VCrO/SiO_2催化剂的制备、表征及催化芳烃氨氧化的活性

以硅胶为载体,用水溶液浸渍法制备了不同质量分数的钒铬复合氧化物催化剂,用BET、XRD、XPS等手段对其进行了表征,发现钒铬形成了Vv-CrⅢ无定形复合氧化物,是催化反应的活性物种,铬的加入及载体硅胶均有利于形成氧化物的无定形相,抑制晶相的生成,从而提高了反应的选择性。硅胶负载的钒铬复合氧化物催化剂对芳烃氨氧化反应表现出较高的催化活性,可使邻二甲苯氨氧化反应高收率得到邻苯二甲酰亚胺,用质量分数为10%的钒铬复合氧化物催化剂在最佳条件下进行小试,收率可达89.1%。

The effect of ethanol on the performance of CrO_x/SiO_2 catalysts during propane dehydrogenation

The effects of ethanol vapor pretreatment on the performance of CrOx/SiO2 catalysts during the dehydrogenation of propane to propylene were studied with and without the presence of CO2.The catalyst pretreated with ethanol vapor exhibited better catalytic activity than the pristine CrOx/SiO2,generating 41.4% propane conversion and 84.8% propylene selectivity.The various catalyst samples prepared were characterized by X-ray diffraction,transmission electron microscopy,temperature-programmed reduction,X-ray photoelectron spectroscopy and reflectance UV-Vis spectroscopy.The data show that coordinative Cr^3＋ species represent the active sites during the dehydrogenation of propane and that these species serve as precursors for the generation of Cr^3＋.Cr^3＋ is reduced during the reaction,leading to a decrease in catalytic activity.Following ethanol vapor pretreatment,the reduced CrOx in the catalyst is readily re-oxidized to Cr^6＋ by CO2.The pretreated catalyst thus exhibits high activity during the propane dehydrogenation reaction by maintaining the active Cr^3＋ states.

Synthesis of Methyl Glycolate by Hydrogenation of Dimethyl Oxalate over Cu-Ag/SiO_2 Catalyst

Methyl glycolate is a good solvent and can be used as feedstock for the synthesis of some important organic chemicals. Catalytic hydrogenation of dimethyl oxalate （DMO） over copper-silver catalyst supported on silica was studied. The Cu-Ag/SiO2 catalyst supported on silica sol was prepared by homogeneous deposition-precipitation of the mixture of aqueous euprammonia complex and silica sol. The proper active temperature of Cu-Ag/SiO2 catalyst for hydrogenation of DMO was 523-623 K. The most preferable reaction conditions for methyl glycolate （MG） were optimized： temperature at 468-478 K, 40-60 mesh catalyst diameter, H2/DMO ratio 40, and 1.0 h^-1 of LHSV.

In_2O_3-modified Cu/SiO_2 as an active and stable catalyst for the hydrogenation of methyl acetate to ethanol

A series of indium oxide‐modified Cu/SiO2catalysts were synthesized and used to produce ethanol via methyl acetate hydrogenation.In‐Cu/SiO2catalyst containing1.0wt%In2O3exhibited the best catalytic activity and stability.The physicochemical properties of the synthesized catalysts were investigated using several characterization methods and the results showed that introducing suitable indium to Cu/SiO2increased the copper dispersion,diminished the copper crystallite size,and enriched the surface Cu+concentration.Furthermore,the Cu/SiO2catalyst gradually deactivated during the stability test,which was mainly attributed to copper sintering and the valence change in surface copper species.In contrast,indium addition can inhibit the thermal transmigration and accumulation of copper nanoparticles to stabilize the catalyst.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

The nature of the deactivation of hydrothermally stable Ni/SiO2–Al2O3 catalyst in long-time aqueous phase hydrogenation of crude 1,4-butanediol

The deactivation of Ni/SiO2-Al2 O3 catalyst in hydrogenation of crude 1,4-butanediol was investigated.During the operation time of 2140 h,the catalyst showed slow activity decay.Characterization results,for four spent catalysts used at different time,indicated that the main reason of the catalyst deactivation was the deposition of carbonaceous species that covered the active Ni and blocked mesopores of the catalyst.The TPO and SEM measurements revealed that the carbonaceous species included both oligomeric and polymeric species with high C/H ratio and showed sheet.Such carbonaceous species might be eliminated through either direct H2 reduction or the combined oxidation-reduction methodologies.

Partial oxidation of methane over SiO2 supported Ni and NiCe catalysts

Nickel and nickel-ceria catalysts supported on high surface area silica, with 6 wt% Ni and 20 wt% CeO2 were prepared by microwave assisted(co) precipitation method. The catalysts were investigated by XRD,TPR and XPS analyses and they were tested in partial oxidation of methane(CPO). The catalytic reaction was carried out at atmospheric pressure in a temperature range of 400–800℃ with a feed gas mixture containing methane and oxygen in a molecular ratio CH4/O2=2. The Ni catalyst exhibited 60% methane conversion with 60% selectivity to CO already at 500℃. On the contrary, the Ni–Ce catalyst was inert to CPO up to 700℃. Moreover, the former catalyst reproduced its activity at the descending temperatures maintaining a good stability at 600℃, over a reaction time of 80 h, whereas the latter one completely deactivated. Test of CH4 temperature programmed surface reaction(CH4-TPSR) revealed a higher methane activation temperature(> 100℃) for the Ni–Ce catalyst as compared to the Ni one. Noticeable improvement of the ceria containing catalyst occurred when the reaction test started at a temperature higher than the methane decomposition temperature. In this case, the sample achieved the same catalytic behavior of the Ni catalyst. As confirmed by XPS analyses, the distinct electronic state of the supported nickel was responsible for the differences in catalytic behavior.

Photocatalytic Synthesis of Hydrocarbon Oxygenates from C_2H_6 and CO_2 over Pd-MoO_3/SiO_2 Catalyst

Pd-MoO3/SiO2 catalyst has been prepared using the method of incipient wetness impregnation. The photo absorbing behaviors and chemisorbing properties of the catalyst have been characterized by UV-vis spectra and TPD-MS experiments. The results indicated that metal Pd loaded on MoOa/SiO2 has a significant effect on the photo absorbing performance of MoOa/SiO2, and an obvious blue shift of the absorption edge is produced. Under UV irradiation, the chemisorption state of CO2 undergoes decomposing process to form CO at 481 K, and a two-site adsorption state of ethane can be formed at around 496 K. Photo-oxidation of ethane using carbon dioxide can mainly produce propanal, ethanol and acetaldehyde in the temperature range of 353-423 K. The presence of metal Pd improves the catalytic activity remarkably.

Characterization and catalytic performance of CeO_2-Co/SiO_2 catalyst for Fischer-Tropsch synthesis using nitrogen-diluted synthesis gas over a laboratory scale fixed-bed reactor

The surface species of CO hydrogenation on CeO2-Co/SiO2 catalyst were investigated using the techniques of temperature programmed reaction and transient response method. The results indicated that the formation of H2O and CO2 was the competitive reaction for the surface oxygen species, CH4 was produced via the hydrogenation of carbon species step by step, and C2 products were formed by the polymerization of surface-active carbon species （-CH2-）. Hydrogen assisted the dissociation of CO. The hydrogenation of surface carbon species was the rate-limiting step in the hydrogenation of CO over CeO2-Co/SiO2 catalyst. The investigation of total pressure, gas hourly space velocity （GHSV）, and product distribution using nitrogen-rich synthesis gas as feedstock over a laboratory scale fixed-bed reactor indicated that total pressure and GHSV had a significant effect on the catalytic performance of CeO2-Co/SiO2 catalyst. The removal of heat and control of the reaction temperature were extremely critical steps, which required lower GHSV and appropriate CO conversion to avoid the deactivation of the catalyst. The feedstock of nitrogen-rich synthesis gas was favorable to increase the conversion of CO, but there was a shift of product distribution toward the light hydrocarbon. The nitrogen-rich synthesis gas was feasible for F-T synthesis for the utilization of remote natural gas.

Effect of CO_2 on the structural variation of Na_2WO_4/Mn/SiO_2 catalyst for oxidative coupling of methane to ethylene

In this work,the influence of CO2 on the structural variation and catalytic performance of Na2WO4/Mn/Si O2 for oxidative coupling of methane to ethylene was investigated. The catalyst was prepared by impregnation method and characterized by XRD,Raman and XPS techniques. Appropriate amount of CO2 in the reactant gases enhanced the formation of surface tetrahedral Na2WO4 species and promoted the migration of O in MOx,Na,W from the catalyst bulk to surface,which were favorable for oxidative coupling of methane. When the molar ratio of CH4/O2/CO2 was 3/1/2,enriched surface tetrahedral Na2WO4 species and high surface concentration of O in MOx,Na,W were detected,and then high CH4 conversion of 33.1% and high C2H4 selectivity of 56.2% were obtained. With further increase of CO2 in the reagent gases,the content of active surface tetrahedral Na2WO4 species and surface concentration of O in MOx,Na,W decreased,while that of inactive species（Mn WO4 and Mn2O3） increased dramatically,leading to low CH4 conversion and low C2H4 selectivity. It could be speculated that Na2WO4 crystal was transformed into Mn WO4 crystal with excessive CO2 added under the reaction conditions. Pretreatment of Na2WO4/Mn/Si O2 catalyst by moderate amount of CO2 before OCM also promoted the formation of Na2WO4 species.

Effects of operating parameters on oxidative coupling of methane over Na-W-Mn/SiO_2 catalyst at elevated pressures

The effects of operating parameters on oxidative coupling of methane （OCM） over Na-W-Mn/SiO2 catalyst have been studied at elevated pressures of 0.2, 0.3 and 0.4 MPa under low gaseous hourly space velocity （GHSV） and low temperature conditions. Experimental results show that when the operating pressure is increased, C2＋ yield slightly decreases, while the maximum ratio of ethylene to ethane remains unchanged. Moreover, it has been found empirically that increase of pressure does not affect the catalyst behavior permanently, the catalyst recovers its original low pressure performance without hysteresis behavior by reducing the pressure. Under the investigated conditions, when oxygen is completely consumed, the increase of GHSV leads to improvement in C2 selectivity, while C3＋ and COx selectivities decrease slightly. The C2＋ selectivity increases by increase of nitrogen diluent in the feed, but the C3＋ hydrocarbons selectivities decrease with increase of nitrogen since it is possible that further dilution at high pressure may reduce the probability of collision between CH3 and C2＋ hydrocarbons. During the stability test at high pressure, the catalyst performance remains unchanged throughout the 20 h running. The fresh and used catalysts were characterized using XRD, SEM and N2 adsorption-desorption methods. It was found that the phase transformation of the support from α-cristobalite to tridymite and quartz does not have obvious effect on catalyst performance at high pressure.

Active Fischer-Tropsch synthesis Fe-Cu-K/SiO_2 catalysts prepared by autocombustion method without a reduction step

The purpose of this study was to prepare iron-based catalysts supported on silica by autocombustion method for directly using for Fischer-Tropsch synthesis（FTS） without a reduction step. The effect of different citric acid（CA）：iron nitrate（N） molar ratios and acid types on the FTS performance of catalysts were investigated. The CA：N molar ratios had an important influence on the formation of iron active phases and FTS activity. The iron carbide（FexC）, which is known to be one of the iron active phases, was demonstrated by the X-ray diffraction and X-ray photoelectron spectroscopy. Increasing the CA：N molar ratios up to 0.1 increased CO conversion of catalyst to 86.5%, which was then decreased markedly at higher CA：N molar ratios. An excess of CA resulted in carbon residues covering the catalyst surface and declined FTS activity. The optimal catalyst（CA：N molar ratio = 0.1） achieved the highest CO conversion when compared with other autocombustion catalysts as well as reference catalyst prepared by impregnation method, followed by a reduction step. The autocombustion method had the advantage to synthesize more efficient catalysts without a reduction step. More interestingly, iron-based FTS catalysts need induction duration at the initial stage of FTS reaction even after reduction, because metallic iron species need time to be transformed to FexC. But here, even if without reduction, FexC was formed directly by autocombustion and induction period was eliminated during FTS reaction.

Influence of catalyst support structure on ethene/decene metathesis and coke formation over WO_3/SiO_2 catalyst

8wt%WO3/SiO2 metathesis （disproportionation） catalysts with different pore structures were prepared by the incipient-wetness-impregnation method. The as-synthesized catalysts were characterized by N2 adsorpfion-desorption, scanning electron microscopy （SEM）, X-ray diffraction （XRD）, UV-visible diffuse reflectance spectroscopy （DRS） and scanning transmission electron microscopy-high-angle annular dark field （STEM HAADF）. The results of STEM HAADF showed that WO3 species were not uniformly distributed on the SiO2 support. The experimental results of 8wt%WO3/SiO2 performance in ethene/decene metathesis revealed that the catalytic effect of 8wt%WO3/SiO2 catalyst and coke formation over it were closely related to the support pore structure： The 8wt%WO3/SiO2 catalyst with a more complicated pore structure showed better catalytic performance but the coke deposition rate was also faster.

In-Situ FT-IR Investigation Methane to Syngas over of Partial Oxidation of Rh/SiO2 Catalyst

Partial oxidation of methane to syngas （POM） over Rh/SiO2 catalyst was investigated using in-situ FT-IR. When methane interacted with 1.0wt%Rh/SiO2 catalyst, it was dissociated to adsorbed hydrogen and CHx species. The adsorbed hydrogen atoms were transferred to SiO2 surface by ＂spill-over＂ and reacted with lattice oxygen to form surface -OH species. POM mechanism was investigated over Rh/SiO2 catalyst using in-situ FT-IR. It was found that CO2 was formed before CO could be detected when CH4 and O2 were introduced over the preoxidized Rh/SiO2 catalyst, whereas CO was detected before CO2 was formed over the prereduced Rh/SiO2 catalyst.

High Activity and Selectivity of Cu/SiO_2 Catalyst for the Direct Synthesis of Indole

Copper supported over silica exhibited very high activity and selectivity for the direct synthesis of indole at atmospheric pressure. Under the reaction temperature of 325C,the yield of indole could obtain 88%.

CO_2 HYDROGENATION OVER SiO_2－SUPPORTED HETEROBINUCLEAR METAL COMPLEX CATALYSTS

The SiO2-Supported (PPh3)2HPt(μ-CO) (μ-PPh2)M(CO) 4 (M-Cr.Mo, W) complel catalysts catalyzing CO2 hydrogenation are reported.The catalysts exhibited high catalytic activity and selectivity toward oxygenates

Vapor-phase synthesis of N-butylaniline from aniline and 1-butanol over Cu/SiO_2 catalyst

The Cu/SiO2 catalyst prepared by incipient wetness method exhibited very high activity and selectivity for the vapor-phase synthesis of N-butylaniline from aniline and 1-butanol. When Cu loading was 0.70 mmol/g-SiO2 and the catalyst precursor was calcined at 500 ℃, 1-butanol conversion reached 99%, and the selectivity of N-butylaniline exceeded 97%.

CATALYTIC PERFORMANCE OF ETHYLENE HYDROFORMYLATION OVER[H_XRu_3(CO)_9(CCO)]^(2-X)/SiO_2-Al_2O_3,SiO_2 AND MgO(X=0-2)CATALYSTS

The various surface species[H_XRu_3(CO)_9(CCO)]^(2-X)(X=0-2)prepared from impregnation of[PPN]_2[Ru_3(CO)_9(CCO)]on SiO_2-Al_2O_3,SiO_2 and MgO show quite different activities and selectivities for oxygenates and ethane in ethylene hydroformylation.

Water/Oil Diphasic Hydroformylation of Higher Olefins over a TPPTS-Rh/SiO_2 Catalyst

A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.

Preparation of Spherical MgCl_2/SiO_2/THF-Supported Late-Transition Metal Catalysts for Ethylene Polymerization

A facile and user friendly technique to immobilize the late-transition metal complexes on spherical MgCl2/SiO2/THF support has been developed. The spherical MgCl2/SiO2/THF-supported late-transition metal catalysts 2,6-bis-[1-(2,6-dimethylphenylimino)ethyl]pyridine iron(II) dichloride(SC-A) and 1,4-bis(2,6-dimethylphenyl)- acenaphthene diimine nickel(II) dibromide(SC-B) for ethylene polymerization has been prepared by spray-drying technique using tetrahydrofuran suspension containing MgCl2, SiO2 and late-transition metal complexes. The catalysts were characterized by BET, XRD, SEM and the polymers were analyzed using GPC, DSC and 13C-NMR. The test results show that spray-drying is a very effective method for immobilizing late-transition metal catalysts for ethylene polymerization. Among six kinds of cocatalysts for olefin polymerization, TMA and TEA were confirmed to be more effective than other compounds for the ethylene polymerization system using the catalyst SC-A. For the case of the catalyst SC-B, DEAC showed the best performance as cocatalysts in ethylene polymerization. The replication of the catalyst morphology was found in the resultant polyethylene.

乙烷在M_xO_y/SiO_2上氧化脱氢制乙烯

在５００—７００℃的温度范围内研究了不同氧化物负载在ＳｉＯ２上乙烷氧化脱氢（ＯＤＨＥ）行为。结果表明过渡金属氧化物负载型催化剂对ＯＤＨＥ反应有很好的活性，碱土金属、ｓｐ区金属氧化物负载型催化剂的活性较低，只有合适的可还原性催化剂才同时具有较高的乙烷转化率和乙烯选择性。通过Ｍｏ基催化剂上引入活性组份Ｆｅ、Ｖ等进行双金属调变可改善催化剂的乙烯选择性。