Removal of heavy metal ions from water by complexation-assisted ultrafiltration

Toxic heavy metals in air, soil and water are global problems that are growing threat to the environment. Therefore, the removal and separation of toxic and environmentally relevant heavy metal ions are a technological challenge with respect to industrial and environmental application. A promising process for the removal of heavy metal ions from aqueous solutions involves bonding the metals to a bonding agent (such as macromolecular species), and then separating the loaded agents from wastewater by separation processes such as membrane filtration. The choice of water-soluble macroligands remains important for developing this technology. The effects of type of complexing agent, pH value and applied pressure on retention coefficients of Zn(II) and Cd(II) complexes were investigated. At best operating conditions (pH=9.0, p=300kPa) using diethylaminoethyl cellulose, the removal of Cd(2+) and Zn(2+) was more than 95% and 99%, respectively.     

PRB技术对地下水中重金属离子的处理研究

实验模拟地下环境,以受重金属离子Pb(Ⅱ)、As(Ⅲ)、Cd(Ⅱ)、Cr(Ⅵ)、Fe(Ⅱ)和总Mn污染的地下水为研究对象,利用还原铁粉、铸铁粉、铸铁粉与颗粒活性炭的混合物为可渗透反应墙(PRB)的主要介质,石英砂为辅助介质,设计了3种反应器.在有效孔隙率为60%～65%、水力停留时间为12.0～14.4 h的条件下,考察其对污染物的去除效果.结果表明:3种反应器对Pb(Ⅱ)、As(Ⅲ)、Cd(Ⅱ)、Cr(Ⅵ)均有较高的去除效果,去除率达98%以上;总Mn的去除率分别达98%、89%和66%;Fe(Ⅱ)的去除率分别达83%、56%和49%.考察了3种反应器内pH、Eh、DO的关系及对重金属离子去除效果的影响,分析了污染物的去除机理.综合考虑处理效果与成本,笔者认为以铸铁粉与石英砂的混合物为PRB的反应介质,应用PRB技术原位处理受上述重金属离子污染的地下水是可行的.     

Removal of heavy metal ions from wastewaters using dendrimer-functionalized multi-walled carbon nanotubes

Dendrimer-functionalized multi-walled carbon nanotubes (MWCNT) for heavy metal ion removal from wastewaters were developed. Triazole dendrimers (TD) were built directly onto the carbon nanotube surface by successive click chemistry reactions affording the zero- and first-generation dendrimer-functionalized MWCNT (MWCNT-TD1 and MWCNT-TD2). The Moedritzer-Irani reaction carried out on the amino groups present on the MWCNT-TD2 sample gave the corresponding α-aminophosphonate nanosystem MWCNT-TD2P. Both MWCNT-TD2 and MWCNT-TD2P nanosystems have been characterized by physical, chemical, and morphological analyses. Their chelating abilities towards the toxic metal ions Pb²⁺, Hg²⁺, and Ni²⁺ and the harmless Ca²⁺ ion have been experimentally evaluated in the two different sets of experiments and at the salt concentrations of 1 mg/mL or 1 μg/mL by inductively coupled plasma mass spectrometry (ICP-MS). The results of these studies pointed out the interesting chelating behavior for the phosphonated nanosystem towards the Hg²⁺ ion. The complexation mode of the best chelating system MWCNT-TD2P with mercury was investigated through density functional theory (DFT) calculations, suggesting a chelation mechanism involving the two oxygen atoms of the phosphate group. The synthesized dendrimers, supported on the multi-walled carbon nanotubes, have shown the potential to be used for the selective toxic metal ion removal and recovery.     

皂化改性橘子皮生物吸附剂对重金属离子的吸附

以生物废料橘子皮(OP)为原料,经乙醇、氢氧化钠处理,得到改性橘子皮生物吸附剂SOP,将其用于对重金属离子Cu2+、Pb2+、Cd2+、Zn2+和Ni2+的吸附。研究了溶液pH、吸附时间和重金属离子初始浓度对SOP吸附性能的影响。结果表明,重金属离子在生物吸附剂上的吸附速率快,符合准二级动力学方程。SOP对重金属离子的吸附等温线符合Lang-muir模型,根据Langmuir模型计算SOP对Cu2+、Pb2+、Cd2+、Zn2+和Ni2+的饱和吸附量分别为56.82、152.4、66.27、33.90和23.02 mg/g,均高于改性前。常见阳离子的存在对重金属离子吸附的影响较小,改性后的橘子皮生物吸附剂可以再生重复使用4次以上,是性能良好的重金属离子吸附剂。     

硅烷化改性沸石对重金属离子的吸附性能

制得一种用于重金属废水处理的新型硅烷化改性沸石吸附剂,成本低、效果显著且稳定。通过对改性沸石表征,分析了改性对沸石结构的影响。结果表明,改性一定程度降低了原沸石的晶体特征,但基本上保持了其结构组成;硅烷化改性成功地在沸石上接枝了氨基。对硅烷化沸石的特性研究,得出硅烷化沸石对Ni2+、Cu2+、Zn2+和Pb2+吸附最佳投加量为1、1、1.6和0.6 g/L,且此时对4种离子的去除率也较好;吸附动力学研究得出,其吸附过程可用二级动力学方程较好地拟合;吸附达到平衡时,4种金属离子的平衡吸附量分别为11.23、17.41、15.45和59.42 mg/g;硅烷化沸石对金属离子的吸附行为更符合Langmuir模型,为化学吸附;在酸性条件下(pH=2～6),硅烷化沸石仍保持一定的吸附能力,具有一定的耐酸性。     

饱和膨润土复合颗粒吸附剂吸附的重金属离子的固定及其再生

采用Na_2S化学再生法对吸附Fe~(2+)、Mn~(2+)、Cu~(2+)和Zn~(2+)饱和的膨润土-钢渣复合颗粒吸附剂分别进行重金属离子的固定及其再生实验研究,探究该吸附剂吸附的重金属离子的固定问题及其再生的可能性和多次再生后的吸附效果,同时根据SEM图进一步揭示固定、再生机理。结果表明:在对Fe~(2+)的固定、再生实验中,可形成Fe S沉淀而实现固定,但再生后再吸附时,膨润土复合颗粒中蒙脱石结构改变使得颗粒坍塌变成粉末状,因此,吸附Fe~(2+)饱和的膨润土复合颗粒吸附剂不适合用Na_2S再生;而对Mn~(2+)、Cu~(2+)和Zn~(2+)的固定、再生实验中,均可形成S化物沉淀而实现固定,颗粒结构未改变,经过3次再生后,吸附剂对Mn~(2+)、Cu~(2+)和Zn~(2+)的去除率还可达到94.22%、83.2%和76.30%,远比未经再生的吸附剂吸附效果好,同时,由SEM表征分析进一步揭示:Na_2S再生溶液既可使重金属离子形成MS沉淀固定,又可使复合颗粒吸附剂获得再生,实现了同步固定、再生的目的,且吸附剂经多次再生后吸附效果保持良好。     

Removal of insoluble heavy metal sulfides from water

The necessity of heavy metal removal from wastewater has led to increasing interest in absorbents. We have developed a new approach to obtain high metal adsorption capacity by precipitating metal sulfides with sodium sulfide on the surface of bentonite and adhere them to the absorbent. This method allowed to remove approximately 90% of cadmium as CdS from 10(-4)-10(-6) M CdCl2 solutions. Additional reactions are related to the removal of excess sodium sulfide by the release of hydrogen sulfide and oxidation to sulfur using carbogen gas (5% CO2, 95% O2) followed by aeration.     

Removal of metal ions and humic acid from water by iron-coated filter media

Iron oxide is an excellent, regenerable adsorbent, and often controls free metals through adsorption reaction. The utilization of heating process for coating iron oxide on sand surface allowed the media to be used in a packed column. Iron-coated sand was investigated for adsorbing metal ions and natural organic matter from water by batch and column experiments. Chemical analysis (energy dispersive analysis of X-ray, EDAX) was used for characterizing the copper and lead adsorption sites on iron-coated sand. From the batch experiment results, the copper and lead ions could be removed simultaneously by the iron-coated sand in the competition adsorption system. The interaction between copper, lead ions and iron oxide on sand surface was primarily the chemical bonds. The maximum adsorption capacities of iron-coated sand for copper and lead were 0.259 mg Cu/g-sand and 1.211 mg Pb/g-sand, respectively. The presence of humic acid led to increase the adsorption of copper and lead. Results from column experiments indicated that the copper ions, lead ions and humic acid could be removed completely before the breakpoint. Consequently, the iron-coated sand may be applied for the adsorption/filtration of metal ions and natural organic matters from water.     

微絮凝深床层过滤去除无机营养物及典型金属离子

在分析了微絮凝深床层过滤机理的基础上,实验研究了以煤矸石燃后残渣为滤料的深床层对微污染矿井水中无机营养物及典型金属离子的去除效果。结果表明,对于微污染矿井水中的NH3-N及COD的去除率仅有20%～40%;对可形成微絮凝体的磷的去除率高达80%以上,对于矿井水中的铁、锰离子的去除率可达75%以上,而絮凝剂的适量加入,不会大幅增加出水中铝离子的含量;分析表明,煤矸石燃后残渣滤料具有良好的吸附、截留作用;对溶解性NH3-N及COD的去除以吸附及生物作用,对铁、锰离子的去除则是以形成絮体沉淀为主,同时金属离子的水合作用、溶度积等对其去除有一定的影响。     

Removal of heavy metal ions from wastewater by a novel HEA/AMPS copolymer hydrogel: preparation, characterization, and mechanism

This study aims to synthesize 2-hydroxyethyl acrylate (HEA) and 2-acrylamido-2-methylpropane sulfonic (AMPS) acid-based hydrogels by gamma radiation and to investigate their swelling behavior and heavy metal ion adsorption capabilities. The copolymer hydrogels prepared were characterized via scanning electron microscopy, Fourier transformed infrared spectra, thermal gravimetric analysis, and X-ray photoelectron spectroscopy. The research showed that the copolymer hydrogel was beneficial for permeation due to its porous structure. In addition, the experimental group A-2-d [70 % water volume ratio and (n (AMPS)/n (HEA))?=?1:1] was an optimal adsorbent. The optimal pH was 6.0 and the optimal temperature was 15 °C. Pb²⁺, Cd²⁺, Cu²⁺, and Fe³+ achieved adsorption equilibriums within 24 h, whereas Cr³⁺ reached equilibrium in 5 h. Pb²+, Cd²⁺, Cr³⁺, and Fe³⁺ maximum load capacity was 1,000 mg L^?1, whereas the Cu²⁺ maximum capacity was 500 mg L^?1. The priority order in the multicomponent adsorption was Cr³⁺>Fe³⁺>Cu²⁺>Cd²⁺>Pb²⁺. The adsorption process of the HEA/AMPS copolymer hydrogel for the heavy metal ions was mainly due to chemisorption, and was only partly due to physisorption, according to the pseudo-second-order equation and Langmuir adsorption isotherm analyses. The HEA/AMPS copolymer hydrogel was confirmed to be an effective adsorbent for heavy metal ion adsorption.     

过渡金属离子活化过硫酸盐去除土壤中的芘

比较研究了Fe2+、Co2+和Ag+活化Na2S2O8及KHSO5对土壤中芘的氧化降解效果,并对上述反应过程进行动力学研究及芘降解产物成分分析。在土水质量比为1：5,氧化剂和过渡金属离子添加摩尔比为10：1,30℃恒温水浴磁力搅拌及反应时间5~120 min条件下开展了系列实验。结果表明,3种离子中Fe2+活化Na2S2O8氧化降解芘的去除效果最优,反应120 min后芘去除率为93.4%;Co2+是活化KHSO5的最佳过渡金属离子,反应5 min后芘去除率达94.5%,在反应120 min后芘去除率增高至97.0%。此外,降解动力学拟合结果表明Fe2+、Co2+和Ag+活化Na2S2O8和KHSO5降解芘的过程符合准一级反应动力学,且土壤中绝大部分芘可被活化过硫酸盐体系氧化降解。     

Pre-concentration and separation of heavy metal ions by chemically modified waste paper gel

Iminodiacetic acid was immobilized on waste paper by chemical modification in order to develop a new type of adsorption gel for heavy metal ions. Adsorption behavior of the gel was investigated for a number of metal ions, specifically Cu(II), Pb(II), Fe(III), Ni(II), Cd(II), and Co(II) at acidic pH. From batch adsorption tests, the order of selectivity was found to be as follows: Cu(II)  Fe(III) > Pb(II) > Ni(II)  Co(II) > Cd(II). Column tests were carried out for pairs of metal ions to understand the separation and pre-concentration behavior of the gel. It was found that mutual separation of Ni(II) from Co(II) and that of Pb(II) from Cd(II) can be achieved at pH 3. Similarly, selective separation of Cu(II) from Cu(II)–Fe(III) and Cu(II)–Pb(II) mixtures at pH 1.5 and 2, respectively, was observed by using this new adsorption gel. In all cases, almost complete recovery of the adsorbed metal was confirmed by elution tests with HCl.     

胶束强化超滤去除水中双酚A

采用截留分子量(MWCO)为5000 Dalton、1000 Dalton的聚砜超滤膜,MWCO为1 kDa的再生纤维素超滤膜;采用十二烷基苯磺酸钠(SDBS)、曲拉通100(TritonX-100)、吐温80(Tween-80)、烷基多苷(APG)为表面活性剂,用胶团强化超滤工艺去除水中双酚A。研究了不同材质和截留分子量的超滤膜、表面活性剂浓度、膜操作压力、溶液pH和溶液中电解质等因素对该工艺的影响。结果表明,SDBS对双酚A有较好的去除效果,去除率在80%以上。在H+和Na+存在的条件下,双酚A的截留率增加,透过液中SDBS浓度降低。SDBS与非离子表面活性剂的复配可以提高双酚A截留率,降低透过液中SDBS的浓度,复配效果优劣顺序为Tween-80TritonX-100APG。     

重金属离子在钠基膨润土中的吸附特征与机理

膨润土是一种天然粘土矿物,比表面积大、吸附能力强。通过钠基膨润土对复合重金属离子Cu2+、Zn2+和Cd2+的竞争吸附实验研究,探讨了钠基膨润土对Cu2+、Zn2+和Cd2+的吸附特征。结果表明,钠基膨润土对Cu2+、Zn2+和Cd2+的吸附随离子浓度增加而增大。吸附具有选择性,Cu2+、Zn2+和Cd2+的吸附能力大小顺序为Cu2+>Zn2+>Cd2+。并通过XRD及IR等分析探讨了钠基膨润土的吸附机理主要表现为离子交换吸附。     

改性磺化泥炭去除水中双酚A的研究

采用十六烷基三甲基澳化铵(HTAB)对磺化泥炭进行接枝改性,并研究了双酚A在改性磺化泥炭上的吸附特性.研究发现,改性磺化泥炭的C元素由40.12%(质量分散,下同)增加到47.91%,其在水中的Zeta电位升高了27.0 mV.双酚A在磺化泥炭和改性磺化泥炭上的吸附过程符合准二级动力学模型和Freundlich等温吸附...     

壳聚糖联合碱改性粉煤灰对重金属离子的吸附特性

采用浸渍法将壳聚糖负载在经NaOH改性的粉煤灰上,制备了联合改性的粉煤灰。随粉煤灰上壳聚糖负载量的增加,粉煤灰对Pb2+和Cd2+的吸附率均提高。当负载壳聚糖的质量分数为8%,吸附温度为30℃,吸附时间为120 min时,粉煤灰对Pb2+的吸附率最高（为98.9%）,对Cd2+的吸附率也最高（为91.5%）。其吸附行为符合Freundlich等温吸附模型,但表现为2个线性区。粉煤灰负载壳聚糖的改性机理是粉煤灰与带正电荷的壳聚糖的化学键合作用。     

Retrieval of heavy metal ions from solution via ferritisation

The paper summarises the results of the studies on retrieval of heavy metal ions in solution by ferritisation and its potential application in waste-water treatment. The optimum procedure for ferritisation of heavy metal ions in solution has been evolved with respect to pH, concentration of Fe2+, rate and time of aeration and temperature. The recommended procedure consists of controlled aeration of the solution containing heavy metal ions and ferrous ions at pH 9.5-10.5 at about 50 degrees C, until the black, granular, magnetic ferrite separates out. The metal ferrites can also be formed, even without heating or forced aeration, by ageing the mixed metal hydroxide precipitate at pH 10 to 11. The metal ferrites formed have been characterised by X-ray diffractometry. The laboratory-scope experiments conducted with synthetic heavy metal solutions as well as actual wastewater from a tanning industry showed that heavy metal ions can be effectively removed from solution to sub-ppm levels. The metal ferrites thus recovered may find commercial application as microwave absorbers, catalysts, metal scavengers, etc. This technique seems to have potential application in simultaneous, one step removal of different heavy metal ions from industrial wastewaters.     

改性γ-聚谷氨酸络合重金属离子性能

研究了不同控制条件(温度、Pb2+浓度、pH)对交联改性γ-聚合谷氨酸(γ-PGA)吸附重金属离子所形成的絮凝颗粒性质的影响,对于治理水中重金属污染的相关研究有一定参考价值。实验表明,C-L-γ-PGA絮凝吸附Pb2+的最佳温度段在30℃附近。随着交联度的增加,不同的Pb2+浓度影响絮凝颗粒的大小,当处于较低浓度时,静电引力成为影响絮凝颗粒粒径最主要的因素,当Pb2+浓度增加到一定程度时,重金属的吸附量成为絮凝颗粒的粒径的决定因素。溶液pH达到7附近时,能够形成粒径最大的絮凝颗粒,并出现了最大的Pb2+去除率。C-L-γ-PGA对其他重金属离子也有类似的吸附絮凝作用,且絮凝吸附强弱顺序为Cu2+>Cr3+>Pb2+>Hg2+。吸附絮凝颗粒的粒径反映了重金属被吸附之后分离的难易程度,因此研究不同条件对絮凝颗粒粒径的影响对重金属离子的吸附和去除有重要意义。     

Sequestering of heavy metal ions from aqueous solutions by using a lignocellulosic material

The ability of Brown Stock Washer (BSW) unbleached kraft pulp and Chemi-Thermo-Mechanical Pulp (CTMP) to sequester heavy metals was studied. The BSW pulp is chemically produced while the CTM one is produced by mechanical treatment aided by some chemicals. The two pulps were rendered in their protonated form and then equilibrated with two aqueous solutions of metals. One was ocean water and the other was a laboratory prepared solution of metal ions. Both pulps were able to remove metal ions from the solution in a one-stage procedure. The overall metal removal efficiency of CTMP was in general greater than that of the BSW pulp for the low concentration metals.     

Selective removal of the heavy metal ions from waters and industrial wastewaters by ion-exchange method

By ion exchange undesirable ions are replaced by others which don't contribute to contamination of the environment. The method is technologically simple and enables efficient removal of even traces of impurities from solutions. Examples of selective removal of heavy metal ions by ion-exchange are presented. They include removal of Pb(II), Hg(II), Cd(II), Ni(II), V(IV,V), Cr(III,VI), Cu(II) and Zn(II) from water and industrial wastewaters by means various modern types of ion exchangers.