Adsorption of heavy metal ions from aqueous solutions by porous polyacrylonitrile beads

The adsorption of Cu(II), Ni(II), Zn(II), and Pb(II) from aqueous solutions on acrylonitrile copolymer sorbents was studied. We prepared five types of sorbents from polyacrylonitrile by varying its concentration in the initial polymer solution and the composition of the coagulation bath, aiming to achieve a different porous structure. The specific area, pore volume, and pore radius of the sorbents were determined on a porosimeter. The porous structure was studied by scanning electron microscopy. Modification of sorbents with sodium hydroxide and hydroxylamine was carried out to form amidooxyme and carboxylic groups with proven complex‐forming properties toward heavy metal ions. The optimal pH of the sorption of metal ions was found. The adsorption kinetics were investigated. The order of polymer sorbents toward the sorption of Pb(II), Cu(II), Ni(II), and Zn(II) ions, and the order of heavy metal uptake were determined for all types of sorbents. The effectiveness of heavy metal desorption and the coefficient of recovery of sorption ability were determined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3036–3044, 2002; DOI 10.1002/app.2334     

High‐retention properties for Hg(II) ions of a resin containing ammonium and pyridine groups

The metal‐ion uptake behavior of the chelating resin poly([(3‐(methacryloylamino)propyl] trimethyl ammonium chloride‐co‐4‐vinyl pyridine) has been investigated. The resin is obtained by radical copolymerization in a yield of 99.6%. The hydrophilic resin shows a high retention capacity and selectivity toward Hg(II) ions in the presence of Cu(II), Pb(II), Cd(II), Zn(II), and Cr(III) ions. A retention of Hg(II) higher than 99% is observed after 5 min. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2595–2599, 2002     

天然气中汞的脱除技术

鉴于环保、设备安全以及人身健康的要求,有效脱除天然气中汞的应用技术日渐受到重视。简述了物理吸附、化学吸附、溶液吸收和低温分离等具有代表性的天然气脱汞的工艺进展。对活性炭汞吸附剂、负载金属吸附剂、卤化或载硫活性炭和其他类型汞吸附剂在天然气中汞脱除的应用进展进行了阐述。研究了入口天然气的温度和湿度对脱汞效果的影响,较低的温度和湿度有利于汞的脱除。     

原料干气脱汞技术的研究进展

汞是重要的毒物和大气染污物。干气中的汞对设备和下游催化剂造成严重危害,必须予以脱除。介绍了干气中汞的脱除情况和脱汞技术的研究进展。     

可循环再生吸附剂脱汞技术现状及发展趋势

总结了当前燃煤烟气脱汞常用的协同脱汞技术和贵金属、金属氧化物基可再生吸附剂技术发展现状,分析了各方法的优势与存在的问题,对未来磁性可回收吸附剂的发展方向和趋势进行了展望。针对现有脱汞技术效率低、易造成二次污染等缺陷,提出了使用飞灰磁珠制备廉价可回收脱汞吸附剂的新思路。通过大量试验开发了负载Co_3O_4或CuCl_2的磁珠改性方法以增强脱汞能力和抗烟气组分干扰能力,从而能够适用于低氯复杂烟气气氛。设计了改性磁珠吸附剂喷射脱汞工艺流程,可兼顾高效脱汞与低廉的运行成本,并通过磁珠回收再利用彻底避免汞进入环境造成污染。     

Hydrogel beads based on carboxymethyl cellulose for removal heavy metal ions

Environment‐friendly carboxymethyl cellulose (CMC) hydrogel beads were successfully prepared using epichlorohydrin (ECH) as a crosslinking agent in the suspension of fluid wax. There was an ether linkage formed between ECH and CMC, which was identified from bands in FTIR spectra of the prepared hydrogel. The prepared hydrogel beads with diameters about 4 mm were apparently spherical and fully transparent. The X‐ray diffraction (XRD) spectra indicated that the adsorption of metal ion onto the oxygen atom of carboxyl group led to change in crystallinity patterns of hydrogels. The scanning electron microscope (SEM) images clearly showed that the hydrogels had an internal porous structure. The adsorption capacity increased as initial concentrations of metal ions and the pH value of metal ion solution increased. Freundlich and Langmuir isotherm models were employed to analyze the data from batch adsorption experiments. There are vey good correlation coefficients of linearized equations for Langmuir model, which indicated that the sorption isotherm of the hydrogel beads for metal ions can be fitted to the Langmuir model. The maximum adsorption amount of hydrogel beads for metal ions is 6.49, 4.06, and 5.15 mmol/g for Cu(II), Ni(II), and Pb(II), respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

污水处理厂污泥制备吸附剂对燃煤烟气中汞的吸附性能研究

以城市污染处理厂的活性污泥作为原料,采用不同的活化方式处理制备出环境友好的吸附剂,可供燃煤电厂烟气中除汞.污泥活化后收率在40%～55%之间,物理活化后收率随活化温度的升高而降低,比表面积、孔隙量和吸汞量随活化温度的升高而逐渐增大,但吸汞量随温度升高而急剧下降,说明物理活化的吸附剂主要以物理吸附的方式除汞;经化学活化处理的吸附剂性能好、收率高,比表面积、空隙率和吸汞量显著增加,且除汞效率受温度影响较小,除汞效率高.淋滤实验结果验证了活化处理后的吸附剂对汞具有较高的吸附稳定性,没有二次污染.     

Removal of chromium (VI) from aqueous solutions using poly(4‐vinyl pyridine) beads

Sorption of hexavalent chromium ions from aqueous solution by poly 4‐vinyl pyridine [Poly(4‐VP)] was studied. The batch method was applied for adsorption processes. The effects of initial ion concentration, time, pH and temperature on adsorption were investigated. A treatment time of 60 min was found to be sufficient to reach equilibrium. pH 3.0 was found as the optimum pH value for the process. The maximum adsorption performance was achieved at 86.7 mg g^?1 using 500 mg L^?1 Cr (VI) solutions. The process of adsorption of Cr (VI) was explained by Langmuir isotherm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2865–2870, 2006     

Preparation of porous polysulfone beads for selective removal of endocrine disruptors

Porous polysulfone (PSf) beads are prepared using a liquid–liquid phase separation technique. The porous PSf beads are then used for the removal of endocrine disruptors, such as Biphenyl (BP), dibenzofuran (DBF), dibenzo-p-dioxin (DBD), biphenol A (BPA), and diethylstylbestrol (DES) from their aqueous solutions. The endocrine disruptors could be removed efficiently by a simple sorption method with hydrophobic porous PSf beads. The removal ratio was high for endocrine disruptors having high octanol–water distribution coefficients. The effect of sorption time, weight of PSf beads, ethanol amount in the solution, and the porosity of the beads on the removal of endocrine disruptors was investigated. The adsorbed endocrine disruptors in the PSf beads could be effectively removed by 2-propanol or ethanol, which indicated that the beads could be reused. The study suggested that the porous PSf beads have a potential ability to be used for the removal of endocrine disruptors in environmental application.     

燃煤烟气汞形态转化及脱除技术

介绍了煤中Hg的含量、不同燃烧时段的形态及其转化,并总结了国内外研究开发的燃煤烟气汞污染物脱除技术,其中着重介绍了活性炭吸附技术和催化氧化技术,最终对该领域的研究方向做了展望。     

Removal and recovery of mercury from chloride solutions by contact deposition on iron felt

This paper deals with the use of iron felt as a reducing agent for the removal of mercury from aqueous dilute solutions containing chloride ions. The kinetic behavior of the mercuric ion reduction was analyzed and its diffusion coefficient was determined with the use of a rotating disk electrode. Experimental results of the removal of mercury from aqueous sodium chloride solutions containing 100 ppm mercury by contact with iron felt are reported. The mercury concentration was decreased to values lower than 0·1 ppm. The recovery of metallic mercury by chemical attack of the residual iron felt was also analyzed.     

Synthesis and characterization of magnetic beads containing aminated fibrous surfaces for removal of Reactive Green 19 dye: kinetics and thermodynamic parameters

BACKGROUND: Poly(HEMA‐co‐MMA) beads were prepared from 2‐hydroxyethyl‐methacrylate (HEMA) and methylmethacrylate (MMA) in the presence of FeCl₃. Thermal co‐precipitation of Fe(III) ions containing beads with Fe(II) ions was carried out under alkaline conditions. The magnetic beads were grafted with poly(glycidylmethacrylate; p(GMA)), and the epoxy groups of the grafted p(GMA) brushes were converted into amino groups by reaction with ammonia. RESULTS: The magnetic beads were characterized by surface area measurement, electron spin resonance (ESR), Mössbauer spectroscopy and scanning electron microscopy (SEM). The maximum adsorption of Reactive Green‐19 (RG‐19) dye on the p(GMA) grafted and amine modified magnetic beads was around pH 3.0. The adsorption capacity of magnetic beads was 84.6 mg dye g^?1. The effects of adsorbent dosage, ionic strength and temperature have also been reported. Batch kinetic sorption experiments showed that a pseudo‐second‐order rate kinetic model was applicable. CONCLUSION: The p(GMA) grafted and amine modified magnetic beads (adsorbent) were expected to have the advantage of mobility of the grafted chains in the removal of acidic dyes from aqueous solutions. The magnetic beads have potential as an adsorbent for removal of pollutants under various experimental conditions without significant reduction in their initial adsorption capacity. Copyright © 2011 Society of Chemical Industry     

Poly(benzoxazine‐co‐sulfur): An efficient sorbent for mercury removal from aqueous solution

A novel sulfur‐rich adsorbent, poly(BA‐ala‐co ‐sulfur), was synthesized by reacting allyl functional benzoxazine (BA‐ala) and elemental sulfur. Simultaneous inverse vulcanization and ring‐opening reactions of benzoxazine generated copolymers in several feed ratios. The adsorption behavior of these copolymers was investigated in aqueous solutions containing Hg²⁺. A three level Box–Behnken design with four factors was applied in order to examine the interactive effect of Hg²⁺ concentration (ppm), S % in adsorbent, temperature, and pH. The optimum adsorption conditions were determined as: 10.33 ppm Hg²⁺, 68% S content, 329 K, and pH 6.3. Common isotherm and kinetic models were applied to the experimental data, where the Langmuir isotherm provided the better fit (q _max = 79.36 mg g^?1) and the pseudo‐second order fit indicated chemisorption as the process‐controlling step. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45306.     

改性褐煤活性焦对模拟烟气中汞的脱除研究

为降低烟气脱汞成本,提高活性焦脱汞性能,以内蒙古锡林浩特褐煤为原料制备活性焦并进行化学改性,分析载硫、Na2S溶液和Zn Cl2溶液浸渍等改性方法对活性焦结构及性能的影响,研究改性方法、吸附温度、负载量和汞渗透量对活性焦脱汞性能的影响。结果表明,活性焦改性后,比表面积和孔容积有所降低,载Na2S、硫、Zn Cl2活性焦对汞的吸附量比原始活性焦分别提高了60%、113%和140%;吸附温度升高,化学反应变快,活性焦的初始脱汞效率由75.8%提高至95%以上,但穿透时间并不呈比例增加;当Zn Cl2负载量由5%提高至15%后,50%穿透率对应时间由75 min延长至120 min,活性焦对汞的吸附值由10.1μg/g增至17.5μg/g。随着汞渗透量的增加,活性焦脱汞效率有所提高,50%穿透率的对应时间由110 min缩短至95 min,最终总吸附值仅由14.4μg/g增至16.2μg/g。     

Crosslinked poly(glycidyl methacrylate)‐based resin for removal of mercury from aqueous solutions

Glycidyl methacrylate–based resin crosslinked beads with acetamide functions were demonstrated to be efficient in the removal of mercury. Beaded polymer supports were prepared by suspension polymerization of glycidyl methacrylate (0.9 mol) and ethylene glycol dimethacrylate (0.1 mol). The resulting copolymer beads were modified through epoxy functions in two steps: (1) by treatment with excess dibutyl amine and (2) by subsequent reaction with chloroacetamide. The resulting polymer resin, which had a chloroacetamide content of 2.5 mmol/g, was effective in extracting mercury from aqueous solutions. The mercury sorption capacity was around 2.2 mmol/g in nonbuffered conditions. Experiments performed in identical conditions with several metal ions revealed that Cd(II), Pb(II), Zn(II), and Fe(III) ions also were extractable in low quantities (0.2–0.8 mmol/g). The sorbed mercury could be eluted by repeated treatment with hot acetic acid without hydrolysis of the amide groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 348–352, 2006     

Simultaneous removal of humic acid and heavy metal from aqueous solutions using charged ultrafiltration membranes

Lab-made negatively charged ultrafiltration (UF) membranes were used for simultaneous removal of humic acid (HA) and heavy metals from water. Effects of the HA/metal ratio, solution pH and ionic strength on rejection coefficients of HA and metals were investigated. The results showed that the rejection coefficients of both HA and metals increase with the increase of pH and the HA/metal ratio, and the decrease of ionic strength. This study indicated that charged UF could be an effective method for the simultaneous removal of HA and heavy metal harnessing the principle of complexation UF and electrostatic repulsion between the membrane and the HA–M complex of the same charges.     

Preparation of poly(acrylamide) grafted onto crosslinked poly (HEMA-MMA-EGDMA) beads for the removal of phenol

ABSTRACT

Poly(acrylamide) (PAAM) was grafted onto crosslinked poly(hydroxy ethyl methacrylate) (HEMA)-based beads for the removal of phenol from aqueous solution. A beaded polymer with a PAAM surface shell was prepared in two steps: synthesis of crosslinked poly (HEMA (50% mol) - MMA (40% mol) - EGDMA (10% mol)) terpolymers spherical beads (200–420 µm) (resin 1) via the suspension polymerization method; and the grafting of PAAM was carried out by redox initiation from hydroxyl groups on resin1 by using cerium (IV) ammonium nitrate as the initiator.

The resulting polymeric sorbent (resin 2) with about 82 wt.% grafted PAAM has been demonstrated to be efficient to remove phenol from water. Moreover, phenol sorption capacities of resin 1 and resin 2 were compared and sorption experiments were performed depending on the initial phenol concentration and pH. Kinetic measurements and models were studied for resin 1 and resin 2.     

氯元素对燃煤烟气脱汞的影响研究进展

燃煤电厂是最主要的人为汞排放污染源,氯元素对汞的形态转化及脱除率有非常重要的影响。本文概述了燃煤电厂汞的释放特性和现有控制技术,从氯元素作为烟气组分、活性炭改性物以及燃料添加剂这3个方面详细阐述了氯对汞排放控制的影响。首先氯化氢作为烟气组分,对单质汞向氧化态汞的形态转化有促进作用,这有利于现有除尘、脱硫装置对烟气汞的脱除。含氯化合物改性活性炭吸附剂时,物理吸附和化学吸附同时存在,这能有效提高吸附剂对汞的吸附性能。氯化物作为燃煤添加剂也能有效促进烟气汞的氧化和脱除,其中氯元素在湿法脱硫废水中富集,如何把其利用到烟气汞的脱除对开发高效脱汞技术有重要的意义。同时,比较了以上3种氯添加方案的优缺点。最后指出,深入研究氯元素对汞作用机理是今后的研究方向。     

金属硫化物吸附剂脱除烟气汞研究进展

工业烟气排放的汞严重危害人体健康及生态环境,金属硫化物是一种新型的高效汞吸附剂,受到广泛关注。本文总结了近年来金属硫化物应用于脱除烟气汞的研究进展。归纳了不同金属硫化物的吸附性能,并对影响吸附性能的常见因素进行了梳理,已有研究表明金属硫化物在复杂的反应条件下仍具有优异的脱汞性能;进一步归纳了金属硫化物的汞吸附机理;总结出活性位和比表面积的调控是当前强化金属硫化物汞吸附性能的常见方法;最后对金属硫化物的再生方法进行了介绍。基于当前研究进展,未来的研究应关注如何强化金属硫化物在高温下的脱汞性能,以及如何在低温条件下实现汞的脱附从而避免当前高温热脱附方法对金属硫化物结构的破坏。     

New sorbent hydrogels for removal of acidic dyes and metal ions from aqueous solutions

Summary Poly(N-hydroxymethylacrylamide), PHMA, hydrogels were prepared by using N-hydroxymethylacrylamide, HMA, monomer and polyethyleneglycol(400)diacrylate as a crosslinking agent in aqueous medium and then amine groups were incorporated onto PHMA hydrogels by amination reaction with different diamines. The obtained hydrogels were characterized by determination of amine value, hydroxymethyl group content and FTIR spectra. The amine value of hydrogels changed from 2.23 to 4.64 mmol/g by depending on the amine compounds used in amination reaction. Their swelling degree increased at acidic pH values and they showed pH dependent swelling behaviour. They were used as sorbent for removal of indigo carmine and Cu(II) ion, as a model dye molecule and metal ion, respectively, from aqueous solutions. The adsorption properties of the hydrogels were investigated by depending on pH, time and initial indigo carmine or Cu(II) ion concentration. It was seen that the amine group incorporated hydrogels have quite high adsorption rate and adsorption capacity, and their adsorption capacities changed with pH of the solution. Langmuir isotherm model was the best fit for adsorption of both indigo carmine and Cu (II) ion.