CN103467344A - 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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- CN103467344A CN103467344A CN2013104422987A CN201310442298A CN103467344A CN 103467344 A CN103467344 A CN 103467344A CN 2013104422987 A CN2013104422987 A CN 2013104422987A CN 201310442298 A CN201310442298 A CN 201310442298A CN 103467344 A CN103467344 A CN 103467344A
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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 a kind of method that reclaims urea recycle from tsiklomitsin urea complex salt crystal mother liquor.
Background technology
Existing tsiklomitsin urea double salt technological process is: tetracycline base (Kg): urea (Kg): water (L)=1:1.5～2.5:1.5～2.5.Add water in crystallisation vessel according to feed ratio, be heated to 35～45 ℃, after add urea, adjust PH1.0～1.4 with concentrated hydrochloric acid, add the tetracycline base stirring and dissolving again, be cooled to 15～25 ℃ in dissolution process, tetracycline base adds the ammoniacal liquor that concentration is 10～12% and adjusts PH to 4.6～5.2 after dissolving, filter to obtain tsiklomitsin urea double salt, the mother liquor environmental protection treatment after stirring 1hr.
Tsiklomitsin urea complex salt crystal is a committed step in the tsiklomitsin treating process, its objective is that the selective reaction by urea and tsiklomitsin removes tsiklomitsin degraded product 4-epitetracycline and dehydration tetracycline.In actual production process, in order to guarantee the level of response of tsiklomitsin double salt, usually the feed ratio that is 10～13:1 by urea and tsiklomitsin according to mol ratio adds, 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, and this result causes the urea 88% or more to waste on the one hand, it is reported, the consumption of the urea in existing tetracycline hydrochloride production process has reached 2Kg/Kg; To enter sewage disposal larger to the impact of Sewage treatment systems for the crystalline mother solution of high concentration COD on the other hand, and cost of sewage disposal is higher.
Summary of the invention
Purpose of the present invention just is to provide a kind of method that reclaims urea recycle from tsiklomitsin urea complex salt crystal mother liquor, the method can reduce the waste of urea, effectively reduce the usage quantity of urea in tsiklomitsin production, reduce intractability and the processing cost of sewage, environmental contamination reduction simultaneously.
The technical scheme taked for achieving the above object is:
A kind of method that reclaims urea recycle from tsiklomitsin urea complex salt crystal mother liquor, it is characterized in that: by tsiklomitsin urea complex salt crystal mother liquor natural subsidence, then its supernatant liquor is filtered with deep bed filter, filtered liquid is acidified with acid, with organic rolled film, filter again, the gained dialyzate is recycled the urea concentrated solution after 1.5～2.5 times of concentrating under reduced pressure under 55～65 ℃ of conditions, according to the ratio that reclaims urea concentrated solution and pure urea 3～4:1, is back to use in tsiklomitsin complex salt crystal process.
Described tsiklomitsin urea complex salt crystal mother liquor natural subsidence 40～80min.
The filter membrane aperture of described deep bed filter is 5～10 μ m.
Described filtered liquid is acidified with acid and refers to concentrated hydrochloric acid filtered liquid is adjusted to PH2.0 ± 0.2.
The molecular weight of described organic rolled film is 180～300.
The mixture of described urea concentrated solution and pure urea first dissolves under 35～45 ℃ of temperature condition, adds concentrated hydrochloric acid and adjusts the rear reuse in PH1.0～1.4.
The present invention is by carrying out purifying treatment to tsiklomitsin urea complex salt crystal mother liquor, screening the nanofiltration membrane of suitable molecular weight separates the urea in mother liquor and impurity, concentrating under reduced pressure makes the urea enrichment in the urea dialyzate, finally the urea concentrated solution is recycled in the crystallisation process of tsiklomitsin urea double salt, thereby reduced the waste of urea, effectively reduced the usage quantity of urea in tsiklomitsin production; Simultaneously, the recovery of urea reduces intractability and the processing cost of sewage, environmental contamination reduction.The present invention can reclaim 88% above urea in mother liquor, and in mother liquor, the concentration of COD reduces more than 60%, and the processing cost of mother liquor waste water reduces more than 50～60%, can make the consumption of urea in the tetracycline hydrochloride production process be reduced to 0.5Kg/Kg by original 2Kg/Kg.
Embodiment
Fig. 1 is that the present invention reclaims the process flow sheet of the method for urea recycle from tsiklomitsin urea complex salt crystal mother liquor.
Embodiment
Embodiment 1
1 urea reclaims: the urea complex salt crystal mother liquor natural subsidence 40min that is first 4.8～5.0 by PH, and supernatant liquor filters through 10 μ m deep bed filter, by the not tolerant removal of solid; Filtered liquid is acidified to PH2.0 ± 0.2 with concentrated hydrochloric acid, and with molecular weight, being then 260, organic rolled film filters, because the urea of urea molecule amount 60.5,80～95% enters in dialyzate.Dialyzate is recycled to the urea concentrated solution after 2.5 times of concentrating under reduced pressure under 55 ℃ of conditions.The urea concentrated solution is cooling, and temperature is controlled at 35～45 ℃, and the concentration of the method detection urea concentrated solution of use GB/T 18204.29-2000 is standby.
The calculating of 2 charging capacitys: press tetracycline base (Kg): urea (Kg): water (L)=1:1.5～2.5:1.5～2.5 feed ratio calculate the input amount of tetracycline base, urea, water in urea complex salt crystal process.Calculate the input amount that reclaims urea and new urea according to the ratio of 3～4:1.Reclaim after urea calculates according to the concentration that reclaims the urea concentrated solution volume that feeds intake and feed intake, new urea can feed intake according to the weight of calculating.New amount of water deducts the urea concentrated solution volume that feeds intake for calculating amount of water.Tetracycline base adds according to calculating charging capacity.
3 urea complex salt crystals: the recovery urea concentrated solution of calculated amount is added in tsiklomitsin urea complex salt crystal tank, then add water and the new urea of calculated amount, stir, add the thermal control solvent temperature at 35～45 ℃, after newly adding the whole dissolvings of urea, add concentrated hydrochloric acid to adjust PH1.0～1.4.Solution is cooled to 15～25 ℃, adds the tetracycline base of calculated amount, continue to be stirred to the lysate clarification, prepare crystallization.
4 other crystallizations, filtration process carry out according to former technique.
Embodiment 2
Urea reclaims: the urea complex salt crystal mother liquor natural subsidence 60min that is first 4.8～5.0 by PH, and supernatant liquor filters through 8 μ m deep bed filter, by the not tolerant removal of solid; Filtered liquid is acidified to PH2.0 ± 0.2 with concentrated hydrochloric acid, and with molecular weight, being then 180, organic rolled film filters, because the urea of urea molecule amount 60.5,80～95% enters in dialyzate.Dialyzate is recycled to the urea concentrated solution after 2.2 times of concentrating under reduced pressure under 65 ℃ of conditions.The urea concentrated solution is cooling, and temperature is controlled at 35～45 ℃, and the concentration of the method detection urea concentrated solution of use GB/T 18204.29-2000 is standby.
Other process is with embodiment 1.
Embodiment 3
Urea reclaims: the urea complex salt crystal mother liquor natural subsidence 70min that is first 4.8～5.0 by PH, and supernatant liquor filters through 7 μ m deep bed filter, by the not tolerant removal of solid; Filtered liquid is acidified to PH2.0 ± 0.2 with concentrated hydrochloric acid, and with molecular weight, being then 300, organic rolled film filters, because the urea of urea molecule amount 60.5,80～95% enters in dialyzate.Dialyzate is recycled to the urea concentrated solution after 1.8 times of concentrating under reduced pressure under 58 ℃ of conditions.The urea concentrated solution is cooling, and temperature is controlled at 35～45 ℃, and the concentration of the method detection urea concentrated solution of use GB/T 18204.29-2000 is standby.
Other process is with embodiment 1.
Embodiment 4
Urea reclaims: the urea complex salt crystal mother liquor natural subsidence 80min that is first 4.8～5.0 by PH, and supernatant liquor filters through 5 μ m deep bed filter, by the not tolerant removal of solid; Filtered liquid is acidified to PH2.0 ± 0.2 with concentrated hydrochloric acid, and with molecular weight, being then 220, organic rolled film filters, because the urea of urea molecule amount 60.5,80～95% enters in dialyzate.Dialyzate is recycled to the urea concentrated solution after 1.5 times of concentrating under reduced pressure under 62 ℃ of conditions.The urea concentrated solution is cooling, and temperature is controlled at 35～45 ℃, and the concentration of the method detection urea concentrated solution of use GB/T 18204.29-2000 is standby.
Other process is with embodiment 1.
Claims (6)
1. a method that reclaims urea recycle from tsiklomitsin urea complex salt crystal mother liquor, it is characterized in that: by tsiklomitsin urea complex salt crystal mother liquor natural subsidence, then its supernatant liquor is filtered with deep bed filter, filtered liquid is acidified with acid, with organic rolled film, filter again, the gained dialyzate is recycled the urea concentrated solution after 1.5～2.5 times of concentrating under reduced pressure under 55～65 ℃ of conditions, according to the ratio that reclaims urea concentrated solution and pure urea 3～4:1, is back to use in tsiklomitsin complex salt crystal process.
2. according to the method that reclaims urea from tsiklomitsin urea complex salt crystal mother liquor claimed in claim 1, it is characterized in that described tsiklomitsin urea complex salt crystal mother liquor natural subsidence 40～80min.
3. according to the method that reclaims urea from tsiklomitsin urea complex salt crystal mother liquor claimed in claim 1, the filter membrane aperture that it is characterized in that described deep bed filter is 5～10 μ m.
4. according to the method that reclaims urea from tsiklomitsin urea complex salt crystal mother liquor claimed in claim 1, it is characterized in that described filtered liquid is acidified with acid to refer to concentrated hydrochloric acid filtered liquid is adjusted to PH2.0 ± 0.2.
5. according to the method that reclaims urea from tsiklomitsin urea complex salt crystal mother liquor claimed in claim 1, the molecular weight that it is characterized in that described organic rolled film is 180～300.
6. according to the method that reclaims urea from tsiklomitsin urea complex salt crystal mother liquor claimed in claim 1, it is characterized in that: the mixture of described urea concentrated solution and pure urea first dissolves under 35～45 ℃ of temperature condition, adds concentrated hydrochloric acid and adjusts the rear reuse in PH1.0～1.4.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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