CN102372666A - Method for synthesizing alfa-methylpyridine through continuous catalytic distillation - Google Patents
Method for synthesizing alfa-methylpyridine through continuous catalytic distillation Download PDFInfo
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- CN102372666A CN102372666A CN201010250545XA CN201010250545A CN102372666A CN 102372666 A CN102372666 A CN 102372666A CN 201010250545X A CN201010250545X A CN 201010250545XA CN 201010250545 A CN201010250545 A CN 201010250545A CN 102372666 A CN102372666 A CN 102372666A
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- acetonitrile
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- jia jibiding
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides a method for synthesizing alfa-methylpyridine through continuous catalytic distillation, comprising the following steps: in the presence of metallocene catalyst, letting liquid phase acetonitrile and gas phase acetylene continuously pass through a filling tubular reactor and be subject to reaction at the reaction temperature of 100-200 DEG C under reaction pressure of 0.5-2.0 MPa with the catalyst addition which accounts for 0.3-0.35 % of the total weight of acetonitrile and acetylene, keeping the reactant in the reactor for 20-60 min, and carrying out double-tower continuous rectification separation on the obtained crude product of alfa-methylpyridine to obtain the high purity alfa-methylpyridine. According to the invention, by using the continuous catalytic distillation technology, the advantages of stable operation, high safety, simple device, recycled catalyst, stable product quality, low energy consumption, no waste water and no exhaust gas generation, environmental friendly, and easy realization of safe and environmentally friendly industrial production.
Description
Technical field
The present invention relates to the compound method of α-Jia Jibiding, relate in particular to the method that adopts the synthetic α-Jia Jibiding of continuous catalyzing rectifying technology.
Background technology
The pyridine that on the α position of ring texture, connects a methyl is called α-Jia Jibiding, 2-picoline or skin Courlene.α-Jia Jibiding is a kind of important fine chemical material; Be mainly used in and produce 2-vinyl pyridine, 2-cyanopyridine; Additive, dyestuff intermediate and the rubber accelerator etc. of nitrogen fertilizer potentiating agent (N-Serve), RP-7522, Toldrin, anti-silicosis medicine, livestock insect repellent, poultry medication, organophosphorus toxinicide, local anesthetic, cathartic, light reaching the film agent also can be used as solvent.α-Jia Jibiding can obtain from the sub product of coal-tar industry or coke production, but output is very low, and maximum extraction element is produced 200 tons per year, and purity has only about 98%, can not satisfy the demand of medicine, agricultural chemicals and chemical industry.The preferred method that obtains pyridine is synthetic through catalysis.
The synthetic for example catalytic gas phase reaction of aldehydes or ketones of ammonia and carbonyl compound that generally passes through of catalysis open and report.Yet these process for catalytic synthesis always have the low and poor selectivity of yield, and operational cycle and the short shortcoming of catalyst life.US4675410 and US4886179 are disclosed to be to be the method for raw material pyridine synthesis and picoline from formaldehyde, acetaldehyde and ammonia, wherein adopts the metal ion-modified ZSM-5 zeolites as catalysts of the 8th group of the periodic table of elements.US4220783 is disclosed to be to be the method for raw material pyridine synthesis and picoline from carbonyl compound and ammonia, wherein adopts cadmium metal ion modification ZSM-5 zeolites as catalysts.All introduced the preparation method of pyridine/picoline among CN1299349A and the CN1332728A; They are catalyzer with the molecular sieve of phosphorus modification all; With ammonia and C1～5 carbonyl reaction agent is raw material; But they all exist the selectivity and the not high problem of yield of product pyridine and picoline, and product yield is the highest to be merely 70%.
It is raw material that CN1506354A discloses with ammonia, formaldehyde and acetaldehyde, is the technical scheme of catalyzer with the molecular sieve of handling through the strong alkali aqueous solution modification.Similar with the technological line of offshore company; Temperature of reaction reaches 350-550 ℃; By product contains 4-picoline, 2-methyl-5 ethylpyridine, pyridine, 3-picoline and senior pyridine etc.; Its shortcoming is that product is numerous and boiling point is close, and the separation purification process of product separation is very complicated, and facility investment is huge.
Since two thousand six, domestic two, three covers of having gone into operation successively are the dingus that raw material route is produced α-Jia Jibiding with acetonitrile and acetylene, are catalyzer with the dicyclopentadienylcobalt, intermittently stir still reaction, batch fractionating purification.In the production process high, the catalyzer of energy consumption can only disposablely consume can't reuse, low, the unstable product quality of production efficiency.Particularly when reaction end, the violent polymerization of excessive acetylene generates benzene, is strong exothermal reaction, and moment produces HTHP, controls the bad security incident that very easily takes place.
Summary of the invention
The present invention wants the technical solution problem to provide a kind of α-Jia Jibiding compound method, to overcome the above-mentioned defective that prior art exists.
The method of the synthetic α-Jia Jibiding of continuous catalyzing rectifying of the present invention comprises the steps:
Liquid phase acetonitrile and gas phase acetylene are in the presence of metallocene catalyst; Through filling tubular reactor, be 100～200 ℃ in temperature of reaction continuously, reaction pressure is 0.5～2.0MPa; The catalyzer addition is to react under 0.3～0.35% the condition of acetonitrile and acetylene total mass; The residence time of reactant in reactor drum is 20～60 minutes, and the α-Jia Jibiding crude product that obtains separates through the double tower continuous rectification, obtains highly purified α-Jia Jibiding.
As preferred version, temperature of reaction is preferably in 150～160 ℃, and reaction pressure is 0.6～0.8MPa, and the residence time of reactant in reactor drum is preferably 35～50 minutes.
Raw material acetonitrile and acetylene molar ratio are 1.0: 1.0～1.9, and acetonitrile is excessive a little.Preferred acetonitrile and acetylene molar ratio are 1.0: 1.7～1.9, guarantee reaction safety.
Said metallocene catalyst is selected from more than one of ferrocene, nickelocene, two luxuriant chromium, dicyclopentadienylcobalt, and preferred catalyzer is the mixture of ferrocene and dicyclopentadienylcobalt, and mass ratio is 1: 2～6, and preferably mass ratio is 1: 3～5.
Be filled with the Pall ring wire packing of diameter 3～20mm in the said filling tubular reactor, and 1～5 gas-liquid mixed sparger is set.Preferred filling diameter is the Pall ring wire packing of 5～6mm, and 2～3 gas-liquid mixed spargers are set.
It is earlier the thick product of said α-Jia Jibiding to be sent into first rectifying tower that said double tower continuous rectification separates; Tower still catalyzer dope returns fills the repeated use of tubular reactor inlet; It is that the α-Jia Jibiding of 65～98wt% gets into second rectifying tower that cat head goes out purity; Isolate unreacted acetonitrile from the cat head of second rectifying tower, return the acetonitrile head tank, by obtaining the α-Jia Jibiding that purity is 99.9wt% at the bottom of the tower.
Fill tubular reactor, Pall ring wire packing, gas-liquid mixed sparger and rectifying tower and all adopt conventional commercially available prod, equipment; For example the diameter 76mm of Wuxi Su Yang chemical equipment ltd production fills tubular reactor; The Pall ring filler of the 5mm that Tianjin Jin Kang chemical plant factory produces and supporting gas-liquid mixed sparger, the rectifying tower of the diameter 500mm that the mechanical Group Plc of Shandong rising sun sun produces.
Advantage of the present invention is to adopt continuous catalyzing rectifying technology, smooth operation, safe; And have that equipment is simple, catalyst recirculation use, constant product quality, characteristic of low energy consumption; There is not waste water and gas to produce, environmentally friendly, realize the suitability for industrialized production of safety, environmental protection easily.
Through embodiment the present invention is done further elaboration below.
Embodiment
Embodiment 1
Acetonitrile and acetylene are raw material; With the molar ratio computing acetonitrile: acetylene=1.0: 1.3, catalyzer are that ferrocene mixes by 1: 3 with dicyclopentadienylcobalt, and addition is 0.3% of a raw material total mass; Be filled with the Pall ring wire packing of diameter 5mm in the tubular reactor, and 2 gas-liquid mixed spargers are set.In temperature of reaction is that 110 ℃, reaction pressure are under the 1.8MPa condition, and through filling tubular reactor, the residence time is 35 minutes continuously, generates the thick product of α-Jia Jibiding; Thick product gets into first tower, is the catalyzer dope at the bottom of the tower, and the Returning reactor inlet is reused; The 65% thick product that cat head comes out continues to get into second tower, obtains the α-Jia Jibiding of purity 99.9% from the bottom of second tower, and overhead product is unreacted acetonitrile, returns raw material acetonitrile jar.
In acetonitrile selectivity 99%, yield 95%.Product appearance: colourless transparent liquid, boiling range: 127-130 ℃, content 99.9%, content detection adopts vapor-phase chromatography, 30M capillary column.
Embodiment 2
Acetonitrile and acetylene molar ratio meter acetonitrile: acetylene=1.0: 1.8; Catalyzer is that ferrocene mixes by 1: 5 with dicyclopentadienylcobalt; Addition is 0.35% of a raw material total mass, is filled with the Pall ring wire packing of diameter 6mm in the tubular reactor, and 3 gas-liquid mixed spargers are set.In temperature of reaction is that 160 ℃, reaction pressure are under the 0.8MPa condition, and through filling tubular reactor, the residence time is 45 minutes continuously, generates the thick product of α-Jia Jibiding; Thick product gets into first tower, is the catalyzer dope at the bottom of the tower, and the Returning reactor inlet is reused; The 90% thick product that cat head comes out continues to get into second tower, obtains the α-Jia Jibiding of purity 99.9% from the bottom of second tower, and overhead product is unreacted acetonitrile, returns raw material acetonitrile jar.
In acetonitrile selectivity 99%, yield 98%.Product appearance: colourless transparent liquid, boiling range: 127-130 ℃, content 99.9%, content detection adopts vapor-phase chromatography, 30M capillary column.
Claims (8)
1. continuous catalyzing rectifying synthesizes the method for α-Jia Jibiding; It is characterized in that liquid phase acetonitrile and gas phase acetylene are in the presence of metallocene catalyst, continuously through filling tubular reactor; In temperature of reaction is 100～200 ℃; Reaction pressure is 0.5～2.0MPa, and the catalyzer addition is to react under 0.3～0.35% the condition of acetonitrile and acetylene total mass, and the residence time of reactant in reactor drum is 20～60 minutes; The α-Jia Jibiding crude product that obtains separates through the double tower continuous rectification, obtains highly purified α-Jia Jibiding.
2. method according to claim 1 is characterized in that, the mol ratio of acetonitrile and acetylene is 1.0: 1.0～1.9.
3. method according to claim 1 is characterized in that, the mol ratio of acetonitrile and acetylene is 1.0: 1.7～1.9.
4. method according to claim 1 is characterized in that, said metallocene catalyst is selected from more than one of ferrocene, nickelocene, two luxuriant chromium, dicyclopentadienylcobalt.
5. method according to claim 1 is characterized in that, said metallocene catalyst is ferrocene and the dicyclopentadienylcobalt mixture by mass ratio 1: 2～6.
6. method according to claim 1 is characterized in that, is filled with the Pall ring wire packing of diameter 3～20mm in the said filling tubular reactor, and 1～5 gas-liquid mixed sparger is set.
7. method according to claim 1 is characterized in that, is filled with the Pall ring wire packing of diameter 5～6mm in the said filling tubular reactor, and 2～3 gas-liquid mixed spargers are set.
8. according to each described method of claim 1～7; It is characterized in that it is earlier the thick product of said α-Jia Jibiding to be sent into first rectifying tower that said double tower continuous rectification separates, tower still catalyzer dope returns fills the repeated use of tubular reactor inlet; It is that the α-Jia Jibiding of 65～98wt% gets into second rectifying tower that cat head goes out purity; Isolate unreacted acetonitrile from the cat head of second rectifying tower, return the acetonitrile head tank, by obtaining the α-Jia Jibiding that purity is 99.9wt% at the bottom of the tower.
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| CN201010250545XA CN102372666A (en) | 2010-08-11 | 2010-08-11 | Method for synthesizing alfa-methylpyridine through continuous catalytic distillation |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351330A (en) * | 2013-07-27 | 2013-10-16 | 新乡市博科精细化工有限公司 | Processing device for producing 2-picoline |
| CN103360304A (en) * | 2013-07-27 | 2013-10-23 | 新乡市博科精细化工有限公司 | Processing production apparatus for 2-methylpyridine |
| CN105820111A (en) * | 2016-04-21 | 2016-08-03 | 鹤壁市赛科化工有限公司 | Preparation method of catalyst and method for preparing 2,2-dipyridyl through catalysis by virtue of catalyst |
| CN106380466A (en) * | 2016-08-31 | 2017-02-08 | 连云港宏业化工有限公司 | Method for synthesizing 2-(2-thiophene)pyridine |
| CN107162959A (en) * | 2017-06-08 | 2017-09-15 | 安徽星宇化工有限公司 | The synthetic method of 2 pyridine carboxylic acids |
| CN108373427A (en) * | 2018-03-13 | 2018-08-07 | 索闻特环保科技(上海)有限公司 | The separation method of the waste liquid of picoline containing 3- and acetonitrile |
| CN108658848A (en) * | 2018-05-05 | 2018-10-16 | 湖北荆洪生物科技股份有限公司 | A kind of production technology of 2,2`- bipyridyls |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4196287A (en) * | 1975-09-18 | 1980-04-01 | Lonza Ltd. | Process for the catalytic production of 2-substituted pyridines |
-
2010
- 2010-08-11 CN CN201010250545XA patent/CN102372666A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4196287A (en) * | 1975-09-18 | 1980-04-01 | Lonza Ltd. | Process for the catalytic production of 2-substituted pyridines |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103351330A (en) * | 2013-07-27 | 2013-10-16 | 新乡市博科精细化工有限公司 | Processing device for producing 2-picoline |
| CN103360304A (en) * | 2013-07-27 | 2013-10-23 | 新乡市博科精细化工有限公司 | Processing production apparatus for 2-methylpyridine |
| CN105820111A (en) * | 2016-04-21 | 2016-08-03 | 鹤壁市赛科化工有限公司 | Preparation method of catalyst and method for preparing 2,2-dipyridyl through catalysis by virtue of catalyst |
| CN105820111B (en) * | 2016-04-21 | 2018-07-24 | 鹤壁市赛科化工有限公司 | The method that a kind of preparation method of catalyst and its catalysis prepare 2,2- bipyridyls |
| CN106380466A (en) * | 2016-08-31 | 2017-02-08 | 连云港宏业化工有限公司 | Method for synthesizing 2-(2-thiophene)pyridine |
| CN106380466B (en) * | 2016-08-31 | 2018-12-21 | 连云港宏业化工有限公司 | A kind of synthetic method of 2- (2- thiophene) pyridine |
| CN107162959A (en) * | 2017-06-08 | 2017-09-15 | 安徽星宇化工有限公司 | The synthetic method of 2 pyridine carboxylic acids |
| CN108373427A (en) * | 2018-03-13 | 2018-08-07 | 索闻特环保科技(上海)有限公司 | The separation method of the waste liquid of picoline containing 3- and acetonitrile |
| CN108373427B (en) * | 2018-03-13 | 2020-11-03 | 索闻特环保科技(上海)有限公司 | Separation method of waste liquid containing 3-methylpyridine and acetonitrile |
| CN108658848A (en) * | 2018-05-05 | 2018-10-16 | 湖北荆洪生物科技股份有限公司 | A kind of production technology of 2,2`- bipyridyls |
| CN108658848B (en) * | 2018-05-05 | 2021-04-02 | 湖北荆洪生物科技股份有限公司 | Production process of 2,2' -bipyridine |
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Application publication date: 20120314 |