CN107987011A - A kind of piperidines is continuously synthesizing to method - Google Patents
A kind of piperidines is continuously synthesizing to method Download PDFInfo
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- CN107987011A CN107987011A CN201711318560.1A CN201711318560A CN107987011A CN 107987011 A CN107987011 A CN 107987011A CN 201711318560 A CN201711318560 A CN 201711318560A CN 107987011 A CN107987011 A CN 107987011A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/02—Preparation by ring-closure or hydrogenation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/08—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms
- C07D211/10—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms
- C07D211/12—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon or substituted hydrocarbon radicals directly attached to ring carbon atoms with radicals containing only carbon and hydrogen atoms attached to ring carbon atoms with only hydrogen atoms attached to the ring nitrogen atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
Method is continuously synthesizing to the present invention provides a kind of piperidines, is comprised the following steps：(1) catalyst is divided in the fixed bed reactors of N sections of series connection, nitrogen or hydrogen is filled with into fixed bed reactors, it is 1.8~4MPa to make the reaction pressure in fixed bed reactors, and heating makes fixed bed reactors temperature be 300~400 DEG C；(2) the preheated vaporization of pyridine once introduces under gas phase state from the air inlet of first segment fixed bed reactors, while hydrogen is introduced from fixed bed reactors first segment to N sections of hydrogen inlet respectively；The condensed pipework condensation of product obtains the piperidines of liquid；Wherein N=2~5；The present invention uses multi-stage fixed-bed serialization hydrogenation reaction, it is possible to achieve the continuous production of piperidines, saves the reaction time, and reactant can recycle, and can improve the time of contact of catalyst and reactant, the effective quality and product yield for improving product.
Description
Technical field
The present invention relates to piperidines synthesis technical field, and in particular to a kind of piperidines is continuously synthesizing to method.
Background technology
Piperidines is also known as hexahydropyridine or piperidine, colourless liquid.There is the smell as pepper.Density 0.8606.Fusing point-
7~-9 DEG C.106 DEG C of boiling point.It is dissolved in water, ethanol and ether.A kind of strong organic base, generation salt is acted on inorganic acid.Energy and steam
Together volatilize.Piperidines is mainly used for organic synthesis raw material, pharmaceutical raw material, solvent, epoxy curing agent, chemical reagent, rubber
Vulcanizing agent etc..The piperidines demand in China is 4000 tons or so at present, and fully relies on import.It is fast with China's chemical engineering industry
Speed development, demand is also in cumulative year after year.
The production method of piperidines mainly has two kinds, and one kind is Furanol or tetrahydrofuran amine in high temperature and pressure hydrogen and catalysis
Piperidines is converted under agent effect, another kind is that pyridine hydro-conversion is piperidines.In the work that current pyridine hydro-conversion is piperidines
In industry production, general to do catalytic hydrogenationization reaction using autoclave, it has the following disadvantages：(1) reaction time is longer, production efficiency
It is low；(2) mechanical agitation can cause material to mix uneven, and localized heat release excessively easily triggers security incident；(3) it is hydrogenated with inadequate kettle
Interior pressure is inadequate, can produce a series of accessory substances such as tetrahydropyridine, the final quality and product yield for influencing product, (4) kettle
Formula reaction response thing cannot come into full contact with catalyst, influence the quality and product yield of product.Thus, a kind of piperidines is developed
New synthetic method, has good market prospects.
The content of the invention
Method is continuously synthesizing to it is an object of the invention to provide a kind of piperidines, is hydrogenated with using multi-stage fixed-bed serialization
Reaction, it is possible to achieve the continuous production of piperidines, saves the reaction time, and reactant can recycle, can improve catalyst with
The time of contact of reactant, the effective quality and product yield for improving product.
In order to achieve the above object, the present invention is achieved by the following technical programs：
A kind of piperidines is continuously synthesizing to method, comprises the following steps：
(1) catalyst is divided in the fixed bed reactors of N sections of series connection, nitrogen or hydrogen is filled with into fixed bed reactors
Gas, it is 1.8~4MPa to make the reaction pressure in fixed bed reactors, and heating makes fixed bed reactors temperature be 300~400 DEG C；
(2) the preheated vaporization of pyridine once introduces under gas phase state from the air inlet of first segment fixed bed reactors, together
When hydrogen respectively from fixed bed reactors first segment to N sections of hydrogen inlet introduce；The condensed pipework condensation of product obtains
The piperidines of liquid；
Wherein N=2~5.
Preferably, the N=3, hydrogen is respectively from first segment, second segment, three-section fixed-bed reactor in step (2)
Hydrogen inlet introduces, wherein the hydrogen that the pyridine being filled with is filled with first segment, second segment, three-section fixed-bed reactor rubs
You are than being respectively 1:3~4,1:2~3,1:1~2.
Preferably, the catalyst is one or several kinds of in platinum carbon, palladium carbon, Raney's nickel.
Preferably, the catalyst is Raney's nickel.
Preferably, in the step (1), hydrogen is filled with into fixed bed reactors, makes the reaction in fixed bed reactors
Pressure is 2~3MPa.
Preferably, the retention time of the fixed bed reaction is 30~150s.
Preferably, the mass ratio of the pyridine and catalyst is 1:1~3.
The beneficial effects of the invention are as follows：The present invention uses multi-stage fixed-bed serialization hydrogenation reaction, relative to still reaction
The reaction time is not only saved, reactant can recycle, and fixed bed tandem energy is improved connecing for catalyst and reactant
Touch the time, ensure that reaction gas comes into full contact with catalyst, can elimination reaction device lower part be not filled by the space of catalyst, and can be effective
Raising reactor the unit volume unit interval product yield and product quality.The present invention can realize continuous metaplasia
Production, reduces the reaction time, improves continuity, the security of production, is more suitable for the serialization industrial production in future.
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 solution 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, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
All other embodiments obtained under the premise of creative work, belong to the scope of protection of the invention.
Embodiment 1：
A kind of piperidines is continuously synthesizing to method, comprises the following steps：
20g Raney's nickel catalysts are divided in 3 sections of fixed bed reactors, nitrogen is filled with into fixed bed reactors, is made
Reaction pressure in fixed bed reactors is 2MPa, and heating makes fixed bed reactors temperature be 300 DEG C；
15g pyridines once draw by heating furnace preheating vaporization under gas phase state from first segment fixed bed reactors air inlet
Enter (pyridine inlet amount per minute is 0.7mL), while hydrogen is in proportion respectively from first segment, second segment, three-section fixed-bed
(pyridine being wherein filled with is filled with first segment, second segment, three-section fixed-bed reactor for the hydrogen inlet introducing of reactor
The molar ratio of hydrogen is respectively 1:4、1:3、1:1), reaction time 60s.Product obtains liquid by condensing tube condensation
Piperidinyl-1 6g, average 6h takes a sample, and the content of piperidines is 6%, and the yield of piperidines is 6%.
Embodiment 2：
A kind of piperidines is continuously synthesizing to method, comprises the following steps：
20g palladium catalysts are divided in 3 sections of fixed bed reactors, nitrogen is filled with into fixed bed reactors, makes fixation
Reaction pressure in bed reactor is 2MPa, and heating makes fixed bed reactors temperature be 300 DEG C；
15.05g pyridines are vaporized under gas phase state from first segment fixed bed reactors air inlet one by heating furnace preheating
It is secondary to introduce (pyridine inlet amount per minute is 0.7mL), while hydrogen divides 3 times in proportion respectively from first segment, second segment, the 3rd
The hydrogen inlet of section fixed bed reactors introduces (pyridine being wherein filled with and first segment, second segment, three-section fixed-bed reaction
The molar ratio for the hydrogen that device is filled with is respectively 1:3、1:2、1:2), reaction time 60s.Product passes through condensing tube condensation
The piperidinyl-1 6.25g of liquid is obtained, average 6h takes a sample, and the content of piperidines is 3%, and the yield of piperidines is 3%.
Apply example 3：
A kind of piperidines is continuously synthesizing to method, comprises the following steps：
25g Raney's nickel catalysts are divided in 3 sections of fixed bed reactors, hydrogen is filled with into fixed bed reactors, is made
Reaction pressure in fixed bed reactors is 2.5MPa, and heating makes fixed bed reactors temperature be 300 DEG C；
15.65g pyridines are vaporized under gas phase state from first segment fixed bed reactors air inlet one by heating furnace preheating
It is secondary to introduce (pyridine inlet amount per minute is 0.7mL), while hydrogen divides 3 times in proportion respectively from first segment, second segment, the 3rd
(pyridine being filled with is filled with first segment, second segment, three-section fixed-bed reactor for the hydrogen inlet introducing of section fixed bed reactors
The molar ratio of the hydrogen entered is respectively 1:3、1:2、1:2), reaction time 60s.Product is obtained by condensing tube condensation
The piperidinyl-1 6.85g of liquid, average 6h take a sample, and the content of piperidines is 10%, and the yield of piperidines is 10%.
Apply example 4：
A kind of piperidines is continuously synthesizing to method, comprises the following steps：
25g Raney's nickel catalysts are divided in 3 sections of fixed bed reactors, hydrogen is filled with into fixed bed reactors, is made
Reaction pressure in fixed bed reactors is 3MPa, and heating makes fixed bed reactors temperature be 400 DEG C；
15.65g pyridines are vaporized under gas phase state from first segment fixed bed reactors air inlet one by heating furnace preheating
It is secondary to introduce (pyridine inlet amount per minute is 0.7mL), while hydrogen divides 3 times in proportion respectively from first segment, second segment, the 3rd
The hydrogen inlet of section fixed bed reactors introduces (pyridine being wherein filled with and first segment, second segment, three-section fixed-bed reaction
The molar ratio for the hydrogen that device is filled with is respectively 1:4、1:3、1:1), reaction time 60s.Product passes through condensing tube condensation
The piperidinyl-1 6.88g of liquid is obtained, average 6h takes a sample, and the content of piperidines is 15%, and the yield of piperidines is 15%.
Apply example 5：
A kind of piperidines is continuously synthesizing to method, comprises the following steps：
30g Raney's nickel catalysts are divided in 3 sections of fixed bed reactors, hydrogen is filled with into fixed bed reactors, is made
Reaction pressure in fixed bed reactors is 3MPa, and heating makes fixed bed reactors temperature be 400 DEG C；
15.05g pyridines are vaporized under gas phase state from first segment fixed bed reactors air inlet one by heating furnace preheating
It is secondary to introduce (pyridine inlet amount per minute is 0.7mL), while hydrogen divides 3 times in proportion respectively from first segment, second segment, the 3rd
The hydrogen inlet of section fixed bed reactors introduces (pyridine being wherein filled with and first segment, second segment, three-section fixed-bed reaction
The molar ratio for the hydrogen that device is filled with is respectively 1:4、1:3、1:2), reaction time 150s.Obtained by condensing tube condensation
The piperidinyl-1 6.25g of liquid, average 6h take a sample, and the content of piperidines is 44%, and the yield of piperidines is 44%.
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 of ordinary skill in the art that：It still can be to foregoing each implementation
Technical solution 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 solution.
Claims (7)
1. a kind of piperidines is continuously synthesizing to method, it is characterised in that comprises the following steps：
(1) catalyst is divided in the fixed bed reactors of N sections of series connection, nitrogen or hydrogen is filled with into fixed bed reactors,
It is 1.8~4MPa to make the reaction pressure in fixed bed reactors, and heating makes fixed bed reactors temperature be 300~400 DEG C；
(2) the preheated vaporization of pyridine once introduces under gas phase state from the air inlet of first segment fixed bed reactors, while hydrogen
Qi leel introduces not from fixed bed reactors first segment to N sections of hydrogen inlet；The condensed pipework condensation of product obtains liquid
Piperidines；
Wherein N=2~5.
2. piperidines according to claim 1 is continuously synthesizing to method, it is characterised in that the N=3, hydrogen in step (2)
Qi leel does not introduce from the hydrogen inlet of first segment, second segment, three-section fixed-bed reactor, wherein the pyridine being filled with and first
The molar ratio for the hydrogen that section, second segment, three-section fixed-bed reactor are filled with is respectively 1:3~4,1:2~3,1:1~2.
3. piperidines according to claim 1 is continuously synthesizing to method, it is characterised in that the catalyst is platinum carbon, palladium
It is one or several kinds of in carbon, Raney's nickel.
4. piperidines according to claim 3 is continuously synthesizing to method, it is characterised in that the catalyst is Raney's nickel.
5. piperidines according to claim 1 is continuously synthesizing to method, it is characterised in that in the step (1), to fixation
Hydrogen is filled with bed reactor, it is 2~3MPa to make the reaction pressure in fixed bed reactors.
6. piperidines according to claim 1 is continuously synthesizing to method, it is characterised in that the reservation of the fixed bed reaction
Time is 30~150s.
7. piperidines according to claim 1 is continuously synthesizing to method, it is characterised in that the matter of the pyridine and catalyst
Amount is than being 1:1~3.
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Cited By (3)
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| GB2576606A (en) * | 2018-06-26 | 2020-02-26 | Johnson Matthey Plc | Hydrogenation process |
| CN111821919A (en) * | 2020-07-10 | 2020-10-27 | 吉林凯莱英制药有限公司 | Continuous catalytic hydrogenation equipment and continuous catalytic hydrogenation method for pyridine compounds |
| 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 |
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Application publication date: 20180504 |