CN106565550A - Method for concentrating and dewatering camphor sulfonic acid solution in production process of L-phenylglycine - Google Patents
Method for concentrating and dewatering camphor sulfonic acid solution in production process of L-phenylglycine Download PDFInfo
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- CN106565550A CN106565550A CN201610966079.2A CN201610966079A CN106565550A CN 106565550 A CN106565550 A CN 106565550A CN 201610966079 A CN201610966079 A CN 201610966079A CN 106565550 A CN106565550 A CN 106565550A
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- phenylglycine
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- reverse osmosis
- camphorsulfonic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/30—Preparation of optical isomers
- C07C227/34—Preparation of optical isomers by separation of optical isomers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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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
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Abstract
The invention discloses a method for concentrating and dewatering a camphor sulfonic acid solution in a production process of L-phenylglycine. A mother liquid produced after a solution produced by using camphor sulfonic acid as a resolving agent in a production process of phenylglycine is subjected to centrifugal separation and water washing is subjected to the following treatment: (1) cooling crystallization pretreatment; (2) first-level high pressure reverse osmosis membrane concentration dewatering; (3) second-level high pressure reverse osmosis membrane concentration dewatering; (4) L-phenylglycine crystallization and separation; and (5) third-level high pressure reverse osmosis membrane concentration dewatering. The concentration of the solution is concentrated from 8%-9% to 30%-32%, the solution can be directly reused in an original resolution process, and produced water is reused to the original production process. The concentration of the camphor sulfonic acid solution is thickened to more than or equal to 30%; compared with conventional multi-effect evaporation, the method has no phase change, energy consumption can be reduced by more than or equal to 60%, the phenylglycine, camphor sulfonic acid and produced water can be reused, and reclamation, energy saving and clean production are achieved.
Description
Technical field
The present invention relates to utilize Camphora sulphur in a kind of solution thickening method, particularly L-Phenylglycine production process
The thickening method of the camphorsulfonic acid solution of resolving agent generation is made in acid, belongs to medication chemistry production technical field.
Background technology
L-Phenylglycine is a kind of important medicine intermediate, is usually used in synthesizing ampicillin, Cefalexin, cephalo
Draw and wait surely beta-lactam antibiotic, be also used for synthesis polypeptide hormone and Multiple Pesticides.In the production process of L-Phenylglycine
In, needing using the camphorsulfonic acid of pharmaceutical grade as resolving agent, the solution that fractionation is produced after terminating is centrifuged and washes
Process, isolates solid levorotatory phenylglycine, and carries out subsequent fine product L-Phenylglycine is obtained, and centrifugation is gone out
Liquid and the liquid of washing are collected i.e. camphorsulfonic acid solution, containing 8%～9% camphorsulfonic acid in this solution, 0.3%～
0.5% phenylglycine, 90%～91% water, due to pharmaceutical grade camphorsulfonic acid it is expensive, need molten to this camphorsulfonic acid
Liquid carries out recycling.At present using decompression multiple-effect evaporation mode, the method steam consumption more than the recovery of camphorsulfonic acid solution
Amount is big, and in still-process, because high temperature makes material propertiess change, viscosity becomes big, is attached on the tubulation of heat exchanger,
Heat transfer efficiency is poor, and steam consumption increases, and hardness is very big after temperature is reduced, it is impossible to remove from heat exchanger tube, needs more
The heat exchanger for renewing, increases cost of investment and operating cost, increases the burden of enterprise.Therefore, a kind of energy-saving and environmental protection, reality are found
Camphorsulfonic acid solution thickening method, realizes energy-saving, reduces cost, is that phenylglycine manufacturing enterprise is urgently to be resolved hurrily
Problem.
The content of the invention
It is an object of the invention to provide in a kind of L-Phenylglycine production process camphorsulfonic acid solution thickening side
Method, so as to reach energy-saving, reduces cost purpose.
The thickening method of camphorsulfonic acid solution in a kind of L-Phenylglycine production process that the present invention is given, including
Following steps：
(1) decrease temperature crystalline pretreatment
The solution for making resolving agent generation using camphorsulfonic acid in phenylglycine production process is produced after being centrifuged and washing
Mother solution be referred to as camphorsulfonic acid original solution, this original solution is cooled to into 15～20 DEG C, keep 40～60min, have a small amount of left-handed benzene
Glycine crystallization is separated out, and is filtered, and obtains the camphorsulfonic acid solution of L-Phenylglycine crystal and mass content 8%～9%；
Wherein, in the camphorsulfonic acid original solution containing 8%～9% camphorsulfonic acid, 0.3%～0.5% L-Phenylglycine,
90%～91% water, pH is 6.5, and temperature is 35 DEG C；
(2) one-level high pressure reverse osmosis membrane thickening
Jing after cartridge filter pre-flock, feeding one-level high pressure reverse osmosis membrane carries out dense the camphorsulfonic acid solution that step (1) is obtained
Contracting dehydration, controls solution after pre-flock and enters film temperature for 30～40 DEG C, and it is 8.0～9.0MPa to enter film pressure, when Camphora in dope side
When the concentration of sulfonic acid reaches mass content 14%～16%, stop thickening process, collect and produce water and mass content 14%～16%
Camphorsulfonic acid solution；
(3) two grades of high pressure reverse osmosis membrane thickenings
The camphorsulfonic acid solution of the mass content 14%～16% that step (2) is collected sends into two grades Jing after cartridge filter pre-flock
High pressure reverse osmosis membrane carries out thickening, controls solution after pre-flock and enters film temperature for 30～40 DEG C, enter film pressure for 10.0～
12.0MPa, when the mass concentration of camphorsulfonic acid in dope side reaches 20%～21%, stops thickening process, collects and produces water
With the camphorsulfonic acid solution of mass concentration 20%～21%；
(4) L-Phenylglycine Crystallization Separation
The camphorsulfonic acid solution of the mass concentration 20%～21% that step (3) is obtained is cooled to 15～20 DEG C, keep 40～
60min, has a small amount of L-Phenylglycine crystallization to separate out, and is filtrated to get L-Phenylglycine crystal and crystalline mother solution, is adjusted with sulphuric acid
Section crystalline mother solution PH to 2～3；
(5) three-level high pressure reverse osmosis membrane thickening
The crystalline mother solution that step (4) is obtained is Jing after cartridge filter pre-flock, and it is de- that feeding three-level high pressure reverse osmosis membrane carries out concentration
Water, control solution after pre-flock enter film temperature for 30～35 DEG C when, enter film pressure for 13.0～16.0MPa, when Camphora in dope side
When the mass concentration of sulfonic acid reaches 30%～32%, stop thickening process, collect the Camphor tree for producing water and mass concentration 30%～32%
Brain sulfonic acid solutions, the camphorsulfonic acid solution of mass concentration 30%～32% can continue to be back to use former resolution process process as resolving agent
In；
The product water collected in step (2) (3) (5) can be back to use in original production process；
The L-Phenylglycine crystal obtained in step (1) (4) is returned in original production process, is finally prepared into the left-handed benzene of product sweet
Propylhomoserin；
In the present invention, one-level, two grades, three-level high pressure reverse osmosis membrane be commercially available MB-160S high-pressure flat plate reverse osmosis membrane products,
Highest operating pressure is 16.0MPa.
In the present invention, the filtering accuracy of filter element is 5～10 μm in cartridge filter.
The method of the present invention can also be used for the phenylglycine solution in camphorsulfonic acid production process after fractionation, centrifugation
In thickening.
The present invention obtains following beneficial effect：
In the present invention, camphorsulfonic acid concentration of polymer solution is concentrated to 30%～32% by 8%～9%, can be straight
During taking back original production resolution process；L-Phenylglycine crystal is reclaimed, product yield and business economic is improve
Benefit；Compared with existing multiple-effect evaporation, energy consumption can reduce by more than 60%, reduce operating cost；Equipment can life-time service, without phase
Become, L-Phenylglycine and camphorsulfonic acid it is all recyclable, high pressure reverse osmosis membrane produce water can reuse, realize resource and cleaning life
Produce；By the way of decrease temperature crystalline, the L-Phenylglycine crystal in camphorsulfonic acid solution is removed, reduce crystal grain anti-to high pressure
The damage of permeable membrane, extends service life.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention.
Specific embodiment
Following examples are used to illustrate the present invention.
Embodiment 1
(1) decrease temperature crystalline pretreatment
After the solution for making resolving agent generation using camphorsulfonic acid in L-Phenylglycine production process is centrifuged and washes
The mother solution of generation is referred to as camphorsulfonic acid original solution, by 100m3This camphorsulfonic acid original solution is cooled to 16 DEG C, keeps 50min, there is few
Amount L-Phenylglycine crystallization is separated out, and is filtrated to get L-Phenylglycine crystal and 99.8 m3Mass content is 8% Camphora sulphur
Acid solution；
Containing 8% camphorsulfonic acid, 0.4% L-Phenylglycine, 91.4% water, PH in wherein described camphorsulfonic acid original solution
For 6.5, temperature is 35 DEG C；
(2) one-level high pressure reverse osmosis membrane thickening
99.8 m that step (1) is obtained3Mass content is 8% camphorsulfonic acid solution, and Jing after cartridge filter pre-flock one is sent into
Level high pressure reverse osmosis membrane carries out thickening, controls solution after pre-flock and enters film temperature for 34～36 DEG C, and it is 8.0MPa to enter film pressure,
When water 45m3 is produced in extraction, stop thickening process, collect the camphorsulfonic acid solution that 54.8m3 mass contents are 14.57%；
(3) two grades of high pressure reverse osmosis membrane thickenings
The camphorsulfonic acid solution that the 54.8m3 mass contents that step (2) is collected are 14.57% is sent Jing after cartridge filter pre-flock
Entering two grades of high pressure reverse osmosis membranes carries out thickening, control solution after pre-flock enter film temperature for 34～36 DEG C when, entering film pressure is
11.5MPa, when water 15m is produced in extraction3When, stop thickening process, collect 39.8m3 Mass content is 20.06% Camphora sulphur
Acid solution；
(4) L-Phenylglycine Crystallization Separation
The 39.8m that step (3) is obtained3 Mass content is that 20.06% camphorsulfonic acid solution is cooled to 16 DEG C, keeps 50min,
There is a small amount of L-Phenylglycine crystallization to separate out, be filtrated to get L-Phenylglycine crystal and crystalline mother solution, adjusted with sulphuric acid and crystallized
Mother solution PH to 2.5；
(5) three-level high pressure reverse osmosis membrane thickening
The crystalline mother solution that step (4) is obtained is Jing after cartridge filter pre-flock, and it is de- that feeding three-level high pressure reverse osmosis membrane carries out concentration
Water, controls solution after pre-flock and enters film temperature for 32～35 DEG C, and it is 15.0MPa to enter film pressure, when water 13m is produced in extraction3When, stop dense
Contracting dehydration, collects 26.6m3 Mass content is 30% camphorsulfonic acid solution, and 30% camphorsulfonic acid solution is used as resolving agent
Continue to be back to use during former resolution process and use.
The present embodiment, the product water collected in step (2) (3) (5) can be back to use in original production process.
The present embodiment, the L-Phenylglycine crystal obtained in step (1) (4) is returned in original production process, final to prepare
Into product L-Phenylglycine.
The present embodiment, one, two, three high pressure reverse osmosis membrane is commercially available MB-160S high-pressure flat plate reverse osmosis membrane products,
Highest operating pressure is 16.0MPa.
The present embodiment, the filtering accuracy of filter element is 5 μm in cartridge filter.
Embodiment 2
(1) decrease temperature crystalline pretreatment
After the solution for making resolving agent generation using camphorsulfonic acid in L-Phenylglycine production process is centrifuged and washes
The mother solution of generation is referred to as camphorsulfonic acid original solution, by 150m3This camphorsulfonic acid original solution is cooled to 17 DEG C, keeps 60min, there is few
Amount L-Phenylglycine crystallization is separated out, and is filtrated to get L-Phenylglycine crystal and 149.7 m3Mass content is 8.5% Camphora
Sulfonic acid solutions；
Containing 8.5% camphorsulfonic acid in wherein described camphorsulfonic acid original solution, 0.35% L-Phenylglycine, 90.85%
Water, PH is 6.5, and temperature is 35 DEG C；
(2) one-level high pressure reverse osmosis membrane thickening
149.7 m that step (1) is obtained3Mass content is 8.5% camphorsulfonic acid solution, is sent Jing after cartridge filter pre-flock
Entering one-level high pressure reverse osmosis membrane carries out thickening, controls solution after pre-flock and enters film temperature for 36～38 DEG C, and entering film pressure is
9.0MPa, when water 70m3 is produced in extraction, stops thickening process, collects the camphorsulfonic acid that 79.7m3 mass contents are 15.96%
Solution,；
(3) two grades of high pressure reverse osmosis membrane thickenings
By camphorsulfonic acid solution that the 79.7m3 mass contents that step (2) is collected are 15.96% Jing after cartridge filter pre-flock,
Send into two grades of high pressure reverse osmosis membranes carry out thickening, control solution after pre-flock enter film temperature be 36～38 DEG C when, enter film pressure
For 11.5MPa, when water 16.5m3 is produced in extraction, stop thickening process, collect 63.2m3 Mass content is 20.13% Camphor tree
Brain sulfonic acid solutions；
(4) L-Phenylglycine Crystallization Separation
The 63.2m that step (3) is obtained3 Mass content is that 20.13% camphorsulfonic acid solution is cooled to 15 DEG C, keeps 60min,
There is a small amount of L-Phenylglycine crystallization to separate out, be filtrated to get L-Phenylglycine crystal and crystalline mother solution, adjusted with sulphuric acid and crystallized
Mother solution PH to 2.5；
(5) three-level high pressure reverse osmosis membrane thickening
The crystalline mother solution that step (4) is obtained is Jing after cartridge filter pre-flock, and it is de- that feeding three-level high pressure reverse osmosis membrane carries out concentration
Water, controls solution after pre-flock and enters film temperature for 32～35 DEG C, and it is 15.5MPa to enter film pressure, when water 20.7m is produced in extraction3When, stop
Thickening process, collects 42.3m3 Mass content is 30.08% camphorsulfonic acid solution, and 30.08% camphorsulfonic acid solution is made
Continue to be back to use during former resolution process for resolving agent and use.
The present embodiment, the product water collected in step (2) (3) (5) can be back to use in original production process.
The present embodiment, the L-Phenylglycine crystal obtained in step (1) (4) is returned in original production process, final to prepare
Into product L-Phenylglycine.
The present embodiment, one, two, three high pressure reverse osmosis membrane is commercially available MB-160S high-pressure flat plate reverse osmosis membrane products,
Highest operating pressure is 16.0MPa.
The present embodiment, the filtering accuracy of filter element is 10 μm in cartridge filter.
Claims (3)
1. in a kind of L-Phenylglycine production process camphorsulfonic acid solution thickening method, comprise the following steps：
(1) decrease temperature crystalline pretreatment
Produce after the solution for making resolving agent generation using camphorsulfonic acid in phenylglycine production process is centrifuged and is washed
Raw mother solution is cooled to 15～20 DEG C, keeps 40～60min, has a small amount of L-Phenylglycine crystallization to separate out, and filters, and obtains left-handed
The camphorsulfonic acid solution of phenylglycine crystal and mass content 8%～9%；
(2) one-level high pressure reverse osmosis membrane thickening
Jing after cartridge filter pre-flock, feeding one-level high pressure reverse osmosis membrane carries out dense the camphorsulfonic acid solution that step (1) is obtained
Contracting dehydration, controls solution after pre-flock and enters film temperature for 30～40 DEG C, and it is 8.0～9.0MPa to enter film pressure, when Camphora in dope side
When the concentration of sulfonic acid reaches mass content 14%～16%, stop thickening process, collect and produce water and mass content 14%～16%
Camphorsulfonic acid solution；
(3) two grades of high pressure reverse osmosis membrane thickenings
The camphorsulfonic acid solution of the mass content 14%～16% that step (2) is collected sends into two grades Jing after cartridge filter pre-flock
High pressure reverse osmosis membrane carries out thickening, controls solution after pre-flock and enters film temperature for 30～40 DEG C, enter film pressure for 10.0～
12.0MPa, when the mass concentration of camphorsulfonic acid in dope side reaches 20%～21%, stops thickening process, collects and produces water
With the camphorsulfonic acid solution of mass concentration 20%～21%；
(4) L-Phenylglycine Crystallization Separation
The camphorsulfonic acid solution of the mass concentration 20%～21% that step (3) is obtained is cooled to 15～20 DEG C, keep 40～
60min, has a small amount of L-Phenylglycine crystallization to separate out, and is filtrated to get L-Phenylglycine crystal and crystalline mother solution, is adjusted with sulphuric acid
Section crystalline mother solution PH to 2～3；
(5) three-level high pressure reverse osmosis membrane thickening
The crystalline mother solution that step (4) is obtained is Jing after cartridge filter pre-flock, and it is de- that feeding three-level high pressure reverse osmosis membrane carries out concentration
Water, controls solution after pre-flock and enters film temperature for 30～35 DEG C, and it is 13.0～16.0MPa to enter film pressure, when Camphora sulphur in dope side
When the mass concentration of acid reaches 30%～32%, stop thickening process, collect the Camphora for producing water and mass concentration 30%～32%
Sulfonic acid solutions, the camphorsulfonic acid solution of mass concentration 30%～32% continues to be back to use during former resolution process as resolving agent；
The high pressure reverse osmosis membrane collected in step (2) (3) (5) produces Water circulation in original production process；
The L-Phenylglycine crystal obtained in step (1) (4) is returned in original production process, is finally prepared into the left-handed benzene of product sweet
Propylhomoserin.
2. method according to claim 1, it is characterised in that three-level high pressure reverse osmosis membrane is commercially available MB-160S high pressure
Flat plate reverse osmosis film product, highest operating pressure is 16.0MPa.
3. method according to claim 1, it is characterised in that the filtering accuracy of filter element is 5～10 μm in cartridge filter.
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| CN110713446A (en) * | 2019-12-04 | 2020-01-21 | 河北美邦膜科技有限公司 | Method for separating dimethyl sulfoxide from amlodipine resolution waste liquid |
| CN111362982A (en) * | 2020-04-07 | 2020-07-03 | 河北美邦工程科技股份有限公司 | Refining method of pyridoxal phosphate |
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| CN110713446A (en) * | 2019-12-04 | 2020-01-21 | 河北美邦膜科技有限公司 | Method for separating dimethyl sulfoxide from amlodipine resolution waste liquid |
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| CN111362982B (en) * | 2020-04-07 | 2023-01-17 | 河北美邦工程科技股份有限公司 | Refining method of pyridoxal phosphate |
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| CN106565550B (en) | 2018-04-13 |
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