Articles in press have been peer-reviewed and accepted, which are not yet assigned to volumes /issues, but are citable by Digital Object Identifier (DOI).
CO2 Assistant Oxidative Dehydrogenation of Isobutane to Isobutene Catalyzed by ZnCaZr Solid Solution
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doi: 10.19906/j.cnki.JFCT.2024003
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doi: 10.1016/S1872-5813(24)60443-3
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doi: 10.19906/j.cnki.JFCT.2024012
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doi: 10.19906/j.cnki.JFCT.2024004
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doi: 10.1016/S1872-5813(23)60390-1
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doi: 10.19906/j.cnki.JFCT.2023084
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doi: 10.1016/S1872-5813(23)60403-7
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doi: 10.19906/j.cnki.JFCT.2023087
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doi: 10.19906/j.cnki.JFCT.2023085
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doi: 10.1016/S1872-5813(23)60402-5
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doi: 10.1016/S1872-5813(24)60444-5
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doi: 10.1016/S1872-5813(24)60435-4
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doi: 10.1016/S1872-5813(24)60445-7
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doi: 10.19906/j.cnki.JFCT.2024014
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doi: 10.1016/S1872-5813(24)60442-1
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doi: 10.19906/j.cnki.JFCT.2024010
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doi: 10.19906/j.cnki.JFCT.2024002
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doi: 10.1016/S1872-5813(23)60408-6
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doi: 10.1016/S1872-5813(23)60410-4
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doi: 10.1016/S1872-5813(24)60433-0
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doi: 10.1016/S1872-5813(23)60412-8
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doi: 10.19906/j.cnki.JFCT.2023082
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doi: 10.1016/S1872-5813(24)60437-8
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doi: 10.19906/j.cnki.JFCT.2024013
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The research progress of formation and control on the N-containing compound of biomass pyrolysis gas
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doi: 10.19906/j.cnki.JFCT.2023090
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doi: 10.1016/S1872-5813(24)60432-9
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doi: 10.1016/S1872-5813(24)60446-9
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doi: 10.19906/j.cnki.JFCT.2023089
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doi: 10.19906/j.cnki.JFCT.2023083
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doi: 10.19906/j.cnki.JFCT.2023079
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doi: 10.1016/S1872-5813(23)60400-1
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doi: 10.1016/S1872-5813(24)60439-1
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doi: 10.1016/S1872-5813(24)60440-8
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doi: 10.19906/j.cnki.JFCT.2024005
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doi: 10.19906/j.cnki.JFCT.2024007
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doi: 10.1016/S1872-5813(23)60411-6
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doi: 10.1016/S1872-5813(24)60438-X
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doi: 10.19906/j.cnki.JFCT.2024008
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doi: 10.19906/j.cnki.JFCT.2023078
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doi: 10.1016/S1872-5813(24)60434-2
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doi: 10.19906/j.cnki.JFCT.2023081
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doi: 10.19906/j.cnki.JFCT.2023076
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doi: 10.19906/j.cnki.JFCT.2024011
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doi: 10.1016/S1872-5813(24)60441-X
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doi: 10.19906/j.cnki.JFCT.2024009
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doi: 10.1016/S1872-5813(23)60409-8
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doi: 10.1016/S1872-5813(24)60436-6
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doi: 10.19906/j.cnki.JFCT.2023088
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doi: 10.1016/S1872-5813(23)60406-2
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doi: 10.1016/S1872-5813(23)60407-4
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doi: 10.1016/S1872-5813(23)60405-0
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doi: 10.19906/j.cnki.JFCT.2024001
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2024, 52(4): 461-480.
doi: 10.19906/j.cnki.JFCT.2023061
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Compared with ethanol, higher alcohols have the advantages of high cetane number, high energy density, non corrosiveness to engine parts, immiscibility with water, good stability, and other advantages as fuel or fuel additive directly. The conversion of fermentation bioethanol into more valuable higher alcohols has attracted widespread attention. This paper reviewed the research progress of bioethanol to higher alcohols at home and abroad in recent years, including the research and development of metal oxides, hydroxyapatite (HAP) and supported metal catalysts. Finally, the current challenges and future research trends of bioethanol to higher alcohols are summarized and prospected, pointing out that the development of multifunctional catalysts is the focus of future research, and Aldol condensation is an effective strategy to further improve the conversion and selectivity of bioethanol to higher alcohols.
Compared with ethanol, higher alcohols have the advantages of high cetane number, high energy density, non corrosiveness to engine parts, immiscibility with water, good stability, and other advantages as fuel or fuel additive directly. The conversion of fermentation bioethanol into more valuable higher alcohols has attracted widespread attention. This paper reviewed the research progress of bioethanol to higher alcohols at home and abroad in recent years, including the research and development of metal oxides, hydroxyapatite (HAP) and supported metal catalysts. Finally, the current challenges and future research trends of bioethanol to higher alcohols are summarized and prospected, pointing out that the development of multifunctional catalysts is the focus of future research, and Aldol condensation is an effective strategy to further improve the conversion and selectivity of bioethanol to higher alcohols.
2024, 52(4): 481-495.
doi: 10.1016/S1872-5813(23)60401-3
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Aromatic hydrocarbons, especially monocyclic aromatic hydrocarbons such as benzene, toluene, and xylene (BTX), are important basic raw materials in the chemical industry, which are mainly derived from the catalytic reforming and thermal cracking of fossil fuels. The co-catalytic pyrolysis of biomass and plastic to produce aromatics has the advantages of high efficiency, environmental protection, low cost, and high selectivity. It can solve the problems of pyrolysis products such as high oxygen content, low aromatics yield, and low selectivity, which are caused by the characteristics of biomass rich in oxygen and poor in hydrogen. This article reviewed the research progress of co-catalytic pyrolysis of biomass and plastics to prepare aromatic compounds. Firstly, the types of raw materials for co-catalytic pyrolysis were introduced, and then the co-catalytic pyrolysis catalysts were emphasized. The reaction mechanisms of co-catalytic pyrolysis of biomass and plastics, such as the synthesis of dienes and hydrocarbon pool synergy were summarized. Finally, the future research focus and development direction of co-catalytic pyrolysis of biomass and plastics were proposed, which is developing the highly active and stable modified molecular sieve catalysts in order to improve the aromatics yield.
Aromatic hydrocarbons, especially monocyclic aromatic hydrocarbons such as benzene, toluene, and xylene (BTX), are important basic raw materials in the chemical industry, which are mainly derived from the catalytic reforming and thermal cracking of fossil fuels. The co-catalytic pyrolysis of biomass and plastic to produce aromatics has the advantages of high efficiency, environmental protection, low cost, and high selectivity. It can solve the problems of pyrolysis products such as high oxygen content, low aromatics yield, and low selectivity, which are caused by the characteristics of biomass rich in oxygen and poor in hydrogen. This article reviewed the research progress of co-catalytic pyrolysis of biomass and plastics to prepare aromatic compounds. Firstly, the types of raw materials for co-catalytic pyrolysis were introduced, and then the co-catalytic pyrolysis catalysts were emphasized. The reaction mechanisms of co-catalytic pyrolysis of biomass and plastics, such as the synthesis of dienes and hydrocarbon pool synergy were summarized. Finally, the future research focus and development direction of co-catalytic pyrolysis of biomass and plastics were proposed, which is developing the highly active and stable modified molecular sieve catalysts in order to improve the aromatics yield.
2024, 52(4): 496-511.
doi: 10.1016/S1872-5813(23)60404-9
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Chemical conversion of greenhouse gas CO2 into value-added oxygenates such as ethanol, acetic acid, propanal, propionic acid, butanol, etc. is challenging due to the complexity of C−C coupling and the uncontrollable bonding. In this review, recent research progresses on the synthesis of multi-carbon oxygenates from CO2 in fixed bed reactor are provided. Firstly, the reaction mechanisms of CO2 hydrogenation are summarized. Then, the potential catalysts applied in one-step or tandem CO2 hydrogenation, dry reforming with light hydrocarbons and hydroformylation were introduced over metal carbides, alkali metal modified single or binary metal catalysts such as Cu, Fe, Co, Rh, etc. The reaction mechanism over different catalysts were further elaborated. Finally, the problems and outlook are discussed.
Chemical conversion of greenhouse gas CO2 into value-added oxygenates such as ethanol, acetic acid, propanal, propionic acid, butanol, etc. is challenging due to the complexity of C−C coupling and the uncontrollable bonding. In this review, recent research progresses on the synthesis of multi-carbon oxygenates from CO2 in fixed bed reactor are provided. Firstly, the reaction mechanisms of CO2 hydrogenation are summarized. Then, the potential catalysts applied in one-step or tandem CO2 hydrogenation, dry reforming with light hydrocarbons and hydroformylation were introduced over metal carbides, alkali metal modified single or binary metal catalysts such as Cu, Fe, Co, Rh, etc. The reaction mechanism over different catalysts were further elaborated. Finally, the problems and outlook are discussed.
2024, 52(4): 512-524.
doi: 10.1016/S1872-5813(23)60397-4
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Ammonia is not only the main raw material of nitrogen fertilizer production, but also one of the energy carriers for the storage and conversion process of renewable energy. Therefore, the development of a mild ammonia synthesis technology has become an important research topic in recent years. The chemical looping ammonia synthesis technology decouples the ammonia synthesis reaction into several steps, including the nitrogen fixation and the ammonia release, which has the advantages of easy operation, mild reaction, and low energy consumption. As the key to the chemical looping ammonia synthesis, nitrogen carriers play the role of transferring energy and nitrogen species. However, the current low nitrogen fixation efficiency of nitrogen carriers severely limits the development of the chemical looping ammonia synthesis technology. Therefore, this article reviews the research on the design, preparation and application of nitrogen carriers for the chemical looping ammonia synthesis. Firstly, the design theory of nitrogen carrier is summarized; secondly, the current research status of nitrogen carrier is introduced, with a focus on how to improve the ammonia production rate of nitrogen carrier and the utilization rate of lattice nitrogen; finally, the opportunities and challenges of chemical looping ammonia synthesis technology are discussed, which provide a reference for the design and development of nitrogen carrier in the future.
Ammonia is not only the main raw material of nitrogen fertilizer production, but also one of the energy carriers for the storage and conversion process of renewable energy. Therefore, the development of a mild ammonia synthesis technology has become an important research topic in recent years. The chemical looping ammonia synthesis technology decouples the ammonia synthesis reaction into several steps, including the nitrogen fixation and the ammonia release, which has the advantages of easy operation, mild reaction, and low energy consumption. As the key to the chemical looping ammonia synthesis, nitrogen carriers play the role of transferring energy and nitrogen species. However, the current low nitrogen fixation efficiency of nitrogen carriers severely limits the development of the chemical looping ammonia synthesis technology. Therefore, this article reviews the research on the design, preparation and application of nitrogen carriers for the chemical looping ammonia synthesis. Firstly, the design theory of nitrogen carrier is summarized; secondly, the current research status of nitrogen carrier is introduced, with a focus on how to improve the ammonia production rate of nitrogen carrier and the utilization rate of lattice nitrogen; finally, the opportunities and challenges of chemical looping ammonia synthesis technology are discussed, which provide a reference for the design and development of nitrogen carrier in the future.
2024, 52(4): 525-535.
doi: 10.1016/S1872-5813(23)60393-7
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Coal and residuum are first co-pyrolyzed, and then hydrogenated into small molecule products during co-liquefaction. Therefore, clarifying influence of residuum on coal pyrolysis performance is an important thermochemical basis for regulating the process. The co-pyrolysis behavior of atmospheric residuum (AR) and Naomaohu coal (NMH) were investigated by TG, TG-FTIR and distributed activation energy model. The results showed that the peak temperature of the maximum rate of weight loss for the co-pyrolysis process was reduced by 7 °C compared with the theoretical value calculated by weighted average of AR and NMH pyrolysis alone, while the weight loss increased by 3%, the average activation energy decreased by 23.6 kJ/mol. In addition, the peak area of alkyl O-containing functional groups such as alcohols and ethers increased, whereas those of CO and CO2 decreased, suggesting that AR had a positive effect on NMH pyrolysis. Meanwhile, alkyl radicals from AR decomposition would combine with O-containing radicals generated from coal pyrolysis, thus resulting in a decrease of CO and CO2 by inhibiting breakage of carboxyl groups. This work will provide a scientific evaluation basis for revealing the influence of residuum on composition of coal liquefaction product during co-liquefaction.
Coal and residuum are first co-pyrolyzed, and then hydrogenated into small molecule products during co-liquefaction. Therefore, clarifying influence of residuum on coal pyrolysis performance is an important thermochemical basis for regulating the process. The co-pyrolysis behavior of atmospheric residuum (AR) and Naomaohu coal (NMH) were investigated by TG, TG-FTIR and distributed activation energy model. The results showed that the peak temperature of the maximum rate of weight loss for the co-pyrolysis process was reduced by 7 °C compared with the theoretical value calculated by weighted average of AR and NMH pyrolysis alone, while the weight loss increased by 3%, the average activation energy decreased by 23.6 kJ/mol. In addition, the peak area of alkyl O-containing functional groups such as alcohols and ethers increased, whereas those of CO and CO2 decreased, suggesting that AR had a positive effect on NMH pyrolysis. Meanwhile, alkyl radicals from AR decomposition would combine with O-containing radicals generated from coal pyrolysis, thus resulting in a decrease of CO and CO2 by inhibiting breakage of carboxyl groups. This work will provide a scientific evaluation basis for revealing the influence of residuum on composition of coal liquefaction product during co-liquefaction.
2024, 52(4): 536-544.
doi: 10.1016/S1872-5813(23)60387-1
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The development of cost-effective and efficient catalysts plays a critical role in the selective hydrodeoxygenation of lignin derivatives for lignin valorization. Herein, we reported “metal-acid” bifunctional catalysts (Ni/Ti-SBA-15) consist of Ni nanoparticles highly dispersed on Ti doped SBA-15, which achieved 100% vanillin conversion and 96.46% selectivity of 2-methoxy-4-methylphenol (MMP) under mild conditions. Characterizations were employed to reveal the morphology and physicochemical properties of the catalysts. The results indicated that doping of Ti species not only increased the number of acidic sites but also promoted the high dispersion of Ni nanoparticles on the support. This research provides a novel concept for the synthesis of cost-effective and efficient catalysts, which contributes to the environmentally friendly and economical conversion of biomass derivatives.
The development of cost-effective and efficient catalysts plays a critical role in the selective hydrodeoxygenation of lignin derivatives for lignin valorization. Herein, we reported “metal-acid” bifunctional catalysts (Ni/Ti-SBA-15) consist of Ni nanoparticles highly dispersed on Ti doped SBA-15, which achieved 100% vanillin conversion and 96.46% selectivity of 2-methoxy-4-methylphenol (MMP) under mild conditions. Characterizations were employed to reveal the morphology and physicochemical properties of the catalysts. The results indicated that doping of Ti species not only increased the number of acidic sites but also promoted the high dispersion of Ni nanoparticles on the support. This research provides a novel concept for the synthesis of cost-effective and efficient catalysts, which contributes to the environmentally friendly and economical conversion of biomass derivatives.
2024, 52(4): 545-552.
doi: 10.1016/S1872-5813(23)60394-9
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Calcium cerium-based catalysts with different Ca:Ce molar ratio prepared by sol-gel method were characterized by XRD, N2 adsorption-desorption, FT-IR, XPS and CO2-TPD, and evaluated the activity for dimethyl carbonate (DMC) synthesis from propylene carbonate (PC) and methanol. The results indicated that more surface oxygen vacancies and more moderate basic sites are beneficial for methanol activation and thus leading to better catalytic activity. The PC conversion was 91.1% with DMC selectivity of 91.72% over 0.9CaCe under the reaction conditions-reaction time of 2 h, reaction temperature of 40 °C, methanol to propylene carbonate molar ratio of 15:1 and catalyst amount of 4% relative to the amount of PC.
Calcium cerium-based catalysts with different Ca:Ce molar ratio prepared by sol-gel method were characterized by XRD, N2 adsorption-desorption, FT-IR, XPS and CO2-TPD, and evaluated the activity for dimethyl carbonate (DMC) synthesis from propylene carbonate (PC) and methanol. The results indicated that more surface oxygen vacancies and more moderate basic sites are beneficial for methanol activation and thus leading to better catalytic activity. The PC conversion was 91.1% with DMC selectivity of 91.72% over 0.9CaCe under the reaction conditions-reaction time of 2 h, reaction temperature of 40 °C, methanol to propylene carbonate molar ratio of 15:1 and catalyst amount of 4% relative to the amount of PC.
2024, 52(4): 553-564.
doi: 10.1016/S1872-5813(23)60399-8
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The costly separation of 1,2-propanediol (1,2-PDO), an unavoidable byproduct in the hydrogenation of dimethyl oxalate (DMO), significantly hampers the economic viability of coal-to-ethylene glycol (EG) technology. To address this challenge, the formation mechanism of the side product 1,2-PDO on the Cu(111) and Cu2O(111) surfaces during DMO hydrogenation was investigated, which focused on the active sites of copper catalyst and the dominant pathway through density functional theory calculation. The thermodynamics of each elementary step and the adsorption behavior of various species involved in the reaction network along with the local density of states and charge density difference were systematically analyzed. The results indicate that 1,2-PDO is generated more favorably on the Cu2O(111) surface than that on the Cu(111) surface, owing to the Lewis acid-base pairs, i.e. ${\rm{Cu}}_{{\rm{us}}}^{+} $ and ${\rm{O}}_{{\rm{suf}}}^- $ sites, present on the Cu2O(111) surface, which strengthens the binding of reactants, products, and reaction intermediates to the substrate. EG reacts primarily with methanol (MeOH) to form 1,2-PDO through Guerbet alcohol condensation reaction through three consecutive steps: alcohol dehydrogenation, aldol condensation, and unsaturated aldehyde hydrogenation. The ${\rm{O}}_{{\rm{suf}}}^- $ sites promote the dehydrogenation of alcohols into aldehydes, the generation of enolates during aldol condensation and the hydrogenation of unsaturated aldehydes, while the ${\rm{Cu}}_{{\rm{us}}}^{+} $ sites are responsible for the C–C coupling reaction. These findings may shed light on the mechanism of 1,2-PDO formation over Cu catalyst and provide fundamental knowledge for the development of more efficient catalysts and process optimization.
The costly separation of 1,2-propanediol (1,2-PDO), an unavoidable byproduct in the hydrogenation of dimethyl oxalate (DMO), significantly hampers the economic viability of coal-to-ethylene glycol (EG) technology. To address this challenge, the formation mechanism of the side product 1,2-PDO on the Cu(111) and Cu2O(111) surfaces during DMO hydrogenation was investigated, which focused on the active sites of copper catalyst and the dominant pathway through density functional theory calculation. The thermodynamics of each elementary step and the adsorption behavior of various species involved in the reaction network along with the local density of states and charge density difference were systematically analyzed. The results indicate that 1,2-PDO is generated more favorably on the Cu2O(111) surface than that on the Cu(111) surface, owing to the Lewis acid-base pairs, i.e. ${\rm{Cu}}_{{\rm{us}}}^{+} $ and ${\rm{O}}_{{\rm{suf}}}^- $ sites, present on the Cu2O(111) surface, which strengthens the binding of reactants, products, and reaction intermediates to the substrate. EG reacts primarily with methanol (MeOH) to form 1,2-PDO through Guerbet alcohol condensation reaction through three consecutive steps: alcohol dehydrogenation, aldol condensation, and unsaturated aldehyde hydrogenation. The ${\rm{O}}_{{\rm{suf}}}^- $ sites promote the dehydrogenation of alcohols into aldehydes, the generation of enolates during aldol condensation and the hydrogenation of unsaturated aldehydes, while the ${\rm{Cu}}_{{\rm{us}}}^{+} $ sites are responsible for the C–C coupling reaction. These findings may shed light on the mechanism of 1,2-PDO formation over Cu catalyst and provide fundamental knowledge for the development of more efficient catalysts and process optimization.
2024, 52(4): 565-576.
doi: 10.19906/j.cnki.JFCT.2023080
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The MnCu/Ce catalyst with a lower Cu content was prepared by co-impregnation method, and then was characterized by XRD, BET, H2-TPR, XPS and CO2-TPD. The effects of calcination temperature on the structure and properties of the catalyst and the preferential oxidation of CO in a hydrogen-rich atmosphere containing CO2 were investigated. The results indicated that Cu/Mn-O-Ce solid solution was formed in all MnCu/Ce catalysts. Of theses sample, the one calcined at 600 ℃ had strong interaction among Mn, Cu and Ce, formed more ternary oxide solid solution with more oxygen vacancies/Ce3+, and revealed good CO-Prox activity. In addition, it was found that the addition of different percentage of Ar had little effects on the CO-Prox activity of the catalyst, while the space velocity and oxygen excess coefficient had great effects on the catalytic performance, and the presence of CO2 in the reaction feedstock gas had a negative effect on the CO-Prox reaction. At an oxygen excess coefficient of 1.2 and the space velocity of 20266−30400 mL/(g·h), the highest CO conversion rate reached 94.7%.
The MnCu/Ce catalyst with a lower Cu content was prepared by co-impregnation method, and then was characterized by XRD, BET, H2-TPR, XPS and CO2-TPD. The effects of calcination temperature on the structure and properties of the catalyst and the preferential oxidation of CO in a hydrogen-rich atmosphere containing CO2 were investigated. The results indicated that Cu/Mn-O-Ce solid solution was formed in all MnCu/Ce catalysts. Of theses sample, the one calcined at 600 ℃ had strong interaction among Mn, Cu and Ce, formed more ternary oxide solid solution with more oxygen vacancies/Ce3+, and revealed good CO-Prox activity. In addition, it was found that the addition of different percentage of Ar had little effects on the CO-Prox activity of the catalyst, while the space velocity and oxygen excess coefficient had great effects on the catalytic performance, and the presence of CO2 in the reaction feedstock gas had a negative effect on the CO-Prox reaction. At an oxygen excess coefficient of 1.2 and the space velocity of 20266−30400 mL/(g·h), the highest CO conversion rate reached 94.7%.
2021, 49(2): 129-136.
doi: 10.1016/S1872-5813(21)60011-7
摘要:
气流床气化过程中产生的细渣含碳量很高,目前多以填埋的方式进行处理,将细渣用于循环流化床锅炉掺烧有望为细渣处理提供有利的技术。本研究选用宁东能源化工基地典型气化工艺GE、OMB及GSP产生的气化细渣为研究对象,利用物理吸附仪、激光拉曼及热重分析仪等仪器,系统研究了气化细渣中残炭的结构特征与燃烧特性。结果表明,原始气化细渣中的物质可分为黏结球形颗粒、多孔不规则颗粒与孤立的大球形颗粒,而酸洗后的气化细渣多以疏松细小的颗粒和多孔不规则块状颗粒存在;细渣中残炭的孔径尺寸主要分布在4−8 nm,且比表面积与残炭的活性位点大小顺序均为:GE > OMB > GSP;GE渣中残炭结构有序度最低,无定形炭结构最多,GSP则相反;GE渣中残炭燃烧速率最快,主要是由于GE渣中残炭有较大的比表面积、较多的无定形炭结构及较高的的活性位点,且GE渣中残炭的综合燃烧指数为5.26 × 10−7%2/(min2·℃3)。
气流床气化过程中产生的细渣含碳量很高,目前多以填埋的方式进行处理,将细渣用于循环流化床锅炉掺烧有望为细渣处理提供有利的技术。本研究选用宁东能源化工基地典型气化工艺GE、OMB及GSP产生的气化细渣为研究对象,利用物理吸附仪、激光拉曼及热重分析仪等仪器,系统研究了气化细渣中残炭的结构特征与燃烧特性。结果表明,原始气化细渣中的物质可分为黏结球形颗粒、多孔不规则颗粒与孤立的大球形颗粒,而酸洗后的气化细渣多以疏松细小的颗粒和多孔不规则块状颗粒存在;细渣中残炭的孔径尺寸主要分布在4−8 nm,且比表面积与残炭的活性位点大小顺序均为:GE > OMB > GSP;GE渣中残炭结构有序度最低,无定形炭结构最多,GSP则相反;GE渣中残炭燃烧速率最快,主要是由于GE渣中残炭有较大的比表面积、较多的无定形炭结构及较高的的活性位点,且GE渣中残炭的综合燃烧指数为5.26 × 10−7%2/(min2·℃3)。
2021, 49(7): 998-1013.
doi: 10.1016/S1872-5813(21)60040-3
摘要:
利用CaO基吸附剂直接从高温烟气中捕集CO2因成本低、吸附性能好等优点成为CCUS(碳捕集、利用与封存)的重要技术之一。但CaO基吸附剂在碳酸化/煅烧吸脱附循环过程中存在易烧结的问题,导致其吸附性能急剧下降。本研究针对CaO基吸附剂全面总结了其吸附CO2的动力学、热力学及烧结机理,并重点综述了世界各国研究者在CaO基吸附剂抗烧结改性方面所做的研究,指出了各种方法的优点及其局限性。结果表明,水合作用改性可使吸附剂崩塌而获得更大的比表面积;酸溶液改性会在制备过程产生更多的气体和小分子物质提高吸附剂孔隙率;掺杂改性可以促进CaO对CO2的吸附和扩散,还可作为骨架分离CaO颗粒。经比较,掺杂改性工艺简单、性能好,是比较有前景的改性方法,以含钙固废制备抗烧结改性吸附剂是发展方向。
利用CaO基吸附剂直接从高温烟气中捕集CO2因成本低、吸附性能好等优点成为CCUS(碳捕集、利用与封存)的重要技术之一。但CaO基吸附剂在碳酸化/煅烧吸脱附循环过程中存在易烧结的问题,导致其吸附性能急剧下降。本研究针对CaO基吸附剂全面总结了其吸附CO2的动力学、热力学及烧结机理,并重点综述了世界各国研究者在CaO基吸附剂抗烧结改性方面所做的研究,指出了各种方法的优点及其局限性。结果表明,水合作用改性可使吸附剂崩塌而获得更大的比表面积;酸溶液改性会在制备过程产生更多的气体和小分子物质提高吸附剂孔隙率;掺杂改性可以促进CaO对CO2的吸附和扩散,还可作为骨架分离CaO颗粒。经比较,掺杂改性工艺简单、性能好,是比较有前景的改性方法,以含钙固废制备抗烧结改性吸附剂是发展方向。
2021, 49(8): 1057-1076.
doi: 10.1016/S1872-5813(21)60093-2
摘要:
Waste gasification has the potential to contribute to China’s transition towards carbon neutrality and zero waste cities via the recirculation of waste as secondary carbon feedstock for the production of chemicals with lower/and or zero carbon footprint, green hydrogen with zero carbon footprint and CO2-neutral synthetic liquid fuels. With China’s significant coal gasification capacity and associated experiences and expertise, Coal-to-X could act as a bridge to Waste-to-X for carbon intensive sectors such as the waste management, chemical production and mobility sectors. To illustrate the opportunities in these areas, this article presented highlights from dynamic global developments in waste gasification, focusing on pioneering industrial developments in Germany between 1980−2000’s as well as current international developments. Lessons learnt from previous and current waste gasification project deployment are shared and enabled the identification of problems which will have to be addressed in the transition from coal gasification towards mono-waste gasification technologies. Additionally, a qualitative evaluation of gasification technologies pointed to the strengths and weaknesses of fixed-bed, fluidized-bed and entrained-flow gasification principles in their application for waste gasification.
Waste gasification has the potential to contribute to China’s transition towards carbon neutrality and zero waste cities via the recirculation of waste as secondary carbon feedstock for the production of chemicals with lower/and or zero carbon footprint, green hydrogen with zero carbon footprint and CO2-neutral synthetic liquid fuels. With China’s significant coal gasification capacity and associated experiences and expertise, Coal-to-X could act as a bridge to Waste-to-X for carbon intensive sectors such as the waste management, chemical production and mobility sectors. To illustrate the opportunities in these areas, this article presented highlights from dynamic global developments in waste gasification, focusing on pioneering industrial developments in Germany between 1980−2000’s as well as current international developments. Lessons learnt from previous and current waste gasification project deployment are shared and enabled the identification of problems which will have to be addressed in the transition from coal gasification towards mono-waste gasification technologies. Additionally, a qualitative evaluation of gasification technologies pointed to the strengths and weaknesses of fixed-bed, fluidized-bed and entrained-flow gasification principles in their application for waste gasification.
2021, 49(9): 1294-1315.
doi: 10.1016/S1872-5813(21)60080-4
摘要:
在NH3选择性催化还原(NH3-SCR)反应中,由于具有宽温度窗口和良好的水热稳定性,金属负载型分子筛是具有广泛应用潜力的脱硝催化剂。本文综述了Cu基和Fe基分子筛催化剂在NH3-SCR领域的研究进展,总结了催化剂的结构特征和NH3-SCR性能指标,并对相应的金属活性位点和反应机理进行了归纳。此外,系统介绍了密度泛函理论(DFT)计算在NH3-SCR反应机理中的应用及反应动力学的研究方法,并对比了不同催化剂体系下的表观动力学参数,为进一步研究金属负载型分子筛催化剂的NH3-SCR反应机理提供方法与思路。
在NH3选择性催化还原(NH3-SCR)反应中,由于具有宽温度窗口和良好的水热稳定性,金属负载型分子筛是具有广泛应用潜力的脱硝催化剂。本文综述了Cu基和Fe基分子筛催化剂在NH3-SCR领域的研究进展,总结了催化剂的结构特征和NH3-SCR性能指标,并对相应的金属活性位点和反应机理进行了归纳。此外,系统介绍了密度泛函理论(DFT)计算在NH3-SCR反应机理中的应用及反应动力学的研究方法,并对比了不同催化剂体系下的表观动力学参数,为进一步研究金属负载型分子筛催化剂的NH3-SCR反应机理提供方法与思路。
2021, 49(8): 1208-1218.
doi: 10.1016/S1872-5813(21)60119-6
摘要:
The chemical and mineralogical characteristics of fly ash from a municipal solid waste incineration (MSWI) in China and the influence of processing parameters on heavy metals removal during leaching were investigated in this work. The fly ash particles had complex surface structure with limited specific surface area. The alkali chloride and metal salts in MSWI fly ash showed evidently impact on leaching efficiency. Metal leachability was related to their properties and speciation in fly ash. Water-soluble salts such as KCl, NaCl and CaCl2 in fly ash were easily washed out. In this study, removal efficiency by water washing was achieved to 93.1% for Cl, 41.4% for Na, 48.5% for K and 24.8% for Ca, respectively. Mineralogical analysis also revealed change of fly ash mineral phases and specification distribution after water washing. Under liquid to solid ratio of 40∶1 L/kg and treatment time of 120 min, the leaching process achieved high dropping yields of toxicity characteristic leaching procedure (TCLP) concentrations for Cu, Zn Cd and Pb (80%−100%), moderate dropping yields for As (30%−80%) and relatively low dropping yields of Ni (< 30%). In addition, heavy metals such as Pb and Zn in fly ash with twice water washing treatment at a low liquid-solid ratio could reach lower TCLP concentrations. The result indicated that the combination process of twice water washing and one acid washing could significantly reduce the environmental risk of MSWI fly ash.
The chemical and mineralogical characteristics of fly ash from a municipal solid waste incineration (MSWI) in China and the influence of processing parameters on heavy metals removal during leaching were investigated in this work. The fly ash particles had complex surface structure with limited specific surface area. The alkali chloride and metal salts in MSWI fly ash showed evidently impact on leaching efficiency. Metal leachability was related to their properties and speciation in fly ash. Water-soluble salts such as KCl, NaCl and CaCl2 in fly ash were easily washed out. In this study, removal efficiency by water washing was achieved to 93.1% for Cl, 41.4% for Na, 48.5% for K and 24.8% for Ca, respectively. Mineralogical analysis also revealed change of fly ash mineral phases and specification distribution after water washing. Under liquid to solid ratio of 40∶1 L/kg and treatment time of 120 min, the leaching process achieved high dropping yields of toxicity characteristic leaching procedure (TCLP) concentrations for Cu, Zn Cd and Pb (80%−100%), moderate dropping yields for As (30%−80%) and relatively low dropping yields of Ni (< 30%). In addition, heavy metals such as Pb and Zn in fly ash with twice water washing treatment at a low liquid-solid ratio could reach lower TCLP concentrations. The result indicated that the combination process of twice water washing and one acid washing could significantly reduce the environmental risk of MSWI fly ash.
2021, 49(1): 113-120.
doi: 10.1016/S1872-5813(21)60003-8
摘要:
考察了Pb对Mn-Ce/TiO2低温选择性催化还原(SCR)脱硝活性的影响,并对Pb中毒的催化剂进行了再生;结合氮吸附、SEM、XRD、FT-IR、H2-TPR和NH3-TPD等表征结果,研究了Mn-Ce/TiO2催化剂Pb中毒和再生活性恢复的原因。结果表明,Pb对Mn-Ce/TiO2催化剂脱硝活性有明显的抑制作用;当Pb的含量为11%时,Mn-Ce/TiO2催化剂在180 ℃下的脱硝效率从原来100%下降至44%。Pb在Mn-Ce/TiO2中的掺杂使得催化剂的比表面积以及活性组分Mn4+和Ce3+的含量降低,影响了氧化还原循环反应(Mn4+ + Ce3+ ↔ Mn3+ + Ce4+)的进行;此外,Pb的加入破坏了催化剂的酸性位点,阻碍了催化剂对NH3的吸附和活化。经硝酸再生后的Mn-Ce/TiO2催化剂的脱硝活性几乎完全恢复,在80–150 ℃下其脱硝活性甚至超过新鲜未中毒的催化剂,其原因主要在于硝酸再生能恢复催化剂的氧化还原能力、增大比表面积、并形成新的酸位点。
考察了Pb对Mn-Ce/TiO2低温选择性催化还原(SCR)脱硝活性的影响,并对Pb中毒的催化剂进行了再生;结合氮吸附、SEM、XRD、FT-IR、H2-TPR和NH3-TPD等表征结果,研究了Mn-Ce/TiO2催化剂Pb中毒和再生活性恢复的原因。结果表明,Pb对Mn-Ce/TiO2催化剂脱硝活性有明显的抑制作用;当Pb的含量为11%时,Mn-Ce/TiO2催化剂在180 ℃下的脱硝效率从原来100%下降至44%。Pb在Mn-Ce/TiO2中的掺杂使得催化剂的比表面积以及活性组分Mn4+和Ce3+的含量降低,影响了氧化还原循环反应(Mn4+ + Ce3+ ↔ Mn3+ + Ce4+)的进行;此外,Pb的加入破坏了催化剂的酸性位点,阻碍了催化剂对NH3的吸附和活化。经硝酸再生后的Mn-Ce/TiO2催化剂的脱硝活性几乎完全恢复,在80–150 ℃下其脱硝活性甚至超过新鲜未中毒的催化剂,其原因主要在于硝酸再生能恢复催化剂的氧化还原能力、增大比表面积、并形成新的酸位点。
2021, 49(2): 211-219.
doi: 10.1016/S1872-5813(21)60014-2
摘要:
采用溶胶-凝胶-超临界干燥法、水热法及共沉淀法分别合成了氧化铈气凝胶(CeO2-A)、纳米棒(CeO2-R)和纳米片(CeO2-F)。考察了不同形貌氧化铈的催化燃烧甲苯性能,通过多种方法分析表征了氧化铈样品的微观结构,讨论了不同方法制得的CeO2形貌结构对催化性能的影响。结果表明,CeO2-R和CeO2-F比表面积较低,并且仅暴露(111)晶面,催化燃烧甲苯活性较低。CeO2-A具有高比表面积和丰富的孔道结构,有利于反应物分子的吸附,而且同时暴露(100)和(111)两种活性晶面,增加了氧空位浓度(Osur/Olatt = 0.25)。此外,CeO2-A由于表面晶格氧移动性较强,有利于Ce3+/Ce4+氧化还原的循环,加快甲苯深度氧化反应的进行。因此,CeO2-A具有更加优异的催化燃烧甲苯活性,t50和t90分别为223 和239 ℃,这主要归因于其大比表面积、高暴露活性晶面以及强晶格氧迁移性。
采用溶胶-凝胶-超临界干燥法、水热法及共沉淀法分别合成了氧化铈气凝胶(CeO2-A)、纳米棒(CeO2-R)和纳米片(CeO2-F)。考察了不同形貌氧化铈的催化燃烧甲苯性能,通过多种方法分析表征了氧化铈样品的微观结构,讨论了不同方法制得的CeO2形貌结构对催化性能的影响。结果表明,CeO2-R和CeO2-F比表面积较低,并且仅暴露(111)晶面,催化燃烧甲苯活性较低。CeO2-A具有高比表面积和丰富的孔道结构,有利于反应物分子的吸附,而且同时暴露(100)和(111)两种活性晶面,增加了氧空位浓度(Osur/Olatt = 0.25)。此外,CeO2-A由于表面晶格氧移动性较强,有利于Ce3+/Ce4+氧化还原的循环,加快甲苯深度氧化反应的进行。因此,CeO2-A具有更加优异的催化燃烧甲苯活性,t50和t90分别为223 和239 ℃,这主要归因于其大比表面积、高暴露活性晶面以及强晶格氧迁移性。
2022, 50(4): 503-512.
doi: 10.1016/S1872-5813(21)60177-9
摘要:
本文采用浸渍法制备了Nb改性的V2O5-WO3/TiO2催化剂,研究了脱硝反应中Nb负载量对催化剂SO2氧化活性的影响。结果表明,在350 °C下,Nb2O5负载量为2%的Nb2O5-V2O5-WO3/TiO2催化剂上的SO2氧化率最低(0.6%),而同时NOx 的转化率仍能达到95%。采用TGA、氮吸附、XRD、H2-TPR、CO2-TPD、XPS和in- situ DRIFTS等对催化剂进行了表征分析,结果显示,Nb改性后V2O5-WO3/TiO2催化剂的晶体结构没有发生明显改变,但是其比表面积小幅度下降,有助于减少对SO2的吸附;同时,改性后催化剂表面的吸附氧含量下降,氧化还原性能也稍微减弱,这有利于降低其对SO2的氧化活性。in-situ DRIFTS结果表明,Nb改性后的Nb-V2O5-WO3/TiO2催化剂反应过程中表面中间产物VOSO4的含量明显下降,从而减少了SO3的生成量。
本文采用浸渍法制备了Nb改性的V2O5-WO3/TiO2催化剂,研究了脱硝反应中Nb负载量对催化剂SO2氧化活性的影响。结果表明,在350 °C下,Nb2O5负载量为2%的Nb2O5-V2O5-WO3/TiO2催化剂上的SO2氧化率最低(0.6%),而同时NOx 的转化率仍能达到95%。采用TGA、氮吸附、XRD、H2-TPR、CO2-TPD、XPS和in- situ DRIFTS等对催化剂进行了表征分析,结果显示,Nb改性后V2O5-WO3/TiO2催化剂的晶体结构没有发生明显改变,但是其比表面积小幅度下降,有助于减少对SO2的吸附;同时,改性后催化剂表面的吸附氧含量下降,氧化还原性能也稍微减弱,这有利于降低其对SO2的氧化活性。in-situ DRIFTS结果表明,Nb改性后的Nb-V2O5-WO3/TiO2催化剂反应过程中表面中间产物VOSO4的含量明显下降,从而减少了SO3的生成量。
2021, 49(12): 1733-1751.
doi: 10.1016/S1872-5813(21)60134-2
摘要:
纤维素的热解技术是一种非常有应用前景的高值转化技术。本综述系统地介绍了纤维素的基础特性,深入讨论了纤维素热解机制、研究方法、催化剂类型及其他影响纤维素热解产物分布的因素。其中,不同类型催化剂的添加和反应装置结构的设计优化可以显著提高纤维素热解转化效率,改善产物种类分布和提高特定高值化学品的选择性,从而有效地提高纤维素热解产物的资源、能源化利用价值。最后,对纤维素热解未来技术研究的发展方向进行了展望。
纤维素的热解技术是一种非常有应用前景的高值转化技术。本综述系统地介绍了纤维素的基础特性,深入讨论了纤维素热解机制、研究方法、催化剂类型及其他影响纤维素热解产物分布的因素。其中,不同类型催化剂的添加和反应装置结构的设计优化可以显著提高纤维素热解转化效率,改善产物种类分布和提高特定高值化学品的选择性,从而有效地提高纤维素热解产物的资源、能源化利用价值。最后,对纤维素热解未来技术研究的发展方向进行了展望。
2021, 49(11): 1609-1619.
doi: 10.1016/S1872-5813(21)60122-6
摘要:
化石资源的大量使用导致CO2的大量排放,带来了严重的环境问题。与此同时,CO2又是一种清洁、无毒的含碳资源。将CO2作为原料,直接转化制备重要化学品,不仅可以减缓温室效应,同时也是一条有效利用含碳资源制备清洁燃料和化学品的新路线。本文概述了近年来关于CO2加氢制备一些烃类化合物(主要包括甲烷、烯烃和芳烃)的相关研究进展;重点分析了CO2加氢制烃类化合物相关过程催化剂的研发状态和对催化反应机理的认识,并对CO2加氢转化利用的未来发展进行了展望。
化石资源的大量使用导致CO2的大量排放,带来了严重的环境问题。与此同时,CO2又是一种清洁、无毒的含碳资源。将CO2作为原料,直接转化制备重要化学品,不仅可以减缓温室效应,同时也是一条有效利用含碳资源制备清洁燃料和化学品的新路线。本文概述了近年来关于CO2加氢制备一些烃类化合物(主要包括甲烷、烯烃和芳烃)的相关研究进展;重点分析了CO2加氢制烃类化合物相关过程催化剂的研发状态和对催化反应机理的认识,并对CO2加氢转化利用的未来发展进行了展望。
2013, 41(08): 1003-1009.
Abstract:
2009, 37(04): 501-505.
Abstract: