The characteristics of the energy structure of rich coal,less oil and less gas,coupling with a high external dependence on oil and natural gas and the emphasis on the efficient and clean utilisation of coal,have broug...The characteristics of the energy structure of rich coal,less oil and less gas,coupling with a high external dependence on oil and natural gas and the emphasis on the efficient and clean utilisation of coal,have brought opportunities for coal chemical industry.However,with the large-scale popularisation of coal gasification technology,the production and resulting storage of coal gasification slag continue to increase,which not only result in serious environmental pollution and a waste of terrestrial resources,but also seriously affect the sustainable development of coal chemical enterprises.Hence,the treatment of coal gasification slag is extremely important.In this paper,the production,composition,morphology,particle size structure and water holding characteristics of coal gasification slag are introduced,and the methods of carbon ash separation of gasification slag,both domestically and abroad,are summarised.In addition,the paper also summarises the research progress on gasification slag in building materials,ecological restoration,residual carbon utilisation and other high-value utilisation,and ultimately puts forward the idea of the comprehensive utilisation of gasification slag.For large-scale consumption to solve the environmental problems of enterprises and achieve high-value utilisation to increase the economic benefits of enterprises,it is urgent to zealously design a reasonable and comprehensive utilisation technologies with simple operational processes,strong adaptability and economic benefits.展开更多
High-pressure impregnation, a new preparation method for sorbents to remove H2S from hot coal gas, is introduced in this paper. Semi-coke (SC) and ZnO is selected as the support and active component of sorbent, respec...High-pressure impregnation, a new preparation method for sorbents to remove H2S from hot coal gas, is introduced in this paper. Semi-coke (SC) and ZnO is selected as the support and active component of sorbent, respectively. The sorbent preparation process includes high-pressure impregnation, filtration, ovendry and calcination. The aim of this research is to primarily study the effects of the impregnation pressure on physical properties and desulfurization ability of the sorbent. The desulfurization experiment was carried out in a fixed-bed reactor at 500°C and a simulated coal gas used in this work was composed of CO (33 vol%), H2 (39 vol%), H2S (300 ppm in volume), and N2 (balance). Experimental results show that the pore structure of the SC support can be improved effectively and ZnO active component can be uniformly dispersed on the support, with the small particle size of 10-500 nm. Sorbents prepared using high-pressure impregnation have better desulfurization capacity and their active components have higher utilization rate. P20-ZnSC sorbent, obtained by high-pressure impregnation at 20 atm, has the best desulfurization ability with a sulfur capacity of 7.54 g S/100g sorbent and a breakthrough time of 44 h. Its desulfurization precision and efficiency of removing H2S from the middle temperature gases can reach <1 ppm and >99.7%, respectively, before sorbent breakthrough.展开更多
Zn-based sorbent (Z20SC) prepared through semi-coke support in 20 wt% zinc nitrate solution by high-pressure impregnation presents an excellent desulfurization capacity in hot coal gas,in which H2 S can not be nearly ...Zn-based sorbent (Z20SC) prepared through semi-coke support in 20 wt% zinc nitrate solution by high-pressure impregnation presents an excellent desulfurization capacity in hot coal gas,in which H2 S can not be nearly detected in the outlet gas before 20 h breakthrough time.The effects of the main operational conditions and the particle size of Z20SC sorbent on its desulfurization performances sorbent were investigated in a fixed-bed reactor and the desulfurization kinetics of Z20SC sorbent removing H2 S from hot coal gas was calculated based on experimental data.Results showed that the conversion of Z20SC sorbent desulfurization reaction increased with the decrease of the particle size of the sorbent and the increases of gas volumetric flow rate,reaction temperature and H 2 S content in inlet gas.Z20SC sorbent obtained from hydrothermal synthesis by high-pressure impregnation possessed much larger surface area and pore volume than semi-coke support,and they were significantly reduced after the desulfurization reaction.The equivalent grain model was reasonably used to analyze experimental data,in which k s=4.382×10-3 exp(-8.270×103/RgT) and Dep=1.262×10-4exp(1.522×104/RgT).It suggests that the desulfurization reaction of the Z20SC sorbent is mainly controlled by the chemical reaction in the initial stage and later by the diffusion through the reacted sorbent layer.展开更多
The Bunsen reaction is the center reaction for both the sulfur–iodine water splitting cycle for hydrogen production and the novel hydrogen sulfide splitting cycle for hydrogen and sulfuric acid production from the su...The Bunsen reaction is the center reaction for both the sulfur–iodine water splitting cycle for hydrogen production and the novel hydrogen sulfide splitting cycle for hydrogen and sulfuric acid production from the sulfur-containing gases.This paper reviews the research progress of the Bunsen reaction in recent 10–15 years.Researches were initially focused on the optimization of the operating conditions of the conventional Bunsen reaction requiring excessive water and iodine to improve the products separation efficiency and to avoid the side reactions and iodine vapor deposition.Alternative methods including electrochemical methods,precipitation methods,and non-aqueous solvent methods had their respective advantages,but still faced challenges.In development of the technology of H2S splitting cycle,dissolving iodine in toluene solvent could render the Bunsen reaction to occur with the flowable I2 stream at ambient temperature such that the side reactions and iodine vaporization can be avoided and the corrosion hazard lessened.It also prevented the Bunsen reaction from using excessive iodine and water.The products from the Bunsen reaction including HI,H2SO4,H2O,and toluene could be directly electrolyzed.展开更多
The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources,and sulfur removal from high-sulfur coal is the most important issue.This paper re...The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources,and sulfur removal from high-sulfur coal is the most important issue.This paper reviews the speciation,forms and distribution of sulfur in coal,the sulfur removal from raw coal,the thermal transformation of sulfur during coal pyrolysis,and the sulfur regulation during coal-blending coking of high organic-sulfur coals.It was suggested that the proper characterization of sulfur in coal cannot be obtained only by either chemical method or instrumental characterization,which raises the need of a combination of current or newly adopted characterization methods.Different from the removal of inorganic sulfur from coal,the organic sulfur can only be partly removed by chemical technologies;and the coal structure and property,particularly high-sulfur coking coals which have caking ability,may be altered and affected by the pretreatment processes.Based on the interactions among the sulfur radicals,sulfur-containing and hydrogen-containing fragments during coal pyrolysis and the reactions with minerals or nascent char,regulating the sulfur transformation behavior in the process of thermal conversion is the most effective way to utilize high organic-sulfur coals in the coke-making industry.An in-situ regulation approach of sulfur transformation during coal-blending coking has been suggested.That is,the high volatile coals with an appropriate releasing temperature range of CH4 overlapping well with that of H2 S from high organic-sulfur coals is blended with high organic-sulfur coals,and the C–S/C–C bonds in some sulfur forms are catalytically broken and immediately hydrogenated by the hydrogencontaining radicals generated from high volatile coals.Wherein,the effect of mass transfer on sulfur regulation during the coking process should be considered for the larger-scale coking tests through optimizing the ratios of different coals in the coal blend.展开更多
With lignite after vacuum drying as the raw material,a series of Zn-based sorbents were prepared by static impregnation,ultrasonic-assisted impregnation,bubbling-assisted impregnation and high-pressure impregnation.Th...With lignite after vacuum drying as the raw material,a series of Zn-based sorbents were prepared by static impregnation,ultrasonic-assisted impregnation,bubbling-assisted impregnation and high-pressure impregnation.The physical properties and the desulfurization performances of Zn-based sorbents were studied systematically by XRD,BET,AAS characterization techniques and the fixed-bed desulfurization evaluation apparatus.The sorbents obtained by high-pressure impregnation method have a larger specific surface area,pore volume and pore diameter comparing with other methods,which is conducive to the sulfidation reaction of hydrogen sulfide gas in the sorbent.The effects of pressure during the high-pressure impregnation and concentration of Zn(NO3)2 precursor solution on the sorbents properties and desulfurization behavior were investigated.The higher the impregnation pressure and the concentration of impregnation solution are,the greater the amount of the active components are uploaded.However,overhigh impregnation pressure can cause collapse and blocking of the carrier pore.The optimal operating condition of high-pressure impregnation method for preparing the sorbents was the impregnation pressure of 20 atm and the solution concentration of 41%.Under that condition,the sorbent had the best desulfurization ability with a sulfur capacity of 13.94 gS/100 gsorbent and a breakthrough time of 54 h.Its desulfurization precision and efficiency of removing H2S before sorbent breakthrough from the middle temperature gases of 400℃ can reach<5 ppm and>99%,respectively.Sorbents could be regenerated under the condition of 1 vol%O2,20 vol% H2O,0.5 vol% NH3,and N2balance gas.The regenerated sorbent could be used for repeated absorption of H2S with a slight decrease in desulfurization effect.展开更多
A series of iron-manganese-based sorbents were prepared by co-precipitation and physical mixing method,and used for H_(2)S removal from hot coal gas.The sulfidation tests were carried out in a fixed-bed reactor with s...A series of iron-manganese-based sorbents were prepared by co-precipitation and physical mixing method,and used for H_(2)S removal from hot coal gas.The sulfidation tests were carried out in a fixed-bed reactor with space velocity of 2000 h^(-1)(STP).The results show that the suitable addition of manganese oxide in iron-based sorbent can decrease H_(2)S and COS concentration in exit before breakthrough due to its simultaneous reaction capability with H_(2)S and COS.Fe3O4 and MnO are the initial active components in iron-manganese-based sorbent,and FeO and Fe are active components formed by reduction during sulfidation.The crystal phases of iron affect obviously their desulfurization capacity.The reducibility of sorbent changes with the content of MnO in sorbent.S7F3M and S3F7M have bigger sulfur capacities(32.68 and 32.30 gS/100 g total active component),while S5F5M has smaller sulfur capacity(21.92 gS/100 g total active component).S7F3M sorbent has stable sulfidation performance in three sulfidation-regeneration cycles and no apparent structure degradation.The sulfidation performance of ironmanganese-based sorbent is also related with its specific surface area and pore volume.展开更多
基金financially supported by the National Key Research and Development Program of China(2019YFC1904302)Foundation of State Key Laboratory of High-efficiency Utilisation of Coal and Green Chemical Engineering(2021-K81)the Technology of Coal-to-liquids Research Institute of National Energy Group([2020]010)。
文摘The characteristics of the energy structure of rich coal,less oil and less gas,coupling with a high external dependence on oil and natural gas and the emphasis on the efficient and clean utilisation of coal,have brought opportunities for coal chemical industry.However,with the large-scale popularisation of coal gasification technology,the production and resulting storage of coal gasification slag continue to increase,which not only result in serious environmental pollution and a waste of terrestrial resources,but also seriously affect the sustainable development of coal chemical enterprises.Hence,the treatment of coal gasification slag is extremely important.In this paper,the production,composition,morphology,particle size structure and water holding characteristics of coal gasification slag are introduced,and the methods of carbon ash separation of gasification slag,both domestically and abroad,are summarised.In addition,the paper also summarises the research progress on gasification slag in building materials,ecological restoration,residual carbon utilisation and other high-value utilisation,and ultimately puts forward the idea of the comprehensive utilisation of gasification slag.For large-scale consumption to solve the environmental problems of enterprises and achieve high-value utilisation to increase the economic benefits of enterprises,it is urgent to zealously design a reasonable and comprehensive utilisation technologies with simple operational processes,strong adaptability and economic benefits.
基金supported by the financial support of National Basic Research Program of China (2012CB723105)National Natural Science Foundation of China (20976117)+1 种基金Shanxi Province Natural Science Foundation(2010011014-3)Shanxi Province Basic Conditions Platform for Science and Technology Project (2010091015)
文摘High-pressure impregnation, a new preparation method for sorbents to remove H2S from hot coal gas, is introduced in this paper. Semi-coke (SC) and ZnO is selected as the support and active component of sorbent, respectively. The sorbent preparation process includes high-pressure impregnation, filtration, ovendry and calcination. The aim of this research is to primarily study the effects of the impregnation pressure on physical properties and desulfurization ability of the sorbent. The desulfurization experiment was carried out in a fixed-bed reactor at 500°C and a simulated coal gas used in this work was composed of CO (33 vol%), H2 (39 vol%), H2S (300 ppm in volume), and N2 (balance). Experimental results show that the pore structure of the SC support can be improved effectively and ZnO active component can be uniformly dispersed on the support, with the small particle size of 10-500 nm. Sorbents prepared using high-pressure impregnation have better desulfurization capacity and their active components have higher utilization rate. P20-ZnSC sorbent, obtained by high-pressure impregnation at 20 atm, has the best desulfurization ability with a sulfur capacity of 7.54 g S/100g sorbent and a breakthrough time of 44 h. Its desulfurization precision and efficiency of removing H2S from the middle temperature gases can reach <1 ppm and >99.7%, respectively, before sorbent breakthrough.
基金supported by the National Basic Research Program of China (2012CB723105)the National Natural Science Foundation of China(20976117)+1 种基金Shanxi Province Natural Science Foundation (2010011014-3)Shanxi Province Basic Conditions Platform for Science and Technology Project(2010091015)
文摘Zn-based sorbent (Z20SC) prepared through semi-coke support in 20 wt% zinc nitrate solution by high-pressure impregnation presents an excellent desulfurization capacity in hot coal gas,in which H2 S can not be nearly detected in the outlet gas before 20 h breakthrough time.The effects of the main operational conditions and the particle size of Z20SC sorbent on its desulfurization performances sorbent were investigated in a fixed-bed reactor and the desulfurization kinetics of Z20SC sorbent removing H2 S from hot coal gas was calculated based on experimental data.Results showed that the conversion of Z20SC sorbent desulfurization reaction increased with the decrease of the particle size of the sorbent and the increases of gas volumetric flow rate,reaction temperature and H 2 S content in inlet gas.Z20SC sorbent obtained from hydrothermal synthesis by high-pressure impregnation possessed much larger surface area and pore volume than semi-coke support,and they were significantly reduced after the desulfurization reaction.The equivalent grain model was reasonably used to analyze experimental data,in which k s=4.382×10-3 exp(-8.270×103/RgT) and Dep=1.262×10-4exp(1.522×104/RgT).It suggests that the desulfurization reaction of the Z20SC sorbent is mainly controlled by the chemical reaction in the initial stage and later by the diffusion through the reacted sorbent layer.
基金financial supports from the National Natural Science Foundation of China(21576183)Natural Science and Technology Research Council of Canada(STPGP-350428-07)
文摘The Bunsen reaction is the center reaction for both the sulfur–iodine water splitting cycle for hydrogen production and the novel hydrogen sulfide splitting cycle for hydrogen and sulfuric acid production from the sulfur-containing gases.This paper reviews the research progress of the Bunsen reaction in recent 10–15 years.Researches were initially focused on the optimization of the operating conditions of the conventional Bunsen reaction requiring excessive water and iodine to improve the products separation efficiency and to avoid the side reactions and iodine vapor deposition.Alternative methods including electrochemical methods,precipitation methods,and non-aqueous solvent methods had their respective advantages,but still faced challenges.In development of the technology of H2S splitting cycle,dissolving iodine in toluene solvent could render the Bunsen reaction to occur with the flowable I2 stream at ambient temperature such that the side reactions and iodine vaporization can be avoided and the corrosion hazard lessened.It also prevented the Bunsen reaction from using excessive iodine and water.The products from the Bunsen reaction including HI,H2SO4,H2O,and toluene could be directly electrolyzed.
基金financial support of National Natural Science Foundation of China(U1910201,21878208)Transformation of Scientific and Technological Achievements Programs of Higher Education Institutions in Shanxi(TSTAP)Shanxi Province Science Foundation for Key Program(201901D111001(ZD))。
文摘The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources,and sulfur removal from high-sulfur coal is the most important issue.This paper reviews the speciation,forms and distribution of sulfur in coal,the sulfur removal from raw coal,the thermal transformation of sulfur during coal pyrolysis,and the sulfur regulation during coal-blending coking of high organic-sulfur coals.It was suggested that the proper characterization of sulfur in coal cannot be obtained only by either chemical method or instrumental characterization,which raises the need of a combination of current or newly adopted characterization methods.Different from the removal of inorganic sulfur from coal,the organic sulfur can only be partly removed by chemical technologies;and the coal structure and property,particularly high-sulfur coking coals which have caking ability,may be altered and affected by the pretreatment processes.Based on the interactions among the sulfur radicals,sulfur-containing and hydrogen-containing fragments during coal pyrolysis and the reactions with minerals or nascent char,regulating the sulfur transformation behavior in the process of thermal conversion is the most effective way to utilize high organic-sulfur coals in the coke-making industry.An in-situ regulation approach of sulfur transformation during coal-blending coking has been suggested.That is,the high volatile coals with an appropriate releasing temperature range of CH4 overlapping well with that of H2 S from high organic-sulfur coals is blended with high organic-sulfur coals,and the C–S/C–C bonds in some sulfur forms are catalytically broken and immediately hydrogenated by the hydrogencontaining radicals generated from high volatile coals.Wherein,the effect of mass transfer on sulfur regulation during the coking process should be considered for the larger-scale coking tests through optimizing the ratios of different coals in the coal blend.
基金supported by the National Basic Research Program of China(2012CB723105)the National Natural Science Foundation of China(20976117)Shanxi Graduates Excellent Innovation Project of China(tyut-rc201018a)
文摘With lignite after vacuum drying as the raw material,a series of Zn-based sorbents were prepared by static impregnation,ultrasonic-assisted impregnation,bubbling-assisted impregnation and high-pressure impregnation.The physical properties and the desulfurization performances of Zn-based sorbents were studied systematically by XRD,BET,AAS characterization techniques and the fixed-bed desulfurization evaluation apparatus.The sorbents obtained by high-pressure impregnation method have a larger specific surface area,pore volume and pore diameter comparing with other methods,which is conducive to the sulfidation reaction of hydrogen sulfide gas in the sorbent.The effects of pressure during the high-pressure impregnation and concentration of Zn(NO3)2 precursor solution on the sorbents properties and desulfurization behavior were investigated.The higher the impregnation pressure and the concentration of impregnation solution are,the greater the amount of the active components are uploaded.However,overhigh impregnation pressure can cause collapse and blocking of the carrier pore.The optimal operating condition of high-pressure impregnation method for preparing the sorbents was the impregnation pressure of 20 atm and the solution concentration of 41%.Under that condition,the sorbent had the best desulfurization ability with a sulfur capacity of 13.94 gS/100 gsorbent and a breakthrough time of 54 h.Its desulfurization precision and efficiency of removing H2S before sorbent breakthrough from the middle temperature gases of 400℃ can reach<5 ppm and>99%,respectively.Sorbents could be regenerated under the condition of 1 vol%O2,20 vol% H2O,0.5 vol% NH3,and N2balance gas.The regenerated sorbent could be used for repeated absorption of H2S with a slight decrease in desulfurization effect.
基金support of the National Basic Research Program of China(2005CB221203)the National Natural Science Foundation of China(Grant No.20976117)+1 种基金Shanxi Province Natural Science Foundation(2010011014-3)Shanxi Province Basic Conditions Platform for Science and Technology Project(2010091015).
文摘A series of iron-manganese-based sorbents were prepared by co-precipitation and physical mixing method,and used for H_(2)S removal from hot coal gas.The sulfidation tests were carried out in a fixed-bed reactor with space velocity of 2000 h^(-1)(STP).The results show that the suitable addition of manganese oxide in iron-based sorbent can decrease H_(2)S and COS concentration in exit before breakthrough due to its simultaneous reaction capability with H_(2)S and COS.Fe3O4 and MnO are the initial active components in iron-manganese-based sorbent,and FeO and Fe are active components formed by reduction during sulfidation.The crystal phases of iron affect obviously their desulfurization capacity.The reducibility of sorbent changes with the content of MnO in sorbent.S7F3M and S3F7M have bigger sulfur capacities(32.68 and 32.30 gS/100 g total active component),while S5F5M has smaller sulfur capacity(21.92 gS/100 g total active component).S7F3M sorbent has stable sulfidation performance in three sulfidation-regeneration cycles and no apparent structure degradation.The sulfidation performance of ironmanganese-based sorbent is also related with its specific surface area and pore volume.
