CN107056696A - A kind of synthetic method of 3 cyanopyridine - Google Patents
A kind of synthetic method of 3 cyanopyridine Download PDFInfo
- Publication number
- CN107056696A CN107056696A CN201710004735.5A CN201710004735A CN107056696A CN 107056696 A CN107056696 A CN 107056696A CN 201710004735 A CN201710004735 A CN 201710004735A CN 107056696 A CN107056696 A CN 107056696A
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- Prior art keywords
- nicotinonitrile
- synthetic method
- fixed bed
- ammonia
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention provides a kind of synthetic method of 3 cyanopyridine, and in the presence of the type catalyst of GXBD 66, using 3 picolines as raw material, catalytic ammoxidation is carried out in fixed bed reactors with ammonia and air, then obtains finished product through washing, extraction, vacuum distillation.The present invention carries out catalytic ammoxidation reaction 3 cyanopyridines of synthesis to make the type catalyst of GXBD 66 by oneself in fixed bed reactors; the catalyst activity is high, stability is good; 3 cyano group yields are up to more than 93%; content is up to more than 97%, and present invention process is simple to operate, and quantity of three wastes is few; clean manufacturing; safety and environmental protection, while avoiding the danger in course of industrialization, is produced on a large scale.
Description
Technical field
The present invention relates to organic synthesis field, and in particular to a kind of synthetic method of nicotinonitrile.
Background technology
Nicotinonitrile also known as 3-cyanopyridine, nicotinic acid nitrile, have a wide range of applications in fields such as medicine, feed, food.In doctor
Medicine field, nicotinonitrile is mainly for the preparation of nicotinic acid, niacinamide and vitamin B series compound；In field of fodder, 3- cyanogen
Yl pyridines are mainly for the preparation of feed addictive；In field of food, nicotinonitrile can as food additives raw material.The world
In the range of, the production of nicotinonitrile is mainly monopolized by foreign enterprise, for example：Switzerland dragon husky (lonza), the Fan Telu in the U.S.
The world such as this (Vertellus) major company.
The production method of nicotinonitrile mostly by raw material of 3- picolines with ammonia and air in the presence of a catalyst
Carry out reaction finished product.At present, it is catalyzed 3- first with the several of the oxide of antimony, titanium, molybdenum, vanadium and zirconium for active constituent catalyst
The existing document report of yl pyridines ammoxidation.But catalyst patented technology is abroad in enterprise's hand, and domestic imitation technology is difficult to reach
Foreign level.It is not high often to there is poor selectivity, conversion ratio in the catalyst that domestic manufacturer uses, and the unstable grade of catalyst activity lacks
Point, causes yield not high, and catalyst change frequently, has larger gap with Foreign Advanced Lerel.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of synthetic method of nicotinonitrile.
To realize object above, the present invention is achieved by the following technical programs：
A kind of synthetic method of nicotinonitrile, in the presence of GXBD-66 type catalyst, using 3- picolines as raw material,
Catalytic ammoxidation is carried out in fixed bed reactors with ammonia and air, then finished product is obtained through washing, extraction, vacuum distillation；
The GXBD-66 types catalyst is the ABO of doping vario-property3Type perovskite, the composition of catalyst is as follows：MmAaBbOx；
Wherein, the one or more combination in M=Sc, Y, La, Ce；
One or more combination in A=Ca, Sr, Mg, Cu, Co；
One or more combination in B=Ti, Zr, Mn, Mo, Cr；
Oxygen atomicity required for m=0.05-0.95, a=0.15-10, b=0.15-8, x=metallic element.
Preferably, the catalytic ammoxidation reaction temperature is 260-450 DEG C.
Preferably, the catalytic ammoxidation reaction temperature is 320 DEG C.
Preferably, the catalytic ammoxidation reaction pressure is 0.3MPa.
Preferably, the mol ratio of the 3- picolines, ammonia and air is 1：2-8：8-20.
Preferably, the mol ratio of the 3- picolines, ammonia and air is 1：5：12.
Preferably, gas space velocity is 0.6-12gh in the fixed bed reactors-1。
Beneficial effect of the present invention：There is provided a kind of synthetic method of nicotinonitrile, be using 3- picolines as raw material, with
Self-control GXBD-66 type catalyst carries out catalytic ammoxidation reaction synthesis nicotinonitrile, the catalyst in fixed bed reactors
Catalytic activity is high, stability is good, and 3- cyano group yield is up to more than 93%, and content is up to more than 97%, present invention process operation letter
Single, quantity of three wastes is few, and clean manufacturing, safety and environmental protection, while avoiding the danger in course of industrialization, is produced on a large scale.
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.
Embodiment 1：
In the lab using the fixed bed reactors that internal diameter is 32mm, catalyst layer filling 10gGXBD-66 type catalysis
Agent, two ends are using quartz sand as filler, and 3- picolines, air, ammonia enter simultaneously in proportion is urged in fixed bed reactors
Change hydrogenation reaction, 320 DEG C of reaction temperature, reaction pressure 0.3MPa, gas space velocity is 6gh-1, the consumption mol ratio of reaction raw materials
For：3- picolines：Ammonia：Air=1:5:12, react fixed bed afterbody and received product, weighed.Yield is 93.61%,
Content is 97.54%.
Embodiment 2：
In the lab using the fixed bed reactors that internal diameter is 32mm, catalyst layer filling 10gGXBD-66 type catalysis
Agent, two ends are using quartz sand as filler, and 3- picolines, air, ammonia enter simultaneously in proportion is urged in fixed bed reactors
Change hydrogenation reaction, 260 DEG C of reaction temperature, reaction pressure 0.3MPa, gas space velocity is 6gh-1, the consumption mol ratio of reaction raw materials
For：3- picolines：Ammonia：Air=1:5:12, react fixed bed afterbody and received product, weighed.Yield is 88.73%,
Content is 98.10%.
Embodiment 3：
In the lab using the fixed bed reactors that internal diameter is 32mm, catalyst layer filling 10gGXBD-66 type catalysis
Agent, two ends are using quartz sand as filler, and 3- picolines, air, ammonia enter simultaneously in proportion is urged in fixed bed reactors
Change hydrogenation reaction, 320 DEG C of reaction temperature, reaction pressure 0.3MPa, gas space velocity is 12gh-1, the consumption mole of reaction raw materials
Than for：3- picolines：Ammonia：Air=1:5:12, react fixed bed afterbody and received product, weighed.Yield is
90.35%, content is 98.76%.
Embodiment 4：
In the lab using the fixed bed reactors that internal diameter is 32mm, catalyst layer filling 10gGXBD-66 type catalysis
Agent, two ends are using quartz sand as filler, and 3- picolines, air, ammonia enter simultaneously in proportion is urged in fixed bed reactors
Change hydrogenation reaction, 320 DEG C of reaction temperature, reaction pressure 0.3MPa, gas space velocity is 6gh-1, the consumption mol ratio of reaction raw materials
For：3- picolines：Ammonia：Air=1:4:12, react fixed bed afterbody and received product, weighed.Yield is 84.89%,
Content is 92.18%.
Embodiment 5：
In the lab using the fixed bed reactors that internal diameter is 32mm, catalyst layer filling 10gGXBD-66 type catalysis
Agent, two ends are using quartz sand as filler, and 3- picolines, air, ammonia enter simultaneously in proportion is urged in fixed bed reactors
Change hydrogenation reaction, 320 DEG C of reaction temperature, reaction pressure 0.3MPa, gas space velocity is 6gh-1, the consumption mol ratio of reaction raw materials
For：3- picolines：Ammonia：Air=1:5:8, react fixed bed afterbody and received product, weighed.Yield is 76.05%, is contained
Measure as 88.61%.
Embodiment 6：
In the lab using the fixed bed reactors that internal diameter is 32mm, catalyst layer filling 10gGXBD-66 type catalysis
Agent, two ends are using quartz sand as filler, and 3- picolines, air, ammonia enter simultaneously in proportion is urged in fixed bed reactors
Change hydrogenation reaction, 400 DEG C of reaction temperature, reaction pressure 0.3MPa, gas space velocity is 0.6gh-1, the consumption mole of reaction raw materials
Than for：3- picolines：Ammonia：Air=1:2:8, react fixed bed afterbody and received product, weighed.Yield is 74.56%,
Content is 85.30%.
Embodiment 7：
In the lab using the fixed bed reactors that internal diameter is 32mm, catalyst layer filling 10gGXBD-66 type catalysis
Agent, two ends are using quartz sand as filler, and 3- picolines, air, ammonia enter simultaneously in proportion is urged in fixed bed reactors
Change hydrogenation reaction, 450 DEG C of reaction temperature, reaction pressure 0.3MPa, gas space velocity is 3gh-1, the consumption mol ratio of reaction raw materials
For：3- picolines：Ammonia：Air=1:8:20, react fixed bed afterbody and received product, weighed.Yield is 80.34%,
Content is 88.25%.
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 (7)
1. a kind of synthetic method of nicotinonitrile, it is characterised in that in the presence of GXBD-66 type catalyst, with 3- methyl pyrroles
Pyridine is raw material, catalytic ammoxidation is carried out in fixed bed reactors with ammonia and air, gas space velocity control is then through washing, extraction
Take, vacuum distillation obtains finished product；
The GXBD-66 types catalyst is the ABO of doping vario-property3Type perovskite, the composition of catalyst is as follows：MmAaBbOx；
Wherein, the one or more combination in M=Sc, Y, La, Ce；
One or more combination in A=Ca, Sr, Mg, Cu, Co；
One or more combination in B=Ti, Zr, Mn, Mo, Cr；
Oxygen atomicity required for m=0.05-0.95, a=0.15-10, b=0.15-8, x=metallic element.
2. the synthetic method of nicotinonitrile as claimed in claim 1, it is characterised in that the catalytic ammoxidation reaction temperature
For 260-450 DEG C.
3. the synthetic method of nicotinonitrile as claimed in claim 2, it is characterised in that the catalytic ammoxidation reaction temperature
For 320 DEG C.
4. the synthetic method of nicotinonitrile as claimed in claim 1, it is characterised in that the catalytic ammoxidation reaction pressure
For 0.3MPa.
5. the synthetic method of nicotinonitrile as claimed in claim 1, it is characterised in that the 3- picolines, ammonia and sky
The mol ratio of gas is 1：2-8：8-20.
6. the synthetic method of nicotinonitrile as claimed in claim 5, it is characterised in that the 3- picolines, ammonia and sky
The mol ratio of gas is 1：5：12.
7. the synthetic method of nicotinonitrile as claimed in claim 1, it is characterised in that gas in the fixed bed reactors
Air speed is 0.6-12gh-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710004735.5A CN107056696A (en) | 2017-01-04 | 2017-01-04 | A kind of synthetic method of 3 cyanopyridine |
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| CN201710004735.5A CN107056696A (en) | 2017-01-04 | 2017-01-04 | A kind of synthetic method of 3 cyanopyridine |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188104A (en) * | 1996-10-24 | 1998-07-22 | 日东化学工业株式会社 | Process for preparing carbocyclic or heterocyclic nitriles by vapor phase ammoxidation |
| CN101602722A (en) * | 2009-04-29 | 2009-12-16 | 南通醋酸化工股份有限公司 | The synthetic method of 3-cyanopyridine |
-
2017
- 2017-01-04 CN CN201710004735.5A patent/CN107056696A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188104A (en) * | 1996-10-24 | 1998-07-22 | 日东化学工业株式会社 | Process for preparing carbocyclic or heterocyclic nitriles by vapor phase ammoxidation |
| CN101602722A (en) * | 2009-04-29 | 2009-12-16 | 南通醋酸化工股份有限公司 | The synthetic method of 3-cyanopyridine |
Non-Patent Citations (1)
| Title |
|---|
| P. KANTA RAO ET AL.: "Highly active titania supported ceria catalysts for ammoxidation of picolines", 《APPLIED CATALYSIS A: GENERAL》 * |
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Application publication date: 20170818 |
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