Catalyst synthesis- picoline condensation of acrolein with ammonia and its preparation

 

(57) Abstract:

The proposed catalyst may be used to obtain b - picoline, which, in turn, is the raw material of certain drugs (e.g., nicotinic acid), pesticides, and other biologically active substances.

The catalyst is alumbramiento composition comprising (mol. %): silicon dioxide - 19 - 50, the aluminum oxide - 50 - 81; obtained either by precipitation of components, or a mixture of silicon - and aluminium-containing substances with subsequent stages of forming, drying and calcination in the temperature range 700 - 1000oC.

The proposed catalysts allow for comparison with the known to increase the output of b-picoline up to 70% vs. 54% and to increase the performance of b-picoline. 3 C.p. f-crystals. table 2.

The present invention relates to catalysts for the synthesis-picoline and how to obtain it.

The need for b-picoline is constantly growing, because it is the raw material of certain drugs (e.g., nicotinic acid), pesticides and other biological active substances.

b-picoline can be obtained by various methods.

1. The rectification of Lech components. In this technology, b-picoline is produced in small quantities for a high price, making it unavailable for use in organic synthesis.

2. Catalytic condensation with ammonia, acetylene, aldehydes (acetaldehyde, formaldehyde, crotonic aldehyde, acrolein), ketones (acetone, ethylmethylketone) and unsaturated hydrocarbons (ethylene, propylene). Of the many methods described in the patent literature, the highest value of acquired those based on the use as a raw material of acetaldehyde, formaldehyde, acrolein, namely:

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The firm'reilly on silica-alumina catalyst promoted with CdF2at temperatures of 400 500oC gets all isomeric pikolines ( - , -) (1, 2] the Amount pikolines depends on the ratio of acetaldehyde to formaldehyde in the reaction mixture. Increasing this ratio increases output and g-pikolines, with the reduction of b-picoline and pyridine. The maximum yield of b-picoline (about 30%) is achieved when the ratio of acetaldehyde/formaldehyde 1,4 1.

In Japan and India used method of obtaining a mixture of b-picoline and pyridine from acrolein [2] In this way, the output of b-picoline increasing the condensation of aldehydes with ammonia, are the oxides of aluminum, promoted by fluorine, Nickel, chromium and zinc [3 5] zeolites of type ZSM [6, 7] the Latter allows to obtain primarily pyridine (70 80%).

Closest to the proposed catalyst receiving the b-picoline condensation of acrolein with ammonia is Aluminiy catalyst [8] containing to 91.6 wt. SiO28.4 wt. Al2O3that match was 94.9 mol. SiO25,1 mol. Al2O3, resulting in the industry as the catalyst for cracking according to THE-38-10226-71 (1988 discontinued). The catalyst was obtained by liquid-phase formation alumbramiento Zola with subsequent stages of washing, drying and calcination at a temperature of 500oC. the Yield of b-picoline this catalyst at a temperature of 400oC and the ratio of acrolein:ammonia 1 3 amounted to 53.9% of

The task of the invention is to find a catalyst and the method of its preparation, allowing to increase the output of b-picoline in the condensation reaction of acrolein with ammonia.

This technical result is achieved by using for the synthesis of b-picoline alumbramiento catalyst containing (19 50) mol. SiO2(50-81) mol. Al2O3received or osaid the Ohm wet mixing the silicon - and aluminium-containing raw materials with a certain humidity mouldable paste with subsequent stages of forming, drying and calcination in the temperature range 700 to 1000oC. using the proposed catalysts output of b-picoline at the reaction temperature of 350 390oC is 55 to 70% higher than in the prototype.

An important characteristic of the proposed catalysts is the performance of b-picoline (see tab. 1).

From this comparison it is seen that the proposed catalysts even at lower load acrolein get the same or better performance, b-picoline, than in the prototype, the increase of the load improves performance.

Distinctive features of the proposed catalyst are:

1. A catalyst composition comprising (19 50) mol. SiO2(50 - 81) mol. Al2O3.

2. The method of preparation of the catalyst, consisting in the deposition or the mixture of the silicon - and aluminium-containing components with subsequent stages of forming, drying and calcination.

3. Other temperature range of formation of the active state of the catalyst.

The catalytic properties of the samples in the condensation reaction of acrolein with ammonia was investigated in a flow setup and was evaluated by the degree of conversion of acrolein and selectcategory fractional composition of 0.25 to 0.50 mm with a bulk velocity: for acrolein - 15-75 h-1, ammonia 80-250 h-1nitrogen 900-2700 h-1. The reaction temperature was varied in the range of 300-420oC. the Composition of the initial reaction mixture with the composition of the reaction products were analyzed by chromatography. The reaction products, in addition to b-picoline and pyridine, were also a resinous substance of unidentified composition.

Source materials used in the synthesis of the catalyst, got:

Al(NO3)39H2O according to GOST 3757-645, followed by dissolving in distilled water at obtaining a solution with a concentration of 100 g Al2O3/l;

Na2SiO3sodium silicate is obtained by dissolution of silicate-rock in alkali when the module is 2.7, and the concentration of SiO2equal to 100 g/l

HA powder of aluminum hydroxide produced according to GOST 11841-76.

The HPA gel aluminum hydroxide obtained by precipitation of a solution of aluminum nitrate ammonia solution under appropriate pH and temperature [9]

Al2O3the alumina powder produced according to GOST 8136-85.

HS hydrated silica obtained by precipitation of low molecular weight silicic acid with aqueous ammonia under appropriate pH and temperature [10]

The essence of the invention is illustrated by the following examples.

Example 1. Salt solution obtained by the mixture of 370 ml of Na2SiO3and 630 ml of Al(NO3)3, precipitated with an aqueous solution of ammonia at pH 8, followed by maintaining the suspension for 1 hour, after which the suspension is filtered, the precipitate washed with distilled water until no nitrate in the filtrate; the resulting paste is molded in the form of cuttings of size a 2 to 3 mm and l 4 5 mm, and then dried at 110oC for 12 hours and calcined in air flow at 700oC 4 hours. The resulting catalyst has the composition: 50 mol. SiO250 mol. Al2O3. The catalytic properties are given in table. 2.

Example 2. to 107.4 g of HA powder is mixed with 37 g of powder SiO2in the presence of 180 ml of water in a Z-shaped mixer for 30 minutes. The resulting paste is molded by extrusion in the form of cuttings size d=3 to 4 mm, l=5 6 mm. Sample dried at 110oC for 12 hours and calcined in air flow at 700oC 4 hours. The resulting catalyst has the composition: 50 mol. SiO2- 50 mol. Al2O3. The catalytic properties are given in table. 2.

Example 3. Similar to example 2, the difference consists in that the annealing is carried out in a muffle furnace at 100 the properties shown in table. 2.

Example 4. Similar to example 2, the difference consists in that the annealing is carried out at a temperature of 1250oC 4 hours. The resulting catalyst has the composition: 50 mol. SiO250 mol. Al2O3. The catalytic properties are given in table. 2.

Example 5. Similar to example 2, the difference is in that mix 218 g of the HPA with 38,8 g GS in the Z-shaped mixer. The resulting catalyst has the composition: 50 mol. SiO250 mol. Al2O3. The catalytic properties are shown in table 2.

Example 6. Similar to example 2, the difference is that the mix of 63 g of a powder of Al2O3with 123,4 ml of the zone in which sodium cations are exchanged for the cations ammonium, and 50 ml of H2O Z-shaped mixer and calcined at 1000oC for 5 hours. The resulting catalyst has the composition: 50 mol. SiO250 mol. Al2O3. The catalytic properties are given in table. 2.

Example 7. Similar to example 2, the difference is in that mix 128 g HA, 23 g of powder SiO2and 160 ml of H2O Z-shaped mixer. The resulting catalyst has the composition: 36 mol. SiO264 mol. Al2O3. The catalytic properties are given in table. 2.

Example 8. Similar to example 2, the difference is that cm is 5 hours. The resulting catalyst has the composition: 36 mol. SiO264 mol. Al2O3. The catalytic properties are given in table. 2.

Example 9. Similar to example 2, the difference is in that mix 128 g HA 25 g of SiO2and 160 ml of H2O Z-shaped mixer and cover in a muffle furnace at 1250oC 4 hours. The resulting catalyst has the composition: 36 mol. SiO264 mol. Al2O3. The catalytic properties are given in table. 2.

Example 10. Similar to example 2, the difference is in that mix 202 g of the HPA from 26.2 g GS in the Z-shaped mixer and calcined at 1000oC for 5 hours. The resulting catalyst has the composition: 36 mol. SiO264 mol. Al2O3. The catalytic properties are given in table. 2.

Example 11. Similar to example 2, the difference is in that mix 155,5 g HA, 12.2 g of powder SiO2and 115 ml of H2O Z-shaped mixer and calcined in a muffle furnace at 1000oC for 5 hours. The resulting catalyst has the composition: 19 mol. SiO281 mol. Al2O3. The catalytic properties are given in table. 2.

Example 12. Similar to example 2, the difference is that the mix of 87.8 g of powder of Al2O3, 40,7 ml CCZ and 90 ml of H2O Z-shaped mixer and calcinate the definition of the properties are given in table. 2.

In table shows catalytic properties of the proposed catalysts and prototype in the condensation reaction of acrolein with ammonia in order to obtain b-picoline. The table shows that the proposed catalysts, calcined at a temperature of 700 1000oC, more efficient prototype, because they allow to increase the output of b-picoline to 55 to 70% versus 53.9% of the prototype.

It should be noted that the proposed catalysts operate with high output b-picoline within 10 to 15 hours, after which the output of b-picoline falls and catalysts require regeneration. Regeneration is carried out at 450 to 500oC oxygen, resulting catalytic properties are completely restored.

Sources of information taken into account

1. H. Y. Franch, J. W. Stadelhofer./ Industrial Aromatic Chemistry Raw Materials Peocesses Products. Berlin, 1988, p. 398-399.

2. L. M. Bova. Some of the issues of the production and use of pyridine and its derivatives in the capitalist countries. /In: "Chemical industry abroad," 1983, V. 9, S. 1-15.

3. Century Yusupov, F.B. Kuchkarov, B. A. Ivanov, E. A. Vlasov, D. K. Babajanov. Kinetics and mechanism of formation of structure synchronological catalysts for the synthesis of pyridine bases. /Heterogeneous to the n Chemie. / "Chem. Ztg.". 1974, 98, N2, s. 61 -69.

5 E. C. Syrlibaev, A. Ikramov, Murtaza, N. In.Kryukov. Heterogeneous catalytic synthesis of alkylpyridine of carbonyl compounds. /In: "Catalysis and catalytic processes himfarmpromyslovosti", H. 2, S. 223.

6. U.S. patent N 4866179, MKI C 07 D 213/08, Appl. 06.06.1988, publ. 12.09.1989.

7. U.S. patent N 4861894, MKI C 07 D 213/10, Appl. 11.07.1987, publ. 29.08.1989.

8. Century Century Antonova, T. I. Smirnova, N. A. Titov, K. P. Bespalov, The Baltic Fleet Of Ustavshikov. Synthesis of 3-alkylpyridine and liquid-phase oxidation them into nicotinic acid. /Journal of applied chemistry, 1977, T. 50, N 2, S. 382 587.

9. C. A. Ziska, A. S. Ivanov, G. P. Vishnyakov. The formation of aluminum hydroxide during aging. /Kinetics and catalysis, 1976, T. 17, N2, S. 483.

10. A. S. Ivanov, B. A., Disco, O. B. Proskurina, E. M. Moroz. The influence of the ratio of components and obtaining conditions on the physico-chemical properties of the system SiO2Al2O3. /Kinetics and catalysis, 1979, No. 3, deposited in VINITI, N 738-79 from back to 28.02.1979.

1. Catalyst synthesis-picoline condensation of acrolein with ammonia containing aluminum oxide and silicon dioxide, characterized in that it contains these components in the following amounts, they say.

Silicon dioxide 19 50

OK, silicon dioxide, characterized in that the oxides are precipitated from a solution of sodium silicate with a concentration of silica 100 g/l solution of aluminum nitrate with a concentration of aluminum oxide 100 g/l aqueous solution of ammonia at pH 7 to 9 at room temperature, followed by molding, drying, and calcination at 700 1000oC, and source components take in a ratio providing a catalyst of the following composition, mol.

Aluminum oxide 50 81

Silicon dioxide 19 50

3. The preparation method of catalyst for the synthesis of b-picoline on the basis of aluminum oxide and silicon dioxide, characterized in that the mixed silicon-containing raw material with a silicon dioxide content of 12 to 37 wt. and aluminium-containing raw materials containing 63 88 wt. aluminum oxide in the presence of water, followed by molding, drying, and calcination at 700 - 1000oC, and source components take in a ratio providing a catalyst of the following composition, mol.

Aluminum oxide 50 81

Silicon dioxide 19 u

 

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