Pathway of the ozonation of 2,4,6-trichlorophenol in aqueous solution

The reaction mechanism and pathway of the ozonation of 2,4,6-trichlorophenol (2,4,6-TCP) in aqueous solution were investigated. The removal efficiency and the variation of H₂O₂, Cl⁻ formic acid, and oxalic acid were studied during the semi-batch ozonation experiments (continuous for ozone gas supply, fixed volume of water sample). The results showed that when there was no scavenger, the removal efficiency of 0.1 mmol/L 2,4,6-TCP could reach 99% within 6 min by adding 24 mg/L ozone. The reaction of molecular ozone with 2,4,6-TCP resulted in the formation of H₂O₂. The maximal concentration of H₂O₂ detected during the ozonation could reach 22.5% of the original concentration of 2,4,6-TCP. The reaction of ozone with H₂O₂ resulted in the generation of a lot of OH• radicals. Therefore, 2,4,6-TCP was degraded to formic acid and oxalic acid by ozone and OH• radicals together. With the inhibition of OH• radicals, ozone molecule firstly degraded 2,4,6-TCP to form chlorinated quinone, which was subsequently oxidized to formic acid and oxalic acid. Two reaction pathways of the degradation of 2,4,6-TCP by ozone and O₃/OH• were proposed in this study. Translated from Acta Scientiae Circumstantiae, 2005, 25(12): 1619–1623 [译自: 环境科学学报]     

Formation control of bromate and trihalomethanes during ozonation of bromide-containing water with chemical addition: Hydrogen peroxide or ammonia?

To ensure the safety of drinking water, ozone (O₃) has been extensively applied in drinking water treatment plants to further remove natural organic matter (NOM). However, the surface water and groundwater near the coastal areas often contain high concentrations of bromide ion (Br^?). Considering the risk of bromate (BrO₃^?) formation in ozonation of the sand-filtered water, the inhibitory efficiencies of hydrogen peroxide (H₂O₂) and ammonia (NH₃) on BrO₃^? formation during ozonation process were compared. The addition of H₂O₂ effectively inhibited BrO₃^? formation at an initial Br^? concentration amended to 350 µg/L. The inhibition efficiencies reached 59.6 and 100% when the mass ratio of H₂O₂/O₃ was 0.25 and > 0.5, respectively. The UV₂₅₄ and total organic carbon (TOC) also decreased after adding H₂O₂, while the formation potential of trihalomethanes (THMsFP) increased especially in subsequent chlorination process at a low dose of H₂O₂. To control the formation of both BrO₃^? and THMs, a relatively large dose of O₃ and a high ratio of H₂O₂/O₃were generally needed. NH₃ addition inhibited BrO₃^? formation when the background ammonia nitrogen (NH₃N) concentration was low. There was no significant correlation between BrO₃^? inhibition efficiency and NH₃ dose, and a small amount of NH₃N (0.2 mg/L) could obviously inhibit BrO₃^? formation. The oxidation of NOM seemed unaffected by NH₃ addition, and the structure of NOM reflected by synchronous fluorescence (SF) scanning remained almost unchanged before and after adding NH₃. Considering the formation of BrO₃^? and THMs, the optimal dose of NH₃ was suggested to be 0.5 mg/L.     

电Fenton法处理难降解有机物的研究进展

评述了电Fenton法在水处理的中的应用状况及国内外研究现状，介绍了各种电Fenton法进行机理及存在的优缺点，并对其今后的发展趋势进行了阐述。     

臭氧氧化法处理城市污水厂出水的实验研究

为了开发污水的回用技术，对北京市某污水处理厂二处理后出水中含有的有机物进行了臭氧无催化氧化、臭氧碱催化氧化、臭氧／过氧化氢氧化和臭氧加过渡性金属离子／过氧化氢催化氧化工艺的实验研究。结果表明，自氧／过氧化氢氧化工艺达到了较好的效果，在Ｈ２Ｏ２＝３ｍｇ／Ｌ时投加臭氧１３ｍｇ／Ｌ，ＣＯＤｃｒ由４５ｍｇ／Ｌ降至２０ｍｇ／Ｌ。     

品红的深度氧化机理研究

选用 2 5 3 7nm的紫外光为激发光源 ,对品红 /过氧化氢体系中的紫外光解离进行了研究 .结果表明 ,该体系中品红的解离近似为表观一级反应 ,解离反应的速率常数为 0 0 386 7s- 1.品红水溶液的脉冲瞬态光谱结果表明 ,品红主要与OH自由基反应而导致脱色 ,其在 5 4 0nm处的脱色与 34 0nm处的瞬态吸收存在很好的相关性 ,品红在5 4 0nm处脱色为一级反应 ,速率常数为 8 1 0× 1 0 5s- 1,34 0nm处新的瞬态物种生成较快而衰减较慢 ,其衰减速率为 5 33× 1 0 3 s- 1.     

粉煤灰-H2O2催化氧化水中对氨基苯酚的试验研究

研究了利用电厂粉煤灰作为非均相催化剂,催化H2O2氧化对氨基苯酚(PAP),讨论了各种因素对PAP去除率的影响.结果表明,在30℃,pH=1.5,H2O2和PAP的起始浓度分别为0.50 mol/L和0.10 mol/L,反应时间为100min,粉煤灰用量为6.0%,搅拌速度为1000r/min的条件下,粉煤灰具有良好的催化活性,能有效地催化H2O2氧化PAP,PAP的去除率可达81%左右.该法可用于预处理含PAP的工业废水.     

甲醛光催化降解与过氧化氢生成的相关性研究

分别采用两种光催化剂(TiO2与Pd/TiO2)和三种紫外光源(黑光灯、杀菌灯、臭氧灯)分解水溶液中的甲醛,同时以酶法测定光催化降解过程中生成的低浓度过氧化氢.发现波长较短的紫外光源生成过氧化氢的浓度较高.当以臭氧灯为光源时,无论是否有催化剂存在,生成的过氧化氢浓度都在50mmol·m-3以上,因为185nm以下的紫外光可以直接由水与溶解氧生成臭氧,而后生成过氧化氢.不管有无催化剂存在,在臭氧灯作用下,甲醛溶液中生成的过氧化氢浓度高于纯水中生成的过氧化氢浓度.但是,在以黑光灯或臭氧灯为光源时,上述结果正好相反.此外,对于每种光源而言,当采用Pd/TiO2代替TiO2时,甲醛的分解和过氧化氢的生成都得到加强.甲醛光催化分解速率与相同条件下纯水中过氧化氢的生成速率呈正比,表明光催化降解的活性与光催化生成过氧化氢的能力近似呈正相关.     

超声波/H2O2/CuO协同氧化降解苯酚

以CuO为催化剂,利用超声波(US)、H2O2及US/H2O2降解苯酚模拟废水,考察了多种因素的影响,并对其降解动力学进行了分析.结果表明,CuO催化作用明显;H2O2投加量的增加对降解反应先促进后抑制;溶液pH值先升高后降低,当溶液初始pH值为5.50时,苯酚的降解效果最好.在溶液初始pH值为5.50,CuO加入量为1mg/mL,H2O2投加量为40mmol/L时,US/H2O2/CuO降解苯酚的速率常数(k)为3.04(10-2min-1,明显大于US、US/H2O2、H2O2/CuO处理下的k值(5.25(10-4,2.31(10-3,2.31(10-2min-1),降解过程均符合表观一级反应动力学.     

H2O2湿式氧化处理含酸性红B染料模拟废水的研究

用H2 O2 作氧化剂 ,在连续式的压力反应器内探索了WPO(过氧化氢湿式氧化法 )、CWPO(催化过氧化氢湿式氧化法 )氧化降解含酸性红B染料模拟废水的过程 ,分别考察温度、压力、氧化剂量及催化剂对反应过程与对象污染物降解的影响规律 .结果表明 ,与常规湿式氧化法相比 ,WPO能在较低的温度和压力下降解结构稳定的有机物 ,在 2 2 0℃、8min、0 1MPa时 ,含1 5 0 0mg·L-1 酸性红B染料模拟废水的COD和色度的去除率分别达到 6 0 5 0 %和 96 80 % .同时发现 ,通过升温和增加过氧化氢的投加量不能够使废水COD和色度的去除率进一步提高 ,故引入Cu2 作催化剂来实现CWPO过程 ,在 2 2 0℃、8min、0 1MPa条件下 ,CWPO对同一废水的COD和色度的去除率分别达到 82 5 0 %和 99 71 % .通过计算得出CWPO与WPO相比基于COD的表观活化能降低了 6 5 93 % .     

Ozonation of refractory chemicals in leachate with hydrogen peroxide

Nearly 97% of organic chemicals in Hong Kong leachate could be effectively removed by the UASB( upflow anaerobic sludge blanket) process followed by the fenton coagulation. The COD of leachate was lowered from an average of 12900 mg/L to 1440 mg/L after the UASB treatment, and was further lowered to 394 mg/L after the fenton coagulation. The remaining refractory residues could be further removed by ozonation with the addition of H2Oz. The ozonation for the supernatant of the fenton coagulation was most effective at pH 7-8, with the addition of 300 mg/L of H202, and 30 min of reaction. The final effluent contained only 85 mg/L of COD and 10 mg/L of BOD5. On the other hand, direct ozonation of UASB effluent lowered the COD to 905 mg/L and BOD5 to 103 mg/L. Ozonation improved the biodegradability of the organic residues, and also converted oart of oruanic-N in the leachate into NH3-N and NO3^- -N.