JP2000185908A - Production of chlorine dioxide water - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing chlorine dioxide water that can be saved in labor, can be remotely operated or unmannedly operated. SOLUTION: This method for producing chlorine dioxide water comprises supplying an aqueous chlorite solution, an aqueous hypochlorite solution, an aqueous acid solution and water into a mixing device, while controllers for controlling the flows of the solutions and the water are controlled by computers through an interface 5, and then passing a mixture of the solutions and water through a reaction column. Therein, the production is carried out in an apparatus which comprises the mixing device 80 connected to an aqueous chlorite solution tank, an aqueous hypochlorite solution tank, an aqueous acid solution tank and a water supply port H via flow-controlling devices respectively; computers C1, C2 in which the concentrations of aqueous chlorite solution, aqueous hypochlorite solution, and aqueous acid solution, the amount of the produced chlorine dioxide, and the molar ratio of the injected raw materials are preliminarily inputted; and a reaction column 90.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing chlorine dioxide water and an apparatus for producing chlorine dioxide water. More particularly, the present invention relates to a method for easily producing chlorine dioxide water having an accurate concentration at any concentration, and an apparatus for producing the chlorine dioxide water.

[0002]

BACKGROUND ART In recent years, large-scale outbreaks of O-157 infection,
Cryptosporidium accidents originating from the water supply in Ogose-machi, Saitama, and legionella infections in the children's ward of university hospitals have frequently occurred, and measures to prevent such accidents are being sought. Because chlorine dioxide has strong oxidizing power and bactericidal properties, as a bactericide for pathogenic bacteria as described above,
It is also used as a biocide containing insecticides, a decolorizing bleach, a deodorant, and an oxidizing agent. This chlorine dioxide has a melting point of -5.
Since it is a gaseous substance at room temperature of 9 ° C. and a boiling point of 11 ° C., it has high chemical reactivity and is unstable when compressed, it is not desirable to transport it as a product, and it must be manufactured at the site of use. However, in general, there are few places where a chemical reaction can be easily performed at a site where chlorine dioxide is used, and it is more difficult to save labor, be unmanned, and control production by remote control.

As a conventional method for producing chlorine dioxide, JP-B-59-53206 discloses a continuous production method in which water, chlorite and hypochlorous acid are individually adjusted after pH adjustment and then reacted. Japanese Patent No. 279707 discloses a method in which a high-concentration aqueous solution of chlorite and chlorine gas are instantaneously reacted with chlorine gas and the generated chlorine dioxide is continuously sucked and collected by a diluting fluid sucked from a venturi extractor. Discloses a method for producing chlorine dioxide water using a reactor equipped with a static mixer or the like having a static mixing effect and using a raw material chemical supply device utilizing the air pressure of a pressure storage tank. Japanese Patent Application Laid-Open No. Hei 9-156902 discloses that an aqueous solution of chlorite, an aqueous solution of hypochlorite, and an aqueous solution of an acid are simultaneously mixed and reacted in the same volume, whereby chlorine as an impurity becomes 2% or less of the amount of chlorine dioxide. A continuous production method of high-purity chlorine dioxide, JP-A-10-81503, discloses that a mineral acid aqueous solution and a chlorite aqueous solution are reacted in a static reaction column by air pressure, and this is diluted with water in a mixing column. Three
A method and apparatus for producing chlorine dioxide water at 000 ppm is disclosed.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to save labor, remote control operation and unmanned operation in a method for producing chlorine dioxide water.

[0005]

SUMMARY OF THE INVENTION The production method of the present invention comprises the steps of producing chlorite, hypochlorite and acid; chlorite and acid; In the production method, the supply amount of each raw material aqueous solution to the reaction column and the supply amount of water are controlled by an electric signal.

[0006] The first method for producing chlorine dioxide water of the present invention comprises:
In the method for producing chlorine dioxide water using chlorite, hypochlorite and acid as raw materials, an interface is provided by a computer which has been preset and set for each raw material aqueous solution concentration, chlorine dioxide production and each raw material injection molar ratio. Each flow controller is interlocked and controlled to adjust the supply amount of each raw material aqueous solution and water to the reaction column. Preferably, one of the water supply amount and the chlorine dioxide water concentration is input and set to the computer. The raw material aqueous solution includes a chlorite aqueous solution (including 200 g / liter or more of chlorite), a hypochlorite aqueous solution (including 80 g / liter or more of hypochlorite), and an aqueous acid solution (including 150 g / liter or more of acid). It is preferable to use The raw material injection molar ratio magnification is 100 to 200 chlorite, 100 to 200 hypochlorite, and 1 acid.
A range from 10 to 500 is preferred. In addition, remote monitoring and control can be performed by computer communication.

According to the second method for producing chlorine dioxide water of the present invention,
In a method for producing chlorine dioxide water using chlorite and acid; or chlorite and chlorine as raw materials, a computer in which a concentration of each raw material aqueous solution, a production amount of chlorine dioxide and a molar ratio of each raw material injection are preset and input. , The respective flow controllers are interlocked and controlled via an interface to adjust the supply amount of each raw material aqueous solution to the reaction column, and to mix the reaction solution from the reaction column with water. Preferably, one of the water supply amount and the chlorine dioxide water concentration is input and set to the computer. Further, the molar ratio of the raw material injection molar ratio is 100 to 500 hydrochloric acid with respect to 100 chlorite. Remote monitoring and control can be performed by computer communication.

[0008] The third method for producing chlorine dioxide water of the present invention comprises:
In a method for producing chlorine dioxide water using chlorite and an acid as raw materials, the flow rate of an aqueous chlorite solution and an aqueous acid solution is controlled by an indicator controller in which a supply amount of chlorite and a supply ratio of both raw materials are set. It is characterized by controlling the flow rate of the vessel.

A first production apparatus of the present invention is a mixer in which a chlorite aqueous solution tank, a hypochlorite aqueous solution tank, an acid aqueous solution tank, and a water supply port are connected via respective flow controllers; A computer in which the concentrations of chlorite, hypochlorite, and acid in each aqueous solution, the amount of chlorine dioxide to be produced, and the molar ratio of each raw material injection are preset and input; and a reaction column. A computer controls the supply amount of each aqueous solution and water to the mixer under the control of the interface, and the aqueous solution and water mixed in the mixer pass through the reaction column to obtain chlorine dioxide water. Consists of Preferably, a digital output signal calculated by a computer is converted into an analog control signal (DC 4 to 20 mA) or a pulse control signal at an interface (program controller) to control the driving of the pump of each flow controller. The manufacturing apparatus described above.

[0010] A second production apparatus of the present invention is a water supply system having a mixer, a reaction column, and a water flow regulator in which a chlorite aqueous solution tank and an acid aqueous solution tank are connected via respective flow regulators. The flow rate of the flow controller is controlled by an indicator controller in which the supply ratio of the chlorite aqueous solution and the acid aqueous solution is set, and the two aqueous solutions whose supply amounts are adjusted by the control are combined by the mixer. It passes through a reaction column and is combined with water from a water supply port having a water flow regulator to obtain chlorine dioxide water. Preferably, the production apparatus is one in which the residence time of the reaction column is 1 to 100 minutes.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The reaction for obtaining chlorine dioxide using chlorite used in the present invention can be exemplified by the following reaction formula, and is an example using hydrochloric acid as an acid. 3 liquid _{method; 2NaClO 2 + NaClO + 2HCl →} 2ClO 2 + 3NaCl + H 2 O (1) 2 -reagent _{method; 5NaClO 2 + 4HCl → 4ClO 2} + 5NaCl + 2H 2 O (2) Gas _{Law; 2NaClO 2 + Cl 2 → 2ClO} 2 + 2NaCl (3) The present invention The raw material injection molar ratio magnification is expressed as follows according to the reaction formula. For example, in the chemical reaction of the three-liquid method represented by the formula (1),
When the molar ratio of ClO ₂ : NaClO: HCl is 2: 1: 2, the raw material injection molar ratio is 100: 100: 1.
00. That is, sodium chlorite (2NaC
(O ₂ ) was defined as 100, and the increase / decrease in the molar ratio of sodium hypochlorite (NaClO) and hydrochloric acid (2HCl) was input to the computer as the molar ratio at the time of injection. For example, as shown in Example 6 below, when the theoretical amount of sodium hypochlorite (NaClO) is increased by 10%, hydrochloric acid (2
HCl) In the case of double the theoretical amount, the molar ratio at the time of injection is 110 for hypochlorite and 110 for hydrochloric acid with respect to 100 for chlorite.
Entered as 00.

The interlocking control in the present invention is to adjust the flow rate of each of the two or three raw material aqueous solutions to the mixer or the reactor by an electric signal using a computer or an indicator controller. For example, when one raw material aqueous solution flow rate is reduced by half, the other raw material aqueous solution flow rate is also reduced by half. As the interlocking control method, a method of controlling the ratio of two flow rates with one indicating controller, a method of controlling the ratio of three flow rates by combining the indicating controllers, and a method of adjusting the flow rates of a plurality of raw material aqueous solutions from a computer There is. The electric signal mentioned here includes a pulse signal, a current signal, a voltage signal, or a signal obtained by replacing these with an optical signal.

As a method of controlling the ratio of the raw material liquids with one indicating controller, one raw material liquid is set, and the remote set values of the other raw material liquids are calculated by a ratio. The raw material liquid ratio will be set. As a method of adjusting the flow rate of the raw material aqueous solution using a computer, the flow rate of the raw material aqueous solution is determined by a computer electric signal via an interface. The interface issues a signal for setting and instructing the flow controller from the computer, and may be any of a pulse signal, a current signal and a voltage signal.
The computer may be a personal computer, a general-purpose computer, a one-chip microcomputer, or any other device having a CPU (central processing function), a storage function, and an input / output function. The interface sets the flow controller by a signal from a computer. In the case of a device having a network communication function, a large number of flow controllers can be compactly linked by connecting two wires.

According to the method for producing chlorine dioxide water which performs remote monitoring and control by computer communication, the monitoring and operation control of the site can be performed from a remote office or the like, so that labor saving and unmanned operation are possible. As the computer communication, there are a dedicated line such as a LAN, an analog line, a digital line ISDN, and a public line including an NS net 64.
In particular, a public line is preferable for monitoring and operation control of a site from a remote place.

In the method for producing chlorine dioxide water of the present invention, the production can be controlled by continuously measuring the amount of water, the amount of chlorine dioxide water, the concentration of chlorine dioxide water or the pH of the chlorine dioxide water. Furthermore, it is desirable to simultaneously and continuously measure the water amount, the concentration of chlorine dioxide water and the pH of the chlorine dioxide water,
It is desirable to input the measured values by computer. The pH of the chlorine dioxide water is preferably 2 to 6, more preferably 2 to 4.
It is.

The method of measuring the amount of water from the water supply port H and the amount of chlorine dioxide water to be produced is as follows: a method in which the rotation speed of a water wheel type is replaced with an electric signal, a gear flow meter, and a float in a tapered pipe are indicated by a differential transformer. And a method of displaying the flow rate from the Karman vortex vibration. Chlorine dioxide water concentration measurement is polarographic analysis method (JIS-K0111), 300-500n
Chlorine dioxide concentration meter (m
ANA-6301). In addition, measurement of pH of chlorine dioxide water,
Use a general-purpose pH meter.

In order to set the amount of the raw material liquid, a method of setting the flow rate of each raw material liquid in a computer, setting and inputting a specific value, and calculating the necessary amounts of the aqueous chlorite solution, the aqueous acid solution, There is a method for determining the amount of chlorate aqueous solution, the amount of chlorine, and the like. In the method of performing the computer arithmetic processing, a method of setting and inputting the amount of water from the water supply port H,
There is also a method of setting the expected production amount of chlorine dioxide water and a method of setting and inputting the chlorine dioxide concentration of the chlorine dioxide water to be produced. Further, the concentration of the raw material liquid such as chlorite, acid, chlorine or hypochlorite can be set and input.

The flow controller according to the present invention may be any one which can control the flow rate by an electric signal, and includes a needle valve, a ball valve, a butterfly valve, a piston / plunger pump, a gear pump, a snake pump, a diaphragm pump, and the like. One using a bellows pump or a tube pump can be exemplified. Particularly, for a small amount, a piston plunger pump, a diaphragm pump, and a tube pump are preferable. DC4-20mA control, 0-5V
Electric signal control such as control is easier, and for large amounts of water, gear pumps, impeller pumps, ball valves,
Needle valves are preferred. For the valve type, the degree of opening and closing of the valve is controlled by an accumulator (driving device), and there is also an air pressure control electrically controlled.
Electric signal control such as 0-5V control is easier.

The reaction column is made of a static mixer, a Raschig ring, a porous material such as a sintered metal, a granular fiber filter, a mesh material such as a stainless steel wire mesh, a Teflon filled with a fiber filter or the like, a plastic made of chlorinated vinyl chloride, glass, or the like. It is a cylindrical container made of ceramics or ceramics. Further, the static mixer is preferably a so-called static mixer in which right-hand twisting elements and left-hand twisting elements are alternately arranged. This element has a rectangular plate twisted by 180 ° and is called a right element or a left element according to the twisting direction. The material is desirably stainless steel, glass, ceramic, or plastic which is hardly corroded. The larger the number of elements, the more uniform the reaction is to generate chlorine dioxide from the chemical solution as the raw material, and the more preferable is four or more.

The water used in the present invention may be any of pure water, ion-exchanged water and tap water as long as it does not hinder the reaction. The amount of water should be such that the concentration of the chlorine dioxide water to be produced is preferably between 10 and 10,000 ppm, more preferably 500 ppm.
It is set to be 3,000 ppm.

The chlorite used in the present invention is a chlorite such as potassium chlorite, sodium chlorite, calcium chlorite, etc., preferably sodium chlorite. Since use in powder is difficult to adjust the amount, it is used as a solution. The chlorite concentration of the aqueous chlorite solution having chlorite ions when formed into a solution is preferably 200
g / liter or more, more preferably 200 to 350 g / liter.

The acid may be any acid required for the reaction for producing chlorine dioxide from chlorite, such as hydrochloric acid,
Examples thereof include sulfuric acid, phosphoric acid, acetic acid, citric acid, and tartaric acid. The concentration of the acid aqueous solution is preferably 150 g / liter or more, more preferably 20 to 600 g / liter.

The chlorine may be either chlorine gas or liquefied chlorine, but liquefied chlorine obtained by cooling and pressurizing chlorine gas is easy to use.

The hypochlorite used in the present invention includes potassium hypochlorite, sodium hypochlorite, calcium hypochlorite, etc., but the quality is stable and easy to obtain and handle. Sodium hypochlorite is preferred from this point. Hypochlorite aqueous solution having a hypochlorite concentration of 100 to 160 g / l or less is commercially available, preferably 80 g / l or more, more preferably 10 g / l or more.
Use more than 0g / liter. Hypochlorite is
Since it is easy to gasify and the concentration tends to decrease, it is preferable to store at low temperature and cool. Even if the concentration of the aqueous hypochlorite solution decreases due to the generation of chlorine gas due to gasification, the flow rate can be accurately adjusted by changing the setting by measuring the concentration appropriately.

The concentration of the produced chlorine dioxide water is 10 to
It is preferably set to be 10,000 ppm, more preferably 500 to 3,000 ppm.

In the method for producing chlorine dioxide water of the present invention, in the case of the first production method (three-liquid method), the raw material molar ratio of the raw material aqueous solution to be injected is 100 parts of hypochlorite and 100 parts of hypochlorite. ~ 200, acid 110 ~ 500, more preferably hypochlorite 110 ~ 160,
The acid is 150-300. In the case of the second production method (two-liquid method), the raw material aqueous solution to be injected has a raw material molar ratio of 100 to 500, more preferably 150 to 400, of hydrochloric acid with respect to 100 of chlorite. In the case of the chlorine method, the molar ratio of the raw material injection molar ratio is 100 parts of chlorite and 1 part of chlorine.
00 to 200, more preferably 110 to 150
It is. When sulfuric acid is used as the acid, the reaction formula is 5NaClO ₂ + 2H ₂ SO ₄ → 4ClO ₂ + 2Na ₂ SO ₄ + NaCl + 2H ₂ O. . . . . . . (4) wherein the molar ratio of the raw material injection is 100 to 500 sulfuric acid with respect to 100 chlorite, and more preferably 15 to 100.
0 to 400.

That is, when chlorine dioxide water according to the production method of the present invention is used for purification of tap water, it is easy to change the amount of chlorine dioxide in the chlorine dioxide water according to the degree of contamination of the raw water of the tap water. is there. The variable amount setting of the chlorine dioxide amount is preferably 10 to 100% of the maximum amount, more preferably 30 to 100% of the maximum amount because the lower limit setting deteriorates the injection amount accuracy of each flow controller.
１００100%. In the purification of tap water with chlorine dioxide water, the chlorine dioxide concentration of tap water is usually 10 to 0.
Perform so that it becomes 1 ppm. In this method, it is preferable to produce chlorine dioxide water having a chlorine dioxide concentration of 100 to 10,000 ppm and inject it into tap water in terms of production. More preferably, 500 to 3,000 ppm of chlorine dioxide water is added to tap water. inject. It can also be used in food washing water and wastewater treatment.

[0028]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a conceptual diagram of an apparatus used in Examples 1 to 4. Each code indicates the following. 1C Computer: A WINDOWS (registered trademark) movable personal computer was used to input data from the following indicating controller. 2 Indicating controller: Yokogawa M &C's indicating controller UT520 (control output is DC4
２０20 mA) was used. One point was set to 100%, and the second point was set to a proportional output between two points with the first point. 3A, B tank: A 20 liter tank made of polyethylene was used.

6A, 6B Flow rate controller: A so-called tube pump of a type in which a polyethylene tube (7 × 5 mmφ) is tightened by a roller pin by rotation of a geared inverter motor (rotation speed: 5 to 100 rpm) to transfer liquid. The roller pin is composed of six pins and has a maximum rotation speed of 75 rpm and a maximum liquid flow of 170 m.
1 / min. In the following experiment, the degree (degree) of the number of rotations of the motor is expressed in% with the case where the maximum rotation speed is 75 rpm as 100. 6C Water flow controller: A combination of a rubber impeller rotor pump and an inverter motor, which adjusts the liquid flow by changing the inverter frequency (Hz). A liquid having a liquid flow rate of 11 liter / min at a maximum of 50 Hz was used. 7 Water flow meter: A device that measures the flow rate by reading a light beam blocked by a windmill-shaped blade rotating by the water flow in a pipe as a pulse signal, and measuring a flow rate of 0.3 to 9 L / min. . (External output: DC 4-20m
A)

8 Mixer: Using a T-type connector, two ports were used as an inlet for an aqueous solution of sodium chlorite and an aqueous acid, and one port was used as an outlet for a mixed solution. 9 Reaction column a: A column in which 24 right-hand twisting elements and left-hand twisting elements were alternately arranged in a polypropylene tube having an inner diameter of 5 mm was used. (here,
Each element is formed by twisting a rectangular plate by 180 °, and is called a right-handed element or a left-handed element depending on the twisting direction. )

10 Chlorine dioxide concentration meter: Tokyo Koden Co., Ltd.
Manufactured by ANA-6301. The light source is emitted from the tungsten lens bulb and absorbed by the measuring cell (chlorine dioxide water).
It is measured by spectroscopy with a 50 nm filter and measuring the amount of light received by the silicon diode. 11 pH meter: A commercially available pH meter for piping and a measurement control device were used.

12 Reaction column b: A column made of a vinyl chloride resin and having a capacity of 1000 ml filled with a ceramic Raschig ring was used. 13 Piping A tube (8 × 6 mmφ) made of Teflon (registered trademark) was used.

The retention times, theoretical concentrations of chlorine dioxide, measured concentrations of chlorine dioxide, and yields of chlorine dioxide shown in the table are as follows. Residence time: The residence time in the reaction column 12 was calculated. Chlorine dioxide concentration of chlorine dioxide water: Theoretical concentration: Determined from the flow rate of the aqueous solution of sodium chlorite based on the reaction formula {Eq. (2) for Table 1 and Eq. (1) for Tables 2 and 3}. It was calculated from the generated amount of chlorine dioxide and the amount of H water. (That is, the concentration when 100% of sodium chlorite has reacted). Measurement concentration: The chlorine dioxide concentration of the produced chlorine dioxide water was determined by a redox titration method (10% KI and PH8 buffer solution were added, and fixed iodine was added dropwise with a 0.1N sodium thiosulfate solution. The inflection point was determined by a polarization titrator). Chlorine dioxide yield: determined by the following equation.

Example 1 Aqueous sodium chlorite solution (NaCl: 150 g + N
5 liters of aClO ₂ : 100 g / liter) were prepared and put into tank A, while an aqueous acid solution (NaCl: 150
g + HCl: 100 g) / liter @ 4 liter was prepared and placed in tank B. The rotation speed of the pump on the A tank side of the indicating controller 2 is 29%, and the supply ratio of the aqueous sodium chlorite solution (A) and the aqueous acid solution (B) is A: B = 100:
By setting and inputting to 80, the flow controllers 6A and 6B
The motor rotation speed was controlled to supply the aqueous sodium chlorite solution to the mixer 8 at a flow rate of 50 ml / min, and the aqueous acid solution to the mixer 8 at a flow rate of 40 ml / min. On the other hand, by controlling the frequency of the inverter motor of the water flow controller 6C to 5.8 Hz,
Water was supplied from the water supply port H at a flow rate of 1 liter / min (at the water flow meter 7). The mixed solution of the aqueous solution of sodium chlorite and the aqueous solution of the acid mixed in the mixer 8 is a reaction column.
From a (9) to reaction column b (12) ｛reaction column (a +
b) The reactor reacts after passing 1 liter in volume and the residence time passes 10 min｝, and merges with water from the water supply port H to produce chlorine dioxide water. C in the obtained chlorine dioxide water (D)
The IO ₂ concentration is 1600 ppm and the pH is 1.5 (pH meter 1
1 measured). The yield was 59%.

Examples 2 to 4 Chlorine dioxide water was produced in the same manner as in Example 1 under the conditions shown in Table 1. Table 1 shows the results.

[0036]

[Table 1] * 1: 6A aqueous solution: (NaCl 150 g + NaClO ₂ 10
0 g) / liter, * 2: 6B aqueous solution: (NaCl 150 g + HCl 10
0 g) / liter * 3: volume ratio

FIG. 2 is a conceptual diagram of the apparatus used in Examples 5 to 13. Each code indicates the following. Reference numerals other than those described below are the same as those in FIG. C1 computer (site): C2 computer (main control room): Microsoft
Using a Windows NT movable personal computer manufactured by ft,
Software to output to the program controller interface was created with Visual Basic. In addition, this personal computer is connected via a hub 10BASE-T: TCP /
A LAN is constructed using the IP protocol, and RAS (remote
Access service) function. Input and output from another personal computer. 4E, 4F, 4G level meter: A load cell type weight scale was used. 5. Computer interface: A program controller (FA-M3 manufactured by Yokogawa Electric Corporation) that converts input / output signals from a personal computer into electric signals of 4-20 mA DC, 0-5 V DC or relay drive signals was used.

6E, 6F, flow controller: maximum discharge amount 3
0 ml / min (max. 150 pulses / min, max.
A diaphragm pulse pump driven by a reciprocating motion of a solenoid (electromagnet) of 20 ml / pulse was used, and a control signal (DC 4 to 2) from a computer interface was used.
0 mV). 6G flow rate controller: using a diaphragm pulse pump driven by a reciprocating motion of a solenoid (electromagnet) having a maximum discharge rate of 15 ml / min (maximum 120 pulses / min, maximum 0.12 ml / pulse), and a control signal from a computer interface ( (DC 4 to 20 mV). 6H-water flow controller: A combination of a bob valve having a nominal diameter of 1/4 and an actuator for driving the valve with a control signal (DC4-20 mA) was used.

80 mixer: polyvinyl chloride pipe 1
3A (inner diameter 13mm, outer diameter 18mm, length 200mm)
Was used. The inlet of the raw material liquid was welded with a polyvinyl chloride tube (8 × 6 mmφ). 90 reaction column: polyvinyl chloride tube (inner diameter 16.6)
mm, an outer diameter of 22 mm, and a length of 190 mm) in which six right-hand twisting elements and left-hand twisting elements are alternately arranged at right angles.

Example 5 The apparatus shown in FIG. 2 was used. The computer C1 was installed at a site where the manufacturing apparatus was located, and the computer C2 was installed at a central control room 100 m away from the site. These two computers have a RAS (Remote Access Service) function, and are connected to a 10BASE-T: T via a hub.
A LAN was constructed using the CP / IP protocol.

20 liters of an aqueous solution of sodium chlorite (290 g / liter of NaClO ₂ ) was placed in tank 3E, and an aqueous solution of sodium hypochlorite (NaC
20 liters of 110 g / l (10 g / l) and 20 liters of an aqueous acid solution (420 g / l of HCl) were charged into the tank 3G, and water was supplied from H.

The following relationship was set and input to the computer C2 in the central control room. (A) A two-variable relational expression obtained by previously preparing a calibration curve of the relationship between the raw material liquid discharge amount of each of the flow rate controllers 6E, 6F, and 6G and the pulse of the diaphragm pump for each specific pump stroke rate (b) ) The following reaction formula: 2NaClO ₂ + NaClO + 2HCl → 2ClO ₂ +3
Raw material NaClO ₂ , NaC based on NaCl + H ₂ O
The molecular weight ratio of 10 and HCl is 90.45: 74.45: 3
6.45. The actual production schedule was set at 5 kg / day, and the raw material injection molar ratio was set to 100 hypochlorite, 50 hypochlorite, and 200 acids.

In the computer having the above settings,
The following values were entered: Scheduled production amount of chlorine dioxide water: 5 Kg (2ClO ₂ conversion) / day Concentration of chlorine dioxide water: 1.157 ppm Concentration of sodium chlorite aqueous solution charged in tank 3E: 290 g (NaClO ₂ ) / liter Sodium hypochlorite charged in tank 3F Aqueous solution concentration: 110 g (NaClO) / liter Tank 3G acid aqueous solution concentration: 420 g (HCl) / liter Flow controller (6E) Pump stroke rate: 45% Flow controller (6F) Pump stroke rate: 68% Flow controller ( 6G) Pump stroke ratio: 48% The raw material injection molar ratio was input as 100 for 2NaClO ₂ , 100 for NaClO, and 200 for 2HCl. A computer to which the above conditions and numerical values have been input calculates the pump pulses of each flow controller, outputs them as digital signals (see Table 2), and outputs analog current control signals (DC 4 to 20 mA DC) at the interface (program controller). )
Each pump is driven according to this signal.

As a result, sodium chlorite aqueous solution 1
6.05 ml / min, sodium hypochlorite aqueous solution 1
It was sent from each tank to the mixer at a discharge rate of 7.4 ml and an aqueous solution of 8.92 ml / min. In addition, by inputting the concentration of chlorine dioxide water (1.157 ppm), the flow rate of water from H is calculated by a computer, the degree of opening and closing of the ball valve of the water flow controller (6H) is determined, and the control signal (DC 18.3 mA) Opening and closing rate of the ball valve 51
%, And water was sent at 3 liter / min. :
The obtained aqueous solution of chlorine dioxide (D) has a ClO ₂ concentration of:
950 ppm, pH: 2.1, yield 82%. Table 2 shows the results.

Example 6-8 The procedure of Example 5 was repeated, except that the amount of sodium hypochlorite was changed as shown in Table 2.

Example 9 The procedure of Example 5 was repeated, except that the amount of sodium hypochlorite and the amount of acid supplied were changed as shown in Table 2.

[0047]

[Table 2] * 4: Ratio to 2NaClO ₂ 100

[0048]

[Table 3] * 4: Ratio to 2NaClO ₂ 100

Examples 10 and 11 The procedure was performed in the same manner as in Example 5 except that the amount of sodium hypochlorite and the amount of water supplied were changed as shown in Table 3.

Example 12 Example 12 was carried out in the same manner as in Example 5 except that the production amount of chlorine dioxide, the amount of sodium hypochlorite, and the supply amount of water were changed as shown in Table 3.

Example 13 The concentration of the aqueous solution of sodium hypochlorite was changed to a decrease in the concentration of sodium hypochlorite.

[0052]

The manufacturing method and the manufacturing apparatus of the present invention include:
The following effects are obtained. The amount of the raw material solution can be easily set by an electric signal, the confirmation can be easily changed, and the chlorine dioxide can be easily and accurately produced in a wide range of concentrations with a high yield. In particular, when a solution whose concentration is reduced by gasification such as sodium hypochlorite is used, it is not necessary to frequently adjust the concentration to a constant concentration, and the chlorine dioxide water can be easily produced only by inputting the measured concentration. Since the production is performed by controlling the flow rate of the raw material liquid, the loss at the time of stopping and restarting the production is small, and the switching can be performed within one minute. A wide variety of computer software is available and the operation can be started easily. Water volume, chlorine dioxide water volume, chlorine dioxide water concentration or chlorine dioxide water p
It is also easy to control chlorine dioxide water by continuously measuring H and performing remote control by computer communication. In the production of chlorine dioxide water using a high concentration solution of a chlorite aqueous solution of 200 g / l or more, a hypochlorite aqueous solution of 100 g / l or more, and an acid aqueous solution of 150 g / l or more, a small raw material liquid tank may be used. Therefore, space saving can be realized. When a commercially available raw material having a high concentration is used, the raw material can be used as it is, so that it is not necessary to take much time to adjust the concentration of the raw material solution as in the related art, and the number of steps can be reduced. Since the operation status of the site can be constantly monitored from a desk in a remote place, operation control and troubleshooting can be easily performed, and labor can be saved. Since it is easy to change the chlorine dioxide concentration of chlorine dioxide water, in the purification of tap water with chlorine dioxide water, the required concentration of chlorine dioxide water is easily provided according to the degree of contamination of tap water raw water. it can. Further, it can be similarly used in food washing water and wastewater treatment. In the method for producing chlorine dioxide water of the present invention, it is easy to change the flow rates of each raw material and the amount of water. The step of adjusting the concentration of the raw material liquid is unnecessary, and particularly when the concentration of the liquid is reduced by gasification as in the case of an aqueous solution of sodium hypochlorite, the operation can be easily performed without a complicated concentration adjustment step.

The method for producing chlorine dioxide water and the apparatus for producing chlorine dioxide water according to the present invention are easy to handle, labor-saving, remote operation and unmanned operation, easy to handle, and compact. In addition, biocides such as fungicides and insecticides, such as tap water sterilization water, drinking water treatment water, food processing water, bleaching water, cooling water, sewage treatment water, medical sterilization water, factory wastewater treatment water, breeding house cleaning water, etc. A wide range of bleaching agents, oxidizing agents, and deodorizing agents can be easily manufactured. Thus, the present invention provides a solution to the recent large-scale outbreak of O-157 infection, the cryptosporidium accident originating from the water supply in Ogose-cho, Saitama, and the infection accident with Legionella in the children's ward of a university hospital. It is.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a first chlorine dioxide water producing apparatus of the present invention.

FIG. 2 is a conceptual diagram of a second apparatus for producing chlorine dioxide water of the present invention.

[Explanation of symbols]

C, C1, C2 Computer 2 Indicating controller 3A, 3B, 3E, 3F, 3G Tank 4E, 4F, 4G Level meter 5 Interface 6A, 6B, 6C, 6E, 6F, 6G, 6H Flow controller 7 Flow meter 8, 80 Mixer 9 Reaction column a 90 Reaction column 10 Concentration meter 11 pH meter 12 Reaction column b H Water supply port D Chlorine dioxide water

[Procedure amendment]

[Submission date] March 3, 1999 (1999.3.3)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

In the method for producing chlorine dioxide water of the present invention, in the case of the first production method (three-liquid method), the raw material injection molar ratio of the raw material aqueous solution to be injected is 100 parts per 100 parts of chlorite.
It is preferable that the hypochlorite is 100 to 200 and the acid is 110 to 500, more preferably, the hypochlorite is 110 to 500.
160, acid 150-300. Also, in the case of the second production method (two-liquid method), raw material note raw solution to be injected
The molar ratio of the chlorite is 100,
５００500, more preferably 150-400. In the case of the chlorine method, the raw material injection molar ratio ratio is 100 to 200 chlorine, and more preferably 110 to 150, relative to 100 chlorite. When sulfuric acid is used as the acid, the reaction formula is 5NaClO ₂ + 2H ₂ SO ₄ → 4ClO ₂ + 2Na ₂ SO ₄ + NaCl + 2H ₂ O. . . . . . . (4) wherein the molar ratio of the raw material injection is 100 to 500 sulfuric acid with respect to 100 chlorite, and more preferably 15 to 100.
0 to 400.

Claims (13)

[Claims] In a method for producing chlorine dioxide water using chlorite, hypochlorite and acid as raw materials, a preset input of each raw material aqueous solution concentration, chlorine dioxide production amount, and each raw material injection molar ratio magnification is provided. A flow controller for controlling the flow rate of each raw material aqueous solution and water supplied to the reaction column by controlling the flow controllers in conjunction with each other via an interface by a computer. 2. The method according to claim 1, wherein one of the water supply amount and the chlorine dioxide water concentration is inputted and set in a computer.
The method for producing chlorine dioxide water according to the above. 3. A raw material aqueous solution includes a chlorite aqueous solution (containing at least 200 g / l of chlorite), a hypochlorite aqueous solution (including at least 80 g / l of hypochlorite), and an aqueous acid solution (containing 150 g of acid). Per liter or more). The method for producing chlorine dioxide water according to any one of claims 1 to 2, comprising: 4. The raw material injection molar ratio magnification is 10 chlorite.
For 0, hypochlorite 100-200, acid 110-5
The method for producing chlorine dioxide water according to any one of claims 1 to 3, wherein 5. The method for producing chlorine dioxide water according to claim 1, wherein remote monitoring and control is performed by computer communication. 6. A method for producing chlorine dioxide water using chlorite and acid; or chlorite and chlorine as raw materials, wherein a concentration of each raw material aqueous solution, a production amount of chlorine dioxide, and a molar ratio of each raw material injection are previously determined. Each of the flow controllers is interlocked and controlled by the computer through the interface by setting and inputting, the supply amount of each raw material aqueous solution to the reaction column is adjusted, and the reaction solution from the reaction column and water are mixed. Method for producing chlorine dioxide water. 7. The computer according to claim 6, wherein one of the water supply amount and the chlorine dioxide water concentration is inputted and set in a computer.
The method for producing chlorine dioxide water according to the above. 8. The method for producing chlorine dioxide water according to claim 6, wherein remote monitoring and control is performed by computer communication. 9. A method for producing chlorine dioxide water using chlorite and an acid as raw materials, wherein the chlorite aqueous solution and the chlorite aqueous solution and the supply ratio of both raw materials are set by an indicator controller. A method for producing chlorine dioxide water, comprising controlling the flow rate of an acid aqueous solution flow controller. 10. A mixer in which a chlorite aqueous solution tank, a hypochlorite aqueous solution tank, an acid aqueous solution tank and a water supply port are connected via respective flow controllers; chlorite of each aqueous solution; A computer in which the concentrations of hypochlorite and acid, the amount of chlorine dioxide to be produced, and the molar ratio of each raw material injection are set in advance; and a reaction column,
Each flow controller is controlled by a computer via an interface to adjust the supply amount of each aqueous solution and water to the mixer, and each aqueous solution and water mixed in the mixer passes through a reaction column, thereby controlling chlorine dioxide. An apparatus for producing chlorine dioxide water, from which water is obtained. 11. A digital output signal calculated by a computer is converted into an analog control signal (DC 4 to 20 m) at an interface (program controller).
11. The chlorine dioxide water producing apparatus according to claim 10, wherein the driving of the pump of each flow controller is controlled by being converted into A) or a pulse control signal. 12. A water supply port having a mixer, a reaction column, and a water flow regulator, wherein a chlorite aqueous solution tank and an acid aqueous solution tank are connected via respective flow regulators. The flow rate is controlled by an indicator controller in which the supply ratio of the chlorite aqueous solution and the acid aqueous solution is set, and the two aqueous solutions whose supply amounts have been adjusted by the control are combined by the mixer, pass through the reaction column, and the water flow rate is controlled. An apparatus for producing chlorine dioxide water, wherein chlorine dioxide water is obtained by merging with water from a water supply port having a regulator. 13. The chlorine dioxide water producing apparatus according to claim 12, wherein the residence time of the reaction column is 1 to 100 minutes.