JP2011508718A - Chlorine dioxide production equipment - Google Patents

Abstract

  The present invention provides an apparatus for producing chlorine dioxide. In the present invention, when the raw material chemicals necessary for chlorine dioxide production are quantitatively charged using a solenoid valve, the inside of the reaction tank is decompressed without using a flow meter or a metering pump, and the necessary chemicals are externally supplied. An apparatus for producing chlorine dioxide is provided which allows a necessary amount to be introduced from a storage container into a reaction vessel through a pipe.

Description

  The present invention relates to an apparatus for producing chlorine dioxide.

  Chlorine dioxide was discovered in 1811 by Humphrey Dary. Chlorine dioxide has a freezing point of −59 ° C. and a boiling point of 11 ° C., and is a greenish yellow gas at room temperature. It smells a little chlorine and can be easily dissolved in water and ether.

  Chlorine dioxide is gradually decomposed during storage and converted into chlorous acid, chloric acid, chlorine ions, etc., and has a bactericidal effect due to its strong oxidizing power (oxidation state: +4).

  Such an advantage of chlorine dioxide is that it does not oxidize organic substances, and in particular does not produce carcinogens such as trihalomethane (THM), HAAs (haloaceticacids), HAN (Haloacetonitol) and other chlorinated organic compounds. Moreover, bactericidal efficacy is maintained in a wide pH range. In addition, there is no generation of carcinogenic substances by by-products, and it is a substance that is rapidly expanding in its use as an alternative to chlorinated disinfectants due to its environmentally friendly properties that are easily decomposed by light.

  Utilizing these characteristics, it was first applied to a water treatment facility in the Niagara Pass (New York, USA) in 1944, and is currently used as a disinfectant in thousands of places in Europe, including over 900 places in the United States. ing.

  In Japan, it is used as a disinfectant (1 ppm or less) and can be used for sterilization of foods such as vegetables and fruits.

  However, chlorine dioxide has a large change over time, and its manufacturing method is complicated, so that storage and analysis are not easy. In addition, in order to mass-produce several hundred tons per day, an acidic liquid starting material chlorate is reduced to sulfurous acid, hydrochloric acid, or hydrogen peroxide by a method such as the following chemical formulas 1 to 3. However, since such a large-scale manufacturing method requires a large facility, it is difficult to apply in a general case other than the bleaching step.

(Formula 1)
2NaClO ₃ + H ₂ SO ₃ → 2ClO ₂ + Na ₂ SO ₄ + H ₂ O

(Formula 2)
2NaClO ₃ + 4HCl → 2ClO ₂ + 2NaCl + Cl ₂ + 2H ₂ O

(Formula 3)
2NaClO ₃ + H ₂ O ₂ + 2HCl → 2ClO ₂ + 2NaCl + O ₂ + 2H ₂ O

  In addition, since the above-mentioned chlorine dioxide is unstable at room temperature, it must be manufactured on site immediately before use, and there are many restrictions on transportation and distribution.

Therefore, it is easy to produce chlorine dioxide water purely by a method that does not contain chlorous acid (ClO ₂ ⁻ ), chloric acid (ClO ₃ ⁻ ), and salts thereof. It is a prerequisite for doing.

JP-A-7-300202

  In order to solve the above problems, an object of the present invention is to provide an apparatus capable of quantitatively generating pure chlorine dioxide gas that does not contain chlorous acid, chloric acid, and salts thereof. is there.

  Another object of the present invention is to generate a high concentration of chlorine dioxide gas in a short time, and even if the high concentration of chlorine dioxide is generated, the chlorine dioxide gas generator is safe without risk of explosion. Is to provide.

  In order to solve the above-described problems, a chlorine dioxide gas generator according to the present invention includes a reaction vessel in which a chlorine dioxide generation reaction occurs, a porous glass filter layer that divides the reaction vessel into a first region and a second region, including.

  The first region of the reaction tank is connected to at least one gas supply unit that supplies chlorine gas and an inert gas to the reaction tank.

  The second region of the reaction tank is connected to at least one raw material supply unit that supplies hypochlorite, chlorite, or acid to the reaction tank.

  A pressure adjusting unit that makes the pressure in the second region smaller than the first region is connected to at least one of the first region and the second region of the reaction vessel.

  A discharge port is connected to the second region of the reaction tank, and chlorine dioxide gas generated in the reaction tank is discharged through the discharge port connected to the reaction tank. The pore size of the porous glass filter layer may be 10 to 100 microns.

  The pressure adjusting unit is a pressure pump that is connected to the first region and pressurizes the first region, or a pressure reducer that is connected to the second region and depressurizes the second region, or a vacuum pump. possible.

  When the pressure adjusting unit is a decompressor, the decompressor is an aspirator using decompressed water or decompressed gas, and the chlorine dioxide is absorbed in the decompressed water passing through the aspirator or is converted into a decompressed gas. Mix.

  The inactive gas may be at least one of nitrogen gas, carbon dioxide gas, and air.

  In the chlorine dioxide manufacturing apparatus according to the present invention, the raw material supply unit may be connected through a solenoid valve. The solenoid valve is controlled by a control unit. The controller may control the solenoid valve to adjust the amount of hypochlorous acid, chlorous acid, or acid supplied.

  The chlorine dioxide production apparatus according to the present invention may include a pressure sensing unit that senses the pressure inside the reaction vessel. The signal of the pressure sensing unit is transmitted to the control unit.

  An adsorption tower may be connected to the discharge port. The adsorption tower includes an organic solvent that dissolves the inert gas and generated chlorine dioxide, and an adsorbing substance. As the organic solvent, any one of n-hexane, methylene chloride, ethyl ether, tert-butyl methyl ether, and petroleum ether can be used. In addition, zeolite or silica gel may be used as the adsorbing material.

  The adsorption tower may be connected to a chlorine dioxide gas removal tower for removing the chlorine dioxide gas remaining after adsorption by the adsorption tower. The gas removal tower may include hydrogen peroxide or sodium thiosulfate for removing the chlorine dioxide gas.

  In the chlorine dioxide production apparatus according to the present invention, the bubbles generated while passing through the fine porous glass filter smoothly stir the reactants, so that a high yield of chlorine dioxide can be obtained.

  Explosion can be suppressed by the reduced pressure inside the reaction tank and fine inactive bubbles ejected from the lower part, and chlorine dioxide can be easily gasified. This pure chlorine dioxide gas is easily absorbed in the vacuum water, and pure chlorine dioxide water can be obtained.

  Further, in the present invention, since a small amount, of course, a large amount of raw material can be introduced quantitatively for an appropriate time using a solenoid valve, the control of reactants and results is easy and inexpensive. It is so economical.

It is a schematic diagram which shows the chlorine dioxide generator which concerns on 1st Embodiment of this invention. It is a schematic diagram which shows the chlorine dioxide generator which concerns on 2nd Embodiment of this invention. It is a schematic diagram which shows the chlorine dioxide generator which concerns on 3rd Embodiment of this invention.

  Hereinafter, the present invention will be described in more detail through embodiments. However, the present invention is not limited to the above-described embodiment, and can be applied to various forms different from each other. The described embodiment is illustrative in all aspects and is not limited. Don't be.

  FIG. 1 is a schematic diagram showing a first embodiment of the chlorine dioxide generator according to the first embodiment of the present invention.

  Referring to FIG. 1, the chlorine dioxide generator according to this embodiment includes a reaction tank 100 in which chlorine dioxide is generated by a reaction.

  The reaction vessel 100 includes a porous glass filter layer 110 that divides the reaction vessel 100 into two regions. That is, the porous glass filter layer 110 separates the reaction tank 100 into the first region R1 and the second region R2.

  The porous glass filter layer 110 can divide the inside of the reaction tank 100 into an upper part, a lower part, a left part, or a right part. The first region R1 is a lower part, and the second region. Most preferably, R2 is the upper part. When the reaction occurs in a liquid state and gas is generated, the gas moves upward, so that the gas generated in the upper part can be easily discharged through the discharge port. The first region R1 of the reaction vessel 100 includes at least one gas supply unit 120 that supplies a chlorine gas that can be used in a chlorine dioxide generation reaction and an inert gas that adjusts the concentration of the chlorine gas. ing. The gas supply unit 120 may be connected to the first region R1 of the reaction tank 100 and the gas supply line 122. One end of the gas supply line 122 connected to the first region R1 may be connected to a gas injection line. An inlet 124 is formed.

The inactive gas and the chlorine gas may be supplied using the same gas inlet 124 as in the present embodiment. However, in other embodiments, the inert gas and the chlorine gas are stored in a separate gas supply unit 120 and separately supplied. Can be supplied to the inlet or simultaneously. For example, a gas inlet for supplying an inert gas so as to move the above chlorine gas from the first region R1 to the second region R2 through the porous glass filter layer 110 and adjust the concentration of the chlorine gas is further formed. Can. FIG. 1 shows an embodiment having one gas inlet 124.
The inert gas supplied at this time is a gas that does not participate in the reaction of chlorine dioxide, and an inert gas such as helium, neon, and argon, and a relatively very stable carbon dioxide gas and air are used. be able to.

  The second region R2 of the reaction vessel 100 is supplied with at least one of chlorite, hypochlorite, and an acid such as sulfuric acid, hydrochloric acid, and nitric acid that can be used for a reaction for generating chlorine dioxide. One or more raw material supply units 130, 140, 150 are provided. In the present embodiment, for convenience of explanation, FIG. 1 shows the first raw material supply unit 130, the second raw material supply unit 140, and the third raw material supply unit 150.

  The first to third raw material supply units 130, 140, and 150 are connected to the second region R2 through first to third raw material supply lines 132, 142, and 152, respectively, and the first to third raw material supply lines 132 are connected. , 142, 152 and the second region R2 are formed with first to third raw material inlets 134, 144, 154, respectively.

  The first to third raw material supply units 130, 140, and 150 may include a raw material supply unit in a tank form (not shown). The first to third raw material supply units 130, 140, and 150 are connected to the second region through first to third raw material supply lines 132, 142, and 152 and first to third raw material inlets 134, 144, and 154, respectively. The raw material is supplied to R2.

  As shown in the drawing, in the present embodiment, a plurality of raw material supply units are formed so as to individually supply each substance, but the present invention is not limited thereto. In another embodiment of the present invention, two or more substances may be supplied to one raw material inlet. Accordingly, the raw material supply lines and the raw material injection ports can be formed in various numbers as necessary. In FIG. 1, the raw material inlets are individually formed, but it is also possible to have a Y-shaped raw material supply line for supplying two kinds of raw materials to one inlet and connecting them to the reaction tank.

  At least one of the first region R1 and the second region R2 of the reaction vessel 100 is provided with a pressure adjusting unit that controls the pressure in the first region R1 and the second region R2. The pressure adjusting unit forms a pressure difference between the first region R1 and the second region R2, so that a fluid flows through the porous glass filter layer 110 between the two regions R1 and R2. To do.

  According to the present embodiment, a decompressor 160 is connected to the second region R2 of the reaction vessel 100 as a pressure adjustment unit for adjusting the pressure inside the reaction vessel 100. The decompressor 160 is connected through the second region R2 and the discharge pipe 162. In the decompressor 160, an aspirator or a vacuum pump can be used. In the present embodiment, an aspirator will be described as an example. At this time, a shutoff valve 166 may be provided between the reaction vessel 100 and the decompressor 160. The decompressor 160 sucks the gas in the reaction tank 100 to lower the pressure in the reaction tank 100, particularly in the second region R2. Here, the decompressor 160 may use various forms of decompressors, for example, a gas decompressor, an air pump, or the like, but preferably uses decompressed water or an aspirator using decompressed gas.

  The decompressor 160 is connected to a discharge port 164 provided in the reaction vessel 100.

  The mechanism for generating chlorine dioxide using the chlorine dioxide production apparatus having the above-described structure is as follows.

  First, if it demonstrates with respect to the method of manufacturing chlorine dioxide, three types can be mention | raise | lifted by a required raw material, for example. The first is the case of using chlorite and acid (sulfuric acid or hydrochloric acid), and the second is chlorite, hypochlorite and acid (sulfuric acid or hydrochloric acid). The third is a case of manufacturing using chlorite and chlorine.

  The above three types of methods are expressed as chemical formulas as follows. Chemical formulas 4 to 5 represent the first case using chlorite, hydrochloric acid, or sulfuric acid, and chemical formulas 6 to 7 represent chlorite, inorganic acid (hydrochloric acid or sulfuric acid), and hypochlorite. This is the second case used, and Chemical Formula 8 is the third case using chlorite and chlorine.

(Formula 4)
5NaClO ₂ + 4HCl → 4ClO ₂ + 5NaCl + 2H ₂ O

(Formula 5)
5NaClO ₂ + 2H ₂ SO ₄ → 4ClO ₂ + 2Na ₂ SO ₄ + NaCl + 2H ₂ O

(Formula 6)
2NaClO ₂ + NaClO + 2HCl → 2ClO ₂ + 3NaCl + H ₂ O

(Formula 7)
2NaClO ₂ + NaClO + H ₂ SO ₄ → 2ClO ₂ + Na ₂ SO ₄ + NaCl + H ₂ O

(Formula 8)
2NaClO ₂ + Cl ₂ → 2ClO ₂ + 2NaCl

  Each of the above-described raw materials is supplied using the gas inlet 124 and the first to third raw material inlets 134, 144, and 154 provided in the first region R1 and the second region R2.

  For example, in the first method, an acid such as sulfuric acid or hydrochloric acid and chlorite are supplied to the second region R2. In the second method, chlorite, hypochlorite, and acid (sulfuric acid or hydrochloric acid) are supplied to the second region R2. In the third method, chlorine gas is supplied to the first region R1, and chlorite is supplied to the second region R2.

  The decompressor 160 reduces the internal pressure of the reaction tank 100 by sucking the gas in the reaction tank 100 before, after, or when the above-described raw materials are input. If depressurized water (not shown) is supplied through the aspirator (decompressor 160), the pressure in the second region R2 becomes lower than the pressure in the first region R1. Accordingly, an inert gas (nitrogen gas, carbon dioxide gas, or air) is sucked into the reaction tank 100 from the outside through the gas inlet 122.

  At this time, the inert gas passes through the fine porous glass filter 110 installed at the lower end of the reaction tank 100 due to the pressure difference, and fine bubbles are generated in the second region R2. By these fine bubbles, the reactants introduced through the raw material inlets 134, 144 and 154 in the second region R2 are uniformly stirred, and at the same time, high concentration and high yield of chlorine dioxide is generated.

  The chlorine dioxide easily becomes a gas due to the reduced pressure inside the reaction tank 100 and fine bubbles.

  The chlorine dioxide gas is absorbed by the decompressor 160 and dissolved in the decompressed water. As a result, an aqueous solution of pure chlorine dioxide can be obtained.

  As described above, in the present invention, a raw material used in a normal chlorine dioxide production method is used. However, the raw material can be used at a higher concentration than in a normal method, and the reaction rate can be increased. Furthermore, high concentration chlorine dioxide gas is generated at the same time.

  The reason why a high yield and high concentration can be maintained without an explosion even if such high concentration of chlorine dioxide is generated is that the reactants installed in the second region of the same reaction tank are continuous. This is because the fine bubble generator installed in the lower part of the same reaction tank as the quantitative charging continuously generates the fine bubbles by the inactive gas flowing from the outside. In order to achieve such conditions, the upper part of the same reaction tank and a decompressor are connected to maintain a constant reduced pressure in the reaction tank.

  At this time, rapid and uniform agitation of the reactant occurs due to such fine bubbles, and the high concentration of chlorine dioxide produced thereby causes fine inert bubbles to gasify chlorine dioxide from the reactant and reaction byproduct solution. Can be extracted.

  In other words, this fine non-active bubble ideally stirs the reactants, and at the same time, easily extracts chlorine dioxide from the mixed reaction solution and by-product reactants in the gaseous state. The explosion can be suppressed by diluting chlorine dioxide gas.

  The extracted pure chlorine dioxide gas is absorbed by the decompressed water flowing out from the decompressor to obtain a pure chlorine dioxide aqueous solution.

  In the production of pure chlorine dioxide aqueous solution, the most important thing can be the pressure inside the reaction vessel, the inactive gas sucked in, and the fine porous glass filter. The pore size of the porous glass filter layer is preferably 10 to 100 microns, more preferably 10 to 40 microns. When the size of the void is smaller than 10 microns, it is difficult for the substance to move between the first region and the second region. When the size is larger than 100 microns, the size of bubbles generated in the porous glass filter layer is large. There is a problem that the reaction becomes too large and the reaction does not occur sufficiently.

  And when adjusting the pressure inside a reaction vessel using a pressure reducer, it reduces pressure to 200 mmHg to 400 mmHg at normal pressure, but preferably 210 mmHg to 240 mmHg is effective. When the diameter is smaller than 200 mmHg, the diameter of the bubbles becomes large and fine bubbles cannot be formed. When the diameter is larger than 400 mmHg, the gas generation rate is lowered and the risk of explosion increases.

  Although each part of the reaction vessel is not described separately, it can be connected by various kinds of connecting devices such as pipes and pipes, and if necessary, each part can be directly connected without a connecting device.

(1-1st Embodiment)
From the top of the reaction vessel, 6.5 mL of 25 wt% sodium chlorite per minute and 30 mL of sulfuric acid of 2 mL per minute are injected using a metering pump.

  An aspirator connected to pressurized water at 3 to 3.5 atm is operated, decompression occurs in the reaction tank, and 400 mL of air per minute is sucked from the outside through a porous fine glass filter installed at the bottom of the reaction tank, Chlorine dioxide generated with rapid mixing of the two compounds while microbubbles are generated is easily vaporized from the reaction mixture and side reaction solution. The vaporized chlorine dioxide is dissolved in reduced pressure water ejected from an aspirator, and a pure chlorine dioxide solution (5.8 L / min) is obtained from the reduced pressure water in which the chlorine dioxide is dissolved.

  The concentration of the chlorine dioxide solution obtained in this embodiment is 172 mg / L, and the yield is 85%.

(1-2 embodiment)
From the top of the reaction vessel, 4.8 mL of 25 wt% sodium chlorite per minute, 4 mL per minute of 12 wt% sodium hypochlorite, and 30 wt% sulfuric acid 2 mL / min are injected using a metering pump.

  If an aspirator connected to pressurized water at 3 to 3.5 atm is operated, a vacuum is generated inside the reaction tank, and a porous fine glass filter installed with nitrogen gas at the lower end of the reaction tank at 400 mL / min from the outside. Inhale through. In the reaction tank, the chlorine dioxide produced by the rapid mixing of the three reaction compounds while producing fine bubbles is easily vaporized from the side reaction products and the impurity solution, and absorbed into the jetted vacuum water to produce pure dioxide. Chlorine water 5.8 L / min can be obtained.

  The concentration of the chlorine dioxide solution obtained in this embodiment is 185 mg / L, and the yield is 95%.

(1-3 embodiment)
An aspirator connected to pressurized water at 3 to 3.5 atm is operated while 25 wt% sodium chlorite is added to the metering pump at 4.9 mL per minute from the upper part of the reaction tank. At this time, a reduced pressure is formed in the reaction tank, and from the outside, carbon dioxide gas 400 mL / min and chlorine gas 170 mL / min are sucked through a porous fine glass filter installed at the lower end of the reaction tank to generate fine air-chlorine mixed bubbles. While being mixed with the sodium chlorite solution instantaneously, chlorine dioxide is produced. The pure chlorine dioxide gas is absorbed by the aspirator jet water to obtain a pure chlorine dioxide aqueous solution of 5.8 L / min.

  The concentration of the chlorine dioxide solution obtained in this embodiment is 180 mg / L, and the yield is 98%.

(First to Fourth Embodiments)
The reaction tank and the reaction reagent used in the 1-1st embodiment to 1-3 are the same, but instead of the liquid decompressor, inactive pressurized gas nitrogen, carbon dioxide, air, etc. are connected to the gas decompressor. Thus, a chlorine dioxide inactive gas mixed gas (16 L / min) can be obtained.

  The concentration of the chlorine dioxide solution obtained in this embodiment is 69 mg / L, and the yield is 90%.

  FIG. 2 shows an apparatus for producing chlorine dioxide according to a second embodiment of the present invention. Hereinafter, in the drawings and description, the description will focus on the parts different from the first embodiment, and the unexplained parts are according to the first embodiment. Similar components in the drawings use similar numbers. In the present embodiment, the reaction vessel 200 is connected to the reaction vessel 200, the porous glass filter layer 210 that divides the reaction vessel 200 into a first region R1 and a second region R2, and the first region R1 of the reaction vessel 200. Is connected to at least one gas supply unit 220 for supplying chlorine gas and inert gas to the second region R2 of the reaction tank 200, and hypochlorous acid, chlorous acid, or acid is supplied to the reaction tank 200. Connected to at least one of the first region R1 and the second region R2 of the reaction vessel 200, and is connected to the first region R1 by the first region R1. A pressure adjusting unit for reducing the pressure in the second region R2, and a discharge port 2 connected to the reaction vessel 200 and from which chlorine dioxide gas generated in the second region R2 of the reaction vessel 200 is discharged. And a 4.

  At this time, a pressure pump 260 is provided as a pressure control unit, and further includes an adsorption tower 270 for obtaining the generated chlorine dioxide gas solution.

  The pressurizing pump 260 is provided between the first region R 1 of the reaction vessel 200 and the gas supply unit 220. The pressurizing pump 260 may be provided on a supply line 222 that supplies an inert gas, and supplies the inert gas to the first region R1 at a high pressure.

  If an inert gas is supplied to the first region R1 in the reaction tank 200 together with chlorine gas by a pressure pump 260 at a high pressure, the pressure in the first region R1 in the reaction tank 200 is changed to the second region in the reaction tank 200. The pressure becomes higher than the pressure of R2, and such a pressure difference becomes a driving force for moving the gas in the first region R1 to the second region R2. As a result, the inert gas and chlorine gas in the first region R1 move to the second region R2 through the porous glass filter layer 210, pass through the porous glass filter layer 210, and fine bubbles in the second region R2. Generated. By these fine bubbles, the reactants introduced through the raw material inlets 234, 244, 254 in the second region R2 are uniformly stirred, and at the same time, high concentration and high yield of chlorine dioxide is generated. The generated chlorine dioxide gas is discharged through the discharge port 264.

  An adsorption tower 270 is connected to the discharge port 264. One adsorption tower 270 may be provided, but a plurality of adsorption towers 270 may be provided and connected in series.

  The adsorption tower 270 includes an organic solvent that dissolves the inert gas and the generated chlorine dioxide and an adsorbing substance. Thus, the generated chlorine dioxide gas is absorbed by the adsorption tower 270, and a pure organic solvent solution of chlorine dioxide can be obtained.

  The organic solvent is a solvent that can be mixed with water, that is, methanol, ethyl alcohol, propanol, isopropanol, tetrahydrofuran, acetone, ethyl acetate, and the like, and is an organic solvent that separates and forms a layer without being mixed with water. n-hexane, methylene chloride, ethyl ether, tert-butyl methyl ether, petroleum ether and the like.

  Among the organic solvents described above, an organic solvent that is highly volatile and forms a layer without being mixed with water can be used by being extracted directly from an aqueous chlorine dioxide solution using a separator.

  Further, zeolite or silica gel can be further added to the organic solvent adsorption tower so that gaseous chlorine dioxide can be adsorbed on the zeolite or silica gel and recovered. Chlorine dioxide adsorbed on zeolite or silica gel can be desorbed later by supplying a large amount of inactive gas.

(2-1 embodiment)
Ethyl alcohol is put into three organic solvent adsorption towers connected in series, and 25 wt% sodium chlorite soda and 30 wt% sulfuric acid are added at 2 mL / min to the inlet of the second region of the reaction tank. Then, inactive nitrogen gas is introduced into the first region of the reaction tank at 350 mL / min for 15 minutes.

  At this time, the concentration of the chlorine dioxide ethyl alcohol solution finally obtained is 2,125 mg / L (yield 85%).

  In the same manner, 2,000 mg / L to 2,200 mg / L of methanol, isobutyl alcohol and acetone can be obtained.

(2-2 embodiment)
6 L of n-hexane was placed in three organic solvent adsorption towers connected in parallel, and 25 wt% chlorite at 6.5 mL / min and 30 wt% sulfuric acid at 2 mL / min at the inlet of the second region of the reaction vessel. The solution is put, and inactive carbon dioxide gas is added to the first region of the reaction tank at 300 mL / min for 15 minutes.

  The concentration of the n-hexane chlorine dioxide solution obtained at this time is 2,250 mg / L (yield 90%).

  In the same manner, an organic solvent solution of ethyl ether 2370 mg / L, tert-butyl methyl ether (2,320 mg / L) in chlorine dioxide is obtained.

(2-3 embodiment)
Silica gel and zeolite are put into three adsorbing towers connected in parallel, 25% chlorite is put at 6.5 mL / min into the inlet of the second region of the reaction tank, and air is fed into the first region at 360 mL / min. And 946 mL / min of chlorine gas are injected simultaneously.

  The chlorine dioxide gas generated at this time is adsorbed on silica gel or zeolite, and finally 95% yield of chlorine dioxide can be obtained.

  FIG. 3 shows an apparatus for producing chlorine dioxide according to a third embodiment of the present invention. In the following, the drawings and description will focus on the parts different from the first embodiment, and the parts not explained will depend on the first embodiment. Similar components in the drawings use similar numbers.

  During the generation reaction of chlorine dioxide, chlorite undergoes an unequal decomposition reaction with acid to produce reactants such as hypochlorous acid, chloric acid and chlorine, so rapid stirring and mixing of the reactants, High yield, high purity chlorine dioxide must be produced, where the exact amount of raw material compound must be injected. Accordingly, the present invention includes a solenoid valve so that the above-described reactants can be reacted in an accurate amount with an appropriate time.

  Referring to FIG. 3, in this embodiment, the reaction tank 300 is connected to a porous glass filter layer 320 that divides the reaction tank 300 into a first region R <b> 1 and a second region R <b> 2, and the first region R <b> 1 of the reaction tank 300. And connected to at least one gas supply unit 320 for supplying chlorine gas and inert gas to the reaction tank 300 and the second region R2 of the reaction tank 300, and the reaction tank 300 is supplied with hypochlorous acid and chlorine. The acid or at least one raw material supply unit 330, 340, 350 for supplying an acid, and the first region R1 or the second region R2 of the reaction tank 300 are connected to the first region R1, and the second region R2. A pressure adjusting unit for reducing the pressure in the second region R2 from the first region R1 and the chlorine dioxide gas generated in the second region R2 of the reaction vessel 300 are connected to the reaction vessel 300. And a discharge port 364 is issued.

  First to third raw material inlets 334 when the raw material is injected into the reaction tank 300 are supplied to the first to third raw material supply units 330, 340, and 350 connected to the first region R1 and the second region R2. First to third solenoid valves S1, S2, S3 for opening and closing 344, 354 are provided. The first to third solenoid valves S1, S2, S3 are valves configured to include a solenoid having a magnetic core and one or more orifices. When a fluid flow passes a current through the solenoid, Alternatively, the valve is controlled while being opened and closed by the movement of the core when no current flows through the solenoid.

  The first to third solenoid valves S1, S2, and S3 can be adjusted so that the opening time is 0.5 seconds to 10 seconds and the closing time is 1 second to 60 seconds. Thereby, the amount of the raw material chemicals can be adjusted, and if necessary, the reaction vessel 300 is also provided at the connecting portion between the reaction vessel 300 and the decompressor 360 to adjust the pressure inside the reaction vessel 300. The fine glass bubbles can be formed by the porous glass filter 310 installed in the filter.

  The reaction tank 300 includes a pressure sensing unit 312 that senses the pressure in the first region R1 and the second region R2, and is preferably provided in the second region R2 to control the pressure in the second region R2. Sense and provide the sensed pressure signal to a control unit 370 to be described later.

  The decompressor 360 may be connected to the reaction tank 300 and the discharge pipe 362, and a solenoid valve S4 may be provided at one end of the discharge pipe 362 on the reaction tank 300 side. At this time, the decompressor 360 is provided with a switch 372 for operating or stopping the decompressor 360 according to an electrical signal, and the switch 372 is electrically connected to the controller 370. The decompressor 360 serves to reduce the pressure inside the reaction tank 300 by sucking the gas inside the reaction tank 300.

  The decompressor 360 is formed with a discharge port 364 through which the gas formed inside the reaction tank 300 is exhausted. When the decompressor 360 is an aspirator, decompressed water or decompressed gas is exhausted. An outlet equal to the outlet can be used. Moreover, pure chlorine dioxide gas is easily absorbed in the reduced pressure water, and a pure chlorine dioxide aqueous solution can be obtained.

  The first, second and third raw material supply units 330, 340 and 350 and the solenoid valves S1, S2 and S3 of the decompressor 360, the switch 372 of the decompressor 360 and the pressure sensing unit 312 are the solenoid valves S1 and S2. , S3, the decompressor 360, and the controller 370 that controls the reaction vessel 300 are electrically connected and controlled.

  The control unit 370 can be mounted on a PCB (Printed Circuit Board) as an electronic control device built in a microprocessor, and controls whether to open or close the component according to each condition. To do.

  The order of producing chlorine dioxide according to this embodiment is as follows.

  First, the internal pressure of the reaction tank 300 is reduced by operating a pressure reducing device 360 such as a vacuum pump or an aspirator connected to an external pipe. In the present embodiment, a case where an aspirator is used as the decompression device 360 will be described as an example.

  First, when the switch 372 of the decompressor 360 is turned on by the controller 370, the decompressor 360 is operated, and the solenoid valve S4 connected to the decompressor 360 is opened to discharge the air in the reaction tank 300. . If the decompression inside the reaction tank 300 is disclosed, the pressure in the second region R2 becomes lower than the pressure in the first region R1, so that gas moves from the first region R1 to the second region R2. . Thereby, fine bubbles are formed from the porous glass filter layer 310.

  If the pressure sensor 312 senses a sufficient and stable reduced pressure state in the reaction tank 300, a signal is given to the control unit 370, and the first raw material supply unit 300 to the third raw material supply are performed according to a predetermined time. The solenoid valves S1, S2, and S3 connected to the unit 500 are opened and closed. As a result, necessary raw materials are quantitatively introduced into the reaction vessel 300.

  The raw material charged in this way is mixed by the air bubbles formed from the porous glass filter 310 and generates chlorine dioxide by the reactions of the above chemical formulas 4 to 8 together with the mixing.

  That is, the inert gas and chlorine gas in the first region R1 move to the second region R2 through the porous glass filter layer 310, pass through the porous glass filter layer 310, and fine bubbles are generated in the second region R2. Is done. Such fine bubbles cause uniform stirring with the reactants introduced through the inlet of the second region R2, and at the same time, high concentration and high yield of chlorine dioxide is generated.

  Chlorine dioxide contained in the reaction mixture and side reaction product solution is easily extracted into gaseous pure chlorine dioxide gas by the reduced pressure and fine bubbles inside the reaction vessel 300.

  This chlorine dioxide gas is absorbed by the decompressor 360 and absorbed by the decompressed water that flows out. As a result, a pure chlorine dioxide aqueous solution can be obtained.

  As described above, in the present invention, by adjusting the opening and closing of the solenoid valve using an electronic control device, the degree of charging can be controlled to a very small amount. There is also an effect of suppressing.

  In the past, raw materials were charged using a metering pump or a flow meter. This was possible because the raw material chemical was a liquid or a gas such as chlorine, but the input amount was not fine and it was difficult to accurately measure the amount of raw material. Also difficult to control. However, the present invention has solved all such problems. In addition, as described above, in the present invention, the raw material used in the ordinary chlorine dioxide production method is used. However, the raw material can be used at a higher concentration than in the usual method, and the reaction rate can be increased. Not only that, it is possible to generate a high concentration of chlorine dioxide gas at the same time.

(3-1 embodiment)
12.5 wt% sodium chlorite is prepared in the first raw material storage container, and 15 wt% sulfuric acid is prepared in the second raw material storage container. Next, after the aspirator was switched on, the solenoid valve of the reaction tank was opened to lower the pressure, and then sodium chlorite was charged into the reaction tank at 1,104 mL / min through the solenoid valve and the sulfuric acid was added. Charge 0.4 mL / min into the reaction vessel.

  The generated chlorine dioxide aqueous solution corresponds to 5.8 L (yield 92%) as a concentration of 17 ppm.

(3-2 embodiment)
Prepare 12.5 wt% sodium chlorite in the first raw material storage container, prepare 6 wt% sodium hypochlorite in the second raw material storage container, and prepare 12.5 wt% sulfuric acid in the third fuel storage container To do. Next, after switching on the aspirator, the solenoid valve of the reaction vessel is opened to lower the pressure, and then the sodium chlorite is 2.66 mL / min and the sodium hypochlorite is 2.18 mL / min. And 1.45 mL / min of the sulfuric acid are charged into the reaction vessel.

  The chlorine dioxide gas generated at this time is absorbed and dissolved in water by an aspirator to show 53 ppm, which corresponds to 5.8 L of chlorine dioxide water (yield 95%).

DESCRIPTION OF SYMBOLS 100: Reaction tank 120: Gas supply part 122: Gas supply line 124: Gas inlet 160: Pressure reducer 164: Outlet R1: 1st area | region

Claims (15)

A reaction vessel;
A porous glass filter layer dividing the reaction vessel into a first region and a second region;
At least one gas supply unit connected to the first region of the reaction vessel and supplying chlorine gas and an inert gas to the reaction vessel;
At least one raw material supply unit connected to the second region of the reaction vessel and supplying hypochlorite, chlorite, or acid to the reaction vessel;
A pressure adjusting unit connected to at least one of the first region and the second region of the reaction tank and configured to reduce the pressure in the second region from the first region;
A chlorine dioxide generator, comprising: a discharge port connected to the reaction tank and from which chlorine dioxide gas generated in the second region of the reaction tank is discharged.   2. The chlorine dioxide generator according to claim 1, wherein the size of the void in the porous glass filter layer is 10 to 100 microns.   The chlorine dioxide generator according to claim 1, wherein the pressure adjusting unit is a pressure pump that is connected to the first region and pressurizes the first region.   2. The chlorine dioxide generator according to claim 1, wherein the pressure adjusting unit is a decompressor that is connected to the second region and depressurizes the second region.   5. The decompressor is an aspirator using decompressed water or decompressed gas, and the chlorine dioxide is absorbed by the decompressed water passing through the aspirator or mixed with the decompressed gas. The chlorine dioxide generator described in 1.   The chlorine dioxide generator according to claim 4, wherein the decompressor is a vacuum pump.   2. The chlorine dioxide generator according to claim 1, wherein the non-active gas is at least one of nitrogen gas, carbon dioxide gas, and air.   The chlorine dioxide generator according to claim 1, wherein the raw material supply unit is connected through a solenoid valve. A control unit for controlling the solenoid valve;
The chlorine dioxide generator according to claim 8, wherein the controller controls the solenoid valve to adjust a supply amount of the hypochlorous acid, chlorous acid, or acid.   The chlorine dioxide generator according to claim 9, further comprising a pressure sensing unit for sensing a pressure inside the reaction vessel in the reaction vessel, and a signal of the pressure sensing unit is transmitted to the control unit. .   The adsorption tower according to claim 1, further comprising an adsorption tower connected to the outlet, wherein the adsorption tower contains an organic solvent that dissolves the inert gas and generated chlorine dioxide and an adsorbent. Chlorine generator.   12. The chlorine dioxide generator according to claim 11, wherein the organic solvent is any one of n-hexane, methylene chloride, ethyl ether, tert-butyl methyl ether, and petroleum ether.   12. The chlorine dioxide generator according to claim 11, wherein the adsorbing substance is zeolite or silica gel.   The chlorine dioxide generator according to claim 11, further comprising a chlorine dioxide gas removal tower connected to the adsorption tower to remove the chlorine dioxide gas remaining after adsorption.   The chlorine dioxide generator according to claim 14, wherein the gas removal tower includes hydrogen peroxide or sodium thiosulfate for removing the chlorine dioxide gas.

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