JP3038673B2 - Ceramic sintered body and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a ceramic sintered product that is recycled using raw materials containing harmful volatile components, especially dioxins, such as incinerated municipal garbage, which has recently been regarded as difficult to improve the environment. At the time of manufacturing, it relates to the technology to make these harmful components harmless, especially for public hygiene.
Broadly relates to new technologies required for the public interest.

[0002]

2. Description of the Related Art Many municipalities and laboratories have developed methods for neutralizing harmful volatile components generated during incineration treatment of municipal garbage incineration ash or removing dioxin particles using a bag filter. Almost no development has been made to reuse incinerated ash. When refired at a high temperature as a ceramic sintered body, the elution of heavy metals is reduced by a factor of ten to make it harmless, but these manufacturing technologies have been published as patents by the inventor of the present invention. Fairness 7-88
No. 248 is the only public technology. However, when producing a ceramic sintered body using these techniques, harmful gases such as dioxins volatilized in the firing process are contained in the exhaust gas of the fired ash. Not only requires a large capital investment, but the treated products are again produced as hazardous wastes, and as such harms public health, so further detoxification is required,
The processing method has not been developed.

[0003]

[Problems to be solved by the invention]
When the material containing synthetic resin material is incinerated, the temperature rises locally due to self-heating, and the consumption of furnace materials and equipment becomes remarkable. Is done. By adding a neutralizing agent such as slaked lime, chlorine is generated as calcium chloride and sulfur is mixed into incinerated ash as calcium sulfate. Dioxins are collected and removed by a bag filter while controlling the exhaust gas to an appropriate temperature. Dioxin is highly toxic as an organochlorine compound, and is said to be adsorbed on unburned carbon and remain in the discharged incineration ash. These dioxins do not regenerate at a temperature of 250 ° C. or lower, but regenerate when residual carbon starts burning at 300 to 470 ° C. The present invention is to create a method and a product for detoxifying and recycling such residual harmful substances to recycle them into valuable and valuable materials.
An object of the present invention is to provide a novel ceramic sintered body and a method for manufacturing the same.

[0004]

Means for Solving the Problems To solve the above problems,
Therefore, the present invention has developed the following means. That is, the first of the present invention
Eyes are characterized by chlorine compounds and / or dioxin compounds
65 to 95 [% by weight] containing a substance and high silica
Otaniishi 5 or more whose main component is clinoptilolite 35
The following [% by weight] are contained uniformly and
It is molded and fired to the desired shape.
The volatile chlorine compound and / or dioxin compound
Chlorine in the material combines with the sodium component in the Otani stone,
It is re-adsorbed in the pores of the Otani stone as sodium
Ceramic sintered body. Next,
The second feature of Ming is that it contains raw materials containing harmful chlorine components, such as
In the case of municipal waste incineration ash, powder particle size 500 [μm] or less
The amount of total chlorine contained in the incinerated ash
At least twice the weight of
Add soil material and sintering adjustment material, add water if necessary,
Adjusted to a uniform composition by kneading and molded into the desired shape
After that, it is dried at a temperature of 250 ° C. or less, and is dried at a temperature of 1000 ° C. or less.
Baking in the temperature range below 1200 [° C]
Contains dioxins adsorbed on unburned carbon in ash
Volatilizes harmful chlorine compounds and removes the chlorine components
To sodium chloride, an ion exchange component of
Thorium is re-adsorbed in the pores of the Otani stone, rendering it harmless
A method for producing a ceramic sintered body
It is. More specifically, the present invention is inspired by the property of dioxin disappearing in only a few seconds at a temperature of 800 ° C. or more and its phenomenon, and is inspired by the phenomenon. That is, the feature as the means is a ceramic sintered body containing a composition containing a chlorine compound and dioxins such as municipal garbage incineration ash and the like, and Otani stone mainly composed of high silica type clinoptilolite. Is 5 [%] or more and 35
[%] It is a ceramic sintered body obtained by adjusting the composition so as to be included in the following range, molding, and firing. In addition, the feature of the production method is that Oya stone crushed to a particle size of 500 [μm] or less from a raw material containing a harmful chlorine component such as municipal waste incineration ash is at least twice as much as the total chlorine content in the incineration ash. After mixing and adding a clay material and a sintering adjustment material as molding aids to adjust the composition, forming the composition into a desired shape, drying at a temperature of 250 ° C. or less,
This is a method for producing a ceramic sintered body that is fired in the range of [° C.] to 1200 [° C.]. In addition, after the dioxin adsorbed on the unburned carbon is heated and heated in the sintered body composition, the substance that has volatilized with the combustion of carbon is re-adsorbed by the zeolitic Oyaishi and carried over to the high temperature region, A means of reacting with sodium component, which is an ion exchange component of Otani stone, to render it harmless as salt is used.

[0005]

DETAILED DESCRIPTION OF THE INVENTION Otani stone is a high silica clinoptilolite mineral of (Na ₂ , K ₂ ) O, Al ₂ O ₃ . 10S
iO ₂ . A zeolite having a chemical composition of 8H ₂ O;
Due to its fine pores of 10 to 10 [Å], it exhibits high adsorption capacity for various gas components and is widely used as a deodorant. In addition, it has a large amount of chemically bonded water,
From 00 [° C.], the release of bound water occurs continuously, and 750
It becomes amorphous between [° C.] and 900 [° C.]. In addition, with respect to the adsorbing action, there is an action of adsorbing the surrounding gas together with the release of the bound water and exerting the maximum adsorbing ability at around 600 [° C.]. Furthermore, it has been developed by the present inventors in Japanese Patent Application No. 5-230633 that the pores of several angstroms possessed by Oya stone become amorphous while adsorbing gas molecules and are sintered. The sodium and potassium components contained in Otaniishi have a high reaction activity as known as ion-exchangeable components, and easily react with acidic gases such as dioxin to produce sodium chloride (NaCl). It is possible.

An example of a chemical component contained in municipal waste incineration ash is as follows. loss 17 [%] (residual carbon 11 [%]), SiO ₂ 38 [%], Al ₂ O ₃ 1
3 [%], CaO 18 [%], Fe ₂ O ₂ 6 [%],
MgO 3 [%], K ₂ O 2 [%], Na ₂ O 3 [%]
In particular, the volatile harmful gas component is Cl ₂ 0.4
[%], SO ₄ 0.6 [%], and a mixture of unburned carbon to which these dioxins are adsorbed as a ceramic sintered body composition starts to be burned by oxygen in a heating and heating process. When the temperature exceeds 350 [° C.], dioxin is regenerated and released in the exhaust gas of the firing furnace.
When it is re-adsorbed by the Oya stone having fine pores of / 5, it can move to the high temperature side without being volatilized and released. Even if released in a temperature range of 800 ° C. or higher, the toxicity as dioxin is already lost, but the present invention seeks a further detoxification direction by a chemical reaction. That, Na ₂ O component in Oya 3 to 4 [%]
When contained and adsorb chlorine gas, 2Na ₂ O + 2C
It is estimated that a reaction of l ₂ → 4NaCl + O ₂ occurs,
When these are theoretically calculated, Na ₂ O can react and fix about 1.34 [%] of Cl ₂ per 1.0 [%]. Therefore, the compounding ratio of Oya stone is sufficient from 5 [%] to 35 [%]. The NaCl produced by the reaction theoretically starts to evaporate as salt vapor when it exceeds the melting point of 776 [° C.], but does not exceed 1100 [° C.] when it is compression-molded at a high pressure as a ceramic sintered body. Was not easily volatilized. In particular, Oya stone is about 80
[%] Activity SiO ₂ to generate when amorphization beyond 900 [° C.] include close SiO ₂ to react with the SiO ₂ · Al ₂ O _3, known as the technical theory of Salt-grilled tile 1 _{.0Na 2 O, 0.5~1.0Al 2 O 3} , 2.8~
A glass having a composition of 5.5 SiO ₂ is produced. The detoxifying effect on dioxins is measured by sampling from exhaust gas in garbage incinerators, etc.
Since it is indicated by an extremely small measured value of 0.5 ng / Nm ^3, it is difficult to make a sufficient judgment for measuring the effect of the present invention. Vinyl resin was mixed as powder with Oya stone powder and baked at 1000 ° C.
The effect was determined based on the generation of Cl.

(Example) (1) The raw material is a sample of 100 [mm] × 50 [mm] 10 [mm] using a powder obtained by pulverizing Oya stone to a particle size of 500 [μm] or less , vinyl chloride resin powder and clay. ]
Under pressure. (2) Mixing ratio 70% of Oya stone, 10% of vinyl chloride resin, 20% of clay 3) Baking is performed using a gas furnace at a heating rate of 10 ° C./minute at 1000 ° C. [° C]. (4) Baking of NaCl by X-ray Diffraction The baked sample was finely pulverized into a powder and subjected to X-ray diffraction, whereby clear NaCl crystals were confirmed. (5) Observation by boiling test When the calcined sample was put into clear water with a particle size of 0.5 [mm] to 1.0 [mm] and boiled, a large amount of bubbles were generated from the particle surface and gas was introduced into the zeolite pores. It was confirmed that the components were sintered while being encapsulated.

[0008]

1) According to the present invention, unresolved chlorine gas, especially dioxins, which has not been solved in order to recycle municipal waste incineration ash as a ceramic sintered body in the ceramics field, is subjected to a rational detoxification treatment. Will be able to do it. 2) In the prior art, harmful gas containing dioxin or chlorine is contained in the exhaust gas generated in the treatment process, so that the treatment required a large equipment cost.
According to the present invention, the cost of equipment is very low because the exhaust gas is also harmless. More specifically,
In the present invention, dioxins which have been a major problem
Detoxification can be achieved, and ceramics such as ceramics and bricks
Municipal waste incineration ash as raw material
One of them is to remove chlorine from dioxins in it.
To make them harmless.
Minutes are the original equipment for producing ceramic products.
Therefore, the cost of detoxifying dioxins is higher than before.
Enormous economic benefits can be obtained
Will be.

Continuation of the front page (56) References JP-A-7-82013 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C04B 35/00 B09B 3/00

Claims (2)

(57) [Claims] 1. A composition containing a chlorine compound and / or a dioxin compound in a range of 65 to 95 [% by weight] and a high silica type clinoptilolite in a proportion of 5 to 3
5% by weight [% by weight] is uniformly contained, and
Molded into a desired shape, which is fired when the firing one
Chlorinated volatile compounds and / or dioxins
The chlorine in the compound combines with the sodium component in the Otani stone,
As sodium chloride, it is re-adsorbed in the pores of the Otani stone.
Ceramic sintered body which is a sintered body which is. 2. Oya stone ground to a raw material containing a harmful chlorine component, for example, municipal garbage incinerated ash, having a powder particle size of 500 [μm] or less, is converted into at least 2 parts by weight of the total chlorine amount contained in the incinerated ash. More than twice, a clay material and a sintering adjusting material are added as molding aids, and if necessary, water is added and kneaded to adjust the composition to a uniform composition.
Dry at a temperature of not more than [° C] and not less than 1000 [° C] and not more than 120
0 [° C.] then calcined at a temperature ranging non of the refuse in the ash
Harmful salts containing dioxins adsorbed on fuel carbon
Volatilizes elemental compounds and converts the chlorine component into ions
Sodium chloride combined with sodium as an exchange component
A method for producing a ceramic sintered body , wherein the porcelain is re-adsorbed in pores of the Oya stone to render it harmless .