Silicon carbide(SiC)was used as a support for SSZ‐13zeolite in an attempt to improve the high‐temperature stability and activity of Cu/SSZ‐13in the selective catalytic reduction(SCR)of NO with NH3.SSZ‐13was grown ...Silicon carbide(SiC)was used as a support for SSZ‐13zeolite in an attempt to improve the high‐temperature stability and activity of Cu/SSZ‐13in the selective catalytic reduction(SCR)of NO with NH3.SSZ‐13was grown via a hydrothermal method using the silicon and silica contained in SiC as the source of silicon,which led to the formation of a chemically bonded SSZ‐13layer on SiC.Characterization using X‐ray diffraction,scanning electron microscopy,and N2adsorption‐desorption isotherms revealed that the alkali content strongly affected the purity of zeolite and the crystallization time affected the coverage and crystallinity of the zeolite layer.Upon ion exchange,the resulting Cu/SSZ‐13@SiC catalyst exhibited enhanced activity in NH3‐SCR in the high‐temperature region compared with the unsupported Cu/SSZ‐13.Thus,the application temperature was extended with the use of SiC as the support.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
The 0.4 nm molecular sieve supported Cu-Ni bimetal catalysts for direct synthesis of dimethyl carbonate (DMC) from CO 2 and CH 3 OH were prepared and investigated. The synthesized catalysts were fully characterized by...The 0.4 nm molecular sieve supported Cu-Ni bimetal catalysts for direct synthesis of dimethyl carbonate (DMC) from CO 2 and CH 3 OH were prepared and investigated. The synthesized catalysts were fully characterized by BET, XRD (X-ray diffraction), TPR (temperature programmed reduction), IR (infra-red adsorption), NH 3-TPD (temperature programmed desorption) and CO 2-TPD (temperature programmed desorption) techniques. The results showed that the surface area of catalysts decreased with increasing metal content, and the metals as well as Cu-Ni alloy co-existed on the reduced catalyst surface. There existed interaction between metal and carrier, and moreover, metal particles affected obviously the acidity and basicity of carrier. The large amount of basic sites facilitated the activation of methanol to methoxyl species and their subsequent reaction with activated carbon dioxide. The catalysts were evaluated in a continuous tubular fixed-bed micro-gaseous reactor and the catalyst with bimetal loading of 20% (by mass) had best catalytic activities. Under the conditions of 393 K, 1.1 MPa, 5 h and gas space velocity of 510 h 1 , the selectivity and yield of DMC were higher than 86.0 % and 5.0 %, respectively.展开更多
Low-carbon light olefins are the basic feedstocks for the petrochemical industry. Catalytic cracking of crude bio-oil and its model compounds (including methanol, ethanol, acetic acid, acetone, and phenol) to light ...Low-carbon light olefins are the basic feedstocks for the petrochemical industry. Catalytic cracking of crude bio-oil and its model compounds (including methanol, ethanol, acetic acid, acetone, and phenol) to light olefins were performed by using the La/HZSM-5 catalyst. The highest olefins yield from crude bio-oil reached 0.19 kg/(kg crude bio-oil). The reaction conditions including temperature, weight hourly space velocity, and addition of La into the HZSM-5 zeolite can be used to control both olefins yield and selectivity. Moderate adjusting the acidity with a suitable ratio between the strong acid and weak acid sites through adding La to the zeolite effectively enhanced the olefins selectivity and improved the catalyst stability. The production of light olefins from crude bio-oil is closely associated with the chemical composition and hydrogen to carbon effective ratios of feedstock. The comparison between the catalytic cracking and pyrolysis of bio-oil was studied. The mechanism of the bio-oil conversion to light olefins was also discussed.展开更多
Composite structures of ZSM‐5 zeolites were prepared by the synthesis of mesopores and mi‐cropores using carbon nanotubes as a template. Dealumination of mesopores was performed selec‐tively using trichloroacetic a...Composite structures of ZSM‐5 zeolites were prepared by the synthesis of mesopores and mi‐cropores using carbon nanotubes as a template. Dealumination of mesopores was performed selec‐tively using trichloroacetic acid, which could only diffuse into the mesopores and not the mi‐cropores owing to the size of the trichloroacetic acid molecules. Empty spaces are created in the catalyst as a result of removal of the Al atoms from the zeolite structure. If Si atoms fill the empty space, then the structure of the mesopores becomes similar to silicates, which do not have any cata‐lytic properties. Silicon containing solution was used to fill the empty spaces, and in doing so, a unique method was developed, by which silicon atoms can directly replace the extracted Al atoms from the mesopore structure. Therefore, by changing the geometry and properties of the mesopores and micropores, the amount of coke reduced from 14%for HZSM‐5 to 3%for the modified zeolite.展开更多
The Na2CO3-modified HZSM-5 zeolites were further treated by tetrapropylammonium hydroxide(TPAOH) solution. The effect of TPAOH concentration on the secondary crystallization process was investigated. The resulting sam...The Na2CO3-modified HZSM-5 zeolites were further treated by tetrapropylammonium hydroxide(TPAOH) solution. The effect of TPAOH concentration on the secondary crystallization process was investigated. The resulting samples were characterized by a complementary combination of X-ray diffraction, N2 adsorption/desorption, scanning electron microscopy, X-ray fluorescence spectroscopy, XPS, 27 Al and 29 Si magic-angle spinning nuclear magnetic resonance spectroscopy, BET and temperature-programmed desorption techniques. The results showed that the secondary crystallization of the HZSM-5 zeolite could result in migration of non-framework species from the internal channels to the zeolite surface and their transformation into framework species. The catalytic activity of these modified samples for thiophene alkylation was evaluated. Both the activity and stability of the catalysts were improved after secondary crystallization.展开更多
Direct syngas conversion to light olefins on bifunctional oxide-zeolite(OX-ZEO)catalysts is of great interest to both academia and industry,but the role of oxygen vacancy(Vo)in metal oxides and whether the key interme...Direct syngas conversion to light olefins on bifunctional oxide-zeolite(OX-ZEO)catalysts is of great interest to both academia and industry,but the role of oxygen vacancy(Vo)in metal oxides and whether the key intermediate in the reaction mechanism is ketene or methanol are still not well-understood.To address these two issues,we carry out a theoretical study of the syngas conversion on the typical reducible metal oxide,CeO2,using density functional theory calculations.Our results demonstrate that by forming frustrated Lewis pairs(FLPs),the VOs in CeO2 play a key role in the activation of H2 and CO.The activation of H2 on FLPs undergoes a heterolytic dissociative pathway with a tiny barrier of 0.01 eV,while CO is activated on FLPs by combining with the basic site(O atom)of FLPs to form CO2^2-.Four pathways for the conversion of syngas were explored on FLPs,two of which are prone to form ketene and the other two are inclined to produce methanol suggesting a compromise to resolve the debate about the key intermediates(ketene or methanol)in the experiments.Rate constant calculations showed that the route initiating with the coupling of two CO*into OCCO*and ending with the formation of ketene is the dominant pathway,with the neighboring FLPs playing an important role in this pathway.Overall,our study reveals the function of the surface FLPs in the activation of H2 and CO and the reaction mechanism for the production of ketene and methanol for the first time,providing novel insights into syngas conversion over OX-ZEO catalysts.展开更多
This paper presents an investigation of a new method of purifying cryogenic liquid using sintered metallic wire-mesh filter, which has the advantages of high purifying efficiency and preferred strength at absolutely l...This paper presents an investigation of a new method of purifying cryogenic liquid using sintered metallic wire-mesh filter, which has the advantages of high purifying efficiency and preferred strength at absolutely low temperature. Experiments are conducted to purify solid CO2 particles from liquid nitrogen. Temperature and pressure in the upstream and downstream of the filter, and the flow rate of carbon dioxide (CO2) gas and liquid nitrogen are measured, with the gas content of filtrate analyzed using a CO2 concentration detector. It is illustrated that after filtration, the purity of liquid nitrogen (volume fraction) is higher than 99.99%, which means that the volume fraction of CO2 is less than 0.01%. Effects of operation parameters on the performance of the filter, such as pressure drop Ap and filtration efficiency E are analyzed quantitatively. The present conclusions will provide a guideline to the optimumal design and operation of sintered metallic wire-mesh filter in cryogenic application.展开更多
基金supported by the INCOEmission project coordinated by BASF SE,Germanythe support from the Fundamental Research Funds for the Central Universities(DC201502080409)~~
文摘Silicon carbide(SiC)was used as a support for SSZ‐13zeolite in an attempt to improve the high‐temperature stability and activity of Cu/SSZ‐13in the selective catalytic reduction(SCR)of NO with NH3.SSZ‐13was grown via a hydrothermal method using the silicon and silica contained in SiC as the source of silicon,which led to the formation of a chemically bonded SSZ‐13layer on SiC.Characterization using X‐ray diffraction,scanning electron microscopy,and N2adsorption‐desorption isotherms revealed that the alkali content strongly affected the purity of zeolite and the crystallization time affected the coverage and crystallinity of the zeolite layer.Upon ion exchange,the resulting Cu/SSZ‐13@SiC catalyst exhibited enhanced activity in NH3‐SCR in the high‐temperature region compared with the unsupported Cu/SSZ‐13.Thus,the application temperature was extended with the use of SiC as the support.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
基金Supported by the National High Technology Research and Development Program of China (2008AA03Z3472294,2009AA302410)the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme (2010)+1 种基金the Guangdong Province Sci & Tech Bureau (2006B12401006, 2008A080800024)the Chinese Universities Basic Research Founding
文摘The 0.4 nm molecular sieve supported Cu-Ni bimetal catalysts for direct synthesis of dimethyl carbonate (DMC) from CO 2 and CH 3 OH were prepared and investigated. The synthesized catalysts were fully characterized by BET, XRD (X-ray diffraction), TPR (temperature programmed reduction), IR (infra-red adsorption), NH 3-TPD (temperature programmed desorption) and CO 2-TPD (temperature programmed desorption) techniques. The results showed that the surface area of catalysts decreased with increasing metal content, and the metals as well as Cu-Ni alloy co-existed on the reduced catalyst surface. There existed interaction between metal and carrier, and moreover, metal particles affected obviously the acidity and basicity of carrier. The large amount of basic sites facilitated the activation of methanol to methoxyl species and their subsequent reaction with activated carbon dioxide. The catalysts were evaluated in a continuous tubular fixed-bed micro-gaseous reactor and the catalyst with bimetal loading of 20% (by mass) had best catalytic activities. Under the conditions of 393 K, 1.1 MPa, 5 h and gas space velocity of 510 h 1 , the selectivity and yield of DMC were higher than 86.0 % and 5.0 %, respectively.
基金This work is supported by the National Key Basic Program of China (No.2013CB228105) and the National Natural Science Foundation of China (No.51161140331).
文摘Low-carbon light olefins are the basic feedstocks for the petrochemical industry. Catalytic cracking of crude bio-oil and its model compounds (including methanol, ethanol, acetic acid, acetone, and phenol) to light olefins were performed by using the La/HZSM-5 catalyst. The highest olefins yield from crude bio-oil reached 0.19 kg/(kg crude bio-oil). The reaction conditions including temperature, weight hourly space velocity, and addition of La into the HZSM-5 zeolite can be used to control both olefins yield and selectivity. Moderate adjusting the acidity with a suitable ratio between the strong acid and weak acid sites through adding La to the zeolite effectively enhanced the olefins selectivity and improved the catalyst stability. The production of light olefins from crude bio-oil is closely associated with the chemical composition and hydrogen to carbon effective ratios of feedstock. The comparison between the catalytic cracking and pyrolysis of bio-oil was studied. The mechanism of the bio-oil conversion to light olefins was also discussed.
基金partly supported by the International Science Foundation~~
文摘Composite structures of ZSM‐5 zeolites were prepared by the synthesis of mesopores and mi‐cropores using carbon nanotubes as a template. Dealumination of mesopores was performed selec‐tively using trichloroacetic acid, which could only diffuse into the mesopores and not the mi‐cropores owing to the size of the trichloroacetic acid molecules. Empty spaces are created in the catalyst as a result of removal of the Al atoms from the zeolite structure. If Si atoms fill the empty space, then the structure of the mesopores becomes similar to silicates, which do not have any cata‐lytic properties. Silicon containing solution was used to fill the empty spaces, and in doing so, a unique method was developed, by which silicon atoms can directly replace the extracted Al atoms from the mesopore structure. Therefore, by changing the geometry and properties of the mesopores and micropores, the amount of coke reduced from 14%for HZSM‐5 to 3%for the modified zeolite.
基金the financial support by the Natural Science Foundation of Liaoning Province of China (Grant No.201202126)the National Natural Science Foundation of China (Grant Nos. 21276253 and 21401093)
文摘The Na2CO3-modified HZSM-5 zeolites were further treated by tetrapropylammonium hydroxide(TPAOH) solution. The effect of TPAOH concentration on the secondary crystallization process was investigated. The resulting samples were characterized by a complementary combination of X-ray diffraction, N2 adsorption/desorption, scanning electron microscopy, X-ray fluorescence spectroscopy, XPS, 27 Al and 29 Si magic-angle spinning nuclear magnetic resonance spectroscopy, BET and temperature-programmed desorption techniques. The results showed that the secondary crystallization of the HZSM-5 zeolite could result in migration of non-framework species from the internal channels to the zeolite surface and their transformation into framework species. The catalytic activity of these modified samples for thiophene alkylation was evaluated. Both the activity and stability of the catalysts were improved after secondary crystallization.
文摘Direct syngas conversion to light olefins on bifunctional oxide-zeolite(OX-ZEO)catalysts is of great interest to both academia and industry,but the role of oxygen vacancy(Vo)in metal oxides and whether the key intermediate in the reaction mechanism is ketene or methanol are still not well-understood.To address these two issues,we carry out a theoretical study of the syngas conversion on the typical reducible metal oxide,CeO2,using density functional theory calculations.Our results demonstrate that by forming frustrated Lewis pairs(FLPs),the VOs in CeO2 play a key role in the activation of H2 and CO.The activation of H2 on FLPs undergoes a heterolytic dissociative pathway with a tiny barrier of 0.01 eV,while CO is activated on FLPs by combining with the basic site(O atom)of FLPs to form CO2^2-.Four pathways for the conversion of syngas were explored on FLPs,two of which are prone to form ketene and the other two are inclined to produce methanol suggesting a compromise to resolve the debate about the key intermediates(ketene or methanol)in the experiments.Rate constant calculations showed that the route initiating with the coupling of two CO*into OCCO*and ending with the formation of ketene is the dominant pathway,with the neighboring FLPs playing an important role in this pathway.Overall,our study reveals the function of the surface FLPs in the activation of H2 and CO and the reaction mechanism for the production of ketene and methanol for the first time,providing novel insights into syngas conversion over OX-ZEO catalysts.
基金the National Natural Science Foundation of China(No.50476022)the Ministries and Commissions of Science and Technology of Shanghai Government(No.03DZ 14014)
文摘This paper presents an investigation of a new method of purifying cryogenic liquid using sintered metallic wire-mesh filter, which has the advantages of high purifying efficiency and preferred strength at absolutely low temperature. Experiments are conducted to purify solid CO2 particles from liquid nitrogen. Temperature and pressure in the upstream and downstream of the filter, and the flow rate of carbon dioxide (CO2) gas and liquid nitrogen are measured, with the gas content of filtrate analyzed using a CO2 concentration detector. It is illustrated that after filtration, the purity of liquid nitrogen (volume fraction) is higher than 99.99%, which means that the volume fraction of CO2 is less than 0.01%. Effects of operation parameters on the performance of the filter, such as pressure drop Ap and filtration efficiency E are analyzed quantitatively. The present conclusions will provide a guideline to the optimumal design and operation of sintered metallic wire-mesh filter in cryogenic application.