异抗坏血酸钠一次结晶母液回收利用研究
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摘要
异抗坏血酸钠、维生素C都与人类健康密切相关,在异抗坏血酸钠生产过程中,产生大量废水,而异抗坏血酸钠结晶过程产生的一次结晶母液中,含有大量的2-酮基-葡萄糖酸、异抗坏血酸钠,直接舍弃不仅造成了发酵产品的大量浪费,而且对环境也带来了很大的污染。本文首先综述了维生素C(抗坏血酸)和异抗坏血酸钠的用途、生产方法和生产废水治理技术,然后在分析测定了一次结晶母液中主要成分的基础上,提出了先采用传统的物化法回收主要产物,再对回收后废水进行脱色处理的工艺,进行了一次结晶母液回收利用技术探索性研究,为异抗坏血酸钠生产过程母液的利用提出新的途径。本文的主要内容和结果如下:
实验第一部分,根据母液组成检测结果,用酸化转化的方法使主要成分向同一目标产物转化。通过正交实验和单因素影响实验,讨论了硝酸用量、反应温度、反应时间对目标产物酸化得率及母液色度的影响。得出最佳工艺条件:硝酸用量为3.5mL,温度为75℃,反应时间为50min。选用离子交换树脂对酸化转化液进一步除杂,考察了830nm、280nm(830nm处反映胶体的含量,280nm处反映色素含量)处的吸光值变化。得出离子交换树脂对胶体去除率达50%,通过交换树脂的收集液的色度与处理前稀释12倍的母液相当。通过离子交换树脂的收集液经过减压浓缩,冷冻结晶最后结晶出纯度为92%左右的维生素C,收率在65%左右。最后将各工序的优化条件,连接成完整的工艺流程,对此工艺进行可靠性验证,结果表明所选定的工艺条件是可靠的,具有较好的稳定性。
实验第二部分,一次结晶母液经过回收处理以后,所得废液含COD值、色度值仍很高,因此做了进一步的处理,本阶段主要研究研究了活性炭吸附、双氧水氧化及活性炭吸附与双氧水氧化联合处理异抗坏血酸钠生产母液的工艺条件。结果表明:用活性炭吸附与双氧水氧化结合处理异抗坏血酸钠生产废液比单独使用活性炭吸附或双氧水氧化处理效果好。异抗坏血酸钠回收母液pH值保持1～2,活性炭用量为0.025g/mL,双氧水用量为100mL/L,母液在350r/min下搅拌50min时,COD去除率达84.9%,脱色率达79.5%。
Sodium erythorbate、vitamin C and human health are closely related in the production process of sodium erythorbate, resulting in a large amount of waste water, and sodium erythorbate, a crystallization process the crystallization mother liquor containing a large number of 2 - keto - gluconic acid, isoleucine ascorbic acid sodium, directly away it, not only resulted in substantial waste fermentation products, but also on the environment has also brought a lot of pollution, this paper summarizes the use the production methods of vitamin C (ascorbic acid) and sodium erythorbate, and the of sodium erythorbate wastewater treatment technologies at first , then on the basis of analysed and determined the main component of the crystallization mother liquor, the study design at first using the traditional method of physico-chemical desposal, and then using decolorization process treatment the recycling wastewater, carried out a explore research of recycling technology to crystallization mother liquor, It provide new use approach for the production process of the mother liquor of sodium erythorbate .The main contents of experiment were as follow:
In the first part of experiment, According to the test results of mother liquor composed, making the major components into a product of the same goal using the method of acid . The influences of the amount of nitrate, reaction time, reaction temperature on the yield of the product were studied. The experimental result shows that the optimum conditions were as follows: Amount of nitricacid was 3.5mL, temperature was 75°C, reaction time was 50min.for the acid into furthe refine selection of ion exchange resin, visited the absorption value change of 830nm, 280nm (830nm reflected the content of colloid, 280nm reflected pigments) result shows colloid removal of up to 50%, Chroma was the same with the diluted 12 times of before the deal with. After decompress concentrating of condensed liquid, The crystallization of vitamin C to be frozen, purity was about 92%, yield was about 65%. Finally, the optimal conditions for the process to connect into a complete process, to verify the reliability of this technology, results showed that the selected process conditions are reliable and have good stability.
The second part of experiment, COD value and chroma were still high of after recycling mother liquor, so to do further processing. This part main study the technological conditions of the dyeing waste water treatment with activated carbon adsorption and H_2O_2 oxidation were studied .The results showed that, when the pH of dyeing wsate water is 1～2, using 0.025g/mL activated carbon, 100 mL / L H_2O_2, and reacting for 50min with 350r/min agotation.the efficiency of COD removal was 84.9%, the color degree removal was 79.5%.Better results were obtained from the combined treatment.
实验第一部分,根据母液组成检测结果,用酸化转化的方法使主要成分向同一目标产物转化。通过正交实验和单因素影响实验,讨论了硝酸用量、反应温度、反应时间对目标产物酸化得率及母液色度的影响。得出最佳工艺条件:硝酸用量为3.5mL,温度为75℃,反应时间为50min。选用离子交换树脂对酸化转化液进一步除杂,考察了830nm、280nm(830nm处反映胶体的含量,280nm处反映色素含量)处的吸光值变化。得出离子交换树脂对胶体去除率达50%,通过交换树脂的收集液的色度与处理前稀释12倍的母液相当。通过离子交换树脂的收集液经过减压浓缩,冷冻结晶最后结晶出纯度为92%左右的维生素C,收率在65%左右。最后将各工序的优化条件,连接成完整的工艺流程,对此工艺进行可靠性验证,结果表明所选定的工艺条件是可靠的,具有较好的稳定性。
实验第二部分,一次结晶母液经过回收处理以后,所得废液含COD值、色度值仍很高,因此做了进一步的处理,本阶段主要研究研究了活性炭吸附、双氧水氧化及活性炭吸附与双氧水氧化联合处理异抗坏血酸钠生产母液的工艺条件。结果表明:用活性炭吸附与双氧水氧化结合处理异抗坏血酸钠生产废液比单独使用活性炭吸附或双氧水氧化处理效果好。异抗坏血酸钠回收母液pH值保持1～2,活性炭用量为0.025g/mL,双氧水用量为100mL/L,母液在350r/min下搅拌50min时,COD去除率达84.9%,脱色率达79.5%。
Sodium erythorbate、vitamin C and human health are closely related in the production process of sodium erythorbate, resulting in a large amount of waste water, and sodium erythorbate, a crystallization process the crystallization mother liquor containing a large number of 2 - keto - gluconic acid, isoleucine ascorbic acid sodium, directly away it, not only resulted in substantial waste fermentation products, but also on the environment has also brought a lot of pollution, this paper summarizes the use the production methods of vitamin C (ascorbic acid) and sodium erythorbate, and the of sodium erythorbate wastewater treatment technologies at first , then on the basis of analysed and determined the main component of the crystallization mother liquor, the study design at first using the traditional method of physico-chemical desposal, and then using decolorization process treatment the recycling wastewater, carried out a explore research of recycling technology to crystallization mother liquor, It provide new use approach for the production process of the mother liquor of sodium erythorbate .The main contents of experiment were as follow:
In the first part of experiment, According to the test results of mother liquor composed, making the major components into a product of the same goal using the method of acid . The influences of the amount of nitrate, reaction time, reaction temperature on the yield of the product were studied. The experimental result shows that the optimum conditions were as follows: Amount of nitricacid was 3.5mL, temperature was 75°C, reaction time was 50min.for the acid into furthe refine selection of ion exchange resin, visited the absorption value change of 830nm, 280nm (830nm reflected the content of colloid, 280nm reflected pigments) result shows colloid removal of up to 50%, Chroma was the same with the diluted 12 times of before the deal with. After decompress concentrating of condensed liquid, The crystallization of vitamin C to be frozen, purity was about 92%, yield was about 65%. Finally, the optimal conditions for the process to connect into a complete process, to verify the reliability of this technology, results showed that the selected process conditions are reliable and have good stability.
The second part of experiment, COD value and chroma were still high of after recycling mother liquor, so to do further processing. This part main study the technological conditions of the dyeing waste water treatment with activated carbon adsorption and H_2O_2 oxidation were studied .The results showed that, when the pH of dyeing wsate water is 1～2, using 0.025g/mL activated carbon, 100 mL / L H_2O_2, and reacting for 50min with 350r/min agotation.the efficiency of COD removal was 84.9%, the color degree removal was 79.5%.Better results were obtained from the combined treatment.
引文
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2 唐世彪,徐岩岩.食品添加剂生产现状及发展趋势[J].技术创新.2006,9x:78-79.
3 徐诗伟.微生物转化在药物合成中的应用前景[J].中国医药工业杂志,1996,27(9):422-430.
4 李晓娜.云南环境科学[J].2006,25(增刊):140-142.
5 唐清海.古龙酸酯转工艺研究(学位论文),天津大学化工学院,2003.
6 Grindley JF,Payton MA,Van de Pol H,et al.Conversion of glucose to 2-keto-L-gulonate,an recombinant strain of Erwinia citreus[J].Appl Environ Microbiol,1988,54:1770.
7 Zimmermann F J.New waste disposal process.Chem Eng,1958,(6):117-120.
8 Huseyin B,T(u丨¨)rker R A,Mustafa L,et al.Separation and speciation of Cr (Ⅲ) and Cr(Ⅵ) with Saccharomyces cerevisiae immobilized on sepiolite and determination of both species in water by FAAS[J].Talanta,2000,51(5):895-902.
9 Castro-Dantas T N,Dantas-Neto A A,Dea M C P,et al.Removal of chromium from aqueous solutions by diatomite treated with microemulion[J].Watres,2001,35(9):2219-2224.
10 潘峰,时蕾,王雪峰,任蓓蕾,崔凤霞.工业水处理[J].2007,27(3);75-77.
11 王汝龙,原正平.化工产品手册-药物(第三版)[M].北京:化学工业出版社.1999,1
12 王晓东,韩国华.维生素C生产技术的进展与发展方向.医药工程设计[J].1995(5):32-34.
13 Gonzalo GIMateos,RosaLazaro Garicia.The value of processing cereal grains for piglets[J]《World poultry》 Vitamin Special,2001,31-33.
14 熊宗贵,白秀峰,镣亲民,等.发酵工艺原理[M].北京:中国医药科技出版社,1995.368-370.
15 田亚红,王丽丽,仪宏.维生素C发酵工艺研究进展[J].2005(5):14-16.
16 仪宏,张华峰,曾志远,等.维生素C生产技术[J].中国食品添加剂,2003,(6):76-81.
17 任凌波,章思规等.生物化工产品生产工艺技术及应用[M].北京:化学工业出版社.2001,6.
18 Reichstein T.Grussner A,Oppenauer R.Nature[J],1933,132-280.
19 李立强,维生素C钠盐结晶工艺优化(学位论文),天津大学研究生院,2003.
20 Reichstein T.Grussner A.Eine ergiebikge synthese der L-seorbinaure[J].Helv Chlm Acta,1934,17:31.
21 王清格.维生素C生产新工艺的探讨.化工论坛[JJ 2000,(4):24-25.
22 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.
23 郑大贵,祝堂永,张前炎.D-异抗坏血酸钠在碱-甲醇-水中稳定性的研究[J].化学世界,2004,(4):192-194.
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