JP2002301485A - Bromine ion removing apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain treated water containing not only no bromine ion but also hypobromous acid, an organochlorine compound or by removing a bromine ion from raw water by solving the problems in a conventional method utilizing chlorine in a method for removing bromine ions dissolved in water or a method for recovering bromine (Br2 ) from bromine ions dissolved in water. SOLUTION: The bromine ion is removed from the water by blowing gas (e.g. oxygen), of which the standard oxidation-reduction potential at 25 deg.C is 1.1-1.5 V, to the water in place of chlorine to obtain the treated water containing not only no bromine ion but also hypobromous acid, an organochlorine compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and a method for removing bromine ions, and more particularly to an apparatus and method for removing bromine ions suitable for use in advanced water treatment such as tap water or sewer water or groundwater. About.

[0002]

2. Description of the Related Art Among advanced water treatment methods, there is a method of decomposing and removing organic substances using hydroxyl radicals (OH ⁺ ). Since bromine ions (Br ⁻ ) become scavengers for hydroxyl radicals, by removing them in advance, the processing efficiency of advanced treatment can be improved.

[0003] Conventionally, a method of removing bromine ions dissolved in water, or a method of removing bromine (B
As a method for recovering r ₂ ), a method utilizing chlorine has been used.

[0004] For example, FIG.
FIG. 1 is a diagram for describing a method disclosed in JP-A-81-180, for recovering bromine ions contained in photographic waste liquid using chlorine. In FIG. 20, 14a is a multi-stage steam distillation column for removing bromine ions dissolved in the water to be treated by supplying chlorine gas 16a. 19a is an aggregator for aggregating the released bromine, and 20a is a decanter.

[0005] treatment water which has flowed into the multi-stage steam distillation tower 14a, than that to supply chlorine gas 16a, "2Br ^- +
Cl ₂ → Br ₂ + 2Cl ⁻ ”occurs, and bromine ions are liberated as bromine. The liberated bromine is supplied to the aggregator 19.
a, is collected in the Br ₂ tank through the decanter 20a.

[0006]

Since the conventional method for removing bromine ions uses chlorine gas, especially when used for water treatment, chlorine must be removed after the treatment, and chlorine is removed. However, there is a problem in that it reacts with organic substances dissolved in the water to be treated and generates harmful substances such as organic chlorine compounds.

[0007] In order to solve this problem, the present inventors have long sought a method for removing bromine ions using a gas other than chlorine. In the conventional method using chlorine, a reaction of “2Br ⁻ + Cl ₂ → Br ₂ + 2Cl ⁻ ” occurs, but this reaction proceeds because the standard oxidation-reduction potential of chlorine is higher than that of bromine. That is, it is considered that a similar reaction occurs even if another substance having a higher standard oxidation-reduction potential than bromine is used, and that bromine ions can be removed. The present inventors have been studying in view of the fact, the use of substances standard oxidation-reduction potential is too high, BrO detrimental substances by oxidation of bromide ion ^- is hypobromous acid, such as product Faced with a new problem.

In order to solve this problem, the present inventors have analyzed the reaction thermodynamically and found that the standard oxidation-reduction potential is 1.
It has been discovered that bromine ions can be removed without producing bromic acid if the gas is in the range of 1 to 1.5 V.
Focusing on the fact that oxygen is a substance that satisfies this condition other than chlorine, and invented a method and apparatus for removing bromine ions using oxygen.

According to the present invention, bromine ions are removed by an apparatus which replaces the conventional apparatus using chlorine, which has a problem that harmful substances are generated during the processing in addition to the necessity of being removed after the processing. It is an object of the present invention to obtain treated water free from harmful substances such as hypobromous acid and organic chlorine compounds.

[0010]

According to a first aspect of the present invention, there is provided a bromine ion removing apparatus comprising: a reaction tank into which water to be treated flows; and a standard oxidation-reduction potential at 25 ° C. of 1 in the water to be treated in the reaction tank. Gas supply means for supplying gas in the range of 0.1 to 1.5 V.

A second bromine ion removing apparatus according to the present invention is the first bromine ion removing apparatus, wherein the dissolved gas concentration means for measuring the dissolved concentration of the gas supplied by the gas supply means in the water to be treated is provided. Gas flow control means for controlling the flow rate of the gas supplied by the supply means based on the difference between the dissolved concentration of the gas measured by the dissolved concentration measurement means and a predetermined target value is provided.

A third bromine ion removing apparatus according to the present invention, in the first bromine ion removing apparatus, is supplied by an ion concentration meter for measuring a bromine ion concentration of the water to be treated in the reaction tank and the gas supply means. Gas flow control means for controlling the flow rate of the gas based on the difference between the measurement result of the bromine ion concentration measured by the ion concentration meter and a predetermined target value is provided.

A fourth bromine ion removing apparatus according to the present invention is the first bromine ion removing apparatus according to the first bromine ion removing apparatus, wherein: a pH meter for measuring the pH of the water to be treated in the reaction tank; Gas flow control means for controlling the flow rate based on the measurement result of pH measured by the pH meter.

A fifth bromide ion removing apparatus according to the present invention is the first bromide ion removing apparatus according to the first bromide ion removing apparatus, wherein the redox potential meter for measuring the oxidation-reduction potential of the water to be treated in the reaction tank is supplied by the gas supply means. Gas flow control means for controlling a flow rate of the gas to be generated based on a difference between a measurement result of the oxidation-reduction potential measured by the oxidation-reduction potential meter and a predetermined target value.

A sixth bromine ion removing apparatus according to the present invention is the first, second, third, fourth or fifth bromine ion removing apparatus, wherein the gas supplied by the gas supply means is oxygen.

In a seventh embodiment of the present invention, there is provided a bromine ion removing apparatus comprising: a reaction tank into which water to be treated flows; and a standard oxidation-reduction potential at 25 ° C. of 1.1 to 1.5 V
Gas (a) supply means for supplying gas (a) in the range of (a), and gas (b) having a standard oxidation-reduction potential at 25 ° C. higher than gas (a) to the water to be treated in the reaction tank. Gas (b) supply means.

According to an eighth aspect of the present invention, there is provided the bromine ion removing apparatus according to the seventh aspect, wherein the dissolved concentration of the gas (a) supplied by the gas (a) supply means is measured in the water to be treated. Measuring means and controlling a flow rate of the gas (a) supplied by the gas (a) supply means based on a difference between a dissolved concentration of the gas (a) measured by the dissolved concentration measuring means and a predetermined target value. And (a) a flow control means.

A ninth bromine ion removing apparatus according to the present invention is the seventh bromine ion removing apparatus, wherein the dissolved concentration of the gas (b) supplied by the gas (b) supply means is measured in the water to be treated. A measuring means, and a flow rate of the gas (b) supplied by the gas (b) supplying means is controlled based on a difference between a dissolved concentration of the gas (b) measured by the dissolved concentration measuring means and a predetermined target value. And (b) a flow control means.

[0019] A tenth bromine ion removing apparatus of the present invention comprises:
In the seventh bromine ion removing apparatus, an ion concentration meter for measuring the bromine ion concentration of the water to be treated in the reaction tank, and a flow rate of the gas (a) supplied by the gas (a) supply means,
A gas (a) flow rate control means for controlling based on a difference between a bromine ion concentration measurement result measured by the ion concentration meter and a predetermined target value is provided.

An eleventh bromine ion removing apparatus according to the present invention comprises:
In a seventh bromine ion removing apparatus, an ion concentration meter for measuring the bromine ion concentration of the water to be treated in the reaction tank, and a flow rate of the gas (b) supplied by the gas (b) supply means,
A gas (b) flow control means for controlling based on a difference between a measurement result of the bromine ion concentration measured by the ion concentration meter and a predetermined target value.

The twelfth bromide ion removing apparatus of the present invention comprises:
In the seventh bromine ion removing apparatus, an ion densitometer for measuring the bromine ion concentration of the water to be treated in the reaction tank, the flow rate of the gas (a) supplied by the gas (a) supply means, and the gas (b) The ratio of the flow rate of the gas (b) supplied by the supply means to the entire flow rate is fixed, and the ratio is controlled based on the difference between the measurement result of the bromine ion concentration measured by the ion concentration meter and a predetermined target value. And flow rate ratio control means.

The thirteenth bromine ion removing apparatus of the present invention comprises:
In the seventh bromine ion removing device, a pH meter for measuring the pH of the inflowing water to be treated and a flow rate of at least one of the gases (a) and (b) are set to the p value.
Flow rate control means for controlling based on the measurement result of pH measured by the H meter.

[0023] A fourteenth bromine ion removing apparatus of the present invention comprises:
In the seventh bromine ion removing device, an oxidation-reduction potentiometer for measuring the oxidation-reduction potential of the water to be treated in the reaction tank, and a flow rate of the gas (a) supplied by the gas (a) supply means,
A gas (a) flow control means for controlling based on a difference between a measurement result of the oxidation-reduction potential measured by the oxidation-reduction potentiometer and a predetermined target value.

According to a fifteenth bromine ion removing apparatus of the present invention,
In the seventh bromine ion removing apparatus, an oxidation-reduction potentiometer for measuring the oxidation-reduction potential of the water to be treated in the reaction tank, and the flow rate of the gas (b) supplied by the gas (b) supply means,
A gas (b) flow control means for controlling based on a difference between a measurement result of the oxidation-reduction potential measured by the oxidation-reduction potentiometer and a predetermined target value is provided.

[0025] A sixteenth bromine ion removing apparatus of the present invention comprises:
In the seventh bromine ion removing device, an oxidation-reduction potentiometer for measuring the oxidation-reduction potential of the water to be treated in the reaction tank, the flow rate of the gas (a) supplied by the gas (a) supply means and the gas (b) A) flow rate control means for controlling the ratio of the gas (b) supplied by the supply means to the flow rate based on the difference between the measurement result of the oxidation-reduction potential measured by the oxidation-reduction potentiometer and a predetermined target value. And characterized in that:

[0026] The seventeenth bromine ion removing apparatus of the present invention comprises:
No. 7, 8, 9, 10, 11, 12, 13, 15 or 1
7. The apparatus for removing bromine ions according to claim 6, wherein the gas (a)
The gas (a) supplied by the supply means is oxygen, and the gas (b) supplied by the gas (b) supply means is chlorine.

An eighteenth bromine ion removing apparatus according to the present invention comprises:
Seventh, eighth, nine, ten, eleven, twelve, thirteen, one of the present invention
17. The bromine ion removing apparatus according to 4, 15, or 16, wherein the gas (a) supplied by the gas (a) supply means is oxygen, and the gas (b) supplied by the gas (b) supply means.
Is ozone.

The nineteenth bromide ion removing apparatus of the present invention comprises:
The first, second, third, fourth, fifth, sixth, seventh, eighth, ninth, ten, eleven,
12, 13, 14, 15, 16, 17 or 18 is characterized in that it comprises an acid adding means for adding a predetermined amount of acid to the water to be treated.

A twentieth bromide ion removing apparatus according to the present invention comprises:
In the nineteenth bromine ion removing apparatus, a pH meter for measuring the pH of the water to be treated in the reaction tank, and the amount of acid added by the acid adding means are determined in advance as the pH measurement result measured by the pH meter. And an acid addition amount control means for controlling based on a difference from the target value.

In the first method for removing bromine ions of the present invention, the water to be treated has a standard oxidation-reduction potential at 25 ° C. of 1.1 to 1.0.
A gas in the range of 1.5 V is supplied.

In the second method for removing bromine ions according to the present invention, the water to be treated has a standard oxidation-reduction potential at 25 ° C. of 1.1 to 1.0.
A gas (a) in the range of 1.5 V and a gas (b) having a standard oxidation-reduction potential at 25 ° C. higher than the gas (a) are supplied.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments of the present invention will be described with reference to the drawings. In the drawings describing the embodiments, the same reference numerals indicate the same or corresponding components.

Embodiment 1 (First or Sixth Bromide Ion Removal Apparatus; First Bromide Ion Removal Method) FIG. 1 schematically shows an apparatus configuration according to Embodiment 1 for carrying out the present invention. FIG. In FIG. 1, reference numeral 1 denotes a reaction tank for removing bromine ions of water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1.

2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is a device for adjusting the flow rate of oxygen gas. The gas diffusing device 2, the oxygen gas storage device 3, and the gas flow regulating device 4 constitute a gas supply means to the water to be treated. In addition, the gas flow control device 4
Connected to the oxygen gas storage device 3,
1 is connected to the air diffuser 2. Although FIG. 1 shows a gas supply unit provided with an air diffuser 2 for dissolving oxygen gas in the water to be treated, other gas-liquid mixing devices such as an ejector may be used.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 1 will be described. The flow rate of the oxygen discharged from the oxygen gas storage device 3 is adjusted by the gas flow rate adjustment device 4, and the oxygen is contacted and mixed with the water to be treated via the pipe 201 and the air diffuser 2. As a result, oxygen is dissolved in the water to be treated, and a reaction of “O ₂ + 4Br ⁻ → 2Br ₂ + 2H ₂ O” occurs with bromine ions dissolved in the water to be treated. As a result, bromine ions dissolved in the water to be treated are released and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water containing no harmful substances such as hypobromous acid and organic chlorine compounds is obtained. This has the effect.

FIG. 2 is a diagram for explaining the effect of the first embodiment.
Oxidation potential and Br ^- removal rate and Br at 0 ° C
O ^- shows a relationship between the generation rate. From FIG.
It is found that when a gas having a standard oxidation-reduction potential at 25 ° C. in the range of 1.1 to 1.5 V is used, a high Br ⁻ removal rate can be obtained, and a BrO ⁻ generation rate can be suppressed low.

In the first embodiment, the gas supplied by the gas supply means is oxygen (a standard oxidation potential of 1.2 at 25 ° C.).
3V), but other gases may be used as long as the standard oxidation-reduction potential at 25 ° C. is 1.1 to 1.5 V. The gas used need not be a single component, but may be a mixture of gases satisfying the above conditions or a mixture of mixed gases satisfying the above conditions. Standard redox potential is 1.
Examples of the gas of 1 to 1.5 include oxygen and chlorine.

In the first embodiment, the case where the water to be treated is continuously treated (that is, the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. The present invention may be applied to the treatment (that is, temporarily storing the treated water in the reaction tank 1 for treatment), and the same effect can be expected.

Second Embodiment (First, Second or Sixth Bromide Ion Removal Apparatus; First Bromide Ion Removal Method) FIG. 3 schematically shows an apparatus configuration according to a second embodiment for carrying out the present invention. FIG. In FIG. 3, reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1. 2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is a gas flow rate for adjusting the flow rate of oxygen gas. The gas diffuser 2, the oxygen gas storage device 3, and the gas flow rate controller 4 constitute a gas supply means to the water to be treated.

The gas flow controller 4 is connected to the oxygen gas storage device 3, while being connected to the air diffuser 2 via a pipe 201. As the gas flow adjusting device 4, a regulator, a flow meter, a mass flow controller, or the like can be used. In addition, although the gas supply means provided with the air diffuser 2 for dissolving the oxygen gas in the water to be treated is shown in FIG. 10, another gas-liquid mixing device such as an ejector may be used.

Reference numeral 14 denotes a dissolved oxygen concentration meter for measuring the dissolved oxygen concentration of the water to be treated, which is connected to the controller (gas flow control means) 15 via a signal line 405. I have. The controller (gas flow control means) 15 is connected to the gas flow controller 4 via a signal line 406.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 3 will be described. The flow rate of the oxygen discharged from the oxygen gas storage device 3 is adjusted by the gas flow rate adjustment device 4, and the oxygen is contacted and mixed with the water to be treated via the pipe 201 and the air diffuser 2. Further, a signal of the measurement result of the dissolved oxygen concentration measured by the dissolved oxygen concentration meter 14 is sent to the controller 15 which is a gas flow rate control means. A signal is sent to the regulator 4 to control the flow rate of oxygen.

Q _O2 = K 1 (X _DO ^* −X _DO ) (2.1) where Q _O2 : rate of change of oxygen flow rate X _DO ^* : target value of dissolved oxygen concentration X _DO : measurement of dissolved oxygen concentration result

As described above, oxygen is dissolved in the water to be treated,
"O ₂ " between the bromine ions dissolved in the water to be treated
+ 4Br ⁻ → 2Br ₂ + 2H ₂ O ”. As a result, bromine ions dissolved in the water to be treated are released and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water containing no harmful substances such as hypobromous acid and organic chlorine compounds is obtained. This has the effect. Further, by controlling the oxygen flow rate as described above, when the measurement result of the dissolved oxygen concentration is lower than the target value, the flow rate of oxygen is increased to further promote the reaction, and the measurement of the dissolved oxygen concentration is performed. When the result is higher than the target value, the flow rate of oxygen can be reduced to suppress the consumption of oxygen, and there is an effect that treated water with stable water quality can be obtained.

In the second embodiment, the gas supplied by the gas supply means is oxygen (a standard oxidation potential of 1.2 at 25 ° C.).
3V), but other gases may be used as long as the standard oxidation-reduction potential at 25 ° C. is 1.1 to 1.5 V. The gas used need not be a single component, but may be a mixture of gases satisfying the above conditions or a mixture of mixed gases satisfying the above conditions.

In the second embodiment, the case where the water to be treated is continuously treated (ie, the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. The present invention may be applied to the treatment (that is, temporarily storing the treated water in the reaction tank 1 for treatment), and the same effect can be expected. The second embodiment
In the above, the case where the controller 15 is used as the gas flow rate control means has been described, but the gas flow rate may be controlled by another method such as control of the flow rate by an operator or control by a computer.

Third Embodiment (First, Third or Sixth Bromide Ion Removal Apparatus; First Bromide Ion Removal Method) FIG. 4 schematically shows an apparatus configuration according to a third embodiment for carrying out the present invention. FIG. In FIG. 4, reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe for flowing the water to be treated into the reaction tank 1, and reference numeral 102 denotes a pipe for flowing the treated water out of the reaction tank 1, and is connected to the reaction tank 1. 2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is a gas flow rate for adjusting the flow rate of oxygen gas. The gas diffuser 2, the oxygen gas storage device 3, and the gas flow rate controller 4 constitute a gas supply means to the water to be treated.

The gas flow control device 4 is connected to the oxygen gas storage device 3, while being connected to the air diffuser 2 via a pipe 201. FIG. 6 shows the gas supply means provided with the air diffuser 2 for dissolving the oxygen gas in the water to be treated, but another gas-liquid mixing device such as an ejector may be used. Reference numeral 12 denotes an ion concentration meter for measuring the bromine ion concentration of the water to be treated, which is mounted in the reaction tank 1, and is connected to a controller (gas flow control means) 13 via a signal line 403. As an ion concentration meter for measuring the bromine ion concentration, ion chromatography can be used. The controller (gas flow control means) 13 is connected to the gas flow controller 4 via a signal line 404.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 4 will be described. The flow rate of the oxygen discharged from the oxygen gas storage device 3 is adjusted by the gas flow rate adjustment device 4, and the oxygen is contacted and mixed with the water to be treated via the pipe 201 and the air diffuser 2. Further, a signal of the measurement result of the bromine ion concentration measured by the ion concentration meter 12 is sent to the controller 13 which is a gas flow rate control means, and the controller 13 adjusts the gas flow rate according to, for example, equation (3.1). A signal is sent to device 4 to control the flow rate of oxygen.

Q _O2 = K 2 (X _Br ^* −X _Br ) (3.1) where, Q _O2 : change rate of oxygen flow rate X _BR ^* : target value of bromine ion concentration X _Br : measurement of bromine ion concentration result

As described above, oxygen is dissolved in the water to be treated,
"O ₂ " between the bromine ions dissolved in the water to be treated
+ 4Br ^- → cause a reaction of 2Br ₂ + 2H ₂ O ". As a result, bromine ions dissolved in the water to be treated are released and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water containing no harmful substances such as hypobromous acid and organic chlorine compounds is obtained. This has the effect. Further, by controlling the oxygen flow rate as described above, when the measurement result of the bromine ion concentration is higher than the target value, the flow rate of oxygen is increased to further promote the reaction, and the measurement of the bromine ion concentration is performed. When the result is lower than the target value, the flow rate of oxygen can be reduced to suppress the consumption of oxygen, and there is an effect that treated water with stable water quality can be obtained.

In the third embodiment, the gas supplied by the gas supply means is oxygen (standard oxidation potential 1.2 at 25 ° C.).
3V), but other gases may be used as long as the standard oxidation-reduction potential at 25 ° C. is 1.1 to 1.5 V. The gas used need not be a single component, but may be a mixture of gases satisfying the above conditions or a mixture of mixed gases satisfying the above conditions.

In the third embodiment, the case where the water to be treated is continuously treated (that is, while the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. The present invention may be applied to the treatment (that is, temporarily storing the treated water in the reaction tank 1 for treatment), and the same effect can be expected. The third embodiment
In the above, the case where the controller 13 is used as the gas flow rate control means has been described. However, the gas flow rate may be controlled by other methods such as flow rate control by an operator or control by a computer.

Fourth Embodiment (First, Fourth, and Sixth Bromide Ion Removal Devices; First Bromide Ion Removal Method) FIG. 5 schematically shows a device configuration according to a fourth embodiment for carrying out the present invention. FIG. In FIG. 5, reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1. 2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is a gas flow rate for adjusting the flow rate of oxygen gas. The gas diffuser 2, the oxygen gas storage device 3, and the gas flow rate controller 4 constitute a gas supply means to the water to be treated.

The gas flow controller 4 is connected to the oxygen gas storage device 3, while being connected to the air diffuser 2 via a pipe 201. FIG. 5 shows the gas supply means provided with the diffuser 2 for dissolving the oxygen gas in the water to be treated, but another gas-liquid mixing device such as an ejector may be used. Reference numeral 9 denotes a pH meter attached to the pipe 101 for measuring the pH of the inflowing water to be treated, and is connected to a controller (gas flow control means) 16 via a signal line 407. The controller (gas flow control means) 16 is connected to the gas flow controller 4 via a signal line 408.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 5 will be described. The flow rate of the oxygen discharged from the oxygen gas storage device 3 is adjusted by the gas flow rate adjustment device 4, and the oxygen is contacted and mixed with the water to be treated via the pipe 201 and the air diffuser 2.

Further, a signal of the measurement result of the pH measured by the pH meter 9 is sent to the controller 16 as the gas flow rate control means, and the controller 16 adjusts the gas flow rate according to the equation (4.1), for example. A signal is sent to device 4 to control the flow rate of oxygen. The target value of the pH can be, for example, 1-6, especially 1-2.

Q _O2 = K 3 × X _H ^* (4.1) where, Q _O2 : rate of change of oxygen flow rate X _H ^* : measurement result of hydrogen ion concentration

As described above, oxygen is dissolved in the water to be treated,
"O ₂ " between the bromine ions dissolved in the water to be treated
+ 4Br ⁻ → 2Br ₂ + 2H ₂ O ”. As a result, bromine ions dissolved in the water to be treated are released and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water containing no harmful substances such as hypobromous acid and organic chlorine compounds is obtained. This has the effect. Further, the above reaction is an oxidation reaction of bromine ions, and is not promoted unless hydrogen ions are present. Therefore, by controlling the oxygen flow rate as described above and supplying the amount of oxygen according to the hydrogen ion concentration, there is an effect that unnecessary consumption of oxygen can be suppressed.

In the fourth embodiment, the gas supplied by the gas supply means is oxygen (a standard oxidation potential of 1.2 at 25 ° C.).
3V), but other gases may be used as long as the standard oxidation-reduction potential at 25 ° C. is 1.1 to 1.5 V. The gas used need not be a single component, but may be a mixture of gases satisfying the above conditions or a mixture of mixed gases satisfying the above conditions.

In the fourth embodiment, the case where the water to be treated is continuously treated (that is, while the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. The present invention may be applied to the treatment (that is, temporarily storing the treated water in the reaction tank 1 for treatment), and the same effect can be expected. Embodiment 4
In the above, the case where the controller 16 is used as the gas flow rate control means has been described. However, the gas flow rate may be controlled by other methods such as flow rate control by an operator or control by a computer.

Embodiment 5 (first, fifth or sixth bromine ion removing apparatus; first bromine ion removing method) FIG. 6 schematically shows an apparatus configuration according to a fifth embodiment for carrying out the present invention. FIG. In FIG. 6, reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1. 2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is a gas flow rate for adjusting the flow rate of oxygen gas. The gas diffuser 2, the oxygen gas storage device 3, and the gas flow rate controller 4 constitute a gas supply means to the water to be treated.

The gas flow controller 4 is connected to the oxygen gas storage device 3, while being connected to the air diffuser 2 via a pipe 201. Although the gas supply means provided with the air diffuser 2 for dissolving oxygen gas in the water to be treated is shown in FIG. 14, another gas-liquid mixing device such as an ejector may be used. Reference numeral 10 denotes an oxidation-reduction potentiometer mounted in the reaction tank 1 for measuring the oxidation-reduction potential of the water to be treated, and is connected to a controller (gas flow rate control means) 17 via a signal line 409. The controller (gas flow control means) 17 is connected to a signal line 410.
Is connected to the gas flow control device 4 via the.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 6 will be described. The flow rate of the oxygen discharged from the oxygen gas storage device 3 is adjusted by the gas flow rate adjustment device 4, and the oxygen is contacted and mixed with the water to be treated via the pipe 201 and the air diffuser 2. Further, a signal of the measurement result of the oxidation-reduction potential measured by the oxidation-reduction potentiometer 10 is sent to the controller 17 serving as the gas flow rate control means. A signal is sent to the regulator 4 to control the flow rate of oxygen.

Q _O2 = K 4 (X _orp ^* −X _orp ) (5.1) where, Q _O2 : change rate of oxygen flow rate X _orp ^* : measurement result of oxidation-reduction potential X _orp : target of oxidation-reduction potential value

As described above, oxygen is dissolved in the water to be treated,
"O ₂ " between the bromine ions dissolved in the water to be treated
+ 4Br ⁻ → 2BR ₂ + 2H ₂ O ”. As a result, bromine ions dissolved in the water to be treated are released and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water containing no harmful substances such as hypobromous acid and organic chlorine compounds is obtained. This has the effect. In addition, by controlling the oxygen flow rate as described above, if the measurement result of the oxidation-reduction potential is lower than the target value, the flow rate of oxygen is increased to further accelerate the reaction, and the measurement of the oxidation-reduction potential is performed. If the result is higher than the target value, it is possible to reduce the oxygen flow rate by reducing the oxygen flow rate, thereby suppressing the wasteful oxygen consumption and supplying the necessary amount of oxygen for the reaction. It works.

In the fifth embodiment, the gas supplied by the gas supply means is oxygen (a standard oxidation potential of 1.2 at 25 ° C.).
3V), but other gases may be used as long as the standard oxidation-reduction potential at 25 ° C. is 1.1 to 1.5 V. The gas used need not be a single component, but may be a mixture of gases satisfying the above conditions or a mixture of mixed gases satisfying the above conditions. At this time, the gas flow rate may be controlled by adjusting the overall flow rate while keeping the composition ratio of the mixed gas constant, or by adjusting the ratio of the mixed gas to adjust the standard oxidation-reduction potential of the entire mixed gas. Similar effects can be expected.

In the fifth embodiment, the case where the water to be treated is continuously treated (that is, while the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. The present invention may be applied to the treatment (that is, temporarily storing the treated water in the reaction tank 1 for treatment), and the same effect can be expected. Embodiment 5
In the above, the case where the controller 17 is used as the gas flow control means has been described. However, the flow rate of the gas may be controlled by another method such as control of the flow rate by an operator or control by a computer.

Embodiment 6 (Seventh or Seventeenth Bromine Ion Removal Device; Second Bromine Ion Removal Method) FIG. 7 is a diagram schematically showing an apparatus configuration according to a sixth embodiment for carrying out the present invention. It is. In FIG. 7, reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1. 2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is oxygen gas for adjusting the flow rate of oxygen gas. It is a flow control device, and the diffuser device 2, the oxygen gas storage device 3, and the oxygen gas flow control device 4 constitute an oxygen gas supply unit to the water to be treated.

Reference numeral 21 denotes an air diffuser for diffusing chlorine gas and dissolving it in the water to be treated, 31 a chlorine gas storage device for storing chlorine gas, and 41 adjusting the flow rate of chlorine gas. And a diffuser 21, a chlorine gas storage 31 and a chlorine gas flow controller 41 constitute a chlorine gas supply means to the water to be treated. The oxygen gas flow control device 4 is connected to the oxygen gas storage device 3, while the diffusion device 2 is connected via a pipe 201.
It is connected to the. In addition, the chlorine gas flow controller 41
Is connected to a chlorine gas storage device 31, while being connected to a diffuser 21 via a pipe 211.

Although FIG. 7 shows the oxygen gas supply means provided with the air diffuser 2 for dissolving the oxygen gas in the water to be treated, other gas-liquid mixing devices such as an ejector may be used. . FIG. 7 shows a chlorine gas supply means provided with an air diffuser 21 for dissolving chlorine gas in the water to be treated, but another gas-liquid mixing device such as an ejector may be used.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 7 will be described. The oxygen discharged from the oxygen gas storage device 3 is adjusted in flow rate by the oxygen gas flow rate control device 4, and is brought into contact with and mixed with the water to be treated via the pipe 201 and the diffuser 2. In addition, chlorine gas storage device 3
The chlorine discharged from 1 is adjusted in flow rate by a chlorine gas flow rate adjusting device 41, and is brought into contact with and mixed with the water to be treated via a pipe 211 and a diffuser 21. As a result, oxygen is dissolved in the water to be treated, and a reaction of “O ₂ + 4Br ⁻ → 2Br ₂ + 2H ₂ O” occurs with bromine ions dissolved in the water to be treated. Further, chlorine is also dissolved in the water to be treated, and “Cl ₂ +2” is present between the chlorine and the bromine ions dissolved in the water to be treated.
Br ⁻ → Br ₂ + 2Cl ⁻ ”occurs.

As a result, bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water free from harmful substances such as hypobromite is obtained. To play. Further, since chlorine has a higher standard oxidation-reduction potential at 25 ° C. than oxygen, the use of chlorine has the effect of promoting the above-mentioned bromine ion removal reaction. As a gas having a higher standard oxidation-reduction potential at 25 ° C. than oxygen, the standard oxidation-reduction potential is 1.23 V to 3.0 V, preferably 1.4 V to
3.0 V gas can be used. Examples of such a gas include chlorine, ozone, and fluorine.

In the sixth embodiment, the supply of oxygen and chlorine to the water to be treated is carried out by using another pipe and a diffuser, but it is also possible to mix either gas from the middle of the pipe. Alternatively, the same aeration device may be used to dissolve the water to be treated, and the same effect can be expected. In the sixth embodiment, the case where the water to be treated is continuously treated (that is, the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. And temporarily treating the water to be treated in the reaction tank 1), and the same effect can be expected.

Embodiment 7 (Seventh, Eighth or Seventeenth Bromide Ion Removal Apparatus; Second Bromide Ion Removal Method) FIG. 8 schematically shows an apparatus configuration according to a seventh embodiment for carrying out the present invention. FIG. In FIG. 8, reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1. 2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is oxygen gas for adjusting the flow rate of oxygen gas. It is a flow control device, and the diffuser device 2, the oxygen gas storage device 3, and the oxygen gas flow control device 4 constitute an oxygen gas supply unit to the water to be treated.

Reference numeral 21 denotes an air diffuser for diffusing chlorine gas and dissolving it in the water to be treated, 31 denotes a chlorine gas storage device for storing chlorine gas, and 41 denotes a flow rate of chlorine gas. And a diffuser 21, a chlorine gas storage 31 and a chlorine gas flow controller 41 constitute a chlorine gas supply means to the water to be treated. The oxygen gas flow control device 4 is connected to the oxygen gas storage device 3, while the diffusion device 2 is connected via a pipe 201.
It is connected to the. In addition, the chlorine gas flow controller 41
Is connected to a chlorine gas storage device 31, while being connected to a diffuser 21 via a pipe 211.

FIG. 8 shows the oxygen gas supply means provided with a diffuser 2 for dissolving the oxygen gas in the water to be treated, but other gas-liquid mixing devices such as an ejector may be used. . FIG. 3 shows a chlorine gas supply unit provided with an air diffuser 21 for dissolving chlorine gas in the water to be treated, but other gas-liquid mixing devices such as an ejector may be used. Numeral 14 denotes a dissolved oxygen concentration meter for measuring the dissolved oxygen concentration of the water to be treated, which is connected to a controller (oxygen gas flow rate control means) 15 via a signal line 405, and is connected to the controller ( The oxygen gas flow control means 15 is connected to the oxygen gas flow controller 4 via a signal line 406.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 8 will be described. The oxygen discharged from the oxygen gas storage device 3 is adjusted in flow rate by the oxygen gas flow rate control device 4, and is brought into contact with and mixed with the water to be treated via the pipe 201 and the diffuser 2. In addition, chlorine gas storage device 3
The chlorine discharged from 1 is adjusted in flow rate by a chlorine gas flow rate adjusting device 41, and is brought into contact with and mixed with the water to be treated via a pipe 211 and a diffuser 21. The controller 15 serving as an oxygen gas flow rate control means includes a dissolved oxygen concentration meter 1.
The controller 15 sends a signal of the measurement result of the dissolved oxygen concentration measured by the controller 4, and sends a signal to the oxygen gas flow controller 4 to control the flow rate of oxygen in accordance with, for example, equation (8.1).

Q _O2 = K 1 _{O 2} (X _DO ^* −X _DO ) (8.1) where Q _{O2 is} the rate of change of the flow rate of oxygen.

As described above, oxygen is dissolved in the water to be treated,
"O" between the bromine ions dissolved in the water to be treated_Two
+ 4Br^-→ 2Br_Two+ 2H_TwoO "reaction. Ma
Chlorine also dissolves in the water to be treated, and
"Cl _Two+ 2Br^-→ Br_Two++
2Cl^-Cause the reaction. As a result,
Brominated ions are liberated and volatilized as bromine, and
Harmful substances such as hypobromite
This produces an effect that treated water containing no is obtained. Ma
In addition, chlorine is a standard oxidation-reduction potential at 25 ° C more than oxygen.
Therefore, the use of chlorine makes it possible to
This has the effect of promoting the on-removal reaction.

Further, by controlling the oxygen flow rate as described above, if the measured result of the dissolved oxygen concentration is lower than the target value, the flow rate of oxygen is increased to further promote the above reaction, and When the measurement result of the concentration is higher than the target value, the flow rate of oxygen can be reduced to suppress the consumption of oxygen, and the effect of obtaining treated water with stable water quality can be obtained. In the seventh embodiment, the supply of oxygen and chlorine to the water to be treated is performed using a separate pipe and a diffuser, but the same applies if either gas is mixed in the middle of the pipe. It may be dissolved in the water to be treated using a diffuser, and the same effect can be expected.

In the seventh embodiment, the case where the water to be treated is continuously treated (that is, while the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. The present invention may be applied to the treatment (that is, temporarily storing the treated water in the reaction tank 1 for treatment), and the same effect can be expected. In addition, the seventh embodiment
In the above, the case where the controllers 15 and 151 are used as the oxygen and chlorine gas flow rate control means has been described. However, the gas flow rate may be controlled by other methods such as flow rate control by an operator or control by a computer.

Embodiment 8 (Seventh, Ninth or Seventeenth Bromide Ion Removal Apparatus) Here, a bromine ion removal apparatus according to an eighth embodiment for carrying out the present invention will be described. A reaction tank, piping for flowing in and out of the water to be treated, oxygen gas supply means,
Since the device configuration such as the chlorine gas supply means is the same as that described in the seventh embodiment, a detailed description thereof will be omitted. However, in the eighth embodiment, instead of the dissolved oxygen concentration meter and the oxygen gas flow rate control means, A dissolved chlorine concentration meter and a chlorine gas flow rate control means, and adjusts the flow rate of the chlorine gas according to the difference between the measurement result of the dissolved concentration of the chlorine gas and a predetermined target value. As a dissolved chlorine concentration meter, ion chromatography or the like can be used.

In the eighth embodiment, the same effects as described in the seventh embodiment can be expected.

Ninth Embodiment (Seventh, Tenth, or Seventeenth Bromine Ion Removal Apparatus) FIG. 9 is a diagram schematically showing an apparatus configuration according to a ninth embodiment for carrying out the present invention. In FIG. 9, reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1. 2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is oxygen gas for adjusting the flow rate of oxygen gas. It is a flow control device, and the diffuser device 2, the oxygen gas storage device 3, and the oxygen gas flow control device 4 constitute an oxygen gas supply unit to the water to be treated.

Reference numeral 21 denotes an air diffuser for diffusing chlorine gas and dissolving it in the water to be treated, 31 a chlorine gas storage device for storing chlorine gas, and 41 adjusting the flow rate of chlorine gas. And a diffuser 21, a chlorine gas storage 31 and a chlorine gas flow controller 41 constitute a chlorine gas supply means to the water to be treated. The oxygen gas flow control device 4 is connected to the oxygen gas storage device 3, while the diffusion device 2 is connected via a pipe 201.
It is connected to the. In addition, the chlorine gas flow controller 41
Is connected to a chlorine gas storage device 31, while being connected to a diffuser 21 via a pipe 211.

FIG. 9 shows an oxygen gas supply means provided with a diffuser 2 for dissolving oxygen gas in the water to be treated, but other gas-liquid mixing devices such as an ejector may be used. . FIG. 9 shows a chlorine gas supply means provided with an air diffuser 21 for dissolving chlorine gas in the water to be treated, but other gas-liquid mixing devices such as an ejector may be used. Reference numeral 12 denotes an ion concentration meter for measuring the bromine ion concentration of the water to be treated, which is connected to a controller (oxygen gas flow rate control means) 13 via a signal line 403, and The gas flow controller 13 is connected to the oxygen gas flow controller 4 via a signal line 404.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 9 will be described. The oxygen discharged from the oxygen gas storage device 3 is adjusted in flow rate by the oxygen gas flow rate control device 4, and is brought into contact with and mixed with the water to be treated via the pipe 201 and the diffuser 2. In addition, chlorine gas storage device 3
The chlorine discharged from 1 is adjusted in flow rate by a chlorine gas flow rate adjusting device 41, and is brought into contact with and mixed with the water to be treated via a pipe 211 and a diffuser 21.

Further, a signal of the measurement result of the bromine ion concentration measured by the ion concentration meter 12 is sent to the controller 13 which is the oxygen gas flow rate control means. A signal is sent to the oxygen gas flow control device 4 to control the flow rate of oxygen.

Q _O2 = K _{2 O 2} (X _Br ^* −X _Br ) (10.1) where, Q _O2 : rate of change of oxygen flow rate

As described above, oxygen is dissolved in the water to be treated,
"O ₂ " between the bromine ions dissolved in the water to be treated
+ Br ^- → cause a reaction of 2Br ₂ + 2H ₂ O ". Also,
Chlorine is also dissolved in the water to be treated, and between the bromine ions dissolved in the water to be treated, “Cl ₂ + 2Br ⁻ → Br ₂ + 2C”
l ^- cause a reaction of ". As a result, the bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, the bromine ions in the water to be treated are removed, and the treated water free from harmful substances such as hypobromous acid is obtained.

Since chlorine has a higher standard oxidation-reduction potential at 25 ° C. than oxygen, the use of chlorine has the effect of accelerating the bromine ion removal reaction. Further, by controlling the oxygen flow rate as described above, when the measurement result of the bromine ion concentration is higher than the target value, the flow rate of oxygen is increased to further promote the reaction, and the measurement of the bromine ion concentration is performed. When the result is lower than the target value, the flow rate of oxygen can be reduced to suppress the consumption of oxygen, and there is an effect that treated water with stable water quality can be obtained.

In the ninth embodiment, the supply of oxygen and chlorine to the water to be treated is carried out by using another pipe and a diffuser, but either gas may be mixed in the middle of the pipe. Alternatively, the same aeration device may be used to dissolve the water to be treated, and the same effect can be expected. In the ninth embodiment, the case where the water to be treated is continuously processed (that is, the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. And temporarily treating the water to be treated in the reaction tank 1), and the same effect can be expected. In the ninth embodiment, the case where the controllers 13 and 131 are used as the oxygen and chlorine gas flow control means has been described. However, the control of the gas flow by another method such as the control of the flow by an operator or the control by a computer is described. You may do it.

Embodiment 10 (Seventh, Eleventh or Seventeenth Bromide Ion Removal Apparatus; Second Bromide Ion Removal Method) Here, a bromide ion removal apparatus according to a tenth embodiment for carrying out the present invention will be described. . The configuration of the reaction tank, piping for inflow and outflow of the water to be treated, oxygen gas supply means, chlorine gas supply means, and the like are the same as those described in Embodiment 9; In the tenth embodiment, a chlorine gas flow rate control means is provided instead of the oxygen gas flow rate control means, and the flow rate of the chlorine gas is adjusted according to the difference between the measurement result of the bromine ion concentration and a predetermined target value. It is. In the tenth embodiment, the same effect as that described in the ninth embodiment can be expected.

Embodiment 11 (Seventh, Tenth, Eleventh or Seventeenth Bromide Ion Removal Apparatus; Second Bromide Ion Removal Method) FIG. 10 is a schematic view of an apparatus configuration according to an eleventh embodiment for carrying out the present invention. FIG. In FIG.
Reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe for flowing the water to be treated into the reaction tank 1, and reference numeral 102 denotes a pipe for flowing the treated water out of the reaction tank 1, and is connected to the reaction tank 1. 2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is oxygen gas for adjusting the flow rate of oxygen gas. It is a flow control device, and the diffuser device 2, the oxygen gas storage device 3, and the oxygen gas flow control device 4 constitute an oxygen gas supply unit to the water to be treated.

Reference numeral 21 denotes an air diffuser for diffusing chlorine gas and dissolving it in the water to be treated, 31 a chlorine gas storage device for storing chlorine gas, and 41 adjusting the flow rate of chlorine gas. And a diffuser 21, a chlorine gas storage 31 and a chlorine gas flow controller 41 constitute a chlorine gas supply means to the water to be treated. The oxygen gas flow control device 4 is connected to the oxygen gas storage device 3, while the diffusion device 2 is connected via a pipe 201.
It is connected to the. In addition, the chlorine gas flow controller 41
Is connected to a chlorine gas storage device 31, while being connected to a diffuser 21 via a pipe 211.

[0097] Although FIG. 3 shows the oxygen gas supply means provided with a diffuser 2 for dissolving oxygen gas in the water to be treated, other gas-liquid mixing devices such as an ejector may be used. . FIG. 10 shows a chlorine gas supply means provided with an air diffuser 21 for dissolving chlorine gas in the water to be treated, but other gas-liquid mixing devices such as an ejector may be used.

Reference numeral 12 denotes an ion concentration meter mounted in the reaction tank 1 for measuring the bromine ion concentration of the water to be treated. The ion concentration meter 12 is connected to a controller (oxygen gas flow control means) 13 via a signal line 403. The controller (oxygen gas flow control means) 13 is connected to the oxygen gas flow controller 4 via a signal line 404. In addition, ion concentration meter 1
2 is also connected to a controller (chlorine gas flow rate control means) 131 via a signal line 413, and the controller (chlorine gas flow rate control means) 131 is connected to a chlorine gas flow rate adjusting device 41 via a signal line 414. .

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 10 will be described. The oxygen discharged from the oxygen gas storage device 3 is adjusted in flow rate by the oxygen gas flow rate control device 4, and is brought into contact with and mixed with the water to be treated via the pipe 201 and the diffuser 2. The chlorine discharged from the chlorine gas storage device 31 is supplied to the chlorine gas flow control device 41.
The flow rate is adjusted, and the water is contacted and mixed with the water to be treated via the pipe 211 and the air diffuser 21.

Further, a signal of the measurement result of the bromine ion concentration measured by the ion concentration meter 12 is sent to the controller 13 as the oxygen gas flow rate control means, and the controller 13 according to the equation (11a.1), for example. A signal is sent to the oxygen gas flow control device 4 to control the flow rate of oxygen.

Q _O2 = K5 _O2 (X _Br ^* −X _Br ) (11a.1) where, Q _O2 : rate of change of oxygen flow rate

Further, a signal of the measurement result of the bromine ion concentration measured by the ion densitometer 12 is also sent to the controller 131 which is a chlorine gas flow rate control means, and the controller 131 calculates, for example, the equation (11a.2) Therefore, a signal is sent to the chlorine gas flow controller 4 to control the flow rate of chlorine.

[0103] _{Q Cl2 = K5 Cl2 (X Br} * -X Br) (11a.2) here, Q _Cl2: flow rate of change of the chlorine

As described above, oxygen is dissolved in the water to be treated,
"O" between the bromine ions dissolved in the water to be treated_Two
+ 4Br^-→ 2Br_Two+ 2H_TwoO "reaction. Ma
Chlorine also dissolves in the water to be treated, and
"Cl _Two+ 2Br^-→ Br_Two+
Cl^-Cause the reaction. As a result, it dissolves in the water to be treated
Bromine ions are liberated and volatilized as bromine, and
Bromine ions are removed, and harmful substances such as hypobromous acid are removed.
This has the effect of obtaining treated water free of water. Also,
Chlorine has a higher standard redox potential at 25 ° C than oxygen
So, by using chlorine, the bromine ion
This has the effect of promoting the removal reaction.

Further, by controlling the oxygen flow rate and the chlorine flow rate as described above, if the measurement result of the bromine ion concentration is higher than the target value, the flow rates of the oxygen and chlorine are increased to improve the reaction. If the measurement result of bromine ion concentration is lower than the target value, the flow rate of oxygen and chlorine can be reduced to suppress the consumption of oxygen and chlorine, and the treated water with stable water quality can be obtained. To play. In the eleventh embodiment, the supply of oxygen and chlorine to the water to be treated is performed using a separate pipe and a diffuser. However, the same applies if either gas is mixed in the middle of the pipe. It may be dissolved in the water to be treated using a diffuser, and the same effect can be expected.

In the eleventh embodiment, the case where the water to be treated is continuously treated (that is, while the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. The present invention may be applied to the treatment (that is, temporarily storing the treated water in the reaction tank 1 for treatment), and the same effect can be expected. In addition, the first embodiment
In 1, the case where the controllers 13 and 131 are used as the oxygen and chlorine gas flow rate control means has been described, but the gas flow rate may be controlled by other methods such as flow rate control by an operator or control by a computer.

Embodiment 12 (Seventh, twelfth or seventeenth bromide ion removing apparatus; second bromide ion removing method) FIG. 11 schematically shows an apparatus structure according to a twelfth embodiment for carrying out the present invention. FIG. In FIG.
Reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe for flowing the water to be treated into the reaction tank 1, and reference numeral 102 denotes a pipe for flowing the treated water out of the reaction tank 1, and is connected to the reaction tank 1. 2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is oxygen gas for adjusting the flow rate of oxygen gas. It is a flow control device, and the diffuser device 2, the oxygen gas storage device 3, and the oxygen gas flow control device 4 constitute an oxygen gas supply unit to the water to be treated.

Reference numeral 21 denotes an air diffuser for diffusing chlorine gas and dissolving it in the water to be treated, 31 a chlorine gas storage device for storing chlorine gas, and 41 adjusting the flow rate of chlorine gas. And a diffuser 21, a chlorine gas storage 31 and a chlorine gas flow controller 41 constitute a chlorine gas supply means to the water to be treated. The oxygen gas flow control device 4 is connected to the oxygen gas storage device 3, while the diffusion device 2 is connected via a pipe 201.
It is connected to the. In addition, the chlorine gas flow controller 41
Is connected to a chlorine gas storage device 31, while being connected to a diffuser 21 via a pipe 211.

FIG. 11 shows the oxygen gas supply means provided with a diffuser 2 for dissolving the oxygen gas in the water to be treated, but other gas-liquid mixing devices such as an ejector may be used. . FIG. 11 shows the chlorine gas supply means provided with the air diffuser 21 for dissolving the chlorine gas in the water to be treated. However, another gas-liquid mixing device such as an ejector may be used. Reference numeral 12 denotes an ion concentration meter which is attached in the reaction tank 1 and measures the bromine ion concentration of the water to be treated. The ion concentration meter 12 is connected to a controller (gas flow rate ratio control means) 18 via a signal line 403, and The flow ratio control means 18 is connected to the oxygen gas flow controller 4 via a signal line 504. The controller (gas flow ratio control means) 18 is also connected to the chlorine gas flow controller 41 via a signal line 514.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 11 will be described. The oxygen discharged from the oxygen gas storage device 3 is adjusted in flow rate by the oxygen gas flow rate control device 4, and is brought into contact with and mixed with the water to be treated via the pipe 201 and the diffuser 2. The chlorine discharged from the chlorine gas storage device 31 is supplied to the chlorine gas flow control device 41.
The flow rate is adjusted, and the water is contacted and mixed with the water to be treated via the pipe 211 and the air diffuser 21. The controller 18 serving as an oxygen gas flow rate control means includes an ion concentration meter 1
The controller 18 sends a signal indicating the result of the measurement of the bromine ion concentration measured by the equation (2).
, The flow ratio of oxygen and chlorine is determined.

[0111] ^{_{R1 = KR1 (X Br * -X}} Br) (12.1) here, R1: the ratio of the chlorine gas flow rate to the total flow rate

Further, the controller 18 determines the flow rates of oxygen and chlorine based on the obtained flow rate ratio R1 and sends signals to the oxygen gas flow rate control device 4 and the chlorine gas flow rate control device 41 to determine the oxygen and chlorine flow rates. Control the flow rate. At this time, the total flow rate of the supplied gas is constant.

The flow rate of oxygen is determined according to the equation (12.2).

[0114] _{Q1 O2 = Q T (1-} R1) (12.2) herein, Q1 _O2: oxygen flow rate Q _T: The total flow rate (constant), the flow rate of chlorine, according to equation (12.3) ,It is determined.

Q1 _Cl2 = Q _T × R1 (12.3) where, Q1 _Cl2 : flow rate of chlorine Q _T : total flow rate (constant)

As described above, oxygen is dissolved in the water to be treated,
"O" between the bromine ions dissolved in the water to be treated_Two
+ 4Br^-→ 2Br_Two+ 2H_TwoO "reaction. Ma
Chlorine also dissolves in the water to be treated, and
"Cl _Two+ 2Br^-→ Br_Two+
2Cl^-Cause the reaction.

As a result, bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water free from harmful substances such as hypobromite is obtained. To play. Further, since chlorine has a higher standard oxidation-reduction potential at 25 ° C. than oxygen, the use of chlorine has the effect of promoting the above-mentioned bromine ion removal reaction. In addition, by controlling the flow ratio of oxygen and chlorine as described above, the oxidation-reduction potential of the supplied mixed gas can be adjusted while keeping the flow rate of the entire mixed gas constant, and stable regardless of the properties of the water to be treated. This has the effect that various processing can be performed. The standard oxidation-reduction potential of the mixed gas can be, for example, 1.1 to 3.0 V, preferably 1.1 to 1.5 V.

In the twelfth embodiment, the supply of oxygen and chlorine to the water to be treated is performed by using another pipe and a diffuser, but it is also possible to mix either gas from the middle of the pipe. Alternatively, the same aeration device may be used to dissolve the water to be treated, and the same effect can be expected. In the twelfth embodiment, the case where the water to be treated is continuously processed (that is, the water to be treated is continuously flowed into and out of the reaction tank 1) is described. And temporarily treating the water to be treated in the reaction tank 1), and the same effect can be expected. In the twelfth embodiment, the case where the controller 18 is used as the gas flow rate ratio control means has been described. However, the flow rate ratio may be controlled by another method such as control by an operator or control by a computer.

Embodiment 13 (Seventh, thirteenth, or seventeenth bromine ion removing apparatus; second bromide ion removing method) FIG. 12 schematically shows an apparatus configuration according to a thirteenth embodiment for carrying out the present invention. FIG. In FIG.
Reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1.
2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is oxygen gas for adjusting the flow rate of oxygen gas. A diffuser 2 and an oxygen gas storage 3 which are flow control devices
The oxygen gas flow control device 4 and the oxygen gas flow control device 4 constitute an oxygen gas supply means to the water to be treated.

Reference numeral 21 denotes an air diffuser for diffusing chlorine gas and dissolving it in the water to be treated, 31 a chlorine gas storage device for storing chlorine gas, and 41 adjusting the flow rate of chlorine gas. And a diffuser 21, a chlorine gas storage 31 and a chlorine gas flow controller 41 constitute a chlorine gas supply means to the water to be treated. The oxygen gas flow control device 4 is connected to the oxygen gas storage device 3, while the diffusion device 2 is connected via a pipe 201.
It is connected to the. In addition, the chlorine gas flow controller 41
Is connected to a chlorine gas storage device 31, while being connected to a diffuser 21 via a pipe 211.

FIG. 12 shows an oxygen gas supply means provided with a diffuser 2 for dissolving oxygen gas in the water to be treated, but other gas-liquid mixing devices such as an ejector may be used. . FIG. 12 shows a chlorine gas supply means provided with a diffuser 21 for dissolving chlorine gas in the water to be treated, but another gas-liquid mixing device such as an ejector may be used. Reference numeral 9 denotes a pH meter attached to the pipe 101 for measuring the pH of the inflowing water to be treated. The pH meter 9 is connected to a controller (oxygen gas flow rate control means) 16 via a signal line 407, and a controller (oxygen gas flow rate control). The means 16 is connected to the oxygen gas flow control device 4 via a signal line 408.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 12 will be described. The flow rate of the oxygen discharged from the oxygen gas storage device 3 is adjusted by the oxygen gas flow control device 4, and the oxygen is brought into contact with and mixed with the water to be treated via the pipe 201 and the air diffuser 2. The chlorine discharged from the chlorine gas storage device 31 is supplied to the chlorine gas flow control device 41.
The flow rate is adjusted, and the water is contacted and mixed with the water to be treated via the pipe 211 and the air diffuser 21.

Further, a signal of the measurement result of the pH measured by the pH meter 9 is sent to the controller 16 which is the oxygen gas flow rate control means, and the controller 16 outputs the oxygen gas flow rate according to the equation (13.1), for example. A signal is sent to the flow control device 4 to control the flow rate of oxygen. The target value of pH is
For example, it can be 1 to 6, especially 1 to 2.

Q _O2 = K 3 _{O 2} × X _H ^* (13.1) where Q _{O2 is} the rate of change of the flow rate of oxygen.

As described above, oxygen is dissolved in the water to be treated,
"O" between the bromine ions dissolved in the water to be treated_Two
+ 4Br^-→ 2Br_Two+ 2H_TwoO "reaction. Ma
Chlorine also dissolves in the water to be treated, and
"Cl _Two+ 2Br^-→ Br_Two+
2Cl^-Cause the reaction. As a result,
Brominated ions are liberated and volatilized as bromine, and
Harmful substances such as hypobromite
This produces an effect that treated water containing no is obtained.

Since chlorine has a higher standard oxidation-reduction potential at 25 ° C. than oxygen, the use of chlorine has the effect of accelerating the bromine ion removal reaction. Further, the above reaction is an oxidation reaction of bromine ions, and is not promoted unless hydrogen ions are present. Therefore, by controlling the oxygen flow rate as described above and supplying the amount of oxygen according to the hydrogen ion concentration, there is an effect that unnecessary consumption of oxygen can be suppressed.

In the thirteenth embodiment, the supply of oxygen and chlorine to the water to be treated is performed by using a separate pipe and a diffuser, but either gas may be mixed in the middle of the pipe. Alternatively, the same effect may be expected by dissolving in the water to be treated using the same air diffuser. Further, in the thirteenth embodiment, among the supplied gases, the one that controls the flow rate of oxygen based on the pH of the water to be treated has been described. However, the flow rate of chlorine and the flow rates of oxygen and chlorine are controlled. The same effect can be expected.

In the thirteenth embodiment, the case where the water to be treated is continuously treated (that is, while the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. The present invention may be applied to the treatment (that is, temporarily storing the treated water in the reaction tank 1 for treatment), and the same effect can be expected. In addition, the first embodiment
3, the controller 16 serves as an oxygen gas flow control means.
Although the description has been given of the case of using, the gas flow rate may be controlled by another method such as control of the flow rate by an operator or control by a computer.

Embodiment 14 (Seventh, Fourteenth or Seventeenth Bromine Ion Removal Apparatus; Second Bromine Ion Removal Method) FIG. 13 schematically shows an apparatus configuration according to a fourteenth embodiment for carrying out the present invention. FIG. In FIG.
Reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1.
2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is oxygen gas for adjusting the flow rate of oxygen gas. A diffuser 2 and an oxygen gas storage 3 which are flow control devices
The oxygen gas flow control device 4 and the oxygen gas flow control device 4 constitute an oxygen gas supply means to the water to be treated.

Reference numeral 21 denotes an air diffuser for diffusing chlorine gas and dissolving it in the water to be treated, 31 a chlorine gas storage device for storing chlorine gas, and 41 adjusting the flow rate of chlorine gas. And a diffuser 21, a chlorine gas storage 31 and a chlorine gas flow controller 41 constitute a chlorine gas supply means to the water to be treated. The oxygen gas flow control device 4 is connected to the oxygen gas storage device 3, while the diffusion device 2 is connected via a pipe 201.
It is connected to the. In addition, the chlorine gas flow controller 41
Is connected to a chlorine gas storage device 31, while being connected to a diffuser 21 via a pipe 211.

FIG. 13 shows the oxygen gas supply means provided with the air diffuser 2 for dissolving the oxygen gas in the water to be treated, but another gas-liquid mixing device such as an ejector may be used. . FIG. 13 shows a chlorine gas supply means provided with an air diffuser 21 for dissolving chlorine gas in the water to be treated, but another gas-liquid mixing device such as an ejector may be used. Reference numeral 10 denotes an oxidation-reduction potentiometer for measuring the oxidation-reduction potential of the water to be treated, which is connected to a controller (oxygen gas flow rate control means) 17 via a signal line 409. The oxygen gas flow control means 17 is connected to the oxygen gas flow controller 4 via a signal line 410.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 13 will be described. The oxygen discharged from the oxygen gas storage device 3 is adjusted in flow rate by the oxygen gas flow rate control device 4, and is brought into contact with and mixed with the water to be treated via the pipe 201 and the diffuser 2. The chlorine discharged from the chlorine gas storage device 31 is supplied to the chlorine gas flow control device 41.
The flow rate is adjusted, and the water is contacted and mixed with the water to be treated via the pipe 211 and the air diffuser 21.

A signal indicating the measurement result of the oxidation-reduction potential measured by the oxidation-reduction potentiometer 10 is sent to the controller 17 as the oxygen gas flow rate control means. Therefore, a signal is sent to the oxygen gas flow control device 4 to control the flow rate of oxygen.

Q _O2 = K 4 _{O 2} (X _orp ^* −X _orp ) (14.1) Where, Q _O2 : the rate of change of the flow rate of oxygen

Thus, oxygen is dissolved in the water to be treated,
"O" between the bromine ions dissolved in the water to be treated_Two
+ 4Br^-→ 2Br_Two+ 2H_TwoO "reaction. Ma
Chlorine also dissolves in the water to be treated, and
"Cl _Two+ 2Br^-→ Br_Two+
2Cl^-Cause the reaction. As a result,
Brominated ions are liberated and volatilized as bromine, and
Harmful substances such as hypobromite
This produces an effect that treated water containing no is obtained.

Since chlorine has a higher standard oxidation-reduction potential at 25 ° C. than oxygen, the use of chlorine has the effect of accelerating the bromine ion removal reaction. In addition, by controlling the oxygen flow rate as described above, if the measurement result of the oxidation-reduction potential is lower than the target value, the flow rate of oxygen is increased to further accelerate the reaction, and the measurement of the oxidation-reduction potential is performed. If the result is higher than the target value, it is possible to reduce the oxygen flow rate by reducing the oxygen flow rate, thereby suppressing the wasteful oxygen consumption and supplying the necessary amount of oxygen for the reaction. It works.

In the fourteenth embodiment, the supply of oxygen and chlorine to the water to be treated is performed by using a separate pipe and a diffuser, but either gas may be mixed in the middle of the pipe. Alternatively, the same aeration device may be used to dissolve the water to be treated, and the same effect can be expected. Further, in the fourteenth embodiment, the case where the to-be-treated water is continuously treated (that is, the to-be-treated water is treated while continuously flowing into and out of the reaction tank 1) has been described. And temporarily treating the water to be treated in the reaction tank 1), and the same effect can be expected. In the fourteenth embodiment, the case where the controller 17 is used as the oxygen gas flow rate control means has been described. However, the gas flow rate may be controlled by other methods such as flow rate control by an operator or control by a computer. .

Embodiment 15 (Seventh, fifteenth or seventeenth bromine ion removing apparatus; second bromide ion removing method) Here, a bromine ion removing apparatus according to a fifteenth embodiment for carrying out the present invention will be described. . The apparatus configuration such as a reaction tank, piping for inflow and outflow of the water to be treated, oxygen gas supply means, and chlorine gas supply means is the same as that described in Embodiment 14; In the fifteenth embodiment, a chlorine gas flow rate control means is provided in place of the oxygen gas flow rate control means, and the chlorine gas flow rate is adjusted according to the difference between the measurement result of the oxidation-reduction potential and a predetermined target value. It is. In the fifteenth embodiment, the same effect as that described in the fourteenth embodiment can be expected.

Embodiment 15a (seventh, fourteenth, fifteenth or seventeenth bromide ion removing apparatus; second bromide ion removing method) FIG. 14 is a schematic view of an apparatus according to a fifteenth embodiment for carrying out the present invention. FIG. In FIG. 14, reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1. 2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is oxygen gas for adjusting the flow rate of oxygen gas. It is a flow control device, and the diffuser device 2, the oxygen gas storage device 3, and the oxygen gas flow control device 4 constitute an oxygen gas supply unit to the water to be treated.

Reference numeral 21 denotes an air diffuser for diffusing chlorine gas and dissolving it in the water to be treated, 31 a chlorine gas storage device for storing chlorine gas, and 41 adjusting the flow rate of chlorine gas. And a diffuser 21, a chlorine gas storage 31 and a chlorine gas flow controller 41 constitute a chlorine gas supply means to the water to be treated. The oxygen gas flow control device 4 is connected to the oxygen gas storage device 3, while the diffusion device 2 is connected via a pipe 201.
It is connected to the. In addition, the chlorine gas flow controller 41
Is connected to a chlorine gas storage device 31, while being connected to a diffuser 21 via a pipe 211.

FIG. 14 shows an oxygen gas supply means provided with a diffuser 2 for dissolving oxygen gas in the water to be treated, but other gas-liquid mixing devices such as an ejector may be used. . FIG. 14 shows a chlorine gas supply means provided with a diffuser 21 for dissolving chlorine gas in the water to be treated, but another gas-liquid mixing device such as an ejector may be used.

Reference numeral 10 denotes an oxidation-reduction potentiometer for measuring the oxidation-reduction potential of the water to be treated, which is connected to the controller (oxygen gas flow rate control means) 17 via a signal line 409. The controller (oxygen gas flow control means) 17 is connected to the oxygen gas flow control device 4 via a signal line 410. Further, the oxidation-reduction potentiometer 10 is also connected to a controller (chlorine gas flow rate control means) 171 via a signal line 419, and the controller (chlorine gas flow rate control means) 171 is connected to a chlorine gas flow rate control device via a signal line 420. 41.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 15 will be described. The oxygen discharged from the oxygen gas storage device 3 is adjusted in flow rate by the oxygen gas flow rate control device 4, and is brought into contact with and mixed with the water to be treated via the pipe 201 and the diffuser 2. The chlorine discharged from the chlorine gas storage device 31 is supplied to the chlorine gas flow control device 41.
The flow rate is adjusted, and the water is contacted and mixed with the water to be treated via the pipe 211 and the air diffuser 21. Further, a signal of the measurement result of the oxidation-reduction potential measured by the oxidation-reduction potentiometer 10 is sent to the controller 17 as the oxygen gas flow rate control means.
According to 1), a signal is sent to the oxygen gas flow control device 4 to control the flow rate of oxygen.

Q _O2 = K7 _O2 (X _orp ^* −X _orp ) (15a.1) where, Q _O2 : rate of change of oxygen flow rate

Further, a signal of the measurement result of the oxidation-reduction potential measured by the oxidation-reduction potentiometer 10 is also sent to the controller 171 as the chlorine gas flow rate control means. , A signal is sent to the chlorine gas flow controller 41 to control the flow rate of chlorine.

Q _Cl2 = K7 _Cl2 (X _orp ^* −X _orp ) (15a.2) where, Q _Cl2 : rate of change of oxygen flow rate

As described above, oxygen is dissolved in the water to be treated,
"O" between the bromine ions dissolved in the water to be treated_Two
+ 4Br^-→ 2Br_Two+ 2H_TwoO "reaction. Ma
Chlorine also dissolves in the water to be treated, and
"Cl _Two+ 2Br^-→ 2Br_Two
+ 2Cl^-Cause the reaction. As a result,
Dissolved bromine ions are released and volatilized as bromine, and are treated
Hazardous substances such as hypobromous acid are removed from bromine ions in water
This has the effect that treated water containing no quality can be obtained. Ma
In addition, chlorine is a standard oxidation-reduction potential at 25 ° C more than oxygen.
Therefore, the use of chlorine makes it possible to
This has the effect of promoting the on-removal reaction.

By controlling the oxygen flow rate and the chlorine flow rate as described above, when the measurement result of the oxidation-reduction potential is lower than the target value, the flow rates of the oxygen and chlorine are increased to make the reaction more efficient. If the measurement result of the oxidation-reduction potential is higher than the target value, the flow rate of oxygen and chlorine can be reduced to suppress the consumption of oxygen and chlorine, and the consumption of unnecessary oxygen and chlorine can be suppressed. This has the effect of supplying oxygen and chlorine in the amounts required for the reaction.

In Embodiment 15a, the supply of oxygen and chlorine to the water to be treated is performed by using another pipe and a diffuser, but either gas may be mixed in the middle of the pipe. Alternatively, the same aeration device may be used to dissolve the water to be treated, and the same effect can be expected. In Embodiment 15a, the case where the water to be treated is continuously treated (that is, the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. And temporarily treating the water to be treated in the reaction tank 1), and the same effect can be expected. In Embodiment 15a, the controllers 17 and 171 serve as oxygen and chlorine gas flow rate control means.
Although the description has been given of the case of using, the gas flow rate may be controlled by another method such as control of the flow rate by an operator or control by a computer.

Embodiment 16 (Seventh, Sixteenth or Eighteenth Bromide Ion Removal Apparatus; Second Bromine Ion Removal Method) FIG. 15 schematically shows an apparatus configuration according to a sixteenth embodiment for carrying out the present invention. FIG. In FIG.
Reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1.
2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is oxygen gas for adjusting the flow rate of oxygen gas. A diffuser 2 and an oxygen gas storage 3 which are flow control devices
The oxygen gas flow control device 4 and the oxygen gas flow control device 4 constitute an oxygen gas supply means to the water to be treated.

Reference numeral 21 denotes an air diffuser for diffusing chlorine gas and dissolving it in the water to be treated, 31 a chlorine gas storage device for storing chlorine gas, and 41 adjusting the flow rate of chlorine gas. And a diffuser 21, a chlorine gas storage 31 and a chlorine gas flow controller 41 constitute a chlorine gas supply means to the water to be treated. The oxygen gas flow control device 4 is connected to the oxygen gas storage device 3, while the diffusion device 2 is connected via a pipe 201.
It is connected to the. In addition, the chlorine gas flow controller 41
Is connected to a chlorine gas storage device 31, while being connected to a diffuser 21 via a pipe 211.

FIG. 15 shows the oxygen gas supply means provided with the air diffuser 2 for dissolving the oxygen gas in the water to be treated. However, another gas-liquid mixing device such as an ejector may be used. . FIG. 15 shows a chlorine gas supply means provided with an air diffuser 21 for dissolving chlorine gas in the water to be treated, but other gas-liquid mixing devices such as an ejector may be used. Reference numeral 10 denotes an oxidation-reduction potentiometer for measuring the oxidation-reduction potential of the water to be treated, which is connected to a controller (gas flow ratio control means) 19 via a signal line 409, and The gas flow rate control means 19 is connected to the oxygen gas flow control device 4 via a signal line 510. The controller (gas flow ratio control means) 19 is also connected to a chlorine gas flow control device 41 via a signal line 520.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 15 will be described. The oxygen discharged from the oxygen gas storage device 3 is adjusted in flow rate by the oxygen gas flow rate control device 4, and is brought into contact with and mixed with the water to be treated via the pipe 201 and the diffuser 2. The chlorine discharged from the chlorine gas storage device 31 is supplied to the chlorine gas flow control device 41.
The flow rate is adjusted, and the water is contacted and mixed with the water to be treated via the pipe 211 and the air diffuser 21. Further, a signal of the measurement result of the oxidation-reduction potential measured by the oxidation-reduction potentiometer 10 is sent to the controller 19 which is the oxygen gas flow rate control means.
, The flow ratio of oxygen and chlorine is determined.

R2 = KR2 (X _orp ^* −X _orp ) (16.1) where: R2: ratio of chlorine gas flow rate to total flow rate

Further, the controller 19 determines the flow rates of oxygen and chlorine based on the obtained flow rate ratio R2, and sends signals to the oxygen gas flow rate control device 4 and the chlorine gas flow rate control device 41 to determine the oxygen and chlorine flow rates. Control the flow rate. At this time, the total flow rate of the supplied gas is constant. The oxygen flow rate is determined according to equation (16.2).

[0156] _{Q1 O2 = Q T (1-} R2) (16.2) here, Q1 _02: oxygen flow rate Q _T: total flow rate (constant)

Further, the flow rate of chlorine is determined according to the equation (16.3).

Q1 _Cl2 = Q _T × R2 (16.3) where, Q1 _Cl2 : flow rate of chlorine Q _T : total flow rate (constant)

As described above, oxygen is dissolved in the water to be treated,
"O" between the bromine ions dissolved in the water to be treated_Two
+ 4Br^-→ 2Br_Two+ 2H_TwoO "reaction. Ma
Chlorine also dissolves in the water to be treated, and
"Cl _Two+ 2Br^-→ Br_Two+
2Cl ”reaction. As a result, it dissolves in the water to be treated
Bromine ions are liberated and volatilized as bromine, and
Bromine ions are removed, and harmful substances such as hypobromous acid are removed.
This has the effect of obtaining treated water free of water.

Since chlorine has a higher standard oxidation-reduction potential at 25 ° C. than oxygen, the use of chlorine has the effect of accelerating the bromine ion removal reaction. In addition, by controlling the flow ratio of oxygen and chlorine as described above, the oxidation-reduction potential of the supplied mixed gas can be adjusted while keeping the flow rate of the entire mixed gas constant, and stable regardless of the properties of the water to be treated. This has the effect that various processing can be performed.

In the sixteenth embodiment, the supply of oxygen and chlorine to the water to be treated is performed using a separate pipe and a diffuser, but either gas may be mixed in the middle of the pipe. Alternatively, the same aeration device may be used to dissolve the water to be treated, and the same effect can be expected. In the sixteenth embodiment, the case where the water to be treated is continuously treated (that is, while the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. And temporarily treating the water to be treated in the reaction tank 1), and the same effect can be expected. In the sixteenth embodiment, the case where the controller 19 is used as the gas flow ratio control means has been described. However, the flow ratio may be controlled by another method such as control by an operator or control by a computer.

Embodiment 17 (Seventh or Eighteenth Bromine Ion Removal Device; Second Bromine Ion Removal Method) FIG. 16 is a diagram schematically showing a device configuration according to a seventeenth embodiment for carrying out the present invention. It is. In FIG.
Reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe for flowing the water to be treated into the reaction tank 1, and reference numeral 102 denotes a pipe for flowing the treated water out of the reaction tank 1, and is connected to the reaction tank 1. 2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is oxygen gas for adjusting the flow rate of oxygen gas. It is a flow control device, and the diffuser device 2, the oxygen gas storage device 3, and the oxygen gas flow control device 4 constitute an oxygen gas supply unit to the water to be treated.

Reference numeral 22 denotes an air diffuser for diffusing ozone gas and dissolving it in the water to be treated; 32, an ozone source gas storage device for storing an ozone source gas such as oxygen or air; 42 is an ozone source gas flow rate adjusting device for adjusting the flow rate of the ozone source gas, 50 is an ozone generator for generating ozone from the source gas, and is a diffuser 22, an ozone source gas storage device 32, and an ozone source gas flow rate. The adjusting device 42 and the ozone generating device 50 constitute an ozone gas supply unit for the water to be treated. The oxygen gas flow control device 4 is connected to the oxygen gas storage device 3, while being connected to the air diffuser 2 via a pipe 201.

The ozone source gas flow rate adjusting device 42
Is connected to an ozone source gas storage device 32, while being connected to an ozone generator 50 via a pipe 212. The ozone generator 50 is connected to the air diffuser 22 via a pipe 213. FIG. 16 shows the oxygen gas supply means provided with the air diffuser 2 for dissolving the oxygen gas in the water to be treated, but another gas-liquid mixing device such as an ejector may be used. FIG. 16 shows the ozone gas supply means provided with the air diffuser 22 for dissolving the ozone gas in the water to be treated. However, another gas-liquid mixing device such as an ejector may be used.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 16 will be described. The oxygen discharged from the oxygen gas storage device 3 is adjusted in flow rate by the oxygen gas flow rate control device 4, and is brought into contact with and mixed with the water to be treated via the pipe 201 and the diffuser 2. The flow rate of the source gas discharged from the ozone source gas storage device 32 is adjusted by the ozone source gas flow rate adjustment device 42, and is sent to the ozone generation device 50 via the pipe 212. The ozone gas or ozone-containing gas generated by the ozone generator 50 is brought into contact with and mixed with the water to be treated via the pipe 213 and the air diffuser 22.

Thus, oxygen is dissolved in the water to be treated,
In between the bromine ions dissolved in the water to be treated "O ₂
+ 4Br ⁻ → 2Br ₂ + 2H ₂ O ”. Further, ozone is also dissolved in the water to be treated, and causes a reaction with bromine ions dissolved in the water to be treated. as a result,
The bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, the bromine ions in the water to be treated are removed, and the treated water containing no harmful substances such as organic chlorine compounds is obtained. Also, ozone is two times more than oxygen and chlorine.
Since the standard oxidation-reduction potential at 5 ° C. is high, there is an effect that the bromine ion removal reaction is further promoted.

In the seventeenth embodiment, the supply of oxygen and ozone to the water to be treated is performed using a separate pipe and a diffuser, but either gas may be mixed in the middle of the pipe. Alternatively, the same aeration device may be used to dissolve the water to be treated, and the same effect can be expected. In the seventeenth embodiment, the case where the water to be treated is continuously treated (that is, while the water to be treated is continuously flowed into and out of the reaction tank 1) is described. And temporarily treating the water to be treated in the reaction tank 1), and the same effect can be expected.

In the seventeenth embodiment, the ozone gas supply means is provided in place of the chlorine gas supply means of the sixth embodiment, but the chlorine gas supply means is similarly applied to the seventh to seventeenth embodiments. Instead, ozone gas supply means may be provided, and the same effects as described in the seventeenth embodiment can be expected.

Eighteenth Embodiment (Seventh, Tenth, Eleventh or Eighteenth Bromide Ion Removal Apparatus; Second Bromide Ion Removal Method) FIG. 17 is a schematic view of an apparatus configuration according to an eighteenth embodiment for carrying out the present invention. FIG. In FIG.
Reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1.

Reference numeral 23 denotes an air diffuser for diffusing ozone gas or ozone-containing gas into the water to be treated, 3 denotes an oxygen gas storage device for storing oxygen gas as a raw material of ozone gas, and 4 denotes an oxygen gas storage device. An oxygen gas flow rate adjusting device for adjusting the flow rate of oxygen gas, 50 is an ozone generator,
The air diffuser 23, the oxygen gas storage device 3, the oxygen gas flow rate adjusting device 4, and the ozone generator 50 constitute an ozone gas supply unit to the water to be treated.

The oxygen gas flow control device 4 is connected to the oxygen gas storage device 3, and is connected to the ozone generator 50 via the pipe 214. Further, the ozone generator 50 is connected to the air diffuser 23 through a pipe 215.
It is connected to the. In addition, as the ozone gas supply means,
FIG. 17 shows an apparatus provided with an air diffuser 23 for dissolving ozone gas or ozone-containing gas in the water to be treated. However, another gas-liquid mixing apparatus such as an ejector may be used.

Numeral 12 denotes an ion concentration meter for measuring the bromine ion concentration of the water to be treated, which is mounted in the reaction tank 1 and is connected to a controller (ozone concentration control means) 20 via a signal line 403. . The controller (ozone concentration control means) 20 is connected to the ozone generator 50 via a signal line 450.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 17 will be described. The oxygen discharged from the oxygen gas storage device 3 has its flow rate adjusted by the oxygen gas flow rate adjusting device 4 and is sent to the ozone generator 50 via the pipe 214. The ozone gas or the ozone-containing gas generated by the ozone generator 50 is brought into contact with and mixed with the water to be treated via the pipe 215 and the diffuser 23.

Further, a signal of the measurement result of the bromine ion concentration measured by the ion concentration meter 12 is sent to the controller 20 as the ozone concentration control means.
0 controls the generated ozone concentration by sending a signal to the ozone generator 50 in accordance with, for example, equation (18a.1).

C _O3 = K _O3 (XBr ^* −XBr) (18a.1) where C _O3 : change rate of ozone concentration XBr ^* : target value of bromine ion concentration XBr: measurement result of bromine ion concentration

As described above, oxygen is dissolved in the water to be treated,
In between the bromine ions dissolved in the water to be treated "O ₂
+ 4Br ⁻ → 2Br ₂ + 2H ₂ O ”. Further, ozone is also dissolved in the water to be treated, and causes a reaction with bromine ions dissolved in the water to be treated. as a result,
The bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, the bromine ions in the water to be treated are removed, and the treated water containing no harmful substances such as organic chlorine compounds is obtained.

Ozone is 25% more than oxygen and chlorine.
Since the standard oxidation-reduction potential at ° C. is high, the effect of further promoting the bromine ion removal reaction is exhibited. Also,
By controlling the ozone concentration as described above,
When the measurement result of the bromide ion concentration is higher than the target value, the ozone concentration is increased to promote the above reaction, and when the measurement result of the bromide ion concentration is lower than the target value, the ozone concentration is reduced. Electric power for ozone generation can be reduced, and the effect of obtaining treated water of stable water quality can be obtained.

In the eighteenth embodiment, the case where the water to be treated is continuously treated (that is, while the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. The present invention may be applied to the treatment (that is, temporarily storing the treated water in the reaction tank 1 for treatment), and the same effect can be expected. In addition, the first embodiment
In FIG. 8, the case where the controller 20 is used as the ozone concentration control means has been described. However, the ozone concentration may be controlled by another method such as control of the generated concentration by an operator or control by a computer.

Further, in the eighteenth embodiment, the control in which the bromine ion concentration is controlled has been described.
Control by dissolved ozone concentration or oxidation-reduction potential may be performed, and the same effect is obtained. Further, as described in Embodiments 6 to 18, the present invention may be applied to a case where two or more kinds of supply gases are used, and similar effects can be expected.

Nineteenth Embodiment (Nineteenth Bromide Ion Removal Apparatus) FIG. 18 is a diagram schematically showing an apparatus configuration according to a nineteenth embodiment for carrying out the present invention. In FIG.
Reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1.
2 is an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 is an oxygen gas storage device for storing oxygen gas, and 4 is a gas flow rate for adjusting the flow rate of oxygen gas. The gas diffuser 2, the oxygen gas storage device 3, and the gas flow rate controller 4 constitute a gas supply means to the water to be treated.

The gas flow control device 4 is connected to the oxygen gas storage device 3, while being connected to the air diffuser 2 via a pipe 201. FIG. 18 shows the gas supply means provided with the air diffuser 2 for dissolving the oxygen gas in the water to be treated, but another gas-liquid mixing device such as an ejector may be used. Reference numeral 7 denotes an acid storage tank for storing acid, and reference numeral 8 denotes a flow rate adjusting device for adjusting the amount of acid added to the water to be treated. The acid storage tank 7 is connected to a flow controller 8 via a pipe 301, and the flow controller 8 is connected to the reaction tank 1 via a pipe 302.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 18 will be described. The flow rate of the oxygen discharged from the oxygen gas storage device 3 is adjusted by the gas flow rate adjustment device 4, and the oxygen is contacted and mixed with the water to be treated via the pipe 201 and the air diffuser 2. Further, the acid discharged from the acid storage tank is added to the water to be treated via the pipe 301, the flow control device 8, and the pipe 302. As the acid, for example,
Hydrochloric acid, sulfuric acid, acetic acid and the like can be used.

As a result, oxygen is dissolved in the water to be treated,
In between the bromine ions dissolved in the water to be treated "O ₂
+ 4Br ⁻ → 2Br ₂ + 2H ₂ O ”. As a result, bromine ions dissolved in the water to be treated are released and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water containing no harmful substances such as hypobromous acid and organic chlorine compounds is obtained. This has the effect. Further, the water to be treated becomes acidic by the addition of an acid, whereby the above-described reaction is promoted.

In the nineteenth embodiment, the gas supplied by the gas supply means is oxygen (standard oxidation potential of 1.degree.
23V), but other gases may be used as long as the standard oxidation-reduction potential at 25 ° C. is 1.1 to 1.5 V. The gas used need not be a single component, but may be a mixture of gases satisfying the above conditions or a mixture of mixed gases satisfying the above conditions.

In the nineteenth embodiment, the case where the water to be treated is continuously treated (that is, the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. The present invention may be applied to the treatment (that is, temporarily storing the treated water in the reaction tank 1 for treatment), and the same effect can be expected. The nineteenth embodiment
In the above, a description has been given of a combination of the device described in Embodiment 1 with the addition of an acid. However, any of the devices in Embodiments 2 to 19 may be combined with the addition of an acid, and similar effects can be expected.

Twentieth Embodiment (Twentieth Bromine Ion Removal Apparatus) FIG. 19 is a diagram schematically showing an apparatus configuration according to a twentieth embodiment for carrying out the present invention. In FIG.
Reference numeral 1 denotes a reaction tank for removing bromine ions of the water to be treated. Reference numeral 101 denotes a pipe through which the water to be treated flows into the reaction tank 1, and reference numeral 102 denotes a pipe through which the treated water flows out of the reaction tank 1, and is connected to the reaction tank 1.

Reference numeral 2 denotes an air diffuser for diffusing oxygen gas and dissolving it in the water to be treated, 3 denotes an oxygen gas storage device for storing oxygen gas, and 4 denotes a device for adjusting the flow rate of oxygen gas. The gas diffusing device 2, the oxygen gas storage device 3, and the gas flow regulating device 4 constitute a gas supply means to the water to be treated. In addition, the gas flow control device 4
Connected to the oxygen gas storage device 3,
1 is connected to the air diffuser 2. FIG. 19 shows the gas supply means provided with the air diffuser 2 for dissolving the oxygen gas in the water to be treated, but another gas-liquid mixing device such as an ejector may be used.

7 is an acid storage tank for storing an acid, 8
Is a flow rate adjusting device for adjusting the amount of acid added to the water to be treated. The acid storage tank 7 is connected to a flow controller 8 via a pipe 301, and the flow controller 8 is connected to the reaction tank 1 via a pipe 302. Reference numeral 9 denotes a pH meter which is mounted in the reaction tank 1 and measures the pH of the water to be treated. The pH meter 9 is connected to a controller (acid addition amount control means) 11 via a signal line 401. Further, the controller (acid addition amount control means) 11 is connected to the flow rate adjusting device 8 via a signal line 402.

Next, the operation of the water treatment apparatus according to the present embodiment shown in FIG. 19 will be described. The flow rate of the oxygen discharged from the oxygen gas storage device 3 is adjusted by the gas flow rate adjustment device 4, and the oxygen is contacted and mixed with the water to be treated via the pipe 201 and the air diffuser 2. Further, the acid discharged from the acid storage tank is added to the water to be treated via the pipe 301, the flow control device 8, and the pipe 302. Further, a signal of the measurement result of the pH measured by the pH meter 9 is sent to the controller 11 which is the acid addition amount control means.
Sends a signal to the flow rate controller 8 to control the amount of acid addition, for example, according to equation (20.1). The target value of the hydrogen ion concentration can be, for example, 1 to 6, particularly 1 to 2.

Q _acid = KpH (X _H ^* −X _H ) (20.1) where, Q _acid : the rate of change of the amount of acid added X _H : the target value of the hydrogen ion concentration

Thus, oxygen is dissolved in the water to be treated,
In between the bromine ions dissolved in the water to be treated "O ₂
+ 4Br ⁻ → 2Br ₂ + 2H ₂ O ”. As a result, bromine ions dissolved in the water to be treated are released and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water containing no harmful substances such as hypobromous acid and organic chlorine compounds is obtained. This has the effect. Further, the water to be treated becomes acidic by the addition of an acid, whereby the above-described reaction is promoted. In addition, by measuring the pH and controlling the amount of acid addition, regardless of the properties of the water to be treated, for example, the water to be treated having a buffer capacity,
An acidic treatment can always be performed, and the effect of promoting the reaction is achieved. At this time, p
H should be kept as low as possible, and preferably 4 or less.

In the twentieth embodiment, the gas supplied by the gas supply means is oxygen (standard oxidation potential of 1.degree.
23 V), but if the standard oxidation-reduction potential at 25 ° C. is 1.1 to 1.5 V gas,
Other gases may be used. The gas used need not be a single component, but may be a mixture of gases satisfying the above conditions or a mixture of mixed gases satisfying the above conditions. Further, in the twentieth embodiment, the case where the water to be treated is continuously treated (that is, the water to be treated is continuously flowed into and out of the reaction tank 1) has been described. And temporarily treating the water to be treated in the reaction tank 1), and the same effect can be expected.

Further, in the twentieth embodiment, the case where the controller 11 is used as the acid addition amount control means has been described. However, the control of the acid addition amount by another method such as control of the addition amount by an operator or control by a computer. May be performed. In the twentieth embodiment, a combination of the device described in the first embodiment with the addition of an acid and the control of the amount of the acid added has been described. Control of the amount of acid addition may be combined, and similar effects can be expected.

[0194]

According to the first bromine ion removing apparatus of the present invention, the standard oxidation-reduction potential at 25 ° C. of the reaction tank into which the water to be treated flows and the water to be treated in the reaction tank are 1.1. ~
Gas supply means for supplying a gas in the range of 1.5 V, so that bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, and bromine ions in the water to be treated are removed. It is possible to obtain treated water free of harmful substances such as bromic acid and organic chlorine compounds.

According to the second apparatus for removing bromine ions of the present invention, the dissolved concentration measuring means for measuring the dissolved concentration of the gas supplied by the gas supplying means in the water to be treated, and the gas supplied by the gas supplying means. Gas flow control means for controlling the flow rate based on the difference between the dissolved concentration of the gas measured by the dissolved concentration measurement means and a predetermined target value,
Bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water free of harmful substances such as hypobromous acid and organic chlorine compounds can be obtained. In addition, stable treatment can be performed without depending on the properties of the water to be treated.

According to the third apparatus for removing bromine ions of the present invention, an ion concentration meter for measuring the concentration of bromine ions in the water to be treated in the reaction tank, Gas flow control means for controlling based on the difference between the measurement result of the bromine ion concentration measured by the meter and a predetermined target value, so that the bromine ions dissolved in the water to be treated are released and volatilized as bromine. By removing bromine ions in the water to be treated, it is possible to obtain treated water free of harmful substances such as hypobromous acid and organic chlorine compounds, and to perform a stable treatment without depending on the properties of the water to be treated. be able to.

According to the fourth bromine ion removing apparatus of the present invention, the pH meter for measuring the pH of the water to be treated in the reaction tank and the flow rate of the gas supplied by the gas supply means are measured by the pH meter. Gas flow control means for controlling based on the pH measurement result, so that bromine ions dissolved in the water to be treated are released and volatilized as bromine, the bromine ions in the water to be treated are removed, and hypobromide is removed. It is possible to obtain treated water that does not contain harmful substances such as acids and organic chlorine compounds.
Stable treatment can be performed without depending on the properties of the water to be treated.

According to the fifth apparatus for removing bromine ions of the present invention, the oxidation-reduction potentiometer for measuring the oxidation-reduction potential of the water to be treated in the reaction tank, and the flow rate of the gas supplied by the gas supply means, Since gas flow control means is provided based on the difference between the measurement result of the oxidation-reduction potential measured by the reduction potentiometer and a predetermined target value, bromine ions dissolved in the water to be treated are released as bromine. , Volatilizes, removes bromine ions in the water to be treated, and obtains treated water free of harmful substances such as hypobromous acid and organic chlorine compounds. Can be performed.

According to the sixth bromine ion removing apparatus of the present invention, since the gas supplied by the gas supply means is oxygen, bromine ions dissolved in the water to be treated are liberated as bromine.
By volatilizing and removing bromine ions in the water to be treated, it is possible to obtain treated water free of harmful substances such as hypobromous acid and organic chlorine compounds.

According to the seventh bromine ion removing apparatus of the present invention, the standard oxidation-reduction potential at 25 ° C. of the reaction tank into which the water to be treated flows is 1.1 to 1.0.
Gas (a) supplying gas (a) in the range of 1.5V
A gas supply means for supplying a gas (b) having a standard oxidation-reduction potential at 25 ° C. higher than the gas (a) to the water to be treated in the reaction vessel; Bromine ions dissolved in water are liberated and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water free of harmful substances such as hypobromous acid and organic chlorine compounds can be obtained. Gas with high redox potential (b)
, The bromine ion removal reaction can be further promoted.

According to the eighth bromine ion removing apparatus of the present invention, a dissolved concentration measuring means for measuring the dissolved concentration of the gas (a) supplied by the gas (a) supplying means in the water to be treated, and the gas (a) a) gas (a) flow control means for controlling the flow rate of gas (a) supplied by the supply means based on the difference between the dissolved concentration of gas (a) measured by the dissolved concentration measurement means and a predetermined target value The bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, and the bromine ions in the water to be treated are removed, and the treated water does not contain harmful substances such as hypobromous acid and organic chlorine compounds. You can get
Furthermore, by using the gas (b) having a high standard oxidation-reduction potential, the above-mentioned bromide ion removal reaction can be further promoted, and a stable treatment can be performed without depending on the properties of the water to be treated. .

According to the ninth bromine ion removing apparatus of the present invention, the dissolved concentration measuring means for measuring the dissolved concentration of the gas (b) supplied by the gas (b) supplying means in the water to be treated, and the gas (b) b) a gas (b) flow control means for controlling the flow rate of the gas (b) supplied by the supply means based on a difference between the dissolved concentration of the gas (b) measured by the dissolved concentration measurement means and a predetermined target value; The bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, and the bromine ions in the water to be treated are removed, and the treated water does not contain harmful substances such as hypobromous acid and organic chlorine compounds. You can get
Furthermore, since the gas (b) having a high standard oxidation-reduction potential is used, the above-mentioned bromide ion removal reaction can be further promoted, and a stable treatment can be performed without depending on the properties of the water to be treated.

According to the tenth bromine ion removing apparatus of the present invention, an ion concentration meter for measuring the bromine ion concentration of the water to be treated in the reaction tank, and the gas (a) supplied by the gas (a) supply means Gas (a) for controlling the flow rate of the gas based on the difference between the measurement result of the bromine ion concentration measured by the ion concentration meter and a predetermined target value. The bromine ions are liberated and volatilized as bromine, and the bromine ions in the water to be treated are removed to obtain treated water free of harmful substances such as hypobromous acid and organic chlorine compounds. Since the gas (b) having a high water content is used, the above-mentioned bromine ion removal reaction can be further promoted, and a stable treatment can be performed without depending on the properties of the water to be treated.

According to the eleventh bromine ion removing apparatus of the present invention, the ion concentration meter for measuring the bromine ion concentration of the water to be treated in the reaction tank, and the gas (b) supplied by the gas (b) supply means (B) flow rate control means for controlling the flow rate of the gas based on the difference between the measurement result of the bromine ion concentration measured by the ion concentration meter and a predetermined target value. The bromine ions are liberated and volatilized as bromine, and the bromine ions in the water to be treated are removed to obtain treated water free of harmful substances such as hypobromous acid and organic chlorine compounds. Since the gas (b) having a high water content is used, the above-mentioned bromine ion removal reaction can be further promoted, and a stable treatment can be performed without depending on the properties of the water to be treated.

According to the twelfth bromine ion removing apparatus of the present invention, an ion concentration meter for measuring the bromine ion concentration of the water to be treated in the reaction tank, and the gas (a) supplied by the gas (a) supply means The ratio of the flow rate of the gas (b) supplied by the gas (b) supply means to the flow rate of the gas (b) is constant, and the flow rate of the gas (b) is constant. Flow rate control means for controlling based on the difference from the value, the bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, the bromine ions in the water to be treated are removed, and hypobromite is removed. And treated water free of harmful substances such as organic chlorine compounds,
Furthermore, since the gas (b) having a high standard oxidation-reduction potential is used, the above-mentioned bromide ion removal reaction can be further promoted, and a stable treatment can be performed without depending on the properties of the water to be treated.

According to the thirteenth bromine ion removing apparatus of the present invention, the flow rate of at least one of the gases (a) and (b) is measured by the pH meter for measuring the pH of the inflowing water to be treated. With the flow rate control means for controlling based on the measurement result of the pH measured by the pH meter, the bromine ions dissolved in the water to be treated are released as bromine, volatilized, and the bromine ions in the water to be treated are removed. It is possible to obtain treated water free of harmful substances such as hypobromous acid and organic chlorine compounds,
Furthermore, since the gas (b) having a high standard oxidation-reduction potential is used, the above-mentioned bromide ion removal reaction can be further promoted, and a stable treatment can be performed without depending on the properties of the water to be treated.

According to the fourteenth bromine ion removing apparatus of the present invention, the oxidation-reduction potentiometer for measuring the oxidation-reduction potential of the water to be treated in the reaction tank, and the gas (a) supplied by the gas (a) supply means (A) a flow rate control means for controlling the flow rate of (a) based on the difference between the measurement result of the oxidation-reduction potential measured by the oxidation-reduction potentiometer and a predetermined target value. The bromine ions dissolved in the water are liberated and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water free of harmful substances such as hypobromous acid and organic chlorine compounds can be obtained. Since the gas (b) having a high reduction potential is used, the above-mentioned bromine ion removal reaction can be further promoted, and a stable treatment can be performed without depending on the properties of the water to be treated.

According to the fifteenth bromine ion removing apparatus of the present invention, the oxidation-reduction potentiometer for measuring the oxidation-reduction potential of the water to be treated in the reaction tank, and the gas (b) supplied by the gas (b) supply means (B) flow rate control means for controlling the flow rate of the gas based on the difference between the measurement result of the oxidation-reduction potential measured by the oxidation-reduction potentiometer and a predetermined target value. The bromine ions dissolved in the water are liberated and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water free of harmful substances such as hypobromous acid and organic chlorine compounds can be obtained. Since the gas (b) having a high reduction potential is used, the bromine ion removal reaction can be further promoted, and a stable treatment can be performed without depending on the properties of the water to be treated.

According to the sixteenth bromine ion removing apparatus of the present invention, the oxidation-reduction potentiometer for measuring the oxidation-reduction potential of the water to be treated in the reaction tank and the gas (a) supplied by the gas (a) supply means ) And the ratio of the flow rate of the gas (b) supplied by the gas (b) supply means, and the flow rate of the gas (b) supplied by the gas (b) supply means is kept constant, and the measurement result of the oxidation-reduction potential measured by the oxidation-reduction potentiometer is predetermined. Flow rate control means for controlling based on the difference from the target value, the bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, the bromine ions in the water to be treated are removed, and It is possible to obtain treated water free of harmful substances such as bromic acid and organic chlorine compounds,
Further, since the gas (b) having a high standard oxidation-reduction potential is used, the above-mentioned bromide ion removal reaction can be further promoted, and a stable treatment can be performed without depending on the properties of the water to be treated. .

According to the seventeenth bromine ion removing apparatus of the present invention, the gas (a) supplied by the gas (a) supply means is oxygen, and the gas (b) supplied by the gas (b) supply means is Since chlorine was used, bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, and bromine ions in the water to be treated are removed to obtain treated water free of harmful substances such as hypobromous acid and organic chlorine compounds. Further, since the gas (b) having a high standard oxidation-reduction potential is used, the bromine ion removal reaction can be further promoted.

According to the eighteenth bromine ion removing apparatus of the present invention, the gas (a) supplied by the gas (a) supply means is oxygen, and the gas (b) supplied by the gas (b) supply means is Since ozone is used, bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, and bromine ions in the water to be treated are removed to obtain treated water free of harmful substances such as hypobromous acid and organic chlorine compounds. Further, since the gas (b) having a high standard oxidation-reduction potential is used, the bromine ion removal reaction can be further promoted.

According to the nineteenth bromine ion removing apparatus of the present invention, since the acid addition means for adding a predetermined amount of acid to the water to be treated is provided, the bromine ions dissolved in the water to be treated are converted into bromine. Release and volatilization, remove the bromine ions in the water to be treated, it is possible to obtain treated water free of harmful substances such as hypobromous acid and organic chlorine compounds, furthermore, since the water to be treated is made acidic, Can further promote the bromine ion removal reaction.

[0213] According to the twentieth bromide ion removing apparatus of the present invention, a pH meter for measuring the pH of the water to be treated in the reaction tank;
Since it comprises acid addition amount control means for controlling the amount of acid added by the acid addition means based on a difference between a measurement result of pH measured by the pH meter and a predetermined target value,
Bromine ions dissolved in the water to be treated are liberated and volatilized as bromine, the bromine ions in the water to be treated are removed, and treated water free of harmful substances such as hypobromous acid and organic chlorine compounds can be obtained. Since the water to be treated is made acidic, the above-mentioned bromine ion removal reaction can be further promoted, and a stable treatment can be performed without depending on the properties of the water to be treated.

[Brief description of the drawings]

FIG. 1 is a layout diagram for explaining a device configuration of a first embodiment.

FIG. 2 is a graph for explaining an effect of the first embodiment.

FIG. 3 is a layout diagram for explaining a device configuration of a second embodiment.

FIG. 4 is a layout diagram for explaining a device configuration of a third embodiment.

FIG. 5 is a layout diagram for explaining a device configuration of a fourth embodiment.

FIG. 6 is a layout diagram for explaining a device configuration of a fifth embodiment.

FIG. 7 is a layout diagram for explaining a device configuration of a sixth embodiment.

FIG. 8 is a layout diagram for explaining a device configuration of a seventh embodiment.

FIG. 9 is a layout diagram for explaining a device configuration of a ninth embodiment.

FIG. 10 is a layout diagram for explaining an apparatus configuration of an eleventh embodiment.

FIG. 11 is a layout diagram for explaining an apparatus configuration of a twelfth embodiment.

FIG. 12 is a layout diagram for explaining a device configuration of a thirteenth embodiment.

FIG. 13 is a layout diagram for explaining a device configuration of a fourteenth embodiment.

FIG. 14 is a layout diagram for explaining an apparatus configuration according to Embodiment 15a.

FIG. 15 is a layout diagram for explaining a device configuration of a sixteenth embodiment.

FIG. 16 is a layout diagram for explaining a device configuration of a seventeenth embodiment.

FIG. 17 is a layout diagram for explaining a device configuration of an eighteenth embodiment.

FIG. 18 is a layout diagram for explaining a device configuration of a nineteenth embodiment.

FIG. 19 is a layout diagram for explaining a device configuration of a twentieth embodiment.

FIG. 20 is a layout diagram for explaining a conventional bromine ion recovery device.

[Explanation of symbols]

REFERENCE SIGNS LIST 1 reaction tank, 2 oxygen gas diffuser, 3 oxygen gas storage device, 4 oxygen gas flow control device, 7 acid storage device, 8
Oxygen gas flow controller, 21 chlorine gas diffuser, 2
2 Ozone gas diffuser, 31 Chlorine gas storage device, 3
2 Ozone source gas storage device, 41 Chlorine gas flow control device, 42 Ozone source gas flow control device, 50 Ozone generator, 9 pH meter, 10 Oxidation reduction potential meter, 1
1,13,15,16,17,18,19,20,13
1,151,171,181,191 controller,
12 ion concentration meter, 14 dissolved oxygen concentration meter, 101,
102, 112, 201, 301, 302, 211,
12,213,214,215 piping, 401-41
0,413 to 416,419,420,450,50
4,510,514,520 Signal line, 14a Multistage steam distillation tower, 16a Chlorine gas, 19a Coagulator, 20a
decanter.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Junji Hirotsuji 2-3-2 Marunouchi, Chiyoda-ku, Tokyo F-term in Mitsubishi Electric Corporation (reference) 4D038 AA02 AA04 AB39 BA04 BA06 4D050 AA02 AA04 AB44 BB01 BB02 BD06 BD08

Claims (22)

[Claims] 1. A reaction tank into which water to be treated flows, and a gas supply for supplying a gas having a standard oxidation-reduction potential in the range of 1.1 to 1.5 V at 25 ° C. to the water to be treated in the reaction tank. Means for removing bromine ions. 2. A dissolved concentration measuring means for measuring a dissolved concentration of a gas supplied by the gas supply means in the water to be treated, and a gas measured by the dissolved concentration measuring means for a flow rate of the gas supplied by the gas supplying means. 2. A bromine ion removing apparatus according to claim 1, further comprising gas flow rate control means for controlling based on a difference between a dissolved concentration of the gas and a predetermined target value. 3. An ion densitometer for measuring a bromine ion concentration of water to be treated in a reaction tank, and a flow rate of a gas supplied by the gas supply means, and a measurement result of a bromine ion concentration measured by the ion densitometer. 2. A bromine ion removing apparatus according to claim 1, further comprising gas flow control means for controlling based on a difference between the gas flow rate and a predetermined target value. 4. A pH for measuring the pH of the inflowing treated water.
Meter, the flow rate of the gas supplied by the gas supply means,
The apparatus for removing bromine ions according to claim 1, further comprising gas flow control means for controlling based on a measurement result of pH measured by the pH meter. 5. An oxidation-reduction potentiometer for measuring an oxidation-reduction potential of water to be treated in a reaction vessel, and a flow rate of a gas supplied by the gas supply means, wherein an oxidation-reduction potential of an oxidation-reduction potential The bromine ion removing device according to claim 1, further comprising gas flow control means for controlling based on a difference between the measurement result and a predetermined target value. 6. The apparatus for removing bromine ions according to claim 1, wherein the gas supplied by said gas supply means is oxygen. 7. A reaction tank into which water to be treated flows, and a gas (a) having a standard oxidation-reduction potential at 25 ° C. in the range of 1.1 to 1.5 V is supplied to the water to be treated in the reaction tank. Gas (a) supplying means, and 25 ° C.
A gas (b) supply means for supplying a gas (b) having a higher standard oxidation-reduction potential than the gas (a). 8. A dissolved concentration measuring means for measuring a dissolved concentration of the gas (a) supplied by the gas (a) supplying means in the water to be treated, and a gas (a) supplied by the gas (a) supplying means.
8. The bromine according to claim 7, further comprising gas (a) flow rate control means for controlling the flow rate of the gas based on the difference between the dissolved concentration of the gas (a) measured by the dissolved concentration measurement means and a predetermined target value. Ion removal device. 9. A dissolved concentration measuring means for measuring a dissolved concentration of the gas (b) supplied in the water to be treated, supplied by the gas (b) supplying means, and a gas (b) supplied by the gas (b) supplying means.
8. The bromine according to claim 7, further comprising gas (b) flow rate control means for controlling the flow rate of the gas (b) based on a difference between the dissolved concentration of the gas (b) measured by the dissolved concentration measurement means and a predetermined target value. Ion removal device. 10. An ion concentration meter for measuring a bromine ion concentration of water to be treated in a reaction tank, and a flow rate of the gas (a) supplied by the gas (a) supply means is measured by the ion concentration meter. 8. The apparatus for removing bromine ions according to claim 7, further comprising a gas (a) flow rate control means for controlling based on a difference between a measurement result of bromine ion concentration and a predetermined target value. 11. An ion densitometer for measuring the bromine ion concentration of the water to be treated in the reaction tank, and a flow rate of the gas (b) supplied by the gas (b) supply means is measured by the ion densitometer. 8. The bromine ion removing apparatus according to claim 7, further comprising a gas (b) flow rate control means for controlling based on a difference between the measurement result of the bromine ion concentration and a predetermined target value. 12. An ion densitometer for measuring a bromine ion concentration of water to be treated in a reaction tank, and a flow rate of the gas (a) supplied by the gas (a) supply means and a flow rate of the gas (b) supplied by the gas (b) supply means. Flow rate control for controlling the ratio of the flow rate of the gas (b) to be performed and the overall flow rate to be constant, based on the difference between the measurement result of the bromine ion concentration measured by the ion concentration meter and a predetermined target value. 8. The apparatus for removing bromine ions according to claim 7, comprising: 13. A method for measuring the pH of inflowing water to be treated.
An H meter and a flow rate of at least one of the gases (a) and (b) are measured by the pH meter.
8. The apparatus for removing bromine ions according to claim 7, further comprising a flow control means for performing control based on the measurement result. 14. An oxidation-reduction potentiometer for measuring an oxidation-reduction potential of water to be treated in a reaction tank, and a flow rate of the gas (a) supplied by the gas (a) supply means is measured by the oxidation-reduction potentiometer. 8. The bromine ion removing apparatus according to claim 7, further comprising a gas (a) flow rate control means for controlling based on a difference between the measured result of the oxidation-reduction potential and a predetermined target value. 15. An oxidation-reduction potentiometer for measuring an oxidation-reduction potential of water to be treated in a reaction tank, and a flow rate of the gas (b) supplied by the gas (b) supply means is measured by the oxidation-reduction potentiometer. 8. The bromine ion removing device according to claim 7, further comprising a gas (b) flow rate control means for controlling based on a difference between the measured result of the oxidation-reduction potential and a predetermined target value. 16. An oxidation-reduction potentiometer for measuring an oxidation-reduction potential of water to be treated in a reaction tank, a flow rate of the gas (a) supplied by the gas (a) supply means, and a flow rate of the gas (b) supplied by the gas (b) supply means. Flow rate control means for controlling the ratio of the supplied gas (b) to the flow rate based on the difference between the measurement result of the oxidation-reduction potential measured by the oxidation-reduction potentiometer and a predetermined target value. The bromine ion removing device according to claim 7. 17. The gas (a) supplied by the gas (a) supply means is oxygen, and the gas (b) supplied by the gas (b) supply means is chlorine. , 1
17. The apparatus for removing bromine ions according to 1, 12, 13, 14, 15, or 16. 18. The gas (a) supplied by the gas (a) supply means is oxygen, and the gas (b) supplied by the gas (b) supply means is ozone. ,
17. The apparatus for removing bromine ions according to 11, 12, 13, 14, 15, or 16. 19. An apparatus according to claim 1, further comprising an acid adding means for adding a predetermined amount of acid to the water to be treated.
7, 8, 9, 10, 11, 12, 13, 14, 15, 1,
19. The apparatus for removing bromine ions according to 6, 17, or 18. 20. A pH meter for measuring the pH of the water to be treated in the reaction tank, and an amount of acid added by the acid adding means, the pH measurement result measured by the pH meter and a predetermined target value. 20. The apparatus for removing bromine ions according to claim 19, further comprising: an acid addition amount control unit that controls the amount of addition based on the difference between the two. 21. A method for removing bromine ions, comprising supplying a gas having a standard oxidation-reduction potential at 25 ° C. in the range of 1.1 to 1.5 V to the water to be treated. 22. A gas (a) having a standard oxidation-reduction potential at 25 ° C. in a range of 1.1 to 1.5 V and a gas (25) having a higher standard oxidation-reduction potential at 25 ° C. than the gas (a). b) supplying a bromine ion.