119,5 ml of distilled water with addition of 1 ml of acetic acid with the concentration of 99.5 wt.%. Next, the impregnated carrier is dried at 110°C for 2 hours and calcined at 500°C for 4 hours. Get the catalyst composition of NiO - 12.0 wt.%, else - γ-Al2O3with srednevyborgskoe size nanocrystallites NiO, equal to 2.8 to nanometers.

Example 6. Active aluminum oxide in the amount of 100 g in the form of balls with a diameter of 4.0 mm, annealed at 500°C for 4 hours. After cooling, the granules of active aluminum oxide is impregnated with an aqueous solution of Nickel nitrate with the addition of oxalic acid with the concentration of Nickel nitrate in terms of NiO 150 g/l and the concentration of oxalic acid 10.0 wt.%, prepared by R is stvorenie 119,1 g of Nickel nitrate setevogo and 27.2 g of oxalic acid in 127 ml of distilled water. Next, the impregnated carrier is dried at 120°C for 2 hours and calcined at a temperature of 450°C for 4 hours. Spend 3 cycles of impregnation-calcination. Get the catalyst composition of NiO - 24,8 wt.%, else - γ-Al2O3with srednevyborgskoe size nanocrystallites NiO equal to 2.5 nanometers.

Example 7. Active aluminum oxide in the amount of 100 g in the form of balls with a diameter of 3.0 mm, annealed at 700°C for 4 hours. After cooling, the granules of active aluminum oxide is impregnated with an aqueous solution of Nickel nitrate with the addition of oxalic acid with the concentration of Nickel nitrate in terms of NiO 250 g/l and the concentration of oxalic acid 10.0 wt.%, which is prepared by dissolving 198,5 g of Nickel nitrate setevogo and 27.2 g of oxalic acid in 87 ml of distilled water. Next, the impregnated carrier is dried at 100°C for 2 hours and calcined at 500°C for 4 hours. Spend 2 cycles of impregnation-calcination. Get the catalyst composition of NiO - of 24.7 wt.%, else - γ-Al2O3with srednevyborgskoe size nanocrystallites NiO equal to 2.5 nanometers.

Example 8. Active aluminum oxide in the amount of 100 g in the form of cylinders with a diameter of 6.0 mm and a height of 6.0 mm, annealed at a temperature of 600°C for 4 hours. After cooling, the granules of active aluminum oxide is impregnated with an aqueous solution of nitrate is Nickel with the addition of oxalic acid with the concentration of Nickel nitrate in terms of NiO 150 g/l and the concentration of oxalic acid 20.0 wt.%, which is prepared by dissolving 119,1 g of Nickel nitrate setevogo and 54.4 g of oxalic acid in 113 ml of distilled water. Next, the impregnated carrier is dried at 120°C for 2 hours and calcined at a temperature of 450°C for 4 hours. Spend 2 cycles of impregnation-calcination. Get the catalyst composition of NiO - by 22.1 wt.%, else - γ-Al2O3with srednevyborgskoe size nanocrystallites NiO, is 3.0 to nanometers.

Example 9. Active aluminum oxide in the amount of 100 kg in the form of cylinders with a diameter of 3.0 mm and a height of 6.0 mm, annealed at 500°C for 4 hours. After cooling, the granules of active aluminum oxide is impregnated with an aqueous solution of Nickel nitrate with the addition of oxalic acid with the concentration of Nickel nitrate 200 g/l in terms of NiO, and the concentration of oxalic acid, and 0.5 wt.%, which is prepared by dissolving 158,8 kg of Nickel nitrate setevogo and 1.36 kg of oxalic acid in 120 l of distilled water. Next, the impregnated carrier is dried at 110°C for 2 hours and calcined at 500°C for 4 hours. Spend 2 cycles of impregnation-calcination. Get the catalyst composition of NiO - 16.2 wt.%, else - γ-Al2O3with srednevyborgskoe size nanocrystallites NiO, equal to 2.5 nanometers.

Example 10. Active aluminum oxide in the amount of 500 g in the form of cylinders with a diameter of 3.0 mm and heights of the th 6.0 mm, annealed at 500°C for 4 hours. After cooling, the granules of active aluminum oxide is impregnated with an aqueous solution of Nickel nitrate with the addition of acetic acid with the concentration of Nickel nitrate in terms of NiO 200 g/l and the concentration of acetic acid of 0.49 wt.%, which is prepared by dissolving 794,2 g of Nickel nitrate setevogo in 598 ml of distilled water with the addition of 4.95 ml of acetic acid with the concentration of 99.5 wt.%. Next, the impregnated carrier is dried at 110°C for 2 hours and calcined at 500°C for 4 hours. Spend 2 cycles of impregnation-calcination. Get the catalyst composition of NiO to 11.2 wt.%, else - γ-Al2O3with srednevyborgskoe size nanocrystallites NiO 3,3 to nanometers.

Example 11. Active aluminum oxide in the amount of 100 g in the form of cylinders with a diameter of 3.0 mm and a height of 6.0 mm, annealed at 500°C for 4 hours. After cooling, the granules of active aluminum oxide is impregnated with an aqueous solution of Nickel nitrate with the addition of oxalic acid with the concentration of Nickel nitrate in terms of NiO 200 g/l and the concentration of oxalic acid to 20.2 wt.%, which is prepared by dissolving 158,8 g of Nickel nitrate setevogo and 54.9 g of oxalic acid in 93 ml of distilled water. Next, the impregnated carrier is dried at 110°C for 2 hours and calcined at 500°C for 4 hours. Spend 2 cycles of impregnation-p is ukalyvaniya. Get the catalyst composition of NiO and 22.6 wt.%, else - γ-Al2O3with srednevyborgskoe size nanocrystallites NiO, equal to 2.7 to nanometers.

Example 12. Active aluminum oxide in the amount of 100 g in the form of cylinders with a diameter of 3.0 mm and a height of 6.0 mm, annealed at 500°C for 4 hours. After cooling, the granules of active aluminum oxide is impregnated with an aqueous solution of Nickel nitrate with the addition of acetic acid with the concentration of Nickel nitrate in terms of NiO 200 g/l and the concentration of acetic acid at 20.2 wt.%, which is prepared by dissolving 158,8 g of Nickel nitrate setevogo in 80 ml of distilled water with the addition of 40.4 ml of acetic acid with the concentration of 99.5 wt.%. Next, the impregnated carrier is dried at 110°C for 2 hours and calcined at 500°C for 4 hours. Spend 2 cycles of impregnation-calcination. Get the catalyst composition of NiO is 22.4 wt.%, else - γ-Al2O3with srednevyborgskoe size nanocrystallites NiO, equal to 2.7 to nanometers.

Example 13. Active aluminum oxide in the amount of 100 g in the form of cylinders with a diameter of 3.0 mm and a height of 6.0 mm, annealed at 500°C for 4 hours. After cooling, the granules of active aluminum oxide is impregnated with an aqueous solution of Nickel nitrate with the addition of oxalic acid with the concentration of Nickel nitrate in terms of NiO 200 g/l and conc is Tracia oxalic acid of 0.49 wt.%, which is prepared by dissolving 158,8 g of Nickel nitrate setevogo and 1.35 g of oxalic acid in 120 ml of distilled water. Next, the impregnated carrier is dried at 110°C for 2 hours and calcined at 500°C for 4 hours. Spend 3 cycles of impregnation-calcination. Get the catalyst composition of NiO is 11.9 wt.%, else - γ-Al2O3with srednevyborgskoe size nanocrystallites NiO, equal to 3.2 to nanometers.

The activity of the samples of the catalysts in the examples is determined by the reaction rate of the hydrogenation of carbon monoxide to methane formation in nitric mixture with a volume ratio of H2/N2- 3/1 at temperatures of 150°C-300°C., an absolute pressure of 0.1 MPa, the volume fraction of CO in the initial mixture of 0.85%-0,90% in laboratory flow-circulation installation. The flow rate of the source gas mixture is set to 10 l/h of the Speed of circulation of the gas mixture in the loop installation is equal to 1000 l/h At the input and output of the gas mixture with a flow rate of 10 l/h in the cycle set the ratio of circulation ~ 100 that provides bigradient test conditions.

Table 1
An example implementation of the methodThe activity of the catalyst, the molCH4/(h·kg) is ri, the process temperature of 200°C and an absolute pressure of 0.1 MPa The concentration of Nickel nitrate in terms of NiO in the impregnating solution, g/lThe drying temperature of the catalyst, °CThe temperature of calcination of the catalyst, °CThe concentration of the modifying agent in the impregnating solution, wt.%Production cost of 1 ton of catalyst, RRThe time period for implementing the method, h
Acetic acidOxalic acid
1 (prototype)4,3200100470472,832
25,515010045010,0330,024
3of 5.4250100500 10,0357,018
45,320012047020,0308,018
54,42001105000,5202,012
65,515012045010,0380,024
7of 5.425010050010,0350,018
85,3200120450 20,0316,018
94,62001105000,5289,518
104,12001105000,49200,018
115,020011050020,2350,518
124,820011050020,2354,318
134,2200110500 0,49245,024

Examples 10 and 13 are shown with the introduction of the acetic and oxalic acid below the lower limit. Examples 11 and 12 are shown with the introduction of oxalic and acetic acid above the upper limit.

From the comparison of examples 2 to 9 of the proposed method with the example 1 by the method prototype can be seen that the proposed method can improve the activity of the catalyst 1,02 of 1.28 times, to reduce the cost of producing 1 ton of catalyst 1.24-2.34 times, to reduce the period of time, the method 1.33-2.67 times.

These effects are caused by the decrease in the number of technological operations in the proposed method compared with the method of the prototype, as well as reduced costs of raw materials (chemicals) and energy to obtain the catalyst. The proposed method can improve the catalyst activity, probably by reducing srednevyborgskoe size nanocrystallites NiO, which is associated with the modifying action of the additive is an organic acid acetic or oxalic.

The decrease medicationbuy supplements - organic acid is less than 0.5 wt.% in example 10 for acetic acid in example 13 for oxalic acid is not possible to achieve uniform distribution of the active component on the catalyst surface, which leads to education is to Finance larger nanocrystallites NiO during annealing of the sample (3.3 nm in example 10 and 3.2 nm in example 13). This increase srednevyborgskoe size nanocrystallites active component leads to a decrease of the surface area of the active component and, consequently, to a reduced activity of the catalyst during catalytic hydrogenation of carbon oxides to methane formation.

The increase in the content of the modifying additive is an organic acid, more than 20.0 wt.% in example 11 for oxalic acid in example 12 for acetic acid leads to unnecessary increase in the cost of manufacture of the catalyst due to the increased consumption of the modifying additive is an organic acid.

Sources of information taken into account in the examination

1. Catalysis in industry, No. 5, 2012, p.50.

2. Copyright certificate №272283, 6 MCI B01J 23/755, 1970.

3. Patent RU 2472587, 6 IPC B01J 37/00, 37/02, 21/04, 23/755, SS 1/04, C9/04.

1. A method of producing a catalyst for the process of mahanirvana, including the impregnation of the carrier on the basis of active aluminum oxide in the form of granules in a solution containing Nickel nitrate, followed by drying at a temperature of 100°C - 120°C and calcination at a temperature of 450°C-500°C, the impregnated carrier, characterized in that a solution of Nickel nitrate introduce the modifying additive is an organic acid with a concentration of 0.5 to 20.0 wt.%, and the finished catalyst contains monocrystalline NiO with srednevyborgskoe size, Agamim in the range of 2-3 nm, with the concentration of NiO 12,0-to 25.0 wt.% and γ-Al2About3- the rest.

2. The method according to claim 1, characterized in that the organic acid using acetic or oxalic acid.

3. The method according to claim 1, characterized in that the applied granules media in the form of balls or cylinders with a diameter and a height lying in the range of 1.5 - 6.0 mm, annealed at a temperature of 500°C-700°C.



 

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21 cl, 3 tbl, 1 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of recuperating hydrogen and methane from a stream of cracking gas in the low temperature part of an ethylene synthesis apparatus, which involves feeding a C2 fraction coming from an ethane separation apparatus (deethaniser) through a heat exchanger (E1) into the first section (A) of a multi-section condensate separator (D1). The condensate is tapped from the first section (A) of the multi-section condensate separator (D1) and fed into a methane separator (T1). Gas from the multi-section condensate separator (D1) is fed into the next heat exchanger (E2) and additionally cooled therein. The additionally cooled gas is fed into the second section (B) of the multi-section condensate separator (D1) in order to separate liquid. The condensate formed is again fed into the methane separator (T1). Gas from the second section (B) of the multi-section condensate separator (D1) is fed into an expander (XI) where it is expanded and then fed into the methane separator (T1) and the C2 fraction from the bottom of the methane separator (T1) is throttled while lowering its pressure to pressure which is predominant in the distillation column for C2 hydrocarbons, partially evaporated in the heat exchanger (E1) and fed into the distillation column for C2 hydrocarbons.

EFFECT: present method significantly lowers power consumption while simultaneously lowering capital investment.

3 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of treating an active Fischer-Tropsch catalyst and an apparatus for preparing and treating said catalyst. The method of treating an active catalyst includes loading a mixture of particles of an active Fischer-Tropsch catalyst and molten wax, which is at a temperature T1 and which sets at a lower temperature T2 lying between 70°C and 140°C, where T2<T1, into a plurality of moulds; at least partial immersion of the moulds into a cooling liquid to cool the organic substance to a temperature T3, where T3≤T2, to obtain cast products in form of candles with a volume of less than 140 ml but more than 2 ml each, having an organic substance matrix in which particles of the active catalyst are dispersed such that the catalyst particles are coated with wax; removing the cast products from the moulds; loading the mixture into moulds, immersing the moulds into a cooling liquid and removing the cast products form the mould in a casting machine. The apparatus includes equipment for preparing or regenerating the catalyst, including a reservoir for applying a coating onto the catalyst; a transportation means for transferring the mixture of particles of the active catalyst and molten organic substance from the reservoir for applying a coating onto the catalyst; a casting machine for producing cast products in form of candles which includes a plurality of moulds into which the transportation means can unload the mixture of particles of the active catalyst and molten organic substance, and a cooling bath capable of holding a cooling liquid into which the moulds can be immersed at least partially.

EFFECT: method and apparatus enables to safely and easily move a catalyst from the production site to the point of use without losing activity.

18 cl, 3 dwg, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to field of synthesis of hydrocarbons from synthesis-gas mixture. Invention deals with method for optimisation of functioning of zone of hydrocarbon synthesis from raw material, which contains synthesis-gas, in which catalyst, containing cobalt, is present, with claimed method including the following stages: a) determination of theoretic value of partial pressure of carbon monoxide in reaction zone, b) regulation of partial CO pressure, determined at stage a), to value, higher or equal 4 bars, c) determination of new value of theoretic value of partial CO pressure CO in reaction zone.

EFFECT: optimisation of device operation, improvement of catalyst stability.

21 cl, 2 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for producing isoparaffin-rich synthetic oil from CO and H2, and a method of producing said catalyst. The catalyst is a granular porous composite material containing a spatial heat-conducting mesh if aluminium metal and Raney cobalt and a linking component containing zeolite in H form. In the composite material, the fraction of macropores in the open porosity of the catalyst granules is 55-79% and the fraction of mesopores with size of 70-500 Е in the open porosity of the catalyst granules is 7-20%. The method of producing the catalyst includes mixing powder of the linking component, peptising the obtained mixture with a solution of nitric acid to obtain a linking component in form of a homogeneous gel, mixing the homogeneous gel with fine Raney cobalt powder, aluminium metal powder and a liquid phase to obtain a homogeneous paste, extruding the obtained paste to obtain granules and calcining the obtained granules. One of the powders of the linking component used is zeolite in H form.

EFFECT: improved mass transfer of reactants into the catalyst granules and high content of isoparaffins in the obtained oil.

13 cl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis. Described is a method of regenerating one or more particles of a cobalt-containing Fischer-Tropsch catalyst in situ in a reactor tube, the method comprising steps: (i) oxidising the catalyst particle(s) at temperature of 20-400°C; (ii) treating the catalyst particle(s) for more than 5 min with a solvent; (iii) drying the catalyst particle(s); and (iv) optionally reducing the catalyst with hydrogen or any hydrogen-containing gas.

EFFECT: high catalyst activity.

10 cl, 4 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to an improved method of producing methanol, dimethyl ether and low-carbon olefin from synthesis gas. The method includes a step of contacting synthesis gas with a catalyst under conditions for converting the synthesis gas into methanol, dimethyl ether, and low-carbon olefins, characterised, wherein the catalyst contains an amorphous alloy consisting of components M-P, M-B or M-B-P, wherein component M represents two or more elements selected from lanthanides and the third, fourth and fifth series of groups IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB and VIII of the Periodic Table of Elements.

EFFECT: method increases selectivity of the target product by conducting the process in conditions which ensure high conversion of CO and availability of carbon.

16 cl, 3 dwg, 3 tbl, 11 ex

Catalysts // 2517700

FIELD: chemistry.

SUBSTANCE: invention relates to catalysis. Described are methods of preparing a catalyst precursor, the first preparation step of which involves impregnating catalyst support particles with an organic cobalt compound in an impregnating liquid to form an impregnated intermediate product, calcining the impregnated intermediate product at calcination temperature not higher than 400°C to obtain a calcined intermediate product; and the second preparation step of which involves impregnating the calcined intermediate product from the first step with an inorganic cobalt salt in an impregnating liquid to form an impregnated support and calcining the impregnated support to obtain a catalyst precursor, wherein neither of the inorganic cobalt salts used at the second preparation step is used at the first preparation step. Described is synthesis of hydrocarbons in the presence of catalysts obtained using said method.

EFFECT: high catalyst activity.

20 cl, 5 tbl, 11 ex

FIELD: chemistry.

SUBSTANCE: claimed invention provides process of production of methanol, dimethyl ether as main products and low-carbon olefin as byproduct from synthesis gas, in which said process contains stage of contact of synthesis-gas with catalyst. Catalyst contains amorphous alloy, consisting of first component A1 and second component, with second component representing one or several elements or their oxides, selected from group IA, IIIA, IVA, VA, IB, IIB, IVB, VB, VIB, VIIB, VIII and a series of lanthanides of periodic table of elements, and said second component is different from first component A1. Conditions for conversion have reaction temperature 200-270°C, reaction pressure 1-6 MPa, volume rate of synthesis-gas supply 1000-10000 ml/g·hour and molar ratio between H2 and CO in synthesis-gas from 1 to 3.

EFFECT: in accordance with said process synthesis-gas can be converted into methanol, dimethyl ether and low-carbon olefin with high degree of CO conversion, high selectivity of target product and high availability of carbon.

19 cl, 3 dwg, 3 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing hydrocarbon gasoline fractions from synthesis gas, having volume ratio H2/(CO+CO2) of 1-3, by contacting, at temperature of 360-440°C and pressure of 100 atm, with a bifunctioanal catalyst containing a ZSM-5 or ZSM-11 zeolite which contains 0.1-1 wt % iron, and a metal oxide component consisting of Zn, Cr and W oxides, wherein content of N2 in the synthesis gas ranges from more than 10 to 20 vol. % and content of CO2 ranges from 1 to 15 vol. %. Wherein total content of N2 and CO2 in the synthesis gas is not more than 30 vol. %, and the volume ratio of components (H2-CO2)/(CO+CO2) is in the range of 1.7-2.3, and the process of converting synthesis gas is carried out with not less than 15 circulations. The invention also relates to a method where a stream of synthesis gas, having volume ratio of components (H2-CO2)/(CO+CO2) less than 1.7, with content of N2 from 20 to 30 vol. % and content of CO2 from 1 to 15 vol. %, is divided into two streams, followed by separating H2 from the first stream and adding to the second stream in an amount which enables to lower content of N2 in the second stream to concentration lower than 20 vol. % and increase volume ratio of components (H2-CO2)/(CO+CO2) in the second stream to 1.7-2.3, which is then fed for contacting with the bifunctional catalyst with not less than 15 circulations, wherein the first stream is taken for burning after separating H2.

EFFECT: obtaining gasoline fractions with low concentration of benzene, high selectivity on C5 hydrocarbons and methane.

3 cl, 1 tbl, 6 ex

FIELD: process engineering.

SUBSTANCE: this invention relates to production of hydrogen-bearing gas and can be used in processing of Fischer-Tropsh process waste products in the presence of porous membrane-catalytic system. Porous catalytic membrane is produced by vibratory compaction of fine mix containing nickel and cobalt at 1:1 ratio and treated in muffle furnace at spontaneous ignition temperature, then cured and cooled. Invention covers also the process of processing Fischer-Tropsh process waste products. Proposed method comprises processing methane, carbonic acid and organic substances diluted in water (methanol, ethanol, methyl ethyl ketone, acetic acid and acetone) by carbonic acid-steam conversion in the presence of said catalytic module at 680-780°C, 1-1.5 atm and the rate of feeding the initial steam-gas mix along with water steam released in the process, 16000-96000 p-1 to obtain conversion products, that is synthesis gas and water cleaned of organic substance impurities.

EFFECT: efficient process, higher yield of valuable hydrocarbons.

4 cl, 1 dwg, 4 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: described is a Fischer-Tropsch synthesis method where: raw gas containing CO and H2, obtained from coal gasification, is desulphurised and then fed as starting gas into a Fischer-Tropsch synthesis apparatus (3) in which hydrocarbons are formed via catalytic reactions from carbon monoxide and hydrogen, wherein the hydrocarbons are removed in form of liquid products (4), a gas stream containing CO and CO2, coming out of the Fischer-Tropsch synthesis apparatus (3) is compressed and fed into a conversion area (6) in which CO is converted with steam to H2 and CO2 and gas coming out of the conversion area (6) after purification (9, 14), from which CO2 and/or other components except H2 are removed, is fed back as gas with high content of H2 together with the desulphurised starting gas into the Fischer-Tropsch synthesis apparatus (3), characterised by that a partial stream (8) of the desulphurised starting gas is removed and fed before a compressor (5) into a loop with a circulation gas stream and that in the gas stream fed into the Fischer-Tropsch synthesis apparatus (3), molar ratio of H2 to CO is set at least equal to 1.5:1. Also described is an installation for carrying out said method, said installation comprising: a Fischer-Tropsch synthesis apparatus (3) with a reactor and an apparatus for separating liquid products, a pre-switched on apparatus (2) for desulphuration of raw gas containing CO and H2, which is formed during coal gasification (1), an apparatus for returning the gas stream coming from the Fischer-Tropsch synthesis apparatus (3) into the desulphurised starting gas, fed into the Fischer-Tropsch synthesis apparatus (3), wherein the apparatus for returning the gas stream has a compressor (5) which operates on steam from a converter (6) for converting CO to H2 and CO2 and an apparatus (9, 14) for removing CO2 from the circulating gas stream, characterised by that the apparatus for returning the gas stream is linked to with a main line for feeding desulphurised starting gas through a branching line (8), wherein the branching line (8) is connected before the compressor (5) in the direction of flow with the returning apparatus, and that in the gas stream fed into the Fischer-Tropsch synthesis apparatus (3), molar ratio of H2 to CO can be at least 1.5:1.

EFFECT: high output of the product without considerably increasing the cost of the equipment.

10 cl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention can be used to obtain modified carbon nanotubes. The method of modifying carbon nanotubes includes treatment of carbon nanotubes with an aqueous solution of an oxidising agent in the form of a persulphate or hypochlorite solution at pH higher than 10, carried out simultaneously with mechanical treatment.

EFFECT: invention enables to obtain modified carbon nanotubes having good dispersability in water and in polar organic solvents with low consumption of reactants compared to known methods.

3 cl, 2 ex

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