混凝沉淀法处理含砷选矿废水

某钨矿含砷选矿废水砷含量高且砷以As(V)为主要存在形态,采用混凝沉淀法处理,详细考察了生石灰、硫酸亚铁和六水三氯化铁3种混凝剂对废水中砷的去除效果。实验结果表明,在PAM投加量40 mg/L,静沉时间60 min条件下,比较分析3种混凝剂对砷的去除效果,三氯化铁为最佳除砷混凝剂。三氯化铁最佳除砷工艺条件为:pH 7.5,三氯化铁投加量986.67 mg/L,混凝反应时间25 min,PAM投加量为40 mg/L,静沉60 min,含砷选矿废水经该工艺处理后,砷去除率可达99.14%,出水砷浓度降至0.361 mg/L,达到国家污水综合排放标准(GB8978-1996)。     

低浓度含砷污酸处理工艺的比较研究

比较研究了石灰中和法和石灰-铁盐法对硫化后含低浓度砷(20～50 mg/L)污酸的处理效果。结果表明,单纯采用石灰法,废水难以达标排放;而两段石灰-铁盐(氯化铁)法满足达标排放的同时,一段及二段沉淀物的浸出液中砷、镉、铜、铅和锌含量均低于危险废物鉴别标准要求(GB 5085.3-2007);其最优工艺参数为一段终了pH=2,反应时间为2 h,二段终了pH=8、Fe/As=8、反应时间为60 min、氧化剂投加量(Ca(ClO)2/As)为6∶1;正交实验结果中各参数对铁盐除砷效果影响顺序为终了pH>反应时间>Fe/As>氧化剂投加量。     

强酸性高浓度含砷废水处理方法与经济性评价

研究了硫化物沉淀和中和沉淀工艺对强酸性体系下As(Ⅲ)和As(Ⅴ)处理效果,考察了沉淀剂种类与投量、酸度(或平衡pH)等因素对除砷效果的影响,结合共沉淀产物的元素组成与价态分析探讨了2种工艺的除砷机理。研究表明,硫化物沉淀对As(Ⅲ)去除效果优于As(Ⅴ),且As(Ⅴ)去除过程中存在As(Ⅴ)转化为As(Ⅲ)的还原过程;中和沉淀对As(Ⅲ)和As(Ⅴ)去除率均可达到98%以上,但不存在砷形态转化过程。进一步以云南某硫精制酸化工厂实际含砷废水为对象,研究了硫化物沉淀(以Na2S为硫源)、中和共沉淀(Fe(Ⅲ)-Ca(OH)2,Fe(Ⅲ)-NaOH,单独Ca(OH)2和Ca(OH)2-Fe(Ⅱ)等)除砷效果和处理成本,发现上述几种工艺砷去除率均可达到99.0%左右;Na2S共沉淀法处理成本最高,单独Ca(OH)2成本最低但废渣产生量大;Ca(OH)2-Fe(Ⅱ)可在不大幅提高成本的基础上确保处理效果并降低废渣产生量。在工程中应综合原水水质特点、处理水质目标、可接受的处理成本以及含砷废渣处置要求等,确定最佳的处理技术方案。     

天然锰砂去除水中的砷

天然锰砂是一种廉价、高效的水处理用材料,但尚未用于水中砷的去除。实验研究了反应时间、砷形态、初始砷浓度、温度、溶液初始pH对吸附过程的影响。结果表明,天然锰砂对As(Ⅲ)的吸附能力大于As(Ⅴ)。25℃时,固液比为10 g/L的条件下,天然锰砂对初始浓度为5.0 mg/L的砷溶液吸附过程经72 h基本达到平衡,平衡时对As(Ⅲ)和As(Ⅴ)的去除率分别达到94.5%和85.9%。吸附过程符合Lagergren准一级反应动力学模型和假二级反应动力学模型。相比之下,假二级动力学模型拟合程度更高。对As(Ⅲ)和As(Ⅴ),45℃时的吸附量均大于25℃时。不同温度下,天然锰砂对As(Ⅲ)和As(Ⅴ)的吸附过程更符合Freundlich等温吸附模型。在溶液初始pH为3～10范围内,锰砂对砷的吸附能力受pH的影响较小。实验结果表明,天然锰砂是一种具有实际应用潜力的除砷材料。     

炼钢废气除尘污水处理的研究

系统地研究了影响石灰中和法处理转炉除尘废水含铜沉降速度的因素.结果表明,在搅拌时间10 min和中等搅拌强度的条件下,pH值控制在8.2～9.0范围内能使废水中铜含量在1 h的沉降时间内降至国家排放标准2 mg/L以下.实验还研究了在石灰中和过程中加入适量絮凝剂的影响因素.结果表明,在搅拌时间3 min和相同pH值范围的条件下,加入絮凝剂能使废水中铜含量在30 min的沉降时间内降至国家排放标准2 mg/L以下.     

炼钢废气除尘污水处理的研究

系统地研究了影响石灰中和法处理转炉除尘废水含铜沉降速度的因素.结果表明,在搅拌时间10 min和中等搅拌强度的条件下,pH值控制在8.2～9.0范围内能使废水中铜含量在1 h的沉降时间内降至国家排放标准2 mg/L以下.实验还研究了在石灰中和过程中加入适量絮凝剂的影响因素.结果表明,在搅拌时间3 min和相同pH值范围的条件下,加入絮凝剂能使废水中铜含量在30 min的沉降时间内降至国家排放标准2 mg/L以下.     

氧化-混凝法处理碱性高砷废水的实验研究

对碱性高砷废水的处理进行了研究 ,针对常规混凝法除砷的缺点提出了氧化 混凝工艺。结果表明 ,用氧化 混凝工艺除砷效果显著 ,废水经处理后砷含量低于 0 5mg/L ,符合国家排放标准。氧化 混凝除砷的最佳工艺条件为 :pH值为 6— 7,H2 O2 用量为 2 5 % ,氧化时间为 10min ,Fe2 (SO4) 3 用量为 2 5g/L ,PAM用量为 11 2 5mg/L。     

氧化-混凝法处理碱性高砷废型的实验研究

对碱性高砷废水的处理进行了研究，针对常规混凝法除砷的缺点提出了氧化一混凝工艺。结果表明，用氧化混凝土工艺除砷效果显著，废水经处理后砷含量低于0.5mg/L,符合国家排放标准，氧化-混凝除砷的最佳工艺条件为：pH值为6-7，H2O2用量为2.5%,氧化时间为10min,Fe2(SO4)3用量为2.5g/L,PAM用量为11.25mg/L。     

应用钙法除磷-碱解-微电解组合工艺预处理吡虫啉农药废水

根据吡虫啉农药废水成分复杂,含有大量有毒有害物质的特点,在小试实验研究的基础上,确定了预处理的组合工艺流程为：钙法除磷-碱解-催化微电解。实验结果表明,预处理的适宜参数为：钙法除磷的pH值11,搅拌速度为100 r/min,钙的投加量为理论计算值的1.4倍;碱解反应的温度70℃,pH值11,反应时间2 h;催化微电解反应的pH值3～4,曝气时间3 h,催化剂与铸铁屑的质量比1∶5。组合工艺对COD、色度、磷的总去除率分别达到81%、90%和99.99%,废水的可生化性能得到很大改善。组合工艺不仅适用于预处理高浓度吡虫啉农药废水,也能为其他高浓度、难生物降解农药废水的治理提供有益的参考。     

磁性纳米吸附剂Fe3O4·ZrO(OH)2的合成及对水中氟和砷的吸附性能

用共沉淀法将ZrOCl2·8H2O包裹在磁性纳米Fe3O4表面,合成了一种针对高浓度含砷含氟废水的高效新型磁性纳米吸附剂Fe3O4·ZrO(OH)2.研究考察了吸附剂对氟和砷的吸附容量、反应平衡时间以及pH对吸附效果的影响.实验表明,磁性纳米Fe3O4·ZrO(OH)2吸附剂对水中F-和As(Ⅲ/Ⅴ)等温吸附模型符合Langmuir和Freundlich模型.对溶液中总氟和总砷的吸附容量分别可达70.42 mg/g和133.33 mg/g.通过拟二级动力学方程可得知吸附过程在20 min左右即可达到平衡.随着pH的不断增加,吸附剂对氟的吸附容量逐渐降低,而对砷的吸附量则是先增加后减少.     

Iron oxide-loaded slag for arsenic removal from aqueous system

An effective adsorbent for arsenic removal from aqueous system was synthesized by loading iron(III) oxide on municipal solid waste incinerator melted slag. The loading was accomplished via chemical processes and thermal coating technique. The key point of the technique was the simultaneous generation of amorphous FeOOH sol and silica sol in-situ and eventually led to the formation of Fe-Si surface complexes which combined the iron oxide with the melted slag tightly. The surface morphology of the iron oxide-loaded slag was examined and the loading mechanisms were discussed in detail. The adsorbent was effective for both arsenate and arsenite removal and its removal capabilities for As(V) and As(III) were 2.5 and 3 times of those of FeOOH, respectively. Both affinity adsorption and chemical reactions contributed to arsenic removal. The effects of solution pH, contact time, arsenic concentration and adsorbent dosage on arsenic removal were examined and the optimum removal conditions were established. Furthermore, leaching of hazardous elements such as Cr(VI), As, Se, Cd and Pb from the adsorbent at a pH range of 2.5-12.5 was below the regulation values. Accordingly, it is believed that the iron oxide-loaded slag developed in this study is environmentally acceptable and industrially applicable for wastewater treatment.     

碳酸根对磷酸钙沉淀反应回收磷的影响

以模拟的厌氧消化液为处理对象,通过小试实验,考察不同初始磷浓度Cp、Ca／P物质的量比、pH和温度下,碳酸根（CO3 2-）对磷酸钙沉淀反应回收磷的影响;利用扫描电镜（SEM）、x射线衍射仪（XRD）和傅里叶变换红外光谱（FT．IR）对沉淀产物进行表征。结果表明,高浓度的CO3 2-对以磷酸钙沉淀反应去除和回收磷的效率影响较大;Cp相同时,CO3 2-浓度（CCO3^2-）越大,P的去除率越低,低C,（20mg／L）时尤为显著;当CCO3^2-相同时,随着Cp的增大,反应速率加快,P的去除率逐渐升高,但升高幅度越来越小;增大Ca／P比和pH能提高P的去除率,降低CO3 2-对磷酸钙沉淀反应的抑制作用,综合考虑实际效果,应选择Ca／P比为3．33,pH为9．0作为适宜的反应条件;升高温度对降低CO3 2-对磷酸钙沉淀反应的抑制作用贡献不大。在Cp为60ITIg／L,Ca／P比为1．67,pH为9．0,温度为20℃的条件下,当CCO3^2-为0时,得到的沉淀产物主要为羟基磷灰石HAP;当CCO3^2-为30mmol／L时,得到的沉淀产物为磷酸钙和碳酸合磷灰石的混合物。     

Arsenic removal from water employing heterogeneous photocatalysis with TiO2 immobilized in PET bottles

Arsenic oxidation (As(III) to As(V)) and As(V) removal from water were assessed by using TiO₂ immobilized in PET (polyethylene terephthalate) bottles in the presence of natural sunlight and iron salts. The effect of many parameters was sequentially studied: TiO₂ concentration of the coating solution, Fe(II) concentration, pH, solar irradiation time; dissolved organic carbon concentration. The final conditions (TiO₂ concentration of the coating solution: 10%; Fe(II): 7.0 mg l⁻¹; solar exposure time: 120 min) were applied to natural water samples spiked with 500 μg l⁻¹ As(III) in order to verify the influence of natural water matrix. After treatment, As(III) and total As concentrations were lower than the limit of quantitation (2 μg l⁻¹) of the voltammetric method used, showing a removal over 99%, and giving evidence that As(III) was effectively oxidized to As(V). The results obtained demonstrated that TiO₂ can be easily immobilized on a PET surface in order to perform As(III) oxidation in water and that this TiO₂ immobilization, combined with coprecipitation of arsenic on Fe(III) hydroxides(oxides) could be an efficient way for inorganic arsenic removal from groundwaters.     

Enhanced removal of arsenic from a highly laden industrial effluent using a combined coprecipitation/nano-adsorption process

Effective arsenic removal from highly laden industrial wastewater is an important but challenging task. Here, a combined coprecipitation/nano-adsorption process, with ferric chloride and calcium chloride as coprecipitation agents and polymer-based nanocomposite as selective adsorbent, has been validated for arsenic removal from tungsten-smelting wastewater. On the basis of operating optimization, a binary FeCl₃ (520 mg/L)–CaCl₂ (300 mg/L) coprecipitation agent could remove more than 93 % arsenic from the wastewater. The resulting precipitate has proved environmental safety based on leaching toxicity test. Fixed-bed column packed with zirconium or ferric-oxide-loaded nanocomposite was employed for further elimination of arsenic in coprecipitated effluent, resulting in a significant decrease of arsenic (from 0.96 to less than 0.5 mg/L). The working capacity of zirconium-loaded nanocomposite was 220 bed volumes per run, much higher than that of ferric-loaded nanocomposite (40 bed volumes per run). The exhausted zirconium-loaded nanocomposite could be efficiently in situ regenerated with a binary NaOH–NaCl solution for reuse without any significant capacity loss. The results validated the combinational coprecipitation/nano-adsorption process to be a potential alternative for effective arsenic removal from highly laden industrial effluent.     

聚硅基复合氯化铁絮凝剂的制备及其在采油废水处理中的应用

采用硅酸钠制备聚硅酸,探讨了活化pH、活化剂、硅酸钠浓度(以SiO_2质量分数计)及聚合温度等因素对聚硅酸稳定性的影响.利用聚硅酸及氯化铁制备聚硅基复合氯化铁(PSiF),并通过正交试验分析了活化pH、Si/Fe(摩尔比)、OH/Fe(摩尔比)、制备时间对PSiF絮凝性能的影响.综合考虑絮凝性能、稳定性以及经济性等因素,确定PSiF适宜的制备条件为SiO_2质量分数2%～3%;活化pH为2～3;Si/Fe为0.50～0.75;OH/Fe为0.50～0.75;制备时间为0.5 h;聚合温度低于25℃.对比PSiF、PAC、FeCl_3对采油废水的处理效果,PSiF除浊、除COD效果以及经济性最好,是一种应用前景广阔的新型絮凝剂.     

复合赤泥在高浓度含磷废水处理中的应用

赤泥与石灰粉（CaO和Ca（OH）₂）按不同比例混合制成复合赤泥,通过投加实验考察了复合赤泥的除磷效果。结果证明,对于磷酸盐浓度为45 000 mg/L左右（以P计）的酸性工业废水,复合赤泥（赤泥与Ca（OH）₂按质量比1：1混合）投加量为240 g/L,去除率为99.97%;对于10 mg/L左右的含磷废水,赤泥的最佳投加浓度为15 g/L,上清液磷浓度可降至0.30 mg/L,出水低于0.5 mg/L的排放标准。根据以上研究结果,提出了对高浓度酸性磷酸盐废水的处理宜采用复合赤泥再加原状赤泥的二级处理方法。     

Effects of solution conditions on the precipitation of phosphate for recovery. A thermodynamic evaluation

To understand the effects of solution conditions on the precipitation of calcium phosphates from wastewater for recovery, a computer programme PHREEQC was employed to calculate the speciation and saturation-index (SI) with respect to hydroxyapatite of a chemically defined precipitation system, which contains phosphate of 1–200 mg P/l, with Ca/P molar ratios of one to 10 times of the stoichiometric calcium to phosphorus molar ratio of hydroxyapatite, at a pH range of 7.0–11.0. The results show that the SI is respectively the logarithmic function of the phosphate concentration and the calcium concentration, increasing with the increase of either of them; the SI is a polynomial function of the solution pH value and increases with its increase, and the effect of solution pH value is due to its influence on base uptake of the precipitation reaction and the speciation of phosphate and calcium ions; the SI is also a logarithmic function of the solution ionic strength but decreases with its increase; at the temperature range of 5–30 °C the SI increases linearly with solution temperature and the effect of temperature is also due to its influence on the speciation of phosphate and calcium ions.     

Calcium-enhanced ferric hydroxide co-precipitation of arsenic in the presence of silicate.

This study focuses on the effectiveness of calcium (Ca2+) improving ferric (hydro)oxides precipitation and its subsequent effects on arsenic co-precipitation with ferric (hydro)oxides. The effects of Ca2+ on surface charge characteristics and precipitating behavior, which are respectively represented as zeta (zeta) potential and R(PDA), are investigated for ferric (hydro)oxides precipitates. The presence of Ca2+ increases the potential of ferric (hydro)oxides, and a more significant effect is observed at higher pH conditions. Calcium apparently facilitates ferric (hydro)oxide floc aggregation, increasing the maximum R(PDA) from 3.19 to 5.27% (in the presence of 3.5 mg/L silicate as silicon). These positive effects contribute to reduce the adverse effects resulting from the presence of silicate and enhance arsenic removal via ferric (hydro)oxides co-precipitation under different conditions. Furthermore, the effect of Ca2+ facilitating ferric precipitation (and therefore providing more precipitated solids for arsenic) is predominant in favoring arsenic removal compared with that of increasing surface charge. Calcium plays an important role in arsenic co-precipitation with ferric (hydro)oxides in the presence of silicate.