CA3110707A1 - Control of toc, perchlorate, and pfas through advanced oxidation and selective ion exchange process - Google Patents
Control of toc, perchlorate, and pfas through advanced oxidation and selective ion exchange process Download PDFInfo
- Publication number
- CA3110707A1 CA3110707A1 CA3110707A CA3110707A CA3110707A1 CA 3110707 A1 CA3110707 A1 CA 3110707A1 CA 3110707 A CA3110707 A CA 3110707A CA 3110707 A CA3110707 A CA 3110707A CA 3110707 A1 CA3110707 A1 CA 3110707A1
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- CA
- Canada
- Prior art keywords
- perchlorate
- aopr
- persulfate
- water
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 title claims abstract description 59
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000005342 ion exchange Methods 0.000 title description 4
- 230000003647 oxidation Effects 0.000 title description 4
- 238000007254 oxidation reaction Methods 0.000 title description 4
- 101150060820 Pfas gene Proteins 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000009303 advanced oxidation process reaction Methods 0.000 claims abstract description 30
- 150000005857 PFAS Chemical class 0.000 claims abstract description 29
- 101001136034 Homo sapiens Phosphoribosylformylglycinamidine synthase Proteins 0.000 claims abstract description 27
- 102100036473 Phosphoribosylformylglycinamidine synthase Human genes 0.000 claims abstract description 27
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 18
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims description 55
- 229920005989 resin Polymers 0.000 claims description 55
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 15
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010977 unit operation Methods 0.000 claims description 6
- -1 persulfate compound Chemical class 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- 238000012544 monitoring process Methods 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 230000003134 recirculating effect Effects 0.000 claims description 2
- 238000009420 retrofitting Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 15
- 230000001590 oxidative effect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- 239000000356 contaminant Substances 0.000 description 5
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003673 groundwater Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 231100000693 bioaccumulation Toxicity 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004886 process control Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 102100027667 Carboxy-terminal domain RNA polymerase II polypeptide A small phosphatase 2 Human genes 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 101000725947 Homo sapiens Carboxy-terminal domain RNA polymerase II polypeptide A small phosphatase 2 Proteins 0.000 description 1
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000002262 irrigation Effects 0.000 description 1
- 238000003973 irrigation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000010841 municipal wastewater Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000011071 total organic carbon measurement Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/04—Processes using organic exchangers
- B01J41/05—Processes using organic exchangers in the strongly basic form
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/326—Lamp control systems
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/32—Details relating to UV-irradiation devices
- C02F2201/328—Having flow diverters (baffles)
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/001—Upstream control, i.e. monitoring for predictive control
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/003—Downstream control, i.e. outlet monitoring, e.g. to check the treating agents, such as halogens or ozone, leaving the process
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/005—Processes using a programmable logic controller [PLC]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/03—Pressure
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/29—Chlorine compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/40—Liquid flow rate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
Abstract
Systems and methods for controlling TOC, perchlorate, and/or PFAS levels in water involving an advanced oxidation process (AOP) combined with ion exchange resin are disclosed.
Description
CONTROL OF TOC, PERCHLORATE, AND PFAS THROUGH ADVANCED
OXIDATION AND SELECTIVE ION EXCHANGE PROCESS
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of priority to -U.S. Provisional Patent Application Serial No. 62/733,149 as filed on September 28, 2018 and titled "CONTROL OF
TOC, PERCHLORATE, AND PFAS THROUGH VAN OX AOP AND SELECTIVE ION
EXCHANGE PROCESS," the entire disclosure of which is hereby incorporated herein by reference in its entirety for all purposes.
FIELD OF THE TECHNOLOGY
Aspects relate generally to water treatment and, more specifically, to controlling the level of one or more target constituents in water.
BACKGROUND
There is rising concern about the presence of various contaminants in municipal wastewater, surface water, drinking water, and groundwater. For example, perchlorate ions in water are of concern, as well as per- and polyfluorinated alkyl substances (PFAS s) and PFAS precursors, along with a general concern with respect to total organic carbon (TOC), PFASs are organic compounds consisting of fluorine, carbon and heteroatoms such as oxygen, nitrogen and sulfur. The hydrophobicity of fluorocarbons and extreme electronegativity of fluorine give these and similar compounds unusual properties. Initially, many of these compounds were used as gases in the fabrication of integrated circuits. The ozone destroying properties of these molecules restricted their use and resulted in methods to prevent their release into the atmosphere. But other PFAS such as fiuoro-surfactants have become increasingly popular. Although used in relatively small amounts, these compounds are readily released into the environment where their extreme hydrophobicity as well as negligible rates of natural decomposition results in environmental persistence and bioaccumulation. It appears as if even low levels of bioaccumulation may lead to serious health consequences for contaminated animals such as human beings, the young being especially susceptible. The environmental effects of these compounds on plants and microbes are as yet largely unknown. Nevertheless, serious efforts to limit the environmental release of PFAS are now commencing.
SUMMARY
In accordance with one or more aspects, a method of treating water including perchlorate and/or per- and polyfluoroalkyl substances (PFASs) is disclosed.
The method may comprise providing feed water having an initial concentration of perchlorate or PFAS, dosing the feed water with an oxidizer, exposing the dosed water to ultraviolet (UV) light to produce a first treated solution, and directing the first treated solution to a selective ion exchange resin to produce product water.
In some aspects, the oxidizer may comprise a persulfate compound. The persulfate compound may comprise ammonium persulfate, sodium persulfate, and/or potassium persulfate. The selective ion exchange resin may comprise a perchlorate selective resin. The perchlorate selective resin may comprise a strong base anion resin. The perchlorate selective resin may comprise a tri-butyl amine resin.
In some aspects, the method may further comprise monitoring a pressure, temperature, pH, concentration, flow rate, or total organic carbon (TOC) level in the feed water, first treated solution, and/or product water. A TOC level of the first treated solution may be less than about 0.5 ppb, A perchlorate concentration in the product water may be less than about 6 ppb, The perchlorate concentration in the product water may be less than about 1 ppb.
In some aspects, the method may further comprise recirculating at least a portion of the first treated solution to the feed water. The method may further comprise delivering the product water to a potable point of use. The method may further comprise replacing the selective ion exchange resin upon detecting perchlorate breakthrough that exceeds a threshold value.
In accordance with one or more aspects, a water treatment system is disclosed.
The system may comprise an advanced oxidation process reactor (AOPR) having an inlet and an outlet, and at least one perchlorate selective resin bed fluidly connected downstream of the AOPR outlet.
In some aspects, the system may further comprise a source of water containing perchlorate and/or PFAS fluidly connected to the AOPR inlet. The AOPR may comprise first and second subreactors arranged in parallel. The AOPR may be fluidly connected to a source of persulfate and may comprise a UV light source. The system may comprise two perchlorate selective resin beds arranged in parallel.
OXIDATION AND SELECTIVE ION EXCHANGE PROCESS
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of priority to -U.S. Provisional Patent Application Serial No. 62/733,149 as filed on September 28, 2018 and titled "CONTROL OF
TOC, PERCHLORATE, AND PFAS THROUGH VAN OX AOP AND SELECTIVE ION
EXCHANGE PROCESS," the entire disclosure of which is hereby incorporated herein by reference in its entirety for all purposes.
FIELD OF THE TECHNOLOGY
Aspects relate generally to water treatment and, more specifically, to controlling the level of one or more target constituents in water.
BACKGROUND
There is rising concern about the presence of various contaminants in municipal wastewater, surface water, drinking water, and groundwater. For example, perchlorate ions in water are of concern, as well as per- and polyfluorinated alkyl substances (PFAS s) and PFAS precursors, along with a general concern with respect to total organic carbon (TOC), PFASs are organic compounds consisting of fluorine, carbon and heteroatoms such as oxygen, nitrogen and sulfur. The hydrophobicity of fluorocarbons and extreme electronegativity of fluorine give these and similar compounds unusual properties. Initially, many of these compounds were used as gases in the fabrication of integrated circuits. The ozone destroying properties of these molecules restricted their use and resulted in methods to prevent their release into the atmosphere. But other PFAS such as fiuoro-surfactants have become increasingly popular. Although used in relatively small amounts, these compounds are readily released into the environment where their extreme hydrophobicity as well as negligible rates of natural decomposition results in environmental persistence and bioaccumulation. It appears as if even low levels of bioaccumulation may lead to serious health consequences for contaminated animals such as human beings, the young being especially susceptible. The environmental effects of these compounds on plants and microbes are as yet largely unknown. Nevertheless, serious efforts to limit the environmental release of PFAS are now commencing.
SUMMARY
In accordance with one or more aspects, a method of treating water including perchlorate and/or per- and polyfluoroalkyl substances (PFASs) is disclosed.
The method may comprise providing feed water having an initial concentration of perchlorate or PFAS, dosing the feed water with an oxidizer, exposing the dosed water to ultraviolet (UV) light to produce a first treated solution, and directing the first treated solution to a selective ion exchange resin to produce product water.
In some aspects, the oxidizer may comprise a persulfate compound. The persulfate compound may comprise ammonium persulfate, sodium persulfate, and/or potassium persulfate. The selective ion exchange resin may comprise a perchlorate selective resin. The perchlorate selective resin may comprise a strong base anion resin. The perchlorate selective resin may comprise a tri-butyl amine resin.
In some aspects, the method may further comprise monitoring a pressure, temperature, pH, concentration, flow rate, or total organic carbon (TOC) level in the feed water, first treated solution, and/or product water. A TOC level of the first treated solution may be less than about 0.5 ppb, A perchlorate concentration in the product water may be less than about 6 ppb, The perchlorate concentration in the product water may be less than about 1 ppb.
In some aspects, the method may further comprise recirculating at least a portion of the first treated solution to the feed water. The method may further comprise delivering the product water to a potable point of use. The method may further comprise replacing the selective ion exchange resin upon detecting perchlorate breakthrough that exceeds a threshold value.
In accordance with one or more aspects, a water treatment system is disclosed.
The system may comprise an advanced oxidation process reactor (AOPR) having an inlet and an outlet, and at least one perchlorate selective resin bed fluidly connected downstream of the AOPR outlet.
In some aspects, the system may further comprise a source of water containing perchlorate and/or PFAS fluidly connected to the AOPR inlet. The AOPR may comprise first and second subreactors arranged in parallel. The AOPR may be fluidly connected to a source of persulfate and may comprise a UV light source. The system may comprise two perchlorate selective resin beds arranged in parallel.
-2-In some aspects, the perchlorate selective resin bed may comprise a strong base anion resin. The perchlorate selective resin bed may comprise a tri-butyl amine resin. The tri-butyl amine resin may comprise a quaternary amine functional group.
In some aspects, the system may further comprise at least one sensor configured to detect a pressure, temperature, pH, concentration, flow rate, or total organic carbon (TOC) level. The system may still further comprise a controller in communication with the at least one sensor and configured to control a rate at which persulfate is introduced to the AOPR
and/or control a dose of irradiation associated with the AOPR.
In some aspects, the system may further comprise a posttreatment unit fluidly connected downstream of at least one of the AOPR and the persulfate selective resin bed.
The posttreatment unit may comprise an activated carbon unit. Likewise, the system may further comprise a pretreatment unit operation fluidly connected upstream of the AOPR.
In accordance with one or more aspects, a method of retrofitting a water treatment system is disclosed. The method may comprise providing a persulfate selective resin bed, and fluidly connecting the persulfate selective resin bed downstream of an AOPR.
In some aspects, the method may further comprise integrating an activated carbon unit operation between the AOPR and the persulfate selective resin bed.
The disclosure contemplates all combinations of any one or more of the foregoing aspects and/or embodiments, as well as combinations with any one or more of the embodiments set forth in the detailed description and any examples.
BRIEF DESCRIPTION OF THE DRAWINGS
Certain illustrative features and examples are described below with reference to the accompanying figures in which:
FIG. 1 presents a schematic of an advanced oxidation process reactor (AOPR) in accordance with one or more embodiments;
FIGS. 2-3 present schematics of water treatment systems involving AOPR paired with ion exchange resin beds in accordance with one or more embodiments; and FIG. 4 presents data discussed in an accompanying Example.
It will be recognized by the person of ordinary skill in the art, given the benefit of this disclosure, that the figures are purely for illustrative purposes. Other features may be present in the embodiments disclosed herein without departing from the scope of the description.
In some aspects, the system may further comprise at least one sensor configured to detect a pressure, temperature, pH, concentration, flow rate, or total organic carbon (TOC) level. The system may still further comprise a controller in communication with the at least one sensor and configured to control a rate at which persulfate is introduced to the AOPR
and/or control a dose of irradiation associated with the AOPR.
In some aspects, the system may further comprise a posttreatment unit fluidly connected downstream of at least one of the AOPR and the persulfate selective resin bed.
The posttreatment unit may comprise an activated carbon unit. Likewise, the system may further comprise a pretreatment unit operation fluidly connected upstream of the AOPR.
In accordance with one or more aspects, a method of retrofitting a water treatment system is disclosed. The method may comprise providing a persulfate selective resin bed, and fluidly connecting the persulfate selective resin bed downstream of an AOPR.
In some aspects, the method may further comprise integrating an activated carbon unit operation between the AOPR and the persulfate selective resin bed.
The disclosure contemplates all combinations of any one or more of the foregoing aspects and/or embodiments, as well as combinations with any one or more of the embodiments set forth in the detailed description and any examples.
BRIEF DESCRIPTION OF THE DRAWINGS
Certain illustrative features and examples are described below with reference to the accompanying figures in which:
FIG. 1 presents a schematic of an advanced oxidation process reactor (AOPR) in accordance with one or more embodiments;
FIGS. 2-3 present schematics of water treatment systems involving AOPR paired with ion exchange resin beds in accordance with one or more embodiments; and FIG. 4 presents data discussed in an accompanying Example.
It will be recognized by the person of ordinary skill in the art, given the benefit of this disclosure, that the figures are purely for illustrative purposes. Other features may be present in the embodiments disclosed herein without departing from the scope of the description.
-3-DETAILED DESCRIPTION
In accordance with one or more embodiments, systems and methods relate to the treatment of water. The level of one or more target constituents may be strategically controlled. Various unit operations may be coupled together as part of an integrated system in order to provide a product water meeting preestablished requirements.
Beneficially, synergies between unit operations may be leveraged to produce a desired product water.
In accordance with one or more embodiments, water to be treated may contain one or more target compounds. For example, process water may contain various organic compounds, i.e. recalcitrant organic contaminants, for example, 1,4-dioxane, trichloroethylene (TCE), perchloroethylene (PCE), urea, isopropanol, chloroform, atrazine, tryptophan, and formic acid. Process water may also contain perchlorate and/or PFAS as described herein.
In accordance with one or more embodiments, PFASs, also referred to as perfluorinated chemicals (PFCs), may be targeted. These man-made chemical compounds .. are very stable and resilient to breakdown in the environment. They may also be highly water soluble because they carry a negative charge when dissolved. They were developed and widely used as a repellant and protective coating. Though they have now largely been phased out, elevated levels are still widespread. For example, water contaminated with PFAS
or PFC may be found in industrial communities where they were manufactured or used, as well as near airfields or military bases where firefighting drills were conducted. PFAS or PFC may also be found in remote locations via water or air migration. Many municipal water systems are undergoing aggressive testing and treatment. In some specific non-limiting embodiments, common PFCs such as perfluorooetanoic acid (PFOA) and/or perfluorooctane sulfonic acid (PFOS) may be removed from water. The U.S. Environmental Protection Agency (EPA) developed revised guidelines in May 2016 of a combined lifetime exposure of 70 parts per trillion (ppt) for PFOS and PFOA. Federal, state, and/or private bodies may also issue relevant regulations.
Likewise, various local, federal, and/or private agencies may establish discharge requirements pertaining to perchlorate levels. EPA Regulations 314, 331, and 332 relate to measuring perchlorate ions. The state of California has a discharge requirement of less than 6 parts per billion (ppb) perchlorate, while the state of Massachusetts has a discharge requirement of less than 1ppb perchlorate.
In accordance with one or more embodiments, product water as described herein may be potable. In at least some embodiments, treatment techniques as described herein may find
In accordance with one or more embodiments, systems and methods relate to the treatment of water. The level of one or more target constituents may be strategically controlled. Various unit operations may be coupled together as part of an integrated system in order to provide a product water meeting preestablished requirements.
Beneficially, synergies between unit operations may be leveraged to produce a desired product water.
In accordance with one or more embodiments, water to be treated may contain one or more target compounds. For example, process water may contain various organic compounds, i.e. recalcitrant organic contaminants, for example, 1,4-dioxane, trichloroethylene (TCE), perchloroethylene (PCE), urea, isopropanol, chloroform, atrazine, tryptophan, and formic acid. Process water may also contain perchlorate and/or PFAS as described herein.
In accordance with one or more embodiments, PFASs, also referred to as perfluorinated chemicals (PFCs), may be targeted. These man-made chemical compounds .. are very stable and resilient to breakdown in the environment. They may also be highly water soluble because they carry a negative charge when dissolved. They were developed and widely used as a repellant and protective coating. Though they have now largely been phased out, elevated levels are still widespread. For example, water contaminated with PFAS
or PFC may be found in industrial communities where they were manufactured or used, as well as near airfields or military bases where firefighting drills were conducted. PFAS or PFC may also be found in remote locations via water or air migration. Many municipal water systems are undergoing aggressive testing and treatment. In some specific non-limiting embodiments, common PFCs such as perfluorooetanoic acid (PFOA) and/or perfluorooctane sulfonic acid (PFOS) may be removed from water. The U.S. Environmental Protection Agency (EPA) developed revised guidelines in May 2016 of a combined lifetime exposure of 70 parts per trillion (ppt) for PFOS and PFOA. Federal, state, and/or private bodies may also issue relevant regulations.
Likewise, various local, federal, and/or private agencies may establish discharge requirements pertaining to perchlorate levels. EPA Regulations 314, 331, and 332 relate to measuring perchlorate ions. The state of California has a discharge requirement of less than 6 parts per billion (ppb) perchlorate, while the state of Massachusetts has a discharge requirement of less than 1ppb perchlorate.
In accordance with one or more embodiments, product water as described herein may be potable. In at least some embodiments, treatment techniques as described herein may find
-4-utility in the municipal water treatment market and may be used to produce drinking water.
In other embodiments, product water may be used for irrigation. In still other embodiments, product water may be returned to surface water or groundwater.
In accordance with one or more embodiments, an advanced oxidation process (AOP) may be implemented to target total organic carbon (TOC) levels in process water.
AOP generally utilizes UV activation of an oxidizing salt for the destruction of various organic species. Any strong oxidant may be used. In some non-limiting embodiments, a persulfate compound may be used. In at least some embodiments, ammonium persulfate, sodium persulfate, and /or potassium persulfate may be used. Other strong oxidants, e.g. ozone or hydrogen peroxide, may also be used. The process water may be dosed with the oxidant.
In accordance with one or more embodiments, process water dosed with an oxidant may be exposed to a source of ultraviolet (UV) light. For instance, the systems and methods disclosed herein may include the use of one or more UV lamps, each emitting light at a desired wavelength in the UV range of the electromagnetic spectrum. For instance, according to some embodiments, the UV lamp may have a wavelength ranging from about 180 to about 280 urn, and in some embodiments, may have a wavelength ranging from about 185 urn to about 254 nm. According to various aspects, the combination of persulfate with UV light is more effective than using either component on its own.
According to some embodiments, a source of persulfate may first be introduced to the contaminated groundwater, which may be followed by exposure of the contaminated groundwater to UV light. According to other embodiments, the persulfate addition and the UV exposure may occur at approximately the same time, i.e., simultaneously or nearly simultaneously. According to various aspects, the persulfate and the UV light function to oxidize organic contaminant into non-hazardous compounds, including carbon dioxide and water.
According to some embodiments, adjusting a dose of the ultraviolet light may comprise at least one of adjusting an intensity of the UV light and adjusting an exposure time of the UV light to the first treated aqueous solution. For instance, the first treated aqueous solution may be held or otherwise contained within a reactor or vessel and be exposed to UV
light for a predetermined exposure time while the solution is housed within the reactor or vessel, According to some embodiments, baffles or other flow control devices positioned within the reactor or vessel may also contribute to containing the first treated aqueous solution for a predetet mined exposure time. According to other embodiments, adjusting a
In other embodiments, product water may be used for irrigation. In still other embodiments, product water may be returned to surface water or groundwater.
In accordance with one or more embodiments, an advanced oxidation process (AOP) may be implemented to target total organic carbon (TOC) levels in process water.
AOP generally utilizes UV activation of an oxidizing salt for the destruction of various organic species. Any strong oxidant may be used. In some non-limiting embodiments, a persulfate compound may be used. In at least some embodiments, ammonium persulfate, sodium persulfate, and /or potassium persulfate may be used. Other strong oxidants, e.g. ozone or hydrogen peroxide, may also be used. The process water may be dosed with the oxidant.
In accordance with one or more embodiments, process water dosed with an oxidant may be exposed to a source of ultraviolet (UV) light. For instance, the systems and methods disclosed herein may include the use of one or more UV lamps, each emitting light at a desired wavelength in the UV range of the electromagnetic spectrum. For instance, according to some embodiments, the UV lamp may have a wavelength ranging from about 180 to about 280 urn, and in some embodiments, may have a wavelength ranging from about 185 urn to about 254 nm. According to various aspects, the combination of persulfate with UV light is more effective than using either component on its own.
According to some embodiments, a source of persulfate may first be introduced to the contaminated groundwater, which may be followed by exposure of the contaminated groundwater to UV light. According to other embodiments, the persulfate addition and the UV exposure may occur at approximately the same time, i.e., simultaneously or nearly simultaneously. According to various aspects, the persulfate and the UV light function to oxidize organic contaminant into non-hazardous compounds, including carbon dioxide and water.
According to some embodiments, adjusting a dose of the ultraviolet light may comprise at least one of adjusting an intensity of the UV light and adjusting an exposure time of the UV light to the first treated aqueous solution. For instance, the first treated aqueous solution may be held or otherwise contained within a reactor or vessel and be exposed to UV
light for a predetermined exposure time while the solution is housed within the reactor or vessel, According to some embodiments, baffles or other flow control devices positioned within the reactor or vessel may also contribute to containing the first treated aqueous solution for a predetet mined exposure time. According to other embodiments, adjusting a
-5-dose of the ultraviolet light may comprise adjusting a flow rate of the first treated aqueous solution. For instance, the first treated aqueous solution may pass through a conduit that is configured to allow UV light to pass through to the conduit to irradiate the first treated aqueous solution. According to other embodiments, the dose of the UV light may be adjusted .. by adjusting a power setting of the UV light, or by adjusting the wavelength of the UV lamp.
According to at least one embodiment, a controller, as discussed further below, may be used to control the oxidant and/or UV dose for batch and flow-through processes, including the lamp power, the exposure time, and the flow rate. Process control may be based on input from one or more sensors monitoring various inlet and outlet concentrations, such as a TOG concentration associated with an AOP reactor. For example, a higher dose of oxidant and/or UV may be appropriate when the concentration of organics is high. Other parameters such as temperature, pressure, pH level, and flow rate, may also be controlling variables.
In some embodiments, AOP may reduce TOC levels to about 1 ppb or less. In at least some embodiments, AOP may reduce TOG levels to about 0.5 ppb or less.
In accordance with one or more embodiments, AOP may typically involve a persulfate feed system in front of UV lamps. AOP is commonly known, including Vanox AOP system commercially available from Evoqua Water Technologies LLC
(Pittsburgh, PA), which may be implemented. Some related patents and patent application publications are hereby incorporated herein by reference in their entireties for all purposes including: U.S.
Patent No. 8,591,730; 8,652,336; 8,961,798; US201602077813; and US20180273412 all to Evoqua Water Technologies LLC.
FIG. 1 presents a schematic illustrating the Vanox AOP system. Feed water is mixed with a persulfate ion and then exposed to UV light. Process control may be implemented with respect to various parameters such as but not limited to pressure, temperature, and recycle volume. Water exiting the AOP system may be further processed as described further herein.
In accordance with one or more embodiments, AOP may generally be effective at removing organic compounds and may be used to control TOG. AOP may have difficulty in removing certain compounds depending on process conditions. For example, AOP
may have difficulty removing PFAS at a neutral pH level.
Notably, it has been recognized that undesirable oxidation byproducts may be generated via AOP. For example, perchlorate may be produced as an AOP
byproduct.
Treatment of difficult to remove TOCs via AOP may be associated with even greater
According to at least one embodiment, a controller, as discussed further below, may be used to control the oxidant and/or UV dose for batch and flow-through processes, including the lamp power, the exposure time, and the flow rate. Process control may be based on input from one or more sensors monitoring various inlet and outlet concentrations, such as a TOG concentration associated with an AOP reactor. For example, a higher dose of oxidant and/or UV may be appropriate when the concentration of organics is high. Other parameters such as temperature, pressure, pH level, and flow rate, may also be controlling variables.
In some embodiments, AOP may reduce TOC levels to about 1 ppb or less. In at least some embodiments, AOP may reduce TOG levels to about 0.5 ppb or less.
In accordance with one or more embodiments, AOP may typically involve a persulfate feed system in front of UV lamps. AOP is commonly known, including Vanox AOP system commercially available from Evoqua Water Technologies LLC
(Pittsburgh, PA), which may be implemented. Some related patents and patent application publications are hereby incorporated herein by reference in their entireties for all purposes including: U.S.
Patent No. 8,591,730; 8,652,336; 8,961,798; US201602077813; and US20180273412 all to Evoqua Water Technologies LLC.
FIG. 1 presents a schematic illustrating the Vanox AOP system. Feed water is mixed with a persulfate ion and then exposed to UV light. Process control may be implemented with respect to various parameters such as but not limited to pressure, temperature, and recycle volume. Water exiting the AOP system may be further processed as described further herein.
In accordance with one or more embodiments, AOP may generally be effective at removing organic compounds and may be used to control TOG. AOP may have difficulty in removing certain compounds depending on process conditions. For example, AOP
may have difficulty removing PFAS at a neutral pH level.
Notably, it has been recognized that undesirable oxidation byproducts may be generated via AOP. For example, perchlorate may be produced as an AOP
byproduct.
Treatment of difficult to remove TOCs via AOP may be associated with even greater
-6-perchlorate generation. A large excess of persulfate may be required in response to a high TOC level and/or low UV transmittance of the water. Also, PFAS may be generated from PFAS precursors during oxidation, Beneficially, perchlorate and/or PFAS may be targeted for removal by one or more downstream processes in accordance with various embodiments.
In accordance with one or more embodiments, AOP product water may be further processed to remove target contaminants not removed by AOP. In some embodiments, AOP
may be supplemented as part of a larger water treatment system in order to remove certain contaminants such as perchlorate and/or PFAS. In at least some embodiments, AOP may be combined with selective ion exchange resin as described further herein.
In accordance with one or more embodiments, AOP product water may be treated with an ion selective resin to remove one or more further target constituents.
In some embodiments, ion selective resin may remove perchlorate and/or PFAS from water. FIG. 2 presents a schematic of a combination system comprising AOP coupled with a selective ion exchange process to remove perchlorate ions and/or PFAS. As illustrated, parallel resin columns may be implemented in order to ensure sufficient processing capability and continuity.
In accordance with one or more embodiments, an ion selective resin bed may be effective to bring perchlorate levels down to regulatory levels. For example, a concentration of perchlorate in treated effluent may be less than about 6 ppb, e.g. about 1 ppb or less.
In accordance with one or more embodiments, the ion selective resin may be an anion selective resin, i.e. a strong base anion resin. In some embodiments, the resin may be a perchlorate selective ion exchange resin. Perchlorate selective resins will generally also target PFAS. In at least some embodiments, the resin may be a tri-butyl amine resin. For example, the resin may be a Dowexe P SR-2 or ResinTeche SIR-110-HP tri-butyl amine resin. In some non-limiting embodiments, a tri-butyl amine resin may have a quaternary amine functional group. Table I provides specifications for one non-limiting example of a perchlorate selective resin effective for removal of both perchlorate ions and PFAS in accordance with various embodiments.
In accordance with one or more embodiments, AOP product water may be further processed to remove target contaminants not removed by AOP. In some embodiments, AOP
may be supplemented as part of a larger water treatment system in order to remove certain contaminants such as perchlorate and/or PFAS. In at least some embodiments, AOP may be combined with selective ion exchange resin as described further herein.
In accordance with one or more embodiments, AOP product water may be treated with an ion selective resin to remove one or more further target constituents.
In some embodiments, ion selective resin may remove perchlorate and/or PFAS from water. FIG. 2 presents a schematic of a combination system comprising AOP coupled with a selective ion exchange process to remove perchlorate ions and/or PFAS. As illustrated, parallel resin columns may be implemented in order to ensure sufficient processing capability and continuity.
In accordance with one or more embodiments, an ion selective resin bed may be effective to bring perchlorate levels down to regulatory levels. For example, a concentration of perchlorate in treated effluent may be less than about 6 ppb, e.g. about 1 ppb or less.
In accordance with one or more embodiments, the ion selective resin may be an anion selective resin, i.e. a strong base anion resin. In some embodiments, the resin may be a perchlorate selective ion exchange resin. Perchlorate selective resins will generally also target PFAS. In at least some embodiments, the resin may be a tri-butyl amine resin. For example, the resin may be a Dowexe P SR-2 or ResinTeche SIR-110-HP tri-butyl amine resin. In some non-limiting embodiments, a tri-butyl amine resin may have a quaternary amine functional group. Table I provides specifications for one non-limiting example of a perchlorate selective resin effective for removal of both perchlorate ions and PFAS in accordance with various embodiments.
-7-
8 Table I: Specifications of Sample Perchlorate Selective Resin Matrix Styrene-divinylbenzene, gel Type Strong base anion Physical Form White to yellow spherical beads Ionic Form as Shipped Cr Form Total Exchange Capacity ;,>. 0.7 eel/
Water Retention Capacity 25- 35%
Particle Size Particle Diameter b 700 50 PM
Uniformity Coefficient <1.1 < 300 pm 1% max Particle Density 1.07 giml_ Bulk Density, as Shipped 690 g/t. (43 IblIP) In accordance with one or more embodiments, a sorption or filtration technology may also be implemented to remove excess oxidizer downstream of the AOP. In some embodiments, an activated carbon unit may process AOP product water in order to remove excess oxidizer. In at least some embodiments the activated carbon unit is directly downstream of the AOPR while in other embodiments the activated carbon unit may be integrated downstream of the ion exchange resin bed.
FIG. 3 presents a detailed schematic of a water treatment system in which an AOPR is coupled to an ion exchange resin bed. The system includes a granular activated carbon (GAC) bed downstream of the AOPR. The illustrated system also optionally includes an effluent break tank.
In accordance with one or more embodiments, one or more sensors may measure a PFAS level upstream and/or downstream of the ion exchange resin bed. A
controller may receive input from the sensor(s) in order to monitor PFAS levels, intermittently or continuously. Monitoring may be in real-time or with lag, either onsite or remotely and either manually or automatically. In some embodiments, samples may be sent offsite for analysis. A detected PFAS level downstream of the ion exchange resin bed may be compared to a threshold level that may be considered unacceptable, such as may be dictated by a controlling regulatory body. The resin bed may be replaced in response to detecting an unacceptable breakthrough level. Parallel resin beds may facilitate continuous opertin during maintenance.
Additional properties such as but not limited to pH, pressure, flow rate, temperature, perchlorate concentration, and TOC levels may be monitored by various interconnected or interrelational sensors throughout the system. The controller may be in communication with these various sensors. The controller may send one or more control signals to adjust various operational parameters. For example, in response to detected levels of organics, one or more properties of the AOPR may be adjusted. In some embodiments, oxidant dosage and/or applied UV levels may be adjusted in response to sensor input as described above.
In accordance with one or more embodiments, an existing water treatment system may be retrofitted. For example, an existing system involving an AOPR may be retrofitted to control perchlorate and/or PFAS levels. An ion exchange resin bed as described herein may be provided. The resin bed may be fluidly connected downstream of the AOPR. An activated carbon unit may also be installed as described herein to address excess oxidant.
The function and advantages of these and other embodiments will be more fully understood from the following examples. The examples are intended to be illustrative in nature and are not to be considered as limiting the scope of the materials, systems, and methods discussed herein.
EXAMPLE
Various categories of anion exchange resins were tested to detelmine their respective perchlorate breakthrough profiles. Associated data is presented in FIG. 4 and indicates that tributylamine resin, generally characterized as being perchlorate selective, provides superior performance. Over 1.2 million gallons of water per cubic foot of resin was processed prior to breakthrough. In comparison, trimethylalamine (type I resin) experienced perchlorate breakthrough prior to processing 200,000 gallons of water per cubic foot.
Triethylamine, known as a nitrate selective resin, experienced perchlorate breakthrough after processing around 400,000 gallons per cubic foot.
A combined AOP and ion exchange resin water treatment system was operated. The process water flow rate to the system was 20 gpm and the water to be treated had a TOC level of 1.4 mg/l. In the AOPR, sodium persulfate was used as the oxidant at a dose of 81 mg/l. A
perchlorate-selective (Dowex0 PSR2 Plus) ion exchange resin was used downstream of the
Water Retention Capacity 25- 35%
Particle Size Particle Diameter b 700 50 PM
Uniformity Coefficient <1.1 < 300 pm 1% max Particle Density 1.07 giml_ Bulk Density, as Shipped 690 g/t. (43 IblIP) In accordance with one or more embodiments, a sorption or filtration technology may also be implemented to remove excess oxidizer downstream of the AOP. In some embodiments, an activated carbon unit may process AOP product water in order to remove excess oxidizer. In at least some embodiments the activated carbon unit is directly downstream of the AOPR while in other embodiments the activated carbon unit may be integrated downstream of the ion exchange resin bed.
FIG. 3 presents a detailed schematic of a water treatment system in which an AOPR is coupled to an ion exchange resin bed. The system includes a granular activated carbon (GAC) bed downstream of the AOPR. The illustrated system also optionally includes an effluent break tank.
In accordance with one or more embodiments, one or more sensors may measure a PFAS level upstream and/or downstream of the ion exchange resin bed. A
controller may receive input from the sensor(s) in order to monitor PFAS levels, intermittently or continuously. Monitoring may be in real-time or with lag, either onsite or remotely and either manually or automatically. In some embodiments, samples may be sent offsite for analysis. A detected PFAS level downstream of the ion exchange resin bed may be compared to a threshold level that may be considered unacceptable, such as may be dictated by a controlling regulatory body. The resin bed may be replaced in response to detecting an unacceptable breakthrough level. Parallel resin beds may facilitate continuous opertin during maintenance.
Additional properties such as but not limited to pH, pressure, flow rate, temperature, perchlorate concentration, and TOC levels may be monitored by various interconnected or interrelational sensors throughout the system. The controller may be in communication with these various sensors. The controller may send one or more control signals to adjust various operational parameters. For example, in response to detected levels of organics, one or more properties of the AOPR may be adjusted. In some embodiments, oxidant dosage and/or applied UV levels may be adjusted in response to sensor input as described above.
In accordance with one or more embodiments, an existing water treatment system may be retrofitted. For example, an existing system involving an AOPR may be retrofitted to control perchlorate and/or PFAS levels. An ion exchange resin bed as described herein may be provided. The resin bed may be fluidly connected downstream of the AOPR. An activated carbon unit may also be installed as described herein to address excess oxidant.
The function and advantages of these and other embodiments will be more fully understood from the following examples. The examples are intended to be illustrative in nature and are not to be considered as limiting the scope of the materials, systems, and methods discussed herein.
EXAMPLE
Various categories of anion exchange resins were tested to detelmine their respective perchlorate breakthrough profiles. Associated data is presented in FIG. 4 and indicates that tributylamine resin, generally characterized as being perchlorate selective, provides superior performance. Over 1.2 million gallons of water per cubic foot of resin was processed prior to breakthrough. In comparison, trimethylalamine (type I resin) experienced perchlorate breakthrough prior to processing 200,000 gallons of water per cubic foot.
Triethylamine, known as a nitrate selective resin, experienced perchlorate breakthrough after processing around 400,000 gallons per cubic foot.
A combined AOP and ion exchange resin water treatment system was operated. The process water flow rate to the system was 20 gpm and the water to be treated had a TOC level of 1.4 mg/l. In the AOPR, sodium persulfate was used as the oxidant at a dose of 81 mg/l. A
perchlorate-selective (Dowex0 PSR2 Plus) ion exchange resin was used downstream of the
-9-AOPR. Data pertaining to measured concentrations of 1,4-dioxane and perchlorate are presented in Table 2.
Table 2: 1,4-Dioxane and Perchlorate Data 1,4-Dioxane Summary (j.1g/L) INF Post Vanox EFF
3.48 0.03 3.17 0.03 3.38 0.03 Perchlorate Summary (lga) INF Post Vanox EFF
0.013 2.70 0.013 0.013 3.28 0.013 0.013 3.04 0.013 The data illustrates that only trace amounts of 1,4-dioxane was present in the treated product effluent. The AOPR appeared to generate perehlorate but the ion exchange resin was consistently effective at bringing the perchlorate levels down to only trace amounts in the treated product effluent.
The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. As used herein, the term "plurality"
refers to two or more items or components. The terms "comprising," "including," "carrying,"
"having,"
"containing," and "involving," whether in the written description or the claims and the like, are open-ended terms, i.e., to mean "including but not limited to." Thus, the use of such terms is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases "consisting of' and "consisting essentially of,"
are closed or semi-closed transitional phrases, respectively, with respect to the claims. Use of ordinal terms such as "first," "second," "third," and the like in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are perfoimed, but are used
Table 2: 1,4-Dioxane and Perchlorate Data 1,4-Dioxane Summary (j.1g/L) INF Post Vanox EFF
3.48 0.03 3.17 0.03 3.38 0.03 Perchlorate Summary (lga) INF Post Vanox EFF
0.013 2.70 0.013 0.013 3.28 0.013 0.013 3.04 0.013 The data illustrates that only trace amounts of 1,4-dioxane was present in the treated product effluent. The AOPR appeared to generate perehlorate but the ion exchange resin was consistently effective at bringing the perchlorate levels down to only trace amounts in the treated product effluent.
The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. As used herein, the term "plurality"
refers to two or more items or components. The terms "comprising," "including," "carrying,"
"having,"
"containing," and "involving," whether in the written description or the claims and the like, are open-ended terms, i.e., to mean "including but not limited to." Thus, the use of such terms is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases "consisting of' and "consisting essentially of,"
are closed or semi-closed transitional phrases, respectively, with respect to the claims. Use of ordinal terms such as "first," "second," "third," and the like in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are perfoimed, but are used
-10-merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements.
Having thus described several aspects of at least one embodiment, it is to be appreciated various alterations, modifications, and improvements will readily occur to those skilled in the art. Any feature described in any embodiment may be included in or substituted for any feature of any other embodiment. Such alterations, modifications, and improvements are intended to be part of this disclosure and are intended to be within the scope of the invention. Accordingly, the foregoing description and drawings are by way of example only.
Those skilled in the art should appreciate that the parameters and configurations described herein are exemplary and that actual parameters and/or configurations will depend on the specific application in which the disclosed methods and materials are used. Those skilled in the art should also recognize or be able to ascertain, using no more than routine experimentation, equivalents to the specific embodiments disclosed.
Having thus described several aspects of at least one embodiment, it is to be appreciated various alterations, modifications, and improvements will readily occur to those skilled in the art. Any feature described in any embodiment may be included in or substituted for any feature of any other embodiment. Such alterations, modifications, and improvements are intended to be part of this disclosure and are intended to be within the scope of the invention. Accordingly, the foregoing description and drawings are by way of example only.
Those skilled in the art should appreciate that the parameters and configurations described herein are exemplary and that actual parameters and/or configurations will depend on the specific application in which the disclosed methods and materials are used. Those skilled in the art should also recognize or be able to ascertain, using no more than routine experimentation, equivalents to the specific embodiments disclosed.
-11-
Claims (28)
1. A method of treating water including perchlorate and/or per- and polyfluoroalkyl substances (PFASs), comprising:
providing feed water having an initial concentration of perchlorate or PFAS;
dosing the feed water with an oxidizer;
exposing the dosed water to ultraviolet (UV) light to produce a first treated solution;
and directing the first treated solution to a selective ion exchange resin to produce product water.
providing feed water having an initial concentration of perchlorate or PFAS;
dosing the feed water with an oxidizer;
exposing the dosed water to ultraviolet (UV) light to produce a first treated solution;
and directing the first treated solution to a selective ion exchange resin to produce product water.
2. The method of claiin 1, wherein the oxidizer comprises a persulfate compound.
3. The method of claim 2, wherein the persulfate compound comprises ammonium persulfate, sodium persulfate, and/or potassium persulfate.
4. The method of claim 1, wherein the selective ion exchange resin comprises a perchlorate selective resin.
5. The method of claim 4, wherein the perchlorate selective resin comprises a strong base anion resin.
6. The method of claim 4, wherein the perchlorate selective resin comprises a tri-butyl amine resin.
7. The method of claim 1, further comprising monitoring a pressure, temperature, pH, concentration, flow rate, or total organic carbon (TOC) level in the feed water, first treated solution, and/or product water.
8. The method of claim 1, wherein a TOC level of the first treated solution is less than about 0.5 ppb.
9. The method of claim 1, wherein a perchlorate concentration in the product water is less than about 6 ppb.
10. The method of claim 9, wherein the perehlorate concentration in the product water is less than about 1 ppb.
11. The method of claim 1, further comprising recirculating at least a portion of the first treated solution to the feed water.
12. The method of claim 1, further comprisingdelivering the product water to a potable point of use.
13. The method of claim 1, further comprising replacing the selective ion exchange resin upon detecting perchlorate breakthrough that exceeds a threshold value.
14. A water treatment system, comprising:
an advanced oxidation process reactor (AOPR) haying an inlet and an outlet;
and at least one perchlorate selective resin bed fluidly connected downstream of the AOPR outlet.
an advanced oxidation process reactor (AOPR) haying an inlet and an outlet;
and at least one perchlorate selective resin bed fluidly connected downstream of the AOPR outlet.
15. The system of claim 14, further comprising a source of water containing perchlorate andJor PFAS fluidly connected to the AOPR inlet.
16. The system of claim 14, wherein the AOPR comprises first and second subreactors arranged in parallel.
17. The system of claim 14, wherein the AOPR is fluidly connected to a source of persulfate and comprises a UV light source.
18. The system of claim 14, wherein the system comprises two perchlorate selective resin beds arranged in parallel.
19. The system of claim 14, wherein the perchlorate selective resin bed comprises a strong base anion resin.
20. The system of claim 19, wherein the perchlorate selective resin bed comprises a tri-butyl amine resin.
21. The system of claim 20, wherein the tri-butyl amine resin comprises a quaternary amine functional group.
22. The system of claim 14, wherein the system further comprises at least one sensor configured to detect a pressure, temperature, pH, concentration, flow rate, or total organic carbon (TOC) level.
23. The system of claim 22, further comprising a controller in communication with the at least one sensor and configured to control a rate at which persulfate is introduced to the AOPR and/or control a dose of irradiation associated with the AOPR.
24. The system of claim 14, further comprising a posttreatment unit fluidly connected downstream of at least one of the AOPR and the persulfate selective resin bed.
25. The system of claim 24, wherein the posttreatment unit comprises an activated carbon unit.
26. The system of claim 14, further comprising a pretreatment unit operation fluidly connected upstream of the AOPR.
27. A method of retrofitting a water treatment system, comprising:
providing a persulfate selective resin bed; and fluidly connecting the persulfate selective resin bed downstream of an AOPR.
providing a persulfate selective resin bed; and fluidly connecting the persulfate selective resin bed downstream of an AOPR.
28. The method of claim 27, further comprising integrating an activated carbon unit operation between the AOPR and the persulfate selective resin bed.
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US62/733,149 | 2018-09-28 | ||
PCT/US2019/051861 WO2020068538A1 (en) | 2018-09-28 | 2019-09-19 | Control of toc, perchlorate, and pfas through advanced oxidation and selective ion exchange process |
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US20210322951A1 (en) * | 2020-04-21 | 2021-10-21 | United States Of America As Represented By The Secretary Of The Army | Mobile system and method for pfas effluent treatment |
AU2022248996A1 (en) * | 2021-04-02 | 2023-10-12 | Emerging Compounds Treatment Technologies, Inc. | System and method for separating competing anions from per- and polyfluoroalkyl substances (pfas) in water |
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US6960301B2 (en) * | 2002-03-15 | 2005-11-01 | New Earth Systems, Inc. | Leachate and wastewater remediation system |
EP1591422A4 (en) * | 2003-01-31 | 2007-10-03 | Idemitsu Kosan Co | Method of treating wastewater containing hardly decomposable harmful substances |
JP2004346299A (en) * | 2003-05-19 | 2004-12-09 | Rohm & Haas Co | Resin for highly selective removal of perchlorate, and method and system using the same |
US7175760B2 (en) * | 2004-07-07 | 2007-02-13 | Innowave, Inc. | Water dispensing apparatus with water recirculation line |
US7875186B2 (en) * | 2005-11-23 | 2011-01-25 | Applied Research Associates, Inc. | Process for regenerating and protonating a weak-base anion exchange resin |
US20130006023A9 (en) * | 2006-11-22 | 2013-01-03 | Siemens Water Technologies Corp | System and method for treating groundwater |
US8241505B2 (en) * | 2009-03-30 | 2012-08-14 | Dow Global Technologies Llc | Perchlorate removal using ion exchange resins comprising interpenetrating polymer networks |
KR100988238B1 (en) * | 2010-03-25 | 2010-10-18 | 주식회사 지오웍스 | Water treatment device and system using low pressure reverse osmosis membrane and ion exchange resin |
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US20140102980A1 (en) * | 2011-06-02 | 2014-04-17 | General Electric Company | Process and apparatus for treating perchlorate in drinking water supplies |
US20150053620A1 (en) * | 2013-08-21 | 2015-02-26 | Temple University Of The Commonwealth System Of Higher Education | Water treatment |
US10494281B2 (en) * | 2015-01-21 | 2019-12-03 | Evoqua Water Technologies Llc | Advanced oxidation process for ex-situ groundwater remediation |
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