CN105838771B - Amoxicillin crystalline mother solution recovery process - Google Patents
Amoxicillin crystalline mother solution recovery process Download PDFInfo
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- CN105838771B CN105838771B CN201510023940.7A CN201510023940A CN105838771B CN 105838771 B CN105838771 B CN 105838771B CN 201510023940 A CN201510023940 A CN 201510023940A CN 105838771 B CN105838771 B CN 105838771B
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Abstract
A kind of Amoxicillin crystalline mother solution recovery process, including enzymatic hydrolysis, filtering, electrodialysis, concentration, isoelectric point crystallization.Technique of the invention realizes the recycling of HPG, 6-APA, reduces the production cost of enzyme process preparation Amoxicillin；The recycling for realizing inorganic salts simultaneously, to more environment-friendly.
Description
Technical field
The present invention relates to three-protection design more particularly to a kind of Amoxicillin crystalline mother solution recovery process.
Background technique
Amoxicillin also known as amoxycillin, chemical name are (2S, 5R, 6R) -3,3- dimethyl -6- ((R)-(-) -
2- methyl -2- (4- p-hydroxybenzene) acetylamino) -7- oxo -4- thia -1- azabicyclo (3.2.0) heptane-two-formic acid
Trihydrate.For beta-lactam broad-spectrum antibiotic, synthesized by inhibition bacteria cell wall, to pneumococcus, hemolytic hammer
The Gram-negative bacterias such as the gram-positive bacterias such as bacterium and escherichia coli, detection of Salmonella have good antibacterial activity.Usual Ah
There are two types of methods, respectively chemical synthesis and Enzyme optrode for the synthesis of Amdinocillin.Enzymatic clarification is parent nucleus 6- aminopenicillanic
Sour (6-APA) is completed under penicillin acylated enzyme catalysis effect with active side chain p-hydroxybenzene glycine methyl ester.It reacts item
Part is mild, and process flow is short, avoids the use of organic solvent and chemical reagent, and whole process is environmentally protective.Its product simultaneously
Quality is better than chemical synthesis.
During using enzymatic clarification Amoxicillin, for the conversion ratio for improving 6-APA, often add during feeding intake
Enter excessive active side chain.And during the reaction, amount of activated side chain, such as: D-para hydroxybenzene glycine methyl ester, in penicillin
Nonactive side chain D-pHPG (HPG) is hydrolyzed under the action of acylase.Therefore in enzymatic clarification Amoxicillin
Crystalline mother solution in, containing nonactive side chain HPG, active side chain D-para hydroxybenzene glycine methyl ester, Amoxicillin and 6- amino
Penicillanic acid.In addition to this still containing a large amount of inorganic salinity.In the enzymatic clarification technique of Amoxicillin, how benefit is effectively recycled
With the mentioned component in mother liquor, become the important topic of enzymatic clarification Amoxicillin.
CN1207742A discloses a kind of crystalline mother solution recycling beta-lactam core of beta-lactam antibiotic enzymatic clarification
Technique.It utilizes the hydrolysis enzyme viability that has in different condition of acylase, by crystalline mother solution active surveyor's chain and β-it is interior
The hydrolysis of amides antibiotic, so that substance classes are reduced in system, the presence of only nonactive side chain and beta-lactam core, thus
Crystallization difficulty is reduced, realizes the recycling of beta-lactam core.
But since synthesis and the change of purifying process, the above method cannot achieve direct recycling.CN102392060 is disclosed
A kind of technique using effective component in nanofiltration recycling enzymatic amoxicillin mother liquor.It uses PA ase to hydrolyze
Active side chain and Amoxicillin in crystalline mother solution, so that in mother liquor system based on HPG and 6-APA.But due to not up to
Crystallisation concentration is concentrated using nanofiltration, until HPG concentration is promoted, obtains solid HPG by reconciling PH.Post mother liquor is crystallized as dissolution
6-APA solvent, is back to use in technique.
But with the improvement of Amoxicillin synthesis technology and extraction process, active side chain and Amoxicillin contains in mother liquor
Amount further decreases, and inorganic salts relative increase therein, using above-mentioned technique, due to nanofiltration be difficult to it is dense needed for being concentrated to crystallization
Degree, leads to the difficulty of disposing mother liquor.
Summary of the invention
The purpose of the present invention provides a kind of Amoxicillin crystallization exactly in order to solve the above-mentioned problems of the prior art
Mother liquid recovery process.
In order to achieve the above object, the invention adopts the following technical scheme: a kind of Amoxicillin crystalline mother solution recycling work
Skill, comprising the following steps:
A, it digests
PA ase is added in the crystalline mother solution of Amoxicillin, by mother liquor Amoxicillin and active side chain water
Solution generates 6-APA and nonactive side chain HPG；
B, it filters
It will be filtered by the mother liquor of enzymatic hydrolysis by millipore filter, and remove suspended particulate therein, under filtered solution enters
One step, the enzyme reuse of retention；
C, electrodialysis
Filtered solution obtained by step B is imported into electrodialysis system and carries out electrodialysis process, obtains fresh water and concentrated water, HPG, 6-
APA and unhydrolysed Amoxicillin and active side chain stay in fresh water, and the ion in liquid enters in concentrated water, realize ion with
The separation of organic matter, while realizing the concentration of ion；Fresh water enters next step, and concentrated water imports evaporator and is evaporated concentration,
Obtain the crystallization of inorganic salts；
D, it is concentrated
Fresh water obtained by step C is imported film concentration systems to be concentrated, filter liquor and concentrate are obtained, under concentrate enters
One step；
E, isoelectric point crystallization
By concentrate inorganic acid for adjusting pH to HPG isoelectric point obtained by step D, HPG crystallization is precipitated, and filtering obtains HPG knot
Crystalline substance recycles HPG, crystalline mother solution reuse.
Filtered solution obtained by step B imports before electrodialysis system, and adjusting pH is 5-9.
Filtered solution obtained by step B imports before electrodialysis system, first passes through the pigment in film separation system removal filtered solution
And colloid.
Fresh water obtained by step C imports before film concentration systems, first pass through pigment in film separation system removal filtered solution and
Colloid.
The pore size filter of the millipore filter filter core is 1 micron -50 microns.
Fresh water obtained by step C imports before film concentration systems, and adjusting pH is 9-10.
The film that the film concentration systems use is greater than 98% to the rejection of magnesium sulfate, or big to the rejection of sodium chloride
In 90%, at 10-40 DEG C, operating pressure is controlled in 1-4Mpa for operation temperature control.
The molecular weight that shuts off of film used by the film separation system is 800-10000, and operation temperature is controlled in 10-40
DEG C, operating pressure is controlled in 0.1-2Mpa.
Pole water in the electrodialysis system uses 0.5%~1.0% sodium-chloride water solution, or purifies by electrodialysis
Concentrated water, initial concentrated water slot using tap water or softened water or pure water or above-mentioned steps D filter liquor.
The electrodialysis system is in such a way that multi-machine parallel connection or multimachine series connection or multi-machine parallel connection series connection combine, to mention
The high mesohalobic concentration of concentrated water.
Electrodialysis system involved in the present invention includes the power supply, delivery pump and electrodialysis for becoming direct current from alternating current
Device.The main component of electric dialyzator is anion-exchange membrane (abbreviation cavity block), cation-exchange membrane (abbreviation anode membrane), partition and electricity
Pole.The compartment that partition is constituted is the channel that liquid stream is passed through.The compartment that material passes through is desalting chamber, and the compartment that concentrated water is passed through is concentration
Room.The salinity of material is removed, while salinity is concentrated in concentrated water room.Usual cavity block, anode membrane and concentrated water and fresh water every
Plate is alternately arranged, and just forms an electric dialyzator plus a pair of electrodes.
Amberplex is the film made of high molecular material to ion with selective penetrated property.Main point of cation
Two kinds of exchange membrane (CM, abbreviation anode membrane) and anion-exchange membrane (AM, abbreviation cavity block).Anode membrane has negative electricity due to the fixed base band of membrane body
Charge ions may be selected through cation；Cavity block may be selected to penetrate anion since the fixed base band of membrane body has positive charge ion.Sun
Film is known as the selective penetrated property of film through the performance of anion through cation, cavity block.
The most basic working cell of electric dialyzator is known as film pair.One film is to one diluting compartment of composition and an enriched chamber.
Under the action of DC electric field, using the selective penetrated property of amberplex, cation permeable anode membrane, anion-permeable cavity block,
The ion of desalting chamber is migrated to enriched chamber, the ion of enriched chamber due to film selective penetrated property and migrated without normal direction desalting chamber.This
The salt concentration of sample diluting compartment gradually decreases, and the salt concentration of adjacent enriched chamber accordingly gradually rises.
Mother liquor is pre-processed using Millipore filtration techniques in this technique.By pretreatment, enzyme hydrolyzate can be removed
In suspended particulate, including immobilized enzyme particle and other suspended matters.
Enter electrodialysis system by pretreated filtered solution.Filtered solution is divided into two parts: concentrated water and fresh water.Wherein side
Chain, 6-APA and unhydrolysed antibiotic and active side chain etc. stay in fresh water, the ion in filtered solution, as sulfate ion,
Chloride ion, sodium ion, ammonium ion etc. enter concentrated water end by film, realize the separation of ion and organic matter under electric drive,
The concentration of ion is realized simultaneously.And the fresh water inorganic salts in fresh water end are removed.And the concentrated water at concentrated water end is gone due to organic matter
Except the overwhelming majority, and pass through initial concentration.The concentrated water enters evaporator and is evaporated concentration, obtains the crystallization of inorganic salts.By
After electrodialysis process, the water outlet at fresh water end is the removal rate of salt in fresh water up to 90% or more.
The fresh water that electrodialysis generates enters film concentration systems after adjusting pH9-10.Under the driving of pressure, water is penetrated, and is formed
Permeate.Organic matter therein includes that the active side chain of HPG, 6-APA, a small amount of Amoxicillin and non-complete hydrolysis is cut
Stream penetrates film with dampening, and concentration increases in the liquid that shuts off, and obtains the concentrate of film.HPG concentration reaches 50mg/ml- in concentrate
65mg/ml。
Technique of the invention realizes the recycling of HPG, 6-APA, reduces being produced into for enzyme process preparation Amoxicillin
This；The recycling of inorganic salts and the recycling of water are realized simultaneously, to more environment-friendly.
Specific embodiment
Embodiment 1
The crystalline mother solution 100L of Amoxicillin contains HPG1-13mg/ml, the sweet ammonia of Amoxicillin 1-5mg/ml, D- para hydroxybenzene
Sour methyl esters 0-5mg/ml, 6 aminopenicillanic acid 0-5mg/ml, conductivity 10-40ms/cm.PA ase is added, in pH8-
Under the conditions of 9, Amoxicillin and D-para hydroxybenzene glycine methyl ester is enabled to be hydrolyzed into HPG and 6-APA.Enzymolysis liquid warp after the completion of hydrolysis
Millipore filter filtering, filtrate are stored in tank.The filtrate tune pH to 6-8.5, is pumped up into electrodialysis system.At electrodialysis
Reason, obtains fresh water 85-98L, conductivity≤2ms/cm.Concentrated water conductivity reaches 110-180ms/cm.It is dense that the fresh water enters film
Compression system.
It is above-mentioned to pass through electrodialytic fresh water, it is pumped up into film concentration systems, controls pressure 1.5-40MPa, temperature 1-40 takes the photograph
Family name's degree, water penetrate film, and HPG and 6-APA etc. are concentrated.It is concentrated into 50mg/ml to HPG, concentrate is collected and enters next step.
The concentrate being concentrated through film, slow acid adding tune pH to 5 or so, HPG are precipitated from mother liquor in the form crystallized.Through dividing
From, obtain HPG crystallization.The crystallization purity reaches 95%.
Embodiment 2
The crystalline mother solution 100L of Amoxicillin contains HPG2.3mg/ml, the sweet ammonia of Amoxicillin 2.1mg/ml, D- para hydroxybenzene
Sour methyl esters 0.8mg/ml, 6 aminopenicillanic acid 0.6mg/ml, conductivity 40ms/cm.PA ase is added, in pH8-9 item
Under part, Amoxicillin and D-para hydroxybenzene glycine methyl ester is enabled to be hydrolyzed into HPG and 6-APA.Enzymolysis liquid after the completion of hydrolysis is through micro-
The filtering of hole filter, filtrate are stored in tank.The filtrate tune pH to 6-8.5, is pumped up into electrodialysis system.By electrodialysis, obtain
To fresh water 90L, conductivity≤2ms/cm.Concentrated water conductivity reaches 110ms/cm.Fresh water enters film concentration systems.
Above-mentioned fresh water adjusts PH9.1-9.3, is pumped up into film concentration systems, controls pressure 1.5-40MPa, temperature 1-40 takes the photograph
Family name's degree, water penetrate film, and HPG and 6-APA etc. are concentrated.It is concentrated into 60-65mg/ml to HPG, concentrate is collected and enters next step
Suddenly.
The concentrate being concentrated through film, slow acid adding tune pH to 5 or so, HPG are precipitated from mother liquor in the form crystallized.Through dividing
From, obtain HPG crystallization.The crystallization purity reaches 95%.Crystallization yield reaches 80-90%.
Embodiment 3:
By the electrodialysis fresh water in embodiment 2, enter film separation system through pump.Use filtering accuracy for the molecular weight that shuts off
The film of 800-2500 controls pressure 1-3Mpa, and 1-40 degrees Celsius of temperature, HPG and 6-APA etc. penetrate film, and pigment colloid etc. is cut
Stream.A small amount of water is added when terminal in concentrate end, the films of dialysing such as the HPG and 6-APA at concentrate end will be deposited in, to improve
The rate of recovery.Permeate is obtained to be concentrated and crystallize through film concentration systems again.Improved technique obtains HPG purity and increases,
Reach 96%, coloration reduces.Crystalline mother solution coloration reduces simultaneously, and advantageous 6-APA is recycled.
Embodiment 4:
, by the filtrate of enzymatic hydrolysis and filtering, film separation system will be directly entered through pump in embodiment 2.Use filtering accuracy for
Shut off the film of molecular weight 800-2500, controls pressure 1-3Mpa, 1-40 degrees Celsius of temperature, HPG and 6-APA etc. penetrate film, pigment
Colloid etc. is trapped.A small amount of water is added when terminal in concentrate end, the HPG and 6-APA etc. that are deposited in concentrate end were dialysed
Film, to improve the rate of recovery.It obtains permeate and enters electrodialysis system and subsequent step.Realize same technological effect.
Embodiment 5:
The crystalline mother solution after HPG is recycled in embodiment 1, wherein HPG20-30mg/ml, 6-APA 7-10mg/ml, conductivity
Greater than 30ms/cm.After the crystalline mother solution enters electrodialysis system progress desalination, 1 subsequent step of embodiment is repeated, is further recycled
HPG therein.
Claims (7)
1. a kind of Amoxicillin crystalline mother solution recovery process, which comprises the following steps:
A, it digests
PA ase is added in the crystalline mother solution of Amoxicillin, by mother liquor Amoxicillin and active side-chain hydrolysis, it is raw
At 6-APA and nonactive side chain HPG；
B, it filters
It will be filtered by the mother liquor of enzymatic hydrolysis by millipore filter, and remove suspended particulate therein, filtered solution enters in next step
Suddenly, the enzyme reuse of retention；
C, electrodialysis
Filtered solution obtained by step B is imported into electrodialysis system and carries out electrodialysis process, obtains fresh water and concentrated water, HPG, 6-APA with
And unhydrolysed Amoxicillin and active side chain stay in fresh water, the ion in liquid enters in concentrated water, realize ion with it is organic
The separation of object, while realizing the concentration of ion；Fresh water enters next step, and concentrated water imports evaporator and is evaporated concentration, obtains
The crystallization of inorganic salts；
D, it is concentrated
Fresh water obtained by step C is imported film concentration systems to be concentrated, obtains filter liquor and concentrate, concentrate enters in next step
Suddenly；
E, isoelectric point crystallization
By concentrate inorganic acid for adjusting pH to HPG isoelectric point obtained by step D, HPG crystallization is precipitated, and filtering obtains HPG crystallization,
Recycle HPG, crystalline mother solution reuse；
Filtered solution obtained by step B imports before electrodialysis system, first passes through pigment and glue in film separation system removal filtered solution
Body；
Fresh water obtained by step C imports before film concentration systems, first passes through pigment and colloid in film separation system removal filtered solution；
Pole water in the electrodialysis system uses 0.5%~1.0% sodium-chloride water solution, or by the dense of electrodialysis purifying
Water, initial concentrated water slot use the filter liquor of tap water or softened water or pure water or above-mentioned steps D.
2. crystalline mother solution recovery process in Amoxicillin according to claim 1, it is characterised in that: filtered solution obtained by step B
It imports before electrodialysis system, adjusting pH is 5-9.
3. crystalline mother solution recovery process in Amoxicillin according to claim 1, it is characterised in that: the millipore filter filter
The pore size filter of core is 1 micron -50 microns.
4. crystalline mother solution recovery process in Amoxicillin according to claim 1, it is characterised in that: fresh water obtained by step C is led
Before entering film concentration systems, adjusting pH is 9-10.
5. crystalline mother solution recovery process in Amoxicillin according to claim 1, it is characterised in that: the film concentration systems are adopted
Film is greater than 98% to the rejection of magnesium sulfate, or is greater than 90% to the rejection of sodium chloride, and operation temperature is controlled in 10-
40 DEG C, operating pressure is controlled in 1-4Mpa.
6. crystalline mother solution recovery process in Amoxicillin according to claim 1, it is characterised in that: the film separation system institute
The molecular weight that shuts off of the film used is 800-10000, and at 10-40 DEG C, operating pressure is controlled in 0.1-2Mpa for operation temperature control.
7. crystalline mother solution recovery process in Amoxicillin according to claim 1, it is characterised in that: the electrodialysis system is adopted
The mode combined with multi-machine parallel connection or multimachine series connection or multi-machine parallel connection series connection, to improve the mesohalobic concentration of concentrated water.
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| CN108084206B (en) * | 2018-02-09 | 2019-04-26 | 国药集团威奇达药业有限公司 | The method of ampicillin is recycled from the mother liquor of enzymatic clarification ampicillin |
| 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 |
| CN113214103B (en) * | 2021-04-23 | 2023-05-02 | 内蒙古常盛制药有限公司 | Subsequent treatment method for synthesizing D-p-hydroxyphenylglycine by using enzymatic method |
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| CN1522997A (en) * | 2003-02-21 | 2004-08-25 | 清华大学 | Process for desalting 1,3-propylene glycol fermentation liquor by electricity dialysis |
| CN102392060A (en) * | 2011-09-16 | 2012-03-28 | 石药集团中润制药(内蒙古)有限公司 | Recovering method of effective components in amoxicillin enzymatic synthesis mother liquor by utilizing nanofiltration |
| CN102816803A (en) * | 2012-09-10 | 2012-12-12 | 华北制药集团先泰药业有限公司 | Method for recycling active ingredients in amoxicillin mother liquor synthesized by enzymatic method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1522997A (en) * | 2003-02-21 | 2004-08-25 | 清华大学 | Process for desalting 1,3-propylene glycol fermentation liquor by electricity dialysis |
| CN102392060A (en) * | 2011-09-16 | 2012-03-28 | 石药集团中润制药(内蒙古)有限公司 | Recovering method of effective components in amoxicillin enzymatic synthesis mother liquor by utilizing nanofiltration |
| CN102816803A (en) * | 2012-09-10 | 2012-12-12 | 华北制药集团先泰药业有限公司 | Method for recycling active ingredients in amoxicillin mother liquor synthesized by enzymatic method |
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