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(12) Patent Application Publication (10) Pub. No.: US 2012/0223022 A1 Hassler Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2012/0223022 A1 Hassler Et Al US 20120223022A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2012/0223022 A1 Hassler et al. (43) Pub. Date: Sep. 6, 2012 (54) CONTAMINANT REMOVAL FROM WATERS Publication Classification USING RARE EARTHS (51) Int. Cl. Inventors: Carl Hassler, Gig Harbor, WA CO2F I/68 (2006.01) (75) CO2F I/52 (2006.01) (US); John Burba, Parker, CO CO2F 9/04 (2006.01) (US); Robert Cable, Las Vegas, C09K 3/00 (2006.01) NV (US) A47K 3/02 (2006.01) (73) Assignee: MOLYCORP MINERALS, LLC, CO2F IOI/30 (2006.01) Greenwood Village, CO (US) CO2F IOI/36 (2006.01) CO2F IOI/38 (2006.01) (21) Appl. No.: 13/410,081 CO2F IOI/34 (2006.01) CO2F IOI/IO (2006.01) (22) Filed: Mar. 1, 2012 (52) U.S. Cl. ......... 210/717; 252/175; 210/767; 210/749; Related U.S. Application Data 210/702; 4/538 (60) Provisional application No. 61/448,021, filed on Mar. 1, 2011, provisional application No. 61/453,446, filed (57) ABSTRACT on Mar. 16, 2011, provisional application No. 61/474, 902, filed on Apr. 13, 2011, provisional application No. The present disclosure is directed to the use of rare earth 61/476,667, filed on Apr. 18, 2011, provisional appli containing additives, particularly rare earth-containing addi cation No. 61/553,809, filed on Oct. 31, 2011, provi tives comprising rare earths of plural oxidation states, to sional application No. 61/558,887, filed on Nov. 11, remove, particularly from recreational waters, various target 2011, provisional application No. 61/538,634, filed on materials, such as disinfectant by-products and precursors Sep. 23, 2011. thereof, phosphates, and organophosphates. 88.888 &S an 88:8: it: Ec: Exx. es:sixx:28:08 ::::::::: 8::::: --- a-- a-- a-------- a -a ------ % :::::::A&:38:38:28:88 88: 888 8:a:: -a- x --- - - - - ---, ---, -- ~~~~ ~~~~ & Patent Application Publication Sep. 6, 2012 Sheet 2 of 6 US 2012/0223022 A1 FIG. 2 Patent Application Publication Sep. 6, 2012 Sheet 3 of 6 US 2012/0223022 A1 pi Dependence on PO. Removal by Ceili Patent Application Publication Sep. 6, 2012 Sheet 4 of 6 US 2012/0223022 A1 - - - 3. - Pre-Treat8ter Form Cerium (IV) . " " " attact Cerita IV 8. and for Rare Earth Cantaining Additive with Water and for Pre-treated Water frn rim m * * * Pre-Removal Treatment es in 20 the Past Removal Treatment Fig. 4 Patent Application Publication Sep. 6, 2012 Sheet 5 of 6 US 2012/0223022 A1 {};&########## §§§ $ xavanopsis Patent Application Publication Sep. 6, 2012 Sheet 6 of 6 US 2012/0223022 A1 30 N Six: - it COAGULATION SEDIMENTATION - 360 N (it DisNFECTION 3. US 2012/0223022 A1 Sep. 6, 2012 CONTAMINANT REMOVAL FROM WATERS treated water. In some configurations, the water contains a USING RARE EARTHS halogenated disinfection by-product. Preferably, the disin fection by-product is one of a trihalomethane, haloacetic acid, CROSS REFERENCE TO RELATED haloacetonitrile, halofuranone, bromate, halonitromethane, APPLICATION haloamide, iodo-acid, iodo-trihalomethane, nitrosamine, and 0001. The present application claims the benefits of U.S. dihaloaldehyde. Preferably, the disinfection by-product pre Provisional Application Ser. Nos. 61/448,021 with a filing cursor is one or more oft-butyl methyl ether, diazomethane, date of Mar. 1, 2011, 61/453,446 with a filing date of Mar. 16, hypohalous acid, aldehyde, carboxylic acid, and chloramines. 2011, 61/474,902 with a filing date of Apr. 13, 2011, 61/476, 0010. In some embodiments, the disinfection-by-product 667 with a filing date of Apr. 18, 2011, 61/538,634 with a comprises one or both of a halogenated hydrocarbon and filing date of Sep. 23, 2011, 61/553,809 with a filing date of halogenated carboxylic acid. Oct. 31, 2011, and 61/558,887 with a filing date of Nov. 11, 2011, all entitled “Process for Treating Waters and Water 0011. In some configurations, the halogenated hydrocar Handling Systems Using Rare Earth Metals', each of which bon comprises one or more of a halogenated methane, chlo are incorporated in their entirety herein by this reference. radane, toxaphene, trihalomethane, endrin, heptachlor, 0002 Cross reference is made to U.S. patent application hexachlorocyclopentadiene, hexachlorobutadiene, lindane, Ser. No. 13/244,117 filed Sep. 23, 2011, entitled “PARTICU aldrin and dieldrin. LATE CERIUMDIOXIDE AND AN INSITU METHOD FORMAKING 0012. In some configuration, the halogenated carboxylic ANDUSING THE SAME' having attorney docket no. 6062-89-4, acid comprises one or more of halogenated acetic acid, triha which is incorporated herein by this reference in its entirety. loacetic acid, trichloroacetic acid, tribromoacetic acid, tri 0003 Cross reference is made to U.S. patent application iodoacetic acid, 2,4-D, dalapon, picloram, and dicamba. Ser. No. 13/356,574 filed Jan. 23, 2012, entitled “RARE 0013 In some configurations, the rare earth-containing EARTH REMOVAL OF PHOSPHORUS-CONTAINING MATERIALS’ additive removes at least most of the disinfection by-product. having attorney docket no. 6062-89-5, which is incorporated In some configurations, the rare earth-containing additive herein by this reference in its entirety. removes at least most of the disinfection by-product precur 0004 Cross reference is made to U.S. patent application sor. In some configurations, the rare earth-containing additive Ser. No. 13/356,581 filed Jan. 23, 2012, entitled “RARE removes at least most of the disinfection by-product and at EARTH REMOVAL OF HYDRATED AND HYDROXYL SPECIES' least most of the disinfection by-product precursor. having attorney docket no. 6062-89-6, which is incorporated 0014. In some configurations, the rare earth-containing herein by this reference in its entirety. additive is a water soluble cerium (III) salt. In some configu rations, the rare earth-containing additive is a cerium (IV)- FIELD containing composition. 0005. The disclosure relates generally to the treatment of 0015. In some embodiments, the rare earth-containing waters to remove target materials and particularly to treat additive removes at least most of target material contained in ment of waters containing disinfection by-products, disinfec the water. Preferably, the target material is one or more of tion by-product precursors and other target materials with alachor (or 2-chloro-N-(2,6-diethylpheynyl)-N-(methoxym rare earths. ethyl)acetamide), benzoapyrene, chlordane (or octachloro 4.7-methanohydroindane), 2,4-D (or 2,4-dichlorophenoxy) BACKGROUND acetic acid), dalapon (or CHC(C1)-COH), bis(2-ethylhexyl 0006. This disclosure relates generally to method and adipate (or hexanedioic acid bis(2-ethylhexyl) ester), endot compositions for removing contaminants from streams and is hal (or 7-Oxabicyclo[2.2.1]heptane-2,3-dicarboxylic acid), particularly concerned with methods and compositions for oxamyl (or Vydate), picloram (or 4-amino-3,5,6-trichloro-2- removing contaminants from municipal waters, recreational pyridinecarboxylic acid), simazine (or 6-chloro-N,N'-dietyl waters, municipal wastewaters, drinking waters (including) 1.3.5-triazine-2,4-diamine), halogentate methane, trihalom municipal drinking waters, industrial waters to name a few. ethane, chloramine, toxaphene, trihalomethane, endrin, 0007 Various techniques have been used to remove con heptachlor, hexachlorocyclopentadiene, hexachlorobutadi taminants from Such waters. Examples of Such techniques ene, lindane, aldrin, dieldrin, halogenated acetic acid, triha include removal Such materials using activated carbon, ion loacetic acid, trichloroacetic acid, tribromoacetic acid, tri exchange resins, electrodialysis and precipitation using tran iodoacetic acid, dicamba, and toxaphen. sition metals. However, these techniques are hindered by the 0016. In some configurations, the target material is one or difficulty that many harmful contaminants are not Substan both of a phosphate and an organophosphate. tially removed. 0017. In some embodiments, the disinfection-by-product comprises one or both of a halogenated hydrocarbon and SUMMARY halogenated carboxylic acid. 0008. These and other needs are addressed by the various 0018. In some configurations, the halogenated hydrocar aspects, embodiments, and configurations of the present dis bon comprises one or more of a halogenated methane, chlo closure. radane, toxaphene, trihalomethane, endrin, heptachlor, 0009. Some embodiments include a method having the hexachlorocyclopentadiene, hexachlorobutadiene, lindane, steps of receiving a water containing at least one of a disin aldrin and dieldrin. fection by-product and a disinfection by-product precursor, 0019. In some configuration, the halogenated carboxylic and contacting the water with a rare earth-containing additive acid comprises one or more of halogenated acetic acid, triha to remove at least one of the disinfection by-product and loacetic acid, trichloroacetic acid, tribromoacetic acid, tri disinfection by-product precursor from the water to form a iodoacetic acid, 2,4-D, dalapon, picloram, and dicamba. US 2012/0223022 A1 Sep. 6, 2012 0020. In some configurations, the disinfection by-product furanone, bromate, halonitromethane, haloamide, iodo-acid, precursor comprises one or more of an aldehyde, carboxylic iodo-trihalomethane, nitrosamine, and dihaloaldehyde. Pref acid and ether. erably, the disinfection by-product precursor is one or more of 0021. Some embodiments include a method having the t-butyl methyl ether, diazomethane, hypohalous acid, alde steps of receiving a water containing at least one of a disin hyde, carboxylic acid, and chloramines. fection by-product, disinfection by-product precursor and a 0029. In some configurations,
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