CN103467344B - Method for recovering urea from tetracycline urea compound salt crystallization mother liquor and recycling urea - Google Patents
Method for recovering urea from tetracycline urea compound salt crystallization mother liquor and recycling urea Download PDFInfo
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- CN103467344B CN103467344B CN201310442298.7A CN201310442298A CN103467344B CN 103467344 B CN103467344 B CN 103467344B CN 201310442298 A CN201310442298 A CN 201310442298A CN 103467344 B CN103467344 B CN 103467344B
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Abstract
The invention relates to a method for recovering urea from tetracycline urea compound salt crystallization mother liquid and recycling the urea. The method for recovering the urea from the tetracycline urea compound salt crystallization mother liquid and recycling the urea is characterized in that the tetracycline urea compound salt crystallization mother liquid naturally settles, then liquid supernatant of the tetracycline urea compound salt crystallization mother liquid is filtered by using a bag filter, filtered fluid is acidized by adding acid and then is filtered by using an organic spiral-wound membrane, obtained dialysis fluid is concentrated under reduced pressure at the temperature of 55-65 DEG C by 1.5-2.5 times so as to obtain recovered urea concentrated solution, and the recovered urea concentrated solution is reused in a tetracycline compound salt crystallization process in a ratio of the recovered urea concentrated solution and the pure urea being (3-4):1. The method for recovering the urea from the tetracycline urea compound salt crystallization mother liquid and recycling the urea has the advantages that the wasting of the urea is reduced, the using amount of the urea in the tetracycline production process is reduced, the treatment difficulty and the treatment cost of wastewater are reduced, the environmental pollution is reduced, and the consumption of the urea in the tetracycline production process is reduced to 0.5Kg/Kg from 2Kg/Kg in past.
Description
Technical field
The invention belongs to technical field of biological fermentation, particularly relate to and a kind ofly from tetracycline urea compound salt crystallization mother liquor, reclaim urea and the method for recycle.
Background technology
Existing tetracycline urea double salt technological process is: tetracycline base (Kg): urea (Kg): water (L)=1:1.5 ~ 2.5:1.5 ~ 2.5.In crystallisation vessel, water is added according to feed ratio, be heated to 35 ~ 45 DEG C, after add urea, PH1.0 ~ 1.4 are adjusted with concentrated hydrochloric acid, add tetracycline base stirring and dissolving again, be cooled to 15 ~ 25 DEG C in dissolution process, tetracycline base adds ammoniacal liquor tune PH to 4.6 ~ 5.2 that concentration is 10 ~ 12% after dissolving, tetracycline urea double salt is filtered to obtain, mother liquor environmental protection treatment after stirring 1hr.
Tetracycline urea compound salt crystallization is a committed step in tsiklomitsin treating process, its objective is to remove tsiklomitsin degraded product 4-epitetracycline and dehydration tetracycline by the selective reaction of urea and tsiklomitsin.In actual production process, in order to ensure the level of response of tsiklomitsin double salt, usually urea and tsiklomitsin are added according to the feed ratio that mol ratio is 10 ~ 13:1, and the mol ratio of real reaction is only 1:1, therefore excessive 9 ~ 12 times of urea in crystallisation process, cause containing a large amount of urea in urea complex salt crystal mother liquor, this result causes the urea of more than 88% to waste on the one hand, it is reported, the consumption of the urea in existing tetracycline hydrochloride production process reaches 2Kg/Kg; The crystalline mother solution of high concentration COD enters sewage disposal to the impact of Sewage treatment systems comparatively greatly on the other hand, and cost of sewage disposal is higher.
Summary of the invention
Object of the present invention is just that provide a kind of reclaims urea and the method for recycle from tetracycline urea compound salt crystallization mother liquor, the method can reduce the waste of urea, the usage quantity of urea in effective reduction tsiklomitsin production, reduce intractability and the processing cost of sewage simultaneously, reduce environmental pollution.
Technical scheme taked for achieving the above object is:
A kind ofly from tetracycline urea compound salt crystallization mother liquor, reclaim urea and the method for recycle, it is characterized in that: by tetracycline urea compound salt crystallization mother liquor natural subsidence, then its supernatant liquor deep bed filter is filtered, filtered liquid is acidified with acid, use organic wound membrane filtration again, gained dialyzate is recycled urea concentration liquid after concentrating under reduced pressure 1.5 ~ 2.5 times under 55 ~ 65 DEG C of conditions, is back to use in tsiklomitsin complex salt crystal process according to the ratio reclaiming urea concentration liquid and pure urea 3 ~ 4:1.
Described tetracycline urea compound salt crystallization mother liquor natural subsidence 40 ~ 80min.
The filter sizes of described deep bed filter is 5 ~ 10 μm.
Described filtered liquid is acidified with acid and refers to, with concentrated hydrochloric acid, filtered liquid is adjusted PH2.0 ± 0.2.
The molecular weight of described organic rolled film is 180 ~ 300.
The mixture of described urea concentration liquid and pure urea first dissolves under 35 ~ 45 DEG C of temperature condition, adds concentrated hydrochloric acid and adjusts reuse behind PH1.0 ~ 1.4.
The present invention is by carrying out purifying treatment to tetracycline urea compound salt crystallization mother liquor, urea in mother liquor separates with impurity by the nanofiltration membrane of screening suitable molecular weight, concentrating under reduced pressure makes the urea enrichment in urea dialysis liquid, finally urea concentration liquid is recycled in the crystallisation process of tetracycline urea double salt, thus decrease the waste of urea, effectively reduce the usage quantity of urea in tsiklomitsin production; Meanwhile, the recovery of urea reduces intractability and the processing cost of sewage, reduces environmental pollution.More than 88% urea in mother liquor can reclaim by the present invention, and in mother liquor, the concentration of COD reduces by more than 60%, and the processing cost of mother liquor waste water reduces by more than 50 ~ 60%, and the consumption of urea in tetracycline hydrochloride production process can be made can be reduced to 0.5Kg/Kg by original 2Kg/Kg.
Embodiment
Fig. 1 is that the present invention reclaims urea and the process flow sheet of the method for recycle from tetracycline urea compound salt crystallization mother liquor.
Embodiment
Embodiment 1
1 urea reclaims: be first the urea complex salt crystal mother liquor natural subsidence 40min of 4.8 ~ 5.0 by PH, supernatant liquor filters through 10 μm of deep bed filter, by not tolerant for solid removal; Filtered liquid concentrated hydrochloric acid is acidified to PH2.0 ± 0.2, is then organic wound membrane filtration of 260 with molecular weight, because the urea of urea molecule amount 60.5,80 ~ 95% enters in dialyzate.Dialyzate is recycled urea concentration liquid after concentrating under reduced pressure 2.5 times under 55 DEG C of conditions.By urea concentration liquid cooling but, temperature controls at 35 ~ 45 DEG C, and the concentration detecting urea concentration liquid by the method for GB/T 18204.29-2000 is for subsequent use.
The calculating of 2 charging capacitys: by tetracycline base (Kg): urea (Kg): water (L)=1:1.5 ~ 2.5:1.5 ~ 2.5 feed ratio calculates the input amount of tetracycline base, urea, water in urea complex salt crystal process.The input amount reclaiming urea and new urea is calculated according to the ratio of 3 ~ 4:1.Reclaim after urea calculates according to the concentration reclaiming urea concentration liquid the volume that feeds intake and feed intake, new urea can feed intake according to the weight calculated.New amount of water deducts urea concentration liquid to feed intake volume for calculating amount of water.Tetracycline base adds according to calculating charging capacity.
3 urea complex salt crystals: the recovery urea concentration liquid of calculated amount is added in tetracycline urea compound salt crystallization tank, then add the water of calculated amount and new urea, stir, computer heating control solvent temperature is at 35 ~ 45 DEG C, after newly adding urea and all dissolving, add concentrated hydrochloric acid and adjust PH1.0 ~ 1.4.Solution is cooled to 15 ~ 25 DEG C, adds the tetracycline base of calculated amount, continue to be stirred to lysate clarification, prepare crystallization.
4 other crystallizations, filtration process are carried out according to former technique.
Embodiment 2
Urea reclaims: be first the urea complex salt crystal mother liquor natural subsidence 60min of 4.8 ~ 5.0 by PH, supernatant liquor filters through 8 μm of deep bed filter, by not tolerant for solid removal; Filtered liquid concentrated hydrochloric acid is acidified to PH2.0 ± 0.2, is then organic wound membrane filtration of 180 with molecular weight, because the urea of urea molecule amount 60.5,80 ~ 95% enters in dialyzate.Dialyzate is recycled urea concentration liquid after concentrating under reduced pressure 2.2 times under 65 DEG C of conditions.By urea concentration liquid cooling but, temperature controls at 35 ~ 45 DEG C, and the concentration detecting urea concentration liquid by the method for GB/T 18204.29-2000 is for subsequent use.
Other process is with embodiment 1.
Embodiment 3
Urea reclaims: be first the urea complex salt crystal mother liquor natural subsidence 70min of 4.8 ~ 5.0 by PH, supernatant liquor filters through 7 μm of deep bed filter, by not tolerant for solid removal; Filtered liquid concentrated hydrochloric acid is acidified to PH2.0 ± 0.2, is then organic wound membrane filtration of 300 with molecular weight, because the urea of urea molecule amount 60.5,80 ~ 95% enters in dialyzate.Dialyzate is recycled urea concentration liquid after concentrating under reduced pressure 1.8 times under 58 DEG C of conditions.By urea concentration liquid cooling but, temperature controls at 35 ~ 45 DEG C, and the concentration detecting urea concentration liquid by the method for GB/T 18204.29-2000 is for subsequent use.
Other process is with embodiment 1.
Embodiment 4
Urea reclaims: be first the urea complex salt crystal mother liquor natural subsidence 80min of 4.8 ~ 5.0 by PH, supernatant liquor filters through 5 μm of deep bed filter, by not tolerant for solid removal; Filtered liquid concentrated hydrochloric acid is acidified to PH2.0 ± 0.2, is then organic wound membrane filtration of 220 with molecular weight, because the urea of urea molecule amount 60.5,80 ~ 95% enters in dialyzate.Dialyzate is recycled urea concentration liquid after concentrating under reduced pressure 1.5 times under 62 DEG C of conditions.By urea concentration liquid cooling but, temperature controls at 35 ~ 45 DEG C, and the concentration detecting urea concentration liquid by the method for GB/T 18204.29-2000 is for subsequent use.
Other process is with embodiment 1.
Claims (2)
1. one kind is reclaimed urea and the method for recycle from tetracycline urea compound salt crystallization mother liquor, it is characterized in that: by tetracycline urea compound salt crystallization mother liquor natural subsidence, then be the deep bed filter filtration of 5 ~ 10 μm by its supernatant liquor aperture, filtered liquid is acidified with acid to pH2.0 ± 0.2, be organic wound membrane filtration of 180 ~ 300 again with molecular weight, gained dialyzate is recycled urea concentration liquid after concentrating under reduced pressure 1.5 ~ 2.5 times under 55 ~ 65 DEG C of conditions, dissolve under 35 ~ 45 DEG C of temperature condition according to after the proportions reclaiming urea concentration liquid and pure urea 3 ~ 4:1, add after concentrated hydrochloric acid adjusts pH1.0 ~ 1.4 and be back to use in tsiklomitsin complex salt crystal process.
2., according to the method reclaiming urea from tetracycline urea compound salt crystallization mother liquor according to claim 1, it is characterized in that described tetracycline urea compound salt crystallization mother liquor natural subsidence 40 ~ 80min.
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103896798A (en) * | 2014-01-14 | 2014-07-02 | 李学强 | Tetracycline purifying process |
| CN106316890A (en) * | 2016-08-19 | 2017-01-11 | 宁夏启元药业有限公司 | Method for preparing urea oxalate from tetracycline urea complex salt crystallization mother liquor |
| CN107540413A (en) * | 2017-09-14 | 2018-01-05 | 精晶药业股份有限公司 | A kind of method that urea is extracted in the crystalline mother solution from aspartic acid ornithine |
| CN116003298A (en) * | 2022-12-23 | 2023-04-25 | 山东汇海医药化工有限公司 | Method for recovering urea from benzimidazolone synthesis reaction mother liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2905662A (en) * | 1956-05-11 | 1959-09-22 | American Cyanamid Co | Preparation of tetracycline-urea compound |
| US3037973A (en) * | 1960-06-16 | 1962-06-05 | Pfizer & Co C | Tetracycline recovery process |
| CN1052849A (en) * | 1989-12-28 | 1991-07-10 | 清华大学 | A kind of treatment process of abricycline crystal mother liquor |
| CN1226278C (en) * | 2003-09-04 | 2005-11-09 | 华北制药集团有限责任公司 | Recovery method of demeclocy cline hydrochloride crystal mother liquor |
| CN101407473A (en) * | 2008-11-28 | 2009-04-15 | 宁夏启元药业有限公司 | Method for recycling abricycline from abricycline crystal mother liquor |
| CN102993043B (en) * | 2012-12-04 | 2015-03-04 | 天津大学 | Method for preparing high-purity tetracycline hydrochloride |
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