Catalytic system for the oxidative ammonolysis of alkylpyridine, its preparation and method of oxidative ammonolysis of alkylpyridine

 

(57) Abstract:

The invention relates to a process for the preparation of cyanopyridines oxidative ammonolysis of alkylpyridine. The method comprises passing a gaseous source mixtures containing alkylpyridine, oxygen-containing gas, ammonia and water on the catalytic system at 330 -440oC. Catalytic system for the oxidative ammonolysis of alkylpyridine formula VaTibOxwhere a = 1, b is from 7.5 to 8, x is the number of oxygen atoms corresponding to the valency presentedin elements, obtained by coprecipitation of compounds of vanadium and titanium from solutions of compounds V5+and Ti4+in water solution of ammonia in water, followed by drying the resulting precipitate, heat treatment and shaping. Get highly selective catalyst, allowing to obtain, in particular, 3-methylpyridin with access 95 - 97%. 3 S. and 13 C.p. f-crystals, 2 tab.

This invention relates to a method for producing a highly selective catalyst for getting cyanopyridines by oxidative ammonolysis of alkylpyridine and the method of production of cyanopyridines. The invention is particularly directed to obtain 3-cyanopyridine or cyanopyridine derivatives, which are flauta key of b group vitamin

In the prior art well-known oxidative ammonolysis of alkylpyridine. Described a large number of catalytic systems and methods for their production, however, is still not known no method that can satisfy the needs of industrial process in a technical scale.

Known patent GB 1317064, in which oxidative ammonolysis of alkylpyridine described mixed oxide catalyst consisting of vanadium oxide and titanium oxide at a molar ratio of from 1:0.6 to 1:32. The maximum yield of cyano, achieved by conversion of 3-methylpyridine, was 89% (example 42: V2O5:TiO2=1:16) and when the conversion of 2-methyl-5-ethylpyridine - 61% (example 55: V2O5:TiO2=1:4).

The results obtained in a known manner, may not be satisfactory, especially in terms of selectivity, yield and flow rates alkylpyridine.

Thus, the purpose of the present invention is to create a highly selective catalyst for amoxilonline and improved way of turning alkylpyridine by oxidative ammonolysis, which allows to overcome the drawbacks.

The catalytic system of equations

Va
get stage coprecipitation of a solution of compound V5+and Ti4+and also, optionally, Zr4+in the water, with a solution of ammonia in water, followed by drying the precipitate and heat treatment, and stage of molding to give a catalytic system suitable form of the catalyst.

Suitable sources of titanium component are preferably water-soluble compounds Ti4+such as titanium chloride, titanium bromide, titanium nitrate or organic compounds of Ti, such as tetraalkyl connection Ti.

Suitable sources of vanadium components are water-soluble compounds V5+for example, ammonium metavanadate.

A suitable source of zirconium component preferably is a water-soluble compound Zr4+such as zirconium oxychloride.

The coprecipitation occurs by simultaneous mixing of dissolved catalyst components with an aqueous solution of ammonia in such a way that after coprecipitation pH of the liquid is between 8 and 9. The precipitate can then be separated by known means, and then, either in the beginning be dried, preferably in a stream of air at temperatures between 120o, predpochtitelno in the presence of air. Then may follow a normal stage shape in order to properly molded catalyst. Preferably form a tablet which is useful subjected to additional heat treatment at temperatures between 740oC and 850oC in the presence of air.

Ready received the catalytic system can then be loaded into the reactor, in which, after activation phase under the reaction conditions it is able to demonstrate high activity and selectivity for large downloads alkylpyridine, as well as a great time of life.

Preferred catalyst systems are:

VTi8Ox< / BR>
VTithe 7.5Zr0,5Ox< / BR>
VTithe 7.5Zr0,125Ox< / BR>
where x is defined above.

The most preferred catalytic system is

VTi8Ox< / BR>
where x is defined above.

The method according to the present invention is used to convert a wide range of alkylpyridine in the cyanopyridines. Suitable alkylpyridine are, for example, 3-methylpyridine, 3-ethylpyridine, 2-methyl-5-ethylpyridine, 2.5-dimethylpyridine and 2-methyl-5-vinylpyridin. The most preferred alkylene the existing process conditions.

Gaseous source material is formed from the corresponding alkylpyridine, oxygen-containing gas, ammonia and water vapor.

Generally, as the oxygen-containing gas is air. The air has the advantage that oxygen diluted with inert components.

In the case of conversion of 3-methylpyridine 3-cyanopyridine gaseous source material suitable to form a 3-methylpyridine, air (based on O2), ammonia, water vapor in a molar ratio from 1:7:3:3 to 1: 40:10:45.

The ratio is preferably in the range from 1:10:4:10 to 1:30:7: 30.

In the case of transformation of 2-methyl-5-ethylpyridine 3-cyanopyridine and, depending on the reaction conditions, also 2.5-dicyanodiamide, gaseous source material suitable to form 2-methyl-5-ethylpyridine, air (based on O2), ammonia, water vapor in a molar ratio of 1:15:5:20 to 1:70:40:140.

The temperature in the reaction zone of the catalyst generally is in the range between 330oC and 440oC, preferably between 350oC and 410oC.

Due to the stable characteristics of the catalyst in relation to the lifetime of the method according to nastothemu molar outputs reach approximately 95-97% for the conversion of 3-methylpyridine and up to about 75% for the conversion of 2-methyl-5-ethylpyridine.

The resulting cyanopyridines, that is, 3-cyanopyridine and/or 2,5-dicyanodiamide, can be directly converted into nicotinic acid by conventional hydrolysis by treatment with a base. Accordingly, it is possible to achieve output of nicotinic acid to 95% based on 3-methyl-pyridine.

Examples

Preparation of catalysts

a) the catalyst VTi8Ox< / BR>
690,4 g (of 3.64 mol) of titanium Chloride is slowly mixed with 400 ml of water at a temperature of about 60-65oC. Add water to a total volume of 800 ml

In a separate vessel 53,19 g (0.45 mol) of metavanadate ammonium dissolved in 850 ml of water and 300 ml of ammonia solution at boiling under reflux. During this procedure, the solution is injected ammonia.

The solution containing V, is added to the solution with Ti at a temperature of about 80-85oC. Add water to a total volume of 4 liters.

In a cylindrical reactor with a stirrer 670 ml Ti-V, having a temperature of 80-85oC, mixed with 670 ml of 5.2% solution of ammonia in water. Formed aoademy material is filtered off, washed with water, and then dried in a stream of air at a temperature of 120-140oC.

Then the resulting powder was treated in a furnace at a temperature of 360ooC for 2 hours. Then a freshly prepared catalyst activated under conditions of oxidative ammonolysis of 3-methylpyridine.

b) the catalyst VTithe 7.5Zr0,5Ox< / BR>
A solution of V-Ti is prepared as described in (a). In a separate vessel 73,27 g (0.23 mol) of zirconium oxychloride - 8 H2O are dissolved in 600 ml of water at temperatures between 40oC and 45oC. the Coprecipitation is carried out in accordance with as specified in (a) by shifting 625 ml Ti-V, 100 Zr solution and 725 ml of the corresponding solution of ammonia in water. Further operations with the obtained precipitate carried out as described in (a).

the catalyst VTithe 7.5Zr0,125Ox:

Repeating the procedure of example b) except that the co-precipitation of mixed 625 ml Ti-V, 25 ml of a solution of Zr and 650 ml of the corresponding solution of ammonia in water.

Way

Example 1

220 cm3The activated catalyst VTi8Oxloaded into a tubular reactor made of stainless steel (inner diameter 20 mm, length 1200 mm).

The gaseous mixture of reactants consisting of 3-methylpyridine 385oC with a feed rate 103,6 g l-1h-13-MP, 2727 g l-1h-1for air, 113,8 g l-1h-1for ammonia and 336,4 g l-1h-1for water vapor. The molar ratio for the source material is: 3-MP: air (O2): NH3: H2O= 1:22,9:6,0:16,8. 114 g 3-MP undergo a transformation in 5 hours. The conversion was complete. Get 119,5 g of 3-cyanopyridine, which corresponds to 93,7% of theoretical. The volume of 3-cyanopyridine output, respectively, is 108 g l-1h-1. Hydrolysis using KOH (boiling under reflux for 2 hours), gives 143,2 g (95% of theory) of nicotinic acid.

Example 2

Using the catalyst described in example 1. The mixture of reactants consisting of 2-methyl-5-ethylpyridine (IEP), air, ammonia and water vapor was passed through the catalyst bed at a temperature of 395oC. the Molar ratio for the source material is: IEP:air (O2):NH3:H2O= 1:25:19:67. 155 g map was made for 10 hours, and got 93,2 g of 3-cyanopyridine, which corresponds to a yield of 70.5% of theoretical. The volume of 3-cyanopyridine output, respectively, was 42.8 g l-1h-1. Hydrolysis using KOH gives nick is), described in example 1. The same reagents that were described in example 2 was passed through the catalyst bed at a temperature of 400oC. the Molar ratio for the source material is: IEP: air (O2): NH3: H2O= 1:16:14:30. 53,2 g map was made for 5 hours and get to 19.7 g of 2,5-dicyanobenzene (34.8% of theory) and 23.0 g of 3-cyanopyridine, (50,3% of theory). Hydrolysis using KOH gives nicotinic acid with a yield of 85.4% of theoretical.

Example 4

100 cm3the activated catalyst VTithe 7.5Zr0,5Oxloaded in a tubular reactor specified in example 1. A gaseous mixture of 3-methylpyridine (3-MP), air, ammonia and water vapor was passed through the catalyst bed at a temperature of 375oC with a feed rate of 225 g l-1h-13-MP, 344,1 g l-1h-1for air, 111 l-1h-1for NH3and 980 g l-1h-1for H2O. 112.3 g of 3-MP has undergone a transformation in 5 hours from receipt of 92.1 3-cyanopyridine (73,2% of theory) and 21.8 g of nicotinamide (14,8% of theory). Hydrolysis using KOH gives 138, 7mm g (93.3% of theory) of nicotinic acid.

Example 5

The same catalyst, which was described in example 4, was used for the oC. the feed Rate of the source materials was 80 g l-1h-1for restoration, 1225 l for air, 180 g of NH3and 1130 g for H2O. 48g IEP has undergone a transformation over 6 hours to obtain 3.6 g of 2,5-dicyanobenzene (7% of theory) and of 28.9 g of 3-cyanopyridine (70% of theory). Hydrolysis using KOH gives nicotinic acid with the release of 79,9% of theoretical.

Example 6

100 cm3the activated catalyst Tithe 7.5Zr0,125Oxused the same way as in example 4. to 112.5 g of 3-MP has undergone a transformation in 5 hours with getting to 100.8 g of 3-cyanopyridine (80.1% of theory) and 17 g of nicotinamide (11.4% of theory). Hydrolysis using KOH gives 139 g (93.3% of theory) of nicotinic acid.

Example 7

The same catalyst (100 cm3), which was described in example 1 was used for gaseous source material containing 3-ethylpyridine (3-EP). The temperature of the catalyst layer was 380oC. the feed Rate of the source materials was 150 g l-1h-1for 3-EP, 3600 l l-1h-1for air, 167 g l-1h-1for NH3and 252 g l-1h-1for H2O. 75 g of 3-EP has undergone a transformation in 5 hours with obtaining 66.5 g of 3-cyanopyridine (91,2% of teoriaerrori source material, containing 2.5-dimethylpyrazine (2,5-DMP). The temperature of the catalyst layer is 400oC. feed Rate: 102 g l-1h-1for 2,5-DMP, 2095 l l-1h-1for air, 227 g l-1h-1for NH3and 650 g l-1h-1for H2O. 52 g of 2,5-DMP turned into 5 hours, leading to an 18.8 g of 2,5-dicyanobenzene (30.6% of theory) and 28.8 g of 3-cyanopyridine (58,1%) of theory). Hydrolysis of NH3in the autoclave gives nicotinic acid with a yield of 87.9% of theory.

Example 9

The same catalyst (100 cm3), as described in example 1 was used for gaseous source material containing 2-methyl-5-vinylpyridine (2-IMP). The temperature of the catalyst is 400oC. the feed Rate is: to 113.4 g l-1h-12 is a profit center, 2095 l l-1h-1for air, 227 g l-1h-1for NH3and 750 g l-1h-1for H2O. 57 g of 2-IMP turned in for 5 hours, resulting to 23.4 g of 2,5-dicyanobenzene (37.9% of theory) and 24.4 g of 3-cyanopyridine (48.9% of theory). Hydrolysis with H3in the autoclave gives nicotinic acid with access to 86.3% of theory.

Example 10

The same catalyst described in example 1 (710 ml) were loaded into a tubular reactor made of stainless stayamerica and water, was passed through the catalyst bed over 1350 hours at a temperature of 385oC with a feed rate that varied between 100 and 150 g l-1h-13-MP. The molar ratio of the source material 3-MP: air (O2): ammonia: water was changed between 1:5,2:10:13 and 1:5,2:16:15. 107 kg of 3-MT were turned into 108 kg of 3-cyanopyridine. The conversion was 97%. The molar yield corresponded to 91%, and the selectivity - 93,5%.

Example 11

The catalyst VTi8Oxprepared according to example (a) preparation of the catalysts, but with the difference that the heat treatment of the pellets is carried out at a temperature of 850oC for 2 hours. 140 cm3this activated catalyst was loaded into a tubular reactor specified in example 1. A gaseous mixture of 2-methyl-5-ethylpyridine (IEP), air, ammonia and water vapor is passed through the catalyst bed at a temperature of 375oC. the Molar ratio of the source material is: IEP : air (O2) : NH3: H2O= 1:34:10:41. 53,2 g IEP turns for 5 hours, resulting of 22.8 g of 2,5-dicyanobenzene (40.2% of theory) and 22.5 g of 3-cyanopyridine (39.7% of theory). Hydrolysis with KOH gives nicotinic acid output by 90.2% of theory.

1. The method for the catalytic system b = 7.5 to 8;

x is the number of oxygen atoms corresponding to the valency of the present elements,

involves coprecipitation compounds of vanadium and titanium from solutions of compounds V5+and Ti4+in water solution of ammonia in water, followed by drying the resulting precipitate, heat treatment and molding.

2. The method according to p. 1, namely, that when the coprecipitation solution of compounds V5+and Ti4+enter the connection Zr4+obtaining the catalytic system of equations

VaTibZrcOx,

where a, b, x are defined above;

c - not more than 0.5.

3. The method according to PP.1 and 2, characterized in that the formed precipitate or first dried in an air stream at 120 - 140oWith, or directly subjected to heat treatment at 360 - 400oC, is then formed and is subjected to additional heat treatment at 740 - 850oC.

4. Catalytic system for the oxidative ammonolysis of alkylpyridine, including vanadium, titanium and oxygen, characterized in that its composition corresponds to the formula

VaTibOx,

where a = 1;

b = 7.5 to 8;

x is the number of oxygen atoms corresponding to the valency of the present elements,

and who but contains zirconium and its composition corresponds to the formula

VaTibZrcOx,

where a, b and x have the meanings indicated above;

c - not more than 0.5.

6. The catalytic system under item 4, characterized in that its composition corresponds to the formula

Vi8Ox,

where x is defined above.

7. The catalytic system under item 5, characterized in that its composition corresponds to the formula

Vithe 7.5Zr0,5Ox,

where x is defined above.

8. The catalytic system under item 5, characterized in that its composition corresponds to the formula

Vithe 7.5Zr0,125Ox,

where x is defined above.

9. The method of obtaining cyanopyridines by oxidative ammonolysis of alkylpyridine comprising passing a gaseous source mixtures containing alkylpyridine, oxygen-containing gas, ammonia and water over a catalyst system comprising a vanadium, titanium and oxygen, with 330 - 440o, Characterized in that the use of a catalytic system obtained by the method according to PP.1 and 2.

10. The method according to p. 9, characterized in that the use of the catalytic system under item 6.

11. The method according to p. 9, characterized in that the use of the catalytic system under item 7.

12. The method according to p. 9, characterized in, Thu choose from 3-methylpyridine, 3 ethylpyridine, 2-methyl-5-ethylpyridine, 2,5-dimethylpyridine and 2-methyl-5-vinylpyridine) - derivatives.

14. The method according to p. 13, characterized in that alkylpyridine choose from 3-methylpyridine or 2-methyl-5-ethylpyridine.

15. The method according to PP.9 to 14, characterized in that for the preparation of 3-cyanopyridine over the catalyst miss gaseous mixture source reagent containing 3-methylpyridin, oxygen-containing gas, in the calculation of the O2, ammonia and water vapor in a molar ratio from 1 : 7 : 3 : 3 to 1 : 40 : 10 : 45.

16. The method according to PP.9 to 14, characterized in that for the preparation of 3-cyanopyridine over the catalyst miss gaseous mixture of reagents containing 2-methyl-5-ethylpyridine, oxygen-containing gas, in the calculation of the O2, ammonia and water vapor in a molar ratio of 1 : 15 : 5 : 20 to 1 : 70 : 40 : 140.

 

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