(12) Patent Application Publication (10) Pub. No.: US 2008/0302728A1 Wang Et Al

US 20080302728A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2008/0302728A1 Wang et al. (43) Pub. Date: Dec. 11, 2008

(54) SULFUR-IMPREGNATED ORGANOCLAY (22) Filed: Jun. 5, 2007 MERCURY AND/OR ARSENC ON REMOVAL MEDIA Publication Classification (51) Int. Cl. (75) Inventors: Zhen Wang, Hoffman Estates, IL CO2F I/28 (2006.01) (US); Robert Abraham, BOLD IS/00 (2006.01) Bolingbrook, IL (US) BOI 20/2 (2006.01) Correspondence Address: (52) U.S. Cl...... 210/688; 210/690: 502/80 MARSHALL, GERSTEIN & BORUN LLP 233 S. WACKER DRIVE, SUITE 6300, SEARS (57) ABSTRACT TOWER The use of a Sulfur-impregnated organoclay provides a mer CHICAGO, IL 60606 (US) cury or arsenic removal media having increased reactivity, stability, and mercury removal ability. The Hg/AS removal (73) Assignee: AMCOL International media described herein is prepared by impregnating an orga Corporation, Arlington Heights, IL nophilic clay with elemental (free state) sulfur. Alternatively, (US) the clay can be made organophilic by onium ion reaction prior to or simultaneously with impregnating the organoclay with (21) Appl. No.: 11/810,363 sulfur.

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SULFUR-IMPREGNATED ORGANOCLAY types of mercury and arsenic, including organic mercury and MERCURY AND/OR ARSENC ON arsenic compounds, mercury metal (Zero Valent); arsenite and REMOVAL MEDIA arsenate compounds; arsenic ions (both III and V valent); and mercury ions (both I and II valent). When the organic-based FIELD OF THE INVENTION mercury and/or arsenic is involved, the adsorption mecha nism of partition could be involved in addition to chemical 0001. The present invention is directed to compositions: bonding. In addition, the Hg/AS removal media described methods of manufacturing the compositions; and methods of herein also is effective to remove oil, grease and other organic using the compositions for removing mercury (organic mer contaminant molecules. The media will be spent eventually cury, Hg, Hg"; and/or Hg") and/or arsenic (As and/or when all of the adsorption sites are saturated. The actual As") from water. The compositions, also identified hereinas media life will depend on the contaminated water composi “media', or “mercury removal media', or “arsenic removal tions and the field operation conditions. media', or “Hg/AS removal media', can be used to remove 0005 Greco U.S. Pat. No. 5,512,526 describes a clay mercury and/or arsenic from any water source and is particu based heavy metal removal media prepared by reacting a fatty larly useful for removal of mercury and/or arsenic from drink mercaptan, e.g., dodecylmercaptan, with a fatty alkyl-con ing water, industrial wastewater, contaminated groundwater, taining quaternary ammonium compound. As described, the contaminated sediment; offshore produced water, so that the mercaptan's hydrophobic fatty alkyl group associates in some produced water can be returned to the ocean; and for removal of mercury and/or arsenic from aqueous mining wastes. The manner with the fatty alkyl group of the quaternary ammo Hg/AS removal media comprises a homogeneous, preferably nium compound. extruded composition comprising a layered phyllosilicate, elemental Sulfur (free state Sulfur), and an organic phyllosili SUMMARY cate surface treating agent, preferably an onium cation, 0006. It has been found in accordance with the present resulting in an organoclay containing Sulfur. The Sulfur is invention that the use of a Sulfur-impregnated organoclay bonded to the phyllosilicate covalently, ionically, physically, provides a mercury and arsenic removal media having or by a combination of mechanisms. increased reactivity, stability, and mercury and arsenic removal ability. The Hg/AS removal media described herein is BACKGROUND AND PRIOR ART prepared by impregnating an organophilic clay with elemen 0002 The technologies available for mercury and arsenic tal (free state) Sulfur. Alternatively, a clay can be made orga removal. Such as precipitation, coagulation/co-precipitation, nophilic by treating the clay with a Surface-treating agent, activated carbon adsorption, ion-exchange and the like, are Such as a polymer capable of increasing the d-spacing of the not sufficiently effective for mercury and arsenic (arsenite clay platelets, or preferably, withonium ions prior to or simul and arsenate compounds) removal. This assignee's organo taneously with impregnating the resulting organoclay with clay has been proven effective on a variety of organic con sulfur. taminants in the last decade. See, for example, this assignee's U.S. Pat. Nos. 6,398,951; 6,398,966; 6,409,924; and 6,749, BRIEF DESCRIPTIONS OF THE DRAWINGS 757, incorporated herein by reference. A new Hg/AS filtration 0007 FIGS. 1 and 2 are graphs showing the mercury media, described herein, can be operated in a similar fashion, removal efficacy of the Hg/AS removal media described in the or together with the organoclay media, but is much more examples; effective for mercury or arsenic removal. 0003. The Hg/AS removal media described herein has a 0008 FIG. 3 is a graph showing the arsenic removal similar physical form to the organoclays used for organic results for the Hg/AS removal media of Example 6: contaminant removal and can be similarly packed in a canis 0009 FIG. 4 is a side view of an offshore oil well drilling ter or cartridge, as described in the above-listed patents. In platform generally showing the Hg/AS removal media held addition, the Hg/AS removal media described herein can be within a canister attached to an offshore oil well drilling deployed in single layer or multi-layer water-permeable mats, platform Support structure with an alternative placement of a as described in this assignee's published applications, Ser. Sump tank; Nos.10/718,128, filed Nov. 19, 2003 (Publication No. 2005 0010 FIG. 5 is a sectional view of an embodiment of a 01.013707 A1), Ser. No. 1 1/221,019, filed Sep. 7, 2005 (Pub vessel containing a plurality of Hg/AS removal media-con lication No. 2006/0000767 A1), Ser. No. 1 1/489,383, filed taining cartridges or canisters for efficient removal of mer Jul. 19, 2006, (Publication No. 2006-0286888A1), Ser. No. cury and arsenic contained in water; 1 1/599,080, filed Nov. 14, 2006 (Publication No. 2007 0011 FIG. 6 is an elevational view of a preferred embodi 0059542 A1); and Ser. No. 1 1/741,376, filed Apr. 27, 2007, all ment of a vessel containing a plurality of Hg/AS removal of which are hereby incorporated by reference. Fundamen media-containing cartridges or canisters; tally, the Hg/AS removal media is based on organoclay tech (0012 FIG. 7 is a top plan view of the header of the vessel nology but it has been Substantially modified using several shown in FIG. 6 and openings within the header for receiving unique chemistries to enhance adsorption of mercury and permeable conduits each of which can extend through a stack arsenic-containing compounds. The mechanism of mercury of cartridges or canisters as shown in FIGS. 5 and 6: adsorption is based upon chemical bonding, ionic bonding, 0013 FIG. 8 is a partially broken-away side view of an mechanical bonding, or a combination thereof. The mercury embodiment of a Hg/AS removal media-containing vessel, and/or arsenic will be bonded to the media's external and containing multiple, stacked cartridges (FIGS. 5 and 6); and internal Surfaces and the bonding process is non-reversible. 0014 FIG. 9 is an elevational view of a preferred embodi 0004. The Hg/AS removal media described herein is effec ment of a mercury removal media-containing cartridge tive on all sources of mercury and arsenic including organic shown in FIGS. 5 and 6. US 2008/0302728A1 Dec. 11, 2008

0015. It should be understood that the drawings are not since the clay is now hydrophobic, and dried in an oven to less necessarily to Scale and that the embodiments are sometimes than about 5% water, preferably bone dry. The onium ion illustrated by graphic symbols, phantom lines, diagrammatic Surface modification agent compound or polymer can be representations and fragmentary views. In certain instances, added as a solid with the addition to the layered material details which are not necessary for an understanding of the surface modification agent blend of preferably about 20% to present invention or which render other details difficult to about 40% water and/or organic solvent, more preferably at perceive may have been omitted. It should be understood, of least about 30% water or more, based on the dry weight of course, that the invention is not necessarily limited to the layered material. Preferably about 30% to about 40% water, particular embodiments illustrated herein. more preferably about 25-35% water, based on the dry weight of the layered material, is included in the onium ion interca DETAILED DESCRIPTION OF THE PREFERRED lating composition, so that less water is sorbed by the inter EMBODIMENT calate, thereby necessitating less drying energy after onium ion intercalation. 0016. It should be understood that while the following 0021. In general, a dry process can be described, as fol description of the preferred embodiment of the invention is lows, for organoclay media preparation or manufacturing. directed to the use of the methods, apparatus and mercury/ The powder form of clay mineral is fed into a mixer through arsenic removal media on an offshore drilling platform, the a major port for Solids, typically an extruder. A separate port invention is also useful for mercury and arsenic removal from for the 2" powder form of solid can also be used besides the any contaminated water, including drinking water, industrial clay feeding port. The liquid forms of the additives, including wastewaters; contaminated ground water Supplies; aqueous water, intercalantagent, and the coupling agentifany, are fed mining wastes; and contaminated underwater and soil sedi into the mixer through the separate ports. Either multiple ments, particularly when contained in a reactive mat, as forms of the solids or the liquids could be pre-mixed, or both described in the applications identified in paragraph I0003, the solids and the liquids can be pre-mixed through a separate or when used in bulk form. mixer, before they are fed into the extender. A preferred liquid 0017. The Hg/AS removal media described herein is a weight is from 10% to 50% based on the total mixture weight, Sulfur-containing layered organophilic phyllosilicate that is more preferably from 20% to 40%, most preferably from 25% (or has been) made organophilic by reaction with an organic to 35%. The intimate mixture from the extruder will be further phyllosilicate surface-treating agent, preferably an onium dried through a dryer, and be ground to the preferred particle ion-liberating compound, and has been made mercury-reac size. A screening process could be used to collect the finished tive and arsenic reactive by impregnation with elemental sul product in the desired particle size distribution. fur. 0022. The onium ions may generally be represented by the Phyllosilicate following formula: 0018. The phyllosilicate can be a smectite clay, e.g., ben tonite, montmorillonite, hectorite, beidellite, Saponite, non tronite, Volkonskoite, Sauconite, Stevensite, and/or a synthetic smectite derivative, particularly fluorohectorite and laponite: a mixed layered clay, particularly rectonite and their synthetic derivatives; Vermiculite, illite, micaceous minerals, and their synthetic derivatives; layered hydrated crystalline polysili cates, particularly makatite, kanemite, octasilicate (illierite), 0023 The preferred phyllosilicate surface-treating agent magadiite and/or kenyaite; attapulgite, palygorskite, sepoi is one or more onium salt compounds, generally represented lite; or any combination thereof. by the following formula: Clay Surface Modification Agents 0019. The surface modification (intercalant) agents used for organoclay formation include but are not limited to pri mary amine, secondary amine, tertiary amine, and onium ions and/or onium salt compounds, polyduat, polyamine, cationic polymers and their derivatives, nonionic polymers, and mix ture of thereof. 0020. In the wet process, the surface modification agent, (0024 wherein Q=N. P. S: e.g., onium ion, is introduced into the layered material gal 0025 wherein A-halide, acetate, methylsulfate, hydrox leries in the form of a Solid or liquid composition (neat or ide, preferably chloride; aqueous, with or without an organic solvent, e.g., isopropanol 0026 wherein R. R. R. and R are independently and/or ethanol, if necessary to aid in dissolving the onium ion organic moieties, or oligomeric moieties or hydrogen. compound) having a Surface modification, e.g., onium ion (Ref. U.S. Pat. No. 6,376,591), hereby incorporated by concentration Sufficient to provide a concentration of about reference. Examples of useful organic moieties include, 5% to about 10% by weight clay (90-95% water) and the but not limited to, linear or branched alkyl, benzyl, aryl or Surface modification agent, e.g., onium ion compound, is aralkyl moieties having 1 to about 24 carbon atoms. added to the clay slurry water, preferably at a molar ratio of onium ions to exchangeable interlayer cations of at least EXAMPLES about 0.5:1, more preferably at least about 1:1. The onium 0027 bis(hydrogenated tallow alkyl)dimethyl ammonium ion-intercalated clay then is separated from the water easily, chloride (Arquad(R) 2HT); benzylbis(hydrogenated tallow US 2008/0302728A1 Dec. 11, 2008

alkyl)methyl ammonium chloride (Arquad(R) M2HTB); ben in order to protect and extend the active life of both the Zyl(hydrogenated tallow alkyl)dimethyl ammonium chloride organoclay, in an initial organoclay stage, and the Hg/AS (ArquadR DMHTB); trihexadecylmethyl ammonium chlo removal media, used after organic contaminant removal. An ride (ArquadR 316); tallowalkyl trimethyl ammonium chlo operation procedure using an initial organoclay media fol ride (Arquad(R) T-27W and ArquadRT-50); hexadecyl trim lowed by contact with the Hg/AS removal media, in series, is ethyl ammonium chloride (Arquad(R) 16-29W and Arquad(R) highly effective. A carbon media can also be used before or 16-50); octadecyl trimethyl ammonium chloride (Arquad(R) after the Hg/AS removal media, if necessary. In general, the 18-50(m)); and dimethylhydrogenated tallow-2-ethylhexyl retention time of contact between Hg-contaminated or AS ammonium methylsulfate. contaminated water and the Hg/AS removal media should be 0028. Additional phyllosilicate surface-treating agents no less than about 10 seconds, preferably at least about 1 include the materials set forth below in paragraphs 0024 minute, more preferably about 2 minutes or more. 0030. 0042. The preferred amount of components of the sulfur 0029 Quaternary ammonium ions containing ester link containing organoclay media are as follows: age: (ref. U.S. Pat. No. 6,787,592, hereby incorporated by reference, see columns 5 and 6) EXAMPLE Phyllosilicate Intercalant Agent Elemental Sulfur 0030 di(ethyl tallowalkylate)dimethyl ammonium chlo Preferably 1-90 1O-SO O.S.-SO More Preferably 3S-83 15-45 2-2O ride (ArquadR DE-T). More Preferably 50-77 20-40 3-10 0031 Quaternary ammonium ions containing amide link More Preferably 59-71 25-35 4-6 age: (ref US patent application 2006/0166840 hereby incor Most Preferably 65 30 5 porated by reference, see page 2) 0032. The onium ions may be functionalized such as pro tonated C.e-amino acid with the general formula (HN Laboratory Study (CH), COOH)". 0033 Alkoxylated quaternary ammonium chloride com 0043. A column study was conducted in order to demon pounds (ref. U.S. Pat. No. 5,366,647 hereby incorporated by strate the mercury removal media's ability to remove mer reference) cury. The influent was composed of ~10 ppm of Hg(NO), solution with dilute nitric acid matrix. The effluent samples EXAMPLES were taken at regular intervals and the mercury content was measured by an ICP analytical test. The flow rate was about 0034 cocoalkylmethylbis(2-hydroxyethyl) ammonium 10 bed volumes (BV) per hour, using a 6-minute retention chloride (Ethoquad(R) C/12); octadecylmethylpolyoxyethyl time. A commercial mercury removal media (Hg-A of SME ene(15) ammonium chloride (EthoquadR 8/25); and octade Associates, Houston, Tex.) containing a mixture of 85-90% cylmethyl (2-hydroxyethyl) ammonium chloride (Ethoquad activated carbon and 10-15% sulfur was also included in this 18/12). study for comparison purposes. 0035 Polyguat (U.S. Pat. No. 6.232,388, hereby incorpo rated by reference) Example 1 EXAMPLE Sample L1S 0036) N.N.N',N',N'-pentamethyl-N-tallowalkyl-1,3-pro 0044 400.0 g of bentonite clay (particle size.<75 um pre pane diammonium dichloride (Duaquad(RT-50). ferred, and ~8% moisture content) was dry-mixed with 28.75 0037 Polyamine: (ref. US patent application 2004/ g of sulfur in the powderform (purchased from Aldrich) using 01.02332 hereby incorporated by reference) the Kitchen Aid mixer for one minute. 80.0 g of deionized water was added to this bentonite-sulfur mixture slowly under EXAMPLES shearing using the same mixer and mixed for ~2 minutes. 209.6 g of melt quat (ARQUADR) 2HT from Akzo Nobel, 0038 N-tallow-1,3-diaminopropane (Duomeen(R) T); bis(hydrogenated tallow alkyl)dimethylammonium chloride, N-tallowalkyl dipropylene triamine (Triameen(R) T); and 83% active) was added to this clay-sulfur-water mixture N-tallowalkyl tripropylene tetramine (Tetrameen(RT). under shearing using the same mixer, and mixed for 5 min 0039 Cationic polymers, non-ionic polymers, including utes. The mixture was extruded three times using a labora homopolymer or copolymer, low molecular weight or high tory-scale extruder with a die-plate, and the final extrudates molecular weight were oven-dried at 85°C. to a moisture content of less than 5% by weight. The dried extrudates were ground and result EXAMPLES ing particles between 18 and 40 mesh (US standard sieves) 0040 Polydially dimethylammonium chloride: Poly(dim were collected and tested for their performance. ethylamine-co-epichlorohydrin); Polyacrylamide; and Copolymers of acrylamide and acryloyloxylethyltrimethyl Example 2 ammonium chloride. 0045. The media material collected in Example 1 was packed in a column having an inner diameter of 1.5" and Hg/As Removal Media having an empty bed volume (BV) of -86 mL. The influent 0041. In a preferred embodiment, particularly in offshore was composed of ~10 ppm of Hg(II) in the presence of nitric environments, the Hg/AS removal media described hereincan acid. The effluent samples were taken at regular intervals and be used after the use of an organoclay for removal of organics the mercury content was measured by the Inductively US 2008/0302728A1 Dec. 11, 2008

Coupled Plasma (ICP) analytical technique. The flow rate minutes and 90 minutes treatment, the effluent had mercury was about 10 BV/hr with a 6-minute retention time. A com concentrations of 3.4 ppb and 3.9 ppb, arsenic concentrations mercial organoclay media Hg-A (without Sulfur) is also of 5.18 ppb and 5.16 ppb, respectively. So a total mercury and included in this study for the comparison purpose. arsenic removal efficiency of greater than 65% and 30% were achieved, respectively. Example 3 0051 Turning now to the drawings, and initially to FIG.4, Production Trial 1 there is shown an offshore drilling platform generally desig nated by reference numeral 10 including a work deck support 0046 Bentonite powder and sulfur powder (from Harwick structure 12 for Supporting a plurality of stacked work decks Standard Distribution Corporation, grade 104) were blended at a substantial height above an ocean water level 14. The in a ratio of 93.3: 6.7 by weight, and then this mixture was fed work decks commonly include a cellar deck 16 at a lowest into a 5" Readco continuous processor at a feed rate of 900 work deck level, a second deck 18 located directly above the 1b/hr. About 0.25 gallon/minute of water and 1.04 gallon/ cellar deck 16, a third deck 20 disposed directly above deck minute of quat (ARQUADR) 2HT from Akzo Nobel, bis(hy 18, and a main deck 22 at an uppermost work deck level. In drogenated tallow alkyl)dimethyl ammonium chloride, -83% extant offshore drilling platforms, a Sump tank 24 has been active) were also fed in the Readco processor through two connected to the drilling platform 10 at the cellar deck level independent ports in sequence. The discharged extrudates 16 and rainwater, including entrained hydrocarbons, particu from the processor were sent to a dryer, the dried extrudates larly oil, paraffins and surfactants have been directed from all were further milled and the granular particles between 18 and deck levels, which are contained so that rainwater and 40 mesh with moisture content less than 5% by weight were entrained hydrocarbons do not spill over to the ocean, to drain colleted as the finished product. by gravity into the Sump tank 24. As described in this assign ee's U.S. Pat. Nos. 6,398,951; 6,398,966; 6,409,924; and Example 4 6,749,757, hereinafter incorporated by reference, further 0047 A similar column testas described in Example 2 was separation of hydrocarbons from rainwater, in addition to conducted on the product sample collected in Example 3. gravity separation, is required for effective elimination of ocean water hydrocarbon contamination by providing a sec Example 5 ondary hydrocarbon recovery apparatus containing an organo-clay after the produced water and/or rainwater has 0048. The media described in Example 2 was tested under been separated by gravity in the Sump tank 24 or 24A. In the offshore platform conditions using actual offshore mercury preferred embodiment of mercury and/or arsenic removal contaminated water. A commercial available organoclay using the methods and apparatus described herein for mer product, CrudeSorbTM, was also used in front of this Hg/As cury and arsenic removal offshore, one or more canisters (not removal media. The influent had a mercury concentration of shown) containing an organoclay, for hydrocarbon removal, 11.4 ppb, and the effluent was 3.4 and 3.9 ppb after the 30 is used in series with one or more canisters containing the minutes and 90 minutes treatment, respectively. A total mer Hg/AS removal media (in any order). It is preferred to remove cury removal efficiency of >65% was achieved. the hydrocarbons with organoclay-containing canister(s) prior to mercury and/or arsenic removal with Hg/AS removal Arsenic Removal Example media-containing cartridges. Example 6 0052. In accordance with a preferred embodiment of the 0049. The media described in Example 3 was examined methods, apparatus and Hg/AS removal media described for its ability to remove arsenic. The media materials were herein, it has been found that the apparatus and methods packed in a column withinner diameter of 1.5" and empty bed described herein function best, in offshore platform use, volume of -86 mL. The influent solution was composed of-5 when the Sump tank 24A is disposed on or near a boat landing ppm of As(V). The As(V) stock solution was prepared by deck level 26 (FIG. 4) of the offshore drilling platform 10. dissolving Na2HAsO.7H2O in the de-ionized water. The However, the Sump tank can also be disposed at an upper effluent samples were taken at regular intervals and the level, such as at reference numeral 24 in FIG. 4. arsenic content was measured by the Inductively Coupled 0053 Mercury and/or arsenic from ocean water that is Plasma (ICP) analytical technique. The flow rate was around collected on the production decks 16, 18, 20 and 22 that may 10 BV/hr with 6-minute retention time. accumulate during dry weather on the inner Surfaces of the conduit 28 and inner Surfaces of Sump tank 24 can be sepa Offshore Field Study Example for Both Hg and AS Removal: rated from the water that flows from the decks to the Hg/As removal media-containing cartridge 44 for recovery and Example 7 separation in accordance with the apparatus and methods 0050. The media material described in Example 3 was described herein. tested under offshore platform conditions using the actual 0054 Water containing mercury and/or arsenic is con wastewater contaminated by both mercury and arsenic. The veyed via conduit 28 from the deck areas 16, 18, 20 and 22 contaminated water was pumped through two columns in along the platform infrastructure or Support leg 12 down to series. Each column had a diameter of 3" and held about 1.5 the sump tank 24 or 24A, preferably sump tank 24A for Liter of media (~1,125 grams). The first column was packed convenient servicing and/or Hg/AS removal media cartridge with the commercial available organoclay media, CrudeS replacement. As stated in this assignee's U.S. Pat. Nos. 6,398, orbTM, and the second column was packed the media material 951, 6,398,966 and 6,409,924, it is expedient to dispose the described in Example 3. The retention time was roughly equal separation apparatus described herein at or near the boat to 5-minute. The influent had mercury and arsenic concentra landing deck level 26 (such that at least a portion of the Sump tion of 11.4 ppb and 7.55 ppb, respectively. After the 30 tank 24A is within about 10 feet of ocean level) since con US 2008/0302728A1 Dec. 11, 2008

taminants collected on the production decks 16, 18, 20 and 22 can be used to collect accumulated Solids, or Solids which do that may accumulate during dry weather on the inner Surfaces not pass through the outer covers 76 of the filter cartridges of the conduit 28 and inner surfaces of sump tank 24A can be 104. A drain 122 is provided for purposes of flushing out the separated from the water that flows from the decks to the accumulated solids which settle in the bottom structure 110 of Sump tank 24A for recovery and separation in accordance the vessel 100, together with the clean water. The clean water with the apparatus and methods described herein. can be passed through a solids filter 123 before being directed 0055. In accordance with an important feature of the meth to the ocean through conduit 125. In contrast, solids will ods, apparatus and mercury removal media described herein, accumulate on top of the tube sheet 111. Thus, the solids must a downwardly extending leg portion 42 of water leg 34 is be removed from above the tube sheet 108 using one or more operatively interconnected to, and in fluid communication nozzle openings shown at 109 in FIG. 5. As shown in FIG. 6, with, one or more mercury and/or arsenic media-containing these additional nozzle openings are not required in the vessel vessels 44. As shown in FIG. 5, the mercury removal media 100 because the accumulated solids are easily flushed down within vessel 44 captures the mercury and thereby separates the drain pipe 122 into solids filter 123. essentially all mercury from the water (less than about 10 0059. As shown in FIG. 6, an extremely dense number of parts per million, preferably less than about 1 part per million stacks of cartridges 104 is provided by the header 108. Spe mercury remains). The treated water flows through the liquid cifically, the header 108, as shown in FIG. 7, includes 23 permeable covers 76 of the cartridges 55 into the vessel 44. openings 120, and therefore 23 porous conduits 106 and The treated water then flows by gravity through water exit therefore 23 stacks 102 of cartridges 104. Accordingly, the opening 46 in the water and coalesced hydrocarbon collection volumetric flow rate that can be handled by the vessel 100 is vessel 44 and through exit conduit 48 back to the ocean water substantially greater than the volumetric flow rate that can be 14. handled by the vessel 44. Of course, smaller vessels with 0056. As shown in FIGS. 5 and 8, vessel 44 includes an fewer stacks of cartridges and large vessels with more stacks outer, fluid-impermeable housing 48 having a water inlet 42 of cartridges are anticipated. interconnected through the housing 48 so that mercury-con 0060 FIG. 8 illustrates a single cartridge 55 containing the taminated water enters vessel 44 and then flows through the Hg/AS removal media 45 that is loosely packed within the Hg/AS removal media-containing cartridges 55, through a canister 55 between liquid-permeable contaminated water plurality of longitudinal, axial, central inlet conduits 56,56A, inlet tube (56,56A, 56B,56C and 56D of FIG.3) and an outer, 56B, 56C and 56D that may form part of a header, described liquid-permeable cartridge cover 76. As shown, the mercury in more detail hereinafter. The mercury removal media-con removal media 45 comprises an organoclay containing Sulfur. taining cartridges 55 are water-permeable by virtue of flow What is claimed: apertures 57, in the cartridge cover 76, that are sized suffi 1. A contaminant removal media for removing mercury ciently small such that the mercury removal media does not and/or arsenic from water by contact comprising: pass therethrough. Water entering vessel 44 through inlet an intimate mixture of an organoclay; and elemental Sulfur. conduit 42 and cartridge inlet conduits 56,56A, 56B,56C and 2. The contaminant removal media of claim 1, wherein the 56D flows radially outwardly through the mercury removal percentage of components is as follows: media 45 where the mercury removal media captures, and a) organoclay: 50 to 99.5 wt.%; removes, the mercury from the contaminated water. The puri b) elemental sulfur: 0.5 to 50 wt.%. fied water flows through the openings 57 in each liquid per 3. The contaminant removal media of claim 2, wherein the meable cartridge cover 76 and collect in vessel 44. The clean organoclay comprises a layered phyllosilicate intercalated water exits the vessel 44 through exit conduit 69 and through with an intercalant agent, and wherein the percentage of valve 71 and then is returned to the ocean 14 via outlet 73. components is as follows: 0057 Turning to FIG. 6, another embodiment of a vessel a) phyllosilicate: 1-90%; intercalant agent 10-50%: 100 is shown containing stacks of cartridges, one of which is b) elemental sulfur: 0.5-50%. shown at 102. Each cartridge stack includes a plurality of 4. The contaminant removal media of claim3, wherein the annular cartridges 104 through which a porous contaminated percentage of components is as follows: liquid inlet conduit 106 extends. The porous inlet conduit 106 a) phyllosilicate: 35-83%; intercalant agent 15-45%: is connected to a header 108 which is disposed within a b) elemental sulfur: 2-20%. bottom section 110 of the vessel 100, similar to the contami 5. The contaminant removal media of claim 4, wherein the nated water inlet conduits 56,56A, 56B,56C and 56D shown percentage of components is as follows: in FIG. 5. a) phyllosilicate: 50-77%; intercalant agent 20-40%: 0058 Turning to FIGS. 6 and 7, the header 108 is con b) elemental sulfur: 3-10%. nected to a mercury-contaminated water inlet 112 which 6. The contaminant removal media of claim 5, wherein the includes a flange 114 which is connected to the flange 116 of percentage of components is as follows: the header 108 by a plurality of fasteners, such as bolts (not a) phyllosilicate: 59-71%; intercalant agent 25-35%; shown). The header is also supported within the bottom struc b) elemental sulfur: 4-6%. ture 110 (see FIG. 6) of the vessel by a plurality of supports 7. The contaminant removal media of claim 6, wherein the shown at 118. The header 108 includes a plurality of openings percentage of components is as follows: 120, each of which receives a permeable conduit 106 (see a) phyllosilicate: 65%; intercalant agent 30%; FIG. 6). In the embodiment illustrated in FIGS. 6 and 7, the b) elemental sulfur 5%. header 108 is connected to 23 permeable conduits and there 8. The contaminant removal media of claim 1, wherein the fore supports 23 stacks 102 of cartridges 104. By providing mixture is compacted in an extruder. the header 108 within the bottom structure 110 of the vessel 9. A method of removing mercury and/or arsenic from 100, a permeable tube sheet 111 shown in FIG.5 is not needed water comprising contacting the water with the contaminant for collecting solids and the bottom section 110 of the vessel removal media of claim 1. US 2008/0302728A1 Dec. 11, 2008

10. A method of removing mercury and/or arsenic from 20. The mercury removal media of claim 16, wherein the water comprising contacting the water with the contaminant elemental sulfur has a particle size such that at least 80% of removal media of claim 2. the particles are finer than 18 mesh, U.S. Sieve Series. 11. The contaminant removal media of claim 1, wherein 21. The mercury removal media of claim 20, wherein the the elemental sulfur has a particle size such that at least 80% of the particles are finer than 18 mesh, U.S. Sieve Series. elemental sulfur has a particle size such that at least 80% of 12. The contaminant removal media of claim 11, wherein the particles are finer than 50 mesh, U.S. Sieve Series. the elemental sulfur has a particle size such that at least 80% 22. The mercury removal media of claim 21, wherein the of the particles are finer than 50 mesh, U.S. Sieve Series. elemental sulfur has a particle size such that at least 80% of 13. The contaminant removal media of claim 12, wherein the particles are finer than 70 mesh, U.S. Sieve Series. the elemental sulfur has a particle size such that at least 80% 23. The mercury removal media of claim 22, wherein the of the particles are finer than 70 mesh, U.S. Sieve Series. elemental sulfur has a particle size such that at least 80% of 14. The contaminant removal media of claim 13, wherein the particles are finer than 80 mesh, U.S. Sieve Series. the elemental sulfur has a particle size such that at least 80% 24. The mercury removal media of claim 23, wherein the of the particles are finer than 80 mesh, U.S. Sieve Series. elemental sulfur has a particle size such that at least 80% of 15. The contaminant removal media of claim 14, wherein the particles are finer than 100 mesh, U.S. Sieve Series. the elemental sulfur has a particle size such that at least 80% 25. A method of regenerating contaminated water contain of the particles are finer than 100 mesh, U.S. Sieve Series. ing an organic contaminant, and mercury, or arsenic contami 16. A contaminant removal media for removing mercury or nants comprising: arsenic from water by contact comprising: an intimate mixture of a layered phyllosilicate intercalated contacting the contaminated water with an organoclay for with a surface-modifying, layer-expanding intercalant; removal of organic contaminants; and and sulfur. contacting the contaminated water with the removal media 17. The contaminant removal media of claim 16, wherein of claim 1 for removal of mercury or arsenic. the mixture is compacted in an extruder. 26. The method of claim 25 wherein the organoclay and 18. The contaminant removal media of claim 16, wherein removal media are contained in separate vessels connected in the layer-expanding intercalant is selected from the group series. consisting of onium ions, a polymer, and a mixture thereof. 27. The method of claim 25 wherein the organoclay and the 19. A method of removing mercury or arsenic from water removal media are contained in the same vessel. comprising contacting the water with the removal media of claim 16. c c c c c