A novel route involving self‐metathesis of1‐butene under mild conditions that gave high yields ofethene and hexene was proposed.The results of thermodynamic analysis revealed that the Gibbsenergy of the target Metat...A novel route involving self‐metathesis of1‐butene under mild conditions that gave high yields ofethene and hexene was proposed.The results of thermodynamic analysis revealed that the Gibbsenergy of the target Metathesis I reaction(1‐butene?ethene+3‐hexene)was much higher thanthat of the main side Metathesis II(1‐butene+2‐butene?propene+2‐pentene).Suppression of1‐butene double‐bond isomerization was the key step to increase the selectivity for the target olefinin the reaction network.The relationship between the catalytic performance and support nature was investigated in detail.On basis of H2‐TPR,UV‐Vis spectra and HRTEM results,an alumina(Al2O3)support with large surface area was beneficial for the dispersion of molybdenum(Mo)species.Both suitable acidity and sufficient Mo dispersion were important to selectively promote the self‐metathesis reaction of1‐butene.On the optimal6Mo/Al2O3catalyst,1‐butene conversion reached47%and ethene selectivity was as high as42%on the premise of good catalytic stability(80°C,1.0MPa,3h?1).?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
Ethylene/1-hexene was copolymerized by an unbridged zirconocene, (2-PhInd)2ZrCl2/MAO (methyl aluminoxane) at 0 °C and 50 °C respectively. High copolymerization activity and 1-hexene incorporation were observ...Ethylene/1-hexene was copolymerized by an unbridged zirconocene, (2-PhInd)2ZrCl2/MAO (methyl aluminoxane) at 0 °C and 50 °C respectively. High copolymerization activity and 1-hexene incorporation were observed at 0 °C, with the co- polymer formed having random sequence distribution and narrow molecular weight distribution. Ethylene polymerization at 50 °C showed high activity, but copolymerization at 50 °C showed much lower activity, which decreased sharply with increasing 1-hexene concentration in the monomer feed. Copolymer formed at 50 °C showed blocky sequence distribution and broad mo- lecular weight distribution. A mechanism model based on ligand rotation hindered by the propagation chain has been proposed to qualitatively explain the observed phenomena.展开更多
The effect of H2S contents on the transformation of 1-hexene with hydrogen over NiMoS/γ-Al2O3 catalyst was investigated.Inhibition of H2S on both hydrogenation and isomerization reactions of olefin has been demonstra...The effect of H2S contents on the transformation of 1-hexene with hydrogen over NiMoS/γ-Al2O3 catalyst was investigated.Inhibition of H2S on both hydrogenation and isomerization reactions of olefin has been demonstrated.And the promotion effect of H2S on the formation of C6 thiols and C12 thioethers has also been observed.It was found out that there was only one type of active site on the NiMoS/γ-Al2O3 for reactions which include hydrogenation reaction,isomerization reaction and sulfides formation reaction,and the formation reactions of sulfides were superior to both hydrogenation and isomerization reactions.The reaction network for the conversion of 1-hexene in the presence of H2S was proposed.展开更多
A series of Ti/Mg supported catalysts are prepared by using ball-milled mixtures of MgCl2-ethanol adducts and NaCl as supports, and 1-hexene polymerizations catalyzed by the novel catalysts are studied. It is found th...A series of Ti/Mg supported catalysts are prepared by using ball-milled mixtures of MgCl2-ethanol adducts and NaCl as supports, and 1-hexene polymerizations catalyzed by the novel catalysts are studied. It is found that the molecular weight distribution of poly(1-hexene) becomes apparently narrower when catalysts with doped supports are used, indicating that changing the structure of the support is an effective way to regulate the active center distribution of heterogeneous Ziegler-Natta catalyst.展开更多
Two different solvents had been used to separate benzene from 1-hexene under atmosphere pressure by employing one of the following two solvents, viz.: dimethyl sulfoxide (DMSO) at 298.15 K and 318.15 K, and furfural a...Two different solvents had been used to separate benzene from 1-hexene under atmosphere pressure by employing one of the following two solvents, viz.: dimethyl sulfoxide (DMSO) at 298.15 K and 318.15 K, and furfural at 298.15 K. A series of liquid-liquid equilibrium (LLE) data had been obtained and the distribution coefficient together with the separation factor were calculated from them. Both the NRTL and the UNIQUAC models could fit in with the experimental data quite well.展开更多
The title compound 5,5-dimethyl-2-（4-chlorophenyl）（3-hydroxy-5,5-dimethyl- 2-cyclohexen-1-one-2-yl）methyl-3-（4-methoxyphenylamino）-2-cyclohexen-1-one has been synthesized, and its crystal structure was character...The title compound 5,5-dimethyl-2-（4-chlorophenyl）（3-hydroxy-5,5-dimethyl- 2-cyclohexen-1-one-2-yl）methyl-3-（4-methoxyphenylamino）-2-cyclohexen-1-one has been synthesized, and its crystal structure was characterized by X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P21/c with a = 9.4193（13）, b = 26.915（4）, c= 21.188（3） A, β = 101.906（3）°, V = 5256.2（13） A3, Z = 4, C60H68C12N2O8, Mr =1016.06, Dc = 1.284 g/cm3, F（000） = 2160, λ（MoKα） = 0.71073 A, μ = 0.182 mm^-1, R = 0.0530 and wR = 0.1131 for 4128 observed reflections （1 〉 2α（Ⅰ））. X-ray analysis reveals that there are two independent molecules in the unit and the cyclohexenone rings adopt different conformations. In addition, there are four intramolecular hydrogen bonds in the title molecule.展开更多
The pyrolysis of 1-hexene can act as a prototype of pyrolytic mechanism in petro- leum processing. Details of C-C bond cleavage in the 1-hexene pyrolysis were investigated at the MP2/6-31 I＋＋G^＊＊ basis set level. ...The pyrolysis of 1-hexene can act as a prototype of pyrolytic mechanism in petro- leum processing. Details of C-C bond cleavage in the 1-hexene pyrolysis were investigated at the MP2/6-31 I＋＋G^＊＊ basis set level. The equilibrium geometries and key thermodynamic parameters such as Gibbs free energies and thermal enthalpies were gained. Our theoretical results show that the entropy effect plays a significant role in dissociative processes. The dissociation of 1-hexene-4-yl radical into C4H6 and C2H5 is not an H-transfer and C-C rupture elementary reaction, but a process involving H-transfer and C-C rupture.展开更多
On October 29, 2014 the hexene-1 package technologyindependently developed by the PetroChina PetrochemicalResearch Institute （PRI） has been applied in commercialscale at the new hexane-1 unit of the DushanzhiPetroch...On October 29, 2014 the hexene-1 package technologyindependently developed by the PetroChina PetrochemicalResearch Institute （PRI） has been applied in commercialscale at the new hexane-1 unit of the DushanzhiPetrochemical Company while cranking out qualifiedproduct with the purity of hexane-1 exceeding 99%. It islearned that the main techno-economic indicators of thisunit are better than those achieved by the overseas similarproduction units.展开更多
文摘A novel route involving self‐metathesis of1‐butene under mild conditions that gave high yields ofethene and hexene was proposed.The results of thermodynamic analysis revealed that the Gibbsenergy of the target Metathesis I reaction(1‐butene?ethene+3‐hexene)was much higher thanthat of the main side Metathesis II(1‐butene+2‐butene?propene+2‐pentene).Suppression of1‐butene double‐bond isomerization was the key step to increase the selectivity for the target olefinin the reaction network.The relationship between the catalytic performance and support nature was investigated in detail.On basis of H2‐TPR,UV‐Vis spectra and HRTEM results,an alumina(Al2O3)support with large surface area was beneficial for the dispersion of molybdenum(Mo)species.Both suitable acidity and sufficient Mo dispersion were important to selectively promote the self‐metathesis reaction of1‐butene.On the optimal6Mo/Al2O3catalyst,1‐butene conversion reached47%and ethene selectivity was as high as42%on the premise of good catalytic stability(80°C,1.0MPa,3h?1).?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
基金Project (Nos. 29734144 and 20274037) supported by the National Natural Science Foundation of China
文摘Ethylene/1-hexene was copolymerized by an unbridged zirconocene, (2-PhInd)2ZrCl2/MAO (methyl aluminoxane) at 0 °C and 50 °C respectively. High copolymerization activity and 1-hexene incorporation were observed at 0 °C, with the co- polymer formed having random sequence distribution and narrow molecular weight distribution. Ethylene polymerization at 50 °C showed high activity, but copolymerization at 50 °C showed much lower activity, which decreased sharply with increasing 1-hexene concentration in the monomer feed. Copolymer formed at 50 °C showed blocky sequence distribution and broad mo- lecular weight distribution. A mechanism model based on ligand rotation hindered by the propagation chain has been proposed to qualitatively explain the observed phenomena.
基金supported by the Natural Science Foundation of Shandong China (No.2009ZRA05107)the Plan of Innovation Team of Ministry of Education China (No.IRT0759)
文摘The effect of H2S contents on the transformation of 1-hexene with hydrogen over NiMoS/γ-Al2O3 catalyst was investigated.Inhibition of H2S on both hydrogenation and isomerization reactions of olefin has been demonstrated.And the promotion effect of H2S on the formation of C6 thiols and C12 thioethers has also been observed.It was found out that there was only one type of active site on the NiMoS/γ-Al2O3 for reactions which include hydrogenation reaction,isomerization reaction and sulfides formation reaction,and the formation reactions of sulfides were superior to both hydrogenation and isomerization reactions.The reaction network for the conversion of 1-hexene in the presence of H2S was proposed.
基金This work was supported by the National Natural Science Foundation of China (grant No. 20174034, 20274037).
文摘A series of Ti/Mg supported catalysts are prepared by using ball-milled mixtures of MgCl2-ethanol adducts and NaCl as supports, and 1-hexene polymerizations catalyzed by the novel catalysts are studied. It is found that the molecular weight distribution of poly(1-hexene) becomes apparently narrower when catalysts with doped supports are used, indicating that changing the structure of the support is an effective way to regulate the active center distribution of heterogeneous Ziegler-Natta catalyst.
基金the financial supports provided by the National Natural Science Foundation of China (No.21177038)
文摘Two different solvents had been used to separate benzene from 1-hexene under atmosphere pressure by employing one of the following two solvents, viz.: dimethyl sulfoxide (DMSO) at 298.15 K and 318.15 K, and furfural at 298.15 K. A series of liquid-liquid equilibrium (LLE) data had been obtained and the distribution coefficient together with the separation factor were calculated from them. Both the NRTL and the UNIQUAC models could fit in with the experimental data quite well.
基金the Foundation of the Key Laboratory of Biotechnology for Medical Plants of Jiangsu Province (No. 02AXL13)
文摘The title compound 5,5-dimethyl-2-（4-chlorophenyl）（3-hydroxy-5,5-dimethyl- 2-cyclohexen-1-one-2-yl）methyl-3-（4-methoxyphenylamino）-2-cyclohexen-1-one has been synthesized, and its crystal structure was characterized by X-ray single-crystal diffraction. The crystal belongs to monoclinic, space group P21/c with a = 9.4193（13）, b = 26.915（4）, c= 21.188（3） A, β = 101.906（3）°, V = 5256.2（13） A3, Z = 4, C60H68C12N2O8, Mr =1016.06, Dc = 1.284 g/cm3, F（000） = 2160, λ（MoKα） = 0.71073 A, μ = 0.182 mm^-1, R = 0.0530 and wR = 0.1131 for 4128 observed reflections （1 〉 2α（Ⅰ））. X-ray analysis reveals that there are two independent molecules in the unit and the cyclohexenone rings adopt different conformations. In addition, there are four intramolecular hydrogen bonds in the title molecule.
基金financially supported by the National Natural Science Foundation of China (No. 11174215)the Foundation of Shandong Province (ZR2012BL10)
文摘The pyrolysis of 1-hexene can act as a prototype of pyrolytic mechanism in petro- leum processing. Details of C-C bond cleavage in the 1-hexene pyrolysis were investigated at the MP2/6-31 I＋＋G^＊＊ basis set level. The equilibrium geometries and key thermodynamic parameters such as Gibbs free energies and thermal enthalpies were gained. Our theoretical results show that the entropy effect plays a significant role in dissociative processes. The dissociation of 1-hexene-4-yl radical into C4H6 and C2H5 is not an H-transfer and C-C rupture elementary reaction, but a process involving H-transfer and C-C rupture.
文摘On October 29, 2014 the hexene-1 package technologyindependently developed by the PetroChina PetrochemicalResearch Institute （PRI） has been applied in commercialscale at the new hexane-1 unit of the DushanzhiPetrochemical Company while cranking out qualifiedproduct with the purity of hexane-1 exceeding 99%. It islearned that the main techno-economic indicators of thisunit are better than those achieved by the overseas similarproduction units.
