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)。     

美国能源部的浆态床F－T合成技术

浆态床Ｆ－Ｔ合成技术是美国能源部Ｆ－Ｔ合成技术的主要开发项目。本文就浆态相Ｆ－Ｔ合成催化剂的开发、中试示范实验和浆态反应器的化工基础研究作一扼要的介绍。     

Bulk and Surface Properties of a VPO Catalyst Used in an Electrochemical Membrane Reactor: Conductivity-, XRD-, TPO- and XPS-study

In the first part of this work, the electrical conductivity of vanadium phosphorous oxide (VPO) catalyst was investigated by means of the 2-probe EIS method. The VPO showed an extremely low conductivity at low oxygen partial pressure, which is the prevailing condition in the anodic compartment in an electrochemical membrane reactor (EMR). In the second part of this study, fresh as well as VPO catalyst already used in an EMR were characterised with XRD, XPS and temperature programmed oxidation (TPO). The XRD measurements revealed an unchanged bulk phase structure after operation in the EMR. Significant differences in the average oxidation states of vanadium in the catalyst layer in the EMR were determined via XPS, where the catalyst surface facing the electrolyte membrane was more oxidised than the surface facing the anodic gas compartment. The lowered uptake and release of oxygen was observed in TPO experiments for the catalyst used in the EMR.     

EVALUATION OF A METHOD FOR MEASURING MIXING TIME USING NUMERICAL SIMULATION AND EXPERIMENTAL DATA

A method for measuring mixing performance in large-scale vessels is investigated. The method is evaluated experimentally in a pilotscale reactor and by using a model based on the three-dimensional calculation of the flow field. The method is based on injection of a tracer and measuring the concentration with several detectors at different locations. The mixing performance is measured as the decay rate of the difference between the concentration at the detectors and the final concentration.

The model predicts a strong dependence on injection point. The assumption of a first-order decay rate of the concentration deviation is more appropriate for some injection points.     

FORMATION AND FLOW OF GAS BUBBLES IN A PRESSURIZED BUBBLE COLUMN WITH A SINGLE ORIFICE OR NOZZLE GAS DISTRIBUTOR

The characteristics of gas bubbles in a 5 cm diameter bubble column equipped with a single orifice of 1,3 or 5 mm diameter were investigated under system pressure of 0.1-15 MPa. The formation of gas bubbles was strongly affected by the system pressure. Under high pressures a dispersed gas jet was formed at gas velocities where spherical gas bubbles would have been formed at atmospheric pressure. The critical gas velocity between the bubbling regime and the jetting regime was correlated with the liquid phase Weber number and the gas phase Reynolds number based on the gas velocity at the orifice. Bubble size and gas holdup in the main part of the bubble column were also affected by the bubble formation pattern at the distributor