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US20090159538A1 - Method of treating water with chlorine dioxide - Google Patents

Method of treating water with chlorine dioxide Download PDF

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Publication number
US20090159538A1
US20090159538A1 US12/339,533 US33953308A US2009159538A1 US 20090159538 A1 US20090159538 A1 US 20090159538A1 US 33953308 A US33953308 A US 33953308A US 2009159538 A1 US2009159538 A1 US 2009159538A1
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Prior art keywords
water
clo
reaction chamber
reactor
solution
Prior art date
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Abandoned
Application number
US12/339,533
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English (en)
Inventor
Hans Duve
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.)
Evonik Operations GmbH
Original Assignee
Infracor GmbH
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Filing date
Publication date
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Application filed by Infracor GmbH filed Critical Infracor GmbH
Assigned to INFRACOR GMBH reassignment INFRACOR GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DUVE, HANS
Publication of US20090159538A1 publication Critical patent/US20090159538A1/en
Priority to US13/109,508 priority Critical patent/US8663481B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/003—Downstream control, i.e. outlet monitoring, e.g. to check the treating agents, such as halogens or ozone, leaving the process
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/05—Conductivity or salinity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection

Definitions

  • the invention relates to a method of treating water with chlorine dioxide (ClO 2 ).
  • Chlorine dioxide is used in water treatment because of its high bactericidal, virucidal and algicidal activity. Due to the explosive tendency of gaseous chlorine dioxide (c>300 g/m 3 ) and chlorine dioxide solutions (c>26 g/l), chlorine dioxide cannot be stored in compressed form or in solutions of relatively high concentration. Owing to these chemical properties, chlorine dioxide must be produced at the point of use. This is conventionally achieved by mixing basic chemicals in special reactors of chlorine dioxide generation systems. The chemical storage vessels, the metering appliances and also the reactor of the chlorine dioxide systems form a locally linked unit of apparatus which is generally erected in rooms accessed by people.
  • a strong acid is used together with sodium chlorite.
  • the strong acid is usually hydrochloric acid or sulphuric acid.
  • hydrochloric acid When hydrochloric acid is used the reaction stoichiometry is as follows:
  • chlorine dioxide can be formed with the use of sulphuric acid in accordance with the following reaction:
  • This method uses gaseous chlorine together with sodium chlorite.
  • the reaction proceeds in two stages, first with the formation of hydrochloric acid.
  • hypochloric acid HOCl
  • sodium chlorite sodium chlorite
  • sodium hypochlorite NaOCl
  • sodium chlorite sodium hypochlorite
  • the synthesis reactions for generating chlorine dioxide are generally carried out in reactors which are operated either continuously or by the batch method.
  • various measures are implemented at the generation systems themselves, and also at the sites where the chlorine dioxide generation systems are erected, e.g. complex servicing work on the generation systems including regular replacement of the reactors, spatially isolated erection sites for the generation systems, forced aeration and air monitoring of the atmosphere of the erection site by continuous gas analysis.
  • one object of the present invention is therefore to design the treatment of water with chlorine dioxide so as to be safer and more efficient.
  • An additional object of the present invention is, at a high time-specific generation rate of the chlorine dioxide methods, to minimize the hazard potential of this type of water treatment and simultaneously to reduce the expenditure on the safety installations.
  • FIG. 1 shows an outline structure of an embodiment of a device for carrying out the method according to the invention, without being restricted to defined starting chemicals (reactants).
  • FIG. 2 shows an outline structure of a further preferred device for carrying out the present invention method.
  • FIG. 3 shows the solubility limits of chlorine dioxide in an aqueous solution as a function of pressure and temperature for the example of chlorine dioxide concentrations of 70 g/l and 80 g/l.
  • the present invention relates to a method of treating water with chlorine dioxide (ClO 2 ), comprising:
  • the combination of the concentrations of the starting chemicals and dilution water used if desired is selected in such a manner that the concentration at the reactor outlet of the chlorine dioxide formed is greater than 3 g/l of solution, preferably greater than 26 g/l of solution, and particularly preferably greater than 80 g/l of solution.
  • the reaction chamber in which the ClO 2 is generated is a reactor without a pressure control appliance and equipped with a free outlet and the combination of the concentrations of the starting chemicals and dilution water used if desired is selected in such a manner that the concentration at the reactor outlet of the chlorine dioxide formed is greater than 3 g/l of solution, preferably greater than 26 g/l of solution, and particularly preferably greater than 80 g/l of solution.
  • the reaction chamber in which the ClO 2 is generated is a reactor without a pressure control appliance and equipped with a free outlet
  • the water surrounding the reaction chamber exerts a pressure on the chlorine dioxide-containing solution in the reaction chamber of a magnitude that the solubility limit of chlorine dioxide in water at a given temperature is not exceeded
  • the combination of the concentrations of the starting chemicals and dilution water used if desired is selected in such a manner that the concentration at the reactor outlet of the chlorine dioxide formed is greater than 3 g/l of solution, preferably greater than 26 g/l of solution, and particularly preferably greater than 80 g/l of solution.
  • the method of the present invention enables safe working by avoiding the escape of ClO 2 into working rooms or the surrounding areas and eliminates adverse consequences of explosive decompositions.
  • the reaction chamber in which the ClO 2 is generated is completely surrounded by water and the water which surrounds the reaction chamber is simultaneously the water which is to be treated.
  • the resultant ClO 2 is passed directly without bypasses from the reaction chamber in which the ClO 2 is formed into the water which is to be treated, since the outlet is directly on the end of the reaction chamber and is therefore likewise surrounded by the water which is to be treated.
  • a leak of the reaction chamber, in particular of the reactor, can be simply and safely handled in the water which is continuously flowing past its wall.
  • the chlorine dioxide, in particular, which escapes in the event of a leak of the reaction chamber is diluted to a non-critical concentration and transported away.
  • reaction chamber leaks up to reaction chamber explosions are virtually neutralized by the large amount of water which is to be treated relative to the amount of chlorine dioxide which is present in the reaction chamber.
  • the features of the present method enable safe working, even with the use of concentrated starting chemicals without dilution water, by avoiding the escape of ClO 2 into working rooms or the surroundings and eliminates adverse consequences of explosive decompositions.
  • reaction chamber The use of one reactor as reaction chamber is preferred.
  • the resultant ClO 2 is passed directly into the water which is to be treated without bypasses or further additional lines directly from the reaction chamber in which the ClO 2 is formed, since the outlet is situated directly at the end of the reaction chamber, preferably the reactor, and is therefore likewise surrounded by the water which is to be treated.
  • This measure is a preferred embodiment of the method.
  • a preferred embodiment of the present invention is a method of treating water with chlorine dioxide (ClO 2 ), comprising:
  • appliances are suitable by which the above described effects can be achieved, such as, for example, fixed mounted lines or flexible tube systems.
  • units for distributing the chlorine dioxide solution e.g. water-jet liquid pump, circulation pump, can also be placed.
  • the expression, passed into the water which is to be treated, means that the ClO 2 from the reaction chamber is introduced into the water which is to be treated more preferably by the starting chemicals introduced directly via an offtake into the reaction chamber and if desired by the dilution water directly or via an offtake introduced into the reaction chamber.
  • the renewal rate at the outlet of the reaction chamber, preferably the reactor outlet, or the offtake, of the water which is to be treated can be increased by technical appliances.
  • the reaction chamber preferably the reactor, is preferably operated without a pressure control appliance.
  • a free outlet at the end of the reaction chamber, preferably the reactor outlet, or the offtake, ensures that the pressure in the reaction chamber can only increase up to the value which is exerted on the reaction chamber by the surrounding water.
  • the concentration of the chlorine dioxide which forms in the reaction chamber preferably the reactor can be set in combination with pressure and temperature of the surrounding water in such a manner that the solubility limit of chlorine dioxide in water is not exceeded. As a result, the formation of a 2-phase system due to a chlorine dioxide gas phase which forms can be prevented.
  • the pressure which is exerted on the reaction chamber by the water which is to be treated can be altered, for example, by the immersion depth of the reaction chamber, preferably the reactor, in a water reservoir.
  • the pressure conditions for a reactor which is used in a pipe can be influenced, for example, by shut-off elements integrated into the pipe.
  • the concentration of the chlorine dioxide solution leaving the reaction chamber, preferably the reactor can be abruptly shifted to a milligram range. This can be achieved, for example, by the reaction chamber, preferably the reactor, being used in a pipe through which water to be treated flows at a rate which corresponds to the desired renewal rate.
  • a reaction chamber preferably a reactor, immersed in a water reservoir can be placed locally in the vicinity of the suction side of a circulation pump in order to ensure the corresponding renewal rate at the end of the reaction chamber, preferably the reactor outlet, or the offtake, of the water to be treated.
  • a circulation pump is not present, a variety of conventional alternatives are available, such as, for example, water-jet liquid pumps or other circulation appliances, which induce the desired renewal rate at the end of the reaction chamber, preferably the reactor outlet or the offtake, of the water which is to be treated.
  • the starting chemicals (reactants) of alkali metal chlorite salt preferably sodium chlorite
  • the acid is preferably hydrochloric acid in a concentration of 3.5% to 42%.
  • concentrated starting chemicals are used and the hydrochloric acid-chlorite method (1) is employed.
  • concentration of hydrochloric acid is then about 33-42% and that of the sodium chlorite solution is about 25-40%.
  • the starting chemicals are not diluted before or in the reaction chamber, preferably the reactor.
  • the material of which the reactor is fabricated comprises materials which exhibit good stability to the respective reaction solutions.
  • the reaction material used is, for example, titanium, alloy 31, glass or chemistry materials e.g. polymers such as e.g. PVDF or PTFE.
  • the ClO 2 is removed from the reactor by any mechanism which is able to remove an aqueous solution from a reactor.
  • the reaction is carried out continuously and ClO 2 is removed continuously from the reactor. After the ClO 2 leaves the reactor, it is metered directly into the water which is to be treated, or transported to one or more other sites via an offtake situated at the reactor outlet.
  • a tubular reactor is preferably used according to the present invention.
  • the tube of the tubular reactor is constructed in such a manner that it has a sufficient length to ensure sufficient residence time in the reactor in order, with respect to flow rate of the reaction solution, its concentration of reactants and the temperature of the reaction solution, to react the components sufficiently.
  • a particularly preferred reactor which can be used for producing a suitable generator of aqueous chlorine dioxide on site is a (temperature-controlled) tubular reactor which contains one or more tube coils.
  • the conductivity value is preferably measured in the solution leaving the reaction chamber before it is released to the water which is to be treated.
  • an inductive measuring method can be used. From the conductivity values measured, information can be obtained with respect to the chemical reaction of the reactants used and also if desired with respect to the amount of dilution water used.
  • the chlorine dioxide solution leaving the reactor outlet, or the offtake, is diluted in such a manner that the renewal rate at the reactor outlet of the water which is to be treated is from about 0.1 m 3 /h to 20 m 3 /h per gram and hour of generated chlorine dioxide, preferably from 1 m 3 /h to 4 m 3 /h per gram and hour of generated chlorine dioxide.
  • the method according to the invention can be carried out, for example, by use of the devices pictured in FIG. 1 and FIG. 2 .
  • FIG. 1 shows an outline structure for carrying out the method according to the invention, without being restricted to defined starting chemicals (reactants).
  • the units having the specified number are therefore to be employed correspondingly generally in their function for all methods having the various possible starting chemicals (reactants) and can readily be recognized by those skilled in the art.
  • the device for treating water with chlorine dioxide comprises two tanks for the starting chemicals (reactants), in particular a chlorite storage tank 1 having a transport pump 4 and an acid storage tank 2 having a transport pump 5 .
  • the water pump 6 is supplied via the water connection 3 .
  • All three transport pumps are connected via an individual line to the bottom side of the reactor 7 .
  • the concentration of the resultant chlorine dioxide solution is set to greater than 3 g/l, preferably greater than 26 g/l, and particularly preferably to greater than 80 g/l.
  • the reactor is completely surrounded by the water which is to be treated 9 which flows through an intermediate store.
  • the treated water is taken off from the intermediate store by a suction line and fed by the circulation pump 10 to the site of use—treated water— 11 .
  • a return line 12 then water which is again to be treated 9 is recycled to the intermediate store and again passes through the reaction outlet 8 or the outflow from the water-jet liquid pump 14 .
  • the reactor outlet 8 can also be placed close in position to the suction side of the circulation pump 10 in order to ensure rapid exchange of the water to be treated 9 at the reactor outlet 8 .
  • FIG. 2 shows an outline structure for carrying out the method according to the invention, without being restricted to defined starting chemicals (reactants).
  • the units having the specified number are therefore to be employed in their function correspondingly generally for all methods having the various possible starting chemicals (reactants) and may be readily recognized by those skilled in the art.
  • the reactor 7 is connected identically as in FIG. 1 to the same feed lines.
  • the reactor 7 is likewise surrounded by the water which is to be treated 9 , but the reactor 7 is situated in a pipe 14 through which water to be treated 9 flows, which pipe feeds the water which is to be treated 9 , after it passes through the reactor outlet 8 , to the site of use—treated water— 11 .
  • the reactor 7 can likewise be supplied with dilution water, but a preferred variant is to allow the reactor 7 to react without dilution of the reactants by water (dilution water transport pump 6 shut off) in the reaction chamber.
  • concentration of the resultant solution at the reactor outlet 8 can be greater than 9 g/l [without dilution water the ClO 2 content increases to 9.1 g/l, even when 3.5% strength reactants are used], preferably greater than 26 g/l, and particularly preferably to greater than 80 g/l, of chlorine dioxide per litre.
  • the device described in FIG. 1 is used.
  • the aqueous solution in the chlorite storage tank 1 contains 25% sodium chlorite and 2.5 l/h of this solution are passed by the transport pump 4 into the reactor 7 .
  • 2.5 l/h of a 32% strength aqueous hydrochloric acid solution are simultaneously fed to the reactor 7 by the transport pump 5 .
  • the concentration of the resultant chlorine dioxide solution is set to 42 g/l [at a yield of 92%].
  • the reactor has a free volume of 0.33 litres and the residence time of the reaction mixture in the reaction chamber is 2 minutes.
  • the water which is to be treated takes up the exiting chlorine dioxide-containing water and rapidly reduces the chlorine dioxide concentration in the mixed water to 0.42 mg/l in this process.
  • the reactor outlet 8 is lowered 4 metres below the water surface in the intermediate store and the temperature of the water which is to be treated is 32° C.
  • the water which is to be treated 9 is recirculation cooling water of a circulation cooling stage which is situated in a cooling tower pond (intermediate store).
  • the cooling water is passed over heat-exchange surfaces of a chemical production plant having exothermic heat sources (site of use—treated water— 11 ) and subsequently trickled over the internals of an evaporative cooling tower before it again reaches the cooling tower pond (intermediate store).
  • the cooling tower pond has a volume of 800 m 3 .
  • the water level in the intermediate store is under level control, in such a manner that the evaporated cooling water is automatically replaced by fresh water.
  • 11 litres of chlorine dioxide solution having a content of 94 g/l are delivered per hour via the reactor outlet 8 into the water which is to be treated 9 flowing around the reactor 7 , as a result of which the concentration of the reaction mixture at the reactor outlet 8 is abruptly reduced to 10 mg/l by mixture with the water which is to be treated 9 .
  • the chlorine dioxide is generated at a yield of 95%.
  • the pressure of the water to be treated 9 in the pipe 14 is 5.5 bar and its renewal rate at the reactor outlet 8 is 0.1 m 3 /h per gram and hour of generated chlorine dioxide.
  • the treated water 11 is provided to the site of use at the end of the pipe.
  • the appliances described in Example 2 are the treatment of 100 m 3 /h of washwater which is used with a chlorine dioxide concentration of 10 mg/l in a cleaning system.
  • the water takes up the chlorine-dioxide-containing water exiting from the reactor outlet 8 and in this process rapidly reduces the chlorine dioxide concentration in the mixed water below the critical concentration of 6 g/l.
  • the concentration of chlorine dioxide is about 0.4 mg per litre of water.

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  • Chemical & Material Sciences (AREA)
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US12/339,533 2007-12-19 2008-12-19 Method of treating water with chlorine dioxide Abandoned US20090159538A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US13/109,508 US8663481B2 (en) 2007-12-19 2011-05-17 Method of treating water with chlorine dioxide

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE102007061360 2007-12-19
DE102007061360.3 2007-12-19
DE102008041081.0 2008-08-07
DE102008041081 2008-08-07
DE102008042424.2 2008-09-29
DE102008042424A DE102008042424A1 (de) 2007-12-19 2008-09-29 Verfahren zur Behandlung von Wasser mit Chlordioxid

Related Child Applications (1)

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US (2) US20090159538A1 (fr)
EP (2) EP2813473A1 (fr)
JP (1) JP5661471B2 (fr)
KR (2) KR20160096722A (fr)
CN (1) CN101555063B (fr)
AU (1) AU2008337695B2 (fr)
BR (1) BRPI0821751A2 (fr)
CA (1) CA2710069C (fr)
DE (1) DE102008042424A1 (fr)
DK (1) DK2234927T3 (fr)
EG (1) EG27077A (fr)
ES (1) ES2525044T3 (fr)
IL (1) IL205188A (fr)
MX (1) MX2010006769A (fr)
PL (1) PL2234927T3 (fr)
PT (1) PT2234927E (fr)
RU (1) RU2497761C2 (fr)
WO (2) WO2009077213A1 (fr)
ZA (1) ZA201005022B (fr)

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US20100155341A1 (en) * 2008-12-19 2010-06-24 Infracor Gmbh Method of treating water and aqueous systems in pipes with chlorine dioxide
US20110220587A1 (en) * 2007-12-19 2011-09-15 Infracor Gmbh Method of treating water with chlorine dioxide
WO2011071862A3 (fr) * 2009-12-07 2011-10-20 Bcr Environmental, Llc Système et procédés de production de dioxyde de chlore
JP2013527028A (ja) * 2010-04-16 2013-06-27 インフラコア ゲゼルシャフト ミット ベシュレンクテル ハフツング 浸漬型反応器
WO2016137723A1 (fr) 2015-02-26 2016-09-01 Chemtreat, Inc. Procédés et systèmes de production de dioxyde de chlore gazeux de haute pureté
US9743670B2 (en) 2011-10-14 2017-08-29 Infracor Gmbh Method of treating water with chlorine dioxide
US10179922B2 (en) * 2009-07-08 2019-01-15 Moustafa Ahmed El-Shafie Method and system for processing a biomass for producing biofuels and other products
US10471165B2 (en) 2016-08-26 2019-11-12 Chemtreat, Inc. Sterilization or disinfection of workpieces, including medical and dental instruments
US10501345B2 (en) 2017-08-17 2019-12-10 Ecolab Usa Inc. Low risk chlorine dioxide onsite generation system
US10508031B2 (en) 2016-12-30 2019-12-17 International Dioxcide, Inc. Chlorine dioxide generation
US11130677B2 (en) 2017-03-24 2021-09-28 Ecolab Usa Inc. Low risk chlorine dioxide onsite generation system
US11535541B2 (en) 2017-02-27 2022-12-27 Ecolab Usa Inc. Method for onsite production of chlorine dioxide
US11970393B2 (en) 2018-07-05 2024-04-30 Ecolab Usa Inc. Decomposition mediation in chlorine dioxide generation systems through sound detection and control

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ITMI20072388A1 (it) * 2007-12-19 2009-06-20 Caffaro Chimica S R L Apparecchiatura e metodo per la disinfezione di acque
WO2011148395A1 (fr) * 2010-05-28 2011-12-01 Isia S.R.L. Appareil de désinfection de l'eau
DE102012200438A1 (de) * 2012-01-12 2013-07-18 Detlef Exner Wechselarmatur für ein Behältnis, Verfahren zum Anbringen einer Wechselarmatur an ein Behältnis und Verwendung einer Wechselarmatur
DE202012006932U1 (de) 2012-07-18 2012-08-31 Infracor Gmbh Radialrohrreaktor
US9156717B2 (en) 2012-07-20 2015-10-13 Infracor Gmbh Radial pipe reactor
CA2901814A1 (fr) 2013-03-15 2014-09-25 Food Safety Technology, Llc Procedes et systemes de commande de microorganismes et de turbidite dans une eau de refroidissement de cornue au moyen d'une solution d'ozone aqueuse
US10442711B2 (en) 2013-03-15 2019-10-15 Sabre Intellectual Property Holdings Llc Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse
MX377911B (es) * 2013-03-15 2025-03-11 Sabre Ip Holdings Llc Metodo y sistema para el tratamiento de agua y fluidos producidos con dioxido de cloro para su reutilizacion.
US9238587B2 (en) 2013-03-15 2016-01-19 Sabre Intellectual Property Holdings Llc Method and system for the treatment of water and fluids with chlorine dioxide
US8789592B2 (en) 2013-04-24 2014-07-29 Sabre Intellectual Property Holdings Llc Flooding operations employing chlorine dioxide
AU2014368266B2 (en) * 2013-12-20 2017-03-09 Sankei Co., Ltd. Method for producing aqueous chlorous acid by adsorption of chlorine dioxide
MX2017011079A (es) 2015-03-02 2018-05-07 Int Dioxcide Inc Método para tratar agua con dióxido de cloro.
JPWO2023171784A1 (fr) * 2022-03-11 2023-09-14
DE102022110015B3 (de) 2022-04-26 2023-08-03 Matthias Weber Vorrichtung und Verfahren zur Herstellung von Chlordioxid

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US8663481B2 (en) 2014-03-04
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US20110220587A1 (en) 2011-09-15
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CN101555063B (zh) 2014-09-17
BRPI0821751A2 (pt) 2015-06-16
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WO2009077309A1 (fr) 2009-06-25
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