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WO2018126126A1 - Génération de dioxyde de chlore - Google Patents

Génération de dioxyde de chlore Download PDF

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Publication number
WO2018126126A1
WO2018126126A1 PCT/US2017/068943 US2017068943W WO2018126126A1 WO 2018126126 A1 WO2018126126 A1 WO 2018126126A1 US 2017068943 W US2017068943 W US 2017068943W WO 2018126126 A1 WO2018126126 A1 WO 2018126126A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction chamber
float
chamber
flow
flow chamber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2017/068943
Other languages
English (en)
Inventor
Neil ANDRE
Aimee E. BELISLE
Randy D. BELISLE
William J. Hulsman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Dioxcide Inc
Original Assignee
International Dioxcide Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by International Dioxcide Inc filed Critical International Dioxcide Inc
Publication of WO2018126126A1 publication Critical patent/WO2018126126A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/022—Chlorine dioxide (ClO2)
    • C01B11/023—Preparation from chlorites or chlorates
    • C01B11/024—Preparation from chlorites or chlorates from chlorites
    • 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
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens

Definitions

  • Chlorine dioxide is a potent oxidizing agent that is commonly used as a water treatment disinfectant.
  • gaseous CIO2 ignites at concentrations greater than 10% by volume. Therefore, CIO 2 cannot be shipped and must be prepared on site.
  • Aqueous solutions of CIO 2 generated at the point of use can be safely handled and applied as long as conditions that may lead to decomposition do not develop.
  • Chlorine dioxide is generally produced from sodium chlorite (NaC10 2 ) and an acid, usually hydrochloric acid (HC1), which can be expressed by the chemical equation:
  • a CIO 2 generator uses pumps or an eductor to properly flow and mix reactants in a preliminary reaction chamber.
  • the generated CIO 2 is diluted at the outlet motive water stream for either short-term storage or direct process application.
  • Eductor-based systems provide safe operation because the reactor is under vacuum while CIO2 is generated.
  • the combined vacuum and flow dynamics of the eductor prevent explosive levels of CIO 2 vapor from forming by rapidly diluting CIO 2 into the motive water supply.
  • a high concentration of CIO 2 is therefore not allowed to develop and persist in the reaction zone at elevated pressure.
  • the motive water driving the eductor operation also promotes immediate CIO 2 dilution, which prevents high concentrations of CIO 2 from persisting or accumulating.
  • the motive water supply may be cycled between an "on” state and an "off state to control CIO 2 administration.
  • Automated valves on each of the reactant precursor feed lines close to halt reactor operation when suitable motive water flow is not provided or process water flow is not detected.
  • Standard eductor operations require enough motive water flow to provide the appropriate suction force for the chemical feeds, and safe operational guidelines limit the final stream CIO2 concentration to no greater than 3,000 ppm.
  • CIO2 concentration in the AC reaction chamber can greatly exceed this value, especially when acid is fed near stoichiometric ratio to chlorite and the reactor is not purged when the system is turned off. Higher reactant precursor concentrations will also elevate the hazards associated with these reactors; therefore, 7.5% sodium chlorite is typically paired with 10-15% HC1 solution for these systems. Larger CIO2 generation capacity requires proportionately larger reaction chamber volumes, leading to increased operational hazards.
  • AC systems are generally limited to lower production levels, such as 50 lb/day CIO2 or lower.
  • US 7,128,879 has incorporated float-dependent valve controls into the operation of a CKVgenerating system. These float sensors or float-dependent valves are used to dispense proper amounts of water and/or CIO2 chemical in response to levels detected in a basin or reservoir. While these float sensors may offer a way to ensure there is a proper amount of dilution water before chemical addition and preventing overflow of a basin, there is no safety mechanism attributed to the reaction chamber itself, which is where destructive failures can be the most severe due to the presence of high concentration of C10 2 . US 7,128,879 also pertains to treatment of a basin whereas the present invention seeks to treat an active process water supply line.
  • the CIO2 generator design combined with the utility of a float-dependent valve described herein is novel and has not been previously. Additionally, the inverted orientation of the floating ball check valve versus how it is typically deployed is non-obvious and is a unique approach to a novel reactor design. Instead of serving as a check valve, it is a safety relief valve during normal operations whereby it remains closed during normal operation but will open in case of elevated pressure in the reaction chamber. Also, it serves as a safety interlock during start-up by ensuring proper dilution water is present in the flow chamber before chemical production initiates.
  • the float-dependent valve being an isolated mechanical device, does not require any wiring or connection to secondary equipment or sensors to perform these functions.
  • the float-dependent check valve will only close and allow chemical flows to commence when there is both a proper amount of dilution water in the flow chamber and a vacuum is being pulled over the reaction chamber.
  • FIG. 1 and FIG. 2 illustrate embodiments of a device 1, including a reaction chamber 10.
  • the reaction chamber 10 may be held under vacuum.
  • An acid feed 102, a chlorite feed 104, and a motive water conduit 108 may open into the reaction chamber 10 to provide the reactants for production of CIO2.
  • the acid feed 102 and the chlorite feed 104 may be mixed in the reaction chamber 10.
  • An eductor 110 may be attached to the reaction chamber 10 and open into a flow chamber 16 to introduce CIO2 produced in the reaction chamber 10 into treatment water passing through the flow chamber 16.
  • the reaction chamber 10 and eductor 110 may be substantially submerged during production of CIO2 by water from the flow chamber 16, and in particular embodiments, the reaction chamber 10 and eductor 108 may be completely submerged in water from the flow chamber 16.
  • the reaction chamber 10 may comprise a material such as, for example, a baffling material or a packing material. In some embodiments, such a material may promote sufficient mixing and residence time to maximize conversion efficiency to C10 2 .
  • the eductor 110 may be connected to the reaction chamber 10 to allow water flowing through the motive water conduit 108 to create a vacuum in the reaction chamber 10.
  • the device may further include a valve 18 that provides a second connection between the reaction chamber 10 and flow chamber 16 and open to the flow chamber 16 to relieve excess pressure during operation of the device 1.
  • the valve 18 may respond to fluid levels in the flow chamber 16, closing the valve and sealing the reaction chamber 10 only when the fluid level is sufficiently high to produce CIO2 safely.
  • the flow chamber 16 When fluid level is sufficiently high, the flow chamber 16 holds enough liquid to safely dilute the entire contents of the reaction chamber 10 to a CIO2 concentration below 3,000ppm, in the case of reaction chamber 10 contents draining entirely into the flow chamber 16 during low or non-flow condition.
  • the fluid may be water.
  • the check valve 18 may act as an emergency vent if excessive pressure is built up in the reaction chamber 10 by opening to the flow chamber 16, allowing reactor contents to empty into the flow chamber 16 and be safely contained.
  • the reaction chamber 10 may be configured to separate from the device and release its contents if a high-pressure event occurs that is beyond the venting capability of the valve 18.
  • valve 18 may be a floating ball check valve.
  • a floating ball within the check valve 18 may close when the flow chamber 16 is sufficiently filled with water and motive water is supplied, thereby sealing the reaction chamber 10 and allowing the motive water conduit 108 to produce a vacuum that initiates draw of chemicals and CIO2 generation.
  • the valve 18 may be actuated by a water level sensor located in the flow chamber (not depicted).
  • the valve may be located on any surface of the reaction chamber.
  • the valve may comprise one or more of a check valve, a ball check valve, a gasket, a flexible gasket, or combinations thereof.
  • the gasket may be a flexible gasket to allow the release of contents into the flow chamber.
  • the reaction chamber may be connected directly to a treatment water flow as illustrated in FIG. 1, having a treatment water flow inlet 130 and a treatment water flow outlet 133.
  • the CIO2 produced in the reaction chamber 10 is introduced into the treatment water flow directly.
  • the reaction chamber 10 may be an accessory to the main treatment water flow.
  • the reaction chamber 10 may be fluidly connected to a treatment water main such that a portion of the water flowing through the main is transported to the reaction chamber 10.
  • the CIO2 produced in the reaction chamber 10 may be diluted, and then transported through an outlet into the treatment water main where the diluted CIO2 treats the treatment water.
  • a device as described herein may further include one or more control systems.
  • control systems may be configured to automate the chemical feed rate of CIO 2 and may employ sensors sensitive to, for example, ORP, pH, and/or CIO 2 concentration or other sensors.
  • a control sensor may be used to turn the device, or a system therein, "on” or “off as necessary.
  • one or more flow rate control valves may be used on the treatment water flow inlet line and/or the treatment water flow outlet line to allow for variable control of a CIO 2 feed rate into the process stream being treated.
  • the components and chambers described herein may be modular in nature, such that they may be individually removed, repaired, or replaced.
  • the device described herein may comprise one or more of each of the components and chambers.
  • the range and flow of CIO 2 production may be modified by changing the eductor, increasing or decreasing the treatment and water flow inlet and outlet, and any other modification apparent to one of skill in the art.
  • the device of embodiments described above provides enhanced safety features. For example, submerging the reaction chamber 10 and eductor 110 in treatment water insulates the reaction chamber 10.
  • a vertically oriented reactor assembly allows an inverted floating ball check valve 18 to prevent chemical eduction when the flow chamber is insufficiently flooded to safely dilute the generated CIO 2 .
  • the eductor 110 will not hold a vacuum and would not draw precursor chemicals to make CIO 2 .
  • Incorporating the eductor flow into the main process flow ensures that CIO 2 generation will only take place when there is also suitable dilution process water for the operation.
  • Further embodiments are directed to methods for treating water with CIO 2 .
  • Such methods may include inducing a vacuum when flow chamber 16 water level reaches the height of the valve 18 and producing CIO 2 under the vacuum.
  • the step of inducing a vacuum may be carried out by closing a check valve between a flow chamber and a reaction chamber and producing a vacuum in the reaction chamber.
  • Closing a check valve can be carried out by any mechanism.
  • a mechanical or electronic valve that is configured to close upon contact of the valve or a sensor with water can be used.
  • the valve 18 can include a float that seals an orifice in the reaction chamber when the treatment water level reaches the reaction chamber.
  • the seal formed by the check valve may become progressively tighter as an increasing vacuum is applied to or produced by the reaction chamber.
  • Producing a vacuum in the reaction chamber can be carried out by any mechanism. For example, producing a vacuum can be carried out using a pump, and in certain embodiments, producing a vacuum can be carried out by Venturi effect, using the motive force of water entering the reaction chamber.
  • the method may include filling at least a portion of the reaction chamber with water while also drawing reactants into the reaction chamber.
  • the step of filling at least a portion of the reaction chamber can be carried out by transporting a portion of the treatment water to the reaction chamber, and in some embodiments, the water used for filling at least a portion of the reaction chamber may include the water used to produce a vacuum by Venturi effect.
  • the step of drawing reactants into the reaction chamber can be carried out as a result of inducing a vacuum.
  • the reactants may include, for example, sodium chlorite (NaClCh) and hydrochloric acid (HC1).
  • the method may further include combining the reactants with water to produce CIO2.
  • combining the reactants with water can be carried out innately upon filling at least a portion of the reaction chamber with water and drawing reactants into the reaction chamber.
  • the reaction chamber may include a mixing device, such as a mechanical stirrer or water jets.
  • the reaction chamber may also contain packing material, baffles, serpentine channels and/or other means to promote suitable reactant mixing and adequate residence time in the reaction chamber before dilution into the motive water supply.
  • the method of various embodiments may include transporting the CIO2 to the treatment water.
  • the transporting can be carried out by pumping the CKVcontaining water from the reaction chamber to the treatment water.
  • transporting can be carried out by siphoning ClC ⁇ -containing water into treatment water through an eductor immersed in the treatment water.
  • FIG. 1 shows a schematic for a two-part reactor assembly with a reaction chamber upstream of the eductor.
  • FIG. 2 shows a detailed view of the eductor and reactant feed lines that reside at the top of the reaction chamber in accordance with the present disclosure.
  • chlorine dioxide C10 2
  • C10 2 chlorine dioxide
  • floating ball check valve means a check valve that uses a ball as the internal component that seals against the valve body to stop flow and in which the ball has a density lower than the fluid medium being processed such that the ball floats.
  • reaction chamber means a vessel that either fully or partially surrounds the reaction chamber and through which a bulk of the process water being treated flows. It is sized to allow for adequate dilution of the reaction chamber, such that in a non-flow condition, complete emptying of the reaction chamber contents into the flow chamber would render a CIO2 concentration no higher than 3,000 ppm.
  • reaction chamber means a vessel in which precursor chemicals are combined to generate CIO2.
  • Example 1 Process flow interruption
  • the acid feed was lowered to simulate a system that had not been properly configured to correct precursor feed ratios.
  • the CIO2 concentration within the reaction chamber can be considerably higher if there is sufficient dwell time to convert the chlorite to CIO2.
  • the CIO2 can continue to form over time after shutdown.
  • the float-dependent valve 18 sufficiently drained and diluted the reaction chamber 10 contents into the flow chamber 16 before any decomposition events occurred.
  • Example 3 Pressure event within the reaction chamber
  • the iteration without the float-dependent valve 18 is similar to traditionally constructed AC CIO2 generators, in which the reaction chamber consists of only two feed inlets and a single outlet being diluted into a process water supply. Therefore, in the case of a decomposition event within the reaction chamber 10, the modified design would readily release its contents into the process water flow, providing much quicker dilution and lower internal shock pressures as compared to a traditionally designed AC CIO2 generator.
  • the float-dependent valve 18 also allows for faster and easier drainage when preparing the device or system for maintenance or inspection. Upon draining the flow chamber 16, the check valve float-dependent valve 18, flow out of the reaction chamber 10 would slow to a trickle, or may even require complete disassembly to empty its contents.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

L'invention concerne des dispositifs et des méthodes pour utiliser en toute sécurité une chimie génératrice d'acide/chlorite ClO2 pour le traitement de l'eau, par lesquels une valve empêche un tirage chimique à moins qu'il y ait à la fois un vide à l'intérieur de la chambre de réaction ainsi qu'un volume d'eau approprié dans la chambre d'écoulement pour une dilution. La valve dépendant du flotteur peut également permettre une ventilation directe de la chambre de réaction à la chambre d'écoulement en cas de pression élevée dans la chambre de réaction. Cette approche fournit une conception de générateur de ClO2 intrinsèquement plus sûr pour des systèmes qui utilisent des zones de réacteur à haute résistance avec une concentration de ClO2 supérieure à 3 000 ppm.
PCT/US2017/068943 2016-12-30 2017-12-29 Génération de dioxyde de chlore Ceased WO2018126126A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201615394885A 2016-12-30 2016-12-30
US15/394,885 2016-12-30

Publications (1)

Publication Number Publication Date
WO2018126126A1 true WO2018126126A1 (fr) 2018-07-05

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PCT/US2017/068943 Ceased WO2018126126A1 (fr) 2016-12-30 2017-12-29 Génération de dioxyde de chlore

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WO (1) WO2018126126A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4269419A (en) * 1979-07-09 1981-05-26 Brant Robert J Fluid pressure sleeve and rubber gasket pipe joint
US5192007A (en) * 1990-12-21 1993-03-09 Continental Plastic Containers, Inc. Valve assembly for inverted dispensing from a container with a pump
US5462100A (en) * 1993-09-15 1995-10-31 General Motors Corporation Fuel fill vapor recovery system with differential pressure control valve
US5803319A (en) * 1996-01-19 1998-09-08 Summit Packaging Systems, Inc. Invertible spray valve and container containing same
US6274009B1 (en) * 1999-09-03 2001-08-14 International Dioxide Inc. Generator for generating chlorine dioxide under vacuum eduction in a single pass
US20050079122A1 (en) * 2003-10-10 2005-04-14 Dimascio Felice Systems and methods for generating chlorine dioxide
US20050079124A1 (en) * 2003-08-06 2005-04-14 Sanderson William D. Apparatus and method for producing chlorine dioxide
US7128879B1 (en) * 2000-03-08 2006-10-31 Bio-Cide International, Inc. Chemical generator using hydro-logic system
US20120148477A1 (en) * 2009-06-23 2012-06-14 Rosenblatt Aaron A Aqueous solutions of chlorine dioxide with enhanced stability and methods for producing and packaging them

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4269419A (en) * 1979-07-09 1981-05-26 Brant Robert J Fluid pressure sleeve and rubber gasket pipe joint
US5192007A (en) * 1990-12-21 1993-03-09 Continental Plastic Containers, Inc. Valve assembly for inverted dispensing from a container with a pump
US5462100A (en) * 1993-09-15 1995-10-31 General Motors Corporation Fuel fill vapor recovery system with differential pressure control valve
US5803319A (en) * 1996-01-19 1998-09-08 Summit Packaging Systems, Inc. Invertible spray valve and container containing same
US6274009B1 (en) * 1999-09-03 2001-08-14 International Dioxide Inc. Generator for generating chlorine dioxide under vacuum eduction in a single pass
US7128879B1 (en) * 2000-03-08 2006-10-31 Bio-Cide International, Inc. Chemical generator using hydro-logic system
US20050079124A1 (en) * 2003-08-06 2005-04-14 Sanderson William D. Apparatus and method for producing chlorine dioxide
US20050079122A1 (en) * 2003-10-10 2005-04-14 Dimascio Felice Systems and methods for generating chlorine dioxide
US20120148477A1 (en) * 2009-06-23 2012-06-14 Rosenblatt Aaron A Aqueous solutions of chlorine dioxide with enhanced stability and methods for producing and packaging them

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