Response surface optimization of a dynamic dye adsorption process: a case study of crystal violet adsorption onto NaOH-modified rice husk

The adsorption of crystal violet from aqueous solution by NaOH-modified rice husk was investigated in a laboratory-scale fixed-bed column. A two-level three factor (2³) full factorial central composite design with the help of Design Expert Version 7.1.6 (Stat Ease, USA) was used for optimisation of the dynamic dye adsorption process and evaluation of interaction effects of different operating parameters: initial dye concentration (100–200 mg L^?1), flow rate (10–30 mL min^?1) and bed height (5–25 cm). A correlation coefficient (R ²) value of 0.999, model F value of 1,936.59 and its low p value (<0.0001) along with lower value of coefficient of variation (1.38 %) indicated the fitness of the response surface quadratic model developed during the present study. Numerical optimisation applying desirability function was used to identify the optimum conditions for a targeted breakthrough time of 12 h. The optimum conditions were found to be initial solution pH?=?8.00, initial dye concentration?=?100 mg L^?1, flow rate?=?22.88 mL min^?1 and bed height?=?18.75 cm. A confirmatory experiment was performed to evaluate the accuracy of the optimised procedure. Under the optimised conditions, breakthrough appeared after 12.2 h and the column efficiency was determined as 99 %. The Thomas model showed excellent fit to the dynamic dye adsorption data obtained from the confirmatory experiment. Thereby, it was concluded that the current investigation gives valuable insights for designing and establishing a continuous wastewater treatment plant.     

涂铁多孔陶瓷对水中亚甲基蓝的动态吸附

研究了涂铁多孔陶瓷填料柱对水中亚甲基蓝（MB）的动态吸附性能。探讨了填料高度、MB初始质量浓度和流速对穿透曲线的影响；分别用BDST模型、Thomas模型和线性回归对动态吸附实验数据拟合，获得了相关参数，并研究了填料的再生性能。结果表明，涂铁多孔陶瓷（IOCPC）能有效去除水中MB，填料层升高，穿透曲线上的穿透点向右移动，穿透时间延长；而随流速、MB初始质量浓度的增大，穿透曲线上的穿透点向左移动，穿透时间缩短。用BDST模型能准确预测穿透时间，误差＜5%；用Thomas模型可较好地描述了MB浓度为10和50 mg/L、初速为2 mL/min时IOCPC对MB的吸附动力学，相关系数分别为0.99和0.93，平衡吸附容量分别为0.078和0.13 mg/g。对吸附饱和后的涂铁多孔陶瓷可用pH=3的硝酸再生，重复使用3次穿透曲线上的穿透点基本不变。     

Heavy metals removal in fixed-bed column by the macro fungus Pycnoporus sanguineus

The ability of Pycnoporus sanguineus to adsorb heavy metals from aqueous solution was investigated in fixed-bed column studies. The experiments were conducted to study the effect of important design parameters such as column bed height, flow rate and initial concentration of solution. The breakthrough profiles were obtained in these studies. A mathematical model based on external mass transfer and pore diffusion was used for the prediction of mass transfer coefficient and effective diffusivity of metals in macro-fungi bed. Experimental breakthrough profiles were compared with the simulated breakthrough profiles obtained from the mathematical model. Bed Depth Service Time (BDST) model was used to analyse the experimental data and evaluated the performance of biosorption column. The BDST model parameters needed for the design of biosorption columns were evaluated for lead, copper and cadmium removal in the column. The columns were regenerated by eluting the metal ions using 0.1 M hydrochloric acid solution after the adsorption studies. The columns were subjected to repeated cycles of adsorption of same metal ions and desorption to evaluate the removal efficiency after adsorption-desorption.     

Low-cost adsorbents from bio-waste for the removal of dyes from aqueous solution

Activated carbons (ACs) were developed from bio-waste materials like rice husk and peanut shell (PS) by various physicochemical activation methods. PS char digested in nitric acid followed by treatment at 673 K resulted in high surface area up to ～585 m²/g. The novelty of the present study is the identification of oxygen functional groups formed on the surface of activated carbons by infrared and X-ray photoelectron spectroscopy and quantification by using temperature programmed decomposition (TPD). Typical TPD data indicated that each activation method may lead to varying amounts of acidic and basic functional groups on the surface of the adsorbent, which may be a crucial factor in determining the adsorption capacity. It was shown that ACs developed during the present study are good adsorbents, especially for the removal of a model textile dye methylene blue (MB) from aqueous solution. As MB is a basic dye, H₂O₂-treated rice husk showed the best adsorption capacity, which is in agreement with the acidic groups present on the surface. Removal of the dye followed Langmuir isotherm model, whereas MB adsorption on ACs followed pseudo-second-order kinetics.     

Column dynamic studies and breakthrough curve analysis for Cd(II) and Cu(II) ions adsorption onto palm oil boiler mill fly ash (POFA)

This paper investigates the adsorption characteristics of palm oil boiler mill fly ash (POFA) derived from an agricultural waste material in removing Cd(II) and Cu(II) from aqueous solution via column studies. The performance of the study is described through the breakthrough curves concept under relevant operating conditions such as column bed depths (1, 1.5, and 2 cm) and influent metal concentrations (5, 10, and 20 mg/L). The Cd(II) and Cu(II) uptake mechanism is particularly bed depth- and concentration-dependant, favoring higher bed depth and lower influent metal concentration. The highest bed capacity of 34.91 mg Cd(II)/g and 21.93 mg Cu(II)/g of POFA was achieved at 20 mg/L of influent metal concentrations, column bed depth of 2 cm, and flow rate of 5 mL/min. The whole breakthrough curve simulation for both metal ions were best described using the Thomas and Yoon–Nelson models, but it is apparent that the initial region of the breakthrough for Cd(II) was better described using the BDST model. The results illustrate that POFA could be utilized effectively for the removal of Cd(II) and Cu(II) ions from aqueous solution in a fixed-bed column system.     

Adsorption behavior of light green anionic dye using cationic surfactant-modified wheat straw in batch and column mode

An agricultural by-product, natural wheat straw (NWS), was soaked in 1 % cationic surfactant (hexadecylpyridinium bromide, CPB) solution for 24 h (at 293 K), and modified wheat straw (MWS) was obtained. Analysis of FTIR, XFR, and nitrogen element showed that CPB was adsorbed onto surface of NWS. Then, MWS was used as adsorbent for the removal of light green dye (LG, anionic dye) from aqueous solution. The experiment was performed in batch and column mode at room temperature (293 K). Sodium chloride (up to 0.1 mol/L) existed in solution was not favor of LG dye adsorption. The equilibrium data were better described by Langmuir isotherm, and adsorption capacity of q _m from Langmuir model was 70.01?±?3.39 mg/g. In fixed-bed column adsorption mode, the effects of initial LG concentration (30, 50, 70 mg/L) and flow rate (6.5, 9.0, 14.5 mL/min) on adsorption were presented. Thomas and modified dose–response models were used to predict the breakthrough curves using nonlinear analysis method, and both models can fit the breakthrough curves. Theoretical and experimental breakthrough curves were drawn and compared. The results implied that MWS can be used as adsorbent material to remove LG from aqueous solution.     

Insights into aqueous carbofuran removal by modified and non-modified rice husk biochars

Biochar has been considered as a potential sorbent for removal of frequently detected pesticides in water. In the present study, modified and non-modified rice husk biochars were used for aqueous carbofuran removal. Rice husk biochars were produced at 300, 500, and 700 °C in slow pyrolysis and further exposed to steam activation. Biochars were physicochemically characterized using proximate, ultimate, FTIR methods and used to examine equilibrium and dynamic adsorption of carbofuran. Increasing pyrolysis temperature led to a decrease of biochar yield and increase of porosity, surface area, and adsorption capacities which were further enhanced by steam activation. Carbofuran adsorption was pH-dependant, and the maximum (161 mg g^?1) occurred in the vicinity of pH 5, on steam-activated biochar produced at 700 °C. Freundlich model best fitted the sorption equilibrium data. Both chemisorption and physisorption interactions on heterogeneous adsorbent surface may involve in carbofuran adsorption. Langmuir kinetics could be applied to describe carbofuran adsorption in a fixed bed. A higher carbofuran volume was treated in a column bed by a steam-activated biochar versus non-activated biochars. Overall, steam-activated rice husk biochar can be highlighted as a promising low-cost sustainable material for aqueous carbofuran removal.     

改性沸石对低浓度氨氮废水的动态吸附

采用氯化钠溶液对甘肃白银天然沸石改性,以低浓度氨氮(NH4+-N)废水为处理对象,对比了天然沸石和改性沸石的动态吸附特性并绘制穿透曲线,利用Origin软件对实验数据分析处理,得出穿透曲线的通式。结果表明:在相同条件下,改性沸石的穿透时间和吸附饱和时间都比天然沸石的长约1.5倍;沸石经氯化钠改性后,对NH4+-N的吸附速率和饱和吸附量都明显提高,吸附性能显著改善。Origin软件对水溶液中NH4+-N的吸附穿透曲线的Logistic模型回归式具有较高的精度,该模型可以很好地反映沸石吸附剂的动态吸附过程。     

Removal of sulfamethoxazole and sulfapyridine by carbon nanotubes in fixed-bed columns

Sulfamethoxazole (SMX) and sulfapyridine (SPY), two representative sulfonamide antibiotics, have gained increasing attention because of the ecological risks these substances pose to plants, animals, and humans. This work systematically investigated the removal of SMX and SPY by carbon nanotubes (CNTs) in fixed-bed columns under a broad range of conditions including: CNT incorporation method, solution pH, bed depth, adsorbent dosage, adsorbate initial concentration, and flow rate. Fixed-bed experiments showed that pH is a key factor that affects the adsorption capacity of antibiotics to CNTs. The Bed Depth Service Time model describes well the relationship between service time and bed depth and can be used to design appropriate column parameters. During fixed-bed regeneration, small amounts of SMX (3%) and SPY (9%) were irreversibly bonded to the CNT/sand porous media, thus reducing the column capacity for subsequent reuse from 67.9 to 50.4 mg g^?1 for SMX and from 91.9 to 72.9 mg g^?1 for SPY. The reduced column capacity resulted from the decrease in available adsorption sites and resulting repulsion (i.e., blocking) of incoming antibiotics from those previously adsorbed. Findings from this study demonstrate that fixed-bed columns packed with CNTs can be efficiently used and regenerated to remove antibiotics from water.     

Biosorption of copper, cobalt and nickel by marine green alga Ulva reticulata in a packed column

Biosorption of copper, cobalt and nickel by marine green alga Ulva reticulata were investigated in a packed bed up-flow column. The experiments were conducted to study the effect of important design parameters such as bed height and flow rate. At a bed height of 25 cm, the metal-uptake capacity of U. reticulata for copper, cobalt and nickel was found to be 56.3+/-0.24, 46.1+/-0.07 and 46.5+/-0.08 mgg(-1), respectively. The Bed Depth Service Time (BDST) model was used to analyze the experimental data. The computed sorption capacity per unit bed volume (N0) was 2580, 2245 and 1911 mgl(-1) for copper, cobalt and nickel, respectively. The rate constant (K(a)) was recorded as 0.063, 0.081 and 0.275 lmg(-1)h(-1) for copper, cobalt and nickel, respectively. In flow rate experiments, the results confirmed that the metal uptake capacity and the metal removal efficiency of U. reticulata decreased with increasing flow rate. The Thomas model was used to fit the column biosorption data at different flow rates and model constants were evaluated. The column regeneration studies were carried out for three sorption-desorption cycles. The elutant used for the regeneration of the biosorbent was 0.1 M CaCl2 at pH 3 adjusted using HCl. For all the metal ions, a decreased breakthrough time and an increased exhaustion time were observed as the regeneration cycles progressed, which also resulted in a broadened mass transfer zone. The pH variations during both sorption and desorption process have been reported.     

Sorption of anionic surfactants on a fixed bed of rubber granules

The performance of a fixed-bed adsorber (FBR) column for the removal of anionic surfactants from aquatic environments has been studied. Waste tyre rubber granules were used as the adsorbent material, and sodium dodecyl sulfate, an anionic surfactant, as the adsorbate. The FBR column design parameters were evaluated using the column breakthrough data at different bed depths. The Bohert and Adams model was used with the bed depth service time approach for the design of the column. The bed efficiency obtained was 90.97%.     

Fixed-bed study for lanthanide (La, Eu, Yb) ions removal from aqueous solutions by immobilized Pseudomonas aeruginosa: experimental data and modelization

A fixed-bed study was carried out by using cells of Pseudomonas aeruginosa immobilized in polyacrylamide gel as a biosorbent for the removal of lanthanide (La, Eu, Yb) ions from aqueous solutions. The effects of superficial liquid velocity based on empty column, particle size, influent concentration and bed depth on the lanthanum breakthrough curves were investigated. Immobilized biomass effectively removed lanthanum from a 6 mM solution with a maximum adsorption capacity of 342 micromolg(-1) (+/-10%) corresponding closely to that observed in earlier batch studies with free bacterial cells. The Bohart and Adams sorption model was employed to determine characteristic parameters useful for process design. Results indicated that the immobilized cells of P. aeruginosa enable removal of lanthanum, europium and ytterbium ions from aqueous effluents with significant and similar maximum adsorption capacities. Experiments with a mixed cation solution showed that the sequence of preferential biosorption was Eu3+ > or = Yb3+ > La3+. Around 96+/-4% of the bound lanthanum was desorbed from the column and concentrated by eluting with a 0.1 M EDTA solution. The feasibility of regenerating and reusing the biomass through three adsorption/desorption cycles was suggested. Neural networks were used to model breakthrough curves performed in the dynamic process. The ability of this statistical tool to predict the breakthrough times was discussed.     

超细粉煤灰基成型吸附剂的动态吸附实验

以粉煤灰为原料制备成型吸附剂，对水溶液中亚甲基蓝和Cr⁶⁺进行动态吸附研究，绘制穿透曲线，利用Origin软件对实验数据分析处理，得出穿透曲线的通式C_t=A₁－A₂〖〗1+(t/t₀)^p+A₁。结果表明，初始浓度C₀=25 mg/L，填料高度不同时，达到穿透点的时间随填料高度的增加而增加；填料高度h=200 mm，初始浓度不同时，达到穿透点的时间随初始浓度的增加而减小；该吸附剂对有机染料和重金属离子均有较好的吸附性能；穿透曲线通式的回归线性相关系数表明，该通式可很好地反映超细粉煤灰成型吸附剂的动态吸附过程。     

Preparation of char from lotus seed biomass and the exploration of its dye removal capacity through batch and column adsorption studies

Char was obtained from lotus seed biomass by a simple single-step acid treatment process. It was used as an adsorbent for the removal of malachite green dye (MG) from simulated dye bath effluent. The adsorbent was characterized for its surface morphology, surface functionalities, and zero point charge. Batch studies were carried out by varying the parameters such as initial aqueous pH, adsorbent dosage, adsorbent particle size, and initial adsorbate concentration. Langmuir and Freundlich isotherms were used to test the isotherm data and the Freundlich isotherm best fitted the data. Thermodynamic studies were carried out and the thermodynamic parameters such as ?G, ?H, and ?S were evaluated. Adsorption kinetics was carried out and the data were tested with pseudofirst-order model, pseudosecond-order model, and intraparticle diffusion model. Adsorption of MG was not solely by intraparticle diffusion but film diffusion also played a major role. Continuous column experiments were also conducted using microcolumn and the spent adsorbent was regenerated using ethanol and was repeatedly used for three cycles in the column to determine the reusability of the regenerated adsorbent. The column data were modeled with the modeling equations such as Adam-Bohart model, Bed Depth Service Time (BDST) model, and Yoon-Nelson model for all the three cycles.     

Efficiency of a cleanup technology to remove mercury from natural waters by means of rice husk biowaste: ecotoxicological and chemical approach

In the present work, the efficiency of rice husk to remove Hg(II) from river waters spiked with realistic environmental concentrations of this metal (μg L^?1 range) was evaluated. The residual levels of Hg(II) obtained after the remediation process were compared with the guideline values for effluents discharges and water for human consumption, and the ecotoxicological effects using organisms of different trophic levels were assessed. The rice husk sorbent proved to be useful in decreasing Hg(II) contamination in river waters, by reducing the levels of Hg(II) to values of ca. 8.0 and 34 μg L^?1, for an Hg(II) initial concentration of 50 and 500 μg L^?1, respectively. The remediation process with rice husk biowaste was extremely efficient in river waters spiked with lower levels of Hg(II), being able to eliminate the toxicity to the exposed organisms algae Pseudokirchneriella subcapitata and rotifer Brachionus calyciflorus and ensure the total survival of Daphnia magna species. For concentrations of Hg(II) tenfold higher (500 μg L^?1), the remediation process was not adequate in the detoxification process, still, the rice husk material was able to reduce considerably the toxicity to the bacteria Vibrio fischeri, algae P. subcapitata and rotifer B. calyciflorus, whose responses where fully inhibited during its exposure to the non-remediated river water. The use of a battery of bioassays with organisms from different trophic levels and whose sensitivity revealed to be different and dependent on the levels of Hg(II) contamination proved to be much more accurate in predicting the ecotoxicological hazard assessment of the detoxification process by means of rice husk biowaste.     

Application of HYDRUS 1D model for assessment of phenol–soil adsorption dynamics

Laboratory-scale batch, vertical, and horizontal column experiments were conducted to investigate the attenuative capacity of a fine-grained clayey soil of local origin in the surrounding of a steel plant wastewater discharge site in West Bengal, India, for removal of phenol. Linear, Langmuir, and Freundlich isotherm plots from batch experimental data revealed that Freundlich isotherm model was reasonably fitted (R ²?=?0.94). The breakthrough column experiments were also carried out with different soil bed heights (5, 10, and 15 cm) under uniform flow to study the hydraulic movements of phenol by evaluating time concentration flow behavior using bromide as a tracer. The horizontal migration test was also conducted in the laboratory using adsorptive phenol and nonreactive bromide tracer to explore the movement of solute in a horizontal distance. The hydrodynamic dispersion coefficients (D) in the vertical and horizontal directions in the soil were estimated using nonlinear least-square parameter optimization method in CXTFIT model. In addition, the equilibrium convection dispersion model in HYDRUS 1D was also examined to simulate the fate and transport of phenol in vertical and horizontal directions using Freundlich isotherm constants and estimated hydrodynamic parameters as input in the model. The model efficacy and validation were examined through statistical parameters such as the coefficient of determination (R ²), root mean square error and design of index (d).     

Adsorptive removal of an acid dye by lignocellulosic waste biomass activated carbon: equilibrium and kinetic studies

Chemically prepared activated carbon material derived from palm flower was used as adsorbent for removal of Amido Black dye in aqueous solution. Batch adsorption studies were performed for the removal of Amido Black 10B (AB10B), a di-azo acid dye from aqueous solutions by varying the parameters like initial solution pH, adsorbent dosage, initial dye concentration and temperature with three different particle sizes such as 100 μm, 600 μm and 1000 μm. The zero point charge was pH 2.5 and the maximum adsorption occurred at the pH 2.3. Experimental data were analyzed by model equations such as Langmuir, Freundlich and Temkin isotherms and it was found that the Freundlich isotherm model best fitted the adsorption data and the Freundlich constants varied from (K_F) 1.214, 1.077 and 0.884 for the three mesh sizes. Thermodynamic parameters such as ΔG, ΔH and ΔS were also calculated for the adsorption processes and found that the adsorption process is feasible and it was the endothermic reaction. Adsorption kinetics was determined using pseudo first-order, pseudo second-order rate equations and also Elovich model and intraparticle diffusion models. The results clearly showed that the adsorption of AB10B onto lignocellulosic waste biomass from palm flower (LCBPF) followed pseudo second-order model, and the pseudo second-order rate constants varied from 0.059 to 0.006 (g mg⁻¹ min) by varying initial adsorbate concentration from 25 mg L⁻¹ to 100 mg L⁻¹. Analysis of the adsorption data confirmed that the adsorption process not only followed intraparticle diffusion but also by the film diffusion mechanism.     

Formation of shaped barium sulfate-dye hybrids: waste dye utilization for eco-friendly treatment of wastewater

Purpose

Owing to the present complexity and difficulty of concentrated dye wastewater treatment, this work aimed to synthesize a reproducible waste-sorbing material for the treatment of wastewater by forming the dye-conjugating complex hybrid.

Methods

The inorganic/organic hybridization was applied to prepare the objective material by immobilizing waster dye-Mordant blue 9 (MB) with barium sulfate (BaSO₄). The composition and pattern of the formed material were determined by spectrometry and characterized by SEM and XRD, and their formation process was clarified. The adsorption of cationic dye-basic blue BO (BB) and copper ion was investigated..

Results

The hybrid of MB alone into growing BaSO₄ formed the pineapple-like particles while that of the MB/BB-conjugating complex was the rhombus material. The adsorption of BB on the MB–BaSO₄ hybrid was probably attributed to ion-pair equilibrium and that of Cu²⁺ may result from the complexation. The treatment of dye and heavy metal wastewaters indicated that the MB hybrid material removed 99.8% BB and 97% Cu²⁺ and the dye-conjugating hybrid with growing BaSO₄ 100% MB, 99.5% BB, and 44% Cu²⁺.

Conclusion

The waste MB–BaSO₄ hybrid material is efficient to treat cationic dye and Cu²⁺ wastewater. The dye-conjugating hybridization method is the first to be advanced for in situ wastewater treatment, and it showed a combined effect for the removal of both organic dyes and heavy metals.     

Synthesis and optimization of spherical nZVI (20–60 nm) immobilized in bio-apatite-based material for efficient removal of phosphate: Box-Behnken design in a fixed-bed column

In the present study, bio-apatite/nZVI composite was synthesized through Fe(III) reduction with sodium borohydride and was fully characterized by FTIR, XRD, SEM–EDX, TEM, BET, BJH, and pH_PZC. Column experiments were carried out for the removal of phosphate as a function of four operational parameters including initial phosphate concentration (100–200 mg L^?1), initial solution pH (2–9), bed height (2–6 cm), and influent flow rate (2.5–7.5 mL min^?1) using a response surface methodology (RSM) coupled with Box-Behnken design (BBD). 2D contour and 3D surface plots were employed to analyze the interactive effects of the four operating parameters on the column performance (e.g., uptake capacity and saturation time). According to ANOVA analysis, the influent flow rate and bed height are the most important factor on phosphate uptake capacity and saturation time, respectively. A quadratic polynomial model was excellently fitted to experimental data with a high coefficient of determination (>?0.96). The RSM-BBD model predicted maximum phosphate adsorption capacity of 85.71 mg g^?1 with the desirability of 0.995 under the optimal conditions of 135.35 mg L^?1, 2, 2 cm, and 7.5 mL min^?1 for initial phosphate concentration, initial solution pH, bed height, and influent flow rate, respectively. The XRD analysis demonstrated that the reaction product between bio-apatite/nZVI composite and phosphate anions was Fe₃ (PO₄)₂. 8H₂O (vivianite). The suggested adsorbent can be effectively employed up to five fixed-bed adsorption–desorption cycles and was also implemented to adsorb phosphate from real samples.

     

Use of carbonised beet pulp carbon for removal of Remazol Turquoise Blue-G 133 from aqueous solution

Carbonised beet pulp (BPC) produced from agricultural solid waste by-product in sugar industry was used as adsorbent for the removal of Remazol Turquoise Blue-G 133 (RTB-G 133) dye in this study. The kinetics and equilibrium of sorption process were investigated with respect to pH, temperature and initial dye concentration. Adsorption studies with real textile wastewater were also performed. The results showed that adsorption was a strongly pH-dependent process, and optimum pH was determined as 1.0. The maximum dye adsorption capacity was obtained as 47.0 mg g^?1at the temperature of 25 °C at this pH value. The Freundlich and Langmuir adsorption models were used for describing the adsorption equilibrium data of the dye, and isotherm constants were evaluated depending on sorption temperature. Equilibrium data of RTB-G 133 sorption fitted very well to the Freundlich isotherm. Mass transfer and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate-controlling steps. It was found that both external mass transfer and intra-particle diffusion played an important role in the adsorption mechanisms of dye and adsorption kinetics followed the pseudo second-order type kinetic model. The thermodynamic analysis indicated that the sorption process was exothermic and spontaneous in nature.