The method of purification of hydrogen from impurities of oxides of carbon and method for producing the catalyst for implementation

 

(57) Abstract:

The invention relates to methods for Nickel-alumina-chromium catalyst and can be used in the chemical industry for fine purification of hydrogen-containing gases from carbon oxides by catalytic hydrogenation of the impurities to methane. The invention consists in a method of producing a Nickel-alumina-chromium catalyst mahanirvana by mixing the basic Nickel carbonate, chromic acid and crushed hydroxide or aluminum oxide, followed by drying, calcination and molding, the calcined catalyst mass is treated with ammonium carbonate solution with a concentration of ammonia (6-12).%. and shaping is done by extrusion into pellets with a subsequent heat treatment of the granules. Processing paste ammonium carbonate solution lead to a residual moisture content 25-32-wt.%. Hydroxide or aluminum oxide is crushed to particles with a size of 100 μm or less. The catalyst contains components in the following ratio, wt.%: Nickel 20-25, chromium oxide 7-10, alumina rest. By running granules of cylindrical shape to receive the catalyst spherical shape. The proposed method allows to replace the non-aligned receive highly active Nickel-alumina-chromium catalyst mahanirvana, having a low bulk weight (less than 1.0 kg/DM3), with the content of the active component of Nickel below 10-20 wt. % compared with katalizatorami obtained in a known manner. 2 S. and 3 C.p. f-crystals, 5 PL.

The invention relates to a method for catalytic purification of hydrogen-containing gas from impurities of carbon oxides and methods of producing the catalyst for this process and can be used in the chemical industry for fine purification of hydrogen and hydrogen-containing gases from carbon oxides by catalytic hydrogenation of the impurities to methane.

A known method of purification of hydrogen-containing gas from impurities of carbon oxides by hydrogenation to methane in the presence of a catalyst containing 32,8-to 50.0 wt. Nickel, 20,4-to 23.8 wt. chromium oxide and alumina rest. The process is carried out at 240aboutWith and volumetric rate of gas supply 5000 h-1(see USSR author's certificate N 780881, CL 01 J 37/02, 1980) prototype.

There is also known a method of producing a catalyst for the implementation of the above method, comprising a mixture of basic Nickel carbonate, ammonium sulphate and reduced to 50 μm hydroxide or aluminum oxide, followed by drying, use the try in a cylindrical shape (matrix) and compress in a tablet at a high pressure.

The catalyst contains components in the following ratio, wt. Nickel 32,8-50.0 chromium Oxide 20,4-23,8 alumina Rest (see author's certificate N 780881, 01 J 37/02, 1980. the prototype).

The disadvantage of these methods is the low activity of the catalyst per unit of its mass with high bulk density. This is due to the following:

This method of preparation of the catalyst allows to produce pellets only to pelletizing. But in the tabletting process creates a pressure of about 100-300 MPa. At this pressure coarsely porous structure (macropores) is almost completely destroyed, the material perepletaetsja, and therefore, increased bulk density and reduced activity of the contact mass per unit mass. Tablets there are residual internal stress, who are not able to relax during tableting. The catalyst in the process of operation more vulnerable to erosion from the influence of the gas flow (the original components of the reaction) and thermal cracking. Strength tablets have a large scatter, resulting in the portion of tablets with low strength is destroyed already when loading the contact apparatus.

It should also be noted that the tablet maginalization mahanirvana, obtained in a known manner, has a high bulk density of more than 1.2 kg/DM3and to increase its activity increase the amount of active component of Nickel from 33 to 50%

The aim of the invention is to increase the efficiency of purification process of the hydrogen-containing gas from impurities of oxides of carbon by increasing the activity of the catalyst and reduce its bulk density.

This is solved by the method of purification of hydrogen from impurities of carbon oxides, including hydrogenation to methane in the presence of nickelchromium catalyst at 240aboutWith that uses granular catalyst cylindrical or spherical shape containing components in the ratio, by weight. Nickel 20-25 chrome Oxide 7-10 alumina Rest, and hydrogenation is carried out at a volumetric rate of gas supply 10000-20000 h-1.

The task is also solved by a method of producing a catalyst for purification of hydrogen from impurities of carbon oxides comprising a mixture of basic Nickel carbonate, chromic acid and crushed hydroxide or aluminum oxide, followed by drying, calcination and molding, in which, after calcination the catalyst mass obrabatyvat. and then carry out molding by extrusion into pellets, heat treated.

While the hydroxide or aluminum oxide is crushed to particle size less than 100 microns.

In addition, the heat treatment of the granules is carried out at 200aboutC.

Running granules of cylindrical shape to carry out the preparation of the catalyst of the spherical shape.

The advantage of the invention is to provide a catalyst with high activity and low bulk density. This is because when using ammonium carbonate solution (AKP), containing about 6-12. ammonia and residual moisture of the paste 25-32 wt. formed plastic-tight mass, from which the granules nicolacopoulos a catalyst having a relatively low bulk density (less than 1.0 kg/nm3) at the optimum mechanical strength. The use of extrusion-forcing plasticized paste through the matrix of holes (die plate) at low pressure (0.8 to-1.5 MPa) allows to obtain granules with an open porous structure. The presence of macropores leads to the reduction of the bulk density of the catalyst. The resulting catalyst has a high activity when the Nickel content is even less than 25 wt.

aboutAllows you to achieve optimum mechanical strength of the catalyst, and running a cylindrical pellets to the spherical shape allows you to get the kind of molded catalyst, lowering the hydraulic resistance and compact packaging layer.

The resulting catalyst contains components in the following ratio, wt. Nickel 20-25 chrome Oxide 7-10 alumina Rest

The use of the above catalyst for the purification of hydrogen-containing gas from impurities of carbon oxides can provide a high cleaning efficiency and high performance process. The hydrogenation is carried out at a volumetric rate of gas supply 10000-20000 h-1that also allows you to reduce the single catalyst loading.

The possibility of obtaining a catalyst according to the claimed method is confirmed by the following examples.

P R I m e R 1. Aluminum oxide (278 g) pre-shredded in a laboratory FWS is mesh within 15 minutes When operating the mixer to the mixture is added in portions a solution of chromic anhydride (42 g CrO3in 144 ml of distilled water). To mass add 270 ml of water and mix until you obtain a creamy, then include the heating of the mixer and continue mixing at a temperature of 90aboutC for 2 h

Then the mass is evaporated, opening the lid of the mixer, unloaded and dried at 120aboutC for 3 h and calcined at 400about4 o'clock the Calcined mixture is again loaded into the mixer, add ammonium carbonate solution containing 6% ammonia, and plastificator the mixture for 15 min Humidity paste 25% More mass is formed into pellets of arbitrary length with a diameter of 5 + 1 on the screw formulatea. The obtained granules were dried at 200aboutC for 4 h the resulting catalyst contains, by weight. Nickel 20.0 chromium Oxide 7,0 alumina Rest

P R I m m e R 2. For the preparation of the catalyst charge, g: Al2O3260; window 204; CrO348. Alumina is crushed to 80 μm, the content of ammonia per ACRE is about 9. residual moisture of the paste 29 wt. The rest analogously to example 1.

The resulting catalyst contains, by weight. Nickel 22,75; chromium oxide 7,9; alumina rest is. The rest is similar to examples 1,2.

The resulting catalyst contains, by weight. Nickel 23,3; chromium oxide 9,2; alumina rest.

P R I m e R 4. Granules of cylindrical shape, obtained in example 3, running to the spherical shape.

P R I m e R 5. For the preparation of the catalyst charge, g: Al2O3240; OKH 224; CrO361. Alumina is crushed to 100 μm. The content of ammonia per ACRE is about 12. residual moisture of the paste 32 wt. The rest is similar to examples 1-3.

The resulting catalyst contains, by weight. Nickel 25,0; chromium oxide 10,0; alumina rest.

In table. 1 shows the values of bulk density and mechanical strength of the catalyst depending on the concentration of ammonia in ammonium carbonate solution, and table. 2 data for the same indicators, depending on the residual moisture of the paste. The composition of the catalyst, wt. Nickel 23,0, chromium oxide 9,1, alumina rest. The mechanical strength of the samples was determined by the method of splitting on the knife with a thick blade knife 0,1 mm

The results imply that the optimal bulk density (0.7-0.9 kg/DM3) and mechanical strength (0.7 to 1.2 kg/mm ) are achieved at the end the jam, and activity depending on the Nickel content is shown in table. 3.

The activity of the catalysts was determined bigradient method and rate of hydrogenation of carbon monoxide. The measurement is conducted on protodesilylation installation at a pressure of 0.1 MPa, temperature (200 1)aboutWith volume concentration of CO in the cycle of 0.3% on the granules (extrudates) the following dimensions: diameter 5 1, length 6 1.

The results imply that the optimal values of the bulk density and mechanical strength at the maximum activity is achieved when the following catalyst composition, wt. Nickel 20-25 chrome Oxide 7-10 alumina Rest

In table. 4 shows the comparative characteristics of the prototype and samples obtained according to the present invention (examples 1-5).

The proposed method allows to replace inefficient molding process by pressing the powder to form pellets by extrusion of the catalyst mass. You get a high-level nicelullaby catalyst mahanirvana with low bulk weight (less than 1.0 kg/DM3), with the content of the active component of Nickel below 10-20 wt. compared with the catalysts obtained in a known manner.

P R I m e R 6 (cleaning gas). The hydrogen containing about. WITH 1,0, CO20,85, purified from carbon oxides by hydrogenation of the latter to methane molded catalyst in the form of cylindrical pellets containing 20 wt. Nickel. The process is conducted on the grain 2-3 mm at a pressure of 0.1 MPa and whole grains at a pressure of 2.5 MPa. The residual content of co and CO2less than 5 cm3/m3each component is achieved under the following conditions: P, MPa 0,1 2,5 (industrial-

nnye conditions,

(grain) (granules)aboutFROM: CO 200 220 CO2240 250 CO + CO2240 250 space velocity, h-110000 10000

The residual content of co and CO2meets the requirements of the regulations for degree of purity when mahanirvana.

P R I m e R 7. The process is conducted on the catalyst containing 250 wt. Nickel. The rest analogously to example 6. P, MPa 0,1 2,5

(grain) (granules)aboutFROM: CO 200 220 CO2240 250 CO + CO2240 250

Objend from oxides of carbon known (prototype) and the catalyst samples, obtained according to the present invention.

The process is carried out on the fine grain in the conditions described in the ed. mon. USSR N 780881, as well as to whole tablets (prototype) and granules.

The invention can be obtained the following advantages:

molded catalyst is effectively used for fine purification of hydrogen-containing gas from impurities oxide and carbon dioxide to a residual content of less than 5 cm3/m3each component, when this process is carried out at a high flow rate of up to 20,000 h-1that allows to reduce single loading of the catalyst volume in the reactor mahanirvana not less than 2 times compared with the preformed catalyst. This leads to a reduction in the cost of loading;

inefficient process of extrusion molding powder is replaced by the process of extrusion mass. You get a catalyst containing the active ingredient Nickel 10-20 wt. lower than the tablets that allows you to save critical raw materials the basic Nickel carbonate;

the catalyst has a low bulk density less than 1.0 kg/DM3, which accounts for the single catalyst loading in the reactor mahanirvana is reduced by approximately 30% pokidov carbon including hydrogenation to methane in the presence of nickelchromium catalyst at a temperature of not more than 240o, Characterized in that use granular catalyst cylindrical or spherical shape containing components in the ratio, wt.%:

Nickel - 20 - 25

The chromium oxide - 7 - 10

Alumina - Rest

and the hydrogenation is carried out at a volumetric rate of gas supply 10000 - 20000 h-1.

2. A method of producing a catalyst for purification of hydrogen from impurities of carbon monoxide, comprising a mixture of basic Nickel carbonate, chromic acid and crushed hydroxide or aluminum oxide, followed by drying, calcination and molding, characterized in that after calcination the catalyst mass is treated with ammonium carbonate solution with a concentration of ammonia 6 to about 12. % to a residual moisture content in the mass 25 to 32 wt.%, and then carry out molding by extrusion into pellets and heat treatment.

3. The method according to p. 2, characterized in that the hydroxide or aluminum oxide is crushed to particle size less than 100 microns.

4. The method according to PP.2 and 3, characterized in that the heat treatment of the granules is carried out at 200oC.

5.

 

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FIELD: hydrocarbon conversion catalysts.

SUBSTANCE: catalyst for generation of synthesis gas via catalytic conversion of hydrocarbons is a complex composite composed of ceramic matrix and, dispersed throughout the matrix, coarse particles of a material and their aggregates in amounts from 0.5 to 70% by weight. Catalyst comprises system of parallel and/or crossing channels. Dispersed material is selected from rare-earth and transition metal oxides, and mixtures thereof, metals and alloys thereof, period 4 metal carbides, and mixtures thereof, which differ from the matrix in what concerns both composition and structure. Preparation procedure comprises providing homogenous mass containing caking-able ceramic matrix material and material to be dispersed, appropriately shaping the mass, and heat treatment. Material to be dispersed are powders containing metallic aluminum. Homogenous mass is used for impregnation of fibrous and/or woven materials forming on caking system of parallel and/or perpendicularly crossing channels. Before heat treatment, shaped mass is preliminarily treated under hydrothermal conditions.

EFFECT: increased resistance of catalyst to thermal impacts with sufficiently high specific surface and activity retained.

4 cl, 1 tbl, 8 ex

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