新型光化学反应器及二氧化碳光解反应研究

研究设计了可产生波长小于200 nm真空紫外光的光化学反应器,首次利用该波段的光在该反应器中进行了CO2光解反应的研究。用氮气为发光介质对其进行光强标定,实验表明主要产生120、149、174 nm波长的光(N原子谱线);实验条件下CO2光解后生成产物CO,结果表明光源电流一定时产生CO的量与光源工作气体的压力有关,在CO2和N2反应物系中,光源内发光介质N2的压力在2 500 Pa左右时CO的产率最大,而在该反应物系中加入甲烷后,CO的产率明显增大。     

自热制氢反应器研究进展

介绍了同心圆式反应器、板式反应器、壁反应器、微通道反应器在自热重整反应制氢中的特点。同心圆式反应器的传热是控制步骤,为强化传热而开发了空间形状不同和流体经过反应器不同腔体的先后顺序不同的反应器;板式反应器易于组装、拆卸和放大,而且热效率也比较高,是目前十分活跃的研究领域,重点在于操作参数和设计的优化及其高效壁载制氢催化剂的研制;壁反应器的反应表面和换热表面不分离,具有较高的热量耦合效果;微通道反应器具有优越的传热性能,但对加工和流体的性质有比较苛刻的要求。另外,不同燃料制氢机理的研究及其过程参数的稳态、瞬态模拟,为反应器的设计提供了理论依据。而制氢过程并行单元的研究为系统的集成奠定了基础。最后,指出开发板式壁反应器以及开展其在CO变换、净化方面的研究有较好的发展前景。     

High-Throughput Experimentation in Oxidation Catalysis

High-throughput experimentation in catalysis comprises the following components: (i) automated high-throughput synthesis, (ii) testing in Stage I and Stage II, for which to some extent novel assays are necessary, (iii) data handling and experimental design tools, and (iv) robotics. This contribution covers these topics, using examples from the research of the authors, but also from the literature, in order to illustrate the problems and opportunities associated with high-throughput experimentation in catalysis, focusing particularly on heterogeneous catalysis.     

UASB-SBR工艺处理城市生活污水的研究

研究了UASB工艺处理城市生活污水的可行性，通过UASB与SBR组合工艺的运行实验，得出在水力停留时间3h时，COD去除率为61．67％-82．32％，出水COD达到国家污水排放二级标准。在氮磷去除效果不佳的情况下，采用SBR工艺处理后，其出水COD、SS、氮、磷等指标均达到国家污水一级排放标准。     

旋转流强化管式微滤膜的分离研究

利用无机盐SiO2在旋转流场中进行的分离实验研究,对进料方式、悬浮液浓度及压力影响渗透通量的规律进行了探索,结果表明旋转流场的过滤效果比普通十字流的过滤效果显著,而且是一种非常有效的强化过滤方法。     

Syngas production from methane reforming with CO2/H2O and O2 over NiO–MgO solid solution catalyst in fluidized bed reactors

Catalyst performance of NiO–MgO solid solution catalysts for methane reforming with CO₂ and H₂O in the presence of oxygen using fluidized and fixed bed reactors under atmospheric and pressurized conditions was investigated. Especially, methane and CO₂ conversion in the fluidized bed reactor in methane reforming with CO₂ and O₂ was higher than those in the fixed bed reactor over Ni_0.15Mg_0.85O catalyst under 1.0 MPa. In contrast, conversion levels in the fluidized and fixed bed reactor were almost the same over MgO-supported Ni and Pt catalysts. It is suggested that the promoting effect of catalyst fluidization on the activity is related to the catalyst reducibility. On a catalyst with suitable reducibility, the oxidized and deactivated catalyst can be reduced with the produced syngas and the reforming activity regenerates in the fluidized bed reactor during the catalyst fluidization. In addition, the catalyst fluidization inhibited the carbon deposition.     

COMPUTER SIMULATION OF HYDRODEMETALLATION IN FIXED-BED REACTORS

An isothermal model for hydrodemetallation (HDM) of crude oils in catalytic fixed-bed reactors is proposed. This model involves a consecutive reaction mechanism, which is capable of accounting for particle deposit profiles with interior maxima. Consistent with the fact that HDM catalysts are conglomerates formed by precipitation, the porous catalyst itself is modeled as randomly overlapping spheres of equal size. The metal is deposited as growing metal sulfide crystallites on the inner surface of the catalyst. These crystallites originate from a certain number of randomly scattered nuclei and increase in size as the deposition proceeds. The random sphere model for the catalyst and the deposit provides the changes in the catalyst pore structure—local porosity and surface area.

The mass transport within the domain of the particle is due to restricted liquid diffusion, since the diameter of the metal bearing compound (porphyrin) and the intermediate are comparable to the pore size. The diffusion restrictions taken into account are the enhanced drag imposed on a molecule by adjacent pore walls and steric partitioning.

Since the deposition process is much slower than diffusion and reaction, the pseudo-steady-state assumption can be justified. The equations of conservation for mass are solved by orthogonal collocation on finite elements. Based on this solution technique a computer simulation program of HDM is designed that allows two modes of operation: constant temperature and constant conversion. The simulation program “SIMULA” is highly flexible with regard to reaction kinetics, catalyst structure, reactor design, and operating conditions. In comparison to a base case with uniform activity, the effect of intraparticle (radial) and bed (axial) activity profiles on the conversion rate is discussed. For the case investigated, a radial distribution of activity higher at the center of the particle than at the edge can increase catalyst life by 25%, but axial distribution was less successful.     

新型热管反应器在轻烃醚化中的研究及应用

将热管技术与催化反应器结合,构建了蛇形回路热管反应器。利用该反应器,进行了轻烃醚化工业侧线试验,考察了进料温度、液相体积空速、冷却水流量、进料浓度对反应结果的影响;测定了催化床层的轴向温度分布。利用反应器数学模型并结合试验数据,采用下山单纯形最优化方法获得了床层对热管的传热膜系数准数关联方程。所开发的新型热管反应器在2万t/a甲基叔丁基醚(MTBE)生产装置的扩能改造中应用成功。     

Propylene epoxidation in a microreactor with electric heating

Gas phase propylene epoxidation on gold catalysts has attracted wide attention from industry and academia due to its high selectivity. However, it suffers from low propylene conversion and rapid catalyst deactivation. Experiments showed that propylene conversion could be increased by raising H₂, O₂, or C₃H₆ concentration in the feed, but the feed compositions were within the explosion limit. It was also shown that the activity of the used catalyst could be fully recovered, but the regeneration temperature was 280 °C, much higher than that for reaction. Therefore a microchannel reactor was devised to suppress explosion and was constructed with Fecralloy, to raise the temperature rapidly for catalyst regeneration by electric heating. In two minutes the temperature of the reactor could be raised from 50 to 300 °C. Catalysts were coated on the alloy belt by dip coating, and the performance of the reactor was evaluated under different operating conditions. Results showed that in the microreactor the overall reaction rate was controlled mainly by the intrinsic reaction rate, and also influenced by film diffusion to a certain extent. The deactivated catalyst was regenerated in the microchannel reactor and the activity was fully recovered.     

Experimental and theoretical study of membrane-aerated biofilm reactor behavior under different modes of oxygen supply for the treatment of synthetic wastewater

This study compares, experimentally and theoretically, five different modes of supplying oxygen to a membrane-aerated biofilm reactor (MABR), and search for the more efficient ways of treating wastewaters. A single-tube MABR was used to measure the decrease of an organic substrate (sodium acetate) in water by supplying oxygen in different modes, namely: (1) by feeding the membrane tube either with oxygen or air (or none of them); (2) in some cases by simultaneous sparging air to the residual water. The dynamics of the substrate and oxygen consumption were measured during the batch experiment, and two mathematical models are developed to predict their transient responses using a Monod kinetic with dual substrate limitation. The models predict biomass growth and the production of extracellular polymer substances (EPS), which in turn causes the biofilm to grow; they account for the counter-diffusion of substrate and oxygen within the EPS structure that contains the cells, and one of them incorporates the mass transport by convection and diffusion in the surrounding liquid contained inside the interconnected pores and channels within the biofilm. Transport and kinetic parameters are estimated from experiments, and both models successfully predict concentration measurements in some of the set of experiments. It was found that all of the modes of oxygen supplied in a MABR were more efficient than the traditional suspended cell process.