Hierarchical SAPO‐34 crystals were synthesized by a facile acid etching post‐treatment. Butterfly‐shaped porous patterns on four side faces and hierarchical pores composed of micropores,mesopores and macropores wer...Hierarchical SAPO‐34 crystals were synthesized by a facile acid etching post‐treatment. Butterfly‐shaped porous patterns on four side faces and hierarchical pores composed of micropores,mesopores and macropores were formed after a nitric acid or oxalic acid treatment. The catalyticperformance of the hierarchical SAPO‐34 for the methanol to olefins (MTO) process showed that thesynergistic effect of the hierarchical pores and acid sites resulted in a longer catalyst lifetime (from210 to 390 min for the acid treated SAPO‐34) and higher selectivity to light olefins of 92%–94%.The ethylene selectivity can be adjusted between 37.4% and 51.5% by the pore size. No hierarchical SAPO‐34 was obtained after a treatment with butanedioic acid, and with this sample, fast deactivation was detected after 100 min.展开更多
The low‐temperature hydrothermal stabilities of Cu‐SAPO‐34samples with various Si contents and Cu loadings were systematically investigated.The NH3oxidation activities and NH3‐selective catalytic reduction(SCR)act...The low‐temperature hydrothermal stabilities of Cu‐SAPO‐34samples with various Si contents and Cu loadings were systematically investigated.The NH3oxidation activities and NH3‐selective catalytic reduction(SCR)activities(mainly the low‐temperature activities)of all the Cu‐SAPO‐34catalysts declined after low‐temperature steam treatment(LTST).These results show that the texture and acid density of Cu‐SAPO‐34can be better preserved by increasing the Cu loading,although the hydrolysis of Si-O-Al bonds is inevitable.The stability of Cu ions and the stability of the SAPO framework were positively correlated at relatively low Cu loadings.However,a high Cu loading(e.g.,3.67wt%)resulted in a significant decrease in the number of isolated Cu ions.Aggregation of CuO particles also occurred during the LTST,which accounts for the decreasing NH3oxidation activities of the catalysts.Among the catalysts,Cu‐SAPO‐34with a high Si content and medium Cu content(1.37wt%)showed the lowest decrease in NH3‐SCR because its Cu2+content was well retained and its acid density was well preserved.展开更多
The utilization of metal oxide‐zeolite catalysts in the syngas‐to‐olefin reaction is a promising strategy for producing C_(2)–C_(4) olefins from non‐petroleum resources.However,the effect of the crystal phase of ...The utilization of metal oxide‐zeolite catalysts in the syngas‐to‐olefin reaction is a promising strategy for producing C_(2)–C_(4) olefins from non‐petroleum resources.However,the effect of the crystal phase of metal oxides on the catalytic activity of these oxides is still ambiguous.Herein,typical metal oxides(ZnO/ZrO_(2))with different crystal phases(monoclinic(m‐ZrO_(2))and tetragonal(t‐ZrO_(2)))were employed for syngas conversion.The(ZnO/m‐ZrO_(2)+SAPO‐34)composite catalyst exhibited 80.5%selectivity for C_(2)–C_(4) olefins at a CO conversion of 27.9%,where the results are superior to those(CO conversion of 16.4%and C_(2)–C_(4) olefin selectivity of 76.1%)obtained over(ZnO/t‐ZrO_(2)+SAPO‐34).The distinct differences are ascribed to the larger number of hydroxyl groups,Lewis acid sites,and oxygen defects in ZnO/m‐ZrO_(2) compared to ZnO/t‐ZrO_(2).These features result in the formation of more formate and methoxy intermediate species on the ZnO/m‐ZrO_(2) oxides during syngas conversion,followed by the formation of more light olefins over SAPO‐34.The present findings provide useful information for the design of highly efficient ZrO_(2)‐based catalysts for syngas conversion.展开更多
基金supported by the National Natural Science Foundation of China (21403279, 21507141, 21506243)the Science and Technology Commission of Shanghai Municipality (14DZ1207602, 14DZ1203700)~~
文摘Hierarchical SAPO‐34 crystals were synthesized by a facile acid etching post‐treatment. Butterfly‐shaped porous patterns on four side faces and hierarchical pores composed of micropores,mesopores and macropores were formed after a nitric acid or oxalic acid treatment. The catalyticperformance of the hierarchical SAPO‐34 for the methanol to olefins (MTO) process showed that thesynergistic effect of the hierarchical pores and acid sites resulted in a longer catalyst lifetime (from210 to 390 min for the acid treated SAPO‐34) and higher selectivity to light olefins of 92%–94%.The ethylene selectivity can be adjusted between 37.4% and 51.5% by the pore size. No hierarchical SAPO‐34 was obtained after a treatment with butanedioic acid, and with this sample, fast deactivation was detected after 100 min.
基金supported by the National Natural Science Foundation of China(21676262,21506207,21606221)the Key Research Program of Frontier Sciences,CAS(QYZDB-SSW-JSC040)~~
文摘The low‐temperature hydrothermal stabilities of Cu‐SAPO‐34samples with various Si contents and Cu loadings were systematically investigated.The NH3oxidation activities and NH3‐selective catalytic reduction(SCR)activities(mainly the low‐temperature activities)of all the Cu‐SAPO‐34catalysts declined after low‐temperature steam treatment(LTST).These results show that the texture and acid density of Cu‐SAPO‐34can be better preserved by increasing the Cu loading,although the hydrolysis of Si-O-Al bonds is inevitable.The stability of Cu ions and the stability of the SAPO framework were positively correlated at relatively low Cu loadings.However,a high Cu loading(e.g.,3.67wt%)resulted in a significant decrease in the number of isolated Cu ions.Aggregation of CuO particles also occurred during the LTST,which accounts for the decreasing NH3oxidation activities of the catalysts.Among the catalysts,Cu‐SAPO‐34with a high Si content and medium Cu content(1.37wt%)showed the lowest decrease in NH3‐SCR because its Cu2+content was well retained and its acid density was well preserved.
文摘The utilization of metal oxide‐zeolite catalysts in the syngas‐to‐olefin reaction is a promising strategy for producing C_(2)–C_(4) olefins from non‐petroleum resources.However,the effect of the crystal phase of metal oxides on the catalytic activity of these oxides is still ambiguous.Herein,typical metal oxides(ZnO/ZrO_(2))with different crystal phases(monoclinic(m‐ZrO_(2))and tetragonal(t‐ZrO_(2)))were employed for syngas conversion.The(ZnO/m‐ZrO_(2)+SAPO‐34)composite catalyst exhibited 80.5%selectivity for C_(2)–C_(4) olefins at a CO conversion of 27.9%,where the results are superior to those(CO conversion of 16.4%and C_(2)–C_(4) olefin selectivity of 76.1%)obtained over(ZnO/t‐ZrO_(2)+SAPO‐34).The distinct differences are ascribed to the larger number of hydroxyl groups,Lewis acid sites,and oxygen defects in ZnO/m‐ZrO_(2) compared to ZnO/t‐ZrO_(2).These features result in the formation of more formate and methoxy intermediate species on the ZnO/m‐ZrO_(2) oxides during syngas conversion,followed by the formation of more light olefins over SAPO‐34.The present findings provide useful information for the design of highly efficient ZrO_(2)‐based catalysts for syngas conversion.
