WO2017030609A1 - Papier d'échange d'ions déchiqueté - Google Patents

Papier d'échange d'ions déchiqueté Download PDF

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Publication number
WO2017030609A1
WO2017030609A1 PCT/US2016/023350 US2016023350W WO2017030609A1 WO 2017030609 A1 WO2017030609 A1 WO 2017030609A1 US 2016023350 W US2016023350 W US 2016023350W WO 2017030609 A1 WO2017030609 A1 WO 2017030609A1
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WO
WIPO (PCT)
Prior art keywords
paper
pei
water
shreds
product
Prior art date
Application number
PCT/US2016/023350
Other languages
English (en)
Inventor
Norman RAINER
Original Assignee
Extractmetal, Inc.
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
Priority claimed from US14/998,586 external-priority patent/US20160151775A1/en
Priority claimed from US14/998,945 external-priority patent/US20170210640A1/en
Application filed by Extractmetal, Inc. filed Critical Extractmetal, Inc.
Publication of WO2017030609A1 publication Critical patent/WO2017030609A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/19—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/16—Cellulose or wood; Derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

Definitions

  • This invention concerns a celiulosic paper product for the selective removal of dissolved ionic metal species from water, and the manner of producing and utilizing such product.
  • the water to be treated is usually caused to flow through a
  • metal-saturated polystyrene beads produce volatile toxic condensed ring hydrocarbon species when disposed of by way of incineration.
  • U.S. Patent 5,002,984 discloses the incorporation into a cellulose sponge of a copolymer produced by the thermally induced condensation reaction of rutrilotriacetic acid (NT A) with pol ethyleneimine (PEI).
  • the PEI contains recurring primary, secondary and tertiary amine groups in a chain structure, and is known to absorb metal cations by way of formation of coordination complexes with the amine groups.
  • the aforesaid incorporation process introduces up to 65% by weight of copolymer into said sponge, causing stiffening of the treated sponge and loss of compressibility. If forceably compacted, the copolymer splits away from the sponge.
  • U.S. Patent 8,809,227 discloses incorporation of the same copolymer into a cotton ten'ycioth fabric.
  • the resultant fabric product is extremely stiff, and although useful in small pieces, has lost the flexibility needed for use in certain filtration applications.
  • the same copolymer when applied to cellulose filter paper, causes the resultant treated paper to lose the porosity requisite for filtration operations.
  • said applications have produced deposits of copolymer which are not chemically bound to the cellulose substrate. As such, the gross physical properties of the substrate are significantly altered, and the copolymer content is removable by physical manipulation.
  • Patent 4,332,916 to Thill discloses the grafting of PEI onto a cellulosic sponge employing a lOOcc aqueous treatment solution containing 8 grams of PEI plus 6 grams of the cross linking agent 2-butenyl-his [1,4 bis (2 hydroxyethyl) sulfoniom chloride]. Following trea tment of said sponge with said solution, and subsequent thermal curing, wasiiing, and dry ing, the treated sponge contained 10,9% PEI. It. should be noted that such treatment involves a large amount of an expensive and toxic cross-linking agent.
  • PEI has been sought to associate PEI with cellulosic substrates, either in a removable manner such as a processing aide, or chemically joined to the cellulose by way of special, bonding agents, it should be noted however, that the mere application of PEI (having a pH of about 12.0), to paper, followed by healing, produces decomposition of the PEI , forming a useless black composition.
  • cellulosic as used herein, is intended to denote substrates which are either entirely or primarily comprised of cellulose.
  • This invention is based in part upon the discovery that a protonated form of PEI, created by addition of acid species to PEI (to produce a pH in the range of 4,5 to 6.8), can undergo thermally induced chemical reaction with cellulose to impart ion exchange properties without decomposition, Furthermore, by utilizing PEI of exceptionally high molecular weight, cellulose substrates thus treated, particularly paper and paper pulp, have sufficient ion exchange capacity to be of commercial value; for example, and not by limitation, they can be shredded and formed into aggregations providing specialized performance in fixed bed absorption operations. BRIEF DESCRIPTION OF THE DRAWING
  • Figure 1 is a side view, with portions broken away, showing apparatus for converting treated paper of the present invention into pulp form, and injecting said pulp into waste water- flowing within a conduit.
  • CEL represents cellulose
  • PPEI represents protonated PEI
  • A- represents tlie anionic component of au acid species which may be an inorganic acid such as HCl or H 2 SO 4 , or an organic carboxylic acid.
  • the process for producing the selective ion exchange paper employed in the present invention starts with the preparation of an aqueous treatment solution containing dissolved PEL
  • a preferred concentration of PEI in the solution is in the range of 2% to 8%, producing an initial solution pH of about 12, It has been found that concentrations below 2% yield inadequate ion exchange functionality in a cellulose paper substrate. At concentrations above about 8%, it has been found that most of the PEI remains unreacted, presumably because of an absence of accepting reactive sites remaining in the cellulose.
  • the PEI-containing treatment solution is then treated with a strong mineral acid, preferably HCl, to produce protonated PEI and consequent solution pH in the range of about 4.5 to 6.8.
  • a strong mineral acid preferably HCl
  • the solution leads to instability in a subsequent thermal curing process.
  • reaction with cellulose has been found to be inefficient.
  • an organic polycarboxylic acid may be dissolved into the treatment solution prior to said treatment with a mineral acid. The ultimate effect of the polycarboxylic acid is to cross link PEI chains attached to the cellulose to produce a stabilized add-on.
  • the amount of said polycarboxylic acid is preferably between about 20% and 70% of the weight of the PEL Suitable polycarboxylic acids include adipic acid, citric acid and tartaric acid.
  • a particularity preferred polycarboxylic acid is n lotriacetic acid (NTA), which augments the metal-holding capacity of the PEI by attachment of chelation groups. It has been discovered that, although NTA is insoluble in plain water, it surprisingly remains dissolved in the treatment, solution even after said solution is acidified to pH levels below 7,0.
  • the aforesaid treatment solution is then applied to a substantially dry cellulosic paper in sheet form in a manner to achieve uniformity with minimal run-off.
  • Preferred papers are those which are marketed as "paper towels", having the ability to absorb at least twice their weight of water, and having a wet tear strength at least 20% of their dry tear strength.
  • the solution- saturated paper is then subjected to a uniform heating operation. Heating temperatures in the range of 250° F to 350° F have been found suitable for time durations of about 60 to 15 minutes respectively. It is desirable, but not necessary to exclude oxygen from the space surrounding the treated paper during heating, preferably by employing a stream of nitrogen gas.
  • the treated paper product is washed with water to remove any unreacted substances.
  • An alkaline compound such as sodium hydroxide may be incorporated into the wash water to adjust the paper pH to about 7.0. If the paper is left in an acidic state, it will have preferential affinity for anionic species.
  • the washed and dried treated paper contain an add-on of between 5% and 30% (dry weight basis) of said PEI or PEI derivative.
  • Such treated paper sheets are considered to be “precursor paper” for the purposes of this invention, and will have a total nitrogen content between about 0.4% and 5.0%, as measured via standard Kjelclahi analysis, method EPA 351.2 R2.0.
  • the expression "PEI derivative” is intended to include protonated PEL and PEI which has interacted with other species, most notably carhoxylic acids. At add-on levels below 5%, the precursor paper is minimally effective for its intended ion exchange function. At add-ons above about 30%, the treated paper may contain PEI or PEI derivatives which are not chemically bound to the paper, and will leach out in the coarse of use.
  • the add-on level can be controlled by suitable variations in the concentration of the treatment solution and/or the amount of solution applied to the starting paper. It has been found that acceptable results are achieved only when the molecular weight of the PEI is above 2000, and preferably above 5000.
  • the expression "chemically bound” is intended to denote covalent bond formation between otherwise separate molecules.
  • the preferred papers to be treated in the aforesaid manner are produced from wood, as in a Kraft process.
  • the starting paper is preferably in the form of a continuous length, such as a spirally wound roll, enablin g the heating operation to be achieved by heated rollers or paired top and bottom rollers within an oven.
  • paper sheets having been treated as described hereinabove generally have a 20%) to 32% increase in lateral area, measured omnidirectionally,
  • the cellulosic substrate starting material is subjected to an oxidation treatment employing oxidizing agents such as ozone or hydrogen peroxide.
  • the PEI is selected to have a molecular weight greater than 2,000, and preferably above 9,000.
  • the preferred cellulosic substrates to be treated in the aforesaid manner are produced from wood, as in a Kraft process, which produces a pulp, and a subsequent paper, which may be produced from said pulp.
  • the pulp may be defined as an aggregation of a massive number of generally flat clusters of 1/8 to 1/2 inch size, each comprised of an intertangled assembly of cellulose fibers of varied length and of less than 50 urn thickness.
  • the fibers have a specific gravity of about 1.4, causing the clusters to sink in wa ter.
  • heating operations When the treatment process of this invention is applied to paper, generally in the form of a continuous spirally wound length, heating operations would be provided by heated rollers or paired top and bottom rollers within an oven. When applied to pulp, heating operations are preferably provided by ovens which confine the pulp in vibrating trays.
  • the treated paper product is best shipped to the site of use in dry, accordion folded stacks or as spirally wound rolls. Treated pulp may be shipped to the user in containers in a damp or dry form..
  • the treated substrate When the treated substrate is a paper, it may be converted back into pulp form at the work site, employing equipment such as shredders or macerating devices equipped with rotating blades. The pulp thus produced may be directly entered into a body of water undergoing remediation.
  • paper having been treated by the process of this invention may be employed in filtration operations, whereby the paper will simultaneously remove suspended particulate and dissolved heavy metal species.
  • the treated, sheet form precursor paper of this invention, and consequently its shredded form, collectively referred to herein as "the paper” have the ability to selectively absorb 60% to 90% of the dissolved cationic and anionic species it encounters within about 8 seconds.
  • the specific rate of absorption is dependent upon the water temperature, pH, nature and
  • the paper When saturated with selected absorbed species, the paper can hold between about 0.4% and 8.0% of its weight of absorbed species (dry weight basis). Expressed alternatively, the paper has an absorption capacity of about 1 -2 milliequivalents (meq)/dry gram. For example, the paper can absorb about 3,6% by weight of Cu+2, which represents about 1 meq of Cu +2 per dry gram of paper, plus 5% by weight of Hg +J , which represents more than. 1/2 meq of Hg +2 per gram of said paper.
  • the aforesaid sheet form treated precursor paper is converted into the shredded format of the present invention by passage of said sheets through a multi-bladed cutting device.
  • Preferred shreds will have an elongated configuration having a substantially uniform width between about 3mm and 6 mm, and an average length between 0.5 inch and 1,5 inch, At lengths shorter than. 0,5 inch, the resultant aggregation of shreds, as a fixed absorption bed, has been found to present undesirably high impedance to the passage of water. At shred lengths greater than 1.5 inch, the aggregation becomes non-uniform, permitting regions where water will bypass significant portions of the bed. in one embodiment, the shreds will be substantially flat. In an alternative embodiment, the shreds may have a textured configuration such as a V-shaped repeated crimp, produced by the shredding of correspondingly textured precursor sheets.
  • the shreds or precursor sheets having PEI or PEi- containing derivatives may be post-treated with carbon disulfide.
  • Such treatment generates sulfur species such as thiourea and dithiocarbamate groups chemically bound to the paper, which enhance ion exchange performance,
  • the extent of such treatment is preferably such as to cause the thus treated precursor paper to have a total elemental sulfur content between about 0.2% and 4.0% .
  • Said post treatment is preferably carried out by exposing moistened precursor sheets to vapor phase CS 2 .
  • stiffening shreds may be blended into the aggregation of the shredded paper so as to increase the crush resistance of the aggregation.
  • stiffening shreds are pieces of shredded plastic film having dimensions similar to the shredded paper, and employed in amounts representing about 1% to 15% by weight of the aggregate. Suitable films include unplasticised PVC at thicknesses of 6-8 mils. Such stiffening shreds can be produced and blended with the paper shreds at the cutting apparatus that creates the shreds.
  • Ail aqueous solution was made containing 4% by weight of PEI having a molecular weight of 10,000.
  • the PEI is a product of Nippon Shokubai of Japan.
  • NTA was then added in an amount representing a 2% concentration in the solution.
  • the solution was then titrated to pH 5.5 with cone. HC1.
  • the resultant solution considered a protonated PEI treatment solution, was applied to Viva f M absorbent toweling paper, arranged in strip form, to cause thorough soaking without run-off.
  • the VivaTM starting paper is capable of absorbing an amount of water about 3.2 times its dry weight, and has a wet tear strength of 0.24 pounds, which is about 60% of its dry tear strength of 0.40 pounds.
  • the soaked paper was then oven-treated at 320° F for 45 minutes, then spray- ashed with water having a pH of 8.0, and dried.
  • the resultant treated paper has an add-on weight of PEI derivative of 19%, with substantially unchanged water uptake and wet tear strength.
  • the paper was found to contain 0.5% nitrogen.
  • Said resultant precursor paper was fed into a commonplace office shredding machine having cross-cut features. An aggregation of pieces of shredded paper was thereby produced, said pieces having an average length of about 1.5 inch and reasonably consistent width of about 3,5 mm.
  • the shreds having initially formed a loose aggregation at the bottom of the tube, were then compacted with a force of 325 grams using a plunger rod, resulting in a compacted bed having a height of 3.75 inch and representing a bed volume of 6.6 cubic inches (or 108 cc).
  • Water was flowed through the bed from a constantly maintained height of 21 inches above the top of the compacted bed.
  • the unrestricted flow rate through the bed was found to be 190 cc/min. This represents a contact time of the water with the bed of 34 seconds (based upon empty bed volume). Slower flow rates were achievable by way of stopcock restriction of exit flow or greater compaction of the bed. ⁇
  • a test solution containing approximately 40 ppm concentrations each of copper, zinc, mercury, and lead in their chloride forms, plus 1% each of sodium and calcium chlorides was run , at gravity force, through the compacted bed of Example 2 at a rate to provide a 45 second contact time.
  • a blue/black absorption band formed atop the bed (and representing only about 8 seconds of contact time) and descended the bed.
  • the sodium arid calcium concentrations were unchanged, thereby illustrating the ionic selectivity of the shreds.
  • Example 1 the wash water employed in Example 1 was caused to contain
  • the paper sheet, in a clamp state can be squeezed in a staffer box, causing a sawtooth, or zigzag crimping effect which can be locked in place by heating.
  • Example 2 An amount of shreds produced as in Example 1 were blended with stiffening shreds of unpiasticized PVC (polyviny!ehioride) of 7 mil thickness and having a length of about 1 inch, and width of 3 mm. The blending was achieved by altematingly running paper and plastic sheets through a single shredding machine, then tumbling the mixture. The amounts of the PVC shreds were varied in separate experiments between 1% and 10% by weight of the mixture. Employing the bed- forming technique of Example 1 with 6.16 grams of the blended mixture of shreds, the following results were obtained Weight % of Stiffening Shreds % increase in bed volume
  • aqueous solution was made containing 4% by weight of PEI having a molecular weight of 10,000.
  • the PEI is a product of Nippon Shokubai of Japan.
  • the solution was then titrated to pH 6.0 with cone. HC1.
  • the resultant solution considered a protonated PEI treatment solution, was applied to Bounty 1 M absorbent toweling paper, arranged in strip form, to cause thorough soaking without run-off.
  • the paper was then oven-treated @ 310° F for 45 minutes, then spray- washed with tap water and dried.
  • the resultant paper has an add-on weight of 5.3%, with unchanged, water permeability or wet tear strength. Neither is there any change In the ease of conversion to a pulp format.
  • the treated sheets were converted into pulp using a kitchen-style blender device.
  • the resultant pulp was poured into an absorption column of 2 inch inside diameter, whereby the pulp particles settled to form an absoiption bed, A weighted grate was placed atop the bed to maintain a uniform bed density.
  • a test solution containing copper chloride, sodium chloride, calcium chloride, zinc chloride, mercury chloride and lead chloride was run through the pulp bed at a rate to provide a 20 second contact time.
  • a blue/black absorption band formed and descended the bed.
  • the effluent water emergent from the bed, upon testing, showed a 96% reduction in copper concentration, and reductions of 70% to 90% of zinc, mercury and lead.
  • the sodium and calcium concentrations were unchanged, thereby il lustrating the ionic selectivity of the treated pulp.
  • Treatment solutions were prepared as in Example 7 with the addition of NT A, and having the characteristics and results shown in Table L Each solution was applied to the aforesaid Bount lM paper, which was then heat-treated and washed as in Example 7. The papers were then soaked in concentrated C11SO4 solution to achieve absorption to saturation, then converted to pulp, re-washed, dried, and submitted for metal analysis.
  • the copper saturation value does not represent the total capacity of the pulp absorbent for all ionic metals, but it does provide an i ndication of the effect eness of production par meters .
  • the starting absorbent paper of Example 7 was moistened with water at pH 8. then treated with an oxidizing stream of 3% ozone in air until substantially dry.
  • the resultant oxidized paper, having increased carboxyi groups, was then treated by the process of Example 7, using the treating solution of Trial #1 of Table 1.
  • the resultant paper was found to have an addon weight of 10.3%, and % copper uptake of 1.3%. Said increased values further indicate that attachment of protonated PEI io cellulose is dependent upon oarboxyl groups in or attached to cellulose.
  • a dried soft wood Kraft process pulp (Weyerhaeuser product CMC-320) was selected for treatment by a treatment solution having a PEI Concentration of 3%, a NTA/PEI ration of 0.6, and varied pH, The trials run and results obtained are shown in Table II.
  • the data indicates that pH values between about 5 and 6.8 provide desired results.
  • a significant use of the treated papers of the instant invention is in being converted back into pulp form and employed for the remediation of industrial and municipal waste waters.
  • the pulp material can be dumped on a regular or sporadic basis into the water. This is in essence opposite to prior art treatments of water with an absorbent species because, in the present invention, the absorbent material is caused to flow through the water, whereas, in prior art treatments, the water is caused to flow through the absorbent.
  • Mechanical means may be employed to control the regularity of addition of the pulp material to flowing waters.
  • a preferred mechanical system is exemplified in Figure 1, wherein a housed turbine-type pulp generating unit 10 is associated with a conduit 11 which conveys a non-pressurized flow of water 12.
  • the pulp generating unit is angled between an upper, intake extremity 13, positioned below the surface 20 of the water and a lower, discharge extremity 14,
  • An enclosure 15, mounted above said intake extremity protectively confines a supply of treated paper 16 of this invention which may be in the form of a spirally wound roll, or a fan-folded stack.
  • turbine 17 which may be powered by compressed air or electricity, draws the paper downwardly through slotted aperture 21 and into intake extremity 13. Passage of the paper through unit 10 produces an output of pulp particles 18.
  • Said pulp particles selectively absorb ionized metal species from the water and accumulate upon a downstream filter unit 19. where their metal absorption function continues until saturation and/or periodic clean-out of the filter unit.
  • the pulp particles will settle to a bottora sediment accumulation, and maintain absorptive activit until the vacuuming or dredging of the sediment layer,
  • Submerged baffles may be utilized to direct the sinking pulp particles to specific sites of accumulation.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)

Abstract

Selon la présente invention, des lambeaux de papier cellulosique traité sont assemblés de façon aléatoire sous la forme d'une agrégation qui permet le passage d'eau. Le papier contient une fonctionnalité chimique qui absorbe sélectivement des espèces métalliques ioniques dissoutes à partir de l'eau. Cette invention est basée en partie sur la découverte qu'une forme protonée de PEI, créée par ajout d'une espèce acide à PEI (pour obtenir un pH dans la plage de 4,5 à 6,8), peut subir une réaction chimique thermiquement induite avec la cellulose pour conférer des propriétés d'échange d'ions sans décomposition. En outre, en utilisant PEI ayant un poids moléculaire exceptionnellement élevé, des substrats de cellulose traités ainsi, en particulier du papier et de la pâte à papier, ont une capacité d'échange d'ions pour avoir une valeur commerciale ; par exemple, et sans limitation, ils peuvent être déchiquetés et formés en agrégats présentant des performances spécialisées dans des opérations d'absorption sur lit fixe.
PCT/US2016/023350 2015-08-17 2016-03-21 Papier d'échange d'ions déchiqueté WO2017030609A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US201562282934P 2015-08-17 2015-08-17
US62/282,934 2015-08-17
US14/998,586 2016-01-27
US14/998,586 US20160151775A1 (en) 2015-08-17 2016-01-27 Ion exchange product and manner of use
US14/998,945 US20170210640A1 (en) 2016-01-27 2016-03-09 Shredded ion exchange paper
US14/998,945 2016-03-09

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3885069A (en) * 1972-08-11 1975-05-20 Us Agriculture Preparation of crosslinked polyethylenimine and impregnation of cellulosic material with in situ crosslink-polymerized ethylenimine
WO1991019675A1 (fr) * 1990-06-20 1991-12-26 Ricoh Kyosan, Inc. Procede et dispositif de purification d'eau
US5096946A (en) * 1989-08-18 1992-03-17 Rainer Norman B Polymer product for the selective absorption of dissolved ions
US20020161122A1 (en) * 2001-03-15 2002-10-31 Rainer Norman B. Sulfur-containing aliphatic polymer for the selective absorption of dissolved metal species
US6676806B1 (en) * 1998-08-14 2004-01-13 Schweitzer-Mauduit International, Inc. Process for increasing the wet strength of porous plug wraps for use in smoking articles
US20120267315A1 (en) * 2011-04-20 2012-10-25 Soane Energy, Llc Treatment of wastewater
US8809227B1 (en) * 2009-06-22 2014-08-19 Norman B. Rainer Metal-absorbing polymer-containing product

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3885069A (en) * 1972-08-11 1975-05-20 Us Agriculture Preparation of crosslinked polyethylenimine and impregnation of cellulosic material with in situ crosslink-polymerized ethylenimine
US5096946A (en) * 1989-08-18 1992-03-17 Rainer Norman B Polymer product for the selective absorption of dissolved ions
WO1991019675A1 (fr) * 1990-06-20 1991-12-26 Ricoh Kyosan, Inc. Procede et dispositif de purification d'eau
US6676806B1 (en) * 1998-08-14 2004-01-13 Schweitzer-Mauduit International, Inc. Process for increasing the wet strength of porous plug wraps for use in smoking articles
US20020161122A1 (en) * 2001-03-15 2002-10-31 Rainer Norman B. Sulfur-containing aliphatic polymer for the selective absorption of dissolved metal species
US8809227B1 (en) * 2009-06-22 2014-08-19 Norman B. Rainer Metal-absorbing polymer-containing product
US20120267315A1 (en) * 2011-04-20 2012-10-25 Soane Energy, Llc Treatment of wastewater

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