WO2006047613A2 - Procede de retrait d'oxyanion des eaux souterraines - Google Patents

Procede de retrait d'oxyanion des eaux souterraines Download PDF

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WO2006047613A2
WO2006047613A2 PCT/US2005/038622 US2005038622W WO2006047613A2 WO 2006047613 A2 WO2006047613 A2 WO 2006047613A2 US 2005038622 W US2005038622 W US 2005038622W WO 2006047613 A2 WO2006047613 A2 WO 2006047613A2
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Prior art keywords
oxyanions
species
organic
group
metal
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PCT/US2005/038622
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English (en)
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WO2006047613A3 (fr
Inventor
Fred S. Cannon
Weifang Chen
Robert Parette
Brian A. Dempsey
Fenglong Sun
Juying Zou
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The Penn State Research Foundation
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Priority claimed from US11/059,733 external-priority patent/US7157006B2/en
Application filed by The Penn State Research Foundation filed Critical The Penn State Research Foundation
Publication of WO2006047613A2 publication Critical patent/WO2006047613A2/fr
Publication of WO2006047613A3 publication Critical patent/WO2006047613A3/fr

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Definitions

  • Th ⁇ present invention relates generally to the a novel activated carbon that is preloaded with at least one ionic organic species and at least one metal or alkaline earth metal, such as a surfactant-iron, and the method of removing an oxyanion, such as arsenic or perchlorate, from a fluid or ground-water.
  • the Penn State team preloaded iron-organic carboxyl complexes onto highly porous activated carbons so as to enhance arsenic removal.
  • This solubilized iron has provided a continuously fresh iron source for complexing arsenic and these complexes have been sorbed and precipitated into the tailored activated carbon.
  • activated carbon systems are durable, rigid, robust, and simple to operate; whereas granular iron systems can crumble and plug, (b) iron, citrate, EDTA (ethylene diamine tetraacetic acid), fatty acids, and activated carbon are all inexpensive and non-toxic materials; (c) activated carbon hosts more surface area and pore volume per bed volume than do inorganic media, (d) The solubilizable iron bed will supply a continuously fresh source of iron to capture arsenic; and it appears that this iron more efficiently captures arsenic than does FeCb coagulation.
  • Perchlorate appears in the groundwater that 10-20 million Americans could drink; and perchlorate might adversely affect people's thyroid gland.
  • the present inventors have uniquely discovered how to both remove perchlorates and other undesirable anions, such as nitrates, chromates, arsenates, and arsenites, and make them available ultimately for destruction by thermally pretreating or chemically preloading granular activated carbons (GACs) prior to use.
  • GACs granular activated carbons
  • Granular ferric hydroxide is a commonly used adsorbent for arsenic removal, but these iron oxide granules can crumble and disintegrate when they experience prolonged use, whereas granular activated carbon does not crumble. Also, after backwashing, there would be significant amount of headloss pressure built up in the GFH system. Although others have loaded iron hydroxide precipitates onto activated carbon, the effectiveness of this iron was minimized because the iron was not distributed within the porous carbon, and thus the higher pounds of iron per pound of As removed was required. The inventors herein have circumvented this limitation by complexing the iron with carboxyl species.
  • Arsenic causes skin cancer at low concentrations. Arsenic exceeds 10 ppb (the new arsenic standard by EPA) in at least 4000 wells that appear in more than 45 U.S. states. Many of these wells service small community water systems.
  • arsenate (+V valence) and arsenite (+111 valence).
  • the arsenate prevails in oxidized or anoxic waters, while the arsenite prevails in reduced waters that also contain hydrogen sulfide.
  • the water pH is between 6.75 and 11.6, the HAsO/ species will prevail in oxidized waters.
  • Iron, citric acid, EDTA, and fatty acids are non-toxic and commonplace in water and foods. No primary drinking water standards exist for any of these species.
  • GAC The large surface area, high pore volume, and rigid structure of GAC renders it an ideal backbone for hosting a considerable quantity of iron-organic carboxyl complexes (or similar metal-organic complexes) that can be dispersed where they are available for oxyanion sorption.
  • solubilized iron and iron- organic tailored GAC have performed considerably better than any other media that the authors herein are aware of.
  • the solubilized iron-tailored GAC system has required only 10-20 pounds of iron to remove a pound of arsenic. This stands considerably better than the 300-4000 Ib Fe / Ib As that the granular iron media have offered.
  • An object of the present invention is to devise a new, cost-effective, and innovative treatment technology for removing oxyanions such as perchlorate and arsenic from drinking water down to 4-10 ppb or less. Provide a durable approach that incurs low capital, operating, and energy costs; while requiring only simple operations, and minimal monitoring.
  • Another object is to develop the most favorable means of preloading GAC with surfactant-iron complexes, so as to greatly extend their arsenic adsorption capacity and bed life.
  • the present invention aims to avoid the abrasion losses and non-durability of conventional granular iron or coated activated alumina processes by adsorbing iron within an activated carbon structure that is rigid and robust.
  • the present invention provides a carbonaceous material that has been loaded or preconditioned with at least one ionic organic species and at least one metal or alkaline earth metal or halide.
  • the present invention also provides a method for diffusing electromagnetic energy comprising passing said electromagnetic energy over a carbonaceous material that has been loaded or preconditioned with at least one ionic organic species and at least one metal or alkaline earth metal or halide.
  • the present invention further provides a method for removing at least one oxyanion from a fluid comprising passing said fluid over a carbonaceous material that has been loaded or preconditioned with at least one ionic organic species and at least one metal or alkaline earth metal.
  • the present invention still further provides a carbonaceous material that has been loaded or preconditioned with at least one ionic organic species or hydroxide species and at least one metal or alkaline earth metal.
  • the present invention also provides a method for diffusing electromagnetic energy comprising passing said electromagnetic energy over a carbonaceous material that has been loaded or preconditioned with at least one ionic organic species and at least one metal or alkaline earth metal or halide.
  • the present invention further provides a method for removing at least one oxyanion from a fluid comprising passing said fluid over a carbonaceous material that has been loaded or preconditioned with at least one ionic organic species or hydroxide species and at least one metal or alkaline earth metal or halide.
  • the present invention further provides a method of removing at least one oxyanion from a fluid comprising passing said fluid through a metal media that dissolves as the fluid passes over it, releasing positive- valent metal species into the fluid, provided that the positive-valent metal species reacts with an oxyanion to form a combined species.
  • the present invention still further provides methods of:
  • (1) removing perchlorate from a fluid comprising: passing said fluid over an activated carbon material selected from the group consisting of: bituminous carbon and lignite carbon that has been loaded with an organic cationic monomer having thereon functional groups wherein said functional groups include at least one selected from the group consisting of: quaternary ammonia, amines, imines, amides, imides, pyrrolic nitrogen, and pyridinic nitrogen; wherein said cationic monomer is selected from the group consisting of: cetylpyridinium chloride (CPC) or bromide (CPB), vinylbenzyltrimethylammonium chloride or bromide and choline chloride or bromide;
  • CPC cetylpyridinium chloride
  • CPB bromide
  • (4) removing perchlorate from a fluid comprising: passing said fluid over an activated carbon material that has been loaded with vinylbenzyltrimethylammonium chloride or bromide; and irradiating with gamma radiation to induced said vinylbenzyltrimethylammonium chloride or bromide to polymerize within the pores of said activated carbon.
  • the present invention also provides a functionalized activated carbon material which exhibits a positive surface charge greater than about 0.09 milliequivalents/gram, as measured in accordance with the Surface Charge Titration Protocol at a pH of 7.5, provided that it also exhibits a BET surface area greater than 850 m 2 /g as measured in accordance with the BET Surface Area protocol; wherein said functionalized activated carbon material is functionalized by loading with cetylpyridinium chloride (CPC) or bromide (CPB), vinylbenzyl ⁇ trimethylammonium chloride or bromide and choline chloride or bromide.
  • CPC cetylpyridinium chloride
  • CPB bromide
  • the present invention uses activated carbon that is derived from parent materials that include bituminous coal, lignite coal, anthracite coal, wood, coconut shells, lignocellulosic material, peat, carbonaceous textiles, chemical vapor deposits, preformed plastics, preformed polymeric resins, and carbon aerosols.
  • parent materials that include bituminous coal, lignite coal, anthracite coal, wood, coconut shells, lignocellulosic material, peat, carbonaceous textiles, chemical vapor deposits, preformed plastics, preformed polymeric resins, and carbon aerosols.
  • Figure 1 shows rapid small-scale column tests (RSSCT) for arsenic with oxidized and iron-loaded wood-based carbons.
  • Figure 2 shows Bed Volumes to Breakthrough for wood-based (PICA) and bituminous-based (Ultracarb) activated carbons that were preconditioned with nitric acid and sulfuric acid oxidation, and then preloaded with ferric or ferrous iron. Influent water contained 50-60 ppb arsenic.
  • PICA wood-based
  • Ultracarb bituminous-based
  • FIG. 3 shows the Adsorption Isotherm of Citrate-Fe preloaded
  • FIG. 4 shows RSSCT's of virgin and Citrate-Fe preloaded GAC.
  • Figure 5 shows RSSCT's of EDTA-Fe and Palmitic acid-Fe preloaded GAC.
  • Figure 6 shows RSSCT's of Fe-oxide coated GAC.
  • Figure 7 shows RSSCT's of Citrate-Fe preloaded GAC augmented with soluble iron.
  • Figure 8 shows RSSCT's of Citrate-Fe (1.07), augmented with soluble iron (duplicate).
  • Figure 9 shows Adsorption of Perchlorate from Redlands water onto cetylpyridinium chloride-tailored GAC.
  • Figure 10 shows Adsorption of perchlorate from Redlands water onto cationic surfactant preloaded wood-based and coconut based GACs.
  • Figure 11 shows Adsorption of perchlorate from University Park Tap Water spiked with 800 ppb perchlorate.
  • the present invention relates to a unique process for removing perchlorate, arsenic and/or other anions from water with activated carbon that has been tailored with metal salt and/or organic complex preloading and/or thermal pretreatment.
  • the organic cation polymers and cationic monomers were dissolved in an aqueous solution and recirculated through a bed of activated carbon for a given time period.
  • the cations can also be loaded via a batch process. Background ionic strength and pH can be adjusted to optimize loading conditions.
  • the pre-loading of these materials onto the activated carbon was at ambient temperature and pressure.
  • Slurry pH represented the pH of a10% slurry of the GAC.
  • Surface charge distribution was appraised by a DL53 Metier Toledo automatic titrator, by first elevating a sample pH to 10-10.5, and then dosing in incremental amounts of acid, as described below.
  • Organic Cation Preloading has also dramatically enhanced perchlorate removal to below 4 ppb.
  • the functional group is at least one selected from: quaternary ammonia, amines, imines, amides, imides, pyrrolic nitrogen, or pyridinic nitrogen.
  • the cationic monomer is at least one selected from: octyltrimethyl- ammonium bromide or chloride, decyltrimethylammonium bromide or chloride, dodecyltrimethylammonium bromide or chloride, tetradecyltrimethylammonium bromide or chloride, tributylheptylammonium bromide or chloride, cetylpyridinium chloride (CPC) or bromide (CPB), ammonium bromide or chloride, diallyldimethlammonium bromide or chloride, acrylamide, domiphen bromide or chloride, tetradecylammonium bromide or chloride, (4-nitrobenzyl)trimethylammonium bromide or chloride, arvinylbenzyl-trimethylammonium bromide or chloride, benzoylcholine bromide or chloride, acetylthiochloine iodide, metha
  • CPC Cetylpyridinium chloride
  • CPB bromide
  • the present invention provides a method of removing perchlorate from a fluid which includes the step of passing the fluid over an activated carbon material selected from: bituminous coal, lignite coal, anthracite coal, wood, coconut shells, lignocellulosic material, peat, carbonaceous textiles, chemical vapor deposits, preformed plastics, preformed polymeric resins, that has been loaded with cationic monomer cetylpyridinium chloride (CPC) or bromide (CPB) or other surfactants as listed above.
  • an activated carbon material selected from: bituminous coal, lignite coal, anthracite coal, wood, coconut shells, lignocellulosic material, peat, carbonaceous textiles, chemical vapor deposits, preformed plastics, preformed polymeric resins, that has been loaded with cationic monomer cetylpyridinium chloride (CPC) or bromide (CPB) or other surfactants as listed above.
  • the present invention still further provides a functionalized activated carbon material which exhibits a positive surface charge greater than about 0.09 milliequivalents/gram, as measured in accordance with the Surface Charge Titration Protocol at a pH of 7.5, provided that it also exhibits a BET surface area greater than 850 m 2 /g as measured in accordance with the BET Surface Area protocol; wherein the activated carbon material is functionalized by loading with cetylpyridinium chloride (CPC) or bromide (CPB).
  • CPC cetylpyridinium chloride
  • CPB bromide
  • the present invention further provides a method for removing perchlorate from a fluid including the step of passing the fluid over an activated carbon material that has been loaded with cetylpyridinium chloride (CPC) or bromide (CPB) or another surfactant as listed above.
  • CPC cetylpyridinium chloride
  • CPB bromide
  • the present invention also provides a carbonaceous material that has been loaded or preconditioned with at least one ionic organic species and at least one metal or alkaline earth metal or halide.
  • preconditioning in the context of the present invention refers to creating an ionic organic species that is affixed to the carbon surface.
  • ionic organic species include solid carbon carboxyl species, solid carbon hydroxyl species, solid carbon sulfonate species, solid carbon phenolic species, solid carbon lactone species, solid carbon amine species, and solid carbon pyridenium species.
  • loading in the context of the present invention refers to coordinating a metal or alkaline earth metal or halide with an ionic organic species and thereafter concurrently sorbing the two onto carbon surfaces from a fluid phase.
  • the ionic organic species is preferably at least one selected from: fatty acids, surfactants, organic carboxyl species, organic sulfonate species, organic hydroxyl species, organic phenolic species, organic lactone species, and organic amine species.
  • the metal or alkaline earth metal is at least one selected from: iron, manganese, aluminum, copper, lead, zinc, calcium, and magnesium.
  • the metal or alkaline earth metal or halide is at least one selected from: sodium, potassium, lithium, rubidium, cesium, beryllium, magnesium, strontium, barium, radium, titanium, zirconium, vanadium, niobium, chromium, osmonium, cobalt, nickel, palladium, platinum, cadmium, boron, gallium, indium, silicon, tin, arsenic, lanthanides, and actinides.
  • the metal or alkaline earth metal is at least one selected from: silver, gold, and mercury.
  • Another embodiment of the present invention pertains to a method for diffusing electromagnetic energy including passing the electromagnetic energy over a carbonaceous material that has been loaded with at least one ionic organic species and at least one metal or alkaline earth metal.
  • the electromagnetic energy is preferably at least one selected from radar and sonar.
  • Still yet another embodiment of the present invention is a method for removing at least one oxyanion from a fluid including passing the fluid over a carbonaceous material that has been loaded with at least one ionic organic species and at least one metal or alkaline earth metal.
  • the oxyanion is at least one selected from arsenic oxyanions, chlorine oxyanions, phosphate oxyanions, nitrogen oxyanions, osmium oxyanions, gallium oxyanions, rubidium oxyanions, and technetium oxyanions.
  • the present invention also provides a carbonaceous material that has been loaded with at least one ionic organic species or hydroxide species and at least one metal or alkaline earth metal.
  • the ionic organic species or hydroxide species is at least one selected from: fatty acids, surfactants, organic carboxyl species, organic sulfonate species, organic hydroxyl species, organic phenolic species, organic lactone species, organic amine species, or hydroxide species.
  • the metal or alkaline earth metal is at least one selected from: iron, manganese, aluminum, copper, lead, zinc, calcium, and magnesium.
  • the metal or alkaline earth metal is at least one selected from: sodium, potassium, lithium, rubidium, cesium, beryllium, strontium, barium, radium, titanium, zirconium, vanadium, niobium, chromium, osmonium, cobalt, nickel, palladium, platinum, cadmium, boron, gallium, indium, silicon, tin, arsenic, lanthanides, and actinides.
  • the metal or alkaline earth metal is at least one selected from: silver, gold, and mercury.
  • the carbonaceous material is derived from at least one selected from the group of bituminous coal, lignite coal, anthracite coal, coconut shells, wood, lignocellulosic material, peat, and carbonaceous textiles.
  • the present invention also provides a method for diffusing electromagnetic energy including passing the electromagnetic energy over a carbonaceous material that has been loaded with at least one ionic organic species and at least one metal or alkaline earth metal.
  • the electromagnetic energy is at least one selected from radar and sonar.
  • the present invention also provides a method for removing at least one oxyanion from a fluid including passing the fluid over a carbonaceous material that has been loaded with at least one ionic organic species or hydroxide species and at least one metal or alkaline earth metal.
  • the metal or alkaline earth metal is at least one selected from: iron, manganese, aluminum, copper, lead, zinc, calcium, and magnesium.
  • the oxyanion is at least one selected from arsenic oxyanions, chlorine oxyanions, phosphate oxyanions, nitrogen oxyanions, osmium oxyanions, gallium oxyanions, rubidium oxyanions, and technetium oxyanions.
  • the fluid is also passed through a metal media that dissolves as the fluid passes over it, releasing positive-valent metal species into the fluid, provided that the positive-valent metal species reacts with an oxyanion to form a combined species.
  • the metal is at least one selected from: iron, manganese, aluminum, copper, lead, zinc, and titanium.
  • the oxyanion is at least one selected from arsenic oxyanions, chlorine oxyanions, phosphate oxyanions, nitrogen oxyanions, osmium oxyanions, gallium oxyanions, rubidium oxyanions, and technetium oxyanions.
  • the present invention also provides a method for removing at least one oxyanion from a fluid including passing the fluid through a metal media that dissolves as the fluid passes over it, releasing positive-valent metal species into the fluid, provided that the positive-valent metal species reacts with an oxyanion to form a combined species.
  • the metal is one selected from: iron, manganese, aluminum, copper, lead, zinc, and titanium.
  • the oxyanion is at least one selected from arsenic oxyanions, chlorine oxyanions, phosphate oxyanions, nitrogen oxyanions, osmium oxyanions, gallium oxyanions, rubidium oxyanions, and technetium oxyanions.
  • the fluid also passes over a carbonaceous material that has been loaded with at least one ionic organic species or hydroxide species and at least one metal or alkaline earth metal.
  • the metal or alkaline earth metal is at least one selected from: iron, manganese, aluminum, copper, lead, zinc, calcium, and magnesium.
  • the oxyanion is at least one selected from arsenic oxyanions, chlorine oxyanions, phosphate oxyanions, nitrogen oxyanions, osmium oxyanions, gallium oxyanions, rubidium oxyanions, and technetium oxyanions.
  • the cation-loaded activated carbon material or functionalized carbonaceous material is capable of treating the fluid containing at least 50 ppb of the perchlorate, such that perchlorate is removed from the fluid to an amount of less than 4 ppb for at least 3,000 bed volumes.
  • Another embodiment according to the present invention includes a method for removing anionic contaminants (e.g., arsenates, arsenites, nitrates, and chromates) from a fluid including: passing the fluid over a cation-loaded activated carbon material or functionalized carbonaceous material.
  • anionic contaminants e.g., arsenates, arsenites, nitrates, and chromates
  • Still another embodiment according to the present invention relates to a functionalized activated carbon material which exhibits a positive surface charge greater than about 0.09 milliequivalents/gram, as measured in accordance with the Surface Charge Titration protocol at a pH of 7.5, provided that it also exhibits a BET surface area greater than 850 m 2 /g as measured in accordance with the BET Surface Area protocol.
  • Yet another embodiment of the present invention includes a functionalized carbonaceous material which exhibits a positive surface charge greater than about 0.09 milliequivalents/gram, as measured in accordance with the Surface Charge Titration protocol at a pH of 7.5, provided that it also exhibits a BET surface area greater than 850 m 2 /g as measured in accordance with the BET Surface Area protocol, wherein the functionalized activated carbon material is formed by: (a) loading the carbonaceous material with an organic cation polymer or cationic monomer;
  • aqueous oxyanions such as H 2 ASO 4 " or HAsO 4 2"
  • undergo a ligand exchange reaction with iron species on the carbon surface One of our goals was to find methods that facilitated the loading of as much iron as possible onto the carbon surface, while also rendering as much of this iron to be surface-exposed in a manner that allowed it to sorb arsenic.
  • pore distribution and specific surface area of these granular activated carbons were determined via ASAP 2010 (Micromeritics, USA), in accordance with US Patent 6,881 ,348.
  • Activated carbon employed included Ultracarb from USFilter- WESTATES, and three wood-based carbons, NORIT C-Grain (from NORIT), Nuchar (from Westvaco) and PICASOL carbon (from PICA). This tailoring protocol could be accomplished with activated carbons derived from lignite coal, bituminous coal, anthracite coal, wood, coconut shells, lignocellulosic materials, polymers, plastics, ion exchange resins, chemical vapor deposition of gaseous carbon, and liquid phase coagulation of dissolved organic carbon.
  • ICP Inductively Coupled Plasma
  • IC-ICP- MS ion chromatography-high resolution-inductively coupled plasma- mass spectrophotometry
  • This instrument is a Finnigan MAT ELEMENT High Resolution ICP-MS with a Merchantek, Nd-YAG Laser. When in normal resolution mode, it can monitor arsenic to below 1 ppb resolution.
  • the arsenic-containing ground water originated from the well of the Cool Sandy Beach Community Water System of Rutland, MA.
  • the perchlorate-containing groundwater originated from the Texas Street well in Redlands, CA, or from University Park, PA groundwater that was spiked with perchlorate.
  • the total Arsenic in the Rutland, MA groundwater was 50-55 ppb; and total perchlorate concentration in the Redlands, CA groundwater was 50-60 ppb. Characteristics of the Rutland groundwater were presented in Table 1.
  • Oxidation by nitric acid 2 g of carbon (US mesh 200 ⁇ 400) was mixed with 100 mL of 70% nitric acid for 1 hour at room temperature.
  • the activated carbon was first oxidized by adding a mixture of 15 g GAC and 10.5 g potassium permanganate to a mixture of 75 mL nitric acid and 100 mL acetic anhydride.
  • the GAC was stirred for one hour and then the GAC/KMnO 4 /HNO 3 /acetic anhydride mixture was dumped into 1.5 L of distilled water.
  • the oxidized GAC was then washed several times with distilled water until the pH of the wash solution neared the pH of the distilled water.
  • Oxidized carbons were thoroughly washed by distilled water to remove acid adsorbed before iron loading in 1 L of 10 "2 M iron solution made from ferric chloride. In some cases, the loading solution (10 "2 M) was made from Ferrous chloride.
  • the reason for using Ferrous iron (Fe(II)) for loading is that Fe(III) hydrolyzes to form hydroxides when the pH is higher than 3. Iron (hydr)oxide cannot diffuse easily into the internal pores of GAC. Carbon and iron solution mixture was put on a shaking table for 24 hours during the loading process.
  • Carbons used in these oxidation plus iron loading tests included Ultracarb from US Filter (Bituminous coal carbon) and three wood-based carbons, NORIT C-Grain (from NORIT), Nuchar (from Westvaco) and PICASOL carbon (from PICA). Other parent sources of activated carbon could be used, as listed above. Table 2 lists the results of iron loading.
  • Results shown in Table 2 indicate that carbon oxidation was generally very effective for iron loading.
  • Nitric acid/sulfuric acid oxidation is better than oxidation by nitric acid alone.
  • the nitric acid/sulfuric acid oxidized NORIT C-Grain carbon was able to facilitate an iron loading as high as 15%.
  • Ultracarb that was oxidized via protocol 3 showed an iron loading of 7.6 to 7.99 %.
  • Figures 1 and 2 are the column test result for arsenic removal by those three carbons. Breakthrough bed volume was set as the bed volume of water passed through column until the As concentration from the effluent first reaches 10 ppb. Figure 1 and 2 shows that oxidized PICA and Ultracarb carbon showed the highest capacity for arsenic removal.
  • the inventors also conducted tests to determine how much iron could be preloaded onto activated carbon when the iron was complexed with organic carboxyl species in the water phase be sorption into the activated carbon.
  • activated carbon has a high surface area, if we can cover this surface with a fine film of iron, then we can get the most efficient removal of arsenic, on the basis of pounds of iron required per pound of arsenic removed.
  • we pre-loaded activated carbon with fatty acid or chelating agent-iron complexes we could increase the GACs capacity to adsorb iron, and hence arsenic.
  • Citrate acid, L-Glutamic acid and EDTA were tested during the period.
  • ferric ammonia citrate was used directly for iron loading instead of citric acid plus ferric chloride.
  • One-step protocol A predetermined amount of carbon was added to a fatty acid or chelating agent-iron solution in which the acid (or chelating agent) and iron (by ferric chloride) had a 1 :1 molar ratio. The carbon and solution mixture was then put on a shaking table for 2 days.
  • the Fe-oxide coated GAC got an extraordinally high iron loading result of 33.6%.
  • Citrate-Fe-Mg (0.81) 5*10- 4 0.81%
  • the carbon used in this test is wood based carbon.
  • EXAMPLE 4 As shown in Figure 3, isotherm results are illustrated.
  • a prescribed amount of activated carbon (10 - 100 mg) was added to 50 ml_ arsenic-spiked Rutland groundwater (Total arsenic concentration is 550 ppb).
  • the water pH had been adjusted to 6 with 0.1 M HCI.
  • the mixtures were then put on the horizontal shaking table and shaken at 120-150 rpm for 48 hours. Then the resulting solution was analyzed for arsenic.
  • the results fit with both Freudlich and Langmuir Isotherm; and the R 2 value is slightly higher with Langmuir Isotherm.
  • the highest q e value obtained is 1.8 mg /g, which was obtained at a Ce value of 178 ppb.
  • RSSCT's Arsenic breakthrough behaviors for virgin carbon and various kinds of tailored carbon are explored with rapid small-scale column tests (RSSCT's), and results are illustrated in Figures 4-6. All RSSCT's herein were operated with the pH adjusted by HCI to pH 6, except as noted otherwise, i.e. except for the citrate-Fe-Mn (1.36) preloaded carbon (pH 5.0).
  • the organic carboxyl species could include many other species that have a carboxyl functional or iron-complexing group.
  • the adsorbent was filtered out and washed with distilled water until no color in the washing water could be discerned.
  • the tailored carbon was dried at 104 0 C overnight and stored in desiccators before use. Sometimes when preloading GAC with organic carboxyl-Fe, the carbon was loaded in two steps-the organic carboxyl species in the first step, and iron in the second step.
  • a wood based activated carbon (#60 X 80) was first soaked in a mixture of concentrated nitric acid and sulfuric acid for 1 day. The carbon were then filtered and dried at 104 0 C for 24 hours. After that, the carbon was kept in a vacuum desiccator until it was used for iron loading. In the loading process, 0.3 gram carbon was added to 25 mL 2M Fe (N ⁇ 3 ) 3 -2H 2 ⁇ solution and agitated on a shaking table for 48 hours. The carbon was then filtered out and washed with distilled water.
  • Table 6 Iron content and Breakthrough bed volume of GACs.
  • the authors also sought to determine whether performace could be enhanced by solubilizing iron into the Rutland groundwater just before it flowed through the GAC bed.
  • the GAC was preloaded with citrate-Fe to an iron content of 1.07%, and this preloaded GAC was inserted into the mini-column chamber.
  • galvanized steel fittings were placed before and after this mini-column; and the groundwater pH was adjusted to pH 6.0.
  • a revised 3-step leaching protocol was introduced here (1) 1 N ammonium acetate (2) 3N hydrochloride (3) 3N nitric acid.
  • arsenic mainly adsorbed onto activated carbon, but it was the iron that dissolved from the fittings and was subsequently captured by the activated carbon that adsorbed most of the arsenic.
  • the variable redox level of the carbon, iron, and sulfur in the GAC may have aided this arsenic removal within the GAC bed.
  • Iron content is an important parameter to look at when choosing the arsenic removal adsorbents. But it's not always true that higher iron content media will perform better than the low iron content media.
  • Palmitic acid-Fe (0.54) GAC contained half the iron content of the Citrate-Fe-Mn (1.36) GAC, but they exhibited very similar arsenic breakthrough curves: they both reached 10 ppb breakthrough at 5500 bed volumes.
  • Fe- oxide (33.6) GAC hosted a 60 times higher iron content than did Palmitic acid-Fe (0.54) GAC; whereas it exhibited 10 ppb arsenic breakthrough at 28,000 BV (i.e. about 5 times longer). What's important is that the iron avails itself to the arsenic sorption.
  • Palmitic acid-Fe GAC (0.54) 0.54 6 9.1 12.2
  • the inventors considered means of chemically linking quaternary ammonium groups onto the surface of activated carbon. This can be achieved by several methods.
  • quaternary ammonium groups can be chemically linked to the surface of the activated carbon by several methods.
  • Halogen atoms F, Cl, I 1 Br, At
  • Halogenation of the activated carbon can be accomplished by treating the activated carbon with the elemental halogens or by halogen containing chemicals (such as chloromethyl ethyl ether, 3,3 bischloromethyl benzoyl peroxide, or thionyl chloride).
  • the introduced halogen group can then be reacted with a tertiary amine (such as trimethylamine) to create a quaternary ammonium group on the activated carbon.
  • the activated carbon can also be nitrated (introduction of -NO 2 groups) or aminated (introduction Of -NH 2 groups).
  • Nitro groups (-NO 2 ) groups can be introduced onto carbon compounds through reactions with fuming nitric acid and acetic anhydride or nitrogen dioxide gas. Nitro groups can then be converted to amine groups (-NH 2 ) by several processes including reaction with hydrazine hydrate or sodium hydrosulfite and ammonium hydroxide. Amine groups can be directly introduced onto the activated through processes such as treatment in ammonia gas or ammonium hydroxide.
  • the -NH 2 groups on the carbon surface can then be reacted with a chemical containing two halogen atoms such as 1 ,2- Dichloroethane.
  • One of the chlorine atoms can react with the amine group to create a N-C linkage and HCI.
  • the remaining halogen atom, in this case Cl can then be reacted with a tertiary amine (as described above) to form the quaternary group.
  • Amine groups can also be converted to a quaternary group via stepwise reaction with alkyl halides.
  • Carboxyl and phenol groups on the carbon surface can be used as a starting point for the creation of quaternary ammonium groups on the activated carbon surface. These acidic groups can easily be introduced on the surface of activated carbon via numerous oxidation processes. Carboxyl or phenol groups can then be reacted with a chemical containing a terminal acyl chloride, hydroxyl, or amine group. For example, a carboxyl group can be reacted with the hydroxyl group of choline chloride (which contains a quaternary ammonium group on the other end ((CH 3 )3N(CI)CH 2 CH 2 ⁇ H) to form an ester linkage between the carbon surface and the chlorine chloride.
  • the terminal amine group on a chemical such as tetraethylenepentamine (NH 2 CH 2 CH 2 NHCH 2 CH 2 ⁇ NH) can be reacted with a surface carboxyl group. These amine sites can then serve as a place in which quaternary ammonium groups can then be linked as described above.
  • acyl chloride groups can also be converted to acyl chloride groups by reaction with thionyl chloride.
  • the acyl chloride groups that are introduced onto the activated carbon surface can then be reacted with a chemical containing a terminal carboxyl or amine group. Quaternary groups can then be added following additional steps described above.
  • Acyl chloride groups can also serve as a site in which quaternary ammonium compounds can be chemically linked via a cationic polymerization reaction.
  • the acyl chloride group is first reacted with silver perchlorate. This reaction exchanges the chloride atom on the activated carbon surface with perchlorate and silver chloride is formed.
  • Polymerization of a vinyl monomer can then occur at the site.
  • Examples of chemicals that contain or through additional steps could contain a quaternary ammonium group are vinylbenzyltrimethylammonium chloride, polyvenylbenzyltrimethylammonium chloride, diallyldimethyl- ammonium chloride, benzylchloride, and styrene. They could also include these same species where bromide, fluoride, or iodide is the carrier halide rather than chloride.
  • the same cationic polymerization reactions can also be performed at a benzylium perchlorate site.
  • Cationic polymerization can also be used to link a chemical such as acrylic acid, which can then be used as sites to which iron can be adsorbed for subsequent arsenic removal.
  • Aldehyde groups on the activated carbon surface can first be converted to a tertiary amine, and then finally to a quaternary ammonium group by reaction with an alkyl halide.
  • Quaternary ammonium compounds lacking a large hydrophobic tail but containing a polymerizable carbon-carbon double bond such as vinylbenzyltrimethylammonium chloride can also be pre-loaded onto activated carbon. These chemicals can be then induced to polymerize within the pores of the activated carbon by methods such as gamma radiation. This will make it harder for individual monomers to desorb from within the pores of the activated carbon.
  • Cetylpyridinium chloride can also be used to pre-load activated carbon to provide a means to increase the capacity for perchlorate.
  • CPC cetylpyridinium chloride
  • 0.25 grams of cetylpyridinium chloride (CPC) was pre-loaded onto SAI GAC by recirculating a 0.4% solution of CPC through a RSSCT column for 2 days. Redlands water (75 ppb CIO 4 " ) was then passed through an RSSCT column containing the CPC-tailored GAC at a flow rate simulating an 8- minute empty bed contact time with full size grains. This GAC was able to remove perchlorate to below detectable levels for 27,000 bed volumes. These results are shown in Figure 9 and compare favorably among the cationic surfactants used.
  • TEPA tetraethylene- pentamine
  • VBTC vinylbenzyltrimethylammonium chloride
  • the GAC modified by TEPA was first oxidized by adding a mixture of 15 g GAC and 10.5 g potassium permanganate to a mixture of 75 mL nitric acid and 100 mL acetic anhydride. The GAC was stirred for one hour and then the GAC/KMnO 4 /HN ⁇ 3 /acetic anhydride mixture was dumped into 1.5 L of distilled water. The oxidized GAC was then washed several times with distilled water until the pH of the wash solution neared the pH of the distilled water.
  • TEPA tetraethylene- pentamine
  • VBTC vinylbenzyltrimethylammonium chloride
  • TEPA + 1 ,2-DCA + TMA activated carbon was able to produce results that appeared to be on par with the virgin GAC, as shown in Figure 11.
  • GAC was also pre-loaded with venylbenzyltrimethylammonium chloride (VBTC) (0.14 grams per gram GAC).
  • VBTC-tailored GAC was then subjected to 4 kGy 60 Cobalt irradiation in an attempt to polymerize the material within the pores of the GAC, making it more difficult for the smaller VBTC molecule to desorb from the GAC in subsequent testing.
  • This VBTC modified GAC was able to treat approximately 3000 BV of the 800 ppb spiked University Park tap water prior to the detection of perchlorate in the effluent (Figure 11). This represents a four-fold increase in comparison to the parent conventional GAC. Subsequent leaching tests indicated that at least some of the VBTC had not fully polymerized to the activated carbon surface.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Treatment Of Sludge (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

L'invention concerne un matériau carboné qui a été chargé avec au moins une espèce organique ionique ou une espèce hydroxyde et au moins un métal ou un métal alcalino-terreux. L'espèce organique ionique ou l'espèce hydroxyde est au moins choisie dans le groupe : acides gras, agents de surface, espèce de carboxyle organique, espèce de sulfonate organique, espèce d'hydroxy organique, espèce phénolique organique, espèce de lactone organique, espèce d'amine organique, ou espèce d'hydroxyde.
PCT/US2005/038622 2004-10-25 2005-10-25 Procede de retrait d'oxyanion des eaux souterraines WO2006047613A2 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US62199304P 2004-10-25 2004-10-25
US60/621,993 2004-10-25
US11/059,733 2005-02-17
US11/059,733 US7157006B2 (en) 2001-06-08 2005-02-17 Method for perchlorate removal from ground water
US69006505P 2005-06-13 2005-06-13
US60/690,065 2005-06-13

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WO2006047613A2 true WO2006047613A2 (fr) 2006-05-04
WO2006047613A3 WO2006047613A3 (fr) 2006-09-28

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101823799B (zh) * 2009-03-06 2012-08-15 昆山工研院华科生物高分子材料研究所有限公司 一种处理酸性含氟废水的方法
CN105467041A (zh) * 2016-01-28 2016-04-06 吴江华衍水务有限公司 一种改进的水中总有机溴的测定方法
US9975787B2 (en) 2014-03-07 2018-05-22 Secure Natural Resources Llc Removal of arsenic from aqueous streams with cerium (IV) oxide compositions
US20210179449A1 (en) * 2018-08-14 2021-06-17 Evoqua Water Technologies Llc Modified Activated Carbon and Methods of Using Same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9233863B2 (en) 2011-04-13 2016-01-12 Molycorp Minerals, Llc Rare earth removal of hydrated and hydroxyl species

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6881348B2 (en) * 2001-06-08 2005-04-19 The Penn State Research Foundation Method for perchlorate removal from ground water

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6881348B2 (en) * 2001-06-08 2005-04-19 The Penn State Research Foundation Method for perchlorate removal from ground water

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101823799B (zh) * 2009-03-06 2012-08-15 昆山工研院华科生物高分子材料研究所有限公司 一种处理酸性含氟废水的方法
US9975787B2 (en) 2014-03-07 2018-05-22 Secure Natural Resources Llc Removal of arsenic from aqueous streams with cerium (IV) oxide compositions
US10577259B2 (en) 2014-03-07 2020-03-03 Secure Natural Resources Llc Removal of arsenic from aqueous streams with cerium (IV) oxide compositions
CN105467041A (zh) * 2016-01-28 2016-04-06 吴江华衍水务有限公司 一种改进的水中总有机溴的测定方法
US20210179449A1 (en) * 2018-08-14 2021-06-17 Evoqua Water Technologies Llc Modified Activated Carbon and Methods of Using Same
US12024442B2 (en) * 2018-08-14 2024-07-02 Evoqua Water Technologies Llc Modified activated carbon and methods of using same

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