Study of Ag/La0.6Sr0.4MnO3 catalysts for complete oxidation of methanol and ethanol at low concentrations

Ag-modified La_0.6Sr_0.4MnO₃-based catalysts with the perovskite-type structure were prepared by using a citric acid sol–gel method, and their catalytic performance for complete oxidation of methanol and ethanol was evaluated and compared with that of the γ-Al₂O₃-supported catalysts, Ag/γ-Al₂O₃, Pt/γ-Al₂O₃, and Pd/γ-Al₂O₃. The results showed that the Ag-modified La_0.6Sr_0.4MnO₃-based catalysts with the perovskite-type structure displayed the activity significantly higher than that of the supported precious metal catalysts, 0.1%Pd/γ-Al₂O₃ and 0.1%Pt/γ-Al₂O₃ in the temperature range of 370–573 K. Over a 6%Ag/20%La_0.6Sr_0.4MnO₃/γ-Al₂O₃ catalyst, the T₉₅ temperature for methanol oxidation can be as low as 413 K. Even at such low reaction temperature, there were little HCHO and CO detected in the reaction exit-gas. However, for the 0.1%Pd/γ-Al₂O₃ and 0.1%Pt/γ-Al₂O₃ catalysts, the HCHO content in the reaction exit-gas reached 200 and 630 ppm at their T₉₅ temperatures. Over a 6%Ag/La_0.6Sr_0.4MnO₃ catalyst, the T₉₅ temperature for ethanol oxidation can be as low as 453 K, with a corresponding content of CH₃CHO in the exit-gas at 782 ppm; when ethanol oxidation is performed at 493 K, the content of acetaldehyde in the exit-gas can be below 1 ppm. Characterization of the catalysts by X-ray diffraction (XRD), TEM, XPS, laser Raman spectra (LRS), hydrogen temperature-programmed reduction (H₂-TPR) and oxygen temperature-programmed desorption (O₂-TPD) methods revealed that both the surface and the bulk phase of the perovskite La_0.6Sr_0.4MnO₃ played important roles in the catalytic oxidation of the alcohols, and that γ-Al₂O₃ as the bottom carrier could be beneficial in creating a large surface area of catalyst. Moreover, a small amount of Ag⁺ doped onto the surface of La_0.6Sr_0.4MnO₃ was able to partially occupy the positions of La³⁺ and Sr²⁺ due to their similar ionic radii, and thus, became stabilized by the perovskite lattice, which would be in favor of preventing the aggregation of the Ag species on the surface and enhancing the stability of the catalyst. On the other hand, modification of the Ag⁺ to the surface of La_0.6Sr_0.4MnO₃ resulted in an increase in relative content of the surface O₂²⁻/O⁻ species highly reactive toward the alcohols and aldehydes as well as CO. Besides, solution of low-valence metal oxides SrO and Ag₂O with proper amounts in the lattice of the trivalent metal perovskite-type oxide LaMnO₃ would also lead to an increase in the content of the reducible Mnⁿ⁺ and the formation of anionic vacancies, which would be favorable for the adsorption-activation of oxygen on the functioning catalyst and the transport of the lattice and surface oxygen species. All these factors would contribute to the pronounced improvement of the catalyst performance.     

Pt/Pt-Ce/γ-Al2O3催化氧化甲苯研究

通过等体积浸渍法制备单贵金属Pt/γ-Al₂O₃和双金属Pt-Ce/γ-Al₂O₃催化剂,考察Ce对催化剂活性的影响,确定催化剂最优配比。结果表明,当Pt的负载量为质量分数0.5%时,Pt/γ-Al₂O₃催化活性最高;当Pt的负载量为质量分数0.2%,Ce的负载量为质量分数1.0%时,Pt-Ce/γ-Al₂O₃催化剂的催化活性最高。Pt-Ce/γ-Al₂O₃催化剂的甲苯转化率高于Pt/γ-Al₂O₃催化剂。随着Pt负载量增大,催化剂孔容、孔径减小。粉体式催化剂性能优于整体式催化剂,但差别不大;Ce的添加有助于催化剂活性的提升。     

K/Ni/β-Mo2C: A highly active and selective catalyst for higher alcohols synthesis from CO hydrogenation

Nickel and potassium promoted β-Mo₂C catalysts were prepared for CO hydrogenation to higher alcohols synthesis. The results revealed that β-Mo₂C produced mainly hydrocarbons, but the addition of potassium resulted in a remarkable selectivity shift from hydrocarbons to alcohols over β-Mo₂C. Moreover, it was found that potassium enhanced the ability of chain propagation of β-Mo₂C catalyst and led to a higher selectivity to C₂⁺OH. The addition of nickel further enhanced higher alcohols synthesis, which showed the optimum at 1/8–1/6 of Ni/Mo molar ratios. The characterization suggested that there might be a synergistic effect of potassium and nickel on β-Mo₂C, which favored the alcohols synthesis. The production of alcohols appeared to be relevant to the presence of Mo⁴⁺ species, whereas the formation of hydrocarbons was closely associated with Mo²⁺ and/or Mo⁰ species on the surface of β-Mo₂C-based catalysts.     

助剂对顺酐加氢制备γ-丁内酯催化剂页硅酸镍性能的影响

采用蒸氨法制备含Mo、Ce、Zn助剂的页硅酸镍催化剂,考察助剂对催化剂催化顺酐加氢制备γ-丁内酯的影响。结合N₂吸附-脱附、XRD、H₂-TPR、NH₃-TPD、TEM 、XPS等表征和活性评价对催化剂的织构性质及其催化性能进行研究。结果表明,不同性质的助剂对催化剂结构及其催化性能具有显著影响。助剂Mo的掺杂,提高催化剂中镍物种的还原,增加催化剂表面金属Ni⁰的数目,在金属和酸性位协同催化下,促进催化剂催化顺酐C≡O基加氢的能力,在反应温度160 ℃、氢气压力5 MPa、反应时间180 min条件下,γ-丁内酯产率可达21.3%,是未掺杂催化剂催化活性的1.5倍。助剂Zn和Ce的加入,降低催化剂酸性,进而降低其催化活性。     

The structures of VOx/MOx and alkali-VOx/MOx catalysts and their catalytic performances for soot combustion

Vanadium oxides supported on γ-Al₂O₃, SiO₂, TiO₂, and ZrO₂ were studied on their molecular structures and reactive performances for soot combustion. To investigate the effect of different alkali metals on the structures and reactivities of supported-vanadium oxide catalysts, they were doped into the V₄/TiO₂ catalyst which had the best intrinsic activity for soot combustion in the selected supported vanadium oxide catalysts. The experimental results demonstrated that the catalytic properties of these catalysts depended on the vanadium loading amount, support nature, and the presence or the absence of alkali metals. The spectroscopic analysis (FT-IR and UV–vis) and H₂-TPR results revealed that the higher activity of alkali-promoted vanadium oxide catalysts could be related to the ability of alkali metal promoting the redox cycle of the active vanadyl species. TG results showed that adding alkali to V_m/TiO₂ catalyst was beneficial to lowering their melting points. Low melting points could ensure the good surface atom migration ability, which would improve the contact between the catalyst and soot. Due to the alkali metal components promoting the redox ability and the mobility of the catalysts, alkali-modified vanadium oxide catalysts could remarkably improve their catalytic activities for soot combustion. The catalytic activity order for soot combustion followed Li > Na > K > Rb > Cs in the catalyst system of alkali-V₄/TiO₂, and the reason why it followed this sequence was discussed.     

K2CO3/γ-A12O3催化剂在棉籽油制备生物柴油中的应用

利用等体积浸渍法制备K₂CO₃/γ-A1₂O₃负载型固体碱催化剂,应用于棉籽油和甲醇酯交换反应制备生物柴油。对催化剂使用前的保存条件、水分、重复使用性能、游离脂肪酸影响以及失活和再生进行了分析。结果表明,固体催化剂K₂CO₃/γ-Al₂O₃具有较好的抗水性,酸度对催化剂影响明显,重复使用4次未经活化的催化剂,催化活性明显降低,催化剂应密封保存。K₂CO₃/γ-A1₂O₃负载型固体碱催化剂经济实惠且催化效果良好。     

The role of the oxidic support on the deactivation of Pt catalysts during the CO2 reforming of methane

Pt supported on γ-Al₂O₃, TiO₂ and ZrO₂ are active catalysts for the CO₂ reforming of methane to synthesis gas. The stability of the catalysts increased in the order Pt/γ-A1₂O₃ < Pt/TiO₂ < Pt/ZrO₂. For all catalysts, the decrease in activity with time on stream is caused by carbon formation, which blocks the active metal sites for reaction. With Pt/TiO₂ and Pt/ZrO₂, deactivation started immediately after the start of the reaction, while the Pt/γ-A1₂O₃ catalyst showed an induction period during which carbon was accumulated without affecting the catalytic activity.     

Hydrogenation of aromatics on modified platinum–alumina catalysts

Using a pulsed-micro catalytic reactor benzene and toluene were hydrogenated to cyclohexane and methylcyclohexane, respectively, in a temperature range 50–250°C. Modified catalysts containing 0.35% Pt–Al₂O₃ were investigated. Modification was carried out via (a) introducing a second metal (Ir, Rh, Re and U) and (b) fluorination and chlorination with different halogen contents of 1,3 and 6 wt%. The study revealed that (1) all catalysts show good catalytic activities in the temperature range 125–150°C, except Rh catalyst which is very active even at room temperature, (2) introducing either Ir or Re enhances Pt activity, while U inhibits this activity, (3) halogenation promotes the catalyst activity and (4) alkyl-substitution enhanced aromatic ring hydrogenation.     

Oxidation of unsymmetrical dimethylhydrazine over heterogeneous catalysts Solution of environmental problems of production, storage and disposal of highly toxic rocket fuels

The catalytic oxidation of unsymmetrical dimethylhydrazine (UDMH) by air has been studied in a vibro-fluidized catalyst bed laboratory kinetic setup over catalysts Cu_xMg_1−xCr₂O₄/γ-Al₂O₃, 32.9%Ir/γ-Al₂O₃ and β-Si₃N₄ in a temperature range 150–400 °C. The catalyst Cu_xMg_1−xCr₂O₄/γ-Al₂O₃ was found to be optimal regarding high yields of CO₂ and low yields of NO_x. A probable mechanism of UDMH heterogeneous catalytic oxidation is proposed. Catalyst Cu_xMg_1−xCr₂O₄/γ-Al₂O₃ has been further used in the pilot plant specially designed for the destruction of UDMH. Results of testing the main fluidized bed catalytic reactor for UDMH oxidation and the reactor for selective catalytic reduction of NO_x with NH₃ are presented. These results prove that the developed UDMH destruction technology is highly efficient and environmentally safe.     

改性铁酸锌催化剂的合成及其丁烯氧化脱氢活性

采用共沉淀法制备铁酸锌催化剂,考察改性元素Mg、B、Zr、Ce、La对铁酸锌催化剂结构和丁烯氧化脱氢性能的影响。采用XRD、TEM和N_2吸附-脱附对镧改性铁酸盐催化剂进行金属元素组成的优化研究,确认镧元素在催化剂中存在的形态和作用。结果表明,La改性铁酸锌催化剂晶粒粒径(20～50) nm,具有较大的比表面,主要活性组分是α-Fe_2O_3和ZnFe_2O_(4,)催化剂的活性随着Fe含量的升高而升高,n(Fe)∶n(Zn)∶n(La)=4∶1∶1催化剂具有最高的催化活性,反应温度380℃时,其TOF值2.1×10~(-3) mol_(butene)·mol_(surface-Fe)·s~(-1)。     

Catalytic activity of zeolites for synthesis reaction of methylenedianiline from aniline and formaldehyde

The catalytic activities of Y-, β-, and ZSM-5-zeolites for methylenedianiline (MDA) synthesis from the condensation reaction of aniline and formaldehyde have been investigated. Among β-zeolites with various Al concentrations (Si/Al ratios from 10 to 120 mol mol⁻¹), β-zeolite with Si/Al ratio of 13.6 mol mol⁻¹ shows the best catalytic performance in MDA synthesis. Y-zeolite exhibited lower catalytic activity than β-zeolites under the identical reaction conditions, however, exhibited the higher selectivity to 4,4′-MDA. Furthermore, it revealed that aniline/formaldehyde and catalyst/formaldehyde ratio, and reaction temperature also influenced on the MDA yield and isomers distribution.     

Preparation and characterization of novel porous metal/ceramic catalytic membrane materials

In order to obtain improved separation or catalytic activity, we propose a method to modify the surface of porous ceramic membranes by modifying the surface of sol particles. The key technical difficulty of this method is how to get appropriate ligands which can make metal ions adsorb on sol particles in the appropriate pH range in which the sol maintains its dynamic stability. Pd/γ-A1₂O₃ catalytic membrane materials with mesopore and a narrow pore size distribution were prepared by this method. Other kinds of metal/ceramic catalytic membrane materials such as Ni/γ-Al₂O₃, Pt/γ-Al₂O₃ can also be obtained by the same method.     

磷改性对NiMo/γ-Al2O3硫化物催化剂硫醚化性能的影响

采用P对NiMo/γ-Al₂O₃硫化物催化剂进行改性,研究P与金属组分浸渍次序对催化剂结构和硫醚化性能的影响。结果表明,P改性通过抑制金属组分与γ-Al₂O₃间相互作用促进金属组分硫化、增加催化剂表面金属位数量,同时P改性也提高了催化剂表面酸量。P改性前后硫化物催化剂中均形成了Ni₃S₂物相,但未检测到MoS₂物相。先浸渍及后浸渍P组分均提高了催化剂硫醚化性能;P物种和金属组分共浸渍制备催化剂利于异戊二烯选择加氢生成异戊烯。此外,P改性催化剂酸量增加促进了烯烃聚合。总体而言,先浸渍Ni-Mo组分后浸渍P组分所制备的硫化物催化剂性能较佳。     

Surfactant-mediated synthesis of metal substituted hexaaluminate from alumina sol

Manganese substituted hexaaluminate has been prepared using environmentally benign surfactants such as Triton X-100, under ambient condition with a commercial alumina sol and metal acetate precursors. The surface area of the pure alumina can be controlled to 10–70 m² g⁻¹ using cetyltrimethylammonium chloride after heating in oxygen flow at 1200°C for 6 h. The crystal structure of the obtained alumina was high purity θ-Al₂O₃. Incorporation of La and Mn leads to the formation of the high purity manganese substituted hexaaluminate with a surface area of 30–40 m² g⁻¹ which is also controllable using organic additives such as urea. The catalytic activity of the manganese substituted hexaaluminate was comparable to the sol–gel derived hexaaluminate catalyst from metal alkoxides.     

TEMPO催化醇氧化反应进展

选择性催化氧化醇类化合物为相应的醛或酮是一类重要的官能团转化反应。四甲基哌啶氧化物(TEMPO)是一种含有稳定的氮氧自由基(NO·)的有机小分子催化剂,NO·可通过自身的强选择性,在加快醛或酮转化的同时不会过氧化成为羧酸。本文阐述了TEMPO催化体系催化醇选择性氧化反应的机理,在此基础上详述了过渡金属/TEMPO、非过渡金属/TEMPO、固载化TEMPO等体系催化醇选择性氧化反应的研究情况,并探讨了TEMPO在电催化以及光催化方面的应用。指出将高活性的TEMPO催化体系改进,在发挥其高选择性、高活性优点的同时,克服其本身价格昂贵的缺点,实现催化体系的重复利用,更符合生态、绿色理念,也是未来发展的趋势。     

浸渍法制备Pt-Sn/γ-Al2O3催化剂及其催化性能

采用等体积共浸渍法和分步浸渍法制备Pt-Sn/γ-Al₂O₃催化剂,并在固定床反应器上进行正丁烷脱氢实验研究。结果表明,与共浸渍法相比,分步浸渍法制备的催化剂表现出更高的催化活性。采用等体积浸渍法制备催化剂时,活性组分与载体之间会发生竞争吸附作用,这会影响活性金属组分在载体表面的分散度,进而影响催化剂活性。     

钌基催化剂用于直接法合成气制低碳烯烃反应

以γ-Al₂O₃为载体,通过等体积浸渍法制备钌基催化剂,用其进行催化CO加氢,研究制低碳烯烃反应中钌基催化剂的催化性能,考察催化剂的焙烧温度、工艺条件及碱金属助剂Na对钌基催化剂CO加氢反应的影响。结果发现,焙烧温度400 ℃制备的钌基催化剂具有最大的比表面积,在反应温度220 ℃、反应压力1.0 MPa和空速1 500 mL·(h·g)^-1条件下,可以保证较高的CO转化率及低碳烯烃选择性。碱金属助剂Na提高了催化剂催化活性,Na质量分数为4%6%时,钌基催化剂表现出最佳的CO转化率及低碳烯烃选择性。     

CDOS渣油裂化催化剂在格尔木炼油厂重催装置的工业应用

在以减压渣油为主要原料的青海省格尔木市格尔木炼油厂重油催化裂化装置进行CDOS渣油裂化催化剂的工业应用,结果表明,在平衡催化剂总重金属污染超过25000μg·g^-1条件下,总液体收率达到81.1%,仍然维持较高的活性和较大的比表面积。     

Structured reactors for kinetic measurements under severe conditions in catalytic combustion over palladium supported systems

The collection of chemical kinetics data in catalytic combustion over very active palladium catalysts under conditions relevant to practical applications (e.g. gas turbine combustors) is extremely difficult, mainly due to strong exothermicity and very fast rate of combustion reactions. Within this purpose in this paper two types of laboratory structured reactors, which closely resemble industrial monolith catalysts, are investigated: (a) the annular reactor, consisting of a catalyst coated ceramic tube, co-axially placed in a quartz tube; (b) the metallic plate-type reactor, consisting of an assembled packet of metallic slabs coated with a ceramic catalytic layer.

The design of the annular reactor configurations for kinetic investigations is first addressed by mathematical modeling. The resulting advantages, including: (i) negligible pressure drops; (ii) minimal impact of diffusional limitations in high temperature–high GHSV experiments; (iii) effective dissipation of reaction heat are then experimentally demonstrated for the case of CH₄ combustion over a PdO/γ-Al₂O₃ catalyst with high noble metal loading (10% (w/w) of Pd).

The feasibility of a near-isothermal operation with the metallic plate-type reactor by an extremely effective dissipation of reaction heat through proper selection of highly conductive support material and of the geometry of the metallic slabs is finally discussed and experimentally demonstrated for the case of combustion of CO at high concentrations over a PdO/γ-Al₂O₃ (3% (w/w) of Pd) catalyst.     

Complete oxidation of benzene on Co---Cr and Co---Cr oxide catalysts

Supported mixture metal oxide systems, Cu---Cr and Co---Cr on γ-A1₂O₃ and γ-A1₂O₃+ SiO₂ were prepared and studied. They exhibited catalytic activity in the complete oxidation of benzene.