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。     

间甲酚臭氧化反应动力学研究

本文采用停流光谱仪研究了溶解臭氧和间甲酚在液相中的均相反应动力学,探讨了反应温度为298K和pH值在3～7范围内,间甲酚臭氧化反应的动力学参数。间甲酚臭氧化总的反应呈二级,对臭氧浓度和间甲酚浓度分别呈一级。臭氧化反应速率常数随溶液pH值的增大而增大,在T为298K时,当pH值从3变化到7,总的反应速率常数从6 28×103(mol L)-1·s-1增大到9 15×105(mol L)-1·s-1。     

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.     

间甲酚臭氧化反应动力学研究

采用停流光谱仪研究了在T=298 K,pH=3～7范围内溶解臭氧与间甲酚在水溶液中的臭氧化反应动力学,初步探讨了间甲酚臭氧化反应的机理。实验结果表明,间甲酚臭氧化总的反应是二级,对臭氧浓度和间甲酚浓度分别为一级。臭氧化反应速率常数随溶液pH的增大而增大,在T=298 K时,当pH从3变化到7,总的反应速率常数从6.28×103(mol/L)-1s-1增大到9.15×105(mol/L)-1s-1。     

苯酐水解速率实验测定

对邻苯二甲酸酐水解反应动力学进行了研究.在线测定了溶液中pH值的变化,根据pH值与溶液浓度之间一一对应的关系,得到苯酐在水解过程中邻苯二甲酸浓度的变化.由水解结束时溶液的平衡浓度与此时溶液的pH值,计算了不同温度下邻苯二甲酸的一级电离常数Ka,从而确定了水解反应级数α和不同温度下反应速率常数k.得到以下结论:随着温度的升高,水解速率常数也随之增加.根据阿伦尼乌斯方程,求得了水解反应的活化能Ea为9.45 kJ/mol、指前因子A为2.30.     

高压低温下H2O-H2O2-CO2三元体系CO2气体水合物的分解动力学

研究了非纯水体系H2O-H2O2-CO2中CO2气体水合物分解的动力学,测定了高压低温条件下CO2气体水合物分解过程的液相组成. 依据实验数据建立了CO2气体水合物分解动力学模型,模型计算值与实验值吻合良好. 确定了3个温度下气体水合物分解的速率常数,计算得出CO2气体水合物分解的活化能为97.17 kJ/mol.     

羟基化锌催化臭氧化水中痕量p-CNB的动力学和机理

以实验室制备的羟基化锌(ZnOOH)为催化剂,探讨了其催化水中臭氧分解和降解水中痕量对氯硝基苯(p-CNB)的途径,并通过ESR实验验证了自由基反应机理。结果表明：ZnOOH可促进水中臭氧分解,使其一级分解速率常数提高了187%。反应20 min时,O₃/ZnOOH对p-CNB的去除可以达到96.1%,比单独O₃提高了1倍多。ZnOOH催化臭氧分解过程中促进了羟基自由基生成,用叔丁醇捕获生成的羟基自由基后,ZnOOH催化臭氧氧化p-CNB的反应速率常数降低了至少10倍。催化剂表面羟基含量与催化臭氧化水中p-CNB的效果之间没有直接的关系。当溶液pH值接近表面零质子电荷点pH_pzc即表面几乎电中性时,O₃/ZnOOH降解p-CNB效果最好。     

羟基化锌催化臭氧化水中痕量p-CNB的动力学和机理

以实验室制备的羟基化锌(ZnOOH)为催化剂,探讨了其催化水中臭氧分解和降解水中痕量对氯硝基苯(p-CNB)的途径,并通过ESR实验验证了自由基反应机理。结果表明:ZnOOH可促进水中臭氧分解,使其一级分解速率常数提高了187%。反应20 min时,O3/ZnOOH对p-CNB的去除可以达到96.1%,比单独O3提高了1倍多。ZnOOH催化臭氧分解过程中促进了羟基自由基生成,用叔丁醇捕获生成的羟基自由基后,ZnOOH催化臭氧氧化p-CNB的反应速率常数降低了至少10倍。催化剂表面羟基含量与催化臭氧化水中p-CNB的效果之间没有直接的关系。当溶液pH值接近表面零质子电荷点pHpzc即表面几乎电中性时,O3/ZnOOH降解p-CNB效果最好。     

固相条件下研磨屑解毒六价铬机理及动力学规律研究

通过改变铬渣的粒径大小,在固相条件下将含铬废渣中的六价铬解毒后稳定化处置.研究了不同温度、pH、铬渣目数、含水率和初始浓度对研磨屑还原六价铬的反应动力学影响,通过实验验证:在pH=2～5,研磨屑与六价铬反应符合准一级动力学规律.pH为2时,速率常数是pH为3、4的1.63、2.47倍;铬渣粒径对反应体系的影响较为明显,R2大于0.98;目数为150目时,还原反应速率常数分别是目数为10、50目的12.1、4.8倍;在初始pH相同的条件下,体系含水率越高,还原剂研磨屑与含铬废渣粉末混合越均匀,固相反应速率常数越大;不同六价铬初始浓度的反应体系中,在铬粉目数相同的前提下,反应速率随六价铬初始浓度的增大而减小;在pH=3、含水率45％的条件下,反应速率常数随温度的升高而增大;温度为35℃时,反应速率常数分别是20℃、5℃的1.68、5.11倍.通过阿伦尼乌斯公式,建立六价铬固相还原反应体系中,反应速率常数随温度变化的函数关系方程.     

甲基丙烯酸-3-三甲氧基硅丙酯的水解-缩合反应速率常数

在甲基丙烯酸-3-三甲氧基硅丙酯（MPS）和苯乙烯的乳液共聚合反应中,MPS与水接触时其SiOR基团会发生水解缩合反应,其反应速率对乳液体系的稳定有很大的影响,而且所得产物的杂化结构也由SiOR基团的水解缩合反应速率决定.通过²⁹Si核磁共振谱,测定了不同pH值下MPS的水解-缩合速率常数.发现MPS的水解速率常数在pH=7时最小,无论是在酸性条件还是碱性条件都使其迅速增大.而MPS的缩合速率常数则在pH=4时达到最小,而在相对较高pH值和更低的pH值时,其缩合速率常数也都迅速增大.并得到了不同pH值时水解-缩合速率常数估算式.为进一步研究MPS乳液聚合的过程机理、反应过程动力学模型的求解以及通过模型对反应结果的预测提供了依据和基础数据.     

Ultraviolet-Enhanced Ozonation of Organic Compounds: 1,2-Dichloroethane and Trichloroethylene as Model Substrates

1,2–Dichloroethane (DCE) and trichloroethylene (TCE) were used as model compounds to study the oxidation of organic chemicals by ozone/ultraviolet radiation, ozone, and hydrogen peroxide/ultraviolet radiation. It was found that ozone/ultraviolet radiation oxidized both 1,2–dichloroethane and trichloroethylene in batch systems, at pH = 2 (phosphate buffer). At ozone concentrations in the 1 to 5 mg/L range, the reaction was first order in both ozone and substrate. At pH = 2 and initial ozone concentration 2.2–2.6 mg/L, rate constants (k)Q = 25 and 130 M^-1sec^-1 were observed for the ozone/ultraviolet radiation oxidation of DCE and TCE, respectively. The rat e constants for ozone oxidation of DCE and TCE without ultraviolet radiation were 4.3 and 47 M^-1sec^-1, respectively.

The higher rate of TCE oxidation implies that direct reaction occurs with the double bond. Finite reaction rate of DCE with ozone, and substantial increases in rate at higher pH imply the participatation of hydroxyl radicals in the oxidation of both compounds. For example, at pH = 7, initial ozone concentration of 2.3 mg/L, the k_o for TCE oxidation by ozone/ultraviolet radiation is approximately 500 M^?1 sec^?1 almost too fast to measure in a batch system.The rate also is increased by increased ultraviolet radiation intensity, and by the presence of hydrogen peroxide, which acts as a catalyst.     

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.     

Kinetics of Heterogeneous Catalytic Ozone Decomposition in Water on an Activated Carbon

Ozone decomposition in water in the presence of an activated carbon has been studied. Variables investigated were agitation speed, carbon particle size, temperature and pH. In all cases, the presence of activated carbon improved the ozone decomposition rate. Between pH 2 and 7 the ozone decomposition rate due to both the homogeneous and heterogeneous mechanisms hardly varied while a significant increase was noticed with increasing pH. A kinetic study based on a Langmuir-Hinselwood type mechanism for the heterogeneous surface reaction was undertaken. According to this mechanism the heterogeneous ozone decomposition kinetics can be simplified to follow a first order process. Fit of experimental results to the kinetic equations derived from the mechanism allowed for the determination of the apparent first order rate constants of the ozone surface heterogeneous reaction and adsorption equilibrium constants.     

Homogeneous Catalyzed Ozone Decomposition in the Presence of Co(II).

The homogeneous decomposition of ozone in the presence of a Co(II) catalyst has been investigated in aqueous solution. Under the conditions investigated (Co(II) concentration: 0.0 – 2.0?ppm, pH: 1.6- 8.4, O₃ concentration: 5 10^?5 – 2.0 10⁴?M) the process can be assumed to follow pseudo first order kinetics with respect to ozone. Cobalt concentration dependency also obeys first order kinetics although it may be considered to reach a steady state concentration. pH exerts a positive influence on the decomposition rate from 1.6 to 7.1, the process leveling off at pH 8.4. An Arrhenius analysis of the temperature effect gave a moderate activation energy of the global reaction (E=10917?cal mol^?1). A more detailed radical mechanism than a simple pseudo first order reaction can be postulated for simulation purposes. By numerical optimization of some unknown kinetic constants the influence of several operating variables can be adequately predicted.     

Decomposition of 2-Chlorophenol in Aqueous Solutions by Ozone and UV/Ozone Processes in the Presence of t-Butanol

The decomposition of 2-chlorophenol in aqueous solutions by ozone and UV/ozone process was studied with the presence of t-butanol. The addition of t-butanol decreased the surface tension of aqueous solutions and subsequently increased the gas-liquid contact area. The presence of t-butanol did not affect the steady-state dissolved ozone concentration in aqueous solution; however, the ozone transfer rate between gas-liquid interface was noticeably enhanced and the time required to reach the steady state was reduced. The presence of t-butanol was found to promote the decomposition of 2-chlorophenol for both ozone and UV/ozone processes. Nonetheless, the presence of excessive dosages of t-butanol might decrease the reaction rates for experiments conducted in alkaline solutions probably because t-butanol also served as the scavenger for hydroxyl free radicals.     

Chemical treatment of cork‐processing wastewaters for potential reuse

The chemical treatment of cork‐processing wastewater by ozonation, alone and in combination with hydrogen peroxide and UV radiation was investigated. A reduction of the chemical oxygen demand (COD) ranging from 42% to 76% was obtained during ozonation after 3 h of reaction, depending on the experimental conditions. The additional presence of hydrogen peroxide and UV radiation enhanced the efficiency of the ozonation treatment due to the contribution of the OH radicals formed in the decomposition of ozone. Thus, final reductions of the COD higher than 90% and a complete elimination of phenolic compounds and absorbance at 254 nm were achieved in both Advanced Oxidation Processes (AOPs), O₃/H₂O₂ and O₃/UV. Therefore the effluent resulting from the ozonation treatments can be reused in the cork‐processing industry. In a second step, the chemical treatment was conducted by means of UV radiation alone and by the action of hydroxyl radicals, which were generated by the following AOPs: UV/H₂O₂, Fenton's reagent, and photo‐Fenton system. The single photochemical process resulted in 9% of the organic matter present being removed, while the AOPs significantly enhanced this reduction with values in the range 20–75%. Kinetic studies for both groups of treatments were performed, and apparent kinetic rate constants were evaluated. In the ozone‐based experiments, the rate constants ranged from 1846 to 10922 dm³ mol^?1 O₃ h^?1, depending on the operating conditions. In the oxidation experiments using oxidants other than ozone, the rate constants varied between 0.06 and 1.19 h^?1. Copyright © 2004 Society of Chemical Industry     

Oxalate Ion Decomposition under UV Light from Low Pressure Mercury Vapor Lamps

Kinetics of oxalate ion decomposition under UV light from low pressure mercury vapor lamps (LPMVL) was studied in a batch reactor. The effects of UV light intensity (1.38×10^?6 to 5.27×10^?6 EL^?1s^?1, where E: Einstein or 1 mole of photons), temperature (15?35°C), initial oxalate concentration ((2.05?21.1)?×?10^?5 M), initial pH (5.45?8.94) and alkalinity (0–50 mg L^?1 as CaCO₃) on the photodecomposition kinetics of oxalate in de-ionized water were investigated. Oxalate decay followed split-rate pseudo-first-order kinetics. The decay rate constants decreased with increasing initial oxalate concentration, initial pH, alkalinity and temperature, but increased with UV light intensity. Solution pH increased during oxalate decomposition and reached a plateau as oxalate reached the analytical detection limit in de-ionized water. Addition of carbonate alkalinity virtually eliminated the pH profile. Time-dependent profiles for non-purgeable organic carbon (NPOC) and total carbon (TC) showed that the carbon not accounted for in NPOC is likely to have been converted to CO₂. The pH profile of oxalate decay was estimated using closed system carbonate equilibrium analysis. The dissolved oxygen (DO) utilization during oxalate decay ranged between 0.3–0.8 mol O₂ / mol oxalate. The effect of DO and the decay of natural dissolved organic carbon (DOC) were also explored. Natural DOC retarded oxalate photodecomposition. The decay rate constants were slightly lower in the absence of DO.     

ELIMINATION OF BENZENE AND CHLOROBENZENES BY PHOTODEGRADATION AND OZONATION PROCESSES

Benzene (B) and two representative chlorobenzenes (1,4-dichlorobenzene (DCB) and 1,2,3-trichlorobenzene (TCB)) were oxidized by means of UV irradiation alone, ozone alone, and the combinations UV/H₂O₂ and O₃/H₂O₂. In the single photolytic process, the influence on the photodegradation of the pH, temperature, and type of radiation source used was established. A kinetic study was performed by evaluating the first-order rate constants and the quantum yields. The effect of the additional presence of hydrogen peroxide was pointed out in the combined process UV/H₂O₂,with the determination of the specific contribution of the radical pathway to the overall photodegradation system. In the oxidation by ozone based systems (ozone alone and the combination O₃/H₂O₂), the rate constants at 20°C for the reaction of each compound with ozone and hydroxyl radicals were determined.     

ELIMINATION OF BENZENE AND CHLOROBENZENES BY PHOTODEGRADATION AND OZONATION PROCESSES

Benzene (B) and two representative chlorobenzenes (1,4-dichlorobenzene (DCB) and 1,2,3-trichlorobenzene (TCB)) were oxidized by means of UV irradiation alone, ozone alone, and the combinations UV/H₂O₂ and O₃/H₂O₂. In the single photolytic process, the influence on the photodegradation of the pH, temperature, and type of radiation source used was established. A kinetic study was performed by evaluating the first-order rate constants and the quantum yields. The effect of the additional presence of hydrogen peroxide was pointed out in the combined process UV/H₂O₂,with the determination of the specific contribution of the radical pathway to the overall photodegradation system. In the oxidation by ozone based systems (ozone alone and the combination O₃/H₂O₂), the rate constants at 20°C for the reaction of each compound with ozone and hydroxyl radicals were determined.     

Kinetic Study and Optimum Control of the Ozone/UV Process Measuring Hydrogen Peroxide Formed In-situ

This study was conducted to develop a kinetic model of the ozone/UV process by monitoring the trend of in-situ hydrogen peroxide formation. A specifically devised setup, which could continuously measure the concentration of hydrogen peroxide as low as 10 μg/L, was used. The kinetic equations, comprised of several intrinsic constants with semi-empirical parameters (k_chain and k_R3) were developed to predict the time varied residual ozone and hydrogen peroxide formed in situ along with the hydroxyl radical concentration at steady state,[OH°]_ss, in the ozone/UV process. The optimum ozone dose was also investigated at a fixed UV dose using the removal rate of UV absorbance at 254 nm (A₂₅₄) in raw drinking water. The result showed that the continuous monitoring of hydrogen peroxide formed in situ in an ozone/UV process could be used as an important tool to optimize the operation of the process.