CN102336706A - Method for producing 3-cyanopyridine - Google Patents
Method for producing 3-cyanopyridine Download PDFInfo
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- CN102336706A CN102336706A CN 201010227301 CN201010227301A CN102336706A CN 102336706 A CN102336706 A CN 102336706A CN 201010227301 CN201010227301 CN 201010227301 CN 201010227301 A CN201010227301 A CN 201010227301A CN 102336706 A CN102336706 A CN 102336706A
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- cyanopyridine
- picoline
- catalyzer
- ammonia
- sulfuric acid
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Abstract
The invention discloses a method for producing 3-cyanopyridine. A 3-methylpyridine aqueous solution, ammonia, air are subjected to an ammoxidation under the effect of a catalyst to obtain 3-cyanopyridine. The invention is characterized in that the catalyst is molten salt. The invention has the advantages that the catalyst used for molten salt has high heat conduction coefficient, high conversion rate and high selectivity, and the usage life can reach more than 5 years, the yield of the product can reach 96% and the product content is more than 99.5%.
Description
Technical field
The present invention relates to a kind of working method of 3-cyanopyridine, specifically is that a kind of 3-picoline aqueous solution and ammonia, air carry out the working method that oxidative ammonolysis gets the 3-cyanopyridine of finished product under the effect of catalyzer.
Background technology
Traditional catalyst is with V-Cr, V-P, and the V-Sb system is main; Different process synthesizes the catalyzer of oneself through adding other component, but the catalyzer that domestic manufacturer adopts, it is not high often to exist poor selectivity, transformation efficiency; Shortcomings such as catalyst activity is unstable, produces prussic acid, and the life-span is short; Cause yield not high, catalyst change is frequent, with external advanced level bigger gap is arranged.
In order to solve the problem that traditional technology is brought, at present about the working method of 3-cyanopyridine mostly all with the vaporization of 3-picoline and ammonia and air mixed, the finished product that in the presence of catalyzer, reacts.Like application number 200910031478 denominations of invention: the compound method of 3-cyanopyridine; Application is artificial: Nantong Acetic Acid Co., Ltd; The compound method of the 3-cyanopyridine of this patent is characterized in that: by the vaporization of 3-picoline and ammonia and air mixed, in the presence of catalyzer, react, absorb extracting rectifying then and obtain 3-cyanopyridine finished product.Technology of the present invention is simple, easy to operate, 3-picoline transformation efficiency greater than 99%, 3-cyanopyridine yield is greater than 95%.
Application number: 200510060203; Denomination of invention: the preparation method of 3-cyanopyridine; Applicant: Zhejiang Aidiya Nutrition Sci. & Tech. Dev. Co., Ltd..The preparation method of the 3-cyanopyridine that this invention provides also is to be employed in the technology of carrying out ammonia oxidation under the existence of catalyzer, mainly is to improve through catalyzer, changes conventional catalysts into active catalyst.The transformation efficiency of above raw materials technology and the yield of product all can reach more than 90%.
Summary of the invention
Main task of the present invention is to provide-working method of kind of 3-cyanopyridine; Specifically be a kind of employing 3-picoline vaporization and ammonia and air mixed; After reacting in the presence of the catalyzer; To the processing of the ammonium sulfate solution that contains the 3-cyanopyridine that generates, thereby reach the characteristic that on original basis, improves yield.
In order to solve above technical problem, the working method of a kind of 3-cyanopyridine of the present invention is mainly the 3-picoline aqueous solution and ammonia, air are carried out oxidative ammonolysis acquisition 3-cyanopyridine under the effect of catalyzer; It is characterized in that: said catalyzer is a fused salt.
The invention has the advantages that: the fused salt catalyzer that this technology is used, thermal conductivity is high, and transformation efficiency is high, and selectivity is high, reach work-ing life more than 5 years, and the yield of product can reach 96%, and product content is more than 99.5%.
Embodiment
The 3-cyanopyridine is colourless transparent liquid or xln, odorlessness.Molecular formula: C
6H
4N
2, molecular weight: 104.116, CAS 100-54-9; Can distil, be dissolved in ethanol, ether, chloroform, benzene and sherwood oil, water-soluble slightly.Fusing point 50-51 ℃, 248 ℃ of boiling points, 84 ℃ of flash-points.
The 3-cyanopyridine is a kind of important chemical midbody, is the main raw material of preparation vitamin B group-nicotinic acid, vitamin PP.Nicotinic acid, vitamin PP are the indispensable vitamin B complex nutritive ingredients of human body and other animals, are widely used in fodder additives, foodstuff additive in recent years.And demand also is the raw material of agricultural chemicals pyrrole aphid ketone, pesticide intermediate 2-chlorine apellagrin constantly going up fast in addition.Market is also increasing to the demand of 3-cyanopyridine.
The preparation method of this product:
The 3-picoline aqueous solution that with the concentration of 100-120g/h is 25%-34% is through volume pump and 0.1-0.12m
3The ammonia of/h, 0.6-0.7m
3The air of/h mixes vaporization in mixing preheater, then through being added with V-Cr, V-P; The V-Sb system is the fixed bed of main catalyzer, between 365-370 ℃, obtains to contain the gas of 3-cyanopyridine through oxidative ammonolysis, absorbs through the secondary spray column; The 3-cyanopyridine is water-soluble, and ammoniated noncondensable gas purifies except that emptying up to standard behind the ammonia through 30% aqueous sulfuric acid, and the ammonium sulfate solution absorption liquid that contains the 3-cyanopyridine is through the toluene continuous extraction; The extraction liquid that contains the 3-cyanopyridine is reclaimed in layering; Carry out continuous rectification then, atmospheric distillation reclaims toluene, and rectification under vacuum obtains 3-cyanopyridine product.The ammonium sulfate solution that layering is simultaneously reclaimed adopts Azotropic distillation method to deviate from the organism (for the 3-picoline) in the waste water, and the front-end volatiles that steam recycle as the process water retrieval system; The water that middle portion distills out can qualified discharge, high-concentration sulfuric acid ammonium hydrothermal solution under the final residual, and after cooling, spinning, the reclaim(ed) sulfuric acid ammonium is applied mechanically when filtrating goes following batch of ammonium sulfate to reclaim.
Instance 1:
With the aqueous solution of 33.3%3-picoline be: 0.6-0.7m through volume pump dominant discharge 100g/h, air speed
3/ h, ammonia amount: 0.11m
3/ h, in 120 ℃ of vaporizations, the fixed-bed reactor that get into through the fused salt heating carry out oxidative ammonolysis at 365-370 ℃ in mixing preheater; The bullion that produces absorbs (30% aqueous sulfuric acid) through the secondary spray water.The sampling analysis molar yield is 98.5%.In 170 hours, be equivalent on catalyzer through 3-picoline 5.67kg.The ammonium sulfate solution absorption liquid that contains the 3-cyanopyridine is through the toluene continuous extraction, and the extraction liquid that contains the 3-cyanopyridine is reclaimed in layering, carries out continuous rectification then; Atmospheric distillation reclaims toluene; Rectification under vacuum obtains the 3-cyanopyridine of 6.14kg, and content is 99.7%, and yield is 96.8%.
The ammonium sulfate solution that layering is simultaneously reclaimed adopts Azotropic distillation method to deviate from the organism (for the 3-picoline) in the waste water, and the front-end volatiles that steam recycle as the process water retrieval system; The water that middle portion distills out can qualified discharge, high-concentration sulfuric acid ammonium hydrothermal solution under the final residual, and after cooling, spinning, the reclaim(ed) sulfuric acid ammonium is applied mechanically when filtrating goes following batch of ammonium sulfate to reclaim.
Instance 2:
With the aqueous solution of 33.3%3-picoline be: 0.6-0.7m through volume pump dominant discharge 120g/h, air speed
3/ h, ammonia amount: 0.12m
3/ h, in 130 ℃ of vaporizations, the fixed-bed reactor that get into through the fused salt heating carry out oxidative ammonolysis at 365-370 ℃ in the pre-heated device; The bullion that produces absorbs (30% aqueous sulfuric acid) through the secondary spray water.The sampling analysis molar yield is 98.3%.In 170 hours, be equivalent on catalyzer through 3-picoline 6.8kg.The ammonium sulfate solution that contains the 3-cyanopyridine is through the toluene continuous extraction, and the extraction liquid that contains the 3-cyanopyridine is reclaimed in layering, carries out continuous rectification then; Atmospheric distillation reclaims toluene; Rectification under vacuum obtains the 3-cyanopyridine of 7.3kg, and content is 99.6%, and yield is 96.1%.
The ammonium sulfate solution that layering is simultaneously reclaimed adopts Azotropic distillation method to deviate from the organism (for the 3-picoline) in the waste water, and the front-end volatiles that steam recycle as the process water retrieval system; The water that middle portion distills out can qualified discharge, high-concentration sulfuric acid ammonium hydrothermal solution under the final residual, and after cooling, spinning, the reclaim(ed) sulfuric acid ammonium is applied mechanically when filtrating goes following batch of ammonium sulfate to reclaim.
Instance 3:
With the aqueous solution of 33.3%3-picoline be: 0.6-0.7m through volume pump dominant discharge 100g/h, air speed
3/ h, ammonia amount: 0.11m
3/ h, in 150 ℃ of vaporizations, the fixed-bed reactor that get into through the fused salt heating carry out oxidative ammonolysis at 365-370 ℃ in the pre-heated device; The bullion that produces absorbs (30% aqueous sulfuric acid) through the secondary spray water.The sampling analysis molar yield is 98.3%.In 170 hours, be equivalent on catalyzer through 3-picoline 5.67kg.The ammonium sulfate solution that contains the 3-cyanopyridine is through the toluene continuous extraction, and the extraction liquid that contains the 3-cyanopyridine is reclaimed in layering, carries out continuous rectification then; Atmospheric distillation reclaims toluene; Rectification under vacuum obtains the 3-cyanopyridine of 6.11kg, and content is 99.6%, and yield is 96.3%.
The ammonium sulfate solution that layering is simultaneously reclaimed adopts Azotropic distillation method to deviate from the organism (for the 3-picoline) in the waste water, and the front-end volatiles that steam recycle as the process water retrieval system; The water that middle portion distills out can qualified discharge, high-concentration sulfuric acid ammonium hydrothermal solution under the final residual, and after cooling, spinning, the reclaim(ed) sulfuric acid ammonium is applied mechanically when filtrating goes following batch of ammonium sulfate to reclaim.
Instance 4:
With the aqueous solution of 25%3-picoline be: 0.6-0.7m through volume pump dominant discharge 100g/h, air speed
3/ h, ammonia amount: 0.1m
3/ h, in 140 ℃ of vaporizations, the fixed-bed reactor that get into through the fused salt heating carry out oxidative ammonolysis at 365-370 ℃ in the pre-heated device; The bullion that produces absorbs (30% aqueous sulfuric acid) through the secondary spray water.The sampling analysis molar yield is 98.1%.In 170 hours, be equivalent on catalyzer through 3-picoline 4.25kg.The ammonium sulfate solution that contains the 3-cyanopyridine is through the toluene continuous extraction, and the extraction liquid that contains the 3-cyanopyridine is reclaimed in layering, carries out continuous rectification then; Atmospheric distillation reclaims toluene; Rectification under vacuum obtains the 3-cyanopyridine of 4.57kg, and content is 99.7%, and yield is 96.1%.
The ammonium sulfate solution that layering is simultaneously reclaimed adopts Azotropic distillation method to deviate from the organism (for the 3-picoline) in the waste water, and the front-end volatiles that steam recycle as the process water retrieval system; The water that middle portion distills out can qualified discharge, high-concentration sulfuric acid ammonium hydrothermal solution under the final residual, and after cooling, spinning, the reclaim(ed) sulfuric acid ammonium is applied mechanically when filtrating goes following batch of ammonium sulfate to reclaim.
Claims (1)
1. the working method of a 3-cyanopyridine is mainly the 3-picoline aqueous solution and ammonia, air are carried out oxidative ammonolysis acquisition 3-cyanopyridine under the effect of catalyzer; It is characterized in that: said catalyzer is a fused salt.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467370A (en) * | 2013-09-12 | 2013-12-25 | 南通天泽化工有限公司 | Synthesis method of cyanopyridine and derivatives thereof |
| CN104402812A (en) * | 2014-10-28 | 2015-03-11 | 常州大学 | Synthetic method for pyridinecarboxylic acid |
| CN108558781A (en) * | 2018-06-28 | 2018-09-21 | 新乡市巨晶化工有限责任公司 | A method of preparing 2 cyano pyrazine |
| CN111138348A (en) * | 2019-12-31 | 2020-05-12 | 南通醋酸化工股份有限公司 | Method for recovering 4-methylpyridine in preparation process of 4-cyanopyridine |
| CN111170931A (en) * | 2019-12-31 | 2020-05-19 | 南通醋酸化工股份有限公司 | Method for recovering 3-methylpyridine in 3-cyanopyridine preparation process |
-
2010
- 2010-07-15 CN CN 201010227301 patent/CN102336706A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467370A (en) * | 2013-09-12 | 2013-12-25 | 南通天泽化工有限公司 | Synthesis method of cyanopyridine and derivatives thereof |
| CN104402812A (en) * | 2014-10-28 | 2015-03-11 | 常州大学 | Synthetic method for pyridinecarboxylic acid |
| CN108558781A (en) * | 2018-06-28 | 2018-09-21 | 新乡市巨晶化工有限责任公司 | A method of preparing 2 cyano pyrazine |
| CN111138348A (en) * | 2019-12-31 | 2020-05-12 | 南通醋酸化工股份有限公司 | Method for recovering 4-methylpyridine in preparation process of 4-cyanopyridine |
| CN111170931A (en) * | 2019-12-31 | 2020-05-19 | 南通醋酸化工股份有限公司 | Method for recovering 3-methylpyridine in 3-cyanopyridine preparation process |
| CN111138348B (en) * | 2019-12-31 | 2023-02-28 | 南通醋酸化工股份有限公司 | Method for recovering 4-methylpyridine in preparation process of 4-cyanopyridine |
| CN111170931B (en) * | 2019-12-31 | 2023-05-23 | 南通醋酸化工股份有限公司 | Recovery method of 3-picoline in preparation process of 3-cyanopyridine |
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Application publication date: 20120201 |