Adsorption of chlorinated organic compounds on activated carbon from water

The adsorption capacities and rates of seven principal chlorinated organic compounds for six commercial GACs were investigated. All the adsorption isotherms were expressed by the Freundlich equation, and the isotherms for the chloroethylenes such as trans - 1,2-dichloroethylene, trichloroethylene and tetrachloroethylene could be shown by the modified Freundlich equation Q′ = k′ (C/C_s)^l/n for each GAC. The magnitude of adsorption of the chlorinated organic compounds was in the order of: tetrachloroethylene > trichloroethylene > trans - 1,2-dichloroethylene > 1,1-dichloroethane > carbontetrachloride > 1.1,1-trichloroethane > chloroform. The value of k for a certain GAC could be predicted from the quantity of pores smaller than 2 nm in diameter. The adsorbed amounts were decreased by 10–20% when humic substances coexisted. The working periods of a fixed bed adsorber before regeneration were predicted by calculating breakthrough curves for various influent concentrations of trichloroethylene and tetrachloroethylene at the space velocities of 5 or 10 h⁻¹, and it was certified that the adsorption method by GAC was feasible for removing these compounds from water.     

Adsorption of cellular peptides of Microcystis aeruginosa and two herbicides onto activated carbon: effect of surface charge and interactions

In this research, the adsorption of two herbicides, alachlor (ALA) and terbuthylazine (TBA), on granular activated carbon (GAC) in the presence of well-characterized peptide fraction of cellular organic matter (COM) produced by cyanobacterium Microcystis aeruginosa was studied. Two commercially available GACs were characterized using nitrogen gas adsorption and surface charge titrations. The COM peptides of molecular weight (MW) < 10 kDa were isolated and characterized using MW fractionation technique and high-performance size exclusion chromatography (HPSEC). The effect of surface charge on the adsorption of COM peptides was studied by means of equilibrium adsorption experiments at pH 5 and pH 8.5. Electrostatic interactions and hydrogen bonding proved to be important mechanisms of COM peptides adsorption. The adsorption of ALA and TBA on granular activated carbon preloaded with COM peptides was influenced by solution pH. The reduction in adsorption was significantly greater at pH 5 compared to pH 8.5, which corresponded to the increased adsorption of COM peptides at pH 5. The majority of the competition between COM peptides and both herbicides was attributed to low molecular weight COM peptides with MW of 700, 900, 1300 and 1700 Da.     

Characterization of natural organic matter adsorption in granular activated carbon adsorbers

The removal of natural organic matter (NOM) from lake water was studied in two pilot-scale adsorbers containing granular activated carbon (GAC) with different physical properties. To study the adsorption behavior of individual NOM fractions as a function of time and adsorber depth, NOM was fractionated by size exclusion chromatography (SEC) into biopolymers, humics, building blocks, and low molecular weight (LMW) organics, and NOM fractions were quantified by both ultraviolet and organic carbon detectors. High molecular weight biopolymers were not retained in the two adsorbers. In contrast, humic substances, building blocks and LMW organics were initially well and irreversibly removed, and their effluent concentrations increased gradually in the outlet of the adsorbers until a pseudo-steady state concentration was reached. Poor removal of biopolymers was likely a result of their comparatively large size that prevented access to the internal pore structure of the GACs. In both GAC adsorbers, adsorbability of the remaining NOM fractions, compared on the basis of partition coefficients, increased with decreasing molecular size, suggesting that increasingly larger portions of the internal GAC surface area could be accessed as the size of NOM decreased. Overall DOC uptake at pseudo-steady state differed between the two tested GACs (18.9 and 28.6 g-C/kg GAC), and the percent difference in DOC uptake closely matched the percent difference in the volume of pores with widths in the 1-50 nm range that was measured for the two fresh GACs. Despite the differences in NOM uptake capacity, individual NOM fractions were removed in similar proportions by the two GACs.     

IMPROVING THE PERFORMANCE OF GRANULAR ACTIVATED CARBON (GAC) VIA PRE-REGENERATION ACID TREATMENT

A lab-scale acid treatment system was developed to Investigate the effects of hydrochloric acid on the removal of calcium from field spent GAC (FSGAC). The effects of acid treatment on the subsequent regeneration process and regenerated GAC properties were also investigated using a lab-scale furnace. A linear relationship between calcium remaining on the GAC following acid treatment and GAC mass losses during regeneration was exhibited. FSGAC treated with 0.1 N hydrochloric acid resulted in 7.5% lower mass losses than non-acid treated GAC. An increase in total surface area of 7.2% and micropore volume of 3.1% was also noted following acid treatment and regeneration. This was due to a reduction in calcium-catalysed gasification of the GAC structure, which may have occurred in samples, which had not received acid treatment. Improvements in porosity, adsorption capacity and surface chemistry indicate that acid treatment is an effective process, which may be used to provide superior regenerated GAC product.     

Adsorption of dissolved natural organic matter by modified activated carbons

Adsorption of dissolved natural organic matter (DOM) by virgin and modified granular activated carbons (GACs) was studied. DOM samples were obtained from two water treatment plants before (i.e., raw water) and after coagulation/flocculation/sedimentation processes (i.e., treated water). A granular activated carbon (GAC) was modified by high temperature helium or ammonia treatment, or iron impregnation followed by high temperature ammonia treatment. Two activated carbon fibers (ACFs) were also used, with no modification, to examine the effect of carbon porosity on DOM adsorption. Size exclusion chromatography (SEC) and specific ultraviolet absorbance (SUVA(254)) were employed to characterize the DOMs before and after adsorption. Iron-impregnated (HDFe) and ammonia-treated (HDN) activated carbons showed significantly higher DOM uptakes than the virgin GAC. The enhanced DOM uptake by HDFe was due to the presence of iron species on the carbon surface. The higher uptake of HDN was attributed to the enlarged carbon pores and basic surface created during ammonia treatment. The SEC and SUVA(254) results showed no specific selectivity in the removal of different DOM components as a result of carbon modification. The removal of DOM from both raw and treated waters was negligible by ACF10, having 96% of its surface area in pores smaller than 1 nm. Small molecular weight (MW) DOM components were preferentially removed by ACF20H, having 33% of its surface area in 1--3 nm pores. DOM components with MWs larger than 1600, 2000, and 2700 Da of Charleston raw, Charleston-treated, and Spartanburg-treated waters, respectively, were excluded from the pores of ACF20H. In contrast to carbon fibers, DOM components from entire MW range were removed from waters by virgin and modified GACs.     

Comparison between thermal and ozone regenerations of spent activated carbon exhausted with phenol

Thermal and ozone regenerations of granular activated carbons (GAC) used in the removal of phenol from aqueous solution have been studied. The phenol isotherms for virgin GAC could be well represented by the Langmuir equation. Direct ozonation of GAC introduced large amounts of acidic surface oxygen groups, which caused a decrease in the phenol uptake. Thermogravimetric methods were used to investigate the mechanism of phenol adsorption onto virgin and ozonated carbons. Thermal regeneration was carried out at 1123K using nitrogen (pyrolysis alone) or nitrogen and carbon dioxide (pyrolysis plus oxidation). Results showed that spent carbons do not recover their adsorption characteristics when heated under inert conditions whereas carbon dioxide regeneration was effective at about 15% wt burn-off. Regeneration of GAC was also carried out with ozone as oxidizing gas at room temperature. Ozone dose and the nature of GAC have much influence on the regeneration performance. For an individual GAC there exits an optimum ozone dose for which phenol is eliminated together with most of its oxidation by-products without incurring in carbon surface chemical alterations. However, if excessive ozone is applied some acidic surface groups are formed on the GAC, thereby decreasing the adsorption capacity for phenol. Results showed that spent carbons can recover most of their adsorption characteristics and specific surface areas when regenerated through a number of adsorption-ozone regeneration cycles.     

Fenton-driven chemical regeneration of MTBE-spent GAC

Methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC) was chemically regenerated utilizing the Fenton mechanism. Two successive GAC regeneration cycles were performed involving iterative adsorption and oxidation processes: MTBE was adsorbed to the GAC, oxidized, re-adsorbed, oxidized, and finally re-adsorbed. Oxidant solutions comprised of hydrogen peroxide (H2O2) (1.7-2.0%) and FeSO4 x 7H2O (3 g/L) (pH 2.5), were recirculated through the GAC column (30% bed expansion). The regeneration efficiency after two full cycles of treatment was calculated to be 91%. The cost of H2O2 was 0.59 dollars/kg GAC (0.27 dollars/lb) per regeneration cycle. There was no loss of sorptive capacity. Small reductions in carbon surface area and pore volume were measured. The lack of carbon deterioration under aggressive oxidative conditions was attributed to the oxidation of the target contaminants relative to the oxidation of carbon surfaces. The reaction byproducts from MTBE oxidation, tertiary butanol and acetone, were also degraded and did not accumulate significantly on the GAC. Excessive accumulation of Fe on the GAC and consequent interference with MTBE sorption and carbon regeneration was controlled by monitoring and adjusting Fe in the oxidative solution.     

Evaluation of granular activated carbon technology for the removal of methyl tertiary butyl ether (MTBE) from drinking water

This study evaluated granular activated carbons (GACs) using rapid small-scale column tests (RSSCTs) on methyl tert-butyl ether (MTBE) levels from 20 to 2000 microg/L, with or without the presence of tert-butyl alcohol, benzene, toluene, p-xylene (BTX) in two groundwater (South Lake Tahoe Utility District [Lake Tahoe, CA] and Arcadia Well Field [Santa Monica, CA]) and a surface water source (Lake Perris, CA). Direct comparison between two GACs was made for RSSCTs conducted with surface water from Lake Perris. The impact of natural organic matter on GAC performance was investigated and found to correspond with total organic carbon concentration in the three source waters. Significant reduction in GAC performance for MTBE due to competitive adsorption from soluble fuel components (e.g., BTX) was observed. Little or no difference in GAC usage rate or bed life was detected as the empty-bed contact time is changed from 10 to 20 min for RSSCTs conducted in the two groundwater sources, whereas the RSSCTs conducted in the surface water source exhibited significant increase in GAC usage rate as the empty-bed contact time is decreased from 20 to 10 min. This finding suggests that the higher NOM content of the surface water over the groundwater sources caused a greater competitive-adsorption effect that made more sites on the GAC to be unavailable to MTBE, thus decreasing its rate of adsorption and GAC performance for MTBE. Finally, the impact of differential influent MTBE concentration on GAC performance was demonstrated.     

Adsorption of tri- and tetra-chloroethylene from aqueous solutions on activated carbon fibers

Recently the contamination of groundwater by trichloroethylene and related compounds have become a new environmental problem. As the first step to clarify the feasibility of applying newly developed adsorbent, activated carbon fiber (ACF), to adsorption treatments of water taken from such a contaminated groundwater source, the adsorption equilibrium and the adsorption rate of trichloroethylene and tetrachloroethylene from aqueous solutions on four ACFs with different pore-size distribution were investigated. The adsorption capacities of ACFs having larger volume of micropores are larger than those of granular activated carbons (GACs) usually used at present. Also, the adsorption rate on ACFs is far more rapid in comparison with GAC adsorption because of smaller diffusion path.     

颗粒活性炭吸附对预臭氧后微污染原水水质影响研究

在不同的预臭氧浓度条件下处理微污染原水,考察了颗粒活性灰（GAC）吸附对处理后水样水质的影响.选择化学需氧量（CODMn）、溶解性有机碳（DOC）、生物可降解溶解性有机碳（BDOC）、UV254和氨氮（NH;-N）含量及有机物分子量分布作为考察吸附效果的检测指标.结果表明,在静态吸附时间达到5天时,颗粒活性炭吸附曲线开始趋于平缓,吸附时间超过5天之后吸附趋于饱和;预臭氧含量为2.5 mg/L时,颗粒活性炭对有机物的吸附效果最佳,对CODMn、DOC、BDOC的去除率分别为53.2％,63.2％和36.2％;在不同预臭氧处理条件下,颗粒活性炭对NH;-N的吸附效果并未表现出较大的差异,吸附去除率约为5％;颗粒活性炭优先吸附水中分子量＞ 10kDa的有机物,其次为分子量＜1 kDa的有机物.     

微波强化Fenton氧化处理垃圾渗滤液的研究

以负载铁(Ⅱ)的颗粒活性炭(GAC)为催化剂,采用微波强化Fenton氧化处理老龄垃圾渗滤液,考察了对垃圾渗滤液的处理效果及微波的作用机理。结果表明,微波对Fenton氧化反应有催化作用,且可促进渗滤液中胶体的絮凝,微波作用时间是影响处理效果的主要因素;当GAC的铁负载量为33.32mg/g、微波功率为720W、微波时间为30min时,对COD和NH3-N的去除率最高,分别达到了95.64%和88.63%;COD主要通过催化氧化作用被去除,而NH3-N主要通过絮凝、吸附作用被去除;另外,微波可使GAC再生,提高了GAC的利用率。     

The effects of dissolved natural organic matter on the adsorption of synthetic organic chemicals by activated carbons and carbon nanotubes

Understanding the influence of natural organic matter (NOM) on synthetic organic contaminant (SOC) adsorption by carbon nanotubes (CNTs) is important for assessing the environmental implications of accidental CNT release and spill to natural waters, and their potential use as adsorbents in engineered systems. In this study, adsorption of two SOCs by three single-walled carbon nanotubes (SWNTs), one multi-walled carbon nanotube (MWNT), a microporous activated carbon fiber (ACF) [i.e., ACF10] and a bimodal porous granular activated carbon (GAC) [i.e., HD4000] was compared in the presence and absence of NOM. The NOM effect was found to depend strongly on the pore size distribution of carbons. Minimal NOM effect occurred on the macroporous MWNT, whereas severe NOM effects were observed on the microporous HD4000 and ACF10. Although the single-solute adsorption capacities of the SWNTs were much lower than those of HD4000, in the presence of NOM the SWNTs exhibited adsorption capacities similar to those of HD4000. Therefore, if released into natural waters, SWNTs can behave like an activated carbon, and will be able to adsorb, carry, and transfer SOCs to other systems. However, from an engineering application perspective, CNTs did not exhibit a major advantage, in terms of adsorption capacities, over the GAC and ACF. The NOM effect was also found to depend on molecular properties of SOCs. NOM competition was more severe on the adsorption of 2-phenylphenol, a nonplanar and hydrophilic SOC, than phenanthrene, a planar and hydrophobic SOC, tested in this study. In terms of surface chemistry, both adsorption affinity to SOCs and NOM effect on SOC adsorption were enhanced with increasing hydrophobicity of the SWNTs.     

Electrochemical regeneration of field spent GAC from two water treatment plants

The effectiveness of on-site thermal regeneration of field-spent granular activated carbon (GAC) from two municipal drinking water facilities was compared with bench-scale electrochemical regeneration, a novel regeneration technology. The regeneration method was evaluated using aqueous natural organic material (NOM) adsorption, iodine number analysis, and surface area analysis. In contrast to the large electrochemical regeneration efficiencies reported in the literature for GAC loaded with phenolics and other individual organic compounds, the electrochemical reactor tested was only able to regenerate 8-15% of the NOM adsorption capacity of the field spent GAC. In contrast, thermal reactivation achieved up to 103% regeneration efficiency. To more accurately assess the efficiency of regeneration processes for water treatment applications, GAC should be loaded in continuous-flow columns and not batch rectors. The iodine number analysis yielded higher efficiency values, however it did not give an accurate estimate of the regeneration efficiency. The small changes in GAC pore size distribution were consistent with the low electrochemical regeneration efficiencies. These low efficiencies appear to be related to the low reversibility of NOM adsorption and to pH-induced adsorbate desorption being the primary mechanism for this type of electrochemical regeneration system.     

Effects of activated carbon characteristics on the simultaneous adsorption of aqueous organic micropollutants and natural organic matter

The overall objective of this research was to determine the effects of physical and chemical activated carbon characteristics on the simultaneous adsorption of trace organic contaminants and natural organic matter (NOM). A matrix of 12 activated carbon fibers (ACFs) with three activation levels and four surface chemistry levels (acid-washed, oxidized, hydrogen-treated, and ammonia-treated) was studied to systematically evaluate pore structure and surface chemistry phenomena. Also, three commercially available granular activated carbons (GACs) were tested. The relatively hydrophilic fuel additive methyl tertiary-butyl ether (MTBE) and the relatively hydrophobic solvent trichloroethene (TCE) served as micropollutant probes. A comparison of adsorption isotherm data collected in the presence and absence of NOM showed that percent reductions of single-solute TCE and MTBE adsorption capacities that resulted from the presence of co-adsorbing NOM were not strongly affected by the chemical characteristics of activated carbons. However, hydrophobic carbons were more effective adsorbents for both TCE and MTBE than hydrophilic carbons because enhanced water adsorption on the latter interfered with the adsorption of micropollutants from solutions containing NOM. With respect to pore structure, activated carbons should exhibit a large volume of micropores with widths that are about 1.5 times the kinetic diameter of the target adsorbate. Furthermore, an effective adsorbent should possess a micropore size distribution that extends to widths that are approximately twice the kinetic diameter of the target adsorbate to prevent pore blockage/constriction as a result of NOM adsorption.     

Adsorptive selenite removal from water using iron-coated GAC adsorbents

Removal of selenite from aqueous phase using iron-coated granular activated carbons (GAC) was investigated in this study. Five different types of GAC were used for iron coating by oxidizing ferrous chloride with sodium hypochlorite and the iron-coated GAC (Fe-GAC) were tested for selenite removal. Nitrogen adsorption-desorption analyses indicated that Brunauer-Emmett-Teller (BET) specific surface area, pore size, and pore volume decreased with the iron coating. The Darco 12x20 GAC was shown to be the most effective adsorbent among the five tested GACs after iron coating. Among the different concentrations used for iron coating, the Darco 12x20 GAC coated with 0.1M ferrous chloride achieved the highest selenite removal (97.3%). High removal efficiency of selenite occurred in a wide range of pH (i.e., 2-8), but the efficiency decreased when pH was higher than 8. Adsorption kinetics showed that selenite removal efficiency reached more than 90% after 6-h adsorption for initial selenium concentration of 2mg/L and equilibrium was obtained after 48h. A pseudo-second-order kinetic model was found to characterize the adsorption kinetics well for all the initial selenium concentrations and temperatures tested (R(2)>/=0.9969). Three temperatures (25, 35, 45 degrees C) were used to examine temperature effect on the adsorption behavior of the Fe-GAC with initial selenium concentration of 1mg/L. Activation energy was calculated to be 30.42kJ/mol. Adsorption isotherms for initial selenium concentration of 2mg/L at various temperatures and ionic strengths were developed and the data generally fit the Langmuir model well (R(2)>/=0.994). The adsorption capacity reached as high as 2.50mg-Se/g-adsorbent at equilibrium for initial concentration of 2mg/L at 25 degrees C. The Gibbs free energy was determined to be negative, indicating the spontaneous nature of the adsorption reaction. Oxyanion competitive adsorption showed that sulfate (0.1-5mM) barely affected selenite adsorption. Other anions (phosphate, silicate and carbonate) impact selenite adsorption to various degrees with phosphate completely excluded selenite adsorption at 5mM. The possible adsorption mechanisms were discussed.     

Application of Granular Activated Carbon in the Water Industry

U ntil the mid 1980s granular activated carbon (GAC) was used in only a small number of water-treatment plants in the UK. Since then the material has been installed in over 30 plants, either as a result of an operational decision to treat the water by GAC or for the purpose of full-scale experiments. GAC is used for a variety of reasons including taste and odour control, removal of a wide range of synthetic organic compounds (for example volatile chlorinated solvents, pesticides, oils) of molecular weight 100–500, and adsorption of trihalomethane precursors (molecular weight 10³-10⁵). The performance of different GACs for a particular duty may vary by a factor of 10, and the best GAC for one application may be the worst for another. Thus, to minimize the cost of GAC treatment, it is essential to identify the purpose for which GAC is being used and then to select, by pilot trials or by more rapid laboratory procedures and mathematical modelling, the most appropriate GAC for that particular application.     

Microwave-assisted regeneration of activated carbons loaded with pharmaceuticals

The purpose of this work was to explore the application of microwaves for the regeneration of activated carbons spent with salicylic acid, a metabolite of a common analgesic frequently found in wastewater from the pharmaceutical industry. The exhausted carbon was treated in a quartz reactor by microwave irradiation at 2450 MHz at different temperatures and atmospheres, the regeneration efficiency being highly dependent on the operating conditions. Quantitative desorption of the pollutant was achieved at high temperature and oxidizing atmosphere, with regeneration efficiencies as high as 99% after six cycles. The stripping efficiency was superior to 95% at high temperatures and decreased at 450 degrees C. The incomplete desorption of the adsorbate at low temperature was further confirmed by the changes in the porosity observed by N2 and CO2 adsorption isotherms. Hence, micropores remain blocked which results in a reduction in loading capacities in successive cycles.     

Influence of microbiological activity in granular activated carbon filters on the removal of organic compounds

In order to show the influence of bacterial activity in GAC filters on the removal of organic matter, experiments were carried out with diluted aqueous solutions of biodegradable and of non-biodegradable compounds under sterile and non sterile conditions. Productions of CO₂ show clearly that the bacterial activity can lead to a complete elimination of the biodegradable solute and to a partial microbiological regeneration of the adsorbent. By its influence on the competitive adsorption, the biological removal of biodegradable compounds leads to an increase of GAC adsorptive capacities for the non-biodegradable organic matter.     

Regeneration of granular activated carbon with adsorbed trichloroethylene using wet peroxide oxidation

The objective of this study is to clarify the regeneration of granular activated carbon (GAC) adsorbed trichloroethylene (TCE) using wet peroxide oxidation (WPO). TCE and TOC concentrations decreased during WPO, whereas Cl(-) accumulated in water indicating that TCE was not only decomposed but was also mineralized to Cl(-) and CO(2) using WPO. Regeneration efficiencies (q/q(0)) of GAC regenerated at 150, 165 and 180 degrees C (initial pH 4) were 0.36, 0.45, 0.48, respectively. In addition, regeneration efficiencies of GAC regenerated in the solution of various initial pH (2.5, 3.0, 4.0) at 180 degrees C were 0.71, 0.60, 0.48, respectively. These results suggest that regeneration of GAC is more effective at higher reaction temperature and lower initial pH of the solution. In the repeated regeneration of GAC, the adsorption capacity of GAC for TCE gradually decreased and regeneration efficiency of the regenerated GAC at sixth step was 0.40. The adsorption capacity loss of regenerated GAC is probably due to oxidation of GAC during WPO.     

Removal of THM precursors by GAC: Ankara case study

The effectiveness of granular activated carbon (GAC) adsorption for the removal of natural organic matter and trihalomethanes from Ivedik Water Treatment Plant of Ankara City is investigated. Freundlich Isotherm constants K and n were determined as 17.61 and 1.66, respectively. Bench-scale GAC columns were run with empty bed contact times (EBCT) varying from 0.40 to 2.67 min to evaluate adsorption performance. 50% exhaustion values were used for comparison. The treated volumes of water increased with EBCT, showing a linear increase in GAC service life. Correspondingly, the carbon usage rate decreased. The capacities calculated by the isotherm equation and achieved by columns were also compared. The column capacities were within 43-65% of the isotherm capacities at complete breakthrough. However, they were only within 8-17% of the isotherm capacities at 50% breakthrough.