EP3938449A1 - Particules pourvues d'un revêtement biocide - Google Patents

Particules pourvues d'un revêtement biocide

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Publication number
EP3938449A1
EP3938449A1 EP20713212.7A EP20713212A EP3938449A1 EP 3938449 A1 EP3938449 A1 EP 3938449A1 EP 20713212 A EP20713212 A EP 20713212A EP 3938449 A1 EP3938449 A1 EP 3938449A1
Authority
EP
European Patent Office
Prior art keywords
polymer
water
polyamine
particles
carrier material
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.)
Pending
Application number
EP20713212.7A
Other languages
German (de)
English (en)
Inventor
Martin Welter
Christian Meyer
Kristian LUNGFIEL
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.)
Instraction GmbH
Original Assignee
Instraction GmbH
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 Instraction GmbH filed Critical Instraction GmbH
Priority to EP23189316.5A priority Critical patent/EP4257556A3/fr
Publication of EP3938449A1 publication Critical patent/EP3938449A1/fr
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3204—Inorganic carriers, supports or substrates
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/04—Nitrogen directly attached to aliphatic or cycloaliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/23—Solid substances, e.g. granules, powders, blocks, tablets
    • A61L2/232—Solid substances, e.g. granules, powders, blocks, tablets layered or coated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/02—Loose filtering material, e.g. loose fibres
    • B01D39/06—Inorganic material, e.g. asbestos fibres, glass beads or fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/321—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions involving only carbon to carbon unsaturated 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/3272—Polymers obtained by reactions otherwise than involving only carbon to carbon unsaturated 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
    • B01J20/3268—Macromolecular compounds
    • B01J20/328—Polymers on the carrier being further modified
    • B01J20/3282—Crosslinked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • 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
    • B01J39/02—Processes using inorganic exchangers
    • 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
    • B01J39/09—Inorganic material
    • 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
    • B01J39/12—Compounds containing phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/05—Processes using organic exchangers in the strongly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/07—Processes using organic exchangers in the weakly basic form
    • 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
    • B01J41/14—Macromolecular compounds obtained 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
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/016—Modification or after-treatment of ion-exchangers
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
    • A61L2101/32—Organic compounds
    • A61L2101/46—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0471—Surface coating material
    • B01D2239/0485—Surface coating material on particles
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection

Definitions

  • the present invention relates to the production of absorber resins for the removal of heavy metals, anions of the element acids or elemental acids as well as special micropollutants and bacteria from aqueous solution, whereby a process is the purely outer coating of commercial ion exchangers or the complete coating of porous polymer particles with an amino group comprising polymer and the subsequent modification of the polymer with functionalizing ligands.
  • the water crisis is defined as the number one global risk that will affect the entire world population.
  • Drinking water sources can be contaminated by various pollutants. These include chemicals, bacteria, micropollutants and heavy metals. These impurities must be removed from the water before drinking for health reasons.
  • Reverse osmosis is one of those filtration methods in which the majority of the water to be filtered is discarded as waste (approx. 90%) with high operating costs (e.g. electricity requirements).
  • electricity requirements e.g. electricity requirements
  • productivity is essentially determined by the required residence time in the absorber resin bed.
  • Small particles for example, are preferable for the contaminants because of the short diffusion paths, but on the other hand, the counterpressure is undesirable Way increase. Larger particles may require a larger bed, as small beds with large particles are difficult to stably pack; on the other hand, they will very likely require a longer residence time due to the longer diffusion paths.
  • RO reverse osmosis
  • RO modules have very poor yield. Only approx. 10-20% of the water used is actually cleaned and is available to the customer.
  • Another disadvantage is the need to use electricity for a required pump and the quality of the water: RO systems deliver pure water without vital salts that then have to be added again (e.g. calcium and magnesium).
  • the distillation process has the disadvantage of extremely high energy consumption in common.
  • the health-promoting elements are removed so that distilled water is created that is not suitable for long-term consumption, and important ingredients such as magnesium salts must be added in a subsequent step.
  • the water purification machines which combine several filter technologies in separate units / cartridges, require complex piping with corresponding valves or connectors / connectors, which are, however, prone to failure and offer the possibility of leakage, etc.
  • connections are exactly the places where bacteria, etc. due to the Flow conditions have particularly good opportunities for growth.
  • a well-known filter medium used on the market is z.
  • B. activated carbon which is used as a bed of particles in cartridges that are flushed through linearly or as a compressed hollow cylinder with radial flushing.
  • the ion exchange resins which also bind heavy metals, compete with calcium and magnesium and are therefore unreliable, or the heavy metals are flushed out of the resin in a small volume in concentrated form, shortly before the total capacity of the ion exchanger is exhausted. At the same time, the status of exhaustion is reached very quickly, especially when there is hard water. From this point on, no more heavy metals are removed. Rather, the heavy metal ions already immobilized on the ion exchanger are eluted in a comparatively small volume due to the displacement by the alkaline earth metals present in excess. At the same time, sodium ions are released into the water by the ion exchanger: A high sodium content in drinking water is increasingly viewed critically in connection with baby food and cardiovascular diseases. In addition to heavy metals, anions of element acids and elemental acids such as selenides, selenates, arsenides and arsenates are to be viewed as critical with regard to the health of consumers and water consumers.
  • steps a) and b) are repeated at least once.
  • the crosslinking takes place in a stirred reactor.
  • the organic carrier polymer is preferably a polystyrene. According to a further embodiment, this is organic
  • Carrier polymer a strong or a weak one
  • Anion exchanger which is only coated with the polymer on its outer surface. Strong anion exchangers are those organic polymers that have
  • Weak anion exchangers are polymers that contain carboxylic acid groups.
  • the organic polymer is selected from polystyrene, polymethacrylate or polyacrylate.
  • the polymer can also be an inorganic polymer selected from silica gel or hydroxyapatite.
  • the polyamine is a
  • the invention also relates to biocidal, porous
  • Particles preferably made of a crosslinked polyamine, which can be obtained or produced by the process described above.
  • the invention also further relates to heavy metal-absorbing porous particles which are produced by the method described above.
  • the invention also relates to absorbent porous particles which absorb the anions of the element acids or elemental acids such as selenite, selenate, arsenite and arsenate, the particles being obtainable or produced by the process described above.
  • the compounds of the 15th and 16th groups (previously 5th and 6th main group) of the periodic table, which have four oxygen atoms, e.g. H 3 ASO 4 or AsC> 4 3 , H 3, are called element acids or anions of element acids Se0 4 or
  • the compounds of groups 15 and 16 of the periodic table which carry three oxygen atoms for example H 3 As0 3 or AS0 3 3 AH 3 Se0 3 or Se0 3 3, are referred to as elemental acids or the anions of elemental acids.
  • ion exchangers Like activated carbon, ion exchangers also suffer from contamination and biofilm formation on their surface. Ultimately, they ensure that even drinking water that is low in germs contains more bacteria than before after the so-called “cleaning". This results in the task of equipping ion exchangers, such as those used in the softening of drinking water, with an anti-bacterial surface without significantly reducing the capacity of the ion exchangers.
  • perfluorinated surfactants e.g. perfluorooctanoic acid, perfluorooctanesulphonic acid
  • perfluorinated surfactants e.g. perfluorooctanoic acid, perfluorooctanesulphonic acid
  • resins can remove heavy metals (W02015EP01754, W02016EP78787) and bacteria (DE102017007273.6) from drinking water.
  • an amino polymer is immobilized on appropriate carriers to form a stable one three-dimensional network implemented with a bifunctional crosslinker.
  • the resins are therefore suitable both as filters for heavy metals in drinking water purification systems and for "police filters" for removing heavy metals at the end of a purification cascade of orthogonal methods.
  • the required coating polymer polyvinylformamide is produced and hydrolyzed to polyvinylamine (PVAm) in a polymer-analogous reaction using sodium hydroxide solution.
  • PVAm polyvinylamine
  • the reagents and cleavage products are then removed by a time-consuming and costly crossflow filtration.
  • This desalinated polymer solution is now used in the second step for coating the carrier material.
  • MetCap® particles can successfully remove bacteria from solutions (DE102017007273.6) that are either based on silica gel or do not require a carrier. Production and detection of the activity are disclosed in DE102017007273.6. There the coating of silica gel particles (as a template) with non-desalinated polymer and subsequent dissolution of the inorganic carrier and its antibacterial activity are described.
  • the simplification of the production process using polystyrene-based resins is achieved by dispensing with the desalination of the polymer hydrolyzate and further process changes, which in particular relate to the addition and drying of the carrier polymers to the polymer solution.
  • Adjustments in the coating process e.g. multiple coating, drying in the Loedige ploughshare mixer, introduction of new washing strategies
  • the coating process made it possible to dispense with the complex and costly process step of desalination of the polymer hydrolyzate without having to accept any restrictions in the performance of the products.
  • the polymer content is now determined by the batch calculation during the polymerization.
  • the coating and pre-crosslinking with ethylene glycol diglycidyl ether in the Lödige vacuum paddle dryer works, to the surprise of the authors, in the same way as with the PVAm polymer solution, which does not contain any salts.
  • the salts contained are then partially dissolved out during the preparation of the suspension for post-crosslinking.
  • all salts (silicates, formates, chlorides, etc.) are rinsed out of the crosslinked, purely organic template material.
  • the BacCap® T or MetCap® T material obtained in this way has the same properties as the absorber resins that were produced using the desalted PVA polymer. This is the first improvement in the process, which comes as a surprise because the previous assumption, also supported by literature data, has prevailed that the volume requirement of the highly concentrated salts in the polymer solution prevents the particles from being effectively and completely filled with polymer by themselves its space requirements.
  • the second process involves coating commercial strong or weak ion exchangers with an anti-bacterial PVA polymer shell.
  • ion exchangers especially the cation exchangers used here, usually have acid groups that are covalently bonded to the polymeric carrier (e.g. polystyrene, acrylates, etc.).
  • the acid groups are carboxylic acids or carboxylates for weak ion exchangers or sulfonic acids or sulfonates for strong ion exchangers. Both types are used in the softening of drinking water.
  • the aim is merely to coat the particles on the outside, without the acid groups in the pores of the particles, where the majority of the capacity-bearing acid groups are located to modify.
  • This goal is achieved by using a corresponding polymer which, due to its size and its hydrodynamic radius, cannot penetrate the pores of the ion exchange particles.
  • the pore sizes in commercial ion exchangers are in the range from 20 nm to 100 nm. These pores are inaccessible for polymers with a size of 10,000-20,000 g / mol.
  • only the outer 2-25% of the particle measured at the radius of the particle is coated. More preferably only the outer 2-10% of the particle measured at the radius of the particle is coated. Most preferably only the outer 2-5% of the particle as measured by the radius is coated.
  • non-desalted polymer of the appropriate size can also be used for this purpose, but this is not a mandatory requirement. Coating with demineralized polymer is also possible, as is the use of non-demineralized polymer.
  • the polymer After hydrolysis of the amide groups of the polyvinylamine with sodium hydroxide solution and subsequent blunting with hydrochloric acid, the polymer contains approx. 15-25% by weight of salt in the form of sodium formate and common salt. In the case of the non-desalted polymer, the polymer content of the aqueous solution corresponds to 9-13% by weight.
  • the salts were laboriously removed by reverse osmosis, and the polymer used with a salt content of less than 2.5% by weight.
  • the new process allows this laborious and expensive desalination step to be dispensed with. It is therefore preferred with the new process to use the polymer in partially demineralized form with a salt content of 2.5-15% by weight. It is more preferred to use a partially desalted polymer with a salt content of 10-15% by weight. It is most preferred to use a non-desalted polymer with a salt content of 15-25% by weight.
  • the polymer-coated ion exchanger was then cooled down to room temperature.
  • the BacCap product is obtained as a water-moist particle.
  • the speed of the mixer is set to 240 rpm and the jacket temperature is left at 4 ° C. After the addition, a further 15 min at 240 rpm mixed. Then the jacket temperature on the dryer is set to 80 ° C and the speed is regulated down to 120 rpm. The particles are then cooled back down to room temperature and are then transferred to a suitable suction filter and washed with the following solvents: 3 BV 0.1 M NaOH, 3 BV DI water, 3 BV 0.1 M HCl, 6 BV water.
  • the BacCap product is obtained as a water-moist particle.
  • 500 g of carrier material of sulfonated polystyrene PRC 15035 (mean pore size 450 ⁇ , mean particle size 500 gm) with a water absorption capacity of 1.35 ml / g are sucked directly into a ploughshare mixer VT5 from Lödige.
  • the product temperature in the dryer is set to 10 ° C.
  • the mixer is operated at 180 revolutions per minute. After the product temperature in the mixing drum has reached 10 ° C, 225 g of non-desalinated polyvinylamine solution, cooled to 10 ° C, are added.
  • PC 16012 polymer content 12%
  • the temperature in the Lödige mixer was then increased again to 65 ° C. for 1 h. 3 L of deionized water were added to the polymer adsorbate. This suspension is used for crosslinking.
  • the coated silica gel suspended in water is transferred to a 10 l glass reactor with automatic temperature control. The suspension is stirred and heated to 80 ° C. Then 317 g of epichlorohydrin CAS no. [106-89-8] was added within 20 min so that the temperature in the reactor does not exceed 85 ° C. 211 g of 1,2-diaminoethane [107-15-3] are then added dropwise over the course of 20 minutes. The second addition of 317 g epichlorohydrin CAS no. [106-89-8] within 20 minutes followed by another 211 g of 1,2-diaminoethane CAS no.
  • the product is obtained as a moist filter cake.
  • An absorber resin prepared according to Example 1, Example 3 or Example 4 is dissolved in a solvent, e.g. B DMF suspended. Then 110 mol% of glycidyl-2, 2, 3, 3, 4, 4, 5, 5-octafluoropentyl ether (based on the amino groups of the starting resin, Figure 2) are added to the stirred suspension of the resin and the suspension for 12 Stirred at 70 ° C. for h. The suspension is then rinsed with the following solvents on a syringe: 3 BV DMF, 3 BV n-heptane, 3 BV 1 M HCl in DMF, 3 BV 1 M NaOH in DMF and 3 BV DMF. Then a 50% suspension in DMF is again prepared.
  • a solvent e.g. B DMF
  • a second reaction step 110 mol% of glycidyl-2, 2, 3, 3, 4, 4, 5, 5-octafluoropentyl ether are again added to this suspension.
  • the reaction mixture is then stirred at 70 ° C. for 12 h.
  • the absorber resin is then rinsed with the following solvents: 3 BV DMF, 3 BV n-heptane, 3 BV 1 M HCl in DMF, 3 BV 1 M NaOH in DMF and 3 BV MeOH.
  • the absorber resin can then be dried in a vacuum to constant weight.
  • the structure of the absorber resin is shown in FIG.
  • a suspension of the instrAction resin (BV 18009, produced as in Example 3 water) is produced and filled into the axial flow-through cartridge in such a way that a bed volume of approx. 100 ml is created (bed dimensions: approx. 6.3 x 9 cm i.d.).
  • a suspension of E. coli (10 4 - 10 5 CFU / 1) is then pumped through the cartridge at a gradually increasing flow rate of 100 - 500 ml / min (60-300 BV / h) per hour.
  • the effluent is collected after approx. 3-5 min at each flow rate level and then examined for remaining bacteria using standard methods.
  • FIG. 5 The result of the examinations is shown in FIG. 5: There are no bacteria in the effluent over the entire examination area verifiable. This means that the bacteria in drinking water relevant concentration are completely removed.
  • Example 3 An instrAction resin prepared as in Example 3 is tested for activity against P. aeruginosa as follows: 500 g of the resin washed with tap water are placed in a
  • the reaction vessel is incubated with a suspension of 10 6 CFU Pseudomonas aeruginosa in 10 ml tap water. After 3, 6, 12 and 24 hours, samples are taken and with
  • the cartridges were initially filled with a 1 L
  • Resins and activated carbon are also none or only one compared to the input quantities strong to hard to the
  • Detection limit reduced number of bacteria detectable.
  • FIG. 3 Chromatographic breakthrough profile on PV 150772 (instrAction resin batch: Batch No. ND 150201); the breakthrough is only achieved after approx. 900 minutes or 220 mg perfluorooctanoic acid per ml of resin.
  • FIG. 4 Test set-up for investigating the bacterial depletion by BacCap resin; 1st storage vessel with bacterial suspension, E. coli, 104 Cfu / L, 2nd pump, 3rd column / cartridge with instrAction BacCap resin, 4th fraction)
  • FIG. 5 Result of the dynamic removal of bacteria on the ion exchanger which is only coated on the outside.
  • FIG. 6 Course of concentration of Pseudomonas aeruginosa over time in the presence of instrAction BacCap resin under static conditions.

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Abstract

L'invention concerne un procédé de production de particules pourvues d'un revêtement antibactérien comprenant les étapes suivantes : (a) la fourniture d'une suspension aqueuse contenant une polyamine, un agent de réticulation et un matériau de support poreux organique ou inorganique sous forme de particules à une température inférieure ou égale à 10°C dans un mélangeur pour revêtir le matériau de support inorganique avec la polyamine ; (b) la réticulation du polymère organique dans les pores du matériau de support inorganique et l'élimination simultanée de l'eau.
EP20713212.7A 2019-03-15 2020-03-13 Particules pourvues d'un revêtement biocide Pending EP3938449A1 (fr)

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DE102019106646.8A DE102019106646A1 (de) 2019-03-15 2019-03-15 Partikel mit biozider Beschichtung
PCT/EP2020/056866 WO2020187746A1 (fr) 2019-03-15 2020-03-13 Particules pourvues d'un revêtement biocide

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US20050263453A1 (en) * 2001-08-23 2005-12-01 The Procter & Gamble Company Water filter materials and water filters containing a mixture of microporous and mesoporous carbon particles
DE102005021221A1 (de) * 2005-05-07 2006-11-09 Geohumus International Gmbh & Co. Kg Superabsorber mit anorganischen und organischen Ballast- und Zusatzstoffen
JP5435708B2 (ja) * 2009-04-27 2014-03-05 日本フイルコン株式会社 金属吸着性焼結多孔体およびその製造方法
EP2570182A1 (fr) * 2011-09-15 2013-03-20 InstrAction GmbH Sorbant comportant à sa surface un résidu aliphatique cationique ou protonisable pour la purification de molécules organiques
CN102872832A (zh) * 2012-09-28 2013-01-16 河海大学 一种负载二氧化钛的壳聚糖分子印迹吸附剂的制备方法
DE102014012566A1 (de) * 2014-08-29 2016-03-03 Instraction Gmbh Sorbens zur Bindung von Metallen und dessen Herstellung
CN107531844A (zh) * 2015-02-25 2018-01-02 巴斯夫欧洲公司 通过聚合单体溶液的液滴制备表面后交联的吸水性聚合物颗粒的方法
EP3173146A1 (fr) * 2015-11-27 2017-05-31 InstrAction GmbH Matériau polymère poreux pour la liaison d'ions métalliques ou pour le nettoyage de molécules organiques
DE102017007273A1 (de) * 2017-08-01 2019-02-07 Instraction Gmbh Entfernung von Bakterien aus Trinkwasser über Filtration

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ZA202106740B (en) 2022-07-27
TW202103788A (zh) 2021-02-01
CN113574125B (zh) 2023-06-27
WO2020187746A1 (fr) 2020-09-24
CA3128958A1 (fr) 2020-09-24
CN113574125A (zh) 2021-10-29
DE102019106646A1 (de) 2020-09-17
US20220159949A1 (en) 2022-05-26
AU2020242757A1 (en) 2021-09-09
EP4257556A3 (fr) 2023-12-06
KR20210142131A (ko) 2021-11-24
EP4257556A2 (fr) 2023-10-11
CN116574405A (zh) 2023-08-11

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