胶原纤维固化黑荆树单宁吸附Cr(Ⅵ)的研究

研究了胶原纤维固化黑荆树单宁对Cr（Ⅵ）的吸附．采用不同温度、pH值等条件进行吸附研究，并进一步探讨了固化黑荆树单宁的吸附动力学和吸附柱动力学及其吸附机理．结果表明，该材料对Cr（Ⅵ）的吸附平衡符合Freundlich方程，温度对吸附平衡的影响不明显；吸附动力学可用拟二级速度方程来描述，该材料同时具有良好的柱动力学特性；Cr（Ⅵ）的吸附过程可能存在3个反应，即Cr（Ⅵ）与吸附剂之间发生氧化还原反应生成Cr（Ⅲ），Cr（Ⅲ）和-COOH之间发生离子交换反应，以及Cr（Ⅲ）与单宁的邻位羟基发生螯合．图8表2参10     

铁(III)-丙酮酸盐配合物光解引发水中铬(Ⅵ)还原

初步研究了含有Fe(III)及丙酮酸盐的溶液在高压汞灯照射下对铬(VI)的光还原反应.考察了溶液pH值、Fe(III)浓度、丙酮酸钠浓度、Cr(VI)浓度对反应的影响.分析了光还原反应的动力学及反应机制.结果表明:铁丙酮酸盐体系能光还原Cr(VI);最佳pH为3.0;Cr(VI)光还原的初始速率随着加入的铁(III)、丙酮酸盐、Cr(VI)初始浓度的增加而增加;实验条件下的表观动力学方程为:-dCCr(VI)/dt=0.021[Cr(VI)]0.39[Fe(III)]1.05[CH3COCOONa]0.39;Fe(III)-丙酮酸盐配合物光解产生的Fe(II)是Cr(VI)的主要还原剂.     

表面印迹材料对水中Cd(Ⅱ)的吸附动力学

采用表面印迹技术,以硅胶为载体、Cd(Ⅱ)为模板离子、γ-脲基丙基三甲氧基硅烷为偶联剂和功能单体、环氧氯丙烷为交联剂,合成了脲基功能化的镉离子表面印迹材料.用制备好的印迹材料为吸附剂进行静态吸附实验,考察了溶液的不同p H值、反应时间、温度和Cd(Ⅱ)的初始浓度等因素对镉离子吸附效果的影响.并用准一级动力学和准二级动力学对实验数据进行拟合,计算出相应的速率常数.结果表明,表面印迹材料对Cd(Ⅱ)的吸附是一个快速的过程,在20 min内即可达到吸附平衡,且准二级动力学方程(R20.99)能更好地描述其吸附动力学行为.吸附等温线符合Langmuir等温吸附模型,这表明了吸附过程是以单层吸附为主.在最佳的吸附条件下,Cr(Ⅱ)的吸附量可达到83 mg·g-1.此外吸附热力学研究表明该吸附过程是一个自发的、吸热过程.     

砖红壤对Cr(Ⅵ)吸附-解吸反应动力学研究

研究了表面覆盖度、H2PO-4等因素对砖红壤吸附Cr(Ⅵ)反应动力学的影响,以及土壤与Cr(Ⅵ)反应时间对表面吸附态C r(Ⅵ)解吸量的影响,还对土壤吸附Cr(Ⅵ)机理进行了初步探讨.在所研究的pH值范围内,砖红壤对Cr(Ⅵ)的吸附量随离子强度增加而减少,这表明砖红壤吸附Cr(Ⅵ)机理中存在静电吸附.动力学实验表明,当Cr(Ⅵ)初始浓度较高时(0.1 mmo.ll-1),吸附反应速率开始比较快,持续约5m in,随后逐渐减缓.而当Cr(Ⅵ)初始浓度较低时(0.05 mmo.ll-1),土壤对其吸附速率十分迅速,5m in内的吸附量占总吸附量的96%以上.该结果表明,表面覆盖度越低,吸附反应速率越快.H2PO-4的存在将降低吸附反应速率和吸附量.H2PO-4对土壤表面吸附态Cr(Ⅵ)的解吸反应动力学也表现出双速率特征,即开始比较迅速而随后逐渐变缓.当延长土壤对Cr(Ⅵ)的吸附时间后,Cr(Ⅵ)吸附量虽然没有增加,但其解吸量却减少,这说明吸附态Cr(Ⅵ)滞留在土壤表面期间,其结合形态向难解吸态方向发生了转变.     

短乳杆菌对Cr3+的吸附及动力学和热力学拟合

研究了Lactobacillus brevis对水溶液中Cr(Ⅲ)的吸附作用.考察了初始pH值、接触时间、初始Cr(Ⅲ)浓度、菌体浓度和温度对Cr(Ⅲ)吸附效果的影响.结果表明,在较低的pH、温度和初始Cr(Ⅲ)离子浓度条件下,菌株对Cr(Ⅲ)离子的吸附量较低.在试验条件下,溶液初始pH、温度和初始Cr(Ⅲ)离子浓度的升高,均能提高菌株对Cr(Ⅲ)离子的吸附量.在温度为40℃、pH 6和初始Cr(Ⅲ)离子浓度为200 mg·L~(-1)时,菌株吸附量最大.随菌体浓度升高,单位浓度菌体对Cr(Ⅲ)离子吸附量降低,但总吸附量增大,菌体浓度为6 g·L~(-1)吸附量最大.菌株对Cr(Ⅲ)离子吸附较快,接触时间为1 h就达到平衡.用Langmuir、Freundlich、Redlich-Peterson和Temkin吸附模型进行拟合,相关的回归系数表明,吸附过程拟合Langmuir吸附模型比Freundlich、Redlich-Peterson和Temkin吸附模型好.用Elovich、准一级、准二级动力学拟合,动力学试验数据与Lagergren准二级动力学方程的拟合度最佳.     

稀水溶液中Cr(Ⅵ)的光催化还原研究

以甲醇、正丙醇、丙三醇和苯酚作为俘获剂,研究稀水溶液中Cr(VI)的光催化还原过程,考察Cr(VI)在催化剂表面上的界面吸附行为及溶液pH值、俘获剂类型等对其光催化还原过程的影响.结果表明,溶液pH值对Cr(VI)吸附的影响为:(1)溶液pH<2.4时,随pH值升高,吸附量减少;(2)pH值在2.4-5.0时,随pH值的升高,吸附量上升,在pH＝5.0时吸附量达到最大;(3)pH>5.0时,吸附量迅速下降.但溶液pH值对Cr(VI)光催化还原的影响与其对Cr(VI)吸附的影响存在显著差异,随pH值的升高,Cr(VI)的还原率下降,在溶液pH＝1.0时60min内可还原完全,而在pH＝9.0时经相同时间后Cr(VI)仍残余65.18%.俘获剂类型对Cr(VI)的还原也有一定影响.     

钛酸盐纳米片光催化-吸附协同去除水中Cr(Ⅵ)和Cr(Ⅲ)

以锐钛型纳米TiO2为原材料,采用水热法合成了钛酸盐纳米片(TNS),系统研究了Cr(Ⅵ)和Cr(Ⅲ)在TNS上的吸附行为,以及不同pH下TNS光催化协同吸附对水体中Cr(Ⅵ)和Cr(Ⅲ)的同步去除.TEM及XRD表征结果表明,制备的TNS呈现出锐钛矿与钛酸盐混合晶相,这对于其光催化和吸附性能的发挥极为重要.吸附实验证实,TNS对Cr(Ⅵ)和Cr(Ⅲ)的吸附显著受pH影响,高pH利于Cr(Ⅲ)的吸附,而Cr(Ⅵ)在低pH下吸附量更大.Cr(Ⅵ)和Cr(Ⅲ)在TNS上的吸附速度较快,吸附动力学符合准二级动力学模型(R20.99).吸附等温线结果符合Langmuir方程(R20.99),pH 5时,Cr(Ⅲ)的最大吸附量(13.19 mg·g-1)远大于Cr(Ⅵ)(0.63 mg·g-1),因此,单一吸附不是有效处理Cr(Ⅵ)的手段,光催化还原是必要的.光催化-吸附实验表明,随着pH的增加,TNS光催化还原Cr(Ⅵ)反应速率逐渐降低,但产生的Cr(Ⅲ)在TNS表面的吸附量显著增加.综合可知,光催化-吸附协同反应最佳pH值为5,Cr(Ⅵ)和总Cr的去除率可达97.6%,且体系中无Cr(Ⅲ)的积累.该研究为同步有效去除水体中的Cr(Ⅵ)和Cr(Ⅲ)提供了一种新的可参照的途径.     

苯胺-2,4-二氨基酚共聚物吸附水中Hg(Ⅱ)的动力学和热力学研究

利用化学氧化法合成苯胺-2,4-二氨基酚共聚物,通过静态吸附实验研究了该共聚物吸附水中汞离子的动力学和热力学.对实验数据采用准一级和准二级动力学方程、Langmuir等温线方程、Freundlich等温线方程进行拟合,并进行相应的热力学分析.研究结果表明,苯胺-2,4-二氨基酚共聚物对水中Hg(Ⅱ)具有很好的去除效果,最大吸附容量达800mg·g-1,吸附等温线符合Langmuir单层吸附模型;动力学过程符合准二级动力学模型;吸附焓变化量ΔH=58.51kJ·mol-1,表明该吸附反应为化学吸附且为吸热反应;三种实验温度下吉布斯自由能变化量均为负值,表明该吸附反应能自发进行。     

棉花秸秆生物炭对水中硫酸根离子的吸附特性

以棉花秸秆生物炭(BCS)为吸附剂,研究了BCS的吸附动力学、热力学特性以及制备温度、投加量和溶液p H等因素对BCS吸附SO_4~(2-)的影响.结果表明,制备温度为500℃的BCS(BCS500)比300℃的BCS(BCS300)更有利于SO_4~(2-)的吸附去除;在20 m L溶液中,BCS500的投加量为0.1000 g时,对SO_4~(2-)的吸附去除最为理想,升高溶液p H值会减小BCS500对SO_4~(2-)的吸附量.动力学拟合表明准二级动力学方程比准一级动力学方程和Elovich方程能更好地描述吸附过程,所得吸附平衡时间为6 h.颗粒内扩散模型拟合发现BCS吸附SO_4~(2-)分为表面吸附和颗粒内扩散两个过程.相比于其他等温吸附方程,Langmuir方程能更好地描述BCS500对SO_4~(2-)的吸附行为,由Langmuir方程拟合所得BCS500的理论最大吸附量(52.13 mg·g~(-1))比BCS300的理论最大吸附量(31.46 mg·g~(-1))大.而计算所得热力学参数,如吉布斯自由能变G_m0,焓变H_m0和熵变S_m0,表明BCS500对SO_4~(2-)的吸附是一个自发、吸热且熵增加的过程;在25、35、45℃时,G_m分别为-9.61、-12.50、-13.96 k J·mol~(-1),介于-20─0 k J·mol~(-1)之间,且反应为吸热反应,表明BCS500吸附SO_4~(2-)主要以物理吸附为主.     

北固山芦苇湿地土壤对铜铬(VI)的吸附研究

北固山芦苇(Phragmites communis)湿地是长江中下游典型湿地类型之一,沿江工业化和城市化的快速发展使其面临严重的重金属污染威胁.然而,目前有关湿地重金属污染的吸附尤其竞争吸附的研究还少见报道.该文以北固山芦苇湿地为对象,采用平衡法对Cu2+、Cr(VI)在湿地土壤中的吸附行为进行了研究,旨在服务于湿地重金属污染的修复与生物学效应评价.研究结果表明(1)湿地土壤吸附Cu2+、Cr(VI)的过程符合Langmuir等温模型;二者的表观最大吸附量(xm)分别为36.10 g·kg-1和178.57 g·kg-1(初始液质量浓度c0＜500 g·m-3),平均吸附率分别达到99.82%± 0.35%和93.17%±1.14%.(2)无论单一吸附或竞争吸附体系,当c0(Cu2+)＞250 g·m-3时,平衡液Cu2+质量浓度快速升高.(3)c0相等的Cu2+、Cr(VI) 竞争吸附体系中,平衡液中Cu2+质量浓度升高,Cr(VI)质量浓度下降;但xm的变化表现为Cu2+增加了2.7倍,Cr(VI)降低了2.4倍.(4)Cu2+、Cr(VI) 的竞争吸附体系中,随Cr(VI)初始液质量浓度的变化(c0(Cu2+)恒定),Cr(VI)的xm下降至其单一吸附时的6%;而随Cu2+初始液质量浓度的变化(c0(Cr(VI))恒定),Cu2+的xm仅为其单一吸附时的1/3.     

Removal of chromium(VI) by ZnCl2 activated coir pith carbon

The adsorption of chromium(VI) onto ZnCl₂ activated carbon developed from coir pith was investigated to assess the possible use of this adsorbent. The influence of contact time, adsorbent dose, Cr(VI) concentration, pH and temperature were investigated. The two theoretical adsorption isotherms, namely, Langmuir and Freundlich were used to describe the experimental results. The Langmuir adsorption capacity (Q ₀) was found to be 120.5?mg Cr(VI) per g of the adsorbent. The adsorption followed the second-order kinetics and was found to be maximum at pH 2.0. The pH effect and the desorption studies showed that ion exchange mechanism might be involved in the adsorption process. The effects of foreign ions such as chloride, sulphate, phosphate, selenite, molybdate, nitrate and perchlorate on the removal of Cr(VI) have been investigated. The removal of Cr(VI) from synthetic ground water was also tested. The results show that ZnCl₂ activated coir pith carbon is effective for the removal of Cr(VI) from water.     

Preparation and characterization of <Emphasis Type="Italic">β</Emphasis>-FeOOH-coated sand and its adsorption of Cr(VI) from aqueous solutions

Batch adsorption experiments were conducted to explore the adsorption of Cr(VI) in aqueous solutions by β-FeOOH-coated sand. We investigated the key factors which affected the adsorption process such as adsorbent dosage, initial pH, initial Cr(VI) ion concentration, contact time and temperature. The uptake of Cr(VI) was very rapid and 44.3%, 51.6%, 58.9% of the adsorption happened during the first 180 minutes at 293K, 303K and 313K, respectively. The pseudo-second-order rate equation successfully described the adsorption kinetics. To study the adsorption isotherm, two equilibrium models, the Langmuir and Freundlich isotherms, were adopted. At 293K, 303K and 313K, the adsorption capacities obtained from the Langmuir isotherm were 0.060, 0.070 and 0.076 mg Cr(VI) per gram of the adsorbent, respectively. Thermodynamic parameters such as the change of energy, enthalpy and entropy were calculated using the equilibrium constants. The negative value of ΔG ⁰ and the positive value of ΔH ⁰ showed that the adsorption of Cr(VI) in aqueous solutions by β-FeOOH-coated sand was spontaneous, endothermic and occurred by physisorption.     

Concurrent adsorption and reduction of chromium(VI) to chromium(III) using nitrogen-doped porous carbon adsorbent derived from loofah sponge

• A high-efficiency N-doped porous carbon adsorbent for Cr(VI) was synthesized. • The maximum adsorption capacity of Cr(VI) reached up to 285.71 mg/g at 318K. • The potential mechanism for Cr(VI) adsorption by NHPC was put forward. • DFT analyzed the adsorption energy and interaction between NHPC and Cr(VI). To develop highly effective adsorbents for chromium removal, a nitrogen-doped biomass-derived carbon (NHPC) was synthesized via direct carbonation of loofah sponge followed by alkali activation and doping modification. NHPC possessed a hierarchical micro-/mesoporous lamellar structure with nitrogen-containing functional groups (1.33 at%), specific surface area (1792.47 m²/g), and pore volume (1.18 cm³/g). NHPC exhibited a higher Cr(VI) adsorption affinity than the HPC (without nitrogen doping) or the pristine loofah sponge carbon (LSC) did. The influence of process parameters, including pH, dosage, time, temperature, and Cr(VI) concentration, on Cr(VI) adsorption by NHPC were evaluated. The Cr(VI) adsorption kinetics matched with the pseudo-second-order model (R²≥0.9983). The Cr(VI) adsorption isotherm was fitted with the Langmuir isotherm model, which indicated the maximum Cr(VI) adsorption capacities: 227.27, 238.10, and 285.71 mg/g at 298K, 308K, and 318K, respectively. The model analysis also indicated that adsorption of Cr(VI) on NHPC was a spontaneous, endothermal, and entropy-increasing process. The Cr(VI) adsorption process potentially involved mixed reductive and adsorbed mechanism. Furthermore, computational chemistry calculations revealed that the adsorption energy between NHPC and Cr(VI) (−0.84 eV) was lower than that of HPC (−0.51 eV), suggesting that nitrogen doping could greatly enhance the interaction between NHPC and Cr(VI).     

Removal of selenite using ‘waste’ Fe(III)/Cr(III) hydroxide: Adsorption kinetics and isotherms

Removal of selenite [Se (IV)] from aqueous solution on to industrial solid ‘waste’ Fe(III)/Cr(III) hydroxide as adsorbent was investigated in the present article. Maximum adsorption was found to be at pH 4.0. Pretreated Fe(III)/Cr(III) hydroxide was found to be more efficient for the removal of selenite compared to untreated adsorbent. Langmuir and Freundlich isotherms have been studied. The Langmuir adsorption capacity (Q ₀) of the pretreated and untreated adsorbents was found to be 15.63 and 6.04?mg?g^?1, respectively. The adsorption process fit into the second-order kinetics. Thermodynamic parameters show that the adsorption process is spontaneous and endothermic in the temperature range 32 to 60°C. Coexisting anions vanadate and phosphate significantly affect the adsorption of selenite for both the pretreated and untreated adsorbents. Molybdate, thiocyanate, sulphate, nitrate and chloride do not significantly affect the removal of selenite for pretreated adsorbent.     

Adsorption of vanadate(V) on Fe(III)/Cr(III) hydroxide waste

Adsorption of vanadate(V) from aqueous solution onto industrial solid ‘waste’ Fe(III)/Cr(III) hydroxide was investigated. HCl treated Fe(III)/Cr(III) hydroxide was found to be more efficient for the removal of vanadate(V) compared to untreated adsorbent. The adsorption follows second-order kinetics. Langmuir and Freundlich isotherms have been studied. The Langmuir adsorption capacity (Q ₀) of the treated and untreated adsorbents was found to be 11.43 and 4.67 mg g⁻¹, respectively. Thermodynamic parameters showed that the adsorption process was spontaneous and endothermic in the temperature range 32–60°C. Maximum adsorption was found at system pH 4.0. The adsorption mechanism was predominantly ion exchange. Effect of other anions such as phosphate, selenite, molybdate, nitrate, chloride, and sulfate on adsorption of vanadium has been examined.     

Biosorption of Cr(VI) from wastewater using Sorghastrum Nutans L. Nash

Sorghastrum Nutans L. Nash is used as an adsorbent for the removal of Cr(VI) from wastewater. Adsorption coupled reduction i.e. indirect reduction is the mechanism of Cr(VI) removal by the biomaterial. The adsorbent surface became highly positively charged at lower pH, adsorption rate of Cr(VI) is faster and reduction reaction also accelerates at lower pH since the binding of negatively charged Cr(VI) ion species to the cationic groups is enhanced and protons take part in this reaction. The adsorbent is characterised by using XRD, FTIR, SEM and EDAX analysis. OH bending, CN stretching/bending and NH stretching play a major role in Chromium adsorption. Experimental values follow pseudo-second order reaction and Langmuir adsorption isotherm. Surface diffusion is the rate controlling mechanism for the process. The maximum percentage of Cr(VI) removal obtained is 75.5% with 7?g/L dosage at pH 1.3 and adsorbate concentration was 100?mg/L. From the normal probability, residual, contour, 3D surface, main effect and interaction plot along with t-test, ANOVA, and F-test, it is observed that pH has the most significant effect on the percentage removal followed by adsorbent dosage and time. The adsorbate concentration has the least effects and interaction effects are found to be significant.     

Preparation and characterization of β-FeOOH-coated sand and its adsorption of Cr(VI) from aqueous solutions

Batch adsorption experiments were conducted to explore the adsorption of Cr(VI) in aqueous solutions by β-FeOOH-coated sand. We investigated the key factors which affected the adsorption process such as adsorbent dosage, initial pH, initial Cr(VI) ion concentration, contact time and temperature. The uptake of Cr(VI) was very rapid and 44.3%, 51.6%, 58.9% of the adsorption happened during the first 180 minutes at 293K, 303K and 313K, respectively. The pseudo-second-order rate equation successfully described the adsorption kinetics. To study the adsorption isotherm, two equilibrium models, the Langmuir and Freundlich isotherms, were adopted. At 293K, 303K and 313K, the adsorption capacities obtained from the Langmuir isotherm were 0.060, 0.070 and 0.076 mg Cr(VI) per gram of the adsorbent, respectively. Thermodynamic parameters such as the change of energy, enthalpy and entropy were calculated using the equilibrium constants. The negative value of ΔG0 and the positive value of ΔH0 showed that the adsorption of Cr(VI) in aqueous solutions by β-FeOOH-coated sand was spontaneous, endothermic and occurred by physisorption.     

Removal of Cr(VI) from aqueous solution using waste weed, Salvinia cucullata

Biosorption studies of Cr(VI) were carried out using waste weed, Salvinia cucullata. Various adsorption parameters were studied, such as agitation speed, contact time, pH, particle size, and concentrations of adsorbent and adsorbate. The equilibrium was achieved in 12 h. A lower pH favoured adsorption of Cr(VI). The kinetics followed pseudo-second-order rate equations. The adsorption isotherm obeyed both the Langmuir and Freundlich models. The calculated activation energy (1.1 kJ mol^-1) suggested that the adsorption followed a diffusion-controlled mechanism. Various thermodynamic parameters such as Δ G^°, Δ H^°, and Δ S^° were also calculated. The positive values of enthalpy indicated the endothermic nature of the reaction, and Δ S^° showed the increasing randomness at the solid liquid interface of Cr(VI) on the adsorbent, which revealed the ease of adsorption reaction. These thermo-dynamic parameters showed the spontaneity of the reaction. The maximum adsorption of uptake (232 mg g^-1) compared well with reported values of similar adsorbents. The rate-determining step was observed to follow an intra-particle diffusion model.     

Biosorption of chromium(VI), nickel(II) and copper(II) ions from aqueous solutions using Pithophora algae

The biosorption of heavy metals is considered to be one of the best alternatives for the treatment of wastewater. The metal binding capacity of algae and acid-treated algae is investigated to find out the removal characteristics of Cr(VI), Ni(II) and Cu(II) ions from single metal solutions. Batch experiments are conducted and the study is extended to investigate the effect of pH, amount of adsorbent and adsorbate concentration on the extent of biosorption. The results indicate that the adsorption capacity of algae depends strongly on pH. The maximum adsorption of Cr(VI), Ni(II) and Cu(II) occurs at pH values of 2, 7 and 4.3, respectively. The adsorption process follows first-order kinetic equation. The data obtained are correlated with Freundlich and Langmuir adsorption isotherms.