混凝-Fenton氧化-Fe0还原预处理高浓度硝基苯生产废水

采用混凝-Fenton氧化-Fe0还原工艺预处理高浓度硝基苯废水,考察各反应阶段硝基苯去除效果及影响因素。研究表明,聚铁混凝性能优于聚铝;初始COD为17 350 mg/L、硝基苯浓度为10 050 mg/L的废水,在pH=4,聚铁投加浓度3 300 mg/L时,COD和硝基苯去除率分别为63%和62%;混凝沉降后的上清液用Fenton试剂氧化,可在较宽pH(3～6)范围内降解硝基苯,当H2O2(30%)浓度为6 000 mg/L,Fe2+浓度为168 mg/L时,氧化效率最高;聚铁混凝-Fenton氧化后的出水用Fe0还原,最佳还原条件为:pH=3,Fe0浓度1 500 mg/L。原水经聚铁混凝-Fenton氧化-Fe0还原后,COD和硝基苯总去除率分别达90%和98%,总药剂成本约12.4元/t。处理后废水硝基苯浓度为168 mg/L,适宜进行后续的厌氧-好氧生物处理。     

气升式反应器中微生物烟气脱硫研究

基于微生物酸性铁溶液烟气脱硫特性,实验构建了一套内循环气升式反应器.在反应器中,利用处于对数生长期的氧化亚铁硫杆菌(Thiobacillus ferrooxidans)酸性铁溶液进行了模拟烟道气SO2脱除实验研究.为寻求高脱硫率,实验研究了铁离子浓度、入口氧含量、细菌数和pH值的变化对脱硫率的影响.考察了反应液中Fe(Ⅱ)离子浓度的变化规律.实验表明,含T.f菌酸性铁溶液的脱硫效果较高;Fe离子浓度在7.67 g/L左右时脱硫率最佳;入口气中氧含量、反应液中细菌数和pH值越高,反应液的脱硫率也就越高.反应液中的Fe(Ⅱ)离子浓度是一先扬后抑的变化过程.     

低品位电镀污泥对氧化亚铁硫杆菌活性的影响

以氧化亚铁硫杆菌（Thiobacillus ferroxidans,以下简称T.f菌）和低品位电镀污泥（干污泥中主要重金属组分低于3%的电镀污泥,以下简称污泥）为主要实验材料,研究了不同污泥浓度、初始pH对T.f菌Fe2＋氧化速率的影响。将实验组中T.f菌重新接种于新鲜9 K液体培养基,以考察T.f菌经实验处理后对新鲜9 K液体培养基中Fe2＋的氧化能力,结果表明,低品位电镀污泥对T.f菌Fe2＋氧化速率具有显著抑制作用,2.5 g/L的污泥浓度即可使T.f菌Fe2＋氧化速率由23.86 mg/（mL·h）降低至10.72 mg/（mL·h）;调节溶液初始pH,可有限改善T.f菌在低污泥浓度条件下的Fe2＋氧化速率,但在较高污泥浓度时,对其Fe2＋氧化速率无促进作用。     

磁性聚合硫酸铁混凝—NaClO氧化处理垃圾渗滤液

采用化学还原法制备的纳米Fe3O4与聚合硫酸铁(PFS)复合制备磁性聚合硫酸铁(MPFS)混凝剂,利用MPFS混凝—NaClO氧化组合工艺处理垃圾渗滤液,用单因素实验确定最佳运行参数。结果表明:MPFS对COD的去除效果优于PFS,在纳米Fe3O4与PFS的质量比为1∶3、MPFS投加质量浓度为3.5g/L、pH为6.5、混凝时间为25 min时,混凝效果最佳;混凝出水在NaClO投加摩尔浓度为140mmol/L、pH为6.0、氧化温度为50℃、氧化时间为65 min时,氧化效果最佳。在最佳运行条件下,MPFS混凝—NaClO氧化组合工艺对垃圾渗滤液COD、色度和氨氮的去除率分别达到88.2%、77.4%、80.3%。     

氧化亚铁硫杆菌菌液脱除SO_2的实验研究

对比了酸性水溶液、酸性Fe3+溶液、含Fe3+的氧化亚铁硫杆菌菌液的SO2脱除效果,分析了氧化亚铁硫杆菌在SO2脱除过程中的主要作用。结果表明:(1)在实验的进气SO2浓度范围内,酸性水溶液对SO2的吸收仅为物理吸收,反应进行到60min时,SO2脱除率均降至15%以下,溶液不再具有SO2脱除能力。(2)对酸性水溶液、酸性Fe3+溶液和含Fe3+的氧化亚铁硫杆菌菌液3种吸收液而言,在实验的进气SO2浓度范围内,进气SO2浓度越高,SO2脱除率越低;Fe3+初始质量浓度为4.44g/L时,SO2脱除效果较好。(3)氧化亚铁硫杆菌在SO2脱除过程中,直接氧化作用不明显,其主要作用是将Fe2+氧化为Fe3+,维持溶液中Fe3+的浓度,这种间接氧化的作用对SO2的有效脱除非常重要。     

一株氧化亚铁硫杆菌的分离及其浸出废旧线路板中铜的效果

从广东某硫铁矿山酸性废水中分离到一株嗜酸性细菌,经形态观察、生理学和近全长16S rRNA基因分析鉴定为氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans,简称A.ferrooxidans),命名为Z1。该菌与GenBank中菌株A.ferrooxidansCMS等处在系统发育树的同一分支,16S rRNA基因序列相似度均为99%。菌株Z1生长的最适pH值和温度分别为2.25和30℃,对数生长期处于第18～30小时,Fe2+平均氧化速率达到0.2307 g/(L.h),经驯化后能耐受15 g/L的废旧线路板金属富集体。浸出实验结果表明,在起始pH值为2.25、起始Fe2+浓度为9 g/L、接种量为10%、金属富集体投加量为15 g/L的条件下,菌株Z1能在62 h内浸出废旧线路板中99.3%的铜。与生物浸出效果类似,过滤除菌的滤菌液处理能在86 h内浸出96.0%的铜。而不接种上述细菌的9K培养基无菌浸出对照134 h铜的浸出率仅为61.3%。因此,菌株Z1可作为浸出废旧线路板中有价金属的潜在有效菌株。     

微生物代谢与Fe3+催化氧化脱除烟气中SO2的研究

利用自制的鼓泡反应器,进行了含氧化亚铁硫杆菌的酸性铁溶液脱除烟气中SO2的实验研究.结果表明,细菌直接脱硫的效果较差;Fe3 在脱硫实验过程中既有催化作用,又有氧化作用;细菌主要起氧化Fe2 为Fe3 的作用,再通过Fe3 脱硫.Fe3 存在一个最佳质量浓度,在7～8 g/L左右.当初始Fe3 质量浓度为7.37 g/L时,脱硫10 h,其效率仍高达80%.     

生物炭对土壤中铁生物还原作用和重金属分布的影响

构建厌氧精瓶培养实验体系,探讨生物炭对土壤中铁的生物还原和其他重金属形态转化的影响。结果表明:生物炭会影响铁还原菌希瓦氏菌(Shewanella oneidensis MR-1)对土壤中铁矿物的还原溶出,降低亚铁离子浓度。培养70d后,土壤-希瓦氏菌(SR)处理组亚铁离子摩尔浓度为(291.0±58.0)μmol/L,土壤-希瓦氏菌-生物炭(SRB)处理组亚铁离子摩尔浓度降为(94.7±32.4)μmol/L。同时,生物炭改变了铁生物还原作用对土壤中重金属迁移性的影响。SRB处理组土壤中可交换态锌、钴和镍含量低于土壤-生物炭(CB)处理组,而铁锰氧化物结合态含量增加;与SR处理组相比,SRB处理组可交换态和铁锰氧化物结合态锌、钴、镍含量均有所增加。因此,在稻田等厌氧环境下应用生物炭修复重金属污染土壤时,生物炭对铁矿物生物还原、重金属形态转化的影响需要引起关注。     

氧化-吸附法处理含铁废盐酸及其资源化

提出并研究了高效氧化与强化吸附相结合的含铁废酸资源化处理新工艺。系统研究了其氧化过程的适宜工艺条件并考察了吸附分离单元中的主要工艺参数对铁离子去除率的影响规律。实验结果显示,采用双氧水氧化废盐酸中Fe2+将不会引入其他污染因子,双氧水的最佳投加摩尔数为Fe2+浓度的1.2倍,氧化时间优选为2 h;氧化后的含铁废盐酸经过强碱阴离子交换树脂NDA900分离去除大部分铁离子,若采用固定床双柱串联方式运行,铁离子分离去除率可达99.9%,处理后盐酸可返回酸洗工序重复利用。吸附饱和后的树脂仅使用自来水就可以实现完全再生,再生液中三氯化铁浓度高达40~50g/L。这一工艺有望实现废盐酸及其中铁离子的综合利用,为相关行业清洁生产水平的提升提供技术支持。     

营养成分对Fe2+生物氧化的影响

在29℃和160 r/min条件下,以广东云浮矿山酸性废水为种源,采用9K培养基,经过富集培养得到氧化亚铁硫杆菌A.f.a。利用分批摇床实验,研究了在A.f.a作用下,溶液初始NH4+-N、PO34--P、Mg2+、Ca2+和Cu2+等基本营养成分对Fe2+生物氧化的影响。结果显示,随着NH4+-N、PO34--P、Ca2+或Cu2+离子浓度增加,Fe2+生物氧化率都先增大后降低,各离子最佳浓度分别为84.8、35.6、2.4和254.5 mg/L;Fe2+生物氧化率随着Mg2+浓度的增加逐渐增大,并趋于稳定,其限制浓度为88.8 mg/L。上述结果可用于控制营养条件促进Fe2+的生物氧化。     

Persulfate oxidation for in situ remediation of TCE. II. Activated by chelated ferrous ion

In situ chemical oxidation (ISCO) is a technique used to remediate contaminated soil and groundwater systems. It has been postulated that sodium persulfate (Na2S2O8) can be activated by transition metal ions such as ferrous ion (Fe2+) to produce a powerful oxidant known as the sulfate free radical (SO4-*) with a redox potential of 2.6 V, which can potentially destroy organic contaminants. In this laboratory study persulfate oxidation of dissolved trichloroethylene (TCE) was investigated in aqueous and soil slurry systems under a variety of experimental conditions. A chelating agent (i.e., citric acid) was used in attempt to manipulate the quantity of ferrous ion in solution by providing an appropriate chelate/Fe2+ molar ratio. In an aqueous system a chelate/Fe2+ molar ratio of 1/5 (e.g., S2O8(2)-/chelate/Fe2+/TCE ratio of 20/2/10/1) was found to be the lowest acceptable ratio to maintain sufficient quantities of Fe2+ activator in solution resulting in nearly complete TCE destruction after only 20 min. The availability of Fe2+ appeared to be controlled by adjusting the molar ratio of chelate/Fe2+. In general, high levels of chelated ferrous ion concentrations resulted in faster TCE degradation and more persulfate decomposition. However, if initial ferrous ion contents are relatively low, sufficient quantities of chelate must be provided to ensure the chelation of a greater percentage of the limited ferrous ion present. Citric acid chelated ferrous ion appeared effective for TCE degradation within soil slurries but required longer reaction times. Additionally, the use of citric acid without the addition of supplemental Fe2+ in soil slurries, where the citric acid apparently extracted native metals from the soil, appeared to be somewhat effective at enhancing persulfate oxidation of TCE over extended reaction times. A comparison of different chelating agents revealed that citric acid was the most effective.     

超声-Fenton法处理偶氮染料橙黄II的研究

以偶氮染料橙黄II为研究对象 ,考察了Fenton反应在超声辐射条件下 ,pH值、H2 O2 浓度、Fe2 + 离子浓度对COD去除率的影响。实验结果表明 ,超声对Fenton试剂处理偶氮染料橙黄II具有强化作用。超声条件下 ,当染料浓度为10 0mg/L、pH为 3.0、Fe2 + 离子浓度为 10mg/L、H2 O2 浓度为 4 0 0mg/L时 ,反应 90min ,COD去除率最高可达 93%。     

Persulfate oxidation for in situ remediation of TCE. I. Activated by ferrous ion with and without a persulfate-thiosulfate redox couple

The objective of the laboratory study is to examine the conditions under which transition metal ions (e.g., ferrous ion, Fe2+) could activate the persulfate anion (S2O8(2)-) to produce a powerful oxidant known as the sulfate free radical (SO4-*) with a standard redox potential of 2.6 V. The SO4-* is capable of destroying groundwater contaminants in situ such as trichloroethylene (TCE). Experiments using Fe2+ as an activator under various molar ratios of S2O8(2)-/Fe2+/TCE in an aqueous system indicated that partial TCE degradation occurred almost instantaneously and then the reaction stalled. Either destruction of SO4-* in the presence of excess Fe2+ or the rapid conversion of all Fe2+ to Fe3+ limited the ultimate oxidizing capability of the system. Sequential addition of Fe2+ in small increments resulted in an increased TCE removal efficiency. Therefore, it appeared that Fe2+ played an important role in generating SO4-*. An observation of oxidation-reduction potential (ORP) variations revealed that the addition of sodium thiosulfate (Na2S2O3) to the ferrous ion activated persulfate system could significantly decrease the strong oxidizing conditions. It was hypothesized that the thiosulfate induced reducing conditions might convert Fe3+ to a lower valence state of Fe2+, making the Fe2+ available to activate persulfate decomposition. The sequential addition of thiosulfate (S2O3(2)-), after the initial stalling of ferrous ion activated persulfate oxidation of TCE, resulted in an improvement in TCE removal. The ferrous ion activated persulfate-thiosulfate redox couple resulted in fairly complete TCE degradation in aqueous systems in a short time frame. In soil slurry systems, TCE degradation was slower in comparison to aqueous systems.     

Oxidation of chlorophenols with hydrogen peroxide in the presence of goethite

The use of goethite (alpha-FeOOH) and hydrogen peroxide was recently found that they could effectively oxidize organic compounds. The study was to investigate the effect of goethite particle size, goethite concentration, Fe2+ and Fe3+ on the 2-chlorophenol oxidation. Results indicated that 2-chlorophenol can be decomposed with hydrogen peroxide catalyzed by goethite and the oxidation rate increased with decreasing goethite particle size. 2-Chlorophenol degradation was almost retarded with 0.8 g/l of goethite because ferrous ions could not be produced at this condition. Addition of Fe2+ and Fe3+ can enhance the catalytic oxidation rate of 2-chlorophenol very efficiently. In conclusion, the main mechanism of goethite catalyzing hydrogen peroxide to oxidize 2-chlorophenol may be due to the catalysis of ferrous ions and goethite surface.     

Hydrogen sulfide gas treatment by a chemical-biological process: chemical absorption and biological oxidation steps

In order to remove high concentrations of hydrogen sulfide (H2S) gas from anaerobic wastewater treatments in livestock farming, a novel process was evaluated for H2S gas abatement involving the combination of chemical absorption and biological oxidation processes. In this study, the extensive experiments evaluating the removal efficiency, capacity, and removal characteristics of H2S gas by the chemical absorption reactor were conducted in a continuous operation. In addition, the effects of initial Fe2+ concentrations, pH, and glucose concentrations on Fe2+ oxidation by Thiobacillus ferrooxidans CP9 were also examined. The results showed that the chemical process exhibited high removal efficiencies with H2S concentrations up to 300 ppm, and nearly no acclimation time was required. The limitation of mass-transfer was verified as the rate-determining step in the chemical reaction through model validation. The Fe2+ production rate was clearly affected by the inlet gas concentration as well as flow rate and a prediction equation of ferrous production was established. The optimal operating conditions for the biological oxidation process were below pH 2.3 and 35 degrees C in which more than 90% Fe3+ formation ratio was achieved. Interestingly, the optimal glucose concentration in the medium was 0.1%, which favored Fe2+ oxidation and the growth of T. ferrooxidans CP9.     

Fenton氧化对硝基苯酚过程中Fe2+/Fe3+的氧化还原机制

Fenton降解对硝基苯酚(PNP)过程中,Fe2+经历一个快速氧化后快速还原,最后在高浓度水平上保持稳定的变化过程。通过分析中间产物的变化过程,发现有机中间产物氢醌和苯醌构成一对氧化还原体系催化Fe3+向Fe2+的转化,本研究从Fe2+/3+转化机制的角度进一步明确了Fenton降解PNP的机理。     

三维电极/电-Fenton法降解苯酚

采用电-Fenton耦合三维电极法处理苯酚模拟废水，研究了活性炭作为第三电极的三维电极体系中苯酚的去除效果，重点考察了常温下初始pH值、电流强度、Fe²⁺浓度等因素对苯酚降解的影响。结果表明：在常温下，曝气速率20 L/min，初始pH=3，电流强度为0.3 A/m²，Fe²⁺浓度为0.1 mmol/L，反应时间60 min时，废水的苯酚的氧化降解率为91%，COD去除率为64%。在此条件下，三维电极/电-Fenton表现出较强的氧化能力，具有较好的去除效果，可应用于含苯酚废水的处理。     

Chemical oxidation of sulfadiazine by the Fenton process: Kinetics,pathways, toxicity evaluation

This paper investigated sulfadiazine oxidation by the Fenton process under various reaction conditions. The reaction conditions tested in the experiments included the initial pH value of reaction solutions, and the dosages of ferrous ions and hydrogen peroxide. Under the reaction conditions with pH 3, 0.25 mM of ferrous ion and 2 mM of hydrogen peroxide, a removal efficiency of nearly 100% was achieved for sulfadiazine. A series of intermediate products including 4-OH-sulfadiazine/or 5-OH-sulfadiazine, 2-aminopyrimidine, sulfanilamide, formic acid, and oxalic acid were identified. Based on these products, the possible oxidation pathway of sulfadiazine by Fenton's reagent was proposed. The toxicity evaluation of reaction solutions showed increased antimicrobial effects following the Fenton oxidation process. The results from this study suggest that the Fenton oxidation process could remove sulfadiazine, but also increase solution toxicity due to the presence of more toxic products.     

Modeling the reaction kinetics of Fenton's process on the removal of atrazine

The degradation of pesticide, atrazine (ATZ), 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine, by Fenton's reagent (FR) was investigated as a function of reagents' concentrations and ratios in a batch reactor. The degradation of ATZ was effectively achieved by hydroxyl radicals, which were generated in the FR process. The decay rates of ATZ and the oxidation capacities of FR were found to depend on the concentrations of hydrogen peroxide and ferrous ion. The removal kinetics of ATZ are initiated by a rapid decay and then followed by a much slower one. After an extended reaction time (5-10 min), the reactions ceased because the Fe(II) and H(2)O(2) were consumed and would be deactivated in the process. A mathematical model was successfully developed to describe the two-stage reaction kinetics by using two simple but critical parameters: the initial ATZ decay rate and the final oxidation capacity of Fenton's process. In general, higher [Fe(II)] or H(2)O(2) concentrations result in faster initial decay rate and higher oxidation capacity. However, the oxidation capacity is more sensitive to the initial [Fe(II)] due to the presence of side reactions as discussed in the paper.     

Degradation of the pharmaceutical metronidazole via UV, Fenton and photo-Fenton processes

Degradation rates and removal efficiencies of Metronidazole using UV, UV/H2O2, H2O2/Fe2+, and UV/H2O2/Fe2+ were studied in de-ionized water. The four different oxidation processes were compared for the removal kinetics of the antimicrobial pharmaceutical Metronidazole. It was found that the degradation of Metronidazole by UV and UV/H2O2 exhibited pseudo-first order reaction kinetics. By applying H2O2/Fe2+, and UV/H2O2/Fe2+ the degradation kinetics followed a second order behavior. The quantum yields for direct photolysis, measured at 254 nm and 200-400 nm, were 0.0033 and 0.0080 mol E(-1), respectively. Increasing the concentrations of hydrogen peroxide promoted the oxidation rate by UV/ H2O2. Adding more ferrous ions enhanced the oxidation rate for the H2O2/Fe2+ and UV/H2O2/Fe2+ processes. The major advantages and disadvantages of each process and the complexity of comparing the various advanced oxidation processes on an equal basis are discussed.