Formation of Bromate Ion Through a Radical Pathway in a Continuous Flow Reactor

The contribution of ozone and hydroxyl radical to the formation of bromate ion was investigated in a continuous flow reactor. Experiments were conducted under a wide range of ozone dose (0.7 ～ 3.8 mgL), pH (6.5 ～ 8.5), and t-butanol concentration (0 ～ 0.5 mM). The formation of bromate ion was found to depend on radical reaction pathway, because the amount of bromate ion formed increased with pH and decreased with t-butanol, a radical scavenger, even when dissolved ozone concentrations were almost the same. In fact, the amount of bromate ion formed was reduced by 90% in the presence of t-butanol. Furthermore, the formation of bromate ion occurred even when dissolved ozone was not significantly detected in the presence of organic matter (TOC of 1 mgCL). The second-order reaction rate constant of hydroxyl radical with bromide ion, k _HO,Br^? of 1.7 × 10⁹ (M^?1s^?1), was obtained on the assumption that the reactions of bromide ion and t-butanol with hydroxyl radical were competitive with each other in the presence of t-butanol and that the formation of bromate ion depended on the reaction of bromide ion with hydroxyl radical. Therefore, it is concluded that the reaction of bromide ion with hydroxyl radical dominated in the overall reaction from bromide ion to bromate ion in the continuous flow reactor.     

反应级数对理想反应器组合方式效率的研究

对于不同级数的不可逆反应,研究了其在全混流反应器(CSTR)与平推流反应器(PFR)不同组合方式中的最终转化率。对两种理想流动反应器的不同组合方式,如CSTR+PFR串联、PFR+CSTR串联及CSTR与PFR并联,反应的最终转化率随反应级数的不同而变化。当反应级数为负值时,CSTR与PFR并联组合方式的最终转化率最高;当反应级数为0~1之间的数值时,CSTR+PFR串联组合方式的最终转化率最高;而当反应级数大于1时,PFR+CSTR串联组合方式的最终转化率最高;当反应级数为0时,三种组合方式具有相同的最终转化率;但当反应为一级不可逆反应时,两种反应器串联时的最终转化率相同,并高于两种反应器并联时的最终转化率。     

Differentiation criteria study for continuous stirred tank reactor and plug flow reactor

All reactors in reality are not ideal plug flow reactor (PFR) or ideal continuous stirred tank reactor (CSTR). They are difficult to differentiate. This study was to investigate the reactor analysis of PFR and CSTR through tracer response curves, residence time distributions (RTD) and several hydraulic performance indexes. We set up the differentiated value of each index. The tracer response curve showed that our lab-scale CSTR was close to ideal CSTR and got 99.9% recovery. In the RTD curves, the results could significantly recognize the PFR nature of high rate pond (HRP). With hydraulic performance indexes study, every selected index demonstrated that the studied HRP was closer to PFR than the studied CSTR. Based on the lab-scale study results, this study established the cutting point between the PFR and CSTR in each index; we were looking through the different types of reactors in literature and we confirmed the criteria with all literature reactors with the “graphic method”. The method helped us to establish those important values to help us to differentiate the reactor types in practice and to understand the designs better.     

共轭双烯聚合物选择性加氢反应器技术进展

对以橡胶、弹性体为代表的含共轭双烯聚合物进行烯属双键的选择性加氢,可显著提高聚合物的稳定性;加氢反应器和反应工艺是制约加氢度和产率的关键技术之一。该文综述了目前共轭双烯聚合物选择性加氢反应器的技术进展,包括以机械搅拌反应器、鼓泡反应器、外循环反应器为代表的全混流型反应器;以填料塔和静态混合管式反应器为代表的平推流型反应器;以及各种反应器的组合技术、特殊操作方式。结合加氢体系的流体力学特征和反应动力学特征,分析了制约加氢度和产率的关键问题,总结了进一步提高加氢度和产率、降低能耗物耗的潜在途径。     

Obtaining Real-Time Kinetic Parameters on Ozone Decay from a Full-Scale Ozone Contactor Using the Axial Dispersion Reactor Model

Ozone decay kinetic parameters, including fast ozone demand ([D]₀), ozone decay rate constant (k_D), and rate constant for ozone reaction with ozone demand (k_R), are required for a numerical simulation targeting the design and operational optimization of an ozone contactor. The kinetic parameters of ozone decay and dispersion number were obtained from a full-scale ozone contactor for the axial dispersion reactor model simulation. The sensitivity analysis showed that the influence of k_R was minor and the constant 13 L mg^?1 min^?1 for k_R was suitable for carrying out simulations for sand-filtered raw water without measuring it. Curve fitting with on-site ozone concentrations and the ADR simulation results using a trial-and-error method could successfully provide kinetic parameters on ozone decay (i.e., k_D and [D]₀). Using these real-time kinetic parameters, we successfully predicted the CT, residual ozone, C. parvum log inactivation, and bromate formation. Compared to a method based on the CSTR in series, this method could provide more accurate CT and residual ozone for an ozone contactor with horizontal meandering flow and low dispersion number.     

A Simple Model to Predict Formation of Bromate Ion and Hypobromous Acid/Hypobromite Ion through Hydroxyl Radical Pathway during Ozonation

A simple model is developed to predict the formation of bromate ion as well as hypobromous acid/hypobromite ion through the hydroxyl radical pathway. For simplicity of the model, hydroxyl radical concentrations are represented by the concentration ratio of hydroxyl radical to dissolved ozone under the different pH conditions. A kinetic analysis is conducted to evaluate the ratio under the different pH conditions based on the experimental data. The different extent of the ratio by one pH unit is found to be 3–4 times. This model can favorably simulate the formations of bromate ion as well as hypobromous acid/hypobromite ion in spite of the simplicity of the model. So it is likely that this model will be applicable to the prediction of bromate ion formation in water purification process such as drinking water treatment by introducing the concentration ratio of hydroxyl radical to dissolved ozone.     

Kinetics and mechanism of the reaction between ozone and hydrogen peroxide in aqueous solutions

A kinetic model has been developed, taking into account both decomposition of ozone molecules and interactions between ozone and hydrogen peroxide for formation of hydroxyl radical and subsequent reactions. Experiments were carried out at 25°C in the pH range of 3 to 13, indicating that the depletion rate of ozone increases with the concentrations of ozone, hydrogen peroxide and hydroxyl ion, as predicted by the kinetic model. Adverse scavenging reactions, however, also play significant roles at sufficient concentration ratios of hydrogen peroxide to ozone and high concentrations of hydroxyl ion in reducing the depletion rate. Results of this research suggest, that it is most desirable to conduct the peroxone oxidation for pollutant destruction by the hydroxyl radical reaction in alkaline solutions of pH below 11, while maintaining about the same concentration of ozone and hydrogen peroxide.     

Continuous emulsion polymerization of vinyl acetate. II Operation in a single Couette–Taylor vortex flow reactor using sodium lauryl sulfate as emulsifier

Continuous emulsion polymerizations of vinyl acetate were conducted at 50°C in a single continuous Couette–Taylor vortex flow reactor (CCTVFR) using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator. The polymerization can be carried out very smoothly and stably, but the steady‐state monomer conversion attained in a CCTVFR is not as high as that in a plug flow reactor (PFR), but only slightly higher than that in a continuous stirred tank reactor (CSTR), even if the Taylor number is adjusted to an optimum value. Also, the effects of operating variables, such as the emulsifier, initiator, and monomer concentrations in the feed and the mean residence time on the kinetic behaviors were almost the same as those observed in a CSTR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2755–2762, 2002     

氯苯反应器数学模型的研究

通过对氯苯反应器中气、液两相传质及反应特征的分析,提出了按照CSTR串联PFR模型设计氯苯反应器的观点。其中CSTR为主要反应区域,约占全塔反应体积的80%。进一步的计算表明,用模型预测的反应器出口转化率与反应器的实际转化率一致。     

Examination of in situ Generation of Hydroxyl Radicals and Ozone in a Flow-through Electrochemical Reactor

Generation of hydroxyl radicals and ozone in a low ionic strength influent (0.001 M Na₂SO₄) treated in a continuous flow electrochemical (EC) reactor equipped with a cobalt-promoted lead dioxide anode was examined using p-chlorobenzoic acid (pCBA) and indigotrisulfonate (ITS) probes. EC generation of hydroxyl radicals via the oxidation of water was determined to precede that of ozone. OH· current yields were affected virtually solely by the current density, with almost negligible effects of variations of pH and carbonate concentrations. Absolute values of the current yields of EC generated OH· radicals were close to 1.0% for current densities > 30 mA/cm². The EC generation of ozone was suppressed in the presence of organic species, primarily due to the interception of OH· radicals that react with oxygen to form ozone. Apparent kinetic constants of major reactions associated with the EC generation of ozone were determined based on a steady-state model of an EC-controlled continuous flow reactor.     

Free Radical and Direct Ozone Reaction Competition to Remove Priority and Pharmaceutical Water Contaminants with Single and Hydrogen Peroxide Ozonation Systems

From the application of concepts derived from the gas-liquid absorption film model, the competition between ozone reactions with 72 water emerging or priority contaminants (pharmaceuticals, pesticides, polynuclear aromatic hydrocarbons, etc.) and the initiation steps of the hydroxyl radical decomposition of ozone in ozone alone and combined with hydrogen peroxide oxidation systems has been studied. With this information, the ozone preferential reaction, that is, the ozone direct reaction or the formation of free radicals and the kinetic absorption regime are known. In a second step, the ratio of removal rates of the contaminants studied by reacting with hydroxyl radical and ozone has also been estimated. With this, the way contaminants are preferentially removed (from their reaction with ozone or from the reaction with free radicals) can also be known and, hence, whether or not an ozone advanced oxidation system is convenient to be applied. For instance, most of the contaminants studied in this work at concentrations lower than 50 μgL^?1 and hydrogen peroxide at concentrations lower than 50 mgL^?1 react with ozone under chemical control regime so that both direct and free radical reactions theoretically compete. However, under chemical control, typical concentration of scavengers present in wastewater or surface water would inhibit the free radical reactions and, at least theoretically, for many contaminants studied here, the direct ozone reaction is the principal removal way. When mass transfer controls the process rate only contaminants with a hydroxyl and ozone rate constant ratio ≥ 1.6x10⁶ M^-1s^-1 would be preferentially removed through free radical way.     

Advanced Oxidation and Degradation of Vinyl Chloride in Water

A kinetic model has been developed for the degradation of organic pollutants, by considering both the decomposition of ozone molecules and the interaction between ozone and hydrogen peroxide in the formation of a hydroxyl radical, and the subsequent reactions. Rate equations were derived for the depletion of ozone and pollutants in the advanced oxidation processes (known as the peroxone oxidation). Experiments were carried out at 298 K in the pH range 3 to 11. Kinetic data obtained experimentally from the hydrogen peroxide‐ozone reaction and advanced oxidation of vinyl chloride were analyzed by using the proposed rate equations, indicating that the depletion rate of ozone increases with the concentrations of ozone, hydrogen peroxide, and hydroxyl ion, as predicted by the kinetic model.     

撞击流气化炉内颗粒停留时间分布的随机模拟

根据多喷嘴对置式气化炉流场测试,将气化炉划分为若干区域,运用时间离散、状态离散的马尔可夫链随机模型,模拟了气化炉内颗粒相的停留时间分布(RTD)。当颗粒在撞击区和射流区间的回流比为0.5,向下撞击流股区和管流区为平推流模型,其他区域按全混流模型处理时,模拟值与实验值吻合较好。随着进料流量的增大,平均停留时间减小,量纲1方差减小;随着回流比的增加,平均停留时间增大;气固两相平均停留时间接近,但RTD存在一定差异。     

模拟乙烷裂解炉管中流体返混对烧焦过程的影响

针对裂解炉管弯头处流体运动状态变化的特点,采用柱塞流反应器(PFR)与串联全混流反应器(CSTR)组合的反应器模型,耦合计算了炉膛传热和辐射段炉管内的烧焦过程.将烧焦时焦炭表面氧分压、烧焦速率、炉管出口气体温度和碳氧化物含量、焦炭层厚度等影响的模拟结果与无返混的PFR模型的模拟结果进行了比较.结果表明:两种模型模拟的炉管出口气体温度和碳氧化物含量均与生产实际基本相合,但有返混的模型能更准确地描述烧焦结束时残碳在管内的分布特点.     

工业渣油催化裂化过程六集总组合反应器模型

工业渣油催化裂化反应主要发生在提升管段和出口的沉降器段的复杂流体动力学区域。通过对工业现场装置流程和过程数据的分析,将发生裂化反应的整个反应器中提升管部分作为活塞流反应器(PFR)和沉降器部分作为全混流反应器(CSTR)的串联组合反应器,并按照渣油催化裂化反应特点建立了简化的6集总组分的串行和并行动力学反应网络模型。所建立的稳态催化裂化反应产率预测模型在数学上表现为提升管部分的微分方程组和沉降器部分的代数方程组。模型设置7个装置因数来校正模型的计算产率与实测产率之间的偏差,并采用工业现场数据回归装置因数。通过对工业装置数据的计算比较,得到的模型产率预测精度很好地满足在线软测量计算要求。     

Practical Design Of A New Ozone Contactor: The Deep U-Tube

This paper presents a practical design of a new ozone contactor (the deep U tube). It is a based on the modeling of upward and downward bubbly flow of air and water, derived from a balanced equation of continuity and momentum. Two hydrodynamic parameters are estimated: the void fraction and the frictional pressure drop. Experimental data carried out on full-scale plant and pilot plant are compared to theoretical results predicted by the model. Flow of the liquid phase is performed from tracer tests in order to determine the detention time which is introduced into the CT concept for disinfection. The influence of flow model shows that a plug flow reactor is more efficient than a CSTR; the DUT is close to plug flow.     

Simulation of hydrodynamics and inhibitor consumption in hydrometallurgical plants

Mathematical models are presented for the consumption of the inhibitors of electrocrystallization in hydrometallurgical plants involved with the copper electrorefining and zinc electrowinning. Continuously-stirred tank reactors (CSTR) and plug flow reactors (PFR) in which first order chemical and electrochemical reactions take place are used in these models. The time dependent behaviours of the industrial plants are predicted. Tests with metallic tracers show the validity of the models. Possible uses in electrocrystallization studies are described.     

Experimental study and model of reaction kinetics of heterogeneously catalyzed methylal synthesis

Reaction kinetics of the heterogeneously catalyzed formation of methylal from aqueous methanolic formaldehyde solutions are studied in a plug flow reactor at 323, 333 and 343 K using the acidic ion exchange resin Amberlyst 15 (Rohm and Haas) as catalyst. Parameters of an activity-based pseudo-homogeneous reaction kinetic model are fitted to the experimental results. The model is based on the true speciation in the reacting solution and explicitly includes the oligomerization reactions of formaldehyde in aqueous methanolic solutions. The reaction kinetic model describes the experimental data well and is suited for process simulations in which both chemical reactions and phase equilibria have to be described simultaneously.     

Switching from water to ionic liquids for the production of methylchloride: Catalysis and reactor issues

The synthesis of methyl chloride from methanol and hydrogen chloride catalysed by zinc chloride was investigated in water and in two room temperature ionic liquids in a CSTR reactor. Both Aliquat336 and BMICl drive to similar rate of reactions as the traditional process albeit at lower temperatures. More importantly, the formation of the side product Me₂O is decreased in ionic liquids. From the reactor point of view and on the basis of kinetics and simulations, a new process involving plug flow behaviour using ionic liquids is proposed which would lead to process intensification, i.e. (50×) productivity increase.     

Investigation of mixing in a rotor shape modified Taylor-vortex reactor by the means of a chemical test reaction

The macro- and micromixing properties of a continuous flow Taylor-vortex reactor can be optimised by changing the conventional cylindrical rotor geometry into a novel ribbed one. A chemical test reaction, the micromixing-sensitive alkaline saponification of ethylacetate with separately fed reactants, was used to probe the mixing performance down to the molecular level. Experiments were performed in a continuous flow Taylor-vortex reactor equipped either with a conventional cylindrical rotor or with a novel ribbed rotor in a wide hydrodynamic range of 150<Ta<8000 and 0.8<Re<2.0.Through increase in the reaction temperature and the feed concentrations, the relaxation times of this reaction were reduced from 680 to 19 s and compared to micromixing times by monitoring the reactor conversion. The results show that a TVR with conventional rotor achieves intense micromixing at high rotor speed, but behaves like a CSTR. In contrast, a device with ribbed rotor shows macromixing features close to those of a plug flow reactor (PFR) in a wide range of rotor speeds; however, segregation of the two feeds could only be dissipated at slow reaction rates, i.e. relaxation times larger than 64 s.