CN103964384B - Chlorine dioxide gas generation system and chlorine dioxide gas decomposer - Google Patents

Abstract

The invention provides a chlorine dioxide gas generation system and a chlorine dioxide gas decomposer, i.e., provides a technology which can generate chlorine dioxide gas and enable the chlorine dioxide gas to be decomposed with shorter time than before. The chloride dioxide gas generation system includes a chlorine dioxide gas generation device which generates chlorine dioxide gas and a chlorine dioxide gas decomposer which inhales and decomposes residual gas of chlorine dioxide gas delivered to indoors from the chlorine dioxide gas generation device, and the chlorine dioxide gas decomposer contains filter material, and the filter material contains at least any one of manganese oxide and permanganate.

Description

Chlorine dioxide generates system and chlorine dioxide decomposer

Technical field

The present invention relates to chlorine dioxide generates system and chlorine dioxide decomposer.

Background technology

Having microorganism is killed using chlorine dioxide or to psocid（チャタテムシ）Enter etc. tiny insect The technology of row parasite killing.If chlorine dioxide and the protein contacts of microbial cell, generate oxygen-derived free radicals, protein is made Oxidation, while the sodium reaction having with microorganism generates NaCl.Chlorine dioxide reacts if with protein contacts.

（Change 1）

ClO₂Protein+NaCl after the Na → oxidation of+protein

Compared with other chlorine, sodium hypochlorite, hydrogen peroxide, small toxicity of the chlorine dioxide to human body, therefore can be with More safely implement sterilization and sterilize.Additionally, chlorine dioxide tool has the advantage that：The 0.1ppm as safe concentration with When lower, compare with ozone with formalin, without pungent abnormal smells from the patient, so unhappy sensation will not be produced, Unit Weight is killed Bacterium ability is strong, can play spore, mould, antibacterial, virus etc. excellent sterilizing and bactericidal effect, and does not generate carcinogen, Etc..

On the other hand, chlorine dioxide reactivity is strong and unstable, it is difficult to continue for a long time with finite concentration keeping.Therefore Since in the past, using following methods：Sodium chlorite and acidic liquid are provided into container, are generated by the chemical reaction of the two Chlorine dioxide.For example, if sodium chlorite solution and malic acid solution are mixed, chlorine dioxide is generated.

As the technology for generating chlorine dioxide, for example, there is the technology described in patent documentation 1,2.Patent documentation 1, In 2 technologies recorded, the powder and acidic liquid reaction of sodium chlorite is made, generate chlorine dioxide.Record in patent documentation 1 Technology in, by into container provide Powdered sodium chlorite be limited in below 10g, the concentration for preventing local is raised.This Outward, in the technology that patent documentation 2 is recorded, except making the concentration of local of chlorine dioxide be less than the 10% of explosion limit In addition, also carry out heating from external container and promote reaction, reaction is terminated at the appointed time.

Chlorine dioxide is unstable and easily with other substance reactions generates salt.For example, with the egg for constituting microorganism Sodium in white matter reacts and decomposes, and generates NaCl.But, if as fumigation, only chlorine dioxide with highly concentrated Degree is placed within the enclosed space, then its decomposition rate is excessively slow.Specifically, the peak concentration in closing space is more than 100ppm's Chlorine dioxide decomposes and is reduced to the maximum safe concentration that allowed of operation in 8 hours in 1 day as WHO regulations 0.1ppm, needs up to 10～15 hours（Non-patent literature 1）.In the experiment of the research facilities in the fields such as pharmacy, food, biology In the case of carrying out fumigation with chlorine dioxide in operating room of room and factory or medical facilities etc., in microorganism Until chlorine dioxide decomposes or is removed so as to reach the degree that can restart safety work after sterilization and sterilizing Till, it has to interrupt production activity, research activitiess, medical act etc..

Therefore, it is necessary on one's own initiative decompose the chlorine dioxide after fumigation or remove the dioxy after fumigation Change chlorine body, so as to be effectively reduced the concentration of chlorine dioxide.In the past, adopting makes chlorine dioxide be adsorbed onto activated carbon Or on sulfurous acid ion type brucite or chlorine dioxide is absorbed into containing the reproducibility compound such as water, DMSO The method removed in absorbing liquid（Patent documentation 3, patent documentation 4）；Or using using not containing outside fumigation object space Air in the air displacement fumigation object space of chlorine dioxide, the method for carrying out diluted chlorine dioxide gas.

It is well known that, manganese oxide, permanganate work as metallic catalyst, ozone and foul gass can be decomposed （Patent documentation 5, patent documentation 6）, then develop the ozone deodorizer using above-mentioned principle（Patent documentation 7）.Additionally, public Know, manganese oxide, permanganate can be used for removing gas shape organic impuritiess and inorganic impurity, manganese oxide, permanganate In being contained in the filter material of air cleaning filter（Patent documentation 8）.

But not know can be carried out chlorine dioxide using at least any one party in manganese oxide and permanganate completely Decomposition reaction.

Prior art literature

Patent documentation

Patent documentation 1：Japanese Laid-Open Patent Publication 2009-234857

Patent documentation 2：Japanese Laid-Open Patent Publication 2010-207539

Patent documentation 3：Japanese Laid-Open Patent Publication is flat No. 10-258215

Patent documentation 4：Japanese Laid-Open Patent Publication is flat No. 10-156134

Patent documentation 5：Japanese Laid-Open Patent Publication 2002-224207

Patent documentation 6：Japan Patent publication Te Xu 4166909

Patent documentation 7：Japanese Laid-Open Patent Publication 2007-136415

Patent documentation 8：Japan Patent publication Te Xu the 3936803rd

Non-patent literature

Non-patent literature 1：Yan Cheng Longchangs, he 3, " two acidifying salt element ガ ス To I Ru Move thing Feeding educate room Smoked steaming disappear Let, STOL Hot Industrial Co., Ltd, November 29 in 2008 day, day are applied in poison ", university of the CiMegumi Huiyi sections experiment Move thing researchs of East capital This experiment Move Wu Ring borders research association シ Application Port ジ ウ ム, experiment Move Wu と Ring borders, 17（1）, 23-27,2009

Chlorine dioxide reactivity is strong and unstable, anti-with the dirt on the surface of the various articles for being present in surrounding space Should, salt as NaCl is generated, so as to decompose.It can be said that being difficult to continue to be taken care of with finite concentration for a long time.The opposing party Face, reported that chlorine dioxide decomposed the required time long.For example record in non-patent literature 1, in fumigation Chlorine dioxide of the peak concentration generated in the confined space of needs more than 100ppm, if keeping the state to place, Needs could decompose and reach the maximum safe concentration allowed of operation in 8 hours in 1 day that specifies as WHO for 10 hours to 15 hours Below 0.1ppm.Therefore, in the spaces such as pharmacy facility, food production facilities, biological study facility, medical surgery room, Hypothesis implement chlorine dioxide disinfection in the case of, from generate chlorine dioxide to become safe concentration so as to Restart to manufacture in space in disinfection, test, perform the operation, need the time of more than half a day.Therebetween, it has to interrupt Production activity in the space, research activitiess, medical act.So, in the past, gas have passed through such as three hours after generating After time required for the disinfection of such object space, active carbon filter adsorption-decomposition function two is used in the space Oxidation chlorine body, with the outdoor displacement of the air without the chlorine dioxide dilution space, tries every possible means as far as possible in the short time The residual chlorine dioxide concentration in space is inside set to reach below the 0.1ppm of safe concentration, it is empty using object to restart as early as possible Between.But, even if in this case, the concentration for reducing residual gas is also required to a few hours.

The content of the invention

In view of described problem, it is an object of the invention to provide one kind can generate chlorine dioxide and can use than ever The technology that the shorter time decomposes chlorine dioxide.

Described in order to solve the problems, such as, the present invention generates chlorine dioxide, and using containing manganese oxide and permanganic acid The filter material of at least any one party in salt is decomposing chlorine dioxide.

In detail, the present invention provides a kind of chlorine dioxide and generates system, and it includes：Chlorine dioxide generates dress Put, generate chlorine dioxide；And chlorine dioxide decomposer, suck and released from the chlorine dioxide generating means It is put into the residual gas of the chlorine dioxide of interior and the residual gas is decomposed, the chlorine dioxide decomposes dress Put comprising filter material, the filter material contains at least any one party in manganese oxide and permanganate.

The present invention chlorine dioxide generate system due to possessing chlorine dioxide generating means, so with others Chlorine, sodium hypochlorite, hydrogen peroxide are compared, and more safely can be implemented to sterilize and be sterilized.Further, since chlorine dioxide does not have The like that strong odour nuisance of chlorine, it is possible to which that reduces that odour nuisance when implementing sterilization and sterilizing causes is unhappy Sense.Additionally, the sterilizing ability of chlorine dioxide Unit Weight is strong, can play excellent for spore, mould, antibacterial, virus etc. Sterilizing and bactericidal effect, and carcinogen will not be produced.Additionally, the chlorine dioxide of the present invention generates system due to possessing Chlorine dioxide decomposer, it is possible to time decomposition chlorine dioxide shorter than ever.Due in filter material Containing at least any one party in manganese oxide and permanganate, so compared with conventional activated carbon, can further improve point The performance of solution chlorine dioxide, can further shorten the resolving time reached required for safe concentration.Safe concentration can be with Enumerate the 0.1ppm of maximum safe concentration that operation in 8 hours in 1 day of WHO regulations is allowed.In manganese oxide and permanganate extremely Few any one party is effectively this discovery to decomposing chlorine dioxide, is discovered by the present inventors.Manganese oxide can be with example Lift manganese dioxide（MnO₂）, manganese sesquioxide managnic oxide（Mn₂O₃）, mangano-manganic oxide（Mn₃O₄）Deng.Permanganate can enumerate M^IMnO₄（M^I Represent alkali metal）、M^II（MnO₄）₂（M^IIRepresent alkaline-earth metal）Deng.Additionally, the present invention can be not only used for spore, mould, antibacterial Etc. sterilized and the inactivation of virus that sterilized, made technology, it is also possible to for carrying out parasite killing to tiny insect as psocid etc. Technology.

Room can illustrate the closed space for needing fumigation.Specifically, room can illustrate pharmacy manufacturing facility, food The closed space of fumigation is needed in product manufacturing facility, biological study facility, medical facilities.

Filter material for example can be packed layer, the granule that manganese oxide powder will be condensed into binding agent（ペレット）, with viscous Knot agent containing the permanganate activated carbon or zeolite porous body piece powder agglomerates into granule, be filled into sky In the hermetic container of air flow inlet and air outflow port the two openings, the packed layer is thus obtained.Additionally, filter material can also It is amplifier case, the powder of the Porous containing manganese oxide powder, the activated carbon of permanganate or zeolite is glued with binding agent On the surface contacted with gas of the honeycomb structured body for having aeration, thus obtain amplifier case.

Manganese oxide decomposes what chlorine dioxide was carried out presumably by dismutation reaction as following reaction equation.According to Following reaction equations, thus it is speculated that the more high de-agglomeration performance of the relative humidity in air is better.

（Change 2）

2ClO₂+ H₂O→HClO₂+ HClO₃

It is preferred, therefore, that the chlorine dioxide of the present invention generates system also includes damping device, the damping device The indoor humidification to specified humidity.Due to possessing damping device, it is possible to indoor humidification to specified humidity.Its knot Really, the performance for decomposing chlorine dioxide can further be improved.Specified humidity be 50%～70%, more preferably 55%～ 65%.As noted previously, as the interior that chlorine dioxide is discharged into can be made to become confined space, if so interior once After humidifying once, indoor humidity can be kept for the regular hour.So, damping device can be generated in chlorine dioxide Indoor humidification to specified humidity before device operating.Additionally, damping device can also operate in chlorine dioxide generating means It is middle indoor humidification to specified humidity.Damping device before the operating of chlorine dioxide generating means indoor humidification to rule In the case of determining humidity, damping device can be humidified to the air from indoor suction.Additionally, in damping device in titanium dioxide In the case of indoor humidification to specified humidity in the operating of chlorine body generating means, damping device can be from indoor suction Air wetting, the air wetting after chlorine dioxide can also being decomposed in addition, in other words, by chlorine dioxide Air wetting after decomposer.

Here, it is preferable that, the chlorine dioxide of the present invention generates system also to be included：First path, from the interior The air of suction is provided with the chlorine dioxide generating means by the first path in the first path；Second tunnel Footpath, is provided with the chlorine dioxide decomposer on second path, by the chlorine dioxide decomposer point Air after solution flows through second path；And the 3rd path, the damping device is provided with the 3rd road Jing, by described Air after damping device humidification flows through the 3rd path.

Chlorine dioxide generating means are provided with the first path.Therefore, in chlorine dioxide generating means In operating, in the ratio chlorine dioxide generating means upstream side of first path, the outdoor air such as air outside room is flow through Or from the air of indoor suction, in first path than chlorine dioxide generating means side farther downstream, flow through from titanium dioxide The chlorine dioxide that chlorine body generating means are generated.Additionally, in the non-operating of chlorine dioxide generating means, it is also possible to only Make the air from indoor suction（Circulation air）Flow in first path.By arranging in chlorine dioxide generating means The filter of the impurity contained in air is caught, the impurity contained in the air for flow through first path can be caught.Make circulation In the case that air is circulated in first path, one end of first path can be arranged on the suction inlet of suction room air, the The other end in one path can be arranged on the air outlet that chlorine dioxide is sent to interior.

Chlorine dioxide decomposer is provided with a second path, in the operating of chlorine dioxide decomposer, In the ratio chlorine dioxide decomposer upstream side in the second path, flow through from the air of indoor suction, in the second path Than chlorine dioxide decomposer side farther downstream, chlorine dioxide is decomposed by chlorine dioxide decomposer after The air for obtaining flows through.In the case that air after decomposition is made returns to interior, the one end in the second path can be located at institute Suction inlet is stated, the other end in the second path is located at the air outlet.I.e., it is possible to constituted by total path first path and The suction inlet side in the second path or a part for air outlet side.

Damping device is provided with the 3rd path, in the ratio damping device upstream side in the 3rd path, from indoor suction The air for entering flows through, and in the ratio damping device side farther downstream in the 3rd path, the air after humidification flows through.Room air is being entered In the case of row humidification, the one end in the 3rd path can be located at the suction inlet, the other end in the 3rd path is located at described Air outlet.Can constitute the suction inlet side in the 3rd path or send by the total path total with first path or the second path A part for air port side.Additionally, the one end in the 3rd path can also be under the chlorine dioxide decomposer in the second path Converge trip side.Thus, damping device can be to air chlorine dioxide is decomposed by chlorine dioxide decomposer after Humidified.Therefore, in the 3rd path than damping device upstream side, chlorine dioxide be decomposed after air stream Cross, in the ratio damping device side farther downstream in the 3rd path, chlorine dioxide be decomposed and it is humidified after air flow through.By This, can prevent damping device from being corroded by chlorine dioxide.

Moreover it is preferred that the chlorine dioxide generating means of the present invention also include：Air outlet, is located at the dioxy Change the top that chlorine body generates system, the chlorine dioxide is sent to the interior；And suction inlet, it is located at described sending Chlorine dioxide below air port generates the bottom of system, the residual gas is sucked, from the air outlet chlorine dioxide Gas is blown upward from level.Thus, top indoors can form from chlorine dioxide and generate system level outwardly upwards Air stream, indoors bottom can be formed towards chlorine dioxide generate system side horizontal direction air stream.As a result, can Efficiently to make indoor air circulation, humidity can be adjusted, fumigation is carried out with chlorine dioxide or reduces chlorine dioxide Gas decomposes the required time.Chlorine dioxide generates system and can be disposed in the outdoor and can also be disposed in the interior, and also may be used So that chlorine dioxide is blown out upwards.

Additionally, in the chlorine dioxide generation system of the present invention, it is preferred that the first path and described second Path, suck a part for the suction inlet side of the residual gas or the chlorine dioxide sent to the interior A part for air outlet side, is made up of total path.Additionally, in the chlorine dioxide generation system of the present invention, preferably Be, a part for the suction inlet side of the suction residual gas in the 3rd path or the chlorine dioxide to described A part for the air outlet side that interior is sent, is made up of the total path total with the first path or second path. It is total path by making the part in path, the space in the chlorine dioxide generation system of the present invention can be expanded, or The chlorine dioxide that the present invention can be made generates system compact.Additionally, the part for making path is the titanium dioxide of common path Chlorine body generates system and can reduce the material for using, and is also excellent in economic aspect.

Moreover it is preferred that the chlorine dioxide of the present invention generates system also including：Humidity sensor, is located at described Near the indoor suction inlet, before chlorine dioxide generating means operating, the phase of the indoor air is detected To humidity；And isolating device, after chlorine dioxide generating means operating, by the humidity sensor from containing State the air insulated of chlorine dioxide.

Due to possessing humidity sensor, it is possible to room air of the detection before the operating of chlorine dioxide generating means Relative humidity.Further, since possess isolating device, it is possible to suppress humidity sensor because contacting with chlorine dioxide and Deterioration.

Additionally, in the chlorine dioxide generation system of the present invention, it is preferred that the chlorine dioxide generates dress The chemical reaction by graininess sodium chlorite and acidic liquid is put, chlorine dioxide, the chlorine dioxide life is generated Have into device：Container, houses the graininess sodium chlorite and the acidic liquid；Heater, is carried out to the container Heating；And filter for installation, in catching the chlorine dioxide generated from the container by the heating devices heat The impurity for containing, the chlorine dioxide generates system also includes fan, and the fan is after the filter for installation Chlorine dioxide be sent to the interior.

Although chlorine dioxide generating means are not limited to described structure, but by using described structure, can be with Avoid mist being worried in the prior art, producing with the generation of chlorine dioxide and the dirt caused by solid particle Dye.

Moreover it is preferred that the chlorine dioxide of the present invention generates system also including：Damping device, the interior Humidify specified humidity；And control device, controlling the chlorine dioxide and generate system, the control device makes described adding Wet device operating, when the interior reaches specified humidity, makes the Chlorine dioxide generator operate, when the interior reaches The chlorine dioxide concentration of regulation and when have passed through the stipulated time, makes the chlorine dioxide decomposer operate.

The control is the example that control device is controlled.Controlled as above by control device, Interior can be sterilized and sterilized safely and with the short time.

Here, the present invention can be specified as described chlorine dioxide decomposer.Specifically, the present invention Chlorine dioxide decomposer, suck from generate chlorine dioxide chlorine dioxide generating means to indoor release Chlorine dioxide residual gas and the residual gas is decomposed, the chlorine dioxide decomposer include filter Material, the filter material sucks and decomposes the residual gas, and containing at least any one party in manganese oxide and permanganate.

According to the chlorine dioxide decomposer of the present invention, time decomposition chlorine dioxide shorter than ever can be used Body.Contain at least any one party in manganese oxide and permanganate by making filter material, compared with conventional activated carbon, one can be entered Step improves the performance for decomposing chlorine dioxide, can further shorten the resolving time reached required for safe concentration.

Moreover it is preferred that the chlorine dioxide decomposer of the present invention is also including at least any in components described below One：Prefilter, in the air-flow of the air of suction, is located at the upstream of the filter material；After-filter, in the sky of the suction In the air-flow of gas, the downstream of the filter material is located at；The fan of decomposer, the air for making the interior passes through the filter material；With And cowling panel, it is located at the entrance side of the filter material.

By prefilter, the dust contained in the air that suction can be caught and waste.Additionally, by after-filter, The dust that filter material can be suppressed disperses.Additionally, the fan for passing through decomposer, can make the air of suction reliably by filter Material.Additionally, by cowling panel, can make the air-flow of the air of suction becomes uniform, can improve the seizure performance of filter material.

Additionally, the present invention can also specify the indoor stifling side that system is generated as described chlorine dioxide Method.For example, fumigating method of the invention includes：The step of making described damping device operate；Specify wet when the interior reaches The step of making the Chlorine dioxide generator operate when spending；And when the interior reaches the chlorine dioxide concentration and Jing of regulation The step of making the chlorine dioxide decomposer operate when having spent the stipulated time.Additionally, so-called fumigating includes sterilizing, goes out Bacterium, parasite killing etc. is carried out to tiny insect as the operation of purpose.

Here, as sterilization effective to microorganism and the method for sterilizing, existing using the demand of chlorine dioxide, separately On the one hand, the method for also seeking to be removed by chlorine dioxide fast decoupled and by chlorine dioxide.To the suction of the solid phase Although attached or be diluted it may be said that shorter than the natural decomposition time to the absorption of liquid phase, by ventilation, chlorine dioxide is made Body becomes low concentration needs a few hours.

In light of this situation, the present invention also makees offer with the means that the shorter time effectively decomposes chlorine dioxide For the technical problem to be solved.

The present inventor is intently studied to solve the problem, be finally found that in manganese oxide and permanganate The catalyst that reacts as chlorine dioxide decomposition of at least any one party, can effectively decompose and remove titanium dioxide with the short time Chlorine, so as to complete the present invention.

That is, the present invention is as follows.

[1] the chlorine dioxide decomposition agent containing at least any one party in manganese oxide and permanganate（Hereinafter also it is denoted as " this The distintegrant of invention "）.

[2] according to the chlorine dioxide decomposition agent described in [1], the manganese oxide be from by manganese dioxide, manganese sesquioxide managnic oxide and Select in the group that mangano-manganic oxide is constituted.

[3] according to [1] or [2] the chlorine dioxide decomposition agent, the permanganate is from by M^IMnO₄（M^IRepresent alkali gold Category）And M^II（MnO₄）₂（M^IIRepresent alkaline-earth metal）Select in the group of composition.

[4] containing the chlorine dioxide decomposition filter material of [1]～chlorine dioxide decomposition agent any one of [3]（Hereinafter also remember Make " the decomposition filter material of the present invention " or be simply denoted as " filter material "）.

[5] possesses the chlorine dioxide decomposition device of the chlorine dioxide decomposition filter material described in [4]（Hereinafter also it is denoted as " the present invention Decomposer "）.

[6] including the dioxy of the operation for making chlorine dioxide contact with [1]～chlorine dioxide decomposition agent any one of [3] Change chlorine decomposition method（Hereinafter also it is denoted as " decomposition method of the present invention "）.

[7] the chlorine dioxide decomposition method according to [6], the operation for making the contact is more than 45% in relative humidity Under conditions of carry out.

[8] according to [6] or [7] the chlorine dioxide decomposition method, the operation for making the contact is less than 50 DEG C in temperature Under conditions of carry out.

According to the distintegrant and the method using it of the present invention, can effectively decompose chlorine dioxide with the short time. Additionally, the distintegrant of the present invention as catalyst due to playing a role, so not consuming in decomposition reaction such that it is able to suppress Time of chlorine dioxide decomposition device repair and maintenance, labour and cost.

Chlorine dioxide according to the present invention generates system and chlorine dioxide decomposer, using the teaching of the invention it is possible to provide can generate Chlorine dioxide and can with the time shorter than ever make chlorine dioxide decompose technology.

Description of the drawings

Fig. 1 is that the chlorine dioxide for representing first embodiment generates the side view of the brief configuration of system.

Fig. 2 is that the chlorine dioxide for representing first embodiment generates the top view of the brief configuration of system.

Fig. 3 is the axonometric chart of the brief configuration of the chlorine dioxide generating means for representing first embodiment.

Fig. 4 is the exploded perspective view of the chlorine dioxide generating means brief configuration for representing first embodiment.

Fig. 5 represents an example of the container of the chlorine dioxide generating means of first embodiment.

Fig. 6 is the perspective view of the brief configuration of the chlorine dioxide decomposer for representing first embodiment.

Fig. 7 represents the motion flow of the gas generation system of first embodiment.

Fig. 8 is the figure of the air-flow for representing explanation humidifying air.

Fig. 9 is the figure of the air-flow for representing explanation chlorine dioxide.

Figure 10 is the figure of the air-flow of the process for representing explanation residual gas.

Figure 11 is the figure of the humidity sensor structure for representing explanation second embodiment.

Figure 12 represents the figure of the relation in chlorine dioxide gas concentration and elapsed time.

Figure 13 represents that the chlorine dioxide of variation generates system.

Figure 14 represents that the food for possessing chlorine dioxide generating means and chlorine dioxide decomposer is defeated with powder body Send the brief configuration of system.

Figure 15 represents an example of powder conveyer.

Figure 16 represents the sterilizing handling process of the food powder delivery system of the 4th embodiment.

Figure 17 is the sketch in the close test room used in embodiment.

Figure 18 is the time dependent figure of chlorine dioxide gas concentration in the close test room of the 10m3 in embodiment.

Description of reference numerals

1 ... casing

2 ... chlorine dioxide generating means

3 ... humidifiers

4 ... fans

5 ... chlorine dioxide decomposers

6 ... control devices

7 ... sterile chambers

52 ... entrances

53 ... prefilters

54 ... main filters

55 ... after-filters

56 ... cowling panels

57 ... outlets

11 ... suction inlets

12 ... air outlets

100 ... chlorine dioxides generate system

Specific embodiment

Embodiments of the present invention are illustrated with reference to the accompanying drawings.Embodiments described below is only shown Example, the invention is not restricted to embodiments described below.For example, in the first embodiment, illustrate by taking sterile chamber as an example, But chlorine dioxide generates system and acts not only as sterilizing spore, mould, antibacterial etc. and being sterilized, makes inactivation of virus Technology use, it is also possible to use as the technology that parasite killing is carried out to tiny insects such as psocids.In this case, according to titanium dioxide Chlorine body generates system, and parasite killing not only can be in itself carried out to psocid, and can be to killing as the mould of its food source Bacterium, it is possible to fundamentally prevent psocid from occurring again.

＜ first embodiments ＞

《Chlorine dioxide generates the structure of system》

Fig. 1 is that the chlorine dioxide for representing first embodiment generates system（Hereinafter also referred to as gas generation system） The side view of 100 brief configuration.Fig. 2 is that the chlorine dioxide for representing first embodiment generates the brief knot of system 100 The top view of structure.

The gas generation system 100 of first embodiment includes chlorine dioxide generating means in the casing 1 of box-shaped （Hereinafter also referred to as gas generating device）2nd, humidifier 3, fan 4, chlorine dioxide decomposer（Hereinafter also referred to as gas Body decomposer）5 and control device 6.Gas generation system 100 is located at the sterile chamber as the confined space for needing fumigation The outside of 7 wall 71, from the air being located in the suction inlet 11 of the bottom of casing 1 suction sterile chamber 7, from being located at the top of casing 1 Air outlet 12 is sent chlorine dioxide to sterile chamber 7.On the wall 71 of sterile chamber 7, with suction inlet 11 and air outlet 12 Corresponding position is provided with opening.Thus, sterile chamber 7 is connected by suction inlet 11 with gas generation system 100 with air outlet 12. According to the air from the point of view of the difference of property states from the suction of suction inlet 11, then according to drive manner, from the sky of the suction of suction inlet 11 Gas bag is included：The air in sterile chamber 7 before the operating of gas generating device 2（Air without chlorine dioxide）；Gas is generated The air containing chlorine dioxide in the operating of device 2；Air after the operating of gas generating device 2（Sky containing residual gas Gas）；And by humidifier 3 plus wet air.The air sent from air outlet 12 includes：Gas generating device 2 operates Front and humidified in humidifier 3 operates air（Here is circulation air）；And contain in gas generating device 2 operates The air of chlorine dioxide.Additionally, air outlet 12, suction inlet 11 can also utilize pipeline and be located on the wall 71 of sterile chamber 7 Open communication.Additionally, gas generation system 100 can be arranged only when in use, as long as when taking off the opening of wall 71 Closing just can be with.For example, as long as arranging the devices to be opened/closed such as air door on the opening of wall 71, it is possible to generated using gas During system 100, air outlet 12, suction inlet 11 are connected with the opening on wall 71, make air door become the state of opening, do not used When gas generation system 100 is taken off from wall 71, make air door become closed mode.Additionally, chlorine dioxide generates system System 100 can also be disposed in the interior.In such a case it is possible to air outlet 12 is located at as described above gas generation system 100 Top side, it is also possible to be arranged on the face of the upside of gas generation system 100, gas be sent to top.

《Gas generating device》

In addition to reference to Fig. 1, Fig. 2 the gas generating device 2 of first embodiment is entered referring also to Fig. 3, Fig. 4 below Row explanation.Fig. 3 is the axonometric chart of the brief configuration of the chlorine dioxide generating means 2 for representing first embodiment.Fig. 4 is table Show the exploded perspective view of the brief configuration of the chlorine dioxide generating means 2 of first embodiment.Gas generating device 2 includes The control device 27 of pedestal 21, heater 22, container 23, tank 24, fan filter unit 25, block piece 26 and heater.

The supports heaters 22 of pedestal 21 and container 23.The pedestal 21 of first embodiment is tetragon, is integrally formed For cuboid, the bottom surface of gas generating device 2 is formed.Additionally, being provided with for gripping on relative two side of pedestal 21 The grip part 28 of gas generating device 2.

Heater 22 is arranged on the central part of pedestal 21, and four containers 23 to carrying are heated.Heater 22 is received From the power supply of the control device 27 of gas generating device, according to the instruction operating of the control device 27 of gas generating device.Gas The control device 27 of body generating means includes power supply, CPU and memorizer, and CPU performs storage control program in memory, control Heater processed 22.Heater 22 can also be received from outside power supply, and by the control device of control gas generation system 100 6 are controlled.

Graininess sodium chlorite is put in container 23, by tank described later 24 acidic liquid is provided.Furthermore, it is possible in advance Graininess sodium chlorite is put into container 23, it is also possible to graininess sodium chlorite is put into container 23 using by Electronic Control Device.Container 23 is heated, and graininess sodium chlorite and acidic liquid occur chemical reaction in the inside of container 23, generate dioxy Change chlorine body.Here, Fig. 5 represents an example of the container of the chlorine dioxide generating means of first embodiment.Fig. 5 institutes The container 23 for showing is divided into multiple rooms 232 by dividing plate 231 the inside of container 23.In Figure 5, container 23 includes：It is centrally located , the central compartment 232a for tetragon viewed from above；And four peripheral chambers 232b around the central compartment 232a.Every Plate 231 can be removed freely from container 23.Additionally, being provided with multiple circular through holes 233 on dividing plate 231, each room is Connection.Although circular through hole 233 can also be formed as rectangle, slit, but it is preferred that by the size of circular through hole 233 Be formed as the intransitable size of graininess sodium chlorite.Graininess sodium chlorite for example can be the granule of cylindrical shape. Granular sodium chlorite can also be other shapes.By binding agent and Powdered sodium chlorite's hybrid process into granule ingot（ペ レ ッ ト Ingot drug）Or piece ingot（タ Block レ ッ ト Ingot drug）, graininess sodium chlorite can be formed as arbitrary size and shape.As Binding agent, it is possible to use carboxymethyl cellulose, hydroxyethyl cellulose, Polyethylene Glycol as water-soluble high-molecular compound etc.. Graininess sodium chlorite is due to being solid, so keeping and transport etc. are easily, even if be attached on human body damaging the load of skin The heart is also little.In addition it is also possible to before acidic liquid is provided into container 23, in advance graininess sodium chlorite is configured in container In 23.

Tank 24 stores acidic liquid.The acidic liquid of storage is provided by nozzle 29 to container 23.Acidic liquid for example may be used With using edible organic acids such as malic acid, citric acid, acetic acid.Thus, compared with the situation using the acid such as hydrochloric acid or sulphuric acid, can be with It is safer and easily produce chlorine dioxide.Such as tartaric acid, fumaric acid, succinic acid, gluconic acid, breast can be used The edible acidic aqueous solution such as acid, acetic acid, adipic acid, phytic acid, ascorbic acid or their mixture is used as acidic liquid.This Outward, in the case of using the acid such as hydrochloric acid or sulphuric acid, preferably use acidic liquids of the pH below 3, thus, it is possible to more reliable and Promptly generate chlorine dioxide.

Fan filter unit 25 is located at the top of container 23, and the chlorine dioxide to generating from container 23 is filtered And granular material is caught, send chlorine dioxide.If fan filter unit 25 from the side, air supply direction is Blow from bottom to top, preferably downside be HEPA filters, upside be built-in fans order.The effect of HEPA filters be from The chlorine dioxide of generation removes the microgranule for being dissolved with the mist of chlorine dioxide and remaining after mist is dried as impurity.Institute If the mist stated and microgranule are attached on metal, with very big corrosivity.Therefore, it is intended that the chlorine dioxide for generating Go after the removal of impurity first to pass through built-in fans again by HEPA filters.If on the position HEPA filters and built-in fans Lower exchange, the chlorine dioxide for generating initially are contacted with built-in fans, then be attached in the metal part of fan in impurity In the case of, corrosion can develop, therefore be undesirable.

By the block piece four tetragons（Such as ethylene curtain etc.）Combine, thus block piece 26 surrounds the week of container 23 Enclose, and the inner space of gas generating device 2 is formed together with pedestal 21 and fan filter unit 25.The three of block piece 26 The bottom in individual direction is provided with the gap 30 for the air of surrounding being incorporated into inside gas generating device 2.If fan mistake The built-in fans operating of filter module 25, then suck the air of surrounding by gap 30.Fill due to needing to suppress to be generated in gas Put the chlorine dioxide and mist generated in 2 to leak from gap 30, so needing to make the speed for sucking air from gap 30 be rule It is more than constant speed degree.For example, it is preferable that make from gap 30 suction around air be by pumping velocity during gap 30 More than 15cm/s, preferably sets the built-in wind of fan filter unit 25 in the way of the pumping velocity described in can realizing The air quantity of fan, the gross area in gap 30.Suction inlet 11, gas generating device 2, fan mistake are flow through from the air of the suction of sterile chamber 7 Filter module 25, the path of air outlet 12 are equivalent to first path of the invention.

《Humidifier》

Humidifier 3 is located at the back side of gas generating device 2, and the air to sucking from sterile chamber 7 is humidified.Here, logical The air that separator lined is imported into the air imported to gas generating device 2 and to humidifier 2 is crossed, the two forms respective stream Road.The relative humidity of sterile chamber 7 can be obtained by being arranged on the humidity sensor 9 near suction inlet 11.Humidifier 3 is received and From outside power supply, operate according to the instruction of control device 6.Control device 6 includes CPU and memorizer, and CPU is performed and is stored in Control program in reservoir, according to the relative humidity control humidifier 3 detected by humidity sensor 9.In addition it is also possible in addition The control device of humidifier of control humidifier 3 is set.Suction inlet 11, humidifier 3, air-supply are flow through from the air of the suction of sterile chamber 7 Threeth path of the path of mouth 12 equivalent to the present invention.

《Fan》

Fan 4 is located at the top of fan filter unit 25 and humidifier 3（Downstream）, after chlorine dioxide or humidification Air be sent to sterile chamber 7 in the horizontal direction.Fan 4 is received from outside power supply, is operated according to the instruction of control device 6. Control device 6 includes CPU and memorizer, and CPU performs storage control program in memory, controls fan 4.

《Gas decomposer》

Below in addition to reference to Fig. 1, Fig. 2, referring also to Fig. 6, the gas decomposer 5 of first embodiment is said It is bright.Fig. 6 is the perspective view of the brief configuration of the chlorine dioxide decomposer for representing first embodiment.Gas decomposer 5 the gas decomposer of box-shaped casing 51 in be configured with entrance 52 successively by the order of the air-flow of air, by punched-plate etc. The cowling panel 56 of formation, prefilter 53, main filter 54, after-filter 55, cowling panel 56, the fan of gas decomposer 58 and outlet 57, gas decomposer 5 suck and decompose in from gas generating device 2 to sterile chamber 7 discharge chlorine dioxide The residual gas of gas.Second path of the present invention is formed to outlet 57 from the entrance 52.

Entrance 52 is arranged on casing 51, the side of sterile chamber 7 a adjacent corner of gas decomposer, here, make into The upper end of mouth 52 contacts with gas generating device 2, and is configured in the lower section of gas generating device 2, connects with suction inlet 11, sucks The air of sterile chamber 7.

In the air-flow of the air of suction, in prefilter 53, main filter 54 and after-filter 55, prefilter 53 Most upstream is arranged on, the dust and waste contained in the air for sucking is caught.For example, by so-called gravimetric method have 70% The prefilter of the performance of the capture rate of left and right is constituting prefilter 53.

Main filter 54 is arranged between prefilter 53 and after-filter 55, in other words, in the gas of the air of suction In stream, it is arranged on than prefilter 53 farther downstream and than the position of the upstream of after-filter 55, contains in the air to suction Some chlorine dioxides（Residual gas）Decomposed.In the example shown in Fig. 6, main filter 54 has straight line repeatedly curved Bent pleated structure, with binding agent the powder containing porous masses such as manganese oxide powder, the activated carbon of permanganate or zeolites Granule is condensed into, the granule is adhered to the plate-like substrate with aeration（Polyurethane foam etc.）Surface on so that angle The mode of alternate change is laminated the base material for being adhered with the granule, is consequently formed the pleated structure.Additionally, main filter 54 Can be amplifier case, with binding agent containing porous masses such as manganese oxide powder, the activated carbon of permanganate or zeolites Powder is adhered on the surface contacted with gas of the honeycomb structured body with aeration, is consequently formed the amplifier case.

After-filter 55 suction air air-flow in, in prefilter 53, main filter 54 and after-filter 55 Most downstream is arranged on, suppresses dust of main filter 54 etc. to disperse.It is used in the chlorine dioxide decomposer of the present invention clean In the case of the sterile chamber of clean room standard, preferably after-filter 55 uses HEPA standards or the high-performance mistake of quasi- HEPA standards Filter.But, in the case of the sterile chamber of the low cleanliness factor beyond for toilet, can be for example, by so-called colorimetry In have 65% or so capture rate performance filter constituting after-filter 55.

Cowling panel 56 is located at the outlet side of the entrance side of main filter 54 and after-filter 55, makes the air-flow of the air of suction Become uniform.Thereby, it is possible to further improve the performance that main filter 54 decomposes chlorine dioxide.In addition it is also possible to whole Stream plate 56 is provided only on the side of entrance 52, makes gas decomposer 5 become simpler structure.

View from above, outlet 57 is located on the same plane of the adjacent corner with the entrance 52 diagonally, add with being provided with The path connection of wet device 3.By making outlet with entrance 52 positioned at position diagonally, so-called short circuit can be suppressed.

The fan 58 of gas decomposer is drawn into the residual gas of sterile chamber 7 in gas decomposer 5, makes residue gas Body passes through prefilter 53, main filter 54 and after-filter 55.Additionally, the air from the suction of sterile chamber 7 flows through entrance 52, gas Second path of the path of body decomposer 5 and outlet 57 equivalent to the present invention.Fan 58 is located under gas decomposer 5 Trip, what is thus flow through in fan 58 is the air after chlorine dioxide is decomposed, it is possible to prevent fan 58 by dioxy Change chlorine body corrosion.

Additionally, gas generation system 100 is in addition to described composition, it is also equipped with making what gas generation system 100 was moved Castor and checked each filter or changed etc. the inspection door of repair and maintenance.

《Control device》

Control device 6 is located at the outside of gas generation system 100, including guidance panel, display, CPU and memorizer, CPU performs storage control program in memory, controls gas generation system 100.

《The action of gas generation system》

Action to the gas generation system of first embodiment below is illustrated.Fig. 7 represents first embodiment The motion flow of gas generation system.In the following description, following situations are illustrated as an example：It is corresponding with action Control program is stored in advance in the memorizer of control device 6, and CPU performs control program, to control gas generation system.But It is that gas generation system 100 can also adopt following manner：CPU receives the instruction of the management personnel from gas generation system, Gas generation system 100 is controlled as indicated.

In step S01, humidifier 3, fan filter unit 25 and fan 4 operate.Can be that CPU receives to carry out Self management The instruction of personnel makes described device operate to perform, and in addition can also be to be built-in with timer in control device 6, if having arrived rule Fix time, automatically make each device operate.If the grade of humidifier 3 device operates, step S02 is entered into.

In step S02, if having reached the relative humidity of regulation in sterile chamber 7, humidifier 3 stops, and gas is generated Device 2 operates.Specifically, CPU obtains the information relevant with the relative humidity in sterile chamber 7, judges whether to have reached set Relative humidity.For example, if the relative humidity in sterile chamber 7 has reached 55%～65%, judge to have reached set Relative humidity.If the relative humidity in sterile chamber 7 has reached set relative humidity, CPU stops humidifier 3, makes gas Body generating means 2 operate.Specifically, CPU makes the acidic liquid being stored in tank 24 be supplied to container 23 by nozzle 29, and And make heater 22 operate, container 23 is heated.If gas generating device 2 operates, step S03 is entered into.

In step S03, if the chlorine dioxide that the such regulations of such as 400ppm have been reached in sterile chamber 7 is dense Degree, then stop gas generating device 2（That is, the heater 22 for making gas generating device 2 stops）, only place such as 3 hours this The stipulated time of sample.Method as the indoor chlorine dioxide concentration for having reached regulation is judged, it is possible to use sell on market Chlorine dioxide concentration meter.Furthermore, it is possible to using following manner：According to the volume for different rooms in advance experimentally It is obtaining, from generating means operating is made reach time of normal concentration, if from gas generating device operating is made through Time, then judge the chlorine dioxide concentration for having reached regulation.

Then, in step S04, the fan 58 of decomposer operates.Specifically, CPU makes the wind of gas decomposer Fan 58 operates the stipulated time.The duration of runs of fan 58 and the reduction speed of chlorine dioxide gas concentration according to gas decomposer Relation, precomputing becomes the time of safe concentration, it is hereby achieved that making what the fan 58 of gas decomposer operated Stipulated time.Safe concentration can enumerate the maximum safe concentration that the operator of 8 hours 1 day of WHO regulations is allowed 0.1ppm.For example, according to the gas generation system 100 of first embodiment, can with 30 minutes or so more than 300ppm is dense The chlorine dioxide of degree is reduced to below 0.1ppm.Thus, the release of gas generation system.Additionally, fan 4 and fan filter Device unit 25 can remain in operation according to the behaviour in service of sterile chamber 7.

《The air-flow of air》

The air-flow of air is illustrated below.Fig. 8 is the figure of the air-flow for representing explanation humidifying air.Fig. 8's（A）It is gas Body generates the front view of system 100, Fig. 8's（B）It is the side view of gas generation system 100, Fig. 8's（C）It is that gas generates system The rearview of system 100.Fig. 8's（a）It is and Fig. 8（A）Corresponding top view, Fig. 8's（b）It is and Fig. 8（B）Corresponding vertical view Figure, Fig. 8's（c）It is and Fig. 8（C）Corresponding top view.

Fig. 8 represents the state of step S01, and humidifier 3, fan filter unit 25 and fan 4 operate.Cause This, the air of suction is flowing through suction inlet 11, the gas generating device 2 of non-operating, fan filter unit 25 from sterile chamber 7 First path and circulation in the 3rd path for flowing through suction inlet 11, humidifier 3 and air outlet 12 with air outlet 12.In the first via In footpath, if the built-in fans operating of fan filter unit 25, by the gap 30 for being formed in three directions, surrounding Air is inhaled into, and the air from sterile chamber 7 passes through first path.By the air of first path due to by fan filter Unit 25, so impurity is captured.Additionally, the gas generating device 2 in the air and first path that pass through the 3rd path is outer The total air suction passage in side, and by being humidified by 3 pairs of air by the 3rd path of humidifier, thus make sterile chamber 7 Interior relative humidity gradually rises.

Fig. 9 is the figure of the air-flow for representing explanation chlorine dioxide.Fig. 9's（A）It is the main view of gas generation system 100 Figure, Fig. 9's（B）It is the side view of gas generation system 100, Fig. 9's（C）It is the rearview of gas generation system 100.Fig. 9's （a）It is and Fig. 9（A）Corresponding top view, Fig. 9's（b）It is and Fig. 9（B）Corresponding top view, Fig. 9's（c）It is and Fig. 9 's（C）Corresponding top view.

Fig. 9 represents the state of described step S02, in addition to fan filter unit 25 and fan 4 operate, gas life Also operating into device 2.Identical with the example of Fig. 8, the air of suction is in first path and the 3rd path from sterile chamber 7 Circulation.But, because gas generating device 2 operates, so the chlorine dioxide generated in gas generating device 2 leads to Cross first path.Additionally, the impurity contained in chlorine dioxide can also be caught in fan filter unit 25.Additionally, Because humidifier 3 stops, so will not be humidified by the air in the 3rd path, simply by the 3rd path.

Figure 10 is the figure of the air-flow of the process for representing explanation residual gas.Figure 10's（A）It is the master of gas generation system 100 View, Figure 10's（B）It is the side view of gas generation system 100, Figure 10's（C）It is the rearview of gas generation system 100.Figure 10（a）It is and Figure 10（A）Corresponding top view, Figure 10's（b）It is and Figure 10（B）Corresponding top view, Figure 10's（c） It is and Figure 10（C）Corresponding top view.

Figure 10 represents the state of described step S04, in addition to fan filter unit 25 and fan 4 operate, gas The fan 58 of decomposer is also operating.Therefore, in the sterile chamber 7 suction air is in first path and flows through suction Mouthfuls 11 with the entrance 52 of the inlet side communication of first path, gas decomposer 5 and going out for connecting near the 3rd path inlet Circulate in second path of mouth 57.But, due to gas generating device 2 be non-operating, so by the air of first path by In new chemicals quality will not be endowed by fan filter unit 25, so impurity is captured.In addition the second tunnel is passed through The air in footpath due to by gas decomposer 5, so residual gas is decomposed.

《Effect》

The chlorine dioxide of first embodiment described above generates system 100 due to possessing gas generating device 2, So compared with other chlorine, sodium hypochlorite, hydrogen peroxide, more safely can implement to sterilize and sterilize.Additionally, chlorine dioxide Gas does not have chlorine odour nuisance strong like that, it is possible to reduce when implementing sterilization and sterilizing because of odour nuisance The unplessantness displeasure for causing.Additionally, the sterilizing ability of chlorine dioxide Unit Weight is strong, spore, mould, antibacterial, virus etc. can be sent out Excellent sterilizing and bactericidal effect are waved, and carcinogen will not be generated.Additionally, the gas generation system 100 of first embodiment Due to possessing gas decomposer 5, it is possible to time decomposition chlorine dioxide shorter than ever.Due in main filtration Filter material comprising the powder containing porous masses such as manganese oxide powder, the activated carbon of permanganate or zeolites, institute used in device 54 Decompose the performance of chlorine dioxide compared with conventional activated carbon, can further improve, and titanium dioxide can be made The chlorine body resolving time required till becoming safe concentration is shorter.

＜ second embodiments ＞

Figure 11 is the figure of the structure of the humidity sensor 9 for representing explanation second embodiment.In this second embodiment, it is wet Degree sensor 9 is located in probe tube 91, probe tube is opened and closed freely by the electromagnetic valve 92 being located on probe tube 91.Probe tube 91 With electromagnetic valve 92 equivalent to isolating device of the invention.Additionally, humidity sensor 9 is connected by cable with control device 6.This Outward, humidity sensor 9 can also show that recorder is connected with humidity sensor.Additionally, the cardinal extremity of suction pump 93 and probe tube 91 Connection, the air in sterile chamber 7 can be drawn in probe tube 91.Aerofluxuss from suction pump 93 can be to the row of sterile chamber 7 Go out.Additionally, by the way that electromagnetic valve 92 and suction pump 93 are electrically connected with control device 6, can be by control device 6 to electromagnetic valve 92 It is controlled with suction pump 93.

Action to the humidity sensor 9 below is illustrated.First, electromagnetic valve 92 is made until gas generating device 2 will operate become open mode before, and make suction pump 93 operate.Thus the air in sterile chamber 7 is drawn into probe tube In 91.Wind speed around humidity sensor 9 is determined by the flow of air when aspirating.It is excellent in order to improve the precision of humidity sensor 9 Choosing, the wind speed is set to the wind speed for being workable moisture sensor 9.For example it is preferably, wind speed is 10cm/s～20cm/ The mild wind speed of s.

Then, before gas generating device 2 will operate, electromagnetic valve 92 is made to become closed mode.Thus, even if thereafter Chlorine dioxide is generated by gas generating device 2, chlorine dioxide and humidity sensor 9 also will not directly contacts.

Then, before electromagnetic valve 92 will become closed mode, the relative humidity detected by humidity sensor 9 Information input is to control device 6.

According to the gas generation system 100 of second embodiment, except the gas generation system with first embodiment Beyond 100 effect, due to possessing probe tube 91 and electromagnetic valve 92, so can also suppress because of humidity sensor 9 and titanium dioxide The deterioration of the humidity sensor 9 that chlorine body contact is caused.

The embodiment ＞ of ＜ the 3rd

Action in step S03 can be carried out as shown below.Specifically, CPU can be such that nozzle 29 opens simultaneously The acidic liquid being stored in tank 24 is supplied to after container 23, after it have passed through the stipulated time, makes heater 22 operate.Can be with The described stipulated time is determined according to the shapes and sizes of sodium chlorite.For example, graininess sodium chlorite and acidic liquid are made In the case of reaction, it is stipulated that the time can adopt 10 minutes or so.

For example, in the case where the room temperature of sterile chamber 7 is 20 DEG C～30 DEG C scopes, the powder Asia chlorine of granule is not being formed Sour sodium and the mixed chlorine dioxide gas concentration of acidic liquid, are just reaching the half of peak value or so in several minutes 200ppm.On the other hand, confirm：In the reaction of graininess sodium chlorite and acidic liquid, under room temperature state, to mixing 10 minutes or so afterwards, the concentration of chlorine dioxide was the concentration to management personnel and operator safety（15 points of such as WHO The exposed pointerforsafety of the temporary transient short-term of clock is 300ppb=0.3ppm）Below.But determines that arriving：In case of heating, pass through Safe concentration is just exceeded within 2 minutes～3 minutes（With reference to Figure 12）.Therefore, after acidic liquid is put into, such as through 5 minutes After heated, thus management personnel and operator can have enough back off times.Additionally, after acidic liquid is put into Jing Heated after having spent more than 10 minutes, thus as shown in figure 12, till 10 minutes or so, chlorine dioxide it is dense Spend for below safe concentration, it can be ensured that more sufficient back off time.

As described above, on the operating opportunity by controlling heater 22, can further improve safety.

＜ variations ＞

In the first embodiment, first path, the second path, the 3rd path are all housed in gas generation system 100, But as shown in figure 13, it is also possible to by the pipeline for being located at the outside of gas generation system 101（The pipe of the upstream of gas decomposer 5 Road 81, the pipeline 82 in the downstream of gas decomposer 5）The part in the second path is constituted, in addition can also be the wind of decomposer Fan 58 is located in the pipeline（For example in the pipeline 82 in the downstream of gas decomposer 5）.Thus, due to gas being decomposed into dress Put the space in 5 and ensure bigger space, it is possible to increase main filter 54, such that it is able to improve gas decomposer 5 Decompose the performance of chlorine dioxide.

Additionally, chlorine dioxide generates system 100 to be not limited to make the mode of indoor air circulation, or full extraneous air Mode：Room air is for example not limited to, makes outdoor air etc. flow into chlorine dioxide generating means 2, can also be following Mode：Gas decomposer 5 is for example arranged on roof portion, indoor chlorine dioxide is sucked and is divided chlorine dioxide Outdoor is discharged to after solution.Additionally, the air for flowing into damping device can also be from outdoor inflow.

The embodiment ＞ of ＜ the 4th

In the 4th embodiment, to gas generating device 2 and gas decomposer 5 for food powder conveying system The situation of the sterilization of system 200 is illustrated.Figure 14 represents possess chlorine dioxide generating means 2 and chlorine dioxide The food of decomposer 5 brief configuration of powder delivery system 200.Additionally, for the embodiment phase having been described above Same structure, using identical reference, and eliminates explanation.

Food includes three powder conveyers 201 with powder delivery system 200（Three powder conveyers 201 have been concentrated Come, also referred to as attract to load unit below）, each powder conveyer 201 connected by delivery pipe 202.4th embodiment party Food powder body in formula（Hereinafter also referred to as powder body）It is mixed powder, three powder conveyers 201 are connected so that can be grain The footpath powder body different with density is maintained and conveyed under uniformly mixed state.Additionally, connecting on each powder conveyer 201 There is service 217, service 217 is the process of powder body introducing technology（Such as food manufacturing）Device（Without expression in figure）. Therefore, the part in the powder body in powder conveyer 201 is sent to process treatment device by service 217（Example Such as specific food manufacturing device）, remaining part is sent to the powder conveyer 201 in downstream by delivery pipe 202.PROCESS FOR TREATMENT Device includes the food manufacturing device of manufacture certain food and constitutes the device of the powder conveyer 201 of conveying powder body.

Additionally, food powder delivery system 200 includes the branched pipe 203 from the branch of delivery pipe 202.Branched pipe 203 is The piping system used in sterilizing described later, is arranged on the attraction loading unit being provided with as one of process treatment device Pipeline entrance and exit midway.In more detail, one end of branched pipe 203 and food powder delivery system 200 The neighbouring connection of powder conveying entrance 204, the other end and food powder conveying of powder delivery system 200 export 205 it is attached Nearly connection.Valve 206,207 is provided with branched pipe 203.In the valve 208 and powder conveying that make near powder conveying entrance 204 The valve 206,207 that valve 209 near outlet 205 becomes closed mode and makes to be located on branched pipe 203 becomes the shape of open mode Under state, the valve near 205 is exported to powder conveying by the position from the valve 208 near than powder conveying entrance 204 farther downstream With branched pipe 203 between 209, a closing space is formed.The closing space is implemented equivalent to " room " of the present invention the 4th In mode, in order to implementing sterilizing in the closing space, gas generating device 2 is provided with branched pipe 203 gentle Body decomposer 5.

Figure 15 represents an example of powder conveyer.Powder conveyer 201 include blower fan 210, loader body 211, Filter 212, air door 213 and gas tank 214.Blower fan 210 is connected by suction tube 215 with loader body 211, suction dress The air of carrier aircraft main body 211 and the delivery pipe 202 being connected with loader body 211, by delivery pipe 202 powder body is aspirated.Load The powder body that the storage suction of owner's body 211 comes.Air door 213 is that hammer discharges air door, if the powder body stored in loader body 211 Amount more than ormal weight is reached and has stopped the suction of blower fan 210, then air door 213 has become open mode.In loader body When the amount and blower fan 210 that the powder body stored in 211 is not reaching to more than ormal weight is aspirated, air door 213 becomes closing shape State.Filter 212 is located in loader body 211, is blocked powder body and is only bypassed air through.It is high pressure in gas tank 214, if beaten Open without the valve for representing in figure, then from the open end injection air of the pipe arrangement 216 configured upward immediately below filter 212.Match somebody with somebody One end of pipe 216 is connected with gas tank 214.The other end of pipe arrangement 216（Open end）Match somebody with somebody in the way of in the face of the inner side of filter 212 Put.

The control device 218 of powder conveyer includes power supply, CPU and memorizer, and CPU is performed and stored in memory Control program, controls powder conveyer 201.Specifically, the control device 218 of powder conveyer is to blower fan 210 and gas tank 214 Valve（Without expression in figure）It is controlled.The function of the control device 218 of powder conveyer can also be generated by control gas The control device 6 of system is performed.

If the action of blower fan 210, powder body is aspirated by the delivery pipe 202 with the neighbouring connection of filter 212, be sucked Powder body contact with filter 212, and be stored in loader body 211.If the powder body in loader body 211 is stored It is more than ormal weight, blower fan 210 stop, then make air door 213 become open mode using the gravity of powder body, powder body falls.From each powder The powder body that the lower section of the respective air door 213 of body conveyer 201 falls a, part is sent at each technique by service 217 Reason device（The manufacture device of such as specific food）, the remaining powder conveyer 201 being partially disposed within farther downstream Blower fan 210 is aspirated, and by delivery pipe 202 powder conveyer 201 in downstream is sent to.When blower fan 210 stops, if from gas tank 214 injection air, then by pipe arrangement 216, the air of injection is discharged from the inner side of filter 212, is attached on filter 212 Powder body falls and is removed.

Additionally, in the example, the intermittent running of blower fan 210 is made, but hammer can also be substituted with rotary valve and discharged Air door 213, and continuously run blower fan 210.Additionally, the powder conveyer 201 shown in Figure 15 uses the suction conveying powder of blower fan 210 Body, but powder conveyer 201 can also use a compressor to pressure conveying powder body.

Gas generating device 2 generates chlorine dioxide.Gas decomposer 5 is sucked and decomposed from gas generating device 2 The residual gas of the chlorine dioxide being discharged in closing space.Control device 6 includes power supply, CPU and memorizer, CPU Perform storage control program in memory, control gas generating device 2 and gas decomposer 5.Additionally, gas generates dress Putting 2 can also be by the control device of the gas generating device of control gas generating device（Gas generating device equivalent to Fig. 4 Control device 27）It is controlled.

Gas generating device 2 and gas decomposer 5 are moved when sterilizing is carried out with powder delivery system 200 to food Make.In other words, when food carries out powder conveying with powder delivery system 200, the valve near powder conveying entrance 204 is made 208 and powder conveying outlet 205 near valve 209 become open mode, become the valve 206,207 being located on branched pipe 203 Closed mode, gas generating device 2 and gas decomposer 5 become the state of stopping.In this condition, if each blower fan 210 Action, then export 205 from powder conveying entrance 204 to powder conveying, and powder body is sucked in food powder delivery system 200 Conveying.

The sterilizing of the food powder delivery system 200 of the 4th embodiment is processed below is illustrated.Figure 16 Represent the sterilizing handling process of the food powder delivery system of the 4th embodiment.In step s 11, powder conveying is made The valve 209 near valve 208 and powder conveying outlet 205 near entrance 204 becomes the state of closing, makes to be located at branched pipe 203 On valve 206,207 become the state of opening.The opening and closing of each valve can also be carried out by management personnel, in addition it is also possible to make each valve For electromagnetic valve, controlled by control device 6.If the opening and closing of each valve terminates, step S12 is entered into.

In step s 12, perform sterilizing to process.By the valve 208 near than powder conveying entrance 204 farther downstream Position to powder conveying outlet 205 near valve 209 between with branched pipe 203, formed a closing space, gas generate dress Put 2 to operate in closing space.Then, if reaching the chlorine dioxide gas concentration of regulation in closing space（For example 400ppm）, then gas generating device 2 stop, for example only place 3 hours as the stipulated time.Then, the wind of decomposer is made Fan 58 operates the stipulated time（Such as 30 minutes）, make gas by the valve 208 near than powder conveying entrance 204 farther downstream Position to powder conveying outlet 205 near valve 209 between with branched pipe 203 formed a closing space interior circulation.By This, sterilizing process terminates.Additionally, the fan of the chlorine dioxide gas concentration of the regulation, standing time and decomposer 58 duration of runs, can be changed according to the equipment of sterilizing.For example, in closing space in the case that bacterium is more, can So that the chlorine dioxide gas concentration of regulation is higher, and shorten the time of placement.In the chlorine dioxide for determining the regulation The duration of runs aspect of the fan 58 of bulk concentration, standing time and decomposer, it is preferred that in a part for closing space （Such as delivery pipe 202）Upper setting probe tube, and the state of bacterium is confirmed in advance.If sterilizing process terminates, enter into Step S13.

In step s 13, the valve 209 near the valve 208 and powder conveying outlet 205 near powder conveying entrance 204 is made Become the state of opening, make the valve 206,207 being located on branched pipe 203 become the state of closing.The opening and closing of each valve can be by managing Reason personnel are carried out, in addition it is also possible to make each valve be electromagnetic valve, are controlled by control device 6.If the opening and closing of each valve terminates, Then restart to convey powder body.

The 4th embodiment described above food with powder delivery system 200, generate dress due to possessing gas 2 are put, so compared with other chlorine, sodium hypochlorite, hydrogen peroxide, more safely can implement to sterilize and sterilize.Further, since Possesses gas decomposer 5, it is possible to time decomposition chlorine dioxide shorter than ever.Filled by decomposing in gas Put and include used in 5 main filter the powder containing porous masses such as manganese oxide powder, the activated carbon of permanganate or zeolites Filter material, compared with conventional activated carbon, can further improve the performance for decomposing chlorine dioxide, further shorten and reach Resolving time required for safe concentration.Additionally, conveying the food of food powder body with powder delivery system 200, worry Produce mould and odour nuisance in delivery pipe 202 to be attached in delivery pipe 202.But, in the 4th embodiment Food with powder delivery system 200, due to possessing gas generating device 2 and gas decomposer 5, it is possible to suppress produce It is mould, it is furthermore possible to remove the odour nuisance of attachment.

Additionally, humidifier can also be arranged in the food powder delivery system 200 of the 4th embodiment.Additionally, The gas generation system 100 of first embodiment can also be connected on the food powder delivery system 200 of the 4th embodiment.

Suitable embodiment of the invention is illustrated above, but gas generation system, the gas generation of the present invention Device and gas decomposer not limited to this, can as far as possible combine including them.Additionally, the gas of the present invention generates system System, gas generating device and gas decomposer can also be used in various fields beyond described embodiment.For example, Can also be so-called draft chamber（ドラフトチャンバ）Generate with harmful substance exhaust apparatus as safety cabinet and gas Device and gas decomposer connect, and carry out the sterilization and sterilizing of harmful substance exhaust apparatus.For example cover cover seal with ethylene Harmful substance exhaust apparatus.Now making the air suction door of harmful substance exhaust apparatus becomes semitight state.From being configured in The chlorine dioxide generating means stated in seal closure generate chlorine dioxide, keep certain concentration.Chlorine dioxide Each corner inside harmful substance exhaust apparatus is diffused into from the air suction door of semitight state, the effect of sterilization is played. Then, after the stipulated time, make the gas decomposer 5 being configured in cover operate, suck and decompose the chlorine dioxide in cover Gas.

Additionally, gas generating device 2 and gas decomposer 5 can be arranged on the midway of pipe arrangement and pipeline.In pipe arrangement In the case of by valve and the space of valve closure（One area of pipe arrangement）And the sky closed by air door and air door in the case of pipeline Between（One area of pipeline）In, sterilizing process and deodorizing process can be carried out.For example, in the example shown in Figure 14, lead to Crossing makes valve 206,207 become closed mode, makes gas generating device 2 and gas decomposer 5 operate, can be to valve 206 and valve Sterilizing process and deodorizing process are carried out in branched pipe 206 between 207.Valve, pipe are usually provided with pipe arrangement and pipeline Road.Therefore, it can to carry out in the pipeline in the pipe arrangement between valve and valve and between air door and air door sterilizing process and Deodorizing process.Sterilizing process can also be carried out to an interval of pipe arrangement and pipeline, in addition it is also possible to from pipe arrangement and pipeline One end carry out sterilizing process to other end order.As noted previously, as being usually provided with valve, pipe on pipe arrangement and pipeline Road, so gas generating device 2 and gas decomposer 5 can be readily applied to configured pipe arrangement, pipeline or possess Their facility.Used as the technology for being sterilized to closing space, being sterilized, the gas that can widely use the present invention generates system System, gas generating device and gas decomposer.

The distintegrant of the ＞ chlorine dioxide of ＜ 1

The distintegrant of the present invention contains at least any one party in manganese oxide and permanganate as effective ingredient.

Here, as manganese oxide, preferably manganese dioxide（MnO₂）, manganese sesquioxide managnic oxide（Mn₂O₃）And mangano-manganic oxide （Mn₃O₄）, it is possible to use any one party in them, can also combine them in addition, because manganese dioxide is readily obtained and valency Lattice are cheap, it is preferred that manganese dioxide.Additionally, manganese monoxide（MnO）Oxidability it is weak, this is not suitable as sometimes Bright distintegrant.Additionally, from the viewpoint such as take precautions against natural calamities, it is preferred that do not use manganese heptoxide as the distintegrant of the present invention （Mn₂O₇）.

Additionally, as permanganate, preferably from by M^IMnO₄（M^IRepresent alkali metal）And M^II（MnO₄）₂（M^IIRepresent alkali Earth metal）Select in the group of composition.

Can be the mode containing manganese oxide and without permanganate, it is also possible to be free from the distintegrant of the present invention Manganese oxide and the mode containing permanganate, can also be the mode containing manganese oxide and permanganate both sides, without special Limit.

The distintegrant of the present invention is decomposed the mechanism of chlorine dioxide and be speculated as being carried out by following reaction.

When chlorine dioxide is contacted with the distintegrant containing at least any one party in manganese oxide and permanganate, if deposited In Organic substance and reducing inorganic thing as ferrum, sulfide, then they consume chlorine dioxide and generate salt so that titanium dioxide Chlorine decomposes.For example, illustrate in case of existing as impurity using ferrum.

First, the chlorine dioxide as strong oxidizer is reduced and becomes free radical（Reaction equation 1）.Here, chlorine dioxide Oxidation-reduction potential（E°）For 0.954V, it is believed that at least any one party in manganese oxide and permanganate is acted as catalyst With the promotion reaction.Then, the ClO of generation₂ ^-It is dissolved in distintegrant and decomposes in the absorption water of surface of filter medium, as sub- chlorine Acid ion and chlorate ions are present（Reaction equation 2）.

ClO₂+ e^-→ClO₂ ^-（Reaction equation 1）

Then, ferrum is oxidized, and is dissolved in absorption water as cation.

Fe→Fe²⁺+ 2e^-Or Fe³⁺+ 3e^-（Reaction equation 3）

Described reaction is used as the overall reaction for carrying out reaction equation 4 or reaction equation 5.

2ClO₂ ^-+ Fe²⁺→FeCl₂+ 2O₂（Reaction equation 4）

6ClO₃ ^-+ 2Fe³⁺→2FeCl₃+ 9O₂（Reaction equation 5）

In the decomposition reaction, because manganese oxide, permanganate work as catalyst, so not being consumed. Therefore manganese oxide, permanganate can suppress the dimension of decomposer described later as chlorine dioxide decomposition agent Reusability Time of guarantor, labour and cost.Additionally, compared with the method to liquid phase scrubbing, it is possible to reduce the weight of decomposer, Ke Yigeng Easily use.

The content of at least any one party in manganese oxide and permanganate in the distintegrant of the present invention is without special limit It is fixed, can arbitrarily adjust in the range of 0.01～99.9 weight %.With regard to manganese oxide, its content is preferably 50～95 weight %. If content is less than 50 weight %, sometimes the decomposition efficiency of chlorine dioxide is reduced, in addition if greater than 95 weight %, although decomposed Efficiency high, but due to binding agent described later etc. others composition content it is few, so can produce dry linting and rise dirt, conduct sometimes The performance of distintegrant deteriorates.With regard to permanganate, due to being readily soluble in water, so as will be described later, preferably make The content of permanganate becomes the content for considering the other compositions and its construction for containing together.

Generally, the by-product of manganese oxide and permanganate as battery materials such as manganese dry cell, alkali manganese aneroid battery, lithium aneroid battery The situation of thing and commercialization is a lot, therefore can obtain from the by-product of the battery material.In the present invention, manganese oxide is pure Degree is preferably more than 85 weight %, more than more preferably 90 weight %.Additionally, generally manganese oxide can be obtained in the way of powder Arrive, its particle diameter distribution at 0.1 μm～60 μm or so, accumulation median particle diameter（Median diameter）Preferably 15 μm～50 μm.Additionally, Its BET specific surface area is preferably 25～100m²/g。

Additionally, under conditions of effect of the present invention is not damaged, the distintegrant of the present invention can also be containing other compositions.Make For other compositions, the adsorbents such as activated carbon and kieselguhr, the binding agent shaped for distintegrant etc. can be enumerated.As bonding Agent, can enumerate Ludox（シリカゾル）And alumina sol（アルミナゾル）Deng inorganic binder, hydrophobicity it is strong and Low macromolecule resin of reactivity etc..The macromolecule resin that reactivity is low as hydrophobicity is strong, can enumerate polyolefin, Buddhist nun Dragon, polyethylene terephthalate, polrvinyl chloride, polyvinylidene chloride etc..

The distintegrant of the present invention can be the powder former state state of at least any one party in manganese oxide and permanganate Form, from from the viewpoint of usability, the distintegrant of the present invention can also be the various forms such as granule, fiber, cloth, lamellar body, In addition various constructions can also be processed into.Especially for permanganate, preferably have in activated carbon or zeolite etc. Contain 0.01～3.0 weight % in punctulate porous body piece, more preferably containing 0.1～1.0 weight %.If fewer than 0.01 Weight %, then occasionally there are the situation of the chlorine dioxide decomposition degradation in efficiency of catalyst reaction, many if being more than 3.0 weight % The pore of hole body piece is easily blocked by permanganate, and sometimes chlorine dioxide is difficult to enter in the pore, so as to impair Catalyst reaction.Additionally, the BET specific surface area of the porous body piece containing permanganate is preferably 25～100m²/g。

The ＞ chlorine dioxide decomposition filter materials of ＜ 2

The distintegrant of the present invention can be contained in chlorine dioxide decomposition filter material.

There is no particular limitation for the form of filter material, from from the viewpoint of the efficiency of the decomposition method of the present invention described later, leads to Frequently with the form of suitable decomposition gas chlorine dioxide.

As described form, from from the viewpoint of the efficiency of decomposition reaction, such as preferably column packing, filter Etc. the form that can increase with the contact area of chlorine dioxide.

More specifically, can enumerate：Manganese oxide powder is condensed into the form of granule with binding agent, containing the height Form that the porous body piece of manganate is filled in the containers such as post, the porous body piece containing the permanganate is filled into many Form of filter configuration etc. is formed in the bag that block non-woven fabrics are formed.

In this case, particularly in the case where being filled in the containers such as post, the size of granule and porous body piece Preferably major diameter is 1～10mm, and more preferably major diameter is 2～5mm.If size is too small, in chlorine dioxide described later In decomposition method, when entering to exercise the air containing chlorine dioxide through the process of the post for making the air contact with distintegrant, relative to Certain process air quantity, aeration resistance increase, occasionally resulting in air-supply power cost increases.If additionally, size is excessive, sometimes Granule easily generates flour when contacting with each other, sometimes due to process object air contact granule surface area diminish and Causing the decomposition efficiency of chlorine dioxide reduces.Accordingly, it is considered to contribute to the sky of the decomposition efficiency of chlorine dioxide and process object The balance of the aeration resistance in the surface area and ventilation treatment of the granule of gas contact, preferably enumerates described scope.

Additionally, the BET specific surface area of granule and porous body piece is preferably 25～100m²/g。

Additionally, the shape of granule and porous body piece whether spheroid, discoid, broken shape etc. can.

Additionally, as the binding agent formed used by granule, the inorganic binders such as Ludox and alumina sol can be enumerated.

Or, it would however also be possible to employ following manner：With binding agent at least appointing in containing manganese oxide powder and permanganate Anticipate the ventilation body of a side（Logical mood body）Adhere on the surface contacted with gas of the structural member with aeration, formed and filtered Device.

For example it is in the way of on inorganic matters are constituted ventilation body so that manganese dioxide powder is carried on inorganic binder Example is illustrated.

Here, the specific surface area of manganese dioxide powder is preferably 25～100m²/g.Additionally, be preferably in practical, The particle diameter of manganese dioxide powder is 0.1～60 μm or so, accumulation median particle diameter（Median diameter）For 15 μm～50 μm.

Additionally, as inorganic binder, being preferably distributed in 15～300 angstroms with fine pore（オングストロー ム）The pore of scope, it is preferred that with N₂In the case that gas adsorption method is measured, the total measurement (volume) of the pore of inorganic binder Specific surface area for more than 0.2cc/g, or the preferably pore of inorganic binder is in the case where being measured with BET method 100m²/ more than g.In the mode, inorganic binder is played and is internally formed the runner that passes through chlorine dioxide in filter material Effect.As inorganic binder, although there is no particular limitation, but due to such as silicon dioxide, aluminium oxide or they Mixture does not need adhesion auxiliary material, it is preferred that using silicon dioxide, aluminium oxide or their mixture.As dioxy SiClx for example uses Silica hydrogel, and as aluminium oxide alumina gel is for example used.

Manganese dioxide powder is preferably with the weight ratio of inorganic binder, manganese dioxide：Inorganic binder=1：1～ 20：1 scope.If manganese dioxide is fewer than the amount of inorganic binder, sometimes the decomposition efficiency of chlorine dioxide is reduced, if two The amount of manganese oxide exceedes 20 times of the amount of inorganic binder, although then the resolution ratio of chlorine dioxide is high, sometimes can not Manganese dioxide powder is fully bonded on ventilation body, dry linting can be produced and dirt is played.

As the inorganic matters for constituting ventilation body, for example, use by ceramic fibre, glass fibre, silicon dioxide fibre, oxidation The cell structure that the inorfils such as aluminum fiber are constituted.The shape of ventilation body is, for example, ojosa or fold building etc., is not had It is special to limit.

In the case where so only filter is constituted with inorganic matters, compared with the filter with compositions such as such as activated carbons, Due to so being safe at aspect of taking precautions against natural calamities, thus being preferred with noninflammability.

In addition it is also possible to pass through thermal welding the porous containing at least any one party in manganese oxide powder and permanganate Body is bonded on the macromolecular fibre that hydrophobicity is strong and reactivity is low, desired being processed into non-woven fabrics made by the fiber Shape, as filter material.Can use polyolefin, nylon, gather as the macromolecular fibre that hydrophobicity is strong and reactivity is low Ethylene glycol terephthalate, polrvinyl chloride, polyvinylidene chloride etc., there is no particular limitation.

As it is explained in detail hereinafter, the decomposition method of the present invention is using the distintegrant by making chlorine dioxide and the present invention（Catalyst） The reaction for contacting and carrying out.Therefore, in the case where chlorine dioxide is gas, from from the viewpoint of being more effectively carried out reacting, Preferably, by the porous body powder containing at least any one party in manganese oxide powder and permanganate, being carried on example Such as on the general zeolite of adsorbent and activated carbon porous material, thus improve in manganese oxide powder and permanganate extremely Chlorine dioxide concentration near few any one party.

The ＞ chlorine dioxide decomposition devices of ＜ 3

The decomposition filter material of the present invention can be arranged on described chlorine dioxide decomposition device（Gas decomposer）In.This Outward, decomposer of the invention can also be combined with various other devices.For example with Japanese Laid-Open Patent Publication It is disclosed in No. 2009-234887 and Japanese Laid-Open Patent Publication 2010-207539 grade, make use of chlorine dioxide The chlorine dioxide generating means combination of body generation method, may be constructed sterilizing and sterilization equipment unit, due to having Effect ground carries out chlorine dioxide generation process, sterilizes and sterilization process, decomposition process this series of operation, so being preferred.

The decomposition method of the ＞ chlorine dioxide of ＜ 4

The chlorine dioxide decomposition agent of the present invention can decompose chlorine dioxide by contacting with chlorine dioxide.Here, although two Chlorine monoxid whether liquid condition or gaseous state can, but from the contact and decomposition reaction with the distintegrant of the present invention From the viewpoint of efficiency and in view of apportioned effort is generally carried out after the sterilization of chlorine dioxide and sterilization processes, lead to Often using the chlorine dioxide of gaseous state as decomposition object.

In the operation for making chlorine dioxide contact with the distintegrant of the present invention, in order to effectively carry out the operation, preferably It is to make the medium containing chlorine dioxide（Typically air）Circulate near the distintegrant of the present invention.

As previously described, because think to need the presence of water in the decomposition reaction of chlorine dioxide, so the sky for being decomposed Between relative humidity be preferably more than 45%RH, more preferably more than 55%RH, it is further preferred that more than 65%RH.This Below 90%RH, more preferably below 80%RH, it is further preferred that below 70%RH are preferably outward.Can connect described It is advance before tactile operation to humidify to implementing space, it is also possible to carry out adding to implementing space simultaneously with the operation of the contact It is wet.

Additionally, generally for the effect of sterilization and the sterilizing for improving chlorine dioxide, it is contemplated that relative humidity is preferably 50% More than RH, more preferably more than 65%RH（With reference to Japanese Laid-Open Patent Publication 2010-207539）, then two are being carried out In the case of chlorine monoxid generation process, sterilization and a series of sterilization process, decomposition process this operation, preferably during operation Space humidity is persistently made in the higher scope.

The temperature in the space decomposed is preferably less than 50 DEG C, more preferably less than 40 DEG C, further preferred It is less than 30 DEG C.

It is well known that, in silica glass surface, under conditions of 22 ± 2 DEG C, in the gas of relative humidity 11% or 33% Under atmosphere, the water on surface is with than 7.6 μm of ol/m²Less amount saturation, under the atmosphere of relative humidity 43% or 51%, with firm on surface Good 7.6 μm of ol/m equivalent to 1 layer²Water saturation, under the atmosphere of relative humidity 75%, with 15 μm of ol/m equivalent to 2 layers²'s Water saturation（Document " silica glass and water " original work K.E.Collins, V.R.Camargo, A.B.Dimiras, D.T.C.Menezes, P.A.Silva, C.H.Collins, J.Colloids＆InterfaceSci., 291,353 (2005)）.

Thus it is speculated that in the manganese oxide powder contained in room temperature, the distintegrant of the present invention and permanganate extremely The surface of the powder and Porous piece of few any one party etc., in more than 45%RH, is completely covered by one layer of absorption water.As it was previously stated, , used as catalyst, promotion is dissolved into the chlorine dioxide in the air in attachment absorption water on the surface for manganese oxide and permanganate Gas forms the reaction of salt in absorption water.With salt is formed, the chlorate ions adsorbed in water is reduced, so in air Chlorine dioxide is according to described（Reaction equation 1）It is dissolved in absorption water and reaches poised state, supplements subtracting for chlorate ions Few part.If relative humidity is covered more than 70%RH, distintegrant surface by multilamellar absorption water, its number of plies has with relatively wet The increase of degree and the tendency that sharply increases.If it exceeds 80%RH, then containing manganese oxide powder and permanganate in it is at least any The space part formed in the gap of the porous body powder of one side starts adsorbed water slug, there is the chlorine dioxide that should be processed Become the tendency for being difficult to ventilate.In the case of more than 90%RH, there is chlorine dioxide in the space part because adsorbing water and saturation The situation that the ventilation of gas significantly suffers damage.Therefore, in the method for the invention, preferably relative humidity is in the scope It is interior.

Additionally, according to the measurement of the present inventor, if in the scope below 50 DEG C, the catalyst activity master of the present invention Will be with relative humidity variations.

Additionally, under conditions of relative humidity is certain, if temperature is high, dissolving of the chlorine dioxide in absorption water Degree is reduced, therefore decomposition efficiency is reduced, and confirms the situation that the decomposition efficiency is reduced if temperature becomes more than 50 DEG C Become apparent from.Therefore in the method for the invention, as described above, the temperature in the space decomposed is preferably less than 50 DEG C, more Preferably less than 40 DEG C, it is further preferred that less than 30 DEG C.

In the present invention, so-called " decomposition of chlorine dioxide " is referred to the chlorine dioxide existed in space in the way of chemistry Decompose, making the concentration of chlorine dioxide reduces, and preferably the concentration of chlorine dioxide is eventually declined to below 0.1ppm.According to this The decomposition method of invention, compared with the decomposition method of conventional chlorine dioxide, can use the very short time chlorine dioxide decomposition, For example, shown in embodiment as be described hereinafter, can be reduced to 30 minutes or so the chlorine dioxide 300ppm concentrations above Below 0.1ppm.

Embodiment

Further the present invention is described in detail to enumerate embodiment below, but the invention is not restricted to this.

Using the close test room of the clean room standards shown in Figure 17, the reality of generation and the decomposition of chlorine dioxide is carried out Test.It is 2m × 2m=4m that close test room is floor area², from floor to roof for 2.5m, volume be 10m³Space.Additionally, Possesses gas decomposer, humidifier, drimeter, gas concentration meter, pass box, the sampling gas shown in gas generating device, Fig. 6 Body suction inlet, gas sampled outlet and circulator.

Pass box is arranged on side wall centers part, for the relative humidity for being adjusted to specify in close test room, transmission Humidity sensor is accommodated with case, volume is about 1 liter.Inner door and outer door are installed on pass box, before gas is generated, After humidity sensor is received in pass box, outer door is closed, open inner door.Become the humidity inductive subordinate of humidity sensor Fall to the state of closed interior.In this condition, the display of humidity sensor represents closed indoor humidity.Transport humidifier Turn, while the indicated value of humidity sensor is seen, while when the relative humidity of regulation is reached, stopping the operating of humidifier.Giving birth to During into gas, the humidity inductive portion of humidity sensor is taken in the inside of pass box, close inner door.The humidity of humidity sensor Induction part for the exposure of chlorine dioxide be it is very fragile, need with closed indoor generation chlorine dioxide every From, in order to it is described isolation and be provided with pass box.

In gas generating device, in sodium chlorite piece（Ami salt element acid Na ト リ ウ system タ Block レ ッ ト）Middle addition Fructus Mali pumilae sour water Solution, by being heated to 60 DEG C with 20 minutes, thus generates chlorine dioxide.Chlorine dioxide is made full of closed closed Test chamber.

Through 180 minutes from gas is generated（According to the volume of different rooms, experimentally obtain in advance from making gas The operating of body generating means reaches the time of normal concentration, accordingly with Jing reaching normal concentration from indoor chlorine dioxide concentration The mode for spending the time that can carry out fully stifling sets the time）Afterwards, chlorine dioxide decomposer is started, closed examination Test the indoor suction chlorine dioxide decomposer of the air containing chlorine dioxide and make to contain dioxy in close test room Change the air of chlorine body by the device.Additionally, in main filter in the apparatus, having used the granule filled with 12L （Specific surface area：50m²/g）Filter material, the granule be by making the broken shaped activated carbon of 2～5mm of major diameter in containing 0.8 weight Obtained from the potassium permanganate powder of amount %（Embodiment）, or replace the granule filled with 12L（Specific surface area：50m²/g）Filter Material has used the filter material filled with 12L granular active carbons（Comparative example）.Close test indoor temperature when device operates is room temperature （25℃）, regulation of relative humidity to 50%RH.

Additionally, closed indoor chlorine dioxide gas concentration is from being located at close test room face side wall, away from floor The gas sampled suction inlet of face 1.5m height, closed indoor gas the chlorine dioxide of Interscan companies manufacture is drawn into Densitometer（Scope of the measurement from 1ppm to 2000ppm）In and measure.Gas sampled after measurement is from being located at gas sampled Gas discharge outlet near suction inlet returns to closed interior.

Figure 18 represents chlorine dioxide gas concentration in the close test room of embodiment and comparative example over time.Dress It is the chlorine dioxide of 330ppm when putting startup, 0.1ppm was dropped to about 30 minutes in embodiment.On the other hand, comparing In example, have passed through 30 minutes and be only reduced to 90ppm.Additionally, chlorine dioxide is because natural decomposition is from generation when device starts The peak concentration of gas is reduced, but is confirmed：Compared with the natural decomposition speed, in embodiment, decomposition rate is very big.

According to the distintegrant and the method using it of the present invention, chlorine dioxide can be decomposed with the short time.Additionally, by Work as catalyst in the distintegrant of the present invention, so not consuming in decomposition reaction, chlorine dioxide decomposition can be suppressed Man-hour of the repair and maintenance of device, labour and cost.Therefore the present invention is highly useful in the industry.

Claims (19)

1. a kind of chlorine dioxide generates system, it is characterised in that

The chlorine dioxide generates system to be included：

Chlorine dioxide generating means, generate chlorine dioxide；And

Chlorine dioxide decomposer, sucks from the chlorine dioxide generating means and is discharged into the chlorine dioxide of interior The residual gas of body simultaneously decomposes to the residual gas,

The chlorine dioxide decomposer includes filter material, and the filter material contains at least any in manganese oxide and permanganate One side.

2. chlorine dioxide according to claim 1 generates system, it is characterised in that

The chlorine dioxide generates system also includes damping device, and the damping device is wet to specifying the indoor humidification Degree.

3. chlorine dioxide according to claim 2 generates system, it is characterised in that

The chlorine dioxide generates system also to be included：

First path, the air from the indoor suction is provided with the dioxy by the first path in the first path Change chlorine body generating means；

Second path, is provided with the chlorine dioxide decomposer, by the chlorine dioxide on second path Air after decomposer decomposes flows through second path；And

3rd path, on the 3rd road Jing the damping device is provided with, and the air after being humidified by the damping device is flowed through 3rd path.

4. chlorine dioxide according to any one of claim 1 to 3 generates system, it is characterised in that

The chlorine dioxide generates system also to be included：

Air outlet, is located at the top that the chlorine dioxide generates system, and the chlorine dioxide is sent to the interior Go out；And

Suction inlet, is located at the bottom that the chlorine dioxide below the air outlet generates system, sucks the residual gas.

5. chlorine dioxide according to claim 3 generates system, it is characterised in that

The first path and second path, suck a part for the suction inlet side of the residual gas or described two A part for the air outlet side that oxidation chlorine body is sent to the interior, is made up of total path.

6. chlorine dioxide according to claim 3 generates system, it is characterised in that

A part for the suction inlet side of the suction residual gas in the 3rd path or the chlorine dioxide to institute A part for the air outlet side that interior is sent is stated, by the total path structure total with the first path or second path Into.

7. chlorine dioxide according to claim 4 generates system, it is characterised in that

The chlorine dioxide generates system also to be included：

Humidity sensor, is located near the suction inlet of the interior, before chlorine dioxide generating means operating, The relative humidity of the detection indoor air；And

Isolating device, after chlorine dioxide generating means operating, by the humidity sensor from containing the dioxy Change the air insulated of chlorine body.

8. chlorine dioxide according to claim 1 generates system, it is characterised in that

The chlorine dioxide generating means generate titanium dioxide by graininess sodium chlorite and the chemical reaction of acidic liquid Chlorine body,

The chlorine dioxide generating means have：

Container, houses the graininess sodium chlorite and the acidic liquid；

Heater, heats to the container；And

Filter for installation, catches what is contained in the chlorine dioxide generated from the container by the heating devices heat Impurity,

The chlorine dioxide generates system also includes fan, and the fan is the titanium dioxide after the filter for installation Chlorine body is sent to the interior.

9. chlorine dioxide according to claim 1 generates system, it is characterised in that

The chlorine dioxide generates system also to be included：

Damping device, the indoor humidification to specified humidity；And

Control device, controls the chlorine dioxide and generates system,

The control device makes the damping device operate, and when the interior reaches specified humidity, gives birth to the chlorine dioxide Into device operating, when the interior reaches the chlorine dioxide concentration of regulation and have passed through the stipulated time, the chlorine dioxide is made Gas decomposer operates.

10. chlorine dioxide according to claim 1 generates system, it is characterised in that

The manganese oxide is selected from the group being made up of manganese dioxide, manganese sesquioxide managnic oxide and mangano-manganic oxide.

11. chlorine dioxides according to claim 1 generate system, it is characterised in that

The permanganate is from by M^IMnO₄And M^II（MnO₄）₂Select in the group of composition, M^IRepresent alkali metal, M^IIRepresent alkaline earth gold Category.

12. chlorine dioxides according to claim 1 generate system, it is characterised in that

The filter material includes chlorine dioxide decomposition agent, and the chlorine dioxide decomposition agent contains the manganese oxide and the permanganate In at least any one party,

The chlorine dioxide decomposer makes chlorine dioxide contact with the chlorine dioxide decomposition agent.

13. chlorine dioxides according to claim 12 generate system, it is characterised in that

The chlorine dioxide decomposer relative humidity be more than 45% under conditions of, make the chlorine dioxide with it is described Chlorine dioxide decomposition agent is contacted.

14. chlorine dioxides according to claim 12 generate system, it is characterised in that

The chlorine dioxide decomposer makes the chlorine dioxide with the dioxy under conditions of temperature is for less than 50 DEG C Change the contact of chlorine distintegrant.

A kind of 15. chlorine dioxide decomposers, suck from the chlorine dioxide generating means for generating chlorine dioxide To the chlorine dioxide of indoor release residual gas and the residual gas decomposed, it is characterised in that

The chlorine dioxide decomposer includes filter material, and the filter material is sucked and decomposes the residual gas, and is contained At least any one party in manganese oxide and permanganate.

16. chlorine dioxide decomposers according to claim 15, it is characterised in that the chlorine dioxide point Solution device also include components described below at least any one：

Prefilter, in the air-flow of the air of suction, is located at the upstream of the filter material；

After-filter, in the air-flow of the air of the suction, is located at the downstream of the filter material；

The fan of decomposer, the air for making the interior passes through the filter material；And

Cowling panel, is located at the entrance side of the filter material.

17. chlorine dioxide decomposers according to claim 15, it is characterised in that

The permanganate is from by M^IMnO₄And M^II（MnO₄）₂Select in the group of composition, M^IRepresent alkali metal, M^IIRepresent alkaline earth gold Category.

18. chlorine dioxide decomposers according to claim 15, it is characterised in that

The filter material includes chlorine dioxide decomposition agent, and the chlorine dioxide decomposition agent contains the manganese oxide and the permanganate In at least any one party,

The chlorine dioxide decomposer makes chlorine dioxide contact with the chlorine dioxide decomposition agent.

19. chlorine dioxide decomposers according to claim 18, it is characterised in that

The chlorine dioxide decomposer relative humidity be more than 45% under conditions of, make the chlorine dioxide with it is described Chlorine dioxide decomposition agent is contacted.