CN109593059A - A kind of azeotropic-variable-pressure rectification separation pyridine-acetonitrile-water system method - Google Patents
A kind of azeotropic-variable-pressure rectification separation pyridine-acetonitrile-water system method Download PDFInfo
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- CN109593059A CN109593059A CN201811511877.1A CN201811511877A CN109593059A CN 109593059 A CN109593059 A CN 109593059A CN 201811511877 A CN201811511877 A CN 201811511877A CN 109593059 A CN109593059 A CN 109593059A
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- acetonitrile
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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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
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Abstract
The present invention is that a kind of azeotropic-variable-pressure rectification separates pyridine-acetonitrile-water system method.The device of this method includes an azeotrope column, a high-pressure tower and a lower pressure column, use the substance acetonitrile that itself contains as entrainer during azeotropic distillation, azeotropic distillation is first passed through to separate acetonitrile and water from ternary system to obtain the pyridine product of purity qualification, pass through the further separating acetonitrile of variable-pressure rectification and aqueous systems again, to the technique combined using azeotropic distillation and variable-pressure rectification, efficiently separating for pyridine, acetonitrile and water is realized.The present invention does not introduce other components, ensure that product purity, and entrainer can be recycled.
Description
Technical field
The invention belongs to chemical separating purification arts, and in particular to a kind of azeotropic-variable-pressure rectification separation pyridine-acetonitrile-water
The method of system.
Background technique
Pyridine and acetonitrile are important chemical industry and medical material, and pyridine-second is formed during controlling hepatitis pharmaceutical synthesis
Nitrile-water mixed waste liquor.115.3 DEG C of pyridine atmospheric boiling point, minimum azeotropic mixture is formed with water, azeotropic group becomes water 57w%, azeotropic temperature
Degree is 94 DEG C.Acetonitrile atmospheric boiling point is 81.6 DEG C, forms minimum azeotropic mixture with water, azeotropic group becomes water 15w%, azeotropic temperature 76
℃.Ternary azeotropic is not formed between pyridine-acetonitrile-water three, but is respectively formed minimum azeotrope between pyridine-water and acetonitrile-water
Object, therefore conventional distillation can not separate this object system, generally use variable-pressure rectification, extracting rectifying to the object system there are azeotropic or be total to
Boiling rectifying is separated.It a kind of rectificating method is used alone separates this ternary system and be not enough to obtain high purity product, Er Qiecui
It takes and needs to introduce other substances using extractant in rectifying, affect product purity, therefore extracting rectifying should not be selected.
Summary of the invention
The object of the present invention is to provide a kind of azeotropic-variable-pressure rectifications to separate pyridine-acetonitrile-water system method, realizes pyrrole
The recycling and reusing of pyridine and acetonitrile.Main device of the invention includes an azeotrope column, a high-pressure tower and a lower pressure column.?
Use the substance acetonitrile itself contained as entrainer during azeotropic distillation, do not introduce other components, ensure that product purity,
And entrainer can be recycled.
Technical scheme is as follows:
A kind of azeotropic-variable-pressure rectification separates pyridine-acetonitrile-water system method, the technique the following steps are included:
(1) pyridine-acetonitrile-water feed liquid is sent into azeotrope column, meanwhile, entrainer acetonitrile is sent into azeotrope column together, is passed through
Azeotropic distillation, tower reactor obtain product pyridine；Overhead vapours is after condenser condenses, and partial reflux to azeotrope column, remaining is pressurized
It is pumped into high-pressure tower；
Wherein, mass ratio is entrainer: material liquid=3.3-4.6:1；The number of theoretical plate of azeotrope column is 13-20 block plate, tower
Pushing up temperature is 75-77 DEG C, and column bottom temperature is 113-116 DEG C, reflux ratio 1.0-3.4, operating pressure 101.325kPa；
(2) high-pressure tower tower reactor obtains product acetonitrile, and partial acetonitrile is recycled into azeotrope column as the entrainer of azeotrope column；Tower
Steam is pushed up after condenser condenses, partial reflux to high-pressure tower, remaining is sent into lower pressure column；
Wherein, the number of theoretical plate of high-pressure tower is 14-22 block plate, and tower top temperature is 131-134 DEG C, column bottom temperature 136-
146 DEG C, reflux ratio 0.4-1.6, operating pressure 450-600kPa；
(3) lower pressure column tower reactor obtains pure water, and overhead vapours obtains acetonitrile-water azeotropic object after condenser condenses, and part is returned
Lower pressure column is flowed to, remaining enters high-pressure tower and carries out circular treatment；
Wherein, the number of theoretical plate of lower pressure column is 7-15 block plate, and tower top temperature is 50-53 DEG C, and column bottom temperature is 74-77 DEG C,
Operating pressure is 40-100kPa, reflux ratio 1-3.
The mass percent of each component is pyridine 14~25%, acetonitrile 26~37%, water 43~55% in the feed liquid.
It is described to obtain acetonitrile and the product purity of pyridine is all larger than 99.5%.
The feed entrance point of the azeotrope column is 7-13 block plate；The feed entrance point of high-pressure tower is 5-13 block plate；Lower pressure column
Feed entrance point is 5-11 block plate.
The entrainer feed entrance point of the azeotrope column is 5-11 block plate.
Substantive distinguishing features of the invention are as follows:
Material of the invention does not form ternary azeotrope, but pyridine-water and acetonitrile-water between pyridine-acetonitrile-water three
Between be respectively formed minimum azeotropic mixture and acetonitrile-water object system to pressure-sensitive characteristic.Since pyridine and water are compared with acetonitrile and water
Be more difficult to separate, thus the first step of the invention be acetonitrile and water are separated to obtain from ternary system by azeotropic distillation it is pure
Qualified pyridine product is spent, then by the further separating acetonitrile of variable-pressure rectification and aqueous systems, thus using azeotropic distillation and transformation
The technique that rectifying combines realizes efficiently separating for pyridine, acetonitrile and water.
The method have the advantages that:
(1) efficiently separating for pyridine, acetonitrile and water is realized, the product purity of pyridine and acetonitrile is up to 99.5% or more,
Raw material cost of investment can be reduced with direct circulation reuse, solve the problems, such as that pyridine-water and acetonitrile-water azeotropic separation are difficult.
(2) the substance acetonitrile that the present invention uses system itself to contain does not introduce other components, ensure that production as entrainer
Quality reduces separating difficulty, reduces equipment investment expense and energy consumption.
(3) present invention realizes the recycling and reusing of pyridine and acetonitrile, avoids discharge of the industrial wastes into environment, subtracts
Small pollution, protects environment.
(4) present invention has simple process, easy to operate, at low cost, low power consumption and other advantages.
Detailed description of the invention
Fig. 1 is flow diagram of the invention.
In figure: T1- azeotropy rectification column；T2- high-pressure tower；T3- lower pressure column；P- force (forcing) pump；Each logistics of digital representation.
The present invention is described in more detail below.But following examples is only simple example of the invention, not generation
Table or limitation the scope of the present invention, protection scope of the present invention are subject to claims.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1:
(1) feed flow rates 5kg/hr, quality form pyridine 19.8%, acetonitrile 31.83%, water 48.37%, entrainer acetonitrile
Dosage 19.5kg/hr.The azeotrope column T1 number of plates 15, reflux ratio 2.2, operating pressure 101.325kPa, feedstock position are the
9 blocks of plates, entrainer feed entrance point are the 7th block of plate, and tower reactor obtains 99.97% pyridine, yield 0.95kg/hr, bottom temperature
It is 115.1 DEG C.Tower top obtains acetonitrile-water mixture, and quality group becomes acetonitrile 89.6%, water 10.4%, partial reflux to azeotropic
Tower, remaining is pressurized to be pumped into high-pressure tower T2, and tower top temperature is 76.6 DEG C.
(2) the high-pressure tower T2 number of plates 18, reflux ratio 1, operating pressure 530kPa, feed entrance point are the 9th block of plate, and tower reactor obtains
99.61% acetonitrile, yield 22.6kg/hr, partial acetonitrile are recycled into azeotrope column T1 as entrainer, and bottom temperature is
144.6℃.Tower top obtains the lower acetonitrile-water mixture of another azeotropic composition, and quality group is as acetonitrile 75.1%, water 24.9%,
Partial reflux is to high-pressure tower, remaining is sent into lower pressure column T3, and tower top temperature is 133.2 DEG C.
(3) the lower pressure column T3 number of plates 11, reflux ratio 2, operating pressure 40kPa, feed entrance point are the 7th block of plate, and tower reactor obtains
99.99% water, flow rate 0.95kg/hr, bottom temperature are 75.8 DEG C.Tower top obtains acetonitrile-water azeotropic object, and quality group becomes
Acetonitrile 83.9%, water 16.1%, partial reflux to lower pressure column, remaining enters high-pressure tower T2 and carries out circular treatment, and tower top temperature is
51.4℃。
Embodiment 2:
(1) feed flow rates 6kg/hr, quality form pyridine 21%, acetonitrile 33%, water 46%, entrainer acetonitrile content
20kg/hr.The azeotrope column T1 number of plates 17, reflux ratio 2, operating pressure 101.325kPa, feedstock position are the 11st block of plate, altogether
Boiling agent feed entrance point is the 9th block of plate, and tower reactor obtains 99.86% pyridine, yield 1kg/hr, and bottom temperature is 115.3 DEG C.Tower
Top obtains acetonitrile-water mixture, and quality group becomes acetonitrile 87.9%, and water 12.1%, partial reflux to azeotrope column, remaining is pressurized
It is pumped into high-pressure tower T2, tower top temperature is 76.7 DEG C.
(2) the high-pressure tower T2 number of plates 20, reflux ratio 0.5, operating pressure 550kPa, feed entrance point are the 11st block of plate, tower reactor
99.63% acetonitrile, yield 23.8kg/hr are obtained, partial acetonitrile is recycled into azeotrope column T1, bottom temperature as entrainer
It is 136.6 DEG C.Tower top obtains the acetonitrile-water mixture under another azeotropic composition, and quality group becomes acetonitrile 76.6%, water
23.4%, partial reflux to high-pressure tower, remaining is sent into lower pressure column T3, and tower top temperature is 133.5 DEG C.
(3) the lower pressure column T3 number of plates 14, reflux ratio 1.2, operating pressure 50kPa, feed entrance point are the 8th block of plate, and tower reactor obtains
To 99.95% water, flow rate 1.2kg/hr, bottom temperature is 75.9 DEG C.Tower top obtains acetonitrile-water azeotropic object, quality composition
For acetonitrile 84.5%, water 15.5%, partial reflux to lower pressure column, remaining enters high-pressure tower T2 and carries out circular treatment, tower top temperature
It is 51.1 DEG C.
Azeotropy rectification column, high-pressure tower and the lower pressure column is plate column or packed tower.
The Applicant declares that the present invention is explained by the above embodiments technique of the invention, but the invention is not limited to
Aforesaid operations step does not mean that the present invention must rely on aforesaid operations step and could implement.The technology of technical field
Personnel it will be clearly understood that any improvement in the present invention, the addition of equivalence replacement and auxiliary element to raw material selected by the present invention,
The selection etc. of concrete mode, all of which fall within the scope of protection and disclosure of the present invention.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Unaccomplished matter of the present invention is well-known technique.
Claims (5)
1. a kind of azeotropic-variable-pressure rectification separates pyridine-acetonitrile-water system method, it is characterized in that this method includes following step
It is rapid:
(1) pyridine-acetonitrile-water feed liquid is sent into azeotrope column, meanwhile, entrainer acetonitrile is sent into azeotrope column together, by azeotropic
Rectifying, tower reactor obtain product pyridine；Overhead vapours is after condenser condenses, partial reflux to azeotrope column, and rest part is pressurized
It is pumped into high-pressure tower；
Wherein, mass ratio is entrainer: material liquid=3.3-4.6:1；The plate number of azeotrope column is 13-20 block plate, and tower top temperature is
75-77 DEG C, column bottom temperature is 113-116 DEG C, reflux ratio 1.0-3.4, operating pressure 101.325kPa；
(2) high-pressure tower tower reactor obtains product acetonitrile, and partial acetonitrile is recycled into azeotrope column as the entrainer of azeotrope column；Tower top steams
Vapour is after condenser condenses, partial reflux to high-pressure tower, and rest part is sent into lower pressure column；
Wherein, the plate number of high-pressure tower is 14-22 block plate, and tower top temperature is 131-134 DEG C, and column bottom temperature is 136-146 DEG C, reflux
Than for 0.4-1.6, operating pressure 450-600kPa；
(3) lower pressure column tower reactor obtains pure water, and overhead vapours obtains acetonitrile-water azeotropic object after condenser condenses, and partial reflux arrives
Lower pressure column, rest part enter high-pressure tower and carry out circular treatment；
Wherein, the plate number of lower pressure column is 7-15 block plate, and tower top temperature is 50-53 DEG C, and column bottom temperature is 74-77 DEG C, operating pressure
For 40-100kPa, reflux ratio 1-3.
2. azeotropic as described in claim 1-variable-pressure rectification separates pyridine-acetonitrile-water system method, it is characterized in that described
Feed liquid in each component mass percent be pyridine 14 ~ 25%, acetonitrile 26 ~ 37%, water 43 ~ 55%.
3. azeotropic as described in claim 1-variable-pressure rectification separates pyridine-acetonitrile-water system method, it is characterized in that described
Obtain acetonitrile and the product purity of pyridine is all larger than 99.5%.
4. azeotropic as described in claim 1-variable-pressure rectification separates pyridine-acetonitrile-water system method, it is characterized in that described
Azeotrope column feed entrance point be 7-13 block plate；The feed entrance point of high-pressure tower is 5-13 block plate；The feed entrance point of lower pressure column is 5-
11 blocks of plates.
5. azeotropic as described in claim 1-variable-pressure rectification separates pyridine-acetonitrile-water system method, it is characterized in that described
Azeotrope column entrainer feed entrance point be 5-11 block plate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811511877.1A CN109593059B (en) | 2018-12-11 | 2018-12-11 | Method for separating pyridine-acetonitrile-water system by azeotropic-pressure swing distillation |
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| CN201811511877.1A CN109593059B (en) | 2018-12-11 | 2018-12-11 | Method for separating pyridine-acetonitrile-water system by azeotropic-pressure swing distillation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113321613A (en) * | 2021-06-24 | 2021-08-31 | 索闻特环保科技(上海)有限公司 | Method for treating mixed liquid containing acetonitrile, 3-methylpyridine and water |
| CN113979925A (en) * | 2021-09-30 | 2022-01-28 | 索闻特环保科技(上海)有限公司 | Method for extracting 3-methylpyridine from pesticide production waste liquid |
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| RU2599132C1 (en) * | 2015-06-30 | 2016-10-10 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский технологический университет" | Method of separating mixture of solvents methanol-tetrahydrofuran-acetonitrile-water-pyridine |
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| RU2599132C1 (en) * | 2015-06-30 | 2016-10-10 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский технологический университет" | Method of separating mixture of solvents methanol-tetrahydrofuran-acetonitrile-water-pyridine |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113321613A (en) * | 2021-06-24 | 2021-08-31 | 索闻特环保科技(上海)有限公司 | Method for treating mixed liquid containing acetonitrile, 3-methylpyridine and water |
| CN113979925A (en) * | 2021-09-30 | 2022-01-28 | 索闻特环保科技(上海)有限公司 | Method for extracting 3-methylpyridine from pesticide production waste liquid |
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Effective date of registration: 20220926 Address after: Room 311(409), Block A, Tianjin Youth Pioneer Park, No. 85 Qingnian Road, Lingdangge Street, Hongqiao District, Tianjin 300131 Patentee after: Tianjin Putong Technology Co.,Ltd. Address before: 300130 No. 8, Hebei University of Technology, Tianjin, Hongqiao No. 330 Patentee before: Hebei University of Technology |