To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from...To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from coal, were investigated. Methane and cyclohexane were chosen as the model compounds. Density functional theory was employed, and many reaction pathways were involved. Calculations were carried out in Gaussian 09 at the B3LYP/6-31G(d,p) level of the theory. The results indicate that the main pyrolysis products of methane and cyclohexane in hydrogen plasma are both hydrogen and acetylene, and the participation of active hydrogen atoms makes dehydrogenation reactions more favorable. H2 mainly comes from dehydrogenation process, while many reaction pathways are responsible for acetylene formation. During coal pyrolysis in hydrogen plasma, three main components in volatiles like aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons lead to the formation of hydrogen and acetylene, but their contributions to products distribution are different.展开更多
A Computational Fluid Dynamics(CFD) model was formulated for DC arc hydrogen/argon plasma jet reactors used in the process of the thermal H_2/Ar plasma pyrolysis of coal to acetylene. In this model, fluid flow, convec...A Computational Fluid Dynamics(CFD) model was formulated for DC arc hydrogen/argon plasma jet reactors used in the process of the thermal H_2/Ar plasma pyrolysis of coal to acetylene. In this model, fluid flow, convective heat transfer and conjugate heat conductivity are considered simultaneously. The error caused by estimating the inner-wall temperature of a reactor is avoided. The thermodynamic and transport properties of the hydrogen/argon mixture plasma system, which are usually expressed by a set of discrete data, are fitted into expressions that can be easily implemented in the program. The effects of the turbulence are modeled by two standard k-εequations. The temperature field and velocity field in the plasma jet reactor were calculated by employing SIMPLEST algorithm. The knowledge and insight obtained are useful for the design improvement and scale-up of plasma reactors.展开更多
The purpose of this paper is to demonstrate a systematic approach to design high performance signal conditioning circuits,and to show how to implement the 4-20 mA analog current-loop transmitter and receiver circuits ...The purpose of this paper is to demonstrate a systematic approach to design high performance signal conditioning circuits,and to show how to implement the 4-20 mA analog current-loop transmitter and receiver circuits by using isolation amplifier.The basic principle and typical applicable circuits of the 4-20 mA current loop isolation chip T1100N,the current-limiting circuit and filter circuit are presented.And the experimental testing data of the circuits are analyzed.展开更多
Coal pyrolysis is a fundamental reaction in the thermal processing and utilization of coal.Investigating the behavior and kinetics of coal pyrolysis is crucial for optimizing,designing,and developing a composite riser...Coal pyrolysis is a fundamental reaction in the thermal processing and utilization of coal.Investigating the behavior and kinetics of coal pyrolysis is crucial for optimizing,designing,and developing a composite riser for the staged pyrolysis gasification process of pulverized coal.In this study,the non-isothermal pyrolysis behavior and kinetics of coal were examined at different heating rates(30,50,100,300,500,700,and 900℃/min)using thermogravimetry(TG)coupled with Fourier-transform infrared spectroscopy.Analysis of the TG/derivative TG(TG/DTG)curves indicated that coal pyrolysis mainly occurred between 300℃ and 700℃.Higher heating rates led to more volatiles being released from the coal,and a higher temperature was required to achieve rapid pyrolysis.Kinetic analysis showed that both the model-free methods(Friedman,Flynn-Wall-Ozawa,and Kissinger-Akahira-Sunose)and the model-based method(Coats-Redfern)effectively describe the coal pyrolysis process.The change in the Ea values between the two kinetic models was consistent throughout the pyrolysis process,and the most probable mechanism was the F2 model(secondary chemical reaction).In addition,the heating rate did not change the overall reaction order of the pyrolysis process;however,a higher heating rate resulted in a decrease in the Ea value during the initial pyrolysis stage.展开更多
The critical issue in developing mature Oxy-Coal Combustion Steam System technology could be the reactivity of deminer-alized coal which,is closely related to its chemical structure.The chemical structures of Liupansh...The critical issue in developing mature Oxy-Coal Combustion Steam System technology could be the reactivity of deminer-alized coal which,is closely related to its chemical structure.The chemical structures of Liupanshui raw coal(LPS-R)and Liupanshui demineralized coal(LPS-D)were analyzed by FTIR and solid-state 13C-NMR.The pyrolysis experiments were carried out by TG,and the pyrolysis kinetics was analyzed by three iso-conversional methods.FTIR and 13C-NMR results suggested that the carbon structure of LPS coal was not altered greatly,while demineralization promoted the maturity of coal and the condensation degree of the aromatic ring,making the chemical structure of coal more stable.The oxygen-containing functional groups with low bond energy were reduced,and the ratio of aromatic carbon with high bond energy was increased,decreasing the pyrolysis reactivity.DTG curve-fitting results revealed that the thermal weight loss of LPS coal mainly came from the cleavage of aliphatic covalent bonds.By pyrolysis kinetics analysis of LPS-R and LPS-D,the apparent activation energies were 76±4 to 463±5 kJ/mol and 84±2 to 758±12 kJ/mol,respectively,under different conversion rates.The reactivity of the demineralized coal was inhibited to some extent,as the apparent activation energy of pyrolysis for LPS-D increased by acid treatment.展开更多
In this paper, a model for fast coal pyrolysis in a cocurrent downer reactor is developed, in which both hydrodynamics and coal pyrolysis kinetics are simultaneously considered. The results of simulations based on thi...In this paper, a model for fast coal pyrolysis in a cocurrent downer reactor is developed, in which both hydrodynamics and coal pyrolysis kinetics are simultaneously considered. The results of simulations based on this model display reasonable agreement with experimental data obtained using Huolinhe coal as the feedstock, and this model is therefore suitable for predicting the fast pyrolysis of specific coal types. A series of simulations of fast coal pyrolysis in a cocurrent downer demonstrated that coal devolatilization is almost complete in the inlet region within a time span of 0.4 s, and that higher temperatures improve the pyrolysis efficiency. However, the yield of liquid products is decreased with increasing pyrolysis temperatures, especially above 670 ℃, because of additional cracking of the liquids.展开更多
ReaxFF molecular dynamic simulation combined with experimental verification was performed to understand the overall reaction mechanism,especially the primary and secondary reactions involving in tar formation of sub-b...ReaxFF molecular dynamic simulation combined with experimental verification was performed to understand the overall reaction mechanism,especially the primary and secondary reactions involving in tar formation of sub-bituminous coal pyrolysis.Quantitative relationship at atomic level is clarified between bond breakage of functional groups and products generation,revealing that the amount and order in forming each product are subject to the number of corresponding functional groups and their bond energies respectively.The primary breakage of-C-O-and-C-C-bridge-bonds present in initial coal macromolecular generates molecular of heavy tar,whereas heavy tar can be converted into light tar through cracking side chain of aromatic rings and cyclic hydrocarbons at increased pyrolysis temperatures.At very high temperatures the cracking of short-chain hydrocarbons and residual atoms connecting to aromatic rings further occurs to generate light tar and gas.The remaining aromatic-ring fragments of heavy tar are likely cross-linked to form char.Furthermore,the simultaneous evolution tendency of tar yield and tar quality under different pyrolysis temperatures and heating rates is obtained at molecular level.For obtaining high yield and quality of tar,appropriately high temperature as well as suitable heating rate are needed to compromise the high yield of primary tar and high quality of secondarily upgraded products.展开更多
Kinetic analyses are important means for understanding the complicated coal pyrolysis process.This work conducted non-isothermal pyrolysis of four low-medium rank coals with thermogravimetric analyzer at different hea...Kinetic analyses are important means for understanding the complicated coal pyrolysis process.This work conducted non-isothermal pyrolysis of four low-medium rank coals with thermogravimetric analyzer at different heating rates(5,10 and 20 K/min).Four model-free fitting approaches including KAS,OFW,Starink and Friedman methods were used to analyze pyrolysis kinetics of the coals.Thermodynamic parameters including enthalpy(ΔH)Gibbs free energy(ΔG)and entropy(ΔS)were calculated with the activation values(E)obtained with KAS method.For the kinetic analysis,the KAS,OFW and Starink methods give close E values over the whole conversion range,but the Friedman method shows more deviant results.The thermodynamic favorability of coal pyrolysis is discussed,bothΔH andΔG increase with conversion consistently with the variation of E,revealing that pyrolysis is endothermic and thermodynamic favorability is reduced with conversion rises.The minusΔS implies that coal structures evolve from disordered to organized ones as universally accepted.These results are expected to deepen our understanding and to optimize the conditions of coal pyrolysis.展开更多
The Pyrolysis behavior of two Chinese coals has been investigated in a laboratory-scale bubbling fluidized bed system in Siegen University, Germany. Experimental equipment and procedure are introduced. The amounts of ...The Pyrolysis behavior of two Chinese coals has been investigated in a laboratory-scale bubbling fluidized bed system in Siegen University, Germany. Experimental equipment and procedure are introduced. The amounts of Pyrolysis species of each coal were measured, calculated and compared. A newmethod was presented to determine the needed parameters in FG-DVC model with the experimentalresults instead of other much more complicated experiments.展开更多
In this study,the Powder River Basin(PRB)coal fast pyrolysis was conducted at 700°C in the atmosphere of syngas produced by CH4-CO2 reforming in two different patterns,including the double reactors pattern(the fi...In this study,the Powder River Basin(PRB)coal fast pyrolysis was conducted at 700°C in the atmosphere of syngas produced by CH4-CO2 reforming in two different patterns,including the double reactors pattern(the first reactor is for syngas production and the second is for coal pyrolysis)and double layers pattern(catalyst was at upper layer and coal was at lower layer).Besides,pure gases atmosphere including N2,H2,CO,H2-CO were also tested to investigate the mechanism of the coal pyrolysis under different atmospheres.The pyrolysis products including gas,liquid and char were characterized,the result showed that,compared with the inert atmosphere,the tar yield is improved with the reducing atmospheres,as well as the tar quality.The hydrogen partial pressure is the key point for that improvement.In the atmosphere of H2,the tar yield was increased by 31.3%and the contained BTX(benzene,toluene and xylene)and naphthalene were increased by 27.1%and 133.4%.The double reactors pattern also performed outstandingly,with 25.4%increment of tar yield and 25.0%and 79.4%for the BTX and naphthalene.The double layers pattern is not effective enough due to the low temperature(700°C)in which the Ni-based catalyst was not fully activated.展开更多
In this paper,13 kinds of transition metals are studied as catalysts for the hydrogen production from coal pyrolysis, and relationships between the catalytic activity of a transition metal and its outer electron confi...In this paper,13 kinds of transition metals are studied as catalysts for the hydrogen production from coal pyrolysis, and relationships between the catalytic activity of a transition metal and its outer electron configuration,d% of transition metals and geometric configuration are summarized.Experimental results show that the same group of transition metals show good similarity for hydrogen production from coal pyrolysis;the d%of transition metals which have activity for hydrogen production from coal pyrolysis is between 40%-50%;all transition metals which have catalytic activity possess either a face-centered cubic or a hexagonal crystal structure.Therefore,it is important to choose a transition metal with an appropriate d%and crystal structure as the catalyst for hydrogen production from coal pyrolysis.展开更多
Nitrogen oxide(NO_(x))pollutants emitted from coal combustion are attracting growing public concern.While the traditional technologies of reducing NO_(x) were mainly focused on terminal treatment,and the research on s...Nitrogen oxide(NO_(x))pollutants emitted from coal combustion are attracting growing public concern.While the traditional technologies of reducing NO_(x) were mainly focused on terminal treatment,and the research on source treatment is limited.This paper proposes a new coal combustion strategy that significantly reduces NO_(x) emissions during coal combustion.This strategy has two important advantages in reducing NO_(x) emissions.First,by introducing iron-based catalyst at the source,which will catalyze the conversion of coke nitrogen to volatile nitrogen during the pyrolysis process,thereby greatly reducing the coke nitrogen content.The second is de-NO_(x) process by a redox reaction between NO_(x) and reducing agents(coke,HCN,NH_(3),etc.)that occurred during coke combustion.Compared to direct combustion of coal,coke prepared by adding iron-based catalyst has 46.1% reduction in NO_(x) emissions.To determine the effect of iron-based additives on de-NO_(x) performance,demineralized coal(de-coal)was prepared to eliminate the effect of iron-based minerals in coal ash.The effects of iron compounds,additive dosages,and combustion temperatures on de-NO_(x) efficiency are systematically studied.The results revealed that the NO_(x) emission of the coke generated by pyrolysis of de-coal loaded with 3%(mass)Fe_(2)O_(3) decreases to 27.3% at combustion temperature of 900℃.Two main reasons for lower NO_(x) emissions were deduced:(1)During the catalytic coal pyrolysis stage,the nitrogen content in the coke decreases with the release of volatile nitrogen.(2)Part of the NO_(x) emitted during the coke combustion was converted into N_(2) for the catalytic effect of the Fe-based catalysts.It is of great practical value and scientific significance to the comprehensive treatment and the clean utilization process of coal.展开更多
Various semicokes were obtained from medium-low temperature pyrolysis of Dongrong long flame coal.The proximate analysis,calorific value and Hardgrove grindability index(HGI) of semicokes were determined,and the ignit...Various semicokes were obtained from medium-low temperature pyrolysis of Dongrong long flame coal.The proximate analysis,calorific value and Hardgrove grindability index(HGI) of semicokes were determined,and the ignition temperature,burnout temperature,ignition index,burnout index,burnout ratio,combustion characteristic index of semicokes were measured and analyzed using thermogravimetry analysis(TGA).The effects of pyrolysis temperature,heating rate,and pyrolysis time on yield,composition and calorific value of long flame coal derived semicokes were investigated,especially the influence of pyrolysis temperature on combustion characteristics and grindability of the semicokes was studied combined with X-ray diffraction(XRD) analysis of semicokes.The results show that the volatile content,ash content and calorific value of semicokes pyrolyzed at all process parameters studied meet the technical specifications of the pulverized coal-fired furnaces(PCFF) referring to China Standards GB/T 7562-1998.The pyrolysis temperature is the most influential factor among pyrolysis process parameters.As pyrolysis temperature increases,the yield,ignition index,combustion reactivity and burnout index of semicokes show a decreasing tend,but the ash content increases.In the range of 400 and 450 °C,the grindability of semicokes is rational,especially the grindability of semicokes pyrolyzed at 450 °C is suitable.Except for the decrease of volatile content and increase of ash content,the decrease of combustion performance of semicokes pyrolyzed at higher temperature should be attributed to the improvement of the degree of structural ordering and the increase of aromaticity and average crystallite size of char.It is concluded that the semicokes pyrolyzed at the temperature of 450 °C is the proper fuel for PCFF.展开更多
The physiochemical properties of chars produced by coal pyrolysis in a laboratory-scale fluidized bed reactor with a continuous coal feed and char discharge at temperatures of 750 to 980 ~ C under N2-based atmospheres...The physiochemical properties of chars produced by coal pyrolysis in a laboratory-scale fluidized bed reactor with a continuous coal feed and char discharge at temperatures of 750 to 980 ~ C under N2-based atmospheres containing 02, H2, CO, CH4, and CO2 were studied. The specific surface area of the char was found to decrease with increasing pyrolysis temperature. The interlayer spacing of the char also decreased, while the average stacking height and carbon crystal size increased at higher temperatures, suggesting that the char generated at high temperatures had a highly ordered structure. The char obtained using an ER value of 0.064 exhibited the highest specific surface area and oxidation reactivity. Rela- tively high 02 concentrations degraded the pore structure of the char, decreasing the surface area. The char produced in an atmosphere incorporating H2 showed a more condensed crystalline structure and consequently had lower oxidation reactivity.展开更多
A new coal staged conversion poly-generation system combined coal combustion and pyrolysis has been developed for clean and high efficient utilization of coal.Coal is the first pyrolysed in a fluidized pyrolyzer.The p...A new coal staged conversion poly-generation system combined coal combustion and pyrolysis has been developed for clean and high efficient utilization of coal.Coal is the first pyrolysed in a fluidized pyrolyzer.The pyrolysis gas is then purified and used for chemical product or liquid fuel production.Tar is collected during purification and can be processed to extract high value product and to make liquid fuels by hydro-refining.Semi-coke from the pyrolysis reactor is burned in a circulating fluidized bed(CFB)combustor for heat or power generation.The system can realize coal multiproduct generation and has a great potential to increase coal utilization value.A 1 MW poly-generation system pilot plant and a 12 MW CFB gas,tar,heat and power poly-generation system was erected.The experimental study focused on the two fluidized bed operation and characterization of gas,tar and char yields and compositions.The results showed that the system could operate stable,and produce about 0.12 m^(3)/kg gas with 22 MJ/m^(3)heating value and about 10 wt%tar when using Huainan bituminous coal under pyrolysis temperature between 500 and 600℃.The produced gases were mainly H_(2),CH_(4),CO,CO_(2),C_(2)H_(4),C_(2)H_(6),C_(3)H_(6)and C_(3)H_(8).The CFB combustor can burn semi-coke steadily.The application prospect of the new system was discussed.展开更多
Depending on advanced technological developments in energy production the low quality coals needed the most economical technologies and even in order to make it possible to produce coal-derived products. Compliance wi...Depending on advanced technological developments in energy production the low quality coals needed the most economical technologies and even in order to make it possible to produce coal-derived products. Compliance with environmental norms of coal pyrolysis or gasification of various type of coals, feasible combustion systems and energy production facilities are needed in today's modern technology, also enable the production of liquid and gaseous coal fuels. However, raw materials and chemical nature of them requires a variety of adaptation methods. This study examined the high sulfur and ash types of Kütahya, Denizli, Aydin, Soma lignite, Sirnak asphaltite and lignite. The representative samples were taken from local areas of the lignites. Fundamentally, the conditions regarding better desulfurization way, the high quality pyrolysis lignite oil production, high value light oil, coal tar and gas products were determined at the goal of high fuel producing yield.展开更多
Red mud(RM)with the high alkalinity as a catalyst was evaluated for coal pyrolysis in a fixed bed as well as CO_(2) gasification of its resultant char in a thermogravimetric analyzer(TGA).The addition of RM into coal ...Red mud(RM)with the high alkalinity as a catalyst was evaluated for coal pyrolysis in a fixed bed as well as CO_(2) gasification of its resultant char in a thermogravimetric analyzer(TGA).The addition of RM into coal could improve the quality of tar during pyrolysis and enhance the reactivity of char during gasification.For catalytic pyrolysis with 12 wt%RM at 600℃,the light fraction in tar was 72.0 wt%,which increased by 20.0%,compared with coal pyrolysis alone.The role of metal oxides in RM on coal pyrolysis was further clarified as well.After catalytic pyrolysis with RM,the specific surface area of resultant char increased,especially for mesoporous surface area,and meanwhile the sodium in RM was proved to migrate to the char surface.These positive factors contributed to the CO_(2) gasification activity of char.RM with the high alkalinity showed a promising catalyst candidate for coal pyrolysis and gasification in terms of its catalytic effects and low cost.展开更多
The utilization of highly reactive and high-strength coke can enhance the efficiency of blast furnace by promoting indirect reduction of iron oxides.Iron compounds,as the main constituent in iron-bearing minerals,have...The utilization of highly reactive and high-strength coke can enhance the efficiency of blast furnace by promoting indirect reduction of iron oxides.Iron compounds,as the main constituent in iron-bearing minerals,have aroused wide interest in preparation of highly reactive iron coke.However,the effects of iron compounds on pyrolysis behavior of coal and metallurgical properties of resultant cokes are still unclear.Thus,three iron compounds,i.e.,Fe;O;,Fe;O;and FeC;O;·2H;O,were adopted to investigate their effects on coal pyrolysis behavior and metallurgical properties of the resultant cokes.The results show that iron compounds have slight effects on the thermal behavior of coal blend originated from thermogravimetric and differential thermogravimetric curves.The apparent activation energy varies with different iron compounds ranging from 94.85 to 110.11 kJ/mol in the primary pyrolysis process,while lower apparent activation energy is required for the secondary pyrolysis process.Iron compounds have an adverse influence on the mechanical properties and carbon structure of cokes.Strong correlations exist among coke reactivity,coke strength after reaction,and the content of metallic iron in cokes or the values of crystallite stacking height,which reflect the dependency of thermal property on metallic iron content and carbon structure of cokes.展开更多
This paper presents a new approach to study the process of coal gasification. Non-linear programming techniques are used to determine the value of the model parameters that depends on coal species and experimental con...This paper presents a new approach to study the process of coal gasification. Non-linear programming techniques are used to determine the value of the model parameters that depends on coal species and experimental conditions and thus minimize the difference between experimental results and model predictions. Model predictions being in good agreement with the experimental results show that this method of combining model with experiment is effective for modeling complex processes.展开更多
The structural optimization of baffle internals for fast pyrolysis of coal with particulate mixing and heat transfer in a downer reactor using the discrete element method(DEM)has been investigated in this research.The...The structural optimization of baffle internals for fast pyrolysis of coal with particulate mixing and heat transfer in a downer reactor using the discrete element method(DEM)has been investigated in this research.The pyrolysis terminal temperature at the exit of the downer reactor is not only decided by the volume-feeding-rate ratio of the coal to the sand,but also is affected by the inner structural design of the baffle internals in the downer reactor.As presented in the previous publication of the author,the inhibition from the baffle internals in a downer reactor can improve the particulate-mixing degree and heat carrier,and increase the mean residence time of the coal and heat-carrier particles in the downer reactor.The structure of the baffle internals in the downer reactor mentioned in this research can be optimized by the independently developed 3D soft-sphere model of the DEM programme of a 40-mm baffle length,a 30°baffle-slope angle and at least four baffles designed in the downer reactor,which is beneficial for the process design of coal pyrolysis with a heat carrier in the downer reactor.展开更多
基金supported by the National High Technology Research and Development Program of China(2009AA044701)the Program for Zhejiang Leading Team of S&T Innovation(2013TD07)
文摘To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from coal, were investigated. Methane and cyclohexane were chosen as the model compounds. Density functional theory was employed, and many reaction pathways were involved. Calculations were carried out in Gaussian 09 at the B3LYP/6-31G(d,p) level of the theory. The results indicate that the main pyrolysis products of methane and cyclohexane in hydrogen plasma are both hydrogen and acetylene, and the participation of active hydrogen atoms makes dehydrogenation reactions more favorable. H2 mainly comes from dehydrogenation process, while many reaction pathways are responsible for acetylene formation. During coal pyrolysis in hydrogen plasma, three main components in volatiles like aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons lead to the formation of hydrogen and acetylene, but their contributions to products distribution are different.
文摘A Computational Fluid Dynamics(CFD) model was formulated for DC arc hydrogen/argon plasma jet reactors used in the process of the thermal H_2/Ar plasma pyrolysis of coal to acetylene. In this model, fluid flow, convective heat transfer and conjugate heat conductivity are considered simultaneously. The error caused by estimating the inner-wall temperature of a reactor is avoided. The thermodynamic and transport properties of the hydrogen/argon mixture plasma system, which are usually expressed by a set of discrete data, are fitted into expressions that can be easily implemented in the program. The effects of the turbulence are modeled by two standard k-εequations. The temperature field and velocity field in the plasma jet reactor were calculated by employing SIMPLEST algorithm. The knowledge and insight obtained are useful for the design improvement and scale-up of plasma reactors.
基金Core-University Program(CUP) and Knowledge Innovation Project and Key Project of CAS(No.KJCX-L07)
文摘The purpose of this paper is to demonstrate a systematic approach to design high performance signal conditioning circuits,and to show how to implement the 4-20 mA analog current-loop transmitter and receiver circuits by using isolation amplifier.The basic principle and typical applicable circuits of the 4-20 mA current loop isolation chip T1100N,the current-limiting circuit and filter circuit are presented.And the experimental testing data of the circuits are analyzed.
基金the financial support from the National Natural Science Foundation of China(Grant No.21576293 and 21576294)。
文摘Coal pyrolysis is a fundamental reaction in the thermal processing and utilization of coal.Investigating the behavior and kinetics of coal pyrolysis is crucial for optimizing,designing,and developing a composite riser for the staged pyrolysis gasification process of pulverized coal.In this study,the non-isothermal pyrolysis behavior and kinetics of coal were examined at different heating rates(30,50,100,300,500,700,and 900℃/min)using thermogravimetry(TG)coupled with Fourier-transform infrared spectroscopy.Analysis of the TG/derivative TG(TG/DTG)curves indicated that coal pyrolysis mainly occurred between 300℃ and 700℃.Higher heating rates led to more volatiles being released from the coal,and a higher temperature was required to achieve rapid pyrolysis.Kinetic analysis showed that both the model-free methods(Friedman,Flynn-Wall-Ozawa,and Kissinger-Akahira-Sunose)and the model-based method(Coats-Redfern)effectively describe the coal pyrolysis process.The change in the Ea values between the two kinetic models was consistent throughout the pyrolysis process,and the most probable mechanism was the F2 model(secondary chemical reaction).In addition,the heating rate did not change the overall reaction order of the pyrolysis process;however,a higher heating rate resulted in a decrease in the Ea value during the initial pyrolysis stage.
基金supported by the National Natural Science Foundation of China (51536002)the Fundamental Research Funds for the Central Universities (2015QNA12)the Open Sharing Fund for the Large-scale Instruments and Equipments of China University of Mining and Technology (CUMT).
文摘The critical issue in developing mature Oxy-Coal Combustion Steam System technology could be the reactivity of deminer-alized coal which,is closely related to its chemical structure.The chemical structures of Liupanshui raw coal(LPS-R)and Liupanshui demineralized coal(LPS-D)were analyzed by FTIR and solid-state 13C-NMR.The pyrolysis experiments were carried out by TG,and the pyrolysis kinetics was analyzed by three iso-conversional methods.FTIR and 13C-NMR results suggested that the carbon structure of LPS coal was not altered greatly,while demineralization promoted the maturity of coal and the condensation degree of the aromatic ring,making the chemical structure of coal more stable.The oxygen-containing functional groups with low bond energy were reduced,and the ratio of aromatic carbon with high bond energy was increased,decreasing the pyrolysis reactivity.DTG curve-fitting results revealed that the thermal weight loss of LPS coal mainly came from the cleavage of aliphatic covalent bonds.By pyrolysis kinetics analysis of LPS-R and LPS-D,the apparent activation energies were 76±4 to 463±5 kJ/mol and 84±2 to 758±12 kJ/mol,respectively,under different conversion rates.The reactivity of the demineralized coal was inhibited to some extent,as the apparent activation energy of pyrolysis for LPS-D increased by acid treatment.
基金financially supported by the International Science & Technology Cooperation Program of MOST(No.2011DFA61360)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDA07080400)the National Nature Science Foundation of China(No.20703047)
文摘In this paper, a model for fast coal pyrolysis in a cocurrent downer reactor is developed, in which both hydrodynamics and coal pyrolysis kinetics are simultaneously considered. The results of simulations based on this model display reasonable agreement with experimental data obtained using Huolinhe coal as the feedstock, and this model is therefore suitable for predicting the fast pyrolysis of specific coal types. A series of simulations of fast coal pyrolysis in a cocurrent downer demonstrated that coal devolatilization is almost complete in the inlet region within a time span of 0.4 s, and that higher temperatures improve the pyrolysis efficiency. However, the yield of liquid products is decreased with increasing pyrolysis temperatures, especially above 670 ℃, because of additional cracking of the liquids.
基金financially supported by the National Natural Science Foundation of China(Grant No.U1908201)the National Key Research and Development Program of China(Grant No.2018YFC0808500).
文摘ReaxFF molecular dynamic simulation combined with experimental verification was performed to understand the overall reaction mechanism,especially the primary and secondary reactions involving in tar formation of sub-bituminous coal pyrolysis.Quantitative relationship at atomic level is clarified between bond breakage of functional groups and products generation,revealing that the amount and order in forming each product are subject to the number of corresponding functional groups and their bond energies respectively.The primary breakage of-C-O-and-C-C-bridge-bonds present in initial coal macromolecular generates molecular of heavy tar,whereas heavy tar can be converted into light tar through cracking side chain of aromatic rings and cyclic hydrocarbons at increased pyrolysis temperatures.At very high temperatures the cracking of short-chain hydrocarbons and residual atoms connecting to aromatic rings further occurs to generate light tar and gas.The remaining aromatic-ring fragments of heavy tar are likely cross-linked to form char.Furthermore,the simultaneous evolution tendency of tar yield and tar quality under different pyrolysis temperatures and heating rates is obtained at molecular level.For obtaining high yield and quality of tar,appropriately high temperature as well as suitable heating rate are needed to compromise the high yield of primary tar and high quality of secondarily upgraded products.
基金the National Key Research and Development Program of China(Grant 2018YFB0604600)the National Natural Science Foundation of China(Grants 21808002,U1710114,21878001 and 22078002 and 21978003).
文摘Kinetic analyses are important means for understanding the complicated coal pyrolysis process.This work conducted non-isothermal pyrolysis of four low-medium rank coals with thermogravimetric analyzer at different heating rates(5,10 and 20 K/min).Four model-free fitting approaches including KAS,OFW,Starink and Friedman methods were used to analyze pyrolysis kinetics of the coals.Thermodynamic parameters including enthalpy(ΔH)Gibbs free energy(ΔG)and entropy(ΔS)were calculated with the activation values(E)obtained with KAS method.For the kinetic analysis,the KAS,OFW and Starink methods give close E values over the whole conversion range,but the Friedman method shows more deviant results.The thermodynamic favorability of coal pyrolysis is discussed,bothΔH andΔG increase with conversion consistently with the variation of E,revealing that pyrolysis is endothermic and thermodynamic favorability is reduced with conversion rises.The minusΔS implies that coal structures evolve from disordered to organized ones as universally accepted.These results are expected to deepen our understanding and to optimize the conditions of coal pyrolysis.
文摘The Pyrolysis behavior of two Chinese coals has been investigated in a laboratory-scale bubbling fluidized bed system in Siegen University, Germany. Experimental equipment and procedure are introduced. The amounts of Pyrolysis species of each coal were measured, calculated and compared. A newmethod was presented to determine the needed parameters in FG-DVC model with the experimentalresults instead of other much more complicated experiments.
基金The author would like to appreciate the funding supports of the State of Wyoming and China Scholarship Council.Without their supports,the international collaboration on clean energy technology development would have been impossible.
文摘In this study,the Powder River Basin(PRB)coal fast pyrolysis was conducted at 700°C in the atmosphere of syngas produced by CH4-CO2 reforming in two different patterns,including the double reactors pattern(the first reactor is for syngas production and the second is for coal pyrolysis)and double layers pattern(catalyst was at upper layer and coal was at lower layer).Besides,pure gases atmosphere including N2,H2,CO,H2-CO were also tested to investigate the mechanism of the coal pyrolysis under different atmospheres.The pyrolysis products including gas,liquid and char were characterized,the result showed that,compared with the inert atmosphere,the tar yield is improved with the reducing atmospheres,as well as the tar quality.The hydrogen partial pressure is the key point for that improvement.In the atmosphere of H2,the tar yield was increased by 31.3%and the contained BTX(benzene,toluene and xylene)and naphthalene were increased by 27.1%and 133.4%.The double reactors pattern also performed outstandingly,with 25.4%increment of tar yield and 25.0%and 79.4%for the BTX and naphthalene.The double layers pattern is not effective enough due to the low temperature(700°C)in which the Ni-based catalyst was not fully activated.
文摘In this paper,13 kinds of transition metals are studied as catalysts for the hydrogen production from coal pyrolysis, and relationships between the catalytic activity of a transition metal and its outer electron configuration,d% of transition metals and geometric configuration are summarized.Experimental results show that the same group of transition metals show good similarity for hydrogen production from coal pyrolysis;the d%of transition metals which have activity for hydrogen production from coal pyrolysis is between 40%-50%;all transition metals which have catalytic activity possess either a face-centered cubic or a hexagonal crystal structure.Therefore,it is important to choose a transition metal with an appropriate d%and crystal structure as the catalyst for hydrogen production from coal pyrolysis.
基金supported by National Natural Science Foundation of China(21878210)Shanxi Provincial Science and Technology Achievement Transformation Guidance Special Program of China(202104021301052)Shanxi Province Patent Transformation Special Program Project(202202054).
文摘Nitrogen oxide(NO_(x))pollutants emitted from coal combustion are attracting growing public concern.While the traditional technologies of reducing NO_(x) were mainly focused on terminal treatment,and the research on source treatment is limited.This paper proposes a new coal combustion strategy that significantly reduces NO_(x) emissions during coal combustion.This strategy has two important advantages in reducing NO_(x) emissions.First,by introducing iron-based catalyst at the source,which will catalyze the conversion of coke nitrogen to volatile nitrogen during the pyrolysis process,thereby greatly reducing the coke nitrogen content.The second is de-NO_(x) process by a redox reaction between NO_(x) and reducing agents(coke,HCN,NH_(3),etc.)that occurred during coke combustion.Compared to direct combustion of coal,coke prepared by adding iron-based catalyst has 46.1% reduction in NO_(x) emissions.To determine the effect of iron-based additives on de-NO_(x) performance,demineralized coal(de-coal)was prepared to eliminate the effect of iron-based minerals in coal ash.The effects of iron compounds,additive dosages,and combustion temperatures on de-NO_(x) efficiency are systematically studied.The results revealed that the NO_(x) emission of the coke generated by pyrolysis of de-coal loaded with 3%(mass)Fe_(2)O_(3) decreases to 27.3% at combustion temperature of 900℃.Two main reasons for lower NO_(x) emissions were deduced:(1)During the catalytic coal pyrolysis stage,the nitrogen content in the coke decreases with the release of volatile nitrogen.(2)Part of the NO_(x) emitted during the coke combustion was converted into N_(2) for the catalytic effect of the Fe-based catalysts.It is of great practical value and scientific significance to the comprehensive treatment and the clean utilization process of coal.
基金support from the Allocated Section of the Basic Fund for the Scientific Research and Operation of Central Universities of China (No.2009KH10)
文摘Various semicokes were obtained from medium-low temperature pyrolysis of Dongrong long flame coal.The proximate analysis,calorific value and Hardgrove grindability index(HGI) of semicokes were determined,and the ignition temperature,burnout temperature,ignition index,burnout index,burnout ratio,combustion characteristic index of semicokes were measured and analyzed using thermogravimetry analysis(TGA).The effects of pyrolysis temperature,heating rate,and pyrolysis time on yield,composition and calorific value of long flame coal derived semicokes were investigated,especially the influence of pyrolysis temperature on combustion characteristics and grindability of the semicokes was studied combined with X-ray diffraction(XRD) analysis of semicokes.The results show that the volatile content,ash content and calorific value of semicokes pyrolyzed at all process parameters studied meet the technical specifications of the pulverized coal-fired furnaces(PCFF) referring to China Standards GB/T 7562-1998.The pyrolysis temperature is the most influential factor among pyrolysis process parameters.As pyrolysis temperature increases,the yield,ignition index,combustion reactivity and burnout index of semicokes show a decreasing tend,but the ash content increases.In the range of 400 and 450 °C,the grindability of semicokes is rational,especially the grindability of semicokes pyrolyzed at 450 °C is suitable.Except for the decrease of volatile content and increase of ash content,the decrease of combustion performance of semicokes pyrolyzed at higher temperature should be attributed to the improvement of the degree of structural ordering and the increase of aromaticity and average crystallite size of char.It is concluded that the semicokes pyrolyzed at the temperature of 450 °C is the proper fuel for PCFF.
文摘The physiochemical properties of chars produced by coal pyrolysis in a laboratory-scale fluidized bed reactor with a continuous coal feed and char discharge at temperatures of 750 to 980 ~ C under N2-based atmospheres containing 02, H2, CO, CH4, and CO2 were studied. The specific surface area of the char was found to decrease with increasing pyrolysis temperature. The interlayer spacing of the char also decreased, while the average stacking height and carbon crystal size increased at higher temperatures, suggesting that the char generated at high temperatures had a highly ordered structure. The char obtained using an ER value of 0.064 exhibited the highest specific surface area and oxidation reactivity. Rela- tively high 02 concentrations degraded the pore structure of the char, decreasing the surface area. The char produced in an atmosphere incorporating H2 showed a more condensed crystalline structure and consequently had lower oxidation reactivity.
基金This work was supported by the National High technology Research and Development Program of China(863 Pro-gram)(No.2007AA05Z334,2013AA051203)International Cooper-ation Project(2011DFR60190)the program of introducing talents of discipline to University(B08026).
文摘A new coal staged conversion poly-generation system combined coal combustion and pyrolysis has been developed for clean and high efficient utilization of coal.Coal is the first pyrolysed in a fluidized pyrolyzer.The pyrolysis gas is then purified and used for chemical product or liquid fuel production.Tar is collected during purification and can be processed to extract high value product and to make liquid fuels by hydro-refining.Semi-coke from the pyrolysis reactor is burned in a circulating fluidized bed(CFB)combustor for heat or power generation.The system can realize coal multiproduct generation and has a great potential to increase coal utilization value.A 1 MW poly-generation system pilot plant and a 12 MW CFB gas,tar,heat and power poly-generation system was erected.The experimental study focused on the two fluidized bed operation and characterization of gas,tar and char yields and compositions.The results showed that the system could operate stable,and produce about 0.12 m^(3)/kg gas with 22 MJ/m^(3)heating value and about 10 wt%tar when using Huainan bituminous coal under pyrolysis temperature between 500 and 600℃.The produced gases were mainly H_(2),CH_(4),CO,CO_(2),C_(2)H_(4),C_(2)H_(6),C_(3)H_(6)and C_(3)H_(8).The CFB combustor can burn semi-coke steadily.The application prospect of the new system was discussed.
文摘Depending on advanced technological developments in energy production the low quality coals needed the most economical technologies and even in order to make it possible to produce coal-derived products. Compliance with environmental norms of coal pyrolysis or gasification of various type of coals, feasible combustion systems and energy production facilities are needed in today's modern technology, also enable the production of liquid and gaseous coal fuels. However, raw materials and chemical nature of them requires a variety of adaptation methods. This study examined the high sulfur and ash types of Kütahya, Denizli, Aydin, Soma lignite, Sirnak asphaltite and lignite. The representative samples were taken from local areas of the lignites. Fundamentally, the conditions regarding better desulfurization way, the high quality pyrolysis lignite oil production, high value light oil, coal tar and gas products were determined at the goal of high fuel producing yield.
基金financed by the National Key Research and Development Program of China(2016YFB0600304)the National Natural Science Foundation of China(21878310).
文摘Red mud(RM)with the high alkalinity as a catalyst was evaluated for coal pyrolysis in a fixed bed as well as CO_(2) gasification of its resultant char in a thermogravimetric analyzer(TGA).The addition of RM into coal could improve the quality of tar during pyrolysis and enhance the reactivity of char during gasification.For catalytic pyrolysis with 12 wt%RM at 600℃,the light fraction in tar was 72.0 wt%,which increased by 20.0%,compared with coal pyrolysis alone.The role of metal oxides in RM on coal pyrolysis was further clarified as well.After catalytic pyrolysis with RM,the specific surface area of resultant char increased,especially for mesoporous surface area,and meanwhile the sodium in RM was proved to migrate to the char surface.These positive factors contributed to the CO_(2) gasification activity of char.RM with the high alkalinity showed a promising catalyst candidate for coal pyrolysis and gasification in terms of its catalytic effects and low cost.
基金supported by the National Natural Science Foundation of China(Grant No.51474042)
文摘The utilization of highly reactive and high-strength coke can enhance the efficiency of blast furnace by promoting indirect reduction of iron oxides.Iron compounds,as the main constituent in iron-bearing minerals,have aroused wide interest in preparation of highly reactive iron coke.However,the effects of iron compounds on pyrolysis behavior of coal and metallurgical properties of resultant cokes are still unclear.Thus,three iron compounds,i.e.,Fe;O;,Fe;O;and FeC;O;·2H;O,were adopted to investigate their effects on coal pyrolysis behavior and metallurgical properties of the resultant cokes.The results show that iron compounds have slight effects on the thermal behavior of coal blend originated from thermogravimetric and differential thermogravimetric curves.The apparent activation energy varies with different iron compounds ranging from 94.85 to 110.11 kJ/mol in the primary pyrolysis process,while lower apparent activation energy is required for the secondary pyrolysis process.Iron compounds have an adverse influence on the mechanical properties and carbon structure of cokes.Strong correlations exist among coke reactivity,coke strength after reaction,and the content of metallic iron in cokes or the values of crystallite stacking height,which reflect the dependency of thermal property on metallic iron content and carbon structure of cokes.
文摘This paper presents a new approach to study the process of coal gasification. Non-linear programming techniques are used to determine the value of the model parameters that depends on coal species and experimental conditions and thus minimize the difference between experimental results and model predictions. Model predictions being in good agreement with the experimental results show that this method of combining model with experiment is effective for modeling complex processes.
文摘The structural optimization of baffle internals for fast pyrolysis of coal with particulate mixing and heat transfer in a downer reactor using the discrete element method(DEM)has been investigated in this research.The pyrolysis terminal temperature at the exit of the downer reactor is not only decided by the volume-feeding-rate ratio of the coal to the sand,but also is affected by the inner structural design of the baffle internals in the downer reactor.As presented in the previous publication of the author,the inhibition from the baffle internals in a downer reactor can improve the particulate-mixing degree and heat carrier,and increase the mean residence time of the coal and heat-carrier particles in the downer reactor.The structure of the baffle internals in the downer reactor mentioned in this research can be optimized by the independently developed 3D soft-sphere model of the DEM programme of a 40-mm baffle length,a 30°baffle-slope angle and at least four baffles designed in the downer reactor,which is beneficial for the process design of coal pyrolysis with a heat carrier in the downer reactor.