JP2002035772A - Method and apparatus for effectively removing dioxins - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and apparatus capable of relatively safely and inexpensively decomposing dioxins in gas, soil or the like containing a very small amount of dioxins to remove them. SOLUTION: Mixing action is applied to gas or fluid containing dioxins having at least two cyclic structures in one moleucle thereof or matter to which dioxins adhere so as to bring a metal phthalocyanine derivative and an oxygen supplying compound such as hydrogen peroxide or the like into contact with the gas or fluid at the same time to effectively remove dioxins. Dioxins can be effectively decomposed at a low temperature by a wet system without relying on an expensive method such as an ultrahigh temperature treatment method or the like. A method for safely treating the metal phthalocyanine derivative accompanied by this dioxin removing method can be provided. This dioxin removing method and apparatus can reply to an emergent and important social demand and can prevent environmental disruption and can be widely and practically applied to industry. Safe standards of dioxins can be lowered to more safe standards.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and effective method for removing or reducing dioxins. The method according to the present invention relates to an effective method for protecting the global environment by recovering normally polluted substances that are becoming a major social problem.

[0002]

2. Description of the Related Art Conventionally, there have been various attempts to remove dioxins, but no effective method has been found. For this reason, low-temperature incinerators and chemical plants, where dioxins are liable to be generated, are shut down or disposed of, and even the surrounding soil is trapped in huge rubber sheets and concrete tanks. The downside of modern science appears, and it is difficult to deal with it, and it is inevitable to proceed assuming that there is little effect if administratively charged.

[0003] The former involves burning at an ultra-high temperature to suppress the generation, reducing the temperature by re-heating at an ultra-high temperature, or trying to reduce the energy by passing through a plasma. , Making implementation more difficult. Public expenditures will further exhaust the economy. The scientific direction alone was that of ultra-high temperature treatment or something similar. It remains unsolved as a fatal problem of being extremely expensive, including the equipment.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have enthusiastically studied to solve the above-mentioned unsolved problems and to provide a method free from disadvantages with enormous cost such as ultra-high temperature processing. As a result, the following invention was reached. In particular, to provide effective low-temperature, relatively inexpensive, earth-friendly methods for removing and reducing dioxins, addressing such urgent problems, and consequently making a significant contribution to human welfare and well-being. Aim.

[0005]

Means for Solving the Problems In the present invention, there is a tendency for many people to avoid the social problem described above, and Shinjuku accepts from the front for human beings who protect the global environment. , Finally achieved. The outline is as follows.

At least a metal phthalocyanine derivative and a solution of an oxygen supply compound that generates oxygen atoms are simultaneously contacted with a solution containing a dioxin having two cyclic structures in one molecule or a solid substance to which the solution is attached. This is an effective method for removing dioxins, characterized by adding a mixing action.

In the above, the metal atom of the metal phthalocyanine derivative is one selected from one or more of iron, cobalt, copper, nickel, manganese, osmium, titanium, molybdenum, and tungsten. Effective removal of dioxins. Is the way.

Further, in the above, a metal phthalocyanine derivative in which two or more of the chemical groups attached to the cyclic compound containing 6 carbon atoms located at the outermost periphery of the phthalocyanine is a carbonyl group or a sulfonic acid group. This is an effective method for removing dioxins.

Further, in the above, two or more of the chemical groups attached to the cyclic compound containing 6 carbon atoms located at the outermost periphery of the phthalocyanine are carbonyl groups. The other residue is -H or another substituent. , An alkyl group, a substituted alkyl group,
Halogen group, nitro group, amino group, thiocyanate group,
Carbonyl group, aldehyde group, carbonyl group, nitrile group, hydroxyl group, alkoxyl group, phenoxyl group, sulfonic acid group, sulfonyl chloride group, sulfonamide group, thiol group, chloromethyl group, alkyl silicon group, vinyl group And a dioxin which is a metal phthalocyanine derivative composed of a chemical group selected from the group consisting of an alkali salt of a sulfonic acid group.

Further, in the above, a particularly preferable solution capable of supplying oxygen atoms is a method for removing dioxins which is a hydrogen peroxide solution.

In the above, the solution of the oxygen supply compound capable of supplying another oxygen atom is selected from the group consisting of peroxides of organic compounds and / or persulfate compounds, titanic oxides and perborates. A method for removing dioxins is also found.

Further, in the above, as a completely different method,
This is an effective method for removing dioxins by mixing in a liquid sandwiched between energized electrolysis electrodes (usually provided as one pair, that is, opposed to each other) as a condition for supplying oxygen.

Further, in the above, gas or flue gas cleaning liquid from an incinerator containing dioxins having at least two cyclic structures in one molecule, soil heating gas or cleaning liquid around the incinerator, incinerator gas or cleaning liquid, around the incinerator Either soil washing liquid, incinerator dismantling cleaning liquid, soil around the incinerator containing water, diesel waste gas or washing liquid, exhaust gas or liquid containing dioxins selected from chemical synthesis, or gas-containing solids And a method for removing dioxins.

A gas or a flue gas cleaning liquid from an incinerator containing dioxins having at least two cyclic structures in one molecule, a soil heating gas or cleaning liquid around the incinerator, an incinerator gas or cleaning liquid, a soil cleaning liquid around the incinerator, or Incinerator demolition cleaning solution, soil around incinerator containing water, diesel waste gas or cleaning solution, gas or liquid containing dioxins selected from exhaust gas or effluent from chemical synthesis, metal solid phthalocyanine derivative Tank containing oxygen-supplying compound mixed with a liquid containing metal phthalocyanine derivative or a substance having a specific surface area adsorbed on a fiber or a fibrous part having a large specific surface area, or circulating or mixing under electrolysis conditions accompanied by oxygen generation conditions And an effective dioxin removal device characterized by comprising a reaction tank.

At least a metal phthalocyanine derivative and an oxygen-supplying compound for generating oxygen atoms are added to a solution containing a dioxin or a halogenated cyclic compound having two cyclic structures in one molecule or to a solid substance to which the solution is attached. After the mixing action is applied so that the solution comes into contact with the solution at the same time, select one of the following: contact with the ion exchange resin or fiber, blowing of ozone, charging of activated alumina or activated carbon, and solidification combustion. This is a method for treating a liquid after a decomposition treatment of dioxins, which is characterized in that the liquid is treated after the decomposition.

Heretofore, the present inventor has focused on the usefulness of the metal phthalocyanine derivative for many years and has been working diligently.
Finally, substances that are not dioxins, such as 2,4
It has already been found that 5-trichlorophenol decomposes into chlorine ions and carbon dioxide gas. On the other hand, dioxins are useful polymers such as polyvinyl chloride and
It is known that chlorine-containing polymers, such as polyvinylidene chloride, are likely to be generated when incinerated at low temperatures.

Dioxins include, in addition to useful polymers such as polyvinyl chloride and polyvinylidene chloride, chlorine (including in the molecule or as an additive) for the purpose of stabilization, heat resistance, flame retardancy and the like. , 2,3,7,8-tetrachlorodibenzo-
For dioxins, such as p-dioxin, in which at least two rings are tightly bound, the challenge of effective removal, as well as its properties, was unknown. Especially 2,3,7,
For the generation of dioxin in which at least two rings are tightly bound, such as 8, -tetrachlorodibenzo-p-dioxin (dioxin). There were few challenges, and the effective removal methods and effects were completely unknown. It is needless to say that the term "dioxins" includes, for example, not all the groups 2, 3, 7, and 8 being chlorine. Similarly, hexachlorophene having at least two cyclic structures in one molecule also belongs to the class.

Regarding the phthalocyanine described below,
Edited by Toshiyoshi Shirai (the present inventor) and Nagao Kobayashi, "Phthalocyanine-Chemistry and Function-" (published by IPC Co., Ltd., published on February 28, 1997: 338 pages in total). The contents described in the present invention are as described in this document level.
It assumes the technical level of the industry. Therefore, here, the complicated chemical structural formula of phthalocyanine is further divided into pages, and need not be described again here.

The metal phthalocyanine derivative used in the present invention is also called a phthalocyanine metal complex, which acts as a specific catalyst for the purpose here. For example, the inventors have invented that 90% of the dioxin was surprisingly decomposed in only 10 minutes at room temperature by adding and mixing dioxin with hydrogen peroxide. That is, it was also confirmed that it was decomposed into chlorine ions and carbon dioxide gas.

This solution is generally poorly soluble,
It is colorful and stable. When it is necessary to remove it after the reaction, it is easy to physically separate it,
For the dissolved component, a method of drying and burning, a method of adsorbing on activated alumina or activated carbon, a method of decomposing by blowing ozone, or a method of supplementing with an anion exchange resin are preferably used. This is unique to the present invention.

Since the metal phthalocyanine derivative is a catalyst, it can be used for an extremely long time if the oxygen supply compound is replenished. On the other hand, for example, a metal phthalocyanine derivative, such as hydrogen peroxide, is adsorbed on an acrylic fiber which is easily oxidized, or reacted, is discharged into the reaction solution as follows. It is preferably used because it does not come or because it comes out very little.
Because it can be used any number of times. A method of increasing the contact area, such as fibrous, cottony, net-like, or multilayer, is employed. The metal phthalocyanine derivative only needs to be resistant to oxidation, and can be supported on fiber, paper, pulp, plastic film, synthetic resin, foamed resin, rubber, activated alumina and the like, and is suitably used in the present invention. The above-mentioned literature describes the characteristics of forming a metal phthalocyanine derivative (complex) into fibers and polymerizing the same, and found that they can be effectively combined.

Here, it has been found that, under similar conditions, potassium hydrogen persulfate, t-butyl hydroperoxide and the like can be similarly used in addition to hydrogen peroxide.
That is, for example, it is well known as a peroxide-based polymerization catalyst of a vinyl-based compound capable of generating (supplying) an oxygen atom. Here, it is clear that there is no need to use a sheet of paper to list these compounds. In particular, in general, hydrogen peroxide which is well-equipped in price, stability, handleability, supply system and the like is preferable.

As a result of an attempt to generate an oxidizing action under electrolysis conditions for generating oxygen, surprisingly, it was found that dioxin was effectively decomposed. This is presumed to result from the strong catalysis of the metal phthalocyanine derivative. In any case,
Fig. 3 shows the industrial utility of the present invention.

In the above, the metal atom of the metal phthalocyanine derivative is preferably selected from one or more of iron, cobalt, copper, nickel, manganese, osmium, titanium, molybdenum, and tungsten. Especially iron,
Manganese is preferred.

Further, in the above, as is apparent from the structural formula of FIG. 1, two or more of the chemical groups attached to the cyclic compound containing 6 carbon atoms located at the outermost periphery of the phthalocyanine are a carboxylic acid group or a sulfonic acid group. It is preferably a certain metal phthalocyanine derivative.

In the above description, for example, in FIG.
M is a metal atom, Y is a substituent, but two or more of the chemical groups attached to the cyclic compound containing 6 carbon atoms located at the outermost periphery of the phthalocyanine are a carbonyl group, The residue is -H or another substituent, an alkyl group,
Substituted alkyl group, halogen group, nitro group, amino group, thiocyanate group, carbonyl chloride group, aldehyde group, carboxamide group, nitrile group, hydroxyl group, alkoxyl group, phenoxyl group, sulfonic acid group, sulfonyl chloride group, sulfonamide group It is preferably a metal phthalocyanine derivative composed of at least one selected from alkanol salts of thiol, chloromethyl, alkylsilicon, vinyl and sulfonic acid groups. In particular, a carboxylic acid group and a salt thereof, and a sulfonic acid group are preferred.

The objects to be treated based on the above-mentioned method are a gas or a flue gas cleaning liquid from an incinerator containing dioxins having at least two cyclic structures in one molecule, a soil heating gas or a cleaning liquid around the incinerator, an incinerator gas Gas or liquid containing dioxins selected from cleaning liquid, soil cleaning liquid around the incinerator, or cleaning liquid for dismantling the incinerator, soil around the incinerator containing water, diesel waste gas or cleaning liquid, exhaust gas or exhaust liquid from chemical synthesis A method for removing dioxins composed of any of the adhered solids is preferred. The waste gas or exhaust gas containing dioxins is supplemented or brought into contact with a shower tower, a spray tower, a bubble bell tower by a chemical engineering technique.

Further, in the above, a gas or a flue gas cleaning liquid from an incinerator containing dioxins having at least two cyclic structures in one molecule, a soil heating gas or a cleaning liquid around the incinerator, an incinerator gas or a cleaning liquid, around the incinerator Soil cleaning liquid or incinerator dismantling cleaning liquid, soil around incinerator containing water, diesel waste gas or cleaning liquid, gas or liquid containing dioxins selected from chemical synthesis exhaust gas or liquid, and solid matter adhering section A reaction vessel in which a metal phthalocyanine derivative is adsorbed on a fiber or a fibrous part having a large specific surface area, or a liquid containing a metal phthalocyanine derivative or a liquid containing particles is mixed and contacted with an oxygen supply compound, or hydrogen peroxide Dioxins consisting of a reaction tank circulated or mixed under electrolysis conditions accompanied by generation conditions Removing apparatus has been found to be effective. In particular, a modified electrolysis method that can decompose dioxins without carrying or handling oxygen-supplying substances
It should be noted as a new method. The modified electrolytic method is, for example, a method in which the surface of an electrode is covered with a metal phthalocyanine derivative.

Since this catalyst preferably has a large contact area, that is, a large specific surface area, such a method is employed. Examples of dioxins having at least two cyclic structures in one molecule include all or partially substituted dioxins of various halogens, and hexachlorophene having two cyclic structures in one molecule. Here, if there is an extremely small amount, it is included in the category of the invention. This is because dioxins have surprisingly high toxicity even in very small amounts. The present invention is extremely effective because even if it does not have two cyclic structures in one molecule, that is, one halogen-substituted cyclic compound is contained in a much larger amount in one molecule, they are also decomposed.

It should be noted that in the present invention, it is not necessary to perform the treatment at an extremely high temperature as in the prior art. Compared to ultra-high temperature treatment, it is extremely economical in terms of equipment costs and operation costs. Even better, even though it was treated at an ultra-high temperature,
In addition, to ensure that the emitted gas is safe and secure,
The method of the present invention can be used for a combination in which a trace amount of dioxins is further decomposed into chlorine ions and carbon dioxide by further processing. The resulting unemployed chlorine ions can be easily neutralized with caustic soda, caustic liquor, and calcium hydroxide, and it is preferable to perform the treatment. It is effective to combine with the above formula.

Examples of the present invention will be described below.
The effectiveness of the present invention is not to be construed as being limited by these, but rather to bring about its application.

[0031]

Example 1 Iron phthalocyanine complex (a mixture of 1 to 8 substituents as sodium carboxylate) as a catalyst in a soil mixed aqueous solution containing 10 ng / ml of dioxin
Was added as a catalyst, and 400 ng / ml was added. A blue soil mixed solution was mixed with hydrogen peroxide 1000 times the amount of the catalyst. After 10 minutes, 90% of the dioxin had been decomposed.

[0032]

Example 2 400 ng / ml of a manganese phthalocyanine complex (a mixture of 1 to 4 sulfonic acid group substituents) as a catalyst was added to a soil mixed aqueous solution containing 1 ng / ml of guioxin, and a green liquid was obtained.・ 100 of catalyst
0 times hydrogen peroxide was added and mixed. After 10 minutes, 88% of the dioxin had been decomposed.

[0033]

Example 3 In Example 1, the soil was separated using wax paper, dried and then burned to confirm the decomposition of phthalocyanine.

[0034]

Example 41 In Example 1, ozone gas was blown after the soil was separated with wax paper. The green color disappeared and decomposition of the phthalocyanine was confirmed. [0035]

Example 5 In Example 2, the soil was separated with a wax paper and then an anion exchange resin was added to separate the soil. It was confirmed that the green liquid almost disappeared and was captured by the ion exchange resin.

[0036]

According to the present invention, highly toxic and dangerous dioxins which are extremely difficult to remove can be decomposed into chlorine ions and carbon dioxide gas at low temperature and efficiently. A method for safely treating the used metal phthalocyanine derivative (complex) can be provided. It can decompose or significantly reduce dioxins generated in industrial waste, emissions, and incineration of household garbage, greatly contribute to the prevention of global environmental destruction, and contribute to human welfare and well-being.

[Brief description of the drawings]

FIG. 1 is an example of a metal phthalocyanine.

[Explanation of symbols]

 M is a metal atom. Y represents a substituent.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C02F 1/28 C07D 319/24 C07B 37/06 B09B 3/00 304K C07D 319/24 (72) Inventor E Kenji 3-15-1, Tsuneta, Ueda City, Nagano Prefecture Shinshu University Graduate School of Engineering (72) Inventor Hamada Shuhiro 3-15-1, Tsuneda, Ueda City, Nagano Prefecture Shinshu University, Department of Materials Development Chemistry ( 72) Inventor Toshihiro Hirai 3-15-1, Tsuneta, Ueda City, Nagano Prefecture F-term (Reference) 2E191 BA12 BB01 BC01 BC05 BD13 4D004 AA41 AB07 CA15 CA36 CA47 CB01 CB21 CC09 CC11 CC15 4D024 AA10 AB04 BA02 BA13 BC04 DB24 4D050 AA13 AB12 AB17 AB19 BB01 BB02 BB09 BB13 BB20 BC06 BC07 BD02 BD04 BD08 CA06 CA08 4H006 AA05 AC13 AC26 BA19 BA34 BE03 BE30 BE32 BE90

Claims (10)

[Claims] At least a solution containing a dioxin having two cyclic structures in one molecule or a solid to which the solution is attached is composed of a solution of a metal phthalocyanine derivative and a solution of an oxygen supply compound for generating an oxygen atom. An effective method for removing dioxins, characterized by adding a mixing action so as to make contact at the same time. 2. The metal atom of the metal phthalocyanine derivative is
Iron, cobalt, copper, nickel, manganese, osmium,
2. The method for removing dioxins according to claim 1, wherein the method is selected from one or more of titanium, molybdenum, and tungsten. 3. The metal phthalocyanine derivative wherein at least two of the chemical groups attached to the cyclic compound containing 6 carbon atoms located at the outermost periphery of the phthalocyanine are carboxyl groups or sulfonic acid groups. The effective method for removing dioxins according to the above. 4. A carboxyl group in which at least two of the chemical groups attached to the cyclic compound containing 6 carbon atoms located at the outermost periphery of phthalocyanine are carboxyl groups. The other residue is -H or another substituent, an alkyl group, a substituted alkyl group, a halogen group, a nitro group, an amino group, a thiocyanate group, a carbonyl chloride group, an aldehyde group, a carboxamide group, a nitrile group, a hydroxyl group, or an alkoxyl group , A metal composed of a chemical group selected from a phenoxyl group, a sulfonic acid group, a sulfonyl chloride group, a sulfonamide group, a thiol group, a chloromethyl group, an alkylsilicon group, a vinyl group, and an alkali salt of a sulfonic acid group 2. The method for removing dioxins according to claim 1, wherein the method is a phthalocyanine derivative. 5. The effective method for removing dioxins according to claim 1, wherein the solution capable of supplying oxygen atoms is a hydrogen peroxide solution. 6. A solution of an oxygen-supplying compound capable of supplying oxygen atoms, which is selected from the group consisting of peroxides of organic compounds and / or persulfate compounds, titanic oxides and perboric acids. The method for effectively removing dioxins according to claim 1, characterized in that: 7. Conditions for supplying oxygen are provided as:
The effective method for removing dioxins according to claim 1, wherein the mixing is performed in a liquid opposed to the electrolysis electrode that is energized. 8. A gas or flue gas cleaning liquid from an incinerator containing dioxins having at least two cyclic structures in one molecule, a soil heating gas or cleaning liquid around an incinerator, an incinerator gas or cleaning liquid, a soil cleaning liquid around an incinerator. Or a liquid containing deoxins selected from the incinerator disintegration cleaning liquid, soil around the incinerator containing water, diesel waste gas or cleaning liquid, exhaust gas or liquid discharged from chemical synthesis, or liquid-attached solid matter 2. The method for effectively removing dioxins according to claim 1, wherein: 9. A gas or flue gas cleaning liquid from an incinerator containing dioxins having at least two cyclic structures in one molecule, a soil heating gas or cleaning liquid around an incinerator, an incinerator gas or cleaning liquid, a soil cleaning liquid around an incinerator. Or incinerator dismantling cleaning liquid, soil around incinerator containing water, diesel waste gas or cleaning liquid, gas or liquid containing solid substances adhering to dioxins selected from exhaust gas or liquid discharged from chemical synthesis, metal A reaction vessel in which a phthalocyanine derivative is adsorbed on a fiber or a fibrous part having a large specific surface area or a liquid containing a metal phthalocyanine derivative, and mixed and contacted with an oxygen supply compound, or circulated under electrolysis conditions accompanied by oxygen generation conditions or An effective dioxin removal device, comprising: a reaction tank for mixing and contacting. 10. An oxygen supply for generating a metal phthalocyanine derivative and an oxygen atom to a solution containing at least a dioxin or a halogenated cyclic compound having two cyclic structures in one molecule or a solid substance to which the solution is attached. For the liquid after adding the mixing action so that the compound solution and the solution simultaneously contact, contact with the ion exchange resin or fiber,
Injection of ozone, injection of activated alumina or activated carbon,
A method for treating a liquid after decomposition treatment of dioxins, wherein one of the solidified combustion is selected and treated.