FUEL
·
2023
·
IF 7.4
Hongxia Fang,Chuncai Zhou,Shihai Xu,Jiaqian Shi,Yunhu Hu,Guijian Liu,Lei Wu
Metal-organic frameworks (MOFs) are considered one of the promising adsorbents for CH 4 /N 2 separation. However, MOFs commercialization is a big challenge since their synthetic materials are expensive and not environmentally friendly. Herein, the dealumination solution obtained from coal fly ash (CFA) using sulfuric acid as an extracting agent through direct leaching and roasting technologies was applied as metal feedstock to prepare CFAx-FumMOF-y and compared to aluminum fumarate MOF (Al-FumMOF) in morphology, surface area, micropore volume, and CH 4 /N 2 selective separation. The results indicated that CFAx-FumMOF-y exhibited closely similar surface area (1164.94–1073.08 m 2 /g) and micropore volume (0.40–0.36 cm 3 /g) to Al-FumMOF (1287.55 m 2 /g, 0.42 cm 3 /g), even there were no detectable differences in CH 4 uptakes (CFAx-FumMOF-y, 21.93–20.69 cm 3 /g; Al-FumMOF, 22.13 cm 3 /g) at 298 K and 1.0 bar, suggesting that the impurity metal species in dealumination solution hardly affect textural properties and gas uptakes. Moreover, the isosteric heat of adsorption (Q st ) and IAST CH 4 /N 2 selectivity of CFAs-FumMOF-1 (19.25–17.84 kJ/mol) and CFAb-FumMOF-1 (18.83–18.64 kJ/mol) were slightly superior to Al-FumMOF (17.83.64–16.86 kJ/mol, 4.87), suggesting that CFAx-FumMOF-1 played an identical role as Al-FumMOF in gases separation. The cyclic regeneration experiments and binary breakthrough tests further confirmed that CFAx-FumMOF-y was feasible for practical application. This study provides a new perspective for reducing the production cost of MOFs as well as realizing high-value utilization of CFA.
研究领域:
材料科学
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环境科学
✓ 已验证
DOI
高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2025
·
IF 3.7
Zhiwei Zhao,Yating Wang,Yuhao Tang,Xiaoqing Wang,Feifei Zhang,Jiangfeng Yang
Unconventional natural gas has become an important supplement to conventional energy sources, and the process of enrichment and purification of methane from low concentration coalbed methane is crucial. To this end, we report a copper-based metal–organic framework (MOF), ZJNU-119Cu, featuring two methane traps constructed with uncoordinated carboxylic acid oxygens and open metal sites. ZJNU-119Cu exhibits a high methane adsorption capacity (58.2 cm 3 ·g –1 ) at 298 K and 0.1 MPa and excellent CH 4 /N 2 separation performance under dynamic conditions. Density-functional theory calculations combined with grand canonical Monte Carlo simulation theory reveal the interaction mechanism for the uncoordinated carboxylic acid oxygen atoms and open metal sites in ZJNU-119Cu with CH 4 . The gas adsorption isotherms, heat of adsorption calculations, and breakthrough separation experiments indicate that this MOF is a very promising adsorbent for CH 4 /N 2 separation.
研究领域:
材料科学
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能源化学
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理论计算
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2018
·
IF 3.927
Shumin Wang,Qingping Guo,Shujun Liang,Peng Li,Jujie Luo
A series of mixed matrix membranes (MMMs) were fabricated with Ni-MOF-74 as filler and poly (styrene-b-butadiene-b-styrene) (SBS) polymer as matrix materials for CH 4 /N 2 separation. MMMs were characterized by Fourier transform infrared (FTIR) spectra, X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). Gas separation behavior was investigated by measuring single and mixed gases. For the single gas, the CH 4 permeability of the MMMs incorporated with 15 wt% Ni-MOF-74 (Ni-MOF-74/SBS-15) reached 83.5 Barrer, which was 116% higher than that of SBS (38.6 Barrer), while its ideal selectivity remained the same. CH 4 permeability can further increase to 176.6 Barrer with the increase in temperature to 55 °C. For the CH 4 /N 2 (50/50 vol%) mixed gas, the Ni-MOF-74/SBS-15 sample exhibited increasing CH 4 permeability (74.7 vs 36.7 Barrer), while selectivity remained unchanged relative to that of the pure SBS membrane.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2024
·
IF 4.8
Kunpeng Liu,Yixuan Yu,Qi Wang,Lingtong Kong,Tianjun Sun
A comprehensive investigation was conducted to explore the adsorption behaviors of CH 4 over N 2 on ultra-microporous Al/Zr-FDCA frameworks, which were synthesized specifically using the eco-friendly and bio-sourced 2,5-furandicarboxylic acid (FDCA). Characterization results revealed that both Al-FDCA and Zr-FDCA exhibited similar specific surface area and surface groups, leading to comparable methane uptake per-unit mass at atmospheric pressure. However, the presence of Zr nodes generated ultra-micropores around 0.43 nm in size, leading to a pronounced affinity for CH 4 . Zr-FDCA demonstrated a higher CH 4 /N 2 selectivity (8.90) calculated from the isotherms compared to Al-FDCA (3.86). Furthermore, breakthrough experiments indicated that under the same dynamic conditions, Zr-FDCA exhibited 1.5 times higher CH 4 uptake per unit volume and 2.5 times higher CH 4 /N 2 selectivity when compared to Al-FDCA. Initially, a four-step VPSA process was simulated to investigate the separation of CH 4 /N 2 mixture, in which the effects of feed-gas flow rate, adsorption time, adsorption pressure, and desorption pressure in VPSA cycle were extensively evaluated to enhance the purity and recovery of methane. Subsequently, a six-step process was employed for further optimization, achieving a purity of 95.9 % and a recovery of 99.1 %. The obtained results demonstrated the reliability of the established model and highlighted the significant potential of Zr-FDCA for CH 4 /N 2 separation.
研究领域:
材料科学
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环境科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION SCIENCE AND TECHNOLOGY
·
2025
·
IF 2.3
Xiaoli Ding,Qiankun Zhang,Hongyong Zhao,Qingping Xin,Yuzhong Zhang
Two series of mixed matrix membranes (MMMs) have been synthesized via in situ UV polymerization for the removal of N2 from CH4. MIL-100(Cr) particles activated at different temperatures were used as fillers. MIL-100(Cr) activated at 150°C with CH4-selective adsorption was incorporated with poly(ethylene oxide)-based polymer to improve the CH4/N2 separation performance, and that activated at 250°C with N2-selective adsorption and diffusion was incorporated with fluoropolymer to improve the N2/CH4 separation performance. The effects of the filler loadings on the gas permeation and separation performances were investigated. The optimum MMMs with 5 wt.% loading of MIL-100(Cr) activated at 150°C exhibited a 70% increased CH4/N2 permselectivity of 5.0 with a 37% increased CH4 permeability of 11.2 Barrer (tested at 0.2 MPa and 35°C). The optimum MMMs with 5 wt.% loading of MIL-100(Cr) activated at 250°C exhibited a 106% increased N2 permeability of 71.5 Barrer with an 89% increased N2/CH4 permselectivity of 1.9.
研究领域:
化学工程
·
材料科学
·
膜技术
·
气体分离
✓ 已验证
产品关联
DOI
高影响因子
REACTIVE & FUNCTIONAL POLYMERS
·
2018
·
IF 2.975
Xing Yang,Tengyang Zhu,Zongxiang Xu,Haiquan Shan,Jujie Luo
Poly(styrene-b-butadiene-b-styrene) triblock co polymer (SBS) crosslinked membranes containing poly(dimethylsiloxane- co -methylhydrosiloxane) (PDMS- co -PMHS) were prepared by hydrosilylation reaction toward CH 4 /N 2 separation. The effect of an additive amount of PDMS- co -PMHS on the structure, morphology, and thermodynamic stability of crosslinked membranes were investigated by using FT-IR, SEM and TGA . Soxhlet extraction experiments were also performed to explore the crosslinking degree of membranes. In this work, the single-gas permeability of CH 4 and N 2 was measured using the constant volume–variable pressure method. Our experimental results showed that crosslinked membranes can significantly enhance CH 4 permeability with increasing PDMS- co -PMHS content, whereas the CH 4 /N 2 selectivity remains unchanged. Among these crosslinked membranes, the SBS-c-PDMS- co -PMHS-70 membrane exhibited optimal CH 4 permeability at room temperature and the pressure of 1 bar. Specifically, the CH 4 permeability was > 10-folds higher than that of the SBS membranes (37.6 barrer versus 443.6 barrer). Moreover, investigation of the effect of test temperature on the gas permeation of crosslinked membranes revealed a preferable CH 4 permeability at 55 °C and 1 bar, at which the CH 4 permeability reaches 679.2 barrer without a substantial compromise in selectivity.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2021
·
IF 7.312
Zhenjie Gu,Zibo Yang,Xiangyu Guo,Zhihua Qiao,Chongli Zhong
CH 4 /N 2 separation, a viable way to purify energy gas and reduce the greenhouse effect, requires the use of highly gas permeable membrane, but acid environment affects the membrane stability. In this work, the ZIF-8@VR nanoparticle was synthesized via a high vacuum resistance sintering method (VRSM), which increased the acid resistance to pH 2.8 because of surface carbonization and stiffening. The structure of the ZIF-8@VR nanoparticle was investigated by XRD, SEM, FTIR, BET and Raman analysis, followed by blending it with polyacrylic acid (PAA) to fabricate PAA/ZIF-8@VR mixed matrix membranes (MMMs). The MMMs exhibited excellent CH 4 permeance and satisfactory CH 4 /N 2 selectivity, with the optimal CH 4 permeance (~1763 GPU) for the MMM with 66.8 wt% ZIF-8@VR filler. Furthermore, compared with pure PAA membrane, the MMMs with ZIF-8@VR filler could improve the CH 4 /N 2 selectivity from 1.3 to 3.1.
研究领域:
材料科学
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化学工程
·
环境科学
✓ 已验证
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2022
·
IF 9.136
Zhenghui Huang,Peng Hu,Jia Liu,Fang Shen,Youquan Zhang,Kungang Chai,Yunpan Ying,Chengjun Kang,Zhaoqiang Zhang,Hongbing Ji
Efficient CH 4 /N 2 separation is necessitated for obtaining purified methane from natural gas. Aluminum-based metal–organic frameworks (Al-MOFs) have potential for industrial separation applications due to their structure-tunable, low-cost, and scalable features. Intrigued by the impressive selectivity of a recently reported Al-MOF (Al-CDC) toward CH 4 over N 2 , we herein further study the potential of Al-MOFs as adsorbent for CH 4 /N 2 separation, mainly considering the effects of pore geometry and linker polarity. Utilization of two bent ligands and two linear ligands with different polarity afforded two one-dimensional square-shaped Al-MOFs i.e., CAU-10-H, MIL-160, and two rhombic-shaped counterparts i.e., Al-Fumarate (Al-Fum), MIL-53(Al)), respectively. Afterward, pure CH 4 and N 2 adsorption experiments were conducted at 273–313 K for assessing the CH 4 /N 2 separation performance. The results indicated that all the Al-MOFs exhibited superior affinity toward CH 4 over N 2 , and the CH 4 uptake followed the sequence of Al-Fum > CAU-10-H > MIL-53(Al) > MIL-160. Exhilaratingly, Al-Fum exhibited unprecedented CH 4 /N 2 selectivity (17.2) and high CH 4 uptake at 273 K and 1.0 bar. The mechanism underlying the disparity of Al-MOFs affinity toward CH 4 was deciphered via theoretical simulation, suggesting that the synergetic effects of accessibility of strong affinity sites (μ 2 -OH) on AlO 6 chains and polar pore surface induced by varying linkers highly promoted the CH 4 uptake. Furthermore, the results of cyclic adsorption–desorption experiments and binary breakthrough tests validated the feasibility of Al-Fum for practical application.
研究领域:
材料科学
·
化学工程
·
气体分离
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Xun Wang,Zewei Liu,Jian Yan,Daofei Lv,Xin Chen,Feng Xu,Xin Zhou,Zhong Li
Developing adsorbents with exceptional CH 4 /N 2 selectivity under high pressure is a crucial commercial requirement and a significant technical challenge for the industrial high-pressure swing adsorption (HPSA) in CH 4 /N 2 separation. Only a few adsorbents were reported to address this issue. In this work, we aimed to explore two microporous MOFs with low-polarity channels for high-pressure CH 4 /N 2 separation. The Ni(BDC)(DABCO) 0.5 and its isostructural analog Ni(TMBDC)(DABCO) 0.5 were synthesized, characterized, and examined for high-pressure CH 4 /N 2 adsorption property. Due to the lower polarity channel originating from tetramethyl groups, Ni(TMBDC)(DABCO) 0.5 exhibited an exceptional methane capacity of 4.23 mmol/g and an IAST selectivity of 5.1 for the CH 4 /N 2 binary mixture at a pressure of 10 bar, surpassing the majority of previously reported materials. The GCMC simulation revealed that the low-polarity pore surfaces in both materials exhibited a higher affinity for CH 4 molecules compared to N 2 molecules, under both ambient and high pressures. The breakthrough experiments showed that Ni(TMBDC)(DABCO) 0.5 exhibited excellent dynamic separation towards CH 4 /N 2 under both 1 bar and 5 bar, indicating great potential as an emerging candidate for the recovery of CH 4 from coal-mine methane in industrial PSA processes.
研究领域:
材料科学
·
化学工程
·
吸附技术
✓ 已验证
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2025
·
IF 9
Yuwei Xie,Kunxiang Lei,Yihao Xiao,Xinxi Huang,Wanbin Li
Natural gas accounts for more than 20 % of the world’s primary energy supply. However, the upgrading of natural gas, especially the separation of CH 4 and N 2 with similar molecular characteristics, remains challenging. Membrane technology is efficient and energy-saving, but the membrane-based CH 4 /N 2 separation usually shows poor performance and hampered by trade-off issue. We report de novo mechanochemical crystallization of metal-organic frameworks (MOFs) within polymers of intrinsic microporosity to design mixed-matrix membranes (MMMs) for CH 4 /N 2 separation. One-pot ball-milling mechanochemistry at room temperature induces in situ crystallization of MOFs and integration of polymers, thereby constructing highly loaded MMMs with ameliorated filler dispersity and interfacial compatibility. As the fillers, consisted of carboxylate linkers and copper centers, improve preferential gas sorption, gas transport process, and polymer arrangement, the MMMs exhibit substantially enhanced separation capability and antiaging property. For CH 4 /N 2 separation, the CH 4 permeability of MMMs before and after aging for 180 days reaches up to 8120 and 7260 Barrer, respectively, which are one to three orders of magnitude larger than that of conventional membranes, while accompanied by greater selectivity of 6.52 and 7.11. Moreover, this strategy is facile and generally applicable for different MOFs, and the MMMs have thermal, humid, and long-term stabilities and show CO 2 permeability over 33,000 Barrer and CO 2 /N 2 selectivity of 20–25. This study illuminates the practicality of mechanochemistry for hybrid membranes and provides an alternative route for gas purification.
研究领域:
材料科学
·
化学工程
·
膜技术
·
气体分离
·
机械化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Tong Li,Xiaoxia Jia,Hui Chen,Zeyu Chang,Libo Li,Yong Wang,Jinping Li
Adsorption separation technology using adsorbents is promising as an alternative to the energy-demanding cryogenic distillation of natural gas (CH4/N2) separation. Although a few adsorbents, such as metal–organic frameworks (MOFs), with high performance for CH4/N2 separation, have been reported, it is still challenging to target the desired adsorbents for the actual CH4/N2 separation under humid conditions because the adsorption capacity and selectivity of the adsorbents might be mainly dampened by water vapor. Except for the high CH4 uptake and CH4/N2 selectivity, the adsorption material should simultaneously have excellent stability against moisture and relatively low-water absorption affinity. Here, we tuned the ligands and metal sites of reticular MOFs, Zn-benzene-1,4-dicarboxylic acid–1,4-diazabicyclo[2.2.2]octane (Zn-BDC–DABCO) (DMOF), affording a series of isostructural MOFs (DMOF-N, DMOF-A1, DMOF-A2, and DMOF-A3). Because of the finely engineered pore size and introduced aromatic rings in the functional DMOF, gas sorption results reveal that the materials show improved performance with a benchmark CH4 uptake of 37 cm3/g and a high CH4/N2 adsorption selectivity of 7.2 for DMOF-A2 at 298 K and 1.0 bar. Moisture stability experiments show that DMOF-A2 is a robust MOF with low water vapor capacity even at ∼40% relative humidity (RH) because of the presence of more hydrophobic aromatic rings. Breakthrough experiments verify the excellent CH4/N2 separation performances of DMOF-A2 under high humidity.
研究领域:
材料科学
·
化学工程
·
环境科学
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2019
·
IF 3.375
Xiao-Wei Liu,Yi-Ming Gu,Tian-Jun Sun,Ya Guo,Xiao-Li Wei,Sheng-Sheng Zhao,Shu-Dong Wang
The highly efficient separation of CH4/N2 remains a great challenge, but it is vital to make the most of diverse natural gas resources and contributes to mitigating global warming. In this work, two isostructural metal–organic frameworks (MOFs), M-MA-BPY where M is Co and Ni, were elaborately selected and synthesized to serve the purpose. These MOFs were thoroughly characterized and found to have favorable framework flexibility, endowing them with narrow and uniform pore networks suitable for the adsorptive separation of CH4/N2. Further studies revealed the M-MA-BPY MOFs’ excellent stability toward water and moist air. Pure gas adsorption experiments suggested they have decent CH4 capacities (0.92 and 1.01 mmol·g–1 for Co- and Ni-MA-BPY), prominent CH4/N2 selectivities (7.2 and 7.4 for Co- and Ni-MA-BPY, IAST selectivity with equimolar CH4/N2 gas mixture) at 298 K and 1 bar, and desirable heats of adsorption for CH4 (22.8 and 23.5 kJ·mol–1 for Co- and Ni-MA-BPY). Dynamic breakthrough experiments and multiple adsorption–desorption cycling tests for CH4/N2 binary mixtures with different gas ratios of 5:95, 15:85, 30:70, and 50:50 (v/v) confirmed the high separation performance of M-MA-BPY MOFs. Together with their relatively simple synthesis and cheap raw reagents, this work demonstrates M-MA-BPY MOFs are very promising adsorbents for the capture of methane from low-quality natural gas resources in ambient conditions.
研究领域:
化学工程
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）