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.     

Nitrate contamination in water resources,human health risks and its remediation through adsorption: a focused review

The level of nitrate in water has been increasing considerably all around the world due to vast application of inorganic nitrogen fertiliser and animal manure. Because of nitrate’s high solubility in water, human beings are getting exposed to it mainly through various routes including water, food etc. Various regulations have been set for nitrate (45–50 mgNO₃^?/L) in drinking water to protect health of the infants from the methemoglobinemia, birth defects, thyroid disease, risk of specific cancers, i.e. colorectal, breast and bladder cancer caused due to nitrate poisoning. Different methods like ion exchange, adsorption, biological denitrification etc. have the ability to eliminate the nitrate from the aqueous medium. However, adsorption process got preference over the other approaches because of its simple design and satisfactory results especially with surface modified adsorbents or with mineral-based adsorbents. Different types of adsorbents have been used for this purpose; however, adsorbents derived from the biomass wastes have great adsorption capacities for nitrate such as tea waste-based adsorbents (136.43 mg/g), carbon nanotube (142.86 mg/g), chitosan beads (104 mg/g) and cetyltrimethylammonium bromide modified rice husk (278 mg/g). Therefore, a thorough literature survey has been carried out to formulate this review paper to understand various sources of nitrate pollution, route of exposure to the human beings, ill effects along with discussing the key developments as well as the new advancements reported in procuring low-cost efficient adsorbents for water purification.

     

Applying Hexagonal Nanostructured Zeolite Particles for Acetone Removal

Abstract

This study examines the performance of a new adsorbent, hexagonal nanostructured zeolite particles (HNZP) for acetone adsorption and compares the results with that of commercial mobil synthetic zeolite-5 (ZSM-5) type zeolite. The HNZP is a pure siliceous adsorbent with different values of pore diameter and surface area being adjustable by the manufacturing condition. The results indicate that a slight increase in the average pore diameter (d) of HNZP from 2 to 2.5 nm leads to an increase in the acetone adsorption capacity, although its surface area is decreased, in which case (d = 2.5 nm) the adsorption capacity of fresh HNZP is better than that of ZSM-5 zeolite. Even for the fresh HNZP (d = 2 nm) of which the adsorption capacity is less than that of the ZSM-5 zeolite at relative humidity (RH) of 0%, its adsorption capacity is not deteriorated after repeated regeneration, but the adsorption capacity of regenerated ZSM-5 zeolite decays markedly. Thus, after only one regeneration, the adsorption capacity of HNZP (d = 2 nm) becomes better than that of the ZSM-5 zeolite. The decrease in the adsorption capacity of regenerated ZSM-5 zeolite might be because of its aluminum content that catalyzes the acetone into coke and, thus, blocks the adsorption sites. Furthermore, result on the moisture effect shows that because the pure siliceous HNZP was more hydrophobic than the ZSM-5 zeolite, the acetone adsorption efficiency of fresh HNZP (d = 2 nm) is better than that of ZSM-5 zeolite at RH = 50%.     

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.     

Adsorption Behavior of Toluene on Modified 1X Molecular Sieves

In this paper, the toluene adsorption/desorption properties of modified 13X molecular sieves (M-13X) are discussed. M-13X molecular sieves were prepared by acidic and steam treatments of 13X molecular sieves. The structural parameters of M-13X were evaluated and compared with those of other molecular sieves (HY, HZSM-5, Cs7NaMOR, and a commercial 13X). The results show that the specific surface area, average pore diameter, and pore volume of M-13X were 414.17 m²/g, 2.98 nm, and 0.31 mL/g, respectively. The pore size distribution of M-13X was 1.8–3.0 nm. Because of its larger Si/Al ratio (Si/Al = 6.77), the hydrophobicity of M-13X is much higher than that of 13X (Si/Al = 1.28), indicating that it is particularly well suited to toluene control applications. The saturation adsorption capacity of M-13X was 0.045 g/g for simulated toluene at a temperature of 293 K and a relative humidity of 50%. The optimal regeneration temperature of M-13X was 473 K for 120 min with a hot air flow rate of 140 L/min.

Implications: The modified 13X molecular sieves (M-13X) are adsorbents with a high adsorption capacity and great hydrophobicity, suitable for the treatment of VOCs. The purpose of the present investigation is to provide a practical guide for their design.     

Adsorption of mesitylene via mesoporous adsorbents

Mesitylene (or 1,3,5-trimethylbenzene) is a volatile organic compound emitted from various industrial processes, e.g., spray coating. Its emissions have become a critical issue because mesitylene is toxic and cannot be removed using traditional adsorbents, e.g., zeolite (H-ZSM-5; the diameter of mesitylene molecules is greater than the pore size of H-ZSM-5). Hence, an adsorbent with a large pore size, MCM-41, is used in this study to investigate its adsorption capacity for mesitylene and compare with that of H-ZSM-5. Experimental results reveal that MCM-41 without Al₂O₃ exhibits a good adsorption capacity (184 mg/g) for the gas stream containing 100 ppm of mesitylene at a relative humidity of 10%. The adsorption kinetics is well described by the Freundlich isotherm. Furthermore, experimental results reveal that MCM-41 is effective for the adsorption of low concentrations (10 ppm) of mesitylene. In addition, adsorption–desorption tests revealed that the sample MCM-41-AS is stable to sustain the adsorption capacity after 10 adsorption–desorption cycles. After 10 adsorption–desorption cycles, MCM-41-AS retains 92.4% of its initial adsorption capacity (170 vs. 184 mg/g). Finally, MCM-41 and H-ZSM-5 in series are effective for the simultaneous removal of mesitylene and toluene in the gas stream.

Implications: This study aims to improve the performance of adsorbent for mesitylene, which is typically applied in the spray-coating industry. The zeolite MCM-41-AS is selected as a candidate for the investigation. Experimental results reveal that MCM-41-AS exhibits a good adsorption capacity for mesitylene and that it can be integrated with H-ZSM-5-25 for the simultaneous adsorption of mesitylene and toluene.     

Applying hexagonal nanostructured zeolite particles for acetone removal

This study examines the performance of a new adsorbent, hexagonal nanostructured zeolite particles (HNZP) for acetone adsorption and compares the results with that of commercial mobil synthetic zeolite-5 (ZSM-5) type zeolite. The HNZP is a pure siliceous adsorbent with different values of pore diameter and surface area being adjustable by the manufacturing condition. The results indicate that a slight increase in the average pore diameter (d) of HNZP from 2 to 2.5 nm leads to an increase in the acetone adsorption capacity, although its surface area is decreased, in which case (d = 2.5 nm) the adsorption capacity of fresh HNZP is better than that of ZSM-5 zeolite. Even for the fresh HNZP (d = 2 nm) of which the adsorption capacity is less than that of the ZSM-5 zeolite at relative humidity (RH) of 0%, its adsorption capacity is not deteriorated after repeated regeneration, but the adsorption capacity of regenerated ZSM-5 zeolite decays markedly. Thus, after only one regeneration, the adsorption capacity of HNZP (d = 2 nm) becomes better than that of the ZSM-5 zeolite. The decrease in the adsorption capacity of regenerated ZSM-5 zeolite might be because of its aluminum content that catalyzes the acetone into coke and, thus, blocks the adsorption sites. Furthermore, result on the moisture effect shows that because the pure siliceous HNZP was more hydrophobic than the ZSM-5 zeolite, the acetone adsorption efficiency of fresh HNZP (d = 2 nm) is better than that of ZSM-5 zeolite at RH = 50%.     

Co-contaminant effects on ofloxacin adsorption onto activated carbon,graphite, and humic acid

Given their voluminous application, significant amounts of fluoroquinolones are discharged into the environment through wastewater effluent. Adsorption has been shown to be a critical process controlling the environmental behaviors of fluoroquinolones. Competition between ofloxacin (OFL) and naphthalene (NAP)/bisphenol A (BPA) and their adsorption on activated carbon (AC), graphite (GP), and humic acid (HA) were investigated. The suppressed adsorption of OFL was observed on AC and GP, but not on HA, by NAP or BPA. Moreover, for AC, the competition by NAP was slightly stronger than that by BPA. However, for GP, the competition with BPA was higher than that with NAP. These observations indicate that competitive adsorption of OFL with respect to NAP/BPA depends on the degree of overlap of adsorption sites, as interpreted by the following: (i) AC can provide overlapping adsorption sites for OFL, BPA, and NAP, which include non-specific adsorption sites, such as hydrophobic sites, π-π interactions, and micropore filling; (ii) π-π interactions and hydrogen bonding might be responsible for the strong competitive adsorption between BPA and OFL on GP; and (iii) OFL adsorbs on HA through specific adsorption force—electrostatic attraction, with which NAP and BPA cannot compete.

     

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.

     

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.

     

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。     

Removal of malachite green dye from wastewater by different organic acid-modified natural adsorbent: kinetics,equilibriums, mechanisms,practical application,and disposal of dye-loaded adsorbent

Natural adsorbent (Cinnamomum camphora sawdust) modified by organic acid (oxalic acid, citric acid, and tartaric acid) was investigated as a potential adsorbent for the removal of hazardous malachite green (MG) dye in aqueous media in a batch process. The extent of MG adsorption onto modified sawdust increased with increasing organic acid concentrations, pH, contact time, and temperature but decreased with increasing adsorbent dosage and ionic strength. Kinetic study indicated that the pseudo-second-order kinetic model could best describe the adsorption kinetics of MG. Equilibrium data were found to fit well with the Langmuir model, and the maximum adsorption capacity of the three kinds of organic acid-modified sawdust was 280.3, 222.8, and 157.5 mg/g, respectively. Thermodynamic parameters suggested that the sorption of MG was an endothermic process. The adsorption mechanism, the application of adsorbents in practical wastewater, the prediction of single-stage batch adsorption system, and the disposal of depleted adsorbents were also discussed.     

Preparation of various thiol-functionalized carbon-based materials for enhanced removal of mercury from aqueous solution

In this work, biochar (BC), activated carbon (AC), and graphene oxide (GO) were thiol-functionalized using 3-mercaptopropyltrimethoxysilane (3-MPTS) (named as BCS, ACS, and GOS, respectively). BCS, ACS, and GOS were synthesized mainly via the interaction between hydrolyzed 3-MPTS and surface oxygen-containing functional groups (e.g., –OH, O–C=O, and C=O) and π-π interaction. The materials before and after modification were characterized and tested for mercury removal, including sorption kinetics and isotherms, the effects of adsorbent dosage, initial pH, and ionic strength. Pseudo-second-order sorption kinetic model (R² = 0.992~1.000) and Langmuir sorption isotherm model (R² = 0.964~0.998) fitted well with the sorption data of mercury. GOS had the most –SH groups with the largest adsorption capacity for Hg²⁺ and CH₃Hg⁺ (449.6 and 127.5 mg/g), followed by ACS (235.7 and 86.7 mg/g) and BCS (175.6 and 30.3 mg/g), which were much larger than GO (96.7 and 4.9 mg/g), AC (81.1 and 24.6 mg/g), and BC (95.6 and 9.4 mg/g). GOS and ACS showed stable mercury adsorption properties at a wide pH range (2~9) and ionic strength (0.01~0.1 mol/L). Mercury maybe removed by ligand exchange, surface complexation, and electrostatic attraction.

     

泥炭对甲苯的吸附-解吸行为研究

用热处理方法对泥炭进行活化改性,探讨了对甲苯的吸附性能及影响因素,并研究了甲苯在泥炭上的吸附/解吸行为。结果表明,粒径在0.6～1 mm之间的泥炭在160℃热处理5 h,在pH为7的条件下对甲苯有良好的吸附效果,对甲苯的吸附量为0.32 mg/g。泥炭对甲苯的吸附在20 min内基本达到平衡,可用二级吸附速率方程进行拟合。甲苯在泥炭上的吸附和解吸均呈现明显的非线性,用Langmuir模型能较好地描述,泥炭对甲苯的饱和吸附量为0.939 mg/g。甲苯在泥炭上的平均解吸率为6.393%,并且出现了滞后现象,表明苯系物与泥炭有较强的结合能力。研究结果为应用泥炭作为PRB装填介质进行原位修复甲苯污染的地下水提供了理论依据。     

Adsorption of sulfamethoxazole on functionalized carbon nanotubes as affected by cations and anions

The environmental risks of antibiotics have attracted lots of research attention, but their environmental behavior is not clear yet. Functionalized carbon nanotubes (CNTs) were used as model adsorbents and sulfamethoxazole (SMX) was used as a model antibiotic to investigate the effect of both cations (Ca²⁺, Cs⁺) and anions (phosphate) on antibiotics adsorption. Various mechanisms (such as electrostatic interaction, hydrophobic interaction, π-π and hydrogen bonds) play roles in SMX adsorption. Cations and anions could “wedge into” these mechanisms and thus alter SMX adsorption. This study emphasized that both increased and decreased SMX adsorption could be observed with the addition of cations/anions, depending on environmental conditions (such as pH in this current study). The net effect is the balance between the increased and decreased effects. The contribution of different mechanisms to the overall antibiotic adsorption on solid particles should be identified to accurately predict the apparent effect by cations and anions.     

Management of hazardous fly-ash energy waste in the adsorptive removal of diclofenac by the use of synthetic zeolitic materials

Zeolite-carbon composites (Na-P1(C), Na-X(C)) and pure zeolites (Na-P1, Na-X) were synthesized from hazardous high-carbon fly ash waste (HC FA) via hydrothermal reaction with sodium hydroxide (NaOH). These solids were applied in the removal of diclofenac (DCF) from aqueous solution, with and without poly(acrylic acid) (PAA). The experiments included adsorption–desorption measurements, as well as electrokinetic and stability analyses. The obtained results showed that HC FA and Na-P1(C) had the greatest adsorption capacity towards DCF, i.e., 26.51 and 21.19 mg/g, respectively. PAA caused considerable decrease in the DCF adsorption due to the competition of both adsorbates of anionic character for active sites. For example, the adsorbed amount of DCF on Na-P1 without PAA was 14.11 mg/g, whereas the one measured with PAA was 5.08 mg/g. Most of prepared solids were effectively regenerated by the use of NaOH. Desorption degree reached even 73.65% in the single systems (with one adsorbate) and 97.24% in the mixed ones (with two adsorbates). Zeolitic materials formed suspensions of rather low stability, which underwent further deterioration in the organic molecules presence. All the results obtained in this study indicated that HC FA can be successfully managed in the removal of organic substances.

     

超高交联吸附树脂对有机物质甲苯的吸附热力学研究

比较了2种超高交联聚苯乙烯吸附树脂NDa99与ZH-04对甲苯的静态吸附行为.结果表明,在288～293 K和研究的浓度范围内,ZH-04、NDa99对甲苯的吸附平衡数据符合Freundlich和Langmuir吸附等温方程.吸附为放热过程,适当降低温度有利于吸附,并计算了甲苯在ZH-04和NDa99树脂上的吸附焓变、自由能变和熵变,对吸附行为进行了合理的解释,为废水处理提供一定的理论依据.     

超高交联吸附树脂对有机物质甲苯的吸附热力学研究

比较了2种超高交联聚苯乙烯吸附树脂NDa99与ZH-04对甲苯的静态吸附行为.结果表明,在288～293 K和研究的浓度范围内,ZH-04、NDa99对甲苯的吸附平衡数据符合Freundlich和Langmuir吸附等温方程.吸附为放热过程,适当降低温度有利于吸附,并计算了甲苯在ZH-04和NDa99树脂上的吸附焓变、自由能变和熵变,对吸附行为进行了合理的解释,为废水处理提供一定的理论依据.     

A Qualitative Analysis of the Effects of Water Vapor on Multi-Component Vapor-Phase Carbon Adsorption

The effects of water vapor on binary vapor adsorption of toluene and methylene chloride by activated carbon were investigated on a bench-scale experimental system. Three levels of relative humidity (15, 65 and 90 percent) in conjunction with different concentrations of individual adsorbates (from 400 to 1200 ppmv) were tested by tracing the breakthrough curves of each adsorbate eluted from a fixed-bed adsorber. The adsorption capacities of the activated carbon tested for each adsorbate under the various conditions were obtained from calculations based on area integration of the breakthrough curves. It was found that with increasing relative humidity, the shape of breakthrough curves was asymmetrically distorted and the width of the breakthrough curves was broadened for toluene and steepened for methylene chloride. The adsorption capacities for both toluene and methylene chloride were decreased with the increase of relative humidity. The magnitude of the effect of water vapor is greater at the lower toluene concentration and at the higher concentration of methylene chloride. The mechanisms of water vapor influence on the process of multicomponent vapor adsorption are discussed.     

Adsorption of Acid Red 73 on copper dithiocarbamate precipitate-type solid wastes

Three solid wastes, copper N,N'-bis(dithiocarboxy)piperazine ([CuBDP](n)), copper diethyldithiocarbamate (Cu(DDTC)(2)) and copper dimethyldithiocarbamate (Cu(DMTC)(2)), were prepared and tested as adsorbents to remove Acid Red 73 from wastewater. It was found that the three precipitates all could effectively adsorb the dye but their adsorption abilities were rather different. The maximum adsorption amounts of the coordination polymer precipitate [CuBDP](n) reached as high as 364mg g(-1), much greater than those of Cu(DDTC)(2) and Cu(DMTC)(2) (42.9 and 37.8mg g(-1), respectively). The investigation of adsorption models showed these adsorption processes followed the pseudo-second-order kinetic equation and the adsorption balances could be described with both Langmuir and Freundlich isotherms, but the latter seemed to be more suitable. Their adsorption nature was inferred to be physical adsorption and mainly depended on the hydrophobic interaction between these precipitates and Acid Red 73. This is the first example for the reutilization of metal dithiocarbamate precipitates as solid wastes to date.