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(12) Patent Application Publication (10) Pub. No.: US 2011/0309017 A1 Hassler Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2011/0309017 A1 Hassler Et Al US 2011 0309017A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/0309017 A1 Hassler et al. (43) Pub. Date: Dec. 22, 2011 (54) METHODS AND DEVICES FOR ENHANCING CO2F I/44 (2006.01) CONTAMINANT REMOVAL BY RARE CO2F I/72 (2006.01) EARTHIS CO2F L/70 (2006.01) CO2F I/52 (2006.01) (75) Inventors: Carl R. Hassler, Gig Harbor, WA CO2F I/42 (2006.01) (US); John L. Burba, III, Parker, CO2F I/26 (2006.01) CO (US); Charles F. Whitehead, CO2F I/68 (2006.01) Henderson, NV (US); Joseph CO2F IOI/30 (2006.01) Lupo, Henderson, NV (US); CO2F IOI/2O (2006.01) Timothy L. Oriard, Issaquah, WA CO2F IOI/22 (2006.01) (US) CO2F IOI/12 (2006.01) CO2F IOI/14 (2006.01) (73) Assignee: MOLYCORP MINERALS, LLC, CO2F IOI/IO (2006.01) Greenwood Village, CO (US) CO2F IOI/38 (2006.01) CO2F IOI/16 (2006.01) (21) Appl. No.: 13/086,247 CO2F IOI/36 (2006.01) CO2F IOI/34 2006.O1 (22) Filed: Apr. 13, 2011 ( ) Related U.S. Application Data (52) U.S. Cl. ......... 210/638; 210/749; 210/753: 210/758: (60) Provisional application No. 61/323,758, filed on Apr. 210/757: 210/723; 210/668; 295.839; 13, 2010, provisional application No. 61/325,996, s filed on Apr. 20, 2010. Publication Classification (57) ABSTRACT (51) Int. Cl. Embodiments are provided for removing a variety of con CO2F I/00 (2006.01) taminants using both rare earth and non-rare earth-containing CO2F I/76 (2006.01) treatment elements. FEED STREAM NON-RAREEARTH-CONTAININGREATMENT ELEMEN RARE EARH-CONTAINMG TREATMENTELEMENT TREATED STREAM Patent Application Publication Dec. 22, 2011 Sheet 1 of 8 US 2011/0309017 A1 100 FEED STREAM 104 NON-RARE EARTH-CONTAINING TREATMENT ELEMENT 108 RARE EARTH-CONTAINING TREATMENTELEMENT 112 TREATED STREAM F.G. 1 Patent Application Publication Dec. 22, 2011 Sheet 2 of 8 US 2011/0309017 A1 1OO FEED STREAM RARE EARTH-CONTAINING TREATMENTELEMENT NON-RARE EARTH-CONTAINING TREATMENT ELEMENT 204 TREATED STREAM FIG 2 Patent Application Publicatication Dec.• 22,4-4- 2011 Sh eet 3 of 8 US 2011/0309017 A1 Retention of humic acid on 20 g of ceria-coated alumina challenged by 6 mg/L using 10 min contact time, 100 90 80 70 60 . 50 AO 30 20 O O 0.0 0.5 1.O 1.5 2.0 2.5 3.0 Volume (L) Y Fig. 3 Patent Application2 o Publicationo Dec. 22, 2011 Sheet 4 of 8 US 2011/03090 17 A1 Fluoride Effects on Residual Arsenic in Solutuin 6O O 0 WI. Fluoride No Fluoride 5O O 4.O O 300 200 100 0.80 1.00 120 14 O 160 180 2.00 Molar Ratio Ce?As Fig. Patent Application Publication Dec. 22, 2011 Sheet 5 of 8 US 2011/0309017 A1 Effect of Molar Ratio on the Loading Capacity R Molar Ratio WIF Molar Ratio No F Q 500 g 450 400350 S 300 p e 250 & 200 4) 150 O 100 E 50 d 0.80O 100 120 140 160 1.80 2.00 2.20 Molar Ratio CelAS Fig. 5 Patent Application Publication Dec. 22, 2011 Sheet 6 of 8 US 2011/0309017 A1 400 ppb Arsenic removal capacity for CMI media (powdered) in Solutions With elevated ion Concentrations (5x w/ respect to NSF recipe). 24 hr isotherms. 20 - Ed As(III) 16 As (V) 12 10X 50X DI NSF SO, F C CO. SiO2 PO FIG 6 Patent Application Publication Dec. 22, 2011 Sheet 7 of 8 US 2011/0309017 A1 Competing ion column studies for CMI media using 300ppb AS(V). Solutions contain 10 X the concentration of the 300 indicated. ionss from the NSF tap water recipe. NSF water is used as a contr. 250 - ExCeSS F, CO3, es and SiO, O s 5, 200 - m 2 o O 150 i rts - Excess PO4 cooooo KXXX E oooooooo ? 100 s & © C o KXXKX 50 - O O 1OOO 2000 3OOO 4000 5000 6000 7OOO Bed Volumes Treated FIG. 7 Patent Application Publication Dec. 22, 2011 Sheet 8 of 8 US 2011/0309017 A1 Removal Capacity of Arsenic by Cerium Chloride As Win D AS II in D 50%/50% As il/V in Di FIG. 8 US 2011/0309017 A1 Dec. 22, 2011 METHODS AND DEVICES FOR ENHANCING following: PO, CO., SiO, bicarbonate, vanadate, and CONTAMINANT REMOVAL BY RARE a halogen, and the target material is one or more of a chemical EARTHIS agent, a colorant, a dye intermediate, a biological material, an organic carbon, a microbe, an oxyanion, and mixtures CROSS REFERENCE TO RELATED thereof. APPLICATION 0012. In one configuration, the downstream treatment ele 0001. The present application is claims the benefits of U.S. ment is the non-rare earth-containing treatment element, the Provisional Patent Application Ser. Nos. 61/323,758, filed upstream treatment element is the rare earth-containing treat Apr. 13, 2010, and 61/325,996, filed Apr. 20, 2010, all of the ment element, and the interferer and target material are each same title and all of which are incorporated herein by this one or more of a chemical agent, a colorant, a dye interme reference in their entirety. diate, a biological material, an organic carbon, a microbe, an oxyanion, a halogen, a halide compound, and mixtures FIELD thereof. 0013 There are a number of examples of applications for 0002 The present disclosure relates generally to treatment this configuration. of target material-containing fluids and particularly to rare 0014. In one example, the non-rare earth-containing treat earth treatment of target material-containing fluids. ment element is a membrane, and the interferer is one or more BACKGROUND of a halogen and a halide compound. 0015. In another example, the non-rare earth-containing 0003. Rare earths and rare earth-containing compositions treatment element comprises an oxidant, and the interferer is are a known way to remove selectively a variety of organic an oxidizable material. The oxidant, relative to the target and inorganic contaminants from liquids. Rare earths are, material, preferentially oxidizes the interferer. however, relatively limited in availability and increasingly 0016. In another example, the non-rare earth-containing expensive. Additionally, rare earths can react preferentially treatment element comprises a reductant, and the interferer is with certain compounds or interferers, thereby preventing a reducible material. The reductant, relative to the target them from reacting with target materials of interest. Certain material, preferentially reduces the interferer. target materials of interest are optimally removed only by rare 0017. In another example, the non-rare earth-containing earths and not by other less expensive sorbents. treatment element comprises a precipitant, and the interferer 0004. There is a need in water purification for greater is co-precipitated with the target material by the precipitant. selectivity in and control of the target materials exposed to a 0018. In another example, the non-rare earth-containing rare earth-containing contaminant removal agent. treatment element comprises an ion exchange medium, and SUMMARY the interferer is, relative to the target material, a competing ion for sites on the ion exchange medium. 0005. These and other needs are addressed by the various 0019. In another example, the non-rare earth-containing aspects, embodiments, and configurations of the present dis treatment element comprises an ion exchange medium, and closure. The disclosure is directed to the removal of various the interferer is a foulant, the at least one of a foulant detri target materials by combinations of rare earths and/or rare mentally impacting operation of the non-rare earth-contain earth compositions with other devices, materials, and pro ing treatment element. cesses (hereinafter "elements'). 0020. In another example, the non-rare earth-containing 0006. In an aspect, an interferer is removed by a non-rare treatment element comprises an organic solvent in a solvent earth-containing treatment element upstream of a rare earth exchange circuit, and the interferer and the target material are, containing treatment element or vice versa. under the selected operating conditions of the Solvent 0007. In an embodiment, a method and system are pro exchange circuit, soluble in the organic solvent. vided that includes the following steps/operations: 0021. In yet another example, the non-rare earth-contain 0008 (a) receiving, by an input, a feed stream comprising ing treatment element comprises a copper/silver ionization a target material and an interferer, the target material and treatment element, and the interferer comprises an oxyanion. interferer being different; 0009 (b) contacting the feed stream with an upstream 0022. In a further example, the non-rare earth-containing treatment element to remove most or all of the interferer while treatment element is a peroxide process, and the interferer leaving most or all of the target material in an intermediate reacts with peroxide to Substantially generate molecular oxy feed stream; and gen. 0010 (c) thereafter contacting the feed stream with a 0023. In yet another example, the interferer is one or more downstream treatment element to remove most or all of the of a phosphorus-containing composition, a carbon- and oxy target material, wherein the interferer interferes with removal gen-containing compound, a halogen, a halogen-containing of the target material by the downstream treatment element, composition, and a silicon-containing composition. the upstream treatment element is one of a rare earth-contain 0024. Other examples will be appreciated by one of ordi ing treatment element and a non-rare earth-containing treat nary skill in the art based on the present disclosure. ment element, and wherein the downstream treatment ele 0025. In a further embodiment, a method and/or system ment is the other of a rare earth-containing treatment element includes the following StepS/operations: and a non-rare earth-containing treatment element.
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