膜法对模拟含氟水蒸气的脱湿研究

文章导读

摘要为解决目前磷肥厂以氟硅酸(15%)生产无水氟化氢(AHF)存在消耗大量的浓硫酸等问题,本研究通过加热分解一定浓度的氟硅酸溶液获得一定浓度的模拟含氟水蒸气,并采用聚砜中空纤维膜组件对此进行脱湿研究,可将高浓度含氟气送入AHF生产装置中。研究发现当膜压差为0.022 MPa、原料气氟含量为4.47%、分离时间为0.47 h时分离效果较好:水蒸气、HF、SiF₄渗透率分别为92.31%、24%、13.62%;分离系数α_H₂O/HF、α_H₂O/SiF₄、α_HF/SiF₄分别为3.85、6.78、1.76。结果表明聚砜中空纤维膜在一定程度上可对含氟水蒸气脱湿浓缩,水蒸气渗透率>HF渗透率>SiF₄渗透率,且该聚砜膜对SiF₄具有相对稳定的分离性能,对非极性气体(SiF₄)的分离效果较好。

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	欧健
	李天祥
	刘松林
	隋岩峰
	史连军
	朱静

关键词：湿法磷酸工艺氟化氢四氟化硅膜法脱湿技术

Abstract： At present, the production of anhydrous hydrogen fluoride (AHF) from fluosilicic acid (15%) in phosphate fertilizer plants consumes a lot of concentrated sulfuric acid and other problems. Therefore, in this paper, a certain concentration of simulated fluorine-containing water vapor was obtained by heating and decomposition of a certain concentration of fluorosilicic acid solution, and a polysulfone hollow fiber membrane module was used to study the dehumidification, then a high concentration of fluorine-containing gas could be sent into the AHF production device. The study found that when the membrane pressure difference is 0.022 MPa, the fluorine content of the raw gas is 4.47%, and the separation time is 0.47 h, the permeation ratio of water vapor, HF and SiF₄ was 92.31%, 24% and 13.62%, respectively, and the separation coefficients of α_H₂O/HF, α_H₂O/SiF₄, and α_HF/SiF₄ were 3.85, 6.78 and 1.76, respectively. The results show that the polysulfone hollow fiber membrane can dehumidify and concentrate fluorine-containing water vapor to a certain extent, and the membrane has relatively stable separation performance for SiF₄. Water vapor has the highest permeation ratio, while SiF₄ has the lowest. And the polysulfone membrane has a relatively stable separation performance for SiF₄, the separation effect of non-polar gas (SiF₄) is good.

Keywords： wet-process phosphoric acid hydrogen fluoride silicon tetrafluoride membrane method dehumidification technique

Received 2021-02-01;

Fund:中低品位磷矿及其共伴生资源高效利用国家重点实验室开放基金项目(WFKF2018-02)。

About author: 欧健(1995-),男,硕士生研究生,研究方向为磷化工及氟化工。

引用本文:

欧健, 李天祥, 刘松林, 隋岩峰, 史连军, 朱静.膜法对模拟含氟水蒸气的脱湿研究[J]. 化学工业与工程, 2023,40(3): 96-103

OU Jian, LI Tianxiang, LIU Songlin, SUI Yanfeng, SHI Lianjun, ZHU Jing.Dehumidification of simulated fluorine-containing water vapor by membrane method[J]. Chemcial Industry and Engineering, 2023,40(3): 96-103

[1] 匡国明. 湿法磷酸工艺路线的探讨[J]. 无机盐工业, 2013, 45(4):1-4 KUANG Guoming. Discussion on process routes of wet-process phosphoric acid[J]. Inorganic Chemicals Industry, 2013, 45(4):1-4(in Chinese)
[2] 孔令发. 湿法磷酸含氟气体回收过程常见问题及建议[J]. 磷肥与复肥, 2005, 20(6):22-26 KONG Lingfa. Common troubles occurred in recovery(scrubbing) of fluoride-containing gas from WPA and some suggestions[J]. Phosphate & Compound Fertilizer, 2005, 20(6):22-26(in Chinese)
[3] DAHLKE T, RUFFINER O, CANT R. Production of HF from H₂SiF₆[J]. Procedia Engineering, 2016, 138:231-239
[4] LIU L, CHEN Y, KANG Y, et al. An industrial scale dehydration process for natural gas involving membranes[J]. Chemical Engineering & Technology, 2001, 24(10):1045-1048
[5] 陈海平, 刘彦达, 周亚男. 中空纤维膜法回收火电厂烟气中水蒸气[J]. 热力发电, 2017, 46(1):100-105, 111 CHEN Haiping, LIU Yanda, ZHOU Yanan. Experimental study on recycling water vapor from flue gas of thermal power plants using hollow fiber membrane[J]. Thermal Power Generation, 2017, 46(1):100-105, 111(in Chinese)
[6] 曹语, 王乐, 季超, 等. 陶瓷膜冷凝器用于烟气脱白烟过程的中试研究[J]. 化工学报, 2019, 70(6):2192-2201 CAO Yu, WANG Le, JI Chao, et al. Pilot-scale application on dissipation of smoke plume from flue gas using ceramic membrane condensers[J]. CIESC Journal, 2019, 70(6):2192-2201(in Chinese)
[7] LIANG C, CHUNG T. Robust thin film composite PDMS/PAN hollow fiber membranes for water vapor removal from humid air and gases[J]. Separation and Purification Technology, 2018, 202:345-356
[8] 魏昶, 王俊中, 姜琪. 氟硅酸及其盐的有关知识[J]. 昆明理工大学学报(自然科学版), 2001, 26(3):97-100 WEI Chang, WANG Junzhong, JIANG Qi. Some knowledge of H₂SiF₆ and its salts[J]. Journal of Kunming University of Science and Technology, 2001, 26(3):97-100(in Chinese)
[9] 蒋明, 王重华, 田森林, 等. 氟离子选择电极测定黄磷尾气中气态氟含量[J]. 分析科学学报, 2014, 30(2):244-246 JIANG Ming, WANG Zhonghua, TIAN Senlin, et al. Determination of gaseous fluorine in yellow phosphorus tail gas by ion selective electrode[J]. Journal of Analytical Science, 2014, 30(2):244-246(in Chinese)
[10] SCHULT K A, PAUL D R. Water sorption and transport in a series of polysulfones[J]. Journal of Polymer Science Part B:Polymer Physics, 1996, 34(16):2805-2817
[11] 吴庸烈, 李国民, 彭曦, 等. 水蒸气的膜法分离用于压缩空气脱湿[J]. 膜科学与技术, 2011, 31(3):239-242 WU Yonglie, LI Guomin, PENG Xi, et al. Separation of water vapor by membranes used for dehumidification of compressed air[J]. Membrane Science and Technology, 2011, 31(3):239-242(in Chinese)
[12] STANNETT V, HAIDER M, KOROS W J, et al. Sorption and transport of water vapor in glassy poly(acrylonitrile)[J]. Polymer Engineering and Science, 1980, 20(4):300-304
[13] KOROS W, PAUL D R. CO₂ sorption in poly(ethylene terephthalate) above and below the glass transition[J]. Journal of Polymer Science Part B, 1978, 16:1947-1963
[14] SCHOLES C A, KENTISH S E, STEVENS G W. Effects of minor components in carbon dioxide capture using polymeric gas separation membranes[J]. Separation & Purification Reviews, 2009, 38(1):1-44
[15] CHEN G, SCHOLES C A, QIAO G, et al. Water vapor permeation in polyimide membranes[J]. Journal of Membrane Science, 2011, 379(1/2):479-487
[16] HODGE R M, BASTOW T J, EDWARD G H, et al. Free Volume and the Mechanism of Plasticization in Water-Swollen Poly(vinyl alcohol)[J]. Macromolecules, 1996, 29(25):8137-8143
[17] MODESTI M, DALL'ACQUA C, LORENZETTI A, et al. Mathematical model and experimental validation of water cluster influence upon vapour permeation through hydrophilic dense membrane[J]. Journal of Membrane Science, 2004, 229(1/2):211-223