Catalytic system for the oxidative ammonolysis of alkylpyridine and method for producing cyanopyridines

 

(57) Abstract:

The catalytic system contains the oxides of vanadium, titanium, zirconium and molybdenum in the following molar ratio of V2O5:TiO2:ZrO2from 1:1:2 to 1: 12 : 25 and the number of Moo3is from 0.54 to 2.6 wt.% with respect to V2O5. A new catalytic system is used in the oxidative ammonolysis of alkylpyridine at 280-400oC. thus, for example, by conversion of 3-methylpyridine does not require the addition of water vapor and also is used in almost stereometrical or a slight molar excess of ammonia. 2 c. and 4 C.p. f-crystals, 2 tab.

The invention relates to catalytic systems, their use in the oxidative ammonolysis of alkylpyridine and to a method for cyanopyridines.

The catalytic system is preferably used for the oxidative ammonolysis of 3-methylpyridine and 2-methyl-5-ethylpyridine in the corresponding 3-cyanopyridine.

3-Cyanopyridine is the intermediate nicotinic acid or its amide, which are the main vitamins of group B.

Oxidative ammonolysis of alkylpyridine well known from the prior art. Described a large number of catbeast industrial process in the technological scale.

Known USSR author's certificate N 891142, which describes the catalyst of ammonolysis of alkylpyridine consisting of oxides of vanadium, tin and titanium. The maximum yield achieved for the conversion, for example, 2-methyl-5-ethylpyridine is 63%. The main drawback of this catalytic system is its low activity and selectivity.

In addition, from Swiss patent 595350 it is known that 2-methyl-5-ethylpyridine can be turned into 3-cyanopyridine over a catalyst of mixed oxides on the substrate, which is formed from oxides of vanadium, zirconium or titanium and, optionally, tungsten. Achieved with this catalyst, the outputs are in the range between 60 and 75%. The catalyst is also not satisfactory because of its low selectivity and activity. An additional disadvantage is a rather complicated procedure of obtaining this catalyst on the substrate.

The aim of the present invention is to provide a catalytic systems with further improved catalytic activity and performance and, thus, to improve the way the oxidative ammonolysis of alkylpyridine, especially, to increase the selectivity and yield.

Rolled the m ratio V2O5: TiO2: ZrO2from 1 : 1 : 2 to 1 : 12 : 25 and the content MoO3from 0.54 to 2.6 wt.% with respect to V2O5.

The preferred catalytic system has a molar ratio of V2O5: TiO2: ZrO21 : 3 : 4 to 1 : 8 : 16 and the content MoO3from 0.54 to 1.15 weight. % with respect to V2O5. In order to prepare the catalytic system, you can use the corresponding oxides by themselves, but you can also use compound precursor, which is then converted into the oxides. Such compounds precursors are, for example, ammonium metavanadate for vanadium oxide; circolare for zirconium oxide; metatitanate acid to titanium oxide and ammonium molybdate to molybdenum oxide.

As a rule, the preparation of the catalytic system can be realized by mixing the compounds in a suitable grinding device, granulating or tabletting mixture and the final drying of the granules or pellets at a temperature of about 100 - 120oC in the air stream. There is an advantage in that the catalyst has undergone subsequent heat treatment at temperatures up to 650oC. you can then download the prepared polucen Yunosti, and selectivity for large downloads alkylpyridine, as well as the service life of the catalyst is extended. The catalytic system of the present invention is particularly suitable for the oxidative ammonolysis of alkylpyridine in the presence of ammonia, oxygen-containing gas and, if necessary, of water vapor. The preferred use of the catalytic system is the conversion of 3-methylpyridine or 2-methyl-5-ethylpyridine in cyanopyridine. It has been proven that suitable are the following process conditions.

As the oxygen-containing gas typically use air. The air has the advantage that oxygen diluted with inert components. There is an advantage in that the partial pressure of oxygen to regulate additional dilution with a suitable inert gas, e.g. nitrogen, or to recycle part or most of the exhaust gases with low oxygen content.

Two advantages compared to the methods known to the prior art is that when the conversion of 3-methylpyridine according to the invention not only does not require the addition of water vapor, but also is used in almost stoichiometric amount or a slight molar I mix reagents formed at a molar ratio of 3-methylpyridine : ammonia : air (oxygen) from 1 : 1 : 1.5 to 1 : 8.5 to 60.

The preferred source of gaseous material is formed at a molar ratio of 3-methylpyridin : ammonia : air (oxygen) from 1 : 1 : 2 to 1 : 4 : 60.

In the case of oxidative ammonolysis of 2-methyl-5-ethylpyridine gaseous starting material reagents formed at a molar ratio of 2-methyl-5-ethylpyridine : ammonia : air (based on O2) : steam 1 : 20 : 20 : 60 to 1 : 60 : 70 : 330. It is advisable that the temperature in the reaction zone of the catalytic layer was between 280 and 400oC and preferably between 310 and 380oC.

Characteristics of the catalytic system, including time of her life, make it possible to continuously carry out the process on a large scale.

The maximum yield of 3-cyanopyridine when applying to 150 g/l/h of the catalyst reaches 99% for 3-methylpyridine and 2-methyl-5-ethylpyridine at a flow rate of up to 120 g/l/hour of catalyst it reaches 85%.

Examples

Example 1. of 36.4 g of vanadium pentoxide, 48,0 g of titanium dioxide, 197,2 g of Zirconia and 0.42 g of molybdenum trioxide in a molar ratio of V2O5: TiO2: ZrO2= 1 : 3 : 8 and when to 1.15 wt.% MoO3on the basis of vanadium pentoxide grind and mixed in a ball mill. The mixture is formed into century. who received the catalyst in the amount of 60 cm3(82 g) are loaded into a tubular reactor made of stainless steel (inner diameter 20 mm, length 1000 mm). The mixture of reactants consisting of 2-methyl-5-ethylpyridine, air, ammonia, water vapor was passed through the catalyst bed at a temperature of 340oC. feed Rate (in g per 1 liter of catalyst per 1 hour = g l-1h-1) is: 2-methyl-5-ethylpyridine - 72 g l-1h-1the air - 1500 liters, ammonia - 228 g l-1h-1and water - 583,3 g l-1h-1that corresponds to a molar ratio of 2-methyl-5-ethylpyridine : oxygen : ammonia : water = 1 : 47 : 45 : 108. Accordingly, within 10 hours serves to 21.6 g of 2-methyl-5-ethylpyridine. The conversion was complete. Obtain 15.0 g of 3-cyanopyridine, which corresponds to the output of 80.5 per cent of theoretical. The volume of 3-cyanopyridine output is 49.8 g l-1h-1.

Example 2. Using the catalyst described in example 1. A mixture consisting of 3-methylpyridine, air and ammonia is passed through the catalyst at a temperature of 330oC. feed Rate (in g per 1 liter of catalyst per 1 hour = g l-1h-1) is: 3-methylpyridin - 84 g l-1h-1the air - 2000 liters, ammonia - 9,92 g l-1-1h-1.

Example 3. The catalyst is prepared from of 36.4 g of vanadium pentoxide, 64,0 g of titanium dioxide, to 98.6 g of zirconium dioxide and 0.2 g MoO3in a molar ratio of V2O5: TiO2: ZrO2= 1 : 4 : 4 and 0.54 wt.% MoO3in the calculation of the V2O5. The catalyst prepared by the method described in example 1. Gaseous source material consisting of 2-methyl-5-ethylpyridine, air, ammonia and water vapor, is passed through the catalyst bed (60 cm3) at a temperature of 320oC. feed Rate (in g per 1 liter of catalyst per 1 hour = g l-1h-1) is: 2-methyl-5-ethylpyridine - 72 g l-1h-1the air - 1500 liters, ammonia - 228 g l-1h-1water - 700 g l-1h-1that corresponds to a molar ratio of 2-methyl-5-ethylpyridine : O2: NH3: H2O 1 : 47 : 45 : 130. Accordingly, within 10 hours serves to 21.6 g of 2-methyl-5-ethylpyridine. The conversion was complete. Gain of 15.3 g of 3-cyanopyridine, which corresponds to the output of 82.2 per cent on the basis of submission of 2-methyl-5-ethylpyridine. R the m value V2O5: TiO2: ZrO2= 1:4:4 and 0.90 wt.% MoO3in the calculation of the V2O5was prepared according to example 1. A mixture consisting of 3-methylpyridine, air and ammonia is passed through the catalyst at a temperature of 330oC. feed Rate (in g per 1 liter of catalyst per 1 hour = g l-1h-1) is: 3-methylpyridin - 84 g l-1h-1the air - 2000 liters, ammonia - 9,92 g l-1h-1that corresponds to a molar ratio of 3-methylpyridin : O2: NH31 : 40 : 1,3. Accordingly, within 10 h serves to 25.2 g of 3-methylpyridine. The conversion was complete. Get 27,3 g of 3-cyanopyridine, which corresponds to the output 97,9% of theoretical. The volume of 3-cyanopyridine output accounted for 91.1 g l-1h-1.

Example 5. The catalyst with a molar ratio of V2O5: TiO2: ZrO2= 1:4:8 and 0.98 wt.% MoO3in the calculation of the V2O5prepared according to example 1. A mixture consisting of 2-methyl-5-ethylpyridine, air, ammonia and water vapor, is passed through the catalyst at a temperature of 320oC. feed Rate (in g per 1 liter of catalyst per 1 hour = g l-1h-1) is: 2-methyl-5-ethylpyridine - 72 g l-1h-1the air - 1500 liters, ammonia pyridine : O2: NH3: H2O 1 : 47 : 45 : 130. Accordingly, within 10 h serves to 21.6 g of 2-methyl-5-ethylpyridine. The conversion was complete. Get to 15.4 g of 3-cyanopyridine, which corresponds to a yield of 83% based on feed 2-methyl-5-ethylpyridine. The volume of 3-cyanopyridine output is 51,3 g l-1h-1.

Example 6. The catalyst with a molar ratio of V2O5: TiO2: ZrO2= 1:4:8 and when to 1.15 wt.% MoO3in the calculation of the V2O5prepared according to example 1. A mixture consisting of 3-methylpyridine, air and ammonia is passed through the catalyst at a temperature of 325oC. feed Rate (in g per 1 liter of catalyst per 1 hour = g l-1h-1) is: 3-methyl-pyridine - 168 g l-1h-1the air - 2000 liters, ammonia and 22.8 g l-1h-1that corresponds to a ratio of 3-methylpyridin : O2: NH31 : 40 of 1.5. Accordingly, in a period of 10 hours served and 50.4 g of 3-methylpyridine. The conversion was complete. Get 55.8 g of 3-cyanopyridine, which corresponds to the output rate of 99.0% of theoretical. The volume of 3-cyanopyridine output is 186 g l-1h-1.

Example 7. The catalyst with a molar ratio of V2O5: TiO2: ZrO2= 1:4:8 and when to 1.15 wt.% MoO3in calc will escaut through the catalyst at a temperature of 350oC. feed Rate (in g per 1 liter of catalyst per 1 hour = g l-1h-1) is: 3-methylpyridin - 218 g l-1h-1the air - 2000 liters, ammonia - 30,35 g l-1h-1that corresponds to a molar ratio of 3-methylpyridin : O2: NH31:16:1,5. Accordingly, within 10 hours serves as 65.5 g of 3-methylpyridine. The conversion was complete. Get 75.2 g of 3-cyanopyridine, which corresponds to the output rate of 99.0% of theoretical. The volume of 3-cyanopyridine output is 241,7 g l-1h-1.

Example 8. 1,167 kg of vanadium Pentoxide, 2,512 kg of titanium dioxide in the form of metatitanate acid, 6,322 kg of zirconium dioxide and 12.4 g of paramolybdate ammonium molybdenum acid) in a molar ratio of V2O5: TiO2: ZrO2= 1: 4:8 and when 1,05% (NH4)6Mo7O244H2O on the basis of vanadium pentoxide kneaded in a two-arm kneader machine, grind and mixed in a ball mill. The mixture is formed into pellets about the size of 3 x 3 mm, and thermally treated at a temperature of 100 - 120oC for 6 hours a Certain amount of catalyst (1 liter, 1.5 kg) loaded into a tubular reactor made of stainless steel (inner diameter 21 mm, length 3 gettemperature 340oC. feed Rate (in g per 1 liter of catalyst per hour = g l-1h-1) is: 3-methylpyridin - 80 g l-1h-1air - 200 liter of h-1nitrogen 1200 liter of h-1ammonia - 37,5 g l-1h-1that corresponds to a molar ratio of 3-methylpyridin : ammonia : oxygen equal to 1:2,6:2,2. Respectively, within 24 h served 1920 3-methylpyridine. The conversion is 99%. Receive 1910 3-cyanopyridine, which corresponds to a yield of 89%. The volume of 3-cyanopyridine output is of 79.6 g l-1h-1.

Example 9. A certain amount of catalyst according to example 8 (985 cm3, 1,46 kg) loaded into a tubular reactor made of stainless steel (inner diameter 21 mm, length 3 meters). The mixture of reactants consisting of 3-methylpyridine, air and recycled exhaust gas and ammonia is passed through the catalyst at a temperature of 345oC. feed Rate (in g per 1 liter of catalyst per 1 hour = g l-1h-1) is: 3-methylpyridin - 80 g l-1h-1the air - 180 liter of h-1, recycled exhaust gas 1200 liter of h-1ammonia - 52,5 g l-1h-1that corresponds to a molar ratio of 3-methylpyridin: ammonia : oxygen equal to 1:3,6:2,0. Regina, which corresponds to the output 88,5%. The volume of 3-cyanopyridine output is 77 g l-1h-1.

Example 10. A certain amount of catalyst according to example 8 (135 cm3, 160 g) thermally treated at 620oC for 6 hours It is loaded into a tubular reactor made of stainless steel (inner diameter 21 mm, length 1000 mm). The mixture of reactants consisting of 3-methylpyridine, air, nitrogen and ammonia, is passed through the catalyst at a temperature of 375oC. the feed Rate is: 3-methylpyridin - 11 g h-1(81 g l-1h-1= g per 1 liter of catalyst per hour), air - 30 liter of h-1nitrogen 285 liter of h-1ammonia - 4 g h-1that corresponds to a molar ratio of 3-methylpyridin : ammonia : oxygen = 1:2:2,6. Respectively, within 24 h served 264 g of 3-methylpyridine. The conversion is 99%. Get 261 g of 3-cyanopyridine, which corresponds to a yield of 89%. The volume of 3-cyanopyridine output is 80 g l-1h-1.

1. Catalytic system for the oxidative ammonolysis of alkylpyridine comprising the oxides of vanadium, titanium, molybdenum, characterized in that it further contains zirconium oxide in the following molar ratio of V2O5.

2. The system under item 1, characterized in that the molar ratio of V2O5: TiO2: ZrO2is from 1 : 3 : 4 : 1 : 8 : 16 and the content MoO3ranges from 0.54 to 1.15 wt.% with respect to V2O5.

3. The method of obtaining cyanopyridines oxidative ammonolysis of alkylpyridine by passing alkylpyridine, ammonia, oxygen-containing gas and optionally water vapor over the catalyst system at 280 - 400oC, characterized in that the use of the catalytic system on the PP.1 and 2.

4. The method according to p. 3, characterized in that for the preparation of 3-cyanopyridine using 3-methylpyridin, ammonia and oxygen-containing gas in the calculation OF2in a molar ratio of from 1 : 1 : 1.5 to 1 : 8.5 to 60 and the process is conducted at 310-380oC.

5. The method according to p. 4, characterized in that take 3-methylpyridin, ammonia and oxygen-containing gas in a molar ratio of from 1 : 1 : 2 to 1 : 4 : 60.

6. The method according to p. 3, characterized in that for the preparation of 3-cyanopyridine using 2-methyl-ethylpyridine, ammonia, oxygen-containing gas, in the calculation of the O2and water vapor in a molar ratio of from 1 : 20 : 20 : 60 to 1 : 60 : 70 : 330 and the process is conducted at 310-380oC.

 

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