In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides her...In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.展开更多
The promotion effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. The hydroformylation reaction in the presence of gemini surfacta...The promotion effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. The hydroformylation reaction in the presence of gemini surfactant occurred with higher turnover frequency and higher selectivity for linear aldehyde than using conventional monomeric surfactant CTAB.展开更多
The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX, BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system. The catalyst system HR...The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX, BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system. The catalyst system HRh(CO)(PPh3)3-BISBI exhibited very high regioselectivity for the formation of linear aldehyde.展开更多
Hydroformylation of 1-dodecene was studied in a biphasic systemusing water-soluble rhodium complex [RhCl(CO)(TPPTS)_2] as catalystin the presence of cetyl trimethyl ammonium bromide as surfactant toenhance the reactio...Hydroformylation of 1-dodecene was studied in a biphasic systemusing water-soluble rhodium complex [RhCl(CO)(TPPTS)_2] as catalystin the presence of cetyl trimethyl ammonium bromide as surfactant toenhance the reaction rate. Efforts were devoted to improve theperformance of hydroformylation by exploring reactor configurationwhich enhanced the mixing, dispersion and interphase mass transfer.Experiments were carried out in a 0.5 L autoclave at the totalpressure of 1.1 Mpa and temperature from 363 K to 373 K.展开更多
The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved...The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved under relatively mild conditions.展开更多
Poly-α-olefin(PAO)synthetic oil,a regular long-chain alkane produced from the catalytic polymerization ofα-olefin,is a high-quality lubricating base oil with huge market potential.In this study,PAO synthesis based o...Poly-α-olefin(PAO)synthetic oil,a regular long-chain alkane produced from the catalytic polymerization ofα-olefin,is a high-quality lubricating base oil with huge market potential.In this study,PAO synthesis based on the catalytic polymerization of 1-decene using the ionic liquid(IL)[Bmim]_(x)[C_(2)H_(5)NH_(3)]_(1-x)[Al_(2)Cl_(7)]as the catalyst was studied.Compared with the conventional catalyst[Bmim][Al_(2)Cl_(7)],the obtained PAO product incorporates more trimers and tetramers of 1-decene and contains few double-bond end groups,demonstrating a better catalytic system for PAO-10 production.The apparent polymerization kinetics of 1-decene in this catalytic system were studied based on the 1-decene concentration,catalyst concentration,and reaction temperature.An apparent kinetic equation for PAO formation was determined,providing a promising strategy for PAO production using 1-decene polymerization.展开更多
Poly-α-olefin(PAO) synthetic oil is the base oil of high-quality lubricants, and has a huge market potential.We illustrate PAO synthesis by catalytic polymerization of 1-decene with a boron trifluoride(BF_3)/alcohol ...Poly-α-olefin(PAO) synthetic oil is the base oil of high-quality lubricants, and has a huge market potential.We illustrate PAO synthesis by catalytic polymerization of 1-decene with a boron trifluoride(BF_3)/alcohol system. Gas chromatography–mass spectrometry, proton nuclear magnetic resonance and ^(13) C nuclear magnetic resonance analysis confirmed dimer, trimer and tetramer structures of PAO. Each component contained branched chains with a 1,2 insertion of a head-to-tail link; a 2,1 insertion of a tail-to-tail link and a methyl-containing linked structure. At a low conversion rate, the reaction rate was related directly with the reaction temperature and the catalyst/1-decene concentration. An apparent kinetic equation for PAO formation was determined during 1-decene polymerization.展开更多
Based on a compulsive mixing-reacting-sepa-rating-recycling small experimental setup,the continuous reaction performances of benzene alkylation with long chain olefins catalyzed by[BMIM]Cl-AlCl 3 ionic liquid were inv...Based on a compulsive mixing-reacting-sepa-rating-recycling small experimental setup,the continuous reaction performances of benzene alkylation with long chain olefins catalyzed by[BMIM]Cl-AlCl 3 ionic liquid were investigated.Three different situations including normal continuous operation mode(reagent materials),sidetrack feeding from different axial positions along the static mixing reactor(reagent materials)and normal con-tinuous alkylation using industrial paraffin and olefins materials were examined.Even under the relatively hype-critical reaction conditions,the single pass conversion of pure 1-dodecene could reach to nearly 100.0%,and the selectivity of 2-phenyl isomer was higher than 37.7%.Although the positions along the reactor for sidetrack feeding were different,the 100.0%single pass conversion of 1-dodecene was also attained before the outlet of the reactor.The refined industrial olefins as raw material could meet with the requirements of continuous alkyla-tion.The influences of impurities such as di-olefins and non-benzene aromatics on the catalytic activity and stability should be studied further.展开更多
文摘In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.
文摘The promotion effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. The hydroformylation reaction in the presence of gemini surfactant occurred with higher turnover frequency and higher selectivity for linear aldehyde than using conventional monomeric surfactant CTAB.
基金We thank the National Basic Research Project of China(G2000048008)for the financial support.
文摘The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX, BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system. The catalyst system HRh(CO)(PPh3)3-BISBI exhibited very high regioselectivity for the formation of linear aldehyde.
基金the National Natural Science Foundation of China (No. 29792074) and SINOPEC.
文摘Hydroformylation of 1-dodecene was studied in a biphasic systemusing water-soluble rhodium complex [RhCl(CO)(TPPTS)_2] as catalystin the presence of cetyl trimethyl ammonium bromide as surfactant toenhance the reaction rate. Efforts were devoted to improve theperformance of hydroformylation by exploring reactor configurationwhich enhanced the mixing, dispersion and interphase mass transfer.Experiments were carried out in a 0.5 L autoclave at the totalpressure of 1.1 Mpa and temperature from 363 K to 373 K.
文摘The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved under relatively mild conditions.
基金supported by the Key Research and Development Program of Ningxia Autonomous Region (No.2023BFE01001)Tianjin Science and Technology Program (Nos.22ZYJDSS00060+2 种基金22YDTPJC00920)Program for Tianjin Innovative Research Team in Universities (No.TD13-5031)Tianjin 131 Research Team of Innovative Talents。
文摘Poly-α-olefin(PAO)synthetic oil,a regular long-chain alkane produced from the catalytic polymerization ofα-olefin,is a high-quality lubricating base oil with huge market potential.In this study,PAO synthesis based on the catalytic polymerization of 1-decene using the ionic liquid(IL)[Bmim]_(x)[C_(2)H_(5)NH_(3)]_(1-x)[Al_(2)Cl_(7)]as the catalyst was studied.Compared with the conventional catalyst[Bmim][Al_(2)Cl_(7)],the obtained PAO product incorporates more trimers and tetramers of 1-decene and contains few double-bond end groups,demonstrating a better catalytic system for PAO-10 production.The apparent polymerization kinetics of 1-decene in this catalytic system were studied based on the 1-decene concentration,catalyst concentration,and reaction temperature.An apparent kinetic equation for PAO formation was determined,providing a promising strategy for PAO production using 1-decene polymerization.
基金supported by the Natural Science Foundation of China(21576048)the PetroChina Innovation Foundation(2014D-5006-0503)
文摘Poly-α-olefin(PAO) synthetic oil is the base oil of high-quality lubricants, and has a huge market potential.We illustrate PAO synthesis by catalytic polymerization of 1-decene with a boron trifluoride(BF_3)/alcohol system. Gas chromatography–mass spectrometry, proton nuclear magnetic resonance and ^(13) C nuclear magnetic resonance analysis confirmed dimer, trimer and tetramer structures of PAO. Each component contained branched chains with a 1,2 insertion of a head-to-tail link; a 2,1 insertion of a tail-to-tail link and a methyl-containing linked structure. At a low conversion rate, the reaction rate was related directly with the reaction temperature and the catalyst/1-decene concentration. An apparent kinetic equation for PAO formation was determined during 1-decene polymerization.
基金This work was supported by the National Program on Key Basic Research Project(G2000048006)Research Foundation of Henan University(05YBZR025).
文摘Based on a compulsive mixing-reacting-sepa-rating-recycling small experimental setup,the continuous reaction performances of benzene alkylation with long chain olefins catalyzed by[BMIM]Cl-AlCl 3 ionic liquid were investigated.Three different situations including normal continuous operation mode(reagent materials),sidetrack feeding from different axial positions along the static mixing reactor(reagent materials)and normal con-tinuous alkylation using industrial paraffin and olefins materials were examined.Even under the relatively hype-critical reaction conditions,the single pass conversion of pure 1-dodecene could reach to nearly 100.0%,and the selectivity of 2-phenyl isomer was higher than 37.7%.Although the positions along the reactor for sidetrack feeding were different,the 100.0%single pass conversion of 1-dodecene was also attained before the outlet of the reactor.The refined industrial olefins as raw material could meet with the requirements of continuous alkyla-tion.The influences of impurities such as di-olefins and non-benzene aromatics on the catalytic activity and stability should be studied further.