JPH08310834A - Production of colored crystalline glass effectively utilizing incineration ash of general waste or the like - Google Patents
Production of colored crystalline glass effectively utilizing incineration ash of general waste or the likeInfo
- Publication number
- JPH08310834A JPH08310834A JP7147983A JP14798395A JPH08310834A JP H08310834 A JPH08310834 A JP H08310834A JP 7147983 A JP7147983 A JP 7147983A JP 14798395 A JP14798395 A JP 14798395A JP H08310834 A JPH08310834 A JP H08310834A
- Authority
- JP
- Japan
- Prior art keywords
- glass
- incineration ash
- general waste
- cao
- ash
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/002—Use of waste materials, e.g. slags
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Glass Compositions (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】「この発明」は、一般廃棄物の焼
却灰等、例えば、都市ゴミで焼却可能な廃棄物を焼却し
た灰を有効に利用して、結晶化ガラスを製造することに
より、無尽蔵といわれる廃棄物をリサイクルとして、多
量に消化可能な着色結晶化ガラスの製造方法に関するも
のである。この結晶化ガラスは、熱処理する前のガラス
でも、有害産業廃棄物またはその化合物の判定基準に充
分に合格して、公害は全くなく、従来のβ−ウオラスト
ナイト(CaO・SiO2)系の結晶化ガラスにより、
比較的低温、例えば1350℃で溶融し、比較的低温で
熱処理、例えば、930℃・2時間で熱処理することに
より、ゴミを多量に使用してこれらの温度が低いので安
価に製造が可能である。その製品は、多量に使用可能な
セメントの骨材として適しているのみならず、付加価値
の高い工芸・装飾ガラス、あるいは板状に成形して内外
装材・床材等の高級建材等に使用することができる。都
市ゴミが焼却される過程で、一般には、消石灰〔Ca
(OH)2〕が加えられており、例えば、β−ウオラス
トナイト(CaO・SiO2)の結晶を析出させるため
に、都市ゴミの焼却灰等を使用した場合、石灰(Ca
O)源は全く加える必要もなく、これらには、塩素(C
l)、カーボン(C)、金属または金属の酸化物等が含
まれているので、結晶核形成剤を加えることなく、結晶
化ガラスを製造することが可能である。また、この焼却
灰等には、前述の如く、金属または金属の酸化物等が含
まれているので、着色剤を加えなくても着色し、所望の
色調を得るためには、着色剤、例えば酸化コバルト(C
o3O4)、酸化ニッケル(NiO)、酸化第二銅(C
uO)等を加えて、多彩な結晶化ガラスが得られる。[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】[0002]
【従来の技術】一般廃棄物の焼却灰等には、従来、多量
のセメントと混合したり、プラズマ法により加熱して、
一般には多く埋立てられているが、埋立地の確保も困難
であり、これらは必ずしも有害産業廃棄物またはその化
合物の判定基準に合格しないものもあり、二次公害を起
こす欠点もあった。β−ウオラスナイトを析出させて、
天然大理石模様結晶化ガラスが製造されたり、天然鉱
物、産業廃棄物の焼却灰を使用して、結晶化ガラスを製
造する特許出願がされているが、「この発明」とは、目
的・構成・効果において著しく異なっていて、そのゆえ
んについても説明する。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.
【0003】発明の名称、「天然大理石模様結晶化ガラ
ス」(特許公開 昭48年第65210号、出願 46
年第99500号)(特許1号と呼称する)に係る発明
の要旨は次のとおりである。〔重量パーセント(wt
%)〕 SiO2 50〜65%、Al2O3 3〜13%、C
aO 15〜25%、ZnO 2〜10%を必須成分と
している。「この発明」との相違点を理解するために、
実施例から特許1号の化学組成の最大・最小を記すと次
のとおりである。SiO2 56.6〜61.7%、A
l2O3 5.3〜7.1%、CaO 18.3〜2
1.8%、ZnO 5.1〜9.9%であり、アルカリ
(Na2O+K2O)は、3.3〜5.3%、アルカリ
以外の融剤のB2O3は、0〜2.2%、BaOは0〜
8.2%である。「この発明」のAl2O3の含有率
は、実施例でみられるように、必須成分とはしていない
が、1.50〜4.20%であり、特許1号は「この発
明」と比べれば、SiO2、Al2O3、CaOが多
く、アルカリは少なくなっている。特許1号の溶融温度
は、1425℃〜1440℃であり、熱処理温度は何れ
も1150℃・2時間で、「この発明」のこれらの温度
に比べればはるかに高温であり、熱処理炉の発熱体は高
価な材質が必要であると思われる。尚、特許1号は、請
求項2において着色剤の添加が述べられているが、必須
成分としては前述の化学組成と変わるものではない。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.
【0004】次に、発明の名称「結晶化ガラスの製造方
法」(特許公開 平3年第75241号、特願 平1年
第206643号)(特許2号と呼称する)に係る要旨
は、次のとおりである。特許2号の原料は、抗火石を1
00として、CaO 20〜40、Na2O 0〜1
0、S 0.5〜2.0、C 0.5〜2.0、ZnO
0〜10を配合したガラスを成形・熱処理することを
特徴とする結晶化ガラスの製造方法に関するものであ
る。この記載は、「この発明」と比較することが困難で
あるため、抗火石の代表的な化学組成を基に、実施例に
記されている配合から算出して、それらの化学組成の最
大・最小を求めると次のとおりである。〔重量パーセン
ト(wt%)〕(特許2号の表2より計算) SiO2 55.1〜56.0%、Al2O3 8.9
9〜9.81%、CaO21.09〜25.67%、S
0.66〜0.69%、C 0.66〜0.67%、
ZnO 0.73〜0.74%、アルカリ(Na2O+
K2O)6.45〜10.89%、Fe2O3 0.6
7〜0.69%である。この組成にあるFe2O3は、
抗火石に含有されている酸化鉄で、外部より添加された
ものではない。特許2号による化学成分は、「この発
明」とは明らかに異なり、溶融温度は明細書の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
【作用】の項に記載されていて、1450℃・2時間で
あり、熱処理温度は800℃〜1200℃・0.5〜4
時間となっていて、少なくとも溶融温度については、
「この発明」より高温であり、主要原料も異なってい
る。「この発明」では、熱処理温度を1200℃に上昇
すれば一度結晶化したガラスがガラス化する。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.
【0005】次に、発明の名称「結晶化ガラスの製造方
法」(特許公開 平4年第317436号 出願 平2
年第413772号)(特許3号と呼称する)に係る発
明の要旨は次のとおりである。〔重量パーセント(wt
%)〕特許3号は、産業廃棄物の下水汚泥の焼却灰を
使用して、アノーサイト(CaO・Al2O3・2Si
O2)とβ−ウオラストナイト(CaO・SiO2)と
の少なくとも一つを合わせ、結晶化ガラスの製造方法に
関するものである。その特許請求範囲の化学組成は、S
iO2 35〜55%、Al2O3 5〜20%、Ca
O 5〜30%、SO 2〜6%(Sに換算した場合、
Sは0.86〜2.57%)、CO 2〜5%(Cに換
算した場合、1.34〜3.34%)であり、且つ、C
aO/Al2O3+SiO2の比が0.15〜0.70
の範囲内にある焼却灰あるいは上記範囲内に調整した焼
却灰を1300℃〜1500℃で溶融し、ついでガラス
質物質を再加熱して熱処理すると記されている。実施例
の溶融温度は1400℃〜1500℃である。この熱処
理は、二段階に分けて実施されている。実施例の化学組
成の最大・最小、熱処理の焼結条件の最大・最小を「こ
の発明」と比較できるように示すと次のとおりである。
SiO2 35.0〜52.7%、Al2O3 5.1
〜19.8%、CaO8.5〜26.9%、S 0.2
〜5.1%、C 0.2〜5.0%である。熱処理につ
いては、熱処理時間を考慮して、最大・最小は、第一次
保持においては、900℃・2時間と800℃・1時間
であり、第二次保持では、1200℃・1時間と100
0℃・30分である。特許3号は、「この発明」と比較
すれば、必須成分も異なっており、溶融温度は高く、熱
処理の機構も変わっており、熱処理の温度が高い。実際
に工業生産をするための大規模な溶解窯・熱処理炉を用
いて熱処理する場合は、温度が高いと一般に経済的でな
く、多量のガラス製品の生産に不向きである場合が多
い。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】[0006]
【発明を解決しようとする問題点】一般廃棄物の焼却灰
等、例えば、都市ゴミで焼却可能な廃棄物を焼却した灰
を経済的に無公害で多量に消化することは困難とされて
いた。以上、述べた結晶化ガラスの製造方法も開発され
ているが、無尽蔵にある都市ゴミの焼却灰の化学成分を
有効に利用して、セメントの骨材として多く使用した
り、人工吹でも製造が可能な工芸・装飾ガラスあるいは
高級建材等のように付加価値の高いガラスが、比較的低
温で溶解・熱処理することで審美性があり、工業製品と
しても強度・硬度等に優れた製品がつくれないのかの問
題点があった。[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】[0007]
【問題を解決するための手段】「この発明」は、都市ゴ
ミの焼却灰等の成分を有効に利用し、CaO、Al2O
3、結晶核形成剤は全く加えることなく、従来のβ−ウ
オラストナイト等を析出させる結晶化ガラスの製造工程
より、溶解温度・熱処理温度を低くして、しかもガラス
の特性値の優れたガラスをつくるために永年研究し、次
のような手段により成果が得られたものである。すなわ
ち、「この発明」は、一般廃棄物の焼却灰等に含有する
化学成分を有効に利用し、これらの成分から着色し、あ
るいは着色剤を加えた結晶化ガラスの製造に際し、重量
パーセント(wt %)で、SiO2 39〜58%、
CaO 8〜24%、アルカリ(Na2O+K2O+L
i2O)8〜17%、アルカリ以外の融剤(F+B2O
3+BaO+ZnO等)3〜9%を含有したガラスに調
整し、これを比較的低温で溶融・熱処理することにより
([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】参照)、主として、β−ウオラストナイト
(CaO・SiO2)の結晶が析出し、強度が高く、硬
度があり、しかも審美性のある結晶化ガラスが得られ
る。[0001], mainly, crystals of β-wollastonite (CaO · SiO 2 ) are deposited, and a crystallized glass having high strength, hardness and aesthetics is obtained.
【0008】[0008]
【実施例】「この発明」で用いられた都市ゴミの焼却灰
の代表的な化学組成は、表1のとおりである。〔重量パ
ーセント(wt %)〕[Examples] Table 1 shows the typical chemical composition of the incineration ash of municipal waste used in "this invention". [Weight percent (wt%)]
【表1】 このゴミの焼却灰等の化学組成のバラツキを少なくする
ためには、回収にあたって厳しい分類をするとか、関係
者の協力が必要になるが、ガラス製造の際もこのバラツ
キが少ないことは勿論望まれる。[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. .
【0009】都市ゴミの焼却灰等を使用して、表2の組
成になるようにし、何れも、1350℃で溶融し、一方
では人工吹により、タンブラー等を成形して除歪を行な
い、一方では溶融炉からどろどろに溶けたガラス(た
ね)を取り出して水冷し、ガラス粒を耐熱石膏型等に詰
めて、型のまま何れも930℃で2時間熱処理してガラ
スを焼結させて、結晶化ガラスをつくり、その特性値を
測定した。セメントの骨材にするのには、水冷したガラ
スを熱処理すればよい。表2の硝種番号のでは、宙吹
き成形が、たねが早く固まるので若干困難であったが、
他は何れも人工吹のガラスとしても使用することができ
た。尚、表2に示すその他には、灼熱減量(Ig.lo
ss)と不純物が含まれている。溶融温度は、1350
℃より高くても差し支えなく(例えば1400℃)、熱
処理温度については、2時間を保持した場合、970℃
まで上昇しても差し支えない。あまり熱処理の温度を上
昇すると一度結晶化した製品がガラス化する傾向にな
る。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.
【表2】 [Table 2]
【0010】着色剤を加えなくても、表2で見られるよ
うに、Fe2O3を含有しているので着色するが、着色
剤を添加することにより、多彩な色調を持つ結晶化ガラ
スが得られる。着色剤としては、例えば、酸化コバルト
(Co3O4)、酸化第二銅(CuO)、酸化ニッケル
(NiO)などを加え、所望の色調を得ることができ
る。例えば、Co3O4を0.10%加えれば、コバル
トブルーがかった結晶化ガラスが得られる。イオン着色
のみならずコロイド着色も可能である。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.
【0011】「この発明」で、特許請求の範囲を限定し
た理由は、次のとおりである。SiO2とCaOとは、
当然のことであるが、回析X線分析を行ない、β−ウオ
ラストナイト(CaO、SiO2)が析出する重量パー
セントが実験データに基づいて、上限・下限が限定され
ており、アルカリ、アルカリ以外の融剤については、こ
れらが下限を越えると、溶融温度が例えば、1350℃
では溶融が困難となり、上限を越えると、β−ウオラス
トナイトの結晶が比較低温、例えば930℃・2時間で
は析出しないためである。「この発明」の組成範囲に調
整すれば、天然鉱物、例えば、火山灰、珪藻土等、産業
廃棄物、例えば下水汚泥の焼却灰等を使用しても、「こ
の発明」の目的が達せられる。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.
【0012】表2に示す、化学組成に調整した調合(バ
ッチ)を溶融して熱処理した結晶化ガラスをJISに準
じて、曲げ試験(3点)、ビッカース硬度ならびに回析
X線分析を行なった結果を表3に示す。曲げ強度につい
ては、天然大理石よりも強く、硬度においては、ソーダ
石灰ガラスよりも硬い結果が得られ、高級建築材料とし
ても充分実用性のある結果が得られている。宙吹きのガ
ラス製品にしてもユニークな色調であり、例えば、ねず
み色、失透するものもあり、結晶化ガラスでは、多く縞
入り模様を生じ、大理石模様のものもあり、外観上審美
である。ガラスの場合より結晶化したほうが白色度を増
し、ゴミの添加量が多い方がβ−ウオラストナイトの析
出が大であるためか、白色度が増加する傾向になる。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.
【表3】 [Table 3]
【0012】[0012]
【発明の効果】「この発明」は、一般廃棄物の焼却灰等
の化学組成を有効に利用し、従来製造されていたβ−ウ
オラストナイト系の結晶化ガラスより、溶解温度・熱処
理温度を低下させ、経済的に結晶化ガラスをつくり、例
えば、都市ゴミの焼却灰等を60%程度消化でき、結晶
化ガラスは、無公害でセメントの骨材としても多量に使
用できるばかりではなく、工芸・装飾用ガラスあるいは
板状に成形して内外装材・床材等の高級建材等として、
強度・硬度・審美性等の特性値に優れた付加価値の高い
製品が得られたことは、ゴミの回収について考慮は必要
になるが、近い将来リサイクル事業としての大々的な活
動が期待される程顕著なる効果である。また、天然鉱物
・産業廃棄物の処理についても、「この発明」は適用で
き、優れた着色結晶化ガラスを製造することが可能であ
る。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)
を有効に利用し、これらの組成から着色し、あるいは着
色剤を加えた着色結晶化ガラスの製造に際し、重量パー
セント(wt %)で、けい酸(SiO2)39〜58
%、酸化カルシウム(CaO)8〜24%、アルカリ
(Na2O+K2O+Li2O)8〜17%、アルカリ
以外の融剤(F+B2O3+BaO+ZnO等)3〜9
%を含有したガラスに調整し、これを比較的低温で溶融
・熱処理することを特徴とする一般廃棄物の焼却灰等を
有効に利用した着色結晶化ガラスの製造方法。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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7147983A JPH08310834A (en) | 1995-05-12 | 1995-05-12 | Production of colored crystalline glass effectively utilizing incineration ash of general waste or the like |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7147983A JPH08310834A (en) | 1995-05-12 | 1995-05-12 | Production of colored crystalline glass effectively utilizing incineration ash of general waste or the like |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH08310834A true JPH08310834A (en) | 1996-11-26 |
Family
ID=15442521
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7147983A Pending JPH08310834A (en) | 1995-05-12 | 1995-05-12 | Production of colored crystalline glass effectively utilizing incineration ash of general waste or the like |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH08310834A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002308646A (en) * | 2001-04-10 | 2002-10-23 | Masatoshi Sato | Wollastonite-based glass ceramic fired at low temperature and method of producing the same |
KR20030079097A (en) * | 2002-04-01 | 2003-10-10 | 윤연흠 | Production of glass-ceramics from waste glass and waste shell |
FR2867400A1 (en) * | 2004-03-10 | 2005-09-16 | Marcadier Eric | Utilization of vitrified residue from the purification of fumes from the incineration of household waste as a secondary compound in cement clinker for road making, railway ballast and fibre |
KR100530355B1 (en) * | 2002-08-16 | 2005-11-22 | 미래화학 주식회사 | Method for manufacturing an aggregate |
JP2008173558A (en) * | 2007-01-17 | 2008-07-31 | Petroleum Energy Center | Water-permeable purifying wall and purification treatment method of polluted underground water |
CN106396410A (en) * | 2016-08-29 | 2017-02-15 | 中国恩菲工程技术有限公司 | Production method of microcrystalline glass |
CN106396411A (en) * | 2016-08-29 | 2017-02-15 | 中国恩菲工程技术有限公司 | Preparation method of microcrystalline glass |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5547246A (en) * | 1978-09-27 | 1980-04-03 | Partek Ab | Glass composition for fiber manufacture |
JPH04317436A (en) * | 1990-12-25 | 1992-11-09 | Tsukishima Kikai Co Ltd | Production of crystallized glass |
-
1995
- 1995-05-12 JP JP7147983A patent/JPH08310834A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5547246A (en) * | 1978-09-27 | 1980-04-03 | Partek Ab | Glass composition for fiber manufacture |
JPH04317436A (en) * | 1990-12-25 | 1992-11-09 | Tsukishima Kikai Co Ltd | Production of crystallized glass |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002308646A (en) * | 2001-04-10 | 2002-10-23 | Masatoshi Sato | Wollastonite-based glass ceramic fired at low temperature and method of producing the same |
KR20030079097A (en) * | 2002-04-01 | 2003-10-10 | 윤연흠 | Production of glass-ceramics from waste glass and waste shell |
KR100530355B1 (en) * | 2002-08-16 | 2005-11-22 | 미래화학 주식회사 | Method for manufacturing an aggregate |
FR2867400A1 (en) * | 2004-03-10 | 2005-09-16 | Marcadier Eric | Utilization of vitrified residue from the purification of fumes from the incineration of household waste as a secondary compound in cement clinker for road making, railway ballast and fibre |
EP1582508A3 (en) * | 2004-03-10 | 2008-07-09 | Eric Marcadier | Method for treating residues resulting from the purification of garbage incineration fumes and product obtained |
JP2008173558A (en) * | 2007-01-17 | 2008-07-31 | Petroleum Energy Center | Water-permeable purifying wall and purification treatment method of polluted underground water |
CN106396410A (en) * | 2016-08-29 | 2017-02-15 | 中国恩菲工程技术有限公司 | Production method of microcrystalline glass |
CN106396411A (en) * | 2016-08-29 | 2017-02-15 | 中国恩菲工程技术有限公司 | Preparation method of microcrystalline glass |
CN106396410B (en) * | 2016-08-29 | 2018-11-09 | 中国恩菲工程技术有限公司 | The preparation method of devitrified glass |
CN106396411B (en) * | 2016-08-29 | 2019-01-08 | 中国恩菲工程技术有限公司 | The preparation method of devitrified glass |
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