非水溶剂分离氯化氢和二氧化硫的研究

南京大学学报(自然科学版) ›› 2016, Vol. 52 ›› Issue (2): 221–.

非水溶剂分离氯化氢和二氧化硫的研究

李旭升，黄宽，胡兴邦*，吴有庭*

出版日期:2016-03-25 发布日期:2016-03-25
作者简介:(南京大学化学化工学院210093)
基金资助:
基金项目:国家自然科学基金(21176110)
收稿日期:2015-08-29
*通讯联系人,E-mail:huxb@nju.edu.cn,ytwu@nju.edu.cn

Separation of ydrogen chloride and sulfur dioxide in non-aqueous solvent

Li Xusheng, Huang Kuan, Hu Xingbang*Wu Youting*

Online:2016-03-25 Published:2016-03-25
About author:(School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China)

摘要/Abstract

摘要： 采用5种不同的溶剂(1-己基-3-甲基咪唑氯盐离子液体、PEG-200、三缩四乙二醇、乙二醇、丙三醇)，分别对HCl、SO2进行了单独吸收与混合吸收，发现丙三醇对HCl和SO2分离效果最好。采用丙三醇作为溶剂对HCl-SO2混合气体(n(HCl):n(SO2)=1:1)进行吸收解吸研究，吸收温度为80 ℃时，解吸气体HCl含量高达96.4%。丙三醇在4次循环使用过程中，吸收量、解吸率和分离效果均不变，为探索工业非水条件下分离HCl和SO2提供了实验基础。

Abstract: To explore a feasible method for the separation of hydrochloric acid (HCl) and sulfur dioxide (SO2) in non-aqueous solvent, the absorption of HCl, SO2 and HCl-SO2 mixture in five different solvents (1-hexyl-3-methylimidazolium chloride, PEG-200, tetraethylene glycol, ethylene glycol, and glycerol) were carefully investigated. It was found that the solubility of both HCl and SO2 in 1-hexyl-3-methylimidazolium chloride is far higher than those in other solvents. However, 1-hexyl-3-methylimidazolium chloride is not a good choice for the separation of HCl-SO2 mixture, because the HCl/SO2 separation selectivity is only 1.40 in this solvent and there is 34.3% of the gas can not be desorbed. For all of the solvents investigated here, the solubility of HCl is obviously higher than that of SO2. Theoretic calculation based on B3LYP/6-31+G* method also shows that the binding energy between HCl and the solvent is obviously larger than that of SO2. These results indicate the possibility to separate the HCl-SO2 mixture by gas absorption in these solvents. For the pure gas under 101 kPa, the HCl/SO2 separation selectivities are 1.13, 2.13, 2.18, 4.13, and 6.99 in 1-hexyl-3-methylimidazolium chloride, PEG-200, tetraethylene glycol, ethylene glycol, and glycerol respectively. Further research on the mixed gas revealed that glycerol was the best choice for the separation of HCl-SO2 mixture. The HCl/SO2 separation selectivity in glycerol is 4.14. When glycerol was used as solvent for the separation of HCl-SO2 mixture (n(HCl):n(SO2)=1:1) at 80 ℃, the HCl content in the desorption gas was 96.4%. When the temperature is 40 ℃, this value is 58.3, 71.6, 76.0, 77.1, 80.5 in 1-hexyl-3-methylimidazolium chloride, PEG-200, tetraethylene glycol, ethylene glycol, and glycerol respectively. The absorption amount, desorption rate and separation efficiency of glycerol remain unchanged after 4 runs. It provides an experimental basis for the industrial separation of HCl-SO2 mixture under non-aqueous conditions

李旭升，黄宽，胡兴邦*，吴有庭*. 非水溶剂分离氯化氢和二氧化硫的研究[J]. 南京大学学报(自然科学版), 2016, 52(2): 221–.

Li Xusheng, Huang Kuan, Hu Xingbang*Wu Youting*. Separation of ydrogen chloride and sulfur dioxide in non-aqueous solvent[J]. Journal of Nanjing University(Natural Sciences), 2016, 52(2): 221–.

参考文献

[1].Oka K. Some applications of thionyl chloride in synthetic organic chemistry. Synthesis, 1981, (9): 661-681.
[2].Nishino Y，Komurasaki T，Yuasa T，et al. Practical large-scale synthesis of the 2-aminomethylpyrrolidin-4-ylthio-containing side chain of the novel carbapenem antibiotic doripenem. Organic Process Research & Development, 2003, 7(5):649-654.
[3].Kaul S，Kumar A, Sain B, et al. A simple and convenient one-pot synthesis of fatty acid esters from hindered alcohols using N,N-dimethylchlorosulfitemethan-iminium chloride as dehydrating agent. Synthetic Communications, 2002, 32(18): 2885-2891.
[4].Fairclough P H, Hough L, Richardson A C. Derivatives of β-D-fructofuranosyl α-D-galactopyranoside. Carbohydrate Research, 1975, 40(2): 285-298.
[5].胡兴邦.一种三氯蔗糖生产废气综合利用的方法中国专利,103113197 A.2013–5–22.
[6].雷世海.氯化亚砜酰化尾气的吸收和利用.环境保护1992, (7): 41.
[7].李娄刚，张汉杰.硫酰氯作氯化剂的尾气回收利用.化学工业与工程技术2012, 33(3): 58-60.
[8].McElvain S M, Walter N J. The preparation of orthoesters. Journal of the American Chemical Society, 1942, 64: 1825–1827.
[9].蒋广生.三氯氢硅制备工艺介绍.化学工业与工程技术2011, 32(6):46–50.
[10].Arun A, Reddy B S R. Photocrosslinkable polymers based on 4-[5-(4-hydroxyphenyl)-3-oxopenta-1,4-dienyl]-phenyl-2-methacrylate: Photocrosslinking studies and reactivity ratios with vinylcyclohexane. European Polymer Journal, 2004, 40:589–597.
[11].Huang K, Feng J, Wu Y T, et al. Absorption of SO2 in aqueous solutions of mixed hydroxylammonium dicarboxylate ionic liquids. Chemical Engineering Science, 2013, 215:36–44.
[12].Huang K, Chen Y L, Zhang X M, et al. SO2 absorption in acid salt ionic liquids/sulfolane binary mixtures: Experimental study and thermodynamic analysis. Chemical Engineering Science, 2014, 237: 478–486.
[13].Wu W, Han B, Gao H, et al. Desulfurization of flue gas: SO2 Absorption by an ionic liquid. Angewandte Chemie International Edition, 2004, 43(18): 2415-2417.
[14].Cui G, Zheng J, Luo X, et al. Tuning anion-functionalized ionic liquids for improved SO2 capture. Angewandte Chemie International Edition, 2013,52: 1–6.
[15].Wang C, Cui G, Luo X, et al. Highly efficient and reversible SO2 capture by tunable azole-based ionic liquids through multiple-site chemical absorption. Journal of the American Chemical Society, 2011,133(31): 11916-11919.
[16].He R H, Long B W, Lu Y Z, et al. Solubility of hydrogen chloride in three 1-alkyl-3- methylimidazolium chloride ionic liquids in the pressure range (0 to 100) kPa and temperature range (298.15 to 363.15)K. Journal of Chemical and Engineering Data,2012,57(11):2936–2941.
[17].Delgado D R, Vargas E F, Martinez F. Thermodynamic study of the solubility of procaine HCl in some ethanol+water cosolvent mixtures. Journal of Chemical and Engineering Data, 2010, 55(8): 2900–2904.
[18].Huang K, Wang G N, Dai Y, et al. Dicarboxylic acid salts as task-specific ionic liquids for reversible absorption of SO2 with a low enthalpy change. Royal Society of Chemistry Advances, 2013, 37(3): 16264–16269.
[19].Ren S, Hou Y, Wu W, et al. Oxidation of SO2 absorbed by an ionic liquid during desulfurization of simulated flue gases. Industrial & Engineering Chemistry Research. 2011, 50: 998–1002.
[20].Tian S, Hou Y, Wu W, et al. Absorption of SO2 by thermal-stable functional ionic liquids with lactate anion. Royal Society of Chemistry Advances, 2013, 3: 3572–3577.
[21].Wang C, Zheng J, Cui G, et al. Highly efficient SO2 capture through tuning the interaction between anion-functionalized ionic liquids and SO2. Chemical Communications, 2013, 49(12), 1166-1169.
[22].Mohammed A I, Mohammed A K, Maksudur R K. Reactive gas solubility in water: An empirical relation. Industrial & Engineering Chemistry Research, 2000, 39: 2627–2630.
[23].何如浩.氯化氢气体在离子液体中溶解性能的研究北京北京化工大学2012:49-50.
[24].Ren S, Hou Y, Wu W, et al. Effect of H2O on the desulfurization of simulated flue gas by an ionic liquid. Industrial & Engineering Chemistry Research, 2009, 48, 4928–4932.
[25].Lever S D, Papadaki M. o-Chlorination of 2-nitrobenzoic acid with thionyl chloride in xylene and acetonitrile - Solubility study of hydrogen chloride and sulphur dioxide in xylene and acetonitrile. Process Safety and Environmental Protection, 2004, 2(B1): 48–60.
[26].Jin M, Hou Y, Wu W, et al. Solubilities and thermodynamic properties of SO2 in ionic liquids. Journal of Physical Chemistry B, 2011, 115 (20), 6585–6591.
[27].Zhang J, Han F, Wei X, et al. Spectral studies of hydrogen bonding and interaction in the absorption processes of sulfur dioxide in poly(ethylene glycol) 400+water binary system. Industrial & Engineering Chemistry Research, 2010, 49: 2025-2030.
[28].张建斌, 李强, 刘占英等.聚乙二醇及其水溶液吸收SO2机理研究.化学工程, 2010, 38(12): 76-79.

Metrics

Viewed

Full text

Abstract

Cited

Shared

Discussed