臭氧氧化法处理焦化废水生化出水的反应动力学简

对臭氧氧化去除焦化废水生化出水COD的反应动力学及其影响因素进行了实验研究,结果表明,在臭氧投加量为8.50 mg/min,反应温度为20℃和初始pH为10.61条件下,对COD的降解符合表观一级反应动力学模型,其相关系数R²=0.9991,表观反应速率常数k_Abs=1.01×10^-3 s^-1。该条件下,臭氧氧化对COD的降解主要来源于高活性羟基自由基的强氧化作用。在不同的臭氧投加量（4.25~12.75 mg/min）、不同的反应温度（10~40℃）和不同的初始pH（3.76~12.53）下,COD的降解也同样遵循一级反应动力学规律。随着臭氧投加量的增大,COD降解的表观反应速率常数从（0.554×10^-3） s^-1增加到（1.06×10^-3） s^-1;随着反应温度的升高,表观反应速率常数从（0.427×10^-3） s^-1增加到（1.40×10^-3） s^-1,温度越高反应速率提高的幅度却越小;在初始pH3.76~10.61范围内,表观反应速率常数从（0.218×10^-3） s^-1增加到（1.01×10^-3） s^-1,在初始pH为12.53时表观反应速率常数下降到（0.857×10^-3） s^-1。     

微波诱导鳞片石墨-H2O2催化氧化处理甲基紫废水

研究微波诱导鳞片石墨-H₂O ₂催化氧化处理甲基紫废水工艺,探讨各种因素的协同作用及对废水脱色效果的影响,并采用SEM、EDX、XRD和FTIR对新鲜及使用6次后的鳞片石墨进行表征。结果表明,微波诱导鳞片石墨-H₂O₂能高效快速降解废水中的甲基紫;在50 mL初始pH为3,质量浓度为10 mg/L的甲基紫废水中, H₂O₂用量1 mL/L,鳞片石墨 3 g/L,微波输出功率259 W,微波辐射时间9 min的最佳处理工艺条件下,甲基紫脱色率达到了98.80%;微波、鳞片石墨、H₂O₂体系对甲基紫废水降解效果明显,产生协同效应。紫外-可见光谱分析表明,废水中甲基紫结构被破坏,但仍含有少量苯环等小分子。动力学研究表明,脱色反应符合一级反应动力学规律,反应速率常数k为0.42613 min^-1,反应半衰期t_1/2为1.626 min。     

碳酸根对磷酸钙沉淀反应回收磷的影响简

以模拟的厌氧消化液为处理对象,通过小试实验,考察不同初始磷浓度C_P、Ca/P物质的量比、pH和温度下,碳酸根（CO₃^2-）对磷酸钙沉淀反应回收磷的影响;利用扫描电镜（SEM）、X射线衍射仪（XRD）和傅里叶变换红外光谱（FTIR）对沉淀产物进行表征。结果表明,高浓度的CO₃^2-对以磷酸钙沉淀反应去除和回收磷的效率影响较大;C_P相同时,CO₃^2-浓度（C_CO3^2-）越大,P的去除率越低,低C_P（20 mg/L）时尤为显著;当C_CO3^2-相同时,随着C_P的增大,反应速率加快,P的去除率逐渐升高,但升高幅度越来越小;增大Ca/P比和pH能提高P的去除率,降低CO₃^2-对磷酸钙沉淀反应的抑制作用,综合考虑实际效果,应选择Ca/P比为3.33,pH为9.0作为适宜的反应条件;升高温度对降低CO₃^2-对磷酸钙沉淀反应的抑制作用贡献不大。在C_P为60 mg/L,Ca/P比为1.67,pH为9.0,温度为20℃的条件下,当C _CO3^2-为0时,得到的沉淀产物主要为羟基磷灰石HAP;当C _CO3^2-为30 mmol/L时,得到的沉淀产物为磷酸钙和碳酸合磷灰石的混合物。     

SBR降解动力学研究

采用SBR工艺处理有机废水,在已有工艺条件下对生物降解动力学进行了研究,得出生物降解反应为一级反应。研究表明,用Monod公式能较好反映出有机物的降解规律,确定了其动力学参数V_max=14.6306 d^-1,K_s=83.2993 mg/L,得出SBR降解动力学模型为V=14.6306X·S/(83.2993+S)。利用以动力学为基础的动态模拟法优化SBR工艺,实验结果表明该方法合理可行,对SBR的设计与运行有一定的指导作用,可作为SBR反应器扩大实验和设计的依据。     

催化湿式氧化法处理高浓度唑螨酯生产废水的研究

对唑螨酯生产过程中产生的高浓度实际废水采用催化湿式氧化技术在鼓泡式固定床反应器连续反应装置上进行处理。实验表明,制备的复合负载型催化剂CuO-MnO₂-Cr₂O₃/ZrO₂-CeO₂在处理该废水时具有较好的催化活性。通过对反应温度、反应压力、反应空速、气液比和进水pH等工艺条件的考察,得出最佳的工艺条件为：反应温度=220℃,反应压力=5.8 MPa,空速＝1.8 h^-1,V（气）∶V（水）＝260∶1,进水pH＝9,在此条件下COD去除率达到95.2％。     

镧负载改性TiO2太阳光催化降解微囊藻毒素的研究

考察了镧负载改性TiO₂催化剂在太阳光下降解微囊藻毒素LR (MCLR)的效果及其影响因素。结果表明,镧负载改性的TiO₂可显著增加MCLR在TiO₂表面的吸附量,同时提高MCLR在太阳光下的降解率。随着镧负载量的增加,太阳光下MCLR降解率可从65%提高到95%,pH降低可促进MCLR的降解。改性TiO₂对藻毒素的降解存在最佳投加量,实验结果表明,在pH=6,MCLR初始浓度为2 mg/L,0.001-La-TiO₂的最佳投量为0.5 g/L,在3 600 μW/cm²太阳光下照射30 min,降解率可达97%。     

粉煤灰沸石负载Ce3+/TiO2光催化降解水中的菲和荧蒽

以钛酸四丁酯为前驱体,粉煤灰合成沸石为载体,采用溶胶-凝胶方法,在低温条件下制备了稀土铈掺杂的TiO₂光催化剂。利用SEM-EDS、XRD、FTIR对催化剂进行了分析和表征。以高压汞灯为灯源,对多环芳烃菲、荧蒽的降解进行了研究。实验考查了稀土铈掺杂质量分数、催化剂用量、溶液pH、目标物初始质量浓度等因素对光催化降解的影响,研究了其光降解动力学。结果表明,当稀土铈含量为0.5%,催化剂用量为3 g/L,pH偏碱性时,催化效果最佳。光催化反应符合Langmuir-Hinshelwood 动力学规律,菲、荧蒽的降解过程符合一级反应动力学,反应速率常数分别为0.0126 min^-1,0.0099 min^-1。     

UV-Fenton光催化氧化处理高浓度邻苯二甲酸二辛酯生产废水

采用UV-Fenton技术光催化氧化高浓度邻苯二甲酸二辛酯（DOP）生产废水，确定最佳操作条件为：初始pH=3.8，H₂O₂浓度为9.99 g/L，H₂O₂/Fe²⁺摩尔比为20∶1，光照反应60 min。此条件下的废水COD去除率为89.1%，出水COD值在570 mg/L左右。经正交试验确定影响处理效果各因素的重要性顺序为：H₂O₂浓度＞H₂O₂/Fe²⁺摩尔比＞光照反应时间＞pH。UV的加入与单独的Fenton体系存在正相关的协同作用。废水降解的表观过程符合一级反应动力学模式。     

废弃印刷线路板碘化法浸金研究

针对碘化法从废弃印刷线路板中提取金的工艺设计,分别考察了碘的质量分数、n(I₂)/n(I^-)比值、固液比、双氧水的质量分数、pH值、浸出时间和浸出温度对金浸出率的影响。结合正交设计优化实验方法,提出了从废弃印刷线路板中碘化法浸取金的最佳工艺条件：碘的质量分数为1.1％,n(I₂)∶n(I^-)=1∶10,双氧水的质量分数为1.5％,浸出时间4 h,固液比为1∶10,浸出温度为常温（25℃）,溶液pH值为中性,此时金浸出率可达97.5％。     

不同基质共代谢降解2,4,6-三硝基苯酚的研究

以葡萄糖、可溶性淀粉、乙酸钠和苯酚作为共基质,通过35℃恒温生化培养箱缺氧驯化污泥,间歇恒温振荡试验研究了在不同共代谢基质条件下,2,4,6-三硝基苯酚（TNP）的缺氧降解性能。结果表明,经过驯化的微生物加入葡萄糖和苯酚作为碳源,在TNP∶苯酚∶葡萄糖为10∶3∶100的比例下,TNP生物降解率可以从不加碳源时的31.2%提高到86.6%;不同共基质条件下TNP的降解均符合一级反应动力学方程,反应速率常数大小依次是K_苯酚＜K_葡萄糖＜K_{葡萄糖+苯酚},其中葡萄糖和苯酚同时作为共基质时TNP降解速率常数最大为0.019 h^-1。     

Combination with catalyzed Fe(0)-carbon microelectrolysis and activated carbon adsorption for advanced reclaimed water treatment: simultaneous nitrate and biorefractory organics removal

A process combining catalyzed Fe(0)-carbon microelectrolysis (IC-ME) with activated carbon (AC) adsorption was developed for advanced reclaimed water treatment. Simultaneous nitrate reduction and chemical oxygen demand (COD) removal were achieved, and the effects of composite catalyst (CC) addition, AC addition, and initial pH were investigated. The reaction kinetics and reaction mechanisms were calculated and analyzed. The results showed that CC addition could enhance the reduction rate of nitrate and effectively inhibit the production of ammonia. Moreover, AC addition increased the adsorption capacity of biorefractory organic compounds (BROs) and enhanced the degradation of BRO. The reduction of NO₃^?–N at different pH values was consistently greater than 96.9%, and NH₄⁺–N was suppressed by high pH. The presence of CC ensured the reaction rate of IC-ME at high pH. The reaction kinetics orders and constants were calculated. Catalyzed iron scrap (IS)-AC showed much better nitrate reduction and BRO degradation performances than IS-AC and AC. The IC-ME showed great potential for application to nitrate and BRO reduction in reclaimed water.

     

Mechanism of decolorization and degradation of CI Direct Red 23 by ozonation combined with sonolysis

The decolorization and degradation of CI Direct Red 23, which is suspected to be carcinogenic, were investigated using ozonation combined with sonolysis. The results showed that the combination of ozonation and sonolysis was a highly effective way to remove color from waste water. The operational parameters, namely concentration of the dye, pH, ozone dose and ultrasonic density, were investigated during the process. The decolorization of the dye followed pseudo-first-order kinetics. Increasing the initial concentration of Direct Red 23 led to a decreasing rate constant. The optimum pH for the reaction was 8.0, and both lower and higher pH decreased the removal rate. The effect of the ozone dose on the dye decolorization was much greater than that of the sonolysis density. Intermediates such as naphthalene-2-sulfonic acid, 1-naphthol, urea and acetamide were detected by gas chromatography coupled with mass spectrometry in the absence of pH buffer, while nitrate and sulfate ions and formic, acetic and oxalic acids were detected by ion chromatography. A tentative degradation pathway was proposed without any further quantitative analyses. During the degradation, all nitrogen atoms and phenyl groups of Direct Red 23 were degraded into urea, nitrate ion, nitrogen and formic, acetic and oxalic acids, etc.     

铁炭微电解法降解TAIC废水

TAIC（三烯丙基异氰脲酸酯）作为过氧化物交联或自由基反应交联的助交联剂被广泛应用。由于TAIC性质稳定难于生物降解,采用铁炭微电解法处理TAIC生产废水,并考察了铁炭比、进水pH值、反应时间对处理效果的影响,以及TAIC降解机理和反应动力学过程。结果表明,影响微电解工艺的因素主次关系为：pH>Fe/C质量比>反应时间;在最佳条件进水pH值为5,铁炭质量比为2：1,反应时间为135 min时,COD的去除率达到46%以上,TAIC的去除率达到48%以上。TAIC去除机理研究表明,微电解对TAIC废水的作用主要通过·H的还原和铁离子的絮凝作用,其中·H的还原作用是TAIC降解的主要原因。反应动力学分析表明,铁炭微电解法处理TAIC的降解过程基本符合二级反应动力学规律,通过建立模型并拟合出了TAIC降解的二级反应动力学方程。     

水体中酮硝基麝香的臭氧氧化降解研究

采用臭氧氧化水体中的酮硝基麝香,考察pH、H2O2等因素对降解程度的影响,结果表明提高初始pH能加快酮硝基麝香的氧化降解,当pH为12时,反应时间1 h,酮硝基麝香几乎完全去除,浓度为2 mol/L和5 mol/L的H2O2存在有利于O3分解生成·OH自由基,使得酮硝基麝香的氧化降解速率加快,当H2O2浓度超过5 mol/L,H2O2会成为·OH的清除剂,降低·OH利用率;无论O3单独作用和O3/H2O2协同作用,酮硝基麝香降解符合准一级动力学规律;酮硝基麝香氧化降解产物包括甲酸、二乙酸和硝酸根等,其中硝基从苯环上脱落降低了硝基麝香对环境的风险.     

钯修饰碳纳米管电极电催化氧化三氯生

采用钯修饰多壁碳纳米管(MWCNTs)电极电催化氧化降解三氯生,考察了极板间距、电流密度、离子强度、pH、初始浓度和电解时间对三氯生去除效率的影响,并探讨了其反应动力学。结果表明:钯修饰多壁碳纳米管(MWCNTs)电极电催化氧化降解三氯生的最佳条件为:三氯生初始浓度为50 mg/L,电流密度约为10 mA/cm2,极板间距为1 cm,pH为11,电解质Na2SO4浓度为1 000 mg/L。此条件下,反应时间为3 h时三氯生的去除率可达到99%以上,三氯生的降解为零级反应。     

脱氮副球菌YF1微生物燃料电池生物阴极脱氮和产电

以脱氮副球菌YF1构建纯种生物阴极微生物燃料电池(microbial fuel cell,MFC)进行脱氮和产电机理的研究。研究结果发现,阴极碳氮比、pH值对产电和脱氮效率有明显影响。当MFC的阴极运行条件pH值为8.0,碳氮比为20时,运行时间15 h时,脱氮率高达100%,输出电压为150 mV。上述结果表明,微生物燃料电池运行过程中,细菌降解硝酸根的机理为将硝酸根还原为N2或者直接将其作为自身的营养物质而利用。循环伏安(CV)与扫描电镜(SEM)的结果表明,在微生物燃料电池运行中,副球菌YF1通过接触导电作为产电的电子供体。     

Photolysis of fluometuron in the presence of natural water constituents

Phototransformation of the herbicide fluometuron (1 microM) in natural sunlight was investigated in neutral Milli-Q water and in synthetic waters containing either fulvic acids, nitrate ions or both in order to mimic reactions taking place in aquatic environments. Fluometuron degradation followed a pseudo-first order kinetics. The reaction was faster in synthetic than in Milli-Q water. Fulvic acids (10 mg l(-1)) increased the rate of fluometuron photolysis by a factor 2.5 and nitrates (25 mg l(-1)) by a factor 15. Identification of major photoproducts was conducted under laboratory conditions using LC-ESI-MS. Numerous photoproducts were detected and tentatively characterized. In the presence of nitrates, hydroxylation of the aromatic ring with or without hydrolysis of CF(3) into CO(2)H and oxidation of the urea chain leading to demethylation were observed. In the presence of fulvic acids, hydroxylation of the aromatic ring was the major reaction route.     

Characteristics of styrene degradation by Rhodococcus pyridinovorans isolated from a biofilter

A novel strain (PYJ-1) of Rhodococcus pyridinovorans that was isolated from a biofilter was able to degrade styrene at a maximum rate of 0.16 mg (mg protein)(-1) h(-1) in batch culture at 97 mg l(-1) of initial styrene gas concentration. The optimum pH and temperature for styrene degradation were 7 and 32 degrees C, respectively. The degradation kinetic constants were obtained using substrate inhibition kinetics. In a perlite-packed biofilter the maximum styrene removal rate by the strain was 279 gm(-3)h(-1). Styrene removal in the biofilter was more sensitive to the temperature than in the batch culture.     

Reductive dechlorination of chlorinated methanes in cement slurries containing Fe(II)

Degradative solidification/stabilization (DS/S) is a novel remediation technology that combines chemical degradation with conventional solidification/stabilization. The applicability of the Fe(II)-based DS/S to treating chlorinated alkanes was tested by characterizing degradation reactions of carbon tetrachloride (CT) and its daughter products in cement slurries containing Fe(II). Degradation kinetics of CT and chloroform (CF) were generally very rapid with reaction rates comparable to rates that can be obtained with zero-valent iron. Dechlorination reactions of CT proceeded primarily via a hydrogenolysis pathway, which yielded CF and methylene chloride (MC) as major products and chloromethane and methane as minor products. However, reaction pathways other than hydrogenolysis also appeared to be important at very high pH conditions. MC apparently was resistant to dechlorination reactions over a period of about two months. Kinetics of CT and CF transformation were strongly dependent on pH with an optimal value around 13, which was higher than found previously for PCE. When the initial CF concentration varied between 0.01 and 1 mM, and the Fe(II) dose was 104 mM, pseudo-first-order kinetics generally described the degradation reactions of CF. However, there was also some indication of substrate saturation kinetics in these experiments. This suggests that a saturation model would better describe the kinetics in systems with higher concentration of substrates or lower concentration of the reactive surfaces.     

Photodegradation of the antimicrobial triclocarban in aqueous systems under ultraviolet radiation

This work aimed to investigate the effectiveness of ultraviolet (UV) radiation on the degradation of the antimicrobial triclocarban (TCC). We investigated the effects of several operational parameters, including solution pH, initial TCC concentration, photocatalyst TiO₂ loading, presence of natural organic matter, and most common anions in surface waters (e.g., bicarbonate, nitrate, and sulfate). The results showed that UV radiation was very effective for TCC photodegradation and that the photolysis followed pseudo-first-order kinetics. The TCC photolysis rate was pH dependent and favored at high pH. A higher TCC photolysis rate was observed by direct photolysis than TiO₂ photocatalysis. The presence of the inorganic ions bicarbonate, nitrate, and sulfate hindered TCC photolysis. Negative effects on TCC photolysis were also observed by the addition of humic acid due to competitive UV absorbance. The main degradation products of TCC were tentatively identified by gas chromatograph with mass spectrometer, and a possible degradation pathway of TCC was also proposed.