双金属氰化物催化剂合成低不饱和度聚醚

以氯化锌、铁氰化钾及含有螯合剂的水溶液为原料合成了铁锌双金属氰化物络合物(DMC)催化剂，为了获得高活性DMC催化剂，需用叔丁醇、聚醚螯合剂螯合至其结构中。并用铁锌DMC催化剂合成了7种数均相对分子质量为2000—15300的聚醚，对其工艺与性能进行了讨论与表征，并用GPC，FTIR，^13C—NMR对此聚醚进行了结构分析表征。结果表明，用此催化剂合成的聚醚与KOH催化剂合成的聚醚相比具有不饱和度低、相时分子质量高、相时分子质量分布窄的特点，同时聚醚的序列结构为头-尾相连的序列结构且呈无规立构分布的特点。     

载体碱性对Fe基催化剂费-托合成反应的影响

低碳烃类化合物是化学工业中重要的有机原料,通过非石油路线由费-托反应(Fischer-Tropsch)制备低碳烃类具有巨大前景,载体对于费-托合成催化剂的反应产物分布具有重要影响。探究了载体碱性对负载型Fe 基催化剂在费-托合成反应中反应性能的影响。通过浸渍法制备了Fe₂₀/AlPO₄、Fe₂₀/γ-Al₂O₃、Fe₂₀/MgAl₂O₄ 催化剂,考评结果表明,载体碱性越强,碳链增长概率(α值)越大,C₅₊选择性上升,烯烷比(O/P)增加。通过Raman 光谱和TPH 实验对由柠檬酸铁铵为前体煅烧后的催化剂表层碳物种进行分析表明,载体碱性越强,催化剂表面碳石墨化程度越高,吸附碳数量越少。并依托XRD、H₂-TPR、CO₂-TPR 表征信息构建了不同碱性载体负载的Fe 基催化剂的构效关系,表明载体给电子能力的强弱引起催化剂表面碳物质含量和金属载体相互作用的差异,最终导致了催化活性和选择性的不同。     

Pd-based bimetallic catalysts prepared by replacement reactions

Several Pd-based bimetallic catalysts, Pd/Co, Pd/Ni and Pd/Cu, were synthesized by replacement reactions. The catalysts were characterized by XRD and CO chemisorption and their catalytic properties were evaluated using cyclohexene self-hydrogenation. The results suggest that the high catalytic activity of Pd/Ni is most likely due to the monolayer-dispersion of Pd on the Ni surface. The results also suggest that Pd is monolayer-dispersed on the Co surface in Pd/Co, whereas Pd forms surface alloy or solid solution with Cu in Pd/Cu.     

The modification of SiO2 by various organic groups and its influence on the properties of cobalt-based catalysts for Fischer-Tropsch synthesis

SiO₂ was modified by various organic groups before the impregnation of cobalt precursor. These modified supports and the corresponding catalysts were characterized by BET, ²⁹Si CP MAS NMR, XRD, Raman, XPS and H₂-TPR. These characterizations clearly show the changes of morphology as well as reducibility of the catalysts. The organic modification of SiO₂ remarkably influences the reducibility and catalytic properties of Co catalysts. Co catalyst supported on (CH₃)₃-modified SiO₂ exhibits high activity and C₅⁺ hydrocarbon selectivity. However, COOH-, NH₂-, and NH₂(CH₂)₂NH-modified SiO₂ distinctly suppress the catalytic activity of Co catalysts.     

New redox deposition-precipitation method for preparation of supported manganese oxide catalysts

A new preparation method has been developed to produce homogeneous coatings of manganese compounds on alumina-coated monoliths by redox deposition-precipitation using acetone as solvent. The deposition is produced by reduction of manganese permanganate with ethanol. The Lewis acid sites on the alumina catalyze this reaction. Thus, the precipitation is produced preferentially on the surface of the monolith and not in the bulk of the solution. Monoliths prepared by this method are very active for the complete oxidation of oxygenated volatile organic compounds (VOCs). These monoliths consist of a mixture of complex phases including aluminum, sulfated alumina, potassium sulfate and manganese oxide.     

Fischer-Tropsch合成钴基催化剂研究进展

综述了近年来钴基催化剂在费托合成反应中的研究进展.重点评述了钴源、负载量、载体、助剂、制备方法、焙烧和还原条件等因素在负载型钴基催化剂制备过程中对催化剂活性、选择性控制等方面的影响,概述了钴基催化剂在费托合成反应中的催化机理,并对今后催化剂的研究提出了一点建议.     

Activity of hydroprocessing catalysts prepared by reprocessing spent catalysts

In this study, two spent catalysts from the 3rd and 4th fixed beds of the atmospheric residue desulfurization (ARDS) process and one spent catalyst from the H-Oil process employing the expanded bed were used as the starting material for preparation of hydroprocessing catalysts. The spent catalysts were used either in a coked or decoked form. The procedures involved pulverizing the spent catalysts before mixing, kneading and extruding with boehmite in the presence of peptizing agent such as HNO₃. The hydrodesufurization (HDS) and hydrodemetallization (HDM) activities of the new catalysts were evaluated in the microreactor using the atmospheric residue derived from Kuwait crude. The new catalysts prepared from the spent catalysts used in the fixed bed reactors exhibited higher activity than that of commercial catalysts. The HDS activity of the new catalysts prepared from spent catalysts used in the ebullated bed reactor was much lower than that of the other catalysts. This was attributed to a high content of vanadium in the former spent catalyst. At the same time, the adverse effect of vanadium on HDM was much less evident.     

The importance of passivation in the study of iron Fischer-Tropsch catalysts

In the study of iron catalysts, careful passivation is necessary for study of microstructure by ex situ analytical techniques. The passivation procedure used in our study consists of heating the sample in He at the reaction temperature, cooling to room temperature and introducing small amounts of O₂ (<1%) in a flowing He stream. A properly passivated sample shows no more than a few nm of surface Fe₃O₄ on-Fe, when examined in a high resolution TEM. Proper passivation is also characterized by an exotherm of no more than 2–3 K. We show that a Fischer-Tropsch catalyst carbided in CO will show substantial amounts of magnetite, if exposed to air without proper passivation. Such surface oxidation may cause errors in determining the relative amounts of the magnetite and carbide phases in Fischer-Tropsch catalysts, which are important for proper identification of the catalytically active phase.     

Highly dispersed MgO-supported model Pd-Mo catalysts prepared from bimetallic clusters: Chemisorption and selective catalytic reduction of NO

Model supported palladium and palladium-molybdenum catalysts prepared from organometallic precursors and previously characterized by a variety of chemical and physical methods were examined by IR spectroscopy of NO chemisorption and tested for their activities as catalysts in the competitive NO + CO + O₂ reaction. The IR results reveal distinctive behavior of the catalyst made from a bimetallic precursor, and the activity results show that this catalyst is more selective for NO reduction than the other catalysts, but its stability is vulnerable to the reaction conditions. The high selectivity is attributed to Pd-Mo interactions, which are inferred to be stronger in the catalyst prepared from a bimetallic precursor than in catalysts prepared from monometallic precursors.     

Synthesis and catalytic properties of eggshell cobalt catalysts for the Fischer-Tropsch synthesis

CO diffusional restrictions decrease C₅₊ synthesis rates and selectivity within large (1–3 mm) catalyst pellets often required in Fischer-Tropsch (FT) synthesis reactors. Eggshell catalysts, where Co is located preferentially near outer pellet surfaces, reduce the severity of these transport restrictions and lead to higher synthesis rates and C₅₊ selectivity. Maximum C₅₊ selectivities occur on catalysts with intermediate shell thickness, within which transport restrictions limit the removal of reactive olefins but not the arrival of reactants at catalytic sites. A new synthetic technique leads to sharp distributions of active sites near outer pellet surfaces by controlling the rate of imbibition of cobalt nitrate melts. Also, slow reduction of the impregnated salt leads to moderate Co dispersions (0.05–0.10) even at high local Co loadings present within shell regions.     

蔗糖基准校准红外吸收法测定非合金钢中超低碳的空白值

按照GB/T 20126-2006测定非合金钢中超低碳含量时,由于分析所使用的纯铁助熔剂没有准确定值,所以无法计算出真正的空白值加以扣除,影响测定结果的准确性。通过实验,采用二次坩埚预处理技术,有效地扣除了空白值;采用蔗糖基准建立了工作曲线,准确地测定了纯铁中质量分数在0.000 6%~0.002 4%的超低碳,标准偏差为0.000 028%~0.000 078%。     

Fischer-Tropsch synthesis on ruthenium supported ETS-10 titanium silicate catalysts

Titanium silicate ETS-10 was found to be a suitable metal catalyst support, having high surface area, high ion exchange capacity and no acidic functions. In this work, ETS-10 was used as a support in preparing ruthenium supported catalyst for Fischer-Tropsch synthesis. Ru/METS-10 catalytic systems (M standing for Na or K) showed some important characteristics, as good metal dispersion and shape selectivity. Moreover, no side reactions due to acidic functions were evidenced; indeed readsorption of olefins on active metal centers was found to control the activity of the catalysts.In part presented at 10th IZC, Garmisch-Partenkirchen, July 1994.     

双金属氰化物催化环氧化物开环聚合的研究进展

综述了近年来双金属氰化物催化剂制备聚醚多元醇的研究进展,详细介绍了双金属氰化物催化剂的制备及其催化环氧化物的聚合机理、聚合工艺方面的研究现状,并展望了催化剂制备及其催化环氧化物合成聚醚今后的研究方向。     

Molybdate catalysts prepared by a novel impregnation method: Effect of citric acid as a ligand on the catalytic activities

Molybdate, nickel-molybdate and cobalt-molybdate/γ-alumina catalysts were prepared by an impregnation method using citric acid as well as ammonia as ligands. Molybdenum structures in the impregnating solutions and on the sulfided catalysts were characterized by EXAFS and XPS. Agglomerated molybdenum octahedra existed in the impregnating solutions containing citric acid, in contrast to the monomeric molybdenum tetrahedra obtained when using ammonia. The nickel-molybdenum catalyst prepared by using citric acid was inferior to the one prepared by using ammonia in terms of both hydrogenation and HDN activities, which might be due to a decrease in the amount of active Ni-Mo-S phase. On the other hand, the cobalt-molybdenum catalyst prepared using citric acid was superior to the one prepared using ammonia in terms of HDS activity. A decrease in the lateral size of MoS₂-like crystallites might attribute to an increase in the HDS activity.     

双金属氰化物催化剂在外循环反应器中的应用研究

介绍了双金属氰化物催化剂在1.5m3外循环生产装置上的工业应用试验情况。结果表明,该催化剂活性高,诱导期短,缩短了生产周期,提高了产品质量。     

Mixed oxides as a support for new CoMo catalysts

Interest in bifunctional catalysts, active in reactions such as hydrodesulphurisation (HDS) of hydrocarbon fractions, is growing in the last years. An improvement of CoMo/Al₂O₃ materials can be obtained by the introduction of other oxides during the sol–gel synthesis. This heavily affects the acid–base characteristics of the catalysts, while textural properties are less influenced. The catalytic performances change as well: a relationship between the density of acid sites and HDS activity has been found.     

Polymerization-filled composites prepared with highly active filler-supported Al/Ti/Mg catalysts. I. Synthesis of homogeneous polyethylene-based composites

When it is attached onto the surface of an inorganic filler (kaolin, barite), the (BuO)₄Ti/BuMgOct/EtAlCl₂/Et₃Al system is a highly efficient and very promising catalyst for the production of high-performance polyethylene-based composites. The surface concentration of the hydroxyl groups, the Al/Ti/Mg ratio, and the purity of the reagents have a major effect on the catalyst efficiency and molecular weight, crystallinity, and physico-mechanical properties of the final composite. Under ca. 4 bar partial pressure of ethylene in heptane at 60°C, the optimum Al/Ti/Mg catalyst composition is 120/0.75/10, the efficiency of which is as high as 300 kgPE/(gTi × h) in the presence of kaolin particles (Satintone W/W). The effect of transfer agents, such as hydrogen and 1-octene, and purity of the α-olefin has been investigated. Actually, the catalyst efficiency is increased in the presence of both hydrogen and octene. Scanning Electron Microscopy (SEM) has shown that the ethylene was polymerized from the filler surface. Special attention has also been paid to the effect of size, density, and surface acidity of the filler particles. The surface of basic filler has to be treated in order to become an efficient catalyst carrier. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 423–438, 1997     

合成气费托合成制重质烃Ru-Co/SiC催化剂的制备及性能

费托合成是以合成气生产清洁燃料和其他化学品的重要途径。传统费托合成产物遵循A-S-F分布,只有甲烷和重质烃的选择性没有极限值。因此,费托合成研究以最大程度地合成重质烃,提高合成产物中重质烃的选择性为目标。基于此,首先详细探究了Al₂O₃、SiO₂和SiC载体对费托反应性能的影响。结果表明 Co/SiC催化剂具有最高的CO转化率（83.5%）和C₅₊选择性（80.3%）。与浸渍法相比,原位还原法更为有效地引入Ru到Co/SiC催化剂,将C₅₊选择性提高至90.1%。Ru助剂能在保持较高催化活性不变的前提下,有效提高Co/SiC催化剂C₅₊选择性。催化剂表征（XRD、H₂-TPR、XPS、H₂-化学吸附和TEM）结果表明,Ru能与Co发生相互作用,提高了催化剂的可还原性和活性组分的分散性,进而改善了Co/SiC催化剂重质烃的选择性。     

On the influence of oxygen on iron catalysts during ammonia synthesis and catalyst characterization

Once again attention is brought to the sensitivity of iron catalysts to poisoning by sub ppm levels of oxygen and a procedure is suggested to evaluate the purity of the gas supply to a steady state flow reactor setup. It is demonstrated that extremely high gas purities are essential, in particular for studies of alkali promoted samples.     

TiO2-coated on Al2O3 support prepared by the CVD method for HDS catalysts

Mo---Co or Mo---Ni catalysts supported on alumina (Al₂O₃) have been widely used for hydrodesulfurization (HDS) of heavy petroleum fractions. In order to enhance the catalytic activities for HDS, a composite type support (TiO₂-Al₂O₃) prepared by the chemical vapor deposition (CVD) method has been studied. We found that Mo catalyst supported on TiO₂-Al₂O₃ showed much higher catalytic activity for HDS of dibenzothiophene derivatives than the catalysts supported on Al₂O₃.