Activated carbon coated palygorskite as adsorbent by activation and its adsorption for methylene blue

An activation process for developing the surface and porous structure of palygorskite/carbon(PG/C) nanocomposite using ZnC l2 as activating agent was investigated. The obtained activated PG/C was characterized by X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR), field-emission scanning electron microscopy(SEM), and Brunauer–Emmett–Teller analysis(BET) techniques. The effects of activation conditions were examined,including activation temperature and impregnation ratio. With increased temperature and impregnation ratio, the collapse of the palygorskite crystal structure was found to accelerate and the carbon coated on the surface underwent further carbonization. XRD and SEM data confirmed that the palygorskite structure was destroyed and the carbon structure was developed during activation. The presence of the characteristic absorption peaks of C_C and C–H vibrations in the FTIR spectra suggested the occurrence of aromatization. The BET surface area improved by more than 11-fold(1201 m2/g for activated PG/C vs. 106 m2/g for PG/C) after activation, and the material appeared to be mainly microporous. The maximum adsorption capacity of methylene blue onto the activated PG/C reached 351 mg/g. The activated PG/C demonstrated better compressive strength than activated carbon without palygorskite clay.     

Influence of sodium dodecyl sulfate coating on adsorption of methylene blue by biochar from aqueous solution

Biochar is regarded as a promising new class of materials due to its multifunctional character and the possibility of effectively coupling different properties. With increasing introduction into the environment, environmental chemicals such as surfactants will load onto the released biochar and change its physicochemical characteristics and adsorption behavior toward pollutants. In this study, sodium dodecyl sulfate(SDS), as one type of anionic surfactant, was coated onto biochar with different loading amounts. The influence of SDS loading onto biochar's physicochemical properties were investigated by Fourier transform infrared(FT-IR) spectroscopy, elemental analysis, zeta potential and Brunauer–Emmett–Teller(BET) surface area and pore size distribution analysis. Results showed that the pore size of the biochar decreased gradually with the increase of SDS loading because of the surface-adsorption and pore-blocking processes; the p H of the point of zero charge(pHPZC) decreased with increasing SDS loading. Although surface-coating with SDS decreased the pore size of the biochar, its adsorption capacity toward Methylene Blue(MB) significantly increased. The biochar-bound SDS introduced functional groups and negative charges to the biochar surface, which could thus enhance the adsorption of MB via hydrogen bonding and electrostatic interaction. The results can shed light on the underlying mechanism of the influence of anionic surfactants on the adsorption of MB by biochar.     

铜藻基载铁活性炭的制备及其对亚甲基蓝的吸附特性研究

以一种大型海藻——铜藻为原料,Fe Cl3·6H2O为活化剂,采用超声浸渍-原位合成法制备了铜藻基载铁活性炭(Fe/SAC),并以活性炭得率和亚甲基蓝吸附值为指标,通过正交法考察了活化温度、活化时间和浸渍比的影响.同时,采用X射线衍射、扫描电镜和比表面积分析仪对最优结果进行表征,并考察了Fe/SAC吸附亚甲基蓝的热力学与动力学特性.结果表明,Fe/SAC的最优制备工艺条件为活化温度600℃、活化时间1 h、浸渍比1∶1,此时的活性炭得率为39.5%,亚甲基蓝吸附值为255.67 mg·g~(-1);最优工艺条件下制得的Fe/SAC比表面积为558.31 m2·g~(-1),其负载的铁组分主要为Fe3O4和Fe O;亚甲基蓝在Fe/SAC上的吸附过程符合准二级动力学模型,Langmuir等温吸附模型能够很好地描述吸附平衡过程,该吸附是熵增加的自发吸热(ΔS0、ΔG0、ΔH0)过程,升温有利于吸附.     

Fenton改性多壁碳纳米管对亚甲基蓝的吸附性能研究

通过催化裂解法制备多壁碳纳米管,利用Fenton试剂对多壁碳纳米管改性,研究了Fenton改性对多壁碳纳米管表面物理化学特性的影响和对亚甲基蓝的吸附特性.投射电镜(TEM)、比表面积(BET)分析表明,Fenton改性多壁碳纳米管纯度高,孔隙均匀,外径为30nm左右,比表面积为120m2/g;且表面引入了大量含氧基团,等电点为1.8.未改性和Fenton改性多壁碳纳米管对亚甲基蓝的吸附动力学均符合Langergren模型,其平衡吸附量分别为24.5,36.4mg/g;吸附等温线均符合Freundlich模型,未改性和Fenton改性多壁碳纳米管的kF分别为7.92和25.37;温度和pH值升高均有利于Fenton改性多壁碳纳米管对亚甲基蓝的吸附.     

镍改性MCM-41介孔分子筛对水中甲基蓝的吸附

通过水热法合成介孔分子筛MCM-41,采用等体积浸渍法制备了Ni负载MCM-41分子筛吸附剂(Ni/MCM-41).小角X-射线粉末衍射(XRD)表征结果显示,Ni/MCM-41保持了纯硅MCM-41有序的介孔结构,并研究了Ni/MCM-41对水中甲基蓝的吸附去除性能,考察了投加量、反应时间、p H值、温度对水中甲基蓝去除率的影响,并从吸附等温线探讨了吸附机理.在优化条件下(25℃,20 mg投加量,6.32 p H,50 mg·L-1甲基蓝),反应120 min后,Ni/MCM-41对甲基蓝吸附量为36.85 mg·g-1,是MCM-41的7.1倍.研究表明吸附等温线符合Freuulich和Dubinin-Radushkevich模型,最大吸附量随着温度的升高而升高,吸附为吸热过程.通过Zeta电位分析认为,静电作用是甲基蓝吸附的主要机理.     

Synthesis of malachite@clay nanocomposite for rapid scavenging of cationic and anionic dyes from synthetic wastewater

Synthesis of malachite@clay nanocomposite was successfully carried out for the removal of cationic (Methylene Blue, MB) and anionic dyes (Congo Red, CR) from synthetic wastewater. Nanocomposite was characterized by TEM, SEM, FT-IR, EDS analysis and zeta potential. TEM analysis indicated that the particle diameter of nanocomposite was in the range of 14 to 23 nm. Various important parameters viz. contact time, concentration of dyes, nanocomposite dosage, temperature and solution pH were optimized to achieve maximum adsorption capacity. In the case of MB, removal decreased from 99.82% to 93.67% while for CR, removal decreased from 88.55% to 75.69% on increasing dye concentration from 100 to 450 mg/L. pH study confirmed the higher removal of CR in acidic range while MB removal was higher in alkaline range. Kinetic study revealed the applicability of pseudo-second-order model for the adsorption of both dyes. Negative values of ΔG⁰ for both systems suggested the feasibility of dye removal and support for spontaneous adsorption of CR and MB on nanocomposite. Nanocomposite showed 277.77 and 238.09 mg/g Langmuir adsorption capacity for MB and CR respectively. Desorption of dyes from the dye loaded nanocomposite was easily carried out with acetone. The results indicate that the prepared malachite@clay nanocomposite is an efficient adsorbent with high adsorption capacity for the aforementioned dyes.     

氨基功能化磁性氧化石墨烯吸附废水中亚甲基蓝机理研究

通过酰胺化一锅法成功制备了三乙烯四胺修饰的磁性氧化石墨烯纳米颗粒(MGO-TETA)吸附剂,并利用傅里叶红外光谱仪(FT-IR)、拉曼光谱仪(Raman)、扫描电子显微镜(SEM)证实了MGO-TETA吸附剂的成功制备.同时,实验研究了吸附剂用量、亚甲基蓝溶液(MB)的pH值、吸附剂的零电点和离子强度对MGO-TETA吸附性能的影响,并考察了MGO-TETA的循环再生和工业模拟应用.最后,通过拟一级动力学、拟二级动力学、颗粒内扩散和液膜扩散4种模型讨论了吸附动力学过程,使用Langmuir、Freundlich和Temkin模型探讨了吸附热力学行为.结果表明：MGO-TETA对MB的吸附是自发可行且吸热的,符合Langmuir等温线模型和拟二级动力学模型.由Langmuir等温线模型计算的最大吸附量为638.90 mg·g-1.经过5次吸附-解吸循环以后,MB的去除率仍然可达87%.经过实验证明在吸附过程中MGO-TETA吸附剂与MB之间存在静电相互作用、氢键相互作用、π-π共轭相互作用.     

废轮胎热解炭黑制备活性炭及处理染料废水

分别采用H₂SO₄和NaOH对废轮胎热解炭黑进行改性处理,考察炭黑与改性剂固液比对染料废水脱色率的影响.实验结果表明,炭黑与H₂SO₄固液比1g/15mL时得到HBC（酸改性活性炭）处理酸性湖蓝溶液,脱色率最高;炭黑与NaOH固液比1g/10mL时得到NBC（碱改性活性炭）处理碱性湖蓝溶液,脱色效果最好.溶液的酸性越强,越有利于HBC对酸性湖蓝溶液的脱色效果;而溶液的碱性增大,有助于提高NBC对碱性湖蓝的脱色率.此外,HBC对酸性湖蓝与NBC对碱性湖蓝的吸附反应变化趋势非常接近,整个吸附反应迅速,20min后基本达到吸附反应平衡.HBC吸附酸性湖蓝和NBC吸附碱性湖蓝的过程均符合准二级动力学方程.对改性前后的固体物质进行了扫描电镜,红外光谱及比表面积分析.     

磁性壳聚糖的制备及处理亚甲基蓝废水

以戊二醛为交联剂,Fe₃O₄为磁核制备磁性壳聚糖,探究了其去除废水中亚甲基蓝的性能,以及吸附动力学、吸附等温线、吸附热力学特征.结果表明,在磁性壳聚糖投加量为0.5g/L、pH=10、反应时间为60min的条件下,对亚甲基蓝的去除率和吸附容量分别达到97.6%和39.0mg/g,远高于天然壳聚糖的59.8%和23.9mg/g.磁性壳聚糖对亚甲基蓝的吸附过程符合准二级反应动力学方程（R²=0.99902）和Langmuir等温线方程（R²=0.99961）,吸附过程是热力学自发过程,吸附反应是放热反应.     

Competitive effects of humic acid and wastewater on adsorption of Methylene Blue dye by activated carbon and non-imprinted polymers

Natural organic matter(NOM), present in natural waters and wastewater, decreases adsorption of micropollutants, increasing treatment costs. This research investigated mechanisms of competition for non-imprinted polymers(NIPs) and activated carbon with humic acid and wastewater. Three different types of activated carbons(Norit PAC 200,Darco KB-M, and Darco S-51) were used for comparison with the NIP. The lower surface area and micropore to mesopore ratio of the NIP led to decreased adsorption capacity in comparison to the activated carbons. In addition, experiments were conducted for single-solute adsorption of Methylene Blue(MB) dye, simultaneous adsorption with humic acid and wastewater, and pre-loading with humic acid and wastewater followed by adsorption of MB dye using NIP and Norit PAC 200. Both the NIP and PAC 200 showed significant decreases of 27% for NIP(p = 0.087) and 29% for PAC 200(p = 0.096) during simultaneous exposure to humic acid and MB dye. There was no corresponding decrease for NIP or PAC 200 pre-loaded with humic acid and then exposed to MB. In fact, for PAC 200, the adsorption capacity of the activated carbon increased when it was pre-loaded with humic acid by 39%(p = 0.0005). For wastewater, the NIP showed no significant increase or decrease in adsorption capacity during either simultaneous exposure or pre-loading. The adsorption capacity of PAC 200 increased by 40%(p = 0.001) for simultaneous exposure to wastewater and MB. Pre-loading with wastewater had no effect on MB adsorption by PAC 200.     

磁性纳米复合物对水中亚甲基蓝的吸附及其机理

利用正硅酸乙酯水解在磁性纳米锰锌铁氧体表面包裹SiO₂,制备了一种新型“核/壳”结构磁性纳米复合物材料Si-Fe-MNCs.采用N₂-吸附脱附法、透射电子显微镜(TEM)、振动样品磁强计(VSM)和傅利叶变换红外技术(FT-IR)分别对Si-Fe-MNCs的织构性能、形貌和磁性能进行了表征.结果表明,该磁性材料对亚甲基蓝表现出良好的吸附性能,318K时平衡吸附量在40.31~184.1mg/g之间,120min可达吸附平衡,符合准二级动力学方程.吸附过程符合Langmuir等温吸附模型,热力学计算结果表明Si-Fe-MNCs对亚甲基蓝的吸附是以表面物理吸附为主的自发吸热过程,红外结果表明氢键是Si-Fe-MNCs表面官能团与亚甲基蓝之间的主要作用力.Si-Fe-MNCs采用H₂O₂进行再生,5次循环使用后,对MB的平衡吸附量仍可维持在93.64mg/g.     

凹凸棒石/氧化锌纳米复合材料对亚甲基蓝的吸附性能

采用化学沉淀法在凹凸棒石的表面负载纳米氧化锌合成了凹凸棒石/氧化锌(ATP/ZnO)纳米复合材料.同时,研究了亚甲基蓝在纳米复合材料上的吸附行为,并从热力学和动力学角度探讨了吸附作用机理.吸附实验表明:纳米复合材料对亚甲基蓝有优异的吸附能力;纳米复合材料对亚甲基蓝的吸附热力学符合Langmuir等温吸附方程,最大吸附量可达110.50mg·g-1,吸附焓变为18.69kJ·mol-1,吸附自由能变为-33.06～-22.74kJ·mol-1,吸附熵变约为146J.mol-1.K-1,是一个自发的吸热过程;纳米复合材料对亚甲基蓝的吸附动力学符合准二级动力学方程,速率常数随着溶液初始浓度的提高而下降.     

GA-g-PAMPS/AA/ST凝胶的制备及对亚甲基蓝吸附性能

采用微波辐射技术,通过接枝共聚反应制备了阿拉伯胶（GA）-g-2-丙烯酰胺-2-甲基丙磺酸（AMPS）/丙烯酸（AA）/海泡石黏土（ST）（GA-g-PAMPS/AA/ST）复合水凝胶,利用FTIR、XRD、SEM对复合水凝胶进行了表征,研究了水凝胶对水溶液中亚甲基蓝（MB）染料的吸附性能.结果显示：GA、ST和AA与AMPS发生了接枝共聚反应,形成具有均匀三维网络结构的复合水凝胶.0.025g水凝胶可以使体积为50mL、pH值为6.4、浓度为600mg/L的MB溶液的吸附量和吸附率分别达1146mg/g和95.5%,水凝胶具有较好的重复利用性能.Freundlich等温模型和准二级动力学模型能更好地描述吸附过程.热力学研究表明水凝胶对亚甲基蓝吸附是自发、吸热和不可逆的过程.该水凝胶可用作阳离子染料和阳离子型污染物的潜在候选生物质吸附剂.     

GA-g-PAMPS/AA/ST凝胶的制备及对亚甲基蓝吸附性能

采用微波辐射技术,通过接枝共聚反应制备了阿拉伯胶（GA）-g-2-丙烯酰胺-2-甲基丙磺酸（AMPS）/丙烯酸（AA）/海泡石黏土（ST）（GA-g-PAMPS/AA/ST）复合水凝胶,利用FTIR、XRD、SEM对复合水凝胶进行了表征,研究了水凝胶对水溶液中亚甲基蓝（MB）染料的吸附性能.结果显示：GA、ST和AA与AMPS发生了接枝共聚反应,形成具有均匀三维网络结构的复合水凝胶.0.025g水凝胶可以使体积为50mL、pH值为6.4、浓度为600mg/L的MB溶液的吸附量和吸附率分别达1146mg/g和95.5%,水凝胶具有较好的重复利用性能.Freundlich等温模型和准二级动力学模型能更好地描述吸附过程.热力学研究表明水凝胶对亚甲基蓝吸附是自发、吸热和不可逆的过程.该水凝胶可用作阳离子染料和阳离子型污染物的潜在候选生物质吸附剂.     

Strong enhancement of methylene blue removal from binary wastewater by in-situ ferrite process

Dye wastewater containing heavy metal ions is a common industrial effluent with complex physicochemical properties.The treatment of metal–dye binary wastewater is difficult.In this work,a novel in-situ ferrite process(IFP) was applied to treat Methylene Blue(MB)–Cu(II)binary wastewater,and the operational parameters were optimized for MB removal.Results showed that the optimum operating conditions were OH/M of 1.72,Cu~(2+)/Fe~(2+)ratio of 1/2.5,reaction time of 90 min,aeration intensity of 320 mL/min,and reaction temperature of40°C.Moreover,the presence of Ca~(2+)and Mg~(2+)moderately influenced the MB removal.Physical characterization results indicated that the precipitates yielded in IFP presented high surface area(232.50 m2/g) and a multi-porous structure.Based on the Langmuir model,the maximum adsorption capacity toward MB was 347.82 mg/g for the precipitates produced in IFP,which outperformed most other adsorbents.Furthermore,IFP rapidly sequestered MB with removal efficiency 5 to 10 times greater than that by general ferrite adsorption,which suggested a strong enhancement of MB removal by IFP.The MB removal process by IFP showed two different high removal stages,each with a corresponding removal mechanism.In the first brief stage(5 min),the initial high MB removal(~95%)was achieved by predominantly electrostatic interactions.Then the sweep effect and encapsulation were dominant in the second longer stage.     

Comparison between linear and non-linear forms of pseudo-first-order and pseudo-second-order adsorption kinetic models for the removal of methylene blue by activated carbon

The best-fit equations of linear and non-linear forms of the two widely used kinetic models, namely pseudo-first-order and pseudo-second-order equations, were compared in this study. The experimental kinetics of methylene blue adsorption on activated carbon was used for this research. Both the correlation coefficient (R ²) and the normalized standard deviation Δq(%) were employed as error analysis methods to determine the best-fitting equations. The results show that the non-linear forms of pseudo-first-order and pseudo-second-order models were more suitable than the linear forms for fitting the experimental data. The experimental kinetics may have been distorted by linearization of the linear kinetic equations, and thus, the non-linear forms of kinetic equations should be primarily used to obtain the adsorption parameters. In addition, the Δq(%) method for error analysis may be better to determine the best-fitting model in this case.     

平行磁场下电极材料对DBD降解亚甲基蓝的影响

采用介质阻挡放电等离子体技术,以镍,铁,钼,不锈钢4种材料作为电极,分别在有平行磁场和无平行磁场的条件下,考察了不同电极材料对亚甲基蓝降解率和能量利用率的影响.实验中发现电极材料的不同会影响亚甲基蓝的降解效果,其中镍电极在处理8min后亚甲基蓝降解率可达99%,降解效果最好,电极材料还会影响平行磁场对亚甲基蓝降解的促进效果,铁和镍电极的能量利用率相比无磁场时提高了约20%,而钼和不锈钢只有5%~10%.通过研究介质阻挡放电等离子体的产生机理和二次电子发射原理,发现这些差异是由电极材料的二次电子发射系数和磁导率的不同导致的,4种材料中铁的二次电子发射系数最大,电子雪崩过程中产生的高能电子更多,因此降解效果最好,铁和镍的磁导率最大,放电空间内的磁感应强度更高,因此平行磁场对亚甲基蓝降解率和能量利用率的提升更大.     

污泥液化生物炭对亚甲基蓝的吸附特性及机理

探讨污泥在乙醇-水混合溶剂中液化产生的生物炭的吸附潜力及其吸附机理（以亚甲基蓝（MB）废水为处理对象）,结果表明：生物炭的吸附容量随着MB溶液起始pH值升高而升高,当pH超过8时,MB的碱性褪色开始显现.吸附温度的上升（30~60℃）对生物炭吸附容量的影响不明显.吸附容量总体上随着吸附时间的增加而上升（240min前）,在240min后趋于稳定.吸附剂用量及初始MB浓度过高或过低都不利于生物炭的吸附,存在一个的临界点,分别是6mg和120mg/L.生物炭吸附MB的过程吻合准二级动力学方程（R²=0.9994）和Langmuir方程（R²=0.9831）,且为自发吸热的过程,受物理吸附和化学吸附联合控制,具体的机理包括：离子交换、官能团络合、π-π吸附等.     

改性生物炭负载纳米零价铁去除水体中头孢噻肟

抗生素对环境的危害已经引起了人们的广泛重视.本实验以改性生物炭(MB)为载体制备了负载纳米零价铁的功能生物炭(Fe/MB).以头孢噻肟(CFX)为目标抗生素,研究了该材料对头孢噻肟的降解特性及影响因素,并探讨了去除机理.实验结果表明,50 min内头孢噻肟的去除率为92%(Fe/MB用量为0.4 g·L~(-1),溶液p H=5.0,头孢噻肟浓度为20 mg·L~(-1),振荡速率为200 r·min~(-1),柠檬酸浓度为1.47 mmol·L~(-1)).头孢噻肟的去除过程存在改性生物炭的吸附和纳米零价铁还原降解的协同作用,数据符合伪二级反应动力学方程(R20.99).采用紫外可见光谱结合质谱分析了降解产物的结构并提出头孢噻肟的降解途径.     

改性活性碳毡电吸附污水中的Zn2+

用20%硝酸改性活性碳毡,利用扫描电镜和傅里叶红外光谱等技术对其改性后的结构进行了表征;利用改性活性碳毡作为吸附电极,进一步研究了其应用于电吸附的除盐效果和影响因素.结果表明,改性后的活性碳毡上的羰基和羧基增多,比表面积增大了32.2%,平均孔径提高了2.5%,微孔体积增大了23.1%.在电压为1.2V,pH值为6~8,极板间距为5mm时电吸附装置对水中Zn²⁺的吸附效果最优,动力学分析表明改性活性碳毡吸附Zn²⁺更符合准二级动力学方程,吸附等温线符合Langmuir等温吸附模型,除此以外,电吸附循环实验表明用20%硝酸为再生液,通过电极反接,改性活性碳毡的再生率> 74%,说明在电吸附Zn²⁺过程中改性活性碳毡具有良好的再生性.