对硝基苯酚臭氧化反应动力学研究

在T=298K,pH=2.1～6,采用停流光谱仪研究了对硝基苯酚与臭氧在水溶液中的臭氧化反应动力学。实验结果表明,对硝基苯酚臭氧化总的反应是2级,对臭氧浓度和对硝基苯酚浓度分别为1级。臭氧化反应速率常数随溶液pH值的增大而增大;T=298K时,当pH值从2.1变化到6,总的反应速率常数从5.88×104L(mol·s)-1增大到1.56×106L(mol·s)-1。为了验证其适用性,对臭氧在搅拌釜中在对硝基苯酚溶液中的吸收过程进行了模拟。采用MATLAB软件求解臭氧在搅拌釜中在对硝基苯酚溶液中吸收过程的质量平衡方程,模拟得到了吸收过程中臭氧和对硝基苯酚浓度的变化,并与实验值进行了比较。结果表明,在85%的对硝基苯酚降解之前,模拟值和实验值能很好地一致。在反应末期,模拟值和实验值出现了一定的偏差。     

化学工程 2005年(第33卷)第1—6期(总第197—202期) 总目次

蒸馏、萃取、吸附、吸收、干燥等过程及设备期页富微孔炭质吸附剂吸附天然气的热效应1 1臭氧在对硝基苯酚溶液中的吸收与模拟过程1 5压力对N-甲基二乙醇胺混合哌嗪水溶液脱碳速率的影响1 9β-萘酚稀溶液萃取动力学研究1 12溶剂抽提法处理炼厂污泥实验1 52闪锌矿氧化浸出与协同萃取分离耦合研究2 1新型固定阀塔板的流体力学和传质性能研究2 4热耦蒸馏及其选用原则2 9纳米多孔材料的超临界干燥新技术2 13鼓泡塔内热质同时传递过程研究2 22陶瓷基硅胶吸附材料的实验研究2 35高比表面积活性炭制备技术的研究进展2 44丙烯酸乙酯脱酸塔流程优化及…     

旋转微气泡反应器强化臭氧降解水中对硝基苯酚

臭氧氧化技术在水处理系统中具有良好的应用前景,但实际应用中受到臭氧传质及氧化选择性的限制。故本研究以对硝基苯酚废水为研究对象,采用一种新型旋转微气泡反应器,通过多孔陶瓷填料的旋转将臭氧气泡尺寸破碎至微米级别,实现对废水降解过程的强化,同时本研究还进一步考察了操作条件对臭氧传质过程和臭氧分解产生羟基自由基过程的影响规律。实验结果表明,提高反应器转速和气体流量可以加快臭氧传质和羟基自由基产率,同时提高溶液pH也可以提高羟基自由基产率进而提高对硝基苯酚的去除率。与其他操作变量相比,反应器转速的影响最为明显,说明改善臭氧气泡流体力学行为能有效地提高对硝基苯酚的去除效果,体现反应器强化臭氧体系的可行性。此外,二甲亚砜的加入抑制了对硝基苯酚的去除,说明臭氧的间接氧化方式是降解对硝基苯酚的一种重要途径。本研究结果为旋转微气泡反应器在臭氧氧化降解过程中开发及应用提供合理指导。     

对硝基苯胺臭氧化反应动力学和吸收过程模拟

采用停流光谱法研究了T＝298 K,pH＝2.1～6范围内对硝基苯胺与臭氧在水溶液中的臭氧化反应动力学.研究结果表明,降解1 mol的对硝基苯胺需要4 mol臭氧,对硝基苯胺臭氧化总的反应是二级,对臭氧浓度和对硝基苯胺浓度分别为一级.臭氧化反应速率常数随溶液pH值的增大而加快:在T=298 K时,当pH值从2.1变化到6,总的反应速率常数从6.17×10⁴ (mol•L^-1)^-1•s^-1增大到1.55×10⁶(mol•L^-1)^-1•s^-1.为了验证其适用性,进行了臭氧在搅拌釜中在对硝基苯胺溶液中吸收过程的模拟.采用Matlab软件求解吸收过程的质量平衡方程,模拟了吸收过程中臭氧和对硝基苯胺浓度的变化,并与实验值进行了比较.结果表明,在80％的对硝基苯胺降解之前,模拟值和实验值能很好地一致.     

促传剂强化臭氧氧化对硝基酚的研究

研究了传质促进剂（促传剂）对臭氧降解水中对硝基酚的影响，筛选出了两种效果较好的促进剂。实验测定了臭氧在鼓泡反应塔中的传质系数以及添加促传剂后传质系数增大的倍数。还测定了添加促传剂后酚溶液表面张力的变化，并初步探讨了促传剂的作用机理。     

超重力法臭氧处理三硝基甲苯碱性废水传质模型

在前期试验研究的基础上建立了超重机中硫酸水溶液物理吸收臭氧的体积传质模型和三硝基甲苯(TNT)碱性废水化学吸收臭氧的体积传质模型。模型计算表明:硫酸水溶液物理吸收臭氧的体积传质系数为0.0191 s-1;臭氧氧化TNT碱性废水的体积传质系数在反应初始达到0.258 s-1,臭氧利用率达到93%,远高于鼓泡塔中臭氧氧化硝基苯类化合物的化学体积传质系数(0.005 88—0.017 s-1),模型的建立为以后的工业放大提供了理论依据。     

臭氧吸收中液相臭氧浓度和增强因子理论预测

研究了臭氧在鼓泡塔中吸收时,水中溶解臭氧浓度随时间的变化规律以及pH值对它的影响。建立了臭氧吸收数学模型,可较准确地预测水中溶解臭氧浓度;同时基于稳态膜理论,提出了带有一个一级臭氧自分解反应和多个一级或二级臭氧氧化反应臭氧吸收过程的增强因子理论预测模型,与文献值比较,结果合理。     

单体Ag纳米流体强化氨水鼓泡吸收特性

为探讨纳米流体对氨水鼓泡吸收传热传质特性的影响,利用自行设计的实验系统进行了不同浓度单体Ag纳米流体基液下的氨水鼓泡吸收实验。实验表明:纳米流体浓度与初始氨水浓度是影响鼓泡吸收过程中传热与传质的关键因素。当单体Ag纳米流体在浓度0.005%～0.020%内、基液中没有添加纳米流体时,5min内随着时间推移,吸收器内溶液温度明显高于添加有纳米流体的情况;氨水鼓泡吸收传质过程中,有效吸收比均大于1.0,随着氨水浓度上升,各浓度纳米流体基液下吸收率逐步减小,有效吸收比逐渐增大,且吸收率和有效吸收比均随着纳米浓度增大而上升,当氨水浓度为20%且纳米流体浓度为0.020%时,单体Ag纳米流体强化氨水鼓泡吸收有效吸收比达到最大值1.55。对实验现象和相关结论进行了可能的机理解释。     

US/O3降解对硝基苯酚的影响因素及机理

研究了US（超声波）/O₃（臭氧）体系中气速、温度、pH值、对硝基苯酚初始质量浓度以及超声声强对对硝基苯酚降解速率的影响.研究结果表明：对硝基苯酚降解速率随着气速、超声声强及pH值（pH≤6时）的提高而提高,随着对硝基苯酚初始质量浓度的提高而下降,而反应温度及在pH>6时影响不明显.对硝基苯酚在US/O₃、US及O₃体系中的降解均遵循拟一级反应动力学规律,其反应速率常数分别为1.50×10^-3 s^-1、3.27×10^-5 s^-1和6.63×10^-4 s^-1,增强因子为216％,具有明显的协同效应,其协同效应主要是由臭氧在空化泡内热解产生•OH引起的.采用液相色谱（HPLC）、离子色谱(IC)、GC-MS等方法测定出对硝基苯酚降解的主要中间产物有邻苯二酚、邻苯醌、对苯二酚、对苯醌、苯酚、反丁烯二酸、顺丁烯二酸、草酸和甲酸等,并依此推导出对硝基苯酚的降解机理.     

固体超强酸SO_4~(2-)/TiO_2-WO_3光催化降解邻硝基苯酚动力学研究

在高压汞灯下,研究了邻硝基苯酚在SO42-/TiO2-WO3光催化剂表面的降解过程,对邻硝基苯酚在SO42-/TiO2-WO3悬浮体系中的降解机理进行了初步的探讨。结果表明,光降解反应速率受邻硝基苯酚的初始浓度、气相氧流量、反应温度、溶液pH值、光强度和催化剂用量等因素的影响。基于Langmuir-Hinshelwood方程和一些假设,分析了邻硝基苯酚光降解的动力学机理,推导了固体超强酸SO42-/TiO2-WO3催化邻硝基苯酚光降解的动力学方程。     

Mass Balance Analysis of Ozone in a Conventional Bubble Column

Ozone transfer into potable water was studied in a conventional bubble column, and ozone mass balances have been calculated to determine ozone utilization efficiencies. Liquid and gas flow rates, as well as inlet ozone concentrations in the gas phase were varied. Using these data, it was possible to determine the ozone mass transfer coefficient, ozone transfer efficiency, and ozone consumption. A model of ozone transfer was established, and procedures for calculating the optimum design parameters and operating conditions are proposed.     

Ammonia absorption from a bubble expanding at a submerged orifice into water

To investigate the mechanism of gas absorption from a bubble containing soluble and insoluble components, a gaseous mixture of ammonia and nitrogen was bubbled into water. The growth curve, volume, surface area and shape of the growing bubbles were measured with parameters such as inlet gas composition, gas flow rate and gas chamber volume. The bubble volume decreased with the increasing composition of ammonia in a bubble, decreasing gas chamber volume and decreasing gas flow rate.To reasonably express the mass transfer from the bulk of a gas in a bubble to the bulk of a liquid, the overall mass transfer resistance was evaluated by the mass transfers in the gas phase, interface and liquid phase.The non-spherical bubble formation model combined with the overall mass transfer resistance estimated well experimental bubble shape, bubble volume at its detachment from an orifice, growth rate and mass transfer rate.Moreover, the change of concentration with bubble growth time and the fractional absorption during bubble formation were simulated.     

Ozonation of C.I. Reactive Black 5 and Indigo

The ozone transfer for the ozonation of the azo dye Reactive Black 5 (RB5) and indigo was investigated using a bubble column at semi-batch conditions. The results were analyzed by applying film theory and surface renewal theory. The ozonation of both dyes was so fast that an instantaneous reaction directly at the bubble surface can be assumed. The ozone balance in the gas phase was used to determine the volumetric mass transfer coefficient k_La and the enhancement factor E. Besides the measured concentrations, temperature and pressure only the Henry coefficient was required for the determination of k_La and E. By varying the ozone inlet and the dye concentration the reaction regime was identified. The Hatta number Ha which requires uncertain parameters did not have to be determined.     

Modeling and scale-up simulation of U-tube ozone oxidation reactor for treating drinking water

In the present study, we developed a novel simulation model of the U-tube reactor for treating drinking water, which is composed of a coaxial inner tube serving as an efficient concurrent down-flow ozone dissolver and an outer column carrying out reactions between ozone and organic substances including odorous materials (2-methylisoborneol: 2-MIB) dissolved in the raw water. We assume that the U-tube is composed of a plug flow section (inner tube) followed by a tanks-in-series section (outer bubble column) and take into account the effect of the hydrostatic pressurization on the flow and absorption equilibrium for the gaseous components including ozone and other inactive species in developing the mass balance models. An algorithm is constructed of the differential multiple mass balance equations for the inner tube sections and multiple difference mass balance equations in the series tanks in the outer column section to enable the scale-up from a pilot plant to a full-scale plant. The gas holdup and gas-liquid mass transfer coefficient were measured in a model reactor and correlated for the use of the simulation calculation. Available literature data and correlations on the rates of reactions between ozone and organic substances including odorous material 2-MIB, gas-liquid equilibrium for active and inactive gases and axial fluid mixing properties are also incorporated in the simulation calculation. The simulation results well explained the available data of the ozone absorption efficiency and the removal efficiency of the odorous material in a pilot U-tube reactor. The simulation procedure was also successfully extended to verify the performance of a full-scale U-tube reactor. It is shown that the ozone absorption is practically a single function of the gas/liquid ratio while the removal efficiency of the odorous material is a single function of the ozone dose for a specified U-tube configuration.     

Hydrodynamics and ozone mass transfer in a tall bubble column

In the paper, major hydrodynamic parameters such as gas hold-up, phase velocities and axial dispersion as well as the ozone mass transfer coefficients in the liquid phase have been investigated in a tall bubble column for co-current, counter-current and semi-batch modes of operation. The major emphasis has been placed on evaluation of the dynamic characteristics of the combined system of experimental column and measuring sensors, which was applied in the subsequent determination of the axial dispersion and ozone mass transfer coefficients in the liquid phase. The ozone mass transfer coefficients have been estimated using two treatment methods of the recorded changes of ozone concentration in the liquid and gas phases with time during ozone absorption or stripping to an inert gas.     

Influence parameters in the ozonation of phenol wastewater treatment using bubble column reactor under continuous circulation

The ozonation of phenol wastewater treatment system has been investigated with effective mass transfer between gas and liquid phase in a bubble column reactor. The designed bubble column reactor was investigated for increasing the rate of mass transfer of ozone, the rate of oxidation of phenol in the solution, the solubility and decomposition rate of ozone in the distilled water were also studied at different flow rates. The decomposition rate constants were calculated based on pseudo first order kinetics. The oxidation of phenol was investigated in order to provide the overall reaction rate constant for the reaction between ozone and phenol at 25 °C. The influence of the operating parameters like initial phenol concentration, ozone flow rate and pH for the destruction of phenol by ozonation were studied. The pseudo first order rate constant was depending on the initial concentration of phenol solution. A comparison of TOC removal percentage between bubble column reactor and bubble diffuser using ozonation were reported.     

HYDRODYNAMICS AND MASS TRANSFER IN DOWNFLOW BUBBLE COLUMN

Gas holdup, effective interfacial area and volumetric mass transfer coefficient were measured in two and three phase downflow bubble columns. The mass transfer data were obtained using the chemical method of sulfite oxidation, and the gas holdup was measured using the hydrostatic technique. Glass beads and Triton 114 were used to study the effects of solids and liquid surface tension on the gas holdup and the mass transfer parameters a and k_La. The gas holdup in three phase systems was measured for non-wettable (glass bead) and wettable (coal and shale particles) solids.

The mass transfer data obtained in the downflow bubble column were compared with the values published for upflow bubble columns. The results indicate that in the range of superficial gas velocities (0.002-0.025) m/s investigated, the values of the mass transfer coefficient were of the same order of magnitude as those observed in upflow systems, but the values of interfacial area were at least two fold greater. Also, the results showed that the operating variables and the physical properties had different influences on a and k_La in the downflow bubble column. Correlations for a and k_La for the downflow bubble column are proposed which predict the data with adequate accuracy in the range of operating conditions investigated.     

鼓泡床反应器内流动与传质行为的研究进展

总结了有关浆态鼓泡床反应器内流动、混合用气液传质特性的研究成果,详细地介绍了鼓泡床反应器内气含率、液速、液体轴向扩散系数、传质系数的测量方法,阐述了鼓泡床反应器性能的主要影响因素,如系统压力、温度、气体表观气速、液体性质及固含率等对流动、液相混合和传质特性的影响,并对鼓泡床反应器的应用前景进行了详述.     

PIV/PLIF Study of Impinging Jet Ozone Bubble Column with Mixing Nozzles

This paper introduces the results obtained from a particle image velocimetry/planer laser-induced fluorescence (PIV/PLIF) system used in characterizing an impinging jet ozone bubble column with mixing nozzles. This research aims at evaluating the mixing effect resulting from the nozzle diffusers attached to the outlets of the impinging jets' injectors. The PIV system was used to study the flow patterns of the liquid and gas phases under different superficial gas and liquid velocities (u_G and u_L, respectively) values (from 0.002 to 0.017 m/s and from 0.008 to 0.024 m/s, respectively). Furthermore, a particle dynamics analyzer (PDA) system was used to characterize the bubble sizes under the same operating conditions. The PLIF system was used to determine the liquid axial dispersion coefficient (D_L, m²/s) for the mentioned range of operating conditions. The column average gas hold-up (?_G) and specific interfacial area (a) were then determined in order to evaluate the column's mass transfer efficiency. The results showed that higher mass transfer rates can be obtained by using this column, as high ?_G, and were achieved.