The reaction characteristics of phenolic hydroxyl group were studied under the conditions of direct coal liquefaction. 2-naphthol was used as a coal model compound in this study. Under the conditions of with and witho...The reaction characteristics of phenolic hydroxyl group were studied under the conditions of direct coal liquefaction. 2-naphthol was used as a coal model compound in this study. Under the conditions of with and without catalysts, a series of experiments were conducted at different temperatures, pressures and reaction time. Gas chromatography-mass spectrometry and gas chromatography were used to identify and quantify the reactants and products respectively. The conversion of 2-naphthol rises with the increase of reaction temperature, initial pressure and catalyst amount. The results indicated that tem- perature had a significant effect on 2-naphthol conversion, which promoted the dehydroxylation reaction. However, initial pressure had an important influence on the hydrogenation of 2-naphthol and naphthalene. The iron catalyst plays a significant role of cracking instead of hydrogenation. It is concluded that the harsh reaction conditions of high temperature, high pressure, and more catalyst are conducive to promoting dehydroxylation of 2-naphthol. The reaction mechanism was put forward based the experimental results, in which 2-tetralone was an intermediate.展开更多
The coal hydrogenation reaction process is simply considered as three steps.In the first step,the smaller molecules associated with coal structure units are released as some gases and water in the condition of solvent...The coal hydrogenation reaction process is simply considered as three steps.In the first step,the smaller molecules associated with coal structure units are released as some gases and water in the condition of solvent and heating.In this step,some weaker bonds of the coal structure units are ruptured to form free radicals.The radicals are stabi- lized by hydrogen atoms from donor solvent and/or H2.In the second step,chain reaction occurs quickly.In the process of chain reaction,the covalent bonds of coal structure units are attacked by the radicals to form some asphaltenes.In the third step,asphaltenes are hydrogenated form more liquids and some gases.In coal liquefaction,the second step of coal hydrogenation reaction should be controlled to avoid integration of radicals,and the third step of coal hydrogenation should be accelerated to increase the coal conversion and the oil yield.A new concept of coal liquefaction process named as China direct coal lique- faction (CDCL) process is presented based on the mechanism study of coal liquefaction.展开更多
To reasonably utilize the coal direct liquefaction residue(DLR), contrasting research on the co-pyrolysis between different low-rank coals and DLR was investigated using a TGA coupled with an FT-IR spectrophotometer a...To reasonably utilize the coal direct liquefaction residue(DLR), contrasting research on the co-pyrolysis between different low-rank coals and DLR was investigated using a TGA coupled with an FT-IR spectrophotometer and a fixed-bed reactor. GC–MS, FTIR, and XRD were used to explore the reaction mechanisms of the various co-pyrolysis processes. Based on the TGA results, it was confirmed that the tetrahydrofuran insoluble fraction of DLR helped to catalyze the conversion reaction of lignite. Also, the addition of DLR improved the yield of tar in the fixed-bed, with altering the composition of the tar. Moreover, a kinetic analysis during the co-pyrolysis was conducted using a distributed activation energy model. The co-pyrolysis reactions showed an approximate double-Gaussian distribution.展开更多
The product distribution and kinetic analysis of low-rank coal vitrinite were investigated during the chemical looping gasification(CLG)process.The acid washing method was used to treat low-rank coal,and the density g...The product distribution and kinetic analysis of low-rank coal vitrinite were investigated during the chemical looping gasification(CLG)process.The acid washing method was used to treat low-rank coal,and the density gradient centrifugation method was adopted to obtain the coal macerals.By combining thermogravimetric analysis and online mass spectrometry,the influence of the heating rate and oxygen carrier(Fe2O3)blending ratio on product distribution was discussed.The macroscopic kinetic parameters were solved by the Kissinger-Akahira-Sunose(KAS)method,and the main gaseous product formation kinetic parameters were solved by the iso-conversion method.The results of vitrinite during slow heating chemical looping gasification showed that the main weight loss interval was 400–600℃,and the solid yield of sample vitrinite-Fe-10 at different heating rates was 64.30%–69.67%.When b=20℃·min^(-1),the maximum decomposition rate of vitrinite-Fe-10 was 0.312%min1.The addition of Fe2O_(3)reduced the maximum decomposition rate,but by comparing the chemical looping conversion characteristic index,it could be inferred that the chemical looping gasification of vitrinite might produce volatile substances higher than the pyrolysis process of vitrinite alone.The average activation energy of the reaction was significantly reduced during chemical looping gasification of vitrinite,which was lower than the average activation energy of 448.69 kJ·mol^(-1) during the pyrolysis process of vitrinite alone.The gaseous products were mainly CO and CO_(2).When the heating rate was 10℃·min^(-1),the highest activation energy for CH4 formation was 21.353 kJ·mol^(-1),and the lowest activation energy for CO formation was 9.7333 kJ·mol^(-1).This study provides basic data for exploring coal chemical looping gasification mechanism and reactor design by studying the chemical looping gasification process of coal macerals。展开更多
Co-carbonization of weakly caking coal and zinc-containing dust to prepare highly reactive ferro-coke and collaboratively recover zinc powder is one of the feasible ways for steel enterprises to recycle zinc-containin...Co-carbonization of weakly caking coal and zinc-containing dust to prepare highly reactive ferro-coke and collaboratively recover zinc powder is one of the feasible ways for steel enterprises to recycle zinc-containing dust.The pyrolysis mass loss behavior of adding blast furnace dust with different zinc contents to different ferro-coke materials was systematically studied by thermogravimetry and differential thermogravimetry analysis,and the kinetic mechanism of pyrolysis-reduction reaction of hybrid briquette was explored.The results of thermogravimetric curve analysis show that the addition of zinc oxide to the sample has no significant effect on the mass loss rate of the sample below 580℃,and the pyrolysis mass loss of zinc oxide mainly occurs between 800 and 1000℃.Kinetic analysis results show that the pyrolysis of zinc-containing samples is controlled by chemical reactions below 580℃.The reaction at 580–700℃ is controlled by the nucleation and growth model,and that above 700℃ is mainly controlled by diffusion.The results of X-ray diffraction analysis show that the pyrolysis process can effectively remove zinc oxide from ferro-coke.展开更多
The characteristics and kinetics of coal and oil shale pyrolysis were comparatively studied by using a micro fluidized bed reaction analyzer(MFBRA).The isothermal differential model was first applied to calculate the ...The characteristics and kinetics of coal and oil shale pyrolysis were comparatively studied by using a micro fluidized bed reaction analyzer(MFBRA).The isothermal differential model was first applied to calculate the kinetic parameters of activation energy and frequency factor according to the major gas components during pyrolysis.The results showed that the major gas components released from coal and oil shale under the isothermal condition had different initiating and ending time points,and the difference was more significant under the programmed heating conditions.The shrinking core model allowed better fitting relevance for the coal pyrolysis,while the three-dimension model was more suitable for oil shale pyrolysis,indicating that the gases from the pyrolysis process of coal and oil shale might go through different reaction paths.The activation energy of oil shale pyrolysis was 36.96 kJ·mol^(−1),larger than the value of pyrolysis of the two coals,which was 21.16 and 32.17 kJ·mol^(−1),respectively.The above results justified that the oil shale pyrolysis with high ash contents was somehow more difficult to take place in terms of higher activation energy and the MFBRA could be a useful tool to give some insight into the intrinsic kinetics and reaction mechanisms of coal and oil shale pyrolysis.展开更多
The gasification reactivity and kinetic parameters of coal chars for non-isothermal steam gasification were investigated.One kind of lignite and three kinds of bituminous coals were used as the samples,and their coal ...The gasification reactivity and kinetic parameters of coal chars for non-isothermal steam gasification were investigated.One kind of lignite and three kinds of bituminous coals were used as the samples,and their coal ranks follow the ascending order:XB<KL<ZJ<GD.As characterized by the comprehensive gasification index,the gasification reactivity of coal chars follows the descending order:XB>KL>ZJ>GD.Through systematically analyzing factors affecting gasification reactivity,it was ascertained that the gasification reactivity is mostly determined by the carbonaceous structure.The gasification reactivity is inversely proportional to the coal rank,and the higher the coal rank,the lower the gasification reactivity.A new kinetic model was proposed to calculate the kinetic parameters,in which the reaction order was considered as an unknown kinetic parameter.The reaction order n follows the ascending order:XB<KL<ZJ<GD,which are n=1.00,n=1.34,n=1.83,and n=2.63,respectively.It is proved that the reaction order is proportional to the coal rank,and the higher the coal rank,the higher the reaction order.展开更多
文摘The reaction characteristics of phenolic hydroxyl group were studied under the conditions of direct coal liquefaction. 2-naphthol was used as a coal model compound in this study. Under the conditions of with and without catalysts, a series of experiments were conducted at different temperatures, pressures and reaction time. Gas chromatography-mass spectrometry and gas chromatography were used to identify and quantify the reactants and products respectively. The conversion of 2-naphthol rises with the increase of reaction temperature, initial pressure and catalyst amount. The results indicated that tem- perature had a significant effect on 2-naphthol conversion, which promoted the dehydroxylation reaction. However, initial pressure had an important influence on the hydrogenation of 2-naphthol and naphthalene. The iron catalyst plays a significant role of cracking instead of hydrogenation. It is concluded that the harsh reaction conditions of high temperature, high pressure, and more catalyst are conducive to promoting dehydroxylation of 2-naphthol. The reaction mechanism was put forward based the experimental results, in which 2-tetralone was an intermediate.
基金the National Basic Research Program of China(973 Program)(2004CB217605)
文摘The coal hydrogenation reaction process is simply considered as three steps.In the first step,the smaller molecules associated with coal structure units are released as some gases and water in the condition of solvent and heating.In this step,some weaker bonds of the coal structure units are ruptured to form free radicals.The radicals are stabi- lized by hydrogen atoms from donor solvent and/or H2.In the second step,chain reaction occurs quickly.In the process of chain reaction,the covalent bonds of coal structure units are attacked by the radicals to form some asphaltenes.In the third step,asphaltenes are hydrogenated form more liquids and some gases.In coal liquefaction,the second step of coal hydrogenation reaction should be controlled to avoid integration of radicals,and the third step of coal hydrogenation should be accelerated to increase the coal conversion and the oil yield.A new concept of coal liquefaction process named as China direct coal lique- faction (CDCL) process is presented based on the mechanism study of coal liquefaction.
基金Supported by National High-tech Research and Development Program of China(2011AA05A2021)the National Natural Science Foundation of China(21536009)Science and Technology Plan Projects of Shaanxi Province(2017ZDCXL-GY-10-03).
文摘To reasonably utilize the coal direct liquefaction residue(DLR), contrasting research on the co-pyrolysis between different low-rank coals and DLR was investigated using a TGA coupled with an FT-IR spectrophotometer and a fixed-bed reactor. GC–MS, FTIR, and XRD were used to explore the reaction mechanisms of the various co-pyrolysis processes. Based on the TGA results, it was confirmed that the tetrahydrofuran insoluble fraction of DLR helped to catalyze the conversion reaction of lignite. Also, the addition of DLR improved the yield of tar in the fixed-bed, with altering the composition of the tar. Moreover, a kinetic analysis during the co-pyrolysis was conducted using a distributed activation energy model. The co-pyrolysis reactions showed an approximate double-Gaussian distribution.
基金support of the National Natural Science Foundation of China(22038011,51976168)the K.C.Wong Education Foundation,China Postdoctoral Science Foundation(2019M653626)+2 种基金Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(2020-KF-06)the Promotion Plan for Young People of Shaanxi Association for Science and Technology(20180402)the Technology Foundation for Selected Overseas Chinese Scholar in Shaanxi Province(2018015).
文摘The product distribution and kinetic analysis of low-rank coal vitrinite were investigated during the chemical looping gasification(CLG)process.The acid washing method was used to treat low-rank coal,and the density gradient centrifugation method was adopted to obtain the coal macerals.By combining thermogravimetric analysis and online mass spectrometry,the influence of the heating rate and oxygen carrier(Fe2O3)blending ratio on product distribution was discussed.The macroscopic kinetic parameters were solved by the Kissinger-Akahira-Sunose(KAS)method,and the main gaseous product formation kinetic parameters were solved by the iso-conversion method.The results of vitrinite during slow heating chemical looping gasification showed that the main weight loss interval was 400–600℃,and the solid yield of sample vitrinite-Fe-10 at different heating rates was 64.30%–69.67%.When b=20℃·min^(-1),the maximum decomposition rate of vitrinite-Fe-10 was 0.312%min1.The addition of Fe2O_(3)reduced the maximum decomposition rate,but by comparing the chemical looping conversion characteristic index,it could be inferred that the chemical looping gasification of vitrinite might produce volatile substances higher than the pyrolysis process of vitrinite alone.The average activation energy of the reaction was significantly reduced during chemical looping gasification of vitrinite,which was lower than the average activation energy of 448.69 kJ·mol^(-1) during the pyrolysis process of vitrinite alone.The gaseous products were mainly CO and CO_(2).When the heating rate was 10℃·min^(-1),the highest activation energy for CH4 formation was 21.353 kJ·mol^(-1),and the lowest activation energy for CO formation was 9.7333 kJ·mol^(-1).This study provides basic data for exploring coal chemical looping gasification mechanism and reactor design by studying the chemical looping gasification process of coal macerals。
基金financially supported by the National Natural Science Foundation of China(No.52274316)the State Key Laboratory of Advanced Metallurgy,University of Science and Technology Beijing(Nos.41620025,41620026,and 41621009)the Interdisciplinary Research Project for Young Teachers of University of Science and Technology Beijing(the Fundamental Research Funds for the Central Universities)(No.FRF-IDRY-20-014).
文摘Co-carbonization of weakly caking coal and zinc-containing dust to prepare highly reactive ferro-coke and collaboratively recover zinc powder is one of the feasible ways for steel enterprises to recycle zinc-containing dust.The pyrolysis mass loss behavior of adding blast furnace dust with different zinc contents to different ferro-coke materials was systematically studied by thermogravimetry and differential thermogravimetry analysis,and the kinetic mechanism of pyrolysis-reduction reaction of hybrid briquette was explored.The results of thermogravimetric curve analysis show that the addition of zinc oxide to the sample has no significant effect on the mass loss rate of the sample below 580℃,and the pyrolysis mass loss of zinc oxide mainly occurs between 800 and 1000℃.Kinetic analysis results show that the pyrolysis of zinc-containing samples is controlled by chemical reactions below 580℃.The reaction at 580–700℃ is controlled by the nucleation and growth model,and that above 700℃ is mainly controlled by diffusion.The results of X-ray diffraction analysis show that the pyrolysis process can effectively remove zinc oxide from ferro-coke.
基金The study was conducted with the research programs financed by the National Natural Science Foundation of China(U1862107,21406264)Science Foundation of China University of Petroleum-Beijing(Grant No.2462018BJC003)R&D Program of China National Petroleum Corporation(LH-17-08-55-05).
文摘The characteristics and kinetics of coal and oil shale pyrolysis were comparatively studied by using a micro fluidized bed reaction analyzer(MFBRA).The isothermal differential model was first applied to calculate the kinetic parameters of activation energy and frequency factor according to the major gas components during pyrolysis.The results showed that the major gas components released from coal and oil shale under the isothermal condition had different initiating and ending time points,and the difference was more significant under the programmed heating conditions.The shrinking core model allowed better fitting relevance for the coal pyrolysis,while the three-dimension model was more suitable for oil shale pyrolysis,indicating that the gases from the pyrolysis process of coal and oil shale might go through different reaction paths.The activation energy of oil shale pyrolysis was 36.96 kJ·mol^(−1),larger than the value of pyrolysis of the two coals,which was 21.16 and 32.17 kJ·mol^(−1),respectively.The above results justified that the oil shale pyrolysis with high ash contents was somehow more difficult to take place in terms of higher activation energy and the MFBRA could be a useful tool to give some insight into the intrinsic kinetics and reaction mechanisms of coal and oil shale pyrolysis.
基金The present work was supported by the National Natural Science Foundation of China(U1960205 and 51574023).
文摘The gasification reactivity and kinetic parameters of coal chars for non-isothermal steam gasification were investigated.One kind of lignite and three kinds of bituminous coals were used as the samples,and their coal ranks follow the ascending order:XB<KL<ZJ<GD.As characterized by the comprehensive gasification index,the gasification reactivity of coal chars follows the descending order:XB>KL>ZJ>GD.Through systematically analyzing factors affecting gasification reactivity,it was ascertained that the gasification reactivity is mostly determined by the carbonaceous structure.The gasification reactivity is inversely proportional to the coal rank,and the higher the coal rank,the lower the gasification reactivity.A new kinetic model was proposed to calculate the kinetic parameters,in which the reaction order was considered as an unknown kinetic parameter.The reaction order n follows the ascending order:XB<KL<ZJ<GD,which are n=1.00,n=1.34,n=1.83,and n=2.63,respectively.It is proved that the reaction order is proportional to the coal rank,and the higher the coal rank,the higher the reaction order.
