CN106565550B - A kind of thickening method of camphorsulfonic acid solution in L-Phenylglycine production process - Google Patents
A kind of thickening method of camphorsulfonic acid solution in L-Phenylglycine production process Download PDFInfo
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- CN106565550B CN106565550B CN201610966079.2A CN201610966079A CN106565550B CN 106565550 B CN106565550 B CN 106565550B CN 201610966079 A CN201610966079 A CN 201610966079A CN 106565550 B CN106565550 B CN 106565550B
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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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- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C07B2200/07—Optical isomers
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Abstract
The invention discloses a kind of thickening method of camphorsulfonic acid solution in L-Phenylglycine production process.By in phenylglycine production process using camphorsulfonic acid make resolving agent generation solution be centrifuged and wash after produce mother liquor process：（1）Decrease temperature crystalline pre-processes；（2）Level-one high pressure reverse osmosis membrane thickening；（3）Two level high pressure reverse osmosis membrane thickening；（4）L-Phenylglycine Crystallization Separation；（5）Three-level high pressure reverse osmosis membrane thickening.Its concentration is concentrated to 30%~32% from 8%~9%, can be returned directly to recycle in former resolution process, production Water circulation is into original production process.The present invention makes camphorsulfonic acid solution enrichment to more than 30%, and compared with existing multiple-effect evaporation, without phase-change, energy consumption can reduce by more than 60%, phenylglycine, camphorsulfonic acid, production water can reuse, realize recycling, energy saving and clean manufacturing.
Description
Technical field
The present invention relates to utilize camphor sulphur in a kind of solution thickening method, particularly L-Phenylglycine production process
Acid makees the thickening method of the camphorsulfonic acid solution of resolving agent generation, 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 beta-lactam antibiotic surely, be also used for synthesis polypeptide hormone and Multiple Pesticides.In the production process of L-Phenylglycine
In, it is necessary to using the camphorsulfonic acid of pharmaceutical grade as resolving agent, the solution produced after fractionation is centrifuged and washes
Process, isolates solid levorotatory phenylglycine, and carries out subsequent fine and product L-Phenylglycine is made, to what is centrifuged 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, it is necessary to molten to this camphorsulfonic acid
Liquid carries out recycling.The recycling of camphorsulfonic acid solution at present is more using decompression multiple-effect evaporation mode, this method steam consumption
Amount is big, and in distillation process, since high temperature makes material properties change, viscosity becomes larger, and is attached on the tubulation of heat exchanger,
Heat transfer efficiency is poor, and steam consumption increase, hardness is very big after temperature reduces, and can not be removed from heat exchanger tube, it is necessary to more
The heat exchanger renewed, increases investment cost and operating cost, aggravates the burden of enterprise.Therefore, a kind of energy-saving and environmental protection, reality are found
Camphorsulfonic acid solution thickening method, realize it is energy-saving, reduce cost, be that phenylglycine manufacturing enterprise is urgently to be resolved hurrily
The problem of.
The content of the invention
The object of the present invention is to provide a kind of thickening side of camphorsulfonic acid solution in L-Phenylglycine production process
Method, thus achieve the purpose that it is energy-saving, reduce cost.
The thickening method of camphorsulfonic acid solution in a kind of L-Phenylglycine production process that the present invention provides, including
Following steps：
(1) decrease temperature crystalline pre-processes
In phenylglycine production process using camphorsulfonic acid make resolving agent generation solution be centrifuged and wash after
The mother liquor of generation is known as camphorsulfonic acid original solution, this original solution is cooled to 15~20 DEG C, 40~60min is kept, there is an a small amount of left side
Revolve phenylglycine crystallization to separate out, filtering, obtains L-Phenylglycine crystal and the camphorsulfonic acid solution of mass content 8%~9%；
Wherein, 8%~9% camphorsulfonic acid, 0.3%~0.5% sweet ammonia of left-handed benzene are contained in the camphorsulfonic acid original solution
Acid, 90%~91% water, pH 6.5, temperature are 35 DEG C；
(2) level-one high pressure reverse osmosis membrane thickening
The camphorsulfonic acid solution that step (1) is obtained after cartridge filter pre-flock, be sent into level-one high pressure reverse osmosis membrane into
Row thickening, it into film temperature is 30~40 DEG C to control after pre-flock solution, is 8.0~9.0MPa into film pressure, when in dope side
When the concentration of camphorsulfonic acid reaches mass content 14%~16%, stop thickening process, collect production water and mass content 14%~
16% camphorsulfonic acid solution；
(3) two level high pressure reverse osmosis membrane thickening
The camphorsulfonic acid solution for the mass content 14%~16% that step (2) is collected into is sent into after cartridge filter pre-flock
Two level high pressure reverse osmosis membrane carries out thickening, and it into film temperature is 30~40 DEG C control after pre-flock solution, is 10.0 into film pressure
~12.0MPa, when the mass concentration of camphorsulfonic acid in dope side reaches 20%~21%, stops thickening process, collects production
The camphorsulfonic acid solution of water and mass concentration 20%~21%；
(4) L-Phenylglycine Crystallization Separation
The camphorsulfonic acid solution for 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, L-Phenylglycine crystal and crystalline mother solution is obtained by filtration, with sulfuric acid tune
Save crystalline mother solution PH to 2~3；
(5) three-level high pressure reverse osmosis membrane thickening
It is dense to be sent into the progress of three-level high pressure reverse osmosis membrane after cartridge filter pre-flock for the crystalline mother solution that step (4) is obtained
Contracting dehydration, control after pre-flock solution into film temperature for 30~35 DEG C when, be 13.0~16.0MPa into film pressure, when in dope side
When the mass concentration of camphorsulfonic acid reaches 30%~32%, stop thickening process, collect production water and mass concentration 30%~32%
Camphorsulfonic acid solution, the camphorsulfonic acid solution of mass concentration 30%~32% can continue to be back to use former resolution process as resolving agent
During；
The production water being collected into 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, and it is left-handed to be finally prepared into product
Phenylglycine；
In the present invention, level-one, two level, three-level high pressure reverse osmosis membrane are commercially available MB-160S high-pressure flat plates reverse osmosis membrane
Product, highest operating pressure are 16.0MPa.
In the present invention, the filtering accuracy of filter core is 5~10 μm in cartridge filter.
The method of the present invention can also be used for splitting in camphorsulfonic acid production process, centrifuge after phenylglycine solution
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 recycled, improves product yield and enterprise
Economic benefit；Compared with existing multiple-effect evaporation, energy consumption can reduce by more than 60%, reduce operating cost；Equipment can long-time service,
Without phase-change, L-Phenylglycine and camphorsulfonic acid are all recyclable, high pressure reverse osmosis membrane production water can reuse, realize recycling and cleaning
Production；By the way of decrease temperature crystalline, the L-Phenylglycine crystal in camphorsulfonic acid solution is removed, reduces crystal grain to high pressure
The damage of reverse osmosis membrane, extends service life.
Brief description of the drawings
Fig. 1 is the process flow diagram of the present invention.
Embodiment
Following embodiments are used to illustrate the present invention.
Embodiment 1
(1) decrease temperature crystalline pre-processes
The solution for being made resolving agent generation in L-Phenylglycine production process using camphorsulfonic acid is centrifuged and water
The mother liquor produced after washing is known as camphorsulfonic acid original solution, by 100m3This camphorsulfonic acid original solution is cooled to 16 DEG C, keeps 50min,
There is a small amount of L-Phenylglycine crystallization to separate out, L-Phenylglycine crystal and 99.8 m is obtained by filtration3 Mass content is 8% camphor tree
Brain sulfonic acid solutions；
Containing 8% camphorsulfonic acid in wherein described camphorsulfonic acid original solution, 0.4% L-Phenylglycine, 91.4%
Water, PH 6.5, temperature are 35 DEG C；
(2) level-one high pressure reverse osmosis membrane thickening
99.8 m that step (1) is obtained3 Mass content is 8% camphorsulfonic acid solution, is sent after cartridge filter pre-flock
Enter level-one high pressure reverse osmosis membrane and carry out thickening, it into film temperature is 34~36 DEG C control after pre-flock solution, is into film pressure
8.0MPa, when water 45m3 is produced in extraction, stops thickening process, collects the camphorsulfonic acid that 54.8m3 mass contents are 14.57%
Solution；
(3) two level high pressure reverse osmosis membrane thickening
The camphorsulfonic acid solution that the 54.8m3 mass contents that step (2) is collected into are 14.57% is through cartridge filter pre-flock
Be sent into two level high pressure reverse osmosis membrane afterwards and carry out thickening, control after pre-flock solution into film temperature for 34~36 DEG C when, into membrane pressure
Power is 11.5MPa, as extraction production water 15m3When, stop thickening process, collect 39.8m3 Mass content is 20.06% camphor tree
Brain sulfonic acid solutions；
(4) L-Phenylglycine Crystallization Separation
The 39.8m that step (3) is obtained3 The camphorsulfonic acid solution that mass content is 20.06% is cooled to 16 DEG C, keeps
50min, has a small amount of L-Phenylglycine crystallization to separate out, L-Phenylglycine crystal and crystalline mother solution is obtained by filtration, with sulfuric acid tune
Save crystalline mother solution PH to 2.5；
(5) three-level high pressure reverse osmosis membrane thickening
It is dense to be sent into the progress of three-level high pressure reverse osmosis membrane after cartridge filter pre-flock for the crystalline mother solution that step (4) is obtained
Contracting dehydration, it into film temperature is 32~35 DEG C control after pre-flock solution, be 15.0MPa into film pressure, water 13m is produced when producing3When, stop
Only thickening process, collects 26.6m3 Mass content is 30% camphorsulfonic acid solution, and 30% camphorsulfonic acid solution, which is used as, to be torn open
Point agent uses during continuing to be back to use former resolution process.
The present embodiment, the production water being collected into 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) are returned in original production process, final to prepare
Into product L-Phenylglycine.
The present embodiment, one, two, three high pressure reverse osmosis membrane are commercially available MB-160S high-pressure flat plates reverse osmosis membrane product,
Highest operating pressure is 16.0MPa.
The present embodiment, the filtering accuracy of filter core is 5 μm in cartridge filter.
Embodiment 2
(1) decrease temperature crystalline pre-processes
The solution for being made resolving agent generation in L-Phenylglycine production process using camphorsulfonic acid is centrifuged and water
The mother liquor produced after washing is known as camphorsulfonic acid original solution, by 150m3This camphorsulfonic acid original solution is cooled to 17 DEG C, keeps 60min,
There is a small amount of L-Phenylglycine crystallization to separate out, L-Phenylglycine crystal and 149.7 m is obtained by filtration3Mass content is 8.5%
Camphorsulfonic acid solution；
Containing 8.5% camphorsulfonic acid in wherein described camphorsulfonic acid original solution, 0.35% L-Phenylglycine,
90.85% water, PH 6.5, temperature are 35 DEG C；
(2) level-one high pressure reverse osmosis membrane thickening
149.7 m that step (1) is obtained3 Mass content is 8.5% camphorsulfonic acid solution, through cartridge filter pre-flock
Be sent into level-one high pressure reverse osmosis membrane afterwards and carry out thickening, control after pre-flock solution into film temperature be 36~38 DEG C, into film pressure
For 9.0MPa, when water 70m3 is produced in extraction, stop thickening process, collect the camphor sulphur that 79.7m3 mass contents are 15.96%
Acid solution,；
(3) two level high pressure reverse osmosis membrane thickening
The camphorsulfonic acid solution that the 79.7m3 mass contents that step (2) is collected into are 15.96% is through cartridge filter pre-flock
Afterwards, be sent into two level high pressure reverse osmosis membrane and carry out thickening, control after pre-flock solution into film temperature for 36~38 DEG C when, into membrane pressure
Power is 11.5MPa, when water 16.5m3 is produced in extraction, stops thickening process, collects 63.2m3 Mass content is 20.13%
Camphorsulfonic acid solution；
(4) L-Phenylglycine Crystallization Separation
The 63.2m that step (3) is obtained3 The camphorsulfonic acid solution that mass content is 20.13% is cooled to 15 DEG C, keeps
60min, has a small amount of L-Phenylglycine crystallization to separate out, L-Phenylglycine crystal and crystalline mother solution is obtained by filtration, with sulfuric acid tune
Save crystalline mother solution PH to 2.5；
(5) three-level high pressure reverse osmosis membrane thickening
It is dense to be sent into the progress of three-level high pressure reverse osmosis membrane after cartridge filter pre-flock for the crystalline mother solution that step (4) is obtained
Contracting dehydration, it into film temperature is 32~35 DEG C control after pre-flock solution, be 15.5MPa into film pressure, water 20.7m is produced when producing3When,
Stop thickening process, collect 42.3m3 Mass content is 30.08% camphorsulfonic acid solution, and 30.08% camphorsulfonic acid is molten
Liquid continues to be back to use during former resolution process as resolving agent to be used.
The present embodiment, the production water being collected into 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) are returned in original production process, final to prepare
Into product L-Phenylglycine.
The present embodiment, one, two, three high pressure reverse osmosis membrane are commercially available MB-160S high-pressure flat plates reverse osmosis membrane product,
Highest operating pressure is 16.0MPa.
The present embodiment, the filtering accuracy of filter core is 10 μm in cartridge filter.
Claims (3)
1. the thickening method of camphorsulfonic acid solution, comprises the following steps in a kind of L-Phenylglycine production process：
(1) decrease temperature crystalline pre-processes
By in phenylglycine production process using camphorsulfonic acid make resolving agent generation solution be centrifuged and wash after produce
Raw mother liquor is cooled to 15~20 DEG C, keeps 40~60min, has a small amount of L-Phenylglycine crystallization to separate out, filtering, obtains left-handed
The camphorsulfonic acid solution of phenylglycine crystal and mass content 8%~9%；
(2) level-one high pressure reverse osmosis membrane thickening
It is dense to be sent into the progress of level-one high pressure reverse osmosis membrane after cartridge filter pre-flock for the camphorsulfonic acid solution that step (1) is obtained
Contracting dehydration, it into film temperature is 30~40 DEG C control after pre-flock solution, is 8.0~9.0MPa into film pressure, when camphor in dope side
When the concentration of sulfonic acid reaches mass content 14%~16%, stop thickening process, collect production water and mass content 14%~16%
Camphorsulfonic acid solution；
(3) two level high pressure reverse osmosis membrane thickening
The camphorsulfonic acid solution for the mass content 14%~16% that step (2) is collected into is sent into two level after cartridge filter pre-flock
High pressure reverse osmosis membrane carries out thickening, control after pre-flock solution into film temperature be 30~40 DEG C, into film pressure be 10.0~
12.0MPa, when the mass concentration of camphorsulfonic acid in dope side reaches 20%~21%, stops thickening process, collects production water
With the camphorsulfonic acid solution of mass concentration 20%~21%；
(4) L-Phenylglycine Crystallization Separation
The camphorsulfonic acid solution for 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, L-Phenylglycine crystal and crystalline mother solution is obtained by filtration, with sulfuric acid tune
Save crystalline mother solution PH to 2~3；
(5) three-level high pressure reverse osmosis membrane thickening
For the crystalline mother solution that step (4) is obtained after cartridge filter pre-flock, it is de- that feeding three-level high pressure reverse osmosis membrane carries out concentration
Water, it into film temperature is 30~35 DEG C to control after pre-flock solution, is 13.0~16.0MPa into film pressure, when camphor sulphur in dope side
When the mass concentration of acid reaches 30%~32%, stop thickening process, collect production water and the camphor of mass concentration 30%~32%
Sulfonic acid solutions, the camphorsulfonic acid solution of mass concentration 30%~32% continue to be back to use during former resolution process as resolving agent；
The high pressure reverse osmosis membrane being collected into step (2) (3) (5) produces Water circulation into original production process；
The L-Phenylglycine crystal obtained in step (1) (4) is returned in original production process, and it is sweet to be finally prepared into the left-handed benzene of product
Propylhomoserin.
2. according to the method described in claim 1, it is characterized in that three-level high pressure reverse osmosis membrane is commercially available MB-160S high pressures
Flat plate reverse osmosis film product, highest operating pressure are 16.0MPa.
3. according to the method described in claim 1, it is characterized in that the filtering accuracy of filter core is 5~10 μm in cartridge filter.
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| CN110713446B (en) * | 2019-12-04 | 2021-07-06 | 河北美邦膜科技有限公司 | Method for separating dimethyl sulfoxide from amlodipine resolution waste liquid |
| 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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| US3819689A (en) * | 1971-06-23 | 1974-06-25 | Lilly Co Eli | Resolution of dl-camphor-10-sulfonic acid |
| CN1552694A (en) * | 2003-05-30 | 2004-12-08 | 上海实业化工有限公司 | Preparation of D-(-)-1-benzene amino acetic acid |
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