Formaldehyde degradation in the presence of methanol by photo-Fenton process

In this study, the photo-Fenton process for the degradation of formaldehyde was investigated in lab-scale experiments. Results showed that methanol, the additive chemical in a commercial product of formaldehyde, was also decomposed during the formaldehyde oxidation reaction. The oxidation reaction was in three-stages. The first stage was the Fe(2+)/H(2)O(2) reaction in which both formaldehyde and methanol were swiftly decomposed. The second and the third stages exerted a somewhat less rapid degradation of both chemicals. The first stage of the oxidation reaction can be discussed by means of the initial average rate and the third stage or Fe(3+)/H(2)O(2) stage was found to follow the first order reaction rate. The reaction was influenced by the initial pH, the concentration of hydrogen peroxide, the amount of ferrous ions. The initial pH at 2.6 provided the highest removal efficiencies in this system. In addition, the competition between formaldehyde and methanol was investigated and described as r(m)/r(f), where r(m) and r(f) were the initial rates of methanol and formaldehyde, respectively. The addition of methanol exhibited a competitive effect on formaldehyde degradation. The removal of formaldehyde decreased with increasing methanol concentration. At the high concentrations of methanol, the oxidation reaction of formaldehyde was repressed. It appears that all values of r(m)/r(f) obtained from the experiments are lower than the theoretical values.     

石油化工企业含苯胺消防污水处理技术研究

针对石油化工企业含苯胺的消防污水,利用基于过氧化氢和氯化铁为氧化剂的深度氧化技术,通过氧化、絮凝、过滤和吸附对消防污水进行处理。实验确定氧化剂的投加量为理论投加量,氧化时间1.0h,消防污水pH值为6.86时,絮凝剂最佳使用浓度约为2%,消防污水中苯胺和COD去除率达到99.5%以上,达到了消防污水处理效果。     

烟气中汞现场监测氧化吸收条件优化研究

以高锰酸钾溶液作为烟气中汞元素的氧化吸收液,通过单因素试验研究了氧化吸收液浓度、反应时间、初始汞浓度、反应温度、pH值对KMnO4对HHg0吸收效率的影响,阐明方法适应性,并将现行采样方法进一步优化.结果 表明,15min后,氧化吸收基本平衡,KMnO4浓度为5mmol/L,反应温度为60℃时KMnO4氧化吸收最佳.强...     

电化学氧化处理焚烧厂渗滤液膜浓缩液混凝出水的研究

为了降低城市生活垃圾焚烧厂渗滤液膜浓缩液混凝出水中的有机物浓度,采用电化学氧化对渗滤液膜浓缩液混凝出水进行了处理.同时,考察了阳极材料、电流密度、初始pH值和电解时间对有机物的去除影响,使用三维荧光光谱分析了有机物的去除特性,并通过氯离子的转化探讨了有机物的降解机理.结果 表明,钌铱(Ru-Ir/Ti)阳极对有机物的去...     

黄磷尾气中PH3液相催化净化研究

以Mn（Ⅱ）与Pd（Ⅱ）为催化剂的吸收净化溶液对黄磷尾气中的PH3进行了液相催化氧化研究。考察了混合气中02浓度、温度、入口PH3浓度、气体流量和吸收液pH变化与磷化氢净化效率曲线的关系。实验结果表明：混合气中较佳的氧含量为5％;在20℃至75℃范围内,低温对催化净化有利,较适宜的反应温度为20℃;较低的PH3入口浓度和低气速均有利于对PH3的净化;吸收液较高的pH有利于吸收液中催化剂催化效能的发挥。吸收液对PH3的净化效率可达100％,但因吸收液中的金属离子易与PH3产生的PO4^3-形成沉淀,使金属离子脱离液相催化氧化系统,吸收液失效较快。     

Reduction of copper(II) by iron(II)

Laboratory and field investigations have clearly demonstrated the important role of reduced iron (Fe(II)) in reductive transformations of first-row transition metal species. However, interactions of Fe(II) and copper (Cu) are not clearly understood. This study examined the reduction of Cu(II) by Fe(II) in stirred-batch experiments at pH 5.2 and 5.5 as influenced by chloride (Cl-) concentration (0.002-0.1 M), initial metal concentration (0.1-9.1 mM), and reaction time (1-60 min) under anoxic conditions. Reduction of Cu(II) to Cu(I) by dissolved Fe(II) was rapid under all experimental conditions and the stability of the products explains the driving force for the redox reaction. Under conditions of low [Cl-] and high initial metal concentration, >40% of total Cu and Fe were removed from solution after 1 min, which accompanied formation of a brownish-red precipitate. X-ray diffraction (XRD) patterns of the precipitates revealed the presence of cuprite (Cu2O), a Cu(I) mineral, based on d-spacings located at 0.248, 0.215, 0.151, and 0.129 nm. Fourier transform infrared (FTIR) spectroscopy corroborated XRD data for the presence of Cu2O, with features located at 518, 625, and 698 cm(-1). Increasing [Cl-] stabilized the dissolved Cu(I) product against Cu2O precipitation and resulted in more Fe precipitated from solution (relative to Cu) that appears to be present as poorly crystalline lepidocrocite (gamma-FeOOH). This process may be important in anoxic soil environments, where dissolved Fe(II) levels can accumulate.     

Bioproduction of ferric sulfate used during heavy metals removal from sewage sludge

Toxic metals removal from wastewater sewage sludge can be achieved through microbial processes involving Acidithiobacillus ferrooxidans. The oxidation of ferrous ions by A. ferrooxidans, cultured in sewage sludge filtrate, was studied in both batch and continuous flow stirred tank reactors. Sewage sludge filtrate containing natural nutrients (phosphorus and nitrogen) was recovered as effluent following the dehydration of a primary and secondary sludge mixture. Batch and continuous flow stirred tank reactor tests demonstrated that A. ferrooxidans were able to grow and completely oxidize ferrous iron in a culture medium containing more than 80% (v v(-1)) sewage sludge filtrate with 10 g Fe(II) L(-1) added. Toxic levels were reached when total organic carbon in the sewage sludge filtrate exceeded 250 mg L(-1). The ferric iron solution produced in the sludge filtrate by A. ferrooxidans was used to solubilize heavy metals in primary and secondary sludge. The solubilization of Cu, Cr, and Zn yielded 71, 49, and 80%, respectively. This is comparable with the yield percentages obtained using a FeCl(3) solution. The cost of treating wastewater sewage sludge by bioproducing a ferric ion solution from sewage sludge is three times less expensive than the conventional method requiring a commercial ferric chloride solution.     

油田含油污水高级氧化技术研究

以气浮—过滤预处理后的污水为处理对象,通过臭氧氧化与Fenton氧化两种方法处理油田含油污水。经实验验证:Fenton在pH为4,H2O2初始浓度为0.08mol/L,Fe2+与H2O2的摩尔比为1:10,H2O2与CODCr的质量比为1:1,反应时间为60min的条件下,去除率达54.3%(CODCr100mg/L),可达到GB8978-1996《污水综合排放标准》二级标准。     

Optimization of Fenton's oxidation of chemical laboratory wastewaters using the response surface methodology

Establishing a treatment process for practical and economic disposal of laboratory wastewaters has become an urgent environmental concern of the Department of Chemical Engineering of the Universidade Estadual de Maringá (State University of Maringá), Brazil. Fenton and related reactions are potentially useful oxidation processes for destroying toxic organic compounds in water. In these reactions, hydrogen peroxide is combined with ferrous or ferric iron in the presence or absence of light to generate hydroxyl radicals (.OH). The feasibility of Fenton's reagent to treat waste chemicals from an academic research laboratory was investigated in this study. A response surface methodology was applied to optimize the Fenton oxidation process conditions using chemical oxygen demand (COD) removal as the target parameter to optimize, and the reagent concentrations, as related to the initial concentration of organic matter in the effluent, and pH as the control factors to be optimized. Maximal COD removal (92.3%) was achieved when wastewater samples were treated at pH 4 in the presence of hydrogen peroxide and iron in the ratios [COD]:[H2O2]=1:9 and [H2O2]:[Fe2+]=4.5:1. Under these conditions, it was possible to obtain simultaneously maximal COD removal and minimal chemical sludge after treatment, which is a residue that needs further processing.     

Experimental oxidative dissolution of sphalerite in the Aznalcollar sludge and other pyritic matrices

After the collapse on 25 Apr. 1998 of the Aznalcóllar mine tailings dike in southwestern Spain, 45 km2 of the Guadiamar valley were covered by a pyritic sludge containing up to 2% sphalerite (ZnS). Later, the sludge was mechanically removed and calcium carbonate was plowed into the soil to immobilize heavy metals. By June 2001 more than 60% of the sulfides in the residual sludge had oxidized and soil Zn contents reached locally phytotoxic levels. Therefore, the oxidative dissolution of sphalerite in the sludge and other pyritic samples was examined. Flow-through oxidation experiments showed that: (i) about 5 and 17% of the sludge Fe and Zn were in soluble form, respectively, because the sludge sample had been partly oxidized in the field; (ii) the oxidation rates of the residual pyrite and sphalerite were similar; (iii) the overall sulfide oxidation rate was relatively unaffected by the addition of calcite; and (iv) poorly crystalline Fe (hydr)oxides containing Zn in occluded form and Zn (hydroxi)carbonates were formed in the presence of calcite. The rate of oxidation of reference sphalerite greatly increased when it was incorporated in the sludge or in a reference pyrite matrix. This enhancement was due to galvanic interaction because pyrite oxidation was depressed in the presence of sphalerite. Oxidation by Fe3+ ions was less important because the oxidation rates of native sphalerite were not greater at low than at high pH. The fast oxidation rate of sphalerite in the Aznalcóllar sludge indicates a need for quick adoption of remediation measures in similar accidents elsewhere. The use of calcite amendments has little influence on the oxidation rate but does result in the accumulation of Zn in relatively insoluble forms.     

吸附-双催化氧化降解苯胺、硝基苯废水

苯胺、硝基苯废水利用吸附树脂吸附后,再利用过氧化氢作氧化剂,在亚铁离子和紫外光的双催化下氧化降解。通过对亚铁离子浓度、过氧化氢浓度等因素对光降解影响的考察,结果表明,在实验条件下,本氧化体系对苯胺、硝基苯废水有明显的降解效果,苯胺、硝基苯废水经该体系处理12h后,去除率最高分别达到99.7%和95.3%。     

Degradation of a commercial textile biocide with advanced oxidation processes and ozone

The occurrence of significant amounts of biocidal finishing agents in the environment as a consequence of intensive textile finishing activities has become a subject of major public health concern and scientific interest only recently. In the present study, the treatment efficiency of selected, well-known advanced oxidation processes (Fenton, Photo-Fenton, TiO(2)/UV-A, TiO(2)/UV-A/H(2)O(2)) and ozone was compared for the degradation and detoxification of a commercial textile biocide formulation containing a 2,4,4'-trichloro-2'-hydroxydiphenyl ether as the active ingredient. The aqueous biocide solution was prepared to mimic typical effluent originating from the antimicrobial finishing operation (BOD(5,o) < or =5 mg/L; COD(o)=200 mg/L; DOC(o) (dissolved organic carbon)=58 mg/L; AOX(o) (adsorbable organic halogens)=48 mg/L; LC(50,o) (lethal concentration causing 50% death or immobilization in Daphnia magna)=8% v/v). Ozonation experiments were conducted at different ozone doses (500-900 mg/h) and initial pH (7-12) to assess the effect of ozonation on degradation (COD, DOC removal), dearomatization (UV(280) and UV(254) abatement), dechlorination (AOX removal) and detoxification (changes in LC(50)). For the Fenton experiments, the effect of varying ferrous iron catalyst concentrations and UV-A light irradiation (the Photo-Fenton process) was examined. In the heterogenous photocatalytic experiments, Degussa P25-type TiO(2) was used as the catalyst and the effect of reaction pH (3, 7 and 12) and H(2)O(2) addition on the photocatalytic treatment efficiency was examined. Although in the photochemical (i.e. Photo-Fenton, TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)) experiments appreciably higher COD and DOC removal efficiencies were obtained, ozonation appeared to be equally effective to achieve dearomatization (UV(280) abatement) at all studied reaction pH. During ozonation of the textile biocide effluent, AOX abatement proceeded significantly faster than dearomatization and was complete after 20 min ozonation (267 mg O(3)). On the other hand, for complete detoxification, ozonation had to be continued for at least 30 min (corresponding to 400mg O(3)). Effective AOX and acute toxicity removal was also obtained after heterogeneous photocatalytic treatment (TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)). The Fenton-based treatment experiments and particularly the dark Fenton reaction resulted in relatively poor degradation, dearomatization, AOX and acute toxicity removals.     

Effects of oxide coating and selected cations on nitrate reduction by iron metal

Under anoxic conditions, zerovalent iron (Fe(0)) reduces nitrate to ammonium and magnetite (Fe3O4) is produced at near-neutral pH. Nitrate removal was most rapid at low pH (2-4); however, the formation of a black oxide film at pH 5 to 8 temporarily halted or slowed the reaction unless the system was augmented with Fe(2+), Cu(2+), or Al(3+). Bathing the corroding Fe(0) in a Fe(2+) solution greatly enhanced nitrate reduction at near-neutral pH and coincided with the formation of a black precipitate. X-ray diffractometry and scanning electron microscopy confirmed that both the black precipitate and black oxide coating on the iron surface were magnetite. In this system, ferrous iron was determined to be a partial contributor to nitrate removal, but nitrate reduction was not observed in the absence of Fe(0). Nitrate removal was also enhanced by augmenting the Fe(0)-H2O system with Fe(3+), Cu(2+), or Al(3+) but not Ca(2+), Mg(2+), or Zn(2+). Our research indicates that a magnetite coating is not a hindrance to nitrate reduction by Fe(0), provided sufficient aqueous Fe(2+) is present in the system.     

再生造纸废水絮凝除浊试验研究

本研究采用絮凝法对再生造纸废水中含细小纤维、无机填料的悬浮物进行处理试验，比较了硫酸亚铁与聚丙烯酰胺复合絮凝剂和聚硅酸氯化铁盐两种絮凝剂的絮凝效果，研究了制备聚硅酸氯化铁盐的铁硅比、pH值、碱化度以及投加量与废水除浊率之间的相互关系。实验结果表明：在最佳条件下，絮凝效果优异，除浊率达到98％，上清液无色透明。     

Sorption of iron-cyanide complexes on goethite in the presence of sulfate and desorption with phosphate and chloride

Soils are contaminated with potentially toxic iron-cyanide complexes by some industrial activities. The influence of sulfate on the sorption of the iron-cyanide complexes ferricyanide, [Fe(CN)6]3-, and ferrocyanide, [Fe(CN)6]4-, on goethite was investigated in batch experiments. The experiments were conducted as influenced by pH and varying sulfate/iron-cyanide complex concentration ratios. Furthermore, the desorption of iron-cyanide complexes sorbed on goethite was studied using phosphate and chloride solutions as influenced by pH and anion concentration. Over the whole pH range (pH 3.5 to 8), ferricyanide and sulfate showed similar affinities for the goethite surface. The extent of ferricyanide sorption strongly depended on sulfate concentrations and vice versa. In contrast, ferrocyanide sorption was only decreased (approximately 12%) by sulfate additions at pH 3.5. Ferricyanide was completely desorbed by 1 M chloride, ferrocyanide not at all. Unbuffered phosphate solutions (pH 8.3) desorbed both iron-cyanide complexes completely. Even in 70-fold excess, pH-adjusted phosphate solutions could not desorb ferrocyanide completely at pH 3.5. For ferricyanide we propose a sorption mechanism that is similar to the sulfate sorption mechanism, including outer-sphere and weak inner-sphere surface complexes on goethite. Ferrocyanide appears to form inner-sphere surface complexes. Additionally, we assume that ferrocyanide precipitates probably as a Berlin Blue-like phase at pH 3.5. Hence, ferrocyanide should be less mobile in the soil environment than ferricyanide or sulfate.     

超声-双氧水和亚铁离子体系处理含酚废水研究

在实验装置上对超声-双氧水和亚铁离子体系联合处理含酚废水进行了实验研究。主要考察了废水初始pH值、初始双氧水浓度、超声功率、反应时间等因素对酚去除率的影响。实验结果表明：超声辐射可以在双氧水和亚铁离子体系氧化过程中起加速反应的作用，而且随着超声功率的增大，加速反应的能力增强；实验条件下废水初始pH值为4～6．8，初始双氧水浓度为140mg／L时酚去除效果最佳；超声-双氧水和亚铁离子体系处理含酚废水过程中苯酚的降解规律符合表现一级反应。     

高锰酸盐氧化-碘量法测定高锰酸盐指数

在高锰酸盐指数的测定方法中,标准碱性法具有较强的抗氯离子干扰能力,但对于高氯离子浓度水样,在酸化后的滴定过程中高锰酸盐可使氯离子氧化导致滴定终点难于辨认。采用高锰酸盐氧化－碘量法（以下简称碘量法）可以较好地解决这一问题。试验得出：碘化钾加入量为４～５ｍＬ（０．５ｍｏｌ／Ｌ）,氯离子浓度在１２０００ｍｇ／Ｌ以下对测定结果基本无影响;Ｆｅ３＋对结果有负干扰,当用氟离子掩蔽后,Ｆｅ３＋浓度对测定结果基本上无影响;碘量法的回收率在９６％～１０２％之间。     

Biodegradation of pentyl amine and aniline from petrochemical wastewater

The objectives of the project were to isolate a bacterial strain capable of degrading pentyl amine and aniline and to define the optimal pentyl amine and aniline degradation conditions for this bacterial strain. The bacterial strain was isolated from activated sludge obtained from a Northeastern China treatment facility for petrochemical wastewater rich in pentyl amine and aniline. Once the strain was isolated, five triplicate (5) batch tests were used to establish the conditions for maximum pentyl amine and aniline degradation, by varying one at a time the following five factors: temperature, pH, reaction time, pollutant concentrations and aeration rate. In a final test, oil refinery sludge was inoculated with the strain and tested for the degradation of pentyl amine and aniline under optimal conditions, while observing the degradation pathway of pentyl amine and aniline. The isolated strain, PN1001, is a member of the Pseudomonas species and it was capable of degrading pentyl amine and aniline. The optimal reactor conditions for the degradation of a mixture of pentyl amine and aniline, at a concentration ranging between 150 and 200mg/L, were found to be 30 degrees C at a pH of 7.0, under a reaction time of 24h and a maximum solution dissolved oxygen level of 6 mgO(2)/L. Under such conditions, the strain PN1001 degraded 93% and 89% of the pentyl amine and aniline, respectively, aniline being more toxic and demonstrating a more complex degradation pathway. The strain PN1001 degraded more contaminants when both were present because of the pi and sigma electron cloud coordination functions of aniline and pentyl amine, respectively, presumed to reduce the toxic effect of aniline. Once inoculated with the strain, oil refinery sludge degraded 93% and 88% of the pentyl amine and aniline, compared to the strain alone which degraded 72% and 82%, likely because of the sludge's buffering effect against the toxic environment.     

Biological mine drainage treatment

Drainage from sulphur mines contains a high concentration of ferrous iron and it is strongly acidic. The mechanism of acid mine drainage formation was briefly explained. As a case study, successful measures taken at the abandoned Matsuo mine, Iwate Prefecture, Japan, for preventing the pollution in receiving rivers was presented in this paper. The measures consisted of the construction works against pollution sources and the construction of a drainage treatment plant in which Thiobacillus ferrooxidans oxidizes ferrous iron under a low pH condition, and produced ferric iron is removed by sedimentation. Then, a laboratory-scale fluidized bed reactor using anion exchange resin as attaching material for the bacteria was examined in order to improve the efficiency of biological oxidation of ferrous iron. More than 90% of oxidation had been maintained for 2 months at 1 h of HRT, which suggests that the size of the oxidation tank could be reduced.     

硫酸盐生物还原的限制性生态因子的影响研究

利用厌氧颗粒污泥对烟气中SO2吸收生成的硫酸盐或亚硫酸盐废水进行处理,考察起始SO4^2-质量浓度、初始COD／SO4^2-、初始pH、接种污泥质量、亚铁离子等限制性生态因子对硫酸盐还原的影响。结果表明：在起始SO4^2-质量浓度800mg／L,初始COD／SO4^2-为3．0,pH值为7．0,接种污泥质量为31．10gVSS／L,添加亚铁离子的条件下,进行半连续试验,硫酸根去除率可迭70％。表明在COD／SO4^2-较低的条件下,各生态因子综合作用下,硫酸盐还原可得较好效果。