CN101967106A - Method for treating L-p-hydroxyphenylglycine desalting mother liquor by adopting bipolar membrane electrodialysis technology - Google Patents
Method for treating L-p-hydroxyphenylglycine desalting mother liquor by adopting bipolar membrane electrodialysis technology Download PDFInfo
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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 treating an L-p-hydroxyphenylglycine desalting mother liquor by adopting a bipolar membrane electrodialysis technology, comprising the following steps of diluting the desalting mother liquor, regulating a pH value thereof to be alkaline, heating, filtering, and using cation exchange resin to remove inpurity ions in the mother liquor; separating the mother liquor after impurity ion removal by adopting bipolar membrane electrodialysis to respectively obtain liquid alkali and a resolution agent; secondly using the obtained liquid alkali in alkali regulation or an activation treatment process of cation exchange resin in the last step, and using the obtained resolution agent for production of L-p-hydroxyphenylglycine again. Therefore, various components reach closed cycle without causing material loss. The method is beneficial to recovering valuable substances in the mother liquor, lowers the environmental pollution and also avoids introduction of new impurities, thereby improving the quality of a product.
Description
Technical field
The present invention relates to a kind of method that waste liquid in the D-pHPG production is carried out recycling, belong to the treatment process that chemical and medicine industry is produced waste liquid.Particularly a kind of method that adopts the left-handed D-pHPG desalination of bipolar membrane electrodialysis technical finesse mother liquor.
Background technology
Left-handed D-pHPG is a kind of white or off-white color crystalline powder, is slightly soluble in water, is soluble in acid or alkaline solution.As important medicine intermediate, the important production technique that is used for synthetic semisynthetic penicillin, cynnematin and beta-lactam semisynthetic antibiotics, still making the important source material of amoxycilline Trihydrate bp, also is the main side chain of cefaparole, general sieve of cephalo etc. simultaneously.The basic technology of producing left-handed D-pHPG is with tosic acid dissolving D-pHPG racemic mixture, obtain DL hydroxyphenylglycine tosilate, obtain left-handed after the fractionation and D-pHPG tosilate two kinds of configurations of dextrorotation, obtain left-handed D-pHPG precipitation with the mineral alkali neutralization then, supernatant liquor is the solution of p-methyl benzenesulfonic acid sodium, general existing production technique is by recycling after being acidified with acid, but acidization can generate inorganic salt simultaneously, impurity is easily introduced in the sepn process of material, also need to consume a large amount of acid simultaneously and carry out acidifying, not only wasted valuable resource and also environment has been produced pollution.
The bipolar membrane electrodialysis technology is a kind of novel membrane separation technique, bipolar membrane is a kind of novel ion-exchange composite membranes, it is composited by cationic exchange layer and anionresin layer usually, the centre is the hydrophilic interface layer, bipolar membrane can separate the water into H+ and OH-under the DC electric field effect, can be respectively combine, generate corresponding bronsted lowry acids and bases bronsted lowry with the negatively charged ion and the positively charged ion of paratoluenesulfonic acid sodium salt in the treatment solution.Existing one piece of bibliographical information (from web search to, medicine community, chemicals pharmacy forum, be published on March 15th, 2010) " bipolar film electrodialysis method transforms the processing condition research of p-methyl benzenesulfonic acid sodium salt ", the method that this report adopted is not considered the pollution problem of film, has just considered Na in the Utopian p-methyl benzenesulfonic acid sodium solution merely
+Remove, and in actual production process, the Fe in the mother liquor
3+, Ca
2+, Mg
2+Can cause very big pollution to film, reduce the work-ing life of film.CN101759583A discloses a kind of DL-D-pHPG waste recovery new technology, be to add water, reclaimed materials, hydrochloric acid, gac by a certain percentage, add activated carbon decolorizing, filtration after the rising temperature for dissolving, transfer pH value to certain limit with ammoniacal liquor in the mother liquor after filtering, centrifugally obtain qualified D-pHPG.
Summary of the invention
Technical problem to be solved by this invention is, a kind of method that adopts the left-handed D-pHPG desalination of bipolar membrane electrodialysis technical finesse mother liquor is provided, this method can reclaim the valuable material in the mother liquor, can reduce environmental pollution again, can also avoid simultaneously the introducing of new impurity, thereby improve the quality of product.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of method that adopts the left-handed D-pHPG desalination of bipolar membrane electrodialysis technical finesse mother liquor is characterized in that it may further comprise the steps:
1. the preprocessing process of desalination mother liquor: at first with the desalination mother liquor with 0.5～1.5 times of pure water dilution, because variation along with disengaging time, cumulative volume in the salt chamber in the bipolar membrane device (sour chamber) can reduce, form the hypersaturated state of solution and separate out crystal, therefore will dilute the desalination mother liquor.Regulate pH value to 11～12 with NaOH, be heated to 60～65 ℃ then, filter, then filtrate is carried out Ca with Zeo-karb
2+Ion, Mg
2+Ionic removes, thereby reduces the pollution to film greatly; 2. bipolar membrane electrodialysis sepn process: adopt two Room methods to experimentize, it is sour chamber that the desalination mother liquor of handling well is placed the salt chamber, alkali adds pure water in the chamber, and then to splash into weight percent concentration be NaOH solution 1～1.5g of 30%, open pump and rectifier, current control is at 7A ± 0.5A, and current density is at 50mA/cm
3The liquid caustic soda that obtains the alkali chamber after the processing respectively is the resolving agent of NaOH solution (weight percent concentration can be 3%～6%) and salt chamber, resolving agent is tosic acid or o-methyl-benzene sulfonic acid or bromo-camphor sulfonic acid or to ethyl phenenyl azochlorosulfonate acid or phenyl ethyl sulfonic acid or Phenylsulfonic acid or sulphosalicylic acid or an acid dimethyl or sulfonaphthol, resolving agent such as the salt chamber can be tosic acid, and concentration can be 240mg/mL; 3. the recycle of valuable material in the treatment solution: the liquid caustic soda that step obtains in 2. is used for step 1. the accent alkali technology of desalination mother liquor or the activation treatment process of ion exchange resin once more, the resolving agent that obtains (can) be used for the production of left-handed D-pHPG once more.
In the technique scheme, described step 1. in the extension rate of desalination mother liquor can be 0.5, regulate pH value to 11 with NaOH, be heated to 60 ℃ then, filter, with the desalination mother liquor after 0.5 times of the atomic absorption spectrophotometer dilution through this step processing, Fe
3+Concentration is reduced to 3.389mg/kg by the 12.12mg/kg before handling, and removes with Zeo-karb that calcium ions and magnesium ions total amount (summation) is reduced to 0.15mg/kg by original 6mg/kg in the back desalination mother liquor.
The resolving agent of above-mentioned steps described in 3. can obtain solid or directly drop into the salt crust technology that left-handed D-pHPG is used for left-handed D-pHPG once more with its aqueous solution by the concentrating under reduced pressure crystallization.
The left-handed D-pHPG desalination mother liquor of above-mentioned processing can also be a L-Phenylglycine desalination mother liquor.
Method of the present invention adopts transfers alkali and Zeo-karb technology that mother liquor is carried out pre-treatment, and then adopt two Room methods that mother liquor is handled, utilize the characteristics of bipolar membrane electrodialysis technology, the bipolar membrane electrodialysis system that bipolar membrane and yin, yang ion-exchange membrane are combined, can be under the situation of not introducing new component, salt in the mother liquor is converted into useful bronsted lowry acids and bases bronsted lowry is used for production technique once more, reduced desalination pollution on the environment after the acidifying.It makes various components reach closed cycle like this, can not cause the loss of material.Method of the present invention had both reclaimed the valuable material in the mother liquor, had reduced environmental pollution again, had also avoided the introducing of new impurity simultaneously, thus improve the quality of product, found comparatively ideal operational path.
Embodiment
The present invention is further described below in conjunction with embodiment:
Embodiment 1: the method for the left-handed D-pHPG desalination of employing bipolar membrane electrodialysis of the present invention technical finesse mother liquor, and it may further comprise the steps:
1. the preprocessing process of desalination mother liquor: at first with the desalination mother liquor with 0.5 times of pure water dilution, because variation along with disengaging time, cumulative volume in the salt chamber in the bipolar membrane device (sour chamber) can reduce, and forms the hypersaturated state of solution and separates out crystal, therefore will dilute the desalination mother liquor.Regulate pH value to 11 with NaOH, be heated to 60 ℃ then, filter, with the desalination mother liquor after 0.5 times of the atomic absorption spectrophotometer dilution through this step processing, Fe
3+Concentration has been reduced to 3.389mg/kg by the 12.12mg/kg before handling, and then filtrate is carried out Ca with Zeo-karb
2+Ion, Mg
2+Ionic removes, and calcium ions and magnesium ions total amount (summation) has been reduced to 0.15mg/kg by original 6mg/kg in the processing back desalination mother liquor, greatly reduces the pollution to film.2. bipolar membrane electrodialysis sepn process: adopt two Room methods to experimentize, it is sour chamber that the desalination mother liquor of handling well is placed the salt chamber, alkali adds pure water in the chamber, and then to splash into weight percent concentration be 30% NaOH solution 1g, open pump and rectifier, current control is at 7A ± 0.5A, and current density is at 50mA/cm
3, the liquid caustic soda that obtains the alkali chamber after the processing respectively is the resolving agent tosic acid (concentration can be 240mg/mL) of NaOH solution (weight percent concentration can be 3%～6%) and salt chamber.3. the recycle of valuable material in the treatment solution: the liquid caustic soda that step obtains in 2. is used for step 1. the accent alkali technology of desalination mother liquor or the activation treatment process of ion exchange resin once more, and the resolving agent tosic acid that obtains can be used for the production of left-handed D-pHPG once more.Be that described resolving agent tosic acid obtains solid or directly drops into the salt crust technology that left-handed D-pHPG is used for left-handed D-pHPG once more with its aqueous solution by the concentrating under reduced pressure crystallization.
Embodiment 2: the method for the left-handed D-pHPG desalination of employing bipolar membrane electrodialysis of the present invention technical finesse mother liquor, it may further comprise the steps: the 1. preprocessing process of desalination mother liquor: at first measure desalination mother liquor 600mL, add pure water 900mL (diluting 1.5 times), regulate desalination mother liquor pH value to 11 with NaOH then, be heated to 60 ℃ (or 65 ℃), filter, then filtrate is crossed post and remove Ca in the mother liquor
2+And Mg
2+2. bipolar membrane electrodialysis sepn process: adopt two Room methods to carry out the recovery of tosic acid in the mother liquor, the desalination mother liquor of handling well is joined in the salt chamber (sour chamber), add pure water 500mL in the alkali chamber, splash into weight percent concentration again and be 30% NaOH solution 1g (perhaps 1.5g), to reduce the energy consumption at separation initial stage, open pump, rectifier, control current is at 7A ± 0.5A, and current density is about 50mA/cm
2The liquid caustic soda that obtains the alkali chamber after the processing respectively is the resolving agent tosic acid of NaOH solution and salt chamber.The every 20min sampling analysis of experimentation, the result shows that the mother liquor of 1.5 times of dilutions separates, when separating 200min, capacity usage ratio is the highest, at this moment Na in the mother liquor
+Decreasing ratio has reached 78%, and energy consumption is 2800kwh/t, and alkali content reaches 3.5% in the alkali chamber.3. the recycle of valuable material in the treatment solution: the liquid caustic soda that step obtains in 2. is used for step 1. the accent alkali technology of desalination mother liquor or the activation treatment process of ion exchange resin once more, and the resolving agent tosic acid that obtains can be used for the production of left-handed D-pHPG once more.Be that described resolving agent tosic acid obtains solid or directly drops into the salt crust technology that left-handed D-pHPG is used for left-handed D-pHPG once more with its aqueous solution by the concentrating under reduced pressure crystallization.
Embodiment 3: the method for the left-handed D-pHPG desalination of employing bipolar membrane electrodialysis of the present invention technical finesse mother liquor, it may further comprise the steps: the 1. preprocessing process of desalination mother liquor: at first measure desalination mother liquor 600mL, add pure water 300mL (diluting 0.5 times), regulate desalination mother liquor pH value to 12 with NaOH then, be heated to 60 ℃, filter, then filtrate is crossed post and remove Ca in the mother liquor
2+And Mg
2+2. bipolar membrane electrodialysis sepn process: adopt two Room methods to carry out the recovery of tosic acid in the mother liquor, the desalination mother liquor of handling well is joined in the salt chamber (sour chamber), add pure water 500mL in the alkali chamber, splash into weight percent concentration again and be 30% NaOH solution 1g (perhaps 1.2g), to reduce the energy consumption at separation initial stage, open pump, rectifier, control current is at 7A ± 0.5A, and current density is about 50mA/cm
2The liquid caustic soda that obtains the alkali chamber after the processing respectively is the resolving agent tosic acid of NaOH solution and salt chamber.The every 20min sampling analysis of experimentation, the result shows that the mother liquor of 0.5 times of dilution separates, when separating 160min, capacity usage ratio is the highest, at this moment Na in the mother liquor
+Decreasing ratio has reached 85%, and energy consumption is 3200kwh/t, and NaOH content reaches 4.0% in the alkali chamber.3. the recycle of valuable material in the treatment solution: the liquid caustic soda that step obtains in 2. is used for step 1. the accent alkali technology of desalination mother liquor or the activation treatment process of ion exchange resin once more, and the resolving agent tosic acid that obtains can be used for the production of left-handed D-pHPG once more.Be that described resolving agent tosic acid obtains solid or directly drops into the salt crust technology that left-handed D-pHPG is used for left-handed D-pHPG once more with its aqueous solution by the concentrating under reduced pressure crystallization.
The resolving agent that obtains among the foregoing description 1, embodiment 2, the embodiment 3 can also for o-methyl-benzene sulfonic acid or bromo-camphor sulfonic acid or to ethyl phenenyl azochlorosulfonate acid or phenyl ethyl sulfonic acid or Phenylsulfonic acid or sulphosalicylic acid or an acid dimethyl or sulfonaphthol, the data among these three embodiment be constant.
Embodiment 4: the method for the left-handed D-pHPG desalination of employing bipolar membrane electrodialysis of the present invention technical finesse mother liquor, it may further comprise the steps: the 1. preprocessing process of desalination mother liquor: at first with the desalination mother liquor with 0.5 times of pure water dilution, because variation along with disengaging time, cumulative volume in the salt chamber in the bipolar membrane device (sour chamber) can reduce, form the hypersaturated state of solution and separate out crystal, therefore will dilute the desalination mother liquor.Regulate pH value to 11 with NaOH, be heated to 60 ℃ then, filter, with the desalination mother liquor after 0.5 times of the atomic absorption spectrophotometer dilution through this step processing, Fe
3+Concentration has been reduced to 3.389mg/kg by the 12.12mg/kg before handling, and then filtrate is carried out Ca with Zeo-karb
2+Ion, Mg
2+Ionic removes, and calcium ions and magnesium ions total amount (summation) has been reduced to 0.15mg/kg by original 6mg/kg in the processing back desalination mother liquor, greatly reduces the pollution to film.2. bipolar membrane electrodialysis sepn process: adopt two Room methods to experimentize, it is sour chamber that the desalination mother liquor of handling well is placed the salt chamber, alkali adds pure water in the chamber, and then to splash into weight percent concentration be 30% NaOH solution 1g, open pump and rectifier, current control is at 7A ± 0.5A, and current density is at 50mA/cm
3The liquid caustic soda that obtains the alkali chamber after the processing respectively is the resolving agent of NaOH solution (weight percent concentration can be 3%～6%) and salt chamber, and resolving agent is o-methyl-benzene sulfonic acid or bromo-camphor sulfonic acid or to ethyl phenenyl azochlorosulfonate acid or phenyl ethyl sulfonic acid or Phenylsulfonic acid or sulphosalicylic acid or an acid dimethyl or sulfonaphthol or tosic acid.3. the recycle of valuable material in the treatment solution: the liquid caustic soda that step obtains in 2. is used for step 1. the accent alkali technology of desalination mother liquor or the activation treatment process of ion exchange resin once more, and the resolving agent that obtains can be used for the production of left-handed D-pHPG once more.Be that described resolving agent obtains solid or directly drops into the salt crust technology that left-handed D-pHPG is used for left-handed D-pHPG once more with its aqueous solution by the concentrating under reduced pressure crystallization.
Embodiment 5: the method for the left-handed D-pHPG desalination of employing bipolar membrane electrodialysis of the present invention technical finesse mother liquor, it may further comprise the steps: the 1. preprocessing process of desalination mother liquor: at first measure desalination mother liquor 600mL, add pure water 900mL (diluting 1.5 times), regulate desalination mother liquor pH value to 11 with NaOH then, be heated to 65 ℃ (or 60 ℃), filter, then filtrate is crossed post and remove Ca in the mother liquor
2+And Mg
2+2. bipolar membrane electrodialysis sepn process: adopt two Room methods to carry out the recovery of tosic acid in the mother liquor, the desalination mother liquor of handling well is joined in the salt chamber (sour chamber), add pure water 500mL in the alkali chamber, splash into weight percent concentration again and be 30% NaOH solution 1.5g (perhaps 1g), to reduce the energy consumption at separation initial stage, open pump, rectifier, control current is at 7A ± 0.5A, and current density is about 50mA/cm
2The liquid caustic soda that obtains the alkali chamber after the processing respectively is the resolving agent of NaOH solution and salt chamber, and resolving agent is o-methyl-benzene sulfonic acid or bromo-camphor sulfonic acid or to ethyl phenenyl azochlorosulfonate acid or phenyl ethyl sulfonic acid or Phenylsulfonic acid or sulphosalicylic acid or an acid dimethyl or sulfonaphthol or tosic acid.The every 20min sampling analysis of experimentation, the result shows that the mother liquor of 1.5 times of dilutions separates, when separating 200min, capacity usage ratio is the highest, at this moment Na in the mother liquor
+Decreasing ratio has reached 78%, and energy consumption is 2800kwh/t, and alkali content reaches 3.5% in the alkali chamber.3. the recycle of valuable material in the treatment solution: the liquid caustic soda that step obtains in 2. is used for step 1. the accent alkali technology of desalination mother liquor or the activation treatment process of ion exchange resin once more, and the resolving agent that obtains can be used for the production of left-handed D-pHPG once more.Be that described resolving agent obtains solid or directly drops into the salt crust technology that left-handed D-pHPG is used for left-handed D-pHPG once more with its aqueous solution by the concentrating under reduced pressure crystallization.
Embodiment 6: the method for the left-handed D-pHPG desalination of employing bipolar membrane electrodialysis of the present invention technical finesse mother liquor, it may further comprise the steps: the 1. preprocessing process of desalination mother liquor: at first measure desalination mother liquor 600mL, add pure water 300mL (diluting 0.5 times), regulate desalination mother liquor pH value to 12 with NaOH then, be heated to 60 ℃, filter, then filtrate is crossed post and remove Ca in the mother liquor
2+And Mg
2+2. bipolar membrane electrodialysis sepn process: adopt two Room methods to carry out the recovery of tosic acid in the mother liquor, the desalination mother liquor of handling well is joined in the salt chamber (sour chamber), add pure water 500mL in the alkali chamber, splash into weight percent concentration again and be 30% NaOH solution 1.2g (perhaps 1g), to reduce the energy consumption at separation initial stage, open pump, rectifier, control current is at 7A ± 0.5A, and current density is about 50mA/cm
2The liquid caustic soda that obtains the alkali chamber after the processing respectively is the resolving agent of NaOH solution and salt chamber, and resolving agent is o-methyl-benzene sulfonic acid or bromo-camphor sulfonic acid or to ethyl phenenyl azochlorosulfonate acid or phenyl ethyl sulfonic acid or Phenylsulfonic acid or sulphosalicylic acid or an acid dimethyl or sulfonaphthol or tosic acid.The every 20min sampling analysis of experimentation, the result shows that the mother liquor of 0.5 times of dilution separates, when separating 160min, capacity usage ratio is the highest, at this moment Na in the mother liquor
+Decreasing ratio has reached 85%, and energy consumption is 3200kwh/t, and NaOH content reaches 4.0% in the alkali chamber.3. the recycle of valuable material in the treatment solution: the liquid caustic soda that step obtains in 2. is used for step 1. the accent alkali technology of desalination mother liquor or the activation treatment process of ion exchange resin once more, and the resolving agent that obtains can be used for the production of left-handed D-pHPG once more.Be that described resolving agent obtains solid or directly drops into the salt crust technology that left-handed D-pHPG is used for left-handed D-pHPG once more with its aqueous solution by the concentrating under reduced pressure crystallization.
Used Zeo-karb can adopt 001*7 type strongly acidic styrene type cation exchange resin in the various embodiments described above, can also adopt the Zeo-karb of other model certainly.
Claims (3)
1. method that adopts the left-handed D-pHPG desalination of bipolar membrane electrodialysis technical finesse mother liquor is characterized in that it may further comprise the steps:
1. the preprocessing process of desalination mother liquor: at first with the desalination mother liquor with 0.5～1.5 times of pure water dilution, regulate pH value to 11～12 with NaOH, be heated to 60～65 ℃ then, filtration is carried out Ca with filtrate with Zeo-karb then
2+Ion, Mg
2+Ionic removes;
2. bipolar membrane electrodialysis sepn process: adopt two Room methods to experimentize, it is sour chamber that the desalination mother liquor of handling well is placed the salt chamber, alkali adds pure water in the chamber, and then to splash into weight percent concentration be NaOH solution 1～1.5g of 30%, open pump and rectifier, current control is at 7A ± 0.5A, and current density is at 50mA/cm
3The liquid caustic soda that obtains the alkali chamber after the processing respectively is the resolving agent of NaOH solution and salt chamber, and resolving agent is tosic acid or o-methyl-benzene sulfonic acid or bromo-camphor sulfonic acid or to ethyl phenenyl azochlorosulfonate acid or phenyl ethyl sulfonic acid or Phenylsulfonic acid or sulphosalicylic acid or an acid dimethyl or sulfonaphthol;
3. the recycle of valuable material in the treatment solution: the liquid caustic soda that step obtains in 2. is used for step 1. the accent alkali technology of desalination mother liquor or the activation treatment process of ion exchange resin once more, and the resolving agent that obtains is used for the production of left-handed D-pHPG once more.
2. the method for the left-handed D-pHPG desalination of employing bipolar membrane electrodialysis according to claim 1 technical finesse mother liquor, it is characterized in that the extension rate of desalination mother liquor was 0.5 during above-mentioned steps 1., regulate pH value to 11 with NaOH, be heated to 60 ℃ then, filter, handle Fe with the desalination mother liquor after 0.5 times of the atomic absorption spectrophotometer dilution through this step
3+Concentration is reduced to 3.389mg/kg by the 12.12mg/kg before handling, and removes with Zeo-karb that the calcium ions and magnesium ions total amount is reduced to 0.15mg/kg by original 6mg/kg in the back desalination mother liquor.
3. the method for the left-handed D-pHPG desalination of employing bipolar membrane electrodialysis according to claim 1 technical finesse mother liquor is characterized in that the resolving agent described in above-mentioned steps 3. obtains solid or directly drops into the salt crust technology that left-handed D-pHPG is used for left-handed D-pHPG once more with its aqueous solution by the concentrating under reduced pressure crystallization.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003830A (en) * | 2014-01-27 | 2014-08-27 | 重庆紫光化工股份有限公司 | Method for separating amino acid and iminodicarboxylic acid from aqueous solution of alkali metal salt of amino acid |
| CN104529801A (en) * | 2014-12-31 | 2015-04-22 | 河南新天地药业股份有限公司 | Synthetic method for p-hydroxyphenyl glycine |
| CN105254520A (en) * | 2015-10-12 | 2016-01-20 | 国药集团威奇达药业有限公司 | Recovery method for D-hydroxyphenylglycine in amoxicillin crystallization mother liquor of enzymatic synthesis |
| CN105646291A (en) * | 2015-12-28 | 2016-06-08 | 江苏远洋药业股份有限公司 | Method for separating and purifying creatine mother liquor |
| CN110776387A (en) * | 2019-09-26 | 2020-02-11 | 四川绵竹新华化工有限责任公司 | Device for preparing salt-free compound amino acid by using cystine production waste liquid |
| CN111269076A (en) * | 2020-03-12 | 2020-06-12 | 山东钧睿科技服务有限公司 | Recovery treatment process for β -lactam antibiotic centrifugal mother liquor synthesized by enzyme method |
| CN112479909A (en) * | 2020-12-02 | 2021-03-12 | 河南大学 | Extraction and recovery method of p-hydroxyphenylglycine |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1201710A (en) * | 1997-01-23 | 1998-12-16 | 阿切尔丹尼尔斯密德兰公司 | Apparatus and process for electrodialysis of salts |
-
2010
- 2010-09-01 CN CN2010102690253A patent/CN101967106A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1201710A (en) * | 1997-01-23 | 1998-12-16 | 阿切尔丹尼尔斯密德兰公司 | Apparatus and process for electrodialysis of salts |
Non-Patent Citations (1)
| Title |
|---|
| 王军等: "双极性膜电渗析法转化对甲基苯磺酸钠盐的工艺条件研究", 《膜科学与技术》, vol. 25, no. 1, 28 February 2005 (2005-02-28) * |
Cited By (10)
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| CN104003830A (en) * | 2014-01-27 | 2014-08-27 | 重庆紫光化工股份有限公司 | Method for separating amino acid and iminodicarboxylic acid from aqueous solution of alkali metal salt of amino acid |
| CN104003830B (en) * | 2014-01-27 | 2016-08-17 | 重庆紫光化工股份有限公司 | Amino acid separation and the method for iminodicarboxylic acid from the aqueous solution of amino acid whose alkali metal salt |
| CN104529801A (en) * | 2014-12-31 | 2015-04-22 | 河南新天地药业股份有限公司 | Synthetic method for p-hydroxyphenyl glycine |
| CN105254520A (en) * | 2015-10-12 | 2016-01-20 | 国药集团威奇达药业有限公司 | Recovery method for D-hydroxyphenylglycine in amoxicillin crystallization mother liquor of enzymatic synthesis |
| CN105254520B (en) * | 2015-10-12 | 2017-07-07 | 国药集团威奇达药业有限公司 | The recovery method of D D-pHPGs in the crystalline mother solution of enzymatic clarification Amoxicillin |
| CN105646291A (en) * | 2015-12-28 | 2016-06-08 | 江苏远洋药业股份有限公司 | Method for separating and purifying creatine mother liquor |
| CN110776387A (en) * | 2019-09-26 | 2020-02-11 | 四川绵竹新华化工有限责任公司 | Device for preparing salt-free compound amino acid by using cystine production waste liquid |
| CN111269076A (en) * | 2020-03-12 | 2020-06-12 | 山东钧睿科技服务有限公司 | Recovery treatment process for β -lactam antibiotic centrifugal mother liquor synthesized by enzyme method |
| CN112479909A (en) * | 2020-12-02 | 2021-03-12 | 河南大学 | Extraction and recovery method of p-hydroxyphenylglycine |
| CN112479909B (en) * | 2020-12-02 | 2021-10-12 | 河南大学 | Extraction and recovery method of p-hydroxyphenylglycine |
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