光催化还原法处理含cr（Ⅵ）废水的研究

采用自制TiO2作为光催化剂,利用光催化-混凝联合处理含Cr（Ⅵ）废水,研究了废水的pH值、催化剂用量、反应时间、有机物和混凝剂种类对含Cr（Ⅵ）废水中Cr（Ⅵ）去除率的影响。结果表明,在添加EDTA,pH值为1,紫外灯120min左右,二氧化钛加入量为0．4g,采用FeCl3和PAM作为混凝剂时,Cr（Ⅵ）的去除效率最好。     

酸催化氧化法处理含对苯二酚废水的方法

本文主要研究用硫酸作催化剂，30％过氧化氢作氧化剂，再经过pH值的调节和活性炭吸附，使对苯二酚化学需氧量值从3615mg／L降至260mg/L。化学需氧量的去除率高达93．3％。     

Oxidation of phenolic acid derivatives by soil and its relevance to allelopathic activity

Previous studies have suggested that phenolic acids from legume green manures may contribute to weed control through allelopathy. The objectives of this study were to investigate the oxidation reactions of phenolic acids in soil and to determine the subsequent effects of oxidation upon phytotoxicity. Soils were reacted for 18 h with 0.25 mmol L(-1) benzoic and cinnamic acid derivative solutions and Mn release from the suspension was used as a marker for phenolic acid oxidation. The extent of oxidation in soil suspensions was in the order of 3,4dihydroxy- > 4-hydroxy-3-methoxy- > 4-hydroxy-approximately 2-hydroxy-substituted benzoic and cinnamic acids. The same ranking was observed for cyclic voltammetry peak currents of the cinnamic acid derivatives. This suggests that the oxidation of phenolic acids is controlled by the electron transfer step from the sorbed phenolic acid to the metal oxide. A bioassay experiment showed that the 4-hydroxy-, 4-hydroxy-3-methoxy-, and 3,4-dihydroxy-substituted cinnamic acids were bioactive at 0.25 mmol L(-1) concentration. Reaction with soil for 18 h resulted in the elimination of bioactivity of these three cinnamic acids at the 5% significance level. The oxidative reactivity of phenolic acids may limit the potential of allelopathy as a component of an integrated weed management system. However, the initial phytotoxicity after soil incorporation may coincide with the early, critical stage of weed emergence and establishment, so that allelopathic phenolic acids may still play a role in weed management despite their reactivity in soil systems.     

Application of Solar Photocatalytic Treatment to Industrial Wastewater from a Chrome Plating Unit

The present study is targeted on the feasibility of photocatalytic treatment of industrial wastewater containing metal ions. Photoreductive deposition of metal ions using solar energy irradiated TiO₂, has been investigated in presence of citric acid as a hole scavenger. Treatment studies have also been performed at pH values 2, 4, 7, 8, and 10 to determine optimum reaction conditions. Results showed that at the pH value of 2, 100% reduction was achieved for Cr(VI) in a minimum time period. A maximum removal of 95.5% was achieved for Ni(II) at the pH value of 10.     

Immobilization of Pb(II), Cd(II) and Ni(II) ions on kaolinite and montmorillonite surfaces from aqueous medium

The present study investigates the immobilization of Pb(II), Cd(II) and Ni(II) on clays (kaolinite and montmorillonite) in aqueous medium through the process of adsorption under a set of variables (concentration of metal ion, amount of clay, pH, time and temperature of interaction). Increasing pH favours the removal of metal ions till they are precipitated as the insoluble hydroxides. The uptake is rapid with maximum adsorption being observed within 180 min for Pb(II) and Ni(II) and 240 min for Cd(II). A number of available models like the Lagergren pseudo first-order kinetics, second-order kinetics, Elovich equation, liquid film diffusion and intra-particle diffusion are utilized to evaluate the kinetics and the mechanism of the immobilization interactions. Two isotherm equations due to Langmuir and Freundlich showed good fits with the experimental data. Kaolinite and montmorillonite have considerable Langmuir monolayer capacity with respect to Pb(II), Cd(II) and Ni(II), the values being in the range of 6.8-11.5mg/g (kaolinite) and 21.1-31.1mg/g (montmorillonite). The Freundlich adsorption capacity follows a similar order. The thermodynamics of the immobilization process indicates the same to be exothermic with Pb(II) and Ni(II), but endothermic with Cd(II). The interactions with Pb(II) and Ni(II) are accompanied by decrease in entropy and Gibbs energy while the endothermic immobilization of Cd(II) is supported by an increase in entropy and an appreciable decrease in Gibbs energy. The results have established good potentiality for kaolinite and montmorillonite to remove heavy metals like Pb(II), Cd(II) and Ni(II) from aqueous medium through adsorption-mediated immobilization.     

Factors controlling sorption of prosulfuron by variable-charge soils and model sorbents

Prosulfuron [1-(4-methoxy-6-methyltriazin-2-yl)-3-[2-(3,3,3-trifluoropropyl) phenylsulfonyl]-urea), a relatively new sulfonylurea herbicide, is a weak acid (pK(a) 3.76), and therefore, will undergo pH-dependent speciation and sorption. Understanding prosulfuron sorption in soils is important for predicting its environmental fate. Soil and solution factors controlling sorption were investigated by measuring prosulfuron sorption on five model sorbents (amorphous silica, alpha-alumina, CaSWy1 montmorillonite, commercial humic acid, and anion exchange resin) and 10 variable-charge soils from CaCl(2) and Ca(H(2)PO(4))(2) solutions as a function of pH and ionic strength. Anion exchange of prosulfuron accounted for up to 82% of overall sorption in the pH range from 3 to 7. The relative importance of anion exchange to prosulfuron sorption was positively correlated to the ratio of anion and cation exchange capacities. Comparison between organic carbon (OC)-normalized sorption (K(oc)) versus pH for humic acid and variable-charge soils show similar trends with sorption decreasing with increasing pH. However, K(oc) values estimated from variable-charge soils in the lower pH range where anion exchange has the greatest contribution to sorption was almost one log unit greater than that estimated from humic acid clearly exemplifying the impact of anion exchange. Similarity in K(oc)-pH curves for humic acid and variable-charge soils may result from the fact that (i) cation exchange capacity increases with increasing OC content, thus effective anion exchange capacity is reduced; and (ii) the relative contribution of hydrophobic and hydrophilic sorption mechanisms was fairly constant. Given that both hydrophilic and hydrophobic sorption of prosulfuron decrease with increasing pH, addition of fertilizer and lime amendments may enhance the potential for off-site leaching of recently applied acidic pesticides.     

Electrocoagulation of vegetable oil refinery wastewater using aluminum electrodes

Electrocoagulation with aluminum electrodes was used to treat the vegetable oil refinery wastewater (VORW) in a batch reactor. The effects of operating parameters such as pH, current density, PAC (poly aluminum chloride) dosage and Na(2)SO(4) dosage on the removal of organics and COD removal efficiency have been investigated. It has been shown that the removal efficiency of COD increased with the increasing applied current density and increasing PAC and Na(2)SO(4) dosage and the most effective removal capacity was achieved at the pH 7. The results indicate that electrocoagulation is very efficient and able to achieve 98.9% COD removal in 90 min at 35 mAcm(-2) with a specific electrical energy consumption of 42 kWh(kgCOD(removed))(-1). The effluent was very clear and its quality exceeded the direct discharge standard.     

Removal of natural organic matter by cationic hydrogel with magnetic properties

Magnetic cationic hydrogel (MCH) was synthesized, and its removal efficiency and mechanisms in regard to natural organic matter (NOM, represented by humic acid and fulvic acid) from the aqueous environment were studied. The effects of time, adsorbent dosage, initial pH, ionic strength, background ions, and NOM types were also investigated. MCH was characterized and found to have a strong magnetic character, yielding an extra advantage for recycling and reuse. Batch studies showed that the removal of Aldrich humic acid (AHA) by MCH was effective. The main mechanism for the removal of NOM is believed to be due to electrostatic interaction. NOM with larger molecular weight tended to be preferentially removed. Solutions with low pH, high ionic strength, and background electrolytes containing calcium, sulfate and bicarbonate were unfavorable for AHA removal. The adsorption-desorption of MCH was evaluated in three cycles, and demonstrated high regeneration rates.     

Transport of cadmium and assessment of phytotoxicity after electrokinetic remediation

The use of ethylene diamine tetraacetic acid (EDTA) on the electrokinetic removal of cadmium-contaminated soil was evaluated. A total of four different tests were conducted using EDTA as a washing solution as well as a purging solution at the electrode compartments. The efficiency of electrokinetic extraction was significantly influenced by the pH of the soil medium. The results show that EDTA was effective in desorbing cadmium at a high pH, with Cd-EDTA(-) anion complexes migrating toward the anode. At low pH values near the anode area, cadmium existed as Cd(2+), migrating toward the cathode. Such contradicting directions of cadmium have resulted in its detrimental removal from the soil cell. However, accumulation of cadmium near the cathode was observed at the end of the tests due to the dominating low pH in the soil cell. The phytotoxicity after the electrokinetic process was investigated using Sorghum saccharatum, Lepidium sativum and Sinapis alba plants. The germination index was a major endpoint estimated by measuring seed germination and shoot elongation. The results obtained show that the phytotoxicity was increased after electrokinetic extraction. Despite, the extensive cadmium removal from two-thirds of the cell, the low pH of the soil was the principal parameter exhibiting the phytotoxicity.     

Removal of Fe(II) from the wastewater of a galvanized pipe manufacturing industry by adsorption onto bentonite clay

Bentonite clay has been used for the adsorption of Fe(II) from aqueous solutions over a concentration range of 80-200 mg/l, shaking time of 1-60 min, adsorbent dosage from 0.02 to 2 g and pH of 3. The process of uptake follows both the Langmuir and Freundlich isotherm models and also the first-order kinetics. The maximum removal (>98%) was observed at pH of 3 with initial concentration of 100 mg/l and 0.5 g of bentonite. The efficiency of Fe(II) removal was also tested using wastewater from a galvanized pipe manufacturing industry. More than 90% of Fe(II) can be effectively removed from the wastewater by using 2.0 g of the bentonite. The effect of cations (i.e. zinc, manganese, lead, cadmium, nickel, cobalt, chromium and copper) on the removal of Fe(II) was studied in the concentration range of 10-500 mg/l. All the added cations reduced the adsorption of Fe(II) at high concentrations except Zn. Column studies have also been carried out using a certain concentration of wastewater. More than 99% recovery has been achieved by using 5 g of the bentonite with 3M nitric acid solution.     

Ammonia stripping of biologically treated liquid manure

A prerequisite for efficient ammonia removal in air stripping is that the pH of the liquid to be stripped is sufficiently high. Swine manure pH is usually around 7. At pH 7 (at 20°C), only 0.4% of ammonium is in ammonia form, and it is necessary to raise the pH of swine slurry to achieve efficient ammonia removal. Because manure has a very high buffering capacity, large amounts of chemicals are needed to change the slurry pH. The present study showed that efficient air stripping of manure can be achieved with a small amount of chemicals and without strong bases like NaOH. Slurry was subjected to aerobic biological treatment to raise pH before stripping. This facilitated 8 to 32% ammonia removal without chemical treatment. The slurry was further subjected to repeated cycles of stripping with MgO and Ca(OH)(2) additions after the first and second strippings, respectively, to raise slurry pH in between the stripping cycles. After three consecutive stripping cycles, 59 to 86% of the original ammonium had been removed. It was shown that the reduction in buffer capacity of the slurry was due to ammonia and carbonate removal during the stripping cycles.     

Advanced oxidation treatment of pulp mill effluent for TOC and toxicity removals

Pulp mill effluent was treated by different advanced oxidation processes (AOPs) consisting of UV, UV/H2O2, TiO2-assisted photo-catalysis (UV/TiO2) and UV/H2O2/TiO2 in lab-scale reactors for total organic carbon (TOC) and toxicity removals. Effects of some operating parameters such as the initial pH, oxidant and catalyst concentrations on TOC and toxicity removals were investigated. Almost every method resulted in some degree of TOC and toxicity removal from the pulp mill effluent. However, the TiO2-assisted photo-catalysis (UV/TiO2) resulted in the highest TOC and toxicity removals under alkaline conditions when compared with the other AOPs tested. Approximately, 79.6% TOC and 94% toxicity removals were obtained by the TiO2-assisted photo-catalysis (UV/TiO2) with a titanium dioxide concentration of 0.75gl(-1) at pH 11 within 60min.     

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.     

不同酸对造纸黑液酸析效果的研究

采用酸析法从造纸黑液中分离木质素,同时去除部分COD和色度,从而完成对黑液的初步处理。实验研究了酸析的最佳pH值,并将硫酸、硝酸、盐酸、磷酸、甲酸和草酸作为酸析剂,分析其分别对黑液色度、COD的去除效果及对木质素提取的影响。介绍了通过快速消解分光光度法来测定COD值,和用分光光度法测定色度值,分别建立COD值和色度对吸光度的工作曲线,使测量更加方便高效快捷,其精确度和准确度都能符合分析方法要求。实验结果表明,酸析效果较好的pH取值范围为2～4,考虑用酸的经济性和处理效果,选择pH=3作为最佳酸析条件;经过对酸析过程规律和原因的分析可得,硫酸、硝酸和磷酸对黑液处理效果较为理想,其中硫酸因其经济性被选为最佳,其色度、COD去除率分别为97.9%和66.1%,木质素的析出量为8.65 g/L。     

Adsorption of phenol and its derivatives from water using synthetic resins and low-cost natural adsorbents: a review

In this article, the technical feasibility of the use of activated carbon, synthetic resins, and various low-cost natural adsorbents for the removal of phenol and its derivatives from contaminated water has been reviewed. Instead of using commercial activated carbon and synthetic resins, researchers have worked on inexpensive materials such as coal fly ash, sludge, biomass, zeolites, and other adsorbents, which have high adsorption capacity and are locally available. The comparison of their removal performance with that of activated carbon and synthetic resins is presented in this study. From our survey of about 100 papers, low-cost adsorbents have demonstrated outstanding removal capabilities for phenol and its derivatives compared to activated carbons. Adsorbents that stand out for high adsorption capacities are coal-reject, residual coal treated with H3PO4, dried activated sludge, red mud, and cetyltrimethylammonium bromide-modified montmorillonite. Of these synthetic resins, HiSiv 1000 and IRA-420 display high adsorption capacity of phenol and XAD-4 has good adsorption capability for 2-nitrophenol. These polymeric adsorbents are suitable for industrial effluents containing phenol and its derivatives as mentioned previously. It should be noted that the adsorption capacities of the adsorbents presented here vary significantly depending on the characteristics of the individual adsorbent, the extent of chemical modifications, and the concentrations of solutes.     

Phenol removal from aqueous environments by natural & chemically modified kaolin clay

Natural, acid and base modified kaolin clays were studied for the sake of phenol and 4-chlorophenol removal from aqueous environments and their application to real ground and industrial wastewater samples. Scanning electron microscope (SEM), infrared spectroscopy (IR), X-ray diffraction (XRD), Thermo Gravimetric Analysis (TGA), Differential Thermal Analysis (DTA), and Surface area analysis were employed for characterization of the adsorbents microstructure. Operating factors such as adsorbent dose, solution pH, initial phenol concentration, and contact time were studied. The experimental data displayed that the increase of the adsorbent dose, contact time, and pH value from 2 to 7 increases the efficiency of the removal process. Optimal conditions for phenolic removal were; contact time of 300 min, primary phenol solution of 25 mg/L, pH 7 and 2.5 g/L as an appropriate adsorbent dose using crude (natural), acid modified and base modified kaolin clays. The higher phenolic removal efficiencies were obtained at 5 mg/L as 90, 97, 96.2%, respectively, for the adsorbents in the previously mentioned order. The adsorption capacity in the removal of phenol and 4-chlorophenol were 7.481 and 4.195, 8.2942 and 3.211, and 8.05185 and 18.565 mg/g, respectively, for the adsorbents in the same mentioned order. The adsorption equilibrium data were fitted and analyzed with four isotherm models, namely, Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich isotherm equations. The adsorption process of phenol on studied adsorbents was exothermic, spontaneous and thermodynamically favorable proved by the negative values of their thermodynamic parameters ΔH° and ΔG°. The correlation coefficient (R²) for all concentrations was higher than 0.94, which indicates that in the studied system, the data suitably fit the first-order kinetics. The % desorption capacity was amounted to 96%, 91.11%, and 87.06% of adsorbed phenol, respectively, for the adsorbents in the previous order using 0.1N NaOH and 10% V/V ethanol solutions as eluents at 25°C, indicating the reusability of the adsorbents. Kaolin and its modified forms can be introduced as eco-friendly and low-cost adsorbents in water remediation implementation.     

Optimization of biodiesel production from waste cooking oil using ion-exchange resins

Waste cooking oil is a potential substitution of refined vegetable oil for the production of biodiesel due to the low cost of raw material and for solving their disposal problem. In this study, optimization of esterification process of free fatty acids in artificially acidified soybean oil with oleic acid has been carried out using methanol as an agent and ion exchange resin as a heterogeneous catalyst. The esterification reaction has been investigated based on the mass balance of the developed model. The model has been validated against experimental data and effects of temperature and catalyst weight have been analyzed. Thereafter, optimization process has been fulfilled for two different objective functions as conversion of acid oil and benefit. Optimization results indicated that the maximum conversion of acid is 95.95%, which is achievable at 4.48-g catalyst loading and reaction temperature of 120°C. Maximum benefit was obtained as US$0.057 per batch of reaction at a catalyst amount of 1 g and temperature of 120°C.     

The application of bioflocculant for the removal of humic acids from stabilized landfill leachates

The evaluation of bioflocculant, in comparison with traditional inorganic coagulants, for the removal of humic acids from landfill leachates stabilized by biological treatment, was performed using conventional jar-test coagulation experiments. The optimized conditions (pH and coagulant dosage) were identified for the treatment of synthetic solutions as well as for biologically pre-treated landfill leachates. It was found that the application of bioflocculant was quite efficient in the removal of humic acids from synthetic solutions as well as in the reduction of COD content from real landfill leachates. The optimal pH value was found to be between 7 and 7.5, while a 20 mg/l bioflocculant dosage was sufficient in providing more than 85% humic acid removal. The results were comparable with those obtained by the application of conventional coagulants such as alum or polyaluminum chloride; therefore, bioflocculant can be considered as a viable alternative in the treatment of landfill leachates applying coagulation.     

Color removal from dye-containing wastewater by magnesium chloride

Color removal by MgCl(2) when treating synthetic waste containing pure dyes was studied. The color removal efficiency of MgCl(2)/Ca(OH)(2) was compared with that of Al(2)(SO(4))(3), polyaluminum chloride (PAC) and FeSO(4)/Ca(OH)(2). The mechanism of color removal by MgCl(2) was also investigated. The experimental results show that the color removal efficiency of MgCl(2) is related to the type of dye and depends on the pH of the waste and the dosage of the coagulants used. Treatment of waste containing reactive dye or dispersed dye with MgCl(2) yielded an optimum color removal ratio when the pH of the solution was equal to or above 12.0. For both the reactive and dispersed dye waste, MgCl(2)/Ca(OH)(2) was shown to be superior to MgCl(2)/NaOH, Al(2)(SO(4))(3), PAC and FeSO(4)/Ca(OH)(2) for color removal. A magnesium hydroxide precipitate formed at pH values greater than 12.0, which provided a large adsorptive surface area and a positive electrostatic surface charge, enabling it to remove the dyes through charge neutralization and an adsorptive coagulating mechanism. So, the MgCl(2)/Ca(OH)(2) system is a viable alternative to some of the more conventional forms of chemical treatment, especially for treating actual textile waste with high natural pH.     

Removing color and chlorinated organics from pulp mill bleach plant effluents by use of flyash

Color and chemical oxygen demand (COD) in bleach plant effluents are of concern. Acidified flyash can effectively remove both color and COD from caustic bleach plant effluents. Equally effective, but quicker and easier, is to acidify the effluent to approximately pH 1 and use untreated flyash. Based on maximum color removal, the required contact time is short, about 10 min, and the optimum ash dosage is that amount which raises the pH of the final effluent to about 5. Sufficient color removal is obtained to easily meet Maine's color regulations. Preliminary tests on samples of deionized water spiked with two arochlors of PCB showed high removal efficiency.The major cost of implementing and operating the cleanup procedure will be the cost of the required acid. This might be minimized by using some of the acidic (chlorine) effluent to lower the pH of the caustic effluent. This will, however, lead to less color reduction, and an unknown effect on the COD.