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    • 专利摘要:
    The present invention relates to a method for disinfecting a space with chlorine dioxide gas, comprising the steps of: generating chlorine dioxide gas in a reaction cell; releasing said chlorine dioxide gas from said reaction cell; and transferring the released chlorine dioxide gas to the area to be treated.
    公开号:BE1023120B1
    申请号:E2015/5694
    申请日:2015-10-27
    公开日:2016-11-24
    发明作者:Rik Daneels；Trees Loncke
    申请人:Aqua Ecologic；
    IPC主号:
    专利说明:

    METHOD AND SYSTEM FOR DISINFECTING WITH CHLORDIOXIDE GAS
    TECHNICAL FIELD
    The present invention relates to a method and a system for disinfecting and / or sterilizing a room and / or equipment installed in a room using chlorine dioxide gas.
    BACKGROUND
    Historically, chlorine dioxide is mainly used as a bleaching agent in the paper and pulp industry, but is also used as a biocide or oxidant, for example for water purification or odor control. Chlorine dioxide has a relatively low oxidation potential compared to other oxidizers, but nevertheless a high oxidation capacity. In addition, when used as a disinfectant it forms fewer by-products compared to chlorine.
    To meet stability requirements, chlorine dioxide is preferably produced in batch. For example, WO 2015/136478 describes an aqueous chlorine dioxide composition with a concentration of at least 4 grams of chlorine dioxide per liter, a method for preparing such an aqueous composition and a kit comprising concentrated solutions of chlorite salt and bisulfate and persulfate salt.
    However, many production methods have limitations in the sense that reagents and / or by-products may be harmful to the space to be disinfected and / or products to be disinfected. For example, chlorate is preferably excluded in the food industry and corrosive substances can have an impact on metals, plastics, electronics, measuring devices or medical equipment. In this way the usability of the chlorine dioxide technology is strongly limited, and then especially for applications where chlorine dioxide is extremely suitable. Thus, there is a need for new ways of releasing high purity chlorine dioxide into the treatment area without reducing generation efficiency.
    The present invention seeks to provide a solution for one or more of the aforementioned problems or shortcomings.
    SUMMARY
    To this end, the invention provides a method and system for disinfecting a space with chlorine dioxide gas.
    To this end, the invention provides in a first aspect a method for disinfecting a space with chlorine dioxide gas, comprising the steps of: - generating chlorine dioxide gas in a reaction cell; - releasing said chlorine dioxide gas from said reaction cell; and - transferring the exempted chlorine dioxide gas into the room to be treated.
    More specifically, the generated chlorine dioxide gas is passed through a gas permeable membrane before being released into the space to be treated. In this way, potentially harmful substances can be partially or completely retained by means of the gas-permeable membrane, so that damage to the space to be disinfected is at least partially and preferably completely suppressed.
    In a second aspect, the present invention provides a system for disinfecting a space with chlorine dioxide gas, comprising a reaction cell for creating and / or storing chlorine dioxide gas, a dispersing unit in fluid communication with said reaction cell for dispersing the chlorine dioxide gas in said reaction cell in a space to be treated and a gas permeable membrane disposed between said reaction cell and said dispersing unit. This offers the advantage that chemical components that may cause damage to equipment in a room to be treated can be retained by said gas-permeable membrane.
    In a third aspect, the present invention provides a use of a method according to the first aspect of the invention for disinfecting a space in which equipment, such as, for example, electrical appliances, are arranged. This offers the advantage that the technology used has no negative impact on the equipment.
    DESCRIPTION OF THE FIGURES
    The explicit characteristics, advantages and objectives of the present invention will further become apparent to those skilled in the art of the invention after reading the following detailed description of the embodiment of the invention and of the figures included herein. To that end, the figures should further illustrate the invention, without thereby limiting the scope of the invention.
    Figure 1 shows a first system for dosing a purified chlorine dioxide gas using a gas permeable membrane 36.
    Figure 2 shows a second system for dosing a purified chlorine dioxide gas using a gas permeable membrane 36.
    Figure 3 is a schematic representation of a system for disinfecting a room.
    DETAILED DESCRIPTION OF THE INVENTION
    Unless defined otherwise, all terms used in the description of the invention, including technical and scientific terms, have the meaning as generally understood by those skilled in the art of the invention. For a better assessment of the description of the invention, the following terms are explicitly explained.
    When "about" or "round" is used in this document for a measurable quantity, a parameter, a duration or moment, and the like, variations are meant of +/- 20% or less, preferably +/- 10% or less, more preferably +/- 5% or less, even more preferably +/- 1% or less, and even more preferably +/- 0.1% or less than and of the quoted value, insofar as such variations of are applicable in the described invention. However, it must be understood here that the value of the quantity at which the term "about" or "round" is used is itself specifically disclosed.
    The citation of numerical intervals by the end points includes all integers, fractions and / or real numbers between the end points, including these end points.
    The term "disinfecting" is to be understood as synonymous with the term "disinfecting" or "purifying" and refers to the at least partial destruction of one or more types of pests, pathogens or germs. Preferably at least 90% of said pathogens or germs are destroyed, more preferably at least 97% and most preferably 100%. The term "pest species" is to be understood as a synonym for the term "harmful organism" and refers to any organism that is undesirably present or has a harmful effect on humans, animals, crops and / or environment. Examples of pests include weeds, microorganisms, pathogens, fungi, larvae, insects, parasites, nematodes, algae, mites, rodents, bacteria, viruses, etc. The term "pathogen" or "pathogens" should be understood as synonymous with the term "pathogen" and refers to various bacteria, viruses, fungi, yeasts and protozoa that can cause disease and / or death in humans, animals, plants or other biological organisms. Pathogenic spores are spores that are produced by a pathogen. Specific examples of pathogens producing spores include, but are not limited to, members of the genera Bacillus, Clostridium, Desulfotomaculans, Sporolactobacillus, and Sporpsarcina, members of the Phylum Apicomplexa (such as Plasmodium falciparum and Cryptosporidium parvum), and phytopathogenic fungi. In the context of the present invention, the term "disinfecting" is to be understood as well as "sterilizing". With sterilization a higher degree of pathogen killing is obtained compared to disinfection: grade 'log 6' with sterilization versus grade 'log 5' with disinfection. The sterilization of a room mainly takes place in applications where a high degree of hygiene is desirable, such as for example in food treatment or production areas, in medical rooms such as for example in hospitals, as well as in veterinary applications.
    The term "chlorine dioxide" or "ClO 2" refers to a molecule designated by CAS number 10049-04-4 and appears as a gas at standard pressure and temperature. Chlorine dioxide has a greenish, yellow color with a characteristic odor similar to chlorine and is an extremely effective biocide that quickly and efficiently kills pathogens such as bacteria, viruses and parasites. Chlorine dioxide gas molecules can also kill atomized germs, and can also spread through cracks and fissures in an article or a building or space, and thus reach any surface that may be contaminated with a pathogen. Chlorine dioxide is very soluble in water, but unlike chlorine, chlorine dioxide does not react with water. It exists in aqueous solution as a dissolved gas. Chlorine dioxide is recognized as oxidizing, potentially explosive, corrosive, toxic and environmentally hazardous. The boiling point of chlorine dioxide is 9.7 ° C at standard pressure.
    The term "sodium chlorite" refers to a chemical molecule with gross formula NaClO2 and is designated by CAS number 7758-19-2. The term "sodium bisulfate" refers to a chemical molecule with gross formula NaHSO 4 and is designated by CAS number 7681-38-1. The term "sodium persulfate" refers to a chemical molecule with gross formula Na 2 S 2 O 8 and is designated by CAS number 7775-27-1. In an alternative embodiment, lithium, potassium, rubidium, cesium and / or francium is used instead of sodium. This offers the advantage that the counter ions minimally interfere with the active components in the aqueous compositions and therefore do not compromise the stability of the chlorine dioxide composition obtained.
    The term "reaction cell" is to be understood as a reaction vessel into which solid, liquid and / or gaseous substances can be loaded and evacuated. Preferably said reaction cell comprises an aqueous solution in which chemical reactions can take place.
    Method
    In a first aspect, the invention provides a method for disinfecting a space with chlorine dioxide gas, comprising the steps of: - generating chlorine dioxide gas in a reaction cell; - releasing said chlorine dioxide gas from said reaction cell; and - transferring the exempted chlorine dioxide gas to the room to be treated.
    Within the context of the present invention, chlorine dioxide can be generated via known methods according to the prior art. Specific examples of combinations of reagents that can be used include, but are not limited to: sodium chlorate, sodium chloride and sulfuric acid; sodium chlorate and hydrochloric acid; sodium chlorate, sodium chlorite, sodium chloride and sulfuric acid; sodium chlorate, sodium chlorite and hydrochloric acid; sodium chlorate, sulfur dioxide and sulfuric acid; sodium chlorate, methanol and sulfuric acid; sodium chlorite and chlorine; sodium chlorite and hydrochloric acid and / or sulfuric acid; sodium chlorite, oxidizing gas and sulfuric acid; sodium chlorate, sodium chloride, hydrogen peroxide and / or methanol and sulfuric acid; sodium chlorite, sodium hypochlorite and hydrochloric acid and / or sulfuric acid; and sodium chlorate, glucose and sulfuric acid. Other suitable combinations of reagents can also be used, such as, for example, electrochemical reactions in which chlorine dioxide is generated from sodium chlorite or sodium chlorate; or photochemical reactions in which chlorine dioxide is generated from sodium chlorite or sodium chlorate under the influence of UV irradiation, e.g. at 254 nm. Such manners are described inter alia in WO 2005/016011, US 4,874,489 and US 8,652,411.
    Preferably chlorine dioxide gas is generated in said reaction cell by reaction of chlorite with an activator in an aqueous solution. To this end, in an aqueous solution, an alkali chlorite, or chlorite for short, is combined - and optionally stirred - with an activator such as preferably bisulfate; bisulfate and persulfate; citric acid; or a combination of one or more of the foregoing substances. The use of a stirrer while combining reagents in said aqueous solution is preferably avoided. Other acids can generally also be used as activators.
    Releasing said chlorine dioxide gas from said aqueous solution can be spontaneously diffused from said chlorine dioxide gas in said aqueous solution to the gas phase above said aqueous solution. The chlorine dioxide gas can then be led away from the aqueous solution. Alternatively, said chlorine dioxide gas can be released from said aqueous solution by purging the aqueous solution with air or nitrogen gas as carrier gas. This purging is also referred to by the term "stripping", referring to the physical separation process in which one or more substances are removed from a liquid and are taken up in the gas or vapor stream which has been brought into contact with said liquid.
    The transfer of the released chlorine dioxide gas to the room to be treated can be carried out by guiding the chlorine dioxide gas and possibly the carrier gas, whereby the outlet flows into the room to be treated.
    More specifically, the invention provides a method for disinfecting a space with chlorine dioxide gas, wherein the released chlorine dioxide gas is passed through a gas permeable membrane before being released into the space to be treated.
    In this way, potentially harmful substances can be partially or completely retained by means of the gas-permeable membrane, so that damage to the space to be disinfected is at least partially and preferably completely suppressed. For example, the presence of chlorate ions in spray drops is undesirable, specifically for disinfecting medical rooms. Chlorate can be present as an impurity in the chlorite raw material, but can also be formed as a by-product during the production of chlorine dioxide from chlorite, certainly when in an acid medium and / or at an elevated temperature. This is because chlorate ions from the spray drops will precipitate in the space and on the equipment present. However, chlorate is considered to be a harmful substance to the human body, and the presence of chlorate in the environment should therefore be avoided. In addition, the presence of corrosive substances in the chlorine dioxide gas preparation reaction mixture is a cause of corrosion of equipment in the room to be treated.
    Any suitable construction material can be used for the membrane, provided that the membrane is sufficiently porous to allow the flow of gases and sufficiently hydrophobic to prevent the passage of the aqueous solution. A suitable gas permeable membrane comprises an expanded polytetrafluoroethylene plate. The membrane can be provided as a composite with supporting or supporting materials to provide the structural strength required for use. Such supporting materials can be selected from a variety of polymeric materials, such as, for example, but not limited to, polyvinyl chloride and polyethylene, and other materials, such as fiberglass fabrics, felt and nonwovens. The pore size of the membrane can vary greatly depending on the desired flow rate of chlorine dioxide through the membrane. The pore size must not be so small that chlorine dioxide gas flow through it is prevented and, moreover, not so large that liquid flow through the membrane becomes possible. Said pore size is preferably comprised between 0.001 µm and 15 µm. The porosity of the membrane can vary greatly, partly depending on the desired flow rate of chlorine dioxide through the membrane. Membrane strength considerations also dictate chosen porosity. In general, the porosity of the membrane ranges from about 50% to about 98%. The thickness of the membrane is determined by the strength of the chosen material. The thickness of the bearing membrane varies from about 0.1 to about 2.0 mm. It is not essential for the present invention that the membrane be made of hydrophobic material over its entire thickness, provided that the surface of the membrane directed to an aqueous solution in the reaction cell is hydrophobic and therefore can prevent the flow of the aqueous medium through the membrane . The membrane can close the mouth of the reaction cell in any desired geometric shape, generally flat shape or in tubular shape, as desired.
    In a preferred embodiment, the present invention provides a method according to the first aspect of the invention, wherein said space is partially or completely closed off prior to disinfection. This offers the advantage that no or only a limited amount of chlorine dioxide gas and / or potentially present harmful substances can leak into the environment, as a result of which the effective concentration of chlorine dioxide in the space to be disinfected remains maximum and there is no risk of undesired contact between said chlorine dioxide and / or or possibly present harmful substances and adjacent or connecting spaces and the equipment present therein. Avoiding or at least significantly reducing chlorine dioxide gas leaks to adjacent rooms contributes to the safety of both professional operators and people in the vicinity of the room to be disinfected. Preferably, said space is closed by means of a substantially gas-tight seal. An enclosed space such as an enclosed article, enclosed space, or a sealed building should be understood as an environment in which substantially all fluid connections with the environment have been or were closed off, for example with the aid of plastic shielding or other sheets, tape, insulation, sealing or combinations thereof, and wherein said shields are preferably gas impermeable. In a further embodiment, said closed space is formed by means of a 'glove bag', a 'gas bag', an 'air bag' or an 'atm bag'. Said closed space is, however, preferably provided with one or more entrances and / or exits which allow specific agents to be moved in and / or out of the enclosed space.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein the chlorine dioxide gas is introduced into the aqueous solution in gas phase, for example by purifying the aqueous solution with air, then passing through a gas permeable membrane and leading to Finally, the room to be treated is exempt. Preferably, after passage through the gas permeable membrane, the chlorine dioxide gas is no longer absorbed in a second aqueous solution, but the chlorine dioxide is led directly to the room to be treated. As a result, the chlorine dioxide in the aqueous solution is exempted with optimum efficiency in the space to be treated, while at the same time spray drops with chlorate ions as well as other potentially harmful substances are not or only greatly reduced in the space.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein said gas permeable membrane has a pore size of less than 5.0 µm, preferably less than 2.5 µm. This offers the advantage that spray drops can be retained by the gas-permeable membrane, while gas molecules can diffuse through the membrane without much resistance. More preferably, said membrane has a pore size of less than 1.0 μη and even more preferably a pore size of between 1 nm and 1000 nm. Most preferably said membrane has a pore size of between 5 nm and 500 nm, such as for example between 10 nm, 20 nm, 50 nm, 75 nm, 100 nm, 125 nm, 150 nm, 200 nm and 250 nm or any value in between located. Gas-permeable membranes with a too small pore size lead to a greater pressure drop over the membrane, so that more energy is needed to transfer the chlorine dioxide through the membrane.
    The term "aqueous solution" is to be understood as an aqueous reaction medium into which reagents for the synthesis of chlorine dioxide gas can be introduced. Reagents can include chlorite and chlorate, as well as one or more activators.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein the chlorite: activator molar ratio is lower than 4: 1, and preferably about 2: 1. A lower molar ratio of chlorite: activator leads to better efficiency for the conversion of chlorite to chlorine dioxide. Preferably said ratio is chlorite: activator greater than 1: 100, more preferably greater than 1:25 and even more preferably greater than 1:10. Too low a chlorite molar ratio: activator leads to a slower activation of the chlorite.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein said activator is a liquid or a solid at standard pressure and temperature. This offers the advantage that the activator has a low vapor pressure, so that the presence of activator in the gas phase above the aqueous solution of chlorine dioxide at standard pressure and temperature is relatively low. This offers the advantage that little or no activator with the chlorine dioxide in the gas phase is released in the room to be treated. This is especially advantageous when the activator may have toxic or harmful properties with respect to the environment or equipment in the room to be treated. For example, hydrogen chloride, which is an activator for chlorite, will simply diffuse through the gas permeable membrane and have a corrosive effect on materials in the space to be treated.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein said activator is a solid at standard pressure and temperature. A solid as activator offers the advantage over a liquid that the vapor pressure is lower at standard pressure and temperature, whereby the presence of activator in the chlorine dioxide gas phase is also lower. Thus, possible damage to the space to be disinfected is avoided.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein said activator in acid form is an acid which does not dissociate in water and an acid gas at standard pressure and temperature. Activators such as, for example, bisulfate will be partially or completely acidified in an acidic environment to, for example, sulfuric acid, which spontaneously dissociates in water and SO3. The SO3 gas can then spontaneously transfer to the gas phase above the aqueous chlorine dioxide solution and diffuse through the gas membrane and then be released into the space to be treated. After reaction with water in the air of the room to be treated, sulfuric acid can be formed again, which has a corrosive effect on the equipment, as well as being irritating and harmful to living organisms. Other examples of activators or additives to be avoided include bicarbonate.
    Preferably, said activator is an acid, such as an organic acid or an inorganic acid, which can bring the pH of the aqueous solution within the pH range of 2 to 6, and preferably from 3 to 5. The suitable pH provides an optimum operating range for the activation of chlorite. Preferably, said organic acid refers to a solid. Organic hydroxy carboxylic acids, such as, for example, but not limited to salicylic acid, lactic acid, acetylsalicylic acid and citric acid, are mainly advantageous in view of their good activity as an activator for generating chlorine dioxide. Most preferably citric acid is used as an activator. Citric acid offers the advantage that it is well soluble in water. Thus, citric acid concentration of up to 500 grams per liter can be easily prepared and a highly concentrated, acidic solution can be added to the aqueous reaction medium to obtain the appropriate acidity. This offers the advantage that no citric acid precipitate is left in the reaction vessel, in the pipes and control valves of the system or on the gas permeable membrane. Such precipitation would prevent the proper functioning of the chlorine dioxide generation system and the gas permeable membrane and eventually require more maintenance work. In addition, because smaller volumes of citric acid can be added, less waste is generated in the fumigation system.
    In a further aspect, the present invention provides a method for making an aqueous solution of chlorine dioxide wherein chlorite and / or chlorate are activated using an activator. The activator can be selected from the group of acids, preferably organic acids and more preferably citric acid; bisulfate and / or persulfate; and hydrogen peroxide; or a mixture of two or more activators such as most preferably citric acid and hydrogen peroxide. This offers the advantage that a concentrated, stable solution of chlorine dioxide is obtained. The solution can then be used for water purification or disinfection applications.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein said chlorine dioxide gas is released from said aqueous solution by purging the aqueous solution with air. Preferably, air from the space to be disinfected is used to purge the aqueous solution with chlorine dioxide. Thus, chlorine dioxide can be stripped with optimum efficiency from said aqueous solution and entrained with the gas stream. The air flow rate for purging is preferably included between 0.001 m 3 / h per liter of aqueous solution and 1,000 m 3 / h per liter of aqueous solution. The air flow rate therefore also depends on the total amount of water. More preferably, said air flow rate is comprised between 0.005 m3 / h per liter of aqueous solution and 0.200 m3 / h per liter of aqueous solution, and even more preferably between 0.01 m3 / h per liter of aqueous solution and 0.10 m3 / h per liter of aqueous solution. An optimum air flow through the aqueous solution leads to an optimum air flow through the gas permeable membrane and is therefore partly responsible for the proper functioning of said gas permeable membrane. As an alternative to air, nitrogen gas can also be used to purge the aqueous chlorine dioxide solution under the same conditions as explained above.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein chlorite is activated by said activator in the presence of hydrogen peroxide. Hydrogen peroxide ensures the rapid conversion of chlorate ions to chlorite ions. Thus, the release of chlorate ions, with or without the use of a gas permeable membrane, can be strongly suppressed in the space to be treated. For some applications, such as mainly the food industry, chlorate is considered to be a contamination that should be avoided and / or remedied. More preferably, chlorite is activated by citric acid in the presence of hydrogen peroxide. In an alternative embodiment, chlorite is activated by persulfate and / or bisulfate in the presence of hydrogen peroxide. In an additional embodiment, the hydrogen peroxide can be prepared in situ.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein hydrogen peroxide and chlorite are mixed in a molar ratio of about 3: 1, such as any ratio between 5: 1 and 1: 1.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein chlorite is metered into said aqueous medium in an amount of more than 0.5% by weight, preferably more than 1.0% by weight. This offers the advantage that the total amount of water in the aqueous reaction medium is smaller, which leads to an increased efficiency of releasing chlorine dioxide gas in the room to be treated.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein the space to be treated is preconditioned at a relative humidity of 50% to 85%, preferably of 55% to 80% and more preferably of 60% to 70%. Most preferably, said space is preconditioned at a relative humidity of 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69% or 70%, or any value in between. Lower values of relative humidity offer the advantage that less water is present in air at a specific ambient temperature. The gaseous substances with corrosive properties that may have diffused through the membrane will be absorbed more slowly in mist droplets at lower relative humidity and will therefore not precipitate or deposit less on the installed equipment in the room to be disinfected.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein the space to be treated is preconditioned at a temperature of 15 ° C to 35 ° C, preferably of 20 ° C to 30 ° C. Most preferably, said space is conditioned at 21 ° C, 22 ° C, 23 ° C, 24 ° C, 25 ° C, 26 ° C, 27 ° C, 28 ° C, 29 ° C or 30 ° C. The use of temperatures higher than 30 ° C ensures that potentially corrosive substances in the exempted chlorine dioxide gas exhibit more corrosive behavior in the room to be treated. The use of temperatures lower than 15 ° C is possible but leads to more difficulties in keeping the relative humidity sufficiently low. Preferably, said process is carried out at a temperature above the boiling point of chlorine dioxide, such as, for example, at a temperature above 10 ° C at standard pressure.
    In a preferred form, the present invention provides a method according to the first aspect of the invention, wherein residual amounts of chlorine dioxide gas in the treated space are removed after disinfection. This can be achieved, for example, by air exchange or by repeated air exchange of the treated room. Alternatively, the chlorine dioxide gas can be neutralized. The term "neutralizing" refers to chemically neutralizing a chemical, preferably by chemisorption, physisorption and / or decomposition. As a result of the neutralization, the concentration of chlorine dioxide in said gas stream is considerably reduced. For example, said chlorine dioxide can be neutralized by means of, preferably intensive, contact with an aqueous solution comprising 10% by weight NaOH and 10% by weight sodium thiosulfate hydrate. Preferably, said chlorine dioxide is neutralized in a gas washer. In an alternative or preferably additional embodiment, a filter with a solid chlorine dioxide adsorbent, preferably activated carbon, is used to adsorb residual chlorine dioxide in the disinfected space. Preferably said filter is suitable for treating an air flow rate higher than 1000 m3 / hour, preferably between 2000 m3 / hour and 10000 m3 / hour, more preferably between 2500 m3 / hour and 5000 m3 / hour and most preferably a 2500, 2750, 3000, 3250, 3500, 3750, or 4000 m3 / hour airflow or any value in between. This offers the advantage that the space to be disinfected can be stripped of the potentially harmful chlorine dioxide faster. Preferably the neutralization of chlorine dioxide in said space lasts less than 2 hours, more preferably less than 1 hour, even more preferably between 5 minutes and 30 minutes and most preferably 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes, or any value in between.
    System
    In a second aspect, the present invention provides a system for disinfecting a space with chlorine dioxide gas, comprising a reaction cell for creating and / or storing chlorine dioxide gas, a dispersing unit in fluid communication with said reaction cell for dispersing the chlorine dioxide gas in said reaction cell in a space to be treated and a gas permeable membrane disposed between said reaction cell and said dispersing unit.
    This offers the advantage that chemical components that may cause damage to equipment in a room to be treated can be retained by said gas-permeable membrane.
    Figure 3 is a schematic representation of a system according to the present invention with indication of a decontamination device 101 comprising a stock solution of chlorite 102 and a stock solution comprising a mixture of activator 103, a batch reactor 104 for mixing both stock solutions 102 and 103, a container and / or stripping reactor 105 for temporarily storing an aqueous solution of chlorine dioxide and / or stripping chlorine dioxide from said solution by means of a carrier gas, preferably supplied air 106, and one or more fluid compounds 107a ', 107a "for guiding a gaseous effluent from said aqueous solution to a space 108 to be disinfected. Finally, the remaining amount of chlorine dioxide after treatment can be led away via one or more fluid compounds 107b to an absorption and / or adsorption unit 109 for reducing the chlorine dioxide content in the effluent gas 110 for discharging the efflu seed gas in the atmosphere. The fluid connection 107 preferably comprises a gas permeable membrane 111 for the selective passage of chlorine dioxide gas close to the outlet of the container / stripping reactor 105. In an alternative but simpler configuration, the batch reactor 104 and the container and / or stripper reactor 105 may be provided as one reaction vessel.
    In a preferred embodiment, the present invention provides said system, comprising one or more storage vessels (12, 13) for at least temporarily storing reagents, at least one reaction vessel (14), and at least one chlorine dioxide vessel (15); a pipe network with one or more pumps for moving gases and / or liquids through said pipe network, said pipe network being configured for transferring reagents to a reaction vessel, for transferring a mixture in said reaction vessel to a chlorine dioxide vessel and for dispensing of chlorine dioxide. In addition, the internal volume of said pipeline network is smaller than the total volume of said chlorine dioxide vessel. Preferably, the internal volume of said pipeline network is 50% smaller than the total volume of said chlorine dioxide vessel, and more preferably 80% smaller. Most preferably, said conduit network volume is 90%, 92%, 94%, 96%, 98%, 99% smaller than the volume of said chlorine dioxide vessel.
    In a preferred embodiment, the present invention provides said system comprising a chlorine dioxide vessel with a liquid sensor for detecting the liquid level in said chlorine dioxide vessel. Thus, the residual volume of chlorine dioxide composition in said chlorine dioxide vessel can be monitored. When the residual volume has fallen below a predetermined value, a new batch of chlorine dioxide composition according to the first aspect of the invention can be created via a control system.
    In a preferred embodiment, the present invention provides said system, further comprising an air pump and aeration compartments for purifying air through said solution comprising chlorine dioxide. More preferably, said aeration compartments for purifying air through said solution comprising chlorine dioxide are provided as a stripping tower, said stripping tower preferably being provided with an active height between 25 cm and 200 cm, and preferably equal to 25 cm 50 cm, 75 cm, 100 cm, 110 cm, 120 cm, 130 cm, 140 cm, or 150 cm, or any value in between. Still preferably said stripping tower has a ratio of height to diameter greater than 2: 1, preferably greater than 5: 1, and most preferably greater than 10: 1. Still preferably said stripping tower has a carrier gas flow rate, preferably an air flow rate, between 250 and 10,000 l per minute, preferably between 400 and 4000 l per minute, even more preferably between 800 and 2000 l per minute and most preferably a flow rate of 800, 1000, 1200, 1400, 1600, 1800, or 2000 l per minute or any value in between. Still preferably said stripping tower has a liquid recirculation flow rate between 10 l per hour and 1000 l per hour, preferably between 20 l per hour and 500 l per hour. The skilled artisan will appreciate that the optimum liquid recirculation rate will depend on the volume of the room to be disinfected and for smaller rooms will be around 20 l per hour, and for larger rooms will be between 150 and 500 l per hour and more preferably between 200 and 400 l per hour. In a specific embodiment, said liquid recycle rate is equal to 0 l per hour. Such an embodiment is workable in situations where chlorine dioxide spontaneously changes from the liquid phase to the gaseous phase of the reactor.
    Figure 1 shows a system for preparing a stable chlorine dioxide composition according to the invention. The system comprises a first 12 and a second 13 storage vessel for reagents, such as, for example, a NaClO2 solution and a solution comprising activator, such as for example citric acid, or sodium bisulfate and / or sodium persulfate, and optionally hydrogen peroxide. Supply of reagents can be controlled by means of shut-off valves 32 and 33, respectively, with the aid of pump 22. The use of a pump becomes optional in cases where water from a water pipe is used under pressure. In this way, reagents can be transferred to a reaction vessel 14, where both reagents are brought into contact with each other during the reaction time. After this reaction time, the chlorine dioxide solution is ready for use, and is transferred to a chlorine dioxide vessel 15. In a simpler configuration, reaction vessel 14 and chlorine dioxide vessel 15 form one physical vessel in which both the mixing and reacting of reagents take place, and where chlorine dioxide gas is stored and later stripped from the reaction medium, specifically from the aqueous solution. The aqueous chlorine dioxide solution can be purged from the aqueous solution of chlorine dioxide in chlorine dioxide vessel 15 using air pump 25 and air line 48. The concentrated chlorine dioxide gases can then be filtered with the aid of a gas permeable membrane 36 before being metered into the room to be treated with the aid of a flow pump 24 and control valve 35. This offers the advantage that any corrosive substances have no harmful influence on flow pump 24 and control valve. 35.
    Figure 2 shows a system for preparing a stable chlorine dioxide composition according to the invention. As a rule, NaClO2 solution can be used in any concentration. As a rule, any chemical in solution or mixture of chemical substances in solution can be used which activate sodium chlorite to at least partially convert to chlorine dioxide. Examples of such activators are, but are not limited to, sodium bisulfate, sodium persulfate, citric acid, hydrogen peroxide, ... or combinations thereof. The concentration of chlorine dioxide of the prepared stable chlorine dioxide solution can e.g. lie between 1 g / L and 10 g / L, according to amperometric determination.
    In a first preferred embodiment, NaClO 2 solution is used at a concentration that is proportionally higher than the concentration of NaClO 2 used at the start of the reaction to form the chlorine dioxide solution. In the above case, the desired sodium chlorite concentration in the reaction mixture in the reaction vessel is achieved by adding water to the reaction vessel. In a second advantageous embodiment, NaClO 2 solution is used at the desired proportional concentration required to achieve the desired concentration of NaClO 2 at the start of the reaction to form the chlorine dioxide solution. In the above case, therefore, no more water needs to be administered.
    The reaction time required for the formation of the stable chlorine dioxide solution is dependent on the chosen precursors, the concentrations of the chosen precursors in the reaction mixture and the required stability over time. It goes without saying that the present invention is not limited to the specified precursors, concentrations of precursors in the reaction mixture or stability.
    The system comprises a first 12 and a second 13 storage vessel for reagents, such as, for example, a NaClO 2 solution and a solution comprising sodium bisulfate and sodium persulfate. These storage vessels are in communication with the main line 42 via the fluid connection 51-52 and 53-54. Supply of reagents is adjustable by means of shut-off valves 32 and 33, respectively. Although not shown in the figure, shut-off valves 32 and 33 are preferably provided with a fluid pump connected in series to control fluid transport of reagents in storage vessels 12 and 13 to main line 42. Alternatively, the storage vessels may be provided with a pressure mechanism for applying a pre-pressure to the liquids in the storage vessels.
    The main line 42 is connected to a water line 11 on the supply side 41 and water supply can be regulated by means of the shut-off valve 31. On the discharge side, the main line 42 is provided with a flow meter 21 and a pump 22. The pump brings the liquid mixture to a pressure of 5 bar. Water and reagents in storage vessels 12 and 13 are conducted via the liquid line 43-44, flow meter 21 and liquid pump 22 to a reaction vessel 14 where the reagents are in contact with each other during the reaction time.
    In a practical methodology, chlorine dioxide is produced in a five-step process. In a first step, a first volume of water is transferred from the water line 11 to a reaction vessel 14. In a second step, sodium chlorite is transferred from a storage vessel 12 to said reaction vessel 14. In a third step, a second volume of water is transferred from the water line 11 to a reaction vessel 14. In a fourth step, an aqueous mixture of activator, such as, for example, citric acid, or sodium bisulfate and / or sodium persulfate, and optionally hydrogen peroxide is transferred from a storage vessel 13 to said reaction vessel 14. In a final step, a third volume of water is transferred from the water line 11 transferred to a reaction vessel 14.
    Upon completion of the reaction, the contents of the reaction vessel 14 are transferred to a chlorine dioxide vessel 15 via the transfer line 45-46, which is controlled by means of a shut-off valve 34 and is optionally provided with a liquid pump to promote liquid transfer.
    The chlorine dioxide vessel 15 is provided with a liquid sensor 23 which is activated when the content of the chlorine dioxide vessel 15 has fallen below a predetermined level. At a liquid level below a predetermined value, for example less than 8 liters, the liquid sensor 23 will transmit a signal to a control system, which is configured to control the adjustable shut-off valves 31, 32 and 33 and the pump 22 so as to create a new volume of chlorine dioxide composition to create. In addition, the chlorine dioxide vessel 15 is connected to an air supply line 48 and air pump 25 for purifying the aqueous chlorine dioxide solution in reaction vessel 15. Concentrated chlorine dioxide gases can be metered via line 47, optionally controlled with the aid of a chlorine dioxide pump 24 with injection valve 35. Before entering the To be exempted from the area to be treated, the concentrated chlorine dioxide gas is filtered using a gas permeable membrane 36.
    In a third aspect, the invention provides a use of a method according to the first aspect of the invention for disinfecting a space in which equipment, such as, for example, electrical and / or electronic devices are arranged.
    EXAMPLES
    The invention will now be further elucidated with reference to the following example, without however being limited thereto. EXAMPLE 1
    Chlorine dioxide gas is produced from an aqueous solution comprising chlorite as a source for chlorine dioxide, persulfate as an oxidant for the conversion of chlorite to chlorine dioxide and hydrogen peroxide for the conversion of chlorate to chlorite. To an amount of 18 L of water is added 1 L of 25 (m / v) -% NaClO 2 in aqueous solution and 1 L of 20 (m / v) -% of Na 2 S 2 O 8 and 5 (m / v) -% of H 2 O 2 in aqueous solution. Persulfate ensures oxidation of chlorite and a good stability of the chlorine dioxide composition obtained. Hydrogen peroxide ensures the conversion of chlorate to the chlorite raw material. The conversion of chlorite to chlorate is completely within the time of 12 hours and the chlorine dioxide concentration is stable at a value of 7000 mg / L ± 100 mg / L for a period of at least 30 days. The reaction progress is summarized in Table 1.
    Table 1. Reaction course for conversion of chlorite to chlorine dioxide according to example 1, values expressed in mg / L.
    Response time ClO2 - ClO3 - ClO2 12 hours 0 0 6900 3 days 0 0 7100 10 days 0 0 6950 30 days 0 0 6925
    The resulting chlorine dioxide composition is thus very pure in chlorine dioxide gas and comprises few or no volatile by-products, such as, for example, hydrogen chloride.
    The chlorine dioxide composition obtained can, after complete conversion of chlorite, be used as a stable solution of chlorine dioxide and can thus be used for disinfection applications. In an alternative embodiment, the chlorine dioxide composition obtained after complete conversion of chlorite can be used to release chlorine dioxide for fumigation applications. In a first step, the room to be treated is conditioned at a relative humidity of approximately 65%. By opting for a lower relative humidity in comparison with the usual humidity according to the prior art, the chlorine dioxide treatment is not experienced as corrosive, so that materials in the space to be treated are not unnecessarily affected. The relative humidity is then maintained for a period of about 10 minutes, so that spray droplets can dissolve in the room and, consequently, the treatment is less corrosive to equipment in the room to be treated. In a second step, the chlorine dioxide gas produced is transported through a gas-selective membrane with a pore size of 1000 nm. To promote the release of chlorine dioxide gas from the aqueous composition, the reaction mixture is purged with air. The room to be treated is then released from chlorine dioxide in an exposure regime of 720 ppm (vol.) H. This means that the room can be exposed to 720 ppm (vol.) For 1 hour or to 360 ppm (vol.) For 2 hours. One or more fans are installed in the room during the disinfection cycle to ensure a good distribution of the chlorine dioxide. In a final step, chlorine dioxide is removed from the space to be treated to a concentration of chlorine dioxide less than 0.1 ppm (vol.). By removing chlorine dioxide, the area to be treated can be put back into use sooner. EXAMPLE 2
    Process according to example 1, wherein to an amount of 17.8 L of water 1 L of 25 (m / v) -% NaClO 2 in aqueous solution is added and 1.2 L 20 (m / v) -% Na 2 S 2 O 8 and 5 (m / v) -% H2O2 in aqueous solution. The conversion of chlorite to chlorate is completely within the time of 12 hours and the chlorine dioxide concentration is stable at a value of 7500 mg / L ± 100 mg / L for a period of at least 30 days. EXAMPLE 3
    Process according to Example 1, wherein 1 L of 25 (m / v) -% NaClO 2 in aqueous solution is added to an amount of 18 L of water and 1 L of 22.5 (m / v) -% Na 2 S 2 O 8 and 5 (m / v) -% H2O2 in aqueous solution. The conversion of chlorite to chlorate is completely within the time of 12 hours and the chlorine dioxide concentration is stable at a value of 7500 mg / L ± 100 mg / L for a period of at least 30 days. EXAMPLE 4
    Chlorine dioxide gas is prepared according to the method of Example 1, wherein bisulfate, persulfate and hydrogen peroxide are added to an aqueous solution of chlorite. Bisulfate ensures a rapid conversion of chlorite to chlorine dioxide. Persulfate ensures good stability of the chlorine dioxide composition obtained. Hydrogen peroxide ensures the conversion of residual amounts of chlorate to the chlorite raw material and of chlorate formed by oxidation of chlorite by bisulfate to chlorine dioxide. EXAMPLE 5
    Chlorine dioxide gas is prepared according to the method of Example 1, wherein citric acid and hydrogen peroxide are added to an aqueous solution of chlorite. Citric acid ensures the conversion of chlorite to chlorine dioxide. Hydrogen peroxide ensures the conversion of residual amounts of chlorate to the chlorite raw material and of chlorate formed by oxidation of chlorite by bisulfate to chlorine dioxide. EXAMPLE 6
    Chlorine dioxide gas is made from an aqueous solution comprising chlorite as a source for chlorine dioxide and persulfate bisulfate as an oxidant and stabilizer, respectively. Alternatively, an acid such as, for example, citric acid can be used as an oxidant. With chlorite oxidation, chlorine dioxide is generated within a period of approximately 5 hours. In the presence of bisulfate, the chlorine dioxide solution remains stable for about 30 days. The reaction composition for a solution comprising 0.45% by weight of chlorite is shown in Table 2.
    Table 2. Reaction course for conversion of chlorite to chlorine dioxide according to comparative example 1, values expressed in mg / L.
    Response time ClO2 "ClO3 - ClO2 1 hour 1100 823 3441 5 hours 0 650 4040 3 days 0 558 4753 30 days 0 0 4344
    During the oxidation of chlorite, chlorate is formed, which after further oxidation is converted to chlorine dioxide. The complete conversion of chlorate to chlorine dioxide, however, takes more than 15 days, which makes it difficult to put the chlorine dioxide composition into practice for some applications, such as in the food industry where chlorate is considered a contaminant. The use of elevated reaction temperatures can also cause the formation of chlorate in the chlorine dioxide composition. In addition, chlorate may be present in the chlorine dioxide composition due to chlorate impurities in the chlorite feedstock.
    Chlorine dioxide gas is released from the solution obtained and passed through a polyvinylidene difluoride gas permeable membrane with a pore size of 1000 nm. Chlorate present in spray droplets is blocked by the membrane in this way and only chlorine dioxide gas can diffuse through the membrane. In this way it is prevented that chlorate in the room to be treated is prevented while the exemption of chlorine dioxide is not impeded. EXAMPLES 7-15
    A room is conditioned at a relative humidity of approximately 70%. Chlorine dioxide is made in an aqueous solution and is released from the aqueous solution. The production of chlorine dioxide occurs from chlorite and bisulfate in a molar ratio of 1: 2, chlorite and hydrogen chloride in a molar ratio of 1: 5 to 2: 1, and chlorite and citric acid in a molar ratio of 1: 2 to 1 : 1. The molar ratios had no noticeable influence on the resulting corrosion behavior. The exemption takes place at different flow rates of purge air, namely 0.2 m3 / h, 1.0 m3 / h and 18.0 m3 / h. Stainless steel 304 species of 5 cm x 10 cm are exposed to the chlorine dioxide gas generated at an exposure regime of 720 ppm (vol.) H.
    Table 3. Corrosive behavior of chlorine dioxide gas with regard to Inox 304 species. Example activator purge flow corrosion behavior a (m3 / h)
    Example 7 bisulfate 18.0 3
    Example 8 bisulfate 1.0 3
    Example 9 bisulfate 0.2 3
    Example 10 hydrogen chloride 18.0 3
    Example 11 hydrogen chloride 1.0 3
    Example 12 hydrogen chloride 0.2 3
    Example 13 citric acid 18.0 3
    Example 14 citric acid 1.0 1
    Example 15 citric acid 0.2 0 a qualitative determination of corrosive behavior with regard to an Inox 304 species where value '3' indicates corrosion of the species, value '2' indicates light corrosion, value '1' indicates corrosion 1 day after the cycle, and value '0' does not indicate corrosion. EXAMPLES 16-24
    The experiments of Examples 7-15 were repeated with a polyvinylidene difluoride gas selective membrane with a pore size of 1000 nm applied to the reactor outlet. The results of the experiments are shown in Table 4. From the results it can be deduced that providing a suitable gas-selective membrane significantly and completely suppresses the corrosive behavior of the disinfection treatment, also at high purge rates. Hydrogen chloride diffuses through the indicated gas permeable membrane so that the corrosive behavior of the treatment cannot be significantly suppressed.
    Table 4. Corrosive behavior of chlorine dioxide gas with regard to Inox 304 species. Example activator purge flow corrosion behavior a (m3 / h)
    Example 16 bisulfate 18.0 0
    Example 17 bisulfate 1.0 0
    Example 18 bisulfate 0.2 0
    Example 19 hydrogen chloride 18.0 3
    Example 20 hydrogen chloride 1.0 3
    Example 21 hydrogen chloride 0.2 1
    Example 22 citric acid 18.0 0
    Example 23 citric acid 1.0 0
    Example 24 citric acid 0.2 0 a qualitative determination of corrosive behavior with regard to an Inox 304 species where value '3' indicates corrosion of the species, value '2' indicates light corrosion, value Ί 'indicates corrosion 1 day after the cycle, and value Ό 'does not indicate corrosion.
    权利要求:
    Claims (13)
    [1]
    CONCLUSIONS
    A method for disinfecting a space with chlorine dioxide gas, comprising the steps of: - generating chlorine dioxide gas in a reaction cell, wherein said reaction cell comprises an aqueous solution and wherein chlorine dioxide gas is generated in said aqueous solution by reaction of chlorite with an activator; - releasing said chlorine dioxide gas from said reaction cell; and - transferring the released chlorine dioxide gas to the room to be treated, characterized in that said activator is a solid at standard pressure and temperature and that the released chlorine dioxide is passed through a gas permeable membrane before being released into the treatment to be treated space.
    [2]
    The method of claim 1, wherein said gas permeable membrane has a pore size of less than 5.0 µm, preferably less than 2.5 µm.
    [3]
    The method according to claim 1 or 2, wherein the chlorite: activator molar ratio is lower than 4: 1.
    [4]
    The method according to at least one of claims 1 to 3, wherein said activator in acid form is an acid which does not dissociate in water and an acid gas at standard pressure and temperature.
    [5]
    The method according to at least one of claims 1 to 4, wherein chlorite is activated by said activator in the presence of hydrogen peroxide.
    [6]
    The method of claim 5, wherein hydrogen peroxide and chlorite are mixed in a molar ratio of about 3: 1.
    [7]
    The method of at least one of claims 1 to 6, wherein said chlorine dioxide gas is released from said aqueous solution by purifying the aqueous solution with air.
    [8]
    The method according to at least one of claims 1 to 7, wherein chlorite is metered into said aqueous medium in an amount of more than 0.5% by weight.
    [9]
    The method according to at least one of claims 1 to 8, wherein the space to be treated is preconditioned at a relative humidity of 50% to 85%.
    [10]
    The method according to at least one of claims 1 to 10, wherein the space to be treated is preconditioned at a temperature of 15 ° C to 35 ° C.
    [11]
    The method according to at least one of claims 1 to 10, wherein residual amounts of chlorine dioxide gas in the treated space are removed after disinfection.
    [12]
    A system for disinfecting a chlorine dioxide gas space, comprising a reaction cell for creating and / or storing chlorine dioxide gas, a dispersing unit in fluid communication with said reaction cell for dispersing the chlorine dioxide gas in said reaction cell in a space to be treated and a gas permeable membrane disposed between said reaction cell and said dispersing unit.
    [13]
    Use of a method according to at least one of claims 1 to 11 for disinfecting a space in which equipment, such as, for example, electrical and / or electronic devices are arranged.
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    同族专利:
    公开号 | 公开日
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP0230737A1|1985-12-18|1987-08-05|Tenneco Canada Inc.|Membrane pervaporation process for obtaining a chlorine dioxide solution|
    WO2007040588A1|2005-09-19|2007-04-12|Avantec Technologies, Inc.|Systems and methods for producing aqueous solutions and gases having disinfecting properties and substantially eliminating purities|
    WO2012084247A1|2010-12-23|2012-06-28|A.P.F. Aqua System Ag|Method for producing an aqueous stable chlorine dioxide solution|
    WO2014056560A2|2012-10-12|2014-04-17|Khs Gmbh|Method for cleaning, disinfecting and/or sterilising packaging means and/or components in container treatment systems|
    法律状态:
    2020-08-13| MM| Lapsed because of non-payment of the annual fee|Effective date: 20191031 |
    优先权:
    申请号 | 申请日 | 专利标题
    BEBE2015/0231|2015-09-16|
    BE201500231|2015-09-16|EP16189173.4A| EP3153184A3|2015-09-16|2016-09-16|Method and system for disinfecting with chlorine dioxide gas|
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