In this paper, the adsorption removal characteristic for 10 species of perfluoroalkyl and polyfluoroalkyl substances (PFAS) was investigated using GAC and modified GAC (GAC-Cu). After modification with Cu(II), the amount of copper was to 1.93 and 4.73 mg/g for GAC and GAC-Cu, respectively. The total amount of 10 species of PFAS per specific area was obtained to 0.548 and 0.612 ng/m2 for GAC and GAC-Cu, respectively. A series of batch test confirmed lower efficiency was observed with a smaller number of carbon chain length and the removal efficiency of PFCA (perfluoroalkyl carboxylic acids) was lower than that of PFSA (perfluoroalkyl sulfonic acids) with the same carbon chain length. Regarding the pH effect, the adsorption capacity was decreased with increase of pH due to the increase of electrostatic repulsion. According to pseudo first and second order (PFO and PSO) kinetic models, while the values of equilibrium uptake and time did not show significant difference, a difference in uptake was observed between 24-48h. Furthermore, based on correlation analysis, Log Kow and uptake have a high correlation with molecular weight (M.W.) and initial concentration, respectively. These results show that long-chain PFAS have higher removal efficiency due to their increased hydrophobicity.
Moso bamboo, as a kind of renewable functional material, exhibits outstanding development potential. It is promising to prepare activated carbon with good mechanical strength and high specific surface area using moso bamboo as raw material. In this work, we employed a hydraulic extruder to extrude the bamboo charcoal and the adhesive to obtain the moso bamboo activated carbon, and improved the specific surface area of the columnar activated carbon through high-temperature water vapor activation. Through the catalytic role of the water vapor activation process, the formation and expansion of the pores were promoted and the internal pores were greatly increased. The obtained columnar activated carbon shows excellent mechanical strength (93%) and high specific surface area (791.54 m2/ g). Polyacrylamide@asphalt is one of the most effective adhesives in the high-temperature water vapor activation. The average pore size (22.99 nm) and pore volume (0.36 cm3/ g) of the prepared columnar activated carbon showed a high mesoporous ratio (83%). Based on the excellent pore structure brought by the activation process, the adsorption capacity of iodine (1135.75 mg/g), methylene blue (230 mg/g) and carbon tetrachloride (64.03 mg/g) were greatly improved. The resultant moso bamboo columnar activated carbon with high specific surface area, excellent mechanical properties, and outstanding adsorption capacity possesses a wide range of industrial applications and environmental protection potential.
In this study, Pitch-derived activated carbon (PAC) pellets were by steam activation for automotive carbon canisters. The crystal structure of PAC was analyzed using X-ray diffraction. The textural properties of PAC were studied by Brunauer– Emmett–Teller (BET), Horvath-Kawazoe (HK), and Non-Localized Density Functional Theory (NLDFT) equations with N2/ 77 K isotherm adsorption/ desorption curves. The butane adsorption capacity of the PAC pellets was analyzed according to the ASTM D5228 standard. With increasing steam activation time, the specific surface area and total pore volume of the PAC increased 650–1950 m2/ g and 0.27–1.02 cm3/ g, respectively. The mesopore ratio of PAC increased with increasing activation time and was observed up to 28.4% at 190 min. The butane adsorption capacity of the PAC increased and was observed to range from 10.86 to 51.55%. A close relationship between butane adsorption capacity and pore size (1.47–2.39 nm) was found. Finally, the butane activity of PAC was found to be 51.55% for the steam activated at 950 ℃ for 190 min; this butane activity is 24% better than that of the coconut-derived activated carbon (41.43%) with a similar specific surface area, indicating that pitch is a suitable material for the activated carbon of automotive carbon canisters.
Modification of the surface of raw activated carbon using chemical solvents can significantly improve the adsorption performance of activated carbon. Triethylenetetramine is one of the most important chemical solvents used to modify raw activated carbon for formaldehyde removal indoor. We conducted the liquid impregnation experiments at different initial concentrations, temperatures, adsorbent dosage and time ranges to fully investigate the adsorption of triethylenetetramine on the surface of raw activated carbon for modification. We found that the Langmuir isotherm model and pseudo-first-order kinetic model fit quite well with the experimental data and the R2 are 0.9883 and 0.9954, respectively. The theoretical maximum adsorption capacity is 166.67 mg/g. The change in Gibbs free energy (ΔG0), enthalpy change (ΔH0) and entropy change (ΔS0) were also calculated to study the direction and driving force of the liquid adsorption process. In order to understand the adsorption process at the molecular level, a new activated carbon model based on the actual physical and chemical properties of activated carbon was carefully established in the Materials Studio to simulate the liquid-phase adsorption. The pore structure, elemental composition, functional group content, density, pore volume, and porosity of the activated carbon model converge close to the actual activated carbon and the adsorption isotherms obtained from the simulation agree well with the experimental results. The results show that the adsorption of triethylenetetramine on activated carbon is a spontaneous, endothermic and monolayer physical adsorption process.
Perfluorooctanoic acid(PFOA) was one of widely used per- and poly substances(PFAS) in the industrial field and its concentration in the surface and groundwater was found with relatively high concentration compared to other PFAS. Since various processes have been introduced to remove the PFOA, adsorption using GAC is well known as a useful and effective process in water and wastewater treatment. Surface modification for GAC was carried out using Cu and Fe to enhance the adsorption capacity and four different adsorbents, such as GAC-Cu, GAC-Fe, GAC-Cu(OH)2, GAC-Fe(OH)3 were prepared and compared with GAC. According to SEM-EDS, the increase of Cu or Fe was confirmed after surface modification and higher weight was observed for Cu and Fe hydroxide(GAC-Cu(OH)2 and GAC-Fe(OH)3, respectively). BET analysis showed that the surface modification reduced specific surface area and total pore volumes. The highest removal efficiency(71.4%) was obtained in GAC-Cu which is improved by 17.9% whereas the use of Fe showed lower removal efficiency compared to GAC. PFOA removal was decreased with increase of solution pH indicating electrostatic interaction governs at low pH and its effect was decreased when the point of zero charges(pzc) was negatively increased with an increase of pH. The enhanced removal of PFOA was clearly observed in solution pH 7, confirming the Cu in the surface of GAC plays a role on the PFOA adsorption. The maximum uptake was calculated as 257 and 345 μg/g for GAC and GAC-Cu using Langmuir isotherm. 40% and 80% of removal were accomplished within 1 h and 48 h. According to R2, only the linear pseudo-second-order(pso) kinetic model showed 0.98 whereas the others obtained less than 0.870.
Removing CO2 gas to address the global climate crisis is one of the most urgent agendas. To improve the CO2 adsorption ability of activated carbon, nitrogen plasma surface treatment was conducted. The effect of nitrogen plasma treatment on the surface chemistry and pore geometry of activated carbon was extensively analyzed. The porosity and surface groups of the activated carbon varied with the plasma treatment time. By plasma treatment for a few minutes, the microporosity and surface functionality could be simultaneously controlled. The changed microporosity and nitrogen groups affected the CO2 adsorption capacity and CO2 adsorption selectivity over N2. This simultaneous surface etching and functionalization effect could be achieved with a short operating time and low energy consumption.
Quality standards of activated carbon for gas-phase applications have been deleted from the Korean national standard list since 2007, and the iodine adsorption test is the only measure currently used for quality assurance. This study was performed to propose a suitable test method and a quality standard for gas-phase activated carbon. The "1/2 saturated vapor adsorption" test has been developed as a simple and convenient method to determine the adsorption capacity of activated carbon. In this study, the developed test method was evaluated using model VOCs including toluene, methyl ethyl ketone (MEK), and ethyl acetate (EA). A virgin activated carbon revealed adsorption capacities of 344mg/g, 322mg/g, and 328mg/g for toluene, EA, and MEK, respectively, and the adsorption capacity for a mixture of the three VOCs was 334 mg/g. When a regenerated activated carbon was applied, the adsorption capacities dramatically decreased to 62 mg/g, 52 mg/g, and 61 mg/ g for toluene, EA, and MEK, respectively. In addition, the 1/2 solvent vapor adsorption tests using 13 different specimens of activated carbon showed that their capacities were closely related to the iodine adsorption numbers, and this study suggested the adsorption capacity of 300 mg/g as a new quality standard. The novel test method and its standard may help to guarantee the quality of gas-phase activated carbon used for VOCs abatement processes.
Though many treatment technologies of contaminated water have been developed for a long time, it is still difficult to find a suitable method for large volumes of low radioactivity tritium-contaminated water. For this reason, most of the tritium-contaminated water been discharged to the biosphere or been stored in a special control area as radioactive waste. Activated carbon is a common material, but since there are few data on the treatment of tritium-contaminated water, its adsorption behavior to HTO is worth studied. In our study, for the tritium-contaminated water having a low radioactivity concentration (350-480 Bq/g), adsorption experiments were performed with activated carbon. The effects on the selective adsorption of HTO were investigated for temperature (5-55°C), hydrogen peroxide (1-10wt%) and activated carbon reuse (1-6 times) under non-equilibrium conditions. The treatment of activated carbon significantly reduced the radioactivity of tritium-contaminated water around 60 minutes of adsorption time. In order to clearly analyze the experimental results, positive factors and negative factors on the HTO selectivity were separately evaluated according to the adsorption time. Temperature and the reuse of activated carbon were evaluated as negative factors for HTO selectivity of activated carbon, whereas hydrogen peroxide (> 5wt%) was evaluated as a positive factor. By the evaluation method of separating the influencing factors into two types, the adsorption experimental results of HTO could be understood more clearly.
In this study, the removal efficiency of PFCs(perfluorinated compounds) in the GAC(granule activated carbon) process based on the superheated steam automatic regeneration system was investigated in laboratory scale and pilot-scale reactor. Among PFCs, PFHxS(perfluorohexyl sulfonate) was most effectively removed. The removal efficiency of PFCs was found to be closely related to the EBCT, and the removal efficiencies of PFOA(perfluorooctanoic acid), PFOS(perfluorooctyl sulfonate), and PFHxS were 43.7, 75, and 100%, respectively, under the condition of EBCT of 6 min. Afterward, PFOA, PFOS, and PFHxS exhibited the earlier breakthrough time in the order. After that, GAC was regenerated, and the removal efficiency of the PFCs before and after regeneration was compared. As a result, it was shown that the PFCs removal efficiency in the regenerated GAC process were higher, and that of PFOA was improved to 75%. The findings of this study indicate the feasibility of the superheated steam automatic regeneration system for the stable removal of the PFCs, and it was verified that this technology can be applied stably enough even in field conditions.
By polymerizing acrylonitrile in the presence of ammonium persulfate as an initiator and Pterocladia capillacea-activated carbon (P-AC) as a filler, a composite material polyacrylonitrile/Pterocladia capillacea-activated carbon (PAN/P- AC) was developed. By reacting hydroxylamine with the composite's nitrile groups, the prepared composite was functionalized by amidoximation. FTIR spectrometry, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and Brunauer–Emmett–Teller (BET) analysis were all applied to thoroughly characterize the fabricated adsorbent. For the treatment of Cr(VI) ions from synthetic solutions, the adsorption properties of amidoximated polyacrylonitrile/Pterocladia capillacea-activated carbon (PAO/P-AC) were investigated. The pH effect, uptake kinetics, adsorption isotherms, and thermodynamics studies were used to characterize adsorption properties. As a kinetic model analysis, the data confirmed that the pseudo-second-order rate equation matched well the adsorption process. With coefficients of determination (R2) of 0.9998, the Tempkin isotherm model had the lowest error, suggesting that it is the best fitted model to describe this adsorption mechanism. Thermodynamic parameters demonstrated that Cr(VI) adsorption was endothermic.
The production of macroalgae-derived adsorbent is of great importance to realize the idea of treating pollutants with invaluable renewable materials. Herein, a novel meso-micro porous nano-activated carbon was prepared from green alga Ulava lactuca in a facile way via chemical activation with zinc chloride. The resultant activated carbon possesses a significant specific surface area 1486.3 m2/ g. The resulting activated carbon was characterized and investigated for the adsorption of Direct Red 23 (DR23) dye from an aqueous environment. Batch method was conducted to study the effects of different adsorption processes on the DR23 dye adsorption from water. Isotherms and kinetics models were investigated for the adsorption process of DR23 dye. It was found that the adsorption data were well fitted by Langmuir model showing a monolayer adsorption capacity 149.26 mg/g. Kinetic experiments revealed that the adsorptions of DR23 dye can be described with pseudo-secondorder model showing a good correlation (R2 > 0.997). The prepared activated carbon from Ulava lactuca was exposed to a total of six regeneration experiments. The regeneration result proved that the fabricated activated carbon only loses 19% of its adsorption capacity after six cycles. These results clearly demonstrated the high ability of the obtained active carbon to absorb anionic dyes from the aqueous environment.
This work reports utilization of apple leaves as a source of activated carbon. Activated carbon from apple leaves is prepared by two different methods, thermal activation where AC1 is obtained and chemical activation using H3PO4 and ZnCl2 where AC2 and AC3 are obtained, respectively. XRD analysis revealed that all types of prepared ACs have a semi-crystalline nature with a mean crystallite size of 13, 21.02, and 39.47 nm for AC1, AC2, and AC3, respectively. To identify the most suitable desorption temperature, the exothermic behavior was discovered for the three types of ACs by DSC. The exothermic onset temperatures are 340 °C, 200 °C, 400 °C, or AC1, AC2, and AC3, respectively. The point of zero charge for the three types of ACs is 8.6, 7.3, and 2.5 for AC1, AC2, and AC3, respectively. The BET surface area analysis data demonstrated that mesoporous structure was developed in AC1 and AC2, while a microporous structure was developed in AC3. Quantum chemical calculations for ACs is carried out using Density Functional Theory (DFT). Application of the prepared ACs in adsorption of basic dye C.I. base blue 47 is studied. The maximum removal efficiency was 65.1%, 96% and 99% for AC1, AC2, and AC3, respectively under the influence of different operating aspects. Adsorption data are modeled by Langmuir, Freundlich, and Temkin isotherms. The data revealed that adsorption of basic dye C.I. base blue 47 on AC1 follows Langmuir isotherm and adsorption on AC2 and AC3 follows Freundlich isotherm.
This work reveals a modified method for the preparation of activated carbon (P-ACA) using low-cost materials (mix natural asphalt: polypropylene waste). The P-ACA was prepared at 600 °C by assisting KOH and HF. The morphological variations and chemical species of the P-ACA were characterized using SEM–EDX and FTIR. The active surface area, density and ash content of the P-ACA were also investigated. Adsorption properties of P-ACA were used for the thermodynamic and kinetic study of 4-((2-hydroxy naphthalenyl) diazenyl) antipyrine (HNDA), which was prepared as a novel azo dye in this work. The optimal conditions (initial concentration, adsorbent dose, contact time and temperature) of the adsorption process were determined. Adsorption isotherms (Freundlich and Langmuir) were applied to the experimental data. These isothermal constants were used to describe the nature of the adsorption system, and the type of interaction between the dye and the P-ACA surface. The results have indicated that the mixture (Natural asphalt-polypropylene waste) is efficient for the synthesis of P-ACA. The synthesized P-ACA demonstrates the presence of pores on the surface with various diameter ranges (from 1.4 to 4.5 μm). Furthermore, P-ACA exhibits an active surface area of 1230 m2 g−1, and shows a high adsorption capacity for HNDA.
Preparation of activated carbon from biomass residue with conventional steam activation was conducted to find the alternative raw materials for meeting the high demand for low-cost porous material in the desiccant application. In this study, activated carbons were produced from dead camphor leaves using two-step methods at different preparation temperatures. The characterization results revealed that the prepared activated carbons have a surface area of 700 m2/g, with 75% of microporosity. The water vapor sorption study reported that the water uptake of camphor leaf-based activated carbons was strongly affected by the pore properties of the materials. Moreover, from the water adsorption kinetics, it was observed that the rate constant of adsorption was varied at each relative pressure, which can be assumed that the water adsorption mechanism is different at each relative pressure. From these results, it was revealed that the prepared camphor leaf-based activated carbons have a promising ability to adsorb water vapor from humid air.
The oxygen-rich activated carbon (AC) was facilely developed using petroleum coke as a raw material by KOH activation under the rapid heating rate. The porosity and surface chemistry of ACs prepared under different heating rates were characterized and their adsorption properties for methylene blue (MB) were investigated. The results showed that the AC5 prepared under the heating rate of 5 °C min−1 had the highest surface area compared with the AC10, AC15 or AC20, while the AC20 prepared under the heating rate of 20 °C min−1 consisted of the highest oxygen content and most –OH functional group compares with the other ACs. These indicated that rapid heating rate was against the formation of more developed porosity, however, it was beneficial to producing more oxygen functional groups. As to MB adsorption, AC15 exhibited the maximum adsorption capacity for MB of 884 mg g−1 due to high surface area of 2803 m2 g−1 and high oxygen content of 23.27%. Moreover, despite the fact that AC20 had much lower surface area than the AC5, the AC20 showed higher MB adsorption capacity than the AC5. This was because the AC20 has the highest content of –OH, which was a positive impetus for MB adsorption. Therefore, rapid heating rate was an effective and simple approach to preparing the oxygen-rich ACs for improving the adsorption capacity of MB.
Numerous chemical modifications on activated carbon such as acidic conditioning, thermal treatment and metal impregnation have been investigated to enhance adsorption capacities of micropollutants in water treatment plants. In this study, chemical modification including acidic, alkaline treatment, and iron-impregnation was evaluated for adsorption of 2,4-dichlorophenol (2,4-DCP). For Fe-impregnation, three concentrations of ferric chloride solutions, i.e., 0.2 M, 0.4 M, and 0.8 M, were used and ion-exchange (MIX) of iron and subsequent thermal treatment (MTH) were also applied. Surface properties of the modified carbons were analyzed by active surface area, pore volume, three-dimensional images, and chemical characteristics. The acidic and alkaline treatment changed the pore structures but yielded little improvement of adsorption capacities. As Fe concentrations were increased during impregnation, the active adsorption areas were decreased and the compositional ratios of Fe were increased. Adsorption capacities of modified ACs were evaluated using Langmuir isotherm. The MIX modification was not efficient to enhance 2,4-DCP adsorption and the MES treatment showed increases in adsorption capacities of 2,4-DCP, compared to the original activated carbon. These results implied a possibility of chemical impregnation modification for improvement of adsorption of 2,4-DCP, if a proper modification procedure is sought.
In this study, we prepared ACFs with a high specific surface area from various precursors (rayon, pitch, and oxidized polyacrylonitrile-based fibers) by a steam-activation technique and investigated the effects of the micropore and mesopore fraction on 2-CEES adsorption behaviors. The activation time was precisely controlled so that the activation yield was in the range of 35–40% to ensure the mechanical properties of the ACFs. The N2 adsorption isotherm characteristics at 77K were confirmed by Brunauer–Emmett–Teller, Barrett–Joyner–Halenda and non-local density functional theory equations. The adsorption capacities of the ACF were measured by breakthrough experiments in the gas phase (750 μg/mL of 2-CEES in N2 flow). The removal efficiency of the ACFs was evaluated and compared with that of AC. From the results, specific surface areas and total pore volume of the ACF were determined to be 1380–1670 m2/g and 0.61–0.82 cm3/g, respectively. It was also observed that various pore characteristics of ACF were found to be dependent on crystallite structure of each precursor. The break through time (C/C0 = 0.10) was in the order of Oxi-Pan-H-9-2 < Saratoga AC < Rayon-H-9-3 < Pitch-H-9-4. This indicates that 2-CEES adsorption capacity could be a function not only of specific surface area or total pore volume, but also of sub-mesopore volume fraction in the range of 1.5–2.5 nm of adsorbents.
Fibrous adsorbents, such as activated carbon fibers (ACF) have acknowledged advantages of rapid adsorption rate and ease of modification compared with granular and powdered adsorbents. Based on the surface modification of lyocell-based ACF, we observed different surface characteristics of ACF samples with variation in the mixing ratio and impregnation time of H3PO4, NaCl, and KMnO4 solution. For an engineering application, we also explored the adsorption characteristics of thusproduced ACF samples onto volatile organic compounds (VOCs). Isothermal adsorption experiments were performed using toluene and benzene as adsorbates. Results indicate that both physical and chemical surface properties have an effect on the adsorption of volatile organic compounds (VOCs).
The present work is aimed at evaluating the kinetics and dynamic adsorption of methylene blue by CO2- activated carbon gels. The carbon gels were characterized by textural properties, thermal degradation and surface chemistry. The result shows that the carbon gels are highly microporous with surface area of 514 m2/g and 745 m2/g for resorcinol-to-catalyst ratios of 1000 (AC1) and 2000 (AC2), respectively. The kinetics data could be described by pseudo-first-order model, with a longer duration to attain equilibrium due to restricted pore diffusion as concentration increases. Also, AC1 exhibits insignificant kinetics with fluctuating adsorption with time at concentrations of 20 and 25 mg/L. However, AC1 reveals a better performance than AC2 in dynamic adsorption due to concentration gradient for molecules diffusion to active sites. The applicability of Yoon–Nelson and Thomas models indicates that the dynamic adsorption is controlled by external and internal diffusion.
In this study, composite PAN-based ACNFs embedded with MgO and MnO2 were prepared by the electrospinning method. The resultant pristine ACNFs, ACNF/MgO and ACNF/MnO2 were characterized in terms of their morphological changes, SSA, crystallinity and functional group with FESEM-EDX, the BET method, XRD and FTIR analysis, respectively. Results from this study showed that the SSA of the ACNF/MgO composite (1893 m2 g–1) is significantly higher than that of the pristine ACNFs and ACNF/MnO2 which is 478 and 430 m2 g–1, respectively. FTIR analysis showed peaks of 476 and 547 cm–1, indicating the presence of MgO and MnO2, respectively. The FESEM micrographs analysis showed a smooth but coarser structure in all the ACNFs. Meanwhile, the ACNF/MgO has the smallest fiber diameter (314.38±62.42 nm) compared to other ACNFs. The presence of MgO and MnO2 inside the ACNFs was also confirmed with EDX analysis as well as XRD. The adsorption capacities of each ACNF toward CH4 were tested with the volumetric adsorption method in which the ACNF/MgO exhibited the highest CH4 adsorption up to 2.39 mmol g–1. Meanwhile, all the ACNF samples followed the pseudo-second order kinetic model with a R2 up to 0.9996.