Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terep...Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.展开更多
Carbonate outcrops were taken from Ma 51 sub-member in the Lower Paleozoic in the Yan’an gas field to conduct true tri-axial hydraulic fracturing experiments with water, liquid CO_(2) and supercritical CO_(2). CT sca...Carbonate outcrops were taken from Ma 51 sub-member in the Lower Paleozoic in the Yan’an gas field to conduct true tri-axial hydraulic fracturing experiments with water, liquid CO_(2) and supercritical CO_(2). CT scan was applied to analyze initiation and propagation laws of hydraulic fractures in carbonate rocks. The experiments show that supercritical CO_(2) has low viscosity, strong diffusivity and large filtration during fracturing, which is more liable to increase pore pressure of rocks around wellbore and decrease breakdown pressure of carbonate rocks. However, it would cost much more volume of supercritical CO_(2) than water to fracture rocks since the former increases the wellbore pressure more slowly during fracturing. For carbonate rocks with few natural fractures, tensional fractures are generated by fracturing with water and liquid CO_(2), and these fractures propagate along the maximum horizontal principal stress direction;while fracturing with supercritical CO_(2) can form shear fractures, whose morphology is rarely influenced by horizontal stress difference. Besides, the angle between propagation direction of these shear fractures near the wellbore and the maximum horizontal principal stress is 45°, and the fractures would gradually turn to propagate along the maximum horizontal principal stress when they extend to a certain distance from the wellbore, leading to an increase of fracture tortuosity compared with the former. For carbonate rocks with well-developed natural fractures, fracturing with fresh water is conducive to connect natural fractures with low approaching angle and form stepped fractures with simple morphology. The key to forming complex fractures after fracturing carbonate rocks is to connect the natural fractures with high approaching angle. It is easier for liquid CO_(2) with low viscosity to realize such connection. Multi-directional fractures with relatively complex morphology would be formed after fracturing with liquid CO_(2).展开更多
基金supported by the National Natural Science Foundation of China (Grant No.22278271)the Key Project of Education Department of Liaoning Province(Grant No.LZGD2020005)
文摘Metal-organic frameworks(MOFs)have attracted considerable research attention as a new type of porous material for catalytic applications.Herein,2,5-dihydroxyterephthalic acid was proposed to replace conventional terephthalic acid and reacted with chromic nitrate nonahydrate to synthesize a functional metal–organic framework(FMIL-101).This was then used to immobilize various compound ionic liquids to prepare three ionic liquids immobilized on FMIL-101 catalysts,namely,FMIL-101-[HeMIM]Cl/(ZnBr_(2))_(2),FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),and FMIL-101-[AeMIM]Br/(ZnBr_(2))_(2).After characterization by Fourier-transform infrared spectroscopy,X-ray diffraction,ultraviolet spectroscopy,thermogravimetry,specific surface area analysis,and scanning electron microscopy,the catalysts were used to mediate cycloaddition reactions between carbon dioxide(CO_(2))and propylene oxide.The effects of reaction temperature,reaction pressure,reaction time,and catalyst dosage on the catalytic performance were investigated.The results revealed that the FMIL-101-supported CIL catalysts afforded the target product propylene carbonate with good catalytic performance and thermal stability.The optimal catalyst,FMIL-101-[CeMIM]Cl/(ZnBr_(2))_(2),displayed a propylene oxide conversion of 98.64%and a propylene carbonate selectivity of 96.63%at a reaction temperature of 110℃,a reaction pressure of 2.0 MPa,a catalyst dosage of 2.0%relative to propylene oxide,and a reaction time of 2.5 h.In addition,the conversion and selectivity of the catalyst decreased slightly after four cycles.Additionally,the catalyst decreased slightly in catalytic performance after being recycled four times.
基金Supported by National Natural Science Foundation of China Project(51704249)The Open Fund Project of the State Key Laboratory Oil and Gas Reservoir Geology and Exploitation(PLN2020-1)。
文摘Carbonate outcrops were taken from Ma 51 sub-member in the Lower Paleozoic in the Yan’an gas field to conduct true tri-axial hydraulic fracturing experiments with water, liquid CO_(2) and supercritical CO_(2). CT scan was applied to analyze initiation and propagation laws of hydraulic fractures in carbonate rocks. The experiments show that supercritical CO_(2) has low viscosity, strong diffusivity and large filtration during fracturing, which is more liable to increase pore pressure of rocks around wellbore and decrease breakdown pressure of carbonate rocks. However, it would cost much more volume of supercritical CO_(2) than water to fracture rocks since the former increases the wellbore pressure more slowly during fracturing. For carbonate rocks with few natural fractures, tensional fractures are generated by fracturing with water and liquid CO_(2), and these fractures propagate along the maximum horizontal principal stress direction;while fracturing with supercritical CO_(2) can form shear fractures, whose morphology is rarely influenced by horizontal stress difference. Besides, the angle between propagation direction of these shear fractures near the wellbore and the maximum horizontal principal stress is 45°, and the fractures would gradually turn to propagate along the maximum horizontal principal stress when they extend to a certain distance from the wellbore, leading to an increase of fracture tortuosity compared with the former. For carbonate rocks with well-developed natural fractures, fracturing with fresh water is conducive to connect natural fractures with low approaching angle and form stepped fractures with simple morphology. The key to forming complex fractures after fracturing carbonate rocks is to connect the natural fractures with high approaching angle. It is easier for liquid CO_(2) with low viscosity to realize such connection. Multi-directional fractures with relatively complex morphology would be formed after fracturing with liquid CO_(2).
