JP4172907B2 - Effective removal method of dioxins - Google Patents

Description

[0001]
[Industrial application fields]
The present invention also 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, which normally recovers polluted materials that are a problem in society, which is a serious social problem.
[0002]
[Prior 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 factories that tend to generate dioxins are shut down and discarded , and even the surrounding soil is confined in huge rubber sheets and concrete tanks. The negative side of modern science appears, and it is difficult to deal with it, and if the amount is administratively charged, there is little impact, and there is no choice but to proceed.
[0003]
The former is burned at very high temperatures, Toka suppress the occurrence, Toka reduced by re-ultra-high-temperature treated through in the plasma, in an attempt to reduce, and both also of the consuming enormous energy, more Implementation was difficult. If done at public expense, it will make the economy even more exhausted. Looking only at the scientific direction, it was the direction of ultra-high temperature treatment or similar. Including the equipment, it remains unresolved as a fatal problem of being extremely expensive.
[0004]
[Problems to be solved by the invention]
As a result of intensive studies aimed at solving the above-mentioned unsolved problems and providing a defect-free method with enormous costs such as ultra-high temperature treatment, the inventors have reached the following invention. . In particular, at low temperatures, relatively inexpensive, to provide a removal method, reduction methods friendly effective dioxins in the earth, to deal with such urgent problems, pulls greatly contributes to welfare and well-being of mankind For the purpose.
[0005]
[Means for Solving the Problems]
The present invention, a social large problems of the above, if there among the trend through to avoid a lot of people, for mankind to protect the global environment, from the front, received in the true 摯, one in which was finally achieved . The outline is as follows.
[0006]
At least 1 for the dioxins with two intramolecular cyclic structure, the following eight two or more chemical groups that are included with cyclic compounds containing 6 carbons located phthalocyanine outermost periphery be sodium carboxylate An effective dioxin characterized by adding a mixing action so that an aqueous solution of a metal phthalocyanine derivative whose other residue is -H and at least 1000 times the amount of hydrogen peroxide of the metal phthalocyanine derivative are in contact with each other simultaneously This is a method of removing the kind.
[0007]
In the above, the metal atom of the metal phthalocyanine derivative is an effective method for removing dioxins, which is a material selected from one or more of iron, cobalt, copper, nickel, manganese, osmium, titanium, molybdenum, and tungsten. .
[0008]
The dioxins having two ring structures in at least one molecule are contained in any one of gas from an incinerator, soil around the incinerator, waste gas from diesel, and exhaust gas accompanying chemical synthesis. This is a method of removing the kind.
[0009]
The dioxins having two ring structures in at least one molecule are any one of incinerator flue gas cleaning liquid, incinerator surrounding soil cleaning liquid, incinerator demolition cleaning liquid, diesel waste gas cleaning liquid, and exhaust gas cleaning liquid accompanying chemical synthesis. It is the removal method of dioxins characterized by being contained in this.
[0010]
In addition above, with respect to the liquid after the addition of mixing action to simultaneously contact, contact with an ion exchange resin or fiber, blowing ozone, characterized that you be on of activated alumina or activated carbon, or solidified combustion This is a method for treating a solution after the decomposition treatment of dioxins.
[0011]
Until now, the present inventor has been intensively researching for many years paying attention to the usefulness of metal phthalocyanine derivatives. Finally, we have already found that substances that are not dioxins , such as 2,4,5 trichlorophenol, decompose into chlorine ions and carbon dioxide. On the other hand, it is known that dioxins are easily generated when a polymer containing chlorine such as polyvinyl chloride and polyvinylidene chloride , which are useful polymers, is incinerated at a low temperature.
[0012]
Dioxins are polymers that contain chlorine (included in the molecule or as an additive) for purposes such as stabilization, heat resistance, and flame resistance in addition to useful polymers such as polyvinyl chloride and polyvinylidene chloride. the butterflies amount generated by incineration at low temperature, 2,3,7, 8-tetrachloro-dibenzo -p- least two, such as dioxin ring against tightly bound dioxins, into effective removal The challenge, as well as its characteristics, was unknown. In particular 2,3,7, 8 against tetrachloro-dibenzo -p- dioxin of at least two dioxin ring tightly bound, such as (dioxin) occurs, it challenges less effective removal methods and effects are completely It was unknown. Note the called dioxins, for example, 2, all groups of 3, 7, 8 is not even Mosu it is also the meaning contained not necessarily the chlorine. Similarly, at least hexachlorophene having two cyclic structures in one molecule also belongs to the class.
[0013]
With respect to the phthalocyanine described below, written and edited by Hiroshi Shirai Fang (the present inventors), Nagao Kobayashi "phthalocyanine - Chemistry and function -" (Ltd. IPC issue: Date of issue 1997 February 28, 2011: all 338 pages) For more information on Are listed. The contents of the description in the present invention are based on the technical level of the industry at the level of this document. Therefore, the complex chemical structure of phthalocyanine is not necessary to be described again here.
[0014]
The metal phthalocyanine derivative used in the present invention is also called a phthalocyanine metal complex, which serves as an intrinsic catalyst for the purpose here. For example, it was invented that 90% of dioxin was surprisingly decomposed in only 10 minutes at room temperature by adding and mixing hydrogen peroxide to dioxin. That is, it was also confirmed that it was decomposed into chlorine ions and carbon dioxide.
[0015]
The solution will generally be poorly soluble and stable colored colorful. When it is necessary to remove it after the reaction, it is easy to physically separate it, but it is easy to dry the dissolved matter and burn it, to adsorb it on activated alumina or activated carbon, to blow in ozone and decompose A method or a method supplemented with an anion exchange resin is preferably used. This is unique to the present invention.
[0016]
Since the metal phthalocyanine derivative is a catalyst, it can be used for a very long time if the oxygen supply compound is replenished. On the other hand, for example, a metal phthalocyanine derivative adsorbed on an acrylic fiber that is resistant to oxidation or reacted with a substance such as hydrogen peroxide does not appear in the reaction solution in this way. Therefore, even if it comes out very little, it is preferably used. This is because it can be used any number of times. A method of increasing the contact area such as fiber, cotton, net 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 preferably used in the present invention. The fiber forming characteristics and polymerization of metal phthalocyanine derivatives (complexes) are described in the above-mentioned documents, and it has been found that they can be combined effectively.
[0017]
Here, it was discovered that under the same conditions, potassium hydrogen persulfate, t-butyl hydroperoxide and the like can be used in addition to hydrogen peroxide. That is, it is well known as a peroxide-based polymerization catalyst for vinyl compounds that can generate (supply) oxygen atoms. Here, it is clear that there is no need to enumerate those compounds one by one using paper. In particular, hydrogen peroxide that is generally well-priced in terms of price, stability, handleability, and supply system is preferred.
[0018]
As occurring an oxidizing effect, under electrolysis conditions of generating oxygen, surprisingly was tried, effectively dioxin to give a knowledge decompose. This can be presumed to have resulted from the strong catalytic action of metal phthalocyanine derivatives. In any case, it shows the high industrial utility and breadth of the present invention.
[0019]
Further, 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. Particularly preferred are iron and manganese.
[0020]
In addition above, as is clear from the structural formula of Figure 1, the metal phthalocyanine is two or more months carboxyl group or a sulfonic acid group of chemical groups that are included with cyclic compounds containing 6 carbons located phthalocyanine outermost A derivative is preferred.
[0021]
Further, in the above, for example, in FIG. 1, M is a metal atom, and Y represents a substituent, but two of the chemical groups attached to the cyclic compound containing 6 carbons located on the outermost periphery of phthalocyanine. or it is mosquitoes carboxyl group, the other residues are -H or another substituent, an alkyl group, a substituted alkyl group, a halogen group, a nitro group, an amino group, a thiocyanate group, carbonyl chloride group, aldehyde group, carboxyl amide group, a nitrile group, a hydroxyl group, an alkoxyl group, selected from phenoxyl group, a sulfonic acid group, sulfonyl chloride group, sulfonamide group, a thiol group, a chloromethyl group, an alkyl silicon group, vinyl group, alkali salts of sulphonic acid groups I want. Or it is preferable that it is a metal phthalocyanine derivative comprised by the group beyond it. In particular, a carboxylic acid group, a salt thereof, and a sulfonic acid group are preferable.
[0022]
The object to be treated under the above method is a gas or flue gas cleaning liquid containing at least one dioxin having two cyclic structures in one molecule, a soil heating gas or cleaning liquid around the incinerator, an incinerator gas or cleaning liquid, Incinerator surrounding soil cleaning liquid, or incinerator dismantling cleaning liquid, soil surrounding incinerator containing moisture, diesel waste gas or cleaning liquid, gas or liquid adhering solids containing dioxins selected from chemical synthesis or exhaust liquid A dioxin removal method comprising any of the above is preferred. Waste gas and exhaust gas containing dioxins are supplemented or brought into contact with each other by chemical engineering techniques such as a shower tower, a spray tower, and a bubble tower.
[0023]
Further, in the above, gas or flue gas cleaning liquid containing dioxins having two ring structures in at least one molecule, incinerator surrounding soil heating gas or cleaning liquid, incinerator gas or cleaning liquid, incinerator peripheral soil cleaning liquid, Or incinerator dismantling cleaning liquid, soil around incinerator containing water, diesel waste gas or cleaning liquid, exhaust gas or chemical adhering gas or liquid adhering solids introduction part selected from chemical synthesis, metal phthalocyanine A reaction vessel in which a derivative is adsorbed on a fiber or a part of a fiber having a large specific surface area, a liquid containing a metal phthalocyanine derivative or a liquid containing particles, and an oxygen supply compound, or a hydrogen peroxide generation condition A dioxin removal device consisting of a reaction vessel that is circulated or mixed and contacted under electrolysis conditions. It was found to be effective. In particular, a modified electrolysis method capable of decomposing dioxins is notable as a new method because it does not carry or handle oxygen supply substances. The modified electrolysis method is, for example, a method in which the surface of the electrode is covered with a metal phthalocyanine derivative.
[0024]
Since this catalyst preferably has a large contact area, that is, a large specific surface area, such a method is adopted. Examples of the dioxins having at least two cyclic structures in one molecule include all of various halogens or all partially substituted dioxins, and hexachlorophene having two cyclic structures in one molecule. In this case, if there is an extremely high amount, it is included in the category of the invention. This is because dioxins are surprisingly highly toxic even in trace amounts. Even if a much larger amount of one halogen-substituted cyclic compound is not contained in one molecule, that is, one halogen-substituted cyclic compound is contained in one molecule, the present invention is very effective because they are decomposed.
[0025]
In the present invention, it should be noted that there is no need for processing at ultra-high temperatures 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 has been treated at ultra-high temperatures, it is further treated with the method of the present invention to ensure that the discharged gas can be reliably and relieved, so that trace amounts of dioxins can be converted into chlorine ions and carbon dioxide. It can also be used for disassembling combinations. Resulting no color chloride ion caustic soda or caustic mosquito Li, can be easily neutralized with calcium hydroxide, it is preferable to perform the treatment. It is effective to combine with the above prescription.
【Example】
[0026]
Although the Example concerning this invention is shown below, the effectiveness of this invention is not limitedly interpreted by these but rather brings about the application development.
[0027]
(Example 1)
400 ng / ml is added to a soil mixed aqueous solution containing 10 ng / ml of dioxin, iron phthalocyanine complex (mixture of 1 to 8 substituents as sodium carboxylate) as a catalyst, and the blue soil mixed solution is added. Then, 1000 times as much hydrogen peroxide as the catalyst was added and mixed. After 10 minutes, 90% of the dioxin was decomposed.
[0028]
(Example 2)
The dioxin in the soil mixed aqueous solution containing 1 ng / ml, manganese phthalocyanine complex (sulfonic acid substituents are 1-4 mixture) as a catalyst as the catalyst, the green liquid added 400 ng / ml, the catalyst 1000 Double hydrogen peroxide was added and mixed. Ten minutes later, 88% of the dioxin was decomposed.
[0029]
Example 3
In Example 1, the soil was separated with a filter paper, dried, and then all burned to confirm the decomposition of phthalocyanine.
[0030]
Example 4
In Example 1, after separating the soil with a filter paper, ozone gas was blown in . The green color disappeared and the decomposition of phthalocyanine was confirmed.
[0031]
(Example 5)
In Example 2, after separating the soil with a filter paper, an anion exchange resin was added and separated. It was confirmed that the green liquid almost disappeared and was captured by the ion exchange resin.
[0032]
【The invention's effect】
Very toxic and dangerous dioxins that are extremely difficult to remove can be efficiently decomposed at low temperatures into chlorine ions and carbon dioxide gas at low cost. A method for safely treating the metal phthalocyanine derivative (complex) used could be provided. Industrial waste, emissions and can decompose and remove or significantly reduce the dioxins generated in the incineration of household waste, can greatly contribute to the prevention of global environmental destruction, it can contribute to the welfare and well-being of mankind.
[Brief description of the drawings]
FIG. 1 is an example of metal phthalocyanine.
[Explanation of symbols]
M is a metal atom. Y represents a substituent.

Claims (5)

At least 1 for the dioxins with two intramolecular cyclic structure, the following eight two or more chemical groups that are included with cyclic compounds containing 6 carbons located phthalocyanine outermost periphery be sodium carboxylate An effective dioxin characterized by adding a mixing action so that an aqueous solution of a metal phthalocyanine derivative whose other residue is -H and at least 1000 times the amount of hydrogen peroxide of the metal phthalocyanine derivative are in contact with each other simultaneously Removal method. Metal atoms of the metal phthalocyanine derivative, iron, cobalt, copper, nickel, manganese, osmium, titanium, molybdenum, effective according to claim 1, characterized in that selected from one or more of tungsten To remove dioxins. Dioxins with two annular structure in said at least one molecule, gas from the incinerator, the incinerator surrounding soil, characterized in that it is included in any exhaust gas, the associated Diesel exhaust gases, chemical synthesis The effective dioxin removal method according to claim 1. The dioxins having two ring structures in at least one molecule are any one of incinerator flue gas cleaning liquid, incinerator surrounding soil cleaning liquid, incinerator demolition cleaning liquid, diesel waste gas cleaning liquid, and exhaust gas cleaning liquid accompanying chemical synthesis. effective dioxin removing method of claim 1, wherein the included characterized Rukoto to or. Features to liquid after the addition of mixing action to simultaneously contact according to claim 1, contacting the ion exchange resin or fiber, blowing ozone, and this for introduction of activated alumina or activated carbon, or solidified combustion The processing method of the solution after the decomposition treatment of dioxins.

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