WO2008088360A1 - Systèmes et procédés de nettoyage de supports de liquide - Google Patents

Systèmes et procédés de nettoyage de supports de liquide Download PDF

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Publication number
WO2008088360A1
WO2008088360A1 PCT/US2007/007515 US2007007515W WO2008088360A1 WO 2008088360 A1 WO2008088360 A1 WO 2008088360A1 US 2007007515 W US2007007515 W US 2007007515W WO 2008088360 A1 WO2008088360 A1 WO 2008088360A1
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Prior art keywords
water
iodine
biofilm
reactants
disrupted
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PCT/US2007/007515
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English (en)
Inventor
Kenneth R. Code
Mark A. Litman
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Biolargo Life Technologies, Incorporated
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Publication of WO2008088360A1 publication Critical patent/WO2008088360A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B9/00—Cleaning hollow articles by methods or apparatus specially adapted thereto 
    • B08B9/02—Cleaning pipes or tubes or systems of pipes or tubes
    • B08B9/027—Cleaning the internal surfaces; Removal of blockages
    • B08B9/04—Cleaning the internal surfaces; Removal of blockages using cleaning devices introduced into and moved along the pipes
    • B08B9/043—Cleaning the internal surfaces; Removal of blockages using cleaning devices introduced into and moved along the pipes moved by externally powered mechanical linkage, e.g. pushed or drawn through the pipes

Definitions

  • the present technology relates to the field of liquid carrying systems and the cleaning of the carrying systems, particularly commercial or residential drain, run-off systems, conduits, aqueducts or rain systems and pipes. These treatments include physical treatment of spurious coatings within the carriers and delivery of active ingredients and/or delayed activity ingredients.
  • Biof ⁇ lms are biological films that develop and persist at interfaces in aqueous environments, especially along the inner walls of conduit material in industrial facilities, in household plumbing systems, on medical implants, or as foci of chronic infections. These biological films are composed of microorganisms embedded in an organic gelatinous structure composed of one or more matrix polymers which are secreted by the resident microorganisms. Biof ⁇ lms can develop into macroscopic structures several millimeters or centimeters in thickness and can cover large surface areas. These biological formations can play a role in restricting or entirely blocking flow in plumbing systems and often decrease the life of materials through corrosive action mediated by the embedded bacteria. Biofilms are also capable of trapping nutrients and particulates that can contribute to their enhanced development and stability.
  • U.S. Patent No. 7,094,394 discloses a method of cleaning or protecting surfaces by treatment with compositions comprising N-(3-oxododecanoyl)- L-homoserine lactone blocking compounds and/or N-butyryl-L-homoserine lactone analogs, either in combination or separately.
  • U.S. Patent No. 6,076,536 (Ludwig et al.) describes a method to chemically clean and immediately passivate a water distribution system to quickly form a passivation layer.
  • the system may be a potable water system, a non-potable water system, a water well or a fire protection system such as a fire sprinkler system and may be treated with a biocide.
  • a section of the system is isolated and chemically cleaned, then is immediately passivated using a high concentration of passivating agent.
  • a passivating layer quickly forms, then the concentrated passivating agent is removed and a maintenance concentration of passivating agent is added. The cleaned and passivated section is restored to the system to provide improved water flow.
  • U.S. Patent No. 6,964,275 (Carl) describes methods and compositions for cleaning and maintaining chemical, biological and radiological countermeasure washdown systems are disclosed.
  • Systems are effectively cleaned by the removal of water scale, including deposits, sediment, microbiological scale, microinvertebrate fouling, and the like, from the inside surfaces of piping in the system.
  • a section of the system is isolated for cleaning and an aqueous acidic cleaning solution is circulated through the fouled pipe section to be cleaned for a sufficient time and at a controlled pH to dissolve and loosen the scale. After cleaning all of the sections, the system is restored to operational readiness.
  • U.S. Patent No. 6,183,646 (Williams) relates to the reduction and prevention of biofouling in facilities utilizing water, e.g. sea water, carrying biological organisms, without causing corrosion, chemical reaction or other detrimental action from the additive or environmental discharge problems.
  • Such operations include, for example, desalination plants, power plants, oilfield water injection facilities and shipboard or ocean platform fire water systems.
  • Flow connectors connect the dosing chamber to various points along the piping in the desalination plant.
  • a controller controls the operation of the dosing chamber and valves along the flow connectors to operate in a sequential target dosing mode to deliver treatment additive of predetermined composition to selected points along the piping at predetermined times and in predetermined concentrations.
  • U.S. Patent No. 4,869,019 (Williams et al.) describes the synergistic effect of low dosage levels of chlorine ions used in conjunction with low dosage levels of copper ions to form a treatment additive sufficient to temporarily stress or disorient (but not "necessarily” kill) both macroorganisms and microorganisms so that they pass through the piping system of a facility without attaching themselves to the system.
  • U.S. Patent No. 6,599,432 (Kross) describes disinfecting compositions (such as chlorine dioxide) for dental unit water lines, particularly effective against microbial flora in biofilms which form on the luminal walls of the piping and reservoir components of dental equipment, as well as methods related to the use of such compositions to reduce microbial numbers in water-bearing dental and other equipment and maintain reduced levels on a continuous basis.
  • compositions such as chlorine dioxide
  • iodine iodine
  • the iodine environment can be provided in numerous and varied tasks and services and even in combination with other additives such as film-breaking compositions such as acids (e.g., sulfamic acid, hydrochloric acid, sulfuric acid, enzymes, etc.).
  • acids e.g., sulfamic acid, hydrochloric acid, sulfuric acid, enzymes, etc.
  • the iodine treatments may be any delivery system that can deliver the iodine-rich environment as needed to an appropriate target.
  • the delivery may be as a gas, liquid, films, powders, concentrates, liquids and the like that may be carried and contacted with as great a surface area as possible within the carrying system.
  • the iodine may be provided as gas or reactants that form the iodine as a free-flowing, injectable, pourable, paintable, sprayable or otherwise deliverable form.
  • the materials may be provided, by way of non-limiting examples such as capsules, packets, powders, coated particles, concentrates, paste, gel or the like and may comprise a water absorbent or viscosity-enhancing material; or a composition that reacts with water to produce molecular iodine.
  • the composition is delivered to provide a local concentration of at least 10 parts per million iodine in water carried by the delivery system.
  • the concentration may ultimately be diluted by local, ambient or added water, but this concentration level of at least lOppm should be present for sufficient time to actively persist in antimicrobial activity, which is minutes (at least two minutes) up to hours, such as up to 24 hours in worst case environments.
  • the total weight of the concentrations should be sufficiently concentrated in air or aqueous material to address antimicrobial requirements or provide sufficient chemical activity to mediate the concentration of the targeted microbes in the environment of the carrying system.
  • Figure 1 shows a representation of a side view of an application and pigging system useful in the practice of the present technology.
  • the iodine environment can be provided in numerous and varied tasks and services and even in combination with other additives such as solvents or reactants for organic deposits that may constitute the film on the interior surface of the carrier.
  • One way of providing molecular iodine (I ⁇ ) on site is with an applicator.
  • the applicator preferably is transported to a site in a manner to provide reactants that can readily produce molecular iodine on-site in a controllable reaction.
  • One format of providing the molecular iodine would be through the oxidation-reduction reaction between two salts or compounds to produce the molecular iodine. It is a readily controlled environment where the reaction can be performed in an aqueous environment.
  • One reaction that can effect this would be generically described as: X + Y " + Z + r ⁇ X + " + Z + Y ' +I 2
  • X is a metal (preferably a multivalent metal and more particularly a divalent metal)
  • n is a valence number appropriate for the oxidation reduction reaction (if any) that occurs in the reaction and is selected from 0, 1 and 2
  • Y is an anion (preferably a multivalent anion and more preferably a divalent anion, and an anion having at least two oxygen atoms)
  • Z is a metal or an alkali metal or alkaline cation.
  • Examples of X are copper, iron, manganese, lead, nickel, tin, and the like
  • Y can be sulfate, sulfite, sulfonate, carbonate, phosphate, phosphate, nitrate, nitrite, borate, and the like
  • Z can be sodium, lithium, potassium, ammonium, magnesium, aluminum, and the like.
  • One preferred reaction would be: Cu +2 SO 4 "2 + K + T " ⁇ Cu (+1 or 2 or 0) + K 2 SO 4 +I 2
  • This reaction takes place readily in an aqueous environment and produces molecular iodine at a controlled rate.
  • the reaction may be used by wetting, dispersing or dissolving the molecular iodide and allowing the iodine in the carrying material to be released and carried to the site (which may be the carrying material itself, such as the fabric, clay, fibers, film etc.) penetrate the area intended to be treated.
  • the iodine may persist for sufficient time to treat the area, particularly within a wetted material on the surface of a particles or carrying medium.
  • the reaction may also be used by dispersing or mixing the two ingredients into a carrying material (e.g., water, aqueous spray, aqueous coating material, paste, gel, fabric, fiber, film, sheet, etc.), either with additional water provided, with water of hydration on the first reactant (e.g., X + Y " • nH 2 0, such as CuSO 4 -SH 2 O) or with ambient water in the carrying material.
  • a carrying material e.g., water, aqueous spray, aqueous coating material, paste, gel, fabric, fiber, film, sheet, etc.
  • water of hydration on the first reactant e.g., X + Y " • nH 2 0, such as CuSO 4 -SH 2 O
  • the two reactants may be physically separated from each other before being combined for application or reaction, as in separate capsules, particle coated droplets, fibers, layers or the like.
  • the two reactants may be provided as a solid carrier medium or separate particulate materials that separate the two reactants until they are in contact with water (as in a soluble carrier such as polyvinyl alcohol, gelatin, amylase, sugars and the like, in pellet, fiber, dust, particle or block form). At least one of the two reactants may be independently coated with a soluble/dispersible coating and the two ingredients kept in a single water-penetrable layer.
  • a soluble carrier such as polyvinyl alcohol, gelatin, amylase, sugars and the like
  • Individually coated particles can be provided in water-soluble containers/coverings by using water-soluble or water-dispersible coating materials that are also organic solvent soluble (alcohol soluble) such as PVA, gels, polyvinylpyrrolidone, silica coatings, poly(ether ketones), poly(ester ketones), and the like are applied to the individual particles (one single reagent) or groups of particles (both or all reagents) and prilled, spray dried, or otherwise dried into separate, agglomerated, or packed coated particles.
  • Polyvinyl alcohol may be coated on particles (even water s-oluble particles as used in the present technology) by use of particle coating technologies such as particle impacting in a fluidized bed or equivalent equipment such as shown in US Patent No. 6,037,019 (Kooyer).
  • the technology described herein is performed by physically disrupting an interior coating on the interior surface of the carrying system (by physical means such as pigging, scraping, abrading, ablating, grooving, etching, and the like) and then applying the iodine antimicrobial system such as by applying a gas, liquid or solid or immediately provided carrier system to a location and either applying or awaiting the presence of sufficient water on or in the carrier system to activate the ingredients and cause the gaseous iodine to form in sufficient concentration in the solid carrier to attenuate, reduce or provide antimicrobial activity in the environment such as a pipe, tunnel, drain or the like.
  • Figure 1 shows a representation of a side view of an application and pigging system 2 useful in the practice of the present technology.
  • a large underground water aqueduct 10 is shown.
  • the applicator system 4 comprising a liquid mixing and applicator cart 12 on wheels 6 delivers the antimicrobial material (not shown) according to the teachings of the present technology.
  • Two unique "Mobius' sealing elements 8 and 14 are shown. These sealing elements 8 and 14 move in front of and behind the applicator system 4 to provide a confined area within which the application of the antimicrobial materials may perform.
  • a cable 20 is shown to both possibly move the delivery system 4 are to control movement of the sealing elements 8 and 14.
  • the 'Mobius' sealing elements 8 and 14 would work as follows.
  • the sealing element 8 is made of a flexible, deformable material such as gel-filled elastomer sheath in the shape of a bagel with the elastomeric sheath extending to the full height and width of the conduit 10 and forming a seal against the interior walls of the conduit 10.
  • a flexible, deformable material such as gel-filled elastomer sheath in the shape of a bagel with the elastomeric sheath extending to the full height and width of the conduit 10 and forming a seal against the interior walls of the conduit 10.
  • the end walls 34a and 34b meet in a relatively central area 16 into which the sides 34a and 34b move as the seal 8 is moved forward along arrow direction 28.
  • the top and bottom contact points 26 and 26a stand to remain relatively stationary, as with the point of contact of a tire with the road.
  • the rear walls 34a move downward along trajectory 30, fold into the crease 16, and move forward along trajectory 32 and then moves upward past center point 18 along trajectory or path 24.
  • This movement thereby provides a continuous moving seal with firm contact points 26 and 26a against the conduit 10.
  • the seal 8 may be advanced by friction, tension, teeth grips or the like by cable 20 as it passes into crease 16. At any points of contact by the cable 20 within the crease 16 between a top half and bottom half of the seal 8, especially if there are friction grips or teeth engaging the cable 20 with the seal 8, there is relatively little or no movement between the cable 20 and the surface of the seal 8 with which the cable 20 is in contact.
  • the elastomeric material could be polysiloxane elastomer, polyurethane elastomer, styrene-butadiene-acrylonitirle elastomer and other synthetic rubbers and elastomers and resins.
  • Mobius seals are defined herein as self-replacing seals as the mass of the seal moves forward and replaces itself within the conduit.
  • Each of the ingredients can be provided as separate uncoated particles.
  • Each of the components preferably in anhydrous or low-moisture containers would be provided to a site.
  • the two solid particles would be injected into, sprayed onto, dusted onto, or otherwise applied onto, or otherwise deposited onto an interior surface within the carrier system.
  • Water would either be simultaneously added, subsequently added, or even applied immediately before the application of particles, which would then react after activation (providing a reactive medium) by the water.
  • each or at least one of the reagents would be coated with a material that is removed or penetrated by water, dissolving at least one component to bring the dissolved reagent into reactive contact with the other reagent.
  • the purpose of the at least one coating is to prevent ambient moisture from causing the two reagents to react if they are stored in the same container. For example, if only the KI were coated, ambient (atmospheric) moisture would not be present in a container in sufficient amounts to dissolve KI and carry it through the coating to the other reagent.
  • the reagents may be added to the soil in a relatively active state, with the reagents provided as solids in a liquid carrier, coated solids in a liquid carrier, or with at least one of the ingredients dissolved at the time of application.
  • Such an active application must be done immediately after mixture of the reagents in an active medium, as the reaction is relatively fast.
  • the two solids may be provided through a single chamber, dispersed into an aqueous medium, and immediately applied (e.g., sprayed, injected, plowed) into the soil so that the majority of the release of the iodine would be within the solid environment and would not be immediately released into the air.
  • iodine gas is generated when metal salts (e.g., such as copper sulfate) and iodide salts (such as potassium iodide) are mixed in the presence of water and/or water gels from superabsorbing polymers (SAP), that this iodine is soluble in the water up to 337 ppm by setting up the chemical equilibria:
  • metal salts e.g., such as copper sulfate
  • iodide salts such as potassium iodide
  • R is any organic moiety, wither aliphatic or aromatic or mixed aliphatic and aromatic.
  • R + may be an acidic organic cation, preferably an organic acidic cation such as C6-C20 carboxylic acid backbones, sulfamyl, and the like.
  • the hydrolytic ionization that occurs during these equilibria leads to several acids which can be characterized as acidizing agents for descaling and cleaning of water and oil wells, sewer and stormwater runoff lines, and anywhere scale and biofilms are desired to be removed by solubilizing.
  • the resulting acidified iodides are much more environmentally friendly for subsequent discharge owing to a well established iodine cycle known to exist between ocean waters and marine lands which receive oxidizing iodine from the ocean and which eventually returns to the ocean where it is restocked as iodate, following production of organic iodides in the watershed.
  • the most widely known and accepted acidizing agents include HCl, sulfamic acid, lactic acid ⁇ citric acid, and acetic acid, all with varying degrees of reactivity for descaling.
  • the effect of acidizing with iodine gas in solution also attends with additive antimicrobial effects, and when the acidized iodine is combined with sulfamic acid, a powerful and effective method is provided for dissolving and remediating biofilms, and chelating heavy metals which may be solubilized by the process, or otherwise contained in water, especially after physical disruption as described herein.
  • Sulfamic acid is also a primitive surfactant, and when added to free iodine in water and stabilized by varying added compounds such as silicates (e.g., sodium metasilicate) and phosphates and sulfonates (e.g., sodium xylene sulfonate or phosphate), yields a disinfecting and biof ⁇ lm removing detergent compound which is active within the technologies described herein for oilfield or watershed applications as a single formulary product.
  • silicates e.g., sodium metasilicate
  • phosphates and sulfonates e.g., sodium xylene sulfonate or phosphate
  • liquid mixture also contained a thickening agent or the like to provide reduced volatility to the water, make the solution of iodine gas adhere to the soil or plants better, and provide greater persistence to the applied liquid and the formed or carried iodine gas.
  • a thickening agent or the like to provide reduced volatility to the water, make the solution of iodine gas adhere to the soil or plants better, and provide greater persistence to the applied liquid and the formed or carried iodine gas.
  • Polymers, gums, resins, silica, and the like are typical thickening agents that might be used.
  • a simple format in considering application to agricultural fields for treatment to prevent nematodes or other ground or water-dwelling pests or for any age or stage of pest animal, would include at least the following formats:
  • particulate reactants may be carried in the same pellets in an anhydrous condition
  • the particulate reactants may be adhered to the same or separate carrier materials such as fertilizer pellets or seeds;
  • the reactants may be carried in carrier materials dispersed throughout or partially constituting a separate carrier material;
  • capsules or microcapsules of the reactants in water-soluble or water- dispersible shells may be dispersed over the ground; and 7) a film or films (water-soluble, water-dispersible or water-leachable) may carry one or more of the reactants, with the other reactant in a location that released or carried first reactant will be placed into contact with the second reactant in the presence of water.
  • the process may use the above reaction to form the molecular iodine represented by
  • XY + ZI -> X ° or +I + ZY +I 2 wherein X is a metal, Y is an anion, Z is an alkali metal or alkaline cation, or where X is a multivalent metal, Y is a multivalent anion, and Z is an alkali metal or alkaline cation, and is preferably represented by
  • the process also may be performed where the two reactants are carried in a _. superabsorbent polymer.
  • the solids carriers for the two reactants may also include compositions of the present that comprise superabsorbent or non-superabsorbent polymers, natural products (e.g., papers, cellulosic solids, water-insoluble porous materials) which absorb or adsorb the film-forming material within the structure, water-soluble porous materials which absorb or adsorb the film-forming material within the structure, porous containers which merely slowly release a volume of the film-forming material, porous containers which both dissolve and physically release volumes of the film-forming composition through pores, and the like.
  • natural products e.g., papers, cellulosic solids, water-insoluble porous materials
  • Superabsorbent polymers are described, by way of non- limiting examples in US Patent Nos. 6,403,674; 4,731,391.
  • Superabsorbent polymers, including starch graft co-polymers are known in the art. See, for example, those described in U.S. Patent Nos. 4,375,535 and 4,497,930 (incorporated herein by reference), which have disclosed uses as adhesives, flocculants, sizes, water-retaining materials for agriculture and water-absorbing materials for sanitary materials.
  • the spectrum of advantages attendant the use of superabsorbent polymers in solid and flowable terrestrial insecticidal, pesticidal or insecticidal/pesticidal delivery compositions have gone unrecognized.
  • the superabsorbent polymers of the present invention are synthetic organic polymers which are solid and hydrophilic, absorbing over 100 times their weight in water. These superabsorbent polymers are typically in a powder, granule, extruded, or flake form, adapted to be blended and/or agglomerated into any shape or form.
  • the superabsorbent polymers may be, for example, acrylamide alkali metal acrylate co-polymers; propenenitrile homo-polymers, hydrolyzed, alkali metal salts; polymers of propenamide and propenoic acid, alkali metal salts; hydrolyzed acrylonitrile co-polymers, and starch graft co-polymers and ter-polymers thereof.
  • AH of these are designed to be hydrophilic, absorbing over 100 times their weight in water.
  • the resulting hydrophilic polymers can absorb from over one hundred to greater than about 5000, more typically around 500 to about 1,000, times their own weight in water (measured using distilled water, pH 7.5, 25, 760 mm Hg. absorption within about 30 seconds).
  • the absorption or swelling capacity and absorption or swelling time typically varies with each specific superabsorbent polymer.
  • One class of superabsorbent polymers include combinations of a starch and organic monomers, oligomers, polymers, co-polymers or ter-polymers. They may be manufactured in a variety of ways, for example, the methods described in U.S. Patent Nos. 4,375,535 and 4,497,930, and can be, for example, the product of grafting corn starch (amylopectin) with acrylonitrile (an acrylic monomer or oligomer).
  • a second class of superabsorbent polymers includes combinations of acrylamide and acrylate polymers, co-polymers and ter-polymers.
  • Land mass such as soil and sand
  • soil contamination can be contaminated by pesticides in a number of manners.
  • the most common manner of soil contamination is from improper handling or disposal of organic wastes and sewage and by animals carrying pests into the region. Excessive rainfall can also stress sewage systems, causing them to overflow and spill raw sewage carrying the pests over the land.
  • the danger to vegetation and animal life can persist for extended periods of time and can severely affect both the medical and economic health of an area. It is therefore essential that methods and plans be developed that can treat a wide variety of pest contaminations, and do so in a rapid manner and at acceptable costs.
  • Land mass can not be moved about readily, and materials added to soil do not disperse as widely as materials added to aqueous systems. Materials added to soil for purposes of pest reduction or elimination must not persist beyond their useful life and must not contribute a contamination effect themselves.
  • the technology disclosed herein is based on the discovery that the provision of molecular iodine into pest contaminated land mass (e.g., soil or sand) can mediate the land mass by killing or at least reducing the concentration of the vast majority of pest that would ordinarily persist in the land mass. Additionally, because of the transient and harmless active agents used, the materials can be used to treat agricultural land with no reasonable fear of contaminating crops.
  • Liquid carrier systems may become contaminated with any variety of microbes that may be harmful to vegetation or fauna that come into contact with the transmitted liquid.
  • the water/liquid carrier system's internal coating is disrupted and is then treated with molecular iodine in vapor or dissolved liquid form to provide a concentration in water or aqueous mass of at least about 10 parts per million, preferably at least 30 parts per million per square meter of disrupted biofilm.
  • the molecular iodine (as opposed to iodide anion) is provided as a) a gas, b) liquid or c) provided as two reactants that form molecular iodide (is a gas or into a liquid) in the water carrier system, either by using an aqueous carrier, water of hydration or ambient water.
  • the source of molecular iodine may be topically applied, ploughed into the biofilm, injected into the disrupted biofilm as solids dispersed solids, liquids or gels, mixed into the disrupted biofilm, injected into the disrupted biofilm separately or contemporaneously with water-removable carrier layers, sprayed onto the disrupted biofilm, or otherwise applied where desired.
  • Elemental iodine is a pesticidally active form of iodine that has been used as a water disinfectant for almost a century. It is also widely used as a sanitizing compound in the food processing industry. Chlorine solution (especially hypochlorites) have been widely using by growers as a sanitizing wash for many fruits and vegetables. However, the strong oxidizing effect of chlorine in water with a moderate to high organic load results in a number of different complex compounds (trihalomethanes or THM) which can become a significant environmental hazard. There are strong reasons to minimize the excessive use of chlorine in the environment.
  • THM complex compounds
  • One way of providing molecular iodine (I 2 ) on site, rather than having to find a way of transporting it to a site) is to provide reactants that can readily produce molecular iodine on-site in a controllable reaction.
  • One format of providing the molecular iodine would be through the oxidation-reduction reaction between two salts to produce the molecular iodine. It is a readily controlled environment where the reaction can be performed in an aqueous environment.
  • One reaction that can effect this would be generically described as:
  • X is a metal (preferably a multivalent metal and more particularly a divalent metal)
  • Y is an anion (preferably a multivalent anion and more preferably a divalent anion, and an anion having at least two oxygen atoms)
  • Z is an alkali metal or alkaline cation.
  • X are copper, iron, manganese, lead, nickel, tin, and the like
  • Y can be sulfate, sulfite, sulfonate, carbonate, phosphate, phosphate, nitrate, nitrie, borate, and the like
  • Z can be sodium, lithium, potassium, ammonium, magnesium, aluminum, and the like.
  • One preferred reaction would be: Cu +2 SO 4 "2 + K + I " ⁇ Cu° or +1 + K 2 SO 4 +I 2
  • This reaction takes place readily in an aqueous environment and produces molecular iodine at a controlled rate.
  • the reaction may be used, as intimated above, by either causing the reaction to occur in a container and directing the iodide into the disrupted film material within or onto the carrying system (as by gas injection or convection or other mass transfer) or by dissolving the molecular iodide and injecting or spraying the dissolved iodide into or onto the disrupted film.
  • the spray of the iodine material is somewhat persistent (as when carried in a thickening agent or SAP, or if the reaction is delayed by withholding water) to apply the reactants or even an initiated reactive I 2 forming composition onto the biofilm and then immediately disrupting the biofilm to distribute the iodine and/or iodine forming composition into the disrupted mass of the biofilm.
  • the reaction may also be used by dispersing or mixing the two ingredients into the land mass, either with additional water provided, with water of hydration on the first reactant (e.g., X + Y " -nP ⁇ O, such as G1SCV5H2O) or with ambient water in the land mass.
  • the two reactants may be physically separated from each other before being combined for application or reaction, as in separate pouches or containers.
  • the two reactants may be provided in a solid carrier medium that separates the two reactants until they are in contact with water (as in a soluble carrier such as polyvinyl alcohol, gelatin, amylase, sugars and the like, in pellet or block form).
  • the two reactants may be provided as liquids in separate containers to be mixed immediately before application.
  • the two reactants may be independently coated with a soluble/dispersible coating and the two ingredients kept in a single water-tight container.
  • the solid is preferably mixed into the biomass of the disrupted biofilm rather than merely spread on top of the film. If the solids are sufficiently large (e.g., at least 1.0mm, preferably at least 2.0mm in diameter), they can be more safely sprinkled on the surface of the damp or pretreated surface of the f ⁇ lmwithout as much concern of being unevenly distributed.
  • the solids may be otherwise roughened into the disrupted film mass, raked into the mass, injected into the mass, mixed with solid disrupted mass or carrier material and deposited onto the disrupted mass or otherwise securely applied.
  • absorbent and superabsorbent carriers have been found to require an additional amount of cupric sulfate over and above that used for the reaction. The reason for this is believed to be that the substrate has a tendency to sequester multivalent ions. With mixing in the vicinity fo workers, care should be taken to consult safety data sheets relating to iodine gas before experimentation of any magnitude is conducted.
  • Soil microorganisms tend to congregate at or underneath the biofilm surface in a shallow layer of approximately 0.5-10 centimeters in depth. This shallow layer is referenced as either the disruptable layer or the carrier layer. Microbial population size bears a direct relationship to the availability of food sources.
  • a distribution of microorganisms may exist in the initial 0-75 centimeters of a biofilm profile (or even deeper) and may include aerobic bacteria, anaerobic bacteria, actinomycetes, fungi, viruses, and algae.
  • the total aerobic and anaerobic bacteria in the upper 8 cm of film may be 77-80 percent of the total bacteria found in the 75 cm profile. 95 percent of all bacteria may be found in the upper 25 cm. of the film profile.
  • Aerobic bacteria may average between 80-90 percent of the total bacteria for the film horizons investigated.
  • the gas or liquid containing the iodine be provided through the major portions of this depth, e.g., at least to 8-25 centimeters.
  • Iodine is the preferred sanitizing agent in the food industry as it is acknowledged as a more effective user friendly sanitizing agent than chlorine. In addition, depending upon the concentrations, it is safe, can be effectively used at reduced concentrations (up to ten times less) than chlorine yet with a higher microbial kill rate. Iodine (unlike chlorine) does not produce any harmful substances such as carcinogens, and if nearly all by-products are removed, can produce an • environmentally safe waste water. Being a solid at room temperatures and supplied, immersed in water, the potentially harmful effects of exposure to a concentrated sanitizing agent such as chlorine are removed, significantly improving environmental work conditions. Furthermore, iodine is less corrosive than chlorine reducing corrosive effects from the use of a biocide.
  • U.S. Patent No. 4,888,118 discloses a water purification process in which the water is passed through a mass of nylon 4 complex with iodine. The treated water is subsequently passed through nylon 4 to remove iodine from the water.
  • Iodine recovery processes are known whose objective is to recover iodine to compensate for gradual reduction of I 2 in the flowing water and to provide a desired iodine residual.
  • the process described in U.S. Patent No. 5,176,836 is distinguished from previous systems by providing a continuous long term microbiological control process in a water supply particularly in space vehicle applications wherein I.sub.2 is released into the water stream flowing through a suitable anion exchange resin.
  • U.S. Patent No. 5,919,374 discloses a method and apparatus for producing bacteria free iodine species containing drinking water for farm animals under continuous dynamic water flow to produce a saturated iodine species containing aqueous solution at a pre selected temperature and blending the saturated solution with a second water flow to produce a diluted iodine species bacterium free aqueous solution.
  • Iodinated resin beds are known as a means for recharging a water supply with a minimum amount of active iodine.
  • the recharging is effected by treatment with an aqueous iodine solution produced by flowing water through a bed of iodine crystals.
  • the iodine residual is monitored and the bed recharged where necessary by adjusting the flow rate of water through the bed of iodine crystals.
  • This is an expensive method of monitoring the level of active iodine and the resin rich in bound iodine is very expensive.
  • the capacity of the resin is limited and reloading techniques in the field would be difficult to maintain in high water flow conditions.
  • this process is best suited to low level ( ⁇ 4 ppm) delivery of active iodine usually in a clean filtered water environment. This is due to the slow dissolving rate of iodine from known iodine beds and the limitation of the release rate and saturation of the anion exchange resins.
  • An ideal level of active iodine to be maintained in the aqueous content in the soil or sand is in the range of at least or greater then 10 ppm to 25 ppm although some applications may require higher concentrations.
  • iodine When iodine is used in large spill sanitizing applications, it may react with organic matter in which case the active iodine can be reduced to the point where there is little left for microbiological control. If resins (e.g., superabsorbing polymers) are used to deliver active iodine, this could necessitate continual monitoring of iodine concentration. It is expensive to use resin in large areas of soil, so it is likely that this mode of delivery would be used in more localized areas.
  • a controlled iodine delivery process would be one in which the level of iodine can be maintained at a predetermined optimum level and without constant manual intervention and monitoring.
  • the process technology of the present disclosure may be practiced in a number of formats, such as a process for reducing the pest content in biofilm mass by providing molecular iodine in the biofilm mass in a concentration in aqueous material in the biofilm mass of at least 10 parts per million.
  • the aqueous material should have a concentration of at least 10 parts per million is applied to the biofilm mass.
  • Specific formats include two reactants are added to the biofilm mass and the two reactants react in the presence of water to generate a concentration of at least 10 parts per million in the water of the molecular iodine, especially where the two reactants are a) mixed with the biofilm mass and at least some of the water present is ambient water; b) mixed with the biofilm mass and at least some of the water present is water of hydration of one of the two reactants; c) mixed with the biofilm mass and at least some of the water present is applied to the biofilm mass at about the same time as the application of the two reactants; d) mixed with the biofilm mass and at least one of the two reactants is coated to prevent premature reaction with water or another reactant.
  • the ways of applying the molecular iodine are at least where molecular iodine gas is injected into the biofilm mass; where the molecular iodine gas is generated in a closed container and injected into the land mass; where the biofilm mass is physically disturbed to assist mixing of molecular iodine into the biofilm mass; where physical disturbance comprises plowing of the land mass; and where solid reactant material to generate the molecular iodine is deposited in the land mass by the physical disturbance.
  • the process may use the above reaction to form the molecular iodine represented by
  • XY + Zl ⁇ X° or+1 + ZY +I 2 wherein X is a metal, Y is an anion, Z is an alkali metal or alkaline cation, or where X is a multivalent metal, Y is a multivalent anion, and Z is an alkali metal or alkaline cation, and is preferably represented by
  • the concentration of the iodine forming material may be selected in the article according the ultimate needs and designs of the manufacturer, and the level of antibacterial effect desired.
  • the concentration of the iodine gas in the liquid in the absorbent material is one measure of the desired results, and a further measure of the desired results is referred to in the art as the kill percentage, a measure of the percent of a specific bacteria (e.g., E. col ⁇ ) in a liquid sample that would be killed in 5 minutes by the level of active ingredient present.
  • An example would be that the presence of about 8 parts per million of gaseous iodine dissolved in the aqueous material in the absorbent material would have a kill percentage over 50%.
  • the liquid may have to be provided with at least 10 parts per million (ppm), at least 15 ppm, at least 20 ppm, or at least 25 ppm by controlling the amount of reagents added, the rate of reaction of the reagents, and other controls aimed at keeping the iodine in solution in the liquid, such as providing thickening agents or other materials that would reduce the volatility of the iodine gas from the solution.
  • ppm parts per million
  • Example I In a first experiment showing the efficacy of the iodine treatment on bacteria in soil, a natural sample from Santa Monica beach was user. This soil sample was taken from an area close to a storm drain. Concentrations started at 1100 MPN enterococci per 100 gram sediment were used. Wash samples having a concentration of greater than 10 parts per million were used on the soil samples. Enterocci concentrations approached zero for all of five consecutive washes. A longer term experiment was then performed with sand dosed with a pure culture of enterococci, the >10 ppm iodine solution imbibed in the soil, and then autoclaving. The bacterial level started at 1050 MPN/100 g, and went to zero immediately upon treatment.
  • Example 2 (Partial Prophetic " )
  • particles of KI and particles of copper sulfate are separately coated in water-removable coating materials comprising hydrophobic fumed silica (e.g., 0.1 — 0.5 microns, although other optional materials include cellulose fibers, lipids, water-softenable waxes, and sugars may be applied with non-aqueous solvents to avoid dissolution of the iodide or sulfate or the like.
  • the separate coated particles might then be carried to an water drain site, the interior surface of the water drain
  • Iodine gas and/or iodine dissolved in water would be generated at concentrations necessary for biocide applications upon the introduction of water (precipitation, direct addition, or from existing ambient moisture in the soil).
  • Example 3 (Partial Prophetic) ( In a prophetic example, particles of KI were blended with 5% by weight Cab- O-SilTM TG 709F hydrophobic fumed silica and blended together for a minimum of 30 seconds. This causes a layer of hydrophobic silica stand off particles to form a discontinuous layer on the KI surface. Old Bridge Chemicals CUSO 4 pentahydrate powder is also used but not treated with silica. Raw materials are mixed in the following ratio of 14.3wt% active CuSO 4 and 85.7wt% active KI. Upon intimate mixing this mixture does not show any discoloration or indication of reaction (iodine release) upon storage in 100% RH environment despite the close proximity of the intimately blended chemical reagent particles.
  • This mixture of reagents would be carried to a water drainage system site, the biof ⁇ lm coating on the interior surface of the water drainage system, rain runoff pipe disrupted and the particles contemporaneously sprayed onto the interior disrupted surface (either immediately before, during or immediately after scraping of the interior surface of the pipe along its length).
  • Iodine gas and/or iodine dissolved in water is generated at concentrations necessary for biocide applications upon the introduction of water (precipitation, direct addition, or from existing ambient moisture in the system).
  • a prophetic example with a rain drain system having a seventy-inch interior diameter was provided with a pigging system and pressurizing system such as those available according to the teachings of US Patent Nos. 7,000,280; 6,067,682; 5,924,158; 5,903,946; 5,384,929; and 5,265,302.
  • the interior of the pipe surface after being treated with such pigging systems, has at least some of the biof ⁇ lm disrupted by the pigging and attendant scraping action of the pigs, so that the film is sufficiently disrupted as to readily enable penetration by liquids and gases.
  • Either attached to a rear end of a pig or in a trailing device is a simple spraying system having a carried source of reactants and/or a feed system from an exterior source of reactants and water.
  • a single container of mixed coated particles of copper sulfate and potassium iodide can be carried in the robot and a hose providing water is connected to the robot to provide an exterior source of liquid.
  • the solids can be fed into a mixing area and the water fed into that same mixing area, and the combination of solids (now having their coatings dissolved, which also tends to render them somewhat tacky, so as to facilitate adherence to the interior of the carrier surface) and water is sprayed onto the pipe or drain (water carrier) surface.
  • This spraying may be done by conventional nozzles of sufficient size as to not get clogged by the carried solids and using the pressure from the water feed to spray the solution/dispersion/suspension of solids and water. It is preferred that a swiveling head be provided to assure coverage of the interior surface. It is to be noted that lower areas of the drain will be covered by runoff of liquid or the gases will disperse in the environment and contact all surfaces.
  • Alternative disrupting means can be the hole/tunnel drilling systems with three overlapping rotating drill heads that revolve as well as rotate to provide a generally circular drilling format.
  • the individual drill bits e.g., the three symmetrical drill bits typically used
  • the individual drill bits are also movable or adjustable radially to comport to the variations in the dimensions of the interior of the pipe and also any joints.
  • thick biof ⁇ lm By setting a maximum radial extension to a centimeter less than the actual minimum interior dimension of the pipe, thick biof ⁇ lm can be assured of disruption without fear of causing significant damage to the pipe itself by the drill bit.
  • softer drill bits can be used that will abrade or disrupt the biofilm coating, but will not readily damage the pipe material.
  • a laser system e.g., pulsed excimer laser may be used with the laser beam transmitted and the redirected in all directions within the interior of the drain
  • Chemical means may be used to physically disrupt the biofilm, but reducing the chemical input into the drain is highly advantageous. Even within the present system the capture, filtering or other means of removing precipitated metals (e.g., the copper iodide) is desirable and may be required.
  • Example 5 Prophetic Particles of KI would be impact coated with smaller particles (1/10 to 1/5 diameter ratio) of polyvinyl alcohol in accordance with the teachings of the processes and equipment shown in US Patent No. 6,037,019 (Kooyer). These PVA coated particles could then be mixed with particles of cupric sulfate with no concern for any immediate reaction between the salts, even in the presence of ambient moisture. These particles could be carried to the application site for admixture into water to provide iodine or into other carrier material for application to conduit surfaces. It is important to appreciate that both water-borne iodine and vapor-bome iodine can be produced in a single environment to address cracks, nooks and crannies in the delivery system where intimate contact with water might be difficult.
  • the activity of the materials may be increased with respect to halogen releasing ability and volume by adding further halogen releasing components, especially iodates, chlorates, bromates, periodates, perchlorates and/or perbromates as a further reagent (e.g., as above 0% to 200% by weight of the further halogen- releasing components to KI.
  • further halogen releasing components especially iodates, chlorates, bromates, periodates, perchlorates and/or perbromates
  • a further reagent e.g., as above 0% to 200% by weight of the further halogen- releasing components to KI.
  • Metal, non-metal, alkaline and alkali halogens compounds may be used.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un procédé d'amélioration d'un système d'acheminement de liquide comprenant la rupture du point de vue physique d'une pellicule biologique sur des surfaces intérieures du système d'acheminement de liquide et par la suite l'apport d'iode moléculaire sur la pellicule biologique rompue dans une concentration dans un milieu aqueux dans la masse de terre d'au moins 10 parties par million. Les réactifs peuvent être fournis également avant la rupture physique. Le iode moléculaire peut être ajouté à l'état solide ou liquide ou gazeux, et peut être formé in situ à l'intérieur du système d'acheminement de liquide en utilisant de l'eau disponible ou ajoutée dans la réaction.
PCT/US2007/007515 2007-01-18 2007-03-27 Systèmes et procédés de nettoyage de supports de liquide WO2008088360A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3436394A4 (fr) * 2016-03-31 2020-04-01 Seoul Viosys Co. Ltd. Traitement de conduite de transport de fluide avec un rayonnement ultraviolet

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4416703A (en) * 1981-11-20 1983-11-22 Shell Oil Company System for removing debris from pipelines
US4561981A (en) * 1984-01-27 1985-12-31 Characklis William G Treatment of fouling with microcapsules
US5753180A (en) * 1995-04-17 1998-05-19 Bio-Technical Resources Method for inhibiting microbially influenced corrosion
US6345632B1 (en) * 1998-10-07 2002-02-12 H.E.R.C. Products Incorporated Method of cleaning and passivating a fire protection system
US6951610B2 (en) * 2002-01-29 2005-10-04 John Alex Leonard Method and device for producing aqueous iodine and other halogen solutions

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4416703A (en) * 1981-11-20 1983-11-22 Shell Oil Company System for removing debris from pipelines
US4561981A (en) * 1984-01-27 1985-12-31 Characklis William G Treatment of fouling with microcapsules
US5753180A (en) * 1995-04-17 1998-05-19 Bio-Technical Resources Method for inhibiting microbially influenced corrosion
US6345632B1 (en) * 1998-10-07 2002-02-12 H.E.R.C. Products Incorporated Method of cleaning and passivating a fire protection system
US6951610B2 (en) * 2002-01-29 2005-10-04 John Alex Leonard Method and device for producing aqueous iodine and other halogen solutions

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Title
KAPUR P. AND VERMA M.: "Determination and Iodate Ion in Presence of Cupric Ion", INDUSTRIAL AND ENGINEERING CHEMISTRY ANALYTICAL EDITION, vol. 13, no. 5, May 1941 (1941-05-01), pages 338 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3436394A4 (fr) * 2016-03-31 2020-04-01 Seoul Viosys Co. Ltd. Traitement de conduite de transport de fluide avec un rayonnement ultraviolet

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