SU954099A1 - Satalyst for preparing methyl formiate - Google Patents

Description

This invention relates to copper-containing catalysts, in particular to catalysts for the synthesis of methyl formate.

Known copper-containing catalyst for the synthesis of methyl formate, containing 51-55 wt.% Copper oxide, 2527 wt.% Zinc oxide, 5-6 wt.% Aluminum oxide, 0.51-1.0 wt.% Potassium oxide, 0.51- 1.0 wt.% Sodium oxide, water and carbon dioxide - the rest is Qlj.

Closest to the present invention is a copper-containing catalyst for the production of methyl formate, containing 63-76 wt.% Copper oxide, 10 t22 wt.% Zinc oxide ,. 2-5 wt.% Alumina, 3-5 wt.% Of phosphorus pentoxide, carbon dioxide and water - up to 100% 2.

The known catalyst is characterized by insufficient performance, namely: at temperatures of 240, 260, 280, 300, 320 ° C - 6.7; 7.5; 6.6;

g methyl formate

6.5; 6.4

ml of catalyst / day

vetstvenno. The volumetric rate at the same time 1000 hours

The purpose of the invention is to increase catalyst productivity.

This goal is achieved by the fact that the catalyst containing 6476 Sec.% Copper oxide, 10-23 wt.% Zinc oxide and 2.0-4.7 wt.% Aluminum oxide, additionally contains 1.0-3.0 weight .% boron oxide and 0.10, 3 wt.% tungsten oxide, carbon dioxide and water - the rest.

The proposed catalyst has

10 increased productivity, which is 5-25% higher than the performance of a known catalyst.

The catalyst is obtained by jointly and sequentially co-precipitating the mixture of copper, zinc and aluminum nitrate salts with soda solution. Copper and zinc carbonates and aluminum hydroxide are formed. Mass jf. washed away from the anion NO, filtered, dried, calcined in air or in nitrogen at 300-400s. At the same time, the main mass of copper and zinc carbonates decomposes to oxides with the release of СО4, aluminum hydroxide during decomposition releases water. As show

X-ray diffraction and analytical studies, calcined katashizatornogo mass contains up to 6 wt.% carbonates in terms of

30 per COj, since compounds, such as solid solutions, are formed. The freshly rolled catalyst does not contain moisture in large quantities, but due to its porosity and highly developed surface it instantly adsorbs water vapor from the air. As a result, the finished catalyst may also contain up to 6.0% H, 0. After calcination, the catalyst is tableted. Additives can be added to both the dried and the calcined mass. The process of the synthesis of methyl formate is carried out by passing methanol vapor on a catalyst at a pressure of, at atmospheric, at a temperature of 220,320 0 and a space velocity of 1,000,3000 h. . Before carrying out the synthesis, the catalyst is reduced with methanol vapors at 100–160 ° C. For the purpose of activation, the catalyst can be overheated in a reducing medium at 400 ° C for 6 h. The condensate resulting from the reaction contains methanol, methiformate and a minor amount of by-products (ethers, water). The gas emitted contains up to 6.5% CO2, up to 25% Co, the rest is hydrogen. Example 1.- 1 liter of a 13% soda solution is introduced into a 2 liter beaker, heated to and, with stirring, gradually, 1 liter of a solution containing 90.5 g of copper, 15.4 g of zinc and 1/14 g of aluminum is poured in terms of scores. The resulting suspension is washed with a tenfold amount of distilled water, filtered, and dried for 8 hours. 100 g of the dried mass is impregnated with 100 ml of a solution containing 0.00847 r (NH) 2W50f72.5 4.0 and 3.99b4, mixed thoroughly, dried, calcined for 6 hours, tableted and tested for productivity. The finished catalyst has the composition (unreduced state), wt.%: CuO 76.0 ZnO 10.0. A1203 2.0 3.0 WO 0.1 CO-2 4.5 NgO 4.4. The catalyst obtained is tested in the preparation of methyl formate. The test results at 280, 290, and a space velocity of 1000 hours are presented in Table 1.

7.0.

7.5 16.7

8.0

.7.5 26.3 Example 2. The catalyst is prepared as in Example 1. 100 g of the dried mass is impregnated with 100 ml of a solution containing 1.264 g of H, BO, and 0.2410 g (2.5 HjO, mixed thoroughly, dried while, calcined at during 6 h, tableted and tested on the installation.The catalyst in tablet form has the following composition, wt.%:

Table 1

5.09,086,0

20.0 22.0

5.19; 985.0 29.8 6.5 16.676.9 5, with the test results for catalyst 240, 260, 280, and volume velocities of 1000, 2000, 3000 hours are given in table 2.

/ 7.0

2000

9.0 8.0 9.5

3000 12.0 7.7

1000 12.5

2000 8.0 14.0

3000 9.0 8.2 24.6

1000 44.5

1000 6.5 Example 3. 175 g of the dried mass, obtained as described in Example 1, is impregnated with a solution containing-2.3268 g of boric acid and 0.4435 g of ammonium tungstic acid. The resulting mass is dried, calcined, tableted as described in Example 1. The finished catalyst has the composition, wt.%: EXAMPLE 4. The catalyst is prepared as in Example 1. 100 g of the dried mass is impregnated with a solution containing , 6643 g of boric acid and 0.1270 g of (NH4) Wp, y.2, 5, thoroughly mixed, dried, calcined for 6 hours ,. tableted and tested for performance. The test is conducted as follows. The catalyst is reduced in methanol vapors, superheated while in a reducing medium, and then performance is determined at 280

table 2

10.0

1.8

7.5

90.7

7.3 2.1

8.0

89.9

23.3

8.7 2.2

89.1

11.5 2.4

9.3

88.3

88, l

8.2 2.3

9.6

29.0 3.3

17.0

79.7 4.1

26.4

26,6

69.5 Performance tests are carried out at 220 and at a space velocity of 1000. The main characteristics of the process are given in Table 3. Table 3,300 ° C and a space velocity of 1000 hours. The composition of the unreduced catalyst is as follows, wt.%: The main characteristics of the process with the indicated catalyst presented in table 4.

6.8

13.7 6.6 29.0

Example 5 A catalyst was prepared as in Example 1.

100 g of the dried mass is impregnated with a solution containing 3.9967 g of H-jBOj and 0.0847 g (liH) 0,, S HgO, thoroughly mixed, dried, and calcined for b. Calcined mass is tabletted and tested in the synthesis of methyl formate. The test is carried out as follows: The catalyst is reduced as described above, overheated for 6 hours in a reducing process, and then the determination is made.

7.2

19.4

7.7 27.0

Example 6 (comparative). 1 liter of 13% soda solution is introduced into a 2 liter beaker, heated to and, with stirring, 1 liter of nitrate solution containing 64.5 g of copper, 21.7 zinc and 1.3 g of aluminum in terms of metal is gradually added. The resulting suspension is washed with a ten-fold amount of distilled water, filtered, dried at 120 ° C for 8 hours. 100 g of the dried mass is impregnated with 100 ml of a solution; containing 6.8 g of phosphoric acid, dried under the same conditions, calcined with b for and h.

Table 4

6.3

15.42.9 17.0 80.1 4.5

17.02.8 21.0 76.2

performance at 300 and and flow rate 1000 h

The composition of the preformed catalyst, wt.%: CuO 64.1 ZnO 22.9 AljO 4.7, 3.0 WO 0.1 COg 2.6 2.6

The main characteristics of the process are listed in Table 5.

Table 5

8.3

24.64.6 11.1 83.8 7.7

28.55.1 16.3 78.6

The gotoyal catalyst has

63.0

SIO 22,0

ZnO 5.0

Ai-Go 5.0

P20f

  Rest

The resulting catalyst is tested for activity by passing methanol vapors over the catalyst at atmospheric pressure, temperatures of 280, 300, and a space velocity of 1000 hours.

The table shows the main 65 characteristics of the process.

formate, including copper oxide, zinc oxide, alumina, carbon dioxide, and water, in order to increase productivity, it additionally contains boron oxide and tungsten oxide in the following content. zhane components, wt.%: Copper oxide 64-76 Zinc oxide alumina 2.0-4.7

Table 6

. Carbon dioxide and water Else

Sources of information taken into account in the examination

1. USSR author's certificate as per 2494940/04,

CL, 01 J 23/78, 1977.

2. USSR Author's Certificate for Application No. 2500527/04,

cl. 01 J 23/78, 1977 (prototype).

Claims (2)

Claim A catalyst for producing methyl25 formate, including copper oxide, zinc oxide, alumina, carbon dioxide and water, with the fact that, in order to increase productivity, it additionally contains boron oxide and Bora’s Oxide Tungsten Oxide Carbon Dioxide and Water Sources 1.0-3.0 0.1-0.3 The rest of the information, tungsten oxide at the following contents of components, Copper oxide Zinc oxide Oxide weight. 64-76 10-23 2.0-4.7 30 taken into account during the examination 1. USSR author's certificate on application No. 2494940/04, class. In 01 J 23/78, 1977. 2. USSR author's certificate □ 5 for application No. 2500527/04, cl. In 01 J 23/78, 1977 (prototype).