Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction)


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The results of single-component herbicide adsorption are presented in Figs. Figures 41 and 42 show the multi- component curves obtained. Tables 23 and 24 present the Freundlich coefcients for the single- and multi-component adsorption isotherms, respectively. All corr- elation coefcients were 0. The Langmuir equation failed to model the data accurately. The pH was measured for every sample before and after equilibration, but no detectable changes were noted.

This is expected at such low adsorbate concentrations. The immediate conclusion drawn from these results is that F is superior to MN for the sorption of highly soluble herbicides. It is also clear that single- component systems show greater adsorption capacity than multicomponent sys- tems. This is expected, although the effect is not as pronounced for MN The adsorption capacity of benazolin, bentazone, imazapyr, and triclopyr on MN is signicantly lower than that of atrazine.

Sweetland [58] postulated that the adsorption of atrazine on MN was predominantly hydrophobic bonding. Benazolin, bentazone, imazapyr, and triclopyr are far more hydrophilic than atrazine, and this explains their lower adsorption capacity. There is no clear indication of the selectivity of the herbicides toward the adsorbents. Figure 41 Multicomponent adsorption isotherms for F pH The molecular dimension of triclopyr is smaller than that of bentazone, so it will diffuse into micropores more easily than bentazone. Figure 42 Multicomponent adsorption isotherms for MN pH Activated Carbons and Carbonaceous Materials 63 The structural formulas of the herbicides reveal that benazolin and bentazone contain aromatic ring p electron systems in their structures as well as nitrogen- containing heterocyclic rings see Table The surface of activated carbon can be visualized as a matrix of organic functional groups containing oxygen.

These groups occur primarily at the edges of broken graphitic and basal planes consisting of large fused aromatic ring systems in a graphite-like structure. Figure 43 Multicomponent adsorption isotherms for F at pH 3. The adsorption force will therefore arise from the dispersion interaction of the p electrons in the respective aromatic systems by a donoracceptor mechanism.

It is well known that the electron density of an aromatic ring is strongly inuenced by the nature of the substituent groups. The chloro Cl group on the aromatic ring of benazolin acts as an electron-withdrawing group, thereby reducing the overall electron density in the p-ring system. Thus, benazolin acts as an acceptor in such complexes and forms stronger donoracceptor complexes with a given donor than bentazone.

The latter has no low-lying acceptor orbitals to form com- plexes with very strong donors. Hence the adsorption capacity of bentazone is lower than that of benazolin. It is also known that the oxygen group dipole moment is the determining fac- tor in the strength of the donoracceptor complex formed.

Carbonyl oxygen has a larger dipole moment than carboxylic acid oxygen and therefore acts as a stronger donor. Thus, it is suggested that benazolin and bentazone molecules adsorb by a donoracceptor complex mechanism involving carbonyl oxygen on the surface of F acting as the electron donor and the aromatic ring of the solute acting as Figure 44 Multicomponent adsorption isotherms for F at pH 3 and Activated Carbons and Carbonaceous Materials 65 the acceptor. Because of the p-system interaction, it is expected that the solute molecules will adsorb in the planar direction.

Similar arguments can be proposed for the adsorption of imazapyr and triclopyr, which contain aromatic rings with a single nitrogen substitution. The selectivity of adsorption on MN is less clear. However, the order changes depending upon pH, as presented in Figs. Triclopyr and bena- zolin are smaller than bentazone and imazapyr, which is thought to be the reason for the comparatively better adsorption of these molecules in the multicomponent system than in the single-component system.

The herbicides adsorb to a greater extent on F with decreasing pH, which suggests that surface charge has a signif- icant role in the adsorption of these particular herbicides. The same trend is gener- ally observed with MN, but to a lesser extent, with the selectivity of adsorption also affected by pH. Figure 45 Multicomponent adsorption isotherms for MN at pH 3. At pH 3, the surface of MN is positively charged, whereas the adsorbates are neutral or partially dissociated.

This will promote adsorption. With increasing pH, the surface of MN becomes negatively charged and the functional groups on the adsorbates will be almost completely dissociated, giving rise to a repulsive effect and thus diminished adsorption. In addition to carboxylic acid functionality, triclopyr and benazolin also contain chlorine groups that enhance the negative charge of the molecules. As a result, the adsorption capacity of these two molecules Figure 46 Multicomponent adsorption isotherms for MN at pH Activated Carbons and Carbonaceous Materials 67 shows the greatest decline with increasing pH.

This explains the changes in the order of selectivity with pH of solution. Therefore, electrostatic interactions such as dipoledipole or hydrogen bonding are likely to play a signicant role in the adsorption of benazolin, bentazone, imazapyr, and triclopyr onto MN No clear trends can be observed from the data, although it is clear that the values for F are consistently lower than those for MN, indicating stronger binding to F The inuence of a high concentration of fulvic acid on the adsorption of trace levels of the herbicides for F and MN is presented in Figs.

Fulvic acid reduces the capacity of the adsorbents for all the herbicides, although the isotherms cannot be modeled by the standard Freundlich or any other equation. The isotherms are of Type II, according to the classical denition. There are few data in the literature that can be used for comparison. The data show reasonable comparison for F The differences are probably due to the different particle size ranges used in the two studies as well as batch variances in the carbon.

The capacity of MN is about one-seventh that of F at an equilibrium olution concentration of 0. The only other relevant adsorption capacity data located in the literature were presented by Hopman et al. The relative molecular mass of bentazone is However, the capacity of MN is just 0. Rapid small-scale column tests are recommended by the American Water Works Association as a protocol for the selection and evaluation of granular acti- vated carbon [60]. Crittenden et al. The experimental rig for minicolumn experiments is illustrated in a simplied ow diagram in Fig.


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Minicolumn experiments were performed using an empty-bed contact time EBCT of approximately 4. The capacity of F is far superior to that of MN because no breakthrough occurred on the carbon column after 28 days of service and nearly L of water treated, whereas the MN column showed instant breakthrough, indicating that the EBCT was too low. The EBCT of the carbon column was reduced and that of the polymeric column increased. The breakthrough curves obtained from the second experiment are shown in Figs.

Breakthrough of the carbon column to the EU legal limit Fig. The selectivity sequence for benazolin and triclopyr is reversed compared to the results obtained in the batch Activated Carbons and Carbonaceous Materials 69 isotherm experiments. This may be due to kinetic effects encountered during the batch equilibrium of 7 days.

During the long duration of the column experiment, triclopyr may have been able to diffuse into the pores to a greater extent than benazolin. The adsorption capacity for benazolin, bentazone, imazapyr, and triclopyr is Figure 49 Simplied ow diagram of column apparatus. The breakthrough curves are shallow, suggesting that the ow rate through the column was too high, thus spreading the mass transfer zone. A slower ow rate and increased EBCT would probably result in a greater lifetime of the columns.

In large-scale practice, an EBCT of 15 min is standard. The concentration used for the breakthrough curves was also exceptionally high, approximately 20 times greater than that found in surface waters. However, the large capacity of the adsorbents and the limited time for experiments necessitated the use of this feed concentration. The minicolumn breakthrough curves in the presence of fulvic acid are presented in Figs.

The introduction of fulvic acid into the herbicide mixture caused instant breakthrough on the F column. MN also showed instant breakthrough, although the reduction in capacity is not as pronounced. Fulvic acid adsorption isotherms presented by Streat et al. Activated Carbons and Carbonaceous Materials 73 molecules adsorb in the mesopores, thus preventing diffusion of the herbicides into the micropore structure of the carbon. Table 28 shows the regeneration efciencies of herbicides from minicolumns using ethanol as eluent. Figures 55 and 56 show the elution curves for F and MN columns, respectively.

The regeneration of MN is virtually complete within 10 BV, because A signicantly greater volume of regenerant is required for F; in all, bed volumes was passed. Figure 55 Elution curves for F at C used in minicolumn runs. Figure 56 Elution curves for MN at Benazolin and imazapyr exhibited two apparent elution maxima, the early peak being attributed to bed equilibration time at the start of the experiment. HPLC chromatograms show a large number of peaks in the early stages of elution that are probably due to impurities in the herbicides and the organic content of the ultrapure water.

The adsorption cycle was repeated for the F column to assess the regen- eration recovery efciency. Figure 57 shows the breakthrough curve in the second cycle. Herbicides start to break through the column between 30, and 60, BV, which is lower than for the virgin carbon. A second regeneration of the column was performed by passing BV of eluent at The recovery efciencies for the second adsorp- tion cycle are presented in Table The gures presented for bentazone and imazapyr represent the recovery efciencies based on the total amount adsorbed after the two cycles.

The gures in parentheses show the recovery efciencies based on the amount adsorbed in the second adsorption cycle only. Using a slightly larger volume or mass of adsorbent, so that the capacity reduction is offset, could compensate for the loss of capacity. In particular, we found that conventional activated carbon can be employed for the removal of heterocyclic aromatic herbicides such as atrazine and also for more water-soluble pesticides that contain hydrophilic carboxylic acid and amino functional groups.

We have presented a rational approach to the repre- sentation of the adsorption isotherms for these species by applying the conventional Langmuir and Freundlich equations. This does not provide a precise description of the adsorption mechanism, which is extremely complex, but does provide us with an adequate basis for the design and development of conventional process equip- ment.

We have found that there is selectivity among the selected herbicides and that it depends on the surface characteristics of the adsorbent material. The underlying principles of adsorption of organic molecules on activated carbon are still the subject of considerable research effort, as can be seen in the comprehensive review of the subject by Radovic et al.

The majority of published work has focused on the sorption of phenol and substituted phenols, and we appear to have performed the most extensive experimental study of herbicides, pesticides, fungicides, etc. Further work is necessary to fully understand the precise mechanisms of adsorption of complex aromatic molecules onto carbon, and this forms the basis of our contin- ued work. From a practical point of view, the regeneration and reactivation of carbon for cyclic use is of equal importance. Here, we nd that the binding energy of aromatics is so strong that arduous regeneration and reactivation techniques are required, i.

Activated Carbons and Carbonaceous Materials 77 cost consideration in the industrial application of these materials in the treatment of water and efuents. To overcome some of these problems, we have embarked on a study of the adsorption of pesticides onto hypercross-linked polymer phases. Our results are most encouraging for atrazine and similar triazine herbicides. We have shown effective adsorption and regeneration of unfunctionalized hypercross- linked hydrocarbon polymers for this case study. Atrazine adsorption in minicol- umns parallels the performance of activated carbon, and moreover we have shown that the binding energies are sufciently low to enable efcient solvent stripping at ambient temperature.

This has already proved an attractive alternative process for the treatment of atrazine-contaminated waters. The adsorption of more highly soluble herbicides with unfunctionalized hydrocarbon hypercross-linked polymers is less favorable, and this has persuaded us to consider tailored polymers for this case study. Further work is in progress to modify the structure of hypercross-linked polymers to remove soluble herbicides without sacricing the favorable low-temperature solvent-stripping regeneration stage. The environment is challenged by other micropollutants: chlorinated hydro- carbons, aliphatic intermediates arising from the chemical industry, and, of course, endocrine disrupters.

Our study of activated carbon and hypercross-linked polymers continues to explore for potential solutions to these important problems. Water pollution arises from many sources. Surface water is contaminated by agricultural runoff, community landlls, polluted runoff, and hazardous waste produced as by-products of manu- facturing. Groundwater is contaminated by leaks of pollutants such as gasoline and methyl tert-butyl ether MTBE from underground storage tanks and the injec- tion of hazardous waste into deep wells.

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The water treatment industry is therefore under pressure to produce a pure product that is free of potentially harmful contaminants. Activated carbon is used primarily for water purication and is essential in water treatment facilities. For example, U. The market for activated carbon remains closely linked to environmental legislation, which has been a primary factor driving growth in key applications for several decades.

ISBN 13: 9780824706012

In particular, legislation has been highly inuential in the choice of treatment procedures used in municipal drinking water and industrial wastewater applications. Activated carbon will continue to nd widespread use in various 78 Streat et al. Activated carbons are especially effective in reducing trace toxic metals such as lead and mercury in water as well as organic compounds such as PCBs and MTBE. They are also likely to reduce contaminants such as antibiotics and other drugs that are now found in drinking water supplies.

New technology is being developed that converts biomass and other carbonaceous wastes and by-products into activated carbon and combustible gas. Bottled water suppliers are being asked to cap off existing multibarrier processes with activated carbon treatment in order to meet the U. FDA revised the existing allow- able levels in bottled water for three residual disinfectantschloramine, chlorine, and chlorine dioxideand disinfectant by-products DBPs , including haloacetic acids HAAs and trihalomethanes THMs. Concurrently, the FDA introduced protocols for testing and enforcement of both source water and nished bottled water products.

In essence, the amendment ensures that the minimum quality of bottled water remains comparable with the quality of public drinking water that meets U. This represents an interesting opportunity for the large-scale application of engineered activated carbons. There are many ongoing studies that implicate a variety of other drinking water contaminants as possible causes of problems with pregnancy or the develop- ing fetus. Engineered activated carbon and advanced formulations could lead to the selective removal of antidepressants and other drugs in poisoning cases.

The admin- istration of activated charcoal AC preparations in acute poisoning is rmly estab- lished as a standard medical treatment because of their ability to adsorb poisons and toxins from the gastrointestinal tract, thereby reducing absorption into the blood- stream of the patient. In commercial preparations, the pore structure and surface chemistry of these carbons have not been tailored to enhance the adsorption of specic drugs.

Our future work is directed toward the development, formulation, and evaluation of novel AC products prepared using synthetic polymer precursors for the adsorption of commonly ingested antidepressants. We propose to make a tailored nonspecic adsorbent with a surface area containing predominantly meso- pores.

The faster kinetics and improved accessibility to the internal surfaces of the AC should result in more efcient use of the adsorbent phase, reducing the dosage amount of carbon that must be controlled and providing signicant benet to the patient. Work is in progress on the manufacture of tailored activated carbons effective in the removal of middle molecular weight and other toxins from blood. Activated Carbons and Carbonaceous Materials 79 Present work could lead to effective and novel adsorbents for the treatment of acute and chronic renal failure and could demonstrate hemo- and biocompa- tibility of uncoated medical adsorbents in the design and manufacture of hemoperfusion columns suitable for augmenting the treatment of renal dialysis patients.

There are two main features of activated carbons that invite their use as biomaterials: the possibility to control, to a large extent, carbon pore structure and thus to control the selectivity and sorption capacity with respect to molecules of dif- ferent sizes and compliance with strict requirements for materials intended for medical use. To ensure that the nal biomaterial grade adsorbent possesses all the requirements for materials used in medicine for detoxication, it is essential that no toxic substances be liberated into blood or any other contacting liquidplasma, lymph, cerebrospinal uid, etc.

The adsorbent must not destroy blood cells or alter the physicochemical properties of perfused solutions; i. In addition, any biomaterial coming into contact with blood must be mechanically robust and must not liberate into the human body or contacting liquids any substance that would cause allergic or pyrogenic reactions. We aim to develop novel nitrogen-containing polymerderived carbons and carbon bers for example, those prepared using polymer precursors including polyacrylonitrile, vinylpyridine, etc.

Their mesopore structure will be optimized to ensure the sorption of high molecular weight substances from biological uids. The biocompatibility of carbon sorbents, i. Water is often referred to as the universal solvent because it dissolves so many substances. Water also contains many materials in suspension and is not particularly selective in what compounds are dissolved or suspended. The water that dissolves our coffee or tea and sugar in the morning or that we use to reconstitute orange juice or an infants formula might have low concentrations of lead from the distri- bution pipes in the home dissolved in it.

If the water is chlorinated it almost cer- tainly contains a few micrograms of chloroform a by-product of the disinfection process. Therefore, the question that needs to be asked is not simply, Does the tap water contain contaminants? The real questions are, What are the contaminants in the water, What are their concentration levels, and Do they pose short- or long- term health risks at those levels?

Finding answers to all these questions is a continu- ing challenge. This chapter has provided some answers to these questions insofar as it relates to processes involving engineered activated carbons and carbonaceous materials. It is our hope that the information presented here will prove helpful to practitioners and moreover stimulate research into the potential of tailored activated carbon for water treatment and environmental remediation. Ofcial Journal of the European Community, , Control: , Streat, M.

Sorption of phenol and para-chloro- phenol from water using conventional and novel activated carbons. Water Res. Adsorption of highly soluble herbicides from water using activated carbon and hypercrosslinked polymers. Part B, Process Safety Environ. Tai, M. Characterisation and sorption performance of a hyper- sol-macronet polymer and an activated carbon.

Rangel-Mendez, J. Removal of cadmium using electrochemi- cally oxidized activated carbon. Part B, , 78, Gabaldon, C. Single and competitive adsorption of Cd and Zn onto granular activated carbon. Bailey P. Application of activated carbon to gold recovery. In: Stanley, G. Sorption of cationic species on acid and air oxidised carbons. Environment Agency, Water Sampling Data, private communication McEnaney, B. Structure and bonding in carbon materials. Puziy, A. Synthetic carbons activated with phosphoric acid. Surface chemistry and ion binding properties. Carbon , 40, Kyotani, T. Control of pore structure in carbon.

Carbon , 38, Tomanek, D. Franklin, R. Proc Roy Soc Lond , A, Byrne, J.

In Porosity in Carbons; Patrick, J. Introductory overview. Activated Carbons and Carbonaceous Materials 81 Matsuda, M. Part A: Polym. Nakagawa, H. Control of micropore formation in the carbonized ion exchange resin by utilising pillar effect. Carbon , 37 9 , Jankowska, H. Chichester, England: Ellis Horwood. Strelko, V. Jr; Malik D. Characterisation of the surface of oxidised carbon adsorbents. Carbon , 40 1 Garten, V. Pure Appl. Puri, B. In: Chemistry and Physics of Carbon. Walker Jr.

Bansal, R. In Active Carbon. Marcel Dekker: New York, Strazhesko, D. Electrophyical properties of active carbons and mechanisms of pro- cesses on their surface Elektrozicheskie svojstva aktivnikh mglej I mekhanizm proces- sov proiskhodyaschik na ikh poverkhnostei. Adsorbtsiya I Adsorbenti Adsorp Adsorb , 4, Radovic, L.


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  • Carbon materials as adsorbents in aqueous solutions. Carbon , 27, Kortum, G. Dissoziationkonstanten organischer sauren in wasseriger losung. In Internationale Vereinigung fur Reine und angewandte Chemie. Butterworths: London, Boehm, H. Chemical identication of functional groups. In Adv Catal; Eley, D. Donnet, J. The chemical reactivity of carbons. Carbon , 6, Mironov, A. Determination of apparent ion exchange constants for oxidised carbons BAU. Adsorbtsiya i Adsorbenti Adsorp Adsorb , 2, Chemical nature of the surface, selective ion exchange and surface complexation on oxidised carbon.

    Adsorbtsiya i Adsorbenti , 1, Electrophysical properties of active carbons and mechanisms of processes on their surface Elektrozicheskie svojstva aktivnikh uglej I mekhanizm processov proiskhodyaschik na ikh poverkhnostei. Adsorbtsiya i Adsorbenti , 4, Ermolenko, I. Adsorption of cadmium by activated carbon cloth: inuence of surface oxidation and solution pH. Adsorption of toxic metals using commercial and modied granular an brous activated carbons. Adsorbtsiya Adsorbenty 11 , Kadirvelu, K. Langmuir , 16, Shim, J. Carbon , 39, Corapcioglu, M. Budinova, T. Seco, A.

    Biniak, S. Langmuir , 15, Mokhosoev, M. USSR , 41, Tomashevskaya, A. In Internationale Verinigung fur reine und ange- wandte Chemie. London: Butterworths, Irving, H. Gerloch, M. In Transition Metal Chemistry. Weinheim: VCH, Winter, M. In d-Block Chemistry. Oxford: Oxford Univ. Press, Martell, A. Stability constants of metal-ion complexes. In Section II: Organic ligands. The Chemical Society: London, Nightingale, E.

    Saha, B. Study of activated carbon after oxidation and subse- quent treatment: characterisation. Part B , 79, Metal sorption performance of an activated carbon after oxidation and subsequent treatment. Newcombe, G. Activated carbon and soluble humic substances: adsorption, desorption, and surface charge effects. Colloid Interface Sci.

    Summers, R. Activated carbon adsorption of humic substances. Het- erodisperse mixtures and desorption. II Exclusion and electrostatic Interactions. Removal of pesticides from water using hypercrosslinked polymer phases: Part 2. Sorption studies. Part B , 76, Speth, T. Water Works Assoc. Removal of pesticides from water using hypercrosslinked polymer phases: Part 3.

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    Mini-column studies and the effect of fulvic and humic substances. Sweetland L. Adsorption of organic micropollutants from water using hypersol- Macronet TM polymers. PhD Thesis, Loughborough Univ. Hopman, R. The prediction and optimization of pesticide removal by GAC ltration. Standardized protocol for the evaluation of GAC.


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    Activated Carbons and Carbonaceous Materials 83 Crittenden, J. Design of rapid small-scale adsorp- tion tests for constant surface diffusivity. Water Pollut. Control Fed.

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    Adsorption of highly soluble herbicides from water using acti- vated carbon and hypercrosslinked polymers. Protect, , 78, Strelko, Jr. The inuence of active carbon oxidation on the preferential removal of heavy metals. As the binding of a solute takes place at the sorption site, the rotational and translational freedom of the solute are reduced.

    Hence, the entropy change DS during sorption is negative. In general, all favorable sorption processes including ion exchange conform to this stipulation, i. Figure 1 illustrates such enthalpy-driven sorption processes. Many synthetic aromatic compounds exhibit acidic characteristics due to the presence of carboxylic, phenolic, and sulfonic acid moieties, and their acidities are often strengthened because of the electron-withdrawing effects of various sub- stituent groups.

    For example, the pK a value i.

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    As a result, PCP, which is extensively used in the wood preservation industry, exists as an anion in contaminated surface water or groundwater at neutral pH. Contrary to other non-ionized hydrophobic aromatic compounds, pentachlorophenate or PCP. Like PCP. Bor Dergisi. Zotero Mendeley EndNote. Anahtar Kelimeler Boron isotope enrichment, continuous annular chromatography, ion exchange resin, inductively coupled plasma-mass spectrometry.

    Construction, Journal of Chromatography, 43, , Journal of Boron , 1 1 , Is this product missing categories? Add more categories. Review This Product. Welcome to Loot. Checkout Your Cart Price. Special order. This item is a special order that could take a long time to obtain. Description Details Customer Reviews "Contains a complete manual with procedures for the implementation and scaling-up of industrial extraction processes.

    Discusses computer-aided molecular design.

    Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction) Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction)
    Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction) Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction)
    Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction) Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction)
    Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction) Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction)
    Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction) Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction)
    Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction) Ion Exchange & Solvent Extraction, Volume 15 (Ion Exchange and Solvent Extraction)

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