WO2011160186A1 - Procédé et appareil pour effectuer une réaction chimique - Google Patents

Procédé et appareil pour effectuer une réaction chimique Download PDF

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Publication number
WO2011160186A1
WO2011160186A1 PCT/AU2011/000778 AU2011000778W WO2011160186A1 WO 2011160186 A1 WO2011160186 A1 WO 2011160186A1 AU 2011000778 W AU2011000778 W AU 2011000778W WO 2011160186 A1 WO2011160186 A1 WO 2011160186A1
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WO
WIPO (PCT)
Prior art keywords
fluid
effecting
light
inlet port
filtration membrane
Prior art date
Application number
PCT/AU2011/000778
Other languages
English (en)
Inventor
Ian Andrew Maxwell
Shane Cox
Original Assignee
Viva Blu Pty Ltd
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Filing date
Publication date
Priority claimed from AU2010902784A external-priority patent/AU2010902784A0/en
Application filed by Viva Blu Pty Ltd filed Critical Viva Blu Pty Ltd
Publication of WO2011160186A1 publication Critical patent/WO2011160186A1/fr

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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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/123—Ultraviolet light
    • 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
    • A61L2/02—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/08—Radiation
    • A61L2/10—Ultraviolet radiation
    • 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
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C02F1/325—Irradiation devices or lamp constructions
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/0004—Processes in series
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0892—Materials to be treated involving catalytically active material
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/305—Endocrine disruptive agents
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • C02F2201/007—Modular design
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/32—Details relating to UV-irradiation devices
    • C02F2201/322—Lamp arrangement
    • C02F2201/3222—Units using UV-light emitting diodes [LED]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/02—Fluid flow conditions
    • C02F2301/026—Spiral, helicoidal, radial
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/10—Photocatalysts

Definitions

  • the present invention relates to an apparatus - and the associated methods and systems in which such an apparatus may be employed, for effecting one or more predetermined chemical and/or biological reactions of pathogen inactivation. More specifically, it relates to a modular apparatus for creating one or more active species in a reaction vessel and to means for delivering such active species to a fluid reactant bearing an organic and/or pathogenic load. Most preferably, the present invention relates to a so-called "hybrid" system, wherein more than one active species is created, such species being active against a corresponding more than one contaminant molecules.
  • the invention has been developed primarily as a means of photocatalytically and/or photolytically and/or chemically remediating wastewater containing a load of small organic molecules such as the carcinogen 1,4-dioxane, and/or endocrine disrupting compounds such as N-nitrosodimethylamine (NDMA), and/or non-aesthetic compounds such as those emitting undesirable odour and/or colour, and/or pathogens/organisms such as bacteria, viruses and protozoa.
  • small organic molecules such as the carcinogen 1,4-dioxane
  • NDMA N-nitrosodimethylamine
  • non-aesthetic compounds such as those emitting undesirable odour and/or colour
  • pathogens/organisms such as bacteria, viruses and protozoa.
  • NDMA N-nitrosodimethylamine
  • 1,4- dioxane pathogens or protozoa
  • Cryptosporidium and Giardia lamblia pathogens or protozoa
  • UV processes such as advanced oxygenation processes (AOPs).
  • AOPs advanced oxygenation processes
  • photo catalysis is the acceleration of a photoreaction in the presence of a catalyst.
  • energy in the form of light is absorbed by an adsorbed substrate.
  • photogenerated catalysis the photocatalytic activity depends on the ability of the catalyst to create electron hole pairs, which generate free radicals able to undergo secondary reactions. This is the essential theory upon which water electrolysis by titanium dioxide (Ti0 2 ) is based.
  • pathogens may be effectively removed from a contaminated fluid through applying a secondary disinfection step or UV.
  • UV-based technologies make it a preferred treatment technology for the various water markets.
  • UV is effective for a wide variety of microorganisms, including bacteria, viruses, and fungi as well as protozoa such as Cryptosporidium and Giardia.
  • the technology is also chemical-free, meaning there are no requirements for chemical transport, storage, handling, removal, or hazardous material management planning. Being chemical-free, it is also non-corrosive and not prone to the effects of accidental overdosing.
  • UV also has relatively low overall capital and operating costs and is easy to maintain and operate.
  • UV-C Ultra-violet
  • UV readily inactivates Cryptosporidium created a huge opportunity for UV-based technologies in the drinking water market, primarily for the disinfection of surface water supplies such as rivers and reservoirs, where Cryptosporidium cysts are prevalent worldwide. Compared with ozonation and membrane separation processes, which are also effective at removing Cryptosporidium, UV is significantly less capital- and operations-intensive. Perhaps most importantly by comparison with chemical- based treatments, UV does not form disinfection by-products (DBPs) and thereby does not impact the aesthetic quality of the treated water (e.g., taste, odour, colour, etc.).
  • DBPs disinfection by-products
  • UV technology does, however, have a few limitations. Principally, that it is difficult to monitor efficacy during operation. Moreover, some in the municipal drinking water market perceive mercury lamps as an environmental detriment and also express concern about the lack of residual protection for the distribution system. In addition, UV is not effective as a pre-oxidant or taste/odour control. Finally, certain viruses, such as adenovirus, require relatively high doses of UV - and the technology is also ineffective with high-solids waters in the municipal wastewater market.
  • UV is used for disinfection purposes, i.e., to inactivate waterborne pathogens such as bacteria, viruses, protozoa and fungi.
  • UV has also been used to remove certain chemicals from water by photolysis. Accordingly, UV has been used to remove total organic carbon in high-purity applications (e.g., pharmaceutical and semiconductor industries) and chemical disinfectants such as chlorine, chloramines, and ozone in certain commercial and industrial applications.
  • UV-based technologies are expected to increase in both the residential and commercial drinking water markets worldwide. The former can be attributed to renewed public awareness about tap water quality issues as well as increasing concerns over the quality, cost and environmental impact of bottled water. UV will be used as either a point-of-use or a point-of-entry device for such applications.
  • Potential commercial users include hospitals, office buildings, schools, restaurants, and camping grounds.
  • the present state of the art in the treatment of secondary effluent to potable standards typically includes a first-pass microfiltration or ultrafiltration process, thereby to remove physical or granular contaminants such as dirt or relatively large molecules. Such processes may also remove certain pathogens from the effluent.
  • the first-pass micro-filtration or ultrafiltration process is typically followed by a Reverse Osmosis (RO) membrane treatment that also removes some remaining pathogens, as well as smaller dissolved organic and inorganic molecules.
  • a disinfection step and/or a UV process may be applied to remove any residual pathogens.
  • Such a step typically utilises chlorine, ozone or UV light as the disinfectant, as related above.
  • Ti0 2 is an effective agent in the remediation of contaminated water due to several factors, which include that the process occurs under ambient conditions; Ti0 2 is not consumed or degraded; oxidation of organic molecule contaminants to water and carbon dioxide can be effected to completion; the photocatalyst is inexpensive and has a high turnover; Ti0 2 can be supported or immobilised on suitable reactor substrates; and the process offers great potential as an industrial technology to detoxify contaminated waters.
  • United States Patent Publication No. 2008/0272050 to Butters, relates to systems and methods for decontaminating a contaminated fluid integrating ultraviolet radiation in an advanced decontamination process, and a honing material, along with a cross-flow membrane filter, into a single closed-loop system.
  • the system of US 2008/0272050 is not modular and does not provide for continuous operation.
  • the membrane is not run in cross flow; it is run in "deadend". This means the removal rate of pollutants will vary as the filter cake forms and compacts.
  • UV can be used in conjunction with oxidants such as ozone and hydrogen peroxide, or semiconductors such as titanium dioxide to oxidise refractory chemicals such as chlorinated solvents, taste-and-odour compounds, nitrosodimethylamine (NDMA), methyl-tert- butyl-ether (MTBE), endocrine disrupting chemicals, and pharmaceuticals.
  • oxidants such as ozone and hydrogen peroxide
  • semiconductors such as titanium dioxide
  • oxidise refractory chemicals such as chlorinated solvents, taste-and-odour compounds, nitrosodimethylamine (NDMA), methyl-tert- butyl-ether (MTBE), endocrine disrupting chemicals, and pharmaceuticals.
  • UV will be part of a multiple-barrier approach, meaning it will be one of multiple combined technologies that complement each other and add a degree of safety and efficiency to drinking water treatment.
  • the modular apparatus is constructed of one or more plastics materials having surfaces exposed to UV and/or chemicals coated with a reflective metallic barrier so as to avoid degradation of the plastic and enhance UV light usage.
  • an "open” circuit is one without a filtration membrane; and a “closed” circuit comprises such a membrane so as to prevent the photocatalyst slurry escaping into the "open” circuit which is in fluid communication with the "closed” circuit.
  • an apparatus for effecting a chemical or biological change upon a fluid comprising: means for providing a feed of said fluid through an inlet port; means for effecting at least one light-enabled process; means for coupling said at least one light-enabled process with said fluid, thereby to actively modify predetermined properties of said fluid; and means for expelling a subsequently modified fluid through an outlet port.
  • the means for effecting said at least one light-enabled process are comprised within a closed circuit in fluid communication with the open circuit.
  • said apparatus is a "hybrid" apparatus wherein one or more of a photocatalytic reaction, a photolytic reaction and a chemical-based reaction (for instance, using peroxide) is employed.
  • said at least one light-enabled process is selected from the group consisting of: photocatalysis, photolysis, disinfection and UV-chemical-based (AOP) processes.
  • the apparatus further comprises means for propagating said contaminated fluid from said inlet port; and said substantially decontaminated fluid from said outlet port.
  • the closed circuit further comprises a filtration membrane defining an interface between said open circuit and said closed circuit.
  • the catalytic substrate is present as a slurry within the contaminated fluid.
  • filtration membrane separates the slurry from the decontaminated fluid.
  • the closed circuit is at least partly coincident with the open circuit.
  • propagation of the fluid from the inlet port, through the means for effecting said at least one light-enabled process, through the filtration membrane and from the outlet port is effected by an impeller.
  • the filtration membrane is a cross-flow filtration membrane.
  • the cross-flow filtration membrane is comprised of ceramic, stainless steel and/or polymeric material.
  • the energy source is light, preferably UV or visible light.
  • the catalytic substrate comprises titanium dioxide.
  • the energy source further provides for a photolytic reaction to at least partly disinfect said contaminated fluid.
  • said at least one light- enabled process comprises a hydrogen peroxide or ozone system.
  • the contaminated fluid is contaminated water.
  • the apparatus further comprises means for a blowdown, the blowdown sufficient to eliminate suspended solids from the closed circuit.
  • the apparatus has an operating pressure of less than about 5 bar, preferably less than about 2 bar.
  • the apparatus is adapted for ease of connection and disconnection within a system comprising one or more such modules.
  • said apparatus is constructed substantially of a plastics material; and having surfaces exposed to said energy source coated in a reflective metallic material.
  • a system for effecting a chemical or biological change upon a fluid comprising at least a pair of apparatus defined according to the first aspect of the invention connected in series such that the outlet port of an upstream apparatus is in fluid communication with the inlet port of a downstream apparatus, thereby to provide for iterative chemical or biological change of said fluid.
  • a system for effecting a chemical or biological change upon a fluid comprising at least a pair of apparatus defined according to the first aspect of the invention connected in parallel such that the outlet port of an upstream apparatus and the outlet port of a downstream apparatus empty into a common conduit; and the inlet port of an upstream apparatus and the inlet port of a downstream apparatus fill from a common conduit, thereby to provide for batch-wise chemical or biological change of said fluid.
  • said system comprises a "hybrid" apparatus wherein one or more of a photocatalytic reaction, a photolytic reaction and a chemical-based reaction (for instance, using peroxide) is employed.
  • the system comprises more than two such modules connected in series, thereby to provide for iterative decontamination/treatment of the contaminated fluid.
  • an apparatus for effecting a chemical or biological change upon a fluid comprising a closed circuit having an inlet port for introducing said fluid to said apparatus; an outlet port for expelling a subsequently modified fluid from said apparatus; means for effecting at least one light-enabled process therebetween; and wherein said inlet port is adapted for fluid communication with a circuit comprising said fluid.
  • said apparatus is a "hybrid" apparatus comprised of at least a pair of modular apparatus wherein individual modules effect different light- enabled process of at least two or more of a photocatalytic reaction, a photolytic reaction and a chemical- based reaction (for instance, using peroxide).
  • said at least one light-enabled process is selected from the group consisting of: photocatalysis, photolysis, disinfection and chemical-based processes.
  • the apparatus further comprises a filtration membrane.
  • the filtration membrane defines an interface between the module and the circuit.
  • the catalytic substrate is present as a slurry within the contaminated fluid.
  • the filtration membrane separates the slurry from the decontaminated fluid.
  • propagation of the fluid from the inlet port, through the means for effecting said at least one light-enabled process, through the filtration membrane and from the outlet port is effected by an impeller.
  • the filtration membrane is a cross-flow filtration membrane.
  • the filtration membrane is comprised of ceramic, stainless steel and/or polymeric material.
  • the energy source is light, preferably UV or visible light source.
  • the catalytic substrate comprises titanium dioxide.
  • the energy source further provides for a photolytic reaction to at least partly disinfect said contaminated fluid.
  • said at least one light-enabled process comprises a hydrogen peroxide or ozone system.
  • the contaminated fluid is contaminated water.
  • the apparatus further comprises means for a blowdown, the blowdown sufficient to eliminate suspended solids from the apparatus.
  • the apparatus preferably further has an operating pressure of less than about 5 bar, preferably less than about 2 bar.
  • the apparatus is adapted for ease of connection and disconnection within a system comprising one or more such modules.
  • a system for effecting a chemical or biological change upon a fluid comprising a first apparatus defined according to the fourth aspect of the invention adapted to be connected in series with a second said apparatus such that said outlet port of said first apparatus is in fluid communication with said inlet port of said second apparatus, thereby to provide for iterative chemical or biological change of said fluid.
  • a system for effecting a chemical or biological change upon a fluid comprising a first apparatus defined according to the fourth aspect of the invention adapted to be connected in parallel with a second said apparatus such that the outlet port of said first apparatus and the outlet port of said second apparatus empty into a common conduit; and the inlet port of said first apparatus and the inlet port of said second apparatus fill from a common conduit, thereby to provide for batch-wise chemical or biological change of said fluid.
  • said system comprises a "hybrid" apparatus wherein one or more of a photo catalytic reaction, a photolytic reaction and a chemical-based reaction (for instance, using peroxide) is employed.
  • the system comprises more than two such modules connected in series, thereby to provide for iterative decontamination/treatment of the contaminated fluid.
  • a method for effecting a chemical or biological change upon a fluid comprising the steps of: providing an inlet port for introducing said fluid to a reaction vessel; providing an outlet port for expelling a modified fluid from said reaction vessel; providing means for effecting at least one light-enabled process between said inlet port and said outlet port; propagating said fluid from said inlet port to said means for effecting said at least one light-enabled process; effecting said at least one light-enabled process upon said fluid, thereby to provide said modified fluid; and subsequently expelling said modified fluid from said outlet port.
  • the means for effecting said at least one light-enabled process are comprised within a closed circuit in fluid communication with the open circuit.
  • said method comprises a "hybrid" apparatus wherein one or more of a photocatalytic reaction, a photo lytic reaction and a chemical-based reaction (for instance, using peroxide) is employed.
  • the means for effecting said at least one light-enabled process are selected from the group consisting of: photocatalysis, photolysis, disinfection and chemical-based processes.
  • the closed circuit further comprises a filtration membrane.
  • the filtration membrane defines an interface between the open circuit and the closed circuit.
  • the catalytic substrate is present as a slurry within the contaminated fluid.
  • the filtration membrane separates the slurry from the decontaminated fluid.
  • the closed circuit is at least partly coincident with the open circuit.
  • the propagation of the fluid from the inlet port, through the means for effecting said at least one light- enabled process, through the filtration membrane and from the outlet port is effected by an impeller.
  • the filtration membrane is a cross-flow filtration membrane.
  • the filtration membrane is comprised of ceramic, stainless steel and/or polymeric material.
  • the energy source is light, preferably UV or visible light source.
  • the catalytic substrate comprises titanium dioxide.
  • the energy source further provides for a photolytic reaction to at least partly disinfect the contaminated fluid.
  • said at least one light-enabled process comprises a hydrogen peroxide or ozone system.
  • the contaminated fluid is contaminated water.
  • the method further comprises means for a blowdown, the blowdown sufficient to eliminate suspended solids from the closed circuit.
  • the method takes place at an operating pressure is less than about 5 bar, preferably less than about 2 bar.
  • a first module is adapted to be connected in series with a second module such that the outlet port of the first module is in fluid communication with the inlet port of the second module, thereby to provide for iterative decontamination of the contaminated fluid.
  • An embodiment of the inventive method comprises connecting more than two such modules in series.
  • the method is adapted for ease of connection and disconnection within a system comprising one or more such modules.
  • a method for effecting a chemical or biological change upon a fluid comprising the steps of: providing an inlet port for introducing said fluid to a closed circuit wherein said inlet port is adapted for fluid communication with a circuit comprising said fluid; providing an outlet port for expelling a modified fluid from said closed circuit; providing means for effecting at least one light-enabled process between said inlet port and said outlet port; propagating said fluid from said inlet port to said means for effecting said at least one light-enabled process; effecting said at least one light-enabled process upon said fluid, thereby to provide said modified fluid; and subsequently propagating said modified fluid from said outlet port.
  • said method comprises a "hybrid" apparatus wherein one or more of a photocatalytic reaction, a photolytic reaction and a chemical-based reaction (for instance, using peroxide) is employed.
  • the means for effecting said at least one light-enabled process is selected from the group consisting of: photocatalysis, photolysis and chemical-based means; and an energy source wherein energy derived therefrom is contactable via one or more transport media with the catalytic substrate, thereby to provide a species active against the contaminant.
  • the closed circuit further comprises a filtration membrane.
  • the filtration membrane defines an interface between the module and the circuit.
  • the catalytic substrate is present as a slurry within the contaminated fluid.
  • the filtration membrane separates the slurry from the decontaminated fluid.
  • the propagation of the fluid from the inlet port, through the means for effecting said at least one light-enabled process, through the filtration membrane and from the outlet port is effected by an impeller.
  • the filtration membrane is a cross-flow filtration membrane.
  • the filtration membrane is comprised of ceramic, stainless steel and/or polymeric material.
  • the energy source is light, preferably UV or visible light source.
  • the catalytic substrate comprises titanium dioxide.
  • the energy source further provides for a photolytic reaction to at least partly disinfect the contaminated fluid.
  • said at least one light-enabled process comprises a hydrogen peroxide or ozone system.
  • the contaminated fluid is contaminated water.
  • the method further comprises a blowdown, the blowdown sufficient to eliminate suspended solids from the closed circuit.
  • the operating pressure of the method is less than about 5 bar, preferably less than about 2 bar.
  • a first module is adapted to be connected in series with a second module such that the outlet port of the first module is in fluid communication with the inlet port of the second module, thereby to provide for iterative decontamination of the contaminated fluid.
  • the modules employed in the method are adapted for ease of connection and disconnection within a system comprising one or more such modules.
  • surfaces exposed to said energy source coated in a reflective metallic material are used to be used.
  • a ninth aspect of the present invention there is provided a modified fluid when so-modified by a method defined according to the seventh or the eighth aspects of the present invention.
  • an apparatus for effecting a chemical or biological change upon a fluid comprising an impeller and an energy source, each operationally engagable with means for effecting at least one light-enabled process between an inlet port and an outlet port in said apparatus.
  • said energy source is adapted to emit UV and/or visible light over one or more wavelengths.
  • the apparatus is modular.
  • the transport medium is a waveguide.
  • the waveguide is a solid waveguide.
  • the waveguide is a liquid waveguide comprising water. More preferably still, said water is the contaminated water undergoing treatment.
  • the energy source is proximal with the catalytic substrate, thereby to selectively control the pathlength therebetween.
  • the proximity of the energy source to the catalytic substrate is such that energy derived from the energy source is not significantly dissipated within the transport medium prior to contacting with the contaminant species.
  • the reaction vessel is provided with interior functionality, thereby to relatively increase the interior surface area and/or provide manipulable flow characteristics within the apparatus.
  • the interior functionality may be one or more discrete discs, one or more discrete or adjoined helical elements, one or more nodules, one or more complex surfaces, and combinations thereof.
  • the waveguide is configured to provide a relatively increased surface area per unit reactor fluid volume.
  • the catalytic substrate is a photocatalytic substrate.
  • the photocatalytic substrate is selected from the group consisting of: Ti0 2 , zinc oxide (ZnO), CdS and tungsten oxide (W0 3 ).
  • the photocatalytic substrate is Ti0 2 .
  • the energy is light, preferably UV or visible light derived from a UV source.
  • the UV source is a UV tube having a power output of about 0.3 W to about 25 W.
  • the UV source is an LED having a power output of about 250 W to about 1400 W, or a plurality of such LEDs.
  • the UV light comprises one or more wavelengths within the range of approximately 200 to 400 nm.
  • the active species is an excited species such as free radicals derived from Ti0 2 electron holes.
  • the contaminated fluid is a liquid, gas, or a combination thereof. More preferably, the fluid is a fluid effluent. In an embodiment, the fluid effluent is a contaminated or polluted liquid, gas and/or steam. Preferably, the liquid, gas and/or steam comprises the one or more contaminant species in solution state. More preferably, the liquid is water. In an embodiment, the solution comprises the one or more contaminant species in aqueous phase. Preferably, the contaminated or polluted liquid comprises one or more organic contaminants.
  • the contaminated fluid may be wet gas from a combustion engine, the method thereby effective to relatively reduce emissions from the engine.
  • the one or more organic contaminants comprise organic molecules and organisms.
  • the one or more organisms comprise bacteria, protozoa and/or viruses.
  • the organic molecules comprise carcinogenic, endocrine-disrupting and/or non-aesthetic compounds.
  • the inventive apparatus preferably further comprises an outlet port remote from an inlet port, thereby to facilitate flow of the feed therebetween.
  • the inventive apparatus alternatively further comprises provision of an outlet port integral with an inlet port, thereby to facilitate the method to operate on a batch basis.
  • the decontamination is effected by photocatalysis and/or photolysis.
  • the photocatalysis is effected from incident light passing through the waveguide and interacting with a photocatalytic substrate, which in one form is a Ti0 2 slurry, and in another form, may be coated upon one or more interior surfaces of the reactor volume prior to it interacting with a contaminant molecule.
  • the photolysis is effected from incident light passing through the waveguide and interacting with a contaminant molecule prior to it interacting with the photocatalytic substrate upon one or more interior surfaces of said reactor volume.
  • titanium dioxide is coated upon one or more surfaces of the catalytic substrate to a uniform or non-uniform thickness of up to approximately 20 microns, preferably about 0.1 to about 15 microns, more preferably about 0.1 to about 5 microns.
  • the waveguide may comprise a lens, thereby to focus the energy in a predetermined manner.
  • the waveguide comprises a reflecting element, thereby to redirect the energy in a predetermined manner.
  • surfaces exposed to said energy source coated in a reflective metallic material are examples of a reflective metallic material.
  • the present invention provides means suitable for the treatment of organic-containing and/or pathogen/micro -organism-containing effluent, such that the organics and/or pathogens are removed with relatively high efficiency.
  • the inventive process is scalable to a treatment plant that has relatively low investment and ongoing running costs, relative to the known engineering solutions.
  • One feature of the inventive apparatus is by way of its construction from relatively low-cost materials, preferably metal or even more preferably plastic.
  • the inventive apparatus can accommodate either flow-through or batch-type operation, the latter has the additional advantage that the degree of remediation required may be selected by simply altering the retention time of the contaminated liquid. Depending upon the precise operational constraints of the system, a stronger intensity lamp/shorter retention time may be desirable, or vice versa.
  • a further feature of the inventive apparatus is the facility to combine a photocatalysis reaction, a photolysis reaction and a chemical reaction within a single modular apparatus. This is especially advantageous in cases where the incident contaminated water is polluted with multiple foulants, as may frequently be the case in developing countries.
  • the inventive apparatus is of significant commercial and indeed social potential.
  • the reactor module according to the present invention is designed to be modular and reflective of other technologies common in the municipal water industry such as reverse osmosis and microfiltration membranes. This is to allow for the widest possible range of application.
  • the components are constructed such that they allow for easy reconditioning of the module.
  • the internal impeller should be sufficient to generate fully turbulent flow within the reactor.
  • the target operating pressure is less than 2 bar , with a maximum operating pressure of 5 bar.
  • operating pressures will be contingent on the type and size of the membranes used in the reactor.
  • the channel thickness shall be sufficient to limit pressure build-up and narrow enough to limit the degree of un- illuminated space in the reactor. In practical terms, the thickness is around 10 mm.
  • Figure 1 is a schematic diagram of a modular apparatus according to the present invention.
  • the contaminated fluid flows from the inlet, through the means for effecting at least one light-enabled process, and from the outlet.
  • Figure 2 is a schematic diagram of a system of modules, such as that illustrated with respect to Figure 1.
  • the treated fluid flows into the inlet port of an adjacent module, thereby to undergo iterative decontamination and produce a relatively decontaminated product.
  • Figure 3 is a schematic diagram of a modular apparatus according to the present invention.
  • the contaminated fluid enters and exits through a combined inlet/outlet, thereby to operate on a batch basis.
  • the means for effecting at least one light-enabled process are remote from the inlet/outlet.
  • Figure 4 is a prototypical pilot plant incorporating the present invention.
  • the present invention provides a modular apparatus 1 for effecting substantially continuous decontamination of a contaminated fluid.
  • the apparatus comprises either an open circuit having an inlet port 2 for introducing said contaminated fluid and an outlet port 3 for expelling a substantially decontaminated fluid; or a closed circuit wherein the inlet port 2 and outlet port 3 are integral, thus facilitating the present invention to operate on a continuous/flow through or batch basis.
  • the apparatus further comprises means 4 in the form of a photocatalytic unit for effecting at least one light-enabled process such as an advanced oxygenation process between the inlet port and the outlet port; means (not shown) for effecting a flow of fluid from said inlet port to said outlet port; and means in the form of an impeller 5 for maintaining a slurry of photocatalytic material in suspension within the photocatalytic unit.
  • a filtration membrane 6 prevents photocatalytic material from exiting the photocatalytic unit 4.
  • photocatalytic material may not be present, in which case the impeller 5 is unnecessary such that there is no slurry to maintain in suspension, unless the impeller provides mixing in addition to that provided by the effect of the inlet and outlet flows that improves UV conversion in the module.
  • the apparatus 1 comprises a substantially centrally located, longitudinally- extending energy source in the form of one or more UV lamps and/or LEDs, preferably adapted to emit energy over one or more wavelengths.
  • the light source is sealed within a solid membrane to avoid contacting with the liquid.
  • the membrane thereby exhibits waveguiding properties by way of transporting incident light from its source to the suspension or slurry of photocatalytic material.
  • the interior walls of the apparatus may be coated with aluminium and/or a photocatalyst, preferably titanium dioxide to provide an additional photocatalytic conversion of contaminant materials, as described above. It will be appreciated that the inventive system also provides for photolytic conversion of other contaminant materials, which occurs where incident light disinfects contaminant species without first contacting with the photocatalytic material.
  • the apparatus comprises interior functionality and/or surface area which is exposed to UV and/or chemical such as peroxide. Accordingly, such surfaces are preferably made of - or at least coated with a reflective material such as aluminium foil whereby the UV/chemicals will not degrade the base material used to construct the apparatus.
  • the apparatus is constructed of a plastics material and the exposed surfaces protected from UV/chemical degradation by a thin coating of aluminium.
  • Means of metallising the plastics material include lamination, sputter coating, liquid coating, powder costing, electrolysis plating, etc., or any other applicable means.
  • the metallisation is optional, depending upon the plastics material employed.
  • the modules can be made out of metal, or any other material that will not degrade under UV radiation.
  • reflective qualities of the metallic coating for the slurry module it is unlikely that the UV will get through the slurry to the module wall. Accordingly, the reflective qualities of the metallic coating are optional.
  • the outlet port of a first such modular apparatus is optionally adapted for modular connection with the inlet port on a second such modular apparatus, thereby to connect said modules in series.
  • series connection of said modules provides for a successive or iterative decontamination to the contaminated fluid.
  • Reaction conditions, reactor volumes, light intensity, residence times - or indeed any other relevant parameter may be the same or different in successive connected modules, thereby to target a relatively high concentration of contaminants, or different contaminants as the case may be in practice.
  • successive modules may be connected in parallel from a common source, thereby to provide for an averaged decontamination of the contaminated fluid.
  • the filtration membrane is preferably a cross-flow filtration membrane comprised of ceramic or stainless steel.
  • the filter membrane can include polymeric material. Although these are degraded by UV, the water absorbs UV and the photocatalyst absorbs and scatters it; these characteristics make polymeric material suitable for use not only in the filter membrane, but in the housing as well.
  • the filtration membrane acts to keep the photocatalytic slurry within the means for conducting the photocatalysis reaction.
  • the membrane and the associated impeller may be optional.
  • the benefits of a pressure drop between the inlet, module and reactor may be created for example by a simple aperture sized to create the required affect.
  • a membrane may still have some benefits for example to keep unwanted solids and pathogens out of the module, or to act as a filter ensuring the outlet fluid itself is not contaminated with unwanted species. Additionally it is known that filter cakes on a membrane can act to remove unwanted species, and therefore add to the efficacy of the system.
  • additional internal surface area may be provided by way of a plurality of discrete discs extending substantially normal to the longitudinal axis of the light source, thereby to define a corresponding plurality of cavities.
  • the cavities may serve to reduce the path length through which the incident light energy must propagate through the liquid medium, thereby increasing overall operational efficiency.
  • the discrete discs are replaced by one or more helical elements, which may be optionally adjoined with each other at their lip portions.
  • the helix may serve to enhance flow-through characteristics such that it may define a conduit through which contaminated liquid may flow from inlet port 2 to outlet port 3.
  • the contaminated fluid is provided as a feed most preferably in the form of a liquid, gas, or a combination thereof. More preferably, the fluid is a liquid effluent, with the method thereby operative to remediate at least a portion of the fluid effluent.
  • said fluid effluent is a contaminated or polluted liquid, gas and/or steam.
  • the liquid, gas and/or steam comprises one or more contaminants in solution and/or undissolved state.
  • the liquid is water and the effluent comprises organic molecules and/or pathogens/micro-organisms.
  • the outlet port 3 is integral with the inlet port 2, thereby to facilitate the method to operate on a batch basis, if desired.
  • reaction conditions e.g., retention time
  • retention times can be varied by way of flow rate through successive modules.
  • the apparatus also comprises an energy source spaced from, or proximal with the catalytic substrate. More preferably, the energy source is directly coupled with the catalytic substrate. This direct coupling may be facilitated by the waveguiding effect of solid and/or liquid media.
  • the waveguide may act both as the transport medium and as a substrate for catalytic material applied to the surface thereof. Alternatively, the waveguide comprises a single material or a plurality of materials of differing refractive indices.
  • the waveguide may comprise scattering centres, reflective elements, diffractive elements, or a combination thereof, thereby to facilitate incident light being shifted out of the plane of the waveguide and contacting with the photo catalyst.
  • the active species is most preferably the free radicals and electron holes in the Ti0 2 .
  • the energy is preferably light, most preferably comprising one or more wavelengths within the range of approximately 200-400 nm and/or spanning the UV- visible range.
  • the light source is a UV lamp of 15 W power.
  • the UV lamp is housed in a channel defined by the central core of the waveguide.
  • one or more LEDs may be used; these may emit light over more than one wavelength.
  • the apparatus also comprises means for contacting said active species with said feed, thereby to actively effect the decontamination.
  • the catalytic material may be applied to one or more surfaces of the catalytic substrate.
  • the catalytic material is provided as a slurry within the photocatalytic unit.
  • the catalytic material is illuminated substantially perpendicular to its longitudinal axis.
  • the inventive apparatus requires sufficient turbulent flow in the module to keep the photocatalyst slurry from settling at the bottom, which in turn requires cross-flow to prevent the membrane/filter from becoming too caked up with photocatalytic material.
  • the inventive module should comprise three easily detachable elements: the impeller; the electricity for the light; and the pipes for inlet and outlet (and any mechanical support).
  • the impeller/s may operate either by a motor for each impeller, or via a manifold drive system comprising a single motor for an entire bank of modules.
  • the feed comprises said one or more predetermined reactants in aqueous phase.
  • the contaminated or polluted liquid generally comprises one or more organic contaminants.
  • the one or more organic contaminants may be organic molecules and/or organisms. Alternatively, the organic molecules may comprise carcinogenic, endocrine- disrupting or non-aesthetic compounds.
  • the one or more organisms may comprise bacteria, protozoa and/or viruses.
  • operating conditions may be adjusted according to factors such as organics load (sensor detected) or flow rate so as to get a specific desired log removal value.
  • flow rate i.e., residence time
  • the banks of modules can be arranged such that the individual modules are able to function either in series or in parallel.
  • a feed will flow from one module to the next, receive substantially equivalent treatment (or even adjusted ratios of photolysis/photocatalysis in each module) before flowing into the next module.
  • each successive module iteratively decreases the level of contamination in the feed such that the end product may be potable water should sufficient modules be included in series.
  • there are exponentially diminishing returns in subjecting the feed to each successive module. Re-oxygenation of the fluid within such a series may also be necessary to maintain the production of the reactive species generated in the photocatalysis reaction.
  • each module treats a discrete flow of feed substantially to completion or to within the required contaminant concentration limit. Whether modules are to be arranged in series or parallel depends upon factors including flow rate; residence time; contaminant composition, load, concentration; photocatalytic area; fluid oxygen concentration; and potable standard of the product required.
  • the surface area per unit volume ratio is optimised with respect to the photocatalyst, and this arrangement also allows less of the waveguide to be coated in Ti0 2 , which itself, facilitates a relatively increased amount of photolysis.
  • the inventive system is adapted to provide for more than one remediation process.
  • a photocatalytic process, a photolytic process and a peroxide-based process can each be accommodated within the single reaction unit containing one or more modules; these processes may take place simultaneously or in a defined sequence.
  • the resultant "hybrid" reactor is expected to be especially advantageous in places such as third- world or dessert-laden countries in which the supply of water is likely to be polluted with more than one species of contaminant.
  • Also related to the present invention is the need to facilitate intermittent chemical and/or physical cleaning to re-activate the catalyst.
  • Iron, for example, in the feed may poison the catalyst.
  • an auto -acid wash in the module may be initiated.
  • oxygen may be desirable to supply oxygen to the feed or directly into the module. In the latter case the modules would also have a gas line going in.
  • cost per quantity of feed treated comprises initial capital expenditure plus ongoing operating and maintenance costs. Also important is the time and expenditure required to develop new water treatment technologies, which directly takes account of the degree to which earlier non-patented engineering technologies may be incorporated, both from photonics and membrane water treatment processes.
  • a further advantage resides in the use of existing filter and membrane cartridge peripheral/support engineering technologies. This results in lower development and unit costs. It also allows a single or low count of UV lamp to illuminate an effectively large volume of water. Yet a further advantage of the present invention resides in it using existing cartridge designs, the ancillary engineering and maintenance and service procedures (pipes, pumps, valves, control systems, management software and hardware) will also be familiar and have relatively low cost. This engineering has a direct effect upon the volume-cost curve. Familiar engineering also lowers the barrier to adoption of this new technology within the marketplace.
  • the association of the catalytic substrate with the waveguide is alternatively such that the catalytic substrate is suspended within the waveguide.
  • the catalytic substrate is dispersed within the feed of contaminated fluid undergoing remediation.
  • any such method would necessarily comprise the further step of retrieving and/or recycling the catalytic substrate from the remediated product.
  • a suspension of photocatalyst was first tested using 1 g/L Ti0 2 (titania) with 1.5 L/min flow rate; an initial turbidity (pre-injection of catalyst) of 4.54 NTU; a backwash frequency of 60 sec; a backwash duration of 1 sec; and an air pressure of 4.5 bar.
  • the Applicant observed significant internal turbidity decrease internally within 60 min; this may be the result of accumulation on the surface of the membrane.
  • the pressure spike on the outlet side is less than the inlet pressure; this may simply be a relaxation of the membrane rather than an actual backwash.
  • Increasing the backwash time did not appear to improve the pressure spike generated during the backwash procedure.
  • An additional 1 g of titania was added at 45 min to increase the suspended loading and attempt to maintain reasonable levels of suspension during the photocatalysis trials. With the additional of further titania, higher turbidities were observed.
  • This experiment was conducted as per Example 1, with the feedwater changed from tap water to 20 ppm phenol solution; 3.62 g titania, with 1.1 L/min flow rate; and a backwash frequency of 60 sec, a backwash duration of 1 sec and an air pressure of 9 bar.
  • the phenol solution (10 L) was allowed to recirculate within the reactor for 10 min.
  • An initial permeate sample was collected and the lamp was switched on.
  • the backwash pressure was 6 bar.
  • the water temperature during the experiment increased from 30 °C to 40 ° C over 120 minutes. This is due to the small initial volume and recirculation of the feed (i.e., batch experiment). The turbidity within the vessel was observed to increase over time.
  • the present invention also provides a modular apparatus for effecting substantially continuous decontamination of a contaminated fluid, the apparatus comprising an impeller and an energy source, each operationally engagable with means for effecting at least one light-enabled process, such as an advanced oxygenation process between an inlet port and an outlet port in the apparatus.
  • a modular apparatus provides a chemical reactor vessel that facilitates contaminants in an aqueous gas or aqueous liquid feed to be destroyed or broken down by an advanced oxidation process, undertaken in a photocatalytic reaction.
  • the reactor vessel enables UV light to be transmitted from a light source, to a waveguide, or series of waveguides optionally having a photocatalytic surface, or comprising a photocatalytic slurry, that enables photocatalysis, which in turn produces a light-enabled process such as an AOP to destroy organics present in the gaseous or fluid feed.
  • a system according to the present invention should have significant cost advantages. For a specific required removal rate of small organic molecules in Reverse Osmosis effluent, lower investment cost should be achieved, together with relatively reduced operating and maintenance costs.
  • the present invention is advantageous in that it creates an efficient means to bring a reaction system together with activating light in a low cost cartridge, with the ability to adjust the relative surface areas and volumes with relative ease, in order to maximise the efficiency of the process.
  • the inventive system may have efficacy for any fluid reaction system where photocatalysis and/or photolysis is required.
  • the means in which the photocatalyst is employed is optional; it can be placed on the surface of the optical transporter, as described, or even in suspension.
  • the effluent phase can be a liquid or a gas.
  • the energy source can be any one or more wavelength/s of light(UV and/or visible) that is suitable to induce photocatalysis.
  • the present invention provides means, preferably in the form of a "hybrid" and/or modular system or apparatus, whereby at least one UV process can be employed upon a contaminated fluid.
  • Such light-enabled processes include UV-photolysis (i.e., the breakdown of chemicals with direct UV), UV- photocatalysis, AOP (i.e., UV-chemical) and UV-disinfection (i.e., the inactivation of bacteria and viruses by direct UV).
  • the hybrid reactor provides for more than one such process to be conducted upon a contaminated fluid.
  • the ratios and proportion of each treatment e.g., UV intensity, retention times, flow rate, etc.
  • inventive modules may be arranged in series or parallel, e.g., where a first module performs photocatalysis; the resultant treated fluid transferred to a second module in which is performed photolysis, etc.
  • separate means for effecting any one of the light-enabled processes may be placed in series within the one module within constraints.
  • means for effecting any or all of the UV processes may be within the same overall "means for effecting at least one UV process" as defined in the claims. It will also be appreciated that some degree of overlap between the light-enabled processes is inevitable, i.e., direct UV may accomplish both photolysis and disinfection in a singular operation.
  • the potential benefits of the present invention include: flexibility to treat feeds with various species that need reducing in the same unit, e.g., viruses and chemicals, rather than separate treatment units; standardisation by way of saving costs and easing operations by having the same module and unit for all types of UV treatment; reduction of manufacturing costs by way of standard module and manifold systems allowing faster tracking down the cost-curve; and the flexibility to change retention times, operational modes and series/parallel modes, in response to changes in water quality and water quality regulations.

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Abstract

La présente invention porte sur un appareil « hybride » servant à distribuer une ou plusieurs espèces actives à un réservoir ou une circulation d'une matière fluide contaminée, pour de cette manière effectuer au moins une transformation chimique ou biologique prédéfinie et pour purifier en grande partie ladite matière fluide contaminée. De préférence, les espèces actives sont des radicaux libres ou un rayonnement ultraviolet. La matière catalytique est de préférence une suspension épaisse de TiO2 et l'énergie est de préférence de la lumière UV ou visible ayant une longueur d'onde approximative de 200 à 400 nm. En variante, les espèces actives peuvent être un ou plusieurs produits chimiques, tels qu'un peroxyde. Le procédé est approprié pour remédier à des contaminants organiques tels que des substances carcinogènes, des composés perturbateurs endocriniens, des pathogènes et des bactéries.
PCT/AU2011/000778 2010-06-24 2011-06-24 Procédé et appareil pour effectuer une réaction chimique WO2011160186A1 (fr)

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AU2010903820A AU2010903820A0 (en) 2010-08-25 Method and apparatus for effecting a chemical reaction II
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US11820655B2 (en) 2017-05-11 2023-11-21 Global Analyzer Systems Limited Method of controlling recombination or back reactions of products and byproducts in a dissociation reaction
US11572286B2 (en) * 2018-02-23 2023-02-07 1934612 Ontario Inc. Systems and methods for a low environmental impact treatment of contaminated fluid
US11548800B2 (en) * 2019-04-26 2023-01-10 Geyser Remediation LLC Water purification apparatus and method

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