络合-陶瓷膜耦合技术处理低浓度含铜废水

采用孔径为200nm的陶瓷膜,以聚丙烯酸(PAA)为络合剂,含Cu2+废水为模拟废水,研究了络合-陶瓷膜耦合技术处理低浓度含铜废水过程。重点考察了运行时间、络合剂浓度、络合剂/金属离子质量浓度比(P/M)、溶液pH、离子强度、操作压力等对膜通量及Cu2+截留率的影响。结果表明,当P/M≥5、pH为5~6时,Cu2+的截留率接近100%,膜通量较高且趋于稳定;外加盐(NaCl和Na2SO4)导致Cu2+截留率下降,可以通过增加P/M值多级处理达到对Cu2+的理想去除。     

电生物反应器降解含Cr6+和Zn2+的高浓度苯酚废水

经驯化得到能适应含Cr^6＋和Zn^2＋离子的高浓度苯酚废水的功能菌，将其在电生物反应器内挂膜并进行废水处理。研究发现，该生物膜对苯酚的降解能力受电场条件的影响显著。与无外加电场情况相比，在最佳电场条件3．0V，17．7V／m和1．98A／m^2下，1200mg／L苯酚降解效率提高了113％。电场条件变化对Cr^6＋的去除效果几乎没有影响，但对Zn^2＋的去除影响显著。实验结果表明：IOL废水中的苯酚（2400mg／L）经65h即可完全降解，而Cr^6＋和Zn^2＋（50mg／L及125mg／L）经12h处理后，去除率分别达到99％和67％；与之相比，相同实验条件下处理不含重金属离子的苯酚废水仅需57h。     

络合-超滤技术处理含铜废水

络合剂为聚丙烯酸钠,超滤膜采用芳香聚酰胺膜,研究了络合.超滤处理含铜废水的工艺条件.研究了不同溶液pH值条件下聚合物/盒属离子质量比(P/M)、溶液PH、操作压力、运行时间等操作参数对铜离子去除率和膜通量的影响.结果表明,在一定pH条件下,Cu~(2+)的截留率随P/M的增加而增加;在一定P/M下,适当提高溶液pH值有利于Cu~(2+)的截留.在溶液pH=6、P/M=22条件下,Cu~(2+)的截留率达到97%以上.     

络合-超滤技术深度处理矿山重金属废水

采用壳聚糖络合-超滤技术深度处理有色金属矿山重金属废水,考察了pH值、壳聚糖/铅离子质量比(P/M)、离子强度、运行时间等因素对Pb2+、Cd2+截留率和膜通量的影响。结果表明,在原水Pb2+、Cd2+的质量浓度分别为1.0、0.1 mg/L,pH值为7,P/M值为6的条件下,Pb2+和Cd2+的截留率分别达到96.62%和96.26%,出水满足GB 3838—2002《地表水环境质量标准》中Ⅲ类标准的要求。NaCl浓度的增大使重金属离子的截留率有所降低;随着运行时间的延长,膜通量逐渐减小最后趋于稳定,而运行时间对Pb2+、Cd2+的截留率影响不大。     

接枝改性木素对含镍废水的絮凝性能研究

研究了木素磺酸钙和丙烯酰胺的接枝共聚物（ LSAM）对含镍废水的絮凝性能及处理效果。同时考察了废水pH值对含镍废水去除效果的影响及镍离子的回收率。结果表明, pH值在pH 5．0～11．0时, Ni2＋去除率＞95％;在pH＝7．0, LSAM的投加量为60 mg／L时,一定浊度下,对镍的去除率＞98％;镍离子可以选用4 mol／L的硝酸进行回收,回收率最高可达到79．7％。     

泥炭对重金属废水中Cu^2＋、Pb^2＋最佳吸附条件的研究

泥炭中富含有机质与腐植酸,其中含有大量的极性基团,对金属离子有较强的吸附性能。本试验通过对泥炭吸附重金属废水中Cu^2＋、Pb^2＋种离子的吸附条件进行研究,得出最佳吸附条件为：当重金属离子浓度为30mg／L时,泥炭投加量分别为7g／L和5g／L,最佳吸附pH值分别为5和8,吸附时间均为30min．且离子浓度越高,表观吸附量越大,但除金属率越低。最佳条件下Cu^2＋、Pb^2＋的表观吸附量分别为4．24mg／g和6．00mg／g,除铜率和除铅率分别为98．8％和999％。     

纳滤去除水中的有害离子

本文综述了纳滤去除饮用水和重金属废水中的有毒有害离子的应用研究，阐述了纳滤膜对无机盐的截留效果主要取决于膜对离子的电荷效应，表现在对多价离子的截留率高于单价离子。利用纳滤膜这种分离性能，可以去除部分饮用水中微量的有害单价离子（如NO2^-、NO3^-、F^-等）和大部分的有毒二价离子（如HAsO4^2-和重金属离子），获取优质安全的饮用水；也可以用于处理重金属废水，能有效去除废水中的重金属离子。将纳滤和反渗透集成用于重金属废水处理，可以做到对有毒重金属离子的回收利用和出水回用，实现清洁生产，既具经济效益，又具环境效益，在工程实际中极具推广应用价值。     

反渗透技术处理压水堆一回路放射性废水试验研究

选用聚酰胺反渗透膜处理核电站一回路放射性废水.对反渗透去除核电站一回路放射性废水及反应堆停堆换料期间一回路排水中的钴离子进行研究.在不同操作压力及浓度下,考察废水中硼酸及镍离子对稳定核素钴的截留率影响.研究表明,一回路废水中含有的硼酸会降低反渗透对钴的截留率,硼酸质量浓度由2 500 mg·L-1下降到500 mg·L-1时,去除率由79.3％上升到88.8％.截留率及膜通量随着膜面压力上升而升高,在1.4 MPa时分别达到86％及30m3·m-2·s-1.结果说明反渗透技术可以有效地去除核电站放射性废水中的钴元素,并且可以获得稳定的膜通量.     

CH型絮凝剂处理废水的研究

研究了ＣＨ型絮凝剂对废水中重金属离子去除效果,结果表明,对废水中Ｎｉ＾２＋、Ｃｒ＾６＋等单一离子（浓度２０￣４０ｍｇ／Ｌ）的去除率大于９０％,对混合废水中的Ｃｕ＾２＋、Ｚｎ＾２＋、Ｎｉ＾２＋、Ｃｒ＾３＋、Ｃｄ＾２＋等（各离子浓度２０￣－４０ｍｇ／Ｌ）的去除率均大于９６％。     

絮凝剂处理含重金属铅锌选矿废水试验研究

以含有单一重金属离子的模拟铅锌选矿废水为研究对象,考察溶液初始pH、絮凝剂种类及投加顺序对重金属离子去除效果的影响,在此基础上对模拟多种重金属选矿废水进行研究。结果表明:①单一重金属离子条件下,pH值为8、加入絮凝剂PAM对铜离子去除效果最好,pH值为6,空白絮凝剂对铅离子去除效果最好,pH值为8,空白絮凝剂对锌离子去除效果最好,pH值为7,絮凝剂PAC对镉离子去除效果最好;絮凝剂PAM-PAC组合对铜离子、锌离子和镉离子的去除效果最好,絮凝剂PFS-PAM组合对铅离子的去除效果最好;②多种重金属离子条件下,pH为9,空白絮凝剂或加入絮凝剂PAM,对铜离子、铅离子、锌离子和镉离子的去除效果最好。     

Polymer assisted ultrafiltration for copper–citric acid chelate removal from wash solutions of contaminated soil

The removal of heavy metals from aqueous systems such as wash-solutions of contaminated soil by using Polymer-Assisted Ultrafiltration (PAUF) has been studied. For the extraction of metal ions from contaminated soil citric acid is used as a chelating agent. Cu²⁺ as metal ion and the polymer polyethylenimine (PEI) as ligand were used in the various experiments. Optimal chemical conditions for copper complexation by citric acid were determined by means of complexation tests. The results showed that citric acid is able to chelate copper ions at pH 5.5, while decomplexation occurs at pH 2. Maximum bonding capacity (saturation condition) was 0.625 mg Cu²⁺ per mg citric acid, meaning 2 mol Cu²⁺ per mol citric acid. Complexation tests in the system polyethylenimine–citric acid–copper showed that the polymer is able to complex the copper–citric acid chelate at pH = 6 while release occurs at pH < 3. The saturation condition was 0.333 mg Cu²⁺ per mg PEI. The ultrafiltration tests, carried out at three trans-membrane pressures (2, 3 and 4 bar), showed the possibility of using the PAUF technique for copper ion removal from aqueous solutions.     

啤酒酵母吸附去除水中Cd~(2+)的影响因素

生物吸附法是一种经济有效的处理大规模低浓度重金属废水的生物技术,其中啤酒酵母(Saccharomyces cerevisiae)是具有实用潜力的生物吸附剂。本文研究了啤酒酵母对Cd2+吸附效果的主要影响因素,结果表明pH值对Cd2+会产生较大的影响,非固定化和固定化啤酒酵母对Cd2+吸附的最佳pH值都为4,过高和过低均不利于吸附的进行。水中常见的K+、Ca2+、Na+、Mg2+四种离子在低浓度时对Cd2+的吸附无显著影响,但当其浓度高于5mg/L时会影响吸附,其影响顺序为K+Na+Ca2+Mg2+;Zn2+、Fe2+、Cu2+、Pb2+对Cd2+的吸附效果影响顺序为Pb2+Zn2+Fe2+Cu2+;当Cu2+浓度≥50mg/L时,啤酒酵母对Cd2+不产生性吸附,而对Cu2+产生专性吸附。     

Simultaneous Recovery of Nickel and Cobalt from Aqueous Solutions using Complexation-Ultrafiltration Process

Simultaneous recovery of nickel and cobalt from aqueous solutions by complexation-ultrafiltration process with polyethylenimine (PEI) was studied. Experiments were performed as a function of polymer/metal ratio (P/M), solution pH, and ionic strength. Effects of concentration time on metal rejection and membrane flux were also studied. At optimum experimental conditions of pH 6.0 and P/M 5.0, the nickel removal efficiency reaches at 99.9% and cobalt removal efficiency goes to 96.4%. Both nickel and cobalt removal efficiencies decreased as the adding salt concentration increases. During 12 h of the ultrafiltration process, the decline of membrane flux was less than 16% and the removal efficiencies for both nickel and cobalt were kept almost constant. Diafiltration was further performed to regenerate PEI. The removal efficiencies for both metals using recycled PEI were found to be close to those with the original PEI. Results from the two-step process of complexation-UF and decomplexation-UF separation showed that it could be a promising method for simultaneous recovery of nickel and cobalt from aqueous solutions.     

疏水性离子液体为溶剂对Co2+和Cd2+废水的萃取性能

研究了疏水性离子液体[Bmim]PF6(1-丁基-3-甲基咪唑六氟磷酸盐)、[Hmim]PF6(1-己基-3-甲基咪唑六氟磷酸盐)和[Omim]PF6(1-辛基-3-甲基咪唑六氟磷酸盐)对Co2+和Cd2+的萃取性能. 结果表明,未加入螯合剂时,离子液体对Co2+和Cd2+的萃取率都很低. 螯合剂的加入大大提高了离子液体对重金属离子的萃取性能,Co2+和Cd2+的萃取率分别由原来的2.06%和1.82%提高到96.37%和93.68%. 不同螯合剂对离子液体萃取Co2+和Cd2+有一定的影响. 离子液体碳链长度的增加有利于Co2+和Cd2+的萃取. 与传统有机溶剂相似,离子液体萃取重金属离子过程中具有很强的pH摆动效应,当pH<2时,Co2+和Cd2+的萃取率几乎为0,而当pH>6时,Co2+和Cd2+的萃取率均大于90%. 运用萃取过程中的pH摆动效应对Cd2+进行反萃取,实现了离子液体的回用.     

Water‐soluble amine and imine polymers with the ability to bind metal ions in conjunction with membrane filtration

The commercial polymers poly(ethylene imine) (PEI), poly(ethylene imine epichlorohydrin), and poly(dimethylamine‐co‐epichlorohydrin) were purified and fractionated by ultrafiltration. Their metal‐ion‐binding properties with respect to different ligand groups and the effect of the concentration on the retention properties were investigated. The amine ligands of the polymers formed the most stable complexes with the metal ions. In general, there was an effect of the pH and polymer fraction size on the retention properties. As the pH and polymer fraction size increased, the affinity to bind metal ions also increased. PEI had the highest metal‐retention values, particularly at higher pHs, at which the amine groups were nonprotonated and could coordinate easily with the metal ions. Only Pb(II) was poorly retained. The affinity for all the metal ions, except Pb(II), increased significantly at pH 5. The metal‐ion retention decreased quickly as the filtration factor increased, except for Cu(II), Co(II), Ni(II), Cd(II), and Zn(II) ions, which were retained by over 40% at a filtration factor of 4. For other metal ions such as Pb(II), Ca(II), and Mg(II), only 10% remained bound to the polymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 222–231, 2005     

Removal of Heavy Metals from Multicomponent Metal Mixtures by Polymer Enhanced Ultrafiltration: Effects of pH,Ionic Strength and Conformational Changes in Polymer Structure

Fractional separation of industrially important heavy metals (cadmium, nickel, zinc) from binary and ternary metal mixtures by continuous mode polymer enhanced ultrafiltration was studied. Polyethyleneimine (PEI) was used as a complexation polymer. Effects of pH and ionic strength on process efficiency were investigated. To gain insight about the characteristics of binding between highly branched PEI and metal ions and effect of salt concentration on this binding were investigated by performing dynamic and static light scattering measurements. It was observed that with optimum pH and salt concentration, fractional separation of metals can be achieved.     

Part 8. Preparation,characterization and metal complexing of poly[(2‐hydroxyethyl)‐DL‐aspartamide] in aqueous solution

Poly[(2‐hydroxyethyl)‐DL ‐aspartamide] was synthesized by polyreaction of aspartic acid and subsequent polymer‐analogous functionalization with ethanolamine. The water‐soluble polymer was characterized by FTIR, NMR, TGA and light‐scattering measurements. The metal complexing properties of the polymer were studied for Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sr(II), Cd(II) and Pb(II) ions in aqueous solution using the liquid‐phase polymer‐based retention (LPR) method. According to the retention profiles of LPR, Cr(III), Fe(III), Cu(II) and Pb(II) showed a strong interaction with this polymer under these conditions, indicated by retention values of about 100 %. In contrast, Co(II), Ni(II), Zn(II), Sr(II) and Cd(II) exhibited retention values of only 50–60 % in dilute solution at pH 5. © 2000 Society of Chemical Industry     

甘氨酸合钴溶液脱除NO

结合乙二胺合钴具高效脱NO的特性,选取与乙二胺合钴配位结构相似的氨羧化合物——甘氨酸,替代乙二胺作钴配合物配体进行脱NO研究,以期解决乙二胺易挥发、难运输等问题.实验表明：甘氨酸合钴的初始浓度对NO脱除影响显著,随浓度的增大NO脱除率提高;吸收剂的pH值和吸收反应温度也对NO脱除率影响显著,最佳pH值为中性至弱碱性,最佳反应温度50℃左右;同时脱硫脱氮时,尿素的加入因其可促进SO^2-₃的氧化,从而提高甘氨酸合钴同时脱硫脱氮能力.     

pH对壳聚糖螯合铜(II)的螯合机理及稳定常数的影响

用紫外分光光度法研究了pH值对壳聚糖螯合Cu(II)的影响。通过显微图像、X衍射图谱及红外光谱对沉淀物进行分析。结果表明,随体系pH值增加,壳聚糖碳链上的活性基团与铜离子的螯合能力增强。溶液体系pH=5~6时,螯合物的稳定常数最大值为1.1×108;当pH接近7时,部分螯合产物析出导致稳定常数降低。酸性条件下pH值的变化对螯合物的配位比(n)无明显影响,壳聚糖–铜螯合物的配位比n=2。通过调节pH值可使溶液中壳聚糖铜螯合物析出,随pH增加,Cu2+浓度降低,当pH约为9时,Cu2+浓度达最小值1.5 mg/L。壳聚糖的主要活性基团–NH2与铜离子发生螯合,反应生成壳聚糖-铜。     

Synthesis,characterization and application of a novel zinc(II) ion-imprinted polymer

In our study, a Zn(II) ion-imprinted polymer (ZnIP) and non-imprinted polymer (NIP) were synthesized via free-radical polymerization. 1-Vinylimidazole, ethylene glycol dimethacrylate, 2-hydroxyethylmethacrylate and 2,2′-azobisisobutyronitrile were used as functional, cross-linking monomers and free-radical initiator, respectively. The obtained polymer was characterized by various analytical methods (Fourier Transform Infrared Spectroscopy, Transmission Electron Microscopy, Wavelength Dispersive X-ray Fluorescence, UV VIS, thermal analysis). The sorption properties of ZnIP and NIP were evaluated after removal of Zn(II) ions from the polymer network. The optimum pH for adsorption was 7.0. The maximum adsorption capacity at the pH was 5.2 and 0.22 mg/g for ZnIP and NIP, respectively. To determine the selectivity, the polymer was equilibrated with the binary mixture of Zn(II) ions and the interfering ions [Cu(II), Ni(II) or Co(II)]. The relative selectivity of ZnIP was 22.57, 5.44 and 46.17 for Cu(II), Ni(II) and Co(II) ions, respectively. The proposed ZnIP sorbent was applied to determine the zinc ions in urine samples by Wavelength Dispersive X-ray Fluorescence.