市政污泥厌氧酸化混合液中有机酸的分离提取研究
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摘要
市政污泥的组成极为复杂,其中含有可为微生物利用、转化的有机营养物质,也有不能转化利用甚至对微生物有毒害的有机或无机物质,导致发酵产酸混合液成分的难以预测。从市政污泥发酵产酸混合液中分离提取有机酸可消除市政污泥发酵产酸的产物抑制,提高污泥转化的效率和速度。因此,研究发酵产酸混合液中目的有机酸的分离提取技术不仅是成功实现市政污泥资源化的关键,而且对提高该工艺的整体效率和加快其产业化进程是现实而有意义的。支撑液膜分离技术是将常规的溶剂萃取和膜分离技术相结合的新型分离提取工艺,具有分离效率高,能耗低,可实现产物的连续、同步的分离和浓缩等优点。本论文首先以有机酸的提取率等为评价依据,对膜组件、萃取剂、有机溶剂和反萃取剂进行选择,在此基础上对支撑液膜法分离提取模拟有机酸混合液的工艺条件进行了优化,最后,研究了其对实际体系中有机酸的提取效果。主要研究结果如下:
(1)从污泥厌氧酸化混合液中分离提取有机酸的支撑液膜体系为:疏水聚丙烯微滤膜、三烷基氧膦、磺化煤油和碳酸氢钠。
(2)少量磺化煤油对污泥产酸有较明显的促进作用,与对照样相比,磺化煤油的添加量为1/32时,总酸和乙酸的产量分别提高20%左右。而过多的磺化煤油对产酸的促进作用不明显。
(3)支撑液膜法提取模拟污泥酸化混合液中有机酸最适条件为:给液相有机酸浓度为20g/L,萃取剂浓度为3%,膜组件高径比为10:1,反萃取相pH值为9,反萃取剂为NaHCO3,反萃取剂浓度为30g/L,提取温度为30℃,提取时间为360min,浓缩倍数为2.0。此时,有机酸的萃取率可达85.0%。
(4)支撑液膜法提取实际污泥酸化混合液中有机酸时,总有机酸和乙酸的提取率分别为69.0%和65.0%,乙酸和总酸的浓缩效率分别是1.3和1.4倍。
The components of anaerobicly acidified broth of sludge are unexpected due to the complexity of municipal sludge with toxic inorganic or organic substances. The separation of organic acids from anaerobicly acidified broth of sludge could avoid the product inhibition and improve the efficiency and rate of sludge conversion to organic acids. The study of the separation of organic acids is of significance. The supported liquid membrane combines the solvent extraction and membrane separation with many advantages, such as high separation efficiency, low energy consumption and concentration of organic acids. This main investigation of this thesis includes: the selections of the appropriately membrane modules, solvent and extractant etc.; the optimization of operating conditions of supported liquid membrane. The major results are summarized as follows:
(1)The supported liquid membrane is composed of hydrophobic PP microfiltration, trialkyl phosphine oxide, sulfonated kerosene and NaHCO3.
(2)The volatile fatty acids production was improved by a slight amount of sulfonated kerosene while the effect was not clear by lots of sulfonated kerosene. The production was improved by 20% with 1/32 sulfonated kerosene.
(3)The optimal conditions of the extraction of organic acids were as follows: the concentration of organic acids in feed was 20 g/L, the concentration of extractant was 3 %, the ratio of length to diameter for membrane module was 10:1, the stripping phase pH was 9, the stripping agent was NaHCO3, its concentration was 30 g/L, the extraction temperature was 30℃, the extraction time was 360min, the concentrate efficiency was 2.0. The total extraction efficiency amounted to 85.0%.
(4)The extraction efficiency of total acids and acetic acids were 69.0% and 65.0% respectively, while the concentrate efficiency was 1.3 and 1.4.
(1)从污泥厌氧酸化混合液中分离提取有机酸的支撑液膜体系为:疏水聚丙烯微滤膜、三烷基氧膦、磺化煤油和碳酸氢钠。
(2)少量磺化煤油对污泥产酸有较明显的促进作用,与对照样相比,磺化煤油的添加量为1/32时,总酸和乙酸的产量分别提高20%左右。而过多的磺化煤油对产酸的促进作用不明显。
(3)支撑液膜法提取模拟污泥酸化混合液中有机酸最适条件为:给液相有机酸浓度为20g/L,萃取剂浓度为3%,膜组件高径比为10:1,反萃取相pH值为9,反萃取剂为NaHCO3,反萃取剂浓度为30g/L,提取温度为30℃,提取时间为360min,浓缩倍数为2.0。此时,有机酸的萃取率可达85.0%。
(4)支撑液膜法提取实际污泥酸化混合液中有机酸时,总有机酸和乙酸的提取率分别为69.0%和65.0%,乙酸和总酸的浓缩效率分别是1.3和1.4倍。
The components of anaerobicly acidified broth of sludge are unexpected due to the complexity of municipal sludge with toxic inorganic or organic substances. The separation of organic acids from anaerobicly acidified broth of sludge could avoid the product inhibition and improve the efficiency and rate of sludge conversion to organic acids. The study of the separation of organic acids is of significance. The supported liquid membrane combines the solvent extraction and membrane separation with many advantages, such as high separation efficiency, low energy consumption and concentration of organic acids. This main investigation of this thesis includes: the selections of the appropriately membrane modules, solvent and extractant etc.; the optimization of operating conditions of supported liquid membrane. The major results are summarized as follows:
(1)The supported liquid membrane is composed of hydrophobic PP microfiltration, trialkyl phosphine oxide, sulfonated kerosene and NaHCO3.
(2)The volatile fatty acids production was improved by a slight amount of sulfonated kerosene while the effect was not clear by lots of sulfonated kerosene. The production was improved by 20% with 1/32 sulfonated kerosene.
(3)The optimal conditions of the extraction of organic acids were as follows: the concentration of organic acids in feed was 20 g/L, the concentration of extractant was 3 %, the ratio of length to diameter for membrane module was 10:1, the stripping phase pH was 9, the stripping agent was NaHCO3, its concentration was 30 g/L, the extraction temperature was 30℃, the extraction time was 360min, the concentrate efficiency was 2.0. The total extraction efficiency amounted to 85.0%.
(4)The extraction efficiency of total acids and acetic acids were 69.0% and 65.0% respectively, while the concentrate efficiency was 1.3 and 1.4.
引文
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2.吕九琢,徐亚贤.乳酸应用生产及需求的现状与预测[J].北京石油化工学院, 2004, 12(2): 33-37.
3.夏景峰,邵守言.国内醋酸生产技术与市场分析[J].化工设计, 2007, 17(3): 40-43.
4.中国聚酯网.亚洲成为世界最大醋酸生产地. http://www .juzhi.com.cn/index Article_ Content.asp/fID_ArticleContent=2999,2006-10-21.
5.王波.醋酸技术市场及产业化评述[J].煤化工, 2007, 2(129): 6-13.
6.赵紫华,仪宏,朱文众等.丙酸发酵的研究进展[J].中国食品添加剂, 2004, (6): 14-18.
7.张华峰,康慧.微生物发酵法生产丙酸[J].发酵工程, 2004, 25(8): 14-18.
8. Gu Z, Glatz BA, Glatz CE. Effects of propionibacterium to acid and low pH: Tolerance and inhibition. Journal of Food Protection, 1998, 61(2): 211-216.
9.彭跃莲,姚仕仲,冯树兰.从柠檬酸发酵液中提取柠檬酸的方法[J].北京工业大学学报, 2002, 28(1): 46-51.
10.秦涛.柠檬酸发酵液提取方法的现状与新技术研究[J].食品与发酵工业, 1995, (2): 62-69.
11.朱亦仁,王锦化,张振超.发酵柠檬酸提取方法的研究进展[J].精细与专用化学品, 2003(14): 18-21.
12.柴红,谭军.乳酸的乳化液膜萃取与有机溶剂萃取比较[J].高校化学工程学报, 1999,
13(1): 56-61.
13.董涛,黄丽萍,陈景文.有机废弃物发酵生产乳酸的研究进展[J].中国资源综合利用, 2006, 24(8): 11-15.
14.闫智慧,高静,周丽亚等.乳酸的应用与发酵生产工艺[J].河北工业大学学报, 2004, 33(3): 15-19.
15. Wang Q, Yamabe K, Narita J, et al. Suppression of growth of putrefactive and food poisoning bacteria by lactic acid fermentation of kitchen waste[J]. Process Biochem., 2001, 37(4): 351-357.
16.汪多仁. L-乳酸的开发与应用进展[J].综述与述评, 2008, 11(2): 11-18.
17.张颖等译.液膜分离技术[M].北京:原子能出版社, 1983, 272-344.
18.邓修,吴俊生.化工分离工程[M].北京:科学出版社, 2000, 221-254.
19.顾忠茂.液膜分离技术进展[J].膜科学与技术, 2003, 23(4): 214-223.
20. Shih YB, Li J, Wiencek JM. Feasibility of surfactant-free supported emulsion liquid membrane extraction[J]. Journal of Colloid and Interface Science, 2003, 266: 430-437.
21. Li J. Feasibility of supported emulsion liquid membrane extraction for fermentation media rejuvenation[D]. United States:Chemical and Biochemical Engineering in the Graduate College of the University of Iowa, 2003.
22.王运东,李屹,李玉鑫等.三烷基氧膦络合萃取一元有机羧酸[J].化学工程, 2003, 31(6): 8-11.
23. Li ZY, Qin W, Dai YY. Liquid–liquid equilibria of acetic,propionic, butyric, and valeric acids with trloctylarnine as extractant[J]. Chem.Eng., 2002, 47(2): 843-848.
24.柴金岭,蒋绪川,温成林等. TBP萃取一元有机酸的研究[J].山东大学学报, 1998, 33(3): 302-308.
25.周洪波,陈坚,赵由才等.长链脂肪酸对厌氧颗粒污泥产甲烷毒性研究[J].水处理技术, 2002, 28(2): 93-96.
26. Yuan HY, Chen YG, Zhang HX, et al. Improved bioproduction of short-chainfatty acids (SCFAs) from excess sludge under alkaline conditions[J]. Environ Sci Technol, 2006, 40: 2025-2029.
27.聂艳秋,刘和,堵国成等.初始pH值对产氢产乙酸/耗氢产乙酸两段耦合工艺定向生产乙酸的影响[J].生物工程学报, 2007, 23(4): 686-691.
28.陈艺阳,刘和,堵国成等. 2–溴乙烷磺酸盐对污泥厌氧发酵过程中乙酸累积及细菌种群的影响[J].应用与环境生物学报, 2007, 13(1): 108-111.
29.嫡丽巴哈,杨义燕,戴猷元.醋酸稀溶液的络合萃取[J].高校化学工程学报, 1993, 7(2): 174-179.
30.张礼平,陈银广,姜苏等.两种表面活性剂对剩余污泥产酸影响的比较研究[J].环境科学报, 2007, 27(1): 96-100.
31.陈燕,李寅,赵丽菁等.环境和营养条件对煤油生物降解的影响[J].应用与环境生物学报, 2002, 8(2): 184-189.
32.张瑛华,张书廷,汪群慧.有机废水厌氧发酵产酸的试验研究[J].中国给水排水, 2007, 23(3): 64-68.
33.赵杰红,张波,蔡伟明.厌氧消化系统中丙酸积累及控制研究进展[J].中国给水排水, 2005, 21(3): 25-27.
34.田凯勋,戴友芝,凌运林.厌氧酸化菌产酸过程研究[J].微生物学通报, 2007, 34(1): 108-111.
35. Gabelman A, Hwang ST. Hollow fiber membrane contactors[J]. Journal of MembraneScience, 1999, (159): 61-106.
36. Solichien MS, OBrien D, Hammond EG.. Membrane-based extractive fermentation to produce propionic and acetic acids: Toxicity and mass transfer considerations[J]. Enzyme and Microbial Technology, 1995, (17): 23-31.
37.左丹英,朱宝库,王绍洪等.聚丙烯中空纤维膜萃取水溶液中铜离子的研究[J].环境化学, 2006, 25(1): 50-54。
38. Lezamiz J, Jonsson JA. Development of a simple hollow fibre supported liquid membrane extraction method to extract and preconcentrate dinitrophenols in environmental samples at ng L?1 level by liquid chromatography[J]. Journal of Chromatography, 2007, (1152): 226-233。
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