Catalytic wet oxidation of the pretreated synthetic pulp and paper mill effluent under moderate conditions

In the present study, catalytic wet oxidation (CWO) was investigated for the destruction of organic pollutants in the thermally pretreated effluent from a pulp and paper mill under moderate temperature and pressure conditions. The thermal pretreatment studies were conducted at atmospheric pressure and 368K using copper sulfate as a catalyst. The thermal pretreatment reduced COD by about 61%. The filtrate of the thermal pretreatment step was used at pH 8.0 for CWO at 383-443K temperature and a total pressure of 0.85MPa for 4h. Catalysts used for the reaction include copper sulfate, 5% CuO/95% activated carbon, 60% CuO/40% MnO(2), and 60% CuO/40% CeO(2). Maximum COD reduction was found to be 89% during CWO step using 5% CuO/95% activated carbon with a catalyst loading of 8gl(-1) at 443K and 0.85MPa total pressure. Overall COD reduction for the pretreatment and the CWO was found to be 96%. Besides this, 60% CuO/40% CeO(2) catalyst also exhibited the similar activity as that of obtained with 5% CuO/95% activated carbon catalyst at 423K temperature and 0.85MPa total pressure. The pH of the solution during the experimental runs decreases initially due to the formation of carboxylic acid and then increases due to the decomposition of acids.     

臭氧氧化法深度处理生活垃圾焚烧厂沥滤液

采用臭氧氧化法对生活垃圾焚烧厂沥滤液经生化处理后的废水(称沥滤液生化处理水)进行深度处理。实验结果表明,COD降解速率随废水pH的提高明显增加,其中pH=10.5时的COD降解速率常数约为pH=4时的5.8倍。在臭氧投量为52.92 mg/min、pH=10.5的条件下反应70 min后,UV254和COD去除率分别达到84.7%和59.3%。向反应体系投加叔丁醇后COD去除率下降了约15%,由羟自由基氧化去除的COD占总COD去除量的26.7%。毒性实验结果表明,沥滤液生化处理水的96 h-EC50为38%,经臭氧氧化进一步处理后出水的96 h-EC50为77%,表明经臭氧深度处理后沥滤液生化处理水的毒性明显降低。     

含固率对牛粪常温厌氧消化的影响

在常温、pH值为7.0下,采用10 L玻璃瓶作为反应器对含固率(TS)分别为2%、6%、10%和14%的4组牛粪溶液进行厌氧消化实验,系统运行48 d,分析了厌氧消化过程中的COD(化学需氧量)、pH、VFA(挥发性脂肪酸)和产气量的变化。结果表明,进料TS是影响牛粪厌氧消化产气效果的重要因素,调节牛粪进料TS至10%,可以使其厌氧消化获得最佳的产气效果,COD去除率为24.6%,产气中甲烷含量为56.1%。     

加热酸化-Fenton氧化处理乳化液废水

采用加热酸化-Fenton氧化处理乳化液废水,在加酸量为1．0mL98％H2SO4／100mL乳化液、加热温度95℃、加热时间1h条件下,初始COD〉20万mg／L,浊度〉8000NTU的乳化液COD降低到46592mg／L,浊度降低到20NTU,加热和酸化的联合过程达到了良好的破乳效果;破乳后的出水在ρ（Fe2＋）／ρ（H2O2）=1：30、ρ（H2O2）和（COD）=1．4、pH=4的条件下进行Fenton氧化,处理后的出水COD可降到18600mg／L,去除率达61．4％,其B／C可由破乳后的0．11提高到0．43,废水的可生化性大大提高,为后续处理创造了可能。     

DNAPL remediation with in situ chemical oxidation using potassium permanganate. Part I. Mineralogy of Mn oxide and its dissolution in organic acids

Previous studies on in situ chemical oxidation of trichloroethylene (TCE) with potassium permanganate indicated that the solid reaction product, Mn oxide, could reduce the permeability of the porous medium and impact the success of dense non-aqueous phase liquid (DNAPL) removal. In order to address the issue of permeability reduction caused by precipitation, this study investigated the mineralogy of Mn oxides and the possibilities of removing the solid precipitates by dissolution. The solid reaction product from the oxidation of TCE by permanganate is semi-amorphous potassium-rich birnessite, which has a layered mineral structure with an interlayer spacing of 7.3 A. The chemical formula is K(0.854)Mn(1.786)O(4).1.55H(2)O. It has a relatively small specific surface area at 23.6+/-0.82 m(2)/g. Its point of zero charge (pzc) was measured as 3.7+/-0.4. This birnessite is a relatively active species and could participate in various reactions with existing organic and inorganic matter. The dissolution kinetics of Mn oxide was evaluated in batch experiments using solutions of citric acid, oxalic acid, and ethylenediaminetetraacetic acid (EDTA). Initial dissolution rates were determined to be 0.126 mM/m(2)/h for citric acid, 1.35 mM/m(2)/h for oxalic acid, and 5.176 mM/m(2)/h for EDTA. These rates compare with 0.0025 mM/m(2)/h for nitric acid at pH=2. Organic acids dissolve Mn oxide quickly. Reaction rates increase with acid concentration, as tested with citric acid. The dissolution mechanism likely involves proton and ligand-promoted dissolution and reductive dissolution. Citric and oxalic acid can induce ligand-promoted dissolution, while EDTA can induce ligand-promoted and reductive dissolutions. At low pH, proton-promoted dissolution seems to occur with all the acids tested, but this process is not dominant. Reductive dissolution appears to be the most effective process in dissolving the solid, followed by ligand-promoted dissolution. These experiments indicate the significant potential in using these organic acids to remove precipitates formed during the oxidation reaction.     

铁及铁铜氧化物对臭氧氧化酸性红B的催化效能

采用自蔓延溶胶凝胶法分别制备了铁氧化物和铁铜复合氧化物催化剂,以酸性红B为降解对象,对比了单独臭氧氧化、铁氧化物和铁铜复合氧化物催化臭氧氧化对酸性红B的降解效果,考察了磁力搅拌速度(500～1 640 r/min)、溶液pH(3～11)、臭氧投加速率(3.55～28.4 mg/min)对铁铜复合氧化物催化性能的影响。结果表明,与单独臭氧氧化比较,铁氧化物和铁铜复合氧化物均能加速酸性红B的降解,促进色度和COD的去除,结合催化剂的表征结果,推断催化剂表面羟基促进臭氧分解产生.OH是其氧化性能较好的主要原因,另外,催化剂的吸附能力对催化性能也有一定影响。随着磁力搅拌速度、溶液pH、臭氧投加速率的增大,铁铜复合氧化物催化臭氧氧化酸性红B的效果越好。     

Zr-Fe双组分复合除砷吸附剂的优化制备及性能评价

实验发现,铁氧化物或铁的羟基氧化物对As(V)有较好的吸附性能,而锆氧化物或锆水合氧化物则对As(Ⅲ)有优异的吸附选择性,但其使用的pH通常要在9的条件下。通过简单的共沉淀法制备了Zr-Fe双组分复合吸附剂,在制备过程中通过优化制备条件如:沉淀剂浓度、金属离子总浓度、金属离子配比、反应温度、反应时间及吸附剂价格等因素,最终合成出了对As(V)和As(Ⅲ)都具有良好吸附能力的吸附剂。这种吸附剂在中性条件下对As(V)和As(Ⅲ)的最大吸附量为62 mg/g和118 mg/g。     

好氧/缺氧消化降解污泥特征分析

为考察好氧/缺氧消化过程中污泥降解的特征,利用2个反应器进行对比试验,研究好氧/缺氧和好氧消化2个过程中VS的去除,pH和碱度变化,消化上清液中COD和氮元素变化等情况。试验结果表明:好氧/缺氧消化能够满足污泥稳定的要求,在常温条件下,消化16 d VS去除率即可达到38.2%,同时比好氧消化节约曝气能耗。好氧/缺氧消化对污泥中总氮的去除率高于传统的好氧消化,达到了36.4%,而且能够降低消化污泥上清液中的氨氮和硝态氮浓度。     

As(V) adsorption on amorphous iron oxide: Triple layer modelling

The adsorption of As(V) by amorphous iron oxide was investigated at 25°C, 0.01 M NaNO₃ background electrolyte as a function of solution pH(4–10) at three initial As(V) concentrations and two Fe(III) concentrations. As(V) adsorption increased with decreasing pH. A modified Langmuir isotherm has been used for describing an equilibrium partition existing between solid and liquid phases. The triple-layer model was used for simulating As(V) adsorption on iron oxide surface. This model was able to describe As(V) adsorption over the pH range 4–10, all at the concentrations of As(V) and Fe(III) studied. =Fe(H₂AsO₄)⁰, = Fe(HAsO₄)⁻ and = Fe(AsO₄)²⁻ have been shown through simulation with inner-sphere complexation products to be more consistent with experimental adsorption observations than complexation with other surface species.     

利用高炉瓦斯泥中的锌制备活性氧化锌的研究

利用高炉炼铁瓦斯泥中的锌,采用火法富集和湿法浸取制取活性氧化锌。考察了温度、时间对火法富集产品中氧化锌含量和原料瓦斯泥中锌挥发率的影响,确定了富集工艺的最佳条件为:在氮气氛围下,温度从常温以10℃/min升温至1 000℃并且在1 000℃下保持1 h,得到的富集产品中氧化锌含量82.24%;瓦斯泥中锌挥发率97%。同时考察了温度、氨水用量、碳酸氢铵用量和液固比等因素对氧化锌浸取率的影响。确定的最佳工艺条件为:浸取温度40℃,氨水用量为理论量的2倍,碳酸氢铵用量为理论量的2倍,液固比4∶1,浸取时间2 h,氧化锌浸取率达99.9%。湿法制得的活性前驱体碱式碳酸锌,经煅烧得到纯度为98.4%的活性氧化锌产品,氧化锌的总回收率达95.3%。     

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%。     

活性炭纤维载体生物膜法处理洗车废水研究

为了实现洗车废水的循环使用,进行了以聚丙烯腈基活性炭纤维(PAN-ACF)为生物膜载体处理洗车废水的实验研究。以LAS、COD和NH3-N等指标考察了活性炭纤维生物膜反应器对洗车废水的处理效果。结果表明:在常温下、pH=6.5~7,当进水流量在30 mL/min时,反应器达到最佳运行参数,活性炭纤维载体生物膜法对LAS、COD和NH3-N等的去除率分别达到了97%、80%和60%。出水水质完全达到《生活杂用水水质标准》(CJ/T48-99)中洗车用水主要水质指标的规定。此外,实验表明PAN-ACF作为生物膜载体具有很好的生物亲和性和再生性。     

活性焦吸附处理一硝基甲苯(MNT)废水

一硝基甲苯(MNT)废水是一种具有高毒性、难降解的火炸药废水。以活性焦为吸附剂,研究了活性焦对MNT废水中COD的吸附性能及pH、时间、温度和活性焦用量对吸附效果的影响,并分析了吸附前后MNT废水水质和急性毒性的变化。实验结果表明,pH、时间和活性焦用量是影响吸附效果的主要因素,吸附过程符合拟二级动力学,吸附速率常数为1.01×10-2g/(mg·min),可以用Freundlich吸附等温线来描述,等温线常数为Kf=1.14×10-4,n=0.58;在pH为3,温度为20℃,活性焦用量为80g/L的条件下吸附MNT废水3 h,COD的去除率达到72.0%,急性毒性下降了98.6%,表明活性焦能有效地吸附处理MNT废水。     

吹脱法预处理皮革废水的实验研究

对某皮革厂综合废水进行吹脱预处理实验,综合考察了影响氨氮去除的各个因素(pH值、汽液比、吹脱温度、氨氮初始浓度),同时对该预处理工艺去除铬、SS(悬浮固体浓度)、COD和硫化物的条件进行了优化,并进行了能耗及运行成本估算。结果表明:该厂皮革废水的最佳吹脱工况为pH=11,气液比=1 800,温度25~35℃,在此条件下,当进水ρ(NH3-N)=304.7 mg/L、ρ(Cr)=65.0 mg/L、ρ(SS)=1 700 mg/L、ρ(COD)=2 700 mg/L、ρ(S2-)=112.3 mg/L时,相应的去除率可达78.1%~83.5%、96.4%、88.2%、45.6%和85.0%,且吹脱法对氨氮具有较高的抗冲击负荷能力,吨水处理成本约为3.61元,可作为皮革废水的预处理工艺。     

Zr—Fe双组分复合除砷吸附剂的优化制备及性能评价

实验发现,铁氧化物或铁的羟基氧化物对As（V）有较好的吸附性能,而锆氧化物或锆水合氧化物则对As（Ⅲ）有优异的吸附选择性,但其使用的pH通常要在〉9的条件下。通过简单的共沉淀法制备了Zr-Fe双组分复合吸附剂,在制备过程中通过优化制备条件如：沉淀剂浓度、金属离子总浓度、金属离子配比、反应温度、反应时间及吸附剂价格等因素,最终合成出了对As（V）和As（Ⅲ）都具有良好吸附能力的吸附剂。这种吸附剂在中性条件下对As（V）和As（Ⅲ）的最大吸附量为62mg／g和118mg／g。     

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%。     

The calcination process in a system for washing, calcinating, and converting treated municipal solid waste incinerator fly ash into raw material for the cement industry

Calcination is the second step in a washing-calcination-conversion system in which treated municipal solid waste incinerator fly ash and bottom ash can be reused as raw material in the cement industry and can decompose or stabilize hazardous compounds, reduce residue amounts, and alter residue characteristics. In this research, only fly ash is discussed. Chloride reduction is important if treated fly ash is to be reused in cement; however, the relationship between washed fly ash properties and chloride reduction by calcination is not well understood. This study used washed residues of three types of fly ash-raw fly ash (RFA) from the boiler or economizer of an incineration system, fly ash collected in a bag filter injected with calcium hydroxide (Ca(OH)2) for acid removal (CaFA), and fly ash collected in a bag filter injected with sodium bicarbonate (NaHCO3) for acid removal (NaFA)-in calcination experiments with varying temperature (400-1100 degrees C) and atmosphere (100% nitrogen [N2] at 25 mL/min or 10% oxygen [O2] [90% N2] at fluxes of 25, 50, and 75 mL/min). From the perspective of chloride reduction, heating to 1000 degrees C with 1-hr heating time, 1-hr holding time, and an atmosphere of 10% O2/90% N2 was most suitable for calcination. Under these conditions, chloride levels were reduced by 91, 52, and 96% in washed residues of RFA, CaFA, and NaFA, respectively. Among the washed residues, the weight of the washed residue of NaFA decreased the most.     

Coagulant recovery from water treatment plant sludge and reuse in post-treatment of UASB reactor effluent treating municipal wastewater

In the present study, feasibility of recovering the coagulant from water treatment plant sludge with sulphuric acid and reusing it in post-treatment of upflow anaerobic sludge blanket (UASB) reactor effluent treating municipal wastewater were studied. The optimum conditions for coagulant recovery from water treatment plant sludge were investigated using response surface methodology (RSM). Sludge obtained from plants that use polyaluminium chloride (PACl) and alum coagulant was utilised for the study. Effect of three variables, pH, solid content and mixing time was studied using a Box–Behnken statistical experimental design. RSM model was developed based on the experimental aluminium recovery, and the response plots were developed. Results of the study showed significant effects of all the three variables and their interactions in the recovery process. The optimum aluminium recovery of 73.26 and 62.73 % from PACl sludge and alum sludge, respectively, was obtained at pH of 2.0, solid content of 0.5 % and mixing time of 30 min. The recovered coagulant solution had elevated concentrations of certain metals and chemical oxygen demand (COD) which raised concern about its reuse potential in water treatment. Hence, the coagulant recovered from PACl sludge was reused as coagulant for post-treatment of UASB reactor effluent treating municipal wastewater. The recovered coagulant gave 71 % COD, 80 % turbidity, 89 % phosphate, 77 % suspended solids and 99.5 % total coliform removal at 25 mg Al/L. Fresh PACl also gave similar performance but at higher dose of 40 mg Al/L. The results suggest that coagulant can be recovered from water treatment plant sludge and can be used to treat UASB reactor effluent treating municipal wastewater which can reduce the consumption of fresh coagulant in wastewater treatment.     

Enhanced stabilisation and methane potential of MSWs in a field-scale landfill with leachate recirculation

This study was carried out on two field scale test cells constructed at Odayeri Sanitary Landfill (OSL) located at the European side of Istanbul city. Approximately 11,000 tons of municipal solid wastes (MSW) were filled at equal quantities to each cell (C1 and C2). Leachate was periodically recirculated to one (C2) of the test cells in various quantities. These cells are compared in terms of leachate quality (pH, BOD and COD), methane potential (MP) of wastes and surface settlement for a monitoring period of 0–400 days. Experimental results showed that optimum pH for anaerobic decomposition was reached in a shorter period of time in C2 compared to C1. Moreover, BOD and COD concentrations were decreased more rapidly in C2 cell than in C1 cell. BOD/COD ratio was determined as 0.25 and 0.17 for C1 and C2 cells consequently after 380 days from placement of refuse to the test cells. In MP tests, first order rate constants for cell C1 and C2 were found be 0.145 year^-1 and 0.222 year^-1, respectively. Topographic measurements revealed that cumulative settlements after 12 months from refuse placement were 0.49 and 0.70 m for C1 and C2 cells, respectively. According to results obtained from this study, it can be concluded that appropriate conditions can cause enhance in the decomposition rate of MSW.