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Molecular simulation study of Cu-based MOFs for CH4/N2 adsorption separation in low-concentration coalbed methane
- Low-Carbon Chemistry and Chemical Engineering Vol. 50, Issue 7, Pages: 83-90(2025)
- 作者机构：
1.太原理工大学 省部共建煤基能源清洁高效利用国家重点实验室，山西 太原 030024
2.太原理工大学 化学工程与技术学院，山西 太原 030024
3.太原理工大学 煤科学与技术教育部重点实验室，山西 太原 030024
- 作者简介：
- 基金信息：
DOI：10.12434/j.issn.2097-2547.20240384
CLC： TQ028Received：11 September 2024，
Revised：12 October 2024，
Published：25 July 2025
- 稿件说明：
移动端阅览
仙梦丹,高学婷,李刚森等.Cu基MOFs在低浓度煤层气CH4/N2吸附分离中的分子模拟研究[J].低碳化学与化工,2025,50(07):83-90.
XIAN Mengdan,GAO Xueting,LI Gangsen,et al.Molecular simulation study of Cu-based MOFs for CH4/N2 adsorption separation in low-concentration coalbed methane[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(07):83-90.
仙梦丹,高学婷,李刚森等.Cu基MOFs在低浓度煤层气CH4/N2吸附分离中的分子模拟研究[J].低碳化学与化工,2025,50(07):83-90. DOI： 10.12434/j.issn.2097-2547.20240384.
XIAN Mengdan,GAO Xueting,LI Gangsen,et al.Molecular simulation study of Cu-based MOFs for CH4/N2 adsorption separation in low-concentration coalbed methane[J].Low-Carbon Chemistry and Chemical Engineering,2025,50(07):83-90. DOI： 10.12434/j.issn.2097-2547.20240384.
摘要
我国目前存在常规天然气产能不足的问题，需要开发煤层气等非常规天然气作为补充。在煤矿开采过程中，会混入大量空气形成低浓度煤层气（CH
4
体积分数低于30%），造成资源浪费等一系列问题，因此，提高低浓度煤层气回收利用率成为亟需解决的问题。采用巨正则蒙特卡洛和密度泛函理论相结合的计算方法，以低浓度煤层气中CH
4
/N
2
的吸附分离为目标，选取Cu基金属-有机骨架材料（MOFs）（Cu-BTC、MOF-143、ATC-Cu和MOF-399）和不同金属（Zn、Co和Mo）改性的ATC-M为吸附材料，研究了不同孔径和金属中心对MOFs的CH
4
/N
2
吸附分离性能的影响。结果表明，MOFs孔径对其吸附量和CH
4
/N
2
吸附选择性具有重要影响，MOFs孔径越接近气体分子动力学直径，CH
4
/N
2
吸附选择性越高。在7种MOFs中，ATC-Zn的孔径（0.4995 nm）更接近CH
4
和N
2
的分子动力学直径（CH
4
：0.380 nm，N
2
：0.364 nm），其CH
4
/N
2
分离性能达到了最优。金属中心改性对ATC-M孔径没有明显影响，改性金属中心的电荷是影响CH
4
/N
2
吸附分离性能的主要因素。当金属离子的bader电荷越大，MOFs的CH
4
/N
2
吸附分离性能越高，在7种MOFs中，ATC-Zn的CH
4
/N
2
吸附分离性能最高。298 K、100 kPa下，当低浓度煤层气
n
(CH
4
):
n
(N
2
) = 1:9时，ATC-Zn的CH
4
/N
2
吸附选择性高达6.46，为低浓度煤层气中CH
4
的回收利用提供了新的研究思路。
Abstract
At present
China has the problem of insufficient capacity of conventional natural gas
and it needs to develop unconventional natural gas such as coalbed methane as a supplement. In the process of coal mining
a large amount of air will be mixed to form low-concentration coalbed
methane (methane volume fraction is less than 30%)
which leads to a series of problems such as resource waste. Therefore
improving the recovery and utilization rate of low-concentration coalbed methane has become an urgent problem to be solved. The adsorption and separation of CH
4
/N
2
in low concentration coalbed methane was studied by using the combination of Grand canonical Monte Carlo and density functional theory. Cu-based metal organic framework (MOFs) (Cu-BTC
MOF-143
ATC-Cu and MOF-399) and ATC-M modified by different metals (Zn
Co and Mo) were selected as adsorption materials.The effects of different pore sizes and metal centers on the adsorption and separation performances of CH
4
/N
2
by MOFs were studied. The results show that the pore size of MOFs has a significant impact on their adsorption capacity and CH
4
/N
2
adsorption selectivity. The closer the pore size of MOFs is to the molecular kinetic diameter of the gas
the higher the CH
4
/N
2
adsorption selectivity. Among the seven MOFs
ATC-Zn has a pore size (0.4995 nm) that is closer to the molecular kinetic diameters of CH
4
and N
2
(CH
4
: 0.380 nm
N
2
: 0.364 nm)
achieving the best CH
4
/N
2
separation performance. Metal center modification has no significant effect on the pore size of ATC-M. The charge of the modified metal center is the main factor affecting the CH
4
/N
2
adsorption and separation performance. The larger the bader charge of the metal ion
the better the CH
4
/N
2
adsorption and separation performance of MOFs. Among the seven MOFs
ATC-Zn has the best CH
4
/N
2
adsorption and separation performance. At 298 K and 100 kPa
when
n
(CH
4
):
n
(N
2
) of low-concentration coalbed methane is 1:9
the CH
4
/N
2
adsorption selectivity of ATC-Zn reaches as high as 6.46
provi
ding a new research idea for the recovery and utilization of CH
4
in low-concentration coalbed methane.
关键词
Keywords
references
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