The self-reforming of coke oven gas(COG)in a gas-based shaft furnace was investigated,employing metallized iron as a catalyst.Thermodynamic analyses,supported by FactSage 8.3 calculations and regression modeling,were ...The self-reforming of coke oven gas(COG)in a gas-based shaft furnace was investigated,employing metallized iron as a catalyst.Thermodynamic analyses,supported by FactSage 8.3 calculations and regression modeling,were used to investigate the effects of temperature(700–1100℃),CO_(2)(3%–10%),and H_(2)O(1%–9%)concentrations on CH_(4) conversion efficiency.Results indicate that CH_(4) conversion exceeds 90%at temperatures above 1000℃,with CO_(2) and H_(2)O concentrations at 9%and 5%,respectively.During the reforming process,introducing CO_(2) provides additional oxygen,facilitating the oxidation of CH_(4),while H_(2)O enhances H_(2) production through the steam reforming pathway.Experimental findings reveal a CH_(4) conversion of 85.83%with a H_(2)/CO ratio of 5.44 at 1050℃.In addition,an optimal H_(2)O concentration of 6%yields the highest CH_(4) conversion of 84.24%,while CO_(2) exhibits minimal effects on promoting the reforming process.Increasing the metallization rate of pellets from 43%to 92%significantly enhances CH_(4) reforming.This is mainly due to the fact that metallized iron is vital in promoting CH_(4) dissociation and improving syngas yield by providing active sites for the redox cycle of CO_(2) and H_(2)O.展开更多
The removal of H_(2)S from coke oven gas (COG) is an important issue for the further utilization of COG. Zeolites could be used for industrial desulfurization owing to their high thermal stability and regenerability. ...The removal of H_(2)S from coke oven gas (COG) is an important issue for the further utilization of COG. Zeolites could be used for industrial desulfurization owing to their high thermal stability and regenerability. However, further analysis on the kinetics of deep desulfurization using zeolites is necessary to provide relevant information for industrial design. In this study, the desulfurization breakthrough curves of faujasite (FAU) zeolite in COG were measured using a fixed bed reactor. The adsorption isotherm was investigated using the Langmuir, Freundlich, Temkin, Dubinin-Radushkevich models. The adsorption saturated capacity of H_(2)S was inversely related to the temperature. The results show that the Langmuir model best fits the adsorption isotherm with a lower value of root-mean-square-error (RMSE) and Chi-Square (χ^(2)), and the calculated activation energy is 14.62 kJ·mol^(−1). The adsorption kinetics were investigated using pseudo-first-order (PFO), pseudo-second-order (PSO), Bangham and Weber-Morris models. The Bangham model fitted the kinetic data well, indicating that pore diffusion is an influential factor in the adsorption process. The Weber-Morris model suggests that the adsorption rate was not solely determined by the pore diffusion, but was also influenced by the active site on the FAU zeolite. The adsorption breakthrough curves under different gas flow rates were fitted using the bed depth service time (BDST) model, and it provides an accurate prediction of the breakthrough time with a small relative error. The results of thermodynamic analysis demonstrated the feasibility and spontaneity (ΔG<0) and exothermic (ΔH<0) nature of the adsorption process of the FAU zeolite for H_(2)S under COG.展开更多
The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets(CVTP)with Cr2O3 addition were studied,and the reduction swelling index(RSI)and compressive strength(CS)of t...The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets(CVTP)with Cr2O3 addition were studied,and the reduction swelling index(RSI)and compressive strength(CS)of the reduced CVTP with simulated coke oven gas(COG)injection were investigated.The results showed that the CS of the CVTP decreases and the porosity of the CVTP increases with increasing amount of Cr2O3 added.The Cr2O3 mainly exists in the form of(Cr,Fe)2O3 solid solution in the CVTP and as Fe-Cr in the reduced CVTP.The CS of the reduced CVTP increases and the RSI of the reduced CVTP decreases with increasing amount of Cr2O3 added.The limited aggregation and diffusion of metallic iron contribute to the formation of dense lamellar crystals,which leads to the slight decrease for reduction swelling behavior of reduced CVTP.This work provides a theoretical and technical basis for the utilization of CVTP and other Cr-bearing ores such as chromite with COG recycling technology.展开更多
Hydrogen amplification from simulated hot coke oven gas （HCOG） was investigated in a BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） membrane reactor combined with a Ru-Ni/Mg（Al）O catalyst by the partial oxidation of hydrocarbon...Hydrogen amplification from simulated hot coke oven gas （HCOG） was investigated in a BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） membrane reactor combined with a Ru-Ni/Mg（Al）O catalyst by the partial oxidation of hydrocarbon compounds under atmospheric pressure. Under optimized reaction conditions, the dense oxygen permeable membrane had an oxygen permeation flux around 13.3 ml/（cm^2·min）. By reforming of the toluene and methane, the amount of H2 in the reaction effluent gas was about 2 times more than that of original H2 in simulated HCOG. The Rn-Ni/Mg（Al）O catalyst used in the membrane reactor possessed good catalytic activity and resistance to coking. After the activity test, a small amount of whisker carbon was observed on the used catalyst, and most of them could be removed in the hydrogen-rich atmosphere, implying that the carbon deposition formed on the catalyst might be a reversible process.展开更多
Perovskite-type oxygen-permeable membrane reactors of BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） packed with Ru-based catalyst had high oxygen permeability and could be used for hydrogen production by partial oxidation of metha...Perovskite-type oxygen-permeable membrane reactors of BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） packed with Ru-based catalyst had high oxygen permeability and could be used for hydrogen production by partial oxidation of methane in coke oven gas （COG）. At 1173 K, 94% of methane conversion, 85% of H2 selectivity, 107% of CO selectivity, and as high as 15.4 mL·cm^-2·min^-1 of oxygen permeation flux were obtained. The BCFNO membrane itself had poor catalytic activity to partial oxidation of CH4 in COG. During continuous operation for 70 h at 1173 K, no degradation of the membrane reaction performance was observed. XRD and SEM characterization also demonstrated that the BCFNO membrane reactor exhibited good stability in partial oxidation of methane in COG.展开更多
基金financially supported by the National Natural Science Foundation of China(No.52004339)the Key Research and Development Project of Hunan Province,China(No.2022SK2075)+1 种基金China Baowu Low Carbon Metallurgy Innovation Foundation(BWLCF202216)Central South University Graduate Student Independent Exploration and Innovation Project(2024ZZTS0378).
文摘The self-reforming of coke oven gas(COG)in a gas-based shaft furnace was investigated,employing metallized iron as a catalyst.Thermodynamic analyses,supported by FactSage 8.3 calculations and regression modeling,were used to investigate the effects of temperature(700–1100℃),CO_(2)(3%–10%),and H_(2)O(1%–9%)concentrations on CH_(4) conversion efficiency.Results indicate that CH_(4) conversion exceeds 90%at temperatures above 1000℃,with CO_(2) and H_(2)O concentrations at 9%and 5%,respectively.During the reforming process,introducing CO_(2) provides additional oxygen,facilitating the oxidation of CH_(4),while H_(2)O enhances H_(2) production through the steam reforming pathway.Experimental findings reveal a CH_(4) conversion of 85.83%with a H_(2)/CO ratio of 5.44 at 1050℃.In addition,an optimal H_(2)O concentration of 6%yields the highest CH_(4) conversion of 84.24%,while CO_(2) exhibits minimal effects on promoting the reforming process.Increasing the metallization rate of pellets from 43%to 92%significantly enhances CH_(4) reforming.This is mainly due to the fact that metallized iron is vital in promoting CH_(4) dissociation and improving syngas yield by providing active sites for the redox cycle of CO_(2) and H_(2)O.
基金support of Ningbo Fareast Tech Catalyst Engineering Co.,Ltd,the National Natural Science Foundation of China(22478275)Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering(2022SX-TD014).
文摘The removal of H_(2)S from coke oven gas (COG) is an important issue for the further utilization of COG. Zeolites could be used for industrial desulfurization owing to their high thermal stability and regenerability. However, further analysis on the kinetics of deep desulfurization using zeolites is necessary to provide relevant information for industrial design. In this study, the desulfurization breakthrough curves of faujasite (FAU) zeolite in COG were measured using a fixed bed reactor. The adsorption isotherm was investigated using the Langmuir, Freundlich, Temkin, Dubinin-Radushkevich models. The adsorption saturated capacity of H_(2)S was inversely related to the temperature. The results show that the Langmuir model best fits the adsorption isotherm with a lower value of root-mean-square-error (RMSE) and Chi-Square (χ^(2)), and the calculated activation energy is 14.62 kJ·mol^(−1). The adsorption kinetics were investigated using pseudo-first-order (PFO), pseudo-second-order (PSO), Bangham and Weber-Morris models. The Bangham model fitted the kinetic data well, indicating that pore diffusion is an influential factor in the adsorption process. The Weber-Morris model suggests that the adsorption rate was not solely determined by the pore diffusion, but was also influenced by the active site on the FAU zeolite. The adsorption breakthrough curves under different gas flow rates were fitted using the bed depth service time (BDST) model, and it provides an accurate prediction of the breakthrough time with a small relative error. The results of thermodynamic analysis demonstrated the feasibility and spontaneity (ΔG<0) and exothermic (ΔH<0) nature of the adsorption process of the FAU zeolite for H_(2)S under COG.
基金financially supported by the National Natural Science Foundation of China (Nos.51674084, 51174051, and 51574082)
文摘The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets(CVTP)with Cr2O3 addition were studied,and the reduction swelling index(RSI)and compressive strength(CS)of the reduced CVTP with simulated coke oven gas(COG)injection were investigated.The results showed that the CS of the CVTP decreases and the porosity of the CVTP increases with increasing amount of Cr2O3 added.The Cr2O3 mainly exists in the form of(Cr,Fe)2O3 solid solution in the CVTP and as Fe-Cr in the reduced CVTP.The CS of the reduced CVTP increases and the RSI of the reduced CVTP decreases with increasing amount of Cr2O3 added.The limited aggregation and diffusion of metallic iron contribute to the formation of dense lamellar crystals,which leads to the slight decrease for reduction swelling behavior of reduced CVTP.This work provides a theoretical and technical basis for the utilization of CVTP and other Cr-bearing ores such as chromite with COG recycling technology.
基金supported by the National High Technology Research and Development Program of China (Grant No. 2006AA11A189)Science and Technology Commission of Shanghai Municipality (Grant Nos. 0952NM01400 and 07DZ12036)
文摘Hydrogen amplification from simulated hot coke oven gas （HCOG） was investigated in a BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） membrane reactor combined with a Ru-Ni/Mg（Al）O catalyst by the partial oxidation of hydrocarbon compounds under atmospheric pressure. Under optimized reaction conditions, the dense oxygen permeable membrane had an oxygen permeation flux around 13.3 ml/（cm^2·min）. By reforming of the toluene and methane, the amount of H2 in the reaction effluent gas was about 2 times more than that of original H2 in simulated HCOG. The Rn-Ni/Mg（Al）O catalyst used in the membrane reactor possessed good catalytic activity and resistance to coking. After the activity test, a small amount of whisker carbon was observed on the used catalyst, and most of them could be removed in the hydrogen-rich atmosphere, implying that the carbon deposition formed on the catalyst might be a reversible process.
基金supported by the National High-Tech Research and Development Program of China (No. 2006AA11A189)the Research on Novel Technology of Hydrogen Production from Oven Gas from Metallurgy Process (No. 07DZ12036)the National Key Technolo-gies Research and Development Program of China (No. 2006BA103A05)
文摘Perovskite-type oxygen-permeable membrane reactors of BaCo0.7Fe0.2Nb0.1O3-δ （BCFNO） packed with Ru-based catalyst had high oxygen permeability and could be used for hydrogen production by partial oxidation of methane in coke oven gas （COG）. At 1173 K, 94% of methane conversion, 85% of H2 selectivity, 107% of CO selectivity, and as high as 15.4 mL·cm^-2·min^-1 of oxygen permeation flux were obtained. The BCFNO membrane itself had poor catalytic activity to partial oxidation of CH4 in COG. During continuous operation for 70 h at 1173 K, no degradation of the membrane reaction performance was observed. XRD and SEM characterization also demonstrated that the BCFNO membrane reactor exhibited good stability in partial oxidation of methane in COG.
