以氢溴酸为吸收剂的气态膜法脱氨过程研究
作者:刘一,秦英杰,许玉壮,贾雨萌,蔡腾豪,于文凯
单位: 1.天津大学化工学院,天津 300350;2.中国船舶重工集团公司第七一八研究所,河北邯郸 056027;3.洁海瑞泉膜技术(天津)有限公司,天津 300350
关键词: 气态膜;PTFE中空纤维;低表面张力;脱氨;氢溴酸
DOI号:
分类号: TQ028.8
出版年,卷(期):页码: 2023,43(4):136-144

摘要:
 本文研究了以氢溴酸为吸收剂的气态膜法料液脱氨过程。该过程通过使用PTFE或PP中空纤维微孔疏水膜制作的膜接触器,从含氨水溶液中脱除/回收氨并相应获得溴化铵副产品。本文研究了料液中氨浓度、料液中电解质浓度、料液表面张力和吸收液pH值等操作条件对传质性能的影响,检验了低表面张力料液对PTFE和PP膜组件性能稳定性的影响。实验结果表明,在提供了最大传质系数的吸收液低pH下氢溴酸的挥发性并没有影响PTFE和PP膜组件的操作稳定性。基于传质机理的数学模型可以描述料液浓度、流速、吸收液pH对总传质系数的影响;料液中的高浓电解质减弱了渗透蒸馏效应,例如当料液中溴化钠浓度为15wt%时,氨在吸收完成液中的富集倍数高达41.25。在连续运行的6个月内,PTFE膜组件对使用挥发性氢溴酸作为吸收剂来处理低表面张力料液表现出了良好的性能稳定性,而PP膜组件的传质系数在十天内值下降了65%。本研究为气态膜技术处理低表面张力的含氨料液或废水并副产溴化铵的工业化应用提供了基本实验数据和基础理论分析。
 The supported-gas-membrane process was investigated for the removal/enrichment of ammonia from aqueous solution, by using membrane contactor made of microporous hydrophobic PTFE or PP hollow fibers and using dilute hydrobromic acid as the stripping solution, in order to obtain ammonium bromide as the by-product correspondingly. The influence of the operation conditions such as feed concentration, other electrolyte concentration in feed, surface tension of feed and pH value of the stripping solution on mass transfer performance were investigated, and the effects of feed with low surface tension on the performance stability of PTFE or PP membrane module were also tested. The experimental results showed that the volatility of hydrobromic acid did not affect the operational stability of PTFE and PP membrane modules at the low pH that the stripping solution provided the maximum mass transfer coefficient. The mathematical model based on mass transfer mechanism can describe well the influence of feed concentration, feed flow rate and pH value of the stripping solution on mass transfer. The highly concentrated electrolyte in the feed weakens the osmotic distillation phenomenon, for example, when the concentration of sodium bromide in the feed solution was as high as 15wt%, the enrichment ratio of ammonia in the final stripping solution was 41.25. In a long-term test of continuous operation for 6 months, PTFE membrane modules had shown good performance stability in dealing with the feed of low surface tension. However the mass transfer coefficient of PP modules decreased significantly within 10 days, with the mass transfer coefficient value decreased by 65%. This study lays a theoretical foundation for the industrial application of supported gas membrane and provides experimental data to remove/ recover ammonia from feed of low surface tension and to obtain ammonium bromide as a by-product.

基金项目:

作者简介:
刘一(1999-),男,山东泰安人,研究方向为新型膜分离技术,通讯联系人邮箱:yjqin@tju.edu.cn

参考文献:
 [1] Liu Y, Ngo H H, Guo W, et al. The roles of free ammonia (FA) in biological wastewater treatment processes: A review[J]. Environment International, 2019, 123:10-19.
[2] Xiang S; Liu Y; Zhang G, et al. New Progress of Ammonia Recovery during Ammonia Nitrogen Removal from Various Wastewaters[J]. World Journal of Microbiology and Biotechnology, 2020, 36(10):144.
[3] Maiti D, Ansari I, Rather M A, et al. Comprehensive review on wastewater characteristics discharged from the coal related industries along with their treatment strategies[J]. Water Science & Technology, 2019, 79(1).
[4] Jin X W, Li E C, Lu S G, et al. Coking wastewater treatment for industrial reuse purpose: Combining biological processes with ultrafiltration, nanofiltration and reverse osmosis[J]. Journal of Environmental Sciences, 2013,25(08):1565-1574.
[5] Imai M , Furusaki S , Miyauchi T. Separation of volatile materials by gas membranes[J]. Industrial & Engineering  Chemistry Process Design and Development, 1982, 21(3): 421-426.
[6] Qin Y J, Cabral J M S, Wang S C. Hollow-fiber gas-membrane process for removal of NH3 from solution of NH3 and CO2 [J]. AIChE Journal, 1996, 42(7): 1945-1956.
[7] 郝兴阁, 王元喜, 秦英杰,等. 稀硝酸作吸收剂的气态膜法回收废水中氨[J]. 化学工业与工程, 2015, 32(2):43-49.
[8] 王雲, 秦英杰, 郝兴阁,等. 可逆气态膜-多效膜蒸馏-精馏过程脱除水相氨副产氨水[J]. 化工学报, 2015, 6(09) :3588-3596. 
[9] 李海庆, 秦英杰, 崔东胜,等. 支撑气膜法脱除/回收垃圾渗滤液中氨[J]. 环境工程学报, 2014, 8(2): 612-618. 
[10] 解利昕, 王元喜, 秦英杰,等. 盐酸作吸收剂用于气态膜法从废水中脱除/回收氨[J]. 化工进展, 2013, 32(10):2507-2513.
[11] 林汉阳, 武春瑞, 吕晓龙. 聚偏氟乙烯膜的超疏水改性研究[J]. 膜科学与技术, 2010,30(02):39-44.
[12] 唐娜, 宋阳阳, 张蕾, 等. 聚丙烯构型对疏水微孔膜的性能影响及共混膜制备研究[J]. 膜科学与技术, 2020,40(01):1-7.
[13] Xlabc D, Hsabc D, Min C, et al. Facile fabrication of omniphobic PVDF composite membrane via a waterborne coating for anti-wetting and anti-fouling membrane distillation[J]. Journal of Membrane Science.2019, 589.
[14] 袁子怡, 樊华, 侯得印,等. 十二烷基硫酸钠对膜蒸馏过程影响[J]. 化工学报, 2019, 70(4):9.
[15] 程认认, 吕晓龙, 武春瑞,等. 疏水膜材料的膜孔润湿与干燥研究[J]. 功能材料, 2015, 46(22):5.
[16] 王可, 樊华, 侯得印,等.XDLVO理论解析有机物在膜蒸馏过程中的膜污染行为机制[J]. 膜科学与技术, 2022,42(02):25-33.
[17] Dupuy A, Athes V, Schenk J, et al. Experimental and theoretical considerations on breakthrough pressure in membrane-based solvent extraction: Focus on citrus essential oil/hydro-alcoholic solvent systems with low interfacial tension[J]. Journal of Membrane Science, 2011, 378( 1–2):203-213.
[18] Tantikhajorngosol P, Laosiripojana N, Jiraratananon R, et al. Analytical study of membrane wetting at high operating pressure for physical absorption of CO2 using hollow fiber membrane contactors[J]. Chemical Engineering Research & Design. 2017, 126: 265-277.
[19] Xu J, Lange S, Bartley J, et al. Alginate-coated microporous PTFE membranes for use in the osmotic distillation of oily feeds[J]. Journal of Membrane Science, 2004, 240(1-2):81-89.
[20]许玉壮,秦英杰,贾雨萌,等.高温下PTFE中空纤维气态膜法脱氨传质过程研究[J].膜科学与技术, 2022,1-13.
[21] Liu Y F, Qin Y J, Li Q, et al. A reversible absorption-based supported gas membrane process for enriching bromine from brine by using thin PTFE hollow fibers[J]. JOURNAL OF MEMBRANE SCIENCE, 2017, 543: 222-232.
[22] Aligwe P A, Sirkar K K, Canlas C J. Hollow fiber gas membrane-based removal and recovery of ammonia from water in three different scales and types of modules[J]. Separation & Purification Technology, 2019, 224: 580-590.
[23] Aligwe P A , Sirkar K K , Canlas C J, et al. Supported gas membrane-based ammonia removal and recovery for a pH-dependent sink: Effect of water vapor transport[J]. Journal of Membrane Science, 2020, 611:118308.
[24] 赵建敏, 秦英杰, 李旭超,等. 料液中盐对气态膜法脱氨过程的影响[J]. 化工学报, 2012, 63(04):1108-1115.
[25] Wang S C, Qin Y J, Xu S C. Mass transfer in membrane absorption-desorption of ammonia from ammonia water[J]. Journal of Chemical Industry and Engineering (China), 1993, 3(1):160.
[26] Qin Y J, Cabral J M S. Lumen Mass Transfer in Hollow Fiber Membrane Processes with Constant External Resistances[J]. AIChE Journal, 1997, 43(8):1975-1988.
[27] Abdulagatov I M , Azizov N D. Experimental study of the effect of temperature, pressure and concentration on the viscosity of aqueous NaBr solutions[J]. J Sol Chem, 2006; 35(5): 705–738.
[28] Abdul G, Takao K. The pervaporation mechanism of dilute ethanol solution by hydrophobic porous membranes[J]. Biochemical Engineering Journal,2004, 18(3):235-238.
 

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