JPH10500892A - Oxidation ammonolysis of alkylpyridines - Google Patents

Abstract

(57) Abstract A process for the preparation of highly selective catalysts and their use in the preparation of cyanopyridines by oxidative ammonolysis of alkylpyridines has been described. The catalyst composition has the formula [Where a = 1, b = 7.5-8, c = 0-0.5. x represents the number of oxygen atoms required to satisfy the required valence of the element present. ].

Description

DETAILED DESCRIPTION OF THE INVENTION                   Oxidation ammonolysis of alkylpyridines   The present invention provides a method for producing cyanopyridine by oxidative ammonolysis of alkylpyridine. And a method for producing a cyanopyridine. .   The present invention is a particularly important precursor of nicotinic acid or nicotinamide For the production of 3-cyanopyridine or cyanopyridine derivatives. nicotine Acids or nicotinamides are important Group B vitamins. Alkylpi Oxidative ammonolysis of lysine is well known in the art. Many types Catalyst systems and methods of manufacture have been disclosed, so far, No known manufacturing method can meet the needs of large-scale commercial processes .   Reference is made to British Patent GB 1 317 064, in which alkylpyridyl Molar ratio of vanadium oxide and titanium oxide for ammonolysis : 0.6 to 1:32 mixed oxide catalysts are disclosed.   The maximum yield of cyanopyridine achieved by conversion of 3-methylpyridine is 89 % (Example 42; V_TwoO_Five: TiO_Two= 1: 16), 2-methyl-5-ethyl The yield from the conversion of pyridine was 61% (Example 54; V_TwoO_Five: TiO_Two= 1: 4 )Met.   The performance of this known method is particularly relevant for selectivity, yield and alkylpyridine supply. Not satisfied with speed.   Therefore, an object of the present invention is to convert alkylpyridines by oxidative ammonolysis. -Selective ammoxidation catalyst and improved method for It is in. The drawbacks mentioned above have been produced by the method according to claim 1. 8. A process for oxidative ammonolysis with a highly active catalyst and according to claim 7. Can overcome it.   Equation V_aTi_bZr_cO_x [Where a = 1, b = 7.5-8, c = 0-0.5. x is the element that exists Indicates the number of oxygen atoms required to satisfy the valence. ] The preparation of the catalyst composition defined by Monia aqueous solution and V^Five+, Ti^Four+ And Zr^FourCo-precipitate the aqueous solution with + (if you choose) And then drying and heat treating the precipitate to obtain a catalyst composition in the form of a suitable catalyst. It is a process of molding into.   Suitable sources of titanium components are aqueous solutions such as titanium chloride, titanium bromide, and titanium nitrate. Properties Ti^Four+ Compounds or organic Ti compounds such as Ti-tetraalkyl compounds preferable.   Suitable sources of the vanadium component include, for example, ammonium metavanadate. , Aqueous solution V^Five+ Compounds are preferred.   A suitable source of the zirconium component is water, such as zirconium oxychloride. Soluble Zr^Four+ Compounds are preferred.   The coprecipitation is carried out in a manner such that the pH of the solution is between 8 and 9 after coprecipitation. This is performed by simultaneously mixing the aqueous solution and the dissolved catalyst component. Formed The precipitated sediment is separated by known means and then firstly preferably at 120 ° C to 140 ° C. Drying in a stream of air at a temperature between 0 ° C or preferably In the presence, heat treatment directly at a temperature between 360 ° C and 400 ° C. then In order to properly shape the catalyst, one enters a normal molding process. Preferably in tablet form Molded, advantageously at a temperature between 740 ° C. and 850 ° C. in the presence of air Further heat treatment is performed.   Fill the reaction vessel with the already prepared catalyst composition, in which High activity and selection at high loadings of alkylpyridine Its properties with regard to properties and with regard to longevity can be revealed.   Preferred catalyst compositions are as follows.     VTi₈O_x     VTi_7.5Zr_0.5O_x     VTi_7.5Zr_0.125O_x Wherein x is as previously defined. ]   The most preferred catalyst composition is as follows.     VTi₈O_x Wherein x is as previously defined. ]   The method of the present invention is applicable to the conversion of various alkylpyridines to cyanopyridines it can. Suitable alkylpyridines are, for example, 3-methylpyridine, 3-ethyl Pyridine, 2-methyl-5-ethylpyridine, 2,5-dimethylpyridine and 2-methyl-5-vinylpyridine. The most preferred alkyl pyridine is 3 -Methylpyridine and 2-methyl-5-ethylpyridine.   The following manufacturing conditions have been found to be appropriate:   Gaseous feeds are alkylpyridine, oxygen-containing gas, ammonia and And steam. Generally, air is used as the oxygen-containing gas. like this Air has the advantage that oxygen is already diluted with inert components.   In the case of conversion of 3-methylpyridine to 3-cyanopyridine, a gaseous feed The product is conveniently 3-methylpyridine, air (O_TwoCalculated with respect to Monia and water vapor, the molar ratio of which is 1: 7: 3: 3 to 1: 40: 10: 45. It is. Preferred molar ratios are in the range of 1: 10: 4: 10 to 1: 30: 7: 30. is there.   In the conversion of 2-methyl-5-ethylpyridine to 3-cyanopyridine, and Gas if conversion to 2,5-dicyanopyridine is required depending on the reaction conditions. The feed in form of is conveniently 2-methyl-5-ethylpyridine, air (O_TwoAbout Calculated), ammonia, water vapor, the molar ratio of which is 1: 15: 5: 20 １ ： 1: 70: 40: 140.   The temperature of the reaction zone of the catalyst is in principle between 330 ° C. and 440 ° C., preferably Ranges between 350 ° C and 410 ° C.   Due to the property of being a stable catalyst with respect to lifetime, the method of the present invention It can be operated continuously for a long period of time.   The maximum molar yields achievable range from about 95% to 97% for the conversion of 3-methylpyridine. The conversion of 2-methyl-5-ethylpyridine reaches about 75%.   The resulting cyanopyridine, for example 3-cyanopyridine and or 2,5-di Cyanopyridine is directly converted to nicotinic acid by hydrolysis with a normal base Is done. The nicotinic acid yield reaches 95%, based on 3-methylpyridine.Example Manufacture of catalyst a) VTi₈O_xcatalyst:   690.4 g (3.64 mol) of titanium chloride is added to water 40 at a temperature of about 60 ° C to 65 ° C. Mix gently with 0 ml. Water is added up to a total of 800 ml.   In a separate vessel, add 53.19 g (0.45 mol) of ammonium metavanadate to water Dissolve in 850 ml and 300 ml of aqueous ammonia solution at reflux temperature. This procedure During this time, ammonia is introduced into the solution.   The solution containing the V compound is added to the Ti solution at about 80C to 85C. 4 water in total Add to l.   In a cylindrical reaction vessel containing the mixed components, a Ti-V solution 6 at a temperature of 80 ° C. to 85 ° C. 70 ml are mixed with 670 ml of a 5.2% aqueous ammonia solution. The formed co-precipitate Filtered, washed with water and then dried in a stream of air at a temperature of 120 ° C to 140 ° C. Let dry.   The obtained powder is treated in a furnace at a temperature of 360 ° C. for 2 hours or more in the presence of air, And crushed with a ball mill, and finally moistened with water to form 4 × 4 mm tablets. Tablets Treat in a Matsufuru furnace for 2 hours at a temperature of 740 ° C. in the presence of air. Just made Is reacted with 3-methylpyridine under oxidative ammonolysis conditions. b) VTi_7.5Z_0.5O_xcatalyst:   A V-Ti solution is prepared as described under a).   In a separate container, place zirconium oxychloride 8H_Two073.27 g (0.23 mol) are dissolved in 600 ml of water at a temperature between 40 ° C. and 45 ° C.   In a method corresponding to the method described in a), 625 ml of a Ti-V solution and 1 00 ml and 725 ml of the respective aqueous ammonia solution are mixed and co-precipitated. Get Further processing of the precipitate obtained is carried out as described under a). c) VTi_7.5Zr_0.125O_xcatalyst:   Except for the following, the procedure of Example b) is repeated. That is, in coprecipitation, Ti-V 625 ml of the solution, 25 ml of the Zr solution and 650 ml of the respective aqueous ammonia solution. mix.process Example 1   Activated VTi₈O_xCatalyst 220cm^ThreeInto a stainless steel tubular reaction vessel (inner diameter 2 0 mm, length 1200 mm).   3-methylpyridine (3-MP), air, ammonia and water vapor The gaseous mixture of the reaction mixture was heated at a temperature of 385 ° C. for 150 hours at a feed rate of 3-MP Is 103.6 gl ~¹h ~¹, The air is 2727 ll ~¹h ~¹, Ammonia is 113.8 gl ~¹h ~¹336.4 gl of steam¹h ~¹And passed through the catalyst layer. The feed molar ratio is 3-MP: air (O_Two): NH_Three: H_TwoO = 1: 22.9: 6 . 0: 16.8.   114 g of 3-MP were converted during 5 hours. The conversion was complete. 3-sh 119.5 g of anopyridine are obtained, which corresponds to a theoretical yield of 93.7%. You. Therefore, the outlet flow rate of 3-cyanopyridine is from 108 gl¹h ~¹Met.   Hydrolysis with KOH (reflux for 2 hours) gives 143.2 g of nicotinic acid (95% of theory) )was gotten.Example 2   The same catalyst as described in Example 1 was used.   2-methyl-5-ethylpyridine (MEP), air, ammonia and steam Was passed through the catalyst bed at a temperature of 395 ° C. Feed mole The ratio is MEP: air (O_Two): NH_Three: H_TwoO = 1: 25: 19: 67.   155 g of MEP are converted over 10 hours to 93.2 g of 3-cyanopyridine Was obtained, which theoretically corresponds to a yield of 70.5%. 3-Cyanopyridine Mouth flow is 42.8 gl ~¹h ~¹Met.   Hydrolysis with KOH gave nicotinic acid in a yield of 72% of theory.Example 3   The same catalyst as described in Example 1 (140 cm^Three)It was used.   The same reactants as described in Example 2 were passed through the catalyst layer at a temperature of 400 ° C. Was. The molar ratio of the feed is MEP: air (O_Two): NH_Three: H_TwoO = 1: 16: 14 : 30.   53.2 g of MEP were converted over 5 hours and 2,5-dicyanopyridine 1 9.7 g (34.8% of theory) and 23.0 g of 3-cyanopyridine (theory) Of 50.3%).   Hydrolysis with KOH gave nicotinic acid in a yield of 85.4% of theory.Example 4   Activated VTi_7.5Zr_0.5O_xCatalyst 100cm^ThreeWas converted to the tubular reaction described in Example 1. The container was filled. 3-methylpyridine (3-MP), air, ammonia and water The gaseous mixture of steam is heated at a temperature of 375 ° C.¹h ~¹, Air is 344.1gl ~¹h ~¹, NH_ThreeIs 111gl ~¹h ~¹, H_TwoO is 980g l ~¹h ~¹To pass through the catalyst layer.   112.3 g of 3-MP were converted over 5 hours and 3-cyanopyridine 92. 1 g (73.2% of theory) and 21.8 g of nicotinamide (14% of theory) . 8%).   Hydrolysis with KOH gave 138.7 g of nicotinic acid (93.3% of theory). .Example 5   The same catalyst as described in Example 4 was used in gaseous form containing MEP instead of 3-MP. Contacted with feed. The temperature of the catalyst layer was 370 ° C. The feed rate is MEP80 gl ~¹h ~¹, Air 1225Q, NH_Three180g, H_TwoO1130 g.   48 g of MEP are converted over 6 hours and 2,5-dicyanopyridine 3.6 g (7% of theory) and 28.9 g (70% of theory) of 3-cyanopyridine Obtained.   Hydrolysis with KOH gave nicotinic acid in a yield of 79.9% of theory.Example 6   Activated VTi_7.5Zr_0.125O_xCatalyst 100cm^ThreeIn the same manner as in Example 4. Used. 112.5 g of 3-MP was converted over 5 hours to give 3-cyanopyridine 100.8 g (80.1% of theory) and 17 g of nicotinamide (of theory) 11.4%).   Hydrolysis with KOH gave 139 g of nicotinic acid (93.3% of theory).Example 7   The same catalyst as described in Example 1 (100 cm^Three) With 3-ethylpyridine ( 3-EP). The temperature of the catalyst layer was 380 ° C. Feeding speed is 3-EP150gl ~¹h ~¹, Air 3600l ~¹h ~¹, NH_Three16 7gl ~¹h ~¹, H_TwoO252gl ~¹h ~¹And   75 g of 3-EP are converted over 5 hours, 66.5 g of 3-cyanopyridine (91.2% of theory).Example 8   The same catalyst as described in Example 1 (100 cm^Three) Is 2,5-dimethylpyri Contact was made with a gaseous feed containing gin (2.5 DMP). The temperature of the catalyst layer is 400 ° C. The feed rate is 2,5 DMP 102 gl ~¹h ~¹, Air 2095 ll ~¹h ~¹, NH_Three227gl ~¹h ~¹, H_TwoO650gl ~¹h ~¹And   52 g of 2,5 DMP are converted over 5 hours and 2,5-dicyanopyridine 1 8.8 g (30.6% of theory) and 28.8 g of 3-cyanopyridine (theory) Of 58.1%).   NH in autoclave_ThreeTo give nicotinic acid at a theoretical value of 87.9. % Yield.Example 9   The same catalyst as described in Example 1 (100 cm^Three) Is 2-methyl-5-vinyl Contact was made with a gaseous feed containing pyridine (2-MVP). The temperature of the catalyst is 400 ° C And The supply speed is 2-MVP113.4gl ~¹h ~¹, Air 2095 ll ~¹h ~¹, NH_Three227gl ~¹h ~¹, H_TwoO750gl ~¹h ~¹And   57 g of 2-MVP are converted over 5 hours and 2,5-dicyanopyridine 23 4 g (37.9% of theory) and 24.4 g of 3-cyanopyridine (4 of theory) 8.9%). In an autoclave, NH_ThreeHydrolyzed by nicotine The acid was obtained in a yield of 86.3% of theory.Example 10   The same catalyst (710 ml) as described in Example 1 was used in a stainless steel tubular reactor. A container (inner diameter 21 mm, length 3 m) was filled. 3-methylpyridine (3-MP), empty A gaseous mixture of reactants consisting of gas, ammonia and water at a temperature of 1350 hours. At 385 ° C., 100 to 150 gl of 3-MP¹h ~¹With a feed rate that varies between Passed through the catalyst bed. The molar ratio of the feeds, 3MP: air (O_Two): Ammo Near: water varied between 1: 5.2: 10: 13 to 1: 5.2: 16: 15 . 107 kg of 3-MP were converted to 108 kg of 3-cyanopyridine. 97% conversion This corresponded to a molar yield of 91% and the selectivity was 93.5%.Example 11   VTi₈O_xThe catalyst was prepared according to the catalyst preparation of example a). The difference is The heat treatment conditions for the tablet were set at a temperature of 850 ° C. for 2 hours.   This activation catalyst 140cm^ThreeWas filled in the tubular reaction vessel described in Example 1. 2 -Methyl-5-ethylpyridine (MEP), air, ammonia and water vapor The body mixture was passed through the catalyst layer at a temperature of 375 ° C. The molar ratio of the feed is M EP: air (O_Two): NH_Three: H_TwoO = 1: 34: 10: 41.   53.2 g of MEP were converted over 5 hours and 2,5-dicyanopyridine 2 2.8 g (40.2% of theory) and 22.5 g of 3-cyanopyridine (theory 39.7%).   Hydrolysis with KOH gave nicotinic acid in a yield of 90.2% of theory.

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, M C, NL, PT, SE), OA (BF, BJ, CF, CG , CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AT, AU, BB, BG, BR, BY, CA, CH, CN, CZ, DE, DK, ES, FI, G B, GE, HU, JP, KE, KG, KP, KR, KZ , LK, LT, LU, LV, MD, MG, MN, MW, NL, NO, NZ, PL, PT, RO, RU, SD, S E, SI, SK, TJ, TT, UA, US, UZ, VN (72) Inventors Stepanova, Lydia Anatolehna             Kazakhstan 480012 Almaty 54−             6 Ur Michulin (72) Inventor Berova, Nadezda Antonovna             Kazakhstan 480096 Almaty 52−             7 Ur Nurmakov (72) Inventor Chuck, Roderick John             Switzerland CH-3902 Brick-Grease               Jeszyttenvek 162 (72) Inventors Pianzola, Daniel             Switzerland CH-3902 Brick-Grease               Velivek 6

Claims (1)

[Claims] 1. Equation V_aTi_bZr_cO_x   [Where a = 1, b = 7.5-8, c = 0-0.5. x is the element that exists Indicates the number of oxygen atoms required to satisfy the valence. ]   A process for producing a catalyst composition defined by^Five+, Ti^Four+ And Zr^FourCo-precipitate the aqueous solution with + (if selected), then dry the precipitate A process comprising drying and heat treating to obtain a catalyst composition in the form of a suitable catalyst. 2. The precipitate formed is first subjected to a stream of air at a temperature between 120 ° C and 140 ° C. Dried in it or heat treated at a temperature between 360 ° C and 400 ° C And then molded into a suitable catalyst and finally to a temperature between 740 ° C and 850 ° C. 2. The method according to claim 1, wherein heat treatment is performed. 3. A catalyst composition obtained by the production method according to claim 1 or 2. 4. Formula VTi₈O_x   Wherein x is as defined above. ]   4. The catalyst composition of claim 3 defined by: 5. Formula VTi_7.5Zr_0.5O_x   Wherein x is as defined above. ]   4. The catalyst composition of claim 3 defined by: 6. Formula VTi_7.5Zr_0.125O_x   Wherein x is as defined above. ]   4. The catalyst composition of claim 3 defined by: 7. Gaseous form of alkylpyridine, oxygen-containing gas, ammonia and water vapor The feed is produced according to claim 1 at a temperature between 330 ° C. and 440 ° C. Oxidized alkyl pyridine, characterized by passing through a co-precipitated catalyst composition. A method for producing cyanopyridine by monomonolysis. 8. Claim 7 wherein the catalyst composition according to claim 4 is used. Term manufacturing method. 9. Claim 7 wherein the catalyst composition according to claim 5 is used. Term manufacturing method. 10. A catalyst composition according to claim 6, wherein the catalyst composition is used. Item 7. The manufacturing method according to Item 7. 11. Alkyl pyridine is converted to 3-methyl pyridine, 3-ethyl pyridine, Tyl-5-ethylpyridine, 2,5-dimethylpyridine and 2-methyl-5 Claims 7 to 10 characterized in that they are selected from vinylpyridine. Manufacturing method. 12. Select 3-methylpyridine or 2-methyl-5-ethylpyridine The method according to claim 11, wherein: 13. The reactant 3-methylpyridine, an oxygen-containing gas (O_TwoCalculated with respect to ), Ammonia and water vapor, the molar ratio of which is 1: 7: 3: 3 to 1:40: Characterized in that a gaseous feed of 10:45 is passed through the catalyst. For the production of 3-cyanopyridine by oxidative ammonolysis of pyridine 13. The manufacturing method according to any one of items 7 to 12. 14． The reactant 2-methyl-5-ethylpyridine, an oxygen-containing gas (O_TwoAbout ), Consisting of ammonia and water vapor, the molar ratio of which is 1:15: Passing the gaseous feed from 5:20 to 1: 70: 40: 140 through the catalyst 3 by oxidative ammonolysis of 2-methyl-5-ethylpyridine, Any one of claims 7 to 12 relating to the production of cyanopyridine Manufacturing method.