TiO2-Al2O3载体的制备及Ni2P/TiO2-Al2O3催化剂上的同时加氢脱硫和加氢脱氮反应

 以溶胶-凝胶法制备的 TiO2-Al2O3 复合氧化物为载体, 采用浸渍法制备了 Ni2P/TiO2-Al2O3 催化剂, 并用 X 射线衍射、N2 吸附脱附、红外和 X 射线光电子能谱等技术对催化剂进行了表征, 考察了载体中 TiO2 含量、焙烧温度及其制备方法对 Ni2P/TiO2-Al2O3 催化剂上同时进行噻吩加氢脱硫和吡啶加氢脱氮反应的影响. 结果表明, 以 Ni/P 摩尔比为 1/2 的前驱体制备的催化剂表面仅出现 Ni2P 物相; 当载体中 TiO2 的含量为 80%, 焙烧温度为 550 oC 时, Ni2P/TiO2-Al2O3 催化剂上加氢脱硫和加氢脱氮的活性最高. 在 360 oC, 3.0 MPa, 氢/油体积比 500, 液时体积空速 2.0 h?1 的条件下, 噻吩和吡啶转化率分别为 61.3%和 64.4%.     

Effect of support on the synergy in HDS of thiophene and HDN of pyridine over Mo sulfide catalysts promoted by Rh

The effect of support (SiO₂-Al₂O₃, Al₂O₃,MgO) of the Rh-Mo(S) sulfide catalysts on the synergy in hydrodesulfurization (HDS) of thiophene and hydrodenitrogenation (HDN) of pyridine was studied. The synergy in HDS was between 7–10 regardless of the kind of support used. The synergy in HDN varied from none over the MgO supported sample to about 3 over SiO₂-Al₂O₃ supported catalyst, in accord with the positive effect of increasing support acidities. This revised version was published online in June 2006 with corrections to the Cover Date.     

碳化钼催化剂加氢脱氮性能研究

MoO3在CH4/H2气氛中程序升温还原碳化反应制备了Mo2C催化剂,用XRD、BET、SEM、XPS进行了表征。以吡啶/环己烷溶液为模型化合物,在高压微反装置上评价了碳化钼催化剂的吡啶加氢脱氮性能。结果表明,MoO3在CH4/H2气氛中程序升温至675℃可制得高纯度的β-Mo2C,SEM表征其形貌为板块状颗粒,平均粒径约3.9μm,比表面积达到了10.7m2/g,高于其前驱体MoO3 的2.7倍。在反应压力3.0MPa,空速为8h－1,H2/原料液体积比为500∶1,体积分数为5%的吡啶/环己烷溶液中,碳化钼催化剂在340℃下的吡啶加氢脱氮转化率达到了86.30%,高于相应MoS2约8%。随还原碳化温度的升高,碳化钼催化剂的比表面积降低,表面积炭增多,导致其吡啶加氢脱氮活性下降。确定的碳化钼催化剂的合成条件以还原碳化温度675℃、还原碳化气体空速1.8×104h－1左右较为适宜。     

络合作用对重油加氢处理催化剂性能的影响

以Ni、W为催化剂的活性金属组分,考察在金属组分浸渍液中加入有机络合剂对催化剂性质及加氢脱硫、脱氮性能的影响。结果表明,络合剂与金属组分共浸渍更有利于金属组分的分散;提高络合剂用量,既有利于提高主活性金属组分WO₃在载体表面的分散,又能促进六配位八面体Ni物种及高加氢活性相NiWO₃的形成;焙烧温度具有调变催化剂金属组分分散性及酸性的双重作用,在适宜的焙烧温度下制得的催化剂具有较好的酸性及加氢活性,主要表现为较高的加氢脱硫及脱氮活性。     

制备条件对磷化钼加氢脱硫催化活性的影响

采用程序升温还原方法制得磷化钼(MoP)催化剂,在常压连续微型化反应装置中,以噻吩为模型化合物,对催化剂的加氢脱硫活性进行评价。考察了还原温度、磷钼摩尔比、不同磷源等制备条件对MoP催化活性的影响。实验结果表明,在MoP生成温度区间内,随着还原温度的升高,催化剂活性降低;磷钼摩尔比为1∶1时,噻吩转化率最高,而磷钼摩尔比为1∶2和2∶1时制备催化剂的催化活性相当;采用磷酸二氢铵、磷酸铵以及磷酸为磷源,均可制得磷化钼,而以磷酸二氢铵为磷源时制备磷化钼催化剂的活性最佳。在噻吩加氢脱硫反应条件下反应后,不同磷源制备的磷化钼整体物相均没有发生变化。     

乙二醇对磷掺杂NiMo/Al_2O_3加氢催化剂性能的影响

采用NiMoP浸渍液中添加乙二醇(EG)的方式制备了不同EG含量的NiMoP(x)/Al_2O_3催化剂,为研究EG及其含量对该系列催化剂催化性能和活性相结构的影响,用二苯并噻吩(DBT)和喹啉(Q)为模型化合物,考察了催化剂的加氢脱硫(HDS)和加氢脱氮(HDN)性能。结果表明,在EG添加量较低的情况下(EG/Ni物质的量比分别为0、0.5、1、2、3),EG能够明显提高催化剂对DBT和Q的HDS和HDN活性,其中,HDN活性提高幅度大于HDS,且随着EG含量提高,催化剂的HDS和HDN活性进一步提高。通过TEM分析和XPS分析可知,EG有助于增加催化剂中MoS_2颗粒的堆积层数和片层长度,且随着EG含量增加,堆积层数和片层长度都有所增加;EG有助于提高Mo表面原子浓度,对Ni表面原子浓度影响较小,但明显提高了Mo和Ni硫化程度。TG表征说明,EG在氧化铝和催化剂表面存在多种相互作用方式,并且存在与活性组分相互作用的耐高温有机物种。     

Sulfided heterogeneous,bimetallic Ru/Mo catalysts derived from mixtures of Ru3(CO)12 (or RuCl3) and a molybdenum heteropolyanion: The reactions of ethanol with tetrahydroquinoline

Efforts have been made to develop Ru/Mo bimetallic catalyst systems for hydrodenitrogenation (HDN) of tetrahydroquinoline (THQ). In the course of these studies, it was discovered that in ethanol, under hydrogen and in the presence of carbon disulfide (CS₂), precatalyst solutions containing ruthenium [as Ru₃(CO)₁₂ or RuCl₃] and molybdenum [as the H₃PMo₁₂O₄₀ heteropolyanion (HPA)] decompose to form bimetallic, sulfided particles. Particle diameters run from 0.1 to 5μm depending on the rate of stirring. Catalyst particles with sizes ranging from 0.1 to 1μm can be prepared reproducibly. BET-measured surface areas for these size particles ranged from 2 to 20m² g^?1. These sulfided particles were found to catalyze, at temperatures of 200–250°C and hydrogen pressures of 200–1000 psig (1.4–6.9 MPa) hydrogen, the N-ethylation of THQ to form N-ethyltetrahydroquinoline (N-Et-THQ), rather than the formation of propylcyclohexane or propylbenzene, reaction products expected for HDN of THQ. Monometallic heterogeneous catalysts prepared from the individual precatalyst complexes, under identical conditions, show minimal activity for N-ethylation by comparison with the bimetallic catalyst. In the absence of hydrogen, the reaction proceeds so that THQ is converted to quinoline, N-Et-THQ, N-C₄H₉-THQ and N-C₆H₁₃-THQ. The latter products appear to arise via acetaldehyde, formed as an intermediate by dehydrogenation of ethanol. Acetaldehyde either condenses with THQ to form N-Et-THQ, or self-condenses (aldol condensation) prior to reaction with THQ, thereby giving higher-homolog alkylation products.     

载Mo和Ni-Mo酚醛树脂基活性炭加氢催化转化羰基硫的研究

将水溶性酚醛树脂与金属盐溶液混合形成均相体系,依次通过减压蒸馏、固化、炭化、活化和预硫化处理制备负载金属硫化物的活性炭脱硫剂;研究其对羰基硫（COS）的加氢转化催化活性,考察了担载金属的种类、担载量、反应温度、反应时间和COS入口浓度等因素对催化反应的影响。研究结果表明,水溶性酚醛树脂是制备催化剂炭载体的理想前驱体;Ni Mo双组分催化剂对COS的加氢催化转化活性明显高于Mo单组分催化剂;在金属硫化物/活性炭催化剂上,COS的催化加氢过程属于内扩散控制,加氢反应气氛中一定浓度含硫组分的存在是抑制催化剂失硫及维持其催化活性的必要条件。     

Preparation and characterization of organotin-oxomolybdate coordination polymers and their use in sulfoxidation catalysis

The organotin-oxomolybdates [(R(3)Sn)(2)MoO(4)].n H(2)O (R=methyl, n-butyl, cyclohexyl, phenyl, benzyl) have been prepared and tested as catalysts for the oxidation of benzothiophene with aqueous hydrogen peroxide, at 35 degrees C and atmospheric pressure. In all cases, the 1,1-dioxide was the only observed product. The kinetic profiles depend on the nature of the tin-bound R group and also on the addition of a co-solvent. For the tribenzyltin derivative, the apparent activation energies for sulfoxidation as a function of the co-solvent are in the order 1,2-dichloroethane (5 kcal mol(-1))相似文献   

ZrO2及其含量对Pd/ZrO2-Al2O3催化剂加氢脱硫性能的影响

采用浸渍法制备了一系列Pd/ZrO2-Al2O3催化剂,并考察了ZrO2-Al2O3复合载体及其ZrO2含量对Pd基催化剂噻吩加氢脱硫(HDS)性能的影响,运用XRD和NH3-TPD等手段对催化剂进行了表征。结果表明,ZrO2-Al2O3复合载体及其ZrO2含量对Pd基催化剂的HDS性能有较大的影响,其中ZrO2含量为12wt%时Pd/ZrO2-Al2O3催化剂的活性最好。ZrO2-Al2O3复合载体及其ZrO2含量对Pd基催化活性的影响是通过增加Pd的分散度、H吸附量和催化剂的酸量、以及降低活性组分与载体的相互作用来实现。     

2,5-Dimethylthiophene coordination to three metal centers in the complexes (η4, S-μ3-2,5-Me2T)(IrCp*) [M(CO)2Cp]2 where MMo or W

The 2,5-dimethylthiophene (2,5-Me₂T) ligand in the isomers Cp*Ir(η⁴-2,5-Me₂T) (1) and Cp*Ir(C,S-2,5-Me₂T) (2) is activated to react with the dimers Cp(CO)₂M?M(CO)₂Cp[M?Mo (3), W (4)] to give complexes (5,6) in which the thiophene is coordinated to three metals. Oxidation of 5 with Cp₂Fe⁺ removes the Mo dimer to give Cp*Ir(η⁵-2,5-Me₂T)²⁺. Reaction of 5 with CO displaces the Mo as [CpMo(CO)₃]₂ to give Cp*Ir(CO)(C,S-2,5-Me₂T) (7). Ultraviolet photolysis of 1 provides a convenient route to the ring-opened isomer 2. Despite the remarkable nature of the thiophene coordination in 5 and 6, its reactivity does not suggest new pathways that would lead to the hydrodesulfurization of thiophenes.     

Study of iron-containing carbon-supported catalysts for oxidative decomposition of hydrogen sulfide: The activity—structure relationship

Clusters of nonstoichiometric magnetite Fe₃O_4+δ and pyrrhotite Fe_1-xS were shown to be the active structures of iron-containing carbon-supported catalysts for oxidative decomposition of hydrogen sulfide. A model of the surface active centers is discussed in terms of the anion vacancies participating in the reaction. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1 pp. 86–90, January 1997     

Ni2P和MoS2催化剂在二苯并噻吩加氢脱硫反应中的氢溢流效应

对分层装填的Ni₂P//MoS₂催化剂上的二苯并噻吩加氢脱硫反应进行了研究。结果表明,分层装填的Ni₂P/Al₂O₃和MoS₂/Al₂O₃催化剂在二苯并噻吩加氢脱硫反应中存在氢溢流效应,氢溢流有助于提高MoS₂催化剂的活性位密度和加氢脱硫反应速率。由于Ni₂P比NiS_x具有更强的氢分子解离能力,Ni₂P//MoS₂催化体系的氢溢流因子略高于NiS_x//MoS₂;相对于NiS_x,Ni₂P对MoS₂催化剂是更好的助剂。     

Utilization of the three-dimensional volcano surface to understand the chemistry of multiphase systems in heterogeneous catalysis

CO hydrogenation is used as a model system to understand why multiphase catalysts are chemically important in heterogeneous catalysis. By including both adsorption and subsequent surface reactions, kinetic equations are derived with two fundamental properties, the chemisorption energies of C and O (DeltaHC and DeltaHO, respectively). By plotting the activity against DeltaHC and DeltaHO, a 3-D volcano surface is obtained. Because of the constraint between DeltaHC and DeltaHO on monophase systems, a maximum can be achieved. However, if multiphase systems are used, such a constraint can be released and the global maximum may be achieved.     

载体性质对Pd催化剂加氢脱硫性能的影响

以Si O2、全硅MCM-41(Si-MCM-41)、通过机械混合Si-MCM-41与ZSM-5得到的Z-MCM-41-M以及通过在ZSM-5外部包覆MCM-41制备得到的Z-MCM-41四种材料为载体,制备了四种负载型Pd催化剂。采用XRD、HRTEM、N2吸附-脱附、NH3-TPD手段对Pd催化剂进行了表征;以二苯并噻吩(DBT)为模型化合物,在固定床反应器上对四种催化剂的加氢脱硫(HDS)活性、加氢路径选择性和加氢裂化活性进行了考察,研究了不同类型载体对Pd催化剂加氢脱硫性能的影响。结果表明,载体的性质会显著影响负载型Pd催化剂的加氢脱硫性能。载体的比表面积对负载型Pd催化剂加氢脱硫活性影响不大,但是HYD路径的选择性与载体的孔道结构有关;具有介孔孔道结构有利于加氢路径选择性的提高。酸性载体负载的Pd催化剂表现出较好加氢脱硫活性和加氢选择性,这与氢溢流有关。介孔材料的孔道结构与微孔沸石的酸性有机结合,所得到的Z-M CM-41复合材料是是潜在的贵金属Pd加氢脱硫催化剂优良载体,可有效提升其加氢脱硫活性。     

On the use of catalysis to bias reaction pathways in out-of-equilibrium systems

Catalysis is an essential function in living systems and provides a way to control complex reaction networks. In natural out-of-equilibrium chemical reaction networks (CRNs) driven by the consumption of chemical fuels, enzymes provide catalytic control over pathway kinetics, giving rise to complex functions. Catalytic regulation of man-made fuel-driven systems is far less common and mostly deals with enzyme catalysis instead of synthetic catalysts. Here, we show via simulations, illustrated by literature examples, how any catalyst can be incorporated in a non-equilibrium CRN and what their effect is on the behavior of the system. Alteration of the catalysts'' concentrations in batch and flow gives rise to responses in maximum conversion, lifetime (i.e. product half-lives and t90 – time to recover 90% of the reactant) and steady states. In situ up or downregulation of catalysts'' levels temporarily changes the product steady state, whereas feedback elements can give unusual concentration profiles as a function of time and self-regulation in a CRN. We show that simulations can be highly effective in predicting CRN behavior. In the future, shifting the focus from enzyme catalysis towards small molecule and metal catalysis in out-of-equilibrium systems can provide us with new reaction networks and enhance their application potential in synthetic materials, overall advancing the design of man-made responsive and interactive systems.

We show, via simulations, how catalytic control over individual paths in a fuel-driven non-equilibrium chemical reaction network in batch or flow gives rise to responses in maximum conversion, lifetime and steady states.     

Catalytic Hydrogenation of Thiophene to Thiolane in the Gas Phase

The hydrogenation of thiophene in the gas phase in the presence of palladium-sulfide catalyst leads to the production of thiolane and hydrogenolysis products (butane and hydrogen sulfide), which are formed during the decomposition of the thiophene and thiolane. The hydrogenation rate of thiophene increases with increase of its content in the reaction mixture and also with increase of the hydrogen pressure and is reduced by thiolane. The yield of thiolane calculated on the reacted thiophene is 70-90% with 30-60% conversion of the thiophene.     

The influence of the support on activity and selectivity of nickel sulfide catalysts in the decarbonylation of stearic acid to heptadecenes

The influence of the support nature on the performance of nickel sulfide catalyst in the decarbonylation of stearic acid to heptadecenes was investigated. The catalyst supported on silica demonstrated higher activity and selectivity in comparison with the catalyst on γ-Al₂O₃ used as a reference. The reaction schemes over these catalysts are nearly the same; however, the contributions from the side reactions of hydrogenation and oligomerization are reasonably different. Introduction of the products of decarbonylation (CO and water vapor) decreases the stearic acid conversion; and in the case of the catalyst supported on silica, the addition of CO strongly reduces the rate of hydrogenation of heptadecenes. The reasons for the observed differences were discussed. It was suggested that the dispersion of the nickel component as well as the nature of support acidity played a significant role.     

The use of thermal analysis in studying catalysis and the chemisorption process

The term catalysis is examined closely and shown in application to a solid phase to be an approximation in that often not only the texture of the catalyst changes but also the composition. However, the action of catalysis still remains perfectly defined in that it opens up a new lower energy path for the reaction considered. The utilisation of thermal analysis tecniques in conjunction with textural studies is shown to be a specially suitable method of investigating catalytic systems. An outline of the necessary thermodynamic and kinetic considerations in catalysis systems is given. Examples of studies on inert supports are given, namely alumina and silica. The occurrence of catalysis in the thermal decomposition of oxysalts is illustrated by reference to oxalates and permanganates. Finally, thermal analysis methods suitable for studying catalysis systems are outlined.