Effect of oxygen addition on the hydrogen production from ethanol steam reforming in a Pd–Ag membrane reactor

In this communication, a porous stainless steel (PSS) tube was electrolessly plated into Pd–Ag membrane reactor which was used for separating hydrogen produced in an ethanol steam reforming reaction with the addition of oxygen, which has not been reported before. Palladium and silver were deposited on porous stainless steel tube via the sequential electroless plating procedure with an overall film thickness of 20 μm and Pd/Ag weight ratio of 78/22. Ethanol–water mixture (n_water/n_ethanol = 1 or 3) and oxygen (n_oxygen/n_ethanol = 0.2 or 0.7) were fed concurrently into the membrane reactor packed with MDC-3. The reaction temperatures were set at 593–723 K and the pressures 3–10 atm. The effect of oxygen addition plays a vital role on the ethanol steam reforming reaction, especially for the Pd–Ag membrane reactor in which a higher flux of hydrogen is required. If oxygen in the feed is not sufficient, it would be possible that steam reforming reaction prevails. Inversely, high O₂ addition will shift the reaction scenario to be partial oxidation dominating, and selectivity of CO₂ increases with increasing oxygen feed. At high pressure, autothermal reaction of ethanol would be easily reached.     

Hydrogen Production by Steam Reforming of Ethanol: A Two Step Process

A two-layer fixed-bed catalytic reactor for hydrogen production by steam reforming of ethanol is proposed. In this reactor ethanol is first converted to acetaldehyde over a Cu-based catalyst and then acetaldehyde is converted to a hydrogen-rich mixture over a Ni-based catalyst. It is shown that the use of such type of reactor prevents coke formation and provides hydrogen yields closed to equilibrium.     

Model‐based design and synthesis of gradient MMA/tBMA copolymers by computer‐programmed semibatch atom transfer radical copolymerization

Methyl methacrylate (MMA)/tert‐butyl methacrylate (tBMA) gradient copolymers having linear and hyperbolic composition profiles were synthesized. These special copolymer products were achieved via a model‐based computer‐controlled semibatch atom transfer radical copolymerization (ATRcoP) process. A simple ATRcoP model was developed based on the terminal model. The equilibrium constants in the ATRP of MMA and tBMA were estimated by the data correlation. The model was verified by batch experiments and was found to give good correlation for the polymerization rate, molecular weight, and copolymer composition data. The model coupled with a reactor model was then applied to the semibatch ATRcoP and was used to calculate comonomer feeding rates for the targeted gradient composition profiles. It was found that the experimental monomer conversion, molecular weight, and cumulative copolymer composition were in good agreement with their targeted theoretical values. The gradient copolymers had low polydispersities close to 1.1. This work demonstrated the feasibility of the model‐based semibatch ATRcoP in fine‐tuning gradient copolymer composition profiles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 69–79, 2009     

Development of a bienzyme reactor sensor system for the determination of ornithine

A bienzyme reactor sensor system with amperometric detection was developed for the determination of ornithine. The system based on the immobilized enzymes (ornithine carbamyl transferase and pyruvate oxidase) consisted of a buffer tank, a peristaltic pump, an enzyme reactor, an oxygen electrode and a recorder. Then, 0.1 M MOPS buffer, containing pyruvic acid (0.5 mM) and carbamyl phosphate (0.5 mM), was continuously transferred into the system at 35 °C. Phosphate ion was formed enzymatically by transformation of ornithine in the presence of carbamyl phosphate. Pyruvate oxidase is activated by the presence of phosphate. Therefore, ornithine was determined from the oxygen consumed upon oxidation of pyruvic acid catalyzed by pyruvate oxidase in the presence of phosphate ion. The limit of detection was 0.05 mM and the response was linear to 3 mM (R²=0.9905). The variation coefficients were 4.9 (n=15) and 3.9% (n=15) for 1.1 and 3.0 mM standard ornithine, respectively. Good comparative results (R²=0.9238) were observed between ornithine contents in prawn muscle determined by the proposed system and by the HPLC. One assay was completed within 4 min. The immobilized enzymes were stable for 2 months at 4 °C and more than 150 samples could be continually determined using this enzyme reactor.     

Oxidative dehydrogenation of propane under steady-state and transient regimes over alumina-supported catalysts prepared from mixed V_2W_4O_（19）~（4-） hexametalate precursors

An integrated approach combining the development of an innovative catalyst and the research of a set of adequate operating conditions for the propane oxidative dehydrogenation (ODH) is described. The experimental set-up, specially designed for steady-state and transient studies is presented. The preparation method, the characterization and the performances in steady-state and transient regimes of catalysts based on V_2W_4O_(19)~(4-) Lindqvist isopolyanion used as a precursor and supported on alumina are reported. The influence of the preparation method of the catalyst and the role of water in the feed gas are more particularly discussed.     

Studies on the structure and catalytic performance of Cu-Zn-Al catalyst prepared by liquid-phase preparation technology under different heat treatment atmosphere

Cu-Zn-Al slurry catalysts were prepared using a complete liquid-phase preparation technology under different heat treatment atmospheres. The catalysts were characterized using X-ray diffraction, X-ray photoelectron spectroscope, and N2 adsorption-desorption. Their application in the single-step synthesis of dimethyl ether from syngas was also investigated. The results indicate that the type of heat treatment atmosphere has an influence on the Cu species and the Cu⁰/Cu⁺ ratio on the catalyst surface. Moreover, the final Cu/Zn ratio on the catalyst surface is mainly dependent on the composition and reaction environment of the catalyst and little on the type of heat treatment atmosphere. The prepared catalysts can suppress sintering of active sites at high temperatures, and the type of heat treatment atmosphere mainly affects the capability of the catalyst for methanol synthesis. The catalysts perform best using N2 as the heat treatment atmosphere.     

Oxidative coupling of methane in a dual-bed reactor comprising of particle/cordierite monolithic catalysts

A dual-bed reactor was constructed comprising of a 5%Na2WO4-2%Mn/SiO2 particle catalyst and a 4%Ce-5%Na2WO4-2%Mn/SiO2/cordierite monolithic catalyst. The reaction performance of the oxidative coupling of methane (OCM) over the dual-bed reactor system was evaluated. The effects of the bed height and operation mode, as well as the reaction parameters such as reaction temperature, CH4/O2 ratio and flowrate of feed gas, on the catalytic performance were investigated. The results indicated that the suggested dual-bed reactor exhibited a good performance for the OCM reaction when the feed gases firstly passed through the particle catalyst bed and then to the monolithic catalyst bed. A CH4 conversion of 38.2% and a C2H4 selectivity of 43.3% could be obtained using the dual-bed reactor with a particle catalyst bed height of 10 mm and a monolithic catalyst bed height of 50 mm. Both the CH4 conversion and C2H4 selectivity have increased by 2.5% and 12.8%, respectively, as compared with the 5%Na2WO4-2%Mn/SiO2 particle catalyst in a conventional single-bed reactor and by 12.9% and 23.0%, respectively, as compared with the 4%Ce-5%Na2WO4-2%Mn/SiO2/cordierite monolithic catalyst in a single-bed reactor. The catalytic performance of the OCM in the dual-bed reactor system has been improved remarkably.     

MgO/Al_2O_3吸附剂对CO_2动态吸附性能的研究

以γ-Al2O3为载体,采用等体积浸渍法制取MgO/Al2O3吸附剂,利用BET、XRD等表征手段对吸附剂进行表征;并通过固定床测量穿透曲线的方法研究其对CO2动态吸附性能的影响,考察了MgO负载量、吸附温度、气体流量等因素对吸附剂吸附CO2性能的影响,同时还通过多次吸脱附实验考察MgO/Al2O3吸附剂的稳定性和再生能力。结果表明,MgO负载量为10%的吸附剂,吸附温度在50℃左右,流量为45 mL/min动态吸附量最大;经数次循环后材料的结构性质和吸附性能未见明显变化,可再生性能比较优异,是一种潜在的可工业化应用的CO2吸附剂。     

浆态床中Cu/ZnO/Al2O3/ZrO2+γ-Al2O3双功能催化剂一步法合成二甲醚

采用共沉淀法,制备了纤维状CD501甲醇合成催化剂,采用SEM、TEM、XRD和BET等手段对催化剂进行了表征;并将其进一步和γ-Al₂O₃进行混合,获得了Cu/ZnO/Al₂O₃/ZrO₂+γ-Al₂O₃双功能催化剂,考察了其在浆态床中一步法合成二甲醚过程的催化特性。结果表明,相比商业催化剂(COM)和LP201催化剂,新型的CD501催化剂具有更大的比表面积和Cu/Zn分散性。对于浆态床中一步法合成二甲醚过程,采用CD501与γ-Al₂O₃双功能催化剂,相比采用COM或LP201与γ-Al₂O₃双功能催化剂,CO转化率提高了一倍,且经过270h测试,CO转化率从61%降至57%,二甲醚时空产率从0.54g/(g·h)降至0.48g/(g·h),稳定性显著优于COM催化剂。当反应温度为250℃,压力为4.0MPa,空速为3000mL/(g·h),氢碳比为1.0时,该催化剂应用在浆态床一步法合成二甲醚时,CO转化率为61%,DME时空产率达到0.54g/(g·h)。