金属离子改性分子筛吸附水的Monte Carlo模拟

doi:10.16085/j.issn.1000-6613.2017-2099

化工进展 ›› 2018, Vol. 37 ›› Issue (09): 3430-3436.DOI: 10.16085/j.issn.1000-6613.2017-2099

金属离子改性分子筛吸附水的Monte Carlo模拟

肖永厚^1,2, 周梦雪¹, 赵颖¹, 王传明³, 贺高红^1,2

1 大连理工大学石油与化学工程学院, 辽宁盘锦 124221;
2 大连理工大学盘锦产业技术研究院, 辽宁盘锦 124221;
3 中国石油化工股份有限公司上海石油化工研究院, 上海 201208

收稿日期:2017-10-12 修回日期:2017-11-15 出版日期:2018-09-05 发布日期:2018-09-05
通讯作者: 贺高红,教授,博士生导师,研究方向为化学工程。
作者简介:肖永厚(1977-),男,高级工程师,研究方向为化学工程、工业催化。E-mail:yonghou.xiao@dlut.edu.cn。
基金资助:
国家自然科学基金（21776028）及大连理工大学盘锦产业技术研究院项科技研发项目（PJYJY2016A006）。

Monte Carlo simulation of water adsorption on metal ions modified molecular sieves

XIAO Yonghou^1,2, ZHOU Mengxue¹, ZHAO Ying¹, WANG Chuanming³, HE Gaohong^1,2

1 School of Petroleum and Chemical Engineering, Dalian University of Technology, Panjin 124221, Liaoning, China;
2 Panjin Industrial Technology Institute, Dalian University of Technology, Panjin 124221, Liaoning, China;
3 Shanghai Research Institute of Petrochemical Technology, SINOPEC, Shanghai 201208, China

Received:2017-10-12 Revised:2017-11-15 Online:2018-09-05 Published:2018-09-05

摘要/Abstract

摘要： 金属离子改性分子筛吸附脱水具有节能环保、吸附容量高、净化精度高等特点，受到广泛关注，但还缺乏平衡吸附量等基础数据。本文利用Materials Studio软件中Sorption模块进行落位计算得到合理的金属离子落位和分子筛构型，同时利用Reflex模块计算分子筛的XRD谱图，计算结果与国际分子筛协会（IZA-SC）的XRD标准谱图一致。采用蒙特卡罗法（Monte Carlo）的"COMPASS"力场对NaX、NaY和NaA 3种分子筛以及Ca²⁺、Fe³⁺、Mg²⁺和K⁺改性分子筛吸附水进行分子模拟。结果表明，水的吸附属于第Ⅰ型Langmuir吸附等温线。NaX、NaY和NaA分子筛对水的平衡吸附量分别为360.3mg/g、393.8mg/g和295.5mg/g，Mg²⁺取代的X型、Y型和A型分子筛对水的吸附能力增加幅度最大。MgX的平衡吸附量达472.6mg/g，较未改性时增加了112.3mg/g。本研究可为高效分子筛脱水吸附剂的筛选及其应用提供一定的理论依据和指导。

关键词: 金属离子, 分子筛, 吸附, COMPASS力场, 蒙特卡罗模拟

Abstract: The adsorption dehydration by the metal ions modified molecular sieves attracted widespread attention, because of their low energy cost, high adsorption capacity and high degree purification, but it is still lack of fundamental data such as the equilibrium water adsorption capacity. The rational metal ion sites and configuration of the molecular sieves were obtained by utilizing the Sorption module in Materials studio software. At the same time, the X-ray diffraction spectra of NaX, NaY and NaA molecular sieves were calculated. The calculated results were consistent with the standard spectra in the International Molecular Sieve Association (IZA-SC) database. The Monte Carlo simulation method with "COMPASS" force field was used to simulate the process of water adsorption on the molecular sieves of NaX, NaY and NaA, and the molecular sieves modified with Ca²⁺, Fe³⁺, Mg²⁺, K⁺. The results showed that the adsorption isotherms of water on the molecular sieves belong to the typeⅠLangmuir adsorption isotherm. The equilibrium adsorption capacities of water on the molecular sieves without modification were 360.3mg/g, 393.8mg/g and 295.5mg/g for NaX, NaY and NaA, respectively. The adsorption performance of the X, Y and A molecular sieves modified with Mg²⁺ improved obviously. The equilibrium adsorption capacity of MgX reached 472.6mg/g, which was 112.3mg/g higher than that of the unmodified ones. This study can provide a theoretical basis and guidance for the research, development and application of the high efficient molecular sieve adsorbents for dehydration.

Key words: metal ions, molecular sieves, adsorption, COMPASS force field, Monte Carlo simulation

中图分类号:

TQ013.1

肖永厚, 周梦雪, 赵颖, 王传明, 贺高红. 金属离子改性分子筛吸附水的Monte Carlo模拟[J]. 化工进展, 2018, 37(09): 3430-3436.

XIAO Yonghou, ZHOU Mengxue, ZHAO Ying, WANG Chuanming, HE Gaohong. Monte Carlo simulation of water adsorption on metal ions modified molecular sieves[J]. Chemical Industry and Engineering Progress, 2018, 37(09): 3430-3436.

参考文献

[1] GABRUS E, NASTAJ J, TABERO P, et al. Experimental studies on 3A and 4A zeolite molecular sieves regeneration in TSA process:aliphatic alcohols dewatering-water desorption[J]. Chemical Engineering Journal, 2015, 259:232-242.
[2] ZHANG K, LIVELY R P, ZHANG C, et al. Investigating the intrinsic ethanol/water separation capability of ZIF-8:an adsorption and diffusion study[J]. Journal of Physical Chemistry C, 2013, 117(14):7214-7225.
[3] CAPUTO D, IUCOLANO F, PEPE F, et al. Modeling of water and ethanol adsorption data on a commercial zeolite-rich tuff and prediction of the relevant binary isotherms[J]. Microporous and Mesoporous Materials, 2007, 105(3):260-267.
[4] SHIRANI B, KAGHAZCHI T, BEHESHTI M. Water and mercaptan adsorption on 13X zeolite in natural gas purification process[J]. Korean Journal of Chemical Engineering, 2010, 27(1):253-260.
[5] YEBOAH S K, DARKWA J. A critical review of thermal enhancement of packed beds for water vapour adsorption[J]. Renewable & Sustainable Energy Reviews, 2016, 58:1500-1520.
[6] LUO Y, FUNKE H H, FALCONER J L, et al. Adsorption of CO₂, CH₄, C₃H₈, and H₂O in SSZ-13, SAPO-34, and T-type zeolites[J]. Industrial & Engineering Chemistry Research, 2016, 55(36):9749-9757.
[7] PIRES J, PINTO M, ESTELLA J, et al. Characterization of the hydrophobicity of mesoporous silicas and clays with silica pillars by water adsorption and DRIFT[J]. Journal of Colloid and Interface Science, 2008, 317(1):206-213.
[8] FERREIRA D, MAGALHAES R, TAVEIRA P, et al. Effective adsorption equilibrium isotherms and breakthroughs of water vapor and carbon dioxide on different adsorbents[J]. Industrial & Engineering Chemistry Research, 2011, 50(17):10201-10210.
[9] WEI X, WANG W, XIAO J, et al. Hierarchically porous aluminosilicates as the water vapor adsorbents for dehumidification[J]. Chemical Engineering Journal, 2013, 228:1133-1139.
[10] KIM J H, LEE C H, KIM W S, et al. Adsorption equilibria of water vapor on alumina, zeolite 13X, and a zeolite X/activated carbon composite[J]. Journal of Chemical and Engineering Data, 2003, 48(1):137-141.
[11] SERBEZOV A. Adsorption equilibrium of water vapor on F-200 activated alumina[J]. Journal of Chemical and Engineering Data, 2003, 48(2):421-425.
[12] 吴晓磊, 孙林兵, 殷孝谦,等. 用于氨气深度脱水的吸附材料[J]. 化工进展, 2013, 32(1):129-155. WU Xiaolei, SUN Linbing, YIN Xiaoqian, et al. Adsorption material for deep dehydration of ammonia[J]. Chemical Industry and Engineering Progress, 2013,32(1):129-155.
[13] 刘海艳, 易红宏, 唐晓龙, 等.分子筛吸附脱除燃煤烟气硫碳硝的研究进展[J]. 化工进展, 2012, 31(6):1347-1352. LIU Haiyan, YI Honghong, TANG Xiaolong, et al. Research progress on removal of sulfur, carbon and nitric oxide from flue gas by molecular sieve adsorption[J]. Chemical Industry and Engineering Progress, 2012, 31(6):1347-1352.
[14] JOVIC S, LAXRNINARAYAN Y, KEURENTJES J, et al. Adsorptive water removal from dichloromethane and vapor-phase regeneration of a molecular sieve 3A packed bed[J]. Industrial & Engineering Chemistry Research, 2017, 56(17):5042-5054.
[15] WANG Y, LEVAN M D. Adsorption equilibrium of carbon dioxide and water vapor on zeolites 5A and 13X and silica gel:pure components[J]. Journal of Chemical and Engineering Data, 2009, 54(10):2839-2844.
[16] METTE B, KERSKES H, DRUCK H, et al. Experimental and numerical investigations on the water vapor adsorption isotherms and kinetics of binderless zeolite 13X[J]. International Journal of Heat and Mass Transfer, 2014, 71:555-561.
[17] LIN R, LIU J, NAN Y, et al. Kinetics of water vapor adsorption on single-layer molecular sieve 3A:experiments and modeling[J]. Industrial & Engineering Chemistry Research, 2014, 53(41):16015-16024.
[18] CHEN H, DING J, WANG W, et al. Water adsorption characteristics of MCM-41 post-modified by Al grafting and cations doping:equilibrium and kinetics study[J]. Adsorption, 2017, 23(1):113-120.
[19] RUSSO P A, CARROTT M M L R, PADRE-ETERNO A, et al. Interaction of water vapour at 298K with Al-MCM-41 materials synthesised at room temperature[J]. Microporous and Mesoporous Materials, 2007, 103(1-3):82-93.
[20] REICHHARDT N V, NYLANDER T, KLOSGEN B, et al. Porosity and surface properites of SBA-15 with grafted pnipaam:a water sorption calorimetry study[J]. Langmuir, 2011, 27(22):13838-13846.
[21] CHANG S C, CHIEN S Y, CHEN C L, et al. Analyzing adsorption characteristics of CO₂, N₂ and H₂ O in MCM-41 silica by molecular simulation[J]. Applied Surface Science, 2015, 331:225-233.
[22] 丁静, 胡玉坤, 杨晓西, 等. 水在ZSM-5型分子筛吸附的Monte Carlo模拟[J]. 化工学报, 2008, 59(9):2276-2282. DING Jin, HU Yukun, YANG Xiaoxi, et al. Monte Carlo simulation of water adsorption on ZSM-5 zeolite[J]. Journal of Chemical Industry and Engineering(China), 2008, 59(9):2276-2282.
[23] DUBBELDAM D, CALERO S, ELLIS D E, et al. RASPA:molecular simulation software for adsorption and diffusion in flexible nanoporous materials[J]. Molecular Simulation, 2016, 42(2):81-101.
[24] ZHAO T, LI X, ZHAO H, et al. Molecular simulation of adsorption and thermodynamic properties on type Ⅱ kerogen:influence of maturity and moisture content[J]. Fuel, 2017, 190:198-207.
[25] 刘航希, 隋红, 李鑫钢, 等. 甲苯分子在铝基金属-有机骨架材料上的吸附特性[J]. 化工进展, 2016, 35(11):3707-3713. LIU Hangxi, SUI Hong, LI Xingang, et al. Adsorption characteristics of toluene molecules on aluminum-based metal-organic skeleton materials[J]. Chemical Industry and Engineering Progress, 2016, 35(11):3707-3713.
[26] 郭向丹, 黄世萍, 腾加伟, 等. 水在Na_n ZSM-5型分子筛中吸附的研究:分子模拟[J]. 物理化学学报, 2006, 22(3):270-274. GUO Xiangdan, HUANG Shiping, TENG Jiawei, et al. Study on adsorption of water in Na_n ZSM-5 molecular sieve:molecular simulation[J]. Acta Physico-Chimica Sinica, 2006, 22(3):270-274.
[27] ARI M U, AHUNBAY M G, YURTSEVER M, et al. Molecular dynamics simulation of water diffusion in MFI-type zeolites[J]. Journal of Physical Chemistry B, 2009, 113(23):8073-8079.
[28] PILLAI R S, JASRA R V. Computational study for water sorption in AlPO₄-5 and AlPO₄-11 molecular sieves[J]. Langmuir, 2010, 26(3):1755-1764.
[29] 谢自立, 郭坤敏. 微孔容积填充吸附理论研究[J]. 化工学报, 1995, 46(4):452-457. XIE Zili, GUO Kunmin. Study on adsorption theory of microporous volume[J]. Journal of Chemical Industry and Engineering(China), 1995, 46(4):452-457.

金属离子改性分子筛吸附水的Monte Carlo模拟

Monte Carlo simulation of water adsorption on metal ions modified molecular sieves

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	崔守成, 徐洪波, 彭楠. 两种MOFs材料用于O₂/He吸附分离的模拟分析[J]. 化工进展, 2023, 42(S1): 382-390.
[2]	陈崇明, 陈秋, 宫云茜, 车凯, 郁金星, 孙楠楠. 分子筛基CO₂吸附剂研究进展[J]. 化工进展, 2023, 42(S1): 411-419.
[3]	许春树, 姚庆达, 梁永贤, 周华龙. 共价有机框架材料功能化策略及其对Hg(Ⅱ)和Cr(Ⅵ)的吸附性能研究进展[J]. 化工进展, 2023, 42(S1): 461-478.
[4]	顾永正, 张永生. HBr改性飞灰对Hg⁰的动态吸附及动力学模型[J]. 化工进展, 2023, 42(S1): 498-509.
[5]	郭强, 赵文凯, 肖永厚. 增强流体扰动强化变压吸附甲硫醚/氮气分离的数值模拟[J]. 化工进展, 2023, 42(S1): 64-72.
[6]	王胜岩, 邓帅, 赵睿恺. 变电吸附二氧化碳捕集技术研究进展[J]. 化工进展, 2023, 42(S1): 233-245.
[7]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[8]	杨莹, 侯豪杰, 黄瑞, 崔煜, 王兵, 刘健, 鲍卫仁, 常丽萍, 王建成, 韩丽娜. 利用煤焦油中酚类物质Stöber法制备碳纳米球用于CO₂吸附[J]. 化工进展, 2023, 42(9): 5011-5018.
[9]	张振, 李丹, 陈辰, 吴菁岚, 应汉杰, 乔浩. 吸附树脂对唾液酸的分离纯化[J]. 化工进展, 2023, 42(8): 4153-4158.
[10]	王晓晗, 周亚松, 于志庆, 魏强, 孙劲晓, 姜鹏. 不同晶粒尺寸Y分子筛的合成及其加氢裂化反应性能[J]. 化工进展, 2023, 42(8): 4283-4295.
[11]	姜晶, 陈霄宇, 张瑞妍, 盛光遥. 载锰生物炭制备及其在环境修复中应用研究进展[J]. 化工进展, 2023, 42(8): 4385-4397.
[12]	于静文, 宋璐娜, 刘砚超, 吕瑞东, 武蒙蒙, 冯宇, 李忠, 米杰. 一种吲哚基超交联聚合物In-HCP对水中碘的吸附作用[J]. 化工进展, 2023, 42(7): 3674-3683.
[13]	李艳玲, 卓振, 池亮, 陈曦, 孙堂磊, 刘鹏, 雷廷宙. 氮掺杂生物炭的制备与应用研究进展[J]. 化工进展, 2023, 42(7): 3720-3735.
[14]	白亚迪, 邓帅, 赵睿恺, 赵力, 杨英霞. 变温吸附碳捕集机组标准化测试方案探讨及性能实验[J]. 化工进展, 2023, 42(7): 3834-3846.
[15]	张雪伟, 黄亚继, 许月阳, 程好强, 朱志成, 李金壘, 丁雪宇, 王圣, 张荣初. 碱性吸附剂对燃煤烟气中SO₃的吸附特性[J]. 化工进展, 2023, 42(7): 3855-3864.