JP3277015B2 - Removal method of organic matter in liquid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for removing organic substances in a liquid, and more particularly, to a halogenated organic compound or a polymer which is a causative substance such as trihalomethane generated in wastewater used as a pollution problem. The present invention relates to a method for removing organic compounds and the like.

[0002]

2. Description of the Related Art Recently, high purity liquids such as ultrapure water and pure water are used as water for the production of semiconductors, liquid crystals and pharmaceuticals. For example, semiconductors such as LSIs are produced. In this case, ultrapure water is used as semiconductor washing water, and this ultrapure water is usually produced by combining an ion exchange device, an ultrafiltration membrane device, a reverse osmosis membrane device, etc. Manufactured by the system.

[0003] However, this ultrapure water production system is suitable for removing various impurity ions, organic substances, suspended particulates, and the like contained in raw water to be treated, but is useful for bacteria, pyrogen ( It is not suitable for removing heat-producing substances), bacteria, and other organic substances, and has a problem of leaking into the ultrapure water, which is a processing liquid. Particularly, when the content of organic substances in the ultrapure water is very small, It is often overlooked and remains in ultrapure water because it cannot be measured with ordinary measuring equipment.If such ultrapure water is used as washing water for semiconductors, organic substances contaminate semiconductors. In some cases, it adheres as an object and causes problems such as contamination of semiconductors and circuit destruction.

On the other hand, in tap water for drinking water, removal of mold odor caused by plankton, floating organisms, algae, etc. has become a problem, but the most important problem is contained in tap water raw water. Halogenated organic compounds and high molecular weight organic compounds, such as trihalomethane and its precursor (humic acid), are added to tap water by chlorine added for oxidative decomposition of organic substances and sterilization of bacteria, pyrogens (pyrogenic substances), bacteria, etc. Acids and their derivatives, fulvic acids,
It is well known that the formation of carcinogens such as cinnamic acid and its derivatives) has been pointed out, and removal of these halogenated organic compounds and high molecular weight organic compounds is an urgent technical problem.

[0005] In order to remove these halogenated organic compounds and high molecular weight organic compounds, various treatment methods such as coagulation filtration have been conventionally employed, but it is difficult to sufficiently remove them. Met. Therefore, the addition of chlorine, which generates halogenated organic compounds and high-molecular organic compounds, is stopped, and the addition of ozone or irradiation of ultraviolet light, which does not generate these organic compounds, is switched to oxidative decomposition of organic substances and sterilization of bacteria, pyrogens, bacteria, and the like. However, in order to achieve sufficient oxidative decomposition and sterilization effects of organic substances, a large amount of ozone addition or ultraviolet irradiation is required, and there is a drawback that the treatment cost is high.

In recent years, it has become a problem that harmful organic compounds released into various industrial wastewaters are mixed into groundwater and river water, thereby contaminating groundwater and river water. For example, tetrachloromethane for dry cleaning or trichloroethylene, trichloroethane, trichloromethane, benzene, carbon tetrachloride and the like for semiconductor cleaning are pointed out.

[0007] In order to prevent these harmful organic compounds from mixing into groundwater and river water, strict regulations have been made. However, in December 1992, the Ministry of Health and Welfare implemented the water quality in 1993. Regulations were announced and 19
In January 1993, the Central Pollution Control Council instructed the Environment Agency
A request was made to add 15 cases including the above-mentioned harmful organic compounds to 25 cases in addition to the conventional monitoring items. A new environmental standard will be set in 1993, and stricter drainage regulations will be enforced.

In addition, Japanese Standard (JIS) K0125
Has established a method for analyzing harmful organic compounds in 1990. However, other organic substances including the harmful organic compounds described above are quite sophisticated when the content in the liquid is very small. There is a problem that it is difficult to measure even with careful measurement with a precision measuring instrument.In addition, the removal of harmful organic compounds is more difficult, and the development of appropriate removal means is eagerly awaited. At present it is not found.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a simple, easy, and low-cost method for removing organic substances that have an adverse effect on production processes and products from liquids used as industrial water when producing various industrial products. It is reduced, removed, and used as high-purity industrial water.

[0010] Another object of the present invention is to remove a halogenated organic compound such as trihalomethane or a high molecular weight organic compound, which is a carcinogen, in tap water or ground water for drinking water. Easier than water,
It is easily and inexpensively reduced and removed, and is used as healthy and safe drinking water.

[0011]

SUMMARY OF THE INVENTION The present invention relates to a method for removing an organic substance in a liquid, and more particularly to a method for removing a primary winding of a primary circuit of a shell-type circular winding transformer using an iron core. Connect to the power supply, and insulate one end of the secondary winding of the secondary circuit of the transformer, and connect the other end to the stainless steel electrode provided in the liquid processing tank made of insulating material. Is configured to be insulated from the ground by an insulator such as an insulator, and a voltage of 500 to 3500 V generated at a stainless steel electrode in the liquid processing tank and a voltage of 0.
A method in which a liquid containing an organic substance is caused to flow into an AC electric field constituted by a current of 5 to 1.5 μA, and dielectric polarization and electronic polarization are performed by electrostatic induction to thereby decompose and decompose the organic substance in the liquid. It is.

In the above-described method for removing organic substances in a liquid, the primary winding of the outer-circle-type circular winding transformer using an iron core may have 200 to 250 primary windings, and the secondary winding of the secondary circuit may have two windings. The next winding is 28000-40000 windings,
Of the secondary windings, the first winding group was set to 16800 to 220
It is characterized in that the number of turns is 00 and the second winding group is 11200 to 18000 turns, and the organic matter in the liquid is efficiently decomposed, reduced and removed by the high voltage and small voltage generated thereby.

Further, the present invention is characterized in that in the above-mentioned method for removing organic substances in a liquid, reduction and removal of halogenated organic compounds and high molecular weight organic compounds which are particularly problematic in terms of pollution as organic substances. is there.

[0014]

When an organic substance in a liquid is treated by the above-described method, an AC electric field generated in a stainless steel electrode in the liquid treatment tank, that is, induced polarization and electronic polarization caused by electrostatic induction, flow into the liquid treatment tank. It imparts rotation and vibration to liquids and molecules in liquids, promotes the dissociation and dispersion of molecular groups, and decomposes and reduces or removes organic substances in liquids into carbon dioxide, chlorine, chlorine gas, low molecular substances, and the like.

An example of an apparatus for carrying out the method for removing an organic substance in a liquid according to the present invention will be described. As shown in FIG. 1, reference numeral 1 denotes a transformer for generating an AC high voltage. The primary winding 3 of the primary circuit of the transformer 1 is connected to an AC power supply, and one end of the secondary winding 4 of the secondary circuit of the transformer 1 is used. 5a is insulated, and the other end 5b of the secondary winding 4 of the secondary circuit is connected to a stainless steel electrode 7 provided in a separately installed liquid processing tank 6. The liquid processing tank 6 is configured to be insulated by an insulator 8 such as an insulator and a ground (earth) 9, and the ground 9 and the primary circuit of the transformer 1 are connected by an electric circuit.

As shown in FIG. 2, the transformer 1 has a cylindrical insulating film 10 fitted in the center of the iron core 2 and further has the above-described primary winding 3 and secondary winding Wind around wire 4. As the primary winding 3, for example, a conductor covered with polyester having a diameter of 0.6 mm is used to make 230 turns, and as the secondary winding 4, for example, a conductor covered with enamel having a diameter of 0.09 mm is used. Out of the 40,000 turns of the secondary winding 4, the first winding group 4a has 22,000 turns, and the second winding group 4b has 18,000 turns. ,
The type, the number of turns of the conducting wire, and the like are appropriately determined according to the treatment conditions for removing organic substances in the liquid.

However, in the ordinary case, the diameter of these conductors can be 0.03 to 3 mm, and the types of conductors other than those coated with polyester or enamel are commonly used as conductors. And the number of turns of the conducting wire, etc.
0, the secondary winding 4 has 28,000 to 40000 windings, and among the secondary windings 4, the first winding group 4
A may be 16800 to 22000 turns, and the second winding group 4B may be 11200 to 18000 turns.

By making a difference between the number of turns of the second winding group 4b and the number of turns of the first winding group 4a among the number of turns of the secondary winding 4, as shown in FIG. The outer diameter of group 4B is smaller than the outer diameter of first winding group 4a,
(B) The cap G2 between the iron core 2 and the cap G1 between the first winding group 4a and the iron core 2 is 1.5 to 2 times larger.

The other end 5b of the secondary winding 4, which is a lead wire on the outer peripheral surface of the first winding group 4a, is connected as an output line to the stainless steel electrode 7 in the liquid treatment tank 6, and As described above, the other end 5a of the secondary winding 4, which is a lead wire on the outer peripheral surface of the group 4B, is set in an insulated state.

When an alternating current is applied to the transformer 1 to raise the primary voltage of the transformer 1 to 100 V, a voltage of about 18000 V is generated on the secondary side in the transformer 1. Since the other end 5a of the second winding group 4b of the secondary winding 4 of the circuit is insulated, the secondary winding which is a lead wire on the outer peripheral surface of the first winding group 4a of the secondary winding 4 is provided. The stainless steel electrode 7 in the liquid processing tank 6 connected to the other end 5b of the wire 4
At a voltage of 500 V, a current of 0.5 to 1.5 μA is generated. That is, between the stainless steel electrode 7 in the liquid processing tank 6 and the ground 9 outside the liquid processing tank 6, organic matter in the liquid flowing into the liquid processing tank 6 is electrostatically induced to induce dielectric polarization (electronic polarization). Configure the AC electric field required for generation.

Approximately 1800 generated on the secondary side in the transformer 1
The voltage of 0 V is applied to the stainless steel electrode 7 in the liquid processing tank 6.
At a voltage of 500-3500 V (0.5-1.5 μ
(A current) from the ground 9 outside the liquid processing tank 6 through the primary winding 3 of the primary circuit of the transformer 1 and the secondary winding 4 of the secondary circuit of the transformer 1 described above. , The other end 5b of the secondary winding 4, the stainless steel electrode 7 in the liquid treatment tank 6
And an AC resistance circuit formed by connecting the AC resistance circuit.

The voltage of the stainless steel electrode 7 in the liquid processing tank 6 generated by the AC resistance circuit as described above is as high as 500-3500 V, but the current is 0.5-1.
Since it is as small as 5 μA, it is safe for the human body and does not cause trouble such as electric shock or fire. The voltage and current generated on the stainless steel electrode 7 are appropriately changed by a voltage regulator (slidac) 11 provided on the AC power supply side according to the conditions for removing organic substances in the liquid. 500 ~ 3500V, current 0.5 ~
At 1.5 μA, an AC electric field suitable for conducting dielectric polarization and electron induction by electrostatically inducing an organic substance in a liquid can be formed.

As shown in FIG. 4, the stainless steel electrode 7 in the liquid treatment tank 6
Becomes positive, a negative charge is conducted to the ground 9, and conversely, if the stainless steel electrode 7 becomes negative, a positive charge is conducted to the ground 9. Thereafter, the stainless steel electrode 7 becomes 1 depending on the frequency of the alternating current. Positive charge and negative charge are switched by the wave number (50 to 60 times) per second, and accordingly, the charge of the ground 9 is also dielectrically switched, so that positive charge and negative charge are switched. The organic matter in the liquid flowing into the liquid processing tank 6 is decomposed by the polarization and the electron induction described later.

A general substance is composed of atoms, and the atoms are composed of nuclei and electrons, and the nuclei are composed of neutrons and protons. Then, electrons with negative charges move in a circular motion around the nucleus, and in a steady state where no electric field or the like is applied from the outside, the amount of positive charges of protons and the amount of negative charges of electrons are equal and stable. It is in a state. However, when an electric field is applied from the outside, the electric field causes the electrons to move to one side and the protons to move to the other side. A dipole is formed, and an internal electric field is generated by the balance of electric charges, causing polarization.

In this case, since the atoms (molecules) are polarized by an external electric field, they are called electron polarization or atomic polarization, and the positively charged molecules including all molecules contained in the liquid including the liquid molecules are Migrating to one side, and negatively charged molecules move to the other. And the movement of this molecule is
The switching between the positive charge and the negative charge due to the electrostatic induction described above is switched 50 to 60 times per second, and this is repeated thereafter.

As described above, the alternating current electric field generated in the stainless steel electrode 7 in the liquid processing tank 6, ie, the liquid flowing into the liquid processing tank 6 and the molecules in the liquid due to induction polarization and electronic polarization based on electrostatic induction. The liquid is applied with rotation and vibration to promote the decoupling and dispersion of the molecular population. In particular, organic substances in the liquid are decomposed and removed into carbon dioxide, chlorine, chlorine gas, low molecular substances, and the like.

The time required for the decomposition and removal of organic substances in the liquid in the liquid processing tank 6 by induction polarization and electronic polarization based on electrostatic induction is appropriately determined according to the type and concentration of the organic substances in the liquid, the voltage and current of the stainless steel electrode 7, and the like. Although it is determined, in a normal case, it is sufficient to perform the organic substance decomposition removal treatment for 2 to 78 hours.

One end 5a of the secondary winding 4 is connected to an end of the secondary winding 4 by wrapping an insulating tape around an end of the secondary winding 4 and filling the transformer with an insulator such as a tar pitch. Insulation is performed so as to cover 5a, but an insulating oil, an unsaturated polyester resin, a polyurethane resin, or the like may be used as the insulating material in addition to the tar pitch.

It is preferable to use a polyethylene resin as the material of the liquid processing tank 6, but any material other than the polyethylene resin may be used as long as the material having an insulating material and the eluted material does not flow out into the liquid. Can be.
The stainless steel electrode 7 is optimally a wire mesh cylindrical shape, but may be a slit shape, a perforated plate shape, or any other shape.

[0030]

Example 1 As a liquid to be treated for removing organic substances by the method of the present invention, three kinds of low-molecular-weight halogenated organic substances of tetrachloroethylene, trichloroethylene and 1.1.1. A specific description will be given by taking a dissolved (15 ° C.) solution as an example. As a transformer for generating an AC high voltage, the transformer having the configuration shown in FIG. 1 is used.
The number of turns was 0, and the secondary winding was a 30,000-turn winding of a conductor covered with 0.09 mm of enamel (the first winding group was 18,000 turns).
And a second winding group of 12,000 windings). As a liquid treatment tank, a 100-ml polyethylene resin tank is provided with a stainless steel electrode in a wire mesh cylindrical shape, and an insulator provided at the lower part of the tank is grounded. And an insulated state was used.

Then, after the above-mentioned solutions of the three kinds of low molecular halogenated organic compounds are caused to flow into the liquid treatment tank,
An AC is applied to the AC high-voltage generating transformer, and a voltage of 1250 V (about 1) is applied to the stainless steel electrode in the liquid processing tank by a voltage of 18000 V generated on the secondary side in the transformer.
An AC electric field of (μA) was generated and the organic substance was decomposed and removed by dielectric polarization and electronic polarization based on electrostatic induction according to the present invention for 60 hours (at a temperature of 15 ° C.). The low molecular weight halogenated organic compound is shown in FIG.
After 48 hours, a treatment liquid free of most low-molecular-weight halogenated organic compounds could be obtained.

[0032]

Embodiment 2 As a liquid to be treated for removing organic substances by the method of the present invention, sodium hypochlorite (effective chlorine amount: 9.10 ml) was dissolved in 100 ml of an aqueous solution containing 50 ppb of humic acid (chemical reagent) as a high molecular organic compound. 83 w / v%) to 0.5
A specific description will be given using the added solution as an example. The primary winding of the AC high-voltage generating transformer is made of a conductor coated with 0.6 mm polyester and has 230 turns.
28,000 turns of a wire covered with 9 mm enamel (16000 turns for the first winding group, 12,000 turns for the second winding group)
The same liquid processing tank as in Example 1 was used.

Next, the voltage of the secondary electrode, that is, the stainless steel electrode in the liquid processing tank is adjusted to 500, 1000, 120 by a voltage regulator (Slidac) of the primary voltage.
0 V, and after the above-mentioned humic acid aqueous solution was allowed to flow into the liquid processing tank, AC was supplied to the AC high-voltage generating transformer, and 500, An AC electric field having a voltage of 1000 or 1200 V (current of about 1 μA) is generated, and the organic substance is decomposed and removed by dielectric polarization and electronic polarization based on electrostatic induction according to the present invention for 100 hours (at a temperature of 25 ° C.). When the amount of chloroform generated by the humic acid and sodium hypochlorite contained in the solution in the tank was measured at 500 ppb as an index (JIS KO125 test method for low molecular weight halogenated hydrocarbons), as shown in FIG. The amount of chloroform decreased with the passage of time, and a treatment solution from which humic acid as a high molecular organic compound was removed was obtained.

[0034]

Embodiment 3 An example of an aqueous solution containing 10 ppb of lipopolysaccharide as a heat-generating substance will be specifically described as a liquid to be treated for removing organic substances by the method of the present invention. The primary winding of the transformer for generating AC high voltage is 230 turns of a conductor coated with 0.6 mm polyester, and the secondary winding is a conductor of 400 mm coated with 0.09 mm enamel.
0 turns (22,000 turns for the first winding group, 18 turns for the second winding group
000 volumes), and the same liquid processing tank as in Example 1 was used.

After the aqueous solution containing the above-mentioned lipopolysaccharide flows into the liquid processing tank, an alternating current is applied to the transformer for generating an AC high voltage, and a voltage of 3300 V is applied to the stainless steel electrode in the liquid processing tank. An AC electric field of about 1 μA) is generated, and the organic substance is decomposed and removed by dielectric polarization and electronic polarization based on electrostatic induction according to the present invention.
0 hours (temperature 25 ° C), Limulus test (12th revised Japanese Pharmacopoeia general test method, endotoxin test method (B-
57)), the change in lipopolysaccharide concentration was measured. As shown in FIG. 7, the amount of lipopolysaccharide decreased over time, and the treatment liquid from which lipopolysaccharide, which was a heat-generating substance, was removed was used. I got it.

[0036]

According to the method for removing organic substances in a liquid of the present invention, any organic substance which has an adverse effect on the production process or the product can be easily, easily, and cost-effectively removed from the liquid used as water for producing various products. It can be safely reduced or removed, and can achieve an industrially excellent effect that it can be used as high-purity industrial water containing no organic matter.

The present invention also provides a simple, easy, low-cost, and safe method for removing halogenated organic compounds and high molecular weight organic compounds such as trihalomethane, which are problematic as carcinogens, from tap water or groundwater for drinking water. It is possible to achieve an excellent effect on life that it can be used as high-purity, healthy drinking water that does not contain harmful organic substances and that does not contain harmful organic substances.

The primary winding of the primary circuit of the transformer is 200 to
250 windings and the secondary winding of the secondary side circuit is 28000
４０40000 turns, and among these secondary windings, the first winding group is set to 16800 to 22,000 turns, and the second winding group is set to 11200 to 18000 turns, thereby removing the organic matter in the liquid. Is further improved.

[0039]

[Brief description of the drawings]

FIG. 1 is an explanatory view of the configuration of a liquid processing tank incorporating a transformer for generating an AC high voltage and a stainless steel electrode, which is an apparatus used in the method for removing organic substances in a liquid of the present invention.

FIG. 2 is an explanatory diagram of a transformer for generating an AC high voltage used in the method for removing an organic substance in a liquid according to the present invention.

FIG. 3 shows the secondary winding of the secondary winding of the AC high voltage generating transformer used in the method for removing organic substances in liquid according to the present invention, in which the outer diameter of the second winding group is smaller than the outer diameter of the first winding group. It is explanatory drawing which shows a state.

FIG. 4 is an explanatory diagram showing a dielectric polarization state of a stainless steel electrode in a liquid processing tank due to electrostatic induction.

FIG. 5 is a graph showing a removal state of three kinds of low molecular halogenated organic substances in a solution in a liquid processing tank.

FIG. 6 is a graph showing the removal state of humic acid, which is a high-molecular-weight organic compound, in a solution by measuring the amount of humic acid and the amount of chloroform generated by chlorine in a solution in a liquid treatment tank. .

FIG. 7 is a graph showing a removal state of lipopolysaccharide, which is an exothermic substance of a solution in a liquid processing tank.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 AC high-voltage generating transformer 2 Iron core 3 Primary winding 4 Secondary winding 4 A First winding group 4 B Second winding group 5 a One end of secondary winding 4 5 b Other than secondary winding 4 End 6 Liquid treatment tank 7 Stainless steel electrode 8 Insulator 9 Ground 11 Voltage regulator

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C02F 1/48

Claims (2)

(57) [Claims] 1. A primary winding of a shell-type circular winding transformer using an iron core having a primary winding of 200 to 250 windings connected to an AC power supply, and a secondary winding of a secondary winding circuit of the transformer. 280 lines
00 to 40,000 turns, and the secondary winding
The first winding group is 16800 to 22000 turns, and the second winding group is
Winding group as 11200 to 18000, Volume, insulates the end of its, the other end connected to the stainless steel electrodes provided in the liquid treatment tank made of insulating material, further by an insulator of the insulator such as the liquid treatment tank It is configured to be insulated from the ground, and a voltage of 500 to 3500 V generated on the stainless steel electrode in the liquid processing tank and 0.5 to
A liquid containing an organic substance is caused to flow into an AC electric field formed by a current of 1.5 μA, and the organic substance in the liquid is decomposed by performing dielectric polarization and electronic polarization by electrostatic induction to decompose the organic substance in the liquid. Method. 2. The organic compound is a halogenated organic compound,
2. The method according to claim 1, wherein the high molecular organic compound is removed. It is about.