CN107056697A - A kind of method for synthesizing 3 cyanopyridines - Google Patents
A kind of method for synthesizing 3 cyanopyridines Download PDFInfo
- Publication number
- CN107056697A CN107056697A CN201710005432.5A CN201710005432A CN107056697A CN 107056697 A CN107056697 A CN 107056697A CN 201710005432 A CN201710005432 A CN 201710005432A CN 107056697 A CN107056697 A CN 107056697A
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- Prior art keywords
- catalyst
- nicotinonitrile
- kmop
- supported
- picolines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
- C07D213/85—Nitriles in position 3
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
Abstract
The invention provides a kind of method for synthesizing 3 cyanopyridines, step is as follows：By γ Al2O3Supported V KMoP loads the beds of fixed bed reactors as catalyst, 3 picolines are added in fixed bed reactors, oxygen, ammonia is then passed to be reacted, after reaction terminates, cool Filtration of catalyst, vacuum distillation precipitation is carried out again and removes unreacted 3 picoline, and remaining solid ether wash cooling obtains 3 cyanopyridines；The γ Al2O3In supported V KMoP catalyst, with γ Al2O3For carrier, using V as major catalyst, using K, Mo, P as auxiliary agent, prepared using infusion process.The present invention is in γ Al2O3In the presence of supported V KMoP catalyst, 3 picolines are directly carried out cyanalation, with very high selectivity, the selectivity of 3 cyanopyridines is up to more than 93%, the conversion ratio of raw material is up to more than 98%, the yield of product is up to more than 92%, and catalyst catalytic performance is stable to be continuously used for a long time, and synthesis technique is reliable and stable.
Description
Technical field
The present invention relates to organic synthesis field, and in particular to a kind of method of synthesis nicotinonitrile.
Background technology
Nicotinonitrile is a kind of important fine-chemical intermediate, is the former material of production medicine, agricultural chemicals and feed industry
Material, can be used for preparing vitamin B, insecticide, cardiotonic etc..Nicotinonitrile is industrially to synthesize nicotinic acid and niacinamide most
Important intermediate, nicotinic acid and its derivative niacinamide belong to the compound of vitamin B series, necessary to being a kind of animal
Chemical substance, the comparision contents in the liver kidney of animal, milk, egg and fresh vegetables are more, and it is primarily involved in organic matter
Redox, enhance metabolism, be applied primarily in life：In food additives, feed addictive, medicine
Mesosome, reactive dye, daily chemical industry product etc..With the improvement of people ' s living standards and animal feed product demand increasing
It is long, the fast development of global nicotinic acid and niacinamide is promoted, the production of nicotinonitrile is also developed therewith.
The production method on nicotinonitrile is mostly mixed with the vaporization of 3- picolines with ammonia and air at present, is being urged
The finished product reacted in the presence of agent.However, often there is poor selectivity, conversion ratio not in the catalyst that domestic manufacturer uses
Height, catalyst activity is unstable, the shortcomings of producing hydrogen cyanide, short life, causes yield not high, and catalyst change is frequent, with state
Outer advanced level has larger gap.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of method for synthesizing nicotinonitrile.
To realize object above, the present invention is achieved by the following technical programs：
A kind of method for synthesizing nicotinonitrile, step is as follows：By γ-Al2O3Supported V KMoP loads solid as catalyst
The beds of fixed bed reactor, 3- picolines are added in fixed bed reactors, are then passed to oxygen, ammonia and are carried out instead
Should, after reaction terminates, cool Filtration of catalyst, then carries out the unreacted 3- picolines of vacuum distillation precipitation removing, remaining
Under solid ether wash cooling, obtain nicotinonitrile；
γ-the Al2O3In supported V KMoP catalyst, with γ-Al2O3For carrier, using V as major catalyst, with K, Mo, P
For auxiliary agent, prepared using infusion process.
Preferably, the γ-Al2O3V load capacity is that 17%, K/V mol ratios are 0.012 in supported V KMoP catalyst,
Mo/V mol ratios are that 0.011, P/V mol ratios are 0.01.
Preferably, the mol ratio of the ammonia, oxygen and 3- picolines is 1.85-1.95：2.9-3.0：1.
Preferably, the reaction temperature is 300-320 DEG C.
Preferably, the temperature of the vacuum distillation is 90-95 DEG C, and vacuum is in 0.07-0.09Mpa.
Preferably, the temperature control of the wash cooling is at 10-15 DEG C.
Beneficial effect of the present invention：The present invention is in γ-Al2O3It is in the presence of supported V KMoP catalyst, 3- picolines is straight
Tap into row it is cyanalation, with very high selectivity, the selectivity of nicotinonitrile is up to more than 93%, and the conversion ratio of raw material is reachable
More than 98%, the yield of product is up to more than 92%, and catalyst catalytic performance is stable to be continuously used for a long time, and synthesis technique is steady
It is fixed reliable.
Embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, belongs to the scope of protection of the invention.
γ-Al2O3In supported V KMoP catalyst, with γ-Al2O3For carrier, using V as major catalyst, using K, Mo, P to help
Agent, is prepared using infusion process, and V load capacity is that 17%, K/V mol ratios are that 0.012, Mo/V mol ratios are in catalyst
0.011, P/V mol ratio is 0.01.
Embodiment 1：
By γ-Al2O3Supported V KMoP catalyst loads the beds of fixed bed reactors, by 93g (1mol) 3-
Picoline is added in fixed bed reactors, is then passed to 1.85mol ammonias, 2.9mol oxygen and is reacted at 300 DEG C, instead
After should terminating, cool Filtration of catalyst, in 90 DEG C of temperature, and under conditions of vacuum is 0.07Mpa, vacuum distillation precipitation is removed
Unreacted 3- picolines are removed, remaining solid, to 10 DEG C, obtains nicotinonitrile with ether wash cooling.3- picolines
Conversion ratio be 98.6%, the selectivity of nicotinonitrile is 93.6%, and the yield of nicotinonitrile is 92.3%.
Embodiment 2：
γ-Al2O3 supported V KMoP catalyst is loaded to the beds of fixed bed reactors, by 93g (1mol) 3-
Picoline is added in fixed bed reactors, is then passed to 1.85mol ammonias, 2.9mol oxygen and is reacted at 310 DEG C, instead
After should terminating, cool Filtration of catalyst, in 90 DEG C of temperature, and under conditions of vacuum is 0.07Mpa, vacuum distillation precipitation is removed
Unreacted 3- picolines are removed, remaining solid, to 10 DEG C, obtains nicotinonitrile with ether wash cooling.3- picolines
Conversion ratio be 98.9%, the selectivity of nicotinonitrile is 94.1%, and the yield of nicotinonitrile is 92.5%.
Embodiment 3：
γ-Al2O3 supported V KMoP catalyst is loaded to the beds of fixed bed reactors, by 93g (1mol) 3-
Picoline is added in fixed bed reactors, is then passed to 1.85mol ammonias, 2.9mol oxygen and is reacted at 320 DEG C, instead
After should terminating, cool Filtration of catalyst, in 90 DEG C of temperature, and under conditions of vacuum is 0.07Mpa, vacuum distillation precipitation is removed
Unreacted 3- picolines are removed, remaining solid, to 10 DEG C, obtains nicotinonitrile with ether wash cooling.3- picolines
Conversion ratio be 98.7%, the selectivity of nicotinonitrile is 93.7%, and the yield of nicotinonitrile is 92.7%.
Embodiment 4：
γ-Al2O3 supported V KMoP catalyst is loaded to the beds of fixed bed reactors, by 93g (1mol) 3-
Picoline is added in fixed bed reactors, is then passed to 1.9mol ammonias, 2.9mol oxygen and is reacted at 300 DEG C, instead
After should terminating, cool Filtration of catalyst, in 90 DEG C of temperature, and under conditions of vacuum is 0.07Mpa, vacuum distillation precipitation is removed
Unreacted 3- picolines are removed, remaining solid, to 10 DEG C, obtains nicotinonitrile with ether wash cooling.3- picolines
Conversion ratio be 98.6%, the selectivity of nicotinonitrile is 93.9%, and the yield of nicotinonitrile is 92.6%.
Embodiment 5：
γ-Al2O3 supported V KMoP catalyst is loaded to the beds of fixed bed reactors, by 93g (1mol) 3-
Picoline is added in fixed bed reactors, is then passed to 1.95mol ammonias, 2.9mol oxygen and is reacted at 300 DEG C, instead
After should terminating, cool Filtration of catalyst, in 90 DEG C of temperature, and under conditions of vacuum is 0.07Mpa, vacuum distillation precipitation is removed
Unreacted 3- picolines are removed, remaining solid, to 10 DEG C, obtains nicotinonitrile with ether wash cooling.3- picolines
Conversion ratio be 98.9%, the selectivity of nicotinonitrile is 93.6%, and the yield of nicotinonitrile is 93.1%.
Embodiment 6：
γ-Al2O3 supported V KMoP catalyst is loaded to the beds of fixed bed reactors, by 93g (1mol) 3-
Picoline is added in fixed bed reactors, is then passed to 1.85mol ammonias, 3.0mol oxygen and is reacted at 300 DEG C, instead
After should terminating, cool Filtration of catalyst, in 90 DEG C of temperature, and under conditions of vacuum is 0.07Mpa, vacuum distillation precipitation is removed
Unreacted 3- picolines are removed, remaining solid, to 10 DEG C, obtains nicotinonitrile with ether wash cooling.3- picolines
Conversion ratio be 98.6%, the selectivity of nicotinonitrile is 93.9%, and the yield of nicotinonitrile is 92.8%.
Embodiment 7：
γ-Al2O3 supported V KMoP catalyst is loaded to the beds of fixed bed reactors, by 93g (1mol) 3-
Picoline is added in fixed bed reactors, is then passed to 1.85mol ammonias, 3.0mol oxygen and is reacted at 300 DEG C, instead
After should terminating, cool Filtration of catalyst, in 95 DEG C of temperature, and under conditions of vacuum is 0.08Mpa, vacuum distillation precipitation is removed
Unreacted 3- picolines are removed, remaining solid, to 10 DEG C, obtains nicotinonitrile with ether wash cooling.3- picolines
Conversion ratio be 98.6%, the selectivity of nicotinonitrile is 93.6%, and the yield of nicotinonitrile is 92.6%.
Embodiment 8：
γ-Al2O3 supported V KMoP catalyst is loaded to the beds of fixed bed reactors, by 93g (1mol) 3-
Picoline is added in fixed bed reactors, is then passed to 1.85mol ammonias, 2.9mol oxygen and is reacted at 300 DEG C, instead
After should terminating, cool Filtration of catalyst, in 90 DEG C of temperature, and under conditions of vacuum is 0.09Mpa, vacuum distillation precipitation is removed
Unreacted 3- picolines are removed, remaining solid, to 15 DEG C, obtains nicotinonitrile with ether wash cooling.3- picolines
Conversion ratio be 98.5%, the selectivity of nicotinonitrile is 93.6%, and the yield of nicotinonitrile is 92.5%.
It should be noted that herein, such as first and second or the like relational terms are used merely to a reality
Body or operation make a distinction with another entity or operation, and not necessarily require or imply these entities or deposited between operating
In any this actual relation or order.Moreover, term " comprising ", "comprising" or its any other variant are intended to
Nonexcludability is included, so that process, method, article or equipment including a series of key elements not only will including those
Element, but also other key elements including being not expressly set out, or also include being this process, method, article or equipment
Intrinsic key element.In the absence of more restrictions, the key element limited by sentence "including a ...", it is not excluded that
Also there is other identical element in process, method, article or equipment including the key element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention is described in detail, it will be understood by those within the art that：It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent substitution to which part technical characteristic；And these modification or
Replace, the essence of appropriate technical solution is departed from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (6)
1. a kind of method for synthesizing nicotinonitrile, it is characterised in that step is as follows：By γ-Al2O3Supported V KMoP is used as catalysis
Agent loads the beds of fixed bed reactors, and 3- picolines are added in fixed bed reactors, oxygen, ammonia is then passed to
Gas is reacted, after reaction terminates, and cool Filtration of catalyst, then carries out the unreacted 3- methyl of vacuum distillation precipitation removing
Pyridine, remaining solid ether wash cooling, obtains nicotinonitrile；
γ-the Al2O3In supported V KMoP catalyst, with γ-Al2O3For carrier, using V as major catalyst, using K, Mo, P to help
Agent, is prepared using infusion process.
2. the method for nicotinonitrile is synthesized as claimed in claim 1, it is characterised in that the γ-Al2O3Supported V KMoP is urged
V load capacity is that 17%, K/V mol ratios are that 0.012, Mo/V mol ratios are that 0.011, P/V mol ratios are 0.01 in agent.
3. the method for nicotinonitrile is synthesized as claimed in claim 1, it is characterised in that the ammonia, oxygen and 3- methyl
The mol ratio of pyridine is 1.85-1.95：2.9-3.0：1.
4. the method for nicotinonitrile is synthesized as claimed in claim 1, it is characterised in that the reaction temperature is 300-320
℃。
5. the method for synthesis nicotinonitrile as claimed in claim 1, it is characterised in that the temperature of the vacuum distillation is
90-95 DEG C, vacuum is in 0.07-0.09Mpa.
6. the method for nicotinonitrile is synthesized as claimed in claim 1, it is characterised in that the temperature control of the wash cooling
At 10-15 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710005432.5A CN107056697A (en) | 2017-01-04 | 2017-01-04 | A kind of method for synthesizing 3 cyanopyridines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710005432.5A CN107056697A (en) | 2017-01-04 | 2017-01-04 | A kind of method for synthesizing 3 cyanopyridines |
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| Publication Number | Publication Date |
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| CN107056697A true CN107056697A (en) | 2017-08-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710005432.5A Pending CN107056697A (en) | 2017-01-04 | 2017-01-04 | A kind of method for synthesizing 3 cyanopyridines |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107857726A (en) * | 2017-12-12 | 2018-03-30 | 安徽瑞邦生物科技有限公司 | The method of 3 picoline one-step synthesis method niacinamide |
| CN113149903A (en) * | 2021-04-30 | 2021-07-23 | 安徽国星生物化学有限公司 | Synthesis method and device of cyanopyridine |
| CN113214148A (en) * | 2021-04-30 | 2021-08-06 | 安徽国星生物化学有限公司 | Synthesis method and device of 2/3-cyanopyridine |
-
2017
- 2017-01-04 CN CN201710005432.5A patent/CN107056697A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 刘振国: "氨氧化法制备3-氰基吡啶的工艺研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107857726A (en) * | 2017-12-12 | 2018-03-30 | 安徽瑞邦生物科技有限公司 | The method of 3 picoline one-step synthesis method niacinamide |
| CN113149903A (en) * | 2021-04-30 | 2021-07-23 | 安徽国星生物化学有限公司 | Synthesis method and device of cyanopyridine |
| CN113214148A (en) * | 2021-04-30 | 2021-08-06 | 安徽国星生物化学有限公司 | Synthesis method and device of 2/3-cyanopyridine |
| CN113149903B (en) * | 2021-04-30 | 2023-02-10 | 安徽国星生物化学有限公司 | Method and device for synthesizing cyanopyridine |
| CN113214148B (en) * | 2021-04-30 | 2023-02-14 | 安徽国星生物化学有限公司 | Synthesis method and device of 2/3-cyanopyridine |
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Application publication date: 20170818 |
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