Removing H_(2)S and CO_(2)is of great significance for natural gas purification.With excellent gas affinity and tunable structure,ionic liquids(ILs) have been regarded as nontrivial candidates for fabricating polymer-...Removing H_(2)S and CO_(2)is of great significance for natural gas purification.With excellent gas affinity and tunable structure,ionic liquids(ILs) have been regarded as nontrivial candidates for fabricating polymer-based membranes.Herein,we firstly reported the incorporation of protic ILs (PILs) having ether-rich and carboxylate sites (ECPILs) into poly(ether-block-amide)(Pebax) matrix for efficient separation H_(2)S and CO_(2)from CH_(4).Notably,the optimal permeability of H_(2)S reaches up to 4310 Barrer (40C,0.50 bar) in Pebax/ECPIL membranes,along with H_(2)S/CH_(4)and (H_(2)StCO_(2))/CH_(4)selectivity of 97.7 and 112.3,respectively.These values are increased by 1125%,160.8%and 145.9%compared to those in neat Pebax membrane.Additionally,the solubility and diffusion coefficients of the gases were measured,demonstrating that ECPIL can simultaneously strengthen the dissolution and diffusion of H_(2)S and CO_(2),thus elevating the permeability and permselectivity.By using quantum chemical calculations and FT-IR spectroscopy,the highly reversible multi-site hydrogen bonding interaction between ECPILs and H_(2)S was revealed,which is responsible for the fast permeation of H_(2)S and good selectivity.Furthermore,H_(2)S/CO_(2)/CH_(4)(3/3/94 mol/mol) ternary mixed gas can be efficiently and stably separated by Pebax/ECPIL membrane for at least 100 h.Overall,this work not only illustrates that PILs with ether-rich and carboxylate hydrogen bonding sites are outstanding materials for simultaneous removal of H_(2)S and CO_(2),but may also provide a novel insight into the design of membrane materials for natural gas upgrading.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
In this work,a series of novel proton-gradient-transfer acid complexes(PGTACs)were developed.Their physicochemical properties,including thermal stability,melting point,and Hammett acidity,were measured.The effects of ...In this work,a series of novel proton-gradient-transfer acid complexes(PGTACs)were developed.Their physicochemical properties,including thermal stability,melting point,and Hammett acidity,were measured.The effects of catalyst loading,reaction temperature,and substrate expansion on the catalytic performance were systematically studied.It is found that the combination of bidentate N-heterocycle and H;SO;(1:2 M ratio)could form simultaneously N–H covalent bond and N…H hydrogen bond,which makes the PGTACs excellent catalysts integrate the advantages of strong acids(high catalytic activity)and ionic liquids(phase separation)in the esterification reaction.Moreover,these PGTACs can be reused by convenient phase separation without obvious diminution of catalytic activity.It is concluded that these PGTACs are potential alternative candidates for esterification reaction in the process of industrial catalysis.展开更多
The resource utilization of hydrogen sulfide(H_(2)S)is of great significance in natural gas chemical industry.Described herein have developed a novel method mediated in tertiary amine-functionalized ionic liquids(ILs)...The resource utilization of hydrogen sulfide(H_(2)S)is of great significance in natural gas chemical industry.Described herein have developed a novel method mediated in tertiary amine-functionalized ionic liquids(ILs)to convert H_(2)S into mercaptan alcohols with enols.The effect of ILs,substra te scope,and regeneration experiments have been investigated.It is found that the conversion of 3-methyl-2-buten-1-ol by H_(2)S can reach 52%with a 50%(mol)catalyst loading of bis(2-dimethylaminoethyl)ether methoxyacetate within 12 hat 90℃.The reaction mechanism was speculated based on theoretical calculation.Besides,a plausible reaction-separation-integrated strategy was further proposed.This work reveals an effective insight into the capture and catalytic conversion of H_(2)S to high valuable mercaptan alcohol,which makes the utilization method of H_(2)S resource universal and has the potentiality for industrial application.展开更多
Selective separation of CO_(2) and H_(2)S from CH_(4) is of importance to the natural gas upgrading because of its cor-rosivity. As is well known, amine group can recognize reversibly CO_(2) and H_(2)S with a moderate...Selective separation of CO_(2) and H_(2)S from CH_(4) is of importance to the natural gas upgrading because of its cor-rosivity. As is well known, amine group can recognize reversibly CO_(2) and H_(2)S with a moderate interaction. Withthis in mind, this work prepared a series of amine-functionalized supported-protic-ionic-liquid membranes(SPILMs) for the selective separation of CO_(2) and H_(2)S from CH_(4) . For comparison, aprotic ionic liquid membranewas also prepared for natural gas sweetening. The effect of temperature and transmembrane pressure differenceon the permeability of single gas and ideal selectivity of CO_(2)/CH_(4) and H_(2)S/CO_(2) were studied. Facilitated transportmechanism was studied by NMR spectra. The permeability of CO_(2) in primary amine functionalized [DMPDAH][Tf_(2)N]-based membrane decreases with the increasing transmembrane pressure, indicating a typical feature offacilitated transport membrane. The permeability of CO_(2) and the ideal selective of CO_(2)/CH_(4) are as high as 2000 barrers and 53.2 at 313.2 K in [DMPDAH][Tf_(2)N] membrane, significantly higher than those in conventional ILsmembrane. It is anticipated that these amine-functionalized SPILMs can provide alternative insight for the se-lective separation of CO_(2) and H_(2)S from CH_(4) .展开更多
基金sponsored by the National Natural Science Foundation of China (Nos. 22308145, 22208140, 22178159, 22078145)Natural Science Foundation of Jiangsu Province (BK20230791)Postgraduate Research Innovation Program of Jiangsu Province (KYCX24_0165)。
文摘Removing H_(2)S and CO_(2)is of great significance for natural gas purification.With excellent gas affinity and tunable structure,ionic liquids(ILs) have been regarded as nontrivial candidates for fabricating polymer-based membranes.Herein,we firstly reported the incorporation of protic ILs (PILs) having ether-rich and carboxylate sites (ECPILs) into poly(ether-block-amide)(Pebax) matrix for efficient separation H_(2)S and CO_(2)from CH_(4).Notably,the optimal permeability of H_(2)S reaches up to 4310 Barrer (40C,0.50 bar) in Pebax/ECPIL membranes,along with H_(2)S/CH_(4)and (H_(2)StCO_(2))/CH_(4)selectivity of 97.7 and 112.3,respectively.These values are increased by 1125%,160.8%and 145.9%compared to those in neat Pebax membrane.Additionally,the solubility and diffusion coefficients of the gases were measured,demonstrating that ECPIL can simultaneously strengthen the dissolution and diffusion of H_(2)S and CO_(2),thus elevating the permeability and permselectivity.By using quantum chemical calculations and FT-IR spectroscopy,the highly reversible multi-site hydrogen bonding interaction between ECPILs and H_(2)S was revealed,which is responsible for the fast permeation of H_(2)S and good selectivity.Furthermore,H_(2)S/CO_(2)/CH_(4)(3/3/94 mol/mol) ternary mixed gas can be efficiently and stably separated by Pebax/ECPIL membrane for at least 100 h.Overall,this work not only illustrates that PILs with ether-rich and carboxylate hydrogen bonding sites are outstanding materials for simultaneous removal of H_(2)S and CO_(2),but may also provide a novel insight into the design of membrane materials for natural gas upgrading.
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.
基金sponsored by the National Natural Science Foundation of China(Nos.21576129 and 21878141)the Natural Science Foundation of Jiangsu Province(BK20190310)for financial supports
文摘In this work,a series of novel proton-gradient-transfer acid complexes(PGTACs)were developed.Their physicochemical properties,including thermal stability,melting point,and Hammett acidity,were measured.The effects of catalyst loading,reaction temperature,and substrate expansion on the catalytic performance were systematically studied.It is found that the combination of bidentate N-heterocycle and H;SO;(1:2 M ratio)could form simultaneously N–H covalent bond and N…H hydrogen bond,which makes the PGTACs excellent catalysts integrate the advantages of strong acids(high catalytic activity)and ionic liquids(phase separation)in the esterification reaction.Moreover,these PGTACs can be reused by convenient phase separation without obvious diminution of catalytic activity.It is concluded that these PGTACs are potential alternative candidates for esterification reaction in the process of industrial catalysis.
基金sponsored by the National Natural Science Foundation of China(22078145,22208140)。
文摘The resource utilization of hydrogen sulfide(H_(2)S)is of great significance in natural gas chemical industry.Described herein have developed a novel method mediated in tertiary amine-functionalized ionic liquids(ILs)to convert H_(2)S into mercaptan alcohols with enols.The effect of ILs,substra te scope,and regeneration experiments have been investigated.It is found that the conversion of 3-methyl-2-buten-1-ol by H_(2)S can reach 52%with a 50%(mol)catalyst loading of bis(2-dimethylaminoethyl)ether methoxyacetate within 12 hat 90℃.The reaction mechanism was speculated based on theoretical calculation.Besides,a plausible reaction-separation-integrated strategy was further proposed.This work reveals an effective insight into the capture and catalytic conversion of H_(2)S to high valuable mercaptan alcohol,which makes the utilization method of H_(2)S resource universal and has the potentiality for industrial application.
基金This work was sponsored by the Natural Science Foundation of Jiangsu Province(BK20190310)China Postdoctoral Science Foundation(2021M691515)+1 种基金the Postdoctoral Science Foundation of Jiangsu Province(2021K211B)the National Natural Science Foundation of China(Nos.22078145 and 21878141)。
文摘Selective separation of CO_(2) and H_(2)S from CH_(4) is of importance to the natural gas upgrading because of its cor-rosivity. As is well known, amine group can recognize reversibly CO_(2) and H_(2)S with a moderate interaction. Withthis in mind, this work prepared a series of amine-functionalized supported-protic-ionic-liquid membranes(SPILMs) for the selective separation of CO_(2) and H_(2)S from CH_(4) . For comparison, aprotic ionic liquid membranewas also prepared for natural gas sweetening. The effect of temperature and transmembrane pressure differenceon the permeability of single gas and ideal selectivity of CO_(2)/CH_(4) and H_(2)S/CO_(2) were studied. Facilitated transportmechanism was studied by NMR spectra. The permeability of CO_(2) in primary amine functionalized [DMPDAH][Tf_(2)N]-based membrane decreases with the increasing transmembrane pressure, indicating a typical feature offacilitated transport membrane. The permeability of CO_(2) and the ideal selective of CO_(2)/CH_(4) are as high as 2000 barrers and 53.2 at 313.2 K in [DMPDAH][Tf_(2)N] membrane, significantly higher than those in conventional ILsmembrane. It is anticipated that these amine-functionalized SPILMs can provide alternative insight for the se-lective separation of CO_(2) and H_(2)S from CH_(4) .
