Fenton试剂处理腐殖酸废水影响特性和降解动力学模型

研究了Fenton试剂降解腐殖酸废水的影响特性,并在理论分析反应过程的基础上建立动力学方程,同时根据实验进行动力学方程参数估算。研究表明,Fenton试剂通过氧化和混凝共同作用有效去除腐殖酸。在初始pH=4,40mmol/L FeSO4和160 mmol/L H2O2投量下,腐殖酸60 min氧化去除率、混凝去除率分别达到78.6%和11.5%,其初始氧化速率达到最大59.6 mg/(L.min)。腐殖酸的氧化降解动力学模型值与实验值吻合良好,说明采用该动力学模型能较好预测腐殖酸废水的氧化降解情况,且Fenton氧化降解腐殖酸的机理符合自由基的理论和实践。     

Fenton试剂氧化苯酚过程中Fe（Ⅱ）浓度的变化

考察了Fenton试剂氧化降解苯酚过程中Fe(Ⅱ)浓度的变化,并通过实验探讨了其变化的原因.实验结果表明,在Fenton反应发生的第1 rain内,Fe(Ⅱ)浓度可降低到初始浓度的60%左右,随着反应的继续Fe(Ⅱ)浓度在大约20min降低到最小值,然后开始增大,说明了Fe(Ⅲ)还原作用的存在;Fenton试剂氧化降解苯酚的中间产物包括对苯二酚、邻苯二酚、间苯二酚和苯醌等,其中前三者能对Fe(Ⅲ)有效还原,是Fenton试剂氧化降解苯酚过程中Fe(Ⅲ)还原的主要途径之一.     

FeAlOx/MMT催化Fenton反应降解高浓度苯酚废水

以蒙脱土为载体制备负载型Fe/Al复合氧化物(FeAlOx/MMT)用于催化Fenton反应降解高浓度苯酚废水。实验结果表明,活性相FeAlOx中Fe/Al摩尔比为0.22时制备所得催化剂对Fenton反应具有最佳活性,且Fe/Al复合氧化物并未嵌入蒙脱土层间。在低温和高pH条件下催化体系存在诱导期,诱导期内FeAlOx/MMT缓释出Fe离子并进而由Fe离子催化溶液中的Fenton反应。通过对非均相催化降解苯酚废水的动力学研究发现,H2O2初始浓度、溶液的pH和反应温度对COD降解效率具有显著影响。调节降解过程中的温度序列和氧化剂引入程序能够缓解高温和高双氧水浓度双重因素耦合导致的HO.自消耗。在优化的降解条件下使用理论用量的H2O2可使得1 g/L的苯酚废水中苯酚降解率达到100%,而COD的降解率则达到97%。     

FeAlO_x/MMT催化Fenton反应降解高浓度苯酚废水

以蒙脱土为载体制备负载型Fe/Al复合氧化物（FeAlOx/MMT）用于催化Fenton反应降解高浓度苯酚废水。实验结果表明,活性相FeAlOx中Fe/Al摩尔比为0.22时制备所得催化剂对Fenton反应具有最佳活性,且Fe/Al复合氧化物并未嵌入蒙脱土层间。在低温和高pH条件下催化体系存在诱导期,诱导期内FeAlOx/MMT缓释出Fe离子并进而由Fe离子催化溶液中的Fenton反应。通过对非均相催化降解苯酚废水的动力学研究发现,H2O2初始浓度、溶液的pH和反应温度对COD降解效率具有显著影响。调节降解过程中的温度序列和氧化剂引入程序能够缓解高温和高双氧水浓度双重因素耦合导致的HO.自消耗。在优化的降解条件下使用理论用量的H2O2可使得1 g/L的苯酚废水中苯酚降解率达到100%,而COD的降解率则达到97%。     

Fenton试剂催化氧化嘧啶废水的特性

研究了Fenton催化氧化法对废水中嘧啶的去除效能,优化了处理体系中的反应条件,分析了各影响因子的作用机理;并用一元线性回归方程对不同温度下,嘧啶相对残余浓度对反应时间的相关性进行了定量分析。结果表明:温度为25℃,pH为3.5,Fe²⁺的投加量64 mmol/L,H₂O₂投加量为300 mmol/L时,反应2 h,Fenton试剂对嘧啶和COD的去除率分别达90%和50%以上;同时发现Fenton试剂对嘧啶的氧化降解具有相对优先性,且符合一级反应动力学模式,并计算表观反应速率常数和活化能。     

强化3级Fenton氧化结合石灰乳中和混凝处理苯系染料中间体废水

采用多级Fenton氧化结合石灰乳中和混凝对苯系染料中间体废水进行强化处理,考察了Fenton试剂投加级数和投加比例对废水处理效果的影响,以及多级Fenton氧化之间石灰乳中和混凝作用效果,并分析了废水中有机成分的变化趋势。结果表明:Fenton氧化过程中,COD去除率随着Fenton试剂投加级数的增加逐渐增大,3级时效果最佳。3级Fenton处理过程中,Fenton试剂的投加比例为1∶2∶3时,COD去除率最高。在Fenton试剂投加比例为1∶2∶3的3级Fenton氧化过程中,石灰乳可有效调节pH由2.5至4.0,同时其混凝作用也可进一步提高COD去除率,最终COD去除率可达97.20%。经GC-MS对各个过程中有机物的分析鉴定,可发现原废水中的苯系有机物逐渐变化为苯酚、对苯醌以及短链小分子脂肪酸等物质。     

光催化-Fenton试剂处理印钞废水

以300w高压汞灯为光源,TiO2为催化剂,对光催化剂用量、酸碱性、H2O2用量以及结合Fenton试剂等因素,对印钞废水光催化氧化降解进行研究.结果表明,酸性条件下,辅以Fenton试剂,对光催化氧化处理印钞废水有较好的效果;并进行了机理探讨.     

光助Fenton氧化法降解水中六氯苯的研究

采用光助Fenton氧化法处理六氯苯模拟废水,考察了反应时间、Fe3 与H2O2摩尔比、Fenton试剂用量、初始pH、六氯苯初始浓度、光强对六氯苯降解效果的影响,并初步探讨了六氯苯的降解动力学规律.结果表明.光助Fenton法降解六氯苯的最佳工艺条件为:紫外灯功率为300 W、Fe3 投加量为1.0 mmol/L、H2O2投加量为5.0 mmol/L、反应时间为60 min、初始pH为3,在此条件下,浓度为500μg/L的HCB的去除率可达91.3%.UV辐射与Fenton氧化对HCB的降解具有协同效应.光助Fenton法对HCB的降解符合一级反应动力学方程,表观速率常数为0.04 min-1,与Fenton法相比,提高了近9倍.     

电解催化氧化法废水处理机制研究

采用电解催化氧化法(electrochemical enhanced catalytic oxidation reaction)处理某高浓度有机废水(COD约10 000mg·L~(-1)),该工艺主要包括电解反应、催化氧化反应以及催化氧化反应后废水内循环进行电解反应等过程。开展了不同因素对废水COD降解效率影响的研究,并对反应降解机制和反应动力学进行了探讨。结果显示,内循环设计结合H_2O_2溶液投加量逐步增加的方式,使得体系在420 min反应时间内均保持着不断削减COD的能力。当FeSO_4·7H_2O初始投加量为0.6 g·L~(-1)、回流比R为0.5时,COD减少量可达9 340 mg·L~(-1)。反应过程中工作电流I及氧化还原电势ORP监测值的不断波动表明反应体系中有机物不断被降解,氧化还原环境不断地变化。该工艺耦合电解氧化和Fenton技术,协同因子约为1.48,且可极大提高废水混凝性能,反应60 min后经废水混凝处理可使COD去除率由4.27%提高至26.21%。     

电生成Fenton试剂光催化降解孔雀石绿的研究

为了提高染料废水的处理效果,采用电生成Fenton试剂光催化氧化系统对孔雀石绿模拟印染废水进行了降解研究,通过与无光照时的对比实验发现:光照能明显加快电生成Fenton试剂对孔雀石绿印染废水的降解脱色速率,20 min内脱色率达到98%以上,40 min内COD去除率达到80%以上,同时通过红外光谱、紫外-可见光谱等手段研究了光照与电生成Fenton试剂的协同作用,初步探讨了电生成Fenton试剂光催化降解孔雀石绿印染废水的反应机理,很好地实现了光催化与电化学氧化降解技术的联合应用。     

超声降解水中的磺胺嘧啶

以磺胺嘧啶(SD)为研究对象,探讨了超声功率、初始浓度、pH值以及超声协同H2O2、Fenton、TiO2等组合工艺对超声降解SD效率的影响。实验结果表明,超声可有效降解水中低浓度的SD,尤其在酸性条件下,超声降解更为显著,降解过程遵循准二级反应动力学模型。加入H2O2或TiO2可在一定程度上促进SD的超声降解,加入Fenton试剂则显著提升SD的去除率。依据量化计算以及LC-MS测定结果,探讨了SD的超声降解机理。超声降解水中SD主要是基于.OH自由基的氧化过程。     

Influence of oxalic acid formed on the degradation of phenol by Fenton reagent

The objective of this work is to examine the influence of oxalic acid formed on the degradation of phenol by Fenton reagent. Oxalic acid formed at initial stage within 30 min significantly suppresses the reduction of ferric ion, thus terminating degradation reaction. The yield of oxalic acid is dependent on the amount of ferrous ion dosed since the minimal amount of oxalic acid is formed after the degradation reaction terminates. Mineralization of phenol by Fenton reagent stagnates after 120 min under the conditions used in this study. The reason why the mineralization stagnated can be assumed to be following two mechanisms other than the depletion of H₂O₂. In the case where a small amount of ferrous ions is dosed, the reduction of ferric ions is minimal by oxalic acid formed. In the case where a large amount of ferrous ions is dosed, the amount of degradable organic compounds is insufficient owing to preferential conversion to oxalic acid. The mineralization can be enhanced by the intermittent dosing of ferrous ions, which facilitates the suppression of oxalic acid formation during the degradation by Fenton reagent.     

Fenton试剂法降解餐厨垃圾异味

自行设计Fenton试剂法降解还原性气体异味的反应器,研究了Fenton试剂法处理餐厨垃圾异味主要成分(苯、乙酸乙酯、苯乙烯)的降解效果。以苯为典型代表物,优化得出该实验的最佳反应条件为:pH=3,FeSO4.7H2O投加量为1 g/L液相,30%H2O2投加量为10 mL/L液相,紫外光源辅助。结果证明,Fenton试剂法处理单一异味气体的效果较理想,在前180 min内能达到90%以上,该法在处理气态异味污染物方面具有广阔的应用前景。     

Degradation of alachlor using an enhanced sono-Fenton process with efficient Fenton's reagent dosages

In this study, an enhanced sono-Fenton process for the degradation of alachlor is presented. At high ultrasonic power, low pH, and in the presence of adequate Fenton's reagent dosages, alachlor degradation can reach nearly 100%. The toxicity of treated alachlor wastewater, which was measured by changes in cell viability, slightly decreased after the Fenton or ultrasound/H₂O₂ process and significantly decreased after the enhanced sono-Fenton process. A satisfactory relationship was observed between the total organic carbon removal and cell viability increment, indicating that alachlor mineralization is a key step in reducing the toxicity of the solution. The formation of alachlor degradation byproducts was observed during the oxidation process, in which the first step was the substitution of a chloride by a hydroxyl group. In conclusion, the enhanced sono-Fenton process was effective in the degradation and detoxification of alachlor within a short reaction time. Thus, the treated wastewater can then be passed through a biological treatment unit for further treatment.     

黄铁矿催化H2O2氧化降解水中三氯生

以三氯生为目标污染物,研究了黄铁矿催化H2O2非均相类Fenton体系对污染物的去除效果,并利用SEM、EDS等手段对天然黄铁矿进行了表征。考察了催化剂、H2O2投加量、溶液初始pH、反应时间等重要因素对催化氧化反应的影响。在H2O2投加量5 mg/L,黄铁矿用量0.1 g/L,溶液初始pH为8,反应10 min后,三氯生的去除率达90%以上。相对于传统Fenton反应,pH对本非均相催化反应的影响较小,在2～10的pH范围内,仍有较高的催化活性。利用GC-MS分析显示,三氯生降解过程能够产生包括2,4-二氯苯酚在内的多种中间产物。     

Treatment of coking wastewater by an advanced Fenton oxidation process using iron powder and hydrogen peroxide

In this study the treatment of coking wastewater was investigated by an advanced Fenton oxidation process using iron powder and hydrogen peroxide. Particular attention was paid to the effect of initial pH, dosage of H₂O₂ and to improvement in biodegradation. The results showed that higher COD and total phenol removal rates were achieved with a decrease in initial pH and an increase in H₂O₂ dosage. At an initial pH of less than 6.5 and H₂O₂ concentration of 0.3 M, COD removal reached 44-50% and approximately 95% of total phenol removal was achieved at a reaction time of 1 h. The oxygen uptake rate of the effluent measured at a reaction time of 1 h increased by approximately 65% compared to that of the raw coking wastewater. This indicated that biodegradation of the coking wastewater was significantly improved. Several organic compounds, including bifuran, quinoline, resorcinol and benzofuranol were removed completely as determined by GC-MS analysis. The advanced Fenton oxidation process is an effective pretreatment method for the removal of organic pollutants from coking wastewater. This process increases biodegradation, and may be combined with a classical biological process to achieve effluent of high quality.     

Vis/Co-TiO_2/KHSO_5体系Fenton-光催化协同降解苯酚

通过溶胶-凝胶法制备了同时具有可见光(Vis)光催化和Fenton催化双重活性的Co-TiO2催化剂。通过对比Vis/Co-TiO2/KHSO5、Co-TiO2/KHSO5和Vis/Co-TiO23种体系对苯酚的降解效果,Vis/Co-TiO2/KHSO5表现出明显的Fenton-光催化协同作用。进一步研究pH值、KHSO5与苯酚摩尔比(nKHSO5∶nC6H6O)和Co-TiO2投加量(mCo-TiO2)对Fenton-光催化协同降解苯酚效果的影响。结果表明,pH=6.9、nKHSO5∶nC6H6O=10∶1、mCo-TiO2=1.0 g/L时,降解率达100%。最后,结合XRD、XPS和UV-DRS等手段和催化活性实验数据分析了Vis/Co-TiO2/KHSO5体系的催化机理。     

臭氧氧化及其他强化技术协同降解聚乙烯醇

采用O₃氧化降解水中聚乙烯醇（PVA），考察了O₃氧化的影响因素及与其他强化技术协同下的降解效果。结果表明，经12 min处理，O₃/超声波、O₃/紫外光协同作用下PVA降解率较直接O₃氧化的63.2%有显著提高，表现出了良好的协同效应。通过比较酸性条件下添加不同量Fenton试剂的作用效果可知，·OH的氧化作用是PVA降解的重要原因。     

Fenton氧化活性深蓝染料B-2GLN的动力学

为了考查H2O2/Fe2+的摩尔比和H2O2的初始剂量、pH值以及活性深蓝染料B-2GLN(RDB B-2GLN)的初始浓度对活性深蓝染料B-2GLN降解过程的影响,采用在线分光光度法对活性深蓝染料B-2GLN的Fenton氧化过程进行了研究,探讨了其动力学过程,并利用气相色谱-质谱联用分析降解中间产物。结果显示,采用Fenton氧化降解水溶液中活性深蓝染料B-2GLN,在H2O2的剂量为2.635 mmol/L,pH值为2.7,H2O2/Fe2+的摩尔比为37.80和活性深蓝染料B-2GLN的初始浓度16 mg/L的条件下,得到300 s后活性深蓝染料B-2GLN的最大色度去除率为85.04%。水溶液中活性深蓝染料B-2GLN与·OH的反应速率常数为2.62×1011L/(mol·s)。活性深蓝B-2GLN染料的分子结构被Fenton试剂分解而未被完全矿化,同时对活性深蓝染料降解产物进行了分析。在线分光光度法是研究染料色度去除率的一种精确、快速与可行的方法。     

Mineralization of dinitrotoluenes and trinitrotoluene of spent acid in toluene nitration process by Fenton oxidation

Fenton's reagent, UV/H2O2 and UV/Fenton's reagent were employed to mineralize dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) of spent acid in toluene nitration process. The bench-scale experiments were conducted to elucidate the influence of various operating variables on the performance of removal of total organic compounds (TOC) from spent acid, including reaction temperature, concentration of ferrous ion and H2O2 dosage. It is remarkable that organic compounds were completely mineralized by Fenton oxidation, of which removal efficiency is superior to that of UV/H2O2. Nevertheless, it makes slight difference between Fenton oxidation and UV/Fenton oxidation. According to the spectra identified by gas chromatograph/mass spectrometer (GC/MS), it is proposed that oxidative degradation of DNT isomers leads to o-, m-, p-mononitrotoluene (MNT) and 1,3-dinitrobenzene respectively. Besides, the oxidation of 2,4,6-TNT gives the 1,3,5-trinitrobenzene intermediate. Apparently, Fenton oxidation is promising for purification of spent acid industrially.