A S 2O 2- 8/ZrO 2 Al 2O 3 type solid superacid catalyst was prepared from ZrOCl 2·8H 2O, AlCl 3· 6H 2O and (NH 4) 2S 2O 8 by coprecipitation, maceration and calcination processes. Their crystal structures an...A S 2O 2- 8/ZrO 2 Al 2O 3 type solid superacid catalyst was prepared from ZrOCl 2·8H 2O, AlCl 3· 6H 2O and (NH 4) 2S 2O 8 by coprecipitation, maceration and calcination processes. Their crystal structures and acidities were determined by XRD and Hammett method, respectively. The activity of the catalyst was studied as function of Al 2O 3 content, calcination temperature and time in the esterification of acetic acid with butanol, and a conversion of 96 5% was obtained. The catalyst gave also higher yields in syntheses of ketals and acetals: cyclohexanone ethylene ketal(86 2%), acetophenone ethylene ketal(78 5%), acetylacetic ester ketal(88 5%), benzaldehyde glycol acetal(76 3%). The chemical structures of the products were confirmed by IR spectra.展开更多
The bimetallic catalyst Ru-Pt/ γ -Al 2O 3 was prepared by impregnating H 2PtCl 6 and RuCl 3 aqueous solution in the presence of PVP(40 000). Its catalytic performance in selective hydrogenation of \{ p -chloronitrobe...The bimetallic catalyst Ru-Pt/ γ -Al 2O 3 was prepared by impregnating H 2PtCl 6 and RuCl 3 aqueous solution in the presence of PVP(40 000). Its catalytic performance in selective hydrogenation of \{ p -chloronitrobenzene\}( p -CNB) was studied. The results indicate that the activity of Ru-Pt/ γ -Al 2O 3[\{ n (ruthenium)\}∶ n (platinum)=4∶1] is much higher than that of Ru/ γ -Al 2O 3,while the amount of dehalogenation product(aniline) and other by-products are much fewer than that by using Pt/ γ -Al 2O 3 as the catalyst. There is synergistic effect of ruthenium and platinum in bimetallic catalyst for selective hydrogenation of p -CNB. Under the reaction conditions t =50 ℃, p H 2 = 1.0 MPa, reaction time 60 min,\{ n (substrate)∶\} n (total amount of metal content)=1000∶1,the conversion of p -CNB and the selectivity to p -chloroaniline( p -CNA) by using Ru-Pt/ γ -Al 2O 3 as the catalyst are 48.2% and 85.9%,respectively. The effect of other metal cations(introduced to the reaction system with the corresponding metal chloride solution) on the reaction was investigated. It was found that catalytic performance of Ru-Pt/ γ -Al 2O 3 could be greatly improved by modfication of some metal cations. When Co 2+ and Ni 2+ were used as modifiers for the catalyst Ru-Pt/ γ -Al 2O 3 under above mentioned reaction conditions,the conversions of p -CNB increase to 74.5% and 87.8%,as well as the selectivities of p -CAN increase to 98.9% and 99.4%,respectively. Fe 3+ and Sn 4+ were the best modifiers for Ru-Pt/ γ -Al 2O 3 under the same reaction conditions. The conversions of p -CNB and the selectivities of p -CAN can reach 100% and >99.0%,respectively. However,the catalysts can be poisoned by Zn 2+ and Sn 2+ .展开更多
Three kinds of new type solid strong acid catalysts S2O 2-8/ZrO2-Al2O3-M2O3（M=Cr,Ce,La） were prepared. Their crystal structure, surface area, acid strength and sulfur content were determined by means of XRD, BET, fl...Three kinds of new type solid strong acid catalysts S2O 2-8/ZrO2-Al2O3-M2O3（M=Cr,Ce,La） were prepared. Their crystal structure, surface area, acid strength and sulfur content were determined by means of XRD, BET, flow Hammett indicator method and chemical analysis. Their catalytic activities in esterification reaction of acetic acid with n-butanol were studied. The results showed that ZrO2 in the catalysts mainly in tetragonal phase and few in monoclinic phase. The tetragonal phase of ZrO2 and S2O 2-8 are the key factors that guarantee the catalytic activity. Incorporation of appropriate amounts of metallic oxides（Cr2O3,Ce2O3,La2O3） into the catalyst favors the stabilization of sulfur species and surface area, which increase the activity sites on the catalyst. The experimental results showed that three catalysts S2O 2-8/ZrO2-Al2O3（2%）-M2O3（1%）（M=Cr,Ce,La） had higher catalytic activity in mentioned esterification, with the conversion of acetic acid reached 96.8%, 95.7% and 96.1%, respectively. The preparation condition of the catalysts showed great influence on the catalytic activity.展开更多
文摘A S 2O 2- 8/ZrO 2 Al 2O 3 type solid superacid catalyst was prepared from ZrOCl 2·8H 2O, AlCl 3· 6H 2O and (NH 4) 2S 2O 8 by coprecipitation, maceration and calcination processes. Their crystal structures and acidities were determined by XRD and Hammett method, respectively. The activity of the catalyst was studied as function of Al 2O 3 content, calcination temperature and time in the esterification of acetic acid with butanol, and a conversion of 96 5% was obtained. The catalyst gave also higher yields in syntheses of ketals and acetals: cyclohexanone ethylene ketal(86 2%), acetophenone ethylene ketal(78 5%), acetylacetic ester ketal(88 5%), benzaldehyde glycol acetal(76 3%). The chemical structures of the products were confirmed by IR spectra.
文摘The bimetallic catalyst Ru-Pt/ γ -Al 2O 3 was prepared by impregnating H 2PtCl 6 and RuCl 3 aqueous solution in the presence of PVP(40 000). Its catalytic performance in selective hydrogenation of \{ p -chloronitrobenzene\}( p -CNB) was studied. The results indicate that the activity of Ru-Pt/ γ -Al 2O 3[\{ n (ruthenium)\}∶ n (platinum)=4∶1] is much higher than that of Ru/ γ -Al 2O 3,while the amount of dehalogenation product(aniline) and other by-products are much fewer than that by using Pt/ γ -Al 2O 3 as the catalyst. There is synergistic effect of ruthenium and platinum in bimetallic catalyst for selective hydrogenation of p -CNB. Under the reaction conditions t =50 ℃, p H 2 = 1.0 MPa, reaction time 60 min,\{ n (substrate)∶\} n (total amount of metal content)=1000∶1,the conversion of p -CNB and the selectivity to p -chloroaniline( p -CNA) by using Ru-Pt/ γ -Al 2O 3 as the catalyst are 48.2% and 85.9%,respectively. The effect of other metal cations(introduced to the reaction system with the corresponding metal chloride solution) on the reaction was investigated. It was found that catalytic performance of Ru-Pt/ γ -Al 2O 3 could be greatly improved by modfication of some metal cations. When Co 2+ and Ni 2+ were used as modifiers for the catalyst Ru-Pt/ γ -Al 2O 3 under above mentioned reaction conditions,the conversions of p -CNB increase to 74.5% and 87.8%,as well as the selectivities of p -CAN increase to 98.9% and 99.4%,respectively. Fe 3+ and Sn 4+ were the best modifiers for Ru-Pt/ γ -Al 2O 3 under the same reaction conditions. The conversions of p -CNB and the selectivities of p -CAN can reach 100% and >99.0%,respectively. However,the catalysts can be poisoned by Zn 2+ and Sn 2+ .
文摘Three kinds of new type solid strong acid catalysts S2O 2-8/ZrO2-Al2O3-M2O3（M=Cr,Ce,La） were prepared. Their crystal structure, surface area, acid strength and sulfur content were determined by means of XRD, BET, flow Hammett indicator method and chemical analysis. Their catalytic activities in esterification reaction of acetic acid with n-butanol were studied. The results showed that ZrO2 in the catalysts mainly in tetragonal phase and few in monoclinic phase. The tetragonal phase of ZrO2 and S2O 2-8 are the key factors that guarantee the catalytic activity. Incorporation of appropriate amounts of metallic oxides（Cr2O3,Ce2O3,La2O3） into the catalyst favors the stabilization of sulfur species and surface area, which increase the activity sites on the catalyst. The experimental results showed that three catalysts S2O 2-8/ZrO2-Al2O3（2%）-M2O3（1%）（M=Cr,Ce,La） had higher catalytic activity in mentioned esterification, with the conversion of acetic acid reached 96.8%, 95.7% and 96.1%, respectively. The preparation condition of the catalysts showed great influence on the catalytic activity.
