SU1243610A3 - Method of preparing catalyst for oxidation of metacrolein and isobutyraldehyde - Google Patents

Description

The invention relates to methods for the preparation of catalysts for the oxidation of organic compounds, in particular for the oxidation of methacroles to isobutyraldehyde to methacrylic acid.

The purpose of the invention is to obtain a catalyst with increased activity due to a specific sequence of preparation stages, modes of their realization, as well as the addition of a nitrogen-containing heterocyclic compound in the preparation of the catalyst.

The action of a nitrogen-containing hetero-1 cyclic compound in the preparation of molybdenum vanadium phosphoric acid, which has a crystalline structure, and approximates the structure of its salt, 5, molybdenum vanadium phosphoric acid, having the composition P: Mo; , is a water-soluble soy. dynenie. X-ray diffraction analysis (Cu-Ka irradiation) shows the presence of diffraction lines at, 9; 26.8 and 27, and the intensity of the diffraction line is very high. When dissolved in water, molybdenum vanadium phosphoric acid forms a reddish-brown solution. When a nitrogen-containing heterocyclic compound is added to this solution, such as pyridine, oracle yellow crystals form. After the addition of the colorless and aqueous solution of the aqueous layer, the crystals are collected. When treated in a stream of nitrogen at 200-600 ° C, the color of the crystals changes to dark blue, indicating a reduction. When they are re-treated in air at 100--. 400 ° C, yellowish-green crystals are formed,

The infrared spectrum of the crystals obtained does not contain a band that can be attributed to pyridine or the pyridinium ion, but contains only the characteristic absorption band of molybdenum vanadium phosphoric acid, X-ray structural analysis, which shows that diffraction lines appear at, 2; 10.5 | 2153 and 30.3, and the intensity diffraction 1: the light near 26.2 is very high. Radiograph of such crystals from

It differs from the X-ray diffraction of free molybdenum vanadium phosphoric acid used as the starting compound, and it is very similar to

X-ray diffraction of the ammonium salt or alkali metal salt of molybdenum-diphosphoric acid. When such crystals are dissolved in water and the aqueous solution is scorched to dryness, the X-ray diffraction pattern of the resulting product has diffraction lines at, 9 | 26.8; 26.8 and 27.1, The radiograph of such a product is very similar to. radiograph free

molybdenum vanadium phosphoric acid used as a starting material.

The function of pyridine is to change the crystal structure of free molybdenum vanadium phosphoric acid, which becomes very close to the crystal structure of the alkali metal salt or ammonium salt of molybdenum vanadium phosphoric acid.

Other nitrogen-containing heterocyclic compounds act like pyridine.

Example 1, Secondary acidic

Sodium phosphate (21.3 g) is dissolved in 300 ml of water. Separate 18.3 g of methanavadata. Sodium is dissolved in AOO ml of hot water. These two solutions are mixed and cooled, after which 15 ml of concentrated sulfuric acid are added. To the resulting solution, a solution of 399 g of sodium molybdate in 600 ml of water is added and, with vigorous stirring, is gradually added

225 MJ-t of concentrated sulfuric acid, after which the mixture is cooled. Then 1200 ml of ethyl ether are added, the mixture is shaken vigorously and allowed to stand, the heteropolyether layer is removed from the medium with liquid and dried in air, the resulting solid is recrystallized from water and dried at 250 ° C to form orange crystals. According to reetgenostructural, fluorescent X-ray diffraction and IR spectroscopic analyzes, it was found that the crystals obtained are free molybdenum vanadium phosphoric acid having the composition P; Mo: V 11.09; 12: 1,09 (atomic ratio without oxygen).

A. Preparation of a catalyst, 60 g of molybdenum-vanadium-phosphoric acid crystals are dissolved in 200 m of water and 18 g of pyridine are added to form a water-insoluble precipitate. The precipitate is collected by filtration, washed with water and formed into cylindrical pellets having a diameter of 5 mm and a height of 5 mm. The molded product is dried at 150, calcined in a stream of nitrogen at 430 ° C for 3 hours and again calcined in a stream of air at 350 ° C for 3 hours to form a catalytic oxide having cocTaEf P: Mo: V: 0 1.09: 12 : 1.09: 41.5 (atomic ratio). The precipitate obtained has good formability and the catalyst has a compressive strength above 3.0 kg / granule, demonstrates sufficient mechanical strength, and has a surface area, measured by the BET method, of the order of 6.00 m2 / g.

The IR spectrum of such a catalyst does not have characteristic absorption frequencies.

inherent in pyridine and pyridine ion, and contains only the absorption lines that are inherent in molybdenum vanadium phosphorus. acid. Catalzato is dissolved in water and has properties. Inherent in free molybdenum-vanadium phosphoric acid, X-ray structural analysis detects the presence of

The number of moles consumed aldehyde

ktlgtt gtgitan-

Mole of aldehyde supplied

Selectivity,%

Passage,%

The test results are presented in Table. one.

Comparative example 1. Crystals of free molybdenum vanadium phosphoric acid having the composition P: Mo: V: 0 1.09: 12: 1.09: 41.5 (atomic ratios) obtained in example 1, when dried in an air of a heteropolyether pulverized and tableted in a cylindrical 10

t5

thirty

2436104

 diffraction lines (Cu-Ka cathode) at, 2; 10.5; 21.3; 30, etc., and the X-ray diffraction pattern of such a sample is completely different from the X-ray patterns of free molybdenum vanadium phosphoric acid and is close to the x-ray pattern of an alkali metal molybdenum vanadium phosphate.

The catalyst is dissolved in water. The aqueous solution is evaporated to dryness and the residue is calcined at 250 s. X-ray structural analysis of the obtained product reveals the main lines (Cu-Ka, irradiation) at, 90; 26.8; 27.1 and 20.1 ° and its X-ray diffraction pattern is close to that of free molybdenum vanadium phosphoric acid. This suggests that pyridine has an effect on the change in the crystal structure of molybdenum vanadium phosphoric acid.

The resulting catalyst (50 ml) is loaded into a Y-shaped stainless steel tube having an internal diameter of 25 mm. This tube is immersed in a molten salt bath at. A gaseous mixture of methacrolein, oxygen, nitrogen, and water in a ratio of 1: 5: 34: 10 is passed through a Y-shaped tube with a bulk velocity of 1000. Conversion, selectivity, and single-pass output are determined as follows:

20

25

 100

. The number of moles of fatty acid formed The number of moles of aldehyde consumed

Mole number of fatty acid formed

Mole number of aldehyde

filed

Comical granules having a diameter of 5 mm and a height of 5 mm, and then they are calcined in a stream of air for 3 hours. This catalyst has a hygroscopicity, low mechanical strength and poor formability. The catalyst has a specific surface area according to the BET method on the order of 2.12.

The same reaction as described in example 1 is carried out using the obtained catalyst, the results are presented in table. 2, Example 2, A catalytic oxide having the composition P: Mo: V: 0 1509: 12: 1.09: 41.5 (atomic ratio) is prepared according to method A, but using piperidine instead of pyridine. The same reaction as in Example 1 was carried out in the presence of the same catalyst, but the reaction temperature was changed to 280 ° C. The results obtained are presented in table. one,

Example 3. A catalytic mixture, containing the composition P: Mo: V: 0 1.09: 12: 1.09: 41.5 (atom ratios), is prepared according to method A, but instead of pyridine, 12 g of piperazine hexahydrate are used. . The reaction, similar to that described in Example 1, was carried out using the obtained catalyst, but the reaction temperature was changed to 300 ° C. EXAMPLE 4. B, Preparation of the catalyst. Ammonium paramolybdate (88.3 g) and 5.3 g of metavanadate. Mm.ok are dissolved in 200 ml of heated water, the resulting solution is stirred, 20.3 g of pyridine and 5.24 g of phosphoric acid are added to this solution: it : Ota (85 May,%) Then 40 Nm of nitric acid are added (specific gravity 1.38; the nitric acid used in the following 1-10 examples has the same specific gravity). While stirring, the mixture is concentrated by heating. The resulting clay-like material is molded into thick-grain granules having a diameter of 5 mm and a height of 5 mm, dried at 250 ° C for 15 hours, burned in a stream of nitrogen at 450 ° C for 4 hours, and then burned in a stream of air. for 3 hours with the formation of a catalytic oxide having the composition P: Mo: V: 0 1.09: 12: 1.09: 41.5 (atomic ratio).

The IR spectrum of the catalyst obtained has characteristic lines, the absorption of molybdenum vanadium phosphoric acid, and does not have absorption bands characteristic of pyridine pyridinium ion. The catalyst is well soluble in water and has properties inherent in free molybdenum vanadium phosphoric acid, its X-ray diffraction pattern is close to that of molybdenum alkali metal.

The same reaction was carried out as in Example 1, using the obtained catalyst, except that the reaction temperature was 300 ° C. The results are presented in Table 1.

Comparative example 2.

Catalytic mixture having. composition JP: Mo: V: 0 1 09: 12: 1.09: 41.5 (atomic ratios), prepared by method B, but pyridine is not used. The same reaction as in Example 1 was carried out using the catalyst obtained, except that the reaction temperature was 300 ° C. The results are presented in Table 2.

PRI me R 5.

С „Crawl catalyst.

Molybdenum trioxide (144.0 g), 8.27 g of vanadium pentoxide and 12.5 g of phosphate (hydrochloric acid (85% by weight) are added to 1 l of water and the mixture is heated under reflux for 24 hours. The resulting the reddish-brown solution is filtered to remove insoluble solids. The solid is concentrated to form reddish-brown crystals. X-ray structural, fluorescent and. IR spectroscopic analyzes show that such crystals are molybdenum; C, phosphoric acid, having the composition P: Mo: V: 0 1.09: 12: 1.09:: 41.5 (atomic e ratio.) The crystals are dried and 81.0 g of the dried product is dissolved in 200 ml of water. A solution of 20 g of pyridine and O ,, 81 I of cesium nitrate IB is added with 50 ml of water and the resulting solution is concentrated by stirring with stirring. clay material is formed into cylindrical pellets having a diameter of 5 mm and a height of 5 mm, dried at 150 ° C, calcined in a stream of nitrogen at 430 C for 3 hours and burned in a stream of air at AOO C for 3 hours with the formation of a catalytic oxide having the composition P: Mo: V: Cs: 0 1.09: 12: 1.09: 0, 1:: 41.5 (atomic ratio),

X-ray diffraction analysis of the detected main diffraction lines nDH, 2, 10.5 | 21.3; 30.3 and

71

18.4. Thus, it was found that the catalyst consists mainly of molybdenum vanadium phosphoric acid, which has a crystalline structure close to the structure of its salt, and contains a small amount of its cesium salt. This catalyst has good formability and has a compressive strength of more than 3.0 kg / granule.

The same reaction was carried out as in Example 1, but the reaction temperature was. The results obtained after carrying out such a reaction for 100 h and 1000 h, respectively, are presented in Table. 3

Comparative example 3.

A catalytic oxide having the composition P: Mo: V: Cs: 0 1.09: 12: 1.09: 0.1:: 41.5 (atomic ratio) is prepared in the same way as in Example 5, except that pyridine is not used and the step of removing pyridine by calcining at 430 ° C for 3 hours is not carried out.

X-ray diffraction analysis detects the presence of OCHOB IX diffraction lines at, 9; 26.1; 10.5; 30.3 and 18.4 °, the diffraction line belonging to molybdenum vanadium phosphoric acid (, 9 °) having a relatively high intensity. The catalyst has good formability and has a compressive strength of less than 0.5 kg / granule.

The same reaction as described in Example 5 was carried out using the obtained catalyst. The results are presented in table. four.

Example 6. A catalytic oxide having the composition P: Mo: V: Sr: 0 1.09: 12: 1.09: 0.1: 41.6 (atomic ratio) is prepared in the same manner as in Example 5, but 0.88 g of strontium J nitrate is used instead of cesium nitrate.

X-ray diffraction analysis of the obtained catalyst detects the main diffraction lines at, 1; 10.5; and 30.3 and its X-ray diffraction pattern is completely separated from the X-ray pattern (, 9; 19; 7; 26.7 and 29.0) partially derived by strontium, a derivative of molybdenum vanadium phosphoric acid.

Part of the catalyst obtained is dispersed in water, the aqueous dispersion is evaporated to dryness, and the residue is calcined. The x-ray diffraction pattern is semi-436108

The product product detects diffraction, lines at, 9; 19.7; 26.5 and 29.0, and such an X-ray diffraction pattern is close to that of a partially 5 strontium-substituted salt of molybdenum vanadium phosphoric acid.

The catalyst has good formability and has a compressive strength of more than 3.0 kg / granule. The same reaction as in Example 5 was carried out using the obtained catalyst. The results are presented in table. 3

Serious example 4.

 5 The catalyst is prepared in the same manner as in Example 6, but pyridine is not used and the pyridine removal stage is calcined in a stream of nitrogen at 430 s for 3 hours. 20 The X-ray analysis of the catalyst detects the main diffraction lines at, 9; 19.7; 26.7 and 29.0. The catalyst is hygroscopic and very fragile. The same reaction as 25 in Example 6 was carried out using the catalyst obtained. The results of the reaction are presented in table. four.

Example 7. A catalytic oxide having the composition P: Mo: V: Sr: 0 30 1.09: 12: 1.09: 1: 42.0 (atomic ratio) is prepared in the same manner as in Example 5, but piperidine is used instead of pyridine, and the amount of cesium nitrate is changed to 8.12 g 5 (method C). X-ray diffraction analysis of the catalyst indicates that the main diffraction lines appear at, 3; 10, 6; 21.4; 30.4 and 18.4. The catalyst has a strength of 0 in compression of more than 30 kg / granule. The reaction described in Example 5 was carried out using the resulting catalyst. The results are presented in table. 3

5 Example 8. A catalytic oxide having the composition P: Mo: V: Sr: 0 1.09: 12: 1.09: 0.6: 42.1 (atomic ratios) is prepared in the same manner as in 9 in Example 6 , except that 0 g of piperazine hexahydrate is used instead of pyridine and the amount of strontium nitrate is changed to 5, 29 g. X-ray analysis of the catalyst shows that the X-ray diffraction pattern of this product is completely identical to that obtained in Example 6. The resulting catalyst has a compressive strength above

91

3.0 kg / granule. The same reaction as in Example 5 was carried out using the obtained catalyst. The results of the reaction are presented: Table 3.

PRI me R 9, D, Obtaining a catalyst. Ammonium paramolybdate (88.3 g) and 5.36 g of ammonium metavanadate are dissolved in 200 ml of hot water and the solution is stirred. 20 pyridine and 5.28 g of phosphoric acid (85% w / w) are added to the solution, after which 40 ml of nitric acid are added with the formation of orange-yellow crystals. These crystals are collected by filtration and dispersed in 100 ml of water. A solution of 5.12 g of rubidium hydroxide in 50 ml of water is added to the dispersion and, with stirring, this mixture is concentrated by heating. The resulting clay material is formed into cylindrical pellets having a diameter of 5 mm and a height of 5 mm, dried at 250 ° C, calcined in a stream of nitrogen for 4 hours and then calcined in an air stream for 2 hours to form a catalytic oxide having composition P ; Mo: V: Rb: 0 1.1: 12: 1.1: 1.2; : 42.1 (atomic ratios). .

The catalyst has a compressive strength of more than 3.0 kg / granule. The same reaction is carried out, as in Example 1, but the reaction temperature is 290 ° C. The results of the reaction are presented in table 3,

Example 10. A catalyst having the composition P: Mo: V., 1: 12: 1.1: 1.2: 42.1 (atomic ratios), is prepared by method D, but 7.0 g of ammonium nitrate is additionally added at the stage of adding an aqueous solution of rubidium hydroxide. The same reaction: s, as in Example 9, is carried out using this catalyst. The results are presented in table. 3

Example 11. A catalytic oxide having the composition P: Mo: V: Be; Ba; 1,151.2; 1.1: 0, 8: 42.6 (atomic ratio), prepared by method D, except that 2.34 g of beryllium nitrate and 8.71 g of nitrate berylium are used instead of rubidium hydroxide. The same reaction is carried out, as in Example 1, but the reaction temperature is: The results are given in the table below. 3

ten

ten

PRI me R 12.

at . Getting a catalyst.

Ammonium paramolybdate (88.3 g) and 4.87 g of ammonium metavanadate are dissolved in 200 ml of hot water and the resulting solution is stirred. 20 g of pyridine, 6.25 g of phosphoric acid 1 lot (95% by weight) and then 40 ml of nitric acid are added to the solution and a solution of 8 ,, 12 g of cesium nitrate in 50 ml of water is added. While stirring, the mixture is concentrated by heating. The resulting clay material is formed into cylindrical granules having a diameter of 5 mm and a height of 5 mm, dried at, calcined in a stream of nitrogen at 450 ° C for 4 hours, and then calcined in a stream of air at 400 ° C for 2 hours to form a catalytic oxide having the composition Р: Мо: „; VsCs: 0 1.3: 12: 1: 1: 42.3 (atomic ratio), X-ray structural analysis of the catalyst shows the presence of the main diffraction lines at 20 26.2, 10.5 °, 21 , 3, 30.3 ° and 18.4. The catalyst has a compressive strength of more than 3.0 kg / granule. The same run as in Example 1 was carried out using the catalyst obtained, and the reaction temperature was 280 seconds. The results are presented in Ta., 3,

Comparative example 5.

The catalytic oxide was prepared in the same manner as in Example 12, but pyridine was not used. The catalyst exhibits poor formability and has a compressive strength of less than 0.5 kg / granule. The same reaction as in Example 12 is carried out using the catalyst obtained. The results are presented in Table. four.

Examples: In each experiment, a catalyst having each of cocTaiiOB, shown in Table 3, is prepared in the same manner as in Example 12, except that pyridine sh: 1 and piperidine are used in as a nitrogen-containing heterocyclic (1CH) compound, the amount of metavanadate and phosphoric acid, at least one compound removed from the group: sodium nitrate, potassium nitrate, rubidium hydroxide, thallium nitrate, magnesium nitrate, calcium nitrate, strontium nitrate and nitrate Bari is used as component X (methods B). Same

111

the reaction as described in tsimer 1 is carried out using the obtained catalyst. The results are presented in table. 3

Example 21. A catalytic oxide having the composition P: Mo: V: Te: 0 1.09: 12: 1.09: 0.2: 41.9 (atomic ratios) is prepared by the method with, except that , 91 g of telluric acid is used instead of cesium nitrate. The same reaction was carried out as in Example 1, but the reaction temperature was 290 ° C. The results are presented in table. five.

Example 22. A catalytic oxide having a composition P: Mo: V: Rb: Cu: 0 1.09: 12: 1.09: 0.1: 41.6 (atomic ratios) was prepared by the method c, but 0.43 g of rubidium hydroxide and 1.0 g of copper nitrate are used instead of cesium nitrate.

X-ray diffraction analysis of the catalyst shows that the main diffraction lines occur at, 3; 10.6; 21.3; 30.5 and 18.5. The catalyst exhibits good formability and has a compressive strength above 3.0 kg / pellet.

The same reaction as in Example 1 was carried out, but the reaction temperature was. The results are presented in table. five.

Comparative Example 6. A catalyst having the same composition as in Example 22 and treated with pyridine is prepared in the same way, then in Example 5, but at a reaction temperature of 270 ° C. 81.0 g of the obtained olibdenum-vanadium phosphoric acid is dissolved in 200 ml of water and a solution of 0.43 g of rubidium hydroxide and 1.0 g of copper nitrate in 20 ml of water are added to the aqueous solution, and the mixture is concentrated by heating. Os. The tatok is formed into cylindrical pellets having a diameter of 5 mm and a height of 5 mm, dried and then calcined in a stream of air at 400 ° C for 3 hours. An X-ray analysis of the catalyst obtained shows that the main diffraction lines occur at, 9; 26.4; 19.7; 30.6 and 18, b, and the diffraction ini, which is inherent in free molybdenum vanadium phosphoric acid (, 9), has a relatively high intensity. The catalyst is very brittle and has less compressive strength

4361012

0.5 kg / pellet. The same. the reaction that in example 22 is carried out using the catalyst obtained. The results are presented in table. 6. 5 Example 23. The catalyst is prepared in the same manner as in Example 22, but that 7.0 g of ammonium nitrate are simultaneously added at the stage of addition of rubidium hydroxide and copper nitrate 10 (method C). The same reaction as in Example 22 was carried out using the catalyst obtained. The results are presented in table. 6. PR, and measure 24. Catalytic oxide 15 having the composition P: Mo: V: Sr: Cu: 0 1.09: 12: 1.09: 0.1: 41.6 (atomic ratios) , prepared by the method of c, except that 0.88 g of strontium nitrate is used instead of hydro-rubidium oxide. X-ray diffraction analysis of the catalyst shows that the main diffraction lines occur at, 1; 10.5; 21.3 and 30.3. A portion of this catalyst is dispersed in water and the dispersion is evaporated to dryness. The residue is calcined and subjected to X-ray analysis. The main diffraction lines were found to occur at, 9; 0 19.7; 26.5 and 29.0 °.

The same run as in Example 1 was carried out, but the boiling point was 260 ° C. The results are presented in table. five.

Comparative Example 7. The catalyst was prepared in the same manner as in Example 24, except that pyridine was not used and the pyridine removal stage was calcined by calcination at 430 ° C for 3 hours in a stream of nitrogen. c jipyKTypHb analysis shows that the main diffraction lines occur at, 9; 19.7; 26.7 and with 29.0, the resulting catalyst is hygroscopic and very fragile. The same reaction as in Example 24 was carried out using the catalyst obtained. The results are presented in table. 6

Examples 25 and 26. Catalysts having the compositions listed in table. 5, prepared by method C, piperidine or piperazine hexahydrate is used instead of pyridine. The same reaction as in example 1 is carried out using each of the resulting catalysts for each of the reactions

0

nf

1312

temperatures as indicated in table. 5. The results are presented in table. 5. Example 27. A catalytic oxide having the composition P: Mo V: Cs: Ag; 0 1.3: 12: 1: 1: 0.1: 42.8 (atomic ratios) 5 1 was recovered by method B, but 0.71 g of silver nitrate is added as part Y in the cesium nitrate addition stage. The same reaction as in Example 12 was carried out using the obtained catalyst. The results are presented in table. -five,

Comparative example 8. Catalytic oxide is prepared in the same manner as in Example 27, but pyridine is not used. The same reaction as in Example 27 was carried out using the catalyst obtained. The results are presented in Table I.b.

Examples 28-41. The catalysts having the compositions listed in table. 5 is prepared according to method B using pyridine as a nitrogen-containing heterocyclic compound, various amounts of ammonium metavanorate and phosphoric acid, at least one compound as component X selected from the group: rubidium hydroxide and sodium, potassium nitrates , cesium, thallium, beryllium, magnesium, kalyz, strontium and barium, and at least one compound as a component V, selected from the group: copper nitrate, silver nitrate, ortomycium acid, sulfuric acid triphosphate, telluric acid, nit atomic cobalt, bismuth nitrate and zirconium nitrate. The same reaction as in Example 1 was carried out using the obtained catalysts. The results of 1presented table, 5,

Example 42 A catalytic oxide having the composition P: Mo: V; Cs; 0 1.3: 12: 1: 055: 42.0 (atomic ratios) was prepared by the method Bb 5, except that the amount of cesium nitrate loaded into the reaction is 4.06 g. The same reaction as in example 1 is carried out using the obtained catalyst, but isomeric aldehyde is used instead of methacrolein, and the reaction temperature is 270 C. . After 100 h, are presented in Table. 7, In tables, methacrolein yield per pass

014

This is the molar percentage of methacrolein obtained as a result of the loaded and oily aldehyde.

Comparative example 9.

The catalyst was prepared in the same manner as in Example 42, but pyriine was not used. The same procedure was carried out as in Example 42, using the catalyst obtained. The results are presented in table, 8,

Example 43. Using the catalyst prepared in Example 13 (method C), the iso-oily aldehyde is oxidized according to the method of Example 42. The results obtained are presented in Table 11. 7

Comparison: th example 10.

The catalyst was prepared according to the method of example 13, but pyri, zing were not used. The same reaction as in example 42 was carried out using the obtained catalyst. The results are presented in Table 8.

EXAMPLE 44. Catalytic oxide., 1: P: Mo: V: Cs: Ag: 0. 1,3 :: 12r1 g055: 0.1: 42., 1 (atomic ratios), prepared by method c, but the amount of cesium nitrate is 4., 06 g. Using the obtained catalyst, isobutyraldehyde is oxidized in the same way As in Example 42. The results are presented in Table 7.

Comparative example 11.

The catalyst is prepared in the same way as in example 44, but pyridine is not used, the same reaction, and in example 42, is carried out using the catalyst obtained. The results are presented in table. eight.

EXAMPLE 45 Using the catalyst prepared in Example 28 (method c), the oil aldehyde is oxidized in the same manner as in Example; re 42, the results are presented in Table 7,

Comparative example 12.

A keP catalyst is prepared according to the method of gfimer 28, but pyridine is not used. Tu. the same reaction as in Example 42, was carried out using the obtained: catalyst. The results are presented in table. eight.

Examples 46 and 47. The catalysts presented in table. 9, is prepared in the same manner as described. 3 at: measure 4, but phosphoric acid

(85%) is used in the amount of 2.4 g and 9.61 g, respectively. Using the thus obtained catalysts, the same reaction is carried out as in Example 1, but the reaction temperature is changed. The results are presented in table. 9.

Examples 48 and 49. The catalysts presented in table. 9, is prepared in the same manner as in Example 4, but ammonium metavanadate is used in an amount of 0.49 tons, 14.59 g, respectively. Using the resulting catalysts, the same reaction was carried out as in Example 1, but the reaction temperature was changed. The results are presented in table. 9.

Example 50. The catalyst. Presented in table. 9, was prepared in the same manner as in Example 12, but using 9.74 g of ammonium metavanadate and 21.07 g of potassium nitrate instead of cesium nitrate. Using the catalyst obtained, the reaction is carried out as in Example 1, but the reaction temperature is changed. The results are presented in Table. 9.

Examples 51 and 52. The catalysts are prepared as in Example 27, except that 0.36 g of silver nitrate and 30.7 g of antimony trioxide are used instead of silver nitrate. Using the resulting catalysts, the same reaction is carried out as in Example 1, but the reaction temperature is changed. The results are presented in table. 9.

EXAMPLE 53 and 54. A catalyst having the composition P: Mo: V: 0 1.09:: 12: 1j09: 41.5, is prepared according to the procedure of Example 4, but with a ratio of 5.08 or 50.8 g.

m 5

15

20 25

so the catalyst is thus carried out {Reaction under the same conditions as in example 4. The results are shown in Table. 9.

Example 55. The catalyst is prepared according to the same preparation method used in Example 1, but calcination is carried out under reduced pressure (110 mm Hg) at 230 ° C for 20 hours instead of calcination in a stream of nitrogen at 430 ° C When using the analyzer thus prepared, the reaction is carried out under the same conditions as in Example 1. The results of the tests are presented in Table. 9.

Example 56. The catalyst is prepared in accordance with the same preparation method used in Example 1, but calcination is carried out under a stream of nitrogen at 550 ° C for 2 hours instead of calcination in a stream of nitrogen for 3 hours. the way the catalyst is carried out under the same conditions as in example 1. The results are shown in table. 9.

Example 57. The catalyst was prepared in the same manner as in Example 1, but using 18 g of pyrrolidine instead of pyridine. An X-ray diffraction analysis having: the catalytic properties of the oxide shows that the main diffraction lines correspond, 2; 10.5; 21.3 and 30.3.

When using the obtained catalyst, the reaction is carried out under the same conditions as indicated in Example 1. The results are presented in table. 9.

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Claims (1)

METHOD FOR PREPARING KATA - LYSATOR FOR THE OXIDATION OF METACROLEIN AND ISOMBAL ALDEHYDE based on molybdenum vanadium phosphoric heteropoly acid corresponding to the empirical formula ^P a ^Mo b ^V cWf> where X is an element selected from the group comprising sodium, potassium, rubidium, cesium, thallium, beryllium, magnesium, calcium, strontium, barium; γ is an element selected from the group comprising copper, silver, arsenic, antimony, tellurium, cobalt, bismuth, zirconium; a = 0.5-2.0 b = 4 2 s = 0.1-3.0 d = 0.1-5.0, e = 0.05-5.0, f are the values determined by atomic valencies and atomic ratios of the constituent elements, including mixing vanadium, molybdenum and phosphorus compounds in an aqueous medium, introducing promoters and activating in an air stream at elevated temperature, characterized in that, in order to obtain a catalyst with increased activity, a nitrogen-containing heterocyclic compound selected from a group comprising pyridine, piperidine, piperazine, pyrrolidine, or the specified nitrogen-containing heterocycle and the §-compound is added to the solution obtained by dissolving in water the dried molybdenum vanadium phosphoric heteropoly acid, in an amount 1.4-14.3 mol of a nitrogen-containing heterocyclic compound per 1 mol of heteropoly acid, water is removed, the mass is molded, dried at 150-250 ^ 0, calcined at 230-550 ° С at atmospheric pressure in an atmosphere of nitrogen or air, and activation is carried out at 350400 ° C. Priority by signs: 04/22/81 at X - an element selected from the group comprising sodium, potassium, rubidium, cesium, thallium; 04.24.81 with X - an element selected from the group including beryllium, magnesium, calcium, strontium, barium. 1243 610 AZ