Despite the long tradition of fossil carbon(coal,char,and related carbon-based materials)for fueling mankind,the science of transforming them into chemicals is still demandingly progressing in the current energy scena...Despite the long tradition of fossil carbon(coal,char,and related carbon-based materials)for fueling mankind,the science of transforming them into chemicals is still demandingly progressing in the current energy scenario,especially when considering its responsibilities to the global climate change.Traditionally,there are four routes of preparing chemicals directly from fossil carbon,including hydrogasification,gasification,direct liquefaction,and oxidation,in the macroscope of gas-solid reaction(hydrogasification and gasification)and liquid-solid reaction(direct liquefaction and oxidation).When the study goes to microscale,the gas-solid reaction can be considered as the reaction between the severe condensed radicals and gas,while the liquid-solid reaction is the direct reaction between the radical and the activated-molecule.To have a full overview of the area,this review systematically summarizes the main factors in these processes and shows our own perspectives as follows,(ⅰ)stabilizing the free radicals generated from coal and then directly converting them has the highest efficiency in coal utilization;(ⅱ)the research on the self-catalytic process of coal structure will have a profound impact on the direct preparation of chemicals from fossil carbon.Further discussions are also proposed to guide the future study of the area into a more sustainable direction.展开更多
In this research,molecular structure models were developed respectively for Shenhua coal vitrinite concentrates(SDV)and inertinite concentrates(SDI),on the basis of information on constitutional unit of Shenhau coal a...In this research,molecular structure models were developed respectively for Shenhua coal vitrinite concentrates(SDV)and inertinite concentrates(SDI),on the basis of information on constitutional unit of Shenhau coal and elemental analysis results obtained from^(13)C-NMR analysis characterization,FTIR analysis characterization,X-ray diffraction XRD and XPS analysis characterization.It can be observed from characterization data and molecular structure models that the structure of SDV and SDI is dominated by aromatic hydrocarbon,with aromaticity of SDI higher than that of SDV;SDV mainly consists of small molecule basic structure unit,while SDI is largely made from macromolecular structure unit.Based on bond-level parameters of the molecular model,the research found through the autoclave experiment that vitrinite liquefaction process goes under thermodynamics control and inertinite liquefaction process under dynamics control.The research developed an efficient directional direct coal liquefaction technology based on the maceral characteristics of Shenhua coal,which can effectively improve oil yield and lower gas yield.展开更多
Gasification of extraction residue(ER) from direct coal liquefaction with pulverized coal is an efficient way for the utilization of carbonaceous wastes, which improve the overall efficiency of direct coal liquefactio...Gasification of extraction residue(ER) from direct coal liquefaction with pulverized coal is an efficient way for the utilization of carbonaceous wastes, which improve the overall efficiency of direct coal liquefaction technology. The discharge characteristics of ER mixing with pulverized coal is important paraments for its gasification process, which is seldom studied in the literature. In this study, the discharge characteristics of the pulverized coal(M1) as well as its mixture with ER(M2) were systematically investigated in an atmospheric pressure partial fluidization silo with different fluidization apparent velocity. It was observed that although M2 is a viscous powder with lower flowability than M1, the mass flow rate of M2 is 65% higher than M1 at the 3.7 mm·s-1apparent gas velocity. M2 exhibits the properties of Geldart A type powder, which improves the mass flow rate and stability of the discharged material. The mass flow rate of both M1 and M2 first increases and then slowly decreases with the increase of apparent gas velocity of the fluidizing air, which means the discharge process of M1 and M2 can be optimized by the apparent gas velocity.展开更多
Radicals are important intermediates in direct coal liquefaction.Certain radicals can cause the cleavage of chemical bonds.At high temperatures,radical fragments can be produced by the splitting of large organic molec...Radicals are important intermediates in direct coal liquefaction.Certain radicals can cause the cleavage of chemical bonds.At high temperatures,radical fragments can be produced by the splitting of large organic molecules,which can break strong chemical bonds through the induction pyrolysis of radicals.The reaction between the formation and annihilation of coal radical fragments and the effect of hydrogen-donor solvents on the radical fragments are discussed in lignite hydrogenolysis.Using the hydroxyl and ether bonds as indicators,the effects of different radicals on the cleavage of chemical bond were investigated employing density functional theory calculations and lignite hydrogenolysis experiments.Results showed that the adjustment of the coal radical fragments could be made by the addition of hydrogendonor solvents.Results showed that the transition from coal radical fragment to H radical leads to the variation of product distribution.The synergistic mechanism of hydrogen supply and hydrogenolysis of hydrogen-donor solvent was proposed.展开更多
Diesel from direct coal liquefaction(DDCL) is a new type of engine alternative energy. But its hydrocarbon composition and physicochemical properties are quite different from those of Petro diesel. In this study, a pr...Diesel from direct coal liquefaction(DDCL) is a new type of engine alternative energy. But its hydrocarbon composition and physicochemical properties are quite different from those of Petro diesel. In this study, a premixed constant volume combustion chamber(CVCC) system with soot particle sampling devices was built. The soot particles in the spray flame were sampled and photographed by thermophoresis probe and transmission electron microscope(TEM). An automatic processing code based on Matlab software was developed to process the TEM images and extract the micro morphology parameters of the soot particles. This study has systematically studied the effects of sampling location, injection pressure, ambient density and oxygen concentration on the micro morphology of soot particles. The ambient density refers to the initial gas density in the CVCC. The results showed that various morphologies and sizes of soot particles coexisted in the upstream of the spray flame. During the evolution of soot particles from upstream to downstream in the flame, the size of soot aggregates gradually decreased, while the maturity of soot aggregates increased. With the increase of injection pressure, ambient density and oxygen concentration, the average sizes of soot aggregates and primary soot particles decreased, but the fractal dimensions of soot aggregates increased gradually. Under the same combustion condition and in-flame sampling location, the average projection area, gyration radius and primary soot diameter of soot aggregates produced by DDCL were significantly lower than those of Petro diesel. The structure of soot particles from DDCL was more compact than that of Petro diesel.展开更多
Utilizing the extraction residue(ER)of direct coal liquefaction residue as a gasification feedstock has significant economic value.But the characteristic of high ash and iron in the ER would increase the risk of corro...Utilizing the extraction residue(ER)of direct coal liquefaction residue as a gasification feedstock has significant economic value.But the characteristic of high ash and iron in the ER would increase the risk of corrosion of the refractory materials and affect the long-term operation of the gasifier.In this work,corrosion experiments of molten slag derived from a mixture of 20 wt%ER and 80 wt%coal on a high-chromia refractory brick and SiC brick were carried out using a rotary-drum furnace in a simulated gasification atmosphere.The experimental results show that the viscosity of the poured slag is larger as compared to the initial ash sample at the same temperature,which suggests that the viscosity-temperature relationship of the poured slag should be used as the reference for the operation temperature of the gasifier to ensure that the slag can flow during operation.For a high-chromia refractory brick,iron oxides in molten slag could react with Cr_(2)O_(3) in the refractory matrix but,because the aggregate was not found to be damaged,the damage to the matrix structure was the key factor for causing the corrosion of the high-chromia refractory brick.Metallic iron was observed in the exposed SiC brick,which indicated that the reaction between the iron oxides in the slag and SiC occurred,forming metallic iron and SiO_(2).The corrosion of a SiC brick by molten slag depended mainly on the dissolution of Al_(2)O_(3) particles and the reaction between iron oxides in the molten slag and SiC particles.Therefore,the high iron content in coal ash had a serious influence on the corrosion of refractory materials.More efforts need to be made on coal blended with ER as a gasification feedstock in the future.展开更多
基金supported by National Natural Science Foundation of China(52161145403 and 22072164)the Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy(Grant.YLU-DNL Fund 2022002)。
文摘Despite the long tradition of fossil carbon(coal,char,and related carbon-based materials)for fueling mankind,the science of transforming them into chemicals is still demandingly progressing in the current energy scenario,especially when considering its responsibilities to the global climate change.Traditionally,there are four routes of preparing chemicals directly from fossil carbon,including hydrogasification,gasification,direct liquefaction,and oxidation,in the macroscope of gas-solid reaction(hydrogasification and gasification)and liquid-solid reaction(direct liquefaction and oxidation).When the study goes to microscale,the gas-solid reaction can be considered as the reaction between the severe condensed radicals and gas,while the liquid-solid reaction is the direct reaction between the radical and the activated-molecule.To have a full overview of the area,this review systematically summarizes the main factors in these processes and shows our own perspectives as follows,(ⅰ)stabilizing the free radicals generated from coal and then directly converting them has the highest efficiency in coal utilization;(ⅱ)the research on the self-catalytic process of coal structure will have a profound impact on the direct preparation of chemicals from fossil carbon.Further discussions are also proposed to guide the future study of the area into a more sustainable direction.
基金Supported by the National Engineering Labo-ratory of Direct Coal Liquefaction(MZY-16).
文摘In this research,molecular structure models were developed respectively for Shenhua coal vitrinite concentrates(SDV)and inertinite concentrates(SDI),on the basis of information on constitutional unit of Shenhau coal and elemental analysis results obtained from^(13)C-NMR analysis characterization,FTIR analysis characterization,X-ray diffraction XRD and XPS analysis characterization.It can be observed from characterization data and molecular structure models that the structure of SDV and SDI is dominated by aromatic hydrocarbon,with aromaticity of SDI higher than that of SDV;SDV mainly consists of small molecule basic structure unit,while SDI is largely made from macromolecular structure unit.Based on bond-level parameters of the molecular model,the research found through the autoclave experiment that vitrinite liquefaction process goes under thermodynamics control and inertinite liquefaction process under dynamics control.The research developed an efficient directional direct coal liquefaction technology based on the maceral characteristics of Shenhua coal,which can effectively improve oil yield and lower gas yield.
文摘Gasification of extraction residue(ER) from direct coal liquefaction with pulverized coal is an efficient way for the utilization of carbonaceous wastes, which improve the overall efficiency of direct coal liquefaction technology. The discharge characteristics of ER mixing with pulverized coal is important paraments for its gasification process, which is seldom studied in the literature. In this study, the discharge characteristics of the pulverized coal(M1) as well as its mixture with ER(M2) were systematically investigated in an atmospheric pressure partial fluidization silo with different fluidization apparent velocity. It was observed that although M2 is a viscous powder with lower flowability than M1, the mass flow rate of M2 is 65% higher than M1 at the 3.7 mm·s-1apparent gas velocity. M2 exhibits the properties of Geldart A type powder, which improves the mass flow rate and stability of the discharged material. The mass flow rate of both M1 and M2 first increases and then slowly decreases with the increase of apparent gas velocity of the fluidizing air, which means the discharge process of M1 and M2 can be optimized by the apparent gas velocity.
基金The authors are grateful to the National Natural Science Foundation of China(Grant No.22038008)the 2030 Major Project Pilot Project from CHN Energy,China(Grant No.GJNY2030XDXM-19-13,2)for the financial suppor。
文摘Radicals are important intermediates in direct coal liquefaction.Certain radicals can cause the cleavage of chemical bonds.At high temperatures,radical fragments can be produced by the splitting of large organic molecules,which can break strong chemical bonds through the induction pyrolysis of radicals.The reaction between the formation and annihilation of coal radical fragments and the effect of hydrogen-donor solvents on the radical fragments are discussed in lignite hydrogenolysis.Using the hydroxyl and ether bonds as indicators,the effects of different radicals on the cleavage of chemical bond were investigated employing density functional theory calculations and lignite hydrogenolysis experiments.Results showed that the adjustment of the coal radical fragments could be made by the addition of hydrogendonor solvents.Results showed that the transition from coal radical fragment to H radical leads to the variation of product distribution.The synergistic mechanism of hydrogen supply and hydrogenolysis of hydrogen-donor solvent was proposed.
基金supported by the National Key Research and Development Program of China(Grant No.2017YFE0130800)National Natural Science Foundation of China(Grant No.91741122)。
文摘Diesel from direct coal liquefaction(DDCL) is a new type of engine alternative energy. But its hydrocarbon composition and physicochemical properties are quite different from those of Petro diesel. In this study, a premixed constant volume combustion chamber(CVCC) system with soot particle sampling devices was built. The soot particles in the spray flame were sampled and photographed by thermophoresis probe and transmission electron microscope(TEM). An automatic processing code based on Matlab software was developed to process the TEM images and extract the micro morphology parameters of the soot particles. This study has systematically studied the effects of sampling location, injection pressure, ambient density and oxygen concentration on the micro morphology of soot particles. The ambient density refers to the initial gas density in the CVCC. The results showed that various morphologies and sizes of soot particles coexisted in the upstream of the spray flame. During the evolution of soot particles from upstream to downstream in the flame, the size of soot aggregates gradually decreased, while the maturity of soot aggregates increased. With the increase of injection pressure, ambient density and oxygen concentration, the average sizes of soot aggregates and primary soot particles decreased, but the fractal dimensions of soot aggregates increased gradually. Under the same combustion condition and in-flame sampling location, the average projection area, gyration radius and primary soot diameter of soot aggregates produced by DDCL were significantly lower than those of Petro diesel. The structure of soot particles from DDCL was more compact than that of Petro diesel.
基金This work was supported by the Science and Technology Innovation Project of CHN Energy(grant number GJNY-21-91)the Science and Technology Innovation Project of CHN Energy(grant number GJNY-20-119)the National Key R&D program of China(grant number 2017YFB0602603).
文摘Utilizing the extraction residue(ER)of direct coal liquefaction residue as a gasification feedstock has significant economic value.But the characteristic of high ash and iron in the ER would increase the risk of corrosion of the refractory materials and affect the long-term operation of the gasifier.In this work,corrosion experiments of molten slag derived from a mixture of 20 wt%ER and 80 wt%coal on a high-chromia refractory brick and SiC brick were carried out using a rotary-drum furnace in a simulated gasification atmosphere.The experimental results show that the viscosity of the poured slag is larger as compared to the initial ash sample at the same temperature,which suggests that the viscosity-temperature relationship of the poured slag should be used as the reference for the operation temperature of the gasifier to ensure that the slag can flow during operation.For a high-chromia refractory brick,iron oxides in molten slag could react with Cr_(2)O_(3) in the refractory matrix but,because the aggregate was not found to be damaged,the damage to the matrix structure was the key factor for causing the corrosion of the high-chromia refractory brick.Metallic iron was observed in the exposed SiC brick,which indicated that the reaction between the iron oxides in the slag and SiC occurred,forming metallic iron and SiO_(2).The corrosion of a SiC brick by molten slag depended mainly on the dissolution of Al_(2)O_(3) particles and the reaction between iron oxides in the molten slag and SiC particles.Therefore,the high iron content in coal ash had a serious influence on the corrosion of refractory materials.More efforts need to be made on coal blended with ER as a gasification feedstock in the future.