CN101970345A - Apparatus for the production of chlorine dioxide - Google Patents
Apparatus for the production of chlorine dioxide Download PDFInfo
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- CN101970345A CN101970345A CN2008801276187A CN200880127618A CN101970345A CN 101970345 A CN101970345 A CN 101970345A CN 2008801276187 A CN2008801276187 A CN 2008801276187A CN 200880127618 A CN200880127618 A CN 200880127618A CN 101970345 A CN101970345 A CN 101970345A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/024—Preparation from chlorites or chlorates from chlorites
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/18—Liquid substances or solutions comprising solids or dissolved gases
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
- A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
- A61L2/20—Gaseous substances, e.g. vapours
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- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
- B01J10/002—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor carried out in foam, aerosol or bubbles
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Abstract
Provided is an apparatus for production of chlorine dioxide. In the apparatus, raw-material chemicals necessary for producing chlorine dioxide are quantitatively supplied to a reaction bath using solenoid valves so that necessary amounts of raw-material chemicals can be exactly supplied to the reaction bath from outside storage vessels through pipes by decompressing the reaction bath without having to use a flow meter or a metering pump.
Description
Technical field
The present invention relates to a kind of device of producing dioxide peroxide.
Background technology
1811, Sir Humphrey Dary found dioxide peroxide.The fusing point of dioxide peroxide is-59 ℃, and boiling point is 11 ℃, is yellow-green colour gas under the room temperature.Dioxide peroxide gives out the smell of slight chlorine, soluble in water, ether etc.
When preserving, dioxide peroxide is decomposed into chlorous acid, chloric acid, chlorion etc. gradually, and (oxidation state :+4), dioxide peroxide can be used as sterilant owing to have stronger oxidation capacity.
Because dioxide peroxide is oxidation of organic compounds matter not, so it has a lot of purposes.Specifically, can not produce such as carcinogenic chlorination organic substances such as trichloromethane (THM), halogenated acetic acids (HAA) and halo acetonitriles from dioxide peroxide.In addition, in very wide pH value scope, dioxide peroxide can be used as sterilant.In addition, dioxide peroxide can not produce carcinogenic by product, easily by photolysis, and because these ecosystem characterizations, dioxide peroxide increases sharply as the purposes of the substituent of chlorine-containing disinfectant.
Because above-mentioned characteristic, nineteen forty-four, dioxide peroxide is used for Niagara Falls (New York, water treating equipment USA) first.At present, in worldwide, comprise about 900 places of the U.S. and a hundreds of place in Europe, dioxide peroxide just is being widely used as sterilizing agent.
In Korea S, concentration is that 1ppm or littler dioxide peroxide also have been used as sterilizing agent.In addition, dioxide peroxide can be used for the sterilization of foods such as vegetables and fruit.
Yet dioxide peroxide can change as time passes, its preparation, preservation and analysis difficulty.In addition, although as shown in following Chemical formula 1～3, can realize the day output of dioxide peroxide hundreds of ton by in liquid acids such as sulfurous acid, hydrochloric acid or hydrogen peroxide, reducing the method for oxymuriate (raw material), but this scale operation of dioxide peroxide needs main equipment.Therefore, except bleaching process, do not use this scale operation usually.
[Chemical formula 1]
2NaClO
3+H
2SO
3→2ClO
2+Na
2SO
4+H
2O
[Chemical formula 2]
2NaClO
3+4HCl→2ClO
2+2NaCl+Cl
2+2H
2O
[chemical formula 3]
2NaClO
3+H
2O
2+2HCl→2ClO
2+2NaCl+O
2+2H
2O
In addition, because dioxide peroxide is at room temperature unstable, so dioxide peroxide should just prepare before use in the workshop, and the transportation of dioxide peroxide and packing are not easy to carry out.
Therefore, need a kind of preparation not contain chlorite (ClO
2 -), chlorate anions (ClO
3 -) and the simple and easy method of the pure chlorine dioxide water of salt, make chlorine dioxide water in fact can be used as for example food sterilisation agent.
Summary of the invention
Technical problem
The invention provides a kind of device that quantitative production does not contain the pure chlorine dioxide of chlorous acid, chloric acid and salt thereof that is used for.
The present invention also provides the chlorine dioxide of a kind of chlorine dioxide that is used for quick production high density and high density not have the device of explosion potential.
Technical scheme
Exemplary embodiment of the present invention provides the device of producing dioxide peroxide, and described device comprises: dioxide peroxide, take place and produce reaction in reactive tank therein; And fritted glass filter, it is divided into first district and second district with described reactive tank.
At least one gas supply unit is connected with first district of described reactive tank, is used for to described reactive tank supply chlorine and inertia (torpescence) gas.
At least one raw material supply unit is connected with second district of described reactive tank, is used for to described reactive tank supply hypochlorite, chlorite or acid.
Pressure regulating unit and first district of described reactive tank are connected with at least one district in second district, and the stress level that is used to keep second district is lower than the stress level in first district.
Reactive tank has connected outlet orifice, is used for discharging the chlorine dioxide that produces in second district of described reactive tank.
In an exemplary embodiment of the present invention, the aperture of described fritted glass filter can be about 10～100 μ m.
In another exemplary embodiment of the present invention, described pressure regulating unit can be a compression pump, and it is connected with first district, is used to compress first district; Perhaps can be decompressing unit or vacuum pump, it be connected with second district, is used to make the decompression of second district.
In other exemplary embodiment, if pressure regulating unit is a decompressing unit, so described decompressing unit can be to utilize the aspirator of decompression water or depressed gas operation, and the chlorine dioxide that produces in second district can be absorbed in through in the decompression water of described aspirator, and perhaps the depressed gas with the described aspirator of process mixes.
In other exemplary embodiment, described rare gas element can be nitrogen, carbon dioxide and airborne at least a.
In other exemplary embodiment, described raw material supply unit can be connected with second district of described reactive tank by magnetic valve.Described magnetic valve can be controlled by controller.Described controller can be regulated the amount of the hypochlorite, chlorite or the acid that are fed to described reactive tank by controlling described magnetic valve.
In other exemplary embodiment, described device can also comprise pressure sensing cell, and it is arranged on the described reactive tank, is used to detect described reactive tank pressure inside.The signal of described pressure sensing cell can be transferred to described controller.
In other exemplary embodiment, described outlet orifice can be connected with adsorption tower.Described adsorption tower can hold organic solvent and sorbing material, and described organic solvent and sorbing material are used to dissolve and adsorb the chlorine dioxide of rare gas element and generation.Described organic solvent can be a kind of in normal hexane, methylene dichloride, ether, methyl tertiary butyl ether and the sherwood oil.Described sorbing material can be zeolite or silica gel.
In other exemplary embodiment, chlorine dioxide is removed tower and can be connected with described adsorption tower, to remove at chlorine dioxide through chlorine dioxide remaining behind the described adsorption tower.Described chlorine dioxide is removed tower can hold hydrogen peroxide or Sulfothiorine, to remove remaining chlorine dioxide.
Beneficial effect
According to the present invention, in chlorine dioxide generator,, make and to produce dioxide peroxide by high productivity because from the bubble that gas produced through fritted glass filter, reactant is evenly stirred.
Because the inside of reactive tank is depressurized and produce bubble from the bottom of reactive tank in reactive tank,, there is not explosion potential so dioxide peroxide can easily evaporate.The pure chlorine dioxide of Huo Deing can easily be dissolved in the decompression water in this way, therefore can obtain pure ClO 2 solution.
In addition,, utilize magnetic valve according to the present invention, can be in the desirable time a small amount of or big content of starting materials of fixed supply, so reactant and its product can easily be controlled at low cost.
Description of drawings
Fig. 1 is the schematic cross sectional views that illustrates according to the device of the production dioxide peroxide of first embodiment of the invention.
Fig. 2 is the schematic cross sectional views that illustrates according to the device of the production dioxide peroxide of second embodiment of the invention.
Fig. 3 is the schematic cross sectional views that illustrates according to the device of the production dioxide peroxide of third embodiment of the invention.
Embodiment
Below, will be described in detail with reference to the attached drawings the preferred embodiments of the invention.Yet the present invention can embody with different forms, should not be considered to only limit to listed embodiment herein.On the contrary, provide these embodiments can make disclosed content, and pass on scope of the present invention fully to those skilled in the art thoroughly with complete.
Fig. 1 is the schematic cross sectional views that illustrates according to the device of the production dioxide peroxide of first embodiment of the invention.
With reference to figure 1, the chlorine dioxide generator of the present embodiment comprises reactive tank 100, is used for producing dioxide peroxide by predetermined reaction.
In reactive tank 100, reactive tank 100 is provided with fritted glass filter 110, is used for the inside of reactive tank 100 is divided into two districts.Specifically, fritted glass filter 110 is divided into the first district R1 and the second district R2 with the inside of reactive tank 100.
Fritted glass filter 110 can be divided into the inside of reactive tank 100 district and inferior segment, Zuo Qu He You district etc.For example, in the present embodiment, fritted glass filter 110 is divided into district and inferior segment (the second district R2 and the first district R1) with the inside of reactive tank 100.In this case, produce gas, and gas moves up, thereby make gas be easy to discharge by venting port by liquid reaction.
The first district R1 is connected with at least one gas supply unit 120, and with supply chlorine and rare gas element, wherein chlorine is used for dioxide peroxide generation reaction, and rare gas element is used for regulating by diluted chlorine gas the concentration of chlorine.Gas supply unit 120 can be connected with the first district R1 of reactive tank 100 by feed tube 122, is formed with gas injection hole 124 in the end of the feed tube 122 that is connected with the first district R1.
In the present embodiment, can pass through same gas injection hole 124 supplying inert gas and chlorine.Yet in another embodiment, rare gas element and chlorine can be kept in the independent gas supply unit, and side by side or not side by side supply by independent gas injection hole.For example, extra gas injection hole can be set with supplying inert gas, rare gas element is used to control the concentration of chlorine, and is used for making chlorine move on to the second district R2 from the first district R1 by fritted glass filter 110.In the embodiment depicted in fig. 1, show single gas injection hole 124.
Do not influence the aitiogenic gas of dioxide peroxide and be supplied to reactive tank 100.For example, can supply rare gas elementes such as helium, neon and argon, and stabilizing gases such as carbonic acid gas and air.
At least one raw material supply unit is connected with the second district R2 of reactive tank 100, with supply chlorite or hypochlorite, and acid such as sulfuric acid, hydrochloric acid or nitric acid, they all are used to carry out dioxide peroxide and produce reaction.In the present embodiment, for convenience of description, the first raw material supply unit 130, the second raw material supply unit 140 and the 3rd raw material supply unit 150 all are connected with the second district R2 of reactive tank 100.
First, second is connected with the second district R2 of reactive tank 100 with 152 with the 3rd raw material supply tube 132,142 by first, second respectively with 150 with the 3rd raw material supply unit 130,140.Be formed with first, second and the 3rd raw material filling orifice 134,144 and 154 in end of first, second and the 3rd raw material supply tube 132,142 that are connected with the second district R2 of reactive tank 100 and 152.
First, second and the 3rd raw material supply unit 130,140 and 150 can comprise raw material supply jar (not shown).By first, second and the 3rd raw material supply tube 132,142 and 152 and by first, second and the 3rd raw material filling orifice 134,144 and 154, each raw material is fed to the second district R2 of reactive tank 100 respectively from first, second and the 3rd raw material supply unit 130,140 and 150.
As shown in Figure 1, in the present embodiment, be provided with a plurality of raw material supplies unit, to supply raw material separately.Yet the present invention is not limited to this.For example, in another embodiment of the present invention, two or more raw materials can be supplied by same raw material filling orifice.That is to say that the number of raw material supply tube and raw material filling orifice can be according to the raw material supply configuration change.In addition, although a plurality of raw material filling orifice independent formation in the present embodiment, Y shape raw material supply tube can be used to by two kinds of raw materials of same raw material filling orifice supply.
The first district R1 of reactive tank 100 and at least one district among the second district R2 are provided with pressure regulating unit.Pressure regulating unit makes and produce pressure reduction between the first district R1 and the second district R2, thereby produces mobile by fritted glass filter 110 between the first district R1 and the second district R2.
In the present embodiment, decompressing unit 160 is connected with the second district R2 of reactive tank 100, as the pressure regulating unit that is used for conditioned reaction groove 100 internal pressures.Decompressing unit 160 is connected with the second district R2 by vent pipe 162.Decompressing unit 160 can be aspirator or vacuum pump.In the present embodiment, aspirator is as decompressing unit 160.
Stopping valve 166 can be arranged between reactive tank 100 and the decompressing unit 160.Decompressing unit 160 to reduce the internal pressure of reactive tank 100, particularly reduces by the internal pressure of the second district R2 from the inside sucking-off gas of reactive tank 100.Can be used as decompressing unit 160 such as various decompressing unit such as gas decompressing unit and pneumatic pumps.For example, the aspirator that utilizes decompression liquid or depressed gas to operate can be used as decompressing unit 160.
The outlet orifice 164 of reactive tank 100 is connected with decompressing unit 160.
The exemplary mechanism of using above-mentioned chlorine dioxide generator to produce dioxide peroxide will be described below.
Three kinds of methods of each dioxide peroxide of the different material system of use at first, are described.In first method, use be chlorite and such as acid such as sulfuric acid or hydrochloric acid; In the second approach, use is chlorite, hypochlorite and such as acid such as sulfuric acid or hydrochloric acid; In the third method, use be muriate and chlorine.
These three kinds of methods can be expressed with following chemical formula.Specifically, use chlorite and can express by chemical formula 4 and chemical formula 5 such as the first method of acid such as sulfuric acid or hydrochloric acid; Use the second method of chlorite, mineral acid (hydrochloric acid or sulfuric acid) and hypochlorite to express by chemical formula 6 and chemical formula 7; Use the third method of muriate and chlorine to express by chemical formula 8.
[chemical formula 4]
5NaClO
2+4HCl→4ClO
2+5NaCl+2H
2O
[chemical formula 5]
5NaClO
2+2H
2SO
4→4ClO
2+2Na
2SO
4+NaCl+2H
2O
[chemical formula 6]
2NaClO
2+NaClO+2HCl→2ClO
2+3NaCl+H
2O
[chemical formula 7]
2NaClO
2+NaClO+H
2SO
4→2ClO
2+Na
2SO
4+NaCl+H
2O
[chemical formula 8]
2NaClO
2+Cl
2→2ClO
2+2NaCl
By gas injection hole 124 that is arranged on the first district R1 and first, second and the 3rd raw material filling orifice 134,144 and 154 that is arranged on the second district R2, above-mentioned raw materials is fed to the inside of reactive tank 100.
For example, in first method, be supplied to the second district R2 such as acid such as sulfuric acid or hydrochloric acid and chlorite.In the second approach, chlorite, hypochlorite and acid (sulfuric acid or hydrochloric acid) is supplied to the second district R2.In the third method, chlorine is supplied to the first district R1, and chlorite is supplied to the second district R2.
Raw material supply before the reactive tank 100, afterwards or during, decompressing unit 160 from the inside sucking-off gas of reactive tank 100 to reduce the internal pressure of reactive tank 100.
When decompression water was allowed to through aspirator (decompressing unit 160), the pressure of the second district R2 became and is lower than the pressure of the first district R1.Then, rare gas element (nitrogen, carbon dioxide or air) is drawn into reactive tank 100 by gas injection hole 122.
Since the pressure reduction between the first district R1 and the second district R2, the horizontal fritted glass filter 110 of rare gas element process of suction at reactive tank 100 downsides, thus in the second district R2, produce microbubble.Because microbubble, the reactant that is fed to the second district R2 by raw material filling orifice 134,144 and 154 can be stirred equably, dioxide peroxide that therefore can high productivity acquisition high density.
Because the lower pressure of microbubble and reactive tank 100 inside, dioxide peroxide can be easy to evaporation.
Chlorine dioxide is drawn onto decompressing unit 160 and is dissolved in the decompression water.Therefore, can obtain pure ClO 2 solution.
As mentioned above, according to the present invention, although the raw material that uses in the raw material that uses and the conventional chlorine dioxide generation is identical, compare with ordinary method, raw material of the present invention can react under greater concn quickly.Thereby, compare with ordinary method, can under the situation that does not increase the treatment time, obtain the chlorine dioxide of high density.
Because reactant (raw material) is fed to second district of reactive tank continuously and quantitatively, and the rare gas element that is fed to first district of reactive tank bottom by utilization produces microbubble continuously in second district, so can obtain the dioxide peroxide of high density by high productivity, and not explode.For this reason, by using the decompressing unit that is connected with second district on reactive tank top, make reactive tank remain on decompression state.
Because microbubble, reactant can be by fast, stir equably, and by utilizing microbubble evaporation dioxide peroxide, can extract the dioxide peroxide of the high density that is produced from the solution that contains reactant and byproduct of reaction.
That is to say that because the rare gas element microbubble, reactant can be stirred ideally, and, can from the solution that contains reactant and byproduct of reaction, easily extract the dioxide peroxide of the high density that is produced by utilizing microbubble evaporation dioxide peroxide.In addition, because microbubble has diluted the chlorine dioxide that is extracted, so can prevent the blast of chlorine dioxide.
By in the decompression water of decompressing unit, dissolving the pure chlorine dioxide that is extracted, can obtain pure ClO 2 solution.
Reactive tank pressure inside, the rare gas element that is fed to reactive tank inside and fritted glass filter are the important factors of producing pure ClO 2 solution.The aperture of fritted glass filter can be about 10～100 μ m.For example, the aperture of fritted glass filter can be about 10～40 μ m.If the aperture, is difficult to shift reaction thing between first district of reactive tank and second district so less than about 10 μ m.If the aperture can produce relatively large bubble so greater than about 100 μ m, thus reactive decline.
When using decompressing unit to make the inner pressure relief of reactive tank, the internal pressure of reactive tank reduces to about 200～400mmHg (for example, pressure of about 210～240mmHg) from barometric point.If the internal pressure of reactive tank less than about 200mmHg, can produce relatively large bubble so and not produce microbubble.If the internal pressure of reactive tank is greater than about 400mmHg, the generation speed of bubble reduces so, thereby the possibility of blast increases.
Although do not describe each parts of reactive tank in detail, what be readily appreciated that is that each parts of reactive tank can directly interconnect, perhaps according to circumstances by interconnecting such as various web members such as conduit and pipelines.
[embodiment 1-1]
Use volume pump, with the speed of 6.5mL/min and 2mL/min the aqueous sulfuric acid of the sodium chlorite aqueous solution of 25wt% and 30wt% is injected into the top of reactive tank respectively.
The aspirator that operation is connected with decompression water under 3～3.5 normal atmosphere, make the reactive tank decompression, so that extraneous air is drawn into reactive tank, and make institute's inhaled air by being arranged on the fritted glass filter of reactive tank bottom, thereby produce the air microbubble with the speed of 400mL/min.Along with the generation of air microbubble, two kinds of compound short mix that are injected into reactive tank top are to produce dioxide peroxide, and the dioxide peroxide that is produced simultaneously is easy to evaporate from the mixture that contains by product.The dioxide peroxide of evaporation is dissolved in from the decompression water that aspirator is discharged.In this way, the speed with 5.8L/min obtains pure ClO 2 solution from the decompression water that is dissolved with dioxide peroxide.
In embodiment 1-1, obtain the ClO 2 solution of the about 172mg/L of concentration, productive rate about 85%.
[embodiment 1-2]
Use volume pump, with the speed of 4.8mL/min, 4mL/min and 2mL/min the sulfuric acid of the clorox of the Textone of 25wt%, 12wt% and 30wt% is injected into the top of reactive tank respectively.
The aspirator that operation is connected with decompression water under 3～3.5 normal atmosphere, make the reactive tank emptying, so that nitrogen is drawn into reactive tank, and make the nitrogen that sucked by being arranged on the fritted glass filter of reactive tank bottom with the speed of 400mL/min, thereby produce microbubble.Along with the generation of microbubble, three kinds of compound short mix that are injected into reactive tank top are to produce dioxide peroxide, and the dioxide peroxide that is produced simultaneously is easy to evaporate from the mixture that contains by product and impurity.The dioxide peroxide of evaporation is dissolved in from the decompression water that aspirator is discharged.In this way, the speed with 5.8L/min obtains pure ClO 2 solution.
In embodiment 1-2, obtain the ClO 2 solution of the about 185mg/L of concentration, productive rate about 95%.
[embodiment 1-3]
When using volume pump the sodium chlorite solution of 25wt% to be fed to reactive tank top with the speed of 4.9mL/min, the aspirator that operation is connected with the water that reduces pressure under 3～3.5 normal atmosphere.Along with the operation aspirator makes the reactive tank decompression, carbon dioxide and chlorine are inhaled into reactive tank, and respectively with the speed of 400mL/min and 170mL/min by being arranged on the fritted glass filter of reactive tank bottom, thereby produce the microbubble of carbon dioxide and chlorine.Microbubble mixes with the sodium chlorite solution immediately, to produce pure chlorine dioxide.The chlorine dioxide that is produced is dissolved in from the decompression water that aspirator is discharged.In this way, the speed with 5.8L/min obtains pure ClO 2 solution.
In embodiment 1-3, obtain the ClO 2 solution of the about 180mg/L of concentration, productive rate about 98%.
[embodiment 1-4]
Adopt with embodiment 1-1 to 1-3 in used identical reactive tank and reagent, but using gas decompressing unit replacement liquid decompressing unit is come sucking-off inertia depressed gas, as nitrogen, carbonic acid gas and air.In this way, obtain the mixture of dioxide peroxide and rare gas element with the speed of 16L/min.
In embodiment 1-4, obtain the ClO 2 solution of the about 69mg/L of concentration, productive rate about 90%.
Other embodiments of the present invention
Fig. 2 is the schematic cross sectional views that illustrates according to the device of the production dioxide peroxide of second embodiment of the invention.Below in the description to second embodiment, with the difference that mainly illustrates between first embodiment and second embodiment, the feature of Miao Shuing identical with described in first embodiment not.In the accompanying drawings, identical Reference numeral is represented same parts.
In the present embodiment, chlorine dioxide generator comprises: reactive tank 200; Fritted glass filter 220 is used for the inside of reactive tank 200 is divided into the first district R1 and the second district R2; At least one gas supply unit 220, it is connected with the first district R1 of reactive tank 200, is used to supply chlorine and rare gas element; At least one raw material supply unit 230,240 and 250, it is connected with the second district R2 of reactive tank 200, is used for to the inside of reactive tank 200 supply hypochlorous acid, chlorous acid or acid; Pressure regulating unit, it is connected with at least one district among the second district R2 with the first district R1, is used to make the pressure of the second district R2 to be lower than the pressure of the first district R1; And outlet orifice 264, it is formed on the reactive tank 200, is used for discharging the chlorine dioxide that produces at the second district R2.
If utilize compression pump 260 that rare gas element and chlorine under high pressure are fed to the first district R1 of reactive tank 200, the pressure of the first district R1 of reactive tank 200 pressure of the second district R2 that is higher than reactive tank 200 that becomes so.Because this pressure reduction, gas is transferred to the second district R2 from the first district R1.That is to say that rare gas element and chlorine move to the second district R2 by fritted glass filter 210 from the first district R1.When rare gas element and chlorine process fritted glass filter 210, in the second district R2, produce microbubble.The reactant (raw material) that is injected into the second district R2 by raw material filling orifice 234,244 and 254 is evenly stirred by microbubble, thereby can high productivity produces the dioxide peroxide of high density.The chlorine dioxide that is produced is discharged by outlet orifice 164.
The example of organic solvent comprises water-soluble solvent and water-insoluble organic solvent, and water-insoluble organic solvent can form the moisture absciss layer.The example of water-soluble solvent comprises methyl alcohol, ethanol, propyl alcohol, Virahol, tetrahydrofuran (THF), acetoneand ethyl acetate.The example of water-insoluble organic solvent comprises normal hexane, methylene dichloride, ether, methyl tertiary butyl ether and sherwood oil.
In these organic solvents, water insoluble but volatile organic solvent that form the moisture absciss layer can utilize separator directly to extract from ClO 2 solution.
The organic solvent adsorption tower can also contain zeolite or silica gel, collects chlorine dioxide by absorption chlorine dioxide to zeolite or silica gel.By supply a large amount of rare gas element to zeolite or silica gel, can from zeolite or silica gel discharge dioxide peroxide thereafter.
[embodiment 2-1]
Ethanol is filled in three organic solvent adsorption towers that are connected in series; With the speed of 6.5mL/min and 2mL/min the sulfuric acid of the Textone of 25wt% and 30wt% is injected into second district of reactive tank respectively by filling orifice; Inert nitrogen is fed to first district of reactive tank with the speed of 350mL/min, continues 15 minutes.
Finally, it is about 2 to obtain concentration, dioxide peroxide-ethanolic soln of 125mg/L, productive rate about 85%.
In the same way, it is about 2,000～2 to obtain concentration, dioxide peroxide-methyl alcohol of 200mg/L, dioxide peroxide-isopropylcarbinol and dioxide peroxide-acetone soln.
[embodiment 2-2]
Normal hexane is filled in three organic solvent adsorption towers that are connected in parallel; With the speed of 6.5mL/min and 2mL/min the sulfuric acid of the Textone of 25wt% and 30wt% is injected into second district of reactive tank respectively by filling orifice; The inert carbon dioxide is fed to first district of reactive tank with the speed of 300mL/min, continues 15 minutes.
Finally, it is about 2 to obtain concentration, dioxide peroxide-hexane solution of 250mg/L, productive rate about 90%.
In the same way, it is about 2 to obtain dioxide peroxide-diethyl ether solution, the concentration of the about 2370mL/L of concentration, the dioxide peroxide of 320mL/L-methyl tertbutyl ethereal solution.
[embodiment 2-3]
Zeolite or silica gel are filled in three organic solvent adsorption towers that are connected in parallel; With the speed of 6.5mL/min the Textone of 25wt% is injected into second district of reactive tank by filling orifice; Air and chlorine are fed to simultaneously first district of reactive tank respectively with the speed of 360mL/min and 946mL/min.
The chlorine dioxide that is produced is adsorbed to zeolite or silica gel, and is final, obtains dioxide peroxide, productive rate about 95%.
Fig. 3 is the schematic cross sectional views that illustrates according to the device of the production dioxide peroxide of third embodiment of the invention.Below in the description to the 3rd embodiment, with the difference that mainly illustrates between first embodiment and the 3rd embodiment, the feature of Miao Shuing identical with described in first embodiment not.In the accompanying drawings, identical Reference numeral is represented same parts.
Produce in the reaction at dioxide peroxide, chlorite is decomposed by sour disproportionation, generates such as products such as hypochlorous acid, chloric acid and chlorine.Therefore, in the starting compound that supply is accurately measured, each reactant should be mixed fast, thereby produces pure chlorine dioxide with high yield.Thereby in the present embodiment, magnetic valve is used to make the reactant of accurate amount to react, and continues the suitable time.
With reference to figure 3, the chlorine dioxide generator of the present embodiment comprises: reactive tank 300; Fritted glass filter 320 is used for the inside of reactive tank 300 is divided into the first district R1 and the second district R2; At least one gas supply unit 320, it is connected with the first district R1 of reactive tank 300, is used to supply chlorine and rare gas element; At least one raw material supply unit 330,340 and 350, it is connected with the second district R2 of reactive tank 300, is used for to the inside of reactive tank 300 supply hypochlorous acid, chlorous acid or acid; Pressure regulating unit, it is connected with at least one district among the second district R2 with the first district R1, is used to make the pressure of the second district R2 to be lower than the pressure of the first district R1; And outlet orifice 364, it is formed on the reactive tank 300, is used for discharging the chlorine dioxide that produces at the second district R2.
First, second is separately positioned on first, second and the 3rd raw material supply unit 330,340 and 350 that are connected with the second district R2 with the first district R1 with the 3rd magnetic valve S1, S2 and S3, is used for opening first, second and the 3rd raw material filling orifice 334,344 and 354 when reactive tank 300 supplies raw material.First, second constitutes by the solenoid coil with magnetic core and one or more holes with the 3rd magnetic valve S1, S2 and S3.When electric current was applied to magnetic core or is not applied to magnetic core, magnetic core was oriented to blocking-up or allows flow.
First, second and the 3rd magnetic valve S1, S2 and S3 can be configured to open about 0.5～10 second and close about 1～60 second.Therefore, can regulate the amount of the raw material chemical substance that is fed to reactive tank 300.If desired, can between reactive tank 300 and decompressing unit 360, magnetic valve be set additionally,, thereby utilize the fritted glass filter 310 that is arranged in the reactive tank 300 to produce microbubble with conditioned reaction groove 300 pressure inside.
Decompressing unit 360 can be connected with reactive tank 300 by vent pipe 362, and magnetic valve S4 can be arranged on the end in abutting connection with reactive tank 300 of vent pipe 362.Switch 372 is located on the decompressing unit 360, and switch 372 is electrically connected with controller 370.Switch 372 utilizes electrical signal to operate or stops decompressing unit 360.By the inside sucking-off gas from reactive tank 300, decompressing unit 360 makes the inner pressure relief of reactive tank 300.
The switch 372 and the pressure sensing cell 312 of magnetic valve S1, the S2 of controller 370 and first, second and the 3rd raw material supply unit 330,340 and 350 and S3, decompressing unit 360, decompressing unit 360 are electrically connected.Controller 370 control magnetic valve S1, S2 and S3, decompressing unit 360 and reactive tank 300.
Utilize the chlorine dioxide generator of the present embodiment can produce dioxide peroxide, as follows.
At first, by operation decompressing unit 360, for example vacuum pump or the aspirator that is connected with reactive tank 300 through pipeline makes the inner pressure relief of reactive tank 300.In the present embodiment, aspirator is as decompressing unit 360; Yet decompressing unit 360 is not restricted to this.For example, decompressing unit 360 can be a vacuum pump.
At first, controller 370 is opened the switch 372 of decompressing unit 360.Then, operation decompressing unit 360 is opened the magnetic valve S4 that is connected with decompressing unit 360 with discharge reactive tank 300 gas inside.Along with the inside of reactive tank 300 is depressurized, the pressure of the second district R2 becomes and is lower than the pressure of the first district R1, thereby produces the air-flow of distinguishing R2 from the first district R1 to the second.Therefore, form microbubble from fritted glass filter 310.
If the inside that can determine reactive tank 300 by applying pressure detecting unit 312 by fully, decompression stably, so according to predetermined sequential, magnetic valve S1, S2 that controller 370 controls and first, second and the 3rd raw material supply unit 330,340 are connected with 350 and the opening and closing of S3 are operated.Therefore, required raw material can be metered into reactive tank 300.
The raw material of the microbubble mixing supply that utilization produces from fritted glass filter 310, and carry out the reaction expressed as chemical formula 4～8, thus can produce dioxide peroxide.
That is to say that rare gas element and chlorine are transferred to the second district R2 by fritted glass filter 310 from the first district R1, thereby produce microbubble from gas through fritted glass filter 310 at the second district R2.Then, each reactant (raw material) that is injected into the second district R2 by the raw material filling orifice is stirred equably by microbubble, thus dioxide peroxide that can high yield production high density.
Because the decompression state and the microbubble of reactive tank 300, the dioxide peroxide that is included in the mixing solutions of reactant and by product can easily be evaporated and extract, thereby can obtain pure chlorine dioxide.
Chlorine dioxide is by decompressing unit 360 sucking-offs, and absorbs from the decompression water that decompressing unit 360 is discharged.Therefore, can obtain pure ClO 2 solution.
As mentioned above, according to the present embodiment,, can control the amount of raw material supply imperceptibly, thereby can control the reaction that needs effectively, and can suppress production of by-products effectively by using electrical control device control magnetic valve.
In device commonly used, use volume pump or under meter to supply raw material.Because each raw material (chemical substance) is liquid or gas (as chlorine), be feasible in this way; Yet, can not accurately supply desirable material quantity, the supply of raw material amount can not accurately be measured.Thereby, can not control the amount of reactant and the degree of reaction imperceptibly.Therefore, the present invention can avoid above-mentioned defective.In addition, although the raw material that uses in the raw material that uses among the present invention and the chlorine dioxide generation commonly used is identical, the present invention can supply the raw material of high density, and raw material can rapid reaction.In addition, in the treatment time identical, can obtain the dioxide peroxide of high density with chlorine dioxide generation commonly used.
[embodiment 3-1]
Preserve the Textone for preparing 12.5wt% in the container at first raw material, preserve the sulfuric acid for preparing 15wt% in the container at second raw material.Subsequently, open aspirator, the magnetic valve of opening reactive tank then is so that the reactive tank decompression.Thereafter, with 1, the speed of 104mL/min is fed to reactive tank with Textone by magnetic valve, simultaneously, with the speed of 0.4mL/min sulfuric acid is fed to reactive tank.
Finally, obtain the ClO 2 solution of 5.8L, its concentration is 17ppm, and productive rate is 92%.
[embodiment 3-2]
Preserve the Textone for preparing 12.5wt% in the container at first raw material; Preserve the clorox for preparing 6wt% in the container at second raw material; Preserve the sulfuric acid for preparing 12.5wt% in the container at the 3rd raw material.Subsequently, open aspirator, the magnetic valve of opening reactive tank then is so that the reactive tank decompression.Respectively with the speed of 2.66mL/min, 2.18mL/min and 1.45mL/min Textone, clorox and sulfuric acid be fed to reactive tank thereafter.
Then, the chlorine dioxide that is produced is dissolved in the water of aspirator.In this way, obtain the ClO 2 solution of 5.8L, its concentration is 53ppm, and productive rate is 95%.
Claims (15)
1. device of producing dioxide peroxide, described device comprises:
Reactive tank;
Fritted glass filter, it is divided into first district and second district with described reactive tank;
At least one gas supply unit, it is connected with first district of described reactive tank, is used for to described reactive tank supply chlorine and rare gas element;
At least one raw material supply unit, it is connected with second district of described reactive tank, is used for to described reactive tank supply hypochlorite, chlorite or acid;
Pressure regulating unit, it is connected with at least one district in second district with first district of described reactive tank, and the stress level that is used to keep second district is lower than the stress level in first district; And
Outlet orifice, it is connected with described reactive tank, is used for discharging the chlorine dioxide that produces in second district of described reactive tank.
2. device according to claim 1, the aperture of wherein said fritted glass filter are about 10～100 μ m.
3. device according to claim 1, wherein said pressure regulating unit is a compression pump, it is connected with first district, is used to compress first district.
4. device according to claim 1, wherein said pressure regulating unit is a decompressing unit, it is connected with second district, is used to make the decompression of second district.
5. device according to claim 4, wherein said decompressing unit is to utilize the aspirator of decompression water or depressed gas operation, the chlorine dioxide that produces in second district is absorbed in through in the decompression water of described aspirator, and perhaps the depressed gas with the described aspirator of process mixes.
6. device according to claim 4, wherein said decompressing unit is a vacuum pump.
7. device according to claim 1, wherein said rare gas element are nitrogen, carbon dioxide and airborne at least a.
8. device according to claim 1, wherein said raw material supply unit is connected with second district of described reactive tank by magnetic valve.
9. device according to claim 8 also comprises the controller of controlling described magnetic valve, and wherein said controller is regulated the amount of the hypochlorite, chlorite or the acid that are fed to described reactive tank by controlling described magnetic valve.
10. device according to claim 9 also comprises pressure sensing cell, and it is arranged on the described reactive tank, is used to detect described reactive tank pressure inside, and the signal of wherein said pressure sensing cell is transferred to described controller.
11. device according to claim 1 also comprises the adsorption tower that is connected with described outlet orifice, wherein said adsorption tower holds organic solvent and sorbing material, with the chlorine dioxide of dissolving and absorption rare gas element and generation.
12. device according to claim 11, wherein said organic solvent are a kind of in normal hexane, methylene dichloride, ether, methyl tertiary butyl ether and the sherwood oil.
13. device according to claim 11, wherein said sorbing material are zeolite or silica gel.
14. device according to claim 11 also comprises the chlorine dioxide removal tower that is connected with described adsorption tower, is used to remove at chlorine dioxide through chlorine dioxide remaining behind the described adsorption tower.
15. device according to claim 14, wherein said chlorine dioxide are removed tower and are held hydrogen peroxide or Sulfothiorine, to remove remaining chlorine dioxide.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20070140906 | 2007-12-28 | ||
| KR10-2007-0140906 | 2007-12-28 | ||
| KR1020080048855A KR100902846B1 (en) | 2008-05-26 | 2008-05-26 | Apparaus for the production of the pure organic chlrorine dioxide solution and the production method using thereof |
| KR10-2008-0048855 | 2008-05-26 | ||
| KR1020080079963A KR100884330B1 (en) | 2008-08-14 | 2008-08-14 | Apparatus and method for the production of pure aqueous chlorine dioxide solution |
| KR10-2008-0079963 | 2008-08-14 | ||
| PCT/KR2008/007649 WO2009084854A2 (en) | 2007-12-28 | 2008-12-24 | Apparatus for the production of chlorine dioxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101970345A true CN101970345A (en) | 2011-02-09 |
| CN101970345B CN101970345B (en) | 2013-05-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200880127618.7A Expired - Fee Related CN101970345B (en) | 2007-12-28 | 2008-12-24 | Apparatus for the production of chlorine dioxide |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2011508718A (en) |
| CN (1) | CN101970345B (en) |
| WO (1) | WO2009084854A2 (en) |
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| CN110577192A (en) * | 2019-10-25 | 2019-12-17 | 东北大学秦皇岛分校 | preparation device and method of high-purity chlorine dioxide solution |
| CN111108325A (en) * | 2017-10-05 | 2020-05-05 | Rasa工业株式会社 | Heat source device and method for using silver zeolite |
| CN112811758A (en) * | 2020-12-31 | 2021-05-18 | 山西大学 | Straw carbon composite material and preparation method and application thereof |
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| KR101119625B1 (en) * | 2011-06-30 | 2012-03-07 | 한국에너지기술연구원 | Advance purification methods for betulonic acid and boc-lysinated betulonic acid, and organic synthesis of betulonic acid amides with piperazine derivatives |
| ES2693119T3 (en) | 2012-05-07 | 2018-12-07 | Erich Schmid | Procedure and device for the generation of chlorine dioxide |
| JP6283551B2 (en) * | 2014-01-20 | 2018-02-21 | 高砂熱学工業株式会社 | Chlorine dioxide gas generator and method |
| SG11201702487WA (en) * | 2014-10-03 | 2017-04-27 | Hungarotex Zrt | Method for producing aqueous solution of chlorine dioxide |
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| EP3992144A1 (en) | 2020-10-29 | 2022-05-04 | Bertram Schmid | Device and method for the production of chlorine dioxide |
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| CN111108325B (en) * | 2017-10-05 | 2021-12-21 | Rasa工业株式会社 | Heat source device and method for using silver zeolite |
| CN110577192A (en) * | 2019-10-25 | 2019-12-17 | 东北大学秦皇岛分校 | preparation device and method of high-purity chlorine dioxide solution |
| CN112811758A (en) * | 2020-12-31 | 2021-05-18 | 山西大学 | Straw carbon composite material and preparation method and application thereof |
| CN112811758B (en) * | 2020-12-31 | 2022-05-31 | 山西大学 | Straw carbon composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009084854A3 (en) | 2009-09-17 |
| CN101970345B (en) | 2013-05-08 |
| WO2009084854A2 (en) | 2009-07-09 |
| JP2011508718A (en) | 2011-03-17 |
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