Cu(II) removal using green adsorbents: kinetic modeling and plant scale-up design

Cu(II) adsorption in continuous column using green adsorbents like peanut and almond shell was investigated. Fourier transform infrared (FTIR) spectroscopy, Brunaer-Emmett-Teller (BET) analysis, scanning electron microscopy (SEM), and Point of Zero charge (pH_pzc) determination have been used for characterization of the adsorbents. Experiments were conducted at various operating conditions to calculate the adsorption capacity of the adsorbents. Adsorption studies signify that both the adsorbents have good adsorptive capacity for Cu(II) ion. Equilibrium of adsorption was described using Langmuir isotherm and the highest q_max value for both the adsorbent were obtained at an operating condition of 20 ml/min flow rate, 15 mg/L influent Cu(II) concentration, and 7 cm bed depth. Regeneration of both the adsorbents suggests that these adsorbents can be used several times for Cu(II) removal. Seven different kinetic models were tested among which the modified dose response model was fitted well for peanut shell and the Thomas model was fitted well for almond shell. These fitted models were further used for scale-up design. Regeneration studies show that peanut shell and almond shell are useful up to the fifth adsorption cycle. Application of these adsorbents with industrial effluent was also reported. This study reveals that peanut and almond shells can be used for Cu(II) removal for industrial wastewater.

     

Synthesis and application of Cu-BTC@ZSM-5 composites as effective adsorbents for removal of toluene gas under moist ambience: kinetics,thermodynamics, and mechanism studies

Metal organic frameworks (MOFs) are excellent adsorbents that provide abundant specific surface area, adjustable pore structure, and rich active sites. The purpose of this study was to prepare composites with hydrophobic and high microporous specific surface area and to adsorb toluene gas in moist ambience. An ethanol activation-assisted hydrothermal method was proposed to synthesize copper-benzene-1,3,5-tricarboxylic acid (Cu-BTC) metal-organic framework, Cu-BTC, and ZSM-5 molecular sieve composites (Cu-BTC@ZSM-5). The dynamic adsorption process of toluene on different adsorbents was investigated, and the results showed that the toluene adsorption capacity of Cu-BTC@ZSM-5 (158.6 mg/g) was 2.53 times higher than Cu-BTC (62.7 mg/g), when the ZSM-5 content is 5% and the humidity is 30%RH. Compared with other factors, the humidity inhibited the adsorption of toluene on Cu-BTC@ZSM-5. Langmuir model and the pseudo-second kinetics model can better describe the adsorption behavior of Cu-BTC@ZSM-5. The thermodynamic results showed the adsorption process was a spontaneous exothermic process at low temperature and mainly physical adsorption. The relative regenerability can still up to 80.4% after six cycles. The adsorption mechanisms of Cu-BTC@ZSM-5 were pore-filling adsorption, π-π interaction, cation-π bonding, and hydrophobic interactions. This study will help to design a systematic route to evaluate the adsorption performance of Cu-BTC@ZSM-5 for toluene.

     

Removal of arsenic(III,V) by a granular Mn-oxide-doped Al oxide adsorbent: surface characterization and performance

In order to remove arsenic (As) from contaminated water, granular Mn-oxide-doped Al oxide (GMAO) was fabricated using the compression method with the addition of organic binder. The analysis results of XRD, SEM, and BET indicated that GMAO was microporous with a large specific surface area of 54.26 m^2/g, and it was formed through the aggregation of massive Al/Mn oxide nanoparticles with an amorphous pattern. EDX, mapping, FTIR, and XPS results showed the uniform distribution of Al/Mn elements and numerous hydroxyl groups on the adsorbent surface. Compression tests indicated a satisfactory mechanical strength of GMAO. Batch adsorption results showed that As(V) adsorption achieved equilibrium faster than As(III), whereas the maximum adsorption capacity of As(III) estimated from the Langmuir isotherm at 25 °C (48.52 mg/g) was greater than that of As(V) (37.94 mg/g). The As removal efficiency could be maintained in a wide pH range of 3~8. The presence of phosphate posed a significant adverse effect on As adsorption due to the competition mechanisms. In contrast, Ca²⁺ and Mg²⁺ could favor As adsorption via cation-bridge involvement. A regeneration method was developed by using sodium hydroxide solution for As elution from saturated adsorbents, which permitted GMAO to keep over 75% of its As adsorption capacity even after five adsorption–regeneration cycles. Column experiments showed that the breakthrough volumes for the treatment of As(III)-spiked and As(V)-spiked water (As concentration = 100 μg/L) were 2224 and 1952, respectively. Overall, GMAO is a potential adsorbent for effectively removing As from As-contaminated groundwater in filter application.

     

Silane removal at ambient temperature by using alumina-supported metal oxide adsorbents

Copper, zinc, and cerium oxide adsorbents supported on alumina were used to remove silane gas (SiH4). The adsorbents were prepared using a coprecipitation method and characterized by the inductively coupled plasma mass spectrometry, X-ray powder diffractometer, and Brunauer-Emmett-Teller method (BET). The silane removal efficiency and adsorption capacity of the adsorbents were investigated in this study. Test results showed that the adsorbents containing active species had a removal efficiency >99.9% for SiH4 before breakthrough. Adsorbents containing mixed oxides (CuO-CeO2/ Al2O3 and CuO-ZnO/Al2O3), which showed well-dispersed active species and high BET surface areas, had a greater adsorption capacity than the adsorbents containing single metal oxide. However, when the CuO-ZnO/ Al2O3 adsorbents contain >40 wt% of active metal oxides, the increase of active species lowered the BET surface area leading to a decrease of the adsorption capacity. Additionally, when the content of the active metal oxides was between 20% and 40%, the CuO-ZnO/Al2O3 adsorbents demonstrated higher adsorption capacity.     

双氯芬酸的吸附去除过程与机制

研究了非甾体抗炎药双氯芬酸的吸附去除过程与机制。对吸附处理效果较好的活性炭与纳米羟基氧化铁（α-FeOOH）进行了比表面积、Zeta电位等表面特性的表征，研究比较了双氯芬酸在活性炭与α—FeOOH2种材料上的吸附去除效果与吸附机制。结果表明，在相同的实验条件下，活性炭与α-FeOOH对双氯芬酸吸附去除率可分别达到97．9％和84．3％；双氯芬酸在活性炭上的吸附主要是由于活性炭较大的比表面积与疏水分配作用，在α-FeOOH上的吸附主要是由于静电引力作用；活性炭与α-FeOOH对双氯芬酸的吸附去除效果均随pH的升高而降低；在pH=6时，活性炭与α-FeOOH对双氯芬酸钠的吸附等温线均符合Langmuir方程，单位饱和吸附量分别为109．98mg／g和58．96mg／g；活性炭对双氯芬酸具有更强的吸附能力。     

Adsorption Kinetic,Thermodynamic, and Desorption Studies of Isopropyl Alcohol Vapor by Oxidized Single-Walled Carbon Nanotubes

Abstract

Single-walled carbon nanotubes (SWCNTs) were oxidized by sodium hypochlorite (NaOCl) solution and used as adsorbents to study adsorption kinetics, thermodynamics, and desorption of isopropyl alcohol (IPA) vapor in an airstream. The adsorption capacity of IPA decreased with temperature, indicating an exothermic nature of the adsorption process, and slightly decreased with relative humidity, showing a hydrophobic nature of the adsorbent surface. The adsorption mechanism appears mainly attributable to physical forces from 5 to 25 °C but appears primarily attributable to chemical forces from 25 to 35 °C. A comparative study on the cyclic IPA adsorption between SWCNTs(NaOCl) and granular activated carbon, GAC(NaOCl), was also conducted and the results revealed that the SWCNTs(NaOCl) show better repeated availability of IPA adsorption during 15 cycles of operation than the GAC(NaOCl). This suggests that the SWCNTs(NaOCl) are efficient IPA adsorbents and can be used in the prolonged cyclic adsorption/desorption operation.     

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.     

纳米四氧化三铁同步去除水中的Pb（Ⅱ）和Cr（Ⅲ）离子

采用共沉淀方法制备纳米四氧化三铁颗粒（MNPs）,通过扫描电镜（SEM）、X射线衍射（XRD）和光电子能谱分析（XPS）等表征手段对材料进行分析。同时考察了不同MNPs投加量、pH值、温度和初始浓度条件下对纳米四氧化三铁同步去除水中Pb（Ⅱ）和Cr（Ⅲ）离子的影响。结果表明,在pH为6.0、温度为25℃、纳米四氧化三铁的投加量为4.0 g/L下,吸附3 h后,Pb（Ⅱ）-Cr（Ⅲ）复合溶液中Pb的去除率为70.5%,Cr的去除率可达77.4%。pH和温度对去除过程影响较大。SEM和XRD分析证实成功制备了纳米级四氧化三铁,XPS结果表明,复合溶液中Pb（Ⅱ）和Cr（Ⅲ）离子的去除过程为同步吸附。吸附等温线研究说明,Pb（Ⅱ）的吸附是放热过程且为单相吸附;相反Cr（Ⅲ）的吸附是吸热过程且为多相吸附。重复利用实验表明,MNPs利用3次后对Pb和Cr的去除率几乎未受影响。因此,MNPs可用于实际工程中多种重金属离子共存废水的原位处理。     

凹凸棒粘土对水中亚甲蓝的吸附性能

用焦磷酸钠和盐酸纯化了地产凹凸棒粘土,SEM、XRD和FT-IR表征其结构。研究了凹凸棒粘土对亚甲蓝的吸附性能及热力学和动力学特征,考察了吸附时间、温度、初始浓度、pH和离子强度下对亚甲蓝吸附的影响。结果表明,不同实验条件下,吸附过程均符合准二级动力学特征。凹凸棒粘土对亚甲蓝是放热的物理吸附过程,吸附符合Langmuir模式,在303 K时最大吸附量为114.02 mg/g。与其他吸附材料相比,凹凸棒粘土对亚甲蓝有较快的吸附速率和较大的吸附量,可以作为价廉的吸附剂用于亚甲蓝的消除。     

Removal of arsenic(V) from aqueous solutions using iron-oxide-coated modified activated carbon.

Removal of arsenic(V) from aqueous solutions was evaluated with the following three different sorption materials: coal-based activated carbon 12 x 40 (activated carbon), iron(II) oxide (FeO)/activated carbon-H, and iron oxide. The apparent characteristics and physical chemistry performances of these adsorbents were investigated by X-ray diffraction, nitrogen adsorption, and scanning electronic microscope. Also, batch experiments for arsenic removal were performed, and the effects of pH value on arsenic(V) removal were studied. The results suggest that the main phases of the iron oxide surface are magnetite, maghemite, hematite, and goethite; fine and uniform iron oxide particles can cover activated carbon surfaces and affect the surface area or pore structures of activated carbon; adsorption kinetics obey a pseudo-first-order rate equation; and adsorption capacities of adsorbents are affected by the values of pH. The optimum value of pH for iron oxide lies in a narrow range between 4.0 and 5.5, and arsenic(V) removal by FeO/activated carbon-H is ideal and stable in the pH range 3 to 7, while activated carbon has the lowest adsorption capacity in the entire pH range. Also, the adsorption characteristics of FeO/activated carbon-H composites and virgin activated carbon match well the Langmuir adsorption model, while those of iron oxide fit well the Freundlich adsorption model.     

Comparative study of adsorption of Pb(II) on native garlic peel and mercerized garlic peel

A comparative study using native garlic peel and mercerized garlic peel as adsorbents for the removal of Pb²⁺ has been proposed. Under the optimized pH, contact time, and adsorbent dosage, the adsorption capacity of garlic peel after mercerization was increased 2.1 times and up to 109.05 mg g^?1. The equilibrium sorption data for both garlic peels fitted well with Langmuir adsorption isotherm, and the adsorbent–adsorbate kinetics followed pseudo-second-order model. These both garlic peels were characterized by elemental analysis, Fourier transform infrared spectrometry (FT-IR), and scanning electron microscopy, and the results indicated that mercerized garlic peel offers more little pores acted as adsorption sites than native garlic peel and has lower polymerization and crystalline and more accessible functional hydroxyl groups, which resulted in higher adsorption capacity than native garlic peel. The FT-IR and X-ray photoelectron spectroscopy analyses of both garlic peels before and after loaded with Pb²⁺ further illustrated that lead was adsorbed on the through chelation between Pb²⁺ and O atom existed on the surface of garlic peels. These results described above showed that garlic peel after mercerization can be a more attractive adsorbent due to its faster sorption uptake and higher capacity.     

Utilization of nSiO2, fly ash, and nSiO2/fly ash composite for the remediation of triphenyltin (TPT) from contaminated seawater

The removal of triphenyltin chloride from contaminated simulated seawater with adsorption method was discussed. The adsorbents used are fly ash, nSiO₂, and nSiO₂/fly ash composite. The results showed that the adsorption of the adsorbents increases with increase in the adsorbent dose, contact time, pH, stirring speed, initial TPT concentration, and decreased with increase in temperature. The adsorption fitted well with the Freundlich isotherm, showing that the adsorbent and TPT combined with function groups and the adsorption kinetics followed the pseudo-second-order kinetic model. The thermodynamic parameters were also evaluated. Optimal conditions for the adsorption of TPT from simulated seawater were applied to TPT removal from natural seawater. A higher removal efficiency of TPT (>99 %) was obtained for the nSiO₂/fly ash composite but not for fly ash and nSiO₂.     

Removal and Destruction of Organic Contaminants in Water Using Adsorption,Steam Regeneration,and Photocatalytic Oxidation: A Pilot-Scale Study

ABSTRACT

The overall objective of this pilot-scale study is to investigate the technical feasibility of the removal and destruction of organic contaminants in water using adsorption and photocatalytic oxidation. The process consists of two consecutive operational steps: (1) removal of organic contaminants using fixed-bed adsorption; and (2) regeneration of spent adsorbent using photocatalysis or steam, followed by decontamination of steam condensate using photocatalysis. The pilot-scale study was conducted to evaluate these options at a water treatment plant in Wausau (Wisconsin) for treatment of groundwater contaminated with tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), toluene, ethylbenzene (EB), and xylenes. The adsorbents used were F-400 GAC and Ambersorb 563.

In the first treatment strategy, the adsorbents were impregnated with photocatalyst and used for the removal of aqueous organics. The spent adsorbents were then exposed to ultraviolet light to achieve photocatalytic regeneration. Regeneration of adsorbents using photocatalysis was observed to be not effective, probably because the impregnated photocatalyst was fouled by background organic matter present in the groundwater matrix.

In the second treatment strategy, the spent adsorbents were regenerated using steam, followed by cleanup of steam condensate using photocatalysis. Four cycles of adsorption and three cycles of steam regeneration were performed. Ambersorb 563 adsorbent was successfully regenerated using saturated steam at 160 °C within 20 hours. The steam condensate was treated using fixed-bed photo-catalysis using 1% Pt-TiO₂ photocatalyst supported on silica gel. After 35 minutes of empty bed contact time, more than 95% removal of TCE, cis-DCE, toluene, EB, and xylenes was achieved, and more than 75% removal of PCE was observed.

In the case of activated carbon adsorbent, steam regeneration was not effective, and a significant loss in adsorbent capacity was observed.     

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.     

Rapid and efficient removal of Ni2+ from aqueous solution by the one-pot synthesized EDTA-modified magnetic nanoparticles

A facile one-pot process has been proposed to prepare the novel ethylenediaminetetraacetic acid (EDTA)-modified magnetite nanoparticles (EDTA-MNPs). The bared Fe₃O₄ magnetite nanoparticles and EDTA-MNPs were characterized using FTIR spectroscopy, TEM, VSM, and X-ray diffraction. The application of the modified magnetite nanoparticles for metal ion uptake was studied using Ni²⁺ as a model. The adsorption was fast and the equilibrium was established within 5 min, and the adsorption kinetics of Ni²⁺ onto EDTA-MNPs followed the pseudo second-order chemisorption mechanism. Maximum adsorption capacity for Ni²⁺ reached as high as 41.3 mg/g at pH 6. The successive adsorption–desorption studies indicated that the EDTA-MNPs kept the adsorption and desorption efficiencies constant over ten cycles. Importantly, EDTA-MNPs were able to remove nearly 100 % of Ni²⁺ from real water.     

Preparation of lactic acid modified cellulose nanoparticles by microwave heating for preconcentration of copper from blood and food samples

In this study, nano-sized cellulose modified with lactic acid (MW-Ce-LA) was prepared with the assistant of microwave then used for the adsorption of Cu²⁺ from real samples. This modified cellulose was characterized by means of FTIR, TEM, XRD, and elemental analysis. ICP-OES was used for determination of Cu²⁺. The effect of pH, adsorption times, temperature, sorbent dose, and initial adsorbate concentration were studied to detect the ideal adsorption condition. Langmuir model proved to be the best to fit the adsorption isotherm experiments with maximum adsorption capacity of 90.3 mg g^?1 Cu²⁺. Calculated thermodynamic parameters (ΔG° and ΔH°) for adsorption of Cu²⁺ on MW-Ce-LA suggested exothermic and nonspontaneous character of the adsorption process. The reusability tests indicated regeneration of the prepared adsorbent simply using 1 mol L^?1 of HCl. The examined method was used effectively to preconcentrate Cu²⁺ from water, blood, and food samples.

     

用于氨氮去除的13X分子筛／PES膜吸附剂的制备与性能表征

针对氨氮排放对环境造成的污染以及给人类带来的危害这一问题，将分子筛吸附与膜技术相结合，以13x分子筛为功能颗粒，以聚醚砜（PES）为膜的基质材料，以二甲基乙酰胺（DMAc）为溶剂，通过相转化法制备了不同13x分子筛填充量的13x／PEs膜吸附剂。研究发现，随着13x分子筛填充量的增加，膜的指状孔变得细密、短小，其吸附容量，断裂强度都在增加，但是水通量逐渐降低。料液温度与pH值对吸附性能的影响表明，该膜吸附剂在293K，pH=7时对氨氮有较好的吸附容量，可达21．69mg／g；吸附热力学研究表明，该类型膜吸附剂对氨氮的吸附等温线符合Langmuir方程。     

Adsorption Characteristics of Benzene on Biosolid Adsorbent and Commercial Activated Carbons

Abstract

This study selected biosolids from a petrochemical waste-water treatment plant as the raw material. The sludge was immersed in 0.5-5 M of zinc chloride (ZnCl₂) solutions and pyrolyzed at different temperatures and times. Results indicated that the 1-M ZnCl₂-immersed biosolids pyrolyzed at 500 °C for 30 min could be reused and were optimal biosolid adsorbents for benzene adsorption. Pore volume distribution analysis indicated that the mesopore contributed more than the macropore and micropore in the biosolid adsorbent. The benzene adsorption capacity of the biosolid adsorbent was 65 and 55% of the G206 (granular-activated carbon) and BPL (coal-based activated carbon; Calgon, Carbon Corp.) activated carbons, respectively. Data from the adsorption and desorption cycles indicated that the benzene adsorption capacity of the biosolid adsorbent was insignificantly reduced compared with the first-run capacity of the adsorbent; therefore, the biosolid adsorbent could be reused as a commercial adsorbent, although its production cost is high.