The method of producing hydrogen and a method of producing a catalyst for producing hydrogen

 

(57) Abstract:

Usage: in the methods for producing hydrogen by catalytic conversion of carbon monoxide, as well as in the compositions and methods of making catalysts for this process. The inventive method enables the production of hydrogen by steam reforming of carbon monoxide in the presence of the oxide copper-zinc-manganese catalyst containing, by weight. 30 65 oxide-copper; 18 31 zinc oxide; 0.1 to 2.7 manganese dioxide; 0,08 - 0,8 carbon and carrier-based alumina rest. The process is carried out at 190 400C and pressures up to 30 MPa. It is also proposed a method of obtaining a catalyst. 2 S. and 1 C. p. F.-ly, 1 table.

The invention relates to chemical technology, in particular to methods of producing hydrogen by catalytic conversion of carbon monoxide, as well as compositions and methods of producing catalysts for this process.

A known method of producing hydrogen by steam reforming of carbon monoxide in the presence of a catalyst NTC-4 based on Pt-group, the process temperature of 200-250aboutC, correlation of vapor-gas 0.4 to 0.8, the pressure up to 30 MPa. (Handbook of apothica. M. Chemistry, 1986, S. 144-146).

The disadvantages of the method are limited woei temperatures up to 400aboutWith, as well as the duration of the recovery process-activation of the catalyst up to 5-7 days and limiting the supply of reducing agent in the activation period of up to about 1-2. hydrogen, the impossibility of carrying out the process in one stage.

There is a method of preparation of the catalyst for carbon monoxide conversion on the basis of the carbonates of copper, zinc and aluminum hydroxide.

The disadvantage of this method is that in the process of preparation of a mixture of copper and zinc components do not interact, which subsequently reduces the catalyst activity. In addition, due to the increased hardening rate of weight hindered the process of its formation.

The task of the invention to develop the method of producing hydrogen by catalytic conversion of carbon monoxide in the low mode on a cheap catalyst with increased activity.

For this method of hydrogen production is carried out by steam conversion of carbon monoxide in the presence of a catalyst containing, by weight. the copper oxide 30-65; zinc oxide 18-31; manganese dioxide 0.1 to 2.7; the carbon 0.08 to 0.8 and the media on the basis of alumina rest. When the conversion process is carried out at 190-400aboutC and pressures up to 30 MPa.

For gaining the ora feed on a mixture of activated carbon and manganese compounds, then separate the precipitate and mix it with a carrier, then the resulting mass is injected Cu-Zn-Al or Cu-Zn-Al-Mn alloy in an amount of 1-40 wt. when the ratio of the components of the alloy Cu-Zn-Al(1-6):(0,3-6):(1-6) or Cu-Zn-Al-Mn(1-6):(0,3-6): (1-6): (0,1-1) accordingly and carry out intensive mixing of the mass to change its color to gray-brown or greenish-brown and odors alcohols, for media use aluminum oxide or shungite or calcium aluminate.

Using the above catalyst composition in the process of producing hydrogen can increase the degree of conversion at low process temperatures and to carry out the process in one stage.

The essence of the process of synthesis of the catalyst is to conduct solid-phase reactions of the original mixture components with alloy type alloy Devarda (Cu-Zn-Al and Cu-Zn-Al-Mn) emitting in the process of intensive mixing of the active atomic hydrogen, activating the initial state of the copper and allow ultimately to increase the activity of the catalyst during operation.

Enter in the composition of the carbon has recovery properties and maintains the active state of the copper in the entire period from the 2 to 8 allow the transfer of oxygen-containing components from the salt forms of metal to metal.

P R I m e R 1 (receipt of catalyst). The reactor is heated and intense mixing, equipped with a flow of carbon dioxide and water, cook the mixture is isomorphic to carbonate salts of copper and zinc in solution, add activated carbon and manganese oxide (number of components see table.1). Then separated from the precipitate, dry it and mix with the carrier (the number and type of vehicle, see the table).

The resulting mass is loaded into a ball mill, fall asleep there, alloy Cu-Zn-Al (1 wt. (the ratio of the components in the alloy, see table).

The molding is injected lubricating component (stearate copper or graphite) in an amount of 1.5 wt. The mass is stirred in a ball mill until the smell of alcohol and change color. Then the pulp, moisturize and formed into pellets. The resulting catalyst has the composition: Cu oxide 40,2; Zn oxide 30,1; carbon 0.8; medium (Al2O3) 28,1.

P R I m e R s 2-6. The process is conducted as in example 1 under the conditions reflected in the table.1.

Examples for hydrogen production. The catalyst after the restore process is operated in an industrial environment in the process of conversion of carbon monoxide to hydrogen in low-temperature mode, the ID of carbon 4,0 1,0 about. In early tests the residual content of carbon monoxide is 0.09. after 240 h of testing 0,1 about. operation catalyst is transferred to the medium temperature mode tests with steam: gas ratio of 1.0 a operating temperature 280aboutWith content in gas 14,0 3,0 about. WITH. The residual content of carbon monoxide in the beginning of the test is 0,28-03,2 about. after 240 h of testing 0,36-0,4 about. the catalyst is transferred to the operation mode at 400aboutWith, the residual content of carbon monoxide in the beginning of the test is 1.3 about. after 240 h of testing 1,48 about.

The subsequent testing of samples according to examples 1-6 are summarized in table.2.

The proposed method of producing hydrogen allows for efficient conversion at low temperatures due to the high activity of the obtained catalyst without using the last of expensive noble metals.

1. The method of producing hydrogen by steam reforming of carbon monoxide in the presence of the oxide copper-zinc-manganese catalyst, characterized in that the conversion is carried out in the presence of a catalyst containing, by weight.

The copper oxide 30 65

Zinc oxide 18 31

Manganese dioxide 0,1 2,7

Carbon 0,08 0,8

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2. A method of producing a catalyst for producing hydrogen steam conversion of carbon monoxide to hydrogen, comprising a mixture of copper compounds and zinc, followed by molding and curing of granules, characterized in that the cook is isomorphic to a mixture of salts of copper and zinc in the solution and the mixture additionally served activated carbon and a compound of manganese, and then separating the precipitate and mix it with a carrier, then the resulting mass is injected Cu Zn Al - or Cu Zn Al Mn-alloy in amounts of 1 to 40 wt. when the ratio of the components of the alloy Cu Zn Al 1 6 0,3 6,0 1 6 or Cu Zn Al Mn 1 6 0,3 6,0 1 6 0.1 to 1.0, respectively, and carry out intensive mixing of the mass to change its color to gray-brown or greenish-brown and the emergence of a smell of spirits.

3. The method according to p. 2, characterized in that as media use aluminum oxide or shungite, or calcium aluminate.

 

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