As a potential methane efficient conversion process,non-oxidative aromatization of methane in fluidized bed requires a catalyst with good attrition resistance,especially in the states of high temperature,longtime rapi...As a potential methane efficient conversion process,non-oxidative aromatization of methane in fluidized bed requires a catalyst with good attrition resistance,especially in the states of high temperature,longtime rapid movement and chemical reaction.Existing evaluation methods for attrition resistance,such as ASTM D5757 and Jet Cup test,are targeted for fresh catalysts at ambient temperature,which cannot well reflect the real process.In this study,spherical-shaped Mo/HZSM-5 catalyst prepared by dipping and spray drying was placed in a self-made apparatus for attrition testing,in which the catalyst attrition under different system temperatures,running time and process factors was investigated with percent mass loss(PML),particle size-mass distribution(PSMD)and scanning electron microscope(SEM).Carbon deposition on the catalyst before and after activation,aromatization and regeneration was analyzed by thermogravimetry(TG),and the attrited catalysts were evaluated for methane dehydro-aromatization(MDA).The results show that the surface abrasion and body breakage of catalyst particles occur continuously,with the increase of system temperature and running time,and make the PML rise gradually.The process factors of activation,aromatization and regeneration can cause the catalyst attrition and carbon deposits,which broaden the PSMD in varying degrees,and the carbon-substances on catalysts greatly improve their attrition resistance at high temperature.Catalyst attrition has a certain influence on its catalytic performance,and the main reasons point to particle breakage and fine powder escape.展开更多
The direct conversion of methane into aromatics under non-oxidative conditions has received considerable attention since 1993^[1-3].Mo/HZSM-5 is the best one among the tested catalysts.It is generally accepted that th...The direct conversion of methane into aromatics under non-oxidative conditions has received considerable attention since 1993^[1-3].Mo/HZSM-5 is the best one among the tested catalysts.It is generally accepted that the activation of the C-H bond of methane and initial C-C bond formation occur on Mocarbides formed from the reduction of Mo O,species,while the further transformation of C^(2+)hydrocarbons occurs on the Bronsted acid sites of HZSM-5 zeolite^[4].The unique channel structure of HZSM-5 plays a crucial role in constraining side reactions and controlling the product distribution^[5].The Bronsted acid sites of HZSM-5 are also responsible for the for-mation of carbonaceous deposits[6].展开更多
The effect of steam-treatment to HZSM-5 zeolite and Mo/HZSM-5 with a steaming time range of 0.5-1 h on the catalytic performance of methane dehydro-aromatization （MDA） over Mo/HZSM-5 catalyst prepared with impregnat...The effect of steam-treatment to HZSM-5 zeolite and Mo/HZSM-5 with a steaming time range of 0.5-1 h on the catalytic performance of methane dehydro-aromatization （MDA） over Mo/HZSM-5 catalyst prepared with impregnation has been studied in detail in combination with the characterization of 1H MAS NMR technique. Both the deactivation rate constant （kd） and the Brtnsted acid sites per unit cell were calculated to quantitatively evaluate the stability of Mo/HZSM-5 catalysts treated with steam at 813 K before and after impregnation of molybdenum species, and the corresponding variation of their Brtnsted acid sites. The results reveal that a V-shape relationship between kd and the number of B 1 acid sites per unit cell is presented on Mo/HZSM-5 catalyst under the tested steam-treatment and reaction conditions.展开更多
The optimum Mo/[H^+] ratio per unit cell of the active precursors in Mo/HZSM-5 catalysts for methane dehydro-aromatization, measured by1H MAS NMR, was found to be about 1 when adjusting the acid sites by altering eith...The optimum Mo/[H^+] ratio per unit cell of the active precursors in Mo/HZSM-5 catalysts for methane dehydro-aromatization, measured by1H MAS NMR, was found to be about 1 when adjusting the acid sites by altering either the SiO2/Al2O3 ratios or the Mo loading. This implies that a concerted interaction between the Mo species and the Bronsted acid sites probably features the bifunctionality of the Mo/HZSM-5 catalyst. On the other hand, it was found that the driving force for Mo species to move into the HSZM-5 zeolite channels and the interaction between the Mo species and the Bronsted acid sites are closely and proportionably related with the amount of Bronsted acid sites per unit cell.展开更多
In this study, the effects of pre-carburization of catalyst, hydrogen addition to methane feed and the space velocity of methane on the catalytic performance in methane to benzene （MTB） reaction were discussed in de...In this study, the effects of pre-carburization of catalyst, hydrogen addition to methane feed and the space velocity of methane on the catalytic performance in methane to benzene （MTB） reaction were discussed in detail over Mo/HZSM-5 catalyst at 1023 K and 0.3 MPa. Compared with the non-precarburized catalyst, the Mo catalyst pre-carburized under the flow of CHa＋4H2 at 973 K was found to have the higher activity and better stability. Further 6% H2 addition to the methane feed suppressed the aromatic type of coke formation effectively, and improved the stability of catalyst markedly, moreover gave a much longer reaction life of catalyst （53 h at 1023 K and 5400 ml/（g-h）） and much more formation amounts of benzene and hydrogen. With increase of methane space velocity, both the naphthalene formation selectivity and the coke formation selectivity were decreased by the shortened contact time; the benzene formation selectivity and total formation amount before the complete deactivation of catalyst were increased markedly, while the total naphthalene and coke formation amounts did not change much. At high methane space velocity （≥5400 ml/（g·h））, a new middle temperature coke derived from the high temperature aromatic coke was formed on the catalyst; all the coke formed could be burnt off at lower temperature in oxygen, compared with those obtained at low space velocity. Considering the benzene formation amount and catalyst stability together, 5400 ml/（g·h） was proved to be the most efficient methane space velocity for benzene production.展开更多
Unraveling the structure-activity relationship and improving the catalytic performance is paramount in propane dehydro-aromatization reactions. Herein, a tandem catalyst with high propane dehydro-aromatization reactio...Unraveling the structure-activity relationship and improving the catalytic performance is paramount in propane dehydro-aromatization reactions. Herein, a tandem catalyst with high propane dehydro-aromatization reaction performance was prepared via coupling the PtFe@S-1 with Zn/ZSM-5 zeolites (PtFe@S-1&1.0Zn/ZSM-5), which exhibits high dehydrogenation activity, aromatics selectivity (~60% at ~78% propane conversion), and stability. The addition of zinc inhibits the cleavage of C_(6)^(=) intermediates on ZSM-5 and promotes the aromatization pathway by weakening zeolite acid strength, significantly improving the selectivity to aromatics. This understanding of the structure-activity relationship in propane dehydro-aromatization reaction helps develop future high-performance catalysts.展开更多
基金supported by Hydrocarbon High-efficiency Utilization Technology Research Center of Shaanxi Yanchang Petroleum(Group)Co.,Ltd.,China(Contract No.HCRC-C13-010)the National Natural Science Foundation of China(No.21536009)。
文摘As a potential methane efficient conversion process,non-oxidative aromatization of methane in fluidized bed requires a catalyst with good attrition resistance,especially in the states of high temperature,longtime rapid movement and chemical reaction.Existing evaluation methods for attrition resistance,such as ASTM D5757 and Jet Cup test,are targeted for fresh catalysts at ambient temperature,which cannot well reflect the real process.In this study,spherical-shaped Mo/HZSM-5 catalyst prepared by dipping and spray drying was placed in a self-made apparatus for attrition testing,in which the catalyst attrition under different system temperatures,running time and process factors was investigated with percent mass loss(PML),particle size-mass distribution(PSMD)and scanning electron microscope(SEM).Carbon deposition on the catalyst before and after activation,aromatization and regeneration was analyzed by thermogravimetry(TG),and the attrited catalysts were evaluated for methane dehydro-aromatization(MDA).The results show that the surface abrasion and body breakage of catalyst particles occur continuously,with the increase of system temperature and running time,and make the PML rise gradually.The process factors of activation,aromatization and regeneration can cause the catalyst attrition and carbon deposits,which broaden the PSMD in varying degrees,and the carbon-substances on catalysts greatly improve their attrition resistance at high temperature.Catalyst attrition has a certain influence on its catalytic performance,and the main reasons point to particle breakage and fine powder escape.
基金Supported by the Ministry of Science and Technology of China(G1999022406)the BP China Joint Center.
文摘The direct conversion of methane into aromatics under non-oxidative conditions has received considerable attention since 1993^[1-3].Mo/HZSM-5 is the best one among the tested catalysts.It is generally accepted that the activation of the C-H bond of methane and initial C-C bond formation occur on Mocarbides formed from the reduction of Mo O,species,while the further transformation of C^(2+)hydrocarbons occurs on the Bronsted acid sites of HZSM-5 zeolite^[4].The unique channel structure of HZSM-5 plays a crucial role in constraining side reactions and controlling the product distribution^[5].The Bronsted acid sites of HZSM-5 are also responsible for the for-mation of carbonaceous deposits[6].
基金supported by Foundation for University Key Teacher by the Education of Heilongjiang Province(No.1152G018)
文摘The effect of steam-treatment to HZSM-5 zeolite and Mo/HZSM-5 with a steaming time range of 0.5-1 h on the catalytic performance of methane dehydro-aromatization （MDA） over Mo/HZSM-5 catalyst prepared with impregnation has been studied in detail in combination with the characterization of 1H MAS NMR technique. Both the deactivation rate constant （kd） and the Brtnsted acid sites per unit cell were calculated to quantitatively evaluate the stability of Mo/HZSM-5 catalysts treated with steam at 813 K before and after impregnation of molybdenum species, and the corresponding variation of their Brtnsted acid sites. The results reveal that a V-shape relationship between kd and the number of B 1 acid sites per unit cell is presented on Mo/HZSM-5 catalyst under the tested steam-treatment and reaction conditions.
文摘The optimum Mo/[H^+] ratio per unit cell of the active precursors in Mo/HZSM-5 catalysts for methane dehydro-aromatization, measured by1H MAS NMR, was found to be about 1 when adjusting the acid sites by altering either the SiO2/Al2O3 ratios or the Mo loading. This implies that a concerted interaction between the Mo species and the Bronsted acid sites probably features the bifunctionality of the Mo/HZSM-5 catalyst. On the other hand, it was found that the driving force for Mo species to move into the HSZM-5 zeolite channels and the interaction between the Mo species and the Bronsted acid sites are closely and proportionably related with the amount of Bronsted acid sites per unit cell.
文摘In this study, the effects of pre-carburization of catalyst, hydrogen addition to methane feed and the space velocity of methane on the catalytic performance in methane to benzene （MTB） reaction were discussed in detail over Mo/HZSM-5 catalyst at 1023 K and 0.3 MPa. Compared with the non-precarburized catalyst, the Mo catalyst pre-carburized under the flow of CHa＋4H2 at 973 K was found to have the higher activity and better stability. Further 6% H2 addition to the methane feed suppressed the aromatic type of coke formation effectively, and improved the stability of catalyst markedly, moreover gave a much longer reaction life of catalyst （53 h at 1023 K and 5400 ml/（g-h）） and much more formation amounts of benzene and hydrogen. With increase of methane space velocity, both the naphthalene formation selectivity and the coke formation selectivity were decreased by the shortened contact time; the benzene formation selectivity and total formation amount before the complete deactivation of catalyst were increased markedly, while the total naphthalene and coke formation amounts did not change much. At high methane space velocity （≥5400 ml/（g·h））, a new middle temperature coke derived from the high temperature aromatic coke was formed on the catalyst; all the coke formed could be burnt off at lower temperature in oxygen, compared with those obtained at low space velocity. Considering the benzene formation amount and catalyst stability together, 5400 ml/（g·h） was proved to be the most efficient methane space velocity for benzene production.
基金supported by the National Natural Science Foundation of China(Grant No.21902019)the Liaoning Revitalization Talent Program(Grant No.XLYC2203126)the Fundamental Research Funds for the Central Universities(Grant Nos.DUT22LK24,DUT22LAB602,and DUT22QN207).
文摘Unraveling the structure-activity relationship and improving the catalytic performance is paramount in propane dehydro-aromatization reactions. Herein, a tandem catalyst with high propane dehydro-aromatization reaction performance was prepared via coupling the PtFe@S-1 with Zn/ZSM-5 zeolites (PtFe@S-1&1.0Zn/ZSM-5), which exhibits high dehydrogenation activity, aromatics selectivity (~60% at ~78% propane conversion), and stability. The addition of zinc inhibits the cleavage of C_(6)^(=) intermediates on ZSM-5 and promotes the aromatization pathway by weakening zeolite acid strength, significantly improving the selectivity to aromatics. This understanding of the structure-activity relationship in propane dehydro-aromatization reaction helps develop future high-performance catalysts.
