Biosorption of chromium (VI) from aqueous solutions and ANN modelling

The use of sustainable, green and biodegradable natural wastes for Cr(VI) detoxification from the contaminated wastewater is considered as a challenging issue. The present research is aimed to assess the effectiveness of seven different natural biomaterials, such as jackfruit leaf, mango leaf, onion peel, garlic peel, bamboo leaf, acid treated rubber leaf and coconut shell powder, for Cr(VI) eradication from aqueous solution by biosorption process. Characterizations were conducted using SEM, BET and FTIR spectroscopy. The effects of operating parameters, viz., pH, initial Cr(VI) ion concentration, adsorbent dosages, contact time and temperature on metal removal efficiency, were studied. The biosorption mechanism was described by the pseudo-second-order model and Langmuir isotherm model. The biosorption process was exothermic, spontaneous and chemical (except garlic peel) in nature. The sequence of adsorption capacity was mango leaf > jackfruit leaf > acid treated rubber leaf > onion peel > bamboo leaf > garlic peel > coconut shell with maximum Langmuir adsorption capacity of 35.7 mg g^?1 for mango leaf. The treated effluent can be reused. Desorption study suggested effective reuse of the adsorbents up to three cycles, and safe disposal method of the used adsorbents suggested biodegradability and sustainability of the process by reapplication of the spent adsorbent and ultimately leading towards zero wastages. The performances of the adsorbents were verified with wastewater from electroplating industry. The scale-up study reported for industrial applications. ANN modelling using multilayer perception with gradient descent (GD) and Levenberg-Marquart (LM) algorithm had been successfully used for prediction of Cr(VI) removal efficiency. The study explores the undiscovered potential of the natural waste materials for sustainable existence of small and medium sector industries, especially in the third world countries by protecting the environment by eco-innovation.     

高比表面积活性炭的制备及对Cr(Ⅵ)吸附的研究

以椰树壳为原料,运用水蒸汽和二氧化碳复合物理活化法在4 h内制备了2 162.84 m2/g的高比表面积活性炭,其孔径分布范围为1.1~2.5 nm。应用此吸附剂考察了溶液pH、吸附剂用量、接触时间和初始浓度对Cr(VI)离子吸附效果的影响,并讨论了固定吸附床中不同溶液流量对Cr(VI)去除效果的影响。结果表明:在温度为298 K、溶液pH为1.96、吸附剂用量为0.10 g、铬离子初始浓度为100 mg/L与接触时间为70 min的条件下,活性炭对铬离子具有较高的吸附容量,去除率高达99.32%;铬离子在吸附床中的穿透曲线具有陡峭的传质锋面,但随着铬离子溶液流量的增大脱除果率降低。     

菌丝体表面分子印迹壳聚糖吸附剂对Cr3+的吸附性能研究

菌丝体表面分子印迹吸附剂所保留的印迹对过渡金属离子有着良好的吸附作用,以Cr3 作为吸附离子,系统研究了该吸附剂的吸附特性和影响因素.结果表明:吸附剂对Cr3 的饱和吸附容量可达60 mg/g;其吸附行为满足Langmuir方程式.初始浓度为200 mg/L时,最佳吸附pH在3～4,吸附容量可达到50 mg/g左右,离子强度对吸附没有影响,用0.5 mol/L硝酸或硫酸解吸Cr3 ,解吸率在90%以上.     

Sorption of Cr(VI) from dilute solutions and wastewater by live and pretreated biomass of Aspergillus flavus

Sorption of Cr(VI) was carried out from dilute solutions using live and pretreated biomass in a batch mode. Effects of agitation time, adsorbent dosage and pH were examined. The autoclaved biomass that showed maximum adsorption capacity (Q(0)=0.335 mg g(-1)) was used as an adsorbent in column studies. The optimized flow rate of 2.5 ml min(-1) and bed height 10 cm were used to determine the effect of metal ion concentration on removal of Cr(VI). Applying the BDST model to calculate the adsorption capacity (N(0)) of column, which showed 4.56 x 10(-5), 7.28 x 10(-5), 6.89 x 10(-5), 3.07 x 10(-5), 2.80 x 10(-5)mg g(-1) for 4, 8, 12, 16 and 20 mg dm(-3) of Cr(VI), respectively. Batch sorption proved to be more efficient than the column sorption and hence batch sorption was used to remove Cr(VI) from a textile dyeing industry wastewater. The phytotoxic effect of treated and untreated wastewater was studied against Zea mays. Toxicity was reduced by 50% in the treated effluent.     

Chromium species behaviour in the activated sludge process

The purpose of this research was to compare trivalent chromium (Cr(III)) and hexavalent chromium (Cr(VI)) removal by activated sludge and to investigate whether Cr(VI) reduction and/or Cr(III) oxidation occurs in a wastewater treatment system. Chromium removal by sludge harvested from sequencing batch reactors, determined by a series of batch experiments, generally followed a Freundlich isotherm model. Almost 90% of Cr(III) was adsorbed on the suspended solids while the rest was precipitated at pH 7.0. On the contrary, removal of Cr(VI) was minor and did not exceed 15% in all experiments under the same conditions. Increase of sludge age reduces Cr(III) removal, possibly because of Cr(III) sorption on slime polymers. Moreover, the decrease of suspended solids concentration and the acclimatization of biomass to Cr(VI) reduced the removal efficiency of Cr(III). Batch experiments showed that Cr(III) cannot be oxidized to Cr(VI) by activated sludge. On the contrary, Cr(VI) reduction is possible and is affected mainly by the initial concentration of organic substrate, which acts as electron donor for Cr(VI) reduction. Initial organic substrate concentration equal to or higher than 1000 mgl(-1) chemical oxygen demand permitted the nearly complete reduction of 5 mgl(-1) Cr(VI) in a 24-h batch experiment. Moreover, higher Cr(VI) reduction rates were obtained with higher Cr(VI) initial concentrations, expressed in mg Cr(VI) g(-1) VSS, while decrease of suspended solids concentration enhanced the specific Cr(VI) reduction rate.     

Removal of Cr(VI) and humic acid by using TiO2 photocatalysis

The removal efficiencies of Cr(VI) and HA, using a TiO(2)-mediated photocatalytic process, were investigated with variations in the pH, TiO(2) dosage and Cr(VI)/HA ratio. During the photocatalytic reaction, the total removal of Cr(VI) occurred through adsorption onto TiO(2), as well as its reduction to Cr(III). However, oxidation and adsorption were identified as important removal processes for the treatment of HA. Due to the anionic type adsorption onto TiO(2) and its acid-catalyzed photocatalytic reduction, the removal of Cr(VI) decreased with increasing pH, while that of HA increased with increasing pH. The TiO(2) dosage was also an important parameter for the removal of Cr(VI). As the TiO(2) dosage was increased to 2.5 g l(-1), the removal of Cr(VI) was continuously enhanced, but decreased at dosages above 3 g l(-1) due to the increased blockage of the incident UV light used for the photocatalytic reaction. The removal of Cr(VI) was greatly enhanced when the system contained both HA and Cr(VI) compared to Cr(VI) alone. Also, the removal of HA was greatly enhanced when the system contained both HA and Cr(VI) compared to HA alone. The removal of Cr(VI) was continuously enhanced as the HA concentration gradually increased; however, no further increase was observed above 20 mg l(-1) HA due to the increased absorption of the UV light. This result supports that the photocatalytic reaction, with illuminated TiO(2), could be applied to more effectively treat wastewater containing both Cr(VI) and HA than that containing a single species only.     

Column study of Cr(VI) removal by cationic hydrogel for in-situ remediation of contaminated groundwater and soil

Column experiments were conducted for examining the effectiveness of the cationic hydrogel on Cr(VI) removal from groundwater and soil. For in-situ groundwater remediation, the effects of background anions, humic acid (HA) and pH were studied. Cr(VI) has a higher preference for being adsorbed onto the cationic hydrogel than sulphate, bicarbonate ions and HA. However, the adsorbed HA reduced the Cr(VI) removal capacity of the cationic hydrogel, especially after regeneration of the adsorbents, probably due to the blockage of adsorption sites. The Cr(VI) removal was slightly influenced by the groundwater pH that could be attributed to Cr(VI) speciation. The 6-cycle regeneration and reusability study shows that the effectiveness of the cationic hydrogel remained almost unchanged. On average, 93% of the adsorbed Cr(VI) was recovered in each cycle and concentrated Cr(VI) solution was obtained after regeneration. For in-situ soil remediation, the flushing water pH had an insignificant effect on the release of Cr(VI) from the soils. Multiple-pulse flushing increased the removal of Cr(VI) from the soils. In contrast, more flushing water and longer operation may be required to achieve the same removal level by continuous flushing.     

废椰壳制备活性炭负载CuO处理活性艳红X-3B废水的工艺优化

为了综合利用废椰壳,进行了废椰壳制备活性炭并负载氧化铜处理活性艳红X-3B废水的研究。采用正交实验法,以COD和色度去除率为目标函数确定了活性炭的最佳制备工艺条件为：磷酸浓度65%（质量百分数）,m（磷酸）/m（椰壳）比3∶1,活化时间2.5 h,活化温度500℃。在该活性炭上负载氧化铜处理活性艳红X-3B染料废水,其COD和色度去除率分别为83.70%和99.72%。用扫描电镜（SEM）和X衍射仪（XRD）对裸活性炭和载铜活性炭样品表面形貌和结构进行了表征和分析。通过单因素实验法确定了废水处理的最佳工艺条件为：pH值5,曝气时间4 h和催化剂用量0.55 g,在此条件下,COD和色度去除率分别为86.70%和99.75%,相应的出水指标为75 mg/L和32稀释倍数。     

Comparative and competitive adsorption of Cr(VI), As(III), and Ni(II) onto coconut charcoal

This study evaluates the behavior of coconut charcoal (AC) to adsorb Cr(VI), As(III), and Ni(II) in mono- and multicomponent (binary and ternary) systems. Batch experiments were carried out for mono- and multicomponent systems with varying metal ion concentrations to investigate the competitive adsorption characteristics. The adsorption kinetics followed the mechanism of the pseudo-second-order equation in both single and binary systems, indicating chemical sorption as the rate-limiting step of adsorption mechanism. Equilibrium studies showed that the adsorption of Cr(VI), As(III), and Ni(II) followed the Langmuir model and maximum adsorption capacities were found to be 5.257, 0.042, and 1.748 mg/g, respectively. In multicomponent system, As(III) and Ni(II) adsorption competed intensely, while Cr(VI) adsorption was much less affected by competition than As(III) and Ni(II). With the presence of Cr(VI), the adsorption capacities of As(III) and Ni(II) on AC were higher than those in single system and the metal sorption followed the order of Ni(II)?>?As(III)?>?Cr(VI). The results from the sequential adsorption–desorption cycles showed that AC adsorbent held good desorption and reusability.     

污泥活性炭的表征及其对Cr（Ⅵ）的吸附特性

以城市污水处理厂污泥为原料,采用磷酸活化一微波热解法制备得到污泥活性炭,并将其用于吸附水溶液中的Cr（Ⅵ）。分别采用元素分析仪（VarioELcube）、比表面积孔径分布测定仪（ASAP2020）、扫描电镜（SEM）和傅里叶红外光谱（FT—IR）等仪器对原污泥及污泥活性炭的表面组成和结构进行表征,探讨污泥活性炭的孔隙结构参数和表面化学性能。通过静态吸附实验,考察了溶液初始pH,接触时间,初始Cr（Ⅵ）浓度对污泥活性炭吸附Cr（Ⅵ）效果的影响,并探讨了污泥活性炭去除Cr（Ⅵ）的机理。实验结果表明,pH越低吸附效果越好,吸附平衡时间为100h。不同温度下吸附过程均符合Langmuir等温吸附模型,30℃时最大吸附容量为27．55mg／g;吸附动力学过程符合准二级速率方程（R2〉0．99）;污泥活性炭对Cr（Ⅵ）的去除是一个吸附-还原耦合的过程。     

Kinetic, equilibrium isotherm and thermodynamic studies of Cr(VI) adsorption onto low-cost adsorbent developed from peanut shell activated with phosphoric acid

A particular agricultural waste, peanut shell, has been used as precursor for activated carbon production by chemical activation with H₃PO₄. Unoxidized activated carbon was prepared in nitrogen atmosphere which was then heated in air at a desired temperature to get oxidized activated carbon. The prepared carbons were characterized for surface area, surface morphology, and pore volume and utilized for the removal of Cr(VI) from aqueous solution. Batch mode experiments were conducted to study the effects of pH, contact time, particle size, adsorbent dose, initial concentration of adsorbate, and temperature on the adsorption of Cr(VI). Cr(VI) adsorption was significantly dependent on solution pH, and the optimum adsorption was observed at pH 2. Pseudo-first-order, pseudo-second-order, and intraparticle diffusion models were used to analyze the kinetic data obtained at different initial Cr(VI) concentrations. The adsorption kinetic data were described very well by the pseudo-second-order model. Equilibrium isotherm data were analyzed by the Langmuir, Freundlich, and Temkin models. The results showed that the Langmuir adsorption isotherm model fitted the data better in the temperature range studied. The adsorption capacity which was found to increase with temperature showed the endothermic nature of Cr(VI) adsorption. The thermodynamic parameters, such as Gibb’s Free energy change (ΔG°), standard enthalpy change (ΔH°), and standard entropy change (ΔS°) were evaluated.     

Competitive adsorption of dye metanil yellow and RB15 in acid solutions on chemically cross-linked chitosan beads

One kind of adsorbent with a high adsorption capacity for anionic dyes was prepared using ionically and chemically cross-linked chitosan beads. A batch system was applied to study the adsorption behavior of one acid dye (MY, metanil yellow) and one reactive dye (RB15, reactive blue 15) in aqueous solutions by the cross-linked chitosan beads. The adsorption capacities was 3.56 mmol g(-1) (1334 mg g(-1)) for dye MY and 0.56 mmol g(-1) (722 mg g(-1)) for dye RB15 at pH4, 30 degrees C. The Langmuir model agreed very well with the experimental data (R(2)>0.996). The kinetics of adsorption for a single dye and the kinetics of removal of ADMI color value in mixture solutions at different initial dye concentrations were evaluated by the nonlinear first-order and second-order models. The first-order kinetic model fits well with the dynamical adsorption behavior of a single dye for lower initial dye concentrations, while the second-order kinetic model fits well for higher initial dye concentrations. The competitive adsorption favored the dye RB15 in the mixture solution (initial conc. (mM): MY=1.34; RB15=1.36); while it favored the dye MY in the mixture solution (initial conc. (mM): MY=3.00; RB15=1.34) and the adsorption kinetics for dye RB15 has the tendency to shift to a slower first order model.     

磷酸活化-微波热解法制备污泥吸附剂

以污泥吸附剂的碘值和其对铬的吸附去除效果为考察指标,对制备污泥吸附剂的各种影响因素进行全面考察和分析。结果表明,其最佳制备工艺条件为微波功率550 W,微波辐照时间330 s,磷酸浓度为40%及磷酸与污泥原料的液固比为2∶1,空气氛围中制备的吸附剂SAA的性能要稍优于氮气氛围中制备的吸附剂SAN,但前者的得率稍低于后者,总体来讲,两者相差不大。在实际应用中可简化制备工艺,无需通入保护气体。     

Predicting adsorptive removal of chlorophenol from aqueous solution using artificial intelligence based modeling approaches

The research aims to develop artificial intelligence (AI)-based model to predict the adsorptive removal of 2-chlorophenol (CP) in aqueous solution by coconut shell carbon (CSC) using four operational variables (pH of solution, adsorbate concentration, temperature, and contact time), and to investigate their effects on the adsorption process. Accordingly, based on a factorial design, 640 batch experiments were conducted. Nonlinearities in experimental data were checked using Brock–Dechert–Scheimkman (BDS) statistics. Five nonlinear models were constructed to predict the adsorptive removal of CP in aqueous solution by CSC using four variables as input. Performances of the constructed models were evaluated and compared using statistical criteria. BDS statistics revealed strong nonlinearity in experimental data. Performance of all the models constructed here was satisfactory. Radial basis function network (RBFN) and multilayer perceptron network (MLPN) models performed better than generalized regression neural network, support vector machines, and gene expression programming models. Sensitivity analysis revealed that the contact time had highest effect on adsorption followed by the solution pH, temperature, and CP concentration. The study concluded that all the models constructed here were capable of capturing the nonlinearity in data. A better generalization and predictive performance of RBFN and MLPN models suggested that these can be used to predict the adsorption of CP in aqueous solution using CSC.     

Purification of industrial phosphoric acid (54 %) using Fe-pillared bentonite

The current problem of excess impurities in industrial phosphoric acid (IPA) 54 % P₂O₅ makes phosphates industries look toward low-cost but efficient adsorbents. In the present study, iron-oxide-modified bentonite (Fe-PILB) was prepared and investigated as a possible adsorbent for the removal of organic matter (OM) like humic acid (HA), chromium (Cr(III)), and zinc (Zn(II)) from IPA aqueous solutions. These adsorbents were characterized using XRD, TEM, and BET. The adsorption of impurities is well described by the pseudo-second-order model. The results indicate that Fe-PILB has a good ability to resist co-existing anions and the low-pH condition of IPA and owns a relatively high-removal capacity of 80.42 and 25 % for OM, Cr(III), and Zn(II). The mechanism of adsorption may be described by the ligand and ion exchange that happened on the active sites. The selected order of adsorption OM?>?Cr³⁺?>?Zn²⁺ showed the importance of the competitive phenomenon onto bentonite materials’ pore adsorption. For the adsorption of OM at the low pH of IPA, H-bond complexation was the dominant mechanism. From the adsorption of heavy metals and OM complex compounds contained in IPA 54 % on Fe-PILB, the bridging of humic acid between bentonite and heavy metals (Zn(II) or Cr(III)) is proposed as the dominant adsorption mechanism (bentonite-HA-Me). Overall, the results obtained in this study indicate Fe-pillared bentonite possesses a potential for the practical application of impurity (OM, Zn(II), and Cr(III)) removal from IPA aqueous solutions.     

壳聚糖双冠醚的合成及其对金属离子的吸附性能研究

将二苯并16－冠－5氯代乙酸酯冠醚分别接枝到西佛碱型壳聚糖冠醚CT－15C和CT－18C上,制备了1,4－壳聚糖双冠醚CT－15CAC和CT－18CAC,经元素分析、FT－IR红外光谱分析和X－射线粉末衍射分析表征了结构。研究了CT－15CAC和CT－18CAC对Pd^2 、Ag^ 、Pt^4 、Au^3 、Cu^2 、Hg^2 的静态吸附性能,并与CT－15C和CT－18C进行了比较。结果表明,这4种吸附剂对贵金属离子如Au^3 、Ag^ 、Pt^4 、Pd^2 都具有较好的吸附性能,并能在Cu^2 和Hg^2 共存的条件下选择吸附Pd^2 ,而且壳聚糖双冠醚CT－15CAC和CT－18CAC比壳聚糖单冠醚CT－15C和CT－18C具有更好的选择性。     

Waste Fe(III)/Cr(III) hydroxide as adsorbent for the removal of Cr(VI) from aqueous solution and chromium plating industry wastewater

Fe(III)/Cr(III) hydroxide, a waste material from the fertilizer industry, has been used for the adsorption of Cr(VI) from aqueous solution, over a range of initial metal ion concentrations (5-30 mg litre(-1)), agitation times (1-180 min), adsorbent dosages (100-1200 mg per 50 ml), temperatures (24, 29 and 38 degrees C) and pH values (4.5-10). The adsorption of Cr(VI) increased with the initial concentration of Cr(VI) and with temperature. The process of uptake follows both the Langmuir and the Freundlich isotherm models. The applicability of Lagergren and empirical kinetic models has also been investigated. Almost quantitative removal of Cr(VI) at 10 mg litre(-1) in a 50-ml solution by 500 mg of adsorbent was found at an equilibrium pH of 5.6. The efficiency of chromium removal was also tested using wastewater from the chromium plating industry.     

氧化树脂的制备及其对水溶液中2,4-二氯苯酚的吸附研究

用H₂O₂或HNO₃氧化的方法制备了新型吸附树脂ZH-07和ZH-08,同时研究了它们对不同温度下水溶液中2,4-二氯苯酚的静态吸附和脱附特征,并对其吸附机理进行了探讨。结果表明,经氧化后的树脂ZH-07和ZH-08对水溶液中2,4-二氯苯酚的吸附过程存在化学吸附作用,可以提高它们对水溶液中2,4-二氯苯酚的吸附容量。