NNI-1型C_5/C_6烷烃异构化催化剂长周期运行分析及建议

中国石化海南炼油化工有限公司0.2 Mt/a C5/C6烷烃异构化装置以连续重整装置的拔头油为原料,使用NNI-1催化剂,采用一次通过流程,不设脱异戊烷塔和稳定塔,经设在连续重整装置内的脱丁烷塔稳定处理后作为汽油调合组分。该装置于2006年9月开工投产,截至2015年3月已连续运行3个周期。长周期运行分析结果表明:前两个周期中NNI-1催化剂具有较高的异构化活性及选择性,C5异构化率为60%左右,C6异构化率为80%左右,C6选择性为15%左右,产品辛烷值基本达到技术指标要求(RON≥78);而在第三周期运行中,催化剂积炭增加等原因导致其异构化活性及选择性降低,异构化产品辛烷值提升能力呈现逐步衰减的趋势,提高反应苛刻度已不能弥补催化剂活性下降造成的产品辛烷值降低。为保证装置长周期运行,建议择机停工对催化剂进行再生,或是直接换用与装置原料性质匹配的异构化催化剂。     

关于征地制度的思考

针对当前农村土地问题的现状．认为调整农村土地关系改革土地制度是解决当前农村问题的关键之一。介绍苏格兰土地改革的经验．提出农村土地转为非农用地的交易中国家应实行限制性措施．可尝试建立“国家失地农民账户”和“国家失地农民保障基金”．从而合理分配土地交易产生的级差收益保障失地农民的合法利益。     

Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.     

连续重整装置仿真系统的设计开发

为提高操作人员对连续重整装置开停工及事故处理的熟练程度，并对生产进行指导，采用半机理模型结合设计和现场数据介发的连续重整装置仿真系统已在现场成功投用。介绍了该仿真系统的软硬件结构、动态模型及仿真功能。     

Hydrogen production in solar reactors

The present work summarizes the recent activities of our laboratory in the field of solar-aided hydrogen production with structured monolithic solar reactors. This reactor concept, “transferred” from the well-known automobile exhaust catalytic after-treatment systems, employs ceramic supports optimized to absorb effectively solar radiation and develop sufficiently high temperatures, that are coated with active materials capable to perform/catalyze a variety of “solar-aided” reactions for the production of hydrogen such as water splitting or natural gas reforming. Our work evolves in an integrated approach starting from the synthesis of active powders tailored to particular hydrogen production reactions, their deposition upon porous absorbers, testing of relevant properties of merit such as thermomechanical stability and hydrogen yield and finally to the design, operation simulation and performance optimization of structured monolithic solar hydrogen production reactors. This approach, among other things, has culminated to the world's first closed, solar-thermochemical cycle in operation that is capable of continuous hydrogen production employing entirely renewable and abundant energy sources and raw materials – solar energy and water, respectively – without any CO₂ emissions and holds, thus, a significant potential for large-scale, emissions-free hydrogen production, particularly for regions of the world that lack indigenous resources but are endowed with ample solar energy.     

Ru-catalyzed anode materials for direct hydrocarbon SOFCs

A solid oxide fuel cell using a thin ceria-based electrolyte film with a Ru-catalyzed anode was directly operated on hydrocarbons, including methane, ethane, and propane, at 600 °C. The role of the Ru catalyst in the anode reaction was to promote the reforming reaction of the unreacted hydrocarbons by the produced steam and CO₂, which avoided interference from steam and CO₂ in the gas-phase diffusion of the fuels. The resulting peak power density reached 750 mW cm⁻² with dry methane, which was comparable to the peak power density of 769 mW cm⁻² with wet (2.9 vol.% H₂O) hydrogen. More important was the fact that the cell performance was maintained at a high level regardless of the change in the methane utilization from 12 to 46% but was significantly reduced by increasing the hydrogen utilization from 13 to 42%. While the anodic reaction of hydrogen was controlled by the slow gas diffusion, the anodic reaction of methane was not subject to the onset of such a gas-diffusion process.     

济钢350m^3高炉高富氧生产技术

分析了济钢350m^3高炉高富氧对产量,理论燃烧温度,炉况顺行状况,焦比和生产效益的影响,高富氧可提高产量,但升高焦比和高炉理论燃烧温度,一定程度上影响高炉顺行,存在富氧效益最大化的适宜富氧率.高炉生产应低富氧高喷煤,根据钢目前的情况,富氧率经2%-3%为宜.     

IFP连续重整新一代催化剂再生技术的改进

介绍了我国引进的采用法国石油研究院 (IFP)三代催化剂连续再生技术的重整装置 ,分析了第二、第三代技术在原有基础上的改进 ,从再生气循环回路、再生操作参数和再生器内部结构三个方面重点介绍了第三代催化剂连续再生技术的特点和优势 :使催化剂的烧焦气循环回路与氧氯化用气、焙烧气循环回路彼此分开 ,烧焦、氧氯化、焙烧的操作参数可分别得到优化 ,使氧氯化及焙烧在高氧条件下进行 ,有利于催化剂金属的再分散 ,保持催化剂的活性。     

3961连续重整催化剂性能考察

新一代高活性，高水热稳定性3961（PS－Ⅳ）型连续重整催化剂于1996年在上海石化芳烃厂400kt/a连续重整装置上首次进行工业应用试验。开工5a，催化剂跟踪分析结果表明，该剂保持了良好的物化性质和反应性能，表现为良好的比表面积稳定性和持氯能力，经过200个以上再生周期的催化剂未发现有明显的相变和金属分散度的变化。     

Cationic ring-opening polymerization of hexamethylcyclodisilazane: General aspects and tentative mechanisms

The ring-opening polymerization of hexamethylcyclodisilazane (D_2NMe), initiated by methyl triflate in 1,2-dichloroethane, forms in the first, fast kinetic step both linear polymer and cyclic dimer (D_4NMe). Subsequently a slow depolymerization process occurs leading to exclusively cyclotrisilazane (D_3NMe). On the basis of kinetic measurements carried out using an adiabatic calorimetric technique and complementary experiments, mechanisms of both propagation, cyclization and back-biting reactions are proposed. The influence of the reaction temperature was also studied; it is demonstrated that, at low temperature, polymerization does not lead to cyclic oligomer formation. In such conditions, the polymerization presents a ‘living’ character.