Kinetics studies of nano-structured iron catalyst in Fischer-Tropsch synthesis

Kinetic parameters of nano-structured iron catalyst in Fischer-Tropsch synthesis (FTS) were studied in a wide range of synthesis gas conversions and compared with conventional catalyst. The conventional Fe/Cu/La catalyst was prepared by co-precipitation of Fe and Cu nitrates in aqueous media and Fe/Cu/La nanostructure catalyst was prepared by co-precipitation in a water-in-oil micro-emulsion. Nano-structured iron catalyst shows higher FTS activity. Kinetic results indicated that in FTS rate expression, the rate constant (k) increased and adsorption parameter (b) decreased by decreasing the catalyst particle size from conventional to nano-structured. Since increasing in the rate constant and decreasing in the adsorption parameter affected the FTS rate in parallel direction, the particle size of catalyst showed complicated effects on kinetic parameters of FTS reaction.     

Isomerisation of butene in isobutene on ferrierite catalyst: A mono- or a bimolecular process?

The isomerisation of n-butene into isobutene has been studied over a ferrierite catalyst being in a selective state (aged catalyst) or non-selective state (fresh catalyst). It is observed, by using ¹³C=C---C---C, that a bimolecular process operates on the non-selective catalyst whereas a monomolecular process exists on the selective catalyst.     

Impact of ageing on the distribution of platinum group elements and catalyst poisoning elements in automobile catalysts

The distribution of platinum group elements (PGEs) and catalyst poisoning elements (Pb, Zn, P and S) on the surface of gasoline and diesel automobile catalysts was investigated within this study. Laser ablation–inductively coupled plasma mass spectrometry (LA–ICPMS) provides both the sensitivity and the spatial resolution required for the surface analysis of sectioned automobile catalysts, and scanning along channels reveals the distribution of longitudinal changes in PGE and catalyst poisoning elements. Changes in catalyst surface features were studied for fresh catalysts and after ageing of the catalyst up to 80 000 km for both types of catalysts studied. The PGEs in the gasoline catalyst were found to decrease at the front of the catalyst after ageing, whereas the diesel catalyst presented a more constant loss along the catalyst. The fraction of poisoning elements (Pb, P and Zn for the gasoline catalyst and P and Zn for the diesel catalyst) retained by the catalyst is distributed non‐uniformly over the length of the catalyst. This could indicate different ageing mechanisms for gasoline and diesel catalysts. Copyright © 2003 John Wiley & Sons, Ltd.     

Deactivation studies of bifunctional Fe-HZSM5 catalyst in Fischer-Tropsch process

A physical mixture of alkali-promoted iron catalyst with binder based on Fischer-Tropsch synthesis and an acidic co-catalyst （HZSM5） for syngas conversion to hydrocarbons was studied in a fixed bed micro reactor. Deactivation data were obtained during the synthesis over a 1400 h period. The deactivation studies on iron catalyst showed that this trend followed the phase transformation Fe2.2C （ ε′） → Fe5C2 （χ） → Fe3C （θ）, and the final predominant phase of the catalyst was Fe3C （θ）. Deactivation of zeolite component in bifunctional catalyst may be caused by coking over the zeolitic component, dealumination of zeolite crystals, and migration of alkali promoters from iron catalyst under synthesis conditions. The deactivation rate of iron catalyst was also obtained.     

Hydrophobic polymer-supported scandium catalyst for carbon-carbon bond-forming reactions in water

It has been revealed that a hydrophobic polymer-supported scandium(III) catalyst prepared from sulfonated polystyrene resin is an effective catalyst for carbon-carbon bond-forming reactions such as Mukaiyama aldol reactions in water. According to studies on loading levels of scandium, hydrophobicity of the catalyst is a key for the efficient catalysis. The scandium catalyst was successfully recovered and reused. Several ketones instead of aldehydes were also used as substrates in the aldol reactions. Some 1,4-addition reactions also occurred using the scandium catalyst in water.     

Study of the early deactivation in pyrolysis of polymers in the presence of catalysts

In this work, the early degradation step of the pyrolysis of some polymers in the presence of certain catalysts has been studied using thermogravimetric analysis (TGA). Three commercial polymers (PE, PP and EVA) and three catalysts were studied (ZSM-5, MCM-41a, and MCM-41b), and the MCM-41a catalyst has been selected for the analysis of the earlier steps of the pyrolysis process carried out in the presence of catalysts. Several cycles of heating–cooling were performed using a thermobalance, in order to analyze the influence of the first stages of decomposition on the activity of the more accessible active sites involved. In this way, the behaviour of the polymer–catalyst mixtures (20% (w/w) of catalyst) was studied and compared with that observed in the corresponding thermal degradation as well as in the pyrolysis in the presence of catalysts, in a single heating cycle.The results obtained clearly show the existence of an early degradation step. For a polymer–catalyst system with low steric hindrances such as PE-MCM-41, this early degradation step causes a noticeable decrease of the catalyst activity for the main decomposition step (i.e., cracking of the chain). The decrease of the catalytic activity is lower for a polymer–catalyst system with higher steric restrictions, as occurs in the EVA-MCM-41 degradation process. However, in this case, the catalyst activity in the first decomposition step (i.e., the loss of the acetoxi groups) is noticeable decreased after one pyrolysis run, thus reflecting that the active sites involved are mainly the most accessible ones.     

浆态床反应器中生物质合成气合成二甲醚的研究

进行了浆态床反应器中,甲醇合成催化剂与分子筛混合制复合催化剂上,生物质制取的合成气(简称生物质合成气)一步法合成二甲醚的研究,重点考察了不同脱水组分和工艺条件对催化剂反应性能的影响,同时,结合NH₃-TPD等手段对催化剂进行了表征。结果表明,含有较弱酸性SAPO-11分子筛的复合催化剂更适合生物质合成气原料气杂质多、氢碳比低的特点,在合成二甲醚反应中具有更高的选择性和稳定性。250℃、5 MPa、500 h^-1时,在甲醇催化剂与SAPO-11分子筛比例为3:1的复合催化剂上,合成气合成二甲醚反应35 h内,CO转化率稳定在40%以上,二甲醚在有机产品中的选择性保持在97%左右。     

A Carbon Nanotube Confinement Strategy to Implement Homogeneous Asymmetric Catalysis in the Solid Phase

A readily recyclable asymmetric catalyst has been developed based on the self‐assembly of a homogeneous catalyst in a fibrous network of multiwalled carbon nanotubes (MWNTs). Dimerization of an amide‐based chiral ligand with a suitable spacer allows for the efficient formation of a heterogeneous catalyst by self‐assembly on addition of Er(OiPr)₃. The self‐assembly proceeds in the MWNT fibrous network and small clusters of assembled catalyst are confined in the MWNTs, producing an easily handled solid‐phase catalyst. The resulting MWNT‐confined catalyst exhibits a good catalytic performance in a catalytic asymmetric Mannich‐type reaction, which can be conducted in a repeated batch system and in a continuous‐flow platform.     

Low Concentration Limitations of Catalyst and Conventional Free Radical Polymerization in ICAR ATRP of Butyl Methacrylate With PMDETA as the Ligand

Low concentration limitations of the catalyst and conventional free radical polymerization are investigated in the system of initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) of butyl methacrylate (BMA), in which 2,2-azobisisobutyronitrile (AIBN) is used as a reducing agent, pentamethyldiethylenetriamine (PMDETA) as a ligand, copper bromide (CuBr₂) as a catalyst and ethyl 2-bromoisobutyrate (EBiB) as an initiator. Results show that conventional radical polymerization happens in the early stage of the ICAR ATRP of BMA when the amounts of AIBN are 3～25 times of the catalyst. And with the increase of the conversion, the BMA polymerization solely conducts the controlled radical polymerization (CRP). The low concentration limitations (based on monomer) of the catalyst required in ICAR ATRP of BMA with good controllability are found to be closely related to the molar ratio of initiator to catalyst, which is determined by the stability of the catalyst/ligand complex. The smaller molar ratio of initiator to catalyst allows lower concentration limitations of the catalyst.     

Catalytic features of a low-temperature reduced alumina-supported platinum catalyst. Activity and selectivity in the liquid-phase hydrogenation of benzaldehyde and nitrobenzene

A low-temperature reduced (LR) supported platinum catalyst was used for the hydrogenation of benzaldehyde, nitrobenzene and their mixture in ethanol, and compared with a high-temperature reduced (HR) catalyst. For benzaldehyde the LR catalyst was highly active to the formation of benzyl alcohol and did not give benzaldehyde diethyl acetal, which was largely formed by the HR catalyst. For the mixture, benzylideneaniline was selectively produced by the LR catalyst, while the HR catalyst gave benzylaniline and the acetal.     

MEA with double-layered catalyst cathode to mitigate methanol crossover in DMFC

Methanol permeation is one of the key problems for direct methanol fuel cell (DMFC) applications. It is necessary to change the structure of the cathode of membrane electrode assembly (MEA). Therefore, a novel MEA with double-layered catalyst cathode was prepared in this paper. The double-layered catalyst consists of PtRu black as inner catalyst layer and Pt black as outer catalyst layer. The inner catalyst layer is prepared for oxidation of the methanol permeated from anode. The results indicate that this double-layered catalyst reduced the effects of methanol crossover and assimilated mixed potential losses. The performance of MEA with double-layered catalyst cathode was 52.2 mW cm⁻², which was a remarkable improvement compared with the performance of MEA with traditional cathode. The key factor responsible for the improved performance is the optimization of the electrode structure.     

Ni-based catalyst derived from Ni/Mg/Al hydrotalcite-like compounds and its activity in the methanation of carbon monoxide

The supported Ni-based catalyst is widely used in the methanation process. Nevertheless, the major disadvantages of this catalyst are a poor behavior in the water-gas-shift (WGS) reaction and the deactivation at higher temperatures. A new kind of catalyst, nickel-containing oxides catalyst (NiMgAl), obtained from thermal treatment of hydrotalcite-like compounds (HTlcs) was prepared using the co-precipitation method. The performance of this catalyst was systematically investigated and compared with that of the Ni/Al₂O₃ catalyst. It was found that the NiMgAl catalyst shows an enhanced methanation activity compared to that of the Ni/Al₂O₃ catalyst and the former catalyst shows a better performance for the methanation especially at temperature over 550°C. Three NiMgAl catalysts with different nickel content were prepared and tested in the methanation operated at a GHSV of 15000 h^?1 and n(H₂)/n(CO) of 1.5. The results indicate that with the NiMg8 catalyst a higher activity and stability could be achieved than with the NiMg5 and NiMg6 samples, the effect mainly attributed to a higher extent of Ni dispersion was confirmed by XRD results.     

Oligomerization of endo-dicyclopentadiene using a mesoporous catalyst in a fixed-bed reactor

The oligomerization of endo-dicyclopentadiene (endo-DCPD) over a mesoporous catalyst in a continuous-flow reactor at elevated pressure was studied to produce tricyclopentadiene (TCPD) and tetracyclopentadiene (TeCPD). The mesoporous material prepared from zeolite beta (MMZ_Hβ) was utilized as a catalyst. In addition, this study focused on the catalytic performance of the regenerated catalyst in comparison with the fresh catalyst. The TCPD and TeCPD were continuously produced through DCPD oligomerization over the MMZ_Hβ catalyst in a fixed bed reactor. At early time-on-stream, the conversion of endo-DCPD, the yield of TCPD and TeCPD, and the isomerization selectivity of TCPD in the fixed bed reactor were comparable to those in the batch-type reactor. The yield of oligomer containing TCPD and TeCPD decreased drastically from 28.5 % at 3 h time-on-stream to 21.5 % at 12 h time-on-stream, indicating that the catalyst was significantly deactivated. The in situ calcination in air flow at 500 °C was found to be effective for the regeneration of the used MMZ_Hβ catalyst.     

Recent advances in automobile exhaust catalyst

Catalysts that were recently developed by Toyota for the control of automobile exhaust are reviewed. (1) A system combining a close-coupled catalyst with high heat resistance and an under-floor catalyst with high oxygen storage capacity were developed for low emission vehicles. (2) Based on a new concept, a three-way catalyst having the ability to store NOx at oxidizing atmosphere and to reduce stored NOx at stoichiometric or reducing atmosphere was developed for automotive lean burn engines. (3) A thin wall ceramic substrate was developed for better catalyst performance.     

Catalytic Conversion of Simulated Biogas Mixtures to Synthesis Gas in a Fluidized Bed Reactor Supported by a DBD

The catalytic conversion of methane and carbon dioxide was studied in a fluidized bed reactor supported by a 13.56?Hz driven coaxial DBD-reactor. Palladium or cupper catalyst which are covered on Al₂O₃ particles were used. The goal was to test whether biogas can be used for the production of synthesis gas. The influences of discharge power, catalysts and temperature of the catalyst bed on the product yield were studied. The starting material and product stream was analyzed by quadrupole mass spectrometry and infrared spectroscopy. H₂/CO ratios can be adjusted in a range between 0.65 (without a catalyst) and 1.75 (using a copper catalyst). The process is highly selective for hydrogen production (up to 83%, using a Palladium catalyst). A copper catalyst increases the H₂/CO ratio can from 1.04 to 1.16 and the palladium catalyst from 1.11 to 1.43 by heating the catalyst to a temperature of 250°C.     

直接甲醇燃料电池的Ir-Fe/C 阴极催化剂性能

合成了直接甲醇燃料电池的Ir-Fe/C阴极催化剂, 用X射线衍射(XRD)谱和X射线能量色散谱(EDS)等方法对该催化剂进行表征, 研究了碳载Ir-Fe(Ir-Fe/C)催化剂对氧还原的电催化活性和抗甲醇能力. 研究发现, 氧在碳载Ir(Ir/C)和Ir-Fe/C催化剂电极上还原的起始氧还原电位分别为0.57和0.65 V. 在0.2 V下的电流密度分别为4.6和5.8 mA/cm², 表明Ir-Fe/C催化剂对氧还原的电催化性能要优于Ir/C催化剂, 而且Ir-Fe/C催化剂也有很好的抗甲醇能力.     

Single and binary catalyst systems based on nickel and palladium in polymerization of ethylene

The catalyst (N,N‐bis(2,6‐dibenzhydryl‐4‐ethoxyphenyl)butane‐2,3‐diimine)nickel dibromide, a late transition metal catalyst, was prepared and used in ethylene polymerization. The effects of reaction parameters such as polymerization temperature, co‐catalyst to catalyst molar ratio and monomer pressure on the polymerization were investigated. The α‐diimine nickel‐based catalyst was demonstrated to be thermally robust at a temperature as high as 90 °C. The highest activity of the catalyst (494 kg polyethylene (mol cat)^?1 h^?1) was obtained at [Al]/[Ni] = 600:1, temperature of 90 °C and pressure of 5 bar. In addition, the performance of a binary catalyst using nickel‐ and palladium‐based complexes was compared with that of the corresponding individual catalytic systems in ethylene polymerization. In a study of the catalyst systems, the average molecular weight and molecular weight distribution for the binary polymerization were between those for the individual catalytic polymerizations; however, the binary catalyst activity was lower than that of the two individual ones. The obtained polyethylenes had high molecular weights in the region of 10⁵ g mol^?1. Gel permeation chromatography analysis showed a narrow molecular weight distribution of 1.44 for the nickel‐based catalyst and 1.61 for the binary catalyst system. The branching density of the polyethylenes generated using the binary catalytic system (30 branches/1000 C) was lower than that generated using the nickel‐based catalyst (51/1000 C). X‐ray diffraction study of the polymer chains showed higher crystallinity with lower branching of the polymer obtained. Also Fourier transform infrared spectra confirmed that all obtained polymers were low‐density polyethylene.     

A heterogeneous and reusable nanopolymer-supported palladium catalyst for the copper- and phosphine-free Sonogashira coupling reaction under aerobic conditions in water

We report here the synthesis of a nanopolymer-supported palladium(II) complex catalyst, [PS-tet-Pd(II)] using a simple protocol. The catalyst was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR, and energy dispersive X-ray spectroscopy (EDS). PS-tet-Pd(II) proves to be a useful heterogeneous catalyst in the copper- and phosphine-free Sonogashira coupling reaction in water. The catalyst can be recovered from the reaction mixture by simple filtration and reused several times without any significant loss of catalytic activity.     

Initiation behaviour in hydrogenation of pyrolysis gasoline over presulphided Ni-Mo-Zn/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst

A presulphided treatment was applied to the oxidic Ni-Mo-Zn/Al₂O₃ catalyst (nickel catalyst) in order to avoid thermal run-away during initiation of the hydrogenation of pyrolysis gasoline. The physico-chemical properties of the prepared oxidic nickel catalyst, the reduced and passivated (RP) nickel catalyst and the sulphided (RPS) nickel catalyst were characterised using N₂ adsorption-desorption, X-ray diffraction, temperature-programmed reduction (TPR) and X-ray photoelectron spectroscopy (XPS). The TPR results showed that the reducibility of the RP Ni-Mo-Zn/Al₂O₃ catalyst was improved over the oxidic nickel catalyst. The XPS spectra confirmed the binding energy of the RPS nickel catalyst to be higher than that of the oxidic nickel catalyst. The catalytic performance was evaluated on a fixed-bed reactor (reaction temperature between 30 °C and 70°C, at 2.8 MPa of total pressure and weight hourly space velocity of 2.0 h^?1, the volume of H₂/pyrogasoline = 200: 1). The rising temperature of the RPS nickel catalyst was almost 20°C lower than that of the oxidic nickel catalyst during the initial stage of the hydrogenation reaction. The results indicated that the RPS nickel catalyst exhibited better stability than the oxidic nickel catalyst during the start-up period, thereby providing a better selectivity in long-term operation.     

PVP-PdCl2-CuCl2/SiO2-PEG600催化芳氯化物水相脱氯研究

PVP(聚乙烯吡咯烷酮)负载双金属催化剂催化芳香氯化物脱氯已有报道[1～3];利用双金属的协同作用,可以大大提高催化剂的脱氯活性和选择性[4]. 但是,这些研究多是在有机相中进行的,催化剂在水相中则会降低甚至失去活性,且难以回收和重复利用. 然而,难溶于水的有毒芳香氯化物,常存在于工业或生活排放的废水中. 由于治理环境的需要,研究芳香氯化物催化水相脱氯,则是极具挑战性的课题. 本文把起相转移作用的聚乙二醇(PEG)键合到硅胶上作为固相载体,制成双负载双金属水相脱氯催化剂PVP-PdCl2-CuCl2/SiO2-PEG600,成功地用于难溶于水的芳香氯化物的水相脱氯. 研究结果表明,这种催化剂对于芳香氯化物有良好的催化脱氯性能,使用中便于分离并能重复利用. 同时,用IR,TEM和XPS等手段对催化剂进行了表征,探讨了催化剂中各组分在催化脱氯中的作用.