Predicting heavy metals’ adsorption edges and adsorption isotherms on MnO2 with the parameters determined from Langmuir kinetics

Although surface complexation models have been widely used to describe the adsorption of heavy metals, few studies have verified the feasibility of modeling the adsorption kinetics,edge, and isotherm data with one p H-independent parameter. A close inspection of the derivation process of Langmuir isotherm revealed that the equilibrium constant derived from the Langmuir kinetic model, K S-kinetic, is theoretically equivalent to the adsorption constant in Langmuir isotherm, K S-Langmuir. The modified Langmuir kinetic model(MLK model) and modified Langmuir isotherm model(MLI model) incorporating p H factor were developed. The MLK model was employed to simulate the adsorption kinetics of Cu(II), Co(II), Cd(II), Zn(II) and Ni(II) on Mn O2 at p H 3.2 or 3.3 to get the values of K S-kinetic. The adsorption edges of heavy metals could be modeled with the modified metal partitioning model(MMP model), and the values of K S-Langmuir were obtained. The values of K S-kinetic and K S-Langmuir are very close to each other, validating that the constants obtained by these two methods are basically the same. The MMP model with K S-kinetic constants could predict the adsorption edges of heavy metals on Mn O2 very well at different adsorbent/adsorbate concentrations. Moreover, the adsorption isotherms of heavy metals on Mn O2 at various p H levels could be predicted reasonably well by the MLI model with the K S-kinetic constants.     

Modification of a magnetic carbon composite for ciprofloxacin adsorption

A magnetic carbon composite, Fe₃O₄/C composite, was fabricated by one-step hydrothermal synthesis, modified by heat treatment under an inert atmosphere (N₂), and then used as an adsorbent for ciprofloxacin (CIP) removal. Conditions for the modification were optimized according to the rate of CIP removal. The adsorbent was characterized by Fourier transform infrared spectroscopy, X-ray diffraction measurements, vibrating-sample magnetometry, scanning electron microscopy, transmission electron microscopy, and N₂ adsorption/desorption isotherm measurements. The results indicate that the modified adsorbent has substantial magnetism and has a large specific area, which favor CIP adsorption. The effects of solution pH, adsorbent dose, contact time, initial CIP concentration, ion strength, humic acid and solution temperature on CIP removal were also studied. Our results show that all of the above factors influence CIP removal. The Langmuir adsorption isotherm fits the adsorption process well, with the pseudo second-order model describing the adsorption kinetics accurately. The thermodynamic parameters indicate that adsorption is mainly physical adsorption. Recycling experiments revealed that the behavior of adsorbent is maintained after recycling for five times. Overall, the modified magnetic carbon composite is an efficient adsorbent for wastewater treatment.     

表面活性剂改性沸石对水中酚类化合物吸附性能研究

使用表面活性剂对2种粉煤灰合成沸石进行改性处理,研究改性沸石对酚类化合物（苯酚、对氯酚和双酚A）的吸附特性.吸附试验结果表明,合成沸石经过阳离子表面活性剂十六烷基三甲基溴化铵改性后,对酚类化合物的吸附性能均有大幅提升,吸附等温线模型均较符合Langmuir模型.2种改性沸石对酚类化合物（苯酚、对氯酚和双酚A）的Langmuir理论最大吸附量分别可达37.7、52.36、90.9 mg.g-1和10.71、22.83、56.8 mg.g-1.当溶液pH值高于酚类化合物的解离系数pKa时,吸附效果随pH升高而增加.结果还表明,酚类化合物的疏水性（辛醇/水分配系数Kow）越强,改性沸石的吸附能力也越高.     

苯胺黑药高效降解菌(Bacillus vallismortis)胞外聚合物去除重金属的研究

微生物胞外聚合物(Extracellular Polymeric Substances,EPS)在废水中重金属的吸附去除过程中起着非常重要的作用.苯胺黑药高效降解菌(Bacillus vallismortis)对苯胺黑药有良好的降解能力,但对其吸附重金属的性能研究还不充分.因此,本文采用3种方法提取苯胺黑药高效降解菌的EPS,主要考察了p H、温度、底物浓度和时间对重金属去除效果的影响.结果表明,热提法提取的效率较高;p H对金属离子吸附影响很大,当p H7时,随着p H变大吸附量逐渐升高,而温度对吸附量影响不大.EPS对Cu~(2+)、Zn~(2+)的去除为快速表面吸附过程,在第8 min时对Cu~(2+)、Zn~(2+)的去除率分别达到了90.7%、52.3%,EPS对Cu~(2+)、Zn~(2+)的吸附表观上符合拟二级动力学规律.在单一体系中,根据Langmuir方程计算出EPS对Cu~(2+)的最大吸附量为2.155 mg·mg-1,对Zn~(2+)的最大吸附量为0.508 mg·mg-1;Cu~(2+)吸附过程与Freundlich方程拟合效果较好,Zn~(2+)吸附过程与Langmuir方程拟合效果较好.红外光谱分析结果表明,EPS表面的羟基、氨基、酰胺基团、羧基和C—O—C基团都参与了吸附,且Cu~(2+)和Zn~(2+)的吸附位点基本一致,本文的研究结果对工程实践具有一定的理论指导意义.     

邻菲罗啉对蒙脱石吸附镍离子性能影响

利用镍离子能与邻菲罗啉反应生成螯合物的性质,研究了加与未加邻菲罗啉条件下,蒙脱石对金属镍离子的吸附行为,考察了镍离子浓度、吸附时间、温度和溶液pH值等因素对吸附性能的影响.结果表明:加入邻菲罗啉后,蒙脱石对镍的螯合离子的吸附量明显增大;吸附平衡时间约为120min;蒙脱石对[Ni(phen)n]2+的吸附性基本不受pH值的影响.动力学研究表明该吸附过程符合准二级反应动力学模型,吸附量随温度升高而增大.二级动力学参数证明加入邻菲罗啉可显著提高蒙脱石对Ni2+的吸附性.蒙脱石对简单Ni2+的吸附符合Langmuir的单层吸附等温式;而蒙脱石对镍的螯合离子的吸附则符合Freundlich等温式.蒙脱石对Ni2+和[Ni(phen)n]2+的吸附均为自发、吸热和更无序的;XRD及FTIR研究表明,蒙脱石对[Ni(phen)n]2+的吸附以层间的物理吸附为主.     

TiO2/Ag modified penta-bismuth hepta-oxide nitrate and its adsorption performance for azo dye removal

A modified hydrophilic penta-bismuth hepta-oxide nitrate (Bi₅O₇NO₃) surface was synthesized via a precipitation method using TiO₂ and Ag as modified agents. The synthesized product was characterized by different analytical techniques. The removal efficiency was evaluated using mono-and di-sulphonated azo dyes as model pollutants. Different kinetic, isotherm and diffusion models were chosen to describe the adsorption process. X-ray photoelectron spectroscopy (XPS) results revealed no noticeable differences in the chemical states of modified adsorbent when compared to pure Bi₅O₇NO₃;however, the presence of hydrophilic centres such as TiO₂ and Ag developed positively charged surface groups and improved its adsorption performance to a wide range of azo dyes. Dyes removal was found to be a function of adsorbent dosage, initial dye concentration, solution pH and temperature. The reduction of Langmuir 1,2-mixed order kinetics to the second or first-order kinetics could be successfully used to describe the adsorption of dyes onto the modified adsorbent. Mass transfer can be described by intra-particle diffusion at a certain stage, but it was not the rate limiting step that controlled the adsorption process. Homogenous behavior of adsorbent surface can be explored by applying Langmuir isotherm to fit the adsorption data.     

Adsorptive removal of heavy metal ions from industrial effluents using activated carbon derived from waste coconut buttons

Removal of heavy metal ions from industrial effluents by the activated carbon prepared by steam activation of waste coconut buttons through batch adsorption process.     

Thermodynamics and kinetics of cadmium adsorption onto oxidized granular activated carbon

Cadmium sorption behavior of granular activated carbon oxidized with nitric acid was systematically studied by sets of the equilibrium and time-based experiments under various conditions.The cadmium adsorption capacity of oxidized granular activated carbon enlarged with an increase in pH,and reduced with an increase in ionic strength.Experimental data were evaluated to find out kinetic characteristics.Adsorption processes were found to follow pseudo-second order rate equation.Adsorption isotherms correlate well with the Langmuir isotherm model and the maximum sorption capacity of cadmium evaluated is 51.02μmol/g.Thermodynamic parameters were calculated based on Van't Hoff equation.Equilibrium constant Kd was evaluated from Freundlich isotherm model constants,Langmnir isotherm model constants,and isotherms,respectively.The average change of standard adsorption heatΔH~0 was -25.29 kJ/mol.NegativeΔH~0 andΔG~0 values indicate the adsorption process for cadmium onto the studied activated carbon is exothermic and spontaneous.The standard entropyΔS~0 was also negative,which suggests a decrease in the freedom of the system.     

Effect of Na+ impregnated activated carbon on the adsorption of NH4+-N from aqueous solution

Two kinds of activated carbons modified by Na+ impregnation after pre-treatments involving oxidation by nitric acid or acidification by hydrochloric acid (denoted as AC/N-Na and AC/HCl-Na, respectively), were used as adsorbents to remove NH4+-N. The surface features of samples were investigated by BET, SEM, XRD and FT-IR. The adsorption experiments were conducted in equilibrium and kinetic conditions. Influencing factors such as initial solution pH and initial concentration were investigated. A possible mechanism was proposed. Results showed that optimal NH4+-N removal efficiency was achieved at a neutral pH condition for the modified ACs. The Langmuir isotherm adsorption equation provided a better fit than other models for the equilibrium study. The adsorption kinetics followed both the pseudo second-order kinetics model and intra-particle kinetic model. Chemical surface analysis indicated that Na+ ions form ionic bonds with available surface functional groups created by pre-treatment, especially oxidation by nitric acid, thus increasing the removal efficiency of the modified ACs for NH4+-N. Na+-impregnated ACs had a higher removal capability in removing NH4+-N than unmodified AC, possibly resulting from higher numbers of surface functional groups and better intra-particle diffusion. The good fit of Langmuir isotherm adsorption to the data indicated the presence of monolayer NH4+-N adsorption on the active homogenous sites within the adsorbents. The applicability of pseudo second-order and intra-particle kinetic models revealed the complex nature of the adsorption mechanism. The intra-particle diffusion model revealed that the adsorption process consisted not only of surface adsorption but also intra-particle diffusion.     

Functionalized CMK-3 mesoporous carbon with 2-amino-5-mercapto-1,3,4-thiadiazole for Hg(II) removal from aqueous media

Ordered mesoporous carbon（CMK-3） was synthesized and functionalized with 2-amino-5-mercapto-1,3,4-thiadiazole groups（AMT-OCMK-3） for Hg（Ⅱ） removal from aqueous solution. The modified CMK-3 was characterized by X-ray diffraction, N2adsorption-desorption isotherm, scanning electron microscopy and Fourier transform infrared spectroscopy. The effects of solution pH, contact time, initial Hg（Ⅱ） concentration and matrix effect were studied. The adsorption data were successfully fitted with the Langmuir model, exhibiting high adsorption capacity of 450.45 mg/g of AMT-OCMK-3. In the solid-phase extraction system a series of experimental parameters such as sample flow rate, sample volume,eluent volume and concentration of the eluent solution have been investigated and established for preconcentration of Hg（Ⅱ） in aqueous solution. The results showed that the enrichment factor for Hg（Ⅱ） was 250, the precision（relative standard deviation（RSD）, %） for six replicate measurements was 2.05% and the limit of detection for Hg（Ⅱ） was achieved at0.17 μg/L.     

一种改性微生物吸附剂的制备及其对镉离子的吸附特性

改性生物吸附剂具有更好的重金属离子去除能力,成为近年来研究热点.本研究通过向菌株拉乌尔菌Raoultella sp. X13生长培养基中添加特定盐获得改性吸附剂,并研究了其镉离子（Cd²⁺）吸附特性.研究结果表明,相比原始菌体X13,经KCl、K₂SO₄、KH₂PO₄、（NH₄）₂SO₄和NH₄Cl改进的生长培养基制备的吸附剂提高了对Cd²⁺吸附效果.其中,NH₄Cl改性的拉乌尔菌Raoultella sp. X13（命名为R5-1）对Cd²⁺吸附能力显著增加,达66.40 mg·g^-1,增加了47.30%.这一显著变化主要依赖于生长代谢引起的细胞表面结构变化.Cd²⁺吸附特性研究结果表明生物吸附过程受溶液pH、初始金属浓度和接触时间的影响.Langmuir等温线模型和伪二级动力学模型更加符合吸附剂R5-l对Cd²⁺的吸附数据. FTIR分析表明R5-l表面存在多种功能位点并可能参与金属离子的结合,例如—OH,—CH₂,N—H, —COO,磷酸盐或硫酸盐等官能团.模拟实验结果表明吸附剂R5-l可以有效修复废水中多种金属离子.因此,本研究获得的改性吸附剂R5-l可以作为重金属Cd²⁺的潜在微生物修复剂,并为高效,简便,环保地制备改性吸附剂提供一定的参考.     

A comparative study and evaluation of sulfamethoxazole adsorption onto organo-montmorillonites

Three organo-montmorillonites were prepared using surfactants, and their adsorption behaviors toward sulfamethoxazole（SMX） were investigated. The surfactants used were cetyltrimethyl ammonium bromide（CTMAB）, 3-（N,N-dimethylhexadecylammonio） propane sulfonate（HDAPS） and 1,3-bis（hexadecyldimethylammonio）-propane dibromide（BHDAP）. The properties of the organo-montmorillonites were characterized by X-ray diffraction, scanning electron microscopy and N2adsorption–desorption isotherm measurements. Results showed that the interlayer spacing of montmorillonite was increased and the surface area as well as the morphology were changed. Batch adsorption experiments showed that the surfactant loading amount had a great effect on the adsorption of SMX. The adsorption process was p H dependent and the maximum adsorption capacity was obtained at p H 3 for HDAPS-Mt, while CTMAB-Mt and BHDAP-Mt showed a high removal efficiency at 3–11. The adsorption capacity increased with the initial SMX concentration and contact time but decreased with increasing solution ionic strength.Kinetic data were best described by the pseudo second-order model. Equilibrium data were best represented by the Langmuir model, and the Freundlich constant（n） indicated a favorable adsorption process. The maximum adsorption capacity of SMX was 235.29 mg/g for CTMAB-Mt, 155.28 mg/g for HDAPS-Mt and 242.72 mg/g for BHDAP-Mt. Thermodynamic parameters were calculated to evaluate the spontaneity and endothermic or exothermic nature. The adsorption mechanism was found to be dominated by electrostatic interaction,while hydrophobic interaction played a secondary role.     

改性稻草吸附铜离子的动力学机理

研究表明稻草改性后吸附铜离子的能力得到很大提高。研究表明吸附相当好地符合假二级吸附速率模型,测定了在4个温度下(15℃,27℃,37℃,50℃)的吸附速率常数。吸附平衡可用Langmiur吸附模型和Freundlich吸附模型处理。讨论了pH对吸附的影响。     

有机改性凹凸棒石对养猪废水中有机物的吸附研究

研究表征了十二烷基二甲基甜菜碱和十六烷基三甲基溴化铵改性凹凸棒石的结构,探讨了改性凹凸棒石对猪粪废水中的有机污染物的吸附性能及机理,并考察了改性剂修饰比例、废水p H、吸附剂的投加量对吸附过程的影响.结果表明,两种改性剂成功结合到了凹凸棒石表面,有机改性凹凸棒石的晶体结构未发生改变,但对有机污染物的吸附能力显著高于原土.两性和阳离子改性凹凸棒石吸附有机污染物的最佳参数为:修饰比例为100%,吸附剂浓度为16 g·L~(-1),p H=4(阳离子改性为6),对猪粪废水中COD的去除率分别达到88%和92%,吸附量分别达到79 mg·g~(-1)和82 mg·g~(-1).吸附过程均符合二级动力学模型(R20.998),两性和阳离子改性凹凸棒石对有机物的吸附分别符合Freundlich和Langmuir等温式.有机改性凹凸棒石的疏水性增强,提高了对有机污染物的吸附能力,其沉降性能良好,这使其作为一种吸附剂用于实际养猪废水的处理成为可能.     

Effective adsorption of quadrivalent cerium by synthesized laurylsulfonate green rust in a central composite design

The layered laurylsulfonate intercalated green rust (lauryl-S GR) was synthesized to evaluate the influence of synthesis parameters and aqueous conditions on the adsorption of Ce^IV. The maximum adsorption capacity of 305.58 mg/g by lauryl-S GR was predictably obtained. The pseudo-first-order kinetic model was appropriate in fitting the whole uptake process in a weak acid environment. Three isotherm models including Langmuir, Freundlich, and Tempkin were all reliable in depicting the isotherm adsorption process. The maximum monolayer adsorption capacity of lauryl-S GR towards Ce^IV was 315.46 mg/g. Ce species including CeO and Ce₂O₃ besides CeO₂ were matched in the XPS distribution, directly indicating the reduction reaction brought by Fe^II in the GR occurred to hydrated Ce^IV ions during the adsorption. Nano-sized Ce particles attached to the lauryl-S GRs after the adsorption experiments were observed in the morphological characterization. Flocculated materials were formed on the surface of the lauryl-S GR at a pH of 7, which further reduced the active sites and disrupted the continuous uptake of Ce^IV to the lauryl-S GR. This study expands the application of GRs and supplies an ideal iron-based material for the construction of the affiliated recovery pathway to the traditional separation of Ce.     

Enhancement of elemental mercury adsorption by silver supported material

Mercury, generally found in natural gas, is extremely hazardous. Although average mercury levels are relatively low, they are further reduced to comply with future mercury regulations, which are stringent in order to avoid releasing to the environment. Herein, vapor mercury adsorption was therefore investigated using two kinds of supports, granular activated carbon (GAC) and titanium dioxide (TiO₂). Both supports were impregnated by silver (5 and 15 wt.%), before testing against a commercial adsorbent (sulfur-impregnated activated carbon, SAC). The adsorption isotherm, kinetics, and its thermodynamics of mercury adsorption were reported. The results revealed that Langmuir isotherm provided a better fit to the experimental data. Pseudo second-order was applicable to describe adsorption kinetics. The higher uniform Ag dispersion was a key factor for the higher mercury uptake. TiO₂ supported silver adsorbent showed higher mercury adsorption than the commercial one by approximately 2 times. Chemisorption of mercury onto silver active sites was confirmed by an amalgam formation found in the spent adsorbents.     

Rapid adsorption of toxic Pb(Ⅱ) ions from aqueous solution using multiwall carbon nanotubes synthesized by microwave chemical vapor deposition technique

Multiwall carbon nanotubes(MWCNTs) were synthesized using a tubular microwave chemical vapor deposition technique, using acetylene and hydrogen as the precursor gases and ferrocene as catalyst. The novel MWCNT samples were tested for their performance in terms of Pb(Ⅱ)binding. The synthesized MWCNT samples were characterized using Fourier Transform Infrared(FT-IR), Brunauer, Emmett and Teller(BET), Field Emission Scanning Electron Microscopy(FESEM) analysis, and the adsorption of Pb(Ⅱ) was studied as a function of p H,initial Pb(Ⅱ) concentration, MWCNT dosage, agitation speed, and adsorption time, and process parameters were optimized. The adsorption data followed both Freundlich and Langmuir isotherms. On the basis of the Langmuir model, Qmaxwas calculated to be 104.2 mg/g for the microwave-synthesized MWCNTs. In order to investigate the dynamic behavior of MWCNTs as an adsorbent, the kinetic data were modeled using pseudo first-order and pseudo second-order equations. Different thermodynamic parameters, viz., ΔH0, ΔS0and ΔG0were evaluated and it was found that the adsorption was feasible, spontaneous and endothermic in nature. The statistical analysis revealed that the optimum conditions for the highest removal(99.9%) of Pb(Ⅱ) are at p H 5, MWCNT dosage 0.1 g, agitation speed 160 r/min and time of 22.5 min with the initial concentration of 10 mg/L. Our results proved that microwave-synthesized MWCNTs can be used as an effective Pb(Ⅱ) adsorbent due to their high adsorption capacity as well as the short adsorption time needed to achieve equilibrium.     

掺杂生物膜组分对黄河乌海段表层沉积物吸附Cd^2＋的影响研究

以生物膜主要组分水铁矿和腐殖酸作为掺杂吸附剂,分析了掺杂前后黄河乌海段表层沉积物对重金属Cd^2＋的吸附特性,探讨了吸附时间、Cd^2＋初始浓度和pH对沉积物吸附Cd^2＋的影响,对吸附动力学和吸附等温线进行了拟合并计算了分配系数。结果表明：腐殖酸和水铁矿掺杂比例的提高增强了沉积物对cd^2＋的吸附能力;掺杂生物膜主要组分对黄河乌海段水体Cd^2＋的吸附过程更符合Langmuir等温吸附曲线（R^2≥0．99,P≤0．02,n=7）;掺杂腐殖酸和水铁矿后沉积物对cd^2＋的分配系数分别为：6．2959和2．7110,二者均高于未掺杂沉积物对Cd^2＋的分配系数（0．8626）,说明掺杂腐殖酸的吸附效果优于掺杂水铁矿的吸附效果;另外,溶液pH对沉积物吸附Cd^2＋影响显著。     

Enhancement of elemental mercury adsorption by silver supported material

Mercury, generally found in natural gas, is extremely hazardous. Although average mercury levels are relatively low, they are further reduced to comply with future mercury regulations, which are stringent in order to avoid releasing to the environment. Herein, vapor mercury adsorption was therefore investigated using two kinds of supports, granular activated carbon (GAC) and titanium dioxide (TiO₂). Both supports were impregnated by silver (5 and 15 wt.%), before testing against a commercial adsorbent (sulfur-impregnated activated carbon, SAC). The adsorption isotherm, kinetics, and its thermodynamics of mercury adsorption were reported. The results revealed that Langmuir isotherm provided a better fit to the experimental data. Pseudo second-order was applicable to describe adsorption kinetics. The higher uniform Ag dispersion was a key factor for the higher mercury uptake. TiO₂ supported silver adsorbent showed higher mercury adsorption than the commercial one by approximately 2 times. Chemisorption of mercury onto silver active sites was confirmed by an amalgam formation found in the spent adsorbents.     

Batch studies of adsorption of copper and lead on activated carbon from Eucalyptus camaldulensis Dehn. Bark

Powdered activated carbon (PAC) prepared from Eucalyptus camaldulensis Dehn. bark was tested for its adsorption capacity for Cu(Ⅱ) and Pb(Ⅱ). The experiment was conducted to investigate the effects of pH, contact time, initial metal concentration, and temperature. The best adsorption of both Cu(Ⅱ) and Pb(Ⅱ) occurred at pH 5, where the adsorption reached equilibrium within 45 min for the whole range of initial heavy metal concentrations (0.1-10 mmol/L). The adsorption kinetics was found to follow the pseudo-...