JPH08310834A - Production of colored crystalline glass effectively utilizing incineration ash of general waste or the like - Google Patents

Abstract

PURPOSE: To effectively utilize the incineration ash of general waste for the aggregate of cement or the like by forming a glass consisting essentially of the incineration ash of general waste or the like, adjusting its composition and fusing and heat-treating it at a relatively low temp. CONSTITUTION: This colored crystalline glass high in strength and hardness, consisting essentially of the incineration ash of general waste is obtained by adjusting the ash to a glass composition containing 39-58wt.% (hereafter called %) SiO2 , 8-24% CaO, 8-17% (Na2 O+K2 O+Li2 O) and 3-9% (F+B2 O3 +BaO+ZnO or the like), if necessary adding a coloring agent, fusing at a low temp. such as 1350 deg.C and heat treating it at a relatively low temp., such as 930 deg.C, for 2hr to precipitate mainly a crystal of β-wollastonite (CaO, SiO2 ). The glass is effectively utilized for the aggregate of cement, art or decorative glass or the like.

Description

Detailed Description of the Invention

[0001]

[Industrial application] "This invention" is to produce crystallized glass by effectively utilizing incineration ash of general waste, for example, ash obtained by incinerating waste that can be incinerated by municipal waste. The present invention relates to a method for producing colored crystallized glass that can be digested in large quantities by recycling waste, which is said to be inexhaustible. This crystallized glass, even before it was heat-treated, passed the criteria of hazardous industrial waste or its compounds sufficiently, and had no pollution, and was of the conventional β-wollastonite (CaO · SiO ₂ ) type. With crystallized glass,
By melting at a relatively low temperature, for example, 1350 ° C., and then heat-treating at a relatively low temperature, for example, 930 ° C. for 2 hours, a large amount of dust is used and these temperatures are low, so that it is possible to manufacture inexpensively. . Not only is the product suitable as an aggregate of cement that can be used in large quantities, but it is also used as a high-value-added craft / decorative glass, or as a high-quality building material such as interior / exterior material / floor material when formed into a plate shape. can do. Generally, slaked lime [Ca
(OH) ₂ ] is added, for example, when incineration ash of municipal waste is used to precipitate β-wollastonite (CaO · SiO ₂ ) crystals, lime (Ca
O) source does not need to be added at all and chlorine (C
Since it contains l), carbon (C), metal or metal oxide, etc., it is possible to produce crystallized glass without adding a crystal nucleating agent. Further, since the incinerated ash or the like contains a metal or a metal oxide as described above, coloring is performed without adding a coloring agent, and in order to obtain a desired color tone, a coloring agent, for example, Cobalt oxide (C
o ₃ O ₄ ), nickel oxide (NiO), cupric oxide (C
uO) and the like are added to obtain various crystallized glasses.

[0002]

2. Description of the Related Art Conventionally, incineration ash of general waste is mixed with a large amount of cement or heated by a plasma method,
Generally, many landfills are available, but it is difficult to secure landfill sites, and some of these do not necessarily pass the criteria for hazardous industrial wastes or their compounds, and they have the drawback of causing secondary pollution. Precipitating β-wollastonite,
A patent application has been filed for producing crystallized glass using natural marble patterned crystallized glass, or using incineration ash of natural minerals and industrial waste. The effect is remarkably different, and its reason will be explained.

The title of the invention, "Natural marble patterned crystallized glass" (Japanese Patent Publication No. SHO 65210, Application No. 46)
The gist of the invention relating to No. 99500) (referred to as Patent No. 1) is as follows. [Weight percent (wt
%)] _{SiO 2 50~65%, Al 2 O} 3 3~13%, C
aO 15 to 25% and ZnO 2 to 10% are essential components. In order to understand the difference from the "this invention",
The maximum and minimum chemical compositions of Patent No. 1 from the examples are as follows. SiO ₂ 56.6~61.7%, A
1 ₂ O ₃ 5.3-7.1%, CaO 18.3-2
1.8%, ZnO 5.1-9.9%, alkali (Na ₂ O + K ₂ O) 3.3-5.3%, B ₂ O ₃ of the flux other than alkali is 0- 2.2%, BaO is 0
It is 8.2%. The content of Al ₂ O _{3 in} “this invention” is 1.50 to 4.20% although it is not an essential component as seen in the examples, and Patent No. 1 is “this invention”. Compared with, the amount of SiO ₂ , Al ₂ O ₃ , and CaO is large, and the amount of alkali is small. The melting temperature of Patent No. 1 is 1425 ° C. to 1440 ° C., and the heat treatment temperature is 1150 ° C. for 2 hours, which is much higher than those of “this invention”. Seems to require expensive materials. It should be noted that Patent Document 1 describes addition of a colorant in claim 2, but the chemical composition is not different from the above-mentioned chemical composition as an essential component.

Next, the gist of the invention, "Method for producing crystallized glass" (Japanese Patent Laid-Open No. Hei 3 No. 75241, Japanese Patent Application No. Hei 1 No. 206643) (referred to as Patent No. 2) is as follows. It is as follows. The raw material of Patent No. 2 is 1 anti-fire stone
00 as CaO 20-40, Na ₂ O 0-1
0, S 0.5 to 2.0, C 0.5 to 2.0, ZnO
The present invention relates to a method for producing crystallized glass, which comprises molding and heat-treating glass containing 0-10. Since this description is difficult to compare with "this invention", it is calculated based on the typical chemical composition of anti-fire stone from the formulation described in the example, and the maximum The minimum is calculated as follows. [Weight percent (wt%)] (calculated from Table 2 of Patent No. 2) SiO ₂ 55.1 to 56.0%, Al ₂ O ₃ 8.9
9-9.81%, CaO21.09-25.67%, S
0.66-0.69%, C 0.66-0.67%,
ZnO 0.73 to 0.74%, alkali (Na ₂ O +
K ₂ O) 6.45 to 10.89%, Fe ₂ O ₃ 0.6
It is 7 to 0.69%. Fe ₂ O _{3 in} this composition is
Iron oxide contained in anti-fire stone, not added from the outside. The chemical composition according to Patent No. 2 is clearly different from the "invention", and the melting temperature is

It is 1450 ° C. for 2 hours and the heat treatment temperature is 800 ° C. to 1200 ° C. for 0.5 to 4 times.
Time, and at least about the melting temperature,
It is hotter than "this invention" and the main raw materials are also different. In this "invention", once the heat treatment temperature is raised to 1200 ° C, the glass once crystallized becomes vitrified.

Next, the title of the invention, "Method for producing crystallized glass" (Japanese Patent Application Laid-Open No. 317436/1992, application No. 2)
No. 413772) (referred to as Patent No. 3) is summarized as follows. [Weight percent (wt
%)] Patent No. 3 uses an incineration ash of sewage sludge of industrial waste to produce anorthite (CaO ・ Al ₂ O ₃・ 2Si).
The present invention relates to a method for producing crystallized glass by combining at least one of O ₂ ) and β-wollastonite (CaO · SiO ₂ ). The chemical composition of the claim is S
iO ₂ 35-55%, Al ₂ O ₃ 5-20%, Ca
O 5-30%, SO 2-6% (when converted to S,
S is 0.86 to 2.57%), CO is 2 to 5% (1.34 to 3.34% when converted to C), and C
The ratio of aO / Al ₂ O ₃ + SiO ₂ is 0.15 to 0.70.
It is described that the incinerated ash within the range or the incinerated ash adjusted within the above range is melted at 1300 ° C to 1500 ° C, and then the glassy material is reheated to be heat-treated. The melting temperature of the example is 1400 ° C to 1500 ° C. This heat treatment is performed in two stages. The maximum and minimum of the chemical composition and the maximum and the minimum of the sintering conditions of the heat treatment of the examples are shown as follows so that they can be compared with "this invention".
_{SiO 2 35.0~52.7%, Al 2 O} 3 5.1
~ 19.8%, CaO 8.5-26.9%, S 0.2
˜5.1% and C 0.2˜5.0%. Regarding the heat treatment, considering the heat treatment time, the maximum and minimum are 900 ° C for 2 hours and 800 ° C for 1 hour in the first holding, and 1200 ° C for 1 hour and 100 in the second holding.
It is 0 ° C for 30 minutes. Compared to “this invention”, Patent No. 3 has different essential components, a high melting temperature, a different heat treatment mechanism, and a high heat treatment temperature. In the case of heat treatment using a large-scale melting kiln / heat treatment furnace for actual industrial production, if the temperature is high, it is generally not economical and it is often unsuitable for the production of a large amount of glass products.

[0006]

[Problems to be Solved by the Invention] It has been considered difficult to economically incinerate a large amount of incinerated ash of general waste, such as ash obtained by incinerating waste that can be incinerated with municipal waste, economically and without pollution. . As mentioned above, the method for producing the crystallized glass described above has also been developed, but by effectively utilizing the chemical components of incinerated ash of municipal waste, which is inexhaustibly used, it is often used as an aggregate of cement, or can be produced by artificial blowing. Possible crafts / decorative glass or high-value-added glass such as high-grade building materials have an aesthetic appeal by being melted / heat-treated at a relatively low temperature, and an industrial product with excellent strength / hardness cannot be made. There was a problem.

[0007]

[Means for Solving the Problems] The "invention" effectively utilizes components such as incinerated ash of municipal waste, and makes use of CaO and Al ₂ O.
_{3. A} glass that has a lower melting temperature and heat treatment temperature than the conventional manufacturing process of crystallized glass that precipitates β-wollastonite without adding a crystal nucleating agent, and that has excellent glass characteristic values. It has been studied for many years in order to produce, and the results have been obtained by the following means. That is, the "invention" effectively utilizes the chemical components contained in the incineration ash of general waste, etc., and when producing a crystallized glass colored from these components or added with a coloring agent, the weight percentage (wt. %), SiO ₂ 39-58%,
CaO 8-24%, alkali (Na ₂ O + K ₂ O + L
i ₂ O) 8 to 17%, flux other than alkali (F + B ₂ O)
₍₃ + BaO + ZnO, etc.) is adjusted to a glass containing 3 to 9%, and this is melted and heat-treated at a relatively low temperature (

[0001], mainly, crystals of β-wollastonite (CaO · SiO ₂ ) are deposited, and a crystallized glass having high strength, hardness and aesthetics is obtained.

[0008]

[Examples] Table 1 shows the typical chemical composition of the incineration ash of municipal waste used in "this invention". [Weight percent (wt%)]

[Table 1] In order to reduce the variation in the chemical composition of the incinerated ash of this garbage, strict classification is required for collection and cooperation of the parties is required, but it is of course desired that this variation be small even during glass manufacturing. .

The composition shown in Table 2 was used using incineration ash of municipal waste, and all were melted at 1350 ° C. On the one hand, a tumbler was molded by artificial blowing to remove strain. Then, take out the melted glass (seeds) from the melting furnace, cool it with water, pack the glass particles in a heat-resistant gypsum mold, etc. and heat the glass as it is at 930 ° C for 2 hours to sinter the glass and crystallize. Foamed glass was made and its characteristic values were measured. Water-cooled glass may be heat-treated to form an aggregate of cement. With the glass type numbers shown in Table 2, it was slightly difficult to perform blow-cast molding because the seeds set quickly.
All others could be used as artificially blown glass. In addition, the ignition loss (Ig.lo
ss) and impurities are included. Melting temperature is 1350
There is no problem even if it is higher than ℃ (for example, 1400 ℃), and the heat treatment temperature is 970 ℃ when holding for 2 hours.
There is no problem even if it rises to. If the temperature of the heat treatment is raised too much, the product once crystallized tends to vitrify.

[Table 2]

As shown in Table 2, Fe ₂ O ₃ is contained even if a coloring agent is not added, so that it is colored. However, by adding a coloring agent, a crystallized glass having various color tones can be obtained. can get. As the colorant, for example, cobalt oxide (Co ₃ O ₄ ), cupric oxide (CuO), nickel oxide (NiO) and the like can be added to obtain a desired color tone. For example, if Co ₃ O ₄ is added in an amount of 0.10%, crystallized glass tinged with cobalt blue is obtained. Not only ionic coloring but also colloidal coloring is possible.

The reason why the scope of the claims is limited in the "present invention" is as follows. SiO ₂ and CaO are
As a matter of course, the diffraction X-ray analysis was performed, and the upper and lower limits of the weight percentage of β-wollastonite (CaO, SiO ₂ ) precipitation were limited based on the experimental data. For the fluxes other than, if these are below the lower limit, the melting temperature is, for example, 1350 ° C.
This is because the melting becomes difficult, and when the content exceeds the upper limit, β-wollastonite crystals do not precipitate at a comparatively low temperature, for example, 930 ° C. for 2 hours. If the composition range of "this invention" is adjusted, the object of "this invention" can be achieved even if natural minerals such as volcanic ash, diatomaceous earth and the like, industrial wastes such as incinerated ash of sewage sludge and the like are used.

Bending test (3 points), Vickers hardness and diffraction X-ray analysis were carried out on the crystallized glass obtained by melting and heat-treating the formulation (batch) adjusted to the chemical composition shown in Table 2 according to JIS. The results are shown in Table 3. Regarding flexural strength, it is stronger than natural marble, and in hardness, it is harder than soda lime glass, and is sufficiently practical as a high-grade building material. Even if it is an air-blown glass product, it has a unique color tone. For example, some are grayish or devitrified, and in crystallized glass, many striped patterns are generated, and some are marbled. The degree of whiteness tends to increase with crystallization as compared with the case of glass, and the degree of whiteness tends to increase as the amount of dust added increases because β-wollastonite precipitates more.

[Table 3]

[0012]

EFFECTS OF THE INVENTION The "invention" effectively utilizes the chemical composition of incineration ash, etc. of general waste, and has a higher melting temperature / heat treatment temperature than β-wollastonite crystallized glass that has been conventionally produced. It can lower the cost and make crystallized glass economically, for example, can incinerate about 60% of the incinerated ash of municipal waste, etc. Crystallized glass is not only pollution-free and can be used in large quantities as an aggregate of cement,・ High-quality building materials such as interior / exterior materials / floor materials that are molded into decorative glass or plates,
The fact that high-value-added products with excellent characteristic values such as strength, hardness, and aesthetics were obtained requires consideration of garbage collection, but it is expected that large-scale activities as a recycling business will be expected in the near future. This is a remarkable effect. Further, the “this invention” can be applied to the treatment of natural minerals and industrial wastes, and it is possible to produce an excellent colored crystallized glass.

Claims (1)

[Claims] 1. A weight percentage (wt%) in the production of a colored crystallized glass that is colored from these compositions by effectively utilizing the chemical composition contained in incineration ash of general waste. Then, silicic acid (SiO ₂ ) 39 to 58
%, Calcium oxide (CaO) 8 to 24%, alkali (Na ₂ O + K ₂ O + Li ₂ O) 8 to 17%, flux other than alkali (F + B ₂ O ₃ + BaO + ZnO, etc.) 3 to 9
% Of glass, and melting and heat treating the glass at a relatively low temperature. A method for producing colored crystallized glass, which effectively utilizes incineration ash of general waste.