The effect of ultrasonic cavitations on the activity of vanadium catalysts atlow temperatures for the oxidation of sulfur dioxide, in which refined carbonized mother liquor hadbeen added, was investigated. Twenty minu...The effect of ultrasonic cavitations on the activity of vanadium catalysts atlow temperatures for the oxidation of sulfur dioxide, in which refined carbonized mother liquor hadbeen added, was investigated. Twenty minutes were needed to produce obvious cavitations when thecatalyst raw material was treated in the 50 W ultrasonic generator. However, only 10 minutes wouldbe needed in a 150 W ultrasonic generator. The higher the temperature of the wet material, the lesstime was needed to produce cavitations, and the optimal temperature was 60℃. The water content inthe wet material mainly affected the quantity of cavitations. Ls-8 catalyst was prepared usingultrasonic. Its activity for conversion of SO_2 reached to 52.5% at 410℃ and 4.2% at 350℃. Thedifferential thermal analyses indicate that both endothermic peaks and exothermic peaks noticeablyshifted forward compared with Ls catalyst prepared without ultrasonic, and SEM results show auniform pore size distribution for Ls-8 catalyst.展开更多
Vanadium-titanium-based catalysts are the most widely used industrial materials for NO_x removal from coal-fired power plants. Owing to their relatively poor low-temperature deNO_x activity, low thermal stability, ins...Vanadium-titanium-based catalysts are the most widely used industrial materials for NO_x removal from coal-fired power plants. Owing to their relatively poor low-temperature deNO_x activity, low thermal stability, insufficient Hg^0 oxidation activity, SO_2 oxidation, ammonia slip, and other disadvantages,modifications to traditional vanadium-titanium-based selective catalytic reduction（SCR）catalysts have been attempted by many researchers to promote their relevant performance. This article reviewed the research progress of modified vanadium-titanium-based SCR catalysts from seven aspects, namely,（1） improving low-temperature deNO_x efficiency,（2） enhancing thermal stability,（3） improving Hg^0 oxidation efficiency,（4） oxidizing slip ammonia,（5） reducing SO_2 oxidation,（6） increasing alkali resistance, and（7） others. Their catalytic performance and the influence mechanisms have been discussed in detail. These catalysts were also divided into different categories according to their modified components such as noble metals（e.g., silver, ruthenium）, transition metals（e.g., manganese, iron, copper, zirconium, etc.）, rare earth metals（e.g., cerium, praseodymium）,and other metal chlorides（e.g., calcium chloride, copper chloride） and non-metals（fluorine,sulfur, silicon, nitrogen, etc.）. The advantages and disadvantages of these catalysts were summarized.Based on previous studies and the author＇s point of view, doping the appropriate modified components is beneficial to further improve the overall performance of vanadium-titanium-based SCR catalysts. This has enormous development potential and is a promising way to realize the control of multiple pollutants on the basis of the existing flue gas treatment system.展开更多
Radio frequency plasma was used to prepare a vanadium catalyst. The resultsshowed that activating time of the catalyst could be shortened quickly and the catalytic activitywas improved to some extent with the use of p...Radio frequency plasma was used to prepare a vanadium catalyst. The resultsshowed that activating time of the catalyst could be shortened quickly and the catalytic activitywas improved to some extent with the use of plasma. Catalyst Ls-9 was prepared under an optimalcondition of 40 W discharge power, 10 min discharge time and 8 Pa gas pressure. The catalyticactivity was up to 54.7% at 410℃, which was 2.2% higher than that of the Ls-8 catalyst. Only 10 minwas needed to activate the catalyst with plasma, which was 1/9 of the traditional calcination time.For Ls-9, both the endothermic as well as the exothermic peaks detected by differential thermalanalysis shifted to higher temperatures obviously, indicating that its crystal phase could melteasily. There existed an apparent endothermic peak at 283℃. SEM photographs showed a uniform sizedistribution. It is inferred that the quadrivalent vanadium compound may exist mainly in the form ofVOSO_4.展开更多
The selective oxidation of n-butane to maleic anhydride (MA) on a vanadium-phosphorus oxide (VPO) catalyst was studied using on-line gas-chromatography combined with mass spectrometry(GC-MS) and transient response tec...The selective oxidation of n-butane to maleic anhydride (MA) on a vanadium-phosphorus oxide (VPO) catalyst was studied using on-line gas-chromatography combined with mass spectrometry(GC-MS) and transient response technique. The reaction intermediates, buterie and furan, were found in the reaction effluent under near industrial feed condition (3% butane+15%O2), while dihydrofuran was detected at high butane concentration (12% butane, 5%O2). Some intermediates of MA decomposition were also identified. Detection of these intermediates shows that the vanadium phosphorus oxides are able to dehydrogenate butane to butene, and butene further to form MA. Based on these observations, a modified scheme of reaction network is proposed. The transient experiments show that butane in the gas phase may directly react with oxygen both on the surface and from the metal oxide lattice, without a proceeding adsorption step. Gas phase oxygen can be adsorbed and transformed to surface lattice oxygen but it can not participate in selective oxidation. Adsorbed oxygen leads to deep oxidation, while lattice oxygen leads to selective oxidation.展开更多
The effect of chemical composition of highly active supported Ziegler-Natta catalysts with controlled morphology on the MWD of PE has been studied.It was shown the variation of transition metal compound in the MgCl_2-...The effect of chemical composition of highly active supported Ziegler-Natta catalysts with controlled morphology on the MWD of PE has been studied.It was shown the variation of transition metal compound in the MgCl_2-supported catalyst affect of MWD of PE produced in broad range:Vanadium-magnesium catalyst(VMC)produce PE with broad and bimodal MWD(M_w/M_n=14-21).MWD of PE,produced over titanium-magnesium catalyst(TMC)is narrow or medium depending on Ti content in the catalyst(M_w/M_n=3.1-4.8).The oxidation ...展开更多
A novel vanadium oxide catalyst supported on active carbon was prepared by an incipient wetness impregnation method, and the precursor was obtained from oxalic acid aqueous solutions of NH4VO3. The catalyst was applie...A novel vanadium oxide catalyst supported on active carbon was prepared by an incipient wetness impregnation method, and the precursor was obtained from oxalic acid aqueous solutions of NH4VO3. The catalyst was applied liquid phase oxidation of glyoxal to glyoxylic acid. It was found that V2O5/C catalyst exhibited obvious activity for glyoxal oxidation. Glyoxylic acid could be obtained without pH regulation during the reaction. By using this catalyst, the conversion of glyoxal and the yield of glyoxalic acid were 29.2% and 13.6%, respectively at 313 K and oxygen flow 0.1 L/rain after reaction for 10 h.展开更多
The nanometer CeO2 powder was prepared by the method of microwave-assisted heating hydrolysis,and the nanometer CeO2-supported or ordinary CeO2-supported vanadia catalysts with different vanadium loadings(atomic ratio...The nanometer CeO2 powder was prepared by the method of microwave-assisted heating hydrolysis,and the nanometer CeO2-supported or ordinary CeO2-supported vanadia catalysts with different vanadium loadings(atomic ratios:100V/Ce=0.1,1,4,10,and 20) were prepared by an incipient-wetness impregnation method.Spectroscopic techniques(XRD,FT-IR,Raman and UV-Vis DRS) were utilized to characterize the structures of VOx/CeO2 catalysts.The results showed that the structures of CeO2-supported vanadium oxide catalysts de...展开更多
Precursor decomposition was used for the preparation of VTeO/SBA-15 catalyst for the selective oxidation of propane to acrolein. The catalyst shows a better performance compared with those prepared by conventional imp...Precursor decomposition was used for the preparation of VTeO/SBA-15 catalyst for the selective oxidation of propane to acrolein. The catalyst shows a better performance compared with those prepared by conventional impregnant method. A yield of 9.3% of acrolein was achieved with 2% V loadings at 500 ℃. XRD, N2-adsorption, H2-TPR, Py-IR and XPS measurements were used to unclose the relationship between the structure and performance of the catalyst.展开更多
Magnesium chloride supported vanadium/titanium bimetallic Ziegler-Natta catalysts with di-i-butyl phthalate as internal donor for copolymerization of ethylene and propylene were prepared. The effects of reaction tempe...Magnesium chloride supported vanadium/titanium bimetallic Ziegler-Natta catalysts with di-i-butyl phthalate as internal donor for copolymerization of ethylene and propylene were prepared. The effects of reaction temperature, ethylene/propylene molar ratio, aluminium/vanadium （Al/V） molar ratio and titanium/vanadium molar ratio on the catalytic activity were investigated. The molecular weight, molecular weight distribution, sequence composition and crystallinity of the products were measured by gel permeation chromatography, ^13C-NMR and differential scanning calorimetry analysis, respectively. In comparison to the vanadium and titanium catalysts, the bimetallic catalyst showed higher catalytic activity and better copolymerization performance. The obtained ethylene/propylene copolymers have high molecular weight （105）, broad molecular weight distribution, high propylene content with random or short blocked sequence structures （rErp = 1.919）, low melting temperatures and low crystallinities （Xc 〈 20%）.展开更多
The Obrochishte deposit located in the Republic of Bulgaria has considerable reserves of relatively poor carbonate manganese ore. At the same time, in the country there are operative outputs for the production of sulp...The Obrochishte deposit located in the Republic of Bulgaria has considerable reserves of relatively poor carbonate manganese ore. At the same time, in the country there are operative outputs for the production of sulphuric acid where vanadium catalyst is deactivated and discharged, polluting the environment. The utilization of these materials requires their consolidation to proper sizes with regard to the next processing, as the most suitable method for joint consolidation is agglomeration. The present work explores the preliminary calculations for obtaining agglomerate and obtaining an alloy with high and low carbon content, through carbothermic and aluminothermic agglomerate reduction.展开更多
Several novel mono（β-enaminoketonato） vanadium complexes bearing constrained [（C6Hs）C6H3C（O）=C（CH2）nCH=N-Ar]VCl2（THF）2 （V3a： n = 1, Ar = C6H5; V4a： n = 2, Ar cyclic skeleton, including C6H5; V4b： n = 2,...Several novel mono（β-enaminoketonato） vanadium complexes bearing constrained [（C6Hs）C6H3C（O）=C（CH2）nCH=N-Ar]VCl2（THF）2 （V3a： n = 1, Ar = C6H5; V4a： n = 2, Ar cyclic skeleton, including C6H5; V4b： n = 2, Ar C6F5; V4c： n = 2, Ar = （C3H7）2C6H3; V5a： n = 3, Ar = C6H5）, were synthesized and their structure and properties were characterized. The structures of V4c and V5a in solid-state were further confirmed by X-ray crystallographic analysis. Density functional theory （DFT） results indicated that these complexes showed enhanced steric hindrance around the metal center as compared with the acyclic analogues. Upon activation with Et2AlCl and in the presence of ethyl trichloroacetate as a reactivator, all of the complexes exhibited high catalytic activities （107 gPE/（molv.h）） toward ethylene polymerization, and the obtained polymers exhibited unimodal distributions （Mw/Mn = 2.0-2.3） even produced at elevated temperatures （70-100 ℃） and prolonged reaction time. When MAO was employed as a cocatalyst, they only showed moderate catalytic activities （10^5 gPE/（molv·h））, but the resulting polymers had higher molecular weights （168-241 kg/mol）. These vanadium complexes with cyclic skeleton also showed high catalytic activities toward ethylene/norbornene copolymerization. The produced copolymers displayed approximate alternating structure at high in-feed concentration of norbornene. The catalytic capabilities of these complexes could be tuned conveniently by varying ligand structure. Furthermore, the cyclic voltammetry results also proved that these complexes exhibited better redox stabilities than the complexes bearing linear skeleton.展开更多
Vanadium（III） complexes bearing thiophenol-phosphine ligands （2a-2b） （2-R-6-PPh2-C6H2S） VC12（THF）2 （2a： R = H; 2b： R = MeaSi） were prepared from VCla（THF）3 by treating with 1.0 equiv of the ligand in tet...Vanadium（III） complexes bearing thiophenol-phosphine ligands （2a-2b） （2-R-6-PPh2-C6H2S） VC12（THF）2 （2a： R = H; 2b： R = MeaSi） were prepared from VCla（THF）3 by treating with 1.0 equiv of the ligand in tetrahydrofuran in the presence of excess triethylamine. The two complexes were characterized by FTIR and mass spectra as well as elemental analyses. On activation with Et2AIC1, these complexes exhibited high catalytic activities （up to 22.1 kg PE/（mmolv.h.bar）） even at high temperature （70 ℃）, and produced high molecular weight polymers with unimodal molecular weight distributions, indicating the polymerization took place in a single-site nature. This result may be attributed to benefits of introduction of second-row donor atoms for adjusting charge density of the vanadium centers. In addition, these complexes also exhibited high catalytic activities for ethylene/1-hexene copolymerization. Catalytic activity, comonomer incorporation and polymer molecular weight can be controlled in a wide range by the variation of catalyst structure and the reaction parameters such as A1/V molar ratio, comonomer feed concentration and polymerization reaction temperature.展开更多
Mono salicylaldiminato vanadium（Ⅲ） complexes （1a-1f） [RN = CH（ArO）]VC12（THF）2 （Ar = C6H4 （1a-1e）, R = Ph, 1a; R = p-CFaPh, 1b; R = 2,6-Me2Ph, 1c; R = 2,6-iPrEPh, 1d; R = eyclohexyl, 1e; Ar = C6HEtBU2（2,4...Mono salicylaldiminato vanadium（Ⅲ） complexes （1a-1f） [RN = CH（ArO）]VC12（THF）2 （Ar = C6H4 （1a-1e）, R = Ph, 1a; R = p-CFaPh, 1b; R = 2,6-Me2Ph, 1c; R = 2,6-iPrEPh, 1d; R = eyclohexyl, 1e; Ar = C6HEtBU2（2,4）, R = 2,6-iPrEPh, 1f） and bis（salicylaldiminato） vanadium（III） complexes （2a-2f） [RN ： CH（ArO）]EVCI（THF）x （Ar = C6H4 （2a-2e）, x = 1 （2a-2e）, R = Ph, 2a; R = p-CF3Ph, 2b; R = 2,6-Me2Ph, 2c; R = 2,6-iPr2Ph, 2d; R = cyclohexyl, 2e; Ar = C6HEtBU2（2,4）, R = 2,6-iPrEPh, x = 0, 2f） have been evaluated as the active catalysts for ethylene/1-hexene copolymerization in the presence of Et2A1C1. The ligand substitution pattern and the catalyst structure model significantly influenced the polymerization behaviors such as the catalytic activity, the molecular weight and molecular weight distribution of the copolymers etc. The highest catalytic activity of 8.82 kg PE/（mmolv.h） was observed for vanadium catalyst 2d with two 2,6-diisopropylphenyl substituted salicylaldiminato ligands. The copolymer with the highest molecular weight was obtained by using mono salieylaldiminato vanadium catalyst 1 f having ligands with tert-butyl at the ortho and para of the aryloxy moiety.展开更多
The need for more active and hydrothermally stable fluid catalytic cracking（FCC）catalysts to combat the effect of metal contaminants has led to an increase in demand for rare earth oxides.Rare earth oxides enhance c...The need for more active and hydrothermally stable fluid catalytic cracking（FCC）catalysts to combat the effect of metal contaminants has led to an increase in demand for rare earth oxides.Rare earth oxides enhance catalyst activity and prevent the loss of acid sites during the FCC unit operation,especially when heavy residue with high metal content is used as feed.In this paper,a review was carried out to show the effects of rare earth elements on the structure,activity,and stability of FCC catalysts.Also,the use of rare earth elements as vanadium traps was analyzed in conjunction with the mechanism of catalyst deactivation by vanadium.The objective was to elucidate the interaction of vanadium species with the zeolite component of the FCC catalysts and the role of rare earth elements in countering the deleterious effects of vanadium on the FCC catalysts.展开更多
基金Project(20176065)supported by the National Natural Science Foundation of China.
文摘The effect of ultrasonic cavitations on the activity of vanadium catalysts atlow temperatures for the oxidation of sulfur dioxide, in which refined carbonized mother liquor hadbeen added, was investigated. Twenty minutes were needed to produce obvious cavitations when thecatalyst raw material was treated in the 50 W ultrasonic generator. However, only 10 minutes wouldbe needed in a 150 W ultrasonic generator. The higher the temperature of the wet material, the lesstime was needed to produce cavitations, and the optimal temperature was 60℃. The water content inthe wet material mainly affected the quantity of cavitations. Ls-8 catalyst was prepared usingultrasonic. Its activity for conversion of SO_2 reached to 52.5% at 410℃ and 4.2% at 350℃. Thedifferential thermal analyses indicate that both endothermic peaks and exothermic peaks noticeablyshifted forward compared with Ls catalyst prepared without ultrasonic, and SEM results show auniform pore size distribution for Ls-8 catalyst.
基金supported by the Science and Technology Plan Project of Hebei Province of China(16273703D)the Fundamental Research Funds for the Central Universities(2015ZD24,2017XS123)~~
文摘Vanadium-titanium-based catalysts are the most widely used industrial materials for NO_x removal from coal-fired power plants. Owing to their relatively poor low-temperature deNO_x activity, low thermal stability, insufficient Hg^0 oxidation activity, SO_2 oxidation, ammonia slip, and other disadvantages,modifications to traditional vanadium-titanium-based selective catalytic reduction（SCR）catalysts have been attempted by many researchers to promote their relevant performance. This article reviewed the research progress of modified vanadium-titanium-based SCR catalysts from seven aspects, namely,（1） improving low-temperature deNO_x efficiency,（2） enhancing thermal stability,（3） improving Hg^0 oxidation efficiency,（4） oxidizing slip ammonia,（5） reducing SO_2 oxidation,（6） increasing alkali resistance, and（7） others. Their catalytic performance and the influence mechanisms have been discussed in detail. These catalysts were also divided into different categories according to their modified components such as noble metals（e.g., silver, ruthenium）, transition metals（e.g., manganese, iron, copper, zirconium, etc.）, rare earth metals（e.g., cerium, praseodymium）,and other metal chlorides（e.g., calcium chloride, copper chloride） and non-metals（fluorine,sulfur, silicon, nitrogen, etc.）. The advantages and disadvantages of these catalysts were summarized.Based on previous studies and the author＇s point of view, doping the appropriate modified components is beneficial to further improve the overall performance of vanadium-titanium-based SCR catalysts. This has enormous development potential and is a promising way to realize the control of multiple pollutants on the basis of the existing flue gas treatment system.
基金The project is supported by the National Natural Science Foundation of China (No.20176065)
文摘Radio frequency plasma was used to prepare a vanadium catalyst. The resultsshowed that activating time of the catalyst could be shortened quickly and the catalytic activitywas improved to some extent with the use of plasma. Catalyst Ls-9 was prepared under an optimalcondition of 40 W discharge power, 10 min discharge time and 8 Pa gas pressure. The catalyticactivity was up to 54.7% at 410℃, which was 2.2% higher than that of the Ls-8 catalyst. Only 10 minwas needed to activate the catalyst with plasma, which was 1/9 of the traditional calcination time.For Ls-9, both the endothermic as well as the exothermic peaks detected by differential thermalanalysis shifted to higher temperatures obviously, indicating that its crystal phase could melteasily. There existed an apparent endothermic peak at 283℃. SEM photographs showed a uniform sizedistribution. It is inferred that the quadrivalent vanadium compound may exist mainly in the form ofVOSO_4.
基金Supported by the National Natural Science Foundation of China (No. 29792073-3).
文摘The selective oxidation of n-butane to maleic anhydride (MA) on a vanadium-phosphorus oxide (VPO) catalyst was studied using on-line gas-chromatography combined with mass spectrometry(GC-MS) and transient response technique. The reaction intermediates, buterie and furan, were found in the reaction effluent under near industrial feed condition (3% butane+15%O2), while dihydrofuran was detected at high butane concentration (12% butane, 5%O2). Some intermediates of MA decomposition were also identified. Detection of these intermediates shows that the vanadium phosphorus oxides are able to dehydrogenate butane to butene, and butene further to form MA. Based on these observations, a modified scheme of reaction network is proposed. The transient experiments show that butane in the gas phase may directly react with oxygen both on the surface and from the metal oxide lattice, without a proceeding adsorption step. Gas phase oxygen can be adsorbed and transformed to surface lattice oxygen but it can not participate in selective oxidation. Adsorbed oxygen leads to deep oxidation, while lattice oxygen leads to selective oxidation.
文摘The effect of chemical composition of highly active supported Ziegler-Natta catalysts with controlled morphology on the MWD of PE has been studied.It was shown the variation of transition metal compound in the MgCl_2-supported catalyst affect of MWD of PE produced in broad range:Vanadium-magnesium catalyst(VMC)produce PE with broad and bimodal MWD(M_w/M_n=14-21).MWD of PE,produced over titanium-magnesium catalyst(TMC)is narrow or medium depending on Ti content in the catalyst(M_w/M_n=3.1-4.8).The oxidation ...
文摘A novel vanadium oxide catalyst supported on active carbon was prepared by an incipient wetness impregnation method, and the precursor was obtained from oxalic acid aqueous solutions of NH4VO3. The catalyst was applied liquid phase oxidation of glyoxal to glyoxylic acid. It was found that V2O5/C catalyst exhibited obvious activity for glyoxal oxidation. Glyoxylic acid could be obtained without pH regulation during the reaction. By using this catalyst, the conversion of glyoxal and the yield of glyoxalic acid were 29.2% and 13.6%, respectively at 313 K and oxygen flow 0.1 L/rain after reaction for 10 h.
基金supported by the National Natural Science Foundation of China (20803093,20833011,20525621)the Doctor Select Foundation for the University of State Education Ministry (200804251016)+1 种基金the Beijing Outstanding Ph.D.Thesis Foundation (YB 20091141401)the Hi-Tech Research and Development Program (863) of China (SQ2009AA06Z3488052)
文摘The nanometer CeO2 powder was prepared by the method of microwave-assisted heating hydrolysis,and the nanometer CeO2-supported or ordinary CeO2-supported vanadia catalysts with different vanadium loadings(atomic ratios:100V/Ce=0.1,1,4,10,and 20) were prepared by an incipient-wetness impregnation method.Spectroscopic techniques(XRD,FT-IR,Raman and UV-Vis DRS) were utilized to characterize the structures of VOx/CeO2 catalysts.The results showed that the structures of CeO2-supported vanadium oxide catalysts de...
基金Supported by the Ministry of Science and Technology of China(No. 2005CB221408)the National Natural Science Founda-tion of China(Nos. 20423002, 20571061)Key Scientific Project of Fujian Province, China(No. 2005HZ01-3)
文摘Precursor decomposition was used for the preparation of VTeO/SBA-15 catalyst for the selective oxidation of propane to acrolein. The catalyst shows a better performance compared with those prepared by conventional impregnant method. A yield of 9.3% of acrolein was achieved with 2% V loadings at 500 ℃. XRD, N2-adsorption, H2-TPR, Py-IR and XPS measurements were used to unclose the relationship between the structure and performance of the catalyst.
基金supported by the Program for New Century Excellent Talents in Universities(NCET-07-0142)the Program for New Century Excellent Talents in Heilongjiang Provincial Universities(NCET-06-010)+1 种基金the National Natural Science Foundation of China(No.20972025)the Science Foundation of Tianjin University of Science & Technology(No.20090420)
文摘Magnesium chloride supported vanadium/titanium bimetallic Ziegler-Natta catalysts with di-i-butyl phthalate as internal donor for copolymerization of ethylene and propylene were prepared. The effects of reaction temperature, ethylene/propylene molar ratio, aluminium/vanadium （Al/V） molar ratio and titanium/vanadium molar ratio on the catalytic activity were investigated. The molecular weight, molecular weight distribution, sequence composition and crystallinity of the products were measured by gel permeation chromatography, ^13C-NMR and differential scanning calorimetry analysis, respectively. In comparison to the vanadium and titanium catalysts, the bimetallic catalyst showed higher catalytic activity and better copolymerization performance. The obtained ethylene/propylene copolymers have high molecular weight （105）, broad molecular weight distribution, high propylene content with random or short blocked sequence structures （rErp = 1.919）, low melting temperatures and low crystallinities （Xc 〈 20%）.
文摘The Obrochishte deposit located in the Republic of Bulgaria has considerable reserves of relatively poor carbonate manganese ore. At the same time, in the country there are operative outputs for the production of sulphuric acid where vanadium catalyst is deactivated and discharged, polluting the environment. The utilization of these materials requires their consolidation to proper sizes with regard to the next processing, as the most suitable method for joint consolidation is agglomeration. The present work explores the preliminary calculations for obtaining agglomerate and obtaining an alloy with high and low carbon content, through carbothermic and aluminothermic agglomerate reduction.
基金the National Natural Science Foundation of China(No.21234006)China National High-tech R&D Program(No.2015AA034002)
文摘Several novel mono（β-enaminoketonato） vanadium complexes bearing constrained [（C6Hs）C6H3C（O）=C（CH2）nCH=N-Ar]VCl2（THF）2 （V3a： n = 1, Ar = C6H5; V4a： n = 2, Ar cyclic skeleton, including C6H5; V4b： n = 2, Ar C6F5; V4c： n = 2, Ar = （C3H7）2C6H3; V5a： n = 3, Ar = C6H5）, were synthesized and their structure and properties were characterized. The structures of V4c and V5a in solid-state were further confirmed by X-ray crystallographic analysis. Density functional theory （DFT） results indicated that these complexes showed enhanced steric hindrance around the metal center as compared with the acyclic analogues. Upon activation with Et2AlCl and in the presence of ethyl trichloroacetate as a reactivator, all of the complexes exhibited high catalytic activities （107 gPE/（molv.h）） toward ethylene polymerization, and the obtained polymers exhibited unimodal distributions （Mw/Mn = 2.0-2.3） even produced at elevated temperatures （70-100 ℃） and prolonged reaction time. When MAO was employed as a cocatalyst, they only showed moderate catalytic activities （10^5 gPE/（molv·h））, but the resulting polymers had higher molecular weights （168-241 kg/mol）. These vanadium complexes with cyclic skeleton also showed high catalytic activities toward ethylene/norbornene copolymerization. The produced copolymers displayed approximate alternating structure at high in-feed concentration of norbornene. The catalytic capabilities of these complexes could be tuned conveniently by varying ligand structure. Furthermore, the cyclic voltammetry results also proved that these complexes exhibited better redox stabilities than the complexes bearing linear skeleton.
基金supported by the National Natural Science Foundation of China (No. 21234006)
文摘Vanadium（III） complexes bearing thiophenol-phosphine ligands （2a-2b） （2-R-6-PPh2-C6H2S） VC12（THF）2 （2a： R = H; 2b： R = MeaSi） were prepared from VCla（THF）3 by treating with 1.0 equiv of the ligand in tetrahydrofuran in the presence of excess triethylamine. The two complexes were characterized by FTIR and mass spectra as well as elemental analyses. On activation with Et2AIC1, these complexes exhibited high catalytic activities （up to 22.1 kg PE/（mmolv.h.bar）） even at high temperature （70 ℃）, and produced high molecular weight polymers with unimodal molecular weight distributions, indicating the polymerization took place in a single-site nature. This result may be attributed to benefits of introduction of second-row donor atoms for adjusting charge density of the vanadium centers. In addition, these complexes also exhibited high catalytic activities for ethylene/1-hexene copolymerization. Catalytic activity, comonomer incorporation and polymer molecular weight can be controlled in a wide range by the variation of catalyst structure and the reaction parameters such as A1/V molar ratio, comonomer feed concentration and polymerization reaction temperature.
基金financially supported by the National Natural Science Foundation of China(No.20734002)
文摘Mono salicylaldiminato vanadium（Ⅲ） complexes （1a-1f） [RN = CH（ArO）]VC12（THF）2 （Ar = C6H4 （1a-1e）, R = Ph, 1a; R = p-CFaPh, 1b; R = 2,6-Me2Ph, 1c; R = 2,6-iPrEPh, 1d; R = eyclohexyl, 1e; Ar = C6HEtBU2（2,4）, R = 2,6-iPrEPh, 1f） and bis（salicylaldiminato） vanadium（III） complexes （2a-2f） [RN ： CH（ArO）]EVCI（THF）x （Ar = C6H4 （2a-2e）, x = 1 （2a-2e）, R = Ph, 2a; R = p-CF3Ph, 2b; R = 2,6-Me2Ph, 2c; R = 2,6-iPr2Ph, 2d; R = cyclohexyl, 2e; Ar = C6HEtBU2（2,4）, R = 2,6-iPrEPh, x = 0, 2f） have been evaluated as the active catalysts for ethylene/1-hexene copolymerization in the presence of Et2A1C1. The ligand substitution pattern and the catalyst structure model significantly influenced the polymerization behaviors such as the catalytic activity, the molecular weight and molecular weight distribution of the copolymers etc. The highest catalytic activity of 8.82 kg PE/（mmolv.h） was observed for vanadium catalyst 2d with two 2,6-diisopropylphenyl substituted salicylaldiminato ligands. The copolymer with the highest molecular weight was obtained by using mono salieylaldiminato vanadium catalyst 1 f having ligands with tert-butyl at the ortho and para of the aryloxy moiety.
基金Program supported by Chemicals R&D Division,Saudi Aramco
文摘The need for more active and hydrothermally stable fluid catalytic cracking（FCC）catalysts to combat the effect of metal contaminants has led to an increase in demand for rare earth oxides.Rare earth oxides enhance catalyst activity and prevent the loss of acid sites during the FCC unit operation,especially when heavy residue with high metal content is used as feed.In this paper,a review was carried out to show the effects of rare earth elements on the structure,activity,and stability of FCC catalysts.Also,the use of rare earth elements as vanadium traps was analyzed in conjunction with the mechanism of catalyst deactivation by vanadium.The objective was to elucidate the interaction of vanadium species with the zeolite component of the FCC catalysts and the role of rare earth elements in countering the deleterious effects of vanadium on the FCC catalysts.
