WO2012088951A1 - 一种制药工业溶媒回收的工艺 - Google Patents

一种制药工业溶媒回收的工艺 Download PDF

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WO2012088951A1
WO2012088951A1 PCT/CN2011/081211 CN2011081211W WO2012088951A1 WO 2012088951 A1 WO2012088951 A1 WO 2012088951A1 CN 2011081211 W CN2011081211 W CN 2011081211W WO 2012088951 A1 WO2012088951 A1 WO 2012088951A1
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solvent
membrane
water
column
vehicle
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PCT/CN2011/081211
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French (fr)
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邢卫红
顾学红
陈纲领
丁晓斌
徐南平
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南京工业大学
南京九思高科技有限公司
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Publication of WO2012088951A1 publication Critical patent/WO2012088951A1/zh

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/36Pervaporation; Membrane distillation; Liquid permeation
    • B01D61/362Pervaporation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D3/00Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14Fractional distillation or use of a fractionation or rectification column
    • B01D3/143Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step

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  • the present invention relates to a solvent recovery process in the pharmaceutical industry, and belongs to the field of solvent resource recycling. Background technique
  • Solvent recovery is an important process in the pharmaceutical industry and ink production.
  • Organic solvents such as extractants, detergents, and reactants used in drug production and refining processes can be reused after being recycled. If solvent recovery is not carried out, environmental pollution is caused on the one hand and production costs are increased on the other hand.
  • water and trace amounts of pharmaceutical ingredients must be removed.
  • the solid impurities in the waste solvent are usually removed by steaming, and then part of the water in the waste solvent is removed by fine boring, and the azeotrope formed by the solvent and water from the fine column is subjected to azeotropic distillation and extraction.
  • the object of the present invention is to provide a solvent recovery process for a pharmaceutical industry, which has the characteristics of simple process, high recovery efficiency, low production cost, and clean and pollution-free.
  • the technical scheme of the present invention is: a pharmaceutical industry solvent recovery process, the specific steps are as follows: the mother liquor from the pharmaceutical production workshop is adjusted to pH 2-4 by acid addition to remove the organic alkaline component in the solvent, and heated Steaming, the temperature is controlled at 50 ° C -150 ° C, the mother liquor distilled from the base is adjusted to pH 8-11 by alkali to further remove the organic acidic components in the solvent, and then enter the fine tower for fine separation, light components in the tower The top collection, heavy components (water and solvent) enter the tower kettle; the catalyst is discharged from the tower to the sub-fine tower to recover the solvent solution; the solvent solution recovered by the sub-fine column is passed to the pervaporation membrane separation unit for alcohol-water separation, after dehydration The solvent product is obtained and enters the pharmaceutical production workshop as a solvent for reuse.
  • the above-mentioned mass percentage of water in the solvent solution for separating the pervaporation membrane separation unit into the pervaporation membrane separation unit by the sub-fine separation tower is 5-30%; the quality of the water in the solvent product after dehydration by the pervaporation membrane separation unit The percentage is 0. 01-3%.
  • the pervaporation membrane separation unit is divided into a permeate side and a liquid side, a permeate side is a vapor phase side, a liquid side is a liquid phase side, a vapor phase side is connected to a vacuum system, and a vapor pump is used to maintain the vapor.
  • the phase side pressure is 1000P a -5000Pa
  • the solvent aqueous solution is separated from the water by the pervaporation membrane separation unit, and a high concentration of the solvent product is obtained at the outlet of the pervaporation membrane separation unit, and the water forms a vapor phase on the permeate side through the membrane at the pressure. It is separated from the solvent solution by vaporization condensation at 1000 Pa to 5000 Pa.
  • the above solvent solution is preheated to 50-150 ° C and then enters the pervaporation membrane separation unit in the form of liquid or vapor.
  • the pervaporation membrane separation unit described above achieves different processing requirements and production capacities by parallel or series combination of 1-200 membrane separators.
  • the membrane used in the membrane separator is a water permeable membrane, preferably a chitosan membrane, a PVA membrane, a PVDF membrane, a sodium alginate membrane or a molecular sieve membrane.
  • the acid for adjusting the pH is sulfuric acid, nitric acid or hydrochloric acid; and the base is sodium oxide or potassium hydroxide.
  • the third component is not required to be added in the solvent recovery process of the present invention, and the environmental pollution caused by the addition of the third component and the reprocessing cost of the third component are omitted.
  • the process of azeotropic distillation and extraction of fine boring is eliminated, the energy consumption for recycling is reduced, the water content of the recovered solvent product reaches the recycling requirement, and the product quality of the solvent is improved.
  • the solvent recovery process does not require the addition of the third component and the ablation of the azeotropic distillation and the extraction of the fine boring process, thereby reducing the production cost, the invention process is compatible with the existing azeotropic distillation and extraction techniques. It is 30% -70% lower than its production cost.
  • the solvent recovery process of the invention has no other waste discharge except water, high resource utilization rate, small whole process area and simple operation, and is a clean and efficient solvent recovery method.
  • Figure 1 is a flow chart of waste solvent recovery process in the pharmaceutical process
  • the light component is mainly ethyl acetate, which is collected at the top of the tower, and the heavy components are mainly water and isopropyl alcohol.
  • the slurry is discharged from the column kettle 9 into the sub-fine column 10, and the isopropanol is recovered and a small amount of high-boiling impurities in the isopropanol are removed.
  • the 17% isopropyl alcohol solution recovered by the sub-fine column 10 is introduced into the raw material tank 12, and the liquid in the raw material tank 12 is pumped into a membrane separator composed of 6 sets of NaA molecular sieve membranes.
  • the pervaporation membrane separation unit 13 performs the separation of the alcohol and water, the pressure of the feed liquid is 0.25 MPa, the pressure on the permeate side is controlled at 2700 Pa, the feed temperature of the pervaporation membrane separator is controlled at 80 ° C, and the isopropyl chloride after the water is removed.
  • the mass percentage of water in the alcohol product reached 1.2%, and was reused as a solvent in the cephalosporin production workshop.
  • the butanol solution with 15% by mass of water recovered by the sub-fine column 10 is vaporized into the pervaporation membrane separation unit 13 composed of 8 membrane separators composed of NaA molecular sieve membranes for separation of alcohol and water, and the liquid is separated.
  • the pressure of the osmotic pressure of the osmotic membrane is controlled at 1500 Pa
  • the feed temperature of the pervaporation membrane separator is controlled at 120 ° C
  • the mass percentage of water in the butanol product after the completion of the water reaches 0.1%, for Antibiotic production workshop reused as solvent
  • the membrane separation unit 13 performs the separation of the alcohol and water, the pressure of the feed liquid is 0.22 MPa, the pressure of the permeate side is controlled at 2000 Pa, the feed temperature of the pervaporation membrane separator is controlled at 100 ° C, and the water of the ethanol product after the water is removed.
  • the mass percentage was 0.05%, and it was reused as a solvent in the Chinese medicine extraction production workshop.

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  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

一种制药工业溶媒回收的工艺 技术领域
[0001 ] 本发明涉及制药工业溶媒回收工艺,属于溶媒资源回收利用领域。 背景技术
[0002] 溶媒回收是制药工业、油墨生产中的重要工序,在药物生产、精制过程中使用的萃 取剂、洗涤剂、反应剂等有机溶媒经过回收环节的处理,可以重复使用。 如果不进行溶媒回 收,一方面造成环境污染,另一方面生产成本提高。 为了使溶媒循环利用,必须将水和微量 药物成分除去。 传统工艺通常是先通过蒸熘除去废溶媒中的固体杂质,然后再通过精熘除 去废溶媒中的部分水分,从精熘塔出来的溶媒与水形成的共沸物再采用恒沸蒸馏、萃取精 熘及片碱脱水等技术进一步脱除其中的水分从而达到再次使用的产品质量要求,这些技术 的共同点是都需要将待脱水的物料体系完全汽化,其消耗的相变潜热巨大,高能耗导致运 行成本居高不下,并且这些方法都存在大量增加另外一种物质(一般是有毒有害的物质) 在生产操作中存在人身危害和环境污染问题。 同时该溶媒回收方法操作复杂,人工费用相 应较高,溶媒回收利用率低。 为了降低溶媒回收能耗,提高溶媒回收效率,简化工艺路线, 提高溶媒的产品质量,降低生产成本,特开发出本申请专利所提出的清洁、高效溶媒回收工 艺。 发明内容
[0003] 本发明的目的在于提供一种制药工业溶媒回收工艺,该方法具有工艺简单,回收 效率高,生产成本低,清洁无污染的特点。
[0004] 本发明的技术方案为:一种制药工业溶媒回收的工艺,其具体步骤如下:对来自 制药生产车间的母液通过加酸调节 pH为 2-4去除溶媒中的有机碱性成分,加热蒸熘,温度 控制在 50°C -150°C,蒸熘出的母液经碱调节 pH为 8-11进一步去除溶媒中的有机酸性成分 后进入精熘塔进行精熘分离,轻组分在塔顶收集,重组分(水和溶媒)进入塔釜;由塔釜出 料进入子精熘塔回收溶媒溶液;通过子精熘塔回收的溶媒溶液进入渗透汽化膜分离机组进 行醇水分离,脱水后得到溶媒产品进入制药生产车间作为溶媒重新使用。
[0005] 上述通过子精熘塔回收进入渗透汽化膜分离机组进行醇水分离的溶媒溶液中水 的质量百分量为 5-30 %;经过渗透汽化膜分离机组脱水后的溶媒产品中水的 质量百分量 为 0. 01-3 %。
[0006] 所述的渗透汽化膜分离机组分为渗透侧和料液侧,渗透侧为汽相侧,料液侧为液 相侧,汽相侧与真空系统相连接,通过真空泵抽吸维持汽相侧压力在 1000Pa-5000Pa,溶媒 水溶液经过渗透汽化膜分离机组将溶媒与水分离,在渗透汽化膜分离机组出口处获得高浓 度的溶媒产品,水经过膜在渗透侧形成汽相,在压力 1000Pa-5000Pa下经汽化冷凝从溶媒 溶液中分离出来。
[0007] 上述的溶媒溶液先预热到 50-150°C后以液体或蒸汽形式进入到渗透汽化膜分离 机组。 [0008] 上述的渗透汽化膜分离机组是由 1-200个膜分离器的并联或串连组合达到不同 的处理要求和生产能力。膜分离器所采用的膜为透水膜,优选壳聚糖膜、 PVA膜、 PVDF膜、海 藻酸钠膜或分子筛膜。
[0009] 上述调节 pH值的酸为硫酸、硝酸或盐酸;所述的碱为氧化钠或氢氧化钾。
[0010] 有益效果:与现有技术相比,本发明溶媒回收过程中无需添加第三组分,省去了第 三组分的添加对环境造成的污染及第三组分的再处理费用,省去了恒沸蒸熘、萃取精熘过 程,降低了回收能耗,回收的溶媒产品中水含量达到回用要求,提高了溶媒的产品质量。 由 于该溶媒回收过程中无需第三组分的添加及恒沸蒸熘、萃取精熘过程的省去,从而降低了 生产成本,该发明工艺与现有的恒沸蒸熘、萃取精熘技术相比其生产成本降低 30 % -70 %。 该发明溶媒回收过程中除水外无其他废弃物的排放,资源利用率高,整套工艺占地面积小, 操作简单,是一种清洁、高效的溶媒回收方法。 附图说明
[001 1 ] 图 1为制药过程中废溶媒回收工艺流程图;
[001 2] 其中 1是供料泵, 2是蒸熘釜, 3是蒸熘塔, 4是冷凝器, 5是母液罐, 6是预热器, 7 是精熘塔, 8是冷凝器, 9是塔釜, 10是子精熘塔, 11是冷凝器, 12是原料罐, 13是渗透汽化 膜分离机组, A为废溶媒, B为蒸熘出的轻组分, C为溶媒产品, D为渗透液。 具体实施方式
[001 3] 实施例 1:
[0014] 将来自头孢生产车间的异丙醇溶媒母液在蒸熘釜 2中加硫酸调节 pH = 3,加 热蒸 熘温度控制在 81 °C,蒸熘出的母液加氢氧化钠调节 pH = 11后,进入溶媒回收车间,精熘塔 7与塔釜 9上来的溶媒蒸汽进行热交换,轻组分主要是乙酸乙酯,在塔顶收集,重组分主要 是水和异丙醇进入塔釜 9,由塔釜 9出料进入子精熘塔 10,回收异丙醇并除去异丙醇中的少 量高沸点杂质。通过子精熘塔 10回收的水质量百分量为 17 %的异丙醇溶液进入原料罐 12, 由泵把原料罐 12中的料液打入由 6组采用 NaA分子筛膜组成的膜分离器构成的渗透汽化 膜分离机组 13进行醇水分离,料液测压力为 0. 25MPa,渗透侧压力控制在 2700Pa,渗透汽化 膜分离器的进料温度控制在 80 °C,脱完水后的异丙醇产品中水的质量百分量达到 1. 2 %, 供头孢生产车间作为溶媒重新使用。
[001 5] 实施例 2:将来自抗生素生产车间的丁醇溶媒母液在蒸熘釜中加盐酸调节 pH = 2, 加热蒸熘温度控制在 98°C,蒸熘出的母液加氢氧化钾调节 pH = 9后,进入溶媒回收车间精 熘塔 7与塔釜 9上来的溶媒蒸汽进行热交换,轻组分如乙酸乙酯等在塔顶收集,重组分主要 是水和丁醇进入塔釜 9,由塔釜 9出料进入子精熘塔 10。 通过子精熘塔 10回收的水质量百 分量为 15 %的丁醇溶液以蒸汽形式进入由 8组采用 NaA分子筛膜组成的膜分离器构成的 渗透汽化膜分离机组 13进行醇水分离,料液测压力为 0. 25MPa,渗透侧压力控制在 1500Pa, 渗透汽化膜分离器的进料温度控制在 120 °C,脱完水后的丁醇产品中水的质量百分量达到 0. 1 %,供抗生素生产车间作为溶媒重新使用
[001 6] 实施例 3:将来自中药提取生产车间的乙醇溶媒母液在蒸熘釜 2中加硫酸调节 pH = 4,加热蒸熘温度控制在 78°C,蒸熘出的母液加氢氧化钠调节 pH = 11后,进入溶媒回收 车间,在精熘塔 7中与塔釜 9上来的溶媒蒸汽进行热交换,轻组分在塔顶收集,重组分主要 是水和乙醇进入塔釜 9,由塔釜 9出料进入子精熘塔 10。 通过子精熘塔 10回收的水质量百 分量为 7 %的乙醇溶液进入原料罐 12,由泵把原料罐 12中的料液打入由 6组采用 PVDF膜 组成的膜分离器构成的渗透汽化膜分离机组 13进行醇水分离,料液测压力为 0. 22MPa,渗 透侧压力控制在 2000Pa,渗透汽化膜分离器的进料温度控制在 100 °C,脱完水后的乙醇产 品中水的质量百分量为 0. 05 %,进入中药提取生产车间作为溶媒重新使用。

Claims

权 利 要 求
1. 一种制药工业溶媒回收的工艺,其具体步骤如下:对来自制药生产车间的母液通过 加酸调节 PH为 2-4去除溶媒中的有机碱性成分,加热蒸熘,温度控制在 50°C -150°C,蒸熘 出的母液经碱调节 pH为 8-11进一步去除溶媒中的有机酸性成分后进入精熘塔进行精熘分 离,轻组分在塔顶收集,重组分(水和溶媒)进入塔釜;由塔釜出料进入子精熘塔回收溶媒 溶液;通过子精熘塔回收的溶媒溶液进入渗透汽化膜分离机组进行醇水分离,脱水后得到 溶媒产品进入制药生产车间作为溶媒重新使用。
2. 根据权利要求 1所述的工艺,其特征在于通过子精熘塔回收进入渗透汽化膜分离机 组进行醇水分离的溶媒溶液中水的质量百分量为 5-30 %;经过渗透汽化膜分离机组脱水后 的溶媒产品中水的质量百分量为 0. 01-3 %。
3. 根据权利要求 1所述的工艺,其特征在于所述的渗透汽化膜分离机组分为渗透侧和 料液侧,渗透侧为汽相侧,料液侧为液相侧,汽相侧与真空系统相连接,通过真空泵抽吸维 持汽相侧压力在 1000Pa-5000Pa。
4. 根据权利要求 1所述的工艺,其特征在于所述的溶媒溶液预热到 50-150 °C,以液体 或蒸汽形式进入到渗透汽化膜分离机组。
5. 根据权利要求 1所述的工艺,其特征在于渗透汽化膜分离机组由 1-200个膜分离器 的并联或串连组合。
6. 根据权利要求 5所述的工艺,其特征在于膜分离器所采用的膜为透水膜,优选壳聚 糖膜、 PVA膜、 PVDF膜、海藻酸钠膜或分子筛膜。
7.根据权利要求 1所述的工艺,其特征在于所述的酸为硫酸、硝酸或盐酸;所述的碱为 氢氧化钠或氢氧化钾。
PCT/CN2011/081211 2010-12-28 2011-10-24 一种制药工业溶媒回收的工艺 WO2012088951A1 (zh)

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