维生素C生产中古龙酸回收工艺研究
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摘要
2-酮基-L-古龙酸又叫古龙酸,是维生素C生产中重要的中间体,古龙酸的收率高低直接影响到维生素C成本,本文研究了吸附法预处理古龙酸母液,母液转型盐析结晶回收古龙酸钠,古龙酸钠用阳离子树脂交换回收古龙酸的工艺。
在实验中,吸附法预处理古龙酸母液与本厂目前工艺进行了比较;通过对四种转型剂、析出剂研究对比,筛选出较为理想的Na2CO3作为转型剂、CH3OH为析出剂。研究了影响古龙酸钠盐析结晶的主要操作条件:加入晶种温度、晶种的用量、析出温度、保温时间对产品收率的影响,筛选出最佳的盐析结晶回收工艺条件,即加入晶种的温度为23～24℃,晶种用量为0.8～1.0g,析出温度为0～﹣2℃,保温时间为1h;研究并筛选出古龙酸钠交换成古龙酸采用X型树脂交换时最佳工艺条件为:15%的古龙酸钠溶液,用床层高径比为10的X型树脂进行交换,出料速度控制3倍柱体积收集PH﹤1.7的溶液,溶液浓缩降温结晶,得到古龙酸。结果表明,采用此回收工艺古龙酸的回收收率可达到77.63%以上,比原工艺提高了二十个百分点,古龙酸干品质量明显提高,含量达到了88.54%,提高了3%;由回收古龙酸经酯化、转化的维生素C钠含量、收率也较目前工艺分别提高1.27%和1.95%。
研究结果表明,采用吸附法处理古龙酸母液、母液转型盐析结晶和X型树脂交换法回收古龙酸工艺与原工艺相比,无论从产品收率及中间体的质量方面都有明显提高。而又具有易分离、无污染、无腐蚀性的优点,是一种极具潜力的绿色环保型回收工艺。
2 -Keto-L-gulonic acid is the important intermediate during producing Vitamin C, and its receiving rate influences the cost of Vitamin C directly. In this article, the salting out crystallization law to recycle gulong sodium, Gulong sodium dissolves and cation exchange resin recovering gulonic acid recovery process has been studied.
Through the transformation of four different agents, precipitation contrast agent research, selected a more ideal agent Na2CO3 as a transition, CH3OH as precipitation agent. In this experiment, the main operating condition which affecting the 2 - keto-L-gulonic sodium salt out and crystal has been studied: Adding crystal seeds of temperature, the amount of seed, precipitation temperature, holding time on the yield of products, Selected the best salt analysis of the crystallization of the recovery process conditions, namely by adding crystal seeds of the temperature of 23 ~ 24℃, the amount of seeds for the 0.8g ~ 1.0g, precipitation temperature of 0 ~ -2℃, holding time for 1h.At the same time, research on using of X-resin exchange to translate sodium gulong sodium into gulonic acid has been done, and the best conditions were as follows: 15% sodium gulong with bed height to diameter ratio of 10 X-exchange resin, the material speed control 3 times the size of the collection of columns PH <1.7 of the solution, the solution concentrated cooling crystallization recovered gulonic acid goods.The results showed that the introduction of new recycling technology of vitamin C intermediates of 2 - Keto-L-gulonic acid recovery yield of 77.63% to reach more than the original 20.00%, The dry goods quality of 2 - Keto-L-gulonic acid was significantly improved and the content has achieved 88.54%, the present craft enhanced 3%.The Vc-Na,s making by gulonic acid recovery content and yield is enhanced1.27% and 1.95%.
The results show that the use of salting-out crystallization transition and X-type exchange resin recycling 2-Keto-L-gulonic acid new technology has markedly improved in terms of product yield and quality of intermediate, comparing with the original process. Easy separation and pollution-free, non-corrosive non-corrosiveness, is one kind of a potential type of green environment-friendly recycling processes.
在实验中,吸附法预处理古龙酸母液与本厂目前工艺进行了比较;通过对四种转型剂、析出剂研究对比,筛选出较为理想的Na2CO3作为转型剂、CH3OH为析出剂。研究了影响古龙酸钠盐析结晶的主要操作条件:加入晶种温度、晶种的用量、析出温度、保温时间对产品收率的影响,筛选出最佳的盐析结晶回收工艺条件,即加入晶种的温度为23～24℃,晶种用量为0.8～1.0g,析出温度为0～﹣2℃,保温时间为1h;研究并筛选出古龙酸钠交换成古龙酸采用X型树脂交换时最佳工艺条件为:15%的古龙酸钠溶液,用床层高径比为10的X型树脂进行交换,出料速度控制3倍柱体积收集PH﹤1.7的溶液,溶液浓缩降温结晶,得到古龙酸。结果表明,采用此回收工艺古龙酸的回收收率可达到77.63%以上,比原工艺提高了二十个百分点,古龙酸干品质量明显提高,含量达到了88.54%,提高了3%;由回收古龙酸经酯化、转化的维生素C钠含量、收率也较目前工艺分别提高1.27%和1.95%。
研究结果表明,采用吸附法处理古龙酸母液、母液转型盐析结晶和X型树脂交换法回收古龙酸工艺与原工艺相比,无论从产品收率及中间体的质量方面都有明显提高。而又具有易分离、无污染、无腐蚀性的优点,是一种极具潜力的绿色环保型回收工艺。
2 -Keto-L-gulonic acid is the important intermediate during producing Vitamin C, and its receiving rate influences the cost of Vitamin C directly. In this article, the salting out crystallization law to recycle gulong sodium, Gulong sodium dissolves and cation exchange resin recovering gulonic acid recovery process has been studied.
Through the transformation of four different agents, precipitation contrast agent research, selected a more ideal agent Na2CO3 as a transition, CH3OH as precipitation agent. In this experiment, the main operating condition which affecting the 2 - keto-L-gulonic sodium salt out and crystal has been studied: Adding crystal seeds of temperature, the amount of seed, precipitation temperature, holding time on the yield of products, Selected the best salt analysis of the crystallization of the recovery process conditions, namely by adding crystal seeds of the temperature of 23 ~ 24℃, the amount of seeds for the 0.8g ~ 1.0g, precipitation temperature of 0 ~ -2℃, holding time for 1h.At the same time, research on using of X-resin exchange to translate sodium gulong sodium into gulonic acid has been done, and the best conditions were as follows: 15% sodium gulong with bed height to diameter ratio of 10 X-exchange resin, the material speed control 3 times the size of the collection of columns PH <1.7 of the solution, the solution concentrated cooling crystallization recovered gulonic acid goods.The results showed that the introduction of new recycling technology of vitamin C intermediates of 2 - Keto-L-gulonic acid recovery yield of 77.63% to reach more than the original 20.00%, The dry goods quality of 2 - Keto-L-gulonic acid was significantly improved and the content has achieved 88.54%, the present craft enhanced 3%.The Vc-Na,s making by gulonic acid recovery content and yield is enhanced1.27% and 1.95%.
The results show that the use of salting-out crystallization transition and X-type exchange resin recycling 2-Keto-L-gulonic acid new technology has markedly improved in terms of product yield and quality of intermediate, comparing with the original process. Easy separation and pollution-free, non-corrosive non-corrosiveness, is one kind of a potential type of green environment-friendly recycling processes.
引文
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[25] Hoffman L.Manufacture of esters of 2-keto-L-gulonic acid[P],EP-0671405, 1995-05-22
[26]张林茂,高永涛,李晶,应用超滤技术改进Vc生产工艺.膜科学与技术,2000,20(5):60～61
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[28]钱卫国,沈金玉,高春满,溶媒萃取氧化-古龙酸的初步工艺研究,中国医药工业杂志,1992,23(6):247～250
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[32]吉爱国,高培基,氧化葡萄糖酸杆菌底物转化特性和与棒杆菌细胞共固定化合成2-酮基-L-古龙酸的研究,药物生物技术,1999,6(1):14～19
[33] Grindley J,Payton M,Van D,et al.Conversion of glucose to 2-keto-L-gulonate,and intermediate recombinant strain of Erwinia citreus,Appl Environ Microbiol,1988,54:1770～1777
[34]许安,姚建铭,余增亮等,离子注入改良维生素C二步发酵混合菌研究,(I)2-酮基-L-古龙酸高产菌系IPPM-1028的选育,工业微生物,1998,28(4):21～24
[35] Anderson S, Berman-Mark C, Lazrus R, et al.Production of 2-keto-L-gulonate,an intermediate in L-ascorbate synthesis,Science,1985, 230:441～447
[36] Sugisawa T,Hoshino T,Normura S,et al. Isolation and characterization of membrane-bound L-sorbose dehydrogenase from Gluconobacter melanogenus UV10.Agric Biol Chem,1991,66(2):363～370
[37] Van H,Bremaeker M,Rouxhet P.Immobilization of yeast by adhesion to support without use of chemical agent.Enzyme Microb Technol, 1984,6:221～227
[38]马成新,焦鹏,胡江春等,蛭弧苗J26转化山梨糖生产2-酮基-b古龙酸发酵条件的研究,微生物学杂志,1998,18(2):1～6
[39] Nishio N,Kayawake E,Nagai S.Rapid methane production from formate or acetate in fixed bed bioreactors.J Ferm Tech.,1985,63:205～209
[40] Rosevear A. Immobilized biocatalysts-acriticalreview. J Chem Biotech, 1984,34:127～150
[41] Halliwell B.Ascorbic acid hype hoax or healer Am.J.Clin.Nutr.,1997,65:1891
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[2]尹光琳,维生素C基因工程菌的构建和研究:利用工程菌从葡萄糖直接发酵产生维生素C前体——2-酮基-L-古龙酸[J],工业微生物,1991,21(1):29～73
[3]王瑾,刘志敏,维生素C生产及应用概况[J],辽宁化工,1995,5:17～19
[4]李梅生,2-酮基-L-古龙酸的回收方法,中国专利,94113360.5,1996-07-10
[5]刘坐镇,谢小华,徐蕙珍,离子交换法提取2-酮基-L-古龙酸的研究,华东理工大学学报,1995,21(2):155～160
[6]王燕,王东智,任伟东,利用古龙酸废母液生产草酸,河北化工,1999,(3):29～31
[7]许演镐,由古龙酸母液制备无磷水基净洗剂,92102329.4,1993-10-06
[8]王辉,刘坐镇,夏杰等,古龙酸结晶母液的回收利用,离子交换与吸附,1998,14(2):175～179
[9]王晓东,韩国华,维生素C生产中古龙酸的提取技术的进展与发展方向,医药工程设计,1995,(5):32～34
[10]徐昌洪,孔太,金抒等,从古龙酸结晶母液中回收2-酮基-L-古龙酸的方法,中国专利,CN200410041060.4,2005-03-16
[11]江南大学,一种从维生素C母液中提取维生素C和古龙酸的方法,中国专利,200510094094.4,2006-02-15
[12]尹光琳,从葡萄糖发酵制备2-酮基-L-古龙酸的新方法,中国专利,96116536.7,1998-05-06
[13]沈阳药学院,古龙酸提取工艺,中国专利,93112075.6,1995-01-25
[14]三达膜科技(厦门)有限公司,古龙酸的提取方法,200410051754.6,2006-04-05
[15] Prazeres D,Cabral J.Enzymatic membrane bioreactors and their applications.Enzyme Microb.Technol,1994, 16:738～750
[16]鲍扬,维生素C与营养,肠与肠内营养,1998,5(3):168～172
[17]陈速荣,赵地顺,维生素C生产技术,河北化工,2001,13(2):7～8
[18]罗青波,我国维生素C产销现状、存在的问题和对策[J],中国医药情报,1998,4(2):93～100
[19]顾觉奋,李丽燕,刘叶青,分离纯化工艺原理[M],北京:中国医药科技出版社,1996,317～320
[20]董文玲等,转化葡萄糖为2-酮基-L-古龙酸的基因工程菌的构建[J],微生物学通报,1991,18(2):107～110
[21]李春艳,夏海平,蓝伟光,维生素C生产工艺进展[J],中国医药工业杂志,2001,32(1):38～41
[22]张骁,束梅英,郭建新,维生素C产销现状和市场前景展望[J],中国药房,1997,8(1):10～12
[23] Takeda.Chemical Industries,Ltd, Process for producing lower alkyl 2-keto-gulonate[P] EP-A-0535927,1993-06-17
[24]王汝龙,原子平,化工产品手册(药物)[M],北京:化学工业出版社,1999
[25] Hoffman L.Manufacture of esters of 2-keto-L-gulonic acid[P],EP-0671405, 1995-05-22
[26]张林茂,高永涛,李晶,应用超滤技术改进Vc生产工艺.膜科学与技术,2000,20(5):60～61
[27]季光辉,燕方龙,苗春等,新型絮凝剂用于维生素C发酵液预处理,沈阳药科大学学报,1997,14(2):88～90
[28]钱卫国,沈金玉,高春满,溶媒萃取氧化-古龙酸的初步工艺研究,中国医药工业杂志,1992,23(6):247～250
[29]严荣庆,李一通,马承继等,超滤应用于维生素C提取工艺,中国医药工业杂志,1990,21(1):1～3
[30]张秋荣,张建革,傅志强等,维生素C提取工艺的改进,河南医科大学学报,1999,34(2):85～86
[31]王毅武,尹光琳,维生素C发酵工艺中2-氧化-L-古洛糖酸发酵液絮凝处理研究,中国医药工业杂志,1997,28(6):243～288
[32]吉爱国,高培基,氧化葡萄糖酸杆菌底物转化特性和与棒杆菌细胞共固定化合成2-酮基-L-古龙酸的研究,药物生物技术,1999,6(1):14～19
[33] Grindley J,Payton M,Van D,et al.Conversion of glucose to 2-keto-L-gulonate,and intermediate recombinant strain of Erwinia citreus,Appl Environ Microbiol,1988,54:1770～1777
[34]许安,姚建铭,余增亮等,离子注入改良维生素C二步发酵混合菌研究,(I)2-酮基-L-古龙酸高产菌系IPPM-1028的选育,工业微生物,1998,28(4):21～24
[35] Anderson S, Berman-Mark C, Lazrus R, et al.Production of 2-keto-L-gulonate,an intermediate in L-ascorbate synthesis,Science,1985, 230:441～447
[36] Sugisawa T,Hoshino T,Normura S,et al. Isolation and characterization of membrane-bound L-sorbose dehydrogenase from Gluconobacter melanogenus UV10.Agric Biol Chem,1991,66(2):363～370
[37] Van H,Bremaeker M,Rouxhet P.Immobilization of yeast by adhesion to support without use of chemical agent.Enzyme Microb Technol, 1984,6:221～227
[38]马成新,焦鹏,胡江春等,蛭弧苗J26转化山梨糖生产2-酮基-b古龙酸发酵条件的研究,微生物学杂志,1998,18(2):1～6
[39] Nishio N,Kayawake E,Nagai S.Rapid methane production from formate or acetate in fixed bed bioreactors.J Ferm Tech.,1985,63:205～209
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