沸石ZSM-5吸附回收低浓度煤层气中CH4

doi:10.11949/j.issn.0438-1157.20151684

化工学报 ›› 2016, Vol. 67 ›› Issue (5): 1931-1941.DOI: 10.11949/j.issn.0438-1157.20151684

沸石ZSM-5吸附回收低浓度煤层气中CH₄

刘海庆, 吴一江, 杨颖, 杨林, 李平, 于建国

华东理工大学化学工程联合国家重点实验室, 上海 200237

收稿日期:2015-11-09 修回日期:2016-01-11 出版日期:2016-05-05 发布日期:2016-05-05
通讯作者: 吴一江
基金资助:
国家国际科技合作专项项目(2015DFG42220);国家自然科学基金项目(21506063);中国博士后科学基金项目(2015M570339);中央高校基本科研业务费专项资金资助项目(222201514307)。

Adsorption and recovery of low concentration coal-bed methane by zeolite ZSM-5

LIU Haiqing, WU Yijiang, YANG Ying, YANG Lin, LI Ping, YU Jianguo

State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2015-11-09 Revised:2016-01-11 Online:2016-05-05 Published:2016-05-05
Supported by:
supported by the International S&T Cooperation Program of China (2015DFG42220), the National Natural Science Foundation of China (21506063), the China Postdoctoral Science Foundation (2015M570339) and the Fundamental Research Funds for the Central Universities (222201514307).

摘要/Abstract

摘要：

利用高硅疏水性沸石ZSM-5吸附回收低浓度煤层气中的甲烷,对其吸附平衡、吸附动力学以及真空变压吸附分离过程进行了理论和实验研究。通过重量法和穿透曲线法测定了CH₄/N₂单组分及双组分的竞争吸附平衡数据,并采用Multisite Langmuir吸附等温线模型对其进行拟合。结合CH₄和N₂稀释穿透曲线实验数据和等温无动量损失的双分散二级孔结构扩散模型,获得CH₄和N₂在沸石ZSM-5上的微孔扩散系数。建立并求解包含质量、动量及能量传递的固定床吸附分离模型方程,预测了CH₄和N₂在沸石ZSM-5上的竞争吸附穿透曲线。进一步采用ZSM-5吸附剂填充床单柱四步真空变压吸附实验考察了进料浓度、进料流速、进料时间以及吹扫比对分离效果的影响。结果发现沸石ZSM-5对CH₄具有较好的选择性,沸石晶粒内的微孔扩散为吸附速率控制步骤,真空变压吸附工艺可将模拟煤层气中20%的CH₄提纯至31%～41%,回收率为93%～98%。

关键词: 煤层气, 吸附, 甲烷, 氮气, 沸石ZSM-5, 真空变压吸附

Abstract:

As a high-silica hydrophobic material, zeolite ZSM-5 was used for the adsorption and recovery of low concentration coal-bed methane. Theoretical and experimental studies were conducted on adsorption equilibrium, adsorption kinetics and vacuum pressure swing adsorption (VPSA). Single and binary competitive adsorption equilibrium experimental data of CH₄/N₂ on zeolite ZSM-5 were measured by gravimetric method and breakthrough-curve method. The multi-site Langmuir model was used to fit the experimental data. Microporous diffusion coefficients were calculated based on the experimental data of diluted breakthrough curves and simulated results of an isothermic mathematical bi-disperse model without momentum loss. Competitive breakthrough curves of CH₄and N₂ on zeolite ZSM-5 were predicted by fixed bed adsorption models with mass, momentum and energy transfer. Effects of CH₄ concentration in feed, feed flow rate, feed time and purge/feed flow rate ratio on separation performances of ZSM-5 packed single column four-step VPSA process were investigated. It showed that ZSM-5 zeolite exhibited a relatively good selectivity for CH₄ and the diffusion in micropores was the rate determining step for both CH4 and N2 adsorption. By the process of VPSA, CH4 purity can be concentrated from 20% to 31%～41% and the recovery can be up to 93%～98%.

Key words: coal-bed methane, adsorption, methane, nitrogen, zeolite ZSM-5, VPSA

中图分类号:

TQ021

刘海庆, 吴一江, 杨颖, 杨林, 李平, 于建国. 沸石ZSM-5吸附回收低浓度煤层气中CH₄[J]. 化工学报, 2016, 67(5): 1931-1941.

LIU Haiqing, WU Yijiang, YANG Ying, YANG Lin, LI Ping, YU Jianguo. Adsorption and recovery of low concentration coal-bed methane by zeolite ZSM-5[J]. CIESC Journal, 2016, 67(5): 1931-1941.

参考文献 24

[1]	靳贝贝. 我国煤层气开采利用存在的问题及建议[J].中国国土资源经济, 2014, (11): 66-69. DOI: 10.3969/j.issn.1 672-6995. 2014.11.017. JIN B B. The problems that China faces in coal-bed methane development and utilization and some suggestions [J]. Natural Resource Economics of China, 2014, (11): 66-69. DOI: 10.3969/j.issn. 1672-6995.2014.11.017.
[2]	International Energy Agency. Coal mine methane in Russia: capturing the safety and environmental benefits [R]. Paris, France: IEA, 2009.
[3]	SALEMAN T L, LI G K, RUFFORD T E, et al. Capture of low grade methane from nitrogen gas using dual-reflux pressure swing adsorption [J]. Chemical Engineering Journal, 2015, 281: 739-748.
[4]	GU M, ZHANG B, QI Z, et al. Effects of pore structure of granular activated carbons on CH4 enrichment from CH4/N2 by vacuum pressure swing adsorption [J]. Separation and Purification Technology, 2015, 146: 213-218.
[5]	SERRA-CRESPO P, WEZENDONK T A, BACH-SAMARIO C, et al. Preliminary design of a vacuum pressure swing adsorption process for natural gas upgrading based on amino-functionalized MIL-53 [J]. Chemical Engineering & Technology, 2015, 38(7): 1183-1194.
[6]	MULGUNDMATH V, TEZEL F, SAATCIOGLU T, et al. Adsorption and separation of CO2/N2 and CO2/CH4 by 13X zeolite [J]. The Canadian Journal of Chemical Engineering, 2012, 90(3): 730-738.
[7]	孔祥明, 杨颖, 沈文龙, 等. CO2/CH4/N2在沸石13X-APG上的吸附平衡[J]. 化工学报, 2013, 64(6): 2117-2124. DOI: 10.3969/j.issn.0438-1157.2013.06.030. KONG X M, YANG Y, SHEN W L, et al. Adsorption equilibrium of CO2, CH4 and N2 on zeolite 13X-APG [J]. CIESC Journal, 2013, 64(6): 2117-2124. DOI: 10.3969/j.issn.0438-1157.2013.06.030.
[8]	BAKHTYARI A, MOFARAHI M. Pure and binary adsorption equilibria of methane and nitrogen on zeolite 5A [J]. Journal of Chemical & Engineering Data, 2014, 59(3): 626-639.
[9]	SETHIA G, SOMANI R S, BAJAJ H C. Sorption of methane and nitrogen on cesium exchanged zeolite-X: structure, cation position and adsorption relationship [J]. Industrial & Engineering Chemistry Research, 2014, 53(16): 6807-6814.
[10]	YAN X, ZHANG L, ZHANG Y, et al. Amine-modified SBA-15: effect of pore structure on the performance for CO2 capture [J]. Industrial & Engineering Chemistry Research, 2011, 50(6): 3220-3226.
[11]	BELMABKHOUT Y, SERNA-GUERRERO R, SAYARI A. Adsorption of CO2-containing gas mixtures over amine-bearing pore-expanded MCM-41 silica: application for gas purification [J]. Industrial & Engineering Chemistry Research, 2009, 49(1): 359-365.
[12]	MELLO M R, PHANON D, SILVEIRA G Q, et al. Amine-modified MCM-41 mesoporous silica for carbon dioxide capture [J]. Microporous and Mesoporous Materials, 2011, 143(1): 174-179.
[13]	WU Y J, YANG Y, KONG X M, et al. Adsorption of pure and binary CO2, CH4, and N2 gas components on activated carbon beads [J]. Journal of Chemical & Engineering Data, 2015, 60(9): 2684-2693.
[14]	KHADDOUR F, KNORST-FOURAN A, PLANTIER F, et al. A fully consistent experimental and molecular simulation study of methane adsorption on activated carbon [J]. Adsorption, 2014, 20(4): 649-656.
[15]	YANG Y, RIBEIRO A M, LI P, et al. Adsorption equilibrium and kinetics of methane and nitrogen on carbon molecular sieve [J]. Industrial & Engineering Chemistry Research, 2014, 53(43): 16840-16850.
[16]	CAVENATI S, GRANDE C A, RODRIGUES A E. Separation of methane and nitrogen by adsorption on carbon molecular sieve [J]. Separation Science and Technology, 2005, 40(13): 2721-2743.
[17]	BHADRA S, FAROOQ S. Separation of methane-nitrogen mixture by pressure swing adsorption for natural gas upgrading [J]. Industrial & Engineering Chemistry Research, 2011, 50(24): 14030-14045.
[18]	GÁNDARA F, FURUKAWA H, LEE S, et al. High methane storage capacity in aluminum metal-organic frameworks [J]. Journal of the American Chemical Society, 2014, 136(14): 5271-5274.
[19]	胡江亮, 孙天军, 刘小伟, 等. CH4-N2在MOFs结构材料中的吸附分离性能[J]. 化工学报, 2015, 66(9): 3518-3528. DOI: 10.11949/j.issn. 0438-1157.20151059. HU J L, SUN T J, LIU X W, et al. Adsorption and separation of CH4-N2 with different structural MOFs [J]. CIESC Journal, 2015, 66(9): 3518-3528. DOI: 10.11949/j.issn.0438-1157.20151059.
[20]	张倬铭, 杨江峰, 陈杨, 等. 一维直孔道MOFs对 CH4/N2和CO2/CH4的分离[J]. 化工学报, 2015, 66(9): 3549-3555. DOI: 10.11949/j.issn.0438-1157.20150892. ZHANG Z M, YANG J F, CHEN Y, et al. Separation of CH4/N2 and CO2/CH4 mixtures in one dimension channel MOFs [J]. CIESC Journal, 2015, 66(9): 3549-3555. DOI: 10.11949/j.issn. 0438-1157. 20150892.
[21]	STAVITSKI E, KOX M H, WECKHUYSEN B M. Revealing shape selectivity and catalytic activity trends within the pores of H-ZSM-5 crystals by time-and space-resolved optical and fluorescence microspectroscopy [J]. Chemistry-A European Journal, 2007, 13(25): 7057-7065.
[22]	沈文龙, 李嘉旭, 杨颖, 等. 基于沸石ZSM-5的CH4/N2/CO2二元体系吸附平衡研究[J]. 化工学报, 2014, 65(9): 3490-3498. DOI: 10.3969/j.issn.0438-1157.201 4.09.025. SHEN W L, LI J X, YANG Y, et al. Binary adsorption equilibrium of CH4, N2 and CO2 on zeolite ZSM-5 [J]. CIESC Journal, 2014, 65(9): 3490-3498. DOI: 10.3969/j.issn.0438-1157.2014.09.025.
[23]	沈春枝. 碳材料捕获燃烧后二氧化碳过程研究[D]. 上海: 华东理工大学, 2011. SHEN C Z. CO2 capture by adsorption process using carbonaceous materials [D]. Shanghai: East China University of Science and Technology, 2011.
[24]	YANG H, YIN C, JIANG B, et al. Optimization and analysis of a VPSA process for N2/CH4 separation [J]. Separation and Purification Technology, 2014, 134: 232-240.

沸石ZSM-5吸附回收低浓度煤层气中CH₄

Adsorption and recovery of low concentration coal-bed methane by zeolite ZSM-5

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 24

相关文章 15

编辑推荐

Metrics

本文评价

[1]	晁京伟, 许嘉兴, 李廷贤. 基于无管束蒸发换热强化策略的吸附热池的供热性能研究[J]. 化工学报, 2023, 74(S1): 302-310.
[2]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[3]	高燕, 伍鹏, 尚超, 胡泽君, 陈晓东. 基于双流体喷嘴的磁性琼脂糖微球的制备及其蛋白吸附性能探究[J]. 化工学报, 2023, 74(8): 3457-3471.
[4]	盛冰纯, 于建国, 林森. 铝基锂吸附剂分离高钠型地下卤水锂资源过程研究[J]. 化工学报, 2023, 74(8): 3375-3385.
[5]	张瑞航, 曹潘, 杨锋, 李昆, 肖朋, 邓春, 刘蓓, 孙长宇, 陈光进. ZIF-8纳米流体天然气乙烷回收工艺的产品纯度关键影响因素分析[J]. 化工学报, 2023, 74(8): 3386-3393.
[6]	刘晓洋, 喻健良, 侯玉洁, 闫兴清, 张振华, 吕先舒. 螺旋微通道对掺氢甲烷爆轰传播的影响[J]. 化工学报, 2023, 74(7): 3139-3148.
[7]	王杰, 丘晓琳, 赵烨, 刘鑫洋, 韩忠强, 许雍, 蒋文瀚. 聚电解质静电沉积改性PHBV抗氧化膜的制备与性能研究[J]. 化工学报, 2023, 74(7): 3068-3078.
[8]	陈吉, 洪泽, 雷昭, 凌强, 赵志刚, 彭陈辉, 崔平. 基于分子动力学的焦炭溶损反应及其机理研究[J]. 化工学报, 2023, 74(7): 2935-2946.
[9]	牛超, 沈胜强, 杨艳, 潘泊年, 李熠桥. 甲烷BOG喷射器流动过程计算与性能分析[J]. 化工学报, 2023, 74(7): 2858-2868.
[10]	王新悦, 王俊杰, 曹思贤, 王翠, 李灵坤, 吴宏宇, 韩静, 吴昊. 玻璃内包材界面修饰对机械应力诱导的单克隆抗体聚集体形成的影响[J]. 化工学报, 2023, 74(6): 2580-2588.
[11]	周小文, 杜杰, 张战国, 许光文. 基于甲烷脉冲法的Fe₂O₃-Al₂O₃载氧体还原特性研究[J]. 化工学报, 2023, 74(6): 2611-2623.
[12]	陈韶云, 徐东, 陈龙, 张禹, 张远方, 尤庆亮, 胡成龙, 陈建. 单层聚苯胺微球阵列结构的制备及其吸附性能[J]. 化工学报, 2023, 74(5): 2228-2238.
[13]	王蕾, 王磊, 白云龙, 何柳柳. SA膜状锂离子筛的制备及其锂吸附性能[J]. 化工学报, 2023, 74(5): 2046-2056.
[14]	蔺彩虹, 王丽, 吴瑜, 刘鹏, 杨江峰, 李晋平. 沸石中碱金属阳离子对CO₂/N₂O吸附分离性能的影响[J]. 化工学报, 2023, 74(5): 2013-2021.
[15]	李辰鑫, 潘艳秋, 何流, 牛亚宾, 俞路. 基于碳微晶结构的炭膜模型及其气体分离模拟[J]. 化工学报, 2023, 74(5): 2057-2066.