The separation of He/H_(2)using membrane technology has gained significant interest in the field of He extraction from natural gas.One of the greatest challenges associated with this process is the extremely close kin...The separation of He/H_(2)using membrane technology has gained significant interest in the field of He extraction from natural gas.One of the greatest challenges associated with this process is the extremely close kinetic diameters of the two gas molecules,resulting in low membrane selectivity.In this study,we investigated the structure-performance relationship of metal-organic framework(MOF)membranes for He/H_(2)separation through molecular simulations and machine learning approaches.By conducting molecular simulations,we identified the potential MOF membranes with high separation performance from the Computation-Ready Experimental(Co RE)MOF database,and the diffusion-dominated mechanism was further elucidated.Moreover,random forest(RF)-based machine learning models were established to identify the crucial factors influencing the He/H_(2)separation performance of MOF membranes.The pore limiting diameter(PLD)and void fraction(φ),are revealed as the most important physical features for determining the membrane selectivity and He permeability,respectively.Additionally,density functional theory(DFT)calculations were carried out to validate the molecular simulation results and suggested that the electronegative atoms on the pore surfaces can enhance the diffusion-based separation of He/H_(2),which is critical for improving the membrane selectivities of He/H_(2).This study offers useful insights for designing and developing novel MOF membranes for the separation of He/H_(2)at the molecular level.展开更多
The deep-processing utility of pure hydrogen sulfide (H_(2)S) is a significant direction in natural gas chemical industry.Herein,a brand-new strategy of H_(2)S conversion by a,β-unsaturated carboxylate esters into th...The deep-processing utility of pure hydrogen sulfide (H_(2)S) is a significant direction in natural gas chemical industry.Herein,a brand-new strategy of H_(2)S conversion by a,β-unsaturated carboxylate esters into thiols or thioethers using task-specific carboxylate ionic liquids (ILs) as catalyst has been developed,firstly accomplishing the phase separation of product and catalyst without introducing the third component.It can be considered as a cascade reaction in which the product selectivity can be controlled by adjusting the molar ratio of H_(2)S to a,β-unsaturated carboxylate esters.Also,the effects of ILs with different anions and cations,intermittent feeding operations,as well as pressure-time kinetic behaviors on cascade reaction were investigated.Furthermore,the proposed interaction mechanism of H_(2)S conversion using butyl acrylate catalyzed by[Emim][Ac]was revealed by DFT-based theoretical calculation.The approach enables the self-phase separation promotion of catalyst and product and achieves 99%quantitative conversion under mild conditions in the absence of solvent,making the entire process ecologically benign.High-efficiency reaction activity can still be maintained after ten cycles of the catalyst.Therefore,the good results,combined with its simplicity of operation and the high recyclability of the catalyst,make this green method environmentally friendly and cost-effective.It is anticipated that this self-separation method mediated by task-specific ILs will provide a feasible strategy for H_(2)S utilization,which will guide its application on an industrial scale.展开更多
氢和氨作为清洁能源受到广泛关注,为深入探究氢-氨混燃的燃烧特性和影响因素,本文借助Chemkin仿真平台建立相关反应模型,以氢-氨混合气体为燃料,空气作为助燃剂,采用Otomo等人提出的一种氨氧化机理对其燃烧过程进行模拟计算,并模拟研究...氢和氨作为清洁能源受到广泛关注,为深入探究氢-氨混燃的燃烧特性和影响因素,本文借助Chemkin仿真平台建立相关反应模型,以氢-氨混合气体为燃料,空气作为助燃剂,采用Otomo等人提出的一种氨氧化机理对其燃烧过程进行模拟计算,并模拟研究了混合气体的点火延迟时间、层流燃烧速度、绝热燃烧温度、NO排放等燃烧特性随当量比、初始压力以及燃料中H_(2)比例的具体变化规律,对不同工况下的层流火焰结构、H和OH自由基的产率(rate of production,ROP)、NO生成的敏感度进行了化学动力学分析。结果表明:纯氨气体的点火延迟时间长、层流燃烧速度慢,掺氢后燃烧特性均有所改善,且提高了火焰的绝热燃烧温度,但掺氢比例越大,NO排放越多。NO摩尔分数随当量比变化的趋势先增后减,在当量比为0.8左右达到峰值。综合考虑氢-氨混燃的一系列燃烧特性以及掺氢、加压的成本和收益情况,推荐H_(2)占比15%、当量比φ=1.1、压力P=0.2 MPa为氢-氨混合燃烧的最优条件。展开更多
基金supported by the National Natural Science Foundation of China(Nos.22141001 and 22108202)
文摘The separation of He/H_(2)using membrane technology has gained significant interest in the field of He extraction from natural gas.One of the greatest challenges associated with this process is the extremely close kinetic diameters of the two gas molecules,resulting in low membrane selectivity.In this study,we investigated the structure-performance relationship of metal-organic framework(MOF)membranes for He/H_(2)separation through molecular simulations and machine learning approaches.By conducting molecular simulations,we identified the potential MOF membranes with high separation performance from the Computation-Ready Experimental(Co RE)MOF database,and the diffusion-dominated mechanism was further elucidated.Moreover,random forest(RF)-based machine learning models were established to identify the crucial factors influencing the He/H_(2)separation performance of MOF membranes.The pore limiting diameter(PLD)and void fraction(φ),are revealed as the most important physical features for determining the membrane selectivity and He permeability,respectively.Additionally,density functional theory(DFT)calculations were carried out to validate the molecular simulation results and suggested that the electronegative atoms on the pore surfaces can enhance the diffusion-based separation of He/H_(2),which is critical for improving the membrane selectivities of He/H_(2).This study offers useful insights for designing and developing novel MOF membranes for the separation of He/H_(2)at the molecular level.
基金sponsored by the National Natural Science Foundation of China (Nos. 22208140 and 22078145)。
文摘The deep-processing utility of pure hydrogen sulfide (H_(2)S) is a significant direction in natural gas chemical industry.Herein,a brand-new strategy of H_(2)S conversion by a,β-unsaturated carboxylate esters into thiols or thioethers using task-specific carboxylate ionic liquids (ILs) as catalyst has been developed,firstly accomplishing the phase separation of product and catalyst without introducing the third component.It can be considered as a cascade reaction in which the product selectivity can be controlled by adjusting the molar ratio of H_(2)S to a,β-unsaturated carboxylate esters.Also,the effects of ILs with different anions and cations,intermittent feeding operations,as well as pressure-time kinetic behaviors on cascade reaction were investigated.Furthermore,the proposed interaction mechanism of H_(2)S conversion using butyl acrylate catalyzed by[Emim][Ac]was revealed by DFT-based theoretical calculation.The approach enables the self-phase separation promotion of catalyst and product and achieves 99%quantitative conversion under mild conditions in the absence of solvent,making the entire process ecologically benign.High-efficiency reaction activity can still be maintained after ten cycles of the catalyst.Therefore,the good results,combined with its simplicity of operation and the high recyclability of the catalyst,make this green method environmentally friendly and cost-effective.It is anticipated that this self-separation method mediated by task-specific ILs will provide a feasible strategy for H_(2)S utilization,which will guide its application on an industrial scale.
文摘氢和氨作为清洁能源受到广泛关注,为深入探究氢-氨混燃的燃烧特性和影响因素,本文借助Chemkin仿真平台建立相关反应模型,以氢-氨混合气体为燃料,空气作为助燃剂,采用Otomo等人提出的一种氨氧化机理对其燃烧过程进行模拟计算,并模拟研究了混合气体的点火延迟时间、层流燃烧速度、绝热燃烧温度、NO排放等燃烧特性随当量比、初始压力以及燃料中H_(2)比例的具体变化规律,对不同工况下的层流火焰结构、H和OH自由基的产率(rate of production,ROP)、NO生成的敏感度进行了化学动力学分析。结果表明:纯氨气体的点火延迟时间长、层流燃烧速度慢,掺氢后燃烧特性均有所改善,且提高了火焰的绝热燃烧温度,但掺氢比例越大,NO排放越多。NO摩尔分数随当量比变化的趋势先增后减,在当量比为0.8左右达到峰值。综合考虑氢-氨混燃的一系列燃烧特性以及掺氢、加压的成本和收益情况,推荐H_(2)占比15%、当量比φ=1.1、压力P=0.2 MPa为氢-氨混合燃烧的最优条件。
