JP3476123B2 - Method for producing artificial zeolite from combustion ash of solid waste fuel - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention heat-treats combustion ash of refuse solidified fuel and a mixture of combustion ash of refuse solidified fuel with at least one or two kinds of glass and diatomaceous earth in an alkaline solution. The present invention relates to a method for producing 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 Society for Soil Fertilizers, 68th)
Volume 4, pages 395-401 (1997)).

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 dust is generally incinerated at an incinerator, but a part of it is used as a solidified fuel (RDF) for heating and fuel for power generation. Further, in the case of non-burnable refuse, glass wastes such as plate glass and bottles are also partially recycled, but the treatment of powder generated during the production of cullet poses 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.

In order to effectively use combustible waste such as municipal waste, it is possible to use it by converting it into fuel. One of them is waste solidified fuel (RDF: REFUSE D).
ERIVED FUEL). However, in the present circumstances, only limited methods such as concrete aggregate have been considered as methods of utilizing combustion ash after burning this solidified waste fuel, and the above problems have not been solved yet.

[0006]

Because of the above-mentioned problems, how to produce artificial zeolite of any quality in artificial zeolite from coal ash, especially zeolite is natural zeolite or synthetic zeolite. Since it has a wide range of uses due to differences in quality, it is an issue to manufacture artificial zeolite of a quality suitable for each use.

On the other hand, in the case of 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, it is desired to effectively use flat glass, glass waste such as bottles, waste diatomaceous earth, and combustion ash of solid waste fuel, so in order to recycle combustible waste such as municipal waste However, the development of new technology is an issue.

[0008]

As a result of various studies to solve these problems, the present inventor has come to provide an artificial zeolite of arbitrary quality from combustion ash of refuse solidified fuel. . That is, in the method for producing an artificial zeolite, which is characterized in that the combustion ash of waste solidified fuel is heat-treated in an alkaline solution, and as the alkaline solution,
It is preferably a 2 to 4N aqueous sodium hydroxide solution.

The second aspect of the present invention is the production of an artificial zeolite characterized by heat-treating a mixture obtained by adding at least one or two of glass and diatomaceous earth to the combustion ash of a solidified waste fuel in an alkaline solution. In the method, the alkaline solution is preferably a 2 to 4N sodium hydroxide aqueous solution.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION
Is the incineration ash of flammable waste such as coal ash and municipal waste.
Artificially by heat-treating
It is the zeolite obtained by conversion and its main component
The component is the ratio of the raw silica, that is, (SiO ₂And Al₂O₃
The ratio of the weight composition of x) x 1.7
Sodalite, Phillipsite, or Forgersa
Ito etc. Therefore, the present invention is thus
That the components of the artificial zeolite obtained by
Let's use it to manufacture artificial zeolite of desired main component
It is what In addition to the main ingredients, other ingredients and
Zeolite A, etc. may be contained in a small amount.
Other parts, that is, non-zeolitic components, unburned
To carbon, iron, other impurities and zeolites
The intermediate product etc. also coexist.

The solid waste fuel (RDF: RE) referred to in the present invention
FUSE DERIVED FUEL) is a combustible waste selected from various human activities, crushed to a certain size, dried to a water content of about 10%, and sometimes mixed with lime. And then solidified, usually 1
It has a calorific value of about 2000 to 3000 kcal per kg, and is attracting attention mainly as a fuel for power generation.

The glass referred to 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 the combustion ash of the solidified fuel of dust, powdery ones having small particles are preferable.

The diatomaceous earth referred to in the present invention is the remains of diatoms, which are mostly single-celled algae, that is, siliceous deposits made of diatom shells, which are usually mixed with clay, volcanic ash, organic matter and the like. However, its essence is hydrous amorphous silicon dioxide. Diatomaceous earth has a wide range of uses, and is used for adsorbents, filter aids, heat insulating materials, cold insulating materials, fillers, abrasives, etc. Depending on the application, the diatomaceous earth raw material is crushed to make it suitable for the intended purpose. It is common to purify. However, in the present invention, not only diatomaceous earth used for various purposes but also waste diatomaceous earth after use can be used. For example, water treatment, sugar, starch syrup, soy sauce, liquor, beer, syrup, vegetable oil, food industry used in the refining process, solvent, machine oil, petroleum, chemical industry used in the refining process, cellulose, Examples include waste diatomaceous earth used as a filter aid in rayon and other textile industries used in the refining process.

The amounts of glass and diatomaceous earth added in the present invention depend on the silica content of the combustion ash of the refuse-solidified fuel used and the quality of the artificial zeolite to be produced. That is, an artificial zeolite obtained by performing heat treatment in an alkaline solution without adding glass and diatomaceous earth using combustion ash of waste solidified fuel as a raw material is a phillipsite, but adding glass and diatomaceous earth and adding diatomaceous earth. The artificial zeolite obtained by heat-treating the mixture having the ratio increased to 4 or more in an alkaline solution has an increased faujasite ratio. For example, by adding approximately 70% by weight of glass or diatomaceous earth to the combustion ash of solid waste fuel, the artificial zeolite obtained becomes almost faujasite. Incidentally, the incinerated ash of municipal waste, which is a general waste, is used as a raw material, and the artificial zeolite obtained by performing heat treatment in an alkaline solution without adding glass and diatomaceous earth is hydroxysodalite, and its pore size is small, It has a large cation exchange capacity but does not have a deodorizing effect.

The mixture obtained by adding glass and diatomaceous earth to the combustion ash of waste solidified fuel according to the present invention means, of course, the mixture obtained by directly adding glass and diatomaceous earth to the combustion ash of solid waste of fuel. , A mixture in which glass and diatomaceous earth are added to the combustion ash produced by spraying glass powder and diatomaceous earth during combustion of solid waste fuel.

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 preferably from 1 to 5 N in order to carry 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. However, in order to shorten the heating time, use a pressure resistant container,
Heating to ℃ is preferable in order to carry out the reaction promptly. The treatment time depends on the composition of the raw material and the quality of the manufactured artificial zeolite, but requires at least 5 hours, usually about 24 hours.

[0017]

The outline of the present invention will be described. Combustion ash of solid waste fuel may be pulverized as it is, and then heat-treated in an alkaline solution, or a mixture obtained by adding one or two of glass and diatomaceous earth is heated in an alkaline solution. Perform processing. Combustion ash of waste solidified fuel, glass and diatomaceous earth are crushed with a particle size of
The thickness is preferably 20 to 100 μm, and the powdery mixture is heat-treated in an alkaline solution. As this alkaline solution, a 1 to 5 N sodium hydroxide aqueous solution is added, and the mixture is heated to 80 to 95 ° C. and reacted. At this time,
An appropriate amount of glass powder or diatomaceous earth is added depending on the silica ratio of the combustion ash of the solid waste fuel used. That is,
When the silica content is less than 1.5, the produced artificial zeolite is mostly hydroxysodalite, and the pore size is 3 to 5Å
It is small and of low quality, so the silicate ratio is 2.0-
When glass powder or diatomaceous earth is added as shown in 2.5, there are many phillipsites and the pore size is 5Å or more, and high quality is obtained. If the amount of glass powder or diatomaceous earth is further increased so that the silicate content exceeds 3.0, 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 1 100 g of combustion ash of solid waste fuel (obtained from the incineration plant of Machida City, Tokyo) was collected and placed in an Erlenmeyer flask having a volume of 1 liter, and water having a concentration of 3.5 N was added thereto. 240 ml of sodium oxide aqueous 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 and air-dried to obtain a powder. From the X-ray diffraction pattern, it was confirmed that hydroxysodalite was produced as an artificial zeolite. The cation exchange capacity of this product was 410 cmol (+) kg ⁻¹ .

(Example 2) 100 g of combustion ash of solid waste fuel (obtained from the incineration plant of Machida City, Tokyo) was collected and placed in a 1 liter Erlenmeyer flask, and water having a concentration of 3.5 N 240 ml of sodium oxide aqueous solution was added. This Erlenmeyer flask was put in a pressure resistant container, heated with saturated steam at 120 to 125 ° C., and reacted for 10 hours. After the reaction, excess sodium hydroxide was washed off with water and air-dried to obtain a powder. From the X-ray diffraction pattern, it was confirmed that hydroxysodalite was produced as an artificial zeolite. The cation exchange capacity of this product is 400 cmol
It was (+) kg ^-1 .

(Example 3) 50 g of glass ash (manufactured by West Japan Environmental Development Cooperative Association) was added to 50 g of combustion ash of solid waste fuel (obtained from the incineration plant of Machida City, Tokyo) and a 1 liter triangle. It was taken in a flask, and 240 ml of a 3.5 N sodium hydroxide aqueous solution was added thereto. A reflux condenser was attached to the Erlenmeyer flask, and the slurry-like mixture was heated at 90 to 95 ° C. on a hot plate and reacted for 24 hours. After the reaction, excess sodium hydroxide was washed off with water and air-dried to obtain a powder. From the X-ray diffraction pattern, it was confirmed that phillipsite was produced as artificial zeolite. The cation exchange capacity of this product is 400c
It was mol (+) kg ^-1 .

(Example 4) Combustion ash of garbage solidified fuel (obtained from the incineration plant of Machida City, Tokyo) was added with 60 g of glass powder (manufactured by West Japan Environmental Development Cooperative Association), and a 1 liter triangle was added. It was taken in a flask, and 240 ml of a 3.5 N sodium hydroxide aqueous solution was added thereto. This Erlenmeyer flask is put in a pressure resistant container, and saturated steam is used for 120 to 1
It was heated at 25 ° C. and reacted for 10 hours. After the reaction, excess sodium hydroxide was washed off with water and air-dried to obtain a powder. From the X-ray diffraction pattern, it was confirmed that faujasite was produced as artificial zeolite. The cation exchange capacity of this product was 320 cmol (+) kg ^-1 .

(Embodiment 5) 70 g of waste diatomaceous earth (produced by Toride Factory of Kirin Brewery Co., Ltd.) was added to 30 g of combustion ash of garbage solidified fuel (obtained from the incinerator of Machida City, Tokyo) to obtain 1
Transfer to a liter Erlenmeyer flask and add a concentration of 3.5N
240 ml of aqueous sodium hydroxide solution was added. A reflux condenser was attached to this Erlenmeyer flask, and the mixture in a slurry state was heated at 90 to 95 ° C. on a hot plate,
Reacted for hours. After the reaction, excess sodium hydroxide was washed off with water and air-dried to obtain a powder. From the X-ray diffraction pattern, it was confirmed that phillipsite was produced as artificial zeolite. The cation exchange capacity of this product is 340
It was cmol (+) kg ⁻¹ .

(Example 6) 70 g of waste diatomaceous earth (produced by Kirin Brewery Co., Ltd. Toride Factory) was added to 30 g of combustion ash of solid waste fuel (obtained from the incinerator of Machida City, Tokyo), and 1
Transfer to a liter Erlenmeyer flask and add a concentration of 3.5N
240 ml of aqueous sodium hydroxide solution was added. Put this Erlenmeyer flask in a pressure resistant container and use saturated steam to
The mixture was heated at 125 ° C. and reacted for 10 hours. After the reaction, excess sodium hydroxide was washed off with water and air-dried to obtain a powder. From the X-ray diffraction pattern, it was confirmed that faujasite was produced as artificial zeolite. The cation exchange capacity of this product was 320 cmol (+) kg ^-1 .

[0024]

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 combustion ash of waste solidified fuel derived from 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 disposal of powder generated when making cullet and disposal of waste diatomaceous earth generated in various industries have become problems.

The present invention is a method for producing an artificial zeolite by heat treating combustion ash of solid waste fuel in an alkaline solution, which has not yet been found to be effectively utilized. The ash is converted to artificial zeolite for effective use. Moreover, by adding glass and diatomaceous earth to the combustion ash of solid waste fuel,
Not only can artificial zeolite of any quality be produced, but high quality artificial zeolite can be produced.

   ─────────────────────────────────────────────────── ─── Continued front page       (56) References Japanese Patent Publication No. 57-15048 (JP, B2)                 "Zero waste incineration ash by alkaline treatment               Olite conversion ”, Journal of soil fertilizer science, 1997               Year, Volume 68, Issue 4, P395-401

Claims (2)

(57) [Claims] 1. At least one or two kinds of glass and diatomaceous earth is added to incineration ash of refuse solidified fuel to adjust the silica content ratio of the mixture to 2.0 to 2.5 and then in an alkaline solution. A method for producing a phillipsite, which comprises heat treatment. 2. At least one or two of glass and diatomaceous earth is added to incineration ash of refuse solidified fuel so that the mixture has a silicate ratio of more than 3.0 and then heated in an alkaline solution. A method for manufacturing a faujasite, which is characterized by processing.