细菌纤维素对重金属离子的吸附机理研究

以细菌纤维素(BC)为吸附剂,对重金属离子Cu2+,Pb2+和Cd2+的吸附等温线和吸附动力学特性进行了研究,并采用红外光谱分析法探讨了吸附作用机理。结果表明:BC对Cu2+,Pb2+和Cd2+吸附更好地符合Langmuir吸附等温方程和准二级反应动力学模型,说明吸附过程为单分子层吸附,化学吸附作用为主。粒子内扩散拟合曲线均不经过原点,证明粒子内扩散并不是唯一速率控制步骤。FT-IR分析表明吸附金属离子后的BC中—OH最大吸收位发生不同程度的蓝移,说明BC中部分—OH参与吸附,即与重金属离子之间发生反应,从而使—OH的数量减少。     

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     

Competitive removal of heavy metal ions by cellulose graft copolymers

The effect of composition of graft chains of four types cellulose graft copolymers on the competitive removal of Pb²⁺, Cu²⁺, and Cd²⁺ ions from aqueous solution was investigated. The copolymers used were (1) cellulose‐g‐polyacrylic acid (cellulose‐g‐pAA) with grafting percentages of 7, 18, and 30%; (2) cellulose‐g‐p(AA–NMBA) prepared by grafting of AA onto cellulose in the presence of crosslinking agent of N,N′‐methylene bisacrylamide (NMBA); (3) cellulose‐g‐p(AA–AASO₃H) prepared by grafting of a monomer mixture of acrylic acid (AA) and 2‐acrylamido‐2‐methyl propane sulphonic acid (AASO₃H) containing 10% (in mole) AASO₃H; and (4) cellulose‐g‐pAASO₃H obtained by grafting of AASO₃H onto cellulose. The concentrations of ions which were kept constant at 4 mmol/L in an aqueous solution of pH 4.5 were equal. Metal ion removal capacities and removal percentages of the copolymers was determined. Metal ion removal capacity of cellulose‐g‐pAA did not change with the increase in grafting percentages of the copolymer and determined to be 0.27 mmol metal ion/g_copolymer. Although the metal removal rate of cellulose‐g‐p(AA–NMBA) copolymer was lower than that of cellulose‐g‐pAA, removal capacities of both copolymers were the same which was equal to 0.24 mmol metal ion/g_copolymer. Cellulose did not remove any ion under the same conditions. In addition, cellulose‐g‐pAASO₃H removed practically no ion from the aqueous solution (0.02 mmol metal ion/g_copolymer). The presence of AASO₃H in the graft chains of cellulose‐g‐p(AA–AASO₃H) created a synergistic effect with respect to metal removal and led to a slight increase in metal ion adsorption capability in comparison to that of cellulose‐g‐pAA. All types of cellulose copolymers were found to be selective for the removal of Pb²⁺ over Cu²⁺ and Cd²⁺. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2034–2039, 2003     

Adsorption for metal ions of chitosan coated cotton fiber

A kind of adsorbent for metal ions, cotton fiber coated by high loading of chitosan (SCCH) was prepared. Its structure was characterized by elemental analysis, scanning electronic microscopy (SEM), Fourier transform infrared spectrum (FTIR), and wide‐angle X‐ray diffraction (WAXD). The adsorption properties of SCCH for Cu²⁺, Ni²⁺, Pb²⁺, Cd²⁺, such as saturated adsorption capacities, static kinetics, and isotherm were investigated. The adsorption for Ni²⁺, Pb²⁺, and Cd²⁺ was controlled by liquid film diffusion, but by particle diffusion for Cu²⁺. The adsorption process for Cu²⁺, Ni²⁺, Cd²⁺ could be described with Langmuir or Freundlich equation, but only with Freundlich equation for Pb²⁺. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of sulfhydryl chitin and its adsorption properties for heavy metal ions

This article discusses the preparation of the water‐insoluble adsorbent sulfhydryl chitin (s‐chitin), by treatment of the chitin with sulfhydryl acetic acid in the presence of sulfuric acid as a catalyst. Its structure was confirmed by elemental analysis, FTIR spectra analysis and near‐IR spectra analysis. We also investigated the adsorption properties of sulfhydryl chitin for Cu^II, Cd^II, Pb^II, Cr^III, and Ni^II. Based on the research results of adsorption capacity, the effect of pH value on adsorption, adsorption kinetics experiments, and selective adsorption experiments were observed. It has been shown that the s‐chitin has much better adsorption for Pb^II, Cu^II, and Cd^II than chitin itself. The adsorption capacities of s‐chitin for Pb^II, Cu^II, and Cd^II were 108.3, 94.7, and 57.1 mg/g, respectively. It also had good adsorption properties for heavy metal ions. The adsorption capacities were also affected by the acidity of medium. The adsorbed Cu^II, Cd^II, and Pb^II could be eluted by diluted chlorhydric acid. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 151–155, 2000     

风化煤对水中重金属离子的吸附

以甘肃景泰风化煤作吸附剂,常温下对水溶液Pb^2＋、Cu^2＋、Zn^2＋进行了吸附实验研究,探讨了吸附动力学、吸附平衡、介质酸度的影响及吸附机理。结果表明,风化煤对几种重金属离子的吸附具有pseudo-second-order Lagergren模型的特征,吸附平衡基本符合Langmuir模型,介质酸度对吸附效果有显著的影响,pH大于5时吸附率均可接近90％。     

Calixarene-based extractants for heavy metal ions removal from aqueous solutions

The article reviews the literature on the possibility of application of the calixarene-based compounds for selective separation of toxic heavy metals from aqueous solutions by the solvent extraction and transport across liquid membranes. The specific three-dimensional structure of calixarenes and their derivatives, simple and low-cost synthesis, and ease of chemical transformation qualify these compounds for the role of selective chemical extractants of toxic heavy metal ions present in industrial wastewater. This article analyses the influence of various process factors, with the greatest emphasis on the structure of the extractants/carriers, on efficient separation of heavy metal ions, primarily those most commonly found in galvanic wastewater.     

分子印迹吸附剂对红景天水煎液中重金属的吸附

采用分子印迹技术,以Pb（Ⅱ）为印迹离子制备了铅印迹壳聚糖包覆硅藻土微球（PbCSDE）。研究了PbCSDE对红景天水煎液中重金属Pb（Ⅱ）、Cu（Ⅱ）的吸附,考察了吸附时间、溶液pH对吸附的影响。与732商业树脂比较,铅印迹壳聚糖包覆硅藻土微球（PbCSDE）对红景天水煎液中Pb（Ⅱ）、Cu（Ⅱ）的吸附能力提高了2倍多。紫外光谱和高效液相色谱分析表明,经PbCSDE吸附后,红景天水煎液中的活性成分红景天苷没有发生改变。     

表面离子印迹聚合物金属离子吸附材料研究进展

离子印迹聚合物吸附材料对模板离子具有强识别能力,对其可实现高选择吸附,因而离子印迹技术常用于制备高选择性吸附材料。但传统方法制备的离子印迹吸附材料,因识别位点容易被包埋导致其吸附容量小、吸附-脱附速率低,而表面离子印迹技术则是采用模板离子和聚合单体直接在载体表面或附近区域构筑选择性识别位点,所有活性位点均暴露,从而有效地解决了上述问题。本文从技术原理与合成原料、制备工艺方法以及载体材料类型等方面对表面印迹聚合物吸附材料近期研究进展情况进行了概述。针对相关研究现状,从载体材料、功能单体、目标离子等角度分析和讨论了表面离子印迹聚合物吸附材料当前发展中的不足及其所面临的挑战,并对表面离子印迹技术发展趋势和前景进行了展望。     

Amidinothiourea-linked covalent organic framework for the adsorption of heavy metal ions

For the first time, a novel amidinothiourea-linked covalent organic framework (COF) (TpAt) has been successfully synthesized by the condensation between 1,3,5-triformylphloroglucinol and amidinothiourea via vacuum solvothermal reaction, and was further utilized for the adsorption of metal ions from aqueous solution. The effects of initial concentration, pH and contact time on the adsorption process were investigated. As a result, the TpAt COF showed maximum binding capacities as high as 95.44, 100.76 and 99.08 mg g^–1 for Cr(III), Cd(II) and Cu(II) within 180 min at the initial concentration of 100 mg L^–1, respectively. The isotherms of metal ions onto TpAt could be described by the Freundlich isotherm equation, and the adsorption kinetics followed the pseudo-second-order model. The TpAt could be reused for more than five adsorption–elution cycles, whilst basically maintaining its original adsorption performance and the structural integrity of the COF layers. The robust adsorption efficiency can be attributed to the coordination between metal ions and N, O and S atoms in the TpAt framework. The TpAt COF represents an ideal candidate for the removal of heavy metal ions in environmental pollution treatment. © 2021 Society of Industrial Chemistry.     

生物膜吸附重金属离子的模型及影响因素的研究

重金属是对生态环境危害极大的一类污染物。去除废水中的重金属元素,生物膜法是一种有效的净化工艺。为了寻找生物膜去除重金属离子的最优操作条件,考察了各种影响因素pH值、温度、吸附时间、生物膜量、共存离子对吸附的影响。从实验结果可知,Cu2+的最优操作条件是pH值为6,温度在30℃左右,吸附时间为15min,生物膜量为12g,吸附率可达到65%;Cr3+的最优操作条件是pH值为3～7,温度在25℃左右,吸附时间为5min,生物膜量为10g,吸附率可达到87%。共存离子的竞争吸附会对吸附能力弱的Cu2+产生很大的影响,Cr3+没有表现出受到抑制或促进作用的影响,对单一Cu2+或Cr3+吸附体系,可以用经典的吸附模型进行拟合。     

Modified polyacrylamide hydrogels and their application in removal of heavy metal ions

Modified crosslinked polyacrylamides having different functional groups were prepared by Mannich reaction using different amine compounds such as ethylenediamine (EDA), diethylenetriamine (DETA) and triethylenetetramine (TETA) and sulfomethylation reaction. Products were characterized by determination of their basic group content (BGC), hydroxymethyl group content (HMG), equilibrium degree of swelling (EDS) and FT-IR spectra. For Mannich reactions, BGC and EDS changed with amount of employed amine compounds, reaction time and temperature. Sulfomethylation reactions gave products with high BGC and very high EDS. FT-IR spectroscopic analysis confirmed that a parallel hydrolysis reaction occurred along with the expected modification reactions. The products were used for removal of Cu(II), Cd(II) and Pb(II) ion under competitive and non-competitive conditions at different pH. The metal ion removal capacities changed depending their BGC and EDS. While the Mannich products were selective towards Cu(II) ion, the sulfomethylation products were highly selective to Pb(II) ions. The polymers were used several times by regeneration without loss of adsorption capacity and changing of selectivity properties.     

Radiation-induced grafting of acrylamide and methacrylic acid individually onto carboxymethyl cellulose for removal of hazardous water pollutants

Carboxymethyl cellulose hydrogels were synthesized by grafting of acrylamide (AAm) and methacrylic acid (MAAc) individually with different concentrations onto carboxymethyl cellulose (CMC) using direct radiation grafting technique. It was found that for both Poly(CMC/AAm) and Poly(CMC/MAAc), the grafting yield and grafting ratio increase with the increasing monomer concentration. Also, it is noted that both grafting ratio and grafting yield of Poly(CMC/AAm) are higher than that of Poly(CMC/MAAc). The effect of different monomer concentrations on gel (%) and swelling behavior was studied. It is found that the increasing monomer concentration increases gel (%). For Poly(CMC/AAm) hydrogels, the swelling behavior decreases with increasing AAm concentration due to high crosslinking hydrogel formation, while as MAAc content increases, swelling behavior increases up to Poly(CMC/MAAc) 1:25 wt%. Swelling kinetics and diffusion mechanism indicate that the water penetration obeys non-Fickian transport mechanism. The structures and properties of the original CMC and the prepared Poly(CMC/MAAc) and Poly(CMC/AAm) were characterized using different analytical tools such as Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and scanning electron microscope (SEM). This study provides a solution to the discharge of different pollutants from wastewater. The adsorption capacity of Poly(CMC/MAAc) and Poly(CMC/AAm) hydrogels toward heavy metals, Cu⁺² and Co⁺², dyes such as acid blue dye and methyl green, and organic contaminants such as 4-chlorophenol and 2,4-Dichlorophenoxy acetic acid has been investigated.     

Heavy metal removal by ion exchanger based on hydroxyethyl cellulose

In the present work, ion exchange resin based on hydroxyethyl cellulose has been synthesized to remove the heavy metals, such as iron, cobalt, copper, and zinc from their aqueous solutions. The conditions in the column and batch modes were investigated for this purpose. The resin, having an average swelling percentage of 75.94 and an exchange capacity of 2.57 meq g⁻¹ resin, is being introduced as a new ion exchange resin in the heavy metal removal process. An investigation of the column operations using aqueous solutions of heavy metal ions indicated that the resin prepared has some advantages, including high total exchange capacity and good chemical stability. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3501–3506, 1999     

活性污泥吸附重金属离子的研究进展

从处理含重金属离子废水的现状出发,简述了活性污泥吸附重金属离子过程中的表面有机络合、离子交换及其它机理;讨论了温度、时间、pH值、污泥种类、预处理、重金属离子浓度等因素对活性污泥吸附重金属离子的影响,并对解吸方式进行了论述;综述了目前国内外有关活性污泥吸附重金属离子的最新研究成果,指明了进一步加强吸附机理和固定化技术以提高活性污泥应用性的研究是今后的方向。     

Polymer brushes on graphene oxide for efficient adsorption of heavy metal ions from water

The pollution of heavy metal ions in water poses a serious threat to human being and ecosystems. Here, we report polyamidoxime (PAO) brush grafted graphene oxide (GO) as a highly efficient adsorbent for extraction of toxic metal cations from water. Surface-initiated atom transfer radical polymerization was used to grow polyacrylonitrile (PAN) brushes on GO, followed by conversion of the nitrile groups in PAN into amidoxime groups, which had high binding affinity toward heavy metal cations. The PAO brush grafted GO demonstrated significantly fast adsorption kinetics and large adsorption capacity. At optimal pH 5, the PAO brush grafted GO can achieve maximum adsorption capacities of 116.7 mg g⁻¹ for Pb(II), 258.6 mg g⁻¹ for Ag(I), 192.2 mg g⁻¹ for Cu(II), and 167.9 mg g⁻¹ for Fe(III), which were significantly larger than those of small molecule functionalized GO. Mechanism analysis suggested that the enhanced adsorption performance was due to the myriads of functional groups in PAO brushes that were easily accessible to metal ions because of the swelling of the polymer brushes in water. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48156.     

Intelligent self-healable electroactive carboxymethyl cellulose hydrogel containing conductive polythiophene and acid hydrolyzed cellulose

Self-healable electroactive carboxymethyl cellulose/polythiophene/acid hydrolyzed cellulose (CMC/PTh/AHC) hydrogels were successfully fabricated. AHC particles dispersed well in the CMC matrix improving hydrogels thermal stability. The electro-responsive performance of the hydrogels was investigated with respect to bending angle and bending sensitivity. The results showed that under an applied electric field, the CMC/PTh/AHC hydrogels bend toward a cathode electrode. In addition, the electroactive performance of the hydrogels decreased with increased AHC content. The CMC/PTh/AHC10 (10 wt.% AHC) hydrogel exhibited the shortest induction time (τ_ind) of 3.35 ± 0.56 s. For self-healing, it was found that the hydrogel with addition of 2 wt.% AHC had the highest self-healing efficiency on both tensile strength and elongation at break (93.37 ± 3.17% and 99.35 ± 12.11%, respectively). While the self-healing efficiency on bending angle was 82.73 ± 14.55%. The results demonstrated that the properties of the CMC/PTh/AHC2 hydrogel were close to its original properties after healing for 24 h. The results demonstrated that the CMC/PTh/AHC hydrogel can be utilized as an actuator or artificial muscle using electrical stimulus.     

三维网络水凝胶在重金属和染料吸附方面的研究进展

近年来,三维网络水凝胶由于具有较高的吸附容量、较快的吸附速率和较好的再生性能,在废水处理方面受到了人们的广泛关注。本文简单介绍了三维网络水凝胶,重点评述了在重金属离子和染料废水方面的研究进展,并探讨了三维网络水凝胶吸附处理中存在的问题,展望了今后重点研究的方向。