JPH10152343A - Production of crystalline glass effectively utilizing natural substance, general and industrial waste, incinerated ash of general and industrial waster or the like - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a building material high in an additional value by effectively utilizing many wastes which increase year after year. SOLUTION: This method for producing crystalline glass comprises effectively utilizing natural materials, general and industrial wastes, the incinerated ash of the general or industrial wastes, etc., using coloring components contained in the materials or adding a coloring agent. Therein, a composition comprising 1.0-12.0wt.% of alumina (Al2 O3 ), 7.0-20.0wt.% of alkali compounds (Na2 I+K2 O+ Li2 O), and boron oxide (B2 O3 ), barium oxide (BaO), zinc oxide (ZnO), etc., as melting agents except the alkali compounds, and, if necessary, further magnesium oxide (MgO), fluorine(F), chlorine(Cl), sulfur(S) and carbon(C) so that the ratio of silicon (SiO2 ) to calcium oxide (CaO) is 13-5.2 is prepared and subsequently melted and thermally treated at a relatively low temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to natural products (for example, volcanic ash, diatomaceous earth, etc.) and general waste (for example,
Glass cullet such as bottle waste), industrial waste (eg, coal ash), incineration ash of general waste (eg, incineration ash of garbage, incineration ash of solid waste made from garbage), and industrial waste It also relates to a method of producing crystallized glass using materials such as incinerated ash (eg, pulp sludge incinerated ash, shredder dust incinerated ash, etc.) as raw materials. By producing high value-added building materials, a large amount of processing is made effective.

[0002] This crystallized glass, even if it is crystallized, as well as the glass before heat treatment, sufficiently passes the criterion for the treatment of hazardous industrial wastes or their compounds, and has no pollution at all. Proven. Further, conventionally produced β-wollastonite (CaO.Si)
The O ₂ ) -based crystallized glass is known as “natural marble patterned crystallized glass” (Patent Publication No. 65210/1972)
As described in the specification, the heat treatment temperature was 1150 ° C., and sintering could not be achieved in a normal nichrome wire electric furnace. However, “this invention”
By subjecting to a heat treatment at a relatively low temperature of 0 ° C. for 2 hours, a target crystallized glass can be obtained, so that an ordinary electric furnace can be used, and it has become possible to produce economically and inexpensively. In this way, by forming granules or spheres, and by precipitating crystals with hydraulic properties (kneaded with water, as found in cement etc.), the components and water combine to form crystals. ), Which is not only suitable as an aggregate that can be used in large quantities, but also molded into a plate,
It can also be used as a high-grade building material such as flooring. The coloring components contained in the waste produce a color tone similar to artificial jewelry (for example, pulp sludge has a whitish color, and coal ash has an emerald green color). Color tone can be obtained. In particular, if a colorless and transparent glass cullet is used, a desired color tone (for example,
When adjusted to copper red glass, a striped color tone of blue and chocolate can be obtained, and an aesthetic crystallized glass can be obtained. Further, by adjusting the composition, in addition to the β- wollastonite (CaO · SiO _2), gehlenite _{(2CaO · Al 2 O 3 ·} SiO 2), akermanite _{(2CaO · MgO · SiO 2)} , Hardesty Knight ( Since crystals such as 2CaO.ZnO.SiO ₂ ) precipitate, hydraulic properties suitable for the above-described aggregate can be obtained, and a new crystallized glass can be produced.

[0003]

2. Description of the Related Art Natural products, incinerated ash of general and industrial wastes, etc. have been conventionally mixed with a large amount of cement or generally landfilled. However, landfill sites are limited. Some of them do not necessarily pass the criterion for the treatment of harmful industrial wastes or their compounds, and have a problem of causing secondary pollution. In addition, glass such as molten slag such as incineration ash, which is a conventional treatment method, has low strength and hardness, has problems such as alkali elution, and is inferior to natural stone aggregate. Applications for producing β-wollastonite-based crystallized glass from natural products and waste have been filed with ash stones and sewage sludge incineration ash, but all have high melting and heat treatment temperatures, and especially heat treatment. The high temperature has the economic disadvantage of costly heating for mass production. Furthermore, no consideration has been given to the composition for producing these crystallized glass as an aggregate capable of being processed in a large amount, or the specific method.

[0004]

Conventionally, it has been difficult to treat large amounts of general and industrial wastes, or incinerated ash of general and industrial wastes, without pollution and economically. Some crystallized glass was developed using these materials, but these are prototypes, which can be used in large quantities as aggregate or as high value-added products such as high-grade building materials. There was a problem that it could not be manufactured in a special way. Aggregates need to be produced at a particularly low cost and in large quantities, and when used, properties such as hydraulic properties are required.

[0005]

Means for Solving the Problems "The present invention" is based on the composition of natural products, general and industrial wastes, incinerated ash of general and industrial wastes, etc., based on the composition contained in each product. By adding and adjusting, the drawbacks of the conventional crystallized glass are eliminated, and the hydraulic property is newly considered. That is, the present invention effectively utilizes natural products, general and industrial wastes, or incinerated ash of general and industrial wastes, and utilizes coloring components contained therein, or crystallization by adding a coloring agent. In producing glass, alumina (Al ₂ O ₃ ) was added in an amount of 1.0 to 12% by weight.
6. 0% alkali (Na ₂ O + K ₂ O + Li ₂ O)
0-20.0%, and as a flux other than alkali, boron oxide (B ₂ O ₃ ), barium oxide (BaO), aene oxide (ZnO) and the like are contained. If desired, magnesium oxide (MgO), It contains fluorine (F), chlorine (Cl), sulfur (S) and carbon (C), and contains silicic acid (S
iO ₂ ) and calcium oxide (CaO) have a ratio of 1.3 to
By adjusting to 5.2, it is possible to melt at a relatively low temperature and heat-treat (

As a result, β-wollastonite (CaO.SiO ₂ ) and other gerenite (2Ca
O.Al ₂ O ₃ .SiO ₂ ), Okermanite (2Ca
O.MgO.SiO ₂ ), hardest night (2CaO)
Crystals such as (ZnO.SiO ₂ ) are precipitated, have high strength and hardness, have hydraulic properties, and provide crystallized glass suitable for aggregate and high-grade building materials.

When a colorless and transparent glass cullet is used, the content of iron oxide (Fe ₂ O ₃ ) alumina (Al ₂ O ₃ ) is small, so that a glass having a desired color tone can be obtained by adding a coloring agent. In addition, the utilization rate of glass cullet is as high as 85%, so that a new crystallized glass can be produced. Crystallized glass used only for aggregates is made of alumina (Al
₂ O ₃ ), magnesium oxide (MgO), aene oxide (ZnO), etc. are added to make the composition to reduce alkali, and it is better to make the composition hard to flow and to have a high softening point in order to form a lump. The composition adjusted at that time does not depart from the scope of the claims of the present invention.

[0007]

EXAMPLES For natural products, an example of volcanic ash (BA-
1), diatomaceous earth (KS-1), glass cullet (GC-1) for general waste, coal ash (CA-1) for industrial waste, and garbage for incinerated ash of general waste. Regarding incinerated ash (DG-1), incinerated ash made from solid waste (SF-1), and incinerated ash of industrial waste, pulp sludge incinerated ash (PS-1) was selected as a representative. Table 1 shows their average chemical compositions in% by weight. (Note 2) The glass cullet of GC-1 shows the composition of a colorless transparent glass such as a milk bottle manufactured by an automatic machine. (Note 3) Since the slaked lime [Ca (OH) ₂ ] is added to the incinerated ash of DG-1 garbage during the treatment, the amount of CaO is large.

[0008] A number of experiments have been conducted on crystallized glass utilizing natural products and wastes effectively. First, as a typical example, a glass using a colorless and transparent glass cullet manufactured by an automatic machine was used. Table 2 shows examples of chemical compositions whose compositions were adjusted. GC-K1 to GC-K
Numeral 6 is a symbol of a chemical composition in which a glass cullet is used and the composition is changed little by little.

The composition is adjusted based on the colorless and transparent glass cullet so that the glass has the chemical composition shown in Table 2, and is melted at a relatively low temperature (for example, 1350 ° C.). Thereafter, the eluted glass is formed into granules or spheres, or is landed and heat-treated at a relatively low temperature (for example, 930 ° C.) for 2 hours, so that β-wollastonite, other gerenite, okermanite, hardest night, etc. Crystals are precipitated and become milky, and a product which is sufficiently practical as an aggregate or a high-grade building material can be obtained. The crystallized glass formed into a granular or spherical shape can be mass-produced by machining. The composition of the bottle glass manufactured by an automatic machine is similar whether it is a colorless transparent glass or a colored glass such as a beer bottle or a liquor bottle. The composition of the sheet glass is the same, and any of these can be used to produce crystallized glass. When a lot of brown beer bottles are used for melting, iron oxide is generally about 0.2% as Fe ₂ O ₃ , and is oxidized to become a greenish light color. Crystallized glass having various colors can be manufactured. Of course, if a colorless and transparent glass cullet is used instead of a beer bottle, a desired color tone can also be obtained by adding a colorant. The composition of the batch to be added must be changed, but colloidal coloring such as copper red, selenium red, and amber glass is also possible.

[0002] Crystallized glass of a new color can be produced, such as the copper red glass described above. Examples of ionic coloring include cobalt oxide (Co) as a coloring agent.
₃ O ₄ ), nickel oxide (NiO), and the like, but the coloring of each of them slightly changes from the color tone when simply melted and vitrified. GC-K5 is a composition for precipitating crystals such as akermanite, and when heat-treated, crystallized glass having hydraulic properties is obtained.

[0010] The chemical composition of crystallized glass using glass cullet produced by a colorless and transparent automatic machine is first described in Table 2, and these chemical compositions are considered as natural products and waste products, considering coloring components excluded. And the like can be similarly applied. Table 3 shows the chemical compositions of Examples in which crystallized glass having excellent characteristic values is obtained by using wastes other than natural products and glass cullet. If each composition is adjusted based on these chemical compositions, and melting, molding, and heat treatment are performed, the crystallized glass such as gray, green, and amber is obtained by the coloring components contained therein, and the coloring agent is used. A variety of crystallized glasses can be obtained by the addition. For more details on this manufacturing method,

The method is the same as that described in the above. The symbols in Table 3 indicate that BA-K1 is volcanic ash and KS-K1.
Haezosoil, CA-K1 is coal ash, DG-K1 is incineration ash of garbage, SF-K1 is incineration ash of solid material made from garbage, and PS-K1 is incineration ash of pulp sludge. Yes, and shows the chemical composition adjusted for each composition. Of course, Table 2. To adjust to the chemical composition shown in Table 3,
Although it is possible to use only commonly used glass raw materials, these chemical compositions have been developed especially for effectively utilizing natural products, wastes, and the like. SF-K
1, PS-K1 is made of inker ash (2CaO.MgO.2) without adding magnesium oxide (MgO) by using incinerated ash of solid waste and pulp sludge made from about 33% of garbage. Crystals such as SiO ₂ ) can be obtained.

The reasons for limiting the scope of the claims in the present invention are as follows. Alumina (Al ₂ O ₃ )
If the upper limit is exceeded, it is difficult to melt at a relatively low temperature,
If the lower limit is exceeded, the precipitation of crystals during heat treatment is poor,
In addition, the glass has poor hydraulic properties. Alkali (Na ₂ O
If (+ K ₂ O + Li ₂ O) exceeds the upper limit, the precipitation of crystals is poor, depending on the addition of a flux other than alkali. If the lower limit is exceeded, melting becomes difficult. The reason for limiting the ratio of silicic acid (SiO ₂ ) to calcium oxide (CaO) is that diffraction X
It is determined by observing the precipitation state of β-wollastonite by a line. Magnesium oxide (MgO)
In some cases, those contained in natural products and wastes are sufficient, but they are necessary components for precipitating crystals of akermanite. Sulfur (S), carbon (C), iron oxide (F
The amount of e ₂ O ₃ ) affects the precipitation and coloration of the crystals,
Fluorine (F), chlorine (C
It has been recognized in the present invention that crystal nuclei grow by containing l).

Table 2. When those having the chemical composition shown in Table 3 are melted and vitrified, for example, CA-K1, PS-
K1 is also a good quality glass for crafts and decorations, and a desired color tone can be obtained by adding a coloring agent to these compositions.
By further heat treatment, β-wollastonite crystals were found to precipitate in these crystallized glasses, and JIS
A bending test, a Biccus hardness and a diffraction X-ray analysis were carried out in accordance with
m ² or more, Vickers hardness was also 550 (Hv) or more. Most of the crystallized glass has a marble pattern because of a striped pattern. However, since it is stronger than natural marble, it can be used as a high-grade building material. Table 2
GC-K5 in Table 3, and PS-K1 in Table 3, in addition to this crystal,
Crystals such as gehlenite, okermanite and hardestonite were observed, and although the fluidity during heat treatment tended to be slightly worse than other compositions, these crystals also exhibited hydraulic properties. When heat treatment is performed with this composition, if the temperature is further lowered (for example, at 800 ° C. for 5 hours), sintering can be performed, so that a round, bulky crystallized glass is formed.
Aggregate can be produced by adjusting the composition or changing the heat treatment conditions. Sulfur (S),
Glass to which carbon (C) has been added changes its color tone depending on the melting temperature and the heat treatment temperature, so that temperature control is necessary to obtain a constant color tone.

[0013]

According to the present invention, natural products, general and industrial wastes, incinerated ash of general and industrial wastes, etc. are taken as specific examples, and these are effectively used to produce β-
By lowering the melting temperature and the heat treatment temperature from a wollastonite-based crystallized glass, a crystallized glass can be produced economically. From the coloring components contained therein, a color tone similar to artificial jewels can be obtained, but if it is a light color or colorless, by adding a coloring agent,
You can make beautiful crystallized glass. "This invention"
Is manufactured from any natural product or waste, but in addition to β-wollastonite,
If necessary, when magnesium oxide (MgO) is added, crystals such as gehlenite, okermanite, hardestonite, etc. are precipitated, so there is no pollution, and there is hydraulicity.
Not only can it be used in large quantities as an aggregate to be mixed with cement, but it is also excellent in strength and hardness, so it can be molded into plates and manufactured as interior and exterior materials, floor materials, and other high-grade building materials. it can. Therefore, this invention is expected to have a large-scale activity as a recycling business in the near future for natural products and wastes that are currently difficult to dispose of, and a great effect is expected especially when adopted in municipalities. You can do it. This time, 2 points for natural products, 3 points for general waste,
Although two specific examples of industrial waste are shown, Table 2 and Table 3 "The present invention" can be applied to other natural products and wastes, and both can produce excellent crystallized glass. .

Claims (1)

[Claims] 1. Effective use of natural products, general and industrial wastes, incinerated ash of general and industrial wastes, etc., use of coloring components contained therein, or of crystallized glass to which a coloring agent is added. In the production, alumina (Al
₂ O ₃ ) from 1.0 to 12.0%, alkali (Na ₂ O +
K ₂ O + Li ₂ O) is set to 7.0 to 20.0%, and as a flux other than alkali, boron oxide (B ₂ O ₃ ), barium oxide (BaO), aene oxide (ZnO), and the like are included. If desired, magnesium oxide (MgO), fluorine (F), chlorine (Cl), phosphorous (S), and carbon (C) may be contained, and silicic acid (SiO ₂ ) and calcium oxide (C) may be contained.
aO) whose composition is adjusted so as to be 1.3 to 5.2, and which is melted and heat-treated at a relatively low temperature. Method.