Dry reforming of methane(DRM) is an attractive technology for utilizing the greenhouse gases(CO_(2) and CH_(4)) to produce syngas. However, the catalyst pellets for DRM are heavily plagued by deactivation by coking, w...Dry reforming of methane(DRM) is an attractive technology for utilizing the greenhouse gases(CO_(2) and CH_(4)) to produce syngas. However, the catalyst pellets for DRM are heavily plagued by deactivation by coking, which prevents this technology from commercialization. In this work, a pore network model is developed to probe the catalyst deactivation by coking in a Ni/Al_(2)O_(3) catalyst pellet for DRM. The reaction conditions can significantly change the coking rate and then affect the catalyst deactivation. The catalyst lifetime is higher under lower temperature, pressure, and CH_(4)/CO_(2) molar ratio, but the maximum coke content in a catalyst pellet is independent of these reaction conditions. The catalyst pellet with larger pore diameter, narrower pore size distribution and higher pore connectivity is more robust against catalyst deactivation by coking, as the pores in this pellet are more difficult to be plugged or inaccessible.The maximum coke content is also higher for narrower pore size distribution and higher pore connectivity, as the number of inaccessible pores is lower. Besides, the catalyst pellet radius only slightly affects the coke content, although the diffusion limitation increases with the pellet radius. These results should serve to guide the rational design of robust DRM catalyst pellets against deactivation by coking.展开更多
Residue conversion by combining catalytic hydrotreating and delayed coking has been evaluated comparatively with both processes alone.Optimal operating conditions are defined to achieve the greatest economic benefit f...Residue conversion by combining catalytic hydrotreating and delayed coking has been evaluated comparatively with both processes alone.Optimal operating conditions are defined to achieve the greatest economic benefit for upgrading an atmospheric residue from a heavy crude oil.A literature model was adapted to simulate the hydrotreating reactor,and for delayed coking,correlations reported in the literature were used.The results with both approaches were employed to calculate the techno-economic feasibility of the combined process scheme.The combination of hydrotreating and delayed coking presented an increase in light fractions of 29% and a reduction in coke production of 47.8%.Based on the calculated net benefit values,it was demonstrated that the combination of hydrotreating and delayed coking is technically and economically better than using each process alone,with highest benefit of 57.7 USD·m^(-3).展开更多
Catalytic oxidation of CH_(4) has been proved to be an attractive option for landfill gas(LFG) upgrading.However, coking of catalysts in catalytic LFG deoxygen has been clearly observed in industrial applications. In ...Catalytic oxidation of CH_(4) has been proved to be an attractive option for landfill gas(LFG) upgrading.However, coking of catalysts in catalytic LFG deoxygen has been clearly observed in industrial applications. In this regard, it is necessary to investigate whether coke deposition originates from CH_(4) or volatile organic compounds present in LFG, and the influence of coke deposition on catalytic performance. Herein,we evaluate the LFG deoxygen on Pt/γ-Al_(2)O_(3) catalyst in simulated LFG(CH_(4), CO_(2), O_(2), N_(2)) and its co-feed with representative volatile organic compounds, ethylbenzene, toluene, benzene and cyclohexane. The results show that the coking of the catalyst is originated from volatile organic compounds rather than CH_(4). The Pt/γ-Al_(2)O_(3) catalyst does not deactivate during LFG deoxygen process, even significant amount of coke deposited, up to 18.15%(mass). Characterization analyses reveal that although coke deposition overall covers the catalyst surface, resulting in mesopores blockage and a reduced number of accessible Pt sites, however, the coke formed, H-rich carbonaceous components, behaves as counterpart for O_(2) elimination. Besides, the coke deposited is mainly filamentous. Thus, coke formation has little negative effect on the overall catalytic performance of Pt/γ-Al_(2)O_(3) catalyst ultimately. The results obtained in this work are helpful for the rational design of robust Pt based catalysts for LFG deoxygen without undue attention to their coking properties, and also favor the innovation of more attractive purification scheme configurations.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
The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were i...The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were investigated in this study.The results showed the drastic effects of barium addition on the physicochemical properties and performances of the catalyst.The solid-phase reaction between alumina and BaO formed BaAl2O4,which re-constructed the alumina structure,resulting in a decrease in the specific surface area and an increase in the resistance of metallic Ni to sintering.The addition of barium was also beneficial for enhancing the catalytic activity,resulting from the changed catalytic reaction network.The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study of the acetic acid steam reforming indicated that barium could effectively suppress the accumulation of the reaction intermediates of carbonyl,formate,and C=C functional groups on the catalyst surface,attributed to its relatively high ability to cause the gasification of these species.In addition,coking was considerably more significant over the Ba-Ni/Al2O3 catalyst.Moreover,the Ba-Ni/Al2O3 catalyst was more stable than the Ni/Al2O3catalyst,owing to the distinct forms of coke formed (carbon nanotube form over the Ba-Ni/Al2O3 catalyst,and the amorphous form over the Ni/Al2O3 catalyst).展开更多
Carbon dioxide and methane are two main greenhouse gases which are contributed to serious global warming.Fortunately,dry reforming of methane(DRM),a very important reaction developed decades ago,can convert these two ...Carbon dioxide and methane are two main greenhouse gases which are contributed to serious global warming.Fortunately,dry reforming of methane(DRM),a very important reaction developed decades ago,can convert these two major greenhouse gases into value-added syngas or hydrogen.The main problem retarding its industrialization is the seriously coking formation upon the nickel-based catalysts.Herein,a series of confined indium-nickel(In-Ni)intermetallic alloy nanocatalysts(In_(x)Ni@SiO_(2))have been prepared and displayed superior coking resistance for DRM reaction.The sample containing 0.5 wt.%of In loading(In_(0.5)Ni@SiO_(2))shows the best balance of carbon deposition resistance and DRM reactivity even after 430 h long term stability test.The boosted carbon resistance can be ascribed to the confinement of core–shell structure and to the transfer of electrons from Indium to Nickel in In-Ni intermetallic alloys due to the smaller electronegativity of In.Both the silica shell and the increase of electron cloud density on metallic Ni can weaken the ability of Ni to activate C–H bond and decrease the deep cracking process of methane.The reaction over the confined InNi intermetallic alloy nanocatalyst was conformed to the Langmuir-Hinshelwood(L-H)mechanism revealed by in situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS).This work provides a guidance to design high performance coking resistance catalysts for methane dry reforming to efficiently utilize these two main greenhouse gases.展开更多
CaO-containing carbon pellets(CCCP)were successfully prepared from well-mixed coking coal(CC)and calcium oxide(CaO)and roasted at different pyrolysis temperatures.The effects of temperature,pore distribution,and carbo...CaO-containing carbon pellets(CCCP)were successfully prepared from well-mixed coking coal(CC)and calcium oxide(CaO)and roasted at different pyrolysis temperatures.The effects of temperature,pore distribution,and carbon structure on the compressive strength of CCCP was investigated in a pyrolysis furnace(350-750℃).The results showed that as the roasting temperature increased,the compressive strength also increased and furthermore,structural defects and imperfections in the carbon crystallites were gradually eliminated to form more organized char structures,thus forming high-ordered CC.Notably,the CCCP preheated at 750℃exhibited the highest compressive strength.A positive relationship between the compressive strength and pore-size homogeneity was established.A linear relationship between the com-pressive strength of the CCCP and the average stack height of CC was observed.Additionally,a four-stage caking mechanism was developed.展开更多
Coking coal dust is extremely hydrophobic;therefore,combination with droplets in the air is difficult and dust suppression is challenging.Here,a dust suppressant spray for coking coal dust was studied in order to impr...Coking coal dust is extremely hydrophobic;therefore,combination with droplets in the air is difficult and dust suppression is challenging.Here,a dust suppressant spray for coking coal dust was studied in order to improve of the combination of droplets and coking coal dust.Based on monomer optimization and compounding analysis,two surfactant monomers,fatty alcohol ether sodium sulfate(AES)and sodium dodecyl benzene sulfonate(SDBS)were selected as the surfactant components of the dust suppressant.The surfactant monomers were combined with four inorganic salts and the reverse osmosis moisture absorption of each solution was determined.By combining the reverse osmosis moisture absorption values with the water retention experimental results,CaCl_(2)was identified as the optimal inorganic salt additive for the dust suppressant.Finally,the optimal concentration of each component was obtained using orthogonal experimental design i.e.,AES(0.03%),SDBS(0.05%),and CaCl_(2)(0.4%).The dust suppressant solution formulated using this method had a high moisture absorption capacity and excellent performance.展开更多
Fresh ZSM-5 zeolite catalysts were pretreated at 460 ℃and 500 ℃with various cumulative amount of water feed(CAWF) in a fixed bed reactor. The catalytic process was carried out under the following conditions: a tempe...Fresh ZSM-5 zeolite catalysts were pretreated at 460 ℃and 500 ℃with various cumulative amount of water feed(CAWF) in a fixed bed reactor. The catalytic process was carried out under the following conditions: a temperature of 480 ℃; a methanol WHSV of 3 h-1; a methanol partial pressure of 30 k Pa; and a time on stream of 12 h, 24 h and 48 h, respectively. The BET parameters of catalysts and diffusion coefficients of toluene showed that there were two types of mesopores generated under different hydrothermal conditions. Mild temperature and moderate CAWF conditions led to external open mesopores which could be entered from the external surface of the zeolite, while a high temperature or a high CAWF condition resulted in the generation of macropores or internal isolated mesopores, which were occluded in the microporous matrix. The TGA results showed that catalyst with external open mesopores had good ability to resist coke accumulation and good performance on propylene selectivity, while the internal isolated mesopores did no contribute to the increased diffusivity of reactants and products.展开更多
In this work,a molecular-level kinetic model was built to simulate the vacuum residue(VR)coking process in a semi-batch laboratory-scale reaction kettle.A series of reaction rules for heavy oil coking were summarized ...In this work,a molecular-level kinetic model was built to simulate the vacuum residue(VR)coking process in a semi-batch laboratory-scale reaction kettle.A series of reaction rules for heavy oil coking were summarized and formulated based on the free radical reaction mechanism.Then,a large-scale molecularlevel reaction network was automatically generated by applying the reaction rules on the vacuum residue molecules.In order to accurately describe the physical change of each molecule in the reactor,we coupled the molecular-level kinetic model with a vapor–liquid phase separation model.The vapor–liquid phase separation model adopted the Peng-Robinson equation of state to calculate vapor–liquid equilibrium.A separation efficiency coefficient was introduced to represent the mass transfer during the phase separation.We used six sets of experimental data under various reaction conditions to regress the model parameters.The tuned model showed that there was an excellent agreement between the calculated values and experimental data.Moreover,we investigated the effect of reaction temperature and reaction time on the product yields.After a comprehensive evaluation of the reaction temperature and reaction time,the optimal reaction condition for the vacuum residue coking was also obtained.展开更多
A comparative numerical study is conducted to evaluate the effect of inlet velocity on the gas-liquid-solid phase change, the separation of phases and the coke formation. The numerical procedure is constructed within ...A comparative numerical study is conducted to evaluate the effect of inlet velocity on the gas-liquid-solid phase change, the separation of phases and the coke formation. The numerical procedure is constructed within the Eulerian framework in which the liquid phase is treated as a continuous phase while gas and solid are both considered as dispersed phases. The simplified reaction net of crude oil is used in order to predict the thermal cracking of the crude oil. The temperature distribution, flow field, liquid–gas phase separation, and coke formation are predicted and discussed for different inlet velocities. The information predicted by the CFD model can be utilized in the optimal design of industrial fired furnaces.展开更多
Main technical and structural characteristics of Tavantolgoi coal from Mongolia are determined. Type, code number and other valuable technological indexes of the coal are estimated according to the international class...Main technical and structural characteristics of Tavantolgoi coal from Mongolia are determined. Type, code number and other valuable technological indexes of the coal are estimated according to the international classification system of coals. Cokes obtained in a laboratory chamber stove and in a reactor was characterized.展开更多
Ni-based anodes of SOFCs are susceptible to coking, which greatly limits practical application of direct methane-based fuels. An indirect internal reformer is an effective way to convert methane-based fuels into synga...Ni-based anodes of SOFCs are susceptible to coking, which greatly limits practical application of direct methane-based fuels. An indirect internal reformer is an effective way to convert methane-based fuels into syngas before they reach anode. In this work, catalytic activity of a redox-stable perovskite La0.7Sr0.3Cr0.8Fe0.2O3-δ(LSCrFO) for methane conversion was evaluated. The catalyst was fabricated as an anodic protective layer to improve coking resistance of a Ni cermet anode. Using wet CH4 as a fuel, the LSCrFO-modified cell showed excellent power output and good coking resistance with peak power density of 1.59 W cm-2 at 800℃. The cell demonstrated good durability lasting for at least 100 h. While the bare cell without the protective layer showed poor durability with the cell voltage fast dropped from 0.75 V to 0.4 V within 30 min. Under wet coal bed methane (CBM) operation, obvious performance degradation within 35 h (1.7 mV h^-1) was observed due to the influence of heavy carbon compounds in CBM. The pre-and post-mortem microstructures and carbon analysis of the anode surface and catalyst surface were further conducted.展开更多
The paper described the coking plant and Lurgi gasifier plant waste water types and characteristics , comparing the COD and ammonia-N level in different source of waste water in the plant.The currently maturity coking...The paper described the coking plant and Lurgi gasifier plant waste water types and characteristics , comparing the COD and ammonia-N level in different source of waste water in the plant.The currently maturity coking plant waste water treatment method was statement in the paper and analyzed the pros and cons of each method.The primary cost analysis of each type of waste water treatment was also completed in the paper.According to these analyses , recommendation was prepared for coking plant and Lurgi gasifier plant waste water treatment.展开更多
The support γ-Al_2O_3 was treated with 1-methylnaphthalene as the model reactant by respectively using the chemical static adsorption method and the accelerated coking method to study the coking sites of γ-Al_2O_3 s...The support γ-Al_2O_3 was treated with 1-methylnaphthalene as the model reactant by respectively using the chemical static adsorption method and the accelerated coking method to study the coking sites of γ-Al_2O_3 surface. The carbon species formed on γ-Al_2O_3 surface were analyzed by CAT-CS, TG-MS, IR-OH, and Py-IR techniques. The results of characterization by CAT-CS and TG-MS techniques indicated that the carbon species formed during the chemical static adsorption process is mainly composed of the reversibly adsorbed coke precursors with a lowly-condensed state, while that formed after the accelerated coking process is probably related with the irreversibly adsorbed coke deposits with a highlycondensed state. The results of characterization by IR-OH and Py-IR techniques further implied that the formation of the two kinds of carbon species, i.e., coke precursors and coke deposits, are closely related with the basic hydroxyl groups and the strong Lewis acid sites on γ-Al_2O_3 surface. The results lead to a deep insight into the coking mechanism on the alumina surface.展开更多
Groundwater pollution in north China is serious, which is mostly caused by complex factors. Aiming at the problems such as the unknown reasons for the differences in the migration characteristics of typical characteri...Groundwater pollution in north China is serious, which is mostly caused by complex factors. Aiming at the problems such as the unknown reasons for the differences in the migration characteristics of typical characteristic pollutants in the same medium and the unknown migration rules of complex pollutants in soil and groundwater, this paper selected a single sample and a mixed sample of typical characteristic pollutants in coking enterprises to carry out the static adsorption test. The results showed that the distribution coefficients of benzene series and aromatic hydrocarbon pollutants in soil-water were K_(d)benzene >K_(d)toluene >K_(d)ethylbenzene >K_(d)pyrene >K_(d)anthracene >K_(d)naphthene, and the distribution coefficients of ammonia nitrogen, phenols and cyanogen were K_(d)ammonia nitrogen >K_(d)phenols >K_(d)cyanogen. The overall distribution coefficient of benzene series was higher than that of PAHs, and it was easier to be adsorbed by silty loam. Different carbon and hydrogen mass and even electron distribution of typical characteristic pollutants led to differences in the migration characteristics of benzene and aromatic pollutants. The more carbon and hydrogen there were, the more even the electron distribution was, and the more difficult it was to migrate in the soil. Among the same kind of pollutants, the migration of complex pollutants was weaker than that of single pollutants. The research could provide the parameter basis for establishing the solute transport model of groundwater and the design basis for developing the related risk control and pollution prevention strategies.展开更多
A type of calcium coke was developed for use in the oxy-thermal process of calcium carbide production.The calcium coke was prepared by the co-pyrolysis of coking coal and calcium carbide slag, which is a solid waste g...A type of calcium coke was developed for use in the oxy-thermal process of calcium carbide production.The calcium coke was prepared by the co-pyrolysis of coking coal and calcium carbide slag, which is a solid waste generated from the chlor-alkali industry.The characteristics of the calcium cokes under different conditions were analyzed experimentally and theoretically.The results show that the thermal strength of calcium coke increased with the increase in the coking coal proportion, and the waterproof property of calcium coke also increased with increased carbonation time.The calcium coke can increase the contact area of calcium and carbon in the calcium carbide production process.Furthermore, the pore structure of the calcium coke can enhance the diffusion of gas inside the furnace, thus improving the efficiency of the oxy-thermal technology.展开更多
Investigation was made on the efficiency of two commercial membranes in removing via forward osmosis(FO)the low molecular weight organic compounds typical of coking wastewater. The membranes were supplied by Poten and...Investigation was made on the efficiency of two commercial membranes in removing via forward osmosis(FO)the low molecular weight organic compounds typical of coking wastewater. The membranes were supplied by Poten and HTI companies. The organics in the simulated coking water were indole and pyrridine. Under FO mode, the rejection to the organics by Poten membrane was around 50%, whereas that for HTI membrane was obviously higher, ranging from 65% to 74%. The response of the two membranes in terms of Water flux and reverse salt flux(RSF) towards changing feed/draw solution(DS) flow rates in FO mode showed similar tendency,but different degree. Generally, the flux in FO using HTI membranes was lower. For HTI membrane, FO operated with pressure retarded osmosis(PRO) mode was also performed and the overall rejection of the organics was slightly lower than that in FO mode. In the long term FO test within 15 days, both Poten and HTI membranes displayed flux reduction and rejection enhancement. But the variation with Poten membrane was much more obvious. Discussion was carried out about the reasons and the mechanisms behind the FO performance difference between two membranes and the variation in flux and rejection with operation conditions. Characterizations by SEM, FTIR, AFM, XRD and XPS were tried to support the proposed explanations.展开更多
The coke deposition on HZSM-5/SAPO-34 composite catalysts has been studied in the conversion of ethanol to propylene. The HZSM-5/SAPO-34 composite catalysts were synthesized by hydrothermal method(ZS-HS) and fully ble...The coke deposition on HZSM-5/SAPO-34 composite catalysts has been studied in the conversion of ethanol to propylene. The HZSM-5/SAPO-34 composite catalysts were synthesized by hydrothermal method(ZS-HS) and fully blending(ZS-MM). The used catalysts were characterized by XRD, N_2 adsorption–desorption, TGA, TPO, elemental analysis, FTIR and XPS. The coking kinetics on both ZS-HS and ZS-MM has been investigated and their coking rate equations were obtained. The used ZS-MM catalyst had higher amount of coke and lower nC:nHthan the used ZS-HS. 90% of the coke was deposited in the micropores of ZS-HS, while almost 45% of the coke located in the micropores of ZS-MM. The coke deposited on ZS-HS catalyst was mainly graphite-like carbon species, whereas dehydrogenated coke species was the major on ZS-MM. The coking activation energy of ZS-MM was lower than that of ZS-HS, and the coking rate on ZS-MM was faster than on ZS-HS. In addition, the regeneration of ZS-MM catalyst showed that it had a good hydrothermal stability. The differences on coking behaviors on the two catalysts were due to their different acidic properties and textures.展开更多
基金financially supported by the National Natural Science Foundation of China (22078090 and 92034301)the Shanghai Rising-Star Program (21QA1402000)+1 种基金the Natural Science Foundation of Shanghai (21ZR1418100)the Open Project of State Key Laboratory of Chemical Engineering (SKL-ChE-21C02)。
文摘Dry reforming of methane(DRM) is an attractive technology for utilizing the greenhouse gases(CO_(2) and CH_(4)) to produce syngas. However, the catalyst pellets for DRM are heavily plagued by deactivation by coking, which prevents this technology from commercialization. In this work, a pore network model is developed to probe the catalyst deactivation by coking in a Ni/Al_(2)O_(3) catalyst pellet for DRM. The reaction conditions can significantly change the coking rate and then affect the catalyst deactivation. The catalyst lifetime is higher under lower temperature, pressure, and CH_(4)/CO_(2) molar ratio, but the maximum coke content in a catalyst pellet is independent of these reaction conditions. The catalyst pellet with larger pore diameter, narrower pore size distribution and higher pore connectivity is more robust against catalyst deactivation by coking, as the pores in this pellet are more difficult to be plugged or inaccessible.The maximum coke content is also higher for narrower pore size distribution and higher pore connectivity, as the number of inaccessible pores is lower. Besides, the catalyst pellet radius only slightly affects the coke content, although the diffusion limitation increases with the pellet radius. These results should serve to guide the rational design of robust DRM catalyst pellets against deactivation by coking.
基金the Mexican Institute of Petroleum(IMP)for the financial support。
文摘Residue conversion by combining catalytic hydrotreating and delayed coking has been evaluated comparatively with both processes alone.Optimal operating conditions are defined to achieve the greatest economic benefit for upgrading an atmospheric residue from a heavy crude oil.A literature model was adapted to simulate the hydrotreating reactor,and for delayed coking,correlations reported in the literature were used.The results with both approaches were employed to calculate the techno-economic feasibility of the combined process scheme.The combination of hydrotreating and delayed coking presented an increase in light fractions of 29% and a reduction in coke production of 47.8%.Based on the calculated net benefit values,it was demonstrated that the combination of hydrotreating and delayed coking is technically and economically better than using each process alone,with highest benefit of 57.7 USD·m^(-3).
基金the financial supports from the National Natural Science Foundation of China (22076077, 21577060)Jiangsu Science and Technology Department (BK20191256)Analysis & Test Fund of Nanjing University。
文摘Catalytic oxidation of CH_(4) has been proved to be an attractive option for landfill gas(LFG) upgrading.However, coking of catalysts in catalytic LFG deoxygen has been clearly observed in industrial applications. In this regard, it is necessary to investigate whether coke deposition originates from CH_(4) or volatile organic compounds present in LFG, and the influence of coke deposition on catalytic performance. Herein,we evaluate the LFG deoxygen on Pt/γ-Al_(2)O_(3) catalyst in simulated LFG(CH_(4), CO_(2), O_(2), N_(2)) and its co-feed with representative volatile organic compounds, ethylbenzene, toluene, benzene and cyclohexane. The results show that the coking of the catalyst is originated from volatile organic compounds rather than CH_(4). The Pt/γ-Al_(2)O_(3) catalyst does not deactivate during LFG deoxygen process, even significant amount of coke deposited, up to 18.15%(mass). Characterization analyses reveal that although coke deposition overall covers the catalyst surface, resulting in mesopores blockage and a reduced number of accessible Pt sites, however, the coke formed, H-rich carbonaceous components, behaves as counterpart for O_(2) elimination. Besides, the coke deposited is mainly filamentous. Thus, coke formation has little negative effect on the overall catalytic performance of Pt/γ-Al_(2)O_(3) catalyst ultimately. The results obtained in this work are helpful for the rational design of robust Pt based catalysts for LFG deoxygen without undue attention to their coking properties, and also favor the innovation of more attractive purification scheme configurations.
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 Natural Science Foundation of China(No.51876080)the Strategic International Scientific and Technological Innovation Cooperation Special Funds of National Key Research and Development Program of China(No.2016YFE0204000)+3 种基金the Program for Taishan Scholars of Shandong Province Governmentthe Recruitment Program of Global Experts(Thousand Youth Talents Plan)the Natural Science Foundation of Shandong Province(ZR2017BB002)the Key Research and Development Program of Shandong Province(2018GSF116014)。
文摘The influence of barium addition to a Ni/Al2O3 catalyst on the reaction intermediates formed,the activity,resistance of the catalyst to coking,and properties of the coke formed after acetic acid steam reforming were investigated in this study.The results showed the drastic effects of barium addition on the physicochemical properties and performances of the catalyst.The solid-phase reaction between alumina and BaO formed BaAl2O4,which re-constructed the alumina structure,resulting in a decrease in the specific surface area and an increase in the resistance of metallic Ni to sintering.The addition of barium was also beneficial for enhancing the catalytic activity,resulting from the changed catalytic reaction network.The in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study of the acetic acid steam reforming indicated that barium could effectively suppress the accumulation of the reaction intermediates of carbonyl,formate,and C=C functional groups on the catalyst surface,attributed to its relatively high ability to cause the gasification of these species.In addition,coking was considerably more significant over the Ba-Ni/Al2O3 catalyst.Moreover,the Ba-Ni/Al2O3 catalyst was more stable than the Ni/Al2O3catalyst,owing to the distinct forms of coke formed (carbon nanotube form over the Ba-Ni/Al2O3 catalyst,and the amorphous form over the Ni/Al2O3 catalyst).
基金supported by the National Natural Science Foundation of China(21976078 and 21773106)the National Key R&D Program of China(2016YFC0205900)+1 种基金the Natural Science Foundation of Jiangxi Province(20202ACB213001)National Engineering Laboratory for Mobile Source Emission Control Technology(NELMS2019A12)。
文摘Carbon dioxide and methane are two main greenhouse gases which are contributed to serious global warming.Fortunately,dry reforming of methane(DRM),a very important reaction developed decades ago,can convert these two major greenhouse gases into value-added syngas or hydrogen.The main problem retarding its industrialization is the seriously coking formation upon the nickel-based catalysts.Herein,a series of confined indium-nickel(In-Ni)intermetallic alloy nanocatalysts(In_(x)Ni@SiO_(2))have been prepared and displayed superior coking resistance for DRM reaction.The sample containing 0.5 wt.%of In loading(In_(0.5)Ni@SiO_(2))shows the best balance of carbon deposition resistance and DRM reactivity even after 430 h long term stability test.The boosted carbon resistance can be ascribed to the confinement of core–shell structure and to the transfer of electrons from Indium to Nickel in In-Ni intermetallic alloys due to the smaller electronegativity of In.Both the silica shell and the increase of electron cloud density on metallic Ni can weaken the ability of Ni to activate C–H bond and decrease the deep cracking process of methane.The reaction over the confined InNi intermetallic alloy nanocatalyst was conformed to the Langmuir-Hinshelwood(L-H)mechanism revealed by in situ diffuse reflectance infrared Fourier transform spectroscopy(in-situ DRIFTS).This work provides a guidance to design high performance coking resistance catalysts for methane dry reforming to efficiently utilize these two main greenhouse gases.
基金This work was financially supported by the National Key R&D Program of China(No.2018YFB0605900).
文摘CaO-containing carbon pellets(CCCP)were successfully prepared from well-mixed coking coal(CC)and calcium oxide(CaO)and roasted at different pyrolysis temperatures.The effects of temperature,pore distribution,and carbon structure on the compressive strength of CCCP was investigated in a pyrolysis furnace(350-750℃).The results showed that as the roasting temperature increased,the compressive strength also increased and furthermore,structural defects and imperfections in the carbon crystallites were gradually eliminated to form more organized char structures,thus forming high-ordered CC.Notably,the CCCP preheated at 750℃exhibited the highest compressive strength.A positive relationship between the compressive strength and pore-size homogeneity was established.A linear relationship between the com-pressive strength of the CCCP and the average stack height of CC was observed.Additionally,a four-stage caking mechanism was developed.
基金The project was supported by the National Natural Science Foundation of China(No.51574123)the Scientific Research Project of Hunan Province Office of Education(No.18A185),which is gratefully acknowledged.
文摘Coking coal dust is extremely hydrophobic;therefore,combination with droplets in the air is difficult and dust suppression is challenging.Here,a dust suppressant spray for coking coal dust was studied in order to improve of the combination of droplets and coking coal dust.Based on monomer optimization and compounding analysis,two surfactant monomers,fatty alcohol ether sodium sulfate(AES)and sodium dodecyl benzene sulfonate(SDBS)were selected as the surfactant components of the dust suppressant.The surfactant monomers were combined with four inorganic salts and the reverse osmosis moisture absorption of each solution was determined.By combining the reverse osmosis moisture absorption values with the water retention experimental results,CaCl_(2)was identified as the optimal inorganic salt additive for the dust suppressant.Finally,the optimal concentration of each component was obtained using orthogonal experimental design i.e.,AES(0.03%),SDBS(0.05%),and CaCl_(2)(0.4%).The dust suppressant solution formulated using this method had a high moisture absorption capacity and excellent performance.
基金supported by the National Natural Science Foundation of China(Grant 21176208&61590925)the National High-Tech R&D Program of China(Grant 2012AA030304)+1 种基金the International S&T Cooperation Projects of China(2015DFA40660)the Fundamental Research Funds for the Central Universities(Grant2015QNA4033)
文摘Fresh ZSM-5 zeolite catalysts were pretreated at 460 ℃and 500 ℃with various cumulative amount of water feed(CAWF) in a fixed bed reactor. The catalytic process was carried out under the following conditions: a temperature of 480 ℃; a methanol WHSV of 3 h-1; a methanol partial pressure of 30 k Pa; and a time on stream of 12 h, 24 h and 48 h, respectively. The BET parameters of catalysts and diffusion coefficients of toluene showed that there were two types of mesopores generated under different hydrothermal conditions. Mild temperature and moderate CAWF conditions led to external open mesopores which could be entered from the external surface of the zeolite, while a high temperature or a high CAWF condition resulted in the generation of macropores or internal isolated mesopores, which were occluded in the microporous matrix. The TGA results showed that catalyst with external open mesopores had good ability to resist coke accumulation and good performance on propylene selectivity, while the internal isolated mesopores did no contribute to the increased diffusivity of reactants and products.
基金supported by the National Natural Science Foun-dation of China(22021004 and U19B2002).
文摘In this work,a molecular-level kinetic model was built to simulate the vacuum residue(VR)coking process in a semi-batch laboratory-scale reaction kettle.A series of reaction rules for heavy oil coking were summarized and formulated based on the free radical reaction mechanism.Then,a large-scale molecularlevel reaction network was automatically generated by applying the reaction rules on the vacuum residue molecules.In order to accurately describe the physical change of each molecule in the reactor,we coupled the molecular-level kinetic model with a vapor–liquid phase separation model.The vapor–liquid phase separation model adopted the Peng-Robinson equation of state to calculate vapor–liquid equilibrium.A separation efficiency coefficient was introduced to represent the mass transfer during the phase separation.We used six sets of experimental data under various reaction conditions to regress the model parameters.The tuned model showed that there was an excellent agreement between the calculated values and experimental data.Moreover,we investigated the effect of reaction temperature and reaction time on the product yields.After a comprehensive evaluation of the reaction temperature and reaction time,the optimal reaction condition for the vacuum residue coking was also obtained.
文摘A comparative numerical study is conducted to evaluate the effect of inlet velocity on the gas-liquid-solid phase change, the separation of phases and the coke formation. The numerical procedure is constructed within the Eulerian framework in which the liquid phase is treated as a continuous phase while gas and solid are both considered as dispersed phases. The simplified reaction net of crude oil is used in order to predict the thermal cracking of the crude oil. The temperature distribution, flow field, liquid–gas phase separation, and coke formation are predicted and discussed for different inlet velocities. The information predicted by the CFD model can be utilized in the optimal design of industrial fired furnaces.
文摘Main technical and structural characteristics of Tavantolgoi coal from Mongolia are determined. Type, code number and other valuable technological indexes of the coal are estimated according to the international classification system of coals. Cokes obtained in a laboratory chamber stove and in a reactor was characterized.
基金supported by the Coal Seam Gas Joint Foundation of Shanxi(2015012016)Shanxi Province Science Foundation(2016011025)+2 种基金Shanxi Scholarship Council of China(2016-010)Shanxi “1331 Project” Key Innovative Research Team(“1331KIRT”)the Open Funding from State Key Laboratory of Materialoriented Chemical Engineering(No.KL16-03)
文摘Ni-based anodes of SOFCs are susceptible to coking, which greatly limits practical application of direct methane-based fuels. An indirect internal reformer is an effective way to convert methane-based fuels into syngas before they reach anode. In this work, catalytic activity of a redox-stable perovskite La0.7Sr0.3Cr0.8Fe0.2O3-δ(LSCrFO) for methane conversion was evaluated. The catalyst was fabricated as an anodic protective layer to improve coking resistance of a Ni cermet anode. Using wet CH4 as a fuel, the LSCrFO-modified cell showed excellent power output and good coking resistance with peak power density of 1.59 W cm-2 at 800℃. The cell demonstrated good durability lasting for at least 100 h. While the bare cell without the protective layer showed poor durability with the cell voltage fast dropped from 0.75 V to 0.4 V within 30 min. Under wet coal bed methane (CBM) operation, obvious performance degradation within 35 h (1.7 mV h^-1) was observed due to the influence of heavy carbon compounds in CBM. The pre-and post-mortem microstructures and carbon analysis of the anode surface and catalyst surface were further conducted.
文摘The paper described the coking plant and Lurgi gasifier plant waste water types and characteristics , comparing the COD and ammonia-N level in different source of waste water in the plant.The currently maturity coking plant waste water treatment method was statement in the paper and analyzed the pros and cons of each method.The primary cost analysis of each type of waste water treatment was also completed in the paper.According to these analyses , recommendation was prepared for coking plant and Lurgi gasifier plant waste water treatment.
基金support from the National Key Basic Research Program of China (Grant 2017YFB0306603)
文摘The support γ-Al_2O_3 was treated with 1-methylnaphthalene as the model reactant by respectively using the chemical static adsorption method and the accelerated coking method to study the coking sites of γ-Al_2O_3 surface. The carbon species formed on γ-Al_2O_3 surface were analyzed by CAT-CS, TG-MS, IR-OH, and Py-IR techniques. The results of characterization by CAT-CS and TG-MS techniques indicated that the carbon species formed during the chemical static adsorption process is mainly composed of the reversibly adsorbed coke precursors with a lowly-condensed state, while that formed after the accelerated coking process is probably related with the irreversibly adsorbed coke deposits with a highlycondensed state. The results of characterization by IR-OH and Py-IR techniques further implied that the formation of the two kinds of carbon species, i.e., coke precursors and coke deposits, are closely related with the basic hydroxyl groups and the strong Lewis acid sites on γ-Al_2O_3 surface. The results lead to a deep insight into the coking mechanism on the alumina surface.
基金Supported by Hebei Natural Science Fund (D2021106004)。
文摘Groundwater pollution in north China is serious, which is mostly caused by complex factors. Aiming at the problems such as the unknown reasons for the differences in the migration characteristics of typical characteristic pollutants in the same medium and the unknown migration rules of complex pollutants in soil and groundwater, this paper selected a single sample and a mixed sample of typical characteristic pollutants in coking enterprises to carry out the static adsorption test. The results showed that the distribution coefficients of benzene series and aromatic hydrocarbon pollutants in soil-water were K_(d)benzene >K_(d)toluene >K_(d)ethylbenzene >K_(d)pyrene >K_(d)anthracene >K_(d)naphthene, and the distribution coefficients of ammonia nitrogen, phenols and cyanogen were K_(d)ammonia nitrogen >K_(d)phenols >K_(d)cyanogen. The overall distribution coefficient of benzene series was higher than that of PAHs, and it was easier to be adsorbed by silty loam. Different carbon and hydrogen mass and even electron distribution of typical characteristic pollutants led to differences in the migration characteristics of benzene and aromatic pollutants. The more carbon and hydrogen there were, the more even the electron distribution was, and the more difficult it was to migrate in the soil. Among the same kind of pollutants, the migration of complex pollutants was weaker than that of single pollutants. The research could provide the parameter basis for establishing the solute transport model of groundwater and the design basis for developing the related risk control and pollution prevention strategies.
基金financially supported by the Natural Science Foundation of China (Nos.U1610101 and 21776288)the Green Process Manufacturing Innovation Research Institute, Chinese Academy of Sciences (No.IAGM-2019-A09)the funding support from Vinnova (Dn: 2018-05293)。
文摘A type of calcium coke was developed for use in the oxy-thermal process of calcium carbide production.The calcium coke was prepared by the co-pyrolysis of coking coal and calcium carbide slag, which is a solid waste generated from the chlor-alkali industry.The characteristics of the calcium cokes under different conditions were analyzed experimentally and theoretically.The results show that the thermal strength of calcium coke increased with the increase in the coking coal proportion, and the waterproof property of calcium coke also increased with increased carbonation time.The calcium coke can increase the contact area of calcium and carbon in the calcium carbide production process.Furthermore, the pore structure of the calcium coke can enhance the diffusion of gas inside the furnace, thus improving the efficiency of the oxy-thermal technology.
基金National Natural Science Foundation of China(Project no.21176265)Hunan Provincial Science and Technology Plan(Project no.2014GK3106).
文摘Investigation was made on the efficiency of two commercial membranes in removing via forward osmosis(FO)the low molecular weight organic compounds typical of coking wastewater. The membranes were supplied by Poten and HTI companies. The organics in the simulated coking water were indole and pyrridine. Under FO mode, the rejection to the organics by Poten membrane was around 50%, whereas that for HTI membrane was obviously higher, ranging from 65% to 74%. The response of the two membranes in terms of Water flux and reverse salt flux(RSF) towards changing feed/draw solution(DS) flow rates in FO mode showed similar tendency,but different degree. Generally, the flux in FO using HTI membranes was lower. For HTI membrane, FO operated with pressure retarded osmosis(PRO) mode was also performed and the overall rejection of the organics was slightly lower than that in FO mode. In the long term FO test within 15 days, both Poten and HTI membranes displayed flux reduction and rejection enhancement. But the variation with Poten membrane was much more obvious. Discussion was carried out about the reasons and the mechanisms behind the FO performance difference between two membranes and the variation in flux and rejection with operation conditions. Characterizations by SEM, FTIR, AFM, XRD and XPS were tried to support the proposed explanations.
基金support for this work from National Ministry of Education(No.NCET-10-878)Shaanxi Province(No.2011ZKC4-08,2009ZDKG-70)Northwest University(10YSY08)
文摘The coke deposition on HZSM-5/SAPO-34 composite catalysts has been studied in the conversion of ethanol to propylene. The HZSM-5/SAPO-34 composite catalysts were synthesized by hydrothermal method(ZS-HS) and fully blending(ZS-MM). The used catalysts were characterized by XRD, N_2 adsorption–desorption, TGA, TPO, elemental analysis, FTIR and XPS. The coking kinetics on both ZS-HS and ZS-MM has been investigated and their coking rate equations were obtained. The used ZS-MM catalyst had higher amount of coke and lower nC:nHthan the used ZS-HS. 90% of the coke was deposited in the micropores of ZS-HS, while almost 45% of the coke located in the micropores of ZS-MM. The coke deposited on ZS-HS catalyst was mainly graphite-like carbon species, whereas dehydrogenated coke species was the major on ZS-MM. The coking activation energy of ZS-MM was lower than that of ZS-HS, and the coking rate on ZS-MM was faster than on ZS-HS. In addition, the regeneration of ZS-MM catalyst showed that it had a good hydrothermal stability. The differences on coking behaviors on the two catalysts were due to their different acidic properties and textures.
