Carbon Monoxide Hydrogenation over Zirconia Supported Ni and Co-Ni Bimetallic Catalysts

Zirconia supported nickel and cobalt-nickel bimetallic catalysts were prepared and characterized for various physico-chemical properties. The hydrogenation of carbon monoxide was studied over these catalysts in the pressure range of 101.3–1654kPa, temperature range of 513–533K, weight hourly space velocity range of 8–14h^–1 and H2/CO mole ratio of 2. Catalysts containing both Co and Ni were found to give higher C₅₊ hydrocarbons selectivity compared to that containing only Ni. A maximum C₅₊ hydrocarbons selectivity of 55wt% was obtained at 655kPa pressure, 523K and 9.6h^–1 of WHSV with catalyst containing 4.03wt% Co and 2.64wt% Ni. The C₂ and C₃ olefin contents of the products decreased with increase in pressure. Improved deactivation behavior of the catalysts was observed when operated at high pressure.     

Impact of Boron Modification on MCM-41-Supported Cobalt Catalysts for Hydrogenation of Carbon Monoxide

Boron modification on MCM-41-supported cobalt (Co) catalysts was found to decrease the catalyst activity during CO hydrogenation. The decreased activities were due to stronger support interaction between Co oxide species and the support with the presence of boron resulting in lower reducibility. However, based on methanation the selectivity to C₂–C₄ products slightly increased with low loading of boron.     

Characterization and Catalytic Oxidation of Carbon Monoxide Over Supported Cobalt Catalysts

Three types of supported cobalt catalysts (CoO_x/SiO₂, CoO_x/TiO₂ and CoO_x/Al₂O₃) were prepared by incipient wetness impregnation with aqueous Co(NO₃)₂·6H₂O solution. The phase composition and the interactions of cobalt with supports under different calcined temperatures were investigated using thermogravimetry (TG), N₂-adsorption at −196 °C, X-ray diffraction (XRD), temperature-programmed reduction (TPR) and diffuse reflectance spectroscopy (DRS). Their catalytic activities towards the CO oxidation were further studied in a continuous flow micro-reactor. The results showed that the interaction of cobalt oxide with supports was much stronger in the kinds of Al₂O₃ and TiO₂, while no conclusive evidence of any interaction was found for SiO₂. Besides the crystalline Co₃O₄ which was formed in three supported catalysts, both high-temperature phases CoAl₂O₄ and CoTiO₃ spinel were also detected under XRD, DRS and TPR analysis. The degree of interaction between cobalt oxide and the support not only affected the surface area and reduction behavior of the catalysts, the catalytic activity toward the CO oxidation also affected simultaneously. As the CoAl₂O₄ and CoTiO₃ spinel formed, both the surface area and catalytic activity decreased significantly.     

Effect of Water Vapor on Carbon Monoxide Oxidation over Promoted Platinum Catalysts

The catalytic behavior of the two kinds of Pd/SiO₂ catalysts prepared from dinitrodiamminepalladium and palladium nitrate are compared for ethene hydroformylation and carbon monoxide hydrogenation. The catalyst prepared from dinitrodiamminepalladium, on which very fine particles of Pd were observed, showed high activity for ethene hydroformylation. On the other hand, the catalyst prepared from palladium nitrate, on which relatively large particles of Pd were observed, showed high activity for CO hydrogenation.     

CO催化合成乙二醇的工业化前景

介绍了从ＣＯ和醇合成草酸酯,再经加氢生成乙二醇的工艺方法,在２００ｍｌ模试成果基础上,预测了该工艺的工业化前景,通过初步技术经济分析,肯定了这条非石油路线的乙二醇生产方法的应用前景。     

采用骨架钴和骨架镍催化剂加氢还原制备糠醇的研究

从钼、铬、铜和铁中筛选金属铬和铁作为助催化剂加入骨架钴或骨架镍催化剂,铬和铁的量分别为催化剂质量的３％和１％。在１００～１２０℃、１０～１２ＭＰａ条件下,用上述骨架钴或骨架镍催化剂在乙醇溶剂中,氢化还原糠醛制备糠醇。用骨架镍催化剂,反应产物含有７８５％的糠醇和１９６％的四氢糠醇;用骨架钴催化剂,反应产物含有９８８％的糠醇和０８％的四氢糠醇,收率９４％。在无乙醇溶剂条件下,反应产物含有９０５％的糠醇、０３％的四氢糠醇和９２％的糠醛。在１８０℃条件下,反应产物含有９０８％的糠醇和８９％的四氢糠醇。     

Characterization of magnesium promoted Co/SiO2 catalysts

Co/SiO₂, Mg-Co/SiO₂, and Co-Mg/SiO₂ catalysts were prepared from nitrate precursors to get more insight into the effect of magnesium promotion on the cobalt catalyst. The desorption characteristics and reactivity of the catalysts towards synthesis gas were evaluated in a pulse micro reactor connected to an on-line quadrupole mass spectrometer. The presence of MgO both decreased the extent of reduction and increased the dispersion of cobalt. The reactivity results suggested that MgO promotion created new types of active sites, probably at the edge sites of cobalt and magnesium. The highest activity per metallic site available was obtained with a Mg: Co molar ratio of 1/2, i.e. with a high amount of edge sites. In accordance with previous results the formation of CO₂ was clearly suppressed in the presence of MgO, and methanol was formed in trace amounts.     

低温CO催化氧化负载型Pd催化剂研究进展

综述了低温CO催化氧化负载型Pd催化剂在制备方法、载体的选用和催化机理等方面的研究进展,并介绍了该类催化剂的最新进展.在文章末对该催化剂领域尚待深入研究的问题进行了探讨.     

A Study of Nitrobenzene Hydrogenation Over Palladium/Carbon Catalysts

The hydrogenation of nitrobenzene has been studied over three palladium/carbon catalysts using methanol and isopropanol as solvents. A solvent and palladium particle size effect have both been observed, with the nature of the particle size effect dependent upon the solvent. This may be related to a change in the rate-determining step.     

CO加氢合成低碳混合醇催化剂研究进展

介绍了低碳混合醇的性质及主要用途,对可用于CO加氢合成低碳混合醇的改性甲醇合成催化剂、改性F-T合成催化剂及Mo系催化剂的最新研究进展进行了介绍,并分析了现有催化剂存在的问题及发展的方向。     

咪唑改性HZSM-5分子筛的制备及其催化CO2加氢合成二甲醚

以咪唑为添加剂,四丙基氢氧化铵为模板剂,采用水热法制备了咪唑改性HZSM-5型分子筛, 用XRD、SEM、EDS、BET、TG和NH3-TPD等手段对合成的分子筛进行了表征,结果表明当在制备分子筛的前驱液中加入少量咪唑时,制备的HZSM-5型分子筛粒径明显减小且分布更加均匀,酸性增强,并具有更好的抗高温性能. 采用浸渍法制备了CuO-ZnO-Al2O3/咪唑改性HZSM-5双功能催化剂,探讨了其催化二氧化碳加氢制备二甲醚的活性,在反应温度270 癈、反应压力3.0 MPa、CO2 : H2 = 1 : 3（体积比）、CuO : ZnO = 2 : 1（摩尔比）和CuO-ZnO2-Al2O3 : 咪唑改性HZSM-5 = 2 : 1（质量比）的条件下,CO2的单程转化率和二甲醚的选择性分别达到了42.3 %和33.1 %.     

Long-Chain-Amine Metal Complexes as Hydrogenation Catalysts. Heterogenisation on Activated Carbon

The catalytic activity of [PdCl₂(NH₂(CH₂)₁₂CH₃)₂] (named [Pd(TDA)]) and [RhCl(NH₂(CH₂)₁₂CH₃)₃] (named [Rh(TDA)]) complexes for the hydrogenation of cyclohexene has been analysed both in homogeneous phase and heterogenised on activated carbon. The [Rh(TDA)] complex has been found to be more active than the [Pd(TDA)], both homogeneous and heterogenised. Experimental and modelled results indicate that these complexes follow a similar reaction mechanism, but with different rates. A clear positive effect of the carbon support has been found in the case of the complex [Rh(TDA)], which has been related to the anchorage of the aliphatic chains of the amine ligands on the activated carbon pores. Experiments in consecutive catalytic runs show that the heterogenised complexes can be used several times giving an acceptable conversion level.     

Carbon monoxide hydrogenation over cobalt catalyst in a tube-wall reactor: Part 1. Experimental studies

Effects of temperature (250?275°C), pressure (0.1-1.03 MPa) and feed gas exposure velocity (139-722 μm/s) were studied on carbon monoxide hydrogenation in a tube-wall reactor using plasma-sprayed cobalt catalyst. The specific catalytic activity and hydrocarbon selectivity increased with an increase in pressure and temperature and a decrease in the exposure velocity. The results showed that the formation of olefins especially ethylene and propylene was favored at low pressures, low temperatures and high exposure velocities. This catalyst was found to be selective for C₅⁺ hydrocarbons (27-34 wt.%) at increased pressures (0.69-1.03 MPa).     

Effect of Carbon Deposits on Carbon Monoxide Hydrogenation over Alumina-Supported Cobalt Catalyst

The carbon deposits on alumina-supported cobalt catalysts and their effects on carbon monoxide hydrogenation were investigated concomitantly. Carbon monoxide hydrogenation was performed in a differential reactor operating at atmospheric pressure, temperature of 250–350°C and a hydrogen: carbon monoxide ratio of 3. Temperature-programmed surface reaction of carbon deposits with hydrogen and Auger electron spectroscopy were employed to obtain a better understanding of the nature of the carbon deposits. With increasing deposition temperature, the amount of carbon deposit increased and the atomic surface carbon transformed morphologically into polymeric and graphitic carbon. Carbon deposits resulted in the reduction of activation energy from 28–32 to 17–18 kcal/mol (117–134 to 71–75 kJ/mol) as well as significantly decreasing activity. Hydrocarbon product distributions were not affected by carbon deposits, but the obvious shift in selectivity from paraffins to olefins was observed with increasing carbon deposits.     

Catalysts for Combustion Containing Tin and Copper Overloaded on ZSM-5 Zeolite

Three samples of modified HZSM-5 zeolite with tin and copper were prepared by ion exchange and coprecipitation under basic conditions. The catalytic activity of prepared catalysts was tested in CO and methane combustion after pretreatments done at 873, 1088 and 1273 K. The XRD analysis and TG-DTA were used to interpret thermal stability of catalysts. Introduction of tin as the third element to well-known copper-overloaded ZSM-5 combustion catalysts improves their thermal stability. It was found that CO combustion is independent of the zeolite structure and probably adjacent sites are necessary to activate carbon monoxide and oxygen in the vicinity. Contrarily, non-dehydroxylated zeolite is indispensable as an active element together with copper or tin to catalyze methane combustion.     

磺酸化碳材料负载Ru催化剂催化纤维素水解/加氢反应

采用纤维素衍生碳、活性炭和介孔碳材料CMK-3为不同碳源前驱体,在不同磺酸化条件下制备磺酸化碳材料负载Ru的双功能催化剂,并用FTIR光谱、XRD、元素分析、热重分析、N₂物理吸附 脱附进行了表征,考察了其对纤维素加氢反应的催化活性。结果表明：相比于纤维素衍生化碳,活性炭和介孔碳CMK-3为碳源经过磺酸化后制备的催化剂具有较强的结合-SO₃H的能力和较高的催化活性,对多元醇具有良好的选择性,170 ℃下反应10 h六元醇的收率可高达84.0%。在循环使用时,磺酸化活性炭负载Ru催化剂催化活性有所降低,但可以保持对多元醇的选择性;而磺酸化介孔碳负载Ru催化剂存在少量S流失,转化率基本不变,但产物的选择性有所降低。     

F-T合成反应机理的研究

对F-T合成反应机理的发展过程,应用范围及研究前景进行了系统综述,着重总结了近期提出的机理模型,讨论了各种反应机理的合理性和欠缺处,并分析了链引发,链增长和链终止在反应机理中的作用,列举了支持各反应机理的直接实验事实。     

In situ FT-IR Spectroscopic Studies on the Mechanism of the Catalytic Oxidation of Carbon Monoxide over Supported Cobalt Catalysts

Three types of supported cobalt catalysts (5% as metal Co loading on SiO₂, Al₂O₃ and TiO₂) were prepared by incipient wetness impregnation with aqueous Co(NO₃)₂·6H₂O solution. Then, all catalysts were calcined in air at 400 °C (assigned as 5Co/Si C400, 5Co/Al C400 and 5Co/Ti C400). Their catalytic activities towards the CO oxidation were studied in a continuous flow micro-reactor. Adsorption of carbon monoxide (CO) and the co-adsorption of CO/O₂ over cobalt oxide were further tested under in situ FT-IR. The results showed that both 5Co/Si C400 and 5Co/Al C400 had higher activity than 5Co/Ti C400. The T₅₀ (50% conversion) for both 5Co/Si C400 and 5Co/Al C400 was reached at temperatures as low as ambient temperature. According to the in situ FT-IR analysis, the variation in oxidation of CO was interpreted with different mechanisms, i.e., the reaction between adsorbed CO and lattice oxygen of cobalt oxide, and part of CO₂ formation via carbonates on 5Co/Si C400; both types of carbonates are formed on 5Co/Al C400 to promote the CO oxidation; while both strong adsorption of CO on TiO₂ and CO₂ on cobalt oxide for 5Co/Ti C400 leads to affect the activity.     

Carbon monoxide hydrogenation over cobalt catalyst in a tube-wall reactor: Part II. Modelling studies

A mathematical model was developed to predict the performance of Fischer-Tropsch Synthesis over cobalt catalyst in a tube-wall reactor. Comparison was made between model predictions and previous experimental results (part 1 of this paper) for pressures 0.35-1.03 MPa, temperatures 250?275°C, and exposure velocities 139-722 μ/s. The agreement was good. The model predicts an increase in methanation activity with temperature. Carbon monoxide and hydrogen conversions, and water and carbon dioxide concentrations increase along the reactor axis. With an increase in exposure velocity, hydrocarbons and carbon dioxide production increase, but water production decreases. However, the water-gas shift activity increases continuously along the reactor axis. The model is based on two-dimensional transport equations, and employs the orthogonal collocation method in its numerical predictions.     

碳二选择加氢催化剂研究进展

简要分析了国内外碳二馏份选择加氢脱乙炔的工艺现状，又从载体、助催化剂和催化剂失活等方面介绍了碳二馏份选择加氢的研究进展，指出提高选择性、降低投资、节能降耗是乙烯工业发展的总趋势。