牛磺酸的制备及电渗析除盐新工艺
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摘要
牛磺酸是名贵中药“牛黄”的重要成分之一，具有广泛的医疗和营养保健作用。该产品需求量很大。本文通过延续国内大多牛磺酸生产厂家的合成路线即用乙醇胺和浓硫酸为酯化原料合成2-氨乙基硫酸酯(AES)，用AES和亚硫酸钠经磺化得牛磺酸母液的工艺路线。但在对牛磺酸母液的处理中，将电渗析技术引用到了除盐纯化牛磺酸过程。对比国内目前大多采用的盐酸-乙醇工艺除盐法，电渗析技术的引用有自己特有的优势。
在合成AES过程中，通过对比实验，首选了正丁醇作脱水剂，该脱水剂与甲苯相比具有较大优点。本文探寻了合成AES的工艺条件，找到了酯化反应的合理加料顺序、硫酸滴加温度、回流时间、配料比等，获得了纯度为95％以上、收率为98％以上的AES。
在合成牛磺酸(磺化)过程中，通过水解实验研究了反应条件下AES水解对牛磺酸产率的影响可忽略不计；发现造成牛磺酸产率低的原因之一是亚硫酸钠的氧化，在实验中采用通入氮气保护、水除氧的方法解决了此问题；实验用用跟踪分析测定亚硫酸钠含量确定了磺化反应进程，得出12小时左右磺化反应基本结束的结论。在磺化过程中，AES和亚硫酸钠的浓度增大都对牛磺酸产率的提高有影响，故亚硫酸钠浓度为近饱和为佳。推测了AES与亚硫酸钠合成牛磺酸的反应动力学，动力学近似方程为dx／dt=0.0241x~2-0.0982(a-x)~2；初步认为反应是按SN2历程进行的。
传统工艺采用盐酸—乙醇法除盐纯化牛磺酸母液。其弊端是成本高、操作繁琐、排放的废液对环境造成污染。本文采用了电渗析膜分离除盐纯化牛磺酸的工艺。设计了二泵式电渗析器，测试了其主要性能参数。实验结果表明：二泵式电渗析器克服了四泵式的诸多缺点，降低了电极电位，节省能源并减少了副产品的产生。经电渗析除盐后蒸馏、脱水、干燥、结晶，得到各项指标符合国家标准的牛磺酸产品。实验用操作电压作为控制指标，操作电压的选择根据除盐阶段的不同相应不同以控制电渗析在极限电流以下运行。用电导率值作为衡量牛磺酸含盐量指标，其优点是可以用电导率仪对脱盐进程进行实时监控。在电渗析过程中存在牛磺酸流失较大这一问题，试验查出了牛磺酸母液含盐量的大小对牛磺酸收率有较大影响这一因素，得出含盐量越高，牛磺酸转移到浓缩室的量就越多，即牛磺酸流失越严重这一结论。
Taurine is one of the vital components of bezoar which is a Chinese traditional medicine that is good for medical treatment and health care. There is a great demand for it. The domestic preparation method for taurine used by most manufacturers is based on the following steps: synthesis of 2-aminoethyl sulfuric ester (AES), following sulfonation with Na2SO3 to get the taurine mother liquid. The paper's work is mainly focused on the above route, but introduces electrodialysis technique into the desalting purifying of taurine. In contrast, this electrodialysis technique has a specific advantage over the domestic technique of hydrochloric acid-ethanol desalting.
In the process of esterification to get 2-aminoethyl sulfuric ester (AES), by contrasting, a series of organic solvents are used to finally select n-butanol as a dehydrant. The dehydrant has much goodness over toluene. The esterification conditions of synthesizing AES are optimized and the best material adding sequence, sulfuric acid dropping temperature, refluxing time, material ratio, etc. The purity of product (AES) and the yield both reaches above 97%.
In the process of sulfonation, it is found that AES hydrolysis at the reaction conditions doesn't have a large effect on the yield of taurine and it is found that one of the factor causing the low yield is the oxidation of Na2SO3. Protection under nitrogen and deoxygenation of water are adopted to solve the problem. Iodine titration is made to trace the content of Na2SO3, and thus the sulfonation state can be known, and the sulfonation ends over a period of 12h. Increases of concentration of AES and Na2SO3 effect favorably the yield of taurine and the nearly saturated Na2SO3 is better. Kinetics of reaction of AES with Na2SO3 is proposed, and the approximate equation is dx/dt = 0.0241x2-0.0982(a-x)2. SN2 kinetics is supposed for the reaction.
Conventional hydrochloric acid-ethanol desalting technique runs on a basis of complex operation, high cost, and some pollution. In our research work, a new technique that adopts electrodialysis membrane separation desalting to purify taurine is introduced. A two-pump electrodialysis device is designed and main parameters of the device are tested. The results show that the two-pump one can overcome some
drawbacks of the existing four-pump device. The electrode potential is reduced, energy is saved, and side-products are decreased. Taurine of high quality is obtained through electrodialysis desalting, distillation, dehydration, drying, crystallization. Experimental voltage is used as a controlling index, which varies at different stage of desalting to control the electrodialysis is working under its utmost electricity. Conductivity is used to represent the content of salt in the taurine product so that the desalting process can be monitored. According to the loss of taurine during electrodialysis, it is found that the content of salt in the taurine mother liquid has a effect on the yield of taurine. The conclusion that high content of salt causes more transfer of taurine into concentrating chamber i.e. more loss of taurine is reached.
在合成AES过程中，通过对比实验，首选了正丁醇作脱水剂，该脱水剂与甲苯相比具有较大优点。本文探寻了合成AES的工艺条件，找到了酯化反应的合理加料顺序、硫酸滴加温度、回流时间、配料比等，获得了纯度为95％以上、收率为98％以上的AES。
在合成牛磺酸(磺化)过程中，通过水解实验研究了反应条件下AES水解对牛磺酸产率的影响可忽略不计；发现造成牛磺酸产率低的原因之一是亚硫酸钠的氧化，在实验中采用通入氮气保护、水除氧的方法解决了此问题；实验用用跟踪分析测定亚硫酸钠含量确定了磺化反应进程，得出12小时左右磺化反应基本结束的结论。在磺化过程中，AES和亚硫酸钠的浓度增大都对牛磺酸产率的提高有影响，故亚硫酸钠浓度为近饱和为佳。推测了AES与亚硫酸钠合成牛磺酸的反应动力学，动力学近似方程为dx／dt=0.0241x~2-0.0982(a-x)~2；初步认为反应是按SN2历程进行的。
传统工艺采用盐酸—乙醇法除盐纯化牛磺酸母液。其弊端是成本高、操作繁琐、排放的废液对环境造成污染。本文采用了电渗析膜分离除盐纯化牛磺酸的工艺。设计了二泵式电渗析器，测试了其主要性能参数。实验结果表明：二泵式电渗析器克服了四泵式的诸多缺点，降低了电极电位，节省能源并减少了副产品的产生。经电渗析除盐后蒸馏、脱水、干燥、结晶，得到各项指标符合国家标准的牛磺酸产品。实验用操作电压作为控制指标，操作电压的选择根据除盐阶段的不同相应不同以控制电渗析在极限电流以下运行。用电导率值作为衡量牛磺酸含盐量指标，其优点是可以用电导率仪对脱盐进程进行实时监控。在电渗析过程中存在牛磺酸流失较大这一问题，试验查出了牛磺酸母液含盐量的大小对牛磺酸收率有较大影响这一因素，得出含盐量越高，牛磺酸转移到浓缩室的量就越多，即牛磺酸流失越严重这一结论。
Taurine is one of the vital components of bezoar which is a Chinese traditional medicine that is good for medical treatment and health care. There is a great demand for it. The domestic preparation method for taurine used by most manufacturers is based on the following steps: synthesis of 2-aminoethyl sulfuric ester (AES), following sulfonation with Na2SO3 to get the taurine mother liquid. The paper's work is mainly focused on the above route, but introduces electrodialysis technique into the desalting purifying of taurine. In contrast, this electrodialysis technique has a specific advantage over the domestic technique of hydrochloric acid-ethanol desalting.
In the process of esterification to get 2-aminoethyl sulfuric ester (AES), by contrasting, a series of organic solvents are used to finally select n-butanol as a dehydrant. The dehydrant has much goodness over toluene. The esterification conditions of synthesizing AES are optimized and the best material adding sequence, sulfuric acid dropping temperature, refluxing time, material ratio, etc. The purity of product (AES) and the yield both reaches above 97%.
In the process of sulfonation, it is found that AES hydrolysis at the reaction conditions doesn't have a large effect on the yield of taurine and it is found that one of the factor causing the low yield is the oxidation of Na2SO3. Protection under nitrogen and deoxygenation of water are adopted to solve the problem. Iodine titration is made to trace the content of Na2SO3, and thus the sulfonation state can be known, and the sulfonation ends over a period of 12h. Increases of concentration of AES and Na2SO3 effect favorably the yield of taurine and the nearly saturated Na2SO3 is better. Kinetics of reaction of AES with Na2SO3 is proposed, and the approximate equation is dx/dt = 0.0241x2-0.0982(a-x)2. SN2 kinetics is supposed for the reaction.
Conventional hydrochloric acid-ethanol desalting technique runs on a basis of complex operation, high cost, and some pollution. In our research work, a new technique that adopts electrodialysis membrane separation desalting to purify taurine is introduced. A two-pump electrodialysis device is designed and main parameters of the device are tested. The results show that the two-pump one can overcome some
drawbacks of the existing four-pump device. The electrode potential is reduced, energy is saved, and side-products are decreased. Taurine of high quality is obtained through electrodialysis desalting, distillation, dehydration, drying, crystallization. Experimental voltage is used as a controlling index, which varies at different stage of desalting to control the electrodialysis is working under its utmost electricity. Conductivity is used to represent the content of salt in the taurine product so that the desalting process can be monitored. According to the loss of taurine during electrodialysis, it is found that the content of salt in the taurine mother liquid has a effect on the yield of taurine. The conclusion that high content of salt causes more transfer of taurine into concentrating chamber i.e. more loss of taurine is reached.
引文
[1] Gmelin, Pogg. Ann., 1927.9:327
[2] Demarcay, Ann., 1838.27:286
[3] Watson, J.Biol. Chem. 1918.33:499
[4] James, J. Biol. Chem. 1927.73: 651
[5] 韩金勇．牛磺酸生产应用及市场前景．化学技术经济．2002第一期：29-32
[6] 特公昭．40—2307
[7] Surer, The Org. Chem. Of Sul, Wiely. 1948. 192：118—126
[8] White, J. Biol. Chem. 1936. 116:457
[9] 特开昭．57—26634
[10] 特开昭．63—243066
[11] 特公昭．38—16462
[12] Alfons, Z.Physiol.Chem. 1933.216:: 193-195
[13] Loeper, Bull Soc.Chem.Biol.1928.10:316
[14] Goldbery, J. Chem. Soc, 1943. 4:05
[15] 特开昭．60—214770
[16] 特开平．7—17943
[17] 崔建兰．吕月仙．牛磺酸的研究进展 华北工学院 1998第19卷第一期：18-20
[18] 特开昭61—44188
[19] 乙醇胺法化学合成牛磺酸．化学世界．1996．9：494-496
[20] FerrazH.C.AlvesT.L.M ElectrodialysisEqipmentMetal Finishing Volume:95,Issue 12December,1997:67
[21] 崛江浩文．交換膜膜分離技術．化学工学，1998，62(5)：32-36
[22] Electrochemical ion exchange Membrane Technology Volume: 1996, Issue: 75,1996,:6-9
[23] 张艳华 田景新 电渗析在化工行业中应用展望 辽宁化工1997，3 Vol．26，No．2 13-17
[24] 华何林 吴光夏等 电渗析技术的新进展 环境污染治理技术与设备2001，6 Vol．2，No．3：16-20
[25] 王芳 混合床离子交换树脂的电再生．工业水处理，1997．2：1-3
[26] 徐铜文．孙树声等．双极膜电渗析的组装方式及其功用．膜科学与技术2002．2：1
[27] 陈平．膜科学与技术2001，12 vol．21 No．6：69-71
[28] Ferraz H. C. Alves T.L.M Electrodialysis Eqipment Metal Finishing Volume:95,Issue 12December, 1997,pp.67
[29] 刘茉蛾等．膜分离技术．1998：6
[30] 时钧．袁权等 膜技术手册：433
[31] Audinos, R.Ion-exchange membrane processes for clean industrial chemistry. Chemical Engineering &Technology, 1997, 20(4):237-258
[32] Rehkamper Mark. A highly sensitive HPLC method for the determination of Th and U 2001.8:16-20
[33] 唐宏科等，乙醇胺脂化法制备牛磺酸的新工艺研究，石油化工，2002-3-14：29-30
[34] 特开昭60-23360
[35] JP63—48259
[36] Redtenbacber, Ann. 1948 65.:37
[37] 时钧．袁权等 膜技术手册：422
[38] Solt George Early Days in ElectroDialysis Desalination Volume: 100, Issue 13, Jan. 1995:15-19
[39] George Solt. Electrodialysis in handbook fo water purification. Waiter lorch(ed)
[40] 冯兴奎．电渗析膜技术的应用 武汉化工学院学报．1996．6：11
[41] 曹连城 离子交换膜选择透过性的测定 武汉化工学院学报vol．21 No．3
[42] 华何林 吴光夏等 电渗析技术的新进展 环境污染治理技术与设备2001，6 Vol．2,No．3：16-20
[43] Electrodialysis membrane Technology Volume: 2002 Issue 5, May, 2002:12
[44] 王佳基．电渗析极化及处理措施．1994，7：341-344
[45] 吴文珊等 电渗析器极限电流的测定 湖北化工1999，3：26-28
[46] 陆九芳等．分离过程化学：233-234
[47] 莫剑雄 诸爱士 生产过程中牛磺酸含量的分析 浙江化工2001，6：36-43
[48] 中华人民共和国国家标准 GB 14759-93(食品添加剂-牛磺酸)
[2] Demarcay, Ann., 1838.27:286
[3] Watson, J.Biol. Chem. 1918.33:499
[4] James, J. Biol. Chem. 1927.73: 651
[5] 韩金勇．牛磺酸生产应用及市场前景．化学技术经济．2002第一期：29-32
[6] 特公昭．40—2307
[7] Surer, The Org. Chem. Of Sul, Wiely. 1948. 192：118—126
[8] White, J. Biol. Chem. 1936. 116:457
[9] 特开昭．57—26634
[10] 特开昭．63—243066
[11] 特公昭．38—16462
[12] Alfons, Z.Physiol.Chem. 1933.216:: 193-195
[13] Loeper, Bull Soc.Chem.Biol.1928.10:316
[14] Goldbery, J. Chem. Soc, 1943. 4:05
[15] 特开昭．60—214770
[16] 特开平．7—17943
[17] 崔建兰．吕月仙．牛磺酸的研究进展 华北工学院 1998第19卷第一期：18-20
[18] 特开昭61—44188
[19] 乙醇胺法化学合成牛磺酸．化学世界．1996．9：494-496
[20] FerrazH.C.AlvesT.L.M ElectrodialysisEqipmentMetal Finishing Volume:95,Issue 12December,1997:67
[21] 崛江浩文．交換膜膜分離技術．化学工学，1998，62(5)：32-36
[22] Electrochemical ion exchange Membrane Technology Volume: 1996, Issue: 75,1996,:6-9
[23] 张艳华 田景新 电渗析在化工行业中应用展望 辽宁化工1997，3 Vol．26，No．2 13-17
[24] 华何林 吴光夏等 电渗析技术的新进展 环境污染治理技术与设备2001，6 Vol．2，No．3：16-20
[25] 王芳 混合床离子交换树脂的电再生．工业水处理，1997．2：1-3
[26] 徐铜文．孙树声等．双极膜电渗析的组装方式及其功用．膜科学与技术2002．2：1
[27] 陈平．膜科学与技术2001，12 vol．21 No．6：69-71
[28] Ferraz H. C. Alves T.L.M Electrodialysis Eqipment Metal Finishing Volume:95,Issue 12December, 1997,pp.67
[29] 刘茉蛾等．膜分离技术．1998：6
[30] 时钧．袁权等 膜技术手册：433
[31] Audinos, R.Ion-exchange membrane processes for clean industrial chemistry. Chemical Engineering &Technology, 1997, 20(4):237-258
[32] Rehkamper Mark. A highly sensitive HPLC method for the determination of Th and U 2001.8:16-20
[33] 唐宏科等，乙醇胺脂化法制备牛磺酸的新工艺研究，石油化工，2002-3-14：29-30
[34] 特开昭60-23360
[35] JP63—48259
[36] Redtenbacber, Ann. 1948 65.:37
[37] 时钧．袁权等 膜技术手册：422
[38] Solt George Early Days in ElectroDialysis Desalination Volume: 100, Issue 13, Jan. 1995:15-19
[39] George Solt. Electrodialysis in handbook fo water purification. Waiter lorch(ed)
[40] 冯兴奎．电渗析膜技术的应用 武汉化工学院学报．1996．6：11
[41] 曹连城 离子交换膜选择透过性的测定 武汉化工学院学报vol．21 No．3
[42] 华何林 吴光夏等 电渗析技术的新进展 环境污染治理技术与设备2001，6 Vol．2,No．3：16-20
[43] Electrodialysis membrane Technology Volume: 2002 Issue 5, May, 2002:12
[44] 王佳基．电渗析极化及处理措施．1994，7：341-344
[45] 吴文珊等 电渗析器极限电流的测定 湖北化工1999，3：26-28
[46] 陆九芳等．分离过程化学：233-234
[47] 莫剑雄 诸爱士 生产过程中牛磺酸含量的分析 浙江化工2001，6：36-43
[48] 中华人民共和国国家标准 GB 14759-93(食品添加剂-牛磺酸)