Method of preparing catalyst for median-temperature carbon monoxide-water steam conversion

FIELD: catalyst manufacture technology.

SUBSTANCE: invention relates to carbon monoxide-water steam conversion to form nitrogen-hydrogen mixture that can be used in ammonia synthesis. Preparation of catalyst comprises precipitation of iron hydroxide from iron nitrate solution with ammonia-containing precipitator, washing of iron hydroxide to remove nitrate ions, mixing with copper compound, granulation, and drying and calcination of granules. Invention is characterized by that iron hydroxide is mixed with copper and calcium oxides at molar ratio Fe2O3/CuO/CaO = 1:(0.03-0.2):(1.0-2.0), after which mechanical activation is performed. Resulting catalyst is 1.8-2.0-fold stronger and by 11.0-15.4% more active than prototype catalyst.

EFFECT: increased strength and catalytic activity.

1 tbl, 3 ex

 

The technical field

The invention relates to a method for preparing catalysts for medium-temperature conversion of carbon monoxide, which can be used in industry for preparation of nitric mixture for the synthesis of ammonia.

The level of technology

There is a method of preparation of the catalyst for conversion of carbon monoxide by precipitation of iron hydroxide from a solution of iron nitrate urea precipitator, which use ammonia water, followed by receiving iron-containing component, representing a suspension of iron hydroxide in the solution of ammonium nitrate. Simultaneously prepare the bichromate of copper dissolution basic carbonate of copper chromic acid, then mixed suspension of iron hydroxide with bichromate of copper and powdered promoters - Al(Oh)3and MgCO3Mg(OH)2, catalyst mass is dried, calcined, form [Technology catalysts / edited Ipomaea. L.: Chemistry, 1997, c.133].

The disadvantages of this method include low activity of the obtained catalyst, and the formation of large quantities of nitrogen oxides by heat treatment of the catalyst, leading to environmental pollution.

There is a method of preparation of the catalyst for conversion of carbon monoxide, comprising smeshivanie iron oxide powder with a solution of chromic acid, extrusion molding the obtained paste into granules, exposure to air, drying and calcination. By this method the mixture of iron oxide powder with a chromic acid is carried out in two stages: first, 20-50 % of iron oxide is pulverized in the presence of chromic acid to achieve the degree of dissolution of iron oxide 5,0-11,0 %, and then, the resulting fine suspension is mixed with the rest of the amount of iron oxide powder to form a paste humidity is 26.0-29.0 percent [As. Su 1235523 AI, B 01 J 37/04, 23/86, publ. BI No. 21, 1986].

A significant disadvantage of this method is used as a precipitant solution of ammonium carbonate, which complicates the technological process, cause undesirable foaming at the stage of receipt of carbonate of iron. The resulting catalyst contains up to 0.3 % sulfur compounds, which during operation causes the deactivation of the low-temperature copper-based catalyst for CO conversion.

Closest to the proposed to the technical essence and the achieved result, i.e. the prototype, is a method for preparing a catalyst for medium-temperature conversion of carbon monoxide with water vapor, including deposition of iron hydroxide from a solution of iron nitrate urea precipitator then receiving iron-containing component, the preparation of the bichromate of copper, mixing with the iron-containing component, drying, calcination, forming the catalyst mass. This method is characterized by the fact that as a precipitator use of ammonium-carbonate solution, the precipitate of iron hydroxide is separated and washed, dried, calcined at a temperature of 380-420°received iron-containing component, representing the iron oxide, mixed with bichromate of copper, the catalyst mass is humidified by water, mold, provalivajut in air, dried and calcined at a gradual rise of temperature with a speed of 30-50° [Patent RU, 2157731, B 01 J 37/04, publ. BI No. 7, 2000].

The disadvantages of the prototype should include the complexity and duration of the technological process of preparation, is not sufficiently high mechanical strength and activity of the obtained catalyst, the use of scarce and toxic chromium compounds. In the process of preparation of the catalyst rather laborious, time-consuming and energy-intensive are the stage of the preparation of a solution of chromic acid, chromate, copper, drying and calcination of the hydroxide of iron, which the proposed technical solution, are excluded. In addition introduces the operation of mechanical activation of iron hydroxide in the presence of oxides of copper and calcium.

The invention

Object of the invention is the creation of the joint venture is soba obtain catalyst for medium-temperature conversion of carbon monoxide with water vapor with high activity and mechanical strength while reducing and removing technological operations and eliminating toxic ingredients.

The problem is solved in the proposed method of preparation of the catalyst for medium-temperature conversion of carbon monoxide with water vapor, including deposition of iron hydroxide urea precipitator, leaching of iron hydroxide water from nitrate ions, a mixture with a compound of copper, molding, drying and calcination of the pellets, and the iron hydroxide is mixed with copper oxide and calcium at a molar ratio of Fe2O3:SiO:Cao=1:0,03-0,2:1,0-2,0, and then subjected to mechanical activation.

Information confirming the possibility of carrying out the invention

Example 1.

For the preparation of the catalyst according to the proposed method using iron hydroxide Fe2O3mo2Oh, obtained by precipitation from a solution of iron nitrate concentration of 380 g/l at a temperature of 60°C, pH 7.8 and constant stirring with 25 % aqueous ammonia solution. In the result of the interaction of a precipitate of Fe2About3mo2On the solution of ammonium nitrate. The precipitate was separated from the mother liquor, washed thoroughly with hot water to a residual content of nitrate-ions of less than 0.5% and remove excess moisture. For the preparation of 102 g of the catalyst take 95 g of iron hydroxide containing 64 g of iron oxide and 31 g of moisture, 4 g of calcium oxide, 2 g of copper oxide (molar ratio of Fe2 O3:CaO:SIO=1:1,5:0,125)that load in the drum vibratory mill VM-4. Then the resulting mass is introduced 25 g of water. The mass is thoroughly stirred for 30 minutes and formed into granules, which are dried at 100°C for 6 hours and then calcined at 45°C for 6 hours. The composition of the catalyst: Fe2O362,7 Million Tons %; CaO-33,3 %; CuO-4,0 %.

Example 2.

The catalyst is prepared analogously to example 1 with the only difference that for the preparation of 104 g of the catalyst charge and 84.6 g of iron hydroxide containing 57 g of iron oxide and 27.6 g of water, 41 g of calcium oxide and 6 g of copper oxide (molar ratio of Fe2O3:CaO:SIO=1:2:0,2), mass activate in a centrifugal planetary mill for 12 minutes. The composition of the catalyst: Fe2About3-54,8%; CaO-39,4 %; CuO-5,8 %.

Example 3.

The catalyst is prepared analogously to example 1 with the only difference that for the preparation of 99 g of the catalyst take 106,9 g of iron hydroxide containing 72 g of iron oxide and is 34.9 g of water, 26 g of calcium oxide and 1 g of copper oxide (molar ratio of Fe2O3:CaO:SIO=1:1:0,03), weight activated in a planetary mill AGO-2 for 5 minutes. The composition of the catalyst: Fe2About3-72,7%; CaO-25,3%; CuO-1,0%.

The mechanical strength of the granules of the catalyst was measured by the method of crushing the butt on the hydraulic hand pump.

The activity of the catalyst samples is assessed and on the degree of conversion of CO in the reaction of conversion of carbon monoxide with water vapor. Test conditions: temperature 350°s, steam:gas ratio=0,6. Space velocity of 5000 h-1. The content input =12,0 % vol.

The test results of physico-chemical properties of the catalysts are presented in the table.

Example # PPMechanical strength at crushing the edge, MPaActivity (degree maturing at t=350 °C
Example 111,0of 89.1
Example 212,492,8
Example 311,290,7
The placeholder6,180,4

The table shows that the use of the claimed invention increases the mechanical strength of 1.8-2.0 times, and activity 11.0-15.4 per cent.

The preparation method of catalyst for medium-temperature conversion of carbon monoxide with water vapor, including deposition of iron hydroxide from a solution of iron nitrate urea precipitator, leaching of iron hydroxide water from nitrate ions, a mixture with a compound of copper, molding, drying and calcination of the pellets, characterized in that the iron hydroxide is mixed with copper oxide and calcium at a molar ratio of Fe2O3:SiO:Cao=1:0,03÷0,2:1,0÷2,0 and then subjected to mechanical is some activation.



 

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