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。     

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。     

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.     

Study of Hydrodynamics,Mixing and Gas‐Liquid Mass Transfer in a Split‐Rectangular Airlift Reactor

Global hydrodynamic characteristics, liquid mixing and gas‐liquid mass transfer for a 63 L split‐rectangular airlift reactor were studied. Correlations for gas holdup and overall liquid circulation velocity were derived for the air‐water system as a function of the specific power input; these were compared to data and correlations for reactor volumes between 4.7 L and 4600 L. A partial recirculation of small bubbles in the riser was observed when U_gr > 0.03 m/s, which was attributed to the use of a single‐orifice nozzle as the gas phase distributor. The dimensionless mixing time and the overall axial dispersion coefficient were nearly constant for the range of gas flow rates studied. However, values of K_L/d_B were greater than those reported in previous studies and this is caused by the partial recirculation of the gas phase in the riser. While scale effects remain slight, the use of a gas distributor favouring this partial recirculation seems adequate for mass transfer in split‐rectangular airlift reactors.     

水解酸化-SBR法处理生物制药废水

对采用水解酸化-SBR法处理生物制药废水的调试运行作了详细说明。工程实践表明，该工艺对处理有机物浓度高、水质水量波动大的生物制药废水是切实可行的，出水水质可达到国家污水综合排放标准一级标准．剩余污泥也得到有效处理处置。该工艺结构简单，操作简便，占地面积小，运行效果稳定，具有推广应用价值。     

CoX催化苯乙烯氧化-膜分离耦合连续反应工艺的研究

将细小的CoX催化苯乙烯氧化悬浮体系与无机膜分离耦合,实现了反应的连续操作,考察了温度、催化剂用量、溶剂量和搅拌速度对反应结果和膜通量的影响。结果表明膜分离过程不会对反应活性造成影响,操作过程中各因素对膜通量的影响归因于此条件下催化剂对膜孔的堵塞及其在膜表面的沉积程度,而超声是一个很好恢复膜通量的手段。在m(CoX)∶m(苯乙烯)=0.16、V(溶剂)∶V(苯乙烯)=3、反应温度100℃、停留时间6 h、搅拌速度800 r/min,跨膜压差0.03 MPa的条件下,苯乙烯的转化率达54.3%,环氧苯乙烷的选择性达到51.4%,苯甲醛选择性达到31.0%,膜通量为28.9 L/(m2.h)。     

Study of mass transfer in a vertically moving particle bed electrode

A study was made of the influence of process parameters on the mass-transfer coefficient in a flow-through cell with a cascade of rotating drums partially filled with conductive particles (called the vertically moving particle bed). Copper deposition from an acidic sodium sulphate solution was used as the model reaction. To evaluate the experimental data a macrohomogeneous mathematical model of potential and current density distribution inside the cell was developed. The electrolyte flow distribution between the empty space above the particle bed and through the bed was evaluated. On the basis of these results the following correlation is proposed: