Improving methane adsorption capacity of HKUST-1 by modified with carboxylic acid

doi:10.11949/j.issn.0438-1157.20180604

Abstract

Abstract:

In order to improve the methane adsorption capacity of adsorbent, the metal-organic frameworks material HKUST-1 was synthesized by solvothermal method and follow by modification research. The optimized synthesis conditions were as follows:n(Cu(NO₃)₂·3H₂O):n(H₃BTC):n(DMF):n(C₂H₅OH):n(H₂O)=1.7:1:46:60:100, the crystallization temperature of 80℃ and the crystallization time of 24 h. The methane adsorption capacity of HKUST-1 was 11.9 mmol/g at 25℃. Acid ligand modification could increase the methane adsorption capacity of HKUST-1. When V_HAc/V_solvent=5.8%, the methane adsorption capacity of HAc-HK-1(5.8%) reached 12.6 mmol/g. Molecular simulation results show that the addition of acetic acid can regulate the pore structure of HKUST-1 crystal, increase the specific surface area and pore volume, and increase the methane adsorption capacity.

Key words: HKUST-1, metal-organic frameworks, methane, natural gas adsorption storage

摘要：

为提高吸附材料对甲烷的吸附容量，采用溶剂热法合成了金属有机骨架材料HKUST-1，并进行了改性研究。HKUST-1的优化合成工艺条件为：原料摩尔比n（Cu（NO₃）₂·3H₂O）：n（H₃BTC）：n（DMF）：n（C₂H₅OH）：n（H₂O）=1.7：1：46：60：100，晶化温度为80℃，晶化时间24 h。合成HKUST-1在25℃、3.5 MPa下的甲烷吸附容量为11.9 mmol/g。乙酸改性HKUST-1可以提高甲烷吸附容量，当反应母液中V_HAc/V_solvent=5.8%时，合成HAc-HK-1（5.8%）的甲烷吸附容量达到12.6 mmol/g。分子模拟结果表明，加入乙酸可以调控HKUST-1晶体孔道结构，增大比表面积和孔容，提高甲烷吸附容量。

关键词: HKUST-1, 金属有机骨架材料, 甲烷, 天然气吸附储存

CLC Number:

TE821

HAN Qiang, CHENG Zhenfei, LIU Jichang, WANG Cheng, OU Suhui, WANG Yuyi, JIAN Yupei, YANG Xiaojuan, WANG Zizhu, YANG Lubin. Improving methane adsorption capacity of HKUST-1 by modified with carboxylic acid[J]. CIESC Journal, 2018, 69(11): 4902-4909.

韩强, 程振飞, 刘纪昌, 汪成, 欧苏慧, 汪瑜懿, 简雨培, 杨小娟, 王紫竹, 杨璐彬. 羧酸改性HKUST-1提高甲烷吸附容量[J]. 化工学报, 2018, 69(11): 4902-4909.

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