The low-temperature catalytic oxidation of heavy crude oil（Xinjiang Oilfield,China） was studied using three types of catalysts including oil-soluble,watersoluble,and dispersed catalysts.According to primary screenin...The low-temperature catalytic oxidation of heavy crude oil（Xinjiang Oilfield,China） was studied using three types of catalysts including oil-soluble,watersoluble,and dispersed catalysts.According to primary screening,oil-soluble catalysts,copper naphthenate and manganese naphthenate,are more attractive,and were selected to further investigate their catalytic performance in in situ upgrading of heavy oil.The heavy oil compositions and molecular structures were characterized by column chromatography,elemental analysis,and Fourier transform infrared spectrometry before and after reaction.An Arrhenius kinetics model was introduced to calculate the rheological activation energy of heavy oil from the viscosity-temperature characteristics.Results show that the two oil-soluble catalysts can crack part of heavy components into light components,decrease the heteroatom content,and achieve the transition of reaction mode from oxygen addition to bond scission.The calculated rheological activation energy of heavy oil from the fitted Arrhenius model is consistent with physical properties of heavy oil（oil viscosity and contents of heavy fractions）.It is found that the temperature,oil composition,and internal molecular structures are the main factors affecting its flow ability.Oil-soluble catalyst-assisted air injection or air huff-n-puff injection is a promising in situ catalytic upgrading method for improving heavy oil recovery.展开更多
Binary metal oxide（MnOx-A/TiO2）catalysts were prepared by adding the second metal to manganese oxides supported on titanium dioxide（TiO2）,where,A indicates Fe2O3,WO3,MoO3,and Cr2O3.Their catalytic activity,N2 sele...Binary metal oxide（MnOx-A/TiO2）catalysts were prepared by adding the second metal to manganese oxides supported on titanium dioxide（TiO2）,where,A indicates Fe2O3,WO3,MoO3,and Cr2O3.Their catalytic activity,N2 selectivity,and SO2 poisonous tolerance were investigated.The catalytic performance at low temperatures decreased in the following order：Mn-W/TiO2〉Mn-Fe/TiO2〉Mn-Cr/TiO2〉Mn-Mo/TiO2,whereas the N2 selectivity decreased in the order：Mn-Fe/TiO2〉Mn-W/TiO2〉Mn-Mo/TiO2〉Mn-Cr/TiO2.In the presence of 0.01%SO2 and 6%H2O,the NOx conversions in the presence of Mn-W/TiO2,Mn-Fe/TiO2,or Mn-Mo/TiO2 maintain 98.5%,95.8%and 94.2%, respectively,after 8 h at 120°C at GHSV 12600 h？ 1 .As effective promoters,WO3 and Fe2O3 can increase N2 selectivity and the resistance to SO2 of MnOx/TiO2 significantly.The Fourier transform infrared（FTIR）spectra of NH3 over WO3 show the presence of Lewis acid sites.The results suggest that WO3 is the best promoter of MnOx/TiO2,and Mn-W/TiO2 is one of the most active catalysts for the low temperature selective catalytic reduction of NO with NH3.展开更多
Formaldehyde（HCHO）is carcinogenic and teratogenic,and is therefore a serious danger to human health.It also adversely affects air quality.Catalytic oxidation is an efficient technique for removing HCHO.The developme...Formaldehyde（HCHO）is carcinogenic and teratogenic,and is therefore a serious danger to human health.It also adversely affects air quality.Catalytic oxidation is an efficient technique for removing HCHO.The development of highly efficient and stable catalysts that can completely convert HCHO at low temperatures,even room temperature,is important.Supported Pt and Pd catalysts can completely convert HCHO at room temperature,but their industrial applications are limited because they are expensive.The catalytic activities in HCHO oxidation of transition-metal oxide catalysts such as manganese and cobalt oxides with unusual morphologies are better than those of traditional MnO2,Co3O4,or other metal oxides.This is attributed to their specific structures,high specific surface areas,and other factors such as active phase,reducibility,and amount of surface active oxygens.Such catalysts with various morphologies have great potential and can also be used as catalyst supports.The loading of relatively cheap Ag or Au on transition-metal oxides with special morphologies potentially improves the catalytic activity in HCHO removal at room temperature.The preparation and development of new nanocatalysts with various morphologies and structures is important for HCHO removal.In this paper,research progress on precious-metal and transition-metal oxide catalyst systems for HCHO oxidation is reviewed; topics such as oxidation properties,structure–activity relationships,and factors influencing the catalytic activity and reaction mechanism are discussed.Future prospects and directions for the development of such catalysts are also covered.展开更多
Changes are needed to improve the efficiency and lower the CO_(2)emissions of traditional coal-fired power generation,which is the main source of global CO_(2)emissions.The integrated gasification fuel cell(IGFC)proce...Changes are needed to improve the efficiency and lower the CO_(2)emissions of traditional coal-fired power generation,which is the main source of global CO_(2)emissions.The integrated gasification fuel cell(IGFC)process,which combines coal gasification and high-temperature fuel cells,was proposed in 2017 to improve the efficiency of coal-based power generation and reduce CO_(2)emissions.Supported by the National Key R&D Program of China,the IGFC for nearzero CO_(2)emissions program was enacted with the goal of achieving near-zero CO_(2)emissions based on(1)catalytic combustion of the flue gas from solid oxide fuel cell(SOFC)stacks and(2)CO_(2)conversion using solid oxide electrolysis cells(SOECs).In this work,we investigated a kW-level catalytic combustion burner and SOEC stack,evaluated the electrochemical performance of the SOEC stack in H2O electrolysis and H2O/CO_(2)co-electrolysis,and established a multiscale and multi-physical coupling simulation model of SOFCs and SOECs.The process developed in this work paves the way for the demonstration and deployment of IGFC technology in the future.展开更多
In this paper,the research status and catalytic mechanism of activated carbon catalysts,molecular sieve catalysts,noble metal catalysts and transition metal oxide catalysts used for NO catalytic oxidation were studied...In this paper,the research status and catalytic mechanism of activated carbon catalysts,molecular sieve catalysts,noble metal catalysts and transition metal oxide catalysts used for NO catalytic oxidation were studied to provide reference for future research.展开更多
MnO_(2)/Melem composites were synthesized with MnO_(2)nanoparticles loaded onto the Melem using the hydrothermal method.As raw materials for C and N carriers,Melem was prepared from melamine roasted at 354℃,and KMnO_...MnO_(2)/Melem composites were synthesized with MnO_(2)nanoparticles loaded onto the Melem using the hydrothermal method.As raw materials for C and N carriers,Melem was prepared from melamine roasted at 354℃,and KMnO_(4)as a raw material for Mn,MnO_(2)nanoparticles were prepared using the hydrothermal synthesis of KMnO_(4).Scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD),and a laser particle size analyzer were used for structural characterization,and the catalytic oxidation performance of the heavy oil was investigated at different reaction temperatures(100℃to 180℃)using MnO_(2)/Melem with an oxidant and donor protonic acid.The results showed that the synthesizedβ-MnO_(2)nanoparticles were successfully loaded onto the Melem surface;the oil samples before and after the reaction at different temperatures were subjected to SARA analysis using Fourier transform infrared(FT-IR),elemental analysis,gas chromatography-mass spectrometry(GC-MS)and viscosity tests,respectively.It was determined that the hydrocarbons in the crude oil were converted to heavy mass by oxidation reactions with the oxidant mainly through a low-temperature oxidation process below 140℃in the heavy oil when the temperature exceeds 140℃,in addition to the oxidation reaction with the oxidant,a cleavage reaction in the carbon chain occurs to form hydrocarbon substances with lower molecular weights.展开更多
To develop more efficient chemical methods for the demineralization of organic pollutants from water bodies, which one was also mimic to the nature, a degradation of methylene blue by Fe(Ⅲ) and H 2O 2 in the absenc...To develop more efficient chemical methods for the demineralization of organic pollutants from water bodies, which one was also mimic to the nature, a degradation of methylene blue by Fe(Ⅲ) and H 2O 2 in the absence of light instead of Fe(Ⅱ) and H 2O 2 was studied. Results showed that use of Fe (Ⅲ) is more promising than Fe(Ⅱ). The present study reflects that Fenton reaction is more efficient, in the presence of a small amount of salicylic acid is added which is a one of the priority pollutant.展开更多
The preparation and catalytic activity of ferric oxide and its composite oxides supported gold catalysts for low-temperature CO oxidation were investigated detailedly, and characterized extensively by XRD, XPS, TPR, E...The preparation and catalytic activity of ferric oxide and its composite oxides supported gold catalysts for low-temperature CO oxidation were investigated detailedly, and characterized extensively by XRD, XPS, TPR, EC and XAFS techniques. It was found that containing highly dispersed Au of partially oxidized state, these nano-structured oxides supported Au/Fe2O3 and Au/NiFe2O4 catalysts had higher low-temperature activities. The possible catalytic active center is the gold of partially oxidized state (Auζ+).展开更多
The structure-activity relationships for vinyl acetate catalytic oxidation are challenging to explore at the atomic scale due to the ambiguity of the structural defect types and sites of manganese oxides.Our work elab...The structure-activity relationships for vinyl acetate catalytic oxidation are challenging to explore at the atomic scale due to the ambiguity of the structural defect types and sites of manganese oxides.Our work elaborates,at the atomic level,through in-situ experimental and theoretical methods,the synergistic effects of two types of structural defect sites of Vo-e(edge-sharing oxygen)and Vo-c(corner-sharing oxygen)and MnO6 structural motifs of manganese oxides.Multi-dimensional manganese oxides,namely those with corner-connected MnOs structural motifs and Vo-c structural oxygen defect sites,significantly improved the activation of vinyl acetate.Enhancement of enol structure formation,acetate and formate intermediate species,and tautomerism between enol structure and acetaldehyde were detected when oxygen vacancies of manganese oxides were present in combination with corner/edge-connected MnO6.Moreover,the activation of chemical bonds and deep catalytic oxidation of vinyl acetate depend on the presence of a redox couple,surface oxygen species,and weakened Mn-O bonds.It provides a valuable notion for investigating and designing catalytic systems and reaction processes for the purpose of emission reduction and the management of environmental contaminants.展开更多
By using the introduced CWO technology and its 200 L/d plant, more than 10 kinds of industrial wastewaters with high concentration in China, such as the waste liquor of coking, the black liquor of paper making, the wa...By using the introduced CWO technology and its 200 L/d plant, more than 10 kinds of industrial wastewaters with high concentration in China, such as the waste liquor of coking, the black liquor of paper making, the waste mother liquor of bio-pharmacy and so on, were treated in this test research. The results showed that the CWO technology and its equipment had a good applicability for treating the industrial wastewaters with high concentration in China. One set of CWO-20 m^3/d industrial plant, as a demonstration engineering installation of CWO technology, was independently designed, made and operated in Kunming city. During the running test, the CWO-20 m^3/d plant displayed a favorable treatment capability for the bio-degradedly difficult industrial wastewaters with high concentration. For the treatment of the waste liquor from coking and the black liquor of paper making, more than 99% of CODcr and NH3-N in the wastewater could be removed. The CWO-20 m^3/d plant could be run continuously and stably. The treated wastewater could meet the discharge standard and the treatment process with CWO technology shown up a good economic advantage.展开更多
A series of N-doped graphene(NG)and TiO_2 supported MnO_x–CeO_2 catalysts were prepared prepared by a hydrothermal method.The catalysts with different molar ratios of Mn/Ce(6:1,10:1,15:1)were investigated for the low...A series of N-doped graphene(NG)and TiO_2 supported MnO_x–CeO_2 catalysts were prepared prepared by a hydrothermal method.The catalysts with different molar ratios of Mn/Ce(6:1,10:1,15:1)were investigated for the low-temperature selective catalytic reduction(SCR)of NO_x with NH_3.The synthesized catalysts were characterized by HRTEM,SEM,XRD,BET,XPS,and NH_3-TPD technologies.The characterization results indicated that manganese and cerium oxide particles dispersed on the surface of the TiO_2–NG support uniformly,and that manganese and cerium oxides existed in different valences on the surface of the TiO_2–NG support.At Mn element loading of 8 wt%,MnO_x–CeO_2(10:1)/TiO_2–1%NG displayed superior activity and improved SO_(2 )resistance.On the basis of the catalyst characterization,excellent catalytic performance and SO_2 tolerance at low temperature were attributed to the high content of manganese with high oxidation valence,extensive oxidation of NO into NO_2 by CeO_2 and strong NO adsorption capacity,and electron transfer of N-doped graphene.展开更多
基金supported by the National Natural Science Foundation of China (No. 51404202)Sichuan Youth Science and Technology Fund (No. 2015JQ0038)the Scientific Research Starting Project of Southwest Petroleum University (No. 2014QHZ001)
文摘The low-temperature catalytic oxidation of heavy crude oil（Xinjiang Oilfield,China） was studied using three types of catalysts including oil-soluble,watersoluble,and dispersed catalysts.According to primary screening,oil-soluble catalysts,copper naphthenate and manganese naphthenate,are more attractive,and were selected to further investigate their catalytic performance in in situ upgrading of heavy oil.The heavy oil compositions and molecular structures were characterized by column chromatography,elemental analysis,and Fourier transform infrared spectrometry before and after reaction.An Arrhenius kinetics model was introduced to calculate the rheological activation energy of heavy oil from the viscosity-temperature characteristics.Results show that the two oil-soluble catalysts can crack part of heavy components into light components,decrease the heteroatom content,and achieve the transition of reaction mode from oxygen addition to bond scission.The calculated rheological activation energy of heavy oil from the fitted Arrhenius model is consistent with physical properties of heavy oil（oil viscosity and contents of heavy fractions）.It is found that the temperature,oil composition,and internal molecular structures are the main factors affecting its flow ability.Oil-soluble catalyst-assisted air injection or air huff-n-puff injection is a promising in situ catalytic upgrading method for improving heavy oil recovery.
文摘Binary metal oxide（MnOx-A/TiO2）catalysts were prepared by adding the second metal to manganese oxides supported on titanium dioxide（TiO2）,where,A indicates Fe2O3,WO3,MoO3,and Cr2O3.Their catalytic activity,N2 selectivity,and SO2 poisonous tolerance were investigated.The catalytic performance at low temperatures decreased in the following order：Mn-W/TiO2〉Mn-Fe/TiO2〉Mn-Cr/TiO2〉Mn-Mo/TiO2,whereas the N2 selectivity decreased in the order：Mn-Fe/TiO2〉Mn-W/TiO2〉Mn-Mo/TiO2〉Mn-Cr/TiO2.In the presence of 0.01%SO2 and 6%H2O,the NOx conversions in the presence of Mn-W/TiO2,Mn-Fe/TiO2,or Mn-Mo/TiO2 maintain 98.5%,95.8%and 94.2%, respectively,after 8 h at 120°C at GHSV 12600 h？ 1 .As effective promoters,WO3 and Fe2O3 can increase N2 selectivity and the resistance to SO2 of MnOx/TiO2 significantly.The Fourier transform infrared（FTIR）spectra of NH3 over WO3 show the presence of Lewis acid sites.The results suggest that WO3 is the best promoter of MnOx/TiO2,and Mn-W/TiO2 is one of the most active catalysts for the low temperature selective catalytic reduction of NO with NH3.
基金supported by the National Natural Science Foundation of China(21325731,51478241,21221004)~~
文摘Formaldehyde（HCHO）is carcinogenic and teratogenic,and is therefore a serious danger to human health.It also adversely affects air quality.Catalytic oxidation is an efficient technique for removing HCHO.The development of highly efficient and stable catalysts that can completely convert HCHO at low temperatures,even room temperature,is important.Supported Pt and Pd catalysts can completely convert HCHO at room temperature,but their industrial applications are limited because they are expensive.The catalytic activities in HCHO oxidation of transition-metal oxide catalysts such as manganese and cobalt oxides with unusual morphologies are better than those of traditional MnO2,Co3O4,or other metal oxides.This is attributed to their specific structures,high specific surface areas,and other factors such as active phase,reducibility,and amount of surface active oxygens.Such catalysts with various morphologies have great potential and can also be used as catalyst supports.The loading of relatively cheap Ag or Au on transition-metal oxides with special morphologies potentially improves the catalytic activity in HCHO removal at room temperature.The preparation and development of new nanocatalysts with various morphologies and structures is important for HCHO removal.In this paper,research progress on precious-metal and transition-metal oxide catalyst systems for HCHO oxidation is reviewed; topics such as oxidation properties,structure–activity relationships,and factors influencing the catalytic activity and reaction mechanism are discussed.Future prospects and directions for the development of such catalysts are also covered.
基金This work was financially supported by the National Key R&D Program of China(2017YFB0601904).
文摘Changes are needed to improve the efficiency and lower the CO_(2)emissions of traditional coal-fired power generation,which is the main source of global CO_(2)emissions.The integrated gasification fuel cell(IGFC)process,which combines coal gasification and high-temperature fuel cells,was proposed in 2017 to improve the efficiency of coal-based power generation and reduce CO_(2)emissions.Supported by the National Key R&D Program of China,the IGFC for nearzero CO_(2)emissions program was enacted with the goal of achieving near-zero CO_(2)emissions based on(1)catalytic combustion of the flue gas from solid oxide fuel cell(SOFC)stacks and(2)CO_(2)conversion using solid oxide electrolysis cells(SOECs).In this work,we investigated a kW-level catalytic combustion burner and SOEC stack,evaluated the electrochemical performance of the SOEC stack in H2O electrolysis and H2O/CO_(2)co-electrolysis,and established a multiscale and multi-physical coupling simulation model of SOFCs and SOECs.The process developed in this work paves the way for the demonstration and deployment of IGFC technology in the future.
基金Supported by General Project of Natural Science Foundation of Liaoning Province in 2019(2019-MS-202)"Double First-Class"Construction Project of Liaoning Province in 2020(Scientific Research)(FWDFGD2020041)。
文摘In this paper,the research status and catalytic mechanism of activated carbon catalysts,molecular sieve catalysts,noble metal catalysts and transition metal oxide catalysts used for NO catalytic oxidation were studied to provide reference for future research.
基金supported by the National Natural Science Foundation of China (51472034)the Key Laboratory Development Fund of Hubei Province (202305904)the Cooperation Project of Petro China Tahe Oilfield Company (2021H10005)。
文摘MnO_(2)/Melem composites were synthesized with MnO_(2)nanoparticles loaded onto the Melem using the hydrothermal method.As raw materials for C and N carriers,Melem was prepared from melamine roasted at 354℃,and KMnO_(4)as a raw material for Mn,MnO_(2)nanoparticles were prepared using the hydrothermal synthesis of KMnO_(4).Scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray diffraction(XRD),and a laser particle size analyzer were used for structural characterization,and the catalytic oxidation performance of the heavy oil was investigated at different reaction temperatures(100℃to 180℃)using MnO_(2)/Melem with an oxidant and donor protonic acid.The results showed that the synthesizedβ-MnO_(2)nanoparticles were successfully loaded onto the Melem surface;the oil samples before and after the reaction at different temperatures were subjected to SARA analysis using Fourier transform infrared(FT-IR),elemental analysis,gas chromatography-mass spectrometry(GC-MS)and viscosity tests,respectively.It was determined that the hydrocarbons in the crude oil were converted to heavy mass by oxidation reactions with the oxidant mainly through a low-temperature oxidation process below 140℃in the heavy oil when the temperature exceeds 140℃,in addition to the oxidation reaction with the oxidant,a cleavage reaction in the carbon chain occurs to form hydrocarbon substances with lower molecular weights.
文摘To develop more efficient chemical methods for the demineralization of organic pollutants from water bodies, which one was also mimic to the nature, a degradation of methylene blue by Fe(Ⅲ) and H 2O 2 in the absence of light instead of Fe(Ⅱ) and H 2O 2 was studied. Results showed that use of Fe (Ⅲ) is more promising than Fe(Ⅱ). The present study reflects that Fenton reaction is more efficient, in the presence of a small amount of salicylic acid is added which is a one of the priority pollutant.
基金BEPC Synchrotron Radiation Laboratory of the Institute of High Energy Physics, Chinese Academy of Sciences.
文摘The preparation and catalytic activity of ferric oxide and its composite oxides supported gold catalysts for low-temperature CO oxidation were investigated detailedly, and characterized extensively by XRD, XPS, TPR, EC and XAFS techniques. It was found that containing highly dispersed Au of partially oxidized state, these nano-structured oxides supported Au/Fe2O3 and Au/NiFe2O4 catalysts had higher low-temperature activities. The possible catalytic active center is the gold of partially oxidized state (Auζ+).
基金financially supported by the National Natural Science Foundation of China(No.22006079)the R&D Program of Beijing Municipal Education Commission(No.KjzD20191443001)+2 种基金the National Key Research and Development Program of China(No.2016YFC0204203)the Project of Ningxia Key Research and Development Plan(No.2020BEB04009)National First-rate Discipline Construction Project of Ningxia(No.NXYLXK2017A04).
文摘The structure-activity relationships for vinyl acetate catalytic oxidation are challenging to explore at the atomic scale due to the ambiguity of the structural defect types and sites of manganese oxides.Our work elaborates,at the atomic level,through in-situ experimental and theoretical methods,the synergistic effects of two types of structural defect sites of Vo-e(edge-sharing oxygen)and Vo-c(corner-sharing oxygen)and MnO6 structural motifs of manganese oxides.Multi-dimensional manganese oxides,namely those with corner-connected MnOs structural motifs and Vo-c structural oxygen defect sites,significantly improved the activation of vinyl acetate.Enhancement of enol structure formation,acetate and formate intermediate species,and tautomerism between enol structure and acetaldehyde were detected when oxygen vacancies of manganese oxides were present in combination with corner/edge-connected MnO6.Moreover,the activation of chemical bonds and deep catalytic oxidation of vinyl acetate depend on the presence of a redox couple,surface oxygen species,and weakened Mn-O bonds.It provides a valuable notion for investigating and designing catalytic systems and reaction processes for the purpose of emission reduction and the management of environmental contaminants.
文摘By using the introduced CWO technology and its 200 L/d plant, more than 10 kinds of industrial wastewaters with high concentration in China, such as the waste liquor of coking, the black liquor of paper making, the waste mother liquor of bio-pharmacy and so on, were treated in this test research. The results showed that the CWO technology and its equipment had a good applicability for treating the industrial wastewaters with high concentration in China. One set of CWO-20 m^3/d industrial plant, as a demonstration engineering installation of CWO technology, was independently designed, made and operated in Kunming city. During the running test, the CWO-20 m^3/d plant displayed a favorable treatment capability for the bio-degradedly difficult industrial wastewaters with high concentration. For the treatment of the waste liquor from coking and the black liquor of paper making, more than 99% of CODcr and NH3-N in the wastewater could be removed. The CWO-20 m^3/d plant could be run continuously and stably. The treated wastewater could meet the discharge standard and the treatment process with CWO technology shown up a good economic advantage.
基金financially supported by the Program of Frontier Exploration Fund of China Building Materials Academy,"the whole process of air pollution control on new technology research" (No. 2016YFC0209302)
文摘A series of N-doped graphene(NG)and TiO_2 supported MnO_x–CeO_2 catalysts were prepared prepared by a hydrothermal method.The catalysts with different molar ratios of Mn/Ce(6:1,10:1,15:1)were investigated for the low-temperature selective catalytic reduction(SCR)of NO_x with NH_3.The synthesized catalysts were characterized by HRTEM,SEM,XRD,BET,XPS,and NH_3-TPD technologies.The characterization results indicated that manganese and cerium oxide particles dispersed on the surface of the TiO_2–NG support uniformly,and that manganese and cerium oxides existed in different valences on the surface of the TiO_2–NG support.At Mn element loading of 8 wt%,MnO_x–CeO_2(10:1)/TiO_2–1%NG displayed superior activity and improved SO_(2 )resistance.On the basis of the catalyst characterization,excellent catalytic performance and SO_2 tolerance at low temperature were attributed to the high content of manganese with high oxidation valence,extensive oxidation of NO into NO_2 by CeO_2 and strong NO adsorption capacity,and electron transfer of N-doped graphene.
