Surface modification of coconut shell based activated carbon for the improvement of hydrophobic VOC removal

In this study, coconut shell based carbons were chemically treated by ammonia, sodium hydroxide, nitric acid, sulphuric acid, and phosphoric acid to determine suitable modification for improving adsorption ability of hydrophobic volatile organic compounds (VOCs) on granular activated carbons (GAC). The saturated adsorption capacities of o-xylene, a hydrophobic volatile organic compound, were measured and adsorption effects of the original and modified activated carbons were compared. Results showed that GAC modified by alkalis had better o-xylene adsorption capacity. Uptake amount was enhanced by 26.5% and reduced by 21.6% after modification by NH₃H₂O and H₂SO₄, respectively. Compared with the original, GAC modified by acid had less adsorption capacity. Both SEM/EDAX and BET were used to identify the structural characteristics of the tested GAC, while IR spectroscopy and Boehm's titration were applied to analysis the surface functional groups. Relationships between physicochemical characteristics of GAC and their adsorption performances demonstrated that o-xylene adsorption capacity was related to surface area, pore volume, and functional groups of the GAC surface. Removing surface oxygen groups, which constitute the source of surface acidity, and reducing hydrophilic carbon surface favors adsorption capacity of hydrophobic VOCs on carbons. The performances of modified GACs were also investigated in the purification of gases containing complex components (o-xylene and steam) in the stream.     

Degradation of recalcitrant compounds from stabilized landfill leachate using a combination of ozone-GAC adsorption treatment

Laboratory experiments were undertaken to investigate the treatment performances of ozonation alone and/or its combination with granular activated carbon (GAC) adsorption for raw leachate from the NENT landfill (in Hong Kong). To improve its removal of recalcitrant contaminants from the leachate, the surface of GAC was oxidized with ozone prior to treatment. With respect to ozone dose and pH, the removal of COD and/or NH(3)-N from ozonation alone and combined ozone-GAC adsorption were evaluated and compared to those of other physico-chemical treatments in some reported studies. The removal mechanism of recalcitrant compounds by ozone-GAC adsorption treatment was presented. Among the various treatments studied, the combination of ozone-GAC adsorption using ozone-modified GAC had the highest removal for COD (86%) and/or NH(3)-N (92%) compared to ozonation alone (COD: 35%; NH(3)-N: 50%) at the same initial COD and/or NH(3)-N concentrations of 8000 and 2620 mg/L, respectively. Although the integrated treatment was more effective than ozonation alone for treating stabilized leachate, the results suggested that it could not generate treated effluent that complied with the COD limit of lower than 200 mg/L and the NH(3)-N discharge standard of less than 5 mg/L. Therefore, further biological treatments to complement the degradation of the leachate are still required to meet the environmental legislation.     

Prediction of simultaneous adsorption of Cu(II) and Pb(II) onto activated carbon by conventional Langmuir type equations

Removal of Cu(II) and Pb(II) by adsorption onto activated carbon was examined in single- and binary-component aqueous solutions representative of contaminated solutions containing heavy metals. Reversibility of adsorption of the heavy metals on the activated carbon was evaluated by desorption experiments. The number of the maximum adsorption sites and adsorption equilibrium constants of Cu(II) and Pb(II) were estimated by the results of single-component systems assuming the Langmuir adsorption model. The adsorption sites per gram of activated carbon resulted in similar values for Cu(II) and Pb(II) from the isotherms. The adsorption constant for Pb(II) was nearly 1.8 times greater than that of Cu(II). Rate constants of adsorption and desorption were also estimated from the kinetic analysis. Using the single set of common parameters obtained from the single-component systems, the experimental results for a binary-component system were quantitatively predicted. Competitive adsorption of Cu(II) and Pb(II) on the same adsorption sites was confirmed by both experimental and predicted results of adsorption in the binary mixture.     

Use of adsorption process to remove organic mercury thimerosal from industrial process wastewater

Carbon adsorption process is tested for removal of high concentration of organic mercury (thimerosal) from industrial process wastewater, in batch and continuously flow through column systems. The organic mercury concentration in the process wastewater is about 1123 mg/L due to the thimerosal compound. Four commercially available adsorbents are tested for mercury removal and they are: Calgon F-400 granular activated carbon (GAC), CB II GAC, Mersorb GAC and an ion-exchange resin Amberlite GT73. The adsorption capacity of each adsorbent is described by the Freundlich isotherm model at pH 3.0, 9.5 and 11.0 in batch isotherm experiments. Acidic pH was favorable for thimerosal adsorption onto the GACs. Columns-in-series experiments are conducted with 30-180 min empty bed contact times (EBCTs). Mercury breakthrough of 30 mg/L occurred after about 47 h (96 Bed Volume Fed (BVF)) of operation, and 97 h (197 BVF) with 120 min EBCT and 180 min EBCT, respectively. Most of the mercury removal is attributed to the 1st adsorbent column. Increase in contact time by additional adsorbent columns did not lower the effluent mercury concentration below 30 mg/L. However, at a lower influent wastewater pH 3, the mercury effluent concentration decreased to less than 7 mg/L for up to 90 h of column operation (183 BVF).     

Enhancing the efficiency of AuCl4 ion removal from aqueous solution using activated carbon and carbon nanomaterials

The removal of AuCl₄⁻ ion from acidic aqueous solutions is studied using a series of non-oxidized and surface oxidized carbon materials (activated carbon, carbon nanotubes, carbon-encapsulated iron nanoparticles and carbon black). The studied sorbents differ in crystallinity, porosity and morphology. In the case of non-oxidized carbon materials the maximum removal efficiency (74%) is found for activated carbon, whilst graphitized nanomaterials (i.e. carbon nanotubes and carbon-encapsulated iron nanoparticles) are able to remove 42–45% of gold ion from the solution. The oxidation in nitric acid significantly improves the removal efficiencies. The uptake of Au(III) increases two times (to 91–92%) for oxidized carbon nanotubes and carbon-encapsulated iron nanoparticles. The same oxidation procedure applied to activated carbon and carbon black moderately enhances the uptake efficiency to 88% and 55%, respectively. The observed substantially distinct uptakes are discussed in the frames of textural properties, morphology, surface chemistry characteristics and crystallinity of the studied carbon materials. Moreover, the possibility of a galvanic exchange reaction between AuCl₄⁻ and metallic Fe in the carbon encapsulate core is also evaluated.     

Experimental and modelling studies of carbon dioxide adsorption by porous biomass derived activated carbon

The goal of the study was to produce a low-cost activated carbon from agricultural residues via single stage carbon dioxide (CO₂) activation and to investigate its applicability in capturing CO₂ flue gas. The performance of the activated carbon was characterized in terms of the chemical composition, surface morphology as well as textural characteristics. The adsorption capacity was investigated at three temperatures of 25, 50 and 100 °C for different types of adsorbate, such as purified carbon dioxide and binary mixture of carbon dioxide and nitrogen. The purified CO₂ adsorption study showed that the greatest adsorption capacity of the optimized activated carbon of 1.79 mmol g^?1 was obtained at the lowest operating temperature. In addition, the adsorption study proved that the adsorption capacity for binary mixtures was lower due to the reduction in partial pressure. The experimental values of the purified CO₂ adsorption were modelled by the Lagergren pseudo-first-order model, pseudo-second-order model, and intra-particle diffusion model. Based on the analysis, it inferred that the adsorption of CO₂ followed the pseudo-second-order model with regression coefficient value higher than 0.995. In addition, the adsorption study was governed by both film diffusion and intra-particle diffusion. The activation energy that was lesser than 25 kJ mol^?1 implied that physical adsorption (physisorption) occurred.     

Granular activated carbon promoted ozonation of a food-processing secondary effluent

This paper reports on the application of a simultaneous combination of ozone and a granular activated carbon (O(3)/GAC) as a tertiary treatment of a wastewater generated from the activity of various food-processing industries. Prior to the O(3)/GAC treatment, the wastewater was subjected to conventional primary and secondary treatments in a full-scale wastewater treatment plant (WWTP). The effluent from the WWTP presented high organic load (COD>500 mg/l and TOC>150 mg/l), which could be much reduced by the O(3)/GAC treatment. Results from the O(3)/GAC experiments were compared with those obtained in single ozonation, single adsorption onto GAC and sequential O(3)-GAC adsorption experiments. While single processes and the sequential one showed limited capacity to remove organic matter for the food-processing effluent (COD removal <40%), the simultaneous O(3)/GAC process led to decreases of COD up to 82% at the conditions here applied. The combined process also improved the ozone consumption, which decreased from about 19 g O(3)/g TOC (single ozonation process) to 8.2-10.7 g O(3)/g TOC (O(3)/GAC process). The reusability of the GAC throughout a series of consecutive O(3)/GAC experiments was studied with no apparent loss of activity for a neutral GAC (PZC = 6.7) but for a basic GAC (PZC = 9.1).     

The effect of functional groups on oligomerization of phenolics on activated carbon

Adsorption of seven phenolic compounds, namely phenol, 2-methylphenol, 2-ethylphenol, 2-chlorophenol, 2-nitrophenol, 4-chlorophenol, and 4-nitrophenol on granular activated carbon (GAC) F400 and two activated carbon fibers (ACFs), ACC-10 and ACC-15 were conducted to study the impact of functional groups on oligomerization. Single solute adsorption and binary solute adsorption were conducted under anoxic (absence of molecular oxygen) and oxic (presence of molecular oxygen) conditions at 23+/-1 degrees C. For F400, the critical oxidation potential (COP), influenced by substitution of functional group, was found to be a limiting factor in oligomerization of adsorbates. For ACC-10, which has narrow pore size distribution (PSD) and small critical pore diameter (8.0A), only phenol and 2-methylphenol showed occurrence of oligomerization under oxic conditions. The degree of oligomerization under oxic conditions was related to the PSD of the adsorbent. The micro-pore diameter of the ACFs effectively reduced the oligomerization process. The oxic and anoxic binary adsorption isotherms of phenol/2-ethylphenol and 2-methylphenol/2-nitrophenol on ACC-10 overlapped indicating hampering of oligomerization by the limited micro-pore diameter of ACFs. The Ideal Adsorbed Solution Theory (IAST), using the Myers equation for correlating the single-solute anoxic isotherms, well predicted both anoxic and oxic binary isotherms.     

粘结剂对颗粒活性炭PSA分离CH4/N2性能的影响

以褐煤为原料,分别采用煤焦油、可溶淀粉和聚丙烯酰胺(PAM)作粘结剂,制备了用于变压吸附(PSA)分离CH4和N2混合气体(CH4/N2)的三种颗粒活性炭GAC-C、GAC-T和GAC-P,对样品的表面官能团和孔结构进行表征,研究了粘结剂对活性炭PSA分离CH4/N2性能的影响.结果表明:粘结剂的种类和用量对样品分离效...     

Removal of nickel ions from water by multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were produced by chemical vapor decomposition using acetylene gas in the presence of Ferrocene catalyst at 800 degrees C, and then oxidized with concentrated nitric acid at 150 degrees C. Both (as-produced and oxidized) CNTs were characterized by TEM, Boehm titration, N2-BET and cation exchange capacity techniques. The adsorption capacity for nickel ions from aqueous solutions increased significantly onto the surface of the oxidized CNTs compared to that on the as-produced CNTs. The effects of adsorption time, solution pH and initial nickel ions concentrations on the adsorption uptake of Ni2+ for both the as-produced and oxidized CNTs were investigated at room temperature. Both Langmuir and Freundlich isotherm models match the experimental data very well. According to the Langmuir model the maximum nickel ions adsorption uptake onto the as-produced and oxidized CNTs were determined as 18.083 and 49.261 mg/g, respectively. Our results showed that CNTs can be used as an effective Ni2+ adsorbent due to the high adsorption capacity as well as the short adsorption time needed to achieve equilibrium.     

Consequence of chitosan treating on the adsorption of humic acid by granular activated carbon

In this work, equilibrium and kinetic adsorption of humic acid (HA) onto chitosan treated granular activated carbon (MGAC) has been investigated and compared to the granular activated carbon (GAC). The adsorption equilibrium data showed that adsorption behaviour of HA could be described reasonably well by Langmuir adsorption isotherm for GAC and Freundlich adsorption isotherm for MGAC. It was shown that pre-adsorption of chitosan onto the surface of GAC improved the adsorption capacity of HA changing the predominant adsorption mechanism. Monolayer capacities for the adsorption of HA onto GAC and MGAC were calculated 55.8 mg/g and 71.4 mg/g, respectively. Kinetic studies showed that film diffusion and intra-particle diffusion were simultaneously operating during the adsorption process for MGAC.     

Adsorption of Ni(II) on oxidized multi-walled carbon nanotubes: Effect of contact time,pH, foreign ions and PAA

The adsorption of Ni(II) on oxidized multi-walled carbon nanotubes (MWCNTs) as a function of contact time, pH and foreign ions in the absence and presence of polyacrylic acid (PAA) was studied using batch technique. The results indicated that adsorption of Ni(II) on oxidized MWCNTs increased from zero to ∼99% at pH 2–9, and then maintained the high level with increasing pH. Kinetic data showed that the adsorption process achieved equilibrium within 2 h and experimental data were fitted well by the pseudo-second-order equation. A positive effect of PAA on Ni(II) adsorption was found at pH < 8, whereas a negative effect was observed at pH > 8. The effect of addition sequences of PAA/Ni(II) on the adsorption of Ni(II) to PAA–MWCNT hybrids were also studied. The results indicated that the adsorption of Ni(II) was influenced by addition sequences obviously. The adsorption of Ni(II) on oxidized MWCNTs may be mainly attributed to surface complexation and ion exchange. Oxidized MWCNTs are suitable material in the solidification and pre-concentration of Ni(II) from aqueous solutions.     

Adsorption of divalent heavy metal ions from water using carbon nanotube sheets

Removal of some divalent heavy metal ions (Cu(2+), Zn(2+), Pb(2+), Cd(2+), Co(2+)) from aqueous solutions using carbon nanotube (CNT) sheets was performed. CNT sheets were synthesized by chemical vapor deposition of cyclohexanol and ferrocene in nitrogen atmosphere at 750°C, and oxidized with concentrated nitric acid at room temperature and then employed as adsorbent for water treatment. Langmuir and Freundlich isotherms were used to describe the adsorption behavior of heavy metal ions by oxidized CNT sheets. The obtained results demonstrated that the oxidized CNT sheets can be used as an effective adsorbent for heavy metal ions removal from water. It was found out that kinetics of adsorption varies with initial concentration of heavy metal ions. Preference of adsorption onto the oxidized CNT sheets can be ordered as Pb(2+)>Cd(2+)>Co(2+)>Zn(2+)>Cu(2+). Using the oxidized CNT sheets, waste water treatment without CNT leakage into water is economically feasible. Therefore, CNT sheets have good potential application in environmental protection.     

Adsorption of aqueous metal ions on cattle-manure-compost based activated carbons

The objective of this study is to examine the suitability and performance of cattle-manure-compost (CMC) based activated carbons in removing heavy metal ions from aqueous solution. The influence of ZnCl₂ activation ratios and solution pH on the removal of Cu(II) and Pb(II) were studied. Pore texture, available surface functional groups, pH of point zero charge (pH_PZC), thermogravimetric analysis and elemental compositions were obtained to characterize the activated carbons. Batch adsorption technique was used to determine the metal-binding ability of activated carbons. The equilibrium data were characterized using Langmuir, Freundlich and Redlich–Peterson models. It was found that the uptake of aqueous metal ions by activated carbons could be well described by Langmuir equation. It is suggested that the increase of surface area and mesopore ratio as a result of increasing activation ratios favored the removal of Cu(II), while activated carbon rich in acidic groups showed selective adsorption towards Pb(II). The preferable removal of Cu(II) over Pb(II) could be due to the rich nitrogen content as well as the higher mesoporous surface area in the CMC activated carbons. The impregnated CMC activated carbons also showed a better performance for Cu(II) removal at varying solution pH than Filtrasorb 400 (F400), while a similar performance was observed for Pb(II) removal.     

Preparation of steam activated carbon from rubberwood sawdust (Hevea brasiliensis) and its adsorption kinetics

Activated carbon was produced from a biowaste product, rubberwood sawdust (RWSD) using steam in a high temperature fluidized bed reactor. Experiments were carried out to investigate the influence of various process parameters such as activation time, activation temperature, particle size and fluidising velocity on the quality of the activated carbon. The activated carbon was characterized based on its iodine number, methylene blue number, Brauner Emmet Teller (BET) surface area and surface area obtained using the ethylene glycol mono ethyl ether (EGME) retention method. The best quality activated carbon was obtained at an activation time and temperature of 1h and 750 degrees C for an average particle size of 0.46 mm. The adsorption kinetics shows that pseudo-second-order rate fitted the adsorption kinetics better than pseudo-first-order rate equation. The adsorption capacity of carbon produced from RWSD was found to be 1250 mg g(-1) for the Bismark Brown dye. The rate constant and diffusion coefficient for intraparticle transport were determined for steam activated carbon. The characteristic of the prepared activated carbon was found comparable to the commercial activated carbon.     

Microwave assisted catalytic oxidation of p-nitrophenol in aqueous solution using carbon-supported copper catalyst

Carbon-supported copper (Cu/GAC) catalyst was prepared by conventional impregnation method and characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD). The sizes of Cu particles dispersing on the surface of GAC were 0.3-1.5 microm, which could be penetrated by microwave so that Cu/GAC catalyst could absorb microwave energy effectively. The catalysis of Cu/GAC in microwave assisted catalytic oxidation of p-nitrophenol (PNP) in aqueous solution was investigated through a fixed bed reactor under ambient pressure and continuous flow mode. PNP removal reached 91.8% under optimized conditions, corresponding to 88% of TOC removal. It showed a higher PNP degradation and total organic carbon (TOC) removal for Cu/GAC catalyst than GAC alone, and Cu/GAC catalyst kept on a high catalysis and a good stability for a long time run, which indicated that GAC structure and catalytic capacity were improved by the load of Cu.     

Removal of copper(II) and lead(II) from aqueous solution by manganese oxide coated sand I. Characterization and kinetic study

The preparation, characterization, and sorption properties for Cu(II) and Pb(II) of manganese oxide coated sand (MOCS) were investigated. A scanning electron microscope (SEM), X-ray diffraction spectrum (XRD) and BET analyses were used to observe the surface properties of the coated layer. An energy dispersive analysis of X-ray (EDAX) and X-ray photoelectron spectroscopy (XPS) were used for characterizing metal adsorption sites on the surface of MOCS. The quantity of manganese on MOCS was determined by means of acid digestion analysis. The adsorption experiments were carried out as a function of solution pH, adsorbent dose, ionic strength, contact time and temperature. Binding of Cu(II) and Pb(II) ions with MOCS was highly pH dependent with an increase in the extent of adsorption with the pH of the media investigated. After the Cu(II) and Pb(II) adsorption by MOCS, the pH in solution was decreased. Cu(II) and Pb(II) uptake were found to increase with the temperature. Further, the removal efficiency of Cu(II) and Pb(II) increased with increasing adsorbent dose and decreased with ionic strength. The pseudo-first-order kinetic model, pseudo-second-order kinetic model, intraparticle diffusion model and Elovich equation model were used to describe the kinetic data and the data constants were evaluated. The pseudo-second-order model was the best choice among all the kinetic models to describe the adsorption behavior of Cu(II) and Pb(II) onto MOCS, suggesting that the adsorption mechanism might be a chemisorption process. The activation energy of adsorption (E(a)) was determined as Cu(II) 4.98 kJ mol(-1) and Pb(II) 2.10 kJ mol(-1), respectively. The low value of E(a) shows that Cu(II) and Pb(II) adsorption process by MOCS may involve a non-activated chemical adsorption and a physical sorption.     

活性炭硝酸表面改性对催化剂分散度的影响

无论是活性炭作为催化剂载体还是在活性炭本身的催化制备过程中,催化剂在活性炭或活性炭前体上的高度分散都是至关重要的。通过X射线能谱(EDX)和扫描电子显微镜(SEM)技术直接观察、研究了活性炭表面经硝酸氧化改性对硝酸铜在煤基活性炭中分散度的影响。此外,将经硝酸表面改性的商品活性炭采用浸渍法负载上硝酸铜催化剂,再经水蒸气二次活化制备了一种新的活性炭。结果表明,硝酸处理造成活性炭吸附性能的下降,并且硝酸处理的强度越高,活性炭吸附性能的下降程度越大。然而,对硝酸处理的活性炭经简单的水洗可恢复其吸附性能。研究结果还表明,活性炭经硝酸氧化提高了炭表面含氧官能团的数量,使催化剂在活性炭的内外表面均能均匀分布,提高了催化剂的分散度和抗烧结能力。活性炭经硝酸改性后再负载硝酸铜进行二次活化制备高性能活性炭,可使硝酸铜的催化性能得到进一步的提升。     

Adsorption of dimethyl methylphosphonate on metal impregnated carbons under static conditions

Active carbon, grade 80 CTC, of surface area 1199m(2)/g, 12x30 BSS particle size and coconut shell origin was impregnated (5%, W/W) with various impregnants such as Cu(II) 1,1,1,5,5,5-hexafluoroacetylacetonate, Cu(II) 1,1,1-trifluoroacetylacetonate, 1-phenylbute-1,3-dione-2-oxime plus Cu(II) using incipient wetness technique. These impregnated carbons along with active carbon (Grade 80 CTC) and whetlerite were studied for the adsorption of dimethyl methylphosphonate (DMMP) at 33+/-1 degrees C under static conditions. Cu(II) 1,1,1,5,5,5-hexafluoroacetylacetonate impregnated carbon system showed highest uptake (68.5%, W/W) of DMMP amongst all the carbon systems, however, active carbon with higher surface area could adsorb 61.5% (W/W) of DMMP under same conditions. It indicated that the adsorption by Cu(II) 1,1,1,5,5,5-hexafluoroacetylacetonate impregnated carbon was not only due to physisorption but chemisorption as well. Kinetics of adsorption was also studied and various parameters such as equilibration time, equilibration capacity, rate constant (k), diffusional exponent (n) and constant (K) were determined. Carbons with and without DMMP exposure were also studied using IR and TGA techniques. Reaction products were analyzed using gas chromatography coupled with mass spectrometry (GC/MS) and found to be methyl methylphosphonic acid (MMPA) and methylphosphonic acid (MPA) for Cu(II) 1,1,1,5,5,5-hexafluoroacetylacetonate impregnated carbon.     

Sorption of lead, mercury and cadmium ions in multi-component system using carbon aerogel as adsorbent

In the present study, adsorption of three metal ions Pb(II), Hg(II) and Cd(II) on carbon aerogel a new form of activated carbon has been investigated in mono- and multi-component (binary and tertiary) system. Batch experiments were also carried out for mono- and multi-component systems with varying metal ion concentration (mg/l) to investigate the competitive adsorption characteristics. Many adsorbents have been studied for their adsorption properties pertaining to mono-component solutions of metal ions. However, to treat wastewater with new materials, their performance needs to be ascertained in multi-component system. The scanning electron micrographs (SEM) and EDAX spectrum of carbon aerogel surfaces before and after the adsorbent was equilibrated with the metal ion solution clearly establishes the presence of the metal ions and some surface modifications can be observed on the carbon aerogel particles adsorption with (i) surface chemistry of the pellets on the surface of carbon aerogel and (ii) inside layers of the carbon aerogel. Applicability of the isotherm models namely Freundlich and Langmuir to predict the equilibrium uptake of Pb(II), Hg(II) and Cd(II) in mono-component, binary and tertiary system has also been tested. Langmuir and Freundlich models are found to generally represent the experimental though but not consistently.