CN102851332A - Recovery method for D(-)phenylglycine in ampicillin mother liquid by using enzyme method - Google Patents
Recovery method for D(-)phenylglycine in ampicillin mother liquid by using enzyme method Download PDFInfo
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Abstract
The present invention discloses a recovery method for D(-)phenylglycine in an ampicillin mother liquid by using an enzyme method. The method comprises the following steps: carrying out enzyme clearage, filtering with a screen, carrying out ultrafiltration concerntration, carrying out nanofiltration concentration, carrying out decolorization with active carbon, carrying out cooling crystallization, and the like. According to the present invention, the recovery rate is more than 80%, the content of the recovered D(-)phenylglycine is more than 98%, and the recovered D(-)phenylglycine can be directly used as a raw material to be used in industrial production so as to reduce environmental pollution and resource waste. In addition, the recovery method has characteristics of low energy consumption and simple operation, can provide considerable economic benefits for enterprises, and is applicable for industrial production.
Description
Technical field
The invention belongs to medical technical field, relate to a kind of recovery method of medicine preparation process Raw, refer to that specifically enzyme process prepares in the process of Ampicillin Trihydrate, reclaims the method for D (-) phenylglycine from mother liquor.
Background technology
D (-) phenylglycine is called for short D-PG, is a kind of intermediate of synthetic β-lactam antibitics, is mainly used in synthetic Ampicillin Trihydrate and cynnematin series products.Because β-lactam antibitics has broad spectrum antibacterial, and has the advantage that fungicidal activity is strong, toxicity is low, indication extensively reaches determined curative effect, clinical application is extensive, therefore, in the industrial production to the demand of D (-) phenylglycine also in continuous increase.
Synthesizing of Ampicillin Trihydrate mainly adopted enzyme process in the industrial production at present, its operational path is: Phenylglycine methyl ester hydrochloride and 6-amino-penicillanic acid (6-APA) generate the Ampicillin Trihydrate under the katalysis of synthetic enzyme, with suitable screen cloth separate solid enzyme and Ampicillin Trihydrate crude product, the Ampicillin Trihydrate crude product carries out recrystallization with the reaction mother liquor after separating and obtains the Ampicillin Trihydrate finished product.Contain a small amount of Ampicillin Trihydrate, 6-APA, Phenylglycine methyl ester and a large amount of by product D (-) phenylglycines in the recrystallization mother liquor of Ampicillin Trihydrate.
D (-) phenylglycine content is generally at 12.0-20.0g/L in the recrystallization mother liquor of Ampicillin Trihydrate, if as discharging of waste liquid, not only bring pressure to environmental protection treatment, also can increase simultaneously the production cost of Ampicillin Trihydrate, therefore, tackle it and carry out recycling, with environmental contamination reduction and the wasting of resources.But not yet find the method for the recovery of D (-) phenylglycine in actual production and bibliographical information, this is still a problem demanding prompt solution.
Summary of the invention
The method that the purpose of this invention is to provide D (-) phenylglycine in a kind of recovery enzyme process Ampicillin Trihydrate, the method yield is high, energy consumption is low, simple to operate, products obtained therefrom content is high, solved that enzyme process prepares the irretrievable problem of D (-) phenylglycine contained in the mother liquor of Ampicillin Trihydrate in the industrial production, be suitable in industrial production, using.
In the process of inventor's D (-) phenylglycine recovery method in the mother liquor of research enzyme process Ampicillin Trihydrate, once attempted the pervaporation method of enrichment, but because the method need to be steamed except a large amount of water, energy consumption is high, and reclaim D (-) the phenylglycine content that obtains and can only reach about 93%, content is lower, can not directly utilize, still need and further process to improve its content, so the inventor has abandoned the method.
Technical problem to be solved by this invention is achieved through the following technical solutions.
D(-in the mother liquor of a kind of enzyme process Ampicillin Trihydrate) recovery method of phenylglycine operates as follows:
A. to contain D(-) the enzyme process Ampicillin Trihydrate recrystallization mother liquor of phenylglycine is raw material, adds penicillin G acylase (PGA) and carries out cracking;
B. ammonification water management pH value in the cracking process, temperature control carries out scission reaction, gets lysate;
C. lysate is crossed screen cloth;
D. add ammoniacal liquor in the lysate of crossing behind the screen cloth and regulate the pH value, then carry out ultrafiltration with tubular ultra-filtration membrane;
E. the solution after the ultrafiltration is carried out nanofiltration with the tubular type nanofiltration membrane;
F. the solution after the nanofiltration is added activated carbon decolorizing, salt adding acid for adjusting pH value in the destainer, the cooling growing the grain, suction filtration, washing, drying gets solid D(-) phenylglycine.
Above-mentioned recovery method, D(-in the recrystallization mother liquor of enzyme process Ampicillin Trihydrate among the step a) solubility of phenylglycine is 12.0-20.0g/L.
Above-mentioned recovery method, the add-on of penicillin G acylase adds 0.5KU-1.0KU in 1L Ampicillin Trihydrate recrystallization mother liquor among the step a.
Above-mentioned recovery method, the concentration of ammoniacal liquor is 3mol/L among the step b, adds ammoniacal liquor adjusting pH value and is 8.0-8.5, temperature control 20-28 ℃, the time of scission reaction is 90-120min.
Above-mentioned recovery method, screen cloth is 400 orders among the step c.
Above-mentioned recovery method, the concentration of ammoniacal liquor is 6mol/L in the steps d, adds ammoniacal liquor adjusting pH value and is 9.0-9.5.
Above-mentioned recovery method, the molecular weight of tubular ultra-filtration membrane is 3000 in the steps d, the film intake pressure is 4-5bar during ultrafiltration, 5-20 ℃ of process temperature control.
Above-mentioned recovery method, the molecular weight of tubular type nanofiltration membrane is 120 among the step e, the film intake pressure is 12-15bar during nanofiltration, 5-20 ℃ of process temperature control.
Above-mentioned recovery method, the concentration of hydrochloric acid is 6mol/L among the step f, the salt adding acid for adjusting pH value is 5.0-5.2.
Recovery method of the present invention, concrete operation step is:
Get the enzyme process Ampicillin Trihydrate crystalline mother solution that D (-) phenylglycine concentration is 12.0-20.0g/L, drop into 0.5KU-1.0KU PGA in 1L Ampicillin Trihydrate mother liquor, add penicillin G acylase and carry out cracking; Dripping concentration is the ammoniacal liquor of 3mol/L, and reaction process control pH value is 8.0-8.5, and temperature is 20-28 ℃, reaction times 90-120min; Reaction by 400 eye mesh screen entrapped enzymes, is told lysate after finishing; It is 9.0-9.5 that lysate is regulated the pH value with the ammoniacal liquor of 6mol/L, carries out ultrafiltration with the tubular ultra-filtration membrane of molecular weight 3000, and the film intake pressure is 4-5 bar, and membrane flux is 8-10L/min, 5-20 ℃ of process temperature control; To carry out nanofiltration with the tubular type nanofiltration membrane of molecular weight 120 concentrated for ultrafiltration dialysis liquid subsequently, and the film intake pressure is 12-15 bar, and membrane flux is 0.5-2.5L/min, 5-20 ℃ of process temperature control; Concentrated solution adds activated carbon decolorizing, and the salt acid for adjusting pH value that destainer adds 6mol/L is 5.0-5.2, and temperature control is below 5 ℃, growing the grain 2h, and suction filtration, washing, drying obtains solid D (-) phenylglycine.
D(-of the present invention) recovery method of phenylglycine, the rate of recovery can reach more than 80%, products obtained therefrom content is more than 98%, can directly be applied to industrial production as raw material, environmental pollution and the wasting of resources have been reduced, and the method energy consumption is low, simple to operate, can also bring considerable economic benefit for enterprise, is fit to suitability for industrialized production and uses.
Embodiment
The present invention will be further described in detail below in conjunction with embodiment.
Embodiment 1The recovery of D (-) phenylglycine
(1) gets the enzyme process Ampicillin Trihydrate crystalline mother solution 180L that D (-) phenylglycine concentration is 12.2g/L, put in the 250L enzyme reaction tank;
(2) take by weighing 0.1MU PGA, with putting in the enzyme reaction tank stirring velocity 80rpm after the salt-free water washing, ammoniacal liquor control pH with 3mol/L is 8.0-8.2,20 ℃ of temperature behind the reaction 90min, are emitted lysate (PGA is held back by enzyme reaction pot bottom 400 eye mesh screens);
(3) lysate drips 6mol/L ammoniacal liquor and regulates pH to 9.0, carries out ultrafiltration dialysis with molecular weight 3000 films, membrane filtration area 10m
2, film intake pressure 4bar, membrane flux 8.2L/min.5-10 ℃ of ultrafiltration dialysis process control temp.Dialysate volumes 250L, D (-) phenylglycine content is 8.66g/L in the dialyzate, the ultrafiltration yield is 98.6%.
(4) it is concentrated that the 250L dialyzate carries out nanofiltration, carries out nanofiltration with molecular weight 120 films and concentrate membrane filtration area 5m
2, film intake pressure 13bar, membrane flux 2.2-0.8L/min.15～20 ℃ of nanofiltration Concentrating Process Control temperature.Concentrated solution volume 31.7L, D (-) phenylglycine content is 67.07g/L in the concentrated solution, the ultrafiltration yield is 98.2%.
(5) in the 31.7L concentrated solution, add gac 31.7g, stir 30min, cross l00um and 0.45um filter membrane; Destainer is regulated pH=5.0 with 6mol/L hydrochloric acid, 2-5 ℃ of temperature control, growing the grain 2h; Suction filtration, washing with acetone, 45 ℃ of dry 2h obtain solid D (-) phenylglycine 1.77kg, total yield 80.60%, product content 98.5%.
Embodiment 2The recovery of D (-) phenylglycine
(1) gets the enzyme process Ampicillin Trihydrate crystalline mother solution 160L that D (-) phenylglycine concentration is 15.5g/L, put in the 250L enzyme reaction tank;
(2) take by weighing 0.13MU PGA, with putting in the enzyme reaction tank stirring velocity 80rpm after the salt-free water washing, ammoniacal liquor control pH with 3mol/L is 8.3-8.4, temperature 20-22 ℃, behind the reaction 100min, lysate is emitted (PGA is held back by enzyme reaction pot bottom 400 eye mesh screens);
(3) lysate drips 6M ammoniacal liquor and regulates pH to 9.3, carries out ultrafiltration dialysis with molecular weight 3000 films, membrane filtration area 10m
2, film intake pressure 4.5bar, membrane flux 9L/min.10-15 ℃ of ultrafiltration dialysis process control temp.Dialysate volumes 260L, D (-) phenylglycine content is 9.42g/L in the dialyzate, the ultrafiltration yield is 98.8%.
(4) it is concentrated that the 260L dialyzate carries out nanofiltration, carries out nanofiltration with molecular weight 120 films and concentrate membrane filtration area 5m
2, film intake pressure 14.1bar, membrane flux 2.0-0.7L/min.10～15 ℃ of nanofiltration Concentrating Process Control temperature.Concentrated solution volume 30.5L, D-is 79.66g/L to hydroxyl D (-) phenylglycine content in the concentrated solution, the ultrafiltration yield is 99.2%.
(5) in the 30.5L concentrated solution, add gac 30.5g, stir 30min, cross l00um and 0.45um filter membrane; Destainer is regulated pH=5.1 with 6M hydrochloric acid, T≤5 ℃, growing the grain 2h; Suction filtration, washing with acetone, 45 ℃ of dry 2h obtain solid D (-) phenylglycine 2.01kg, total yield 81.05%, product content 99.1%.
Embodiment 3The recovery of D (-) phenylglycine
(1) gets the enzyme process Ampicillin Trihydrate crystalline mother solution 150L that D (-) phenylglycine concentration is 19.96g/L, put in the 250L enzyme reaction tank;
(2) take by weighing 0.15MU PGA, with putting in the enzyme reaction tank stirring velocity 80rpm after the salt-free water washing, ammoniacal liquor control pH with 3mol/L is 8.4-8.5, temperature 25-28 ℃, behind the reaction 120min, lysate is emitted (PGA is held back by enzyme reaction pot bottom 400 eye mesh screens);
(3) lysate drips 6mol/L ammoniacal liquor and regulates pH to 9.5, carries out ultrafiltration dialysis with molecular weight 3000 films, membrane filtration area 10m
2, film intake pressure 5.0bar, membrane flux 10L/min.15-20 ℃ of ultrafiltration dialysis process control temp.Dialysate volumes 245L, D (-) phenylglycine content is 12.10g/L in the dialyzate, the ultrafiltration yield is 99.0%.
(4) the 245L dialyzate is carried out nanofiltration and concentrate, it is concentrated to carry out nanofiltration with molecular weight 120 films, membrane filtration area 5m
2, film intake pressure 15bar, membrane flux 2.2-0.5L/min.5-10 ℃ of nanofiltration Concentrating Process Control temperature.Concentrated solution volume 31.5L, D (-) phenylglycine content is 93.45g/L in the concentrated solution, the ultrafiltration yield is 99.3%.
(5) in the 31.5L concentrated solution, add gac 31.5g, stir 30min, cross l00um and 0.45um filter membrane; Destainer is regulated pH=5.2 with 6mol/L hydrochloric acid, T≤5 ℃, growing the grain 2h; Suction filtration, washing with acetone, 45 ℃ of dry 2h obtain solid D (-) phenylglycine 2.45kg, total yield 81.83%, product content 99.4%.
Embodiment 4The analytical procedure of removal process intermediate controlled
1.HPLC testing conditions
Chromatographic column: Yi Lite filler: ODS 25 μ m
Detect wavelength: 230nm
The moving phase preparation:
A: damping fluid: 4.08g KH
2PO
4→ 1000ml H
2O pH=4.5
B: methyl alcohol
Gradient: function of time parameter
0 solvent composition A:B=98:2
1 solvent composition A:B=98:2
15 solvent composition A:B=70:30
15 flow 1.5mL/min
18 solvent composition A:B=98:2
18 flow 1mL/min
25 solvent composition A:B=98:2
Retention time: 6-APA 5.8min, D-PG 3.9min,
PGM.HCL 12.7min ，Ampicillin 15.5min
The comparative example 1Evaporation concentration method reclaims D(-) phenylglycine
(1) get the enzyme process Ampicillin Trihydrate crystalline mother solution 500ml that D (-) phenylglycine concentration is 15.7g/L, add PGA enzyme 280U, controlling pH with the ammoniacal liquor of 3mol/L is 8.0-8.3, and 20 ℃ of temperature behind the reaction 90min, leach lysate.
(2) lysate is transferred pH=10.6 with 5M sodium hydroxide.
(3) carry out underpressure distillation 1.5h with Rotary Evaporators, T=80 ℃.
(4) be cooled to room temperature, transfer pH=5.0 with ammoniacal liquor, obtain D (-) phenylglycine solid.
(5) with the water washing of 50ml acetone, 45 ℃ of dryings obtain finished product 5.6g, yield 78.3%, content 93.1%.
Claims (10)
1. D(-in the enzyme process Ampicillin Trihydrate mother liquor) recovery method of phenylglycine is characterized in that, operates as follows:
A. to contain D(-) the enzyme process Ampicillin Trihydrate recrystallization mother liquor of phenylglycine is raw material, adds penicillin G acylase and carries out cracking;
B. ammonification water management pH value in the cracking process, temperature control carries out scission reaction, gets lysate;
C. lysate is crossed screen cloth;
D. add ammoniacal liquor in the lysate of crossing behind the screen cloth and regulate the pH value, then carry out ultrafiltration with tubular ultra-filtration membrane;
E. the solution after the ultrafiltration is carried out nanofiltration with the tubular type nanofiltration membrane;
F. the solution after the nanofiltration is added activated carbon decolorizing, salt adding acid for adjusting pH value in the destainer, the cooling growing the grain, suction filtration, washing, drying gets solid D(-) phenylglycine.
2. recovery method according to claim 1 is characterized in that, D(-in the recrystallization mother liquor of enzyme process Ampicillin Trihydrate among the step a) solubility of phenylglycine is 12.0-20.0g/L.
3. recovery method according to claim 1 is characterized in that, the add-on of penicillin G acylase adds 0.5KU-1.0KU in 1L Ampicillin Trihydrate recrystallization mother liquor among the step a.
4. recovery method according to claim 1 is characterized in that, the concentration of ammoniacal liquor is 3mol/L among the step b, adds ammoniacal liquor adjusting pH value and is 8.0-8.5, and temperature control 20-28 ℃, the time of scission reaction is 90-120min.
5. recovery method according to claim 1 is characterized in that, screen cloth is 400 orders among the step c.
6. recovery method according to claim 1 is characterized in that, the concentration of ammoniacal liquor is 6mol/L in the steps d, adds ammoniacal liquor adjusting pH value and is 9.0-9.5.
7. recovery method according to claim 1 is characterized in that, the molecular weight of tubular ultra-filtration membrane is 3000 in the steps d, and the film intake pressure is 4-5bar during ultrafiltration, 5-20 ℃ of process temperature control.
8. recovery method according to claim 1 is characterized in that, the molecular weight of tubular type nanofiltration membrane is 120 among the step e, and the film intake pressure is 12-15bar during nanofiltration, 5-20 ℃ of process temperature control.
9. recovery method according to claim 1 is characterized in that, the concentration of hydrochloric acid is 6mol/L among the step f, and the salt adding acid for adjusting pH value is 5.0-5.2.
10. recovery method according to claim 1 is characterized in that, concrete operation step is:
Get the enzyme process Ampicillin Trihydrate crystalline mother solution that D (-) phenylglycine concentration is 12.0-20.0g/L, drop into 0.5KU-1.0KU in 1L Ampicillin Trihydrate mother liquor, add penicillin G acylase and carry out cracking; Dripping concentration is the ammoniacal liquor of 3mol/L, and reaction process control pH value is 8.0-8.5, and temperature is 20-28 ℃, reaction times 90-120min; Reaction by 400 eye mesh screen entrapped enzymes, is told lysate after finishing; It is 9.0-9.5 that lysate is regulated the pH value with the ammoniacal liquor of 6mol/L, carries out ultrafiltration with the tubular ultra-filtration membrane of molecular weight 3000, and the film intake pressure is 4-5 bar, and membrane flux is 8-10L/min, 5-20 ℃ of process temperature control; To carry out nanofiltration with the tubular type nanofiltration membrane of molecular weight 120 concentrated for ultrafiltration dialysis liquid subsequently, and the film intake pressure is 12-15 bar, and membrane flux is 0.5-2.5L/min, 5-20 ℃ of process temperature control; Concentrated solution adds activated carbon decolorizing, and the salt acid for adjusting pH value that destainer adds 6mol/L is 5.0-5.2, and temperature control is below 5 ℃, growing the grain 2h, and suction filtration, washing, drying obtains solid D (-) phenylglycine.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108129339A (en) * | 2018-01-12 | 2018-06-08 | 河北华旭化工有限公司 | The decolorising agent of L-Phenylglycine production |
| CN108191687A (en) * | 2018-01-12 | 2018-06-22 | 河北华旭化工有限公司 | L-Phenylglycine decoloration process |
| CN114105797A (en) * | 2021-09-10 | 2022-03-01 | 上海城建职业学院 | Method for recovering D-p-hydroxyphenylglycine from crystallization mother liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108129339A (en) * | 2018-01-12 | 2018-06-08 | 河北华旭化工有限公司 | The decolorising agent of L-Phenylglycine production |
| CN108191687A (en) * | 2018-01-12 | 2018-06-22 | 河北华旭化工有限公司 | L-Phenylglycine decoloration process |
| CN108191687B (en) * | 2018-01-12 | 2020-05-12 | 河北华旭化工有限公司 | Process for decoloring L-phenylglycine |
| CN108129339B (en) * | 2018-01-12 | 2020-05-12 | 河北华旭化工有限公司 | Decolorizing agent for producing L-phenylglycine |
| CN114105797A (en) * | 2021-09-10 | 2022-03-01 | 上海城建职业学院 | Method for recovering D-p-hydroxyphenylglycine from crystallization mother liquor |
| CN114105797B (en) * | 2021-09-10 | 2024-05-14 | 上海城建职业学院 | Method for recovering D-p-hydroxyphenylglycine from crystallization mother liquor |
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Application publication date: 20130102 |