Preparation Method for Ruthenium Catalysts Supported by Carbon‐Coated Aluminum Foams

A preparation method is proposed for coating aluminum and aluminum alloy foams with a porous carbon layer for application as a catalyst support. The polymerization of furfuryl alcohol with diluted oxalic acid was used as precursor for the carbon layer. The polymer layer was distributed by applying centrifugal forces via spinning foam substrates during the polymerization process to prevent clogging and for homogeneous growth of the polymer layer. A homogeneous deposition precipitation method was applied for incorporation of ruthenium on carbon‐coated foam substrates. The carbon coating was characterized by X‐ray tomography to measure the thickness distribution. The specific surface and pore volume distribution were determined by gas adsorption (BET) and mercury porosimetry. The prepared Ru/C foam catalysts were adopted as a stirrer in a rotating foam reactor for hydrogenation of glucose, a simple biomass model substance.     

负载型纳米钌催化剂的制备方法及应用

负载型纳米金属催化剂在化学工业中发挥着重要作用。纳米金属颗粒的结构、组成、形貌以及与载体的相互作用影响负载型纳米金属催化剂的催化活性和稳定性,而纳米金属催化剂的物化性质与催化剂的制备方法密切相关。与其他贵金属相比,负载型纳米钌催化剂对芳环加氢具有很高的催化活性,在化工材料、制药以及有机液体储氢等领域具有较为广泛的应用。综述了负载型纳米钌催化剂的基本制备方法及应用,为今后研究工作提供了参考。     

国外柴油加氢脱硫催化剂的研究进展

硫含量是柴油燃料质量升级最主要的制约因素.与其他方式相比,最为经济简便的脱硫手段是采用更高活性的加氢脱硫催化剂.重点介绍了国外在开发柴油深度加氢脱硫催化剂方面所取得的进展.     

FCC汽油加氢脱硫催化剂研究进展

介绍了国内外FCC汽油中硫存在形式、加氢脱硫反应原理以及研究进展。通过对加氢脱硫活性相结构和其与催化剂活性关系的分析,对不同加氢脱硫制备方法进行分析,对加氢脱硫催化剂的载体、活性组分、助剂方面加以分析,可知发展高活性、高选择性的催化剂仍是现今研究的热点。     

负载型臭氧氧化催化剂研究进展

多相催化臭氧化技术是一种高效的污水净化技术。其中负载型臭氧氧化催化剂因其催化效果好、易分离、重复率用率高等优点而成为研究热点之一。依据不同的载体类型,将负载型臭氧氧化催化剂进行归纳分类,并综述了不同载体的催化剂在催化臭氧氧化水处理中的最新应用。     

FCC汽油加氢脱硫反应过程及其催化剂研究进展

综述了国内外有关FCC汽油中硫的存在形态、HDS反应原理及其催化剂的研究进展.一般认为,FCC汽油中的硫化物形态主要为噻吩类化合物,且主要集中在重馏分中,汽油的HDS反应原理的研究也都集中在噻吩的加氢脱硫反应上.传统的HDS催化剂由于烯烃饱和率过高不适于FCC汽油的HDS,可通过改变催化剂的酸性来调整其HDS/HYD选...     

免焙烧对加氢脱硫催化剂选择性影响研究

采用免焙烧方式制备了CoMo/Al_2O_3免焙烧加氢脱硫催化剂,相比于焙烧样催化剂,催化剂分析表征结果表明CoMo/Al_2O_3免焙烧催化剂硫化程度高、活性相分散度适中。在微型固定床加氢装置上考察了催化剂的加氢脱硫选择性能,在反应50 h后,CoMo/Al_2O_3免焙烧催化剂选择性优于CoMo/Al_2O_3焙烧样催化剂反应100h的选择性。在反应100 h后,CoMo/Al_2O_3免焙烧样、焙烧样催化剂在保持较高脱硫率的同时,烯烃加氢饱和率分别降至20.2%、36.2%,选择性因子SF分别上升至14.0、6.6。上述实验结果表明免焙烧的CoMo/Al_2O_3催化剂具有更高的加氢脱硫选择性。     

Ozone Decomposition over Cobalt Supported on Olive Stones Activated Carbon: Effect of Preparation Method on Catalyst Activity

Aqueous ozone decomposition was studied over highly dispersed cobalt nanoparticles supported on olive stones activated carbon (AC) prepared by: wetness impregnation (Co/AC_w) and incipient wetness impregnation (Co/AC_iw) with respect to pore volume. Nitrogen adsorption-desorption at 77K, SEM, XRD and XPS analyses were used to characterize the catalysts. Analyses results show that Co/AC_w was more uniformly dispersed on the AC than Co/AC_iw. The effect of the presence of tert-butanol as radical scavenger was also studied. Higher catalytic activity was measured for Co/AC_w than Co/AC_iw. Ozone decomposition extent goes to 99% in only 3 min in the presence of Co/AC_w compared to 60% and 58% using Co/AC_iw catalyst and AC, respectively.     

Carbon black composites—supports of HDS catalysts

HDS activity of sulfided Mo (W) catalysts supported on carbon black composites (CBC) is affected by kind of functional groups present on the CBC surface. Oxidation of CBC with (NH₄)₂S₂O₈ produce functionalities with the highest acid strength and corresponding catalyst exhibits the highest HDS activity. Sulfided W/CBC is less active in thiophene HDS than corresponding Mo counterpart. The rate of thiophene HDS over Mo/“basic” CBC does not depend on the method of Mo deposition.     

Preparation of Co–Mo/B2O3/Al2O3 catalysts for hydrodesulfurization: Effect of citric acid addition

The effect of citric acid (CA) addition was studied on the HDS of thiophene over Co–Mo/(B)/Al₂O₃ catalysts. The catalysts were characterized by means of LRS, Mo K-edge EXAFS, NO adsorption capacity measurements, and UV–vis spectra. The catalysts were subjected to a chemical vapor deposition (CVD) technique using Co(CO)₃NO as a precursor of Co in order to get deeper insights into the effect of citric acid addition. It was shown that the HDS activity was enhanced by the citric acid addition up to the CA/Mo mole ratio of around 1 and leveled off with further addition. The amount of Co anchored by the CVD was increased by the addition of citric acid, suggesting an increase in the dispersion of MoS₂ particles on the catalyst by the simultaneous presence of Co, Mo and citric acid, in conformity with the increase in the NO adsorption capacity. In contrast to Co–Mo catalysts, the edge dispersion of MoS₂ particles in Mo/B/Al₂O₃ was not affected by the addition of citric acid. The LRS, UV–vis spectra and Mo K-edge EXAFS showed that Co–CA and Mo–CA surface complexes are formed by the addition of citric acid. The Co–CA surface complex is more preferentially formed on CoMo/Al than on CoMo/B/Al, in agreement with a greater promoting effect of citric acid at a lower CA/Mo mole ratio for CoMo/Al than for CoMo/B/Al.     

负载型非茂金属催化剂聚合制备UHMWPE

在淤浆聚合条件下采用新型负载型非茂金属催化剂(SSTU)制备了超高相对分子质量聚乙烯(UHMWPE),考察了聚合温度、预聚合、助催化剂用量等聚合条件对催化剂活性、UHMWPE堆密度、粒径分布、粘均相对分子质量、力学性能、结晶性能和微观形貌等的影响.结果表明,提高聚合温度和助催化剂用量有利于催化剂活性发挥,而降低聚合温度和不预络合时可以得到高粘均相对分子质量的UHMWPE.由SSTU聚合得到的UHMWPE粒径分布均匀,细粉含量低(质量分数小于0.5%),结晶性能和力学性能好,在微观形貌上与齐格勒-纳塔催化剂制备的UHMWPE有显著区别.     

HYDRODESULFURIZATION OF THIOPHENE OVER MILDLY DEACTIVATED COAL-LIQUID HYDROTREATMENT CATALYST: EFFECT OF TEMPERATURE

The hydrodesulfurization (HDS) of thiophene was carried out over mildly deactivated NiMo/ahimina catalysts used for the hydrotreatment of coal-derived liquids. Arrhenius plots were obtained covering a wide temperature range, 180-54O°C. The observed rate constant is found to level off at the highest temperatures. This phenomenon cannot be explained by further catalyst deactivation, catalyst desulfiding, external mass transfer control, formation of an inert external shell or thermodynamic equilibrium for the HDS of thiophene. A modified two-step reaction mechanism is suggested to explain these results. Step 2 has a higher activation energy and controls the reaction rate at lower temperatures. Step 1 has a low activation energy and controls the rate at the highest temperatures. The proposed mechanism successfully predicts the experimental observations. Increasing deactivation affects the effective diffusivity to a greater extent than it does the intrinsic reaction rate constants.     

负载型Ru催化剂的制备及加氢性能

通过Ru固载同水滑石修饰的Al2O3（HTc-Al2O3）合成的同步化，制得Ru-HTc-Al2O3，对其进行XRD、ICP-AES、SEM、HRTEM、BET、NH3-TPD和XPS表征，并将其用于对苯二甲酸二甲酯催化加氢制取1,4-环己烷二甲酸二甲酯。以溶液浸渍法制得Ru/HTc-Al2O3和Ru/Al2O3对照。结果表明：相较于Ru/Al2O3和Ru/HTc-Al2O3，Ru-HTc-Al2O3具有更大的比表面积（105.4 m2/g）；其大粒径Ru粒子的形成和Ru的损失受到明显抑制、Ru粒子尺寸分布集聚区间向小尺寸方向偏移，并可提供更多的表面酸性位，尤其是中性强度的酸性位。通过考察催化剂质量与原料DMT初始摩尔量的比例（CRR）、压力和温度的影响以及循环使用反应性能，发现催化反应活性顺序为：Ru-HTc-Al2O3 > Ru/HTc-Al2O3 > Ru/Al2O3；在CRR为100 g/mol，反应温度为180 ℃，反应压力为8 MPa时，Ru-HTc-Al2O3的催化性能达到最佳：DMT转化率为98.2%，DMCD选择性为96.9%。     

负载型Ru催化剂的制备及其催化加氢性能

通过Ru固载与水滑石修饰的Al2O3(HTc-Al2O3)合成同步化,制得Ru-HTc-Al2O3,对其进行了XRD、ICP-AES、SEM、HRTEM、BET、NH3-TPD和XPS表征,并将其用于对苯二甲酸二甲酯(DMT)催化加氢制取1,4-环己烷二甲酸二甲酯(DMCD)。以溶液浸渍法制得Ru/HTc-Al2O3和Ru/Al2O3进行对照。结果表明,相较于Ru/Al2O3和Ru/HTc-Al2O3,Ru-HTc-Al2O3具有更大的比表面积(105.4 m2/g);其大粒径Ru粒子的形成和Ru的损失受到明显抑制,Ru粒子尺寸分布集聚区间向小尺寸方向偏移,并可提供更多的表面酸性位,尤其是中等强度的酸性位。通过考察催化剂质量与原料DMT初始物质的量比(CRR)、压力和温度的影响以及循环使用反应性能发现,催化反应活性顺序为:Ru-HTc-Al2O3 Ru/HTc-Al2O3 Ru/Al2O3;在CRR为100 g/mol、反应温度为180℃、反应压力为8 MPa时,Ru-HTc-Al2O3的催化性能达到最佳:DMT转化率为98.2%,DMCD选择性为96.9%。     

Mesocellular Foam‐Supported Catalysts: Enhanced Activity and Recyclability for Ring‐Closing Metathesis

Although ring‐closing metathesis (RCM) has been one of the most powerful methodologies for creating cyclic compounds, the pharmaceutical industry has not yet widely adopted this process commercially due to the high costs and leaching problems of homogeneous ruthenium catalysts. To circumvent these problems, we have immobilized the second‐generation Hoveyda–Grubbs catalyst effectively onto siliceous mesocellular foam (MCF). The open and interconnected pores of MCF facilitated ligand immobilization and substrate diffusion. We have observed that the ligand and metal loadings significantly affected the catalytic activity and recyclability. Enhanced recyclability by suppression of ruthenium leaching was achieved by using excess immobilized ligands. The resulting novel heterogenized catalysts demonstrated excellent activity and reusability for the RCM of various types of substrates.     

Magnetic Nanoparticle‐Supported Morita–Baylis–Hillman Catalysts

A magnetic nanoparticle‐supported quinuclidine was prepared and evaluated as a recoverable Morita–Baylis–Hillman catalyst. The supported catalyst 2 demonstrated comparable activity with that of DABCO and could be simply recycled with the assistance of an external magnet. The thus recycled catalyst could be reused for 7 times without significant loss of activity.     

低不饱和度聚醚多元醇及其催化剂的制备工艺

论述了低不饱和度高分子量聚醚多元醇的特性,对双金属氰化物络合物（DMC）催化剂的类型及其制备方法、低不饱和度聚醚多元醇的制备技术进行了介绍。     

The 2014 Murray Raney Award Lecture: Architecture and Preparation of Supported Nickel Catalysts

The so-called method of sequential co-precipitation allows the production of Ni or Co catalysts varying in metal content, metal dispersion, structure and texture. In this method at first the metal is precipitated and subsequently the support precursor or “stabilizer”. Deposition–precipitation of base metals (Ni, Co, Cu) starting from metal ammine complexes yields highly dispersed metals, uniformly distributed across the carrier surface.

     

Selective Hydrogenation of 5‐Ethoxymethylfurfural over Alumina‐Supported Heterogeneous Catalysts

We report here the synthesis and testing of a set of 48 alumina‐supported catalysts for hydrogenation of 5‐ethoxymethylfurfural. This catalytic reaction is very important in the context of converting biomass to biofuels. The catalysts are composed of one main metal (gold, copper, iridium, nickel, palladium, platinum, rhodium, ruthenium) and one promoter metal (bismuth, chromium, iron, sodium, tin, tungsten). Using a 16‐parallel trickle‐flow reactor, we tested all 48 catalyst combinations under a variety of conditions. The results show that both substrate conversion and product selectivity are sensitive towards temperature changes and solvent effects. The best results of >99% yield to the desired product, 5‐ethoxymethylfurfuryl alcohol, are obtained using an iridium/chromium (Ir/Cr) catalyst. The mechanistic implications of different possible reaction pathways in this complex hydrogenation system are discussed.     

Planar Metal‐Supported SOFC with Novel Cermet Anode

Metal‐supported solid oxide fuel cells are expected to offer several potential advantages over conventional anode (Ni‐YSZ) supported cells. For example, increased resistance against mechanical and thermal stresses and a reduction in material costs. When Ni‐YSZ based anodes are used in metal supported SOFC, elements from the active anode layer may inter‐diffuse with the metallic support during sintering. This work illustrates how the inter‐diffusion problem can be circumvented by using an alternative anode design based on porous and electronically conducting layers, into which electrocatalytically active materials are infiltrated after sintering. The paper presents the electrochemical performance and durability of the novel planar metal‐supported SOFC design. The electrode performance on symmetrical cells has also been evaluated. The novel cell and anode design shows a promising performance and durability at a broad range of temperatures and is especially suitable for intermediate temperature operation at around 650 °C.