US20020011446A1 - Process for modifying the metal ion sorption capacity of a medium and modified medium - Google Patents

Process for modifying the metal ion sorption capacity of a medium and modified medium Download PDF

Info

Publication number
US20020011446A1
US20020011446A1 US09/199,296 US19929698A US2002011446A1 US 20020011446 A1 US20020011446 A1 US 20020011446A1 US 19929698 A US19929698 A US 19929698A US 2002011446 A1 US2002011446 A1 US 2002011446A1
Authority
US
United States
Prior art keywords
medium
ions
solution
metal ions
sodium
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.)
Granted
Application number
US09/199,296
Other versions
US6436294B2 (en
Inventor
Susan H. Lundquist
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Innovative Properties Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to US09/199,296 priority Critical patent/US6436294B2/en
Assigned to MINNESOTA MINING AND MANUFACTURING COMPANY reassignment MINNESOTA MINING AND MANUFACTURING COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LUNDQUIST, SUSAN H.
Assigned to MINNESOTA MINING AND MANUFACTURING COMPANY reassignment MINNESOTA MINING AND MANUFACTURING COMPANY CORRECTIVE DOCUMENT REEL 9840, FRAME 0878, RE-RECORD TO CORRECT EXECUTION DATE ON PREVIOUSLY RECORDED DOCUMENT. Assignors: LUNDQUIST, SUSAN H.
Publication of US20020011446A1 publication Critical patent/US20020011446A1/en
Assigned to ENERGY, UNITED STATES DEPARTMENT OF reassignment ENERGY, UNITED STATES DEPARTMENT OF CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: MINNESOTA MINING AND MANUFACTURING COMPANY
Assigned to 3M INNOVATIVE PROPERTIES COMPANY reassignment 3M INNOVATIVE PROPERTIES COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MINNESOTA MINING AND MANUFACTURING COMPANY, A CORPORATION OF THE STATE OF DELAWARE
Assigned to ENERGY, UNITED STATES DEPARTMENT OF reassignment ENERGY, UNITED STATES DEPARTMENT OF CONFIRMATORY LICENSE (SEE DOCUMENT FOR DETAILS). Assignors: MINNESOTA MINING & MANUFACTURING COMPANY
Application granted granted Critical
Publication of US6436294B2 publication Critical patent/US6436294B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/0203Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0211Compounds of Ti, Zr, Hf
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28026Particles within, immobilised, dispersed, entrapped in or on a matrix, e.g. a resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28033Membrane, sheet, cloth, pad, lamellar or mat
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/281Sorbents specially adapted for preparative, analytical or investigative chromatography
    • B01J20/286Phases chemically bonded to a substrate, e.g. to silica or to polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3007Moulding, shaping or extruding
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3035Compressing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3042Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/3078Thermal treatment, e.g. calcining or pyrolizing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204Inorganic carriers, supports or substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244Non-macromolecular compounds
    • B01J20/3246Non-macromolecular compounds having a well defined chemical structure
    • B01J20/3248Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one type of heteroatom selected from a nitrogen, oxygen or sulfur, these atoms not being part of the carrier as such
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3244Non-macromolecular compounds
    • B01J20/3265Non-macromolecular compounds with an organic functional group containing a metal, e.g. a metal affinity ligand
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30Processes for preparing, regenerating, or reactivating
    • B01J20/32Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3295Coatings made of particles, nanoparticles, fibers, nanofibers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J45/00Ion-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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/50Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/52Sorbents specially adapted for preparative chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/50Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/54Sorbents specially adapted for analytical or investigative chromatography
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/50Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/58Use in a single column
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00Aspects relating to sorbent materials
    • B01J2220/50Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/62In a cartridge
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/281Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/28Treatment of water, waste water, or sewage by sorption
    • C02F1/285Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/68Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683Treatment 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
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/006Radioactive compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/20Heavy metals or heavy metal compounds

Definitions

  • the invention relates to modifying the metal ion sorption capacity of a medium.
  • Water from waste streams, ground water, holding ponds, water treatment facilities, storage tanks, rivers, and streams can contain metals such as iron, zinc, cesium, plutonium, strontium, technetium, uranium, and americium. For environmental compliance, it is often desirable or necessary to remove these metals from the water.
  • a variety of methods have been developed for removing metals from the water in waste streams, ground water, holding ponds, water treatment facilities, storage tanks, rivers, and streams. Some of these methods include passing the water containing through a medium that removes the metal.
  • the medium may be an ion exchange medium that is capable of sorbing the metal ions in the liquid. The medium is often packed in a column and once the medium is saturated with metal ions, the medium and/or column is discarded.
  • a method for removing metals from the medium involves eluting the metal ions from the medium with a strong acid followed by regenerating the medium with a strong base. These methods, however, do not always perform with the same level of effectiveness for all metals. For example, ion exchange media used for the removal of strontium frequently have a relatively low capacity for strontium due to large excesses of calcium and magnesium, which compete with the strontium for sites on the medium. Large excesses of calcium and magnesium relative to strontium are often present in waste streams and ground water.
  • Nitric acid and hydrochloric acid are often used to elute strontium from a strontium absorber.
  • Nitric acid and hydrochloric acid tend to cause a gradual increase in back pressure in systems in which they are employed as the eluant and in systems in which the medium is reconditioned.
  • the invention features a process for modifying a medium to increase its capacity to sorb (i.e., adsorb, absorb and combinations thereof) metal ions, as well as processes for regenerating the metal ion sorption capacity of a medium that has been exposed to metal ions, as well as the modified media, itself.
  • the invention features a process for modifying a medium that includes treating a medium having a metal ion sorption capacity with a solution that includes (a) an agent capable of forming a complex with metal ions, and (b) ions selected from the group consisting of sodium ions, potassium ions, magnesium ions or a combination thereof, to create a medium having an increased capacity to sorb metal ions relative to the untreated medium.
  • the complexing agent is an organic acid (e.g., citric acid) and the ions are sodium ions.
  • the solution includes sodium azide.
  • the solution includes an organic acid and sodium hydroxide.
  • the treating solution has a pH of between about 6 and 10, more preferably a pH of between about 7.5 and 8.5.
  • the medium is capable of sorbing strontium ions. In other embodiments the medium is capable of sorbing mercury ions.
  • the medium includes a membrane filled with particles, e.g., particles selected from the group consisting of particles of sodium titanate (i.e., sodium titanate, sodium nonatitanate, and combinations thereof), crystalline silico titanate, mixed salts of titanium silicate, sulfonated styrene divinyl benzene, SAMMS self-assembled monolayers on mesoporous supports specific for mercury analytes having a formula SiO 2 —CH 2 CH 2 —SH, and combinations thereof.
  • particles of sodium titanate i.e., sodium titanate, sodium nonatitanate, and combinations thereof
  • crystalline silico titanate i.e., mixed salts of titanium silicate, sulfonated styrene divinyl benzene, SAMMS self-assembled monolayers on mesoporous supports specific for mercury analytes having a formula SiO 2 —CH 2 CH 2 —SH, and combinations thereof.
  • the medium includes sorbed metal ions.
  • the process further includes contacting the treated medium with a liquid that includes metal ions such that the metal ions sorb onto the medium.
  • the medium that includes sorbed metal ions can then be treated with an agent capable of forming a complex with metal ions for a period sufficient to elute the metal ions.
  • an agent capable of forming a complex with metal ions is a solution that includes an organic acid, e.g., citric acid and sodium hydroxide.
  • the invention features a process in which the back pressure produced during the process remains relatively constant during the process.
  • the process further includes providing a medium that includes sorbed metal ions, prior to treating the medium.
  • the process is useful for treating a medium (e.g., a solid phase ion exchange medium) that has sorbed metal ions (e.g., heavy metals, rare earth metals, and radioactive elements).
  • a medium e.g., a solid phase ion exchange medium
  • the processes can regenerate (i.e., restore or increase) the metal ion sorption capacity of articles that have been previously contacted with a source of metal ions.
  • the process is particularly useful in regenerating the ion sorption capacity of articles that are used to remove metal ion contaminates, and to treat aqueous streams from sources such as ground water, storage tanks, holding ponds, waste water treatment facilities, and nuclear waste storage tanks.
  • the process of the present invention improves the metal ion sorption capacity of an article relative to its metal ion adsorption capacity without treatment. In another embodiment, the process of the invention improves the metal ion sorption capacity of an article that includes sorbed metal ions.
  • the processes according to the present invention also permit the maintenance of a relatively constant back pressure throughout the process.
  • Certain preferred processes according to the present invention are particularly well suited and can be optimized for the selective removal and recovery of strontium from a medium.
  • the process includes treating a medium having a metal ion adsorption capacity with a solution that includes: A) an agent capable of forming a complex with at least one metal ion; and B) ions selected from the group consisting of sodium, potassium, magnesium and combinations thereof, to increase the capacity of the medium to sorb metal ions relative to the untreated medium.
  • the treating solution is a buffer preferably having a pH in the range of about 5 to about 11, more preferably a pH in the range of about 6 to about 10, most preferably a pH in the range of about 7.5 to about 8.5.
  • the treating solution includes a complexing agent capable of forming a complex with at least one metal ion.
  • Preferred agents are capable of forming complexes with ions of, e.g., heavy metals, rare earth metals, actinides, and combinations thereof.
  • Examples of useful complexing agents include organic acids having more than one carboxyl group including citric acid, tartaric acid, oxalic acid, succinic acid, malonic acid, and ethylenediaminetetraacetic acid (“EDTA”).
  • organic acids having more than one carboxyl group including citric acid, tartaric acid, oxalic acid, succinic acid, malonic acid, and ethylenediaminetetraacetic acid (“EDTA”).
  • Other useful complexing agents include lactic acid, sulphosalicylates, acetylacetonante, and azides (e.g., sodium azide).
  • the treating solution also includes ions, e.g., sodium ions, potassium ions, magnesium ions and combinations thereof.
  • the treating solution is brought to the desired pH by the addition of an appropriate amount of buffer adjusting solution, e.g., base, which also provides the ions.
  • buffer adjusting solution e.g., base
  • useful bases include metal hydroxides including, e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide, and sodium azide.
  • the sodium azide can function as both the complexing agent and a source of sodium ions.
  • ions can be used to convert substantially all of the particles in the medium to a single salt form, e.g., the sodium form, such that the medium exhibits an increased propensity to selectively sorb predetermined ions, e.g., cations or anions.
  • ions are added to convert substantially all of the medium to the sodium salt form.
  • the medium exhibits a propensity to selectively sorb strontium ions.
  • the treating solution is used to treat a medium that is capable of sorbing metal ions.
  • the medium includes particles capable of removing ions from fluids through mechanisms such as, e.g., ion exchange (e.g., solid phase ion exchange), chelation, covalent bond formation, and sorption (e.g., adsorption, absorption and combinations thereof).
  • the medium is capable of sorbing ions of radioactive particles, metals (e.g., heavy metals, rare earth metals, alkaline earth metals, and combinations thereof) and combinations thereof.
  • Useful media sorb ions of metals from Groups IA, IIA, IB, IIB, IIIB, and VIII of the periodic table.
  • the medium is capable of sorbing ions of metals such as, e.g., cesium strontium, silver, cobalt, chromium, gold, mercury, uranium, americium, plutonium, copper, iron, technetium, lead, zinc, and rhenium.
  • metals such as, e.g., cesium strontium, silver, cobalt, chromium, gold, mercury, uranium, americium, plutonium, copper, iron, technetium, lead, zinc, and rhenium.
  • the medium consists of finely divided, microporous particles.
  • the particles Preferably have a relatively large area of active surface and a uniform size distribution.
  • Useful particles have an average particle size in the range of about 1 ⁇ m to about 100 ⁇ m, preferably about 2 ⁇ m to about 75 ⁇ m, more preferably about 9 ⁇ m to about 18 ⁇ m.
  • Suitable particles include inorganic, organic, and combinations thereof.
  • the particles are ionically charged (e.g., cationic and anionic particles).
  • Useful inorganic media include metal titanates, where the metal is selected form Group IA and Group IIA metals (e.g., sodium titanate which includes nonatitanate), silicotitanates (e.g., crystalline silico titanate, and mixed salts of titanium silicates) and combinations thereof.
  • metal titanates where the metal is selected form Group IA and Group IIA metals (e.g., sodium titanate which includes nonatitanate), silicotitanates (e.g., crystalline silico titanate, and mixed salts of titanium silicates) and combinations thereof.
  • Examples of commercially available inorganic particles include sodium titanates (available from Allied Signal Corp., Chicago, Ill.), crystalline silico titanates (available under the trade designation IONSIV from UOP of Tarrytown, N.Y.), sorbent particles available under the trade designation ATS from Engelhard Corporation, Iselin, N.J., and high capacity resins available under the trade designation NALCITE from Nalco Chemical Co., Naperville, Ill.
  • Examples of useful organic media include sulfonated styrene divinyl benzene resins (commercially available, e.g., under the trade designation CATEX from Sarasep Corp., Santa Clara, Calif.)), organic anion sorber (commercially available under the trade designation ANEX from Serasep), and organic cation sorber (commercially available under the trade designation DIPHONIX from Ichrome Industries of Chicago, Ill.).
  • the medium can also include derivatized particles.
  • useful derivatized particles include polymeric coated oxide particles and organic moieties covalently bonded to inorganic oxide particles. Derivatized particles are described, e.g., in U.S. Pat. Nos. 5,393,892 (Krakowiak), 5,334,326 (Bostick), 5,316,679 (Bruening), 5,273,660 (Bruening), and 5,244,856 (Bruening) and incorporated herein by reference.
  • the particles can be enmeshed in a variety of fibrous, nonwoven webs, which preferably are porous.
  • fibrous, nonwoven webs which preferably are porous.
  • Such webs include polymer pulps, fibrillated polytetrafluoroethylene (PTFE), microfibrous webs, and macrofibrous webs.
  • PTFE fibrillated polytetrafluoroethylene
  • Examples of particle filled webs are described in U.S. Pat. Nos. 5,328,758 (Markell et al.), 5,071,610 (Hagen et al.), 5,082,720 (Hayes), and 3,971,373 (Braun), the disclosures of which are incorporated herein by reference.
  • Other useful media may include those media described in U.S. Ser. No. 08/791,205 entitled, “Spiral Wound Extraction Cartridge,” which was filed on Feb.
  • Another useful medium includes sponge-like (i.e., porous) medium prepared by compacting spray dried particles under low pressure (e.g., hand pressure) into a confined space and heating the compacted particles to a temperature of about 130° C. for about 72 hours results.
  • sponge-like media exhibit excellent separating ability and relatively low back pressure during use.
  • Useful sponge-like media are described in U.S. Ser. No. 08/960,528 filed on Oct. 31, 1997 and incorporated herein by reference.
  • the medium can be in the form of an article such as, e.g., membranes (e.g., particle embedded membranes, and particle filled membranes), particle filled microfiber webs, particle coated filter paper, cartridges, columns (e.g., chromatography columns, short packed columns), disks and sheets.
  • membranes e.g., particle embedded membranes, and particle filled membranes
  • particle filled microfiber webs e.g., particle coated filter paper, cartridges, columns (e.g., chromatography columns, short packed columns), disks and sheets.
  • Example 1 and Comparative Example A show the Sr ion loading of a solid phase extraction (“SPE”) media disk preconditioned with a pH 8 buffer solution (Example 1) and a SPE disk that had not been preconditioned with the pH 8 buffer solution (Comparative Example A).
  • SPE solid phase extraction
  • the pH 8 buffer solution was prepared as follows.
  • a 0.23 Molar citric acid solution was prepared by dissolving 48.33 grams of citric acid monohydrate (obtained from J.T. Baker, Phillipsburg, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution.
  • a 0.5 Molar NaOH solution was prepared by dissolving 20 grams of NaOH (obtained from E.M. Science, Gibbstown, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution.
  • About 564 grams of the 0.5 M NaOH solution were added to 404 grams of the 0.23 M citric acid solution to provide the pH 8 buffer solution.
  • An extraction medium was prepared by first mixing 13.20 grams (dry weight) of aramid fiber pulp (obtained under the trade designation “KEVLAR IF306” from E.I. Dupont, Inc., Wilmington, Del.) with 2000 ml of hot water in a 4 liter laboratory Waring blender at low speed for 30 seconds to form a slurry. About 0.25 gram of a nonionic dispersant (obtained under the trade designation “TAMOL 850” from Rohm and Haas, Philadelphia, Pa.) was added to the slurry and blended in at the low speed setting for 30 seconds.
  • KEVLAR IF306 from E.I. Dupont, Inc., Wilmington, Del.
  • TAMOL 850 nonionic dispersant
  • sorbent particles obtained under the trade designation “ATS” from Engelhard Corporation, Iselin, N.J.
  • ATS Engelhard Corporation, Iselin, N.J.
  • a mixed salt of titanium silicate were added to the slurry and blended in at the low speed setting for 30 seconds.
  • latex binder 3.0 grams of styrene-butadiene (obtained under the trade designation “GOODRITE 1800 ⁇ 73” from B.F. Goodrich Co., Cleveland, Ohio) dissolved in 4.5 grams of deionized water were added to the slurry and blended in at low speed for 30 seconds.
  • a handsheet was prepared by pouring a portion of the resulting slurry into a sheet mold apparatus (obtained from Williams Apparatus Co., Watertown N.Y.). The apparatus was equipped with a 413 square centimeter porous screen having a pore size of 80 mesh (177 micrometers) at the bottom to allow for drainage. The poured slurry was allowed to drain for 15 seconds. The resulting wet sheet was pressed for 5 minutes at 620 kPa using in a pneumatic press (Mead Fluid Dynamics, Chicago, Ill.). The pressed handsheet was then dried for 120 minutes at 135° C.
  • a pump (Model 7553-80 with a Model 7518-00 pump head both from (Cole Parmer Instrument Company, Vernon Hills, Ill.) was used to pump the pH 8 buffer solution through tubing (obtained under the trade designation “MASTERFLEX PHARMED TUBING #6485-14” from Cole-Parmer Instrument Company, Vernon Hills, Ill.) from a bottle to the disk holder assembly.
  • a pressure gauge (obtained under the trade designation “ASHCROFT PRESSURE GAUGE,” (Model #3NA22422-013 from Dressler Industries, Stratford, Conn.) was in line between the bottle containing the pH 8 buffer solution and the disk holder assembly.
  • the buffer solution was pumped through the extraction medium for 30 minutes at a flow rate of 5 ml per minute.
  • the flow diameter of the 25 mm disk extraction medium disk was about 22 mm.
  • An analyte matrix solution (also referred to as a “challenge solution”) was prepared by adding (and then mixing) a sufficient amount of each of various salts (see Table 1, below) to deionized water to provide the concentration of ions shown in Table 1.
  • the total volume of the resulting challenge solution was 20 liters.
  • the pH of the challenge solution was adjusted to 7.5 with 1 N sodium hydroxide (obtained from Fisher Scientific, Fair Lawn, N.J.).
  • the analyte matrix solution which was continually stirred, was pumped through each of the Example 1 and Comparative Example A disk holders at a rate of about 5 ml/minute.
  • the solution passed through the respective disks was collected in a collection bottle.
  • Six ml sample fractions of the passed solution were taken after 2, 10, 20, 30, 45, 60, 80, 100, 120, 140, 160 and 180 minutes of flow. Further, sample fractions of the initial and final feed solution were also taken. Two 6 ml samples were taken from each of the respective collection bottles.
  • One drop of 1M nitric acid (Fisher Scientific) was added as a preservative to each sample.
  • the samples were analyzed for Sr ions using an inductively coupled plasma analyzer (obtained under the trade designation “PERKIN-ELMER OPTIMA 3000DV” from Perkin Elmer, Norwalk, Conn.) and EPA Test Method 200.7 (“Determination of Metals and Trace Elements In Water And Wastes By Inductively Coupled Plasma-Atomic Emission-Spectroscopy”, Revision 4.4, EMMC Version, Environmental Monitoring Systems Laboratory, Office of Research And Development, U.S. Environmental Protection Agency, 1994), the disclosure of which is incorporated herein by reference.
  • inductively coupled plasma analyzer obtained under the trade designation “PERKIN-ELMER OPTIMA 3000DV” from Perkin Elmer, Norwalk, Conn.
  • EPA Test Method 200.7 Determination of Metals and Trace Elements In Water And Wastes By Inductively Coupled Plasma-Atomic Emission-Spectroscopy”, Revision 4.4, EMMC Version, Environmental Monitoring Systems Laboratory, Office of Research And Development, U.S. Environmental Protection Agency, 1994
  • Example 1 disk maintained a lower back pressure than did the Comparative Example A disk.
  • the Example 1 disk had a 50% break through occur at a bed volume of about 1100 ml of challenge solution.
  • Example 2 and Comparative Example B show the Hg ion loading of a solid phase extraction (“SPE”) media disk preconditioned with a pH 8 buffer solution (Example 1) and a SPE disk that had not been preconditioned with the pH 8 buffer solution (Comparative Example A).
  • SPE solid phase extraction
  • Example 2 and Comparative Example B were carried out as described for Example 1 and Comparative Example B, respectively, except (a) the sorbent particles were a mercury sorbent (SAMMS (Self-assembled monolayers on mesoporous supports) obtained from Pacific Northwest National Laboratory, Richland, Wash.) rather than the sorbent particles containing a mixed salt of titanium silicate; (b) the analyte matrix solution was prepared by dissolving a sufficient amount of mercuric chloride (obtained from salt Fisher Scientific Company, Fair Lawn, N.J.) in deionized water to provide a solution containing 100 ppm Hg ions; and (c) the concentration of Hg ions was analyzed using Method 3112, “Metals by Cold-Vapor Atomic Absorption Spectrometry”, Standard Methods for the Examination of Water and Wastewater, 19 th edition, 1995, and an analyzer obtained under the trade designation “LEEMAN LABS PS200 AUTOMATED MERCURY ANALYZER” from Lee
  • Example 2 disk maintained a lower back pressure than the Comparative Example B disk.
  • Examples 3-5 and Comparative Example C showed the Sr ion loading of a SPE disk preconditioned with a pH 8 buffer solution neutralized by 0.5 M sodium hydroxide solution (i.e., using the Example 1 buffer solution) (Example 3), potassium hydroxide (Example 4), and magnesium hydroxide (Example 5), respectively, and a SPE disk that had not been preconditioned with a buffer solution (Comparative Example C).
  • Examples 3-5 and Comparative Example C were carried out as described for Example 1 and Comparative Example C, respectively, except the respective buffer solutions for Examples 4 and 5 were prepared as described below.
  • a pH 8 buffer solution was prepared as follows.
  • a 0.23 Molar citric acid solution was prepared by dissolving 48.33 grams of citric acid monohydrate (obtained from J.T. Baker, Phillipsburg, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution.
  • a 0.5 Molar KOH solution was prepared by dissolving 28.1 grams of KOH (obtained from EM Science, Gibbstown, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution.
  • About 637.71 grams of the 0.5 M KOH solution were added to 400 grams of the 0.23 M citric acid solution to provide the pH 8 buffer solution.
  • a pH 8 buffer solution was prepared as follows.
  • a 0.23 Molar citric acid solution was prepared by dissolving 48.33 grams of citric acid monohydrate (obtained from J.T. Baker, Phillipsburg, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution.
  • a 0.5 Molar magnesium hydroxide solution was prepared by dissolving 29.2 grams of Mg(OH) 2 (obtained from Fisher Scientific, Fair Lawn, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution.
  • About 329.7 grams of the 0.5 M magnesium hydroxide solution were added to 404.85 grams of the 0.23 M citric acid solution to provide the pH 8 buffer solution.
  • Example 6 was carried out as described for Example 1 except (a) the initial treatment (i.e., the preconditioning) of the SPE disk with the buffer solution was for 45 minutes at a flow rate of 5 ml/min; and (b) the steps of loading the disk with the analyte matrix at a flow rate of 5 ml/min. for 60 minutes and then eluting the disk with the buffer solution at a flow rate of 1.2 ml/min. for 30 minutes, were each successively repeated four times (i.e., four cycles).
  • the back pressure as measured with the pressure gauge 5 cm from the disk, at the end of each loading with the analyte matrix was measured and is reported in Table 7, below. TABLE 7 Cycle Back pressure, kPa 1 24.1 2 34.5 3 68.9 4 124 5 124
  • Example 7 was carried out as described for Example 1 except (a) the initial treatment (i.e., the preconditioning) of the SPE disk with the buffer solution was for 45 minutes at a flow rate of 5 ml/min; and (b) the steps of loading the disk with the analyte matrix at a flow rate of 5 ml/min. for 60 minutes, eluting the disk with the buffer solution at a flow rate of 1.2 ml/min. for 30 minutes, and then rinsing the disk with deionized water for 30 minutes at a flow rate of 1.2 ml/min., were each successively repeated four times (i.e., four cycles).
  • the initial treatment i.e., the preconditioning
  • Examples 8 and 9 were carried out as described for Example 1 except (a) the buffer solutions and eluants for Examples 8 and 9 were prepared as described below; (b) the sorbent particles were particles containing sodium nonatitanate (obtained from Allied Signal, Morristown, N.J.); (c) the initial treatment (i.e., the preconditioning) of the SPE disk with the buffer solution was for 45 minutes at a flow rate of 5 ml/min; and (d) the steps of loading the disk with the analyte matrix at a flow rate of 5 ml/min. for 60 minutes and then eluting the disk with the buffer solution at a flow rate of 1.2 ml/min. for 30 minutes, were each successively repeated four times (i.e., four cycles).
  • a pH 8 buffer solution was prepared as follows.
  • a 0.23 Molar tartaric acid solution was prepared by dissolving 34.5 grams of tartaric acid (obtained from Aldrich Chemical, Milwaukee, Wis.) in a sufficient amount of deionized water to provide 1 liter of solution.
  • a 0.5 Molar NaOH solution was prepared by dissolving 20 grams of NaOH (obtained from E.M. Science, Gibbstown, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution.
  • About 342.5 grams of the 0.5 M NaOH solution were added to 366 grams of the 0.23 M tartaric acid solution to provide the pH 8 buffer solution.
  • a pH 8 buffer solution was prepared as follows.
  • a 0.23 Molar Ethylenediaminetetraacetic acid (“EDTA”) solution was prepared by dissolving 67.21 grams of EDTA (obtained from Aldrich Chemical Company, Milwaukee, Wis.) in a sufficient amount of deionized water to provide 1 liter of solution.
  • a 0.5 Molar NaOH solution was prepared by dissolving 20 grams of NaOH (obtained from E.M. Science, Gibbstown, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution. About 315 grams of the 0.5 M NaOH solution were added to 400.6 grams of the 0.23 M EDTA solution to provide the pH 8 buffer solution.
  • Example 10 was carried out as described for Example 1 except (a) the buffer solution and eluant was a pH 8.0 organic acid/base buffer solution prepared as described below; (b) the sorbent particles were particles containing sodium nonatitanate (obtained from Allied Signal, Morristown, N.J.); (c) the initial treatment (i.e., the preconditioning) of the SPE disk with the buffer solution was for 60 minutes at a flow rate of 5 ml/min; and (d) the steps of loading the disk with the analyte matrix at a flow rate of 5 ml/min. for 60 minutes and then eluting the disk with the buffer solution at a flow rate of 1.2 ml/min. for 30 minutes, were each successively repeated three times (i.e., three cycles).
  • the buffer solution and eluant was a pH 8.0 organic acid/base buffer solution prepared as described below; (b) the sorbent particles were particles containing sodium nonatitanate (obtained from Allied Signal, Morris
  • the organic acid/base buffer solution was prepared as follows.
  • a 0.23 Molar sodium azide solution was prepared by dissolving 14.95 grams of sodium azide (obtained from Aldrich Chemical Company) in a sufficient amount of deionized water to provide 1 liter of solution.
  • the solution had a pH of 8.

Abstract

A process for modifying a medium is disclosed that includes treating a medium having a metal ion sorption capacity with a solution that includes: A) an agent capable of forming a complex with metal ions; and B) ions selected from the group consisting of sodium ions, potassium ions, magnesium ions, and combinations thereof, to create a medium having an increased capacity to sorb metal ions relative to the untreated medium.

Description

    STATEMENT AS TO FEDERALLY SPONSORED RESEARCH
  • [0001] The invention was made with Government support under Contract DE-AR2 1-96MC-33089 awarded by the Department of Energy. The Government has certain rights in the invention.
  • BACKGROUND OF THE INVENTION
  • The invention relates to modifying the metal ion sorption capacity of a medium. [0002]
  • Water from waste streams, ground water, holding ponds, water treatment facilities, storage tanks, rivers, and streams can contain metals such as iron, zinc, cesium, plutonium, strontium, technetium, uranium, and americium. For environmental compliance, it is often desirable or necessary to remove these metals from the water. [0003]
  • A variety of methods have been developed for removing metals from the water in waste streams, ground water, holding ponds, water treatment facilities, storage tanks, rivers, and streams. Some of these methods include passing the water containing through a medium that removes the metal. The medium may be an ion exchange medium that is capable of sorbing the metal ions in the liquid. The medium is often packed in a column and once the medium is saturated with metal ions, the medium and/or column is discarded. [0004]
  • A method for removing metals from the medium involves eluting the metal ions from the medium with a strong acid followed by regenerating the medium with a strong base. These methods, however, do not always perform with the same level of effectiveness for all metals. For example, ion exchange media used for the removal of strontium frequently have a relatively low capacity for strontium due to large excesses of calcium and magnesium, which compete with the strontium for sites on the medium. Large excesses of calcium and magnesium relative to strontium are often present in waste streams and ground water. [0005]
  • A variety of agents can be used to elute metal ions from an ion exchange medium. Nitric acid and hydrochloric acid, for example, are often used to elute strontium from a strontium absorber. Nitric acid and hydrochloric acid, however, tend to cause a gradual increase in back pressure in systems in which they are employed as the eluant and in systems in which the medium is reconditioned. [0006]
  • SUMMARY OF THE INVENTION
  • The invention features a process for modifying a medium to increase its capacity to sorb (i.e., adsorb, absorb and combinations thereof) metal ions, as well as processes for regenerating the metal ion sorption capacity of a medium that has been exposed to metal ions, as well as the modified media, itself. [0007]
  • In one aspect, the invention features a process for modifying a medium that includes treating a medium having a metal ion sorption capacity with a solution that includes (a) an agent capable of forming a complex with metal ions, and (b) ions selected from the group consisting of sodium ions, potassium ions, magnesium ions or a combination thereof, to create a medium having an increased capacity to sorb metal ions relative to the untreated medium. [0008]
  • In preferred embodiments, the complexing agent is an organic acid (e.g., citric acid) and the ions are sodium ions. In some embodiments, the solution includes sodium azide. In other embodiments, the solution includes an organic acid and sodium hydroxide. [0009]
  • In preferred embodiments, the treating solution has a pH of between about 6 and 10, more preferably a pH of between about 7.5 and 8.5. [0010]
  • In one embodiment, the medium is capable of sorbing strontium ions. In other embodiments the medium is capable of sorbing mercury ions. [0011]
  • In another embodiment, the medium includes a membrane filled with particles, e.g., particles selected from the group consisting of particles of sodium titanate (i.e., sodium titanate, sodium nonatitanate, and combinations thereof), crystalline silico titanate, mixed salts of titanium silicate, sulfonated styrene divinyl benzene, SAMMS self-assembled monolayers on mesoporous supports specific for mercury analytes having a formula SiO[0012] 2—CH2CH2—SH, and combinations thereof.
  • In other embodiments, the medium includes sorbed metal ions. [0013]
  • In one embodiment, the process further includes contacting the treated medium with a liquid that includes metal ions such that the metal ions sorb onto the medium. The medium that includes sorbed metal ions can then be treated with an agent capable of forming a complex with metal ions for a period sufficient to elute the metal ions. One example of an agent capable of forming a complex with metal ions is a solution that includes an organic acid, e.g., citric acid and sodium hydroxide. [0014]
  • In one aspect, the invention features a process in which the back pressure produced during the process remains relatively constant during the process. In one embodiment, the process further includes providing a medium that includes sorbed metal ions, prior to treating the medium. [0015]
  • The process is useful for treating a medium (e.g., a solid phase ion exchange medium) that has sorbed metal ions (e.g., heavy metals, rare earth metals, and radioactive elements). The processes can regenerate (i.e., restore or increase) the metal ion sorption capacity of articles that have been previously contacted with a source of metal ions. The process is particularly useful in regenerating the ion sorption capacity of articles that are used to remove metal ion contaminates, and to treat aqueous streams from sources such as ground water, storage tanks, holding ponds, waste water treatment facilities, and nuclear waste storage tanks. [0016]
  • The process of the present invention improves the metal ion sorption capacity of an article relative to its metal ion adsorption capacity without treatment. In another embodiment, the process of the invention improves the metal ion sorption capacity of an article that includes sorbed metal ions. The processes according to the present invention also permit the maintenance of a relatively constant back pressure throughout the process. [0017]
  • Certain preferred processes according to the present invention are particularly well suited and can be optimized for the selective removal and recovery of strontium from a medium. [0018]
  • Other features and advantages of the invention will be apparent from the following description of the preferred embodiments thereof, and from the claims. [0019]
  • DETAILED DESCRIPTION
  • The process includes treating a medium having a metal ion adsorption capacity with a solution that includes: A) an agent capable of forming a complex with at least one metal ion; and B) ions selected from the group consisting of sodium, potassium, magnesium and combinations thereof, to increase the capacity of the medium to sorb metal ions relative to the untreated medium. [0020]
  • The treating solution is a buffer preferably having a pH in the range of about 5 to about 11, more preferably a pH in the range of about 6 to about 10, most preferably a pH in the range of about 7.5 to about 8.5. The treating solution includes a complexing agent capable of forming a complex with at least one metal ion. Preferred agents are capable of forming complexes with ions of, e.g., heavy metals, rare earth metals, actinides, and combinations thereof. [0021]
  • Examples of useful complexing agents include organic acids having more than one carboxyl group including citric acid, tartaric acid, oxalic acid, succinic acid, malonic acid, and ethylenediaminetetraacetic acid (“EDTA”). [0022]
  • Other useful complexing agents include lactic acid, sulphosalicylates, acetylacetonante, and azides (e.g., sodium azide). [0023]
  • The treating solution also includes ions, e.g., sodium ions, potassium ions, magnesium ions and combinations thereof. The treating solution is brought to the desired pH by the addition of an appropriate amount of buffer adjusting solution, e.g., base, which also provides the ions. Examples of useful bases include metal hydroxides including, e.g., sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide, and sodium azide. The sodium azide can function as both the complexing agent and a source of sodium ions. [0024]
  • The addition of ions can be used to convert substantially all of the particles in the medium to a single salt form, e.g., the sodium form, such that the medium exhibits an increased propensity to selectively sorb predetermined ions, e.g., cations or anions. Preferably ions are added to convert substantially all of the medium to the sodium salt form. Preferably the medium exhibits a propensity to selectively sorb strontium ions. [0025]
  • The treating solution is used to treat a medium that is capable of sorbing metal ions. The medium includes particles capable of removing ions from fluids through mechanisms such as, e.g., ion exchange (e.g., solid phase ion exchange), chelation, covalent bond formation, and sorption (e.g., adsorption, absorption and combinations thereof). Preferably the medium is capable of sorbing ions of radioactive particles, metals (e.g., heavy metals, rare earth metals, alkaline earth metals, and combinations thereof) and combinations thereof. Useful media sorb ions of metals from Groups IA, IIA, IB, IIB, IIIB, and VIII of the periodic table. Preferably the medium is capable of sorbing ions of metals such as, e.g., cesium strontium, silver, cobalt, chromium, gold, mercury, uranium, americium, plutonium, copper, iron, technetium, lead, zinc, and rhenium. [0026]
  • Typically the medium consists of finely divided, microporous particles. Preferably the particles have a relatively large area of active surface and a uniform size distribution. Useful particles have an average particle size in the range of about 1 μm to about 100 μm, preferably about 2 μm to about 75 μm, more preferably about 9 μm to about 18 μm. Suitable particles include inorganic, organic, and combinations thereof. Preferably the particles are ionically charged (e.g., cationic and anionic particles). [0027]
  • Useful inorganic media include metal titanates, where the metal is selected form Group IA and Group IIA metals (e.g., sodium titanate which includes nonatitanate), silicotitanates (e.g., crystalline silico titanate, and mixed salts of titanium silicates) and combinations thereof. Examples of commercially available inorganic particles include sodium titanates (available from Allied Signal Corp., Chicago, Ill.), crystalline silico titanates (available under the trade designation IONSIV from UOP of Tarrytown, N.Y.), sorbent particles available under the trade designation ATS from Engelhard Corporation, Iselin, N.J., and high capacity resins available under the trade designation NALCITE from Nalco Chemical Co., Naperville, Ill. [0028]
  • Examples of useful organic media include sulfonated styrene divinyl benzene resins (commercially available, e.g., under the trade designation CATEX from Sarasep Corp., Santa Clara, Calif.)), organic anion sorber (commercially available under the trade designation ANEX from Serasep), and organic cation sorber (commercially available under the trade designation DIPHONIX from Ichrome Industries of Chicago, Ill.). [0029]
  • Other useful commercially available particles include SAMMS self-assembled monolayers on mesoporous supports specific for mercury analytes having a formula SiO[0030] 2—CH2CH2—SH (from Batelle Memorial Institute, Pacific Northwest National Labs, Richland, Wash.), and Clinoptolite.
  • The medium can also include derivatized particles. Useful derivatized particles include polymeric coated oxide particles and organic moieties covalently bonded to inorganic oxide particles. Derivatized particles are described, e.g., in U.S. Pat. Nos. 5,393,892 (Krakowiak), 5,334,326 (Bostick), 5,316,679 (Bruening), 5,273,660 (Bruening), and 5,244,856 (Bruening) and incorporated herein by reference. [0031]
  • The particles can be enmeshed in a variety of fibrous, nonwoven webs, which preferably are porous. Examples of such webs include polymer pulps, fibrillated polytetrafluoroethylene (PTFE), microfibrous webs, and macrofibrous webs. Examples of particle filled webs are described in U.S. Pat. Nos. 5,328,758 (Markell et al.), 5,071,610 (Hagen et al.), 5,082,720 (Hayes), and 3,971,373 (Braun), the disclosures of which are incorporated herein by reference. Other useful media may include those media described in U.S. Ser. No. 08/791,205 entitled, “Spiral Wound Extraction Cartridge,” which was filed on Feb. 13, 1997; U.S. Ser. No. 08/918,113 entitled, “Absorbent for Metal Ions and Method for Making and Using,” which was filed on Aug. 27, 1997; and PCT publication WO96/29146 published Sep. 26, 1996 and incorporated herein by reference. [0032]
  • Another useful medium includes sponge-like (i.e., porous) medium prepared by compacting spray dried particles under low pressure (e.g., hand pressure) into a confined space and heating the compacted particles to a temperature of about 130° C. for about 72 hours results. Such sponge-like media exhibit excellent separating ability and relatively low back pressure during use. Useful sponge-like media are described in U.S. Ser. No. 08/960,528 filed on Oct. 31, 1997 and incorporated herein by reference. [0033]
  • The medium can be in the form of an article such as, e.g., membranes (e.g., particle embedded membranes, and particle filled membranes), particle filled microfiber webs, particle coated filter paper, cartridges, columns (e.g., chromatography columns, short packed columns), disks and sheets. [0034]
  • The invention will now be described further by way of the following examples. [0035]
  • Objects and advantages of this invention are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention.[0036]
  • EXAMPLES Example 1 and Comparative Example A
  • Example 1 and Comparative Example A show the Sr ion loading of a solid phase extraction (“SPE”) media disk preconditioned with a pH 8 buffer solution (Example 1) and a SPE disk that had not been preconditioned with the pH 8 buffer solution (Comparative Example A). [0037]
  • The pH 8 buffer solution was prepared as follows. A 0.23 Molar citric acid solution was prepared by dissolving 48.33 grams of citric acid monohydrate (obtained from J.T. Baker, Phillipsburg, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution. A 0.5 Molar NaOH solution was prepared by dissolving 20 grams of NaOH (obtained from E.M. Science, Gibbstown, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution. About 564 grams of the 0.5 M NaOH solution were added to 404 grams of the 0.23 M citric acid solution to provide the pH 8 buffer solution. [0038]
  • An extraction medium was prepared by first mixing 13.20 grams (dry weight) of aramid fiber pulp (obtained under the trade designation “KEVLAR IF306” from E.I. Dupont, Inc., Wilmington, Del.) with 2000 ml of hot water in a 4 liter laboratory Waring blender at low speed for 30 seconds to form a slurry. About 0.25 gram of a nonionic dispersant (obtained under the trade designation “TAMOL 850” from Rohm and Haas, Philadelphia, Pa.) was added to the slurry and blended in at the low speed setting for 30 seconds. Next, 43.80 grams of sorbent particles (obtained under the trade designation “ATS” from Engelhard Corporation, Iselin, N.J.), containing a mixed salt of titanium silicate, were added to the slurry and blended in at the low speed setting for 30 seconds. About 7.5 grams latex binder (3.0 grams of styrene-butadiene (obtained under the trade designation “GOODRITE 1800×73” from B.F. Goodrich Co., Cleveland, Ohio) dissolved in 4.5 grams of deionized water were added to the slurry and blended in at low speed for 30 seconds. Next, 25 grams of a 25% aluminum sulfate aqueous solution (obtained from Aldrich Chemicals of Milwaukee, Wis.) were added to the slurry and blended at low speed for 30 seconds. About 1.4 gram of a 10% acrylamide modified cationic copolymer solution, a flocculating agent (obtained under the trade designation “NALCO 7530” from Nalco Chemical Company, Naperville, Ill.) were added to the slurry and blended in at low speed for about 4 seconds. [0039]
  • A handsheet was prepared by pouring a portion of the resulting slurry into a sheet mold apparatus (obtained from Williams Apparatus Co., Watertown N.Y.). The apparatus was equipped with a 413 square centimeter porous screen having a pore size of 80 mesh (177 micrometers) at the bottom to allow for drainage. The poured slurry was allowed to drain for 15 seconds. The resulting wet sheet was pressed for 5 minutes at 620 kPa using in a pneumatic press (Mead Fluid Dynamics, Chicago, Ill.). The pressed handsheet was then dried for 120 minutes at 135° C. [0040]
  • Two 25 mm diameter disks were cut out of the extraction medium (i.e., the dried handsheet). For each of Example 1 and Comparative Example A, one of the 25 mm diameter disks were placed in a stainless steel disk holder (#1209; obtained from Pall/Gelman Sciences, Ann Arbor, Mich.). The disk holder was attached to the top of a flask. A pump (Model 7553-80 with a Model 7518-00 pump head both from (Cole Parmer Instrument Company, Vernon Hills, Ill.) was used to pump the pH 8 buffer solution through tubing (obtained under the trade designation “MASTERFLEX PHARMED TUBING #6485-14” from Cole-Parmer Instrument Company, Vernon Hills, Ill.) from a bottle to the disk holder assembly. A pressure gauge (obtained under the trade designation “ASHCROFT PRESSURE GAUGE,” (Model #3NA22422-013 from Dressler Industries, Stratford, Conn.) was in line between the bottle containing the pH 8 buffer solution and the disk holder assembly. The buffer solution was pumped through the extraction medium for 30 minutes at a flow rate of 5 ml per minute. The flow diameter of the 25 mm disk extraction medium disk was about 22 mm. [0041]
  • An analyte matrix solution (also referred to as a “challenge solution”) was prepared by adding (and then mixing) a sufficient amount of each of various salts (see Table 1, below) to deionized water to provide the concentration of ions shown in Table 1. The total volume of the resulting challenge solution was 20 liters. The pH of the challenge solution was adjusted to 7.5 with 1 N sodium hydroxide (obtained from Fisher Scientific, Fair Lawn, N.J.). [0042]
    TABLE 1
    Molarity,
    ppm in solution moles/liter Salt Manufacturer
    54.5 Ca ions 1.36 × 10−3 Ca(NO3)24 H2O EM Science,
    Gibbstown, NJ
    0.074 Cu ions 1.01 × 10−6 Cu(NO3)22.5 H2O J. T Baker,
    Phillipsburg, NJ
    1.75 Fe ions 1.16 × 10−6 Fe(NO3)39 H2O J. T Baker
    0.0248 Pb ions 3.13 × 10−5 Pb(NO3)2 Aldrich Chemical
    Co., Milwaukee, WI
    0.0332 Cr ions 8.11 × 10−4 Cr(NO3)29H2O Fisher Scientific,
    Fair Lawn, NJ
    0.399 Zn ions 1.20 × 10−7 Zn(NO3)2xH2O Mallinckrodt Inc,
    Paris, KY
    0.139 Ba ions 6.39 × 10−7 Ba(NO3)2 Mallinckrodt, Inc,
    19.7 Mg ions 3.87 × 10−3 Mg(NO3)26H2O Fisher Chemical
    89 Na ions 6.10 × 10−6 NaNO3 J. T. Baker
    0.3 Sr ions 3.42 × 10−6 Sr(NO3)2 Aldrich Chemical
    Co.
  • The analyte matrix solution, which was continually stirred, was pumped through each of the Example 1 and Comparative Example A disk holders at a rate of about 5 ml/minute. The solution passed through the respective disks was collected in a collection bottle. Six ml sample fractions of the passed solution were taken after 2, 10, 20, 30, 45, 60, 80, 100, 120, 140, 160 and 180 minutes of flow. Further, sample fractions of the initial and final feed solution were also taken. Two 6 ml samples were taken from each of the respective collection bottles. One drop of 1M nitric acid (Fisher Scientific) was added as a preservative to each sample. The samples were analyzed for Sr ions using an inductively coupled plasma analyzer (obtained under the trade designation “PERKIN-ELMER OPTIMA 3000DV” from Perkin Elmer, Norwalk, Conn.) and EPA Test Method 200.7 (“Determination of Metals and Trace Elements In Water And Wastes By Inductively Coupled Plasma-Atomic Emission-Spectroscopy”, Revision 4.4, EMMC Version, Environmental Monitoring Systems Laboratory, Office of Research And Development, U.S. Environmental Protection Agency, 1994), the disclosure of which is incorporated herein by reference. [0043]
  • The results and other details are shown in Table 2, below. [0044]
    TABLE 2
    Comparative Example A Example 1
    Disk weight: 0.61 gram Disk weight: 0.78 gram
    % particle in medium: 68.9% % particle in medium: 68.9%
    Weight particle in medium: Weight particle in medium:
    0.420 gram 0.537 gram
    Disk thickness: 0.198 cm Disk thickness: 0.213 cm
    Bed volume @ 22 mm: 0.752 ml Bed volume @ 22 mm: 0.810 ml
    Bed Concen- C/Co for Sr Bed Concen- C/Co for Sr
    volumes tration (Co = 0.28 volumes tration (Co = 0.29
    passed of Sr, ppm ppm) passed of Sr, ppm ppm)
    0 0.01 0.035 0 0.00 0.035
    66 0.03 0.107 62 0.00 0.035
    132 0.09 0.321 123 0.00 0.035
    199 0.11 0.393 185 0.01 0.035
    302 0.14 0.500 277 0.05 0.172
    402 0.15 0.535 370 0.06 0.207
    535 0.17 0.607 493 0.09 0.310
    668 0.19 0.679 616 0.10 0.345
    793 0.19 0.679 740 0.12 0.414
    925 0.20 0.714 863 0.13 0.448
    1058 0.20 0.714 986 0.14 0.483
    1191 0.21 0.750 1110 0.15 0.517
    Capacity @ 50% breakthrough*: Capacity @ 50% breakthrough
    0.0106 g Sr/100 g particle 0.0344 g Sr/100 g particle
  • The Example 1 disk maintained a lower back pressure than did the Comparative Example A disk. The Example 1 disk had a 50% break through occur at a bed volume of about 1100 ml of challenge solution. [0045]
  • Example 2 and Comparative Example B
  • Example 2 and Comparative Example B show the Hg ion loading of a solid phase extraction (“SPE”) media disk preconditioned with a pH 8 buffer solution (Example 1) and a SPE disk that had not been preconditioned with the pH 8 buffer solution (Comparative Example A). [0046]
  • Example 2 and Comparative Example B were carried out as described for Example 1 and Comparative Example B, respectively, except (a) the sorbent particles were a mercury sorbent (SAMMS (Self-assembled monolayers on mesoporous supports) obtained from Pacific Northwest National Laboratory, Richland, Wash.) rather than the sorbent particles containing a mixed salt of titanium silicate; (b) the analyte matrix solution was prepared by dissolving a sufficient amount of mercuric chloride (obtained from salt Fisher Scientific Company, Fair Lawn, N.J.) in deionized water to provide a solution containing 100 ppm Hg ions; and (c) the concentration of Hg ions was analyzed using Method 3112, “Metals by Cold-Vapor Atomic Absorption Spectrometry”, [0047] Standard Methods for the Examination of Water and Wastewater, 19th edition, 1995, and an analyzer obtained under the trade designation “LEEMAN LABS PS200 AUTOMATED MERCURY ANALYZER” from Leeman Labs, Hudson, N.H. The results and other details are shown in Table 3, below.
    TABLE 3
    Comparative Example B Example 2
    Disk weight 0.34 gram Disk weight: 0.32 gram
    % particle in medium: 73.1% % particle in medium: 73.1%
    Weight particle in medium: Weight particle in medium:
    0.249 gram 0.234 gram
    Disk thickness: 0.072 inch Disk thickness: 0.072 inch
    0.0283 cm 0.0283 cm
    Bed volume @ 22 mm: 0.695 ml Bed volume @ 22 mm: 0.695 ml
    Bed Concen- C/Co for Hg Bed Concen- C/Co for
    volumes tration of (Co = 80. volumes tration of Hg (Co =
    passed Hg, ppm ppm) passed Hg, ppm 160 ppm)
    0 0 0 0 0 0
    36 13.64 0.17 37 0 0
    72 17.38 0.21 75 0.11 0.0007
    108 19.69 0.24 112 2.2 0.0138
    144 21.89 0.27 149 5.4 0.0338
    180 23.32 0.29 187 9.2 0.0575
    216 25.74 0.32 224 20 0.125
    433 37.40 0.46 449 37 0.231
    649 49.39 0.61 898 54 0.337
    866 56.21 0.69 1122 69 0.431
    1082 61.38 0.76 1347 72 0.45
    1297 64.68 0.80 1459 64 0.40
    Capacity @ 50% breakthrough: Capacity @ 50% breakthrough:
    7.67 g Hg/100 g particle 64.87 g Hg/100 g particle
  • The Example 2 disk maintained a lower back pressure than the Comparative Example B disk. [0048]
  • Examples 3-5 and Comparative Example C
  • Examples 3-5 and Comparative Example C showed the Sr ion loading of a SPE disk preconditioned with a pH 8 buffer solution neutralized by 0.5 M sodium hydroxide solution (i.e., using the Example 1 buffer solution) (Example 3), potassium hydroxide (Example 4), and magnesium hydroxide (Example 5), respectively, and a SPE disk that had not been preconditioned with a buffer solution (Comparative Example C). [0049]
  • Examples 3-5 and Comparative Example C were carried out as described for Example 1 and Comparative Example C, respectively, except the respective buffer solutions for Examples 4 and 5 were prepared as described below. [0050]
  • For Example 4, a pH 8 buffer solution was prepared as follows. A 0.23 Molar citric acid solution was prepared by dissolving 48.33 grams of citric acid monohydrate (obtained from J.T. Baker, Phillipsburg, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution. A 0.5 Molar KOH solution was prepared by dissolving 28.1 grams of KOH (obtained from EM Science, Gibbstown, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution. About 637.71 grams of the 0.5 M KOH solution were added to 400 grams of the 0.23 M citric acid solution to provide the pH 8 buffer solution. [0051]
  • For Example 5, a pH 8 buffer solution was prepared as follows. A 0.23 Molar citric acid solution was prepared by dissolving 48.33 grams of citric acid monohydrate (obtained from J.T. Baker, Phillipsburg, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution. A 0.5 Molar magnesium hydroxide solution was prepared by dissolving 29.2 grams of Mg(OH)[0052] 2 (obtained from Fisher Scientific, Fair Lawn, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution. About 329.7 grams of the 0.5 M magnesium hydroxide solution were added to 404.85 grams of the 0.23 M citric acid solution to provide the pH 8 buffer solution.
  • The results and other details are shown in Table 4, below. [0053]
    TABLE 4
    Comparative Example C Example 3 Example 4 Example 5
    Disk weight: 0.76 gram Disk weight: 0.78 gram Disk weight: 0.75 gram Disk weight: 0.73 gram
    % particle in medium: 68.9% % particle in medium: 68.9% % particle in medium: 68.9% % particle in medium: 68.9%
    Weight particle in medium; Weight particle in medium Weight particle in medium Weight particle in medium
    0.524 gram 0.537 gram 0.517gram 0.502 gram
    Disk thickness: 0.082 inch Disk thickness: 0.084 inch 0.033 Disk thickness: 0.090 inch Disk thickness: 0.078 inch 0.0307
    0.0322 cm cm 0.035 cm cm
    Bed volume @ 22 mm: 0.791 ml Bed volume @ 22 mm: 0.810 ml Bed volume @ 22 mm: 0.869 ml Bed volume @ 22 mm: 0.753 ml
    C/Co for C/Co for C/Co for
    Bed Conc. Sr Bed Conc. Sr Bed Conc. Sr Bed Conc. C/Co for
    volumes of Sr, (Co = 0.35 volumes of Sr, (Co = 0.29 volumes of Sr, (Co = 0.37 Volumes of Sr, Sr (Co = 0.
    passed ppm ppm) passed) ppm ppm) passed ppm ppm) passed ppm ppm)
    0 0 0 0 0 0 0 0 0 0 0 0
    32 0.1 0.28 30.5 0.01 0.035 25 0.1 0.27 35 0.06 0.16
    64 0.12 0.34 61 0.01 0.035 52 0.1 0.27 70 0.09 0.25
    128 0.16 0.45 123 0.01 0.035 104 0.12 0.32 138 0.09 0.25
    193 0.18 0.51 185 0.01 0.035 160 0.14 0.37 205 0.10 0.28
    290 0.21 0.6 277 0.05 0.17 242 0.17 0.46 307 0.12 0.33
    386 0.22 0.62 370 0.06 0.20 327 0.19 0.51 411 0.14 0.38
    515 0.26 0.74 493 0.09 0.31 442 0.22 0.59 549 0.17 0.47
    644 0.27 0.77 616 0.1 0.34 558 0.23 0.62 687 0.20 0.55
    773 0.26 0.74 740 0.12 0.41 675 0.24 0.64 825 0.21 0.58
    902 0.28 0.80 863 0.13 0.44 791 0.25 0.67 963 0.22 0.61
    1031 0.28 0.80 986 0.14 0.48 907 0.26 0.70 1101 0.23 0.63
    1160 0.28 0.80 1110 0.15 0.51 1024 0.26 0.70 1240 0.28 0.78
    Capacity @ 50% breakthrough: Capacity @ 50% breakthrough: Capacity @ 50% breakthrough: Capacity @ 50% breakthrough:
    0.00602 g Sr/100 g particle 0.0344 g Sr/100 g particle 0.0133 g Sr/100 g particle 0.0194 g Sr/100 g particle
  • Example 6
  • Example 6 was carried out as described for Example 1 except (a) the initial treatment (i.e., the preconditioning) of the SPE disk with the buffer solution was for 45 minutes at a flow rate of 5 ml/min; and (b) the steps of loading the disk with the analyte matrix at a flow rate of 5 ml/min. for 60 minutes and then eluting the disk with the buffer solution at a flow rate of 1.2 ml/min. for 30 minutes, were each successively repeated four times (i.e., four cycles). The back pressure, as measured with the pressure gauge 5 cm from the disk, at the end of each loading with the analyte matrix was measured and is reported in Table 7, below. [0054]
    TABLE 7
    Cycle Back pressure, kPa
    1 24.1
    2 34.5
    3 68.9
    4 124
    5 124
  • Example 7
  • Example 7 was carried out as described for Example 1 except (a) the initial treatment (i.e., the preconditioning) of the SPE disk with the buffer solution was for 45 minutes at a flow rate of 5 ml/min; and (b) the steps of loading the disk with the analyte matrix at a flow rate of 5 ml/min. for 60 minutes, eluting the disk with the buffer solution at a flow rate of 1.2 ml/min. for 30 minutes, and then rinsing the disk with deionized water for 30 minutes at a flow rate of 1.2 ml/min., were each successively repeated four times (i.e., four cycles). The back pressure, as measured with the pressure gauge 5 cm from the disk, at the end of each loading with the analyte matrix was measured and is reported in Table 8, below. [0055]
    TABLE 8
    Cycle Back pressure, kPa
    1 10.3
    2 6.9
    3 10.3
    4 10.3
    5 20.6
  • Examples 8 and 9
  • Examples 8 and 9 were carried out as described for Example 1 except (a) the buffer solutions and eluants for Examples 8 and 9 were prepared as described below; (b) the sorbent particles were particles containing sodium nonatitanate (obtained from Allied Signal, Morristown, N.J.); (c) the initial treatment (i.e., the preconditioning) of the SPE disk with the buffer solution was for 45 minutes at a flow rate of 5 ml/min; and (d) the steps of loading the disk with the analyte matrix at a flow rate of 5 ml/min. for 60 minutes and then eluting the disk with the buffer solution at a flow rate of 1.2 ml/min. for 30 minutes, were each successively repeated four times (i.e., four cycles). [0056]
  • For Example 8, a pH 8 buffer solution was prepared as follows. A 0.23 Molar tartaric acid solution was prepared by dissolving 34.5 grams of tartaric acid (obtained from Aldrich Chemical, Milwaukee, Wis.) in a sufficient amount of deionized water to provide 1 liter of solution. A 0.5 Molar NaOH solution was prepared by dissolving 20 grams of NaOH (obtained from E.M. Science, Gibbstown, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution. About 342.5 grams of the 0.5 M NaOH solution were added to 366 grams of the 0.23 M tartaric acid solution to provide the pH 8 buffer solution. [0057]
  • For Example 9, a pH 8 buffer solution was prepared as follows. A 0.23 Molar Ethylenediaminetetraacetic acid (“EDTA”) solution was prepared by dissolving 67.21 grams of EDTA (obtained from Aldrich Chemical Company, Milwaukee, Wis.) in a sufficient amount of deionized water to provide 1 liter of solution. A 0.5 Molar NaOH solution was prepared by dissolving 20 grams of NaOH (obtained from E.M. Science, Gibbstown, N.J.) in a sufficient amount of deionized water to provide 1 liter of solution. About 315 grams of the 0.5 M NaOH solution were added to 400.6 grams of the 0.23 M EDTA solution to provide the pH 8 buffer solution. [0058]
  • The back pressure, as measured with the pressure gauge 5 cm from the disk, at the end of each loading with the analyte matrix was measured and are reported in Table 9, below. [0059]
    TABLE 9
    Example 8 Example 9
    Cycle Back pressure, kPa Back pressure, kPa
    1 6.9 6.9
    2 6.9 6.9
    3 10.3 6.9
    4 10.3
  • Example 10
  • Example 10 was carried out as described for Example 1 except (a) the buffer solution and eluant was a pH 8.0 organic acid/base buffer solution prepared as described below; (b) the sorbent particles were particles containing sodium nonatitanate (obtained from Allied Signal, Morristown, N.J.); (c) the initial treatment (i.e., the preconditioning) of the SPE disk with the buffer solution was for 60 minutes at a flow rate of 5 ml/min; and (d) the steps of loading the disk with the analyte matrix at a flow rate of 5 ml/min. for 60 minutes and then eluting the disk with the buffer solution at a flow rate of 1.2 ml/min. for 30 minutes, were each successively repeated three times (i.e., three cycles). [0060]
  • The organic acid/base buffer solution was prepared as follows. A 0.23 Molar sodium azide solution was prepared by dissolving 14.95 grams of sodium azide (obtained from Aldrich Chemical Company) in a sufficient amount of deionized water to provide 1 liter of solution. The solution had a pH of 8. [0061]
  • The back pressure, as measured with the pressure gauge 5 cm from the disk, at the end of each loading with the analyte matrix was measured and are reported in Table 10, below. [0062]
    TABLE 10
    Cycle Back pressure, kPa
    1 6.9
    2 20.6
    3 20.6
  • Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit of this invention, and it should be understood that this invention is not to be unduly limited to the illustrative embodiments set forth herein. [0063]
  • Other embodiments are within the claims.[0064]

Claims (18)

What is claimed is:
1. A process for modifying a medium comprising:
treating a medium having a metal ion sorption capacity with a solution comprising
(a) an agent capable of forming a complex with metal ions, and
(b) ions selected from the group consisting of sodium ions, potassium ions, magnesium ions or a combination thereof,
to create a medium having an increased capacity to sorb metal ions relative to said untreated medium.
2. The process of claim 1, wherein said agent comprises an organic acid and said ions are sodium ions.
3. The process of claim 1, wherein said agent is citric acid and ions are sodium ions.
4. The process of claim 1, wherein said solution comprises sodium azide.
5. The process of claim 1, wherein said solution comprises an organic acid and sodium hydroxide.
6. The process of claim 1, wherein said solution has a pH of between about 6 and 10.
7. The process of claim 1, wherein said solution has a pH of between about 7.5 and 8.5.
8. The process of claim 1, wherein said medium is capable of sorbing strontium ions.
9. The process of claim 1, wherein said medium is capable of sorbing mercury ions.
10. The process of claim 1 wherein said medium comprises a membrane filled with particles.
11. The process of claim 10, wherein said particles are selected from the group consisting of particles of sodium titanate, crystalline silico titanate, mixed salts of titanium silicate, sulfonated styrene divinyl benzene, SAMMS or a combination thereof.
12. The process of claim 1, wherein said medium comprises sorbed metal ions.
13. The process of claim 1, further comprising contacting said treated medium with a liquid comprising metal ions such that said metal ions sorb onto said medium.
14. The process of claim 13, further comprising treating said medium comprising sorbed metal ions with an agent capable of forming a complex with metal ions for a period sufficient to elute said metal ions.
15. The process of claim 14, wherein said the agent capable of forming a complex with metal ions comprises a solution comprising citric acid and sodium hydroxide.
16. The process of claim 13, further comprising treating said medium comprising sorbed metal ions with a solution comprising an organic acid and sodium hydroxide for a period sufficient to elute said metal ions.
17. The process of claim 13, wherein a back pressure produced during said process remains relatively constant during said process.
18. The process of claim 1 further comprising providing a medium comprising sorbed metal ions, prior to treating said medium.
US09/199,296 1998-11-24 1998-11-24 Process for modifying the metal ion sorption capacity of a medium Expired - Fee Related US6436294B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US09/199,296 US6436294B2 (en) 1998-11-24 1998-11-24 Process for modifying the metal ion sorption capacity of a medium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US09/199,296 US6436294B2 (en) 1998-11-24 1998-11-24 Process for modifying the metal ion sorption capacity of a medium

Publications (2)

Publication Number Publication Date
US20020011446A1 true US20020011446A1 (en) 2002-01-31
US6436294B2 US6436294B2 (en) 2002-08-20

Family

ID=22736983

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/199,296 Expired - Fee Related US6436294B2 (en) 1998-11-24 1998-11-24 Process for modifying the metal ion sorption capacity of a medium

Country Status (1)

Country Link
US (1) US6436294B2 (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009002915A1 (en) * 2007-06-22 2008-12-31 Steward Environmental Solutions, Llc System amd methods for the removal of soft heavy metals from streams
US20090144644A1 (en) * 2004-06-25 2009-06-04 Chaudhri Imran A Web View Layer For Accessing User Interface Elements
US8302020B2 (en) 2004-06-25 2012-10-30 Apple Inc. Widget authoring and editing environment
CN102814164A (en) * 2012-09-17 2012-12-12 工信华鑫科技有限公司 Method for implementing copper-cobalt-zinc separation, enrichment and purification by using heavy metal adsorbing material
CN102815763A (en) * 2012-09-17 2012-12-12 工信华鑫科技有限公司 Method for implementing copper-cobalt separation, enrichment and purification by using heavy metal adsorbing material
CN102872807A (en) * 2012-09-17 2013-01-16 工信华鑫科技有限公司 Method for separating, enriching and purifying nickel and ferrous iron through heavy metal absorbing material
CN102872808A (en) * 2012-09-17 2013-01-16 工信华鑫科技有限公司 Method for separating, enriching and purifying copper and nickel by using heavy metal adsorption material
US20130277295A1 (en) * 2006-12-01 2013-10-24 Perry Equipment Corporation Filter Element and Methods of Manufacturing and Using Same
WO2015101071A1 (en) * 2014-01-03 2015-07-09 上海交通大学 Silicon-based titanate composite adsorbent for removing radioactive strontium and preparation method therefor
CN104923193A (en) * 2015-06-15 2015-09-23 中国石油大学(华东) Acid and alkali treatment reactivating method for S-Zorb spent sorbent
US9417888B2 (en) 2005-11-18 2016-08-16 Apple Inc. Management of user interface elements in a display environment
US9483164B2 (en) 2007-07-18 2016-11-01 Apple Inc. User-centric widgets and dashboards
US9513930B2 (en) 2005-10-27 2016-12-06 Apple Inc. Workflow widgets
EP3098817A4 (en) * 2014-03-27 2017-10-18 Nippon Chemical Industrial Co., Ltd. Adsorbent and method for manufacturing crystalline silicotitanate
EP3190087A4 (en) * 2014-10-02 2018-05-23 Nippon Chemical Industrial Co., Ltd. Method for producing crystalline silicotitanate
JP2018205276A (en) * 2017-06-09 2018-12-27 日立Geニュークリア・エナジー株式会社 Treatment method and treatment device for radioactive waste liquid
CN113816509A (en) * 2021-09-28 2021-12-21 石文建 Method for adsorbing rare metal ions in aqueous solution by using calcium sulfate whiskers

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040122141A1 (en) * 2000-10-19 2004-06-24 Todd Terry A Composite media for ion processing and a method for making the composite media
US7629292B2 (en) * 2000-10-19 2009-12-08 Battelle Energy Alliance, Llc Composite media for ion processing
US6514566B2 (en) * 2000-10-19 2003-02-04 Bechtel Bwxt Idaho, Llc Ion processing element with composite media
US6946077B2 (en) * 2000-11-30 2005-09-20 Envirotrol, Inc. pH stable activated carbon
WO2004085708A1 (en) * 2002-08-21 2004-10-07 Battelle Memorial Institute Photolytic oxygenator with carbon dioxide and/or hydrogen separation and fixation
WO2007035622A1 (en) * 2005-09-15 2007-03-29 Battelle Memorial Institute Photolytic generation of hydrogen peroxide
BRPI0710098A2 (en) * 2006-03-31 2011-08-02 Perry Equipment Corp layered filter for treating contaminated fluids
WO2007117415A2 (en) * 2006-03-31 2007-10-18 Perry Equipment Corporation Systems and methods for flow-through treatment of contaminated fluids
WO2007117416A2 (en) * 2006-03-31 2007-10-18 Perry Equipment Corporation Composite adsorbent block for the treatment of contaminated fluids
WO2007117420A2 (en) * 2006-03-31 2007-10-18 Perry Equipment Corporation Canister for treatment of contaminated fluids
EP2183192A4 (en) * 2007-07-31 2011-08-31 Perry Equipment Corp Systems and methods for removal of heavy metal contaminants from fluids
US20090032472A1 (en) * 2007-07-31 2009-02-05 Perry Equipment Corporation Systems and methods for removal of heavy metal contaminants from fluids
US8663361B1 (en) * 2010-05-06 2014-03-04 Sandia Corporation Methods of recovering alkali metals
US8507284B2 (en) * 2011-07-14 2013-08-13 Uchicago Argonne, Llc Method and apparatus for extraction of strontium from urine
US11484875B2 (en) 2019-07-09 2022-11-01 Uop Llc Process for removing mercury ions from bodily fluids using titanium metallate ion exchange compositions

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1031084A (en) * 1973-03-12 1978-05-09 Robert Kunin Water conditioning process
US3971373A (en) 1974-01-21 1976-07-27 Minnesota Mining And Manufacturing Company Particle-loaded microfiber sheet product and respirators made therefrom
US3928192A (en) * 1974-06-06 1975-12-23 Aerojet General Co Buffered, weak ion-exchange water demineralization process
US3957698A (en) * 1974-11-05 1976-05-18 The Dow Chemical Company Thermally reversible, amphoteric ion exchange resins consisting of crosslinked microbeads embedded in crosslinked matrix of opposite exchange group type
US4437271A (en) 1979-03-14 1984-03-20 Minnesota Mining And Manufacturing Company Surface treating pad having a renewable surface
US4893439A (en) 1987-04-14 1990-01-16 Minnesota Mining And Manufacturing Company Abrasive article containing helically crimped fibers
US5082720A (en) 1988-05-06 1992-01-21 Minnesota Mining And Manufacturing Company Melt-bondable fibers for use in nonwoven web
US4933229A (en) 1989-04-21 1990-06-12 Minnesota Mining And Manufacturing Company High wet-strength polyolefin blown microfiber web
US5030496A (en) 1989-05-10 1991-07-09 Minnesota Mining And Manufacturing Company Low density nonwoven fibrous surface treating article
US5770090A (en) * 1989-07-28 1998-06-23 Lewis, Iii; Tom Method for recovery of heavy metal from waste water
US5071610A (en) 1990-02-23 1991-12-10 Minnesota Mining And Manufacturing Company Method of making a controlled pore composite polytetrafluoroethylene
US5026456A (en) 1990-06-14 1991-06-25 E. I. Du Pont De Nemours And Company Aramid papers containing aramid paper pulp
US5328758A (en) 1991-10-11 1994-07-12 Minnesota Mining And Manufacturing Company Particle-loaded nonwoven fibrous article for separations and purifications
US5292456A (en) 1992-03-20 1994-03-08 Associated Universities, Inc. Waste site reclamation with recovery of radionuclides and metals
US5474704A (en) * 1993-07-30 1995-12-12 Jacam Chemical Partners, Ltd. Regeneration compositions for cationic exchange resins
WO1997005480A1 (en) * 1995-07-27 1997-02-13 Massachusetts Institute Of Technology Separation and/or concentration of an analyte from a mixture using a two-phase aqueous micellar system

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9507503B2 (en) 2004-06-25 2016-11-29 Apple Inc. Remote access to layer and user interface elements
US9753627B2 (en) 2004-06-25 2017-09-05 Apple Inc. Visual characteristics of user interface elements in a unified interest layer
US20110078616A1 (en) * 2004-06-25 2011-03-31 Chaudhri Imran A Configuration bar for launching layer for accessing user interface elements
US7984384B2 (en) 2004-06-25 2011-07-19 Apple Inc. Web view layer for accessing user interface elements
US8266538B2 (en) 2004-06-25 2012-09-11 Apple Inc. Remote access to layer and user interface elements
US8291332B2 (en) 2004-06-25 2012-10-16 Apple Inc. Layer for accessing user interface elements
US8302020B2 (en) 2004-06-25 2012-10-30 Apple Inc. Widget authoring and editing environment
US20090144644A1 (en) * 2004-06-25 2009-06-04 Chaudhri Imran A Web View Layer For Accessing User Interface Elements
US8464172B2 (en) 2004-06-25 2013-06-11 Apple Inc. Configuration bar for launching layer for accessing user interface elements
US10489040B2 (en) 2004-06-25 2019-11-26 Apple Inc. Visual characteristics of user interface elements in a unified interest layer
US11150781B2 (en) 2005-10-27 2021-10-19 Apple Inc. Workflow widgets
US9513930B2 (en) 2005-10-27 2016-12-06 Apple Inc. Workflow widgets
US9417888B2 (en) 2005-11-18 2016-08-16 Apple Inc. Management of user interface elements in a display environment
US8845899B2 (en) * 2006-12-01 2014-09-30 Pecofacet (Us), Inc. Filter element and methods of manufacturing and using same
US20130277295A1 (en) * 2006-12-01 2013-10-24 Perry Equipment Corporation Filter Element and Methods of Manufacturing and Using Same
WO2009002915A1 (en) * 2007-06-22 2008-12-31 Steward Environmental Solutions, Llc System amd methods for the removal of soft heavy metals from streams
US9483164B2 (en) 2007-07-18 2016-11-01 Apple Inc. User-centric widgets and dashboards
CN102814164A (en) * 2012-09-17 2012-12-12 工信华鑫科技有限公司 Method for implementing copper-cobalt-zinc separation, enrichment and purification by using heavy metal adsorbing material
CN102872808A (en) * 2012-09-17 2013-01-16 工信华鑫科技有限公司 Method for separating, enriching and purifying copper and nickel by using heavy metal adsorption material
CN102872807A (en) * 2012-09-17 2013-01-16 工信华鑫科技有限公司 Method for separating, enriching and purifying nickel and ferrous iron through heavy metal absorbing material
CN102815763A (en) * 2012-09-17 2012-12-12 工信华鑫科技有限公司 Method for implementing copper-cobalt separation, enrichment and purification by using heavy metal adsorbing material
WO2015101071A1 (en) * 2014-01-03 2015-07-09 上海交通大学 Silicon-based titanate composite adsorbent for removing radioactive strontium and preparation method therefor
EP3098817A4 (en) * 2014-03-27 2017-10-18 Nippon Chemical Industrial Co., Ltd. Adsorbent and method for manufacturing crystalline silicotitanate
EP3190087A4 (en) * 2014-10-02 2018-05-23 Nippon Chemical Industrial Co., Ltd. Method for producing crystalline silicotitanate
CN104923193A (en) * 2015-06-15 2015-09-23 中国石油大学(华东) Acid and alkali treatment reactivating method for S-Zorb spent sorbent
JP2018205276A (en) * 2017-06-09 2018-12-27 日立Geニュークリア・エナジー株式会社 Treatment method and treatment device for radioactive waste liquid
CN113816509A (en) * 2021-09-28 2021-12-21 石文建 Method for adsorbing rare metal ions in aqueous solution by using calcium sulfate whiskers

Also Published As

Publication number Publication date
US6436294B2 (en) 2002-08-20

Similar Documents

Publication Publication Date Title
US6436294B2 (en) Process for modifying the metal ion sorption capacity of a medium
Chen et al. A review on emerging composite materials for cesium adsorption and environmental remediation on the latest decade
Wen et al. application of zeolite in removing salinity/sodicity from wastewater: A review of mechanisms, challenges and opportunities
Reed et al. As (III), As (V), Hg, and Pb removal by Fe-oxide impregnated activated carbon
US5397476A (en) Purification of solutions
Anirudhan et al. Removal of uranium (VI) from aqueous solutions and nuclear industry effluents using humic acid-immobilized zirconium-pillared clay
Xu et al. Adsorption and removal of arsenic (V) from drinking water by aluminum-loaded Shirasu-zeolite
Thirunavukkarasu et al. Arsenic removal from drinking water using iron oxide-coated sand
US20050029198A1 (en) Heavy metals absorbent and method of use
Inglezakis et al. Effects of pretreatment on physical and ion exchange properties of natural clinoptilolite
US9409147B2 (en) Method for granulation of absorbent and adsorbent granules prepared by the same
Kim et al. Adsorption of organic compounds by synthetic resins
Jinfang et al. Synthesis of a novel Ce (III)-incorporated cross-linked chitosan and its effective removal of fluoride from aqueous solution
Dai et al. Highly ordered macroporous silica dioxide framework embedded with supramolecular as robust recognition agent for removal of cesium
Krajnak et al. Kinetics, thermodynamics and isotherm parameters of uranium (VI) adsorption on natural and HDTMA-intercalated bentonite and zeolite
Mimura et al. Selective removal of cesium from highly concentrated sodium nitrate neutral solutions by potassium nickel hexacyanoferrate (II)-loaded silica gels
Chen et al. Desorption trials and granular stability of chromium loaded aerobic granular sludge from synthetic domestic wastewater treatment
Mahmoud et al. Adsorption behavior of samarium (III) from aqueous solutions onto PAN@ SDS core-shell polymeric adsorbent
Peng et al. Rapid and highly selective removal of cesium by Prussian blue analog anchored on porous collagen fibers
Kluczka et al. Boron removal from wastewater using adsorbents
EP0047785B1 (en) Silica removal process and alumina composition used therein
US10752522B2 (en) Compositions and methods for selenium removal
Barrera-Díaz et al. Cd (II) and Pb (II) separation from aqueous solution using clinoptilolite and Opuntia ectodermis
JP3643873B2 (en) Heavy metal ion adsorbent, method for producing the same, and method for removing heavy metal ions using the same
JP2000342962A (en) Heavy metal adsorbent and production thereof

Legal Events

Date Code Title Description
AS Assignment

Owner name: MINNESOTA MINING AND MANUFACTURING COMPANY, MINNES

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:LUNDQUIST, SUSAN H.;REEL/FRAME:009840/0878

Effective date: 19990319

AS Assignment

Owner name: MINNESOTA MINING AND MANUFACTURING COMPANY, MINNES

Free format text: CORRECTIVE DOCUMENT REEL 9840, FRAME 0878, RE-RECORD TO CORRECT EXECUTION DATE ON PREVIOUSLY RECORDED DOCUMENT.;ASSIGNOR:LUNDQUIST, SUSAN H.;REEL/FRAME:010721/0629

Effective date: 19990318

AS Assignment

Owner name: ENERGY, UNITED STATES DEPARTMENT OF, DISTRICT OF C

Free format text: CONFIRMATORY LICENSE;ASSIGNOR:MINNESOTA MINING AND MANUFACTURING COMPANY;REEL/FRAME:012870/0053

Effective date: 20020409

AS Assignment

Owner name: 3M INNOVATIVE PROPERTIES COMPANY, MINNESOTA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MINNESOTA MINING AND MANUFACTURING COMPANY, A CORPORATION OF THE STATE OF DELAWARE;REEL/FRAME:012902/0739

Effective date: 20020423

AS Assignment

Owner name: ENERGY, UNITED STATES DEPARTMENT OF, DISTRICT OF C

Free format text: CONFIRMATORY LICENSE;ASSIGNOR:MINNESOTA MINING & MANUFACTURING COMPANY;REEL/FRAME:012904/0120

Effective date: 20020409

FPAY Fee payment

Year of fee payment: 4

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20100820