Catalyst for steam reforming of carbon monoxide

 

(57) Abstract:

Usage: in the chemical and petrochemical industries. The essence: a catalyst for steam reforming of carbon monoxide containing the following ratio of components, wt.%: the chromium oxide of 6.5 - 7.5; copper oxide 2,0 - 10,0; aluminum oxide, 1.0 to 4.0; iron oxide - rest. table 1.

The invention relates to catalysts for steam reforming of carbon monoxide and can be used in chemical, petrochemical industry, for example in the production of ammonia, hydrogen and other industries, where on the stage of conversion of carbon monoxide as catalysts contacts on the basis of oxide compounds of iron.

A known catalyst for steam reforming of carbon monoxide containing oxides of iron and chromium [Guide apothica. M. Chemistry, 1986, S. 140] At the present time all over the world are working on upgrading the existing large-capacity units ammonia to reduce their energy consumption, developed and introduced new cost-saving installation. One of the effective ways to reduce energy consumption is to reduce the consumption of process steam, which raised the issue of the possibility isporaka contact in the process of medium-temperature conversion of carbon monoxide with steam:gas ratio of less than 0.5:1, the formation of organic compounds, on the synthesis of which is consumed hydrogen. The number of the resulting impurities can reach values at which the flow of hydrogen on their hydrogenation will correspond to a decrease in the performance of the ammonia unit 3%

Many of the resulting compounds are poisons for catalysts subsequent stages (such as the catalyst of low-temperature conversion of carbon monoxide and other). The catalysts are expensive and replacing them in the process is costly.

In addition, during operation at low steam:gas ratio gelatobaby catalyst completely or partially destroyed, which leads to increased resistance of the Converter and, as a consequence, the overload of the catalyst.

Closest to the invention is a catalyst for steam reforming of carbon monoxide containing oxides of iron, chromium and oxides of metals I, II, IV, VII, VIII group, preferably zinc oxide. This catalyst is inherent in the above-mentioned disadvantages of the catalyst based on oxides of iron and chromium, although during the process of steam conversion of carbon monoxide at low steam:gas ratio in the catalyst of the formation of impurities is negligible Syracuse steam conversion of carbon monoxide at low steam:gas ratio of less than 0.5:1 does not form a side of organic impurities, and not destroyed in the process, with this steam:gas ratio.

This object is achieved in that the catalyst for steam reforming of carbon monoxide containing chromium oxide, iron oxide and the oxide of the metal of group I of the Periodic system further comprises aluminum oxide, and the oxide of a metal of group I of the Periodic system of the copper oxide in the following ratio of these components, wt.

The chromium oxide of 6.5-7.5

The copper oxide 2,0-10,0

Aluminum oxide, 1.0 to 4.0

Iron oxide Rest

Comparative analysis of the claimed invention with the prototype showed that the proposed catalyst further comprises an oxide of aluminum, the new ratio of components. Thus, the claimed catalyst meets the criteria of the invention of "novelty."

Comparison of the invention not only prototype, but also with other technical solutions in this field of technology is not allowed to reveal in them the features distinguishing the claimed solution to the prototype that allows to conclude that the criterion of "inventive step".

P R I m e R 1. To 300 g of washed from the sulfate ion paste carbonate of iron, obtained by deposition of carbon Ammon 26N2About the amount of 14 g and aluminum nitrate Al(NO3)3N2About 15 g dissolved in 100 ml of water. The paste is thoroughly mixed, calcined at a temperature of 300aboutC for 2 hours, the Obtained iron oxide with the addition of copper oxide and aluminum mixed with a calculated amount of a solution of chromic anhydride (10 g in 35 ml of water) and the pasty mass is thoroughly mixed, and then dried for 3 hours at 100-105aboutC. the Mass is ground and pressed into pills the size of 5 x 5 mm. Ready tablets calcined at 450aboutC for 5 h

Get catalyst the weight of the composition based on oxides of metals, wt. Cu 5; Al2O32; Cr2O37,5; Fe2O385,5.

P R I m m e R 2. To 300 g of washed from the sulfate ion paste carbonate of iron, obtained by precipitation of ammonium carbonate from a solution of ferrous sulphate iron (humidity paste 70%) add copper nitrate in the amount of 19.5 g and aluminum nitrate in the amount of 14.3 g dissolved in 100 ml of water.

The paste is thoroughly mixed, calcined at a temperature of 300aboutC for 2 hours, the Obtained iron oxide with the addition of copper oxide and aluminum is mixed with the calculated kolichestvennie 1.

Get catalyst the weight of the composition based metal oxides, wt. CuO 7; Al2O32; Cr2O36,5; Fe2O384,5.

P R I m e R 3. To 300 g of washed from the sulfate ion paste carbonate of iron, obtained by precipitation of ammonium carbonate from a solution of ferrous sulphate iron (humidity paste 70%) add copper-ammonium-carbonate solution composition, g/l: Cu 94,7; NH4102,5; CO276,8 in the number 42,23 Jr. Then add the aluminum hydroxide in the amount of 4.6 g of chromic anhydride in the amount of 9.8, this mass is added to 1000 ml of water, thoroughly stirred for 3 hours. Then the mass is sucked off over a Buechner funnel, washed with water. Dried at a temperature of 105aboutC for 4 hours, calcined at 400aboutC for 5 h

Get catalyst the weight of the composition based metal oxides, wt. CuO 2,0; Al2O33,0; Cr2O37,0; Fe2O388,0.

P R I m e R 4. To 280 g washed from the sulfate ion paste carbonate of iron, obtained by precipitation of ammonium carbonate from a solution of ferrous sulphate iron (humidity paste 70%) add copper-ammonium-carbonate solution composition, g/l: Cu 94,7; NH4102,5; CO2with 76.8 g/l, in the amount of 211,2 annoy weight add 1000 ml of water, carefully stirred for 3 hours Then the mass is sucked off over a Buechner funnel, washed with water. Dried at a temperature of 105aboutC for 4 h, and calcined at 400aboutC for 5 h

Get catalyst the weight of the composition based metal oxides, wt. CuO 10,0; Al2O32,0; Cr2O37,0; Fe2O381,0.

P R I m e R 5. To 300 g of washed from the sulfate ion paste carbonate of iron, obtained by precipitation of ammonium carbonate from a solution of ferrous sulphate iron (humidity paste 70%) add copper nitrate Cu(NO2)36 H2About the number of 19.5 grams aluminum nitrate Al(NO3)39 H2O number of 7.35 g dissolved in 100 ml of water. The paste is thoroughly mixed, calcined at a temperature of 300aboutC for 2 hours, the Obtained iron oxide with the addition of copper oxide and aluminum mixed with a calculated amount of a solution of chromic anhydride (9.2 grams in 35 ml of water) and the pasty mass is thoroughly mixed, and then, as in example 1. Get catalyst mass comprising metals, wt. Cr2O37,0; CuO 7,0; Al2O31,0; Fe2O385,0.

P R I m e R 6. To 292 g of washed from the sulfate ion paste carbonate of iron, obtained ookiku copper in the amount of 13.9 g and aluminum nitrate in the amount of 29,25 g, dissolved in 100 ml of water. The paste is thoroughly mixed, calcined at a temperature of 300aboutC for 2 hours, the Obtained iron oxide with the addition of copper oxide and aluminum mixed with a calculated amount of a solution of chromic anhydride (7 g in 35 ml of water) and the pasty mass is thoroughly mixed, and then, as in example 1.

Get catalyst the weight of the composition based metal oxides, wt. CuO 5,0; Al2O34,0; Cr2O37,0; Fe2O384,0.

The test results of the catalysts described in examples 1-6, as well as analog and prototype shown in the table.

As the table shows, the formation of organic compounds in the process of conversion of carbon monoxide on low steam:gas ratio on the proposed catalyst is practically absent. In addition, in the process of working under these conditions the catalyst almost destroyed, that was an unexpected effect.

CATALYST FOR STEAM reforming of CARBON MONOXIDE containing chromium oxide, iron oxide and the oxide of the metal of group I of the Periodic system, characterized in that it additionally contains aluminum oxide, and the oxide of a metal of group I of the copper oxide with aluminium led 1,0 4,0

Iron oxide Rest

 

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