Approaches to mitigate the impact of dissolved organic matter on the adsorption of synthetic organic contaminants by porous carbonaceous sorbents

Adsorption of trichloroethylene (TCE) and atrazine, two synthetic organic contaminants (SOCs) having different optimum adsorption pore regions, by four activated carbons and an activated carbon fiber (ACF) was examined. The selected adsorbents had a wide range of pore size distributions but similar surface acidity and hydrophobicity. Single solute and preloading (with a dissolved organic matter (DOM)) isotherms were performed. Single solute adsorption results showed that (i) the adsorbents having higher amounts of pores with sizes about the dimensions of the adsorbate molecules exhibited higher uptakes, (ii) there were some pore structure characteristics, which were not completely captured by pore size distribution analysis, that also affected the adsorption, and (iii) the BET surface area and total pore volume were not the primary factors controlling the adsorption of SOCs. The preloading isotherm results showed that for TCE adsorbing primarily in pores < 10 angstroms, the highly microporous ACF and GACs, acting like molecular sieves, exhibited the highest uptakes. For atrazine with an optimum adsorption pore region of 10-20 angstroms, which overlaps with the adsorption region of some DOM components, the GACs with a broad pore size distribution and high pore volumes in the 10-20 angstroms region had the least impact of DOM on the adsorption.     

Trichloroethylene adsorption by fibrous and granular activated carbons: aqueous phase, gas phase, and water vapor adsorption studies

The important adsorption components involved in the removal of trichloroethylene (TCE) by fibrous and granular activated carbons from aqueous solutions were systematically examined. Namely, adsorption of TCE itself (i.e., TCE vapor isotherms), water molecules (i.e., water vapor isotherms), and TCE in water (i.e., TCE aqueous phase isotherms) were studied, side-by-side, using 20 well-characterized surface-modified activated carbons. The results showed that TCE molecular size and geometry, activated carbon surface hydrophilicity, pore volume, and pore size distribution in micropores control adsorption of TCE at relatively dilute aqueous solutions. TCE adsorption increased as the carbon surface hydrophilicity decreased and the pore volume in micropores of less than 10 A, especially in the 5-8 A range, increased. TCE molecules appeared to access deep regions of carbon micropores due to their flat geometry. The results indicated that characteristics of both adsorbate (i.e., the molecular structure, size, and geometry) and activated carbon (surface hydrophilicity, pore volume, and pore size distribution of micropores) control adsorption of synthetic organic compounds from water and wastewaters. The important micropore size region for a target compound adsorption depends on its size and geometry.     

Effects of powdered activated carbon pore size distribution on the competitive adsorption of aqueous atrazine and natural organic matter

The pore size distribution (PSD) of adsorbents has been found to be an important factor that affects adsorption capacity for organic compounds; consequently, it should influence competitive adsorption in multisolute systems. This research was conducted to show howthe PSD of activated carbon affects the competition between natural organic matter (NOM) and the trace organic contaminant atrazine, with a primary emphasis on quantifying the pore blocking mechanism of NOM competition. Isotherm tests were performed for both atrazine and NOM from a groundwater on five powdered activated carbons (PACs) with widely different PSDs. The capacity for NOM correlated best with the surface area of pores in the diameter range of 15-50 A, although some NOM also adsorbed in the smaller pores as evidenced by a reduction in capacity for atrazine when NOM was present. Kinetic tests for atrazine on PACs with various levels of preadsorbed NOM showed that the magnitude of the pore blockage effect by NOM was lower for PACs with higher surface area of pores with diameter in the range of 15-50 A. Therefore increasing pores in the size range where NOM adsorb can reduce the extent of the pore blockage competitive effect on the target compound atrazine. The effect of PSD was further studied with a flow-through PAC-membrane hybrid watertreatment system, in which experimental results successfully verified model simulations by the COMPSORB model.     

Modeling trichloroethylene adsorption by activated carbon preloaded with natural dissolved organic matter using a modified IAST approach

A model was developed, using an approach based on the Ideal Adsorbed Solution Theory (IAST), to predict trichloroethylene (TCE) adsorption by granular activated carbon (GAC) preloaded with natural dissolved organic matter (DOM) isolated from three surface water sources. The IAST model was formulated for a bi-solute system in which TCE and DOM single-solute uptakes were described by the Langmuir-Freundlich and Freundlich isotherms, respectively. The effect of DOM molecular size and polarity (as measured by XAD 8 resin fractionation) on TCE uptake by preloaded GAC was assessed to identify a reactive fraction of natural water DOM for the purpose of modeling competitive adsorption. Consistent with previous work that identified low molecular weight species as the most reactive with regard to preloading effects (i.e., reducing target compound uptake), the low molecular weight components of the polar (hydrophilic) and nonpolar (hydrophobic) DOM fractions, isolated using ultrafiltration (1 kDa molecular weight cutoff membrane), exhibited significant competitive effects. Furthermore, the effects of these fractions on TCE uptake were similar; therefore, theywere considered together to represent a single "reactive fraction" of DOM. On the basis of this finding, isotherms for the <1 kDa low molecular weight DOM fraction of the whole water were measured, and molar concentrations were computed based on an average molecular weight determined using size-exclusion chromatography. The IAST model was modified to incorporate surface area reduction due to pore blockage by DOM and to reflectthe hypothesis thatTCE molecules can access adsorption sites which humic molecules cannot, thus preventing competition on these sites. The model was calibrated with data for TCE uptake by carbon preloaded with the <1 kDa low molecular weight DOM fraction and was verified by predicting TCE uptake by carbon preloaded with whole natural waters for both constant GAC dose (hence constant DOM loading) and variable GAC dose (hence variable DOM loading) TCE isotherms. Preloading by DOM reduced volume in GAC pores having widths smaller than 1.25 nm (likely accessible only to TCE) to a greater extent than total pore volume, suggesting preferential blockage of micropores. Such preferential pore blockage may explain, in part, why increased DOM loading decreases the fraction of the total surface area on which no competition between TCE and DOM occurs.     

Experimental and molecular mechanics and ab initio investigation of activated adsorption and desorption of trichloroethylene in mineral micropores

This research investigated activated adsorption of a hydrophobic organic contaminant(HOC) in mineral micropores using experimental and molecular modeling techniques. Adsorption of trichloroethylene (TCE) on a silica gel adsorbent was measured using a frontal analysis chromatography technique at atmospheric and elevated fluid pressures. Increasing the fluid pressure yielded increased TCE uptake that was not released upon lowering the pressure back to atmospheric conditions. This showed that the increase in pressure was able to rapidly induce the formation of a desorption-resistant fraction that previous investigations have shown requires months to develop at atmospheric pressure. Grand Canonical Monte Carlo (GCMC) modeling was then used to elucidate the nature of water and TCE behavior within silica micropores. The GCMC modeling showed that molecular scale packing restrictions resulted in pore fluid densities that ranged from 0.28 to 0.78 of those in the bulk solution. The modeling also showed that TCE was able to displace water from hydrophilic mineral pores due to molecular scale packing restrictions. Exothermic isosteric heats for TCE adsorption up to -27 kJ/mol were observed and were greatest in pores of 7 and 8 A. This indicated that TCE adsorption was energetically most favorable in pores that were minimally large enough to accommodate a TCE molecule. The pressure-induced uptake appeared to result primarily from an increase in the packing density in the smallest pores. Ab initio calculations showed that small distortions of a TCE molecule from its low energy conformation require high activation energies. Results from this study indicate that activated adsorption requiring bond angle distortions in the adsorbate may be responsible forthe slow attainment of adsorptive equilibrium of HOCs on microporous solids. Likewise, activated desorption from molecular-sized adsorption sites may contribute to the slow release of HOCs from aquifer sediments.     

Impact of natural organic matter on monochloramine reduction by granular activated carbon: the role of porosity and electrostatic surface properties

Steady-state monochloramine reduction in fixed-bed reactors (FBRs) was quantified on five types of granular activated carbon (GAC) using two background waters-one natural source water (LAW) containing 2.5-3.5 mg/L organic carbon and one synthetic organic-free water (NW). While more monochloramine was reduced at steady-state using NW compared to LAW for each GAC and empty-bed contact time studied, the differences in removal varied considerably among the GACs tested. Physical characterization of the GACs suggested that the degree of interference caused by natural organic matter (NOM) increased with increasing GAC surface area contained within pores greater than 2 nm in width. Acid/base and electrostatic properties of the GACs were not found to be significant in terms of NOM uptake, which indicated that size exclusion effects of the GAC pores overwhelmed the impact of the GAC surface chemistry. Therefore, selection of GAC to limit the impact of NOM on monochloramine reduction in FBRs should be based on pore size distribution alone, with the impact of NOM decreasing with decreasing mesoporosity and macroporosity.     

Enhancement of the performance of activated carbons as municipal odor removal media by addition of a sewage-sludge-derived phase

Two commercial low-cost activated carbons and wood-based char were mixed with dewatered sludge and pyrolized at 950 degrees C. The sludge content on a dry basis was 23%. The obtained composite adsorbents were characterized from the point of view of surface chemistry (pH) and texture (adsorption of nitrogen at its boiling point: surface area, pore volume, pore size distributions). Then hydrogen sulfide breakthrough capacities were measured using the home-designed dynamic test. The results revealed a significant increase in the capacity of the composite adsorbents compared to the unmodified carbons. Moreover, that increase was a few times greater than the hypothetical one predicted when desulfurization performance would be the sum of the contributions of both the sludge-derived and carbon phases. This is attributed to a synergetic effect related to the dispersion of the catalysts and the presence of small pores. Mixing activated carbon provides the active centers for oxidation (coming from sludge) and the developed pore system (from the activated carbon) where products of oxidation can be stored. Moreover, in the hydrophobic pore space the volatile organic compounds present in effluent air from a municipal waste treatment plant can be adsorbed. The selectivity for H2S oxidation, as in the case of pure activated carbon, depends on the pore sizes. Smaller pores lead to a higher yield of sulfuric acid; larger pores lead to a higher yield of sulfur.     

聚丙烯腈基活性碳纤维及其应用

活性碳纤维(ACF)是一种多孔材料,它可以通过物理或化学的方式从液体或气体中吸附多种成分,因此被用于许多应用中,特别是污染气体的净化、有毒气体的吸收、气体的分离、空调的除臭和水的净化等,ACF还可应用于医药领域。活性碳的另一种类粒状活性碳(GAC)同样可应用于以上各领域。尽管ACF的价格很高,但ACF的使用却更为广泛,这主要是因为其蓬松度大、孔径均匀,使它的吸收量和传质系数比粒状活性碳高12～15倍。原材料性能及碳化与活化工艺影响最终ACF的微孔数量和总表面积。由聚丙烯腈(PAN)原丝制得的ACF有着独特的吸收性能和相当高的强度。     

活性炭结构特性对烟气羰基物过滤效率的影响

测定了不同结构特性活性炭对烟气羰基化合物的过滤效率,讨论了活性炭结构特性及烟气化合物性质对烟气过滤效率的影响.结果表明:1)活性炭的过滤效率主要与活性炭的比表面积和微孔容积有关,在用量一定的情况下,微孔含量越多、比表面积越大,则过滤效率越高;2)过滤效率受孔径分布的影响,不同的孔在吸附中所起的作用不同,微孔滞留小分子的能力强,在气相吸附中起主要的吸附作用,同时微孔传质阻力大,在微孔含量接近的情况下,适当增加大中孔等过渡孔有利于化合物的吸附;3)在不显著增加滤嘴吸阻的前提下,活性炭的粒度越小越好;4)过滤效率与化合物的分子量和沸点密切相关,在不受传质阻力限制的情况下,化合物的沸点越高,则过滤效率越高.     

Effect of pore-blocking background compounds on the kinetics of trace organic contaminant desorption from activated carbon

This study examined the effect of pore-blocking (PB) background organic matter, which is known to hinder adsorption kinetics, on the rate of trace contaminant desorption. Adsorption, displaced desorption (DD) and nondisplaced desorption (NDD) kinetic tests were performed using powdered activated carbon (PAC) that was preloaded with natural organic matter (NOM). Since the NOM contained both strongly competing (SC) and PB components, the proposed model separated the contributions of the SC and PB NOM to the overall diffusion coefficient of the target contaminant. By factoring outthe SC NOM contribution, which increases the overall diffusion coefficient it was found that the relationship used to model the effect of PB NOM on adsorption kinetics could also describe desorption kinetics. The results highlighted the substantial influence of competitive SC NOM on the kinetics of adsorption and desorption. SC NOM competition aids contaminant removal by offsetting the undesirable effects of pore blocking on adsorption kinetics. However, for desorption events, PB NOM serves a practical benefit of reducing the rate of release of adsorbed micropollutants, while SC NOM counters that gain by both displacing contaminants and accelerating their diffusion.     

Bisphenol A removal from water by activated carbon. Effects of carbon characteristics and solution chemistry

The present study aimed to analyze the behavior of different activated carbons in the adsorption and removal of bisphenol A (2-2-bis-4-hydroxypheniyl propane) from aqueous solutions in order to identify the parameters that determine this process. Two commercial activated carbons and one prepared in our laboratory from almond shells were used; they were texturally and chemically characterized, obtaining the surface area, pore size distribution, mineral matter content, elemental analysis, oxygen surface groups, and pH of the point of zero charge (pH(PZC)), among other parameters. Adsorption isotherms of bisphenol A and adsorption capacities were obtained. The capacity of the carbons to remove bisphenol A was related to their characteristics. Thus, the adsorption of bisphenol A on activated carbon fundamentally depends on the chemical nature of the carbon surface and the pH of the solution. The most favorable experimental conditions for this process are those in which the net charge density of the carbon is zero and the bisphenol A is in molecular form. Under these conditions, the adsorbent-adsorbate interactions that govern the adsorption mechanism are enhanced. Influences of the mineral matter present in the carbon samples and the solution chemistry (pH and ionic strength) were also analyzed. The presence of mineral matter in carbons reduces their adsorption capacity because of the hydrophilic nature of the matter. The presence of electrolytes in the solution favor the adsorption process because of the screening effect produced between the positively charged carbon surface and the bisphenol A molecules, with a resulting increase in adsorbent-adsorbate interactions.     

Competitive effects of natural organic matter: parametrization and verification of the three-component adsorption model COMPSORB

Natural organic matter (NOM) hinders adsorption of trace organic compounds on powdered activated carbon (PAC) via two dominant mechanisms: direct site competition and pore blockage. COMPSORB, a three-component model that incorporates these two competitive mechanisms, was developed in a previous study to describe the removal of trace contaminants in continuous-flow hybrid PAC adsorption/membrane filtration systems. Synthetic solutions containing two model compounds as surrogates for NOM were used in the original study to elucidate competitive effects and to verify the model. In the present study, a quantitative method to characterize the components of NOM that are responsible for competitive adsorption effects in natural water was developed to extend the application of COMPSORB to natural water systems. Using batch adsorption data, NOM was differentiated into two fictive fractions, representing the strongly competing and pore blocking components, and each was treated as a single compound. The equilibrium and kinetic parameters for these fictive compounds were calculated using simplified adsorption models. This parametrization procedure was carried out on two different natural waters, and the model was verified with experimental data obtained for atrazine removal from natural water in a PAC/membrane system. The model predicted the system performance reasonably well and highlighted the importance of considering both direct site competition and pore blockage effects of NOM in modeling these systems.     

Pesticide adsorption by granular activated carbon adsorbers. 1. Effect of natural organic matter preloading on removal rates and model simplification

The adsorptive removal of periodic spikes of the trace synthetic organic chemicals (SOCs) simazine and asulam from water containing natural organic matter (NOM) was studied in pilot-scale granular activated carbon (GAC) adsorbers over a period of nearly 3 years. The SOC removal percentage obtained at any preloading time and bed depth was independent of the liquid-phase SOC concentration, and equations derived from the ideal adsorbed solution theory and a pore surface diffusion model validated this observation. The pseudo-steady-state SOC removal rate, (dC/dz), at each preloading time and bed depth was therefore first order with respectto the liquid-phase SOC concentration, C. Furthermore, the removal modulus, k, in the resulting SOC removal rate expression was a reflection of the solid-phase concentration of the NOM fraction that interfered with the adsorption of SOCs. Analysis of the removal modulus values indicated that the mass transfer zone of the NOM fraction competing with asulamtraveled more rapidlythrough the GAC adsorber than that competing with simazine. Given the similar molecular sizes of the targeted SOCs, this result was primarily explained by differences in SOC adsorbabilities, where the more weakly adsorbing asulam was less capable of displacing preloaded NOM. Consequently, the NOM fraction competing with asulam constituted a larger percentage of the total NOM than that competing with simazine.     

负载金属改性活性碳纤维材料制备及吸碘性能

以活性碳纤维（ACF）为原料,采用浸渍法制备了负载金属银的改性活性碳纤维（Ag-ACF）,并通过测定吸附材料在77 K的氮气吸附等温线对改性前后材料的比表面积和孔结构进行了表征.研究并比较了活性碳纤维在负载金属银后对碘的吸附性能,结果表明,在活性碳纤维上负载适量的金属银,可以显著地提高活性碳纤维对碘的吸附容量,原因是由于金属银对活性碳纤维比表面积和表面化学性质的修饰,并提高了活性碳纤维对碘的吸附势.     

基于吸附理论分析活性炭对卷烟烟气的吸附

为了解活性炭孔隙结构及被吸附化合物的性质对吸附效率的影响,测定了纯丙酮气体在活性炭上的吸附特性及不同结构活性炭对烟气羰基物的吸附效率。分别用Langmuir模型和D-R模型对活性炭上丙酮气体的吸附数据进行拟合,从模型拟合精度及吸附热预测角度对Langmuir模型及D-R模型进行了比较。进一步分析了吸附效率与模型参数间的关系以及模型参数与活性炭结构和被吸附化合物性质间的关系。结果表明:①与Langmuir模型相比,D-R模型对活性炭上纯丙酮气体吸附数据的拟合相关系数更高,平均相对标准偏差更低,拟合结果更好。②由10-4-3型势函数计算得到活性炭上纯丙酮气体的理论吸附热为17.9 kJ/mol,吸附热较小,说明此吸附以物理吸附为主。D-R模型吸附热预测值为15.8 kJ/mol,与理论计算值较为接近;Langmuir模型吸附热预测值为40.7 kJ/mol,比理论计算值偏大较多。③实现活性炭对不同化合物吸附效率预测的关键是对化合物吸附热的预测。吸附效率主要与吸附温度,活性炭的用量、孔容,化合物的分子量,碰撞直径和能量参数有关。通过分析吸附能可以推断孔径对吸附效率及吸附选择性的影响。     

Modeling effective diffusivity of volatile organic compounds in activated carbon fiber

Volatile organic compounds (VOCs) comprise 67% of total hazardous air pollutants (HAPs) that are emitted by major industrial point sources into the U.S. atmosphere (1). Adsorption by activated carbon fiber (ACF) has been recognized as one of the feasible regenerative control processes to separate and recover VOCs for reuse. Characteristics of VOCs transport in ACFs are required to efficiently design ACF sorption systems. However, extensive resources are spent experimentally obtaining transient sorption data to design adsorption systems. As an alternative, this work develops a new model that predicts effective diffusivities of VOCs into ACFs. The diffusion process is modeled as Knudsen transport into the ACF open pore spaces coupled with activated surface diffusion on the ACF's internal surface area. Temperature and Darken's factors are included in the surface diffusion model to provide corrections for thermodynamic state and deviation from Fick's Law, respectively. Depth of the adsorption potential well is considered as the product of the heat of adsorption of a reference VOC, an adsorption similarity factor, and a surface diffusion energy factor. Introduction of the adsorption similarity factor in the effective diffusivity model is a new concept providing a means to predict effective diffusivity of similar adsorption systems from a reference system. Experimental data from a short length column are used to determine effective diffusivity of acetone in ACF. Results from this diffusivity model are compared to experimental values for the acetone/ACF system to describe the degree of closure between modeled and experimental results.     

Gas-phase formaldehyde adsorption isotherm studies on activated carbon: correlations of adsorption capacity to surface functional group density

Formaldehyde (HCHO) adsorption isotherms were developed for the first time on three activated carbons representing one activated carbon fiber (ACF) cloth, one all-purpose granular activated carbon (GAC), and one GAC commercially promoted for gas-phase HCHO removal. The three activated carbons were evaluated for HCHO removal in the low-ppm(v) range and for water vapor adsorption from relative pressures of 0.1-0.9 at 26 °C where, according to the IUPAC isotherm classification system, the adsorption isotherms observed exhibited Type V behavior. A Type V adsorption isotherm model recently proposed by Qi and LeVan (Q-L) was selected to model the observed adsorption behavior because it reduces to a finite, nonzero limit at low partial pressures and it describes the entire range of adsorption considered in this study. The Q-L model was applied to a polar organic adsorbate to fit HCHO adsorption isotherms for the three activated carbons. The physical and chemical characteristics of the activated carbon surfaces were characterized using nitrogen adsorption isotherms, X-ray photoelectron spectroscopy (XPS), and Boehm titrations. At low concentrations, HCHO adsorption capacity was most strongly related to the density of basic surface functional groups (SFGs), while water vapor adsorption was most strongly influenced by the density of acidic SFGs.     

Predicting adsorption isotherms for aqueous organic micropollutants from activated carbon and pollutant properties

A method based on the Polanyi-Dubinin-Manes (PDM) model is presented to predict adsorption isotherms of aqueous organic contaminants on activated carbons. It was assumed that trace organic compound adsorption from aqueous solution is primarily controlled by nonspecific dispersive interactions while water adsorption is controlled by specific interactions with oxygen-containing functional groups on the activated carbon surface. Coefficients describing the affinity of water for the activated carbon surface were derived from aqueous-phase methyl tertiary-butyl ether (MTBE) and trichloroethene (TCE) adsorption isotherm data that were collected with 12 well-characterized activated carbons. Over the range of oxygen contents covered by the adsorbents (approximately 0.8-10 mmol O/g dry, ash-free activated carbon), a linear relationship between water affinity coefficients and adsorbent oxygen content was obtained. Incorporating water affinity coefficients calculated from the developed relationship into the PDM model, isotherm predictions resulted that agreed well with experimental data for three adsorbents and two adsorbates [tetrachloroethene (PCE), cis-1,2-dichloroethene (DCE)] that were not used to calibrate the model.     

活性炭孔隙结构对活性炭过滤纸吸附性能的影响

用氮气吸附法、扫描电镜对4种不同活性炭(木质活性炭AC1、AC2,煤质活性炭AC3,椰壳质活性炭AC4)的孔隙结构进行表征,通过抄纸方法制备活性炭过滤纸,用亚甲基蓝和苯酚吸附效率表征活性炭过滤纸的吸附性能,研究了活性炭孔隙结构对过滤纸吸附性能的影响.结果表明,两种木质活性炭的比表面积和总的孔容积较高,分别为1054 m2/g、1.165 cm3/g和1125 m2/g、1.083 cm3/g;4种活性炭微孔平均孔径相差不大,但两种木质活性炭的大中孔平均孔径较大;其中,木质活性炭AC2的微孔和大中孔孔容积均较大,孔径在0.64、1.2和2.3 nm附近的孔隙发达,具有较强的选择性吸收能力,用其抄造的过滤纸对亚甲基蓝和苯酚均有较好的吸附效率,3次过滤吸附效率分别为92.2%和93.8%.