响应面法优化空气氛围下制备S-nZVI对水中Cr(Ⅵ)的去除

在空气氛围下制备硫化纳米零价铁(S-nZVI),通过SEM、XRD等进行表征,并对其去除水中Cr(VI)进行研究。以Cr(VI)去除率为响应值建立了4因素5水平的响应面模型。SEM和XRD结果显示S-nZVI具有片状结构,主要成分为Fe~0并含有少量的FeS和铁氧化物。响应面法分析结果表明模型可信度高,适用于模拟4种因素对S-nZVI去除Cr(VI)的影响。以伪一级、伪二级动力学模型拟合S-nZVI去除Cr(VI),结果显示伪二级动力学模型R~2为0.999,拟合度更好,说明S-nZVI对Cr(VI)的去除主要以化学吸附为主,平衡吸附量达到156.3 mg/g。     

硫化纳米零价铁去除水中三氯乙烯的研究

通过硫化对纳米零价铁 (nZVI) 进行改性, 制备了硫化纳米零价铁 (S-nZVI), 而后对三氯乙烯 (TCE) 进行降 解实验研究。利用 SEM、XRD 对 S-nZVI 进行材料的结构表征, 进而研究不同材料、不同 S/Fe 摩尔比、不同初始 TCE 浓度、不同初始 pH 条件下, S-nZVI 对 TCE 的降解效果。结果表明, S-nZVI 主要成分为 Fe⁰ 并含有少量的 FeS, 制得的 S-nZVI 为球状结构, 表面有片层状的 FeS 生成；当 S/Fe 摩尔比为 0.6, 初始浓度为 20 mg/L 时, TCE 的降解 率为 87.2%, 远高于 nZVI (降解率为 56.4%)。经动力学分析后, S-nZVI 去除 TCE 符合伪二级动力学过程, 表明其降 解过程以化学还原为主。nZVI 经过硫化后提高了材料的电子选择性, 使其成为修复受污染土壤和地下水的有前途 的功能材料。     

烟末对铀(Ⅵ)的吸附性能

以卷烟生产过程中产生的烟末为原料,进行静态实验,观察烟末用量、溶液的pH、吸附时间、初始浓度及温度等因素对烟末吸附U （Ⅵ）的影响,采用傅里叶变换红外光谱（FTIR）、扫描电子显微镜（SEM）、X射线能谱分析（EDS）对烟末进行表征,并探讨其吸附U （Ⅵ）的机理。结果表明：当温度30℃、烟末用量为4 g/L、溶液pH=5、U （Ⅵ）浓度为25 mg/L、吸附时间为100 min时,烟末吸附U （Ⅵ）成效最佳。吸附过程较好的拟合了准二级动力学模型（R²≈1）和Langmuir等温模型（R²≈1）。扫描电镜、X-射线衍射、红外光谱等结果表明,烟末对U （Ⅵ）有很好的吸附性能,其吸附U （Ⅵ）前后使表面形态发生变化,而与U （Ⅵ）互相作用的基团主要是羟基、羧基。     

改性钢渣的制备及其吸附除磷性能

研究了改性钢渣吸附除磷影响因素、等温吸附线特征和吸附动力学,并对生物处理后的出水进行吸附除磷研究。结果表明：在初始磷浓度10 mg/L,投加量10 g/L、pH为7时,改性钢渣吸附后总磷浓度为0.687 mg/L,去除率达93%;改性钢渣对磷的吸附符合Langmuir模型,理论饱和吸附量是1.977 mg/g,吸附动力学符合准二级动力学模型（R²>0.99）;实际生活污水的吸附除磷中,投加量为50 g/L,反应2 h后出水总磷浓度达到《城镇污水处理厂污染物排放标准》（GB 18918-2002）一级B标的排放要求。     

柚子皮对水中六价铬的吸附性能研究

采用柚子皮制备生物吸附剂用于去除水中的Cr（VI）,考察了pH值、柚子皮投加量、柚子皮粒径、溶液离子强度、反应温度等因素对吸附效果的影响。结果表明,当溶液中Cr（VI）离子初始浓度15mg／L、pH 1．5、反应温度25℃、柚子皮投加量1．Og／100mL、吸附时间7h时,Cr（VI）离子去除率可达90％以上。柚于皮对Or（VI）离子的吸附过程可以用Langmuir和Freundlich吸附等温模型来描述,吸附等温线线性相关性均较显著,吸附过程符合准二级动力学方程。柚子皮对水中Cr（VI）离子吸附性能较好,且运行成本低,可推广应用于水中重金属离子的治理。     

稻秆生物炭负载Fe/Ca对化粪池中磷的吸附特性

实现磷资源的高效回收和农业废弃物的资源化利用具有重要意义。采用氯化铁、硫酸铁、氯化钙对水稻秸秆生物炭（RSB）进行改性,得到3种改性稻秆生物炭（PRSB-Fe、PRSB-FS和PRSB-Ca）,采用SEM、XPS、FTIR和BET对其进行表征,并通过批量实验探究其对模拟废水和化粪池粪污分离液中磷酸盐的吸附特性。模拟废水实验结果表明：伪二级动力学方程能更好地描述改性生物炭对磷的吸附过程（R²>0.99）,吸附机制以化学吸附为主,吸附等温线均更符合Freundlich方程（20 ℃）,表明多层吸附可能起主导作用。共存的Cl^-基本不会影响3种改性生物炭对磷的吸附效果;对于初始磷浓度为（12.94±1.51） mg/g、pH值为7.4±0.2的化粪池粪污分离液,PRSB-Fe-5、PRSB-FS-5和PRSB-Ca-5对磷的吸附量分别是10.77、23.35、0.85 mg/g,其中PRSB-FS-5对磷的吸附效果最好,去除率高达97.31%,剩余磷浓度仅有0.37 mg/L,达到《城镇污水处理厂污染物排放标准》（GB 18918—2002）一级A标准。     

零价铁/阳离子表面活性剂/生物炭对水体Cr(VI)的吸附研究

以常见柳条为生物炭原料,通过十六烷基三甲基氯化铵（CTMAC）进行阳离子表面活化,与零价铁、海藻酸钠混合制备了零价铁/阳离子表面活性剂/生物炭（Fe⁰?MBC）凝胶微球,探讨了其对水体Cr（VI）的吸附能力。借助XRF、FTIR、XRD以及Zeta电位等分析手段,对Fe⁰?MBC凝胶微球的结构与性能进行研究。通过分析反应时间、环境温度及pH对吸附的影响,在吸附动力学、等温线模型的基础上,初步探讨了吸附机制。通过吸附?解析循环实验,研究了Fe⁰?MBC凝胶微球的再生性能。结果表明,Fe⁰?MBC凝胶微球对Cr(VI)的吸附与准一级动力学和Langmuir等温吸附模型拟合度较高;Cr初始质量浓度100 mg/L、负载质量分数分别为5%和10%的零价铁的CTMAC活化生物炭对Cr（VI）的去除率在2 h时分别为89%、97%,最大饱和吸附量分别为33.777 9、42.562 0 mg/g;Fe⁰?MBC凝胶微球作为一种成本低、效率高的环境功能材料,对去除废水中的Cr(VI)具有良好的应用前景。     

Fe/Cu双金属可渗透反应墙体系对Cr(VI)的去除研究

基于零价铁可渗透反应墙技术,采用化学沉积法制备了Fe/Cu双金属颗粒材料,对Fe/Cu材料进行表征,发现其表观非均匀,化学组成为Cu涂覆在铁颗粒表面;通过静态试验系统地考察了反应温度、溶液pH值、平均流速、等温吸附、双金属材料与河砂的配比等条件对Cr（Ⅵ）去除效果的影响,同时调节进水流速,实现了动态试验的模拟。Cr（Ⅵ）去除的静态试验表明,当mFe：mCu=10：2、投加量40 mg/mL、Cr（Ⅵ）初始浓度50 mg/L、pH=7.5、反应温度298 K时,对水中Cr（Ⅵ）的去除效果最佳,在反应15 min左右时,对Cr（Ⅵ）去除率高达99.4%;动态试验表明,快流速组（104 mL/h）的Cr（Ⅵ）的平均吸附量为0.869 mg/g,慢流速组（28 mL/h）的Cr（Ⅵ）平均吸附量为0.920 mg/g,慢流速组的总吸附量较高。采用Langmuir和Freundlich模型拟合表明,该吸附反应属于单层吸附过程,且升温有利于该吸附反应的进行。实现了Fe/Cu双金属颗粒材料的制备,并对Cr（Ⅵ）有很好的去除效果,结合PRB技术,有望实现地下水等水体中Cr（Ⅵ）的有效去除。     

水热辅助溶胶凝胶法制备纳米钛酸锌及其光催化性能

采用水热辅助的溶胶凝胶法制备纳米钛酸锌（ZnTiO₃）光催化剂,以罗丹明B为目标降解物,运用动力学模型分析罗丹明B（RhB）初始浓度对降解效果的影响。通过SEM、XRD、XPS、UV-Vis DRS对ZnTiO₃进行表征,并使用自由基捕获试验分析其降解机理。结果表明,ZnTiO₃为纯六方相,形貌为类球形,粒径50 nm左右。在催化剂用量为1 g/L、RhB初始浓度为5 mg/L、pH值为3的条件下,光催化反应150 min后,RhB降解率为93.2%。其动力学方程为k=0.132C₀^-1.253。ZnTiO₃光催化剂降解过程中,·OH、h⁺、·O₂^-均起到催化作用,产生·OH、h⁺的量相近且多于·O₂^-,说明·OH、h⁺在催化反应中起主要作用。     

泥煤对铬（VI）吸附动力学研究

对泥煤吸附Cr（VI）的动力学过程进行了研究。结果表明,pH值和初始Cr（VI）质量浓度对Cr（VI）的吸附率有明显的影响,pH值越小,泥煤表面正电性越高,Cr（VI）吸附率越高;初始Cr（VI）质量浓度越小,Cr（VI）吸附率越高;初始Cr（VI）质量浓度位于10～20mg／L,新型L—F动力学模型能很好地描述泥煤吸附过程;新型L—F动力学方程直线化截距导出的参数Go／（Go—Ce）可以反映吸附剂的吸附强弱,“多化一”法推出了Cr（VI）初始浓度与吸附常数k拟合函数关系。     

Removal of anionic ions from single material solution by bauxite tailings modified with FeCl3·6H2O

The adsorbabilities of the unmodified and modified bauxite tailings for Cr（Ⅵ）, As（Ⅴ） and F（Ⅰ） ions were investigated. Batch experiments were carried out to determine the removal rate as a function of adsorbent dosage, solution pH value and shaking time. The results show that the maximum removal rates of Cr（Ⅵ）, As（Ⅴ） and F（Ⅰ ） are respectively 99%, 99% and 90% by using the modified bauxite tailings. The isoelectric point of the unmodified bauxite tailings is 3.6, and that of the modified bauxite tailings is 5.0, which shifts to lower pH values in Cr（Ⅵ） solution. This indicates a specific adsorption of the anionic species on the modified bauxite railings. A new band of Cr2O72 appears in the FTIR, showing that Cr（Ⅵ） is adsorbed on the modified bauxite railings in the form of chemistry adsorption. The adsorption data of Cr（Ⅵ） on the modified bauxite tailings are well described by Freundlich model. The investigations of kinetic models show that pseudo-second-order kinetic model provides the best correlation for the experimental data.     

Removal of Cr（Ⅲ） and Cr（Ⅵ） from aqueous solution by adsorption on sugarcane pulp residue

Sugarcane pulp residue (SPR), a waste from sugar-refinery, which possesses a large surface area, can be used for removing chromium (Cr(III) and Cr(VI)) from wastewater. In this work, the kinetics, isotherms of Cr(III) and Cr(VI) adsorption and their removal by SPR were investigated. The results show that the removal percentages of Cr(VI) and Cr(III) increase with increasing SPR dosage and temperature and decrease with increasing SPR particle size and the initial concentration of chromium ions. However, the influence of pH value on the Cr(VI) removal differs from that of the Cr(III) removal. The Cr(VI) removal percentage decreases with increasing pH values, while the Cr(III) removal percentage increases with increasing pH value. The adsorption kinetics of Cr(VI) and Cr(III) well fits with pseudo-second-order model. Langmuir adsorption isotherm can well describe the adsorption phenomena of chromium ions with the maximum adsorption capacity of 0.567 mg/g for Cr(VI) and 3.446 mg/g for Cr(III). Moreover, SPR reveals higher adsorption capacity for Cr(III) than that for Cr(VI), which implies that SPR has more potential application for Cr(III)-containing wastewater treatment than that for Cr(VI)-containing wastewater treatment. Foundation item: Projects(2006AA06Z374, 2007AA021304) supported by the National High-Tech Research and Development Program of China; Project(2008SK2007) supported by the Key Program of Science and Technology of Hunan Province, China     

Removal of Cr (VI) from aqueous solution using ultrafine coal fly ash

Coal fly ashes WSRA and BQRA were ball milled for 5 h to produce their ultrafine coal fly ashes WSUA and BQUA, respectively. Batch kinetic, isotherm and pH effect on adsorption were studied to evaluate removal of Cr (VI) from aqueous solutions by ultrafine coal fly ashes comparing with raw coal fly ashes. The kinetics of adsorption indicates the process to be intraparticle diffusion controlled and follows the Lagergren first-order kinetics for all coal fly ashes. The first-order rate constants (k ₁) of Cr (VI) adsorption onto WSRA, WSUA, BQRA and BQUA are 1.981, 1.497, 2.119 and 1.500 (×10⁻²) min⁻¹, respectively. The adsorption capacities of WSUA and BQUA are much better than those of WSRA and BQRA. Equilibrium adsorption data of all coal fly ashes well satisfy the Langmuir isotherm. The adsorbed amounts of Cr (VI) onto WSUA and BQUA decrease from pH 2 to pH 6 and then increase up to pH 12.     

CNTs 改性及水体中 Cr（VI）离子的吸附性能研究

为了脱除水体Cr（VI）,600℃下于Fe2Ni/γ-Al2O3上苯催化化学气相分解（catalytic chemical vapor decomposition ）制备碳纳米管（ carbon nanotubes , CNTs ）,粗 CNTs 经混酸（H2SO4/HNO3,3∶1, volume ratio,体积比）,超声氧化纯化,纯化的同时赋予其表面功能基团,进一步地,表面包覆功能分子聚乙烯醇（ polyvinyl alcohol ,PVA）。系统探讨了改性CNTs对高浓度水体Cr（ VI）离子的吸附脱除,结果表明,CNTs的氧化纯化使其表面植入-COOH、-OH等功能基团,进一步地,富含羟基功能基团的PVA分子在CNTs表面包覆,赋予CNTs表面活性的同时,显著提高CNTs的亲水性能。观察到了随氧化纯化和PVA修饰的CNTs上高浓度Cr（ VI）离子吸附的逐步和明显提升,吸附热力学和动力学研究表明,CNTs表面Cr（ VI）的吸附符合Freundlich热力学和准二级动力学特征。随氧化纯化和PVA修饰, CNTs对水体Cr （ VI ）吸附性能的提高可能与CNTs亲水性能的提升以及表面功能化基团对Cr（ VI）的化学吸附的促进相关联。     

Biosorption mechanism of Cr （Ⅳ） onto cells of Synechococcus sp.

The biosorption mechanism of Cr （Ⅳ） ions on Synechococcus sp. biosorbent was studied by analyzing the biosorption kinetics as well as speciation change and bond formation during the biosorption process. The kinetics study shows that the adsorption process of Cr （Ⅳ） consists of a very fast stage in the first several minutes, in which more than half of the saturation adsorption is attained, and a slower stage that approximately follows the first order kinetic model, basically Freundlich isotherm models were observed. Comparative studies of FT-LR spectra of K2Cr2O7, free cells of Synechococcus sp., and Cr-bound cells of Synechococcus sp show that the speciation of chromium that binds to the cells ofSynechococcus sp. is Cr （Ⅲ）, instead of Cr （Ⅳ）, and the carboxylic, alcoholic, amido and amino groups may be involved in the binding of Cr （Ⅲ）. Integrative analyses of the surface electric potential, the effect of pH value on adsorption behavior of Cr （Ⅵ）, and the results of FT-IR show that the biosorption of Cr （Ⅵ） follows two subsequent steps, biosorption of Cr2O7 ^2- by electrostatical force at the protonated active sites and reduction of Cr2O7^2- to Cr^3＋ by the reductive groups on the surface of the biosorbents.     

Selective leaching of chromium-containing slag by HCl

A batch of column experiments was carried out to investigate the change of Cr（Ⅵ） concentration leached out from chromium-containing slag with HCI as leaching agent, and to study influences of pH, ratio of solid mass to solution volume, flow velocity and temperature on Cr（Ⅵ） leaching. The optimal parameters were obtained for Cr（Ⅵ） leaching and a fitting model was established to describe the procedure of Cr（Ⅵ） leaching. The results show that Cr（Ⅵ） concentration in leachate increases with decreasing pH and increasing flow velocity and temperature. Moreover, Cr（Ⅵ） leaching percentage increases with increasing ratio of solid mass to solution volume. The optimal parameters for Cr（Ⅵ） selective leaching are as follows： pH=3.0, 1：5 of ratio of solid mass to solution volume, 180 mL/min of flow velocity and 40 ℃ of temperature. The procedure of Cr（Ⅵ） leaching fits well with the model： v= 1.87t^-0.54, indicating that the leaching rate of Cr（Ⅵ） declines in an exponential order of-0.54.