Comparison of natural organic matter adsorption capacities of super-powdered activated carbon and powdered activated Carbon

We examined the natural organic matter (NOM) adsorption characteristics of super-powdered activated carbon (S-PAC) produced by pulverizing commercially available, normal PAC to a submicron particle size range. The adsorption capacities of S-PAC for NOM and polystyrene sulfonates (PSS) with molecular weights (MWs) of 1.1, 1.8, and 4.6 kDa, which we used as model compounds, were considerably higher than those of PAC. The adsorption capacity increases were observed for all five types of carbon tested (two wood-based, two coconut-based, and one coal-based carbon). The adsorption capacities of S-PAC and PAC for polyethylene glycols (PEGs) with MWs of 0.3 and 1.0 were the same. The adsorption capacities of S-PAC for PEGs with MWs of 3.0 and 8.0 kDa were slightly higher than the adsorption capacities of PAC, but the difference in adsorption capacity was not as large as that observed for NOM and the PSSs, even though the MW ranges of the adsorbates were similar. We concluded that the adsorption capacity differences between S-PAC and PAC observed for NOM and PSSs were due to the difference in particle size between the two carbons, rather than to differences in internal pore size or structure, to differences in activation, or to non-attainment of equilibrium that resulted from the change in particle size. The difference in adsorption capacity between S-PAC and PAC was larger for NOM with a high specific UV absorbance (SUVA) value than for low-SUVA NOM. The larger adsorption capacities of S-PAC compared with PAC were explained by the larger specific external surface area per unit mass. We hypothesize that a larger fraction of the internal pore volume is accessible with carbon of smaller particle size because the NOM and PSS molecules preferentially adsorb near the outer surface of the particle and therefore do not completely penetrate the adsorbent particle.     

Characteristics of competitive adsorption between 2-methylisoborneol and natural organic matter on superfine and conventionally sized powdered activated carbons

When treating water with activated carbon, natural organic matter (NOM) is not only a target for adsorptive removal but also an inhibitory substance that reduces the removal efficiency of trace compounds, such as 2-methylisoborneol (MIB), through adsorption competition. Recently, superfine (submicron-sized) activated carbon (SPAC) was developed by wet-milling commercially available powdered activated carbon (PAC) to a smaller particle size. It was reported that SPAC has a larger NOM adsorption capacity than PAC because NOM mainly adsorbs close to the external adsorbent particle surface (shell adsorption mechanism). Thus, SPAC with its larger specific external surface area can adsorb more NOM than PAC. The effect of higher NOM uptake on the adsorptive removal of MIB has, however, not been investigated. Results of this study show that adsorption competition between NOM and MIB did not increase when NOM uptake increased due to carbon size reduction; i.e., the increased NOM uptake by SPAC did not result in a decrease in MIB adsorption capacity beyond that obtained as a result of NOM adsorption by PAC. A simple estimation method for determining the adsorbed amount of competing NOM (NOM that reduces MIB adsorption) is presented based on the simplified equivalent background compound (EBC) method. Furthermore, the mechanism of adsorption competition is discussed based on results obtained with the simplified EBC method and the shell adsorption mechanism. Competing NOM, which likely comprises a small portion of NOM, adsorbs in internal pores of activated carbon particles as MIB does, thereby reducing the MIB adsorption capacity to a similar extent regardless of adsorbent particle size. SPAC application can be advantageous because enhanced NOM removal does not translate into less effective removal of MIB. Molecular size distribution data of NOM suggest that the competing NOM has a molecular weight similar to that of the target compound.     

Direct observation of solid-phase adsorbate concentration profile in powdered activated carbon particle to elucidate mechanism of high adsorption capacity on super-powdered activated carbon

Decreasing the particle size of powdered activated carbon (PAC) by pulverization increases its adsorption capacities for natural organic matter (NOM) and polystyrene sulfonate (PSS, which is used as a model adsorbate). A shell adsorption mechanism in which NOM and PSS molecules do not completely penetrate the adsorbent particle and instead preferentially adsorb near the outer surface of the particle has been proposed as an explanation for this adsorption capacity increase. In this report, we present direct evidence to support the shell adsorption mechanism. PAC particles containing adsorbed PSS were sectioned with a focused ion beam, and the solid-phase PSS concentration profiles of the particle cross-sections were directly observed by means of field emission-scanning electron microscopy/energy-dispersive X-ray spectrometry (FE-SEM/EDXS). X-ray emission from sulfur, an index of PSS concentration, was higher in the shell region than in the inner region of the particles. The X-ray emission profile observed by EDXS did not agree completely with the solid-phase PSS concentration profile predicted by shell adsorption model analysis of the PSS isotherm data, but the observed and predicted profiles were not inconsistent when the analytical errors were considered. These EDXS results provide the first direct evidence that PSS is adsorbed mainly in the vicinity of the external surface of the PAC particles, and thus the results support the proposition that the increase in NOM and PSS adsorption capacity with decreasing particle size is due to the increase in external surface area on which the molecules can be adsorbed.     

Elucidating competitive adsorption mechanisms of atrazine and NOM using model compounds

Based on the relative adsorbability of natural organic matter (NOM) fractions with different molecular weights (MWs), two model compounds, poly(styrene sulfonate) (PSS) (nominal MW=1800 Dalton) and p-dichlorobenzene (DCB), were chosen to study the competitive effect of large and small NOM molecules on atrazine adsorption by two powdered activated carbons (PACs) with different pore size distributions. Both isotherm and kinetic tests of atrazine adsorption were conducted using fresh PAC and PAC preloaded with the model compounds. The model compounds were found to affect atrazine adsorption through two different mechanisms due to their size difference: direct competition for sites by p-DCB and pore constriction/blockage by PSS-1.8k. p-DCB was found to significantly reduce atrazine adsorption capacity but to have no effect on atrazine adsorption kinetics. In contrast, the effect of PSS-1.8k on atrazine adsorption capacity was very small. Furthermore, during simultaneous adsorption, PSS-1.8k had no effect on atrazine surface diffusion. However, preloading PAC with PSS-1.8k lowered the atrazine surface diffusion coefficient, D(s), by more than three orders of magnitude; D(s) decreased with increasing solid phase PSS-1.8k concentration. The pore size distribution of the PAC was found to play an important role in competitive adsorption. A high mesopore surface area could alleviate pore blockage significantly.     

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.     

Pore distribution effect of activated carbon in adsorbing organic micropollutants from natural water

Adsorption isotherms of organic micropollutants in coexistence with natural organic matter (NOM) were analyzed to evaluate the impacts of pore size distribution of activated carbon (AC) on the competition effects of the NOM. Single solute adsorption experiments and simultaneous adsorption experiments with NOM contained in a coagulation-pretreated surface water were performed for four agricultural chemicals and three coal-based activated carbons (ACs) having different pore distributions. The results showed that, for all the carbons used, the adsorption capacity of the chemicals was reduced distinctly in the presence of NOM. Such a reduction was more apparent for AC with a larger portion of small pores suitable for the adsorption of small organic molecules and for the agricultural chemicals with a more hydrophilic nature. Ideal adsorbed solution theory (IAST) incorporated with the Freundlich isotherm expression (IAST-Freundlich model) could not interpret the impact of NOM on the adsorption capacity of the chemicals unless a pore blockage effect caused by the adsorption of NOM was also considered. By taking into account this effect, the adsorption isotherm of the chemicals in the presence of NOM was well described, and the capacity reduction caused by the NOM was quantitatively assessed from the viewpoints of the site competition and the pore blockage. Analytical results clearly indicated that pore blockage was an important competition mechanism that contributed to 10-99% of the total capacity reductions of the chemicals, the level depended greatly on the ACs, the chemicals and the equilibrium concentrations, and could possibly be alleviated by broadening the pore size distributions of the ACs to provide a large volume percentage for pores with sizes above 30 A.     

An overall isotherm for activated carbon adsorption of dissolved natural organic matter in water

Design and analysis of activated carbon processes in water treatment often requires the adsorption isotherm for dissolved natural organic matter (NOM). Of the isotherm models available, the Summers and Roberts (SR) equation, capable of describing the adsorbent dose effect with the fewest parameters, has been successfully used to normalize NOM isotherm data. In this study, we show that the adsorbent dose in the SR equation can be eliminated as an intermediate variable and the initial concentration effect on NOM adsorption is then described explicitly. Comparing with the original SR equation, the derived isotherm equation is in a form more amenable to analysis. To ensure that the prediction is physically attainable, we introduced the limiting adsorption capacity by taking the adsorbent pore volume and size exclusion into consideration. Subsequently, we develop a simple relationship that can be used to determine the minimum adsorbent usage required for any desirable level of treatment. By comparing with extensive isotherm data previously published by Li et al. [2003a. Polydisperse adsorbability composition of several natural and synthetic organic matrices. J. Colloid Interface Sci. 265(2), 265-275], we demonstrated that the isotherm equation derived herein yields predictions that agree with the much more complicated fictive component-ideal adsorbed solution theory (IAST)-based model for NOM from different sources and over a range of initial concentrations.     

Effect of natural organic matter on powdered activated carbon adsorption of trace contaminants: characteristics and mechanism of competitive adsorption

Batch adsorption experiments using powdered activated carbon (PAC) to remove trace synthetic organic chemicals (SOCs) from water containing natural organic matter (NOM) were conducted. The percentage of SOC removed at any contact time and at any PAC dose was observed to be independent of the initial SOC concentration. Equations derived from the ideal adsorbed solution theory and the pore surface diffusion model validated this observation. For the strongly adsorbing SOCs (simazine and simetryn), the percentage of SOC removed was independent only at low initial SOC concentrations. The NOM fraction competing with the weakly adsorbing SOC (asulam) constituted a larger percentage of the total NOM than that competing with the strongly adsorbing SOCs. Although the adsorptive capacities of the SOCs were greatly reduced in water containing NOM compared with those in pure water, the change in the pore diffusion coefficient was insignificant. Therefore, NOM competed with the SOCs for adsorption sites, reducing the adsorptive capacity, but the amount of NOM loading was not so severe that it blocked or filled the pores, hindering the internal diffusion of the SOCs.     

Branched pore kinetic model analysis of geosmin adsorption on super-powdered activated carbon

Super-powdered activated carbon (S-PAC) is activated carbon of much finer particle size than powdered activated carbon (PAC). Geosmin is a naturally occurring taste and odor compound that impairs aesthetic quality in drinking water. Experiments on geosmin adsorption on S-PAC and PAC were conducted, and the results using adsorption kinetic models were analyzed. PAC pulverization, which produced the S-PAC, did not change geosmin adsorption capacity, and geosmin adsorption capacities did not differ between S-PAC and PAC. Geosmin adsorption kinetics, however, were much higher on S-PAC than on PAC. A solution to the branched pore kinetic model (BPKM) was developed, and experimental adsorption kinetic data were analyzed by BPKM and by a homogeneous surface diffusion model (HSDM). The HSDM describing the adsorption behavior of geosmin required different surface diffusivity values for S-PAC and PAC, which indicated a decrease in surface diffusivity apparently associated with activated carbon particle size. The BPKM, consisting of macropore diffusion followed by mass transfer from macropore to micropore, successfully described the batch adsorption kinetics on S-PAC and PAC with the same set of model parameter values, including surface diffusivity. The BPKM simulation clearly showed geosmin removal was improved as activated carbon particle size decreased. The simulation also implied that the rate-determining step in overall mass transfer shifted from intraparticle radial diffusion in macropores to local mass transfer from macropore to micropore. Sensitivity analysis showed that adsorptive removal of geosmin improved with decrease in activated carbon particle size down to 1 μm, but further particle size reduction produced little improvement.     

应对突发氯苯污染的粉末炭吸附工艺实验研究

考察了模拟常规工艺对水中氯苯的去除效能,测定了粉末炭(PAC)对原水中氯苯的吸附等温线和吸附动力学曲线,并采用Freundlich吸附等温式和假二级动力学模型进行拟合.结果表明,常规工艺难以有效去除水中氯苯;PAC可快速地吸附水中氯苯,5min吸附量可达平衡吸附量的80％以上,30 min吸附量可达98％以上.建立了P...     

Evaluation of Victorian low rank coal-based adsorbents for the removal of organic compounds from aqueous systems

Three activated carbons and two chars made from low rank coal were evaluated in terms of their ability to remove the organic compound 4-nitrophenol (4-NP) and natural organic matter (NOM) from aqueous systems. The adsorption equilibrium capacities of all adsorbents for 4-NP correlated with the micropore area of the adsorbents. Adsorption rates showed improved removal with decreasing particle size and higher carbon mass loadings. A pseudo first order model was used to fit the kinetic data, with a correlation coefficient of 0.995–0.999 for all systems.

The adsorption capacity for NOM, as measured by UV-absorbing DOC, correlated well with the pore volume and pore surface areas for pores with diameters in the range 2.7–21 nm. The trend in the adsorption capacities and removal rates of the adsorbents for NOM provided evidence that the pore size distribution is one of the most important physical characteristics of activated carbon for the adsorption of NOM.

The performance of activated low rank coal based materials was comparable to a high quality coconut-based commercial carbon in batch systems. Although the non-activated char adsorbents gave poor performance, they have potential for use in applications where poor performance can be outweighed by lower cost.     

Pore blockage effect of NOM on atrazine adsorption kinetics of PAC: the roles of PAC pore size distribution and NOM molecular weight

Natural organic matter (NOM) in natural water has been found to have negative effects on the adsorption of various trace organic compounds by activated carbon through two major mechanisms: direct competition for sites and pore blockage. In this study, the pore blockage effect of NOM on atrazine adsorption kinetics was investigated. Two types of powdered activated carbon (PAC) and three natural waters were tested to determine the roles of PAC pore size distribution and NOM molecular weight distribution in the pore blockage mechanism. When PAC was preloaded with natural water, the pore blockage effect of the NOM was found to cause a reduction of up to more than two orders of magnitude in the surface diffusion rate of atrazine compared to simultaneous adsorption of atrazine and NOM with fresh PAC. The surface diffusion coefficient of atrazine for preloaded PAC decreased with a decrease in PAC dose or an increase in NOM surface concentration. Because of the pore blockage effect of NOM, a 30% drop in atrazine removal was observed in a continuous flow PAC/microfiltration (MF) system after 7 days of contact compared to the removal predicted from the batch isotherm test. Large micropores and mesopores were found to play an important role in alleviating the effect of pore blockage. A PAC with a relatively large fraction of large micropore and mesopores was shown to suffer much less from the pore blockage effect compared with a PAC that had a much smaller fraction of large pores. Natural waters with different NOM molecular weight distribution caused different extent of pore blockage. The NOM molecules with molecular weight between 200 and 700 Dalton appeared to be responsible for the pore blockage effect.     

Removal of 2,4,6-trichlorophenol and natural organic matter from water supplies using PAC in floc-blanket reactors

The objective of this study was to evaluate the addition of powdered activated carbon (PAC) to upflow floc-blanket reactors for the adsorption of natural and synthetic organic chemicals. A 15.5-1. bench-scale floc-blanket reactor was operated with PAC addition for the adsorption of 2,4,6-trichlorophenol (TCP) and natural organic matter from one groundwater and two surface waters under laboratory and field conditions, respectively. Influent TCP concentrations ranged from 21 to 415 μg/l. The PAC doses ranged from 2 to 12 mg/l. While the hydraulic residence time in the floc-blanket reactor varied from 15 to 30 min, the carbon residence time ranged from 9 to 34 h. This is due to the high solids concentration in the floc blanket, which ranged from 1200 to 8700 mg/l. Comparison between the extent of TCP adsorption through the floc-blanket reactor and the equilibrium adsorption isotherms of TCP on PAC showed that the maximum adsorption capacity of PAC for TCP was utilized in the reactor. However, this study showed that the maximum adsorptive capacity of the carbon in a continuous process is dependent on the influent adsorbate concentration. This was in agreement with isotherm studies conducted with varying initial TCP concentration. The maximum PAC adsorption capacity for natural organic matter was also achieved in the floc-blanket reactor.     

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.     

Sorption of perfluorooctane sulfonate and perfluorooctanoate on activated carbons and resin: Kinetic and isotherm study

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have increasingly attracted global concerns in recent years due to their global distribution, persistence, strong bioaccumulation and potential toxicity. The feasibility of using powder activated carbon (PAC), granular activated carbon (GAC) and anion-exchange resin (AI400) to remove PFOS and PFOA from water was investigated with regard to their sorption kinetics and isotherms. Sorption kinetic results show that the adsorbent size influenced greatly the sorption velocity, and both the GAC and AI400 required over 168 h to achieve the equilibrium, much longer than 4 h for the PAC. Two kinetic models were adopted to describe the experimental data, and the pseudo-second-order model well described the sorption of PFOS and PFOA on the three adsorbents. The sorption isotherms show that the GAC had the lowest sorption capacity both for PFOS and PFOA among the three adsorbents, while the PAC and AI400 possessed the highest sorption capacity of 1.04 mmol g⁻¹ for PFOS and 2.92 mmol g⁻¹ for PFOA according to the Langmuir fitting. Based on the sorption behaviors and the characteristics of the adsorbents and adsorbates, ion exchange and electrostatic interaction as well as hydrophobic interaction were deduced to be involved in the sorption, and some hemi-micelles and micelles possibly formed in the intraparticle pores.     

粉末活性炭去除水中氯丁二烯的研究

试验研究了粉末活性炭对氯丁二烯的去除效果以及吸附时间、投加量和水质对粉末活性炭吸附性能的影响。结果表明,粉末活性炭对氯丁二烯的去除率在90%以上,吸附规律符合Langmuir吸附等温线和Freunlich吸附等温线;最佳吸附时间为120min;随着投炭量的增加,氯丁二烯的去除率提高,粉末活性炭的吸附容量降低;在不同水质条件下,粉末活性炭的吸附等温线不同,因此在应急处理中,首先应确定原水水质下的吸附等温线,然后计算出投炭量。     

Natural organic matter (NOM) and pesticides removal using a combination of ion exchange resin and powdered activated carbon (PAC)

The combination of anion exchange resins (AERs) and powdered activated carbon (PAC) was studied to remove both natural organic matter (NOM) and pesticides. Experiments were conducted with high dissolved organic carbon (DOC) surface water (about 6.0mg DOC/L) spiked with both atrazine and isoproturon. AERs, like MIEX and IRA938, showed up to 75% removal of DOC after 30min contact time. The addition of PAC after treatment with these AERs only slightly decreased the residual DOC from 1.4 to 1.2mg/L. Experiments conducted with high (200microg/L) and low (1microg/L) initial pesticide concentrations showed that simultaneous and successive combinations of AER and PAC significantly improve the removal of both pesticides compared with PAC treatment on raw water. The improvement of short-term adsorption kinetics was explained by the adsorption of pesticides on AERs (about 5%) and the removal of high molecular weight (MW) NOM structures by AERs that reduce pore blockage phenomena. For 24h contact time with PAC (adsorption isotherms), the benefit of AER treatment was lower, which indicates that the refractory DOC to AER treatment still competes through direct site competition mechanism. MIEX resin had a distinct behavior since the simultaneous treatment with PAC showed no benefit on pesticide adsorption. The presence of fine residues of MIEX was shown to interfere with PAC adsorption.     

Adsorption of Cr(III) on ozonised activated carbon. Importance of Cpi-cation interactions

The adsorption of Cr(III) in aqueous solution was investigated on a series of ozonised activated carbons, analysing the effect of oxygenated surface groups on the adsorption process. A study was carried out to determine the adsorption isotherms and the influence of the pH on the adsorption of this metal. The adsorption capacity and affinity of the adsorbent for Cr(III) increased with the increase in oxygenated acid groups on the surface of the activated carbon. These findings imply that electrostatic-type interactions predominate in the adsorption process, although the adsorption of Cr(III) on the original (basic) carbon indicates that other forces also participate in the adsorption process. Thus, the ionic exchange of protons in the -Cpi-H3O(+) interaction for Cr(III) accounts for the adsorption of cationic species in basic carbons with positive charge density. Study of the influence of pH on the adsorption of Cr(III) showed that, in each system, the maximum adsorption occurred when the charge of the carbon surface was opposite that of the species of Cr(III) present at the pH of the experiment. These results confirmed that electrostatic interactions predominate in the adsorption process.     

Adsorption of basic dyes on granular activated carbon and natural zeolite

The adsorption of basic dyes from aqueous solution onto granular activated carbon and natural zeolite has been studied using an agitated batch adsorber. The influence of agitation, initial dye concentration and adsorbent mass has been studied. The parameters of Langmuir and Freundlich adsorption isotherms have been determined using the adsorption data. Homogeneous diffusion model (solid diffusion) combined with external mass transfer resistance is proposed for the kinetic investigation. The dependence of solid diffusion coefficient on initial concentration and mass adsorbent is represented by the simple empirical equations.     

饮用水中粉末活性炭应急处理技术研究

以遭受突发性2,4滴污染的水体作为研究对象,考察了粉末活性炭技术对受2,4滴污染原水的应急处理效果.结果显示,粉末活性炭可有效去除2,4滴污染物,吸附时间越长,去除率越高.与准一级动力学方程相比,准二级动力学方程拟合曲线能更好地与数据点重合,相关系数为0.99,由准二级动力学方程计算得出的吸附容量值与试验中实际得到的吸附容量值很接近.粉末活性炭吸附2,4滴的Freundlich模型拟合度优于Langmuir模型,且对2,4滴的吸附存在多分子层吸附.