EP1660544A2 - Arsenic removal - Google Patents
Arsenic removalInfo
- Publication number
- EP1660544A2 EP1660544A2 EP04783276A EP04783276A EP1660544A2 EP 1660544 A2 EP1660544 A2 EP 1660544A2 EP 04783276 A EP04783276 A EP 04783276A EP 04783276 A EP04783276 A EP 04783276A EP 1660544 A2 EP1660544 A2 EP 1660544A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- chelate
- bead
- forming
- crosslinked polymeric
- mmol
- 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.)
- Withdrawn
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Classifications
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- 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
- B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
Definitions
- This invention pertains to polymer beads for removing arsenic from aqueous fluids such as groundwater.
- Arsenic is a toxic and ubiquitous metalloid element that can be found in groundwaters around the world at levels well above the maximum containment level of 10 ⁇ g/L recommended by the World Health Organization (WHO). Arsenic poses a serious threat to millions of people worldwide, and geogenic (natural) contamination has been reported in many countries, including countries having large populations such as India and China. In the U.S., the Environmental Protection Agency (EPA) has recently decreased the limit of arsenic in drinking water from 50 ⁇ g/L to 10 ⁇ g/L, and all systems for treating drinking water must comply with the new standard by January 2006.
- WHO World Health Organization
- Arsenic occurs mainly as arsenate As(V) (having a +5 oxidation state) and arsenite As(III) (having a +3 oxidation state) in groundwaters.
- arsenate As(V) having a +5 oxidation state
- arsenite As(III) having a +3 oxidation state
- Different compounds can be formed with arsenic in groundwater depending on the arsenic oxidation state.
- the distribution of As(III)/As(V) varies significantly in groundwater.
- As(III) can represent in the range of about 30% to about 98% of the total arsenic in groundwaters.
- An embodiment of the invention provides a chelate-forming material comprising a crosslinked polymeric bead having bound chelate-forming groups and a volume capacity of about 1.5 mmol/mL or less, wherein the chelate-forming groups comprise protonated N- methyl-D-glucamine, and have the capability of forming a chelate with As(V) and/or compounds thereof.
- another embodiment of the invention provides a chelate-forming material comprising a crosslinked polymeric bead having bound chelate- forming groups and a nitrogen content of about 2.4 mmol/g or more, wherein the chelate- forming groups comprise protonated N-methyl-D-glucamine, and have the capability of forming a chelate with As(V) and/or compounds thereof.
- the protonated N-methyl-D-glucamine is in chloride form, or in sulfate form.
- An embodiment of a method for treating an arsenic-containing aqueous fluid according to the invention comprises contacting an As(V)-containing fluid with crosslinked polymeric beads each having bound chelate-forming groups and a volume capacity of about 1.5 mmol/mL or less, wherein the chelate-forming groups comprise protonated N-methyl- D-glucamine and have the capability of forming a chelate with arsenate(V) and/or compounds thereof, forming the chelate with As(V) and/or a compound thereof, and separating the chelated As(V) and/or compound thereof from the fluid.
- Yet another embodiment of a method for treating an arsenic-containing aqueous fluid according to the invention comprises contacting an As(V)-containing fluid with crosslinked polymeric beads each having bound chelate-forming groups and a nitrogen content of about 2.4 mmol/g or more, wherein the chelate-forming groups comprise protonated N-methyl-D-glucamine and have the capability of forming a chelate with arsenic(V) and/or compounds thereof, forming the chelate with As(V) and/or a compound thereof, and separating the chelated As(V) and/or compound thereof from the fluid.
- a process for preparing a chelate-forming crosslinked polymeric bead having a volume capacity of about 1.5 mmol/mL or less and/or a nitrogen content of about 2.4 mmol/g or more, wherein the bead is comprised of a crosslinked polymer bound to chelate-forming groups comprises obtaining a crosslinked polymeric bead having functional groups, reacting the functional groups with N-methyl-D-glucamine, and producing a protonated N-methyl-D-glucamine.
- An embodiment of the invention provides a crosslinked polymeric bead having bound chelate-forming groups and a volume capacity of about 1.5 mmol/mL or less, wherein the chelate-forming groups comprise protonated N-methyl-D-glucamine, and have the capability of forming a chelate with As(V) and/or compounds thereof.
- the bead has a volume capacity of about 1.3 mmol/mL or less.
- another embodiment of the invention provides a crosslinked polymeric bead having bound chelate-forming groups and a nitrogen content by dry weight basis of about 2.4 mmol/g or more, wherein the chelate-forming groups comprise protonated N-methyl-D-glucamine, and have the capability of forming a chelate with As(V) and/or compounds thereof.
- the bead has a nitrogen content by dry weight basis of about 2.5 mmol/g or more.
- the protonated N-methyl-D-glucamine is in chloride form, or sulfate form.
- the crosslinked polymeric bead comprises poly(vinylbenzylchloride) or chloromethylated styrene wherein the chelate-forming groups are bound to at least a portion of the -CH 2 groups of the benzyl moieties.
- the crosslinked polymeric bead comprises poly(glycidyl methacrylate) wherein the chelate forming groups are bound to at least a portion of the glycidal groups of the acrylate moieties.
- the crosslinked polymeric bead comprises a polymerized bi-, tri-, or tetra-functional monomer, or any combination thereof, to provide the crosslinks.
- the bi-, tri-, or tetra-functional monomer can be selected from the group consisting of ethylene glycol diacrylate, di(ethylene glycol) diacrylate, tetra(ethylene glycol) diacrylate, ethylene glycol dimethacrylate, di(ethylene glycol) dimethacrylate, tri(ethylene glycol) dimethacrylate, butanediol diacrylate, hexanediol diacrylate, N,N-methylenebisacrylamide, N,N-(l,2-dihydroxyethylene) bisacrylamide, and divinylbenzene, or any combination thereof.
- a system for treating arsenic-containing aqueous fluid comprises a bed comprising crosslinked polymeric beads each bead having bound chelate-forming groups, and a volume capacity of about 1.5 mmol/mL or less and/or a nitrogen content by dry weight basis of about 2.4 mmol/g, wherein the chelate-forming groups comprise protonated N-methyl-D-glucamine, and have the capability of forming a chelate with As(V) and/or compounds thereof.
- An embodiment of a method for treating an arsenic-containing aqueous fluid according to the invention comprises contacting an As(V)-containing fluid with crosslinked polymeric beads, each bead having bound chelate-forming groups, and a volume capacity of about 1.5 mmol/mL or less and/or a nitrogen content by dry weight basis of about 2.4 mmol/g or more, wherein the chelate-forming groups comprise protonated N-methyl-D- glucamine, and having the capability of forming a chelate with arsenic(V) and/or compounds thereof, forming the chelate with As(V) and/or a compound thereof, and separating the chelated As(V) or compound thereof from the fluid.
- a preferred embodiment of the invention comprises separating As(V) from groundwater.
- a process for preparing a chelate-forming crosslinked polymeric bead having a volume capacity of about 1.5 mmol/mL or less and/or a nitrogen content of about 2.4 mmol/g or more, wherein the bead is comprised of a crosslinked polymer bound to chelate-forming groups comprises obtaining a crosslinked polymeric bead having functional groups, reacting the functional groups with N-methyl-D-glucamine, and producing a protonated N-methyl-D-glucamine.
- the crosslinked polymeric bead having functional groups comprises a poly(vinylbenzylchloride) bead, a chloromethylated polystyrene bead, or a poly(glycidyl methacrylate) bead.
- the functional groups on the crosslinked polymer bead can be haloalkyl groups or epoxy groups.
- the present invention is preferably used to treat source water, such as municipal drinking water, water from natural sources such as lakes, rivers, reservoirs, surface water, groundwater and storm water runoff, or industrial source water, or wastewater, such as industrial wastewater or municipal wastewater.
- Source water may also include treated wastewater which has, for example, been purified after industrial use.
- Embodiments of the invention can also be used to treat As(V)-containing brine.
- beds including the beads can be used to treat greater volumes of water and/or treat the water for longer periods of time, before replacement and/or regeneration, than beds including conventionally available beads.
- the invention provides for the removal of As(V) from influent aqueous fluids, typically source water having a pH in the range of from about 1 to about 11 , preferably, having a pH in the range of from about 4 to about 6.5.
- removal of As(V) includes removal of the arsenic-containing negatively charged compounds typically formed in natural waters at a pH in the range of 2 to 11, i.e., H 2 AsO 4 " and HAsO " .
- the invention provides for the removal of the arsenic-containing uncharged compound, H 3 AsO 2 , formed in aqueous fluids at a pH of about 1 to about 1.5.
- Embodiments of the invention can efficiently remove As(V) from groundwater having a sulfate concentration of greater than 120 mg/L, e.g., up to about 800 mg/L, or more and/or can efficiently remove As(V) from groundwater having a phosphate concentration of up to about 400 mg/L, or more.
- embodiments of the invention can remove As(V) from aqueous fluids in the presence of 1M NaCl.
- the chelate-forming groups of the present invention comprise protonated N- methyl-D-glucamine represented by formula (I):
- the chelate-forming group N-methyl-D-glucamine (NMDG)
- NMDG N-methyl-D-glucamine
- Elemental analysis is performed to determine the amount of nitrogen, or equivalents of nitrogen, present in the chelate-forming group. Since the chelate-forming group is the sole group that contains nitrogen, the equivalents of nitrogen are directly related to the equivalents of the chelate-forming group present on the bead. This can be further defined as "theoretical specific capacity", (IUPAC Compendium of Analytical Nomenclature, section 9.2.5.4, 1997, 3rd ed.) which is the amount (mmol) of ionogenic group per mass (g) of dry ion exchanger.
- Illustrative elemental analytical techniques for determining the nitrogen content of beads according to the invention are ASTM D 5373 (2002) “Test Methods for Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Laboratory Samples of Coal and Coke” and ASTM D 5291 (2003) “Test Method for Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants.”
- ASTM D 5373 crosslinked beads according to embodiments of the invention, comprising the protonated N-methyl-D-glucamine, have a nitrogen content, on a dry weight basis, of 2.35 mmol/g or more.
- crosslinked beads according to embodiments of the invention have a nitrogen content, on a dry weight basis, of 2.46 mmol/g or more.
- the crosslinked bead comprising the protonated N-methyl-D-glucamine, has a nitrogen content, on a dry weight basis, of about 2.4 mmol/g or more, preferably, a nitrogen content of about 2.5 mmol/g or more, more preferably, a nitrogen content of about 2.6 mmol/g or more, and in some embodiments, a nitrogen content of about 2.7 mmol/g or more.
- the bead (or particle) is preferably a non-porous bead, although it may have pores having diameters of 50 Angstroms or less, e.g., micropores. The bead is crosslinked.
- Preferred crosslinked polymeric beads comprise poly(vinylbenzylchloride) copolymer beads and poly(glycidyl methacrylate) copolymer beads.
- Other embodiments include, for example, crosslinked chloromethylated polystyrene copolymer beads, and crosslinked polymer beads functionalized with amine reactive chemistries such as epichlorohydrin and azlactone.
- the crosslinked polymeric bead comprises a polymerized bi-, tri-, or tetra-functional monomer, or any combination thereof, to provide the crosslinks.
- the bi-, tri-, or tetra-functional monomer can be selected from the group consisting of ethylene glycol diacrylate, di(ethylene glycol) diacrylate, tetra(ethvlene glycol) diacrylate, ethylene glycol dimethacrylate, di(ethylene glycol) dimethacrylate, tri(ethylene glycol) dimethacrylate, butanediol diacrylate, hexanediol diacrylate, N,N-methylenebisacrylamide, N,N-(l,2-dihydroxyethylene) bisacrylamide, and divinylbenzene (DVB), or any combination thereof.
- crosslinkers can be used in preparing beads according to the invention.
- Preferred crosslinking agents include compounds with two or more groups.
- Exemplary crosslinkers include ethylene glycol di(meth)acrylate (EGDMA), ethylene glycol diacrylate, di(ethylene glycol) diacrylate, tetra(ethylene glycol) diacrylate, ethylene glycol dimethacrylate, di(ethylene glycol) dimethacrylate, tri(ethylene glycol) dimethacrylate; butanediol diacrylate, hexanediol diacrylate, methylenebisacrylamide, N,N methylenebisacrylamide, N,N-(l,2-dihydroxyethylene)bisacrylamide), and divinylbenzene (DVB).
- EGDMA ethylene glycol di(meth)acrylate
- ethylene glycol diacrylate di(ethylene glycol) diacrylate
- tetra(ethylene glycol) diacrylate ethylene glycol dimethacrylate
- the degree of crosslinking is preferably about 7% or less, more preferably, about 5% or less, and in some embodiments, about 3% or less.
- the desired range can be varied depending on, for example, the hydrophilicity of the backbone polymer and the structure of the crosslinking agent.
- the degree of crosslinking can be in the range of from about 2% to about 7% (e.g., wherein the bead includes a more hydrophilic backbone polymer such as, for example, poly(glycidyl methacrylate)), or from about 2% to about 5% (e.g., wherein the bead includes a more hydrophobic backbone polymer, such as, for example, poly(vinylbenzylchloride) or chloromethylated polystyrene).
- the polymer chains e.g., polystyrene backbone
- this flexibility, and the level of crosslinking are important, so that the lower level of crosslinking (about 7% or less) allows increased swelling of the bead, allowing more reactive groups to bind NMDG to the bead, providing more available surface area allowing a greater amount of the NMDG to be bound to the bead, and allowing more of the protonated NMDG to be accessed by the As(V) in the fluid to be treated.
- the crosslinked polymeric bead having bound chelate-forming groups has volume capacity of about 1.5 mmol/mL or less, preferably, about 1.3 or less. In some embodiments, the volume capacity is in the range of from about 1.5 mmol/mL to about 1.1 mmol/mL. Without being bound to any particular mechanism, it is believed the volume capacity can be generally correlated with the degree of crosslinking.
- the volume capacity is, as defined in 1UPAC Compendium of Analytical Nomenclature, section 9.2.5.4, 1997, 3rd ed., the amount (mmol) of ionogenic group per volume (cm ) of swollen ion exchanger.
- the ionic form of the ion exchanger and the medium should be stated.
- the ionic form of the ion exchanger is the protonated amine, and the medium is water.
- the swelling ratio is about 1.5 or more, preferably about 2.3 or more. Typically, the swelling ratio is in the range of from about 1.5 to about 2.5, and in some embodiments, can be greater than about 2.5.
- the swelling ratio refers to the increase in volume when comparing the volume of the beads after a specified time in water to the volume of vacuum dried beads.
- the specific swelling ratios referenced in the Examples section herein were determined using 2 mL of vacuum dried beads that were placed in a 10 mL cylinder of water, wherein the volume was determined after 19 hours.
- the process for preparing a chelate-forming crosslinked polymeric bead comprises obtaining a crosslinked polymeric bead having functional groups, and reacting these functional groups with NMDG to bind the NMDG to the crosslinked bead.
- Preferred functional groups are haloalkyl groups, i.e., chloromethyl, or epoxy groups.
- the crosslinked polymeric bead comprises poly(vinylbenzylchloride) or chloromethylated polystyrene
- the reactive functional groups are chloromethyl groups
- the NMDG becomes bonded to the -CH 2 groups of the benzyl moieties via a nucleophilic substitution reaction at the chloromethyl group.
- the reactive functional groups are epoxy groups, and the N-methyl-D-glucamine becomes bonded to the glycidal groups of the acrylate moieties via a ring-opening reaction of an epoxy group.
- the resulting bead is conditioned with a dilute acidic solution such as, for example, HCl or H 2 SO , to produce a protonated amine moiety on the chelate-forming group.
- a dilute acidic solution such as, for example, HCl or H 2 SO
- the bead can be conditioned with HCl to provide protonated N-methyl- D-glucamine in chloride form, or conditioned with H SO to provide protonated N-methyl- D-glucamine in sulfate form.
- one form can be exchanged to the other, e.g., the sulfate form can be exchanged to the chloride form, or the chloride form can be exchanged to the sulfate form.
- the chloride form can be soaked in water, and subsequently conditioned with NaOH, water, H 2 SO 4 , and water
- EXAMPLE 1 [0044] This example describes of the preparation of chelate-forming beads according to an embodiment of the invention.
- EXAMPLE 2 [0046] This example describes of the preparation of chelate-forming beads according to another embodiment of the invention.
- EXAMPLE 4 This example demonstrates the volume capacity of chelate-forming beads according to an embodiment of the invention.
- Beads are prepared as described in Example 1. Elemental analysis is performed, and combined with the swelling ratio determined as in Example 3, it is determined the beads have a volume capacity of 1.19 mmol Nitrogen/mL.
- EXAMPLE 5 This example demonstrates the selective formation of chelates with As(V) of chelate-forming beads according to an embodiment of the invention as compared to commercially available beads and fibers including NMDG, particularly in the presence of sulfate.
- Polymerized VBC-DVB crosslink level 2 wt.% beads including NMDG are prepared as described in Example 1. Additionally, the following commercially available beads including NMDG are obtained: Diaion CRB-02 (Mitsubishi Chemical), Purolite S-108 (Purolite Co.), and Amberlite IRA-743 (Rohm and Haas). The following commercially available cotton fibers including NMDG are also obtained: GCP, GRY, and GRY-L (Chelest Corp.). Each set of beads and fibers is placed in contact with As(V) solutions as described below.
- As(V) solutions as described below.
- the beads and fibers are all conditioned with IL each of water, 4% NaOH, water, 4% HCl and water, and vacuum dried at 70 °C. Nitrogen elemental analysis is performed on each set of beads and fibers, and beads and fibers containing 0.3 meq of nitrogen are placed in contact with the As(V) solutions.
- Two sets of As(V) solutions are prepared using sodium hydrogen arsenate Na 2 HAsO 4 , 7H 2 O (AlfaAesar).
- the solutions are 20 mL As(V) 100 ppm.
- One set of As(V) solutions includes a concentration of 560 mg/L SO 4 2" (pH 6.0).
- the set of As(V) solutions without SO 2" has a pH of 5.8.
- Each set of As(V) solutions is placed in contact with a separate set of beads and fibers, i.e., beads prepared in accordance with Example 1 are contacted with the solutions, and each of the commercially available beads and fibers are contacted with the solutions.
- 20 mL of the solution is placed in a Nalgene 40 mL bottle containing the beds or fibers, on a shaker. The total contact time is 3 days.
- Arsenate concentrations are analyzed by the molybdenum blue method (Chariot) using a spectrophotometer Spectronic 21 D (Milton Roy) equipped with l A " test tube. For lower concentrations, solutions are analyzed by ICP-MS (Hewlet Packard) [0058] All of the beads and the GRY and GRY-L fibers remove more than 99% (the GCP fibers remove 98.6%) of the arsenic present in solution from the solution without S0 2" .
- CRB-02 achieves a residual As(V) concentration of 80 ppb
- S-108 achieves a residual As(V) concentration of 890 ppb
- IRA-743 achieves a residual concentration of 300 ppb
- the VBC-DVB beads prepared in accordance with Example 1 remove 99.9% of the arsenic with a residual As(V) concentration of less than 50 ppb.
- the equilibrium solution concentrations (mg/L) and sorption capacities (mg/g) at equilibrium solution concentration are, respectively: 0.03 mg/L and 16.4 mg/g (VBC-2% DVB bead), 0.30 mg/L and 14.7 mg/g (IRA-741), 0.08 mg/L and 14.9 mg/g (CRB-02), 0.89 mg/L and 14.8 mg/g (S-108), 1.42 mg/L and 8.88 mg/g (GCP), 0.04 mg/L and 6.92 mg/g (GRY), and 0.04 mg/L and 7.45 mg/g (GRY-L).
- the efficiency of removal of As(V) drops for the commercially available beads when compared to the solution without SO 4 2" , i.e., CRB-02 drops from 99.9% to 90.3%, S-108 drops from 99.1% to 77.9%, and IRA-743 drops from 99.7% to 79.4%.
- the efficiency of removal for each of the GCP, GRY, and GRY-L fibers is, respectively, 98.8%, 97.8%, and 98.9%.
- the equilibrium solution concentrations (mg/L) and sorption capacities (mg/g) at equilibrium solution concentration are, respectively: 20.7 mg/L and 13.3 mg/g (IRA-741), 9.70 mg/L and 13.7 mg/g (CRB-02), 22.2 mg/L and 11.8 mg/g (S-108), 1.21 mg/L and 9.06 mg/g (GCP), 2.22 mg/L and 6.87 mg/g (GRY), and 1.04 mg/L and 7.46 mg/g (GRY-L).
- VBC-2% DVB beads prepared in accordance with Example 1 essentially maintain the removal efficiency and sorption capacity, in that the removal efficiency is 99.4%, and the sorption capacity (at an equilibrium solution concentration of 0.63 mg/L) is 16.6 mg/g.
- EXAMPLE 6 This example describes of the preparation of chelate-forming beads according to another embodiment of the invention, and the selective formation of chelates with As(V) of the chelate-forming beads.
- Nitrogen elemental analysis is performed in accordance with ASTM D 5373 and beads containing 0.3 meq of nitrogen are placed in contact with the As(V) solutions as described in Example 5.
- the beads remove 99.9% of the As(V) present in solution from the solution without SO 4 " , and achieve a residual As(V) concentration of 65 ppb.
- the beads remove
- EXAMPLE 7 [0067] This example describes of the preparation of chelate-forming beads according to another embodiment of the invention.
- EXAMPLE 8 This example demonstrates the selective formation of chelates with As(V) using crosslinked beads having the sulfate form of protonated NMDG according to another embodiment of the invention.
- Beads are prepared as described in Example 7 to provide beads having the chloride form of protonated NMDG.
- the beads are treated to exchange the chloride form for the sulfate form by soaking the beads in IL of water for 2 hours, followed by conditioning with IL of IN NaOH, IL of water, IL of IN H 2 SO 4 , and IL of water.
- EXAMPLE 9 This example describes of the selective formation of chelates with As(V) of chelate-forming beads according to an embodiment of the present invention in the presence of different concentrations of chloride or sulfate ions.
- crosslinked beads comprising VBC and polymerized DVB (crosslink level 2 wt.%) are swelled and placed in a 250 mL round bottom flask equipped with a condenser and overhead stirrer. 20 g of NMDG (Arcos Organics) is added to 10 mL of water, and 100 mL of dioxane. The mixture is refluxed for 17 hours. After washing, the beads are conditioned with 1 L each of water, 1M NaOH, water, 1 M HCl, and water, then vacuum dried at 70°C for 17 hours and characterized by FTIR and nitrogen elemental analysis.
- NMDG Arcos Organics
- Amberlite IRA-900 beads (Rohm and Haas) are obtained and conditioned and dried as set forth above.
- Arsenate is analyzed by the molybdenum blue method using a Spectronic 21D spectrophotometer. At lower concentrations, and in the presence of phosphate, solutions are analyzed by ICP-MS (Hewlett-Packard 4500 series).
- EXAMPLE 10 This example describes the preparation of chelate-forming beads according to other embodiments of the invention, and the selective formation of chelates with As(V) of the chelate-forming beads as compared to commercially available resins including NMDG, particularly in the presence of sulfate.
- crosslinked beads comprising VBC and polymerized DVB (crosslink levels 2 wt.%, 5 wt.%, 8 wt.%, and 12 wt.%) are swelled and placed in a 250 mL round bottom flask equipped with a condenser and overhead stirrer.
- 20 g of NMDG (Arcos Organics) is added to 10 mL of water, and 100 mL of dioxane. The mixture is heated at reflux for 17 hours. After washing, the beads are conditioned with 1 L each of water, 1M NaOH, water, 1 M HCl, and water, then vacuum dried at 70°C for 17 hours and characterized by FTIR and nitrogen elemental analysis.
- Two sets of As(V) solutions are prepared.
- One solution is 20mL As(V), 100 mg/L, pH 6.
- the other solution is 20 mL As(V), 100 mg/L + 560 mg/L SO 4 2" , pH 6.
- Each set of As(V) solutions is placed in contact with a separate set of beads, i.e. NMDG beads prepared as described above at each crosslink density are contacted with the solutions, CRB-02 beads are contacted with the solutions, S-108 beads are contacted with the solutions, and IRA-743 beads are contacted with the solutions.
- Arsenate is analyzed by the molybdenum blue method using a Spectronic 2 ID spectrophotometer. At lower concentrations, solutions are analyzed by ICP-MS (Hewlett- Packard 4500 series).
- EXAMPLE 11 This example describes of the higher nitrogen content by dry weight basis of the chelate-forming beads according to other embodiments of the invention as compared to three commercially available products.
- Crosslinked beads comprising polymerized VBC and DVB (crosslink levels 2 wt.%, 5 wt.%, 8 wt.%, and 12 wt.%) including NMDG are prepared as described in Example 10.
- Crosslinked beads comprising polymerized VBC crosslinked with EGDMA (crosslink levels 2% and 4%) including NMDG are prepared as described in Example 7.
- the following commercially available beads including NMDG are also obtained: Amberlite IRA-743, Diaion CRB-02, and Purolite S-108.
- the table shows that, when analyzed in accordance with ASTM D 5373, prepared beads having less than 8% crosslinking have a nitrogen content by dry weight basis of greater than 2.35 mmol/g, and commercially available beads have a nitrogen content by dry weight basis of 2.27 mmol/g or less.
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- General Chemical & Material Sciences (AREA)
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- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
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Applications Claiming Priority (2)
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US50025903P | 2003-09-05 | 2003-09-05 | |
PCT/US2004/028977 WO2005023409A2 (en) | 2003-09-05 | 2004-09-07 | Arsenic removal |
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EP1660544A2 true EP1660544A2 (en) | 2006-05-31 |
EP1660544A4 EP1660544A4 (en) | 2007-07-11 |
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EP04783276A Withdrawn EP1660544A4 (en) | 2003-09-05 | 2004-09-07 | Arsenic removal |
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CA (1) | CA2536178A1 (en) |
WO (1) | WO2005023409A2 (en) |
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EP1568660B1 (en) | 2004-02-24 | 2010-12-15 | Rohm And Haas Company | Method for removal of arsenic from water |
CN113272058A (en) * | 2018-11-27 | 2021-08-17 | Ddp特种电子材料美国第5有限公司 | Method for producing resin for semiconductor production |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD279377A3 (en) * | 1984-10-26 | 1990-06-06 | Chemiekomb Bitterfeld Veb | PROCESS FOR THE PREPARATION OF ANION EXCHANGERS WITH POLYOL GROUPS |
FR2844509A1 (en) * | 2002-09-12 | 2004-03-19 | Gervais Danone Sa | Treatment of mineral water to reduce boron content uses contact with ion exchange resin and recuperation of treated water to reduce losses |
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DE69824286T2 (en) * | 1997-03-25 | 2005-07-07 | Chelest Corp. | Chelating fiber, process for its preparation and use thereof |
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2004
- 2004-09-07 WO PCT/US2004/028977 patent/WO2005023409A2/en active Application Filing
- 2004-09-07 EP EP04783276A patent/EP1660544A4/en not_active Withdrawn
- 2004-09-07 CA CA002536178A patent/CA2536178A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DD279377A3 (en) * | 1984-10-26 | 1990-06-06 | Chemiekomb Bitterfeld Veb | PROCESS FOR THE PREPARATION OF ANION EXCHANGERS WITH POLYOL GROUPS |
FR2844509A1 (en) * | 2002-09-12 | 2004-03-19 | Gervais Danone Sa | Treatment of mineral water to reduce boron content uses contact with ion exchange resin and recuperation of treated water to reduce losses |
Non-Patent Citations (4)
Title |
---|
GROBOSCH T ET AL: "ABTRENNUNG VON ARSEN(V) AUS GRUNDWASSER MITTELS IONENAUSTAUSCHER = SEPARATION OF ARSENE(V) FROM THE GROUNDWATER BY MEANS OF ION EXCHANGE" CHEMISCHE TECHNIK, LEIPZIG, DE, vol. 48, no. 4, August 1996 (1996-08), pages 203-211, XP009077139 * |
KORNGOLD E ET AL: "Removal of arsenic from drinking water by anion exchangers" DESALINATION, ELSEVIER, AMSTERDAM, NL, vol. 141, no. 1, 1 December 2001 (2001-12-01), pages 81-84, XP004333330 ISSN: 0011-9164 * |
SCHILDE U ET AL: "SEPARATION OF THE OXOANIONS OF GERMANIUM, TIN, ARSENIC, ANTIMONY, TELLURIUM, MOLYBDENUM AND TUNGSTEN WITH A SPECIAL CHELATING RESIN CONTAINING METHYLAMINOGLUCITOL GROUPS" REACTIVE POLYMERS, ELSEVIER SCIENCE PUBLISHERS, AMSTERDAM, NL, vol. 22, no. 2, 1 April 1994 (1994-04-01), pages 101-106, XP000461750 ISSN: 0923-1137 * |
See also references of WO2005023409A2 * |
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WO2005023409A3 (en) | 2005-12-01 |
EP1660544A4 (en) | 2007-07-11 |
CA2536178A1 (en) | 2005-03-17 |
WO2005023409A2 (en) | 2005-03-17 |
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