JP3370267B2 - Artificial zeolite made from a mixture of incinerated ash of urban garbage and glass and a method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a mixture obtained by adding glass to incineration ash of combustible waste such as municipal waste,
The present invention relates to an artificial zeolite produced by heat treatment in an alkaline solution and a method for producing the artificial zeolite.

[0002]

2. Description of the Related Art The conventional method for producing artificial zeolite mainly uses fly ash, which is produced when coal is burned in a thermal power plant, as its raw material, and its quality depends on the composition of the raw material coal. The quality was also limited. Further, a method of producing an artificial zeolite by heating the refuse incinerated ash in an aqueous sodium hydroxide solution has been proposed, but the produced artificial zeolite is limited to sodalite or hydroxysodalite, and there is a problem in quality. Yes (Journal of Japan Soil Fertilizer Society, Vol. 68, No. 4, 395-401 (1997)). On the other hand, glass wastes such as plate glass and bottles are also partially recycled, but the disposal of powder generated during crushing has become a problem.

In municipalities all over the country, when disposing of garbage, it is separated into several kinds of garbage and collected. For example, it is classified into burnable garbage, non-burnable garbage, oversized garbage, harmful garbage, etc., but the classification method differs depending on the municipality. Of these, burning garbage is generally incinerated at an incinerator, but the disposal of the incinerated ash is a problem. In non-burnable garbage, some of glass, metal and synthetic resin are recycled, but processing of glass such as bottles, metal such as cans, synthetic resin products such as trays and PET bottles is a problem. .

At present, the total amount of domestic waste discharged is 5
The amount exceeds 10 million tons, of which about 85% is incinerated, crushed, and recycled. But,
The amount of landfill including waste that is directly landfilled and incinerated ash from waste processing facilities is increasing year by year. Therefore, in each municipality, most of this incinerated ash, which has been increasing year by year, has been used for landfills or solidified with cement or the like and disposed of, but it has been a serious social problem such as difficulty in securing the disposal site. Has become.

[0005]

Because of the above problems, how to produce artificial zeolite of arbitrary quality, especially zeolite has a wide range of applications due to the difference in quality from natural zeolite to synthetic zeolite. Therefore, it is an issue to manufacture artificial zeolite of quality suitable for various uses. On the other hand, regarding artificial zeolite from incineration ash of combustible waste such as municipal waste, how to manufacture high quality artificial zeolite has been a problem, and its manufacturing method has been studied. Furthermore, since the effective use of glass waste such as plate glass and bottles is also desired, the development of new technology becomes an issue in order to recycle combustible waste such as municipal waste. There is.

[0006]

As a result of various studies to solve these problems, the present inventor has come to provide an artificial zeolite of any quality from incineration ash such as municipal waste. That is, it is an artificial zeolite produced by heating a mixture obtained by adding glass to incinerated ash of municipal waste, in an alkaline solution.

A second aspect of the present invention is a method for producing an artificial zeolite, characterized in that glass is added to the incineration ash of municipal waste and heat treatment is carried out in an alkaline solution. It is preferable that it is 20 to 100% by weight with respect to the incinerated ash in order to produce the artificial zeolite.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The artificial zeolite referred to in the present invention is a zeolite obtained by artificially converting incineration ash of combustible waste such as municipal waste by heat treatment in an alkaline solution. Therefore, its main component is hydroxysodalite, phillipsite, faujasite, etc., depending on the silica ratio of the raw material, that is, (ratio of the weight composition of SiO ₂ and Al ₂ O ₃ ) × 1.7. . Therefore, the present invention, by utilizing the fact that the components of the artificial zeolite obtained by the silica content is different,
It is intended to produce a desired main component artificial zeolite. In addition to the main component, a small amount of other components, such as zeolite A, may be included, and as a non-zeolite component, that is, unburned carbon, iron, other impurities, and intermediate products up to zeolite as a non-zeolitic component. And so on.

The flammable waste referred to in the present invention means flammable wastes generated by various human activities, and may be general wastes or industrial wastes. Examples of the industrial waste include wood produced in civil engineering and construction work, combustible waste such as paper, and sludge produced in the paper manufacturing process. In addition, the municipal waste referred to in the present invention means, among the combustible wastes, raw wastes and other combustible wastes produced at home as general wastes.

The glass in the present invention means silicate glass, and examples thereof include silicate glass, soda lime glass, potassium lime glass, lead glass, barium glass and borosilicate glass. Further, as the soda-lime glass, plate glass, bottle glass, crown glass and the like can be exemplified. Therefore, in the present invention, plate glass, bottle glass, tableware glass, household glass,
Wastes after using electrical glass, lighting glass, physicochemical glass, medical glass, optical glass, etc. can be used. Furthermore, it also includes glass powder generated when the glass as waste is crushed to be recovered. In order to carry out the present invention, since glass is added to and mixed with combustible waste such as municipal waste,
A powdery form with small particles is preferable.

The amount of glass added in the present invention depends on the silica content of the raw materials used and the quality of the artificial zeolite to be produced. That is, using the incineration ash of municipal waste that is a general waste as a raw material, an artificial zeolite obtained by performing a heat treatment in an alkaline solution without adding glass,
It is hydroxy sodalite, its pore size is small,
It has a large cation exchange capacity but does not have a deodorizing effect. By adding glass in an amount of 20% by weight or more to the incineration ash of combustible waste such as municipal waste or the solid content of combustible waste such as municipal waste, the silica content becomes 2 or more, resulting in artificial The proportion of phillipsite in the zeolite increases. Artificial zeolite when glass is added to the incineration ash of combustible waste such as municipal waste or solid content of combustible waste such as municipal waste in an amount of 40 to 50% by weight and a silica content ratio of 2.5 or more. Most of them will be Philippe sites. Furthermore, if the silica content is increased to 4 or more by increasing the amount of glass added to 60% by weight or more, the ratio of faujasite in the artificial zeolite increases.

The incineration ash of municipal waste referred to in the present invention is ash produced when incinerating combustible waste such as municipal waste in an incinerator, and is a fine fly ash (fly ash) attached to a flue. ) And incinerator ash stored at the bottom of the incinerator. In the case of incineration ash of municipal waste, the production ratio of fly ash and incinerator ash is about 1: 4. The components of this incineration ash are
In the case of municipal waste, the silicic acid content is 18 to ₃ as SiO ₂ .
0%, and the alumina content is 10 to 15 as Al ₂ O _3.
%. Therefore, at this time, the silicate ratio is about 1.5, and it is one of the objects of the present invention to supplement the silicic acid content by adding glass in order to improve the quality of the artificial zeolite.

The mixture obtained by adding the glass to the incineration ash referred to in the present invention means not only the mixture obtained by directly adding the glass to the produced incineration ash, but also the glass obtained during the incineration of combustible wastes. A mixture of glass was added to the incineration ash produced by spraying the powder, and the glass was added before incinerating the combustible waste, the mixture was incinerated, and the glass was added to the incinerator ash. A mixture.

The alkaline solution referred to in the present invention means an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide, and the concentration of the alkali is 1 to 5 N,
It is preferable for carrying out the present invention. As for the heat treatment, if the temperature is 80 ° C. or higher, there is no problem in carrying out the present invention, but if the temperature is 100 ° C. or higher, a pressure vessel is required for the reaction, so the temperature is usually 90 to 95 ° C. It is preferable to maintain it in order to promote the reaction. The treatment time varies depending on the composition of the raw materials and the quality of the manufactured artificial zeolite, but may take at least 5 hours, usually about 24 hours, and in some cases 90 hours or more.

[0015]

The outline of the present invention will be described. If the incineration ash of combustible waste such as municipal waste is fly ash, the mixture obtained by adding glass as it is can be heat-treated in an alkaline solution. If the incinerator ash is an incinerator ash, it has to be crushed because it has large particles. The particle size after crushing is 20 to 1
It is desirable to set it to 00 μm.
The mixture obtained by adding the glass powder is heat-treated in an alkaline solution. As this alkaline solution, a 1-5 normal sodium hydroxide aqueous solution is added, and the mixture is heated to 80 to 90 ° C. and reacted. At this time, an appropriate amount of glass powder is added according to the silica content of the incineration ash used. That is, when the silicate ratio is 1.5 or less, the produced artificial zeolite has a large amount of hydroxysodalite and has a small pore size of 3 to 5Å and is of low quality, so that the silicate ratio is 2.0 to
When the glass powder is added so as to be 2.5, there are many phillipsites and the pore size is 5Å or more, so that a high quality product is obtained. Further increase the glass powder, the silica content ratio is 3.
If it exceeds 0, faujasite can be obtained. Next, details of the present invention will be described based on examples, but the gist of the present invention is not limited to these examples.

(Example 1) Of the refuse incinerated ash from general households, fly ash was collected, washed with water, and 20 g of a sample from which soluble components were removed was placed in a 1-liter Erlenmeyer flask. It was taken, and 10 g of glass powder was added thereto and mixed well. To this mixture was added 240 ml of a 3.5 M sodium hydroxide aqueous solution. A reflux condenser was attached to the Erlenmeyer flask, and the slurry mixture was heated on a hot plate at 80 to 90 ° C. and reacted for 60 hours. After the reaction, excess sodium hydroxide was washed out with water to remove the sodium hydroxide.
It was washed with a 5M magnesium chloride solution, washed again with water, and then air-dried to obtain a powder. From the X-ray diffraction pattern, it was confirmed that phillipsite was produced as artificial zeolite.

(Example 2) Of the incinerated ash from general households, fly ash was collected, washed with water, and 20 g of the sample from which soluble components had been removed was placed in a 1-liter Erlenmeyer flask. 20 g of glass powder was added to this, and mixed well. To this mixture was added 280 ml of a 3.5 M aqueous sodium hydroxide solution. A reflux condenser was attached to the Erlenmeyer flask, and the slurry mixture was heated on a hot plate at 80 to 90 ° C. and reacted for 60 hours. After the reaction, excess sodium hydroxide was washed out with water to remove the sodium hydroxide.
It was washed with a 5M magnesium chloride solution, washed again with water, and then air-dried to obtain a powder. From the X-ray diffraction pattern, it was confirmed that faujasite was produced as an artificial zeolite.

(Example 3) 10% by weight of glass powder was mixed well with combustible waste from general households, incinerated, and then fly ash was collected and washed with water. Then, 20 g of the sample from which the soluble components were removed was placed in a 1-liter Erlenmeyer flask, and 160 ml of a 3.5 M aqueous sodium hydroxide solution was added thereto. A reflux condenser was attached to the Erlenmeyer flask, and the slurry mixture was stirred on a hot plate.
It heated at 0-90 degreeC and was made to react for 60 hours. After the reaction, excess sodium hydroxide was washed off with water, washed with a 0.5 M magnesium chloride solution, washed again with water, and then air-dried to obtain a powder. From the X-ray diffraction pattern, it was confirmed that phillipsite was produced as artificial zeolite.

Comparative Example 1 20 g of coal ash (fly ash) was sampled and placed in a 1 liter Erlenmeyer flask, and 240 ml of a 3.5 M aqueous sodium hydroxide solution was added. A reflux condenser was attached to the Erlenmeyer flask, and the slurry mixture was heated on a hot plate at 80 to 90 ° C. and reacted for 60 hours. After the reaction, excess sodium hydroxide was washed off with water, washed with a 0.5 M magnesium chloride solution, washed again with water, and then air-dried to obtain a powder. From the X-ray diffraction pattern, it was confirmed that phillipsite was produced as artificial zeolite.

(Comparative Example 2) Of the refuse incinerated ash from general households, fly ash was collected, washed with water, and 20 g of the sample from which soluble components had been removed was placed in a 1-liter Erlenmeyer flask. 280m with a 3.5M aqueous sodium hydroxide solution
1 was added. A reflux condenser was attached to the Erlenmeyer flask, and the mixture in a slurry state was mixed on a hot plate at 80 to 9
The mixture was heated at 0 ° C. and reacted for 60 hours. After the reaction, excess sodium hydroxide was washed off with water, washed with a 0.5 M magnesium chloride solution, washed again with water, and then air-dried to obtain a powder. From the X-ray diffraction pattern, it was confirmed that hydroxysodalite was produced as an artificial zeolite.

[0021]

EFFECT OF THE INVENTION Zeolites have a wide range of uses due to the difference in quality from natural zeolites to synthetic zeolites. Moreover, the artificial zeolite can be manufactured at a lower cost than the synthetic zeolite, and the quality can be changed depending on the raw material used, so that it is possible to manufacture the zeolite having a quality suitable for various uses. . However, the quality of the artificial zeolite from the incinerated ash depends on the components of the incinerated ash as the raw material, and there has been a problem how to produce the artificial zeolite of any quality. In particular, when the incineration ash of combustible waste such as municipal waste was used as a raw material, a high quality artificial zeolite could not be obtained. On the other hand, glass wastes such as plate glass and bottles are also partially recycled, but the problem is the disposal of powder generated during crushing.

The present invention is to produce artificial zeolite by adding glass to the incinerated ash obtained by incinerating combustible waste such as municipal waste and heating the mixture with an alkaline solution. Therefore, an artificial zeolite having a desired quality can be produced by changing the amount of glass added based on the composition of the incinerated ash, particularly the silicate ratio. Further, in combustible waste such as municipal waste, glass can be added before incineration to obtain incinerated ash having a desired silica content. Therefore, the present invention aims to effectively utilize incineration ash of combustible waste and glass waste, and the obtained artificial zeolite is a soil conditioner,
It can be widely used as a cation exchanger and a deodorant.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C01B 39/02

Claims (3)

(57) [Claims] 1. An artificial zeolite produced by subjecting a mixture obtained by adding glass to incinerated ash of municipal waste to heat treatment in an alkaline solution. 2. A method for producing an artificial zeolite, which comprises adding glass to incinerated ash of municipal waste and heat-treating it in an alkaline solution. 3. The amount of the glass according to claim 2 added is 20 to 100% by weight based on the incineration ash of municipal waste.
Method for producing artificial zeolite.