CN108059291A - 头孢他啶侧链酸酯废水中dmf及无机盐的回收方法 - Google Patents

头孢他啶侧链酸酯废水中dmf及无机盐的回收方法 Download PDF

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CN108059291A
CN108059291A CN201711012946.XA CN201711012946A CN108059291A CN 108059291 A CN108059291 A CN 108059291A CN 201711012946 A CN201711012946 A CN 201711012946A CN 108059291 A CN108059291 A CN 108059291A
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waste water
dmf
inorganic salts
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张艳红
张立明
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SHANDONG XINQUAN PHARMACEUTICAL Co.,Ltd.
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
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    • C01D3/00Halides of sodium, potassium or alkali metals in general
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00Preparation of carboxylic acid amides
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2103/34Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2301/08Multistage treatments, e.g. repetition of the same process step under different conditions

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Abstract

本发明涉及一种头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,属于废水处理回收技术领域。本发明所述的头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,对头孢他啶侧链酸酯废水进行萃取,得到水相和有机相,然后对水相利用刮板蒸发器蒸出水分,收集无机盐,并向无机盐中通入HBr气体,将过量的K2CO3全部转化为KBr;对有机相进行减压精馏得到DMF和萃取剂,以重复使用。本发明所述的头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,操作简单便捷,提高了溶剂及无机盐的回收率,降低了企业成本,减少了对环境的污染。

Description

头孢他啶侧链酸酯废水中DMF及无机盐的回收方法
技术领域
本发明涉及一种头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,属于废水处理回收技术领域。
背景技术
头孢他啶侧链酸酯是头孢他啶活性酯合成过程中的一类重要中间体,其质量与成本对原料药具有重要的影响。在头孢他啶侧链酸酯的合成过程中使用DMF作为溶剂,K2CO3作为缚酸剂,废水中含有一定量的DMF和无机盐(KBr和过量的K2CO3),如果将废水直接排放,将会造成严重的环境污染和经济损失。
DMF废水毒性强,需经过一定的处理再进行排放。目前回收DMF的方法主要有:化学法(碱化法)、生化法、物化法(吸附、精馏、萃取)、超临界水氧化法等。鉴于国内DMF回收装置简单,能耗高,回收成本昂贵,对于一些企业来说回收意义不大。在无机盐回收过程中,采用传统工艺设备进行回收,容易堵塞管道而存在回收难度大,效率低的问题,因此寻求一种高效回收DMF及无机盐的方法将会降低企业成本及缓解环境压力。
据相关文献报道,许杰文等研究含量低的DMF废水时采用活性炭吸附法,此法仅适用于较低浓度的DMF回收;徐明仙等利用超临界水氧化法处理DMF废水,去除了大量的CODcr,提高了废水的可生化降解性,此法较适合于处理高浓度、难生化降解的有机废水,但使用条件苛刻,难以大规模使用。
发明内容
本发明的目的在于提供一种头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,其操作简单便捷,提高了溶剂及无机盐的回收率,降低了企业成本,减少了对环境的污染。
本发明所述的头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,对头孢他啶侧链酸酯废水进行萃取,得到水相和有机相,然后对水相利用刮板蒸发器蒸出水分,收集无机盐,并向无机盐中通入HBr气体,将过量的K2CO3全部转化为KBr;对有机相进行减压精馏得到DMF和萃取剂,以重复使用。
对头孢他啶侧链酸酯废水进行萃取时,所用的萃取剂与废水的体积比为2~3:1。
所述萃取时间为10~15min,静置时间为10min。
所述萃取级数为3~5次。
减压精馏时,加入碳酸钙防止DMF的分解。
减压精馏时,控制压力为-0.08MPa~-0.1MPa。
减压精馏时,控制温度为10~60℃,且保持温度的缓慢上升,升温速率为1℃/min;升温至60℃后保温至无馏分流出。
本发明在回收无机盐时采用刮板蒸发器,大大缩短回收盐分的时间,提高盐分的回收率。
本发明向回收到的无机盐中通入一定量的HBr气体,将过量的K2CO3全部转化为KBr。
本发明与现有技术相比,具有以下有益效果:
(1)工艺简单,回收率高,利于工业化生产;
(2)本发明回收DMF的回收率高达87~89.5%,纯度高达99%以上,水分低于0.1%,完全达到DMF溶剂重复使用的标准;
(3)本发明使用刮板蒸发器进行无机盐的回收,大大缩短了回收时间,并将回收到的无机盐通入一定量的HBr气体,将过量的K2CO3全部转化为KBr。
具体实施方式
下面结合实施例对本发明作进一步的说明,但其并不限制本发明的实施。
实施例1
取1000mL醚化废水,加入2000mL的氯仿进行萃取,共萃取三次,萃取时间均为10min,静置时间均为10min,合并氯仿相及水相备用。
将合并的氯仿相进行减压蒸馏,并将蒸馏瓶底部放入少量的CaCO3,压力不低于-0.08MPa,温度范围为35±25℃,至馏出相无液体馏出,将收集的馏出液氯仿继续作为萃取剂重复使用,底部烧瓶中所余有机相即为DMF(约131mL),回收率为87.3%,纯度为99.2%,水分为0.07%;将合并的水相加入到刮板蒸发器中,减压蒸馏压力为-0.08MPa,夹套温度不低于75℃,至将水分全部蒸出,将底部烧瓶中的盐分进行收集,所得盐分为KBr和K2CO3的混合无机盐,再通入一定的HBr气体,将混合无机盐中的K2CO3转化为KBr,共计回收KBr 40.6g。
实施例2
取1000mL醚化废水,加入2500mL的氯仿进行萃取,共萃取四次,萃取时间均为15min,静置时间均为10min,合并氯仿相及水相备用。
将合并的氯仿相进行减压蒸馏,并将蒸馏瓶底部放入少量的CaCO3,压力不低于-0.08MPa,温度范围为35±25℃,至馏出相无液体馏出,将收集的馏出液氯仿继续作为萃取剂重复使用,底部烧瓶中所余有机相即为DMF(约132mL),回收率为88%,纯度为99.5%,水分为0.06%;将合并的水相加入到刮板蒸发器中,减压蒸馏压力为-0.08MPa,夹套温度不低于75℃,至将水分全部蒸出,将底部烧瓶中的盐分进行收集,所得盐分为KBr和K2CO3的混合无机盐,再通入一定的HBr气体,将混合无机盐中的K2CO3转化为KBr,共计回收KBr 41.3g。
实施例3
取1000mL醚化废水,加入3000mL的氯仿进行萃取,共萃取五次,萃取时间均为15min,静置时间均为10min,合并氯仿相及水相备用。
将合并的氯仿相进行减压蒸馏,并将蒸馏瓶底部放入少量的CaCO3,压力不低于-0.08MPa,温度范围为35±25℃,至馏出相无液体馏出,将收集的馏出液氯仿继续作为萃取剂重复使用,底部烧瓶中所余有机相即为DMF(约134mL),回收率为89.3%,纯度为99.1%,水分为0.09%;将合并的水相加入到刮板蒸发器中,减压蒸馏压力为-0.08MPa,夹套温度不低于75℃,至将水分全部蒸出,将底部烧瓶中的盐分进行收集,所得盐分为KBr和K2CO3的混合无机盐,再通入一定的HBr气体,将混合无机盐中的K2CO3转化为KBr,共计回收KBr 42.5g。

Claims (7)

1.一种头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,其特征在于:对头孢他啶侧链酸酯废水进行萃取,得到水相和有机相,然后对水相利用刮板蒸发器蒸出水分,收集无机盐,并向无机盐中通入HBr气体;对有机相进行减压精馏得到DMF和萃取剂。
2.根据权利要求1所述的头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,其特征在于:对头孢他啶侧链酸酯废水进行萃取时,所用的萃取剂与废水的体积比为2~3:1。
3.根据权利要求1所述的头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,其特征在于:萃取时间为10~15min,静置时间为10min。
4.根据权利要求1所述的头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,其特征在于:萃取级数为3~5次。
5.根据权利要求1所述的头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,其特征在于:减压精馏时加入碳酸钙。
6.根据权利要求1所述的头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,其特征在于:减压精馏时,控制压力为-0.08MPa~-0.1MPa。
7.根据权利要求1所述的头孢他啶侧链酸酯废水中DMF及无机盐的回收方法,其特征在于:减压精馏时,控制温度为10~60℃,升温速率为1℃/min;升温至60℃后保温至无馏分流出。
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108862795A (zh) * 2018-07-16 2018-11-23 兰博尔开封科技有限公司 一种氰霜唑废水中dmf的综合回收处理方法
CN113880351A (zh) * 2020-07-01 2022-01-04 山东理工大学 含有有机物、dmf和盐类的废水的处理方法和装置
CN114735872A (zh) * 2022-03-17 2022-07-12 佛山市南海北沙制药有限公司 一种对磺胺喹噁啉工艺废水回收再循环利用方法
WO2023198484A1 (en) 2022-04-12 2023-10-19 BASF Agro B.V. Improved process for recovering n,n-dimethylformamide (dmf) from an aqueous process stream
EP4306508A1 (en) 2022-07-14 2024-01-17 BASF Agro B.V. Improved process for recovering n,n-dimethylformamide (dmf) from an aqueous process stream

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CN108862795A (zh) * 2018-07-16 2018-11-23 兰博尔开封科技有限公司 一种氰霜唑废水中dmf的综合回收处理方法
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WO2023198484A1 (en) 2022-04-12 2023-10-19 BASF Agro B.V. Improved process for recovering n,n-dimethylformamide (dmf) from an aqueous process stream
EP4306508A1 (en) 2022-07-14 2024-01-17 BASF Agro B.V. Improved process for recovering n,n-dimethylformamide (dmf) from an aqueous process stream

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Denomination of invention: Recovery of DMF and inorganic salts from ceftazidime side chain ester wastewater

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Denomination of invention: Recovery method of DMF and inorganic salts from ceftazidime side-chain ester wastewater

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