CN105985300B - A kind of continuous producing method of piperidines - Google Patents
A kind of continuous producing method of piperidines Download PDFInfo
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- CN105985300B CN105985300B CN201510064231.3A CN201510064231A CN105985300B CN 105985300 B CN105985300 B CN 105985300B CN 201510064231 A CN201510064231 A CN 201510064231A CN 105985300 B CN105985300 B CN 105985300B
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Abstract
The present invention discloses the low pressure continuous producing method of piperidines product.This method produces piperidines product as raw material using pyridines and hydrogen and is converted into piperidines product after contacting the pyridines raw material and hydrogen of gas phase with hydrogenation catalyst, process is continuous, and reaction pressure is low using fixed bed reactors.Mild reaction condition of the invention, yield is high, and product quality is high, and by-product is few, live free from extraneous odour, Environmental Safety.
Description
Technical field
The invention belongs to field of fine chemical, are related to a kind of production method of piperidines product, more specifically, this method
Piperidines product is produced using pyridines and hydrogen as raw material, using fixed bed reactors, by the pyridines raw material and hydrogen of gas phase
Piperidines product is converted into after contacting with hydrogenation catalyst.
Background technique
Piperidines product is that one kind is widely used in medicine, pesticide, plastic additive, organic catalyst, curing agent, solvent
The fine chemical product in equal fields, especially its bioactivity with higher, good market prospect.Piperidines of the present invention
Class product includes piperidines, 3- methyl piperidine, 4- methyl piperidine, pipecoline, 2,4- lupetidine, 3,5- dimethyl piperazine
Pyridine, 2,2,6,6- tetramethyl piperidines, 2,6- lupetidine.The following are the introductions of portioned product:
Piperidines also known as hexahydropyridine or piperidine are widely used in manufacture local anesthetic, anodyne, fungicide, profit
The curing agent of humectant and epoxy resin, thiofide etc., derivative is widely present in natural products and drug
In mesosome.
Important original of 3, the 5- lupetidines as the synthesis novel antibiotic Tilmicosin of the dedicated macrolides of livestock and poultry
Material is used as centre wherein cis- -3,5- lupetidine is highly useful in preparing antifungal agent and plant growth regulator
Body prepares ammonia first heterocyclic pesticidal compounds and can adjust the compound of dietary behavior and related disease and prepare greatly
It is also particularly useful in double hydrogen-dehydrogenation-(ring type amidogen) derivatives of the carbon -20- of cyclic lactone class antibiotic.The medicine is successively in the big benefit of Australia
The countries such as Asia, Brazil, France, Malaysia, Italy, Spain, the U.S. go through clinical application, to all gram sun
Property bacterium and part Gram-negative bacteria, Mycoplasma, conveyor screw etc. have inhibiting effect, for treat ox, goat, sheep, milk cow,
The animals such as pig, chicken infectious diseases as caused by sensitivity, especially livestock and poultry respiratory tract infection.
The production method of piperidines product substantially passes through pyridines raw material and hydrogen is added to obtain, as described in CN101723877
A kind of production method of piperidines, using the nickel catalyst of support type, carrier is silica-alumina, pyridine conversion ratio
100%, for piperidines yield 95% or more, reaction pressure 4.0-10.0MPa, reaction temperature is 140-220 DEG C.Du Xi etc. is open
A kind of Ru-Pd/C catalyst, at (Ru+Pd): substrate=1: 200 (molar ratios), 150 DEG C of reaction temperature, hydrogen presses 4MPa, and reduction is anti-
Answer 3h, under conditions of 3- picoline 1ml, ethyl alcohol 4ml, selectivity of the 3- picoline conversion ratio up to 100%, 3- methyl piperidine
Up to 99% (apply chemical industry, 2007, V36, No.1,41-43 pages).
Conventional process techniques are characterized in that, using autoclave reactor, coke deposition is liquid phase, and use larger dose
The solvent of amount, there is following apparent disadvantages for this technology: first, reaction pressure is high, generally in 4.0MPa, in actual life
7.0MPa or more is more up in production；This undoubtedly will increase dramatically equipment investment pressure, and also make the security performance of device
Decline；Second, it needs using solvent, this undoubtedly will cause the quality decline of product and energy consumption increases；Third, autoclave are interval
Property operation, frequent material switching and nitrogen displacement in will cause the waste of bulk gas and the life of volatile organic matter
At polluting severe with site operation personnel's working environment.4th, the catalyst used is separated with liquid needs mating work
Journey, loss is larger, and especially in use noble metal catalyst, cost allowance is bigger, and when the common Raney's nickel catalyst of use
There are biggish danger for time.
The present invention describes a kind of production method of piperidines product, it is characterised in that reaction process is that low pressure and serialization are grasped
Make, and the pyridines feed stock conversion of reaction process is high (> 99.8%), compared with the prior art: first, reaction pressure highest
No more than 3.0MPa, further, it is no more than 2.0MPa, is further no more than 1.0MPa, to belong to low pressure scope；The
Two, process is continuous, and volatile organic matter is few, and no three wastes generates, environment-friendly and green；Third, product quality height, especially coloration,
Impurity and moisture are low, therefore can increase substantially application field；4th, products application face is closed wealthy；5th, reaction heat can obtain
To making full use of.
Summary of the invention
Piperidines product is that one kind is widely used in medicine, pesticide, plastic additive, organic catalyst, curing agent, solvent
The fine chemical product in equal fields, especially its bioactivity with higher, good market prospect.Piperidines of the present invention
Class product is very extensive, specifically selects from piperidines, 3- methyl piperidine, 4- methyl piperidine, pipecoline, 2,4- diformazan
Phenylpiperidines, 3,5- lupetidine, one of 2,2,6,6- tetramethyl piperidines, 2,6- lupetidine.
In order to overcome the difficulty faced in existing piperidines production: hydrogen and nitrogen consumption are big, scene peculiar smell, produce
Product purity is low to provide a kind of novel piperidines production with various problems, the present invention such as moisture height, poor safety performances
Method.
The reactor that the present invention uses is fixed bed reactors, and the fixed bed reactors are selected from calandria type fixed bed anti-
Answer one of device, multistage insulation bed reactor, self-heating reactor.Flow of Goods and Materials mode after vaporization is selected from radial, journal axle
To combine perhaps one of axial radial flow can be selected from one of from top to bottom or from bottom to top.
The reaction pressure of traditional technology is minimum to be reported in 3.0MPa or more, and actual production is higher than 6.0MPa, therefore reactor
Design pressure be even higher than 10.0MPa, for huge autoclave (> 2.0NM3) deposited in production, installation and use process
In huge security risk, high cost.The present invention is found surprisingly that, required when reaction carries out under gas phase condition
Pressure can be reduced to 2.0MPa hereinafter, can further be reduced to 1.5MPa hereinafter, can further be reduced to 1.0Pa hereinafter, more into
One step can be reduced to 0.6MPa and also not send one's regards to topic hereinafter, reacting in atmospheric conditions.This discovery is undoubtedly the improvement of technique
Apparent with progress meaning: this greatly improves the safety coefficient of equipment, and investment cost also declines.
The reaction temperature that the present invention uses is 80-220 DEG C, and advanced optimizing is 90-200 DEG C, is further optimized for
110-180 DEG C, reaction temperature action pane is very big, this can enable the adjustable space of operator is big, device tolerance fluctuation
Ability is obvious.
Pyridine adds the main reaction of hydrogen for production piperidines, and side reaction is that open loop generates n-amylamine, and then generates N- amyl piperidine
(NPP).Wherein that be to product quality be is unfavorable for the generation of by-product amylamine and pyridine residual, because of amylamine and pyridine and piperidines
Boiling point it is very close (only 2 DEG C of difference), this can undoubtedly to separate extremely difficult, and for N- amyl piperidine, separation is opposite
Simply.Another inventive point of the invention is highly selective and high activity catalyst.Hydrogenation catalyst of the present invention
Active component be one of cobalt, nickel, palladium, platinum, ruthenium, two or more composition, further active component be palladium,
One of platinum, ruthenium or two kinds.Further, the hydrogenation catalyst contains one in alkali or alkaline earth metal oxide
Kind and more than one.This is the key that highly selective place, and the amount of amylamine may be significantly inhibition.Further, described
Hydrogenation catalyst contains one of sodium, potassium, caesium, magnesium, calcium and more than one.Catalyst carrier for hydrgenating is also key, be may be selected
From for one of silica, aluminium oxide, active carbon, zirconium oxide, diatomite, titanium oxide and more than one combination, into one
Step selects certainly as one of silica and aluminium oxide.
The present invention, which is found surprisingly that during low-pressure vapor phase, not to be needed using solvent, and solvent will cause selection instead
The decline of property；This conclusion obtained with traditional technology is as being different, such as " fuel and chemical industry " third phase P151- in 2000
Use a large amount of methanol (1: 1) as solvent described in 152.
The present invention is characterized in that conversion ratio is close to 100%, piperidines content is even at least in 99.5% or more, crude product
Can be 99.5% or more, this numerical value is higher than existing Chinese Industrial Standards (CIS), therefore separative unit of the invention may be only one
A flash tank.Generally, for commercialization demand, piperidines may be may require that 99.9% or more.Before obtaining qualified products,
Impurity can be separated by rectifying column and obtain higher quality product.
Specific embodiment
Following embodiment is to describe to more detailed citing of the invention, but the invention is not limited to these embodiments.
Embodiment 1
Pyridine (Shandong is deep up to production, content 99.9%) is taken to enter by metering pump, pyridine inlet amount is 10L/h, hot
Enter in vaporizer after hydrogen mixing, hydrogen inlet amount is 30NM3/ h, and by superheater (140~170 DEG C of temperature of control) mistake
Enter in hydrogenator R101 after heat, R101 is shell and tube reactor, hydrogenation catalyst loadings 30L (the permanent auspicious new continuous heavy rain in Beijing
Scientific & technical corporation's production, catalytic component are containing 1.5wt%CaO, 0.2wt%Ru, 5wt%Ni, and surplus is aluminium oxide).Reaction
Device temperature is 160 DEG C, pressure 1.0MPa, exports pyridine conversion ratio 99.89%, piperidines selectivity 96%, amylamine selectivity
0.04%, exported product is sent to vacuum batch distillation tower (number of theoretical plate 30), tower top pressure is controlled in 112kpa, is controlled first
Tower top temperature is in 100 DEG C of extraction light components, in tower top temperature gradually to 108~120 DEG C or so extraction product piperidines, product purity
99.72%.
Embodiment 2
Pyridine (Shandong is deep up to production, content 99.9%, water content 0.02%) is taken to enter by metering pump, pyridine feed position
It sets there are two, amount respectively is 4L/h and 6L/h, and for hydrogen feed entrance point there are two, inlet amount is respectively 8NM3/ h and
20NM3/ h, R102 are self-heating reactor, hydrogenation catalyst loadings 20L (production of Beijing Heng Ruixin continuous heavy rain scientific & technical corporation, catalysis
Agent group is divided into containing 1.0wt%K2O, 0.5wt%Rt, 8wt%Co, surplus are aluminium oxide).Temperature of reactor is 110 DEG C, pressure
For 0.15MPa, pyridine conversion ratio 100%, piperidines selectivity 98% are exported, exported product is sent to by amylamine selectivity 0.03%
Continuous vacuum rectification tower (number of theoretical plate 20), piperidine product purity 99.90%, water content 0.02%.
Embodiment 3
According to the reactor of embodiment 1, difference be catalytic component be containing 0.5wt%MgO, 0.5wt%Rd,
0.1wt%Pt, surplus are silica (production of Beijing Heng Ruixin continuous heavy rain scientific & technical corporation).Pyridine inlet amount is 15L/h, hot hydrogen
Enter in vaporizer after mixing, hydrogen inlet amount is 50NM3/ h exports pyridine conversion ratio 99.90%, piperidines selectivity
94.5%, exported product is sent to continuous vacuum rectification tower (number of theoretical plate 20), piperidine product purity by amylamine selectivity 0.09%
99.69%.
Comparative example 3
The method of the embodiment 1 referring to described in patent of invention authorization authorization specification CN200910234328, catalyst use
Commercialized Raney nickel (NCG-98H), 50 grams of loadings, 500 grams of pyridine additional amount, maintain reaction pressure 5.0~
8.0MPa no longer inhales hydrogen, pyridine conversion ratio 99.94%, piperidines selectivity after reacting 20 hours at 150~170 DEG C of reaction temperature
90.5%, amylamine selectivity 0.25%.Exported product is sent to continuous vacuum rectification tower (number of theoretical plate 20), piperidine product purity
99.53%.
Claims (2)
1. a kind of continuous producing method of Piperidine Series product, it is characterised in that: pyridines raw material passes through vapour after mixing with hydrogen
Enter in hydrogenator after changing device vaporization, 110-180 DEG C of hydrogenator temperature, reaction pressure 0.1-1.0MPa, pyridines
Raw material is converted into piperidines product on hydrogenation catalyst, then after the crude product condensation containing piperidines product, gas-liquid separation
Enter separative unit afterwards, obtains piperidines product；The pyridines raw material be selected from pyridine, 3- picoline, 4- picoline,
2- picoline, 2,4- lutidines, 3,5- lutidines, in 2,2,6,6- tetramethyl pyridines, 2,6- lutidines
One kind；The hydrogenator be fixed bed reactors, selected from calandria type fixed bed reactor, multistage insulation bed reactor,
One of self-heating reactor；The active component of the hydrogenation catalyst is one of cobalt, nickel, palladium, platinum, ruthenium, two kinds
Or two or more compositions；The hydrogenation catalyst contain one of alkali or alkaline earth metal oxide or it is a kind of with
On；The carrier of the hydrogenation catalyst is silica, aluminium oxide, active carbon, zirconium oxide, diatomite, one in titanium oxide
Kind or more than one combination；The piperidines product is selected from piperidines, 3- methyl piperidine, 4- methyl piperidine, pipecoline, 2,
4- lupetidine, 3,5- lupetidine, one of 2,2,6,6- tetramethyl piperidines, 2,6- lupetidine.
2. the method as described in claim 1, it is characterised in that: the active component of the hydrogenation catalyst is palladium, platinum, ruthenium, cobalt
One of or two kinds.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107987011A (en) * | 2017-12-12 | 2018-05-04 | 安徽国星生物化学有限公司 | A kind of piperidines is continuously synthesizing to method |
| GB201810449D0 (en) * | 2018-06-26 | 2018-08-08 | Johnson Matthey Plc | Hydrogenation process |
| CN111205246A (en) * | 2020-01-09 | 2020-05-29 | 内蒙古世杰化工有限公司 | Method for synthesizing piperidine by using umbrella-shaped microchannel mixer and tubular reactor |
| WO2022006869A1 (en) * | 2020-07-10 | 2022-01-13 | 吉林凯莱英制药有限公司 | Continuous catalytic hydrogenation apparatus and method for pyridine compounds |
| CN112979583B (en) * | 2021-02-03 | 2022-06-28 | 鹤壁中昊新材料科技有限公司 | Method for synthesizing piperidine by continuous liquid-phase hydrogenation of pyridine in microreactor |
| CN115850205B (en) * | 2022-12-29 | 2024-06-11 | 重庆中邦科技有限公司 | Method for synthesizing N-methylpiperidine by pyridine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723877A (en) * | 2009-11-24 | 2010-06-09 | 南京第一农药集团有限公司 | Method for preparing piperidines compound by using pyridine base through catalytic hydrogenation |
| CN102093283A (en) * | 2009-12-10 | 2011-06-15 | 中国科学院大连化学物理研究所 | Method for preparing piperidine and piperidine derivative |
| CN104725299A (en) * | 2015-04-15 | 2015-06-24 | 西安凯立化工有限公司 | Method for preparing 3-hydroxypiperidine through liquid phase catalytic hydrogenation of 3-hydroxypyridine |
-
2015
- 2015-02-09 CN CN201510064231.3A patent/CN105985300B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723877A (en) * | 2009-11-24 | 2010-06-09 | 南京第一农药集团有限公司 | Method for preparing piperidines compound by using pyridine base through catalytic hydrogenation |
| CN102093283A (en) * | 2009-12-10 | 2011-06-15 | 中国科学院大连化学物理研究所 | Method for preparing piperidine and piperidine derivative |
| CN104725299A (en) * | 2015-04-15 | 2015-06-24 | 西安凯立化工有限公司 | Method for preparing 3-hydroxypiperidine through liquid phase catalytic hydrogenation of 3-hydroxypyridine |
Non-Patent Citations (2)
| Title |
|---|
| Hydrogenation of arenes, N-heteroaromatic compounds, and alkenes catalyzed by rhodium nanoparticles supported on magnesium oxide;Antonio Sánchez et al.;《Applied Catalysis A: General》;20140314;第477卷;117-124 |
| Ruthenium nanoparticles supported on magnesium oxide: A versatile and recyclable dual-site catalyst for hydrogenation of mono- and poly-cyclic arenes, N-heteroaromatics, and S-heteroaromatics;Minfeng Fang et al.;《Journal of Catalysis》;20140129;第311卷;357-368 |
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Inventor after: Huang Long Inventor after: Xu Dapeng Inventor after: Shao Shuqiang Inventor after: Jia Songyu Inventor after: Gao Shuai Inventor before: Xu Xuefeng Inventor before: Jiang Zhaokun Inventor before: Shi Haoyuan Inventor before: Jia Songyu Inventor before: Gao Shuai Inventor before: Other inventor requests not to publish the name |
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Effective date of registration: 20161213 Address after: 276000 Yishui Economic Development Zone, Shandong, Linyi Applicant after: Gunther bio tech ltd, Shandong Applicant after: SHANDONG HONGDA BIOTECHNOLOGY CO., LTD. Applicant after: BEIJING HENGRUI XINLIN TECHNOLOGY CO., LTD. Address before: 276400 Shandong province Yishui County Economic Development Zone, the Biological Technology Co. Ltd. Applicant before: SHANDONG HONGDA BIOTECHNOLOGY CO., LTD. Applicant before: BEIJING HENGRUI XINLIN TECHNOLOGY CO., LTD. |
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