JP2012153557A - Artificial aggregate and method of manufacturing the same - Google Patents

Artificial aggregate and method of manufacturing the same Download PDF

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JP2012153557A
JP2012153557A JP2011013506A JP2011013506A JP2012153557A JP 2012153557 A JP2012153557 A JP 2012153557A JP 2011013506 A JP2011013506 A JP 2011013506A JP 2011013506 A JP2011013506 A JP 2011013506A JP 2012153557 A JP2012153557 A JP 2012153557A
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molten slag
raw material
added
artificial aggregate
artificial
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Hiroyuki Ono
浩之 小野
Kouji Fujita
浩示 藤田
Tomoya Suzuki
智也 鈴木
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Dowa Eco Systems Co Ltd
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Dowa Eco Systems Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Abstract

PROBLEM TO BE SOLVED: To provide an artificial aggregate that has a novel composition including gehlenite shown by 2CaO-AlO-SiOas a principal ingredient, and to provide a method of manufacturing the same.SOLUTION: The artificial aggregate includes gehlenite shown by 2CaO-AlO-SiO, wherein Al is 10-22 mass% by an alumina conversion, CaO/SiOis at most 1.2. In addition, NaO and/or MgO may be contained, NaO is at most 8 mass%. and MgO is at most 5 mass%. The artificial aggregate may further include at least one chosen from a group consisting of FeO, POand TiO.

Description

本発明は、人工骨材及びその製造方法に関する。さらに詳しくは、本発明は、２ＣａＯ・Ａ１２０３・ＳｉＯ２からなるゲーレナイトを主成分とする人工骨材及びその製造方法に関する。 The present invention relates to an artificial aggregate and a method for manufacturing the same. More specifically, the present invention relates to an artificial bone material composed mainly of gehlenite composed of 2CaO · A1 2 0 3 · SiO 2 and a method for producing the same.

生活ごみ等の一般廃棄物の燃えがら、つまり焼却灰が人工骨材等の原料として使用されている。具体的には、一般廃棄物の焼却灰が再度溶融されて溶融液とされ、この溶融液が冷却されることで、溶融スラグが得られる。この溶融スラグが人工骨材として利用される。一般廃棄物の焼却灰を溶融スラグとすることによって、焼却灰に含まれる重金属類や還元可能な酸化物を溶融還元して除去すると共に、ＳｉＯ２やＡｌ２Ｏ３等の鉱物質を主成分とする溶融スラグが得られる。このような溶融スラグから天然岩石に極めて近い組成のコンクリート用人工骨材が製造されている（特許文献１参照）。人工骨材の原料となる焼却灰としては、上記した一般廃棄物に加えて、産業廃棄物や下水道で回収される汚泥等の焼却灰も使用されている。 Combustion of general waste such as household waste, that is, incinerated ash, is used as a raw material for artificial aggregates and the like. Specifically, incineration ash of general waste is melted again to form a molten liquid, and this molten liquid is cooled to obtain molten slag. This molten slag is used as an artificial aggregate. By making incineration ash of general waste into molten slag, heavy metals and reducible oxides contained in incineration ash are removed by melting reduction, and mineral substances such as SiO 2 and Al 2 O 3 are the main components A molten slag is obtained. An artificial aggregate for concrete having a composition very close to that of natural rock is produced from such molten slag (see Patent Document 1). As incineration ash used as a raw material for artificial aggregates, incineration ash such as industrial waste and sludge collected in sewers is used in addition to the above general waste.

人工骨材の製造において、従来は、一般廃棄物由来の燃えがらを原料としていたので、原料の安定性は確保されていた。しかしながら、近年、原料となる一般廃棄物由来の焼却灰に対して添加される産業廃棄物由来の焼却灰の比率が増加している。このため、産業廃棄物由来の焼却灰に含まれるＮａやＭｇ等が混入するようになり、原料の組成変動が大きくなってきている。   In the production of artificial aggregates, conventionally, since the waste derived from general waste was used as a raw material, the stability of the raw material was ensured. However, in recent years, the ratio of industrial waste-derived incineration ash added to general waste-derived incineration ash as a raw material has increased. For this reason, Na, Mg, etc. contained in the incineration ash derived from industrial waste are mixed, and the composition fluctuation of the raw material is increasing.

このため、人工骨材となる溶融スラグの原料として、一般廃棄物由来の焼却灰に産業廃棄物由来の焼却灰が混入された原料を使用した場合、処理後の融液を水冷あるいは空冷して得られる溶融スラグはガラス質となることが多かった。   For this reason, when using raw materials in which incineration ash derived from industrial waste is mixed with incineration ash derived from general waste as a raw material for molten slag to be used as an artificial aggregate, the treated melt is cooled with water or air. The obtained molten slag was often glassy.

得られた溶融スラグを砂、砂利、平板等の建設資材として再利用する場合、溶融スラグがガラス質の溶融スラグでは強度が低い。このため、ガラス質の溶融スラグは結晶質の溶融スラグに比較して再利用の範囲が狭い。このように様々な組成を持つ廃棄物に対して、安定して高い強度を持つ、結晶性の高い溶融スラグを得ることが難しかった。   When the obtained molten slag is reused as construction materials such as sand, gravel, and flat plate, the strength is low when the molten slag is glassy molten slag. For this reason, the range of reuse of glassy molten slag is narrower than that of crystalline molten slag. As described above, it has been difficult to obtain a highly crystalline molten slag having a stable and high strength for waste having various compositions.

特開平０９−１９４２４０号公報JP 09-194240 A

従来の一般廃棄物由来の原料を用いた人工骨材の製造方法では、製造管理の指標として原料となる焼却灰の組成分析を行い、ＣａＯ／ＳｉＯ２の重量比、所謂塩基度を基準として人工骨材の組成管理を行ってきた。しかしながら、ＮａやＭｇといった他の元素のバラツキも大きくなってきているため、結晶化されずにガラス質の人工石ができてしまう場合が増えているという課題がある。 In the conventional method for producing artificial aggregate using raw materials derived from general waste, composition analysis of incinerated ash as a raw material is performed as an index for production control, and the artificial weight is calculated based on the CaO / SiO 2 weight ratio, so-called basicity. We have been managing the composition of aggregates. However, since the variation of other elements such as Na and Mg is also increasing, there is a problem that the number of cases where a vitreous artificial stone is formed without being crystallized increases.

さらに、操業時の溶融液の粘性変動が大きいため、出滓の安定性が保てなくなってきているという課題がある。   Furthermore, since the viscosity fluctuation of the melt during operation is large, there is a problem that the stability of the brewing cannot be maintained.

本発明は上記課題に鑑み、２ＣａＯ・Ａｌ２Ｏ３・ＳｉＯ２で表されるゲーレナイトを主成分とした組成を有する人工骨材を提供することを第１の目的とし、人工骨材の製造方法を提供することを第２の目的としている。 In view of the above problems, the first object of the present invention is to provide an artificial aggregate having a composition mainly composed of gehlenite represented by 2CaO.Al 2 O 3 .SiO 2. The second purpose is to provide the above.

上記第１の目的を達成するために、本発明の人工骨材は、２ＣａＯ・Ａｌ２Ｏ３・ＳｉＯ２で表されるゲーレナイトを含み、Ａｌはアルミナ換算で１０〜２２質量％を含有し、ＣａＯ／ＳｉＯ２を１．２以下で含むことを特徴とする。 In order to achieve the first object, the artificial aggregate of the present invention includes galenite represented by 2CaO.Al 2 O 3 .SiO 2 , Al contains 10 to 22% by mass in terms of alumina, CaO / SiO 2 is contained in 1.2 or less.

上記構成において、Ｎａ２Ｏ及び／又はＭｇＯが含有され、Ｎａ２Ｏは８質量％以下で含有し、ＭｇＯは５質量％以下で含むようにしてもよい。
さらに、Ｆｅ２Ｏ３、Ｐ２Ｏ５及びＴｉＯ２から成る群より選ばれた少なくとも１種が含有されていてもよい。
Ｆｅ２Ｏ３は、好ましくは１０質量％以下含有されている。Ｐ２Ｏ５は、好ましくは３質量％以下含有されている。ＴｉＯ２は、好ましくは５質量％以下含有されている。 In the above configuration, Na 2 O and / or MgO may be contained, Na 2 O may be contained at 8% by mass or less, and MgO may be contained at 5% by mass or less.
Furthermore, at least one selected from the group consisting of Fe 2 O 3 , P 2 O 5 and TiO 2 may be contained.
Fe 2 O 3 is preferably contained in an amount of 10% by mass or less. P 2 O 5 is preferably contained in an amount of 3% by mass or less. TiO 2 is preferably contained in an amount of 5% by mass or less.

上記第２の目的を達成するために、本発明の人工骨材骨材の製造方法は、上記の何れかに記載の人工骨材を製造するに当たり、人工骨材の原料及び還元剤を所定の溶融温度まで昇温して溶融液とする還元溶融工程と、溶融液を溶融温度で所定時間保持する工程と、所定時間保持した後溶融液を徐冷して溶融液を結晶化する工程と、を備えていることを特徴とする。   In order to achieve the second object described above, the method for producing an artificial aggregate according to the present invention, when producing the artificial aggregate according to any one of the above, provides a raw material for the artificial aggregate and a reducing agent in a predetermined manner. A reduction melting step of raising the temperature to the melting temperature to obtain a melt, a step of holding the melt at a melting temperature for a predetermined time, a step of holding the melt for a predetermined time and then slowly cooling the melt to crystallize the melt; It is characterized by having.

上記構成において、原料は、好ましくは、一般廃棄物の焼却灰、又は一般廃棄物及び産業廃棄物を混合した焼却灰からなる。還元剤は、好ましくはコークスである。原料にさらにＣａ化合物を添加してもよい。   In the above configuration, the raw material is preferably made of incineration ash of general waste or incineration ash obtained by mixing general waste and industrial waste. The reducing agent is preferably coke. A Ca compound may be further added to the raw material.

本発明によれば、ゲーレナイトを主成分とし結晶性が高く、強度が高い人工骨材を提供することができる。   According to the present invention, it is possible to provide an artificial aggregate having gehlenite as a main component, high crystallinity, and high strength.

本発明の人工骨材の製造方法によれば、溶融スラグの原料を一般廃棄物由来の焼却灰だけではなく、産業廃棄物由来の焼却灰等も使用して、強度が高い人工骨材を製造することができる。従来の溶融スラグでは、原料となる焼却灰のＣａＯ／ＳｉＯ２の重量比、所謂塩基度を基準にして組成管理を行ってきた。本発明の人工骨材の製造方法によれば、Ｎａ、Ｍｇ、Ｆｅ、Ｐ、Ｔｉ等の結晶化に寄与する原料を考慮した組成管理を行うことで、結晶質の人工骨材を再現性良く製造することができる。 According to the method for producing an artificial aggregate of the present invention, not only incineration ash derived from general waste but also incineration ash derived from industrial waste is used as a raw material for molten slag to produce an artificial aggregate having high strength. can do. In conventional molten slag, composition management has been carried out based on the so-called basicity of CaO / SiO 2 weight ratio of the incinerated ash used as a raw material. According to the method for producing an artificial aggregate of the present invention, a crystalline artificial aggregate can be reproduced with good reproducibility by performing composition management in consideration of raw materials contributing to crystallization such as Na, Mg, Fe, P, and Ti. Can be manufactured.

本発明の人工骨材の基本組成を説明する２ＣａＯ・Ａｌ２Ｏ３・ＳｉＯ２の３元系相図であり、（Ａ）は全体図、（Ｂ）は部分拡大図である。A ternary phase diagram of 2CaO · Al 2 O 3 · SiO 2 illustrating the basic composition of the artificial bone material of the present invention, (A) is an overall view, (B) is a partially enlarged view. 本発明の人工骨材を製造するための温度プログラムの一例を示す図である。It is a figure which shows an example of the temperature program for manufacturing the artificial aggregate of this invention. 本発明の実施例１の溶融スラグを作製する際の温度プログラムを示す図である。It is a figure which shows the temperature program at the time of producing the molten slag of Example 1 of this invention. 実施例１の還元溶融した場合における溶融スラグのＸＲＤの測定結果を示す図である。It is a figure which shows the measurement result of XRD of the molten slag in the case of carrying out the reduction melting of Example 1. FIG. 比較例１の酸化溶融した場合における溶融スラグのＸＲＤの測定結果を示す図である。It is a figure which shows the measurement result of XRD of the molten slag in the case of carrying out the oxidation melting of the comparative example 1.

以下、本発明を実施形態に即して詳細に説明する。
本発明の人工骨材は、２ＣａＯ・Ａｌ２Ｏ３・ＳｉＯ２で表されるゲーレナイトを含み、Ａｌの質量％（ｗｔ％と表記する）がアルミナ換算で１０〜２５ｗｔ％で含有され、ＣａＯ／ＳｉＯ２が１．２以下で含有される。Ａｌは、好ましくは、１０〜２２．５質量％、より好ましくは１０〜２０質量％、さらに好ましくは１０〜１５質量％で含有される。人工骨材には、上記の組成に、さらに、Ｎａ２Ｏ、ＭｇＯのいずれか一方又は双方を、Ｎａ２Ｏを８質量％以下、ＭｇＯを５質量％以下の割合で含めることが好ましい。人工骨材には、上記ゲーレナイト又はゲーレナイトにＮａ２Ｏ及び又はＭｇＯに、さらに、Ｆｅ２Ｏ３、Ｐ２Ｏ５及びＴｉＯ２からなる群より選ばれた少なくとも１種が含有されることが好ましい。本発明の人工骨材は、主成分がゲーレナイトであり、結晶性の溶融スラグからなる。以下、本発明では、質量％はｗｔ％とも表記する。
なお、ゲーレナイトの組成は、Ｃａ２Ａｌ２ＳｉＯ７とも表記される。ＣａＯ／ＳｉＯ２は、塩基度とも呼ばれている。 Hereinafter, the present invention will be described in detail according to embodiments.
The artificial aggregate of the present invention contains gehlenite represented by 2CaO.Al 2 O 3 .SiO 2 , the mass% of Al (expressed as wt%) is contained at 10 to 25 wt% in terms of alumina, and CaO / SiO 2 is contained in 1.2 or less. Al is preferably contained at 10 to 22.5% by mass, more preferably 10 to 20% by mass, and still more preferably 10 to 15% by mass. It is preferable that the artificial aggregate further includes one or both of Na 2 O and MgO in the above-described composition in a ratio of Na 2 O of 8% by mass or less and MgO of 5% by mass or less. The artificial aggregate preferably contains at least one selected from the group consisting of Fe 2 O 3 , P 2 O 5 and TiO 2 in addition to Na 2 O and / or MgO in the above-mentioned gelenite or gehlenite. . The artificial aggregate of the present invention is mainly composed of gehlenite and is made of crystalline molten slag. Hereinafter, in the present invention, mass% is also expressed as wt%.
The composition of gehlenite is also expressed as Ca 2 Al 2 SiO 7 . CaO / SiO 2 is also called basicity.

本発明の人工骨材において、Ｎａ２Ｏは、ゲーレナイトにさらに結晶化のために含有される原料である。Ｎａ２Ｏを８ｗｔ％以下とすれば、本発明の人工骨材の結晶化ができ、人工骨材の強度を増加することができる。Ｎａ２Ｏが８ｗｔ％より多い場合は、結晶化を阻害するため好ましくない。 In the artificial aggregate of the present invention, Na 2 O is a raw material further contained in gerenite for crystallization. When Na 2 O is 8 wt% or less, the artificial aggregate of the present invention can be crystallized, and the strength of the artificial aggregate can be increased. When Na 2 O is more than 8 wt%, it is not preferable because crystallization is inhibited.

ＭｇＯは、人工骨材の結晶化のためにゲーレナイトに含有される原料である。ＭｇＯを５ｗｔ％以下とすれば、本発明の人工骨材の結晶化ができ、人工骨材の強度を増すことができる。ＭｇＯが５ｗｔ％より多い場合は、結晶化を阻害するため好ましくない。
なお、上記の人工骨材の組成においては、Ｎａ２ＯとＭｇＯの組成分析をしたとき、Ｎａ２ＯとＭｇＯの含有量が定量限界以下程度の値であるときにはＮａ２ＯとＭｇＯを共に０ｗｔ％とする。この場合、人工骨材の組成はゲーレナイトに近い組成となるが、結晶性であるので、人工骨材としての使用には支障がない。さらに、人工骨材の組成分析をしたときにＮａ２Ｏ又はＭｇＯが定量の限界以下程度の場合も、Ｎａ２Ｏ又はＭｇＯの含有量を０ｗｔ％とする。この場合の人工骨材の組成は、ゲーレナイトを主成分として、さらにＮａ２Ｏ又はＭｇＯが含有されている組成であり、本発明の人工骨材の組成に含まれる。 MgO is a raw material contained in gehlenite for crystallization of artificial aggregate. If MgO is 5 wt% or less, the artificial aggregate of the present invention can be crystallized, and the strength of the artificial aggregate can be increased. When MgO is more than 5 wt%, crystallization is inhibited, which is not preferable.
In the composition of the artificial bone material, when the composition analysis of Na 2 O and MgO, when the content of Na 2 O and MgO is a value lower than about the quantitation limit Na 2 O and MgO together 0wt %. In this case, the composition of the artificial aggregate is a composition close to that of gehlenite, but since it is crystalline, there is no hindrance to its use as an artificial aggregate. Further, when the composition of the artificial aggregate is analyzed, the content of Na 2 O or MgO is set to 0 wt% even when Na 2 O or MgO is less than the limit of quantification. The composition of the artificial aggregate in this case is a composition containing gehlenite as a main component and further containing Na 2 O or MgO, and is included in the composition of the artificial aggregate of the present invention.

上記人工骨材には、Ｆｅ２Ｏ３、Ｐ２Ｏ５及びＴｉＯ２から成る群より選ばれた少なくとも１種が含有されてもよい。Ｆｅ２Ｏ３は、好ましくは１０ｗｔ％以下であり、この範囲内であれば、本発明の人工骨材の結晶化ができ、人工骨材の強度を増すことができる。Ｆｅ２Ｏ３が１０ｗｔ％より多い場合は、結晶化を阻害するため好ましくない。 The artificial aggregate may contain at least one selected from the group consisting of Fe 2 O 3 , P 2 O 5 and TiO 2 . Fe 2 O 3 is preferably 10 wt% or less, and within this range, the artificial aggregate of the present invention can be crystallized and the strength of the artificial aggregate can be increased. When Fe 2 O 3 is more than 10 wt%, it is not preferable because crystallization is inhibited.

Ｐ２Ｏ５は、好ましくは３ｗｔ％以下であり、この範囲内であれば本発明の人工骨材のガラス化を効果的に防止することができる。Ｐ２Ｏ５が３ｗｔ％より多い場合は、結晶化を阻害するため好ましくない。 P 2 O 5 is preferably 3 wt% or less, and within this range, vitrification of the artificial aggregate of the present invention can be effectively prevented. If P 2 O 5 is more than 3 wt% is not preferable because of inhibiting crystallization.

ＴｉＯ２は、好ましくは５ｗｔ％以下であり、この範囲内であれば本発明の人工骨材のガラス化を効果的に防止することができる。ＴｉＯ２が５ｗｔ％より多い場合は、結晶化を阻害するため好ましくない。 TiO 2 is preferably not more than 5 wt%, it is possible to prevent the glass of the artificial bone material of the present invention as long as it is within this range effectively. If TiO 2 is more than 5 wt% is not preferable because of inhibiting crystallization.

図１は、本発明の人工骨材の基本組成を説明する２ＣａＯ・Ａｌ２Ｏ３・ＳｉＯ２の３元系相図であり、（Ａ）が全体図、（Ｂ）は部分拡大図である。
図１（Ａ）に示すように、略５角形の領域Ａは、１４００℃の液相範囲である。図１（Ｂ）の部分拡大した図中に示す上記領域Ａ内の(1)、(2)、(3)、(4)、(5)、(6)、(7)は、Ａｌ組成を１０〜２５ｗｔ％とした基本組成を示している。さらに、塩基度が０．７、０．８、０．９、１．０、１、２となる領域を点線で示している。 Figure 1 is a ternary phase diagram of 2CaO · Al 2 O 3 · SiO 2 illustrating the basic composition of the artificial bone material of the present invention is the overall view, (B) is a partial enlarged diagram (A) .
As shown in FIG. 1A, the substantially pentagonal region A is a liquid phase range of 1400 ° C. (1), (2), (3), (4), (5), (6), (7) in the region A shown in the partially enlarged view of FIG. The basic composition is 10 to 25 wt%. Furthermore, regions where the basicity is 0.7, 0.8, 0.9, 1.0, 1, 2 are indicated by dotted lines.

本発明の人工骨材によれば、ゲーレナイトを主成分とするので強度が高い。この人工骨材は、建設資材等として利用することができる。   According to the artificial aggregate of the present invention, the strength is high because gehlenite is a main component. This artificial aggregate can be used as a construction material or the like.

次に、本発明の人工骨材の製造方法について説明する。
人工骨材は、人工骨材の原料及び還元剤を、所定の溶融温度まで昇温して溶融液とする還元溶融工程と、
溶融液を溶融温度で所定時間保持する工程と、
所定時間保持した後溶融液を徐冷して、溶融液を結晶化する工程と、
を順に行うことによって製造することができる。 Next, the manufacturing method of the artificial aggregate of this invention is demonstrated.
Artificial aggregate is a reducing and melting step in which the raw material of artificial aggregate and the reducing agent are heated to a predetermined melting temperature to form a melt,
Holding the melt at a melting temperature for a predetermined time;
A step of slowly cooling the melt after holding for a predetermined time to crystallize the melt;
Can be manufactured in order.

具体的には、人工骨材の原料と還元剤を調製し、この原料及び還元剤を溶融炉に投入した後昇温して溶融液とし、この溶融液を所定の溶融温度で所定時間溶融した後、金属製の型に流し入れ、冷却することで、結晶化した溶融スラグが得られる。この溶融スラグが本発明の人工骨材となる。必要に応じて、溶融スラグの粉砕処理を行うことによって所定の粒径をもった人工骨材としてもよい。原料としては、一般廃棄物や、一般廃棄物の焼却灰に産業廃棄物の焼却灰が一部混合された焼却灰を用いることができる。原料の組成は、人工骨材の上記組成、つまりゲーレナイトを主成分として、Ａｌはアルミナ換算で１０〜２２ｗｔ％であり、ＣａＯ／ＳｉＯ２が１．２以下である。さらに、添加剤として、Ｎａ２Ｏ、ＭｇＯのいずれか一方又は双方を、Ｎａ２Ｏを８質量％以下、ＭｇＯを５質量％以下となる組成が得られるように調製できる。原料には、上記したＦｅ２Ｏ３、Ｐ２Ｏ５、ＴｉＯ２の何れかの含有物を添加剤として添加してもよい。さらに、原料には、ＣａＯ／ＳｉＯ２を調整するために調整剤としてＣａ又はＣａを含む化合物を添加してもよい。調整剤として生石灰（ＣａＯ）等を用いることができる。 Specifically, a raw material and a reducing agent for an artificial aggregate are prepared, and after the raw material and the reducing agent are put into a melting furnace, the temperature is raised to a molten liquid, and the molten liquid is melted at a predetermined melting temperature for a predetermined time. Thereafter, it is poured into a metal mold and cooled to obtain crystallized molten slag. This molten slag becomes the artificial aggregate of the present invention. If necessary, an artificial bone material having a predetermined particle size may be obtained by pulverizing molten slag. As a raw material, incineration ash in which incineration ash of industrial waste is partially mixed with incineration ash of general waste or general waste can be used. The composition of the raw material is the above composition of the artificial aggregate, that is, gehlenite as a main component, Al is 10 to 22 wt% in terms of alumina, and CaO / SiO 2 is 1.2 or less. Further, as an additive, Na 2 O, one or both of MgO, Na 2 O to 8% by weight or less, can be prepared as MgO and 5 mass% or less composition is obtained. Any of the above-described contents of Fe 2 O 3 , P 2 O 5 and TiO 2 may be added as an additive to the raw material. In addition, the raw material may be added a compound containing Ca or Ca as an adjusting agent for adjusting the CaO / SiO 2. Quick lime (CaO) etc. can be used as a regulator.

原料の組成は、周知の元素分析装置によって測定することができる。このような元素分析装置としては、蛍光Ｘ線測定装置等を用いることができる。   The composition of the raw material can be measured by a known elemental analyzer. As such an elemental analyzer, a fluorescent X-ray measuring device or the like can be used.

還元剤としてはコークスを用いることができる。還元剤の添加量としては、原材料１トン（ｔ）に対して５０ｋｇ以上とすればよい。還元剤の添加量が５０ｋｇよりも少ない場合には、還元が十分されないので好ましくない。   Coke can be used as the reducing agent. The addition amount of the reducing agent may be 50 kg or more with respect to 1 ton (t) of the raw material. When the amount of the reducing agent added is less than 50 kg, the reduction is not sufficient, which is not preferable.

溶融温度は原料が液相となる温度であり、１３００〜１７００℃の範囲とすることができる。溶融温度で保持する時間、つまり溶融時間は、３０分〜１８０分の範囲とすることができる。   The melting temperature is a temperature at which the raw material becomes a liquid phase, and can be in the range of 1300 to 1700 ° C. The time for holding at the melting temperature, that is, the melting time can be in the range of 30 minutes to 180 minutes.

図２は、本発明の人工骨材を製造するための温度プログラムの一例を示す図である。図２の横軸は時間（分）であり、縦軸は溶融炉の温度（℃）である。
図２に示すように、２０℃から１６００℃まで３０分で昇温した。このときの昇温速度は約５３℃／分である。次に、昇温開始３０分から６０分迄は１６００℃で３０分保持し、次に最初から９０分経過後迄、つまり３０分で１４００℃まで徐冷した後、出滓した。出滓までの降温速度は−６．７℃／分である。出滓の後、２７０分経過後までに４３０℃まで徐冷した。型ばらしは、１６５分経過後の８７０℃で行った。 FIG. 2 is a diagram showing an example of a temperature program for manufacturing the artificial aggregate of the present invention. The horizontal axis in FIG. 2 is time (minutes), and the vertical axis is the melting furnace temperature (° C.).
As shown in FIG. 2, the temperature was raised from 20 ° C. to 1600 ° C. in 30 minutes. The temperature rising rate at this time is about 53 ° C./min. Next, the temperature was maintained at 1600 ° C. for 30 minutes from 30 minutes to 60 minutes, and then gradually cooled to 1400 ° C. after 90 minutes from the beginning, that is, 30 minutes. The rate of temperature decrease until tapping is −6.7 ° C./min. After brewing, it was gradually cooled to 430 ° C. by 270 minutes. Mold release was performed at 870 ° C. after 165 minutes.

本発明の人工骨材の製造方法によれば、一般廃棄物由来の焼却灰だけではなく、産業廃棄物由来の焼却灰等も原料の一部として使用することができる。従来の一般廃棄物由来の焼却灰だけを原料とした溶融スラグの製造方法では、ＣａＯ／ＳｉＯ２の重量比、つまり、塩基度だけで組成管理を行ってきた。本発明の人工骨材の製造方法によれば、さらにＮａ、Ｍｇ、Ｆｅ、Ｐ、Ｔｉ等の結晶化に寄与する原料を考慮した組成管理を行うことで、結晶質の溶融スラグからなる人工骨材を再現性良く製造することができる。 According to the method for producing an artificial aggregate of the present invention, not only incineration ash derived from general waste but also incineration ash derived from industrial waste can be used as a part of the raw material. In a conventional method for producing molten slag using only incineration ash derived from general waste as a raw material, composition management has been performed only by the weight ratio of CaO / SiO 2 , that is, basicity. According to the method for producing an artificial aggregate of the present invention, an artificial bone made of crystalline molten slag is obtained by performing composition management in consideration of raw materials contributing to crystallization such as Na, Mg, Fe, P, and Ti. The material can be manufactured with good reproducibility.

以下、本発明の実施例についてさらに詳細に説明する。
原料の基本組成比（ｗｔ％）を、ＳｉＯ２：Ａｌ２Ｏ３：ＣａＯ＝４０：２０：４０とした。ＣａＯ／ＳｉＯ２の重量比である塩基度は１である。溶融スラグ中に含まれるＳｉＯ２の原料として、試薬ＳｉＯ２（無水ケイ酸、Ｐｒ．Ｇグレード）を用いた。溶融スラグ中に含まれるＡｌ２Ｏ３の原料としては、試薬Ａｌ２Ｏ３（酸化アルミニウム、特級）を用いた。溶融スラグ中に含まれるＣａＯの原料としては、試薬Ｃａ（ＯＨ）２（水酸化カルシウム、特級）を用いた。これらの試薬と後述する試薬は何れも和光純薬工業製である。還元溶融の還元剤となるコークスとしては、試薬活性炭素（活性炭素、粉末）を用いた。ここで、原料として試薬を用いたのは、溶融スラグが結晶性及びガラス質になる組成を正確に把握するためである。Ｎａ２Ｏ及びＭｇＯの含有量は、他の添加剤等の効果を確かめるため上記試薬に含有される程度とした。蛍光Ｘ線測定装置によって測定した実施例１の原料のＮａ２Ｏ及びＭｇＯの含有量は、定量限界の０．１ｗｔ％以下であった。 Hereinafter, examples of the present invention will be described in more detail.
The basic composition ratio (wt%) of the raw material was SiO 2 : Al 2 O 3 : CaO = 40: 20: 40. The basicity which is the weight ratio of CaO / SiO 2 is 1. Reagent SiO 2 (anhydrous silicic acid, Pr. G grade) was used as a raw material for SiO 2 contained in the molten slag. Reagent Al 2 O 3 (aluminum oxide, special grade) was used as a raw material for Al 2 O 3 contained in the molten slag. Reagent Ca (OH) 2 (calcium hydroxide, special grade) was used as a raw material for CaO contained in the molten slag. These reagents and the reagents described later are all manufactured by Wako Pure Chemical Industries. Reagent activated carbon (activated carbon, powder) was used as coke as a reducing agent for reduction melting. Here, the reagent was used as the raw material in order to accurately grasp the composition in which the molten slag becomes crystalline and vitreous. The content of Na 2 O and MgO was set to the extent contained in the reagent in order to confirm the effects of other additives. The contents of Na 2 O and MgO of the raw material of Example 1 measured by a fluorescent X-ray measurement device were 0.1 wt% or less, which is the limit of quantification.

上記の各試薬をｍｇ単位まで測定し、合計で約２０ｇとなるように秤量した。これらの原料をチャック付きビニール袋内に封入し、１０秒×５回の条件で振とう攪拌して混合した。   Each of the above reagents was measured to the nearest mg, and weighed to a total of about 20 g. These raw materials were enclosed in a plastic bag with a chuck and mixed by shaking and stirring under conditions of 10 seconds × 5 times.

上記原料を、容積が２０ｍｌ（ｃｍ３）のアルミナ製の坩堝（アズワン製、純度
９９％、ＡＲＣ−２０、φ３８ｍｍ×４４ｍｍ）に充填し、空気中で昇温した。 The raw material was charged into an alumina crucible (Azuwan, purity 99%, ARC-20, φ38 mm × 44 mm) having a volume of 20 ml (cm 3 ), and heated in air.

アルミナ製の坩堝は、ガス流通なしで電気炉（光洋サーモシステム製、ＫＢＦ３１４Ｎ１）で加熱し、所定の溶融温度で所定時間加熱した後で徐冷した。電気炉の炉内寸法は、１２５ｍｍ（Ｗ）×１２３ｍｍ（Ｈ）×１５５ｍｍ（Ｄ）であった。電気炉の熱電対位置は、背面から５０ｍｍ、上面から１５ｍｍの位置とした。   The alumina crucible was heated by an electric furnace (manufactured by Koyo Thermo Systems, KBF314N1) without gas flow, heated at a predetermined melting temperature for a predetermined time, and then gradually cooled. The in-furnace dimensions of the electric furnace were 125 mm (W) × 123 mm (H) × 155 mm (D). The thermocouple position of the electric furnace was 50 mm from the back and 15 mm from the top.

溶融固化して得た溶融固化物、つまり溶融スラグの結晶性は、下記のようにして評価した。
溶融スラグの結晶性を、粉末Ｘ線回折（ＸＲＤ）を用いて評価した。Ｘ線回折装置（リガク製、MiniFlex）を使用し、Ｘ線ターゲットは銅（Ｃｕ）を用いた。Ｘ線管は、管電圧４０ｋＶ、管電流４０ｍＡで測定した。スキャンスピードは２度／分であり、スキャン範囲は２θ＝２０〜８０度とした。 The melt-solidified product obtained by melt-solidification, that is, the crystallinity of the molten slag was evaluated as follows.
The crystallinity of the molten slag was evaluated using powder X-ray diffraction (XRD). An X-ray diffractometer (manufactured by Rigaku, MiniFlex) was used, and the X-ray target was copper (Cu). The X-ray tube was measured at a tube voltage of 40 kV and a tube current of 40 mA. The scan speed was 2 degrees / minute, and the scan range was 2θ = 20 to 80 degrees.

溶融スラグの組成は、波長分散型の蛍光Ｘ線測定装置（リガク製、Rigaku Supermini、Ezscanモード）で評価した。   The composition of the molten slag was evaluated with a wavelength dispersive X-ray fluorescence measurement apparatus (Rigaku, Rigaku Supermini, Ezscan mode).

図３は、本発明の実施例１の溶融スラグを作製する際の温度プログラムを示す図である。図３に示すように、２０℃から１６００℃まで８０分で昇温した。このときの昇温速度は、約２０℃／分である。１６００℃で４０分保持した後、第１の降温として、１６００℃から１４００℃迄３０分で降温した。このときの第１の降温速度は、−６．７℃／分である。さらに、第２の降温として１４００℃から５００℃まで３００分で降温した。このときの第２の降温速度は、−３℃／分である。第２の降温は、冷却速度の影響を排し、原料の組成の影響を明らかにするため、徐冷速度を十分低く設定した。   FIG. 3 is a diagram showing a temperature program when producing the molten slag of Example 1 of the present invention. As shown in FIG. 3, the temperature was raised from 20 ° C. to 1600 ° C. in 80 minutes. The temperature rising rate at this time is about 20 ° C./min. After holding at 1600 ° C. for 40 minutes, the temperature was lowered from 1600 ° C. to 1400 ° C. in 30 minutes as the first temperature drop. The first temperature drop rate at this time is −6.7 ° C./min. Further, the temperature was decreased from 1400 ° C. to 500 ° C. in 300 minutes as the second temperature decrease. The second temperature drop rate at this time is −3 ° C./min. In the second temperature decrease, the cooling rate was set sufficiently low in order to eliminate the effect of the cooling rate and clarify the effect of the composition of the raw material.

Ｆｅ２Ｏ３、Ｐ２Ｏ５、ＴｉＯ２の何れの添加剤も添加しない場合の溶融スラグは、ゲーレナイトが主成分であった。ＸＲＤの測定から、このゲーレナイトのＸ線のピーク強度は２４６３であった。蛍光Ｘ線測定装置によって測定した実施例１の溶融スラグにおけるＮａ２Ｏ及びＭｇＯの含有量は、定量限界の０．１ｗｔ％以下であった。 The molten slag when no additive of Fe 2 O 3 , P 2 O 5 and TiO 2 was added was mainly gehlenite. From the XRD measurement, the peak intensity of X-ray of this gelenite was 2463. The content of Na 2 O and MgO in the molten slag of Example 1 measured by a fluorescent X-ray measurement device was 0.1 wt% or less, which is the limit of quantification.

図４は、実施例１の還元溶融した場合における溶融スラグのＸＲＤの測定結果を示す図である。図４の横軸は、Ｘ線の回折角度θの２倍である２θ（°）であり、縦軸は回折Ｘ線強度（ｃｐｓ）である。図４において、２θ＝３１．５°のピークがゲーレナイトからのＸ線回折を示している。   FIG. 4 is a diagram showing the XRD measurement results of the molten slag when the reduction melting of Example 1 is performed. The horizontal axis in FIG. 4 is 2θ (°), which is twice the diffraction angle θ of X-rays, and the vertical axis is the diffraction X-ray intensity (cps). In FIG. 4, the peak at 2θ = 31.5 ° indicates X-ray diffraction from gehlenite.

実施例２の溶融スラグの原料には、Ｆｅ２Ｏ３を５ｗｔ％添加した。これ以外の条件は実施例１と同様にした。溶融スラグ中に含まれるＦｅ２Ｏ３の原料として、試薬Ｆｅ２Ｏ３（酸化鉄（III）、１級）を用いた。ＸＲＤの測定から、Ｆｅ２Ｏ３を５ｗｔ％添加した場合、溶融スラグは結晶性を有しており、Ｆｅ２Ｏ３を５ｗｔ％添加したゲーレナイトのピーク強度は２１００であった。 As a raw material for the molten slag of Example 2, 5 wt% of Fe 2 O 3 was added. The other conditions were the same as in Example 1. The reagent Fe 2 O 3 (iron (III) oxide, first grade) was used as a raw material for Fe 2 O 3 contained in the molten slag. From the XRD measurement, when 5 wt% of Fe 2 O 3 was added, the molten slag had crystallinity, and the peak intensity of gehlenite with 5 wt% of Fe 2 O 3 added was 2100.

実施例３の溶融スラグの原料には、Ｆｅ２Ｏ３を１０ｗｔ％添加した。これ以外の条件は実施例１と同様にした。ＸＲＤの測定から、Ｆｅ２Ｏ３を１０ｗｔ％添加した実施例３の溶融スラグは結晶性を有しており、Ｆｅ２Ｏ３を１０ｗｔ％添加したゲーレナイトのピーク強度は１２７１であった。 10 wt% of Fe 2 O 3 was added to the raw material for the molten slag of Example 3. The other conditions were the same as in Example 1. From the XRD measurement, the molten slag of Example 3 to which 10 wt% of Fe 2 O 3 was added had crystallinity, and the peak intensity of gehlenite to which 10 wt% of Fe 2 O 3 was added was 1271.

実施例４の溶融スラグの原料には、Ｔｉ２Ｏ３を５ｗｔ％添加した。これ以外の条件は実施例１と同様にした。溶融スラグ中に含まれるＴｉ２Ｏ３の原料としては、試薬ＴｉＯ２（酸化チタン（IV）、アナターゼ型）を用いた。ＸＲＤの測定から、Ｔｉ２Ｏ３を５ｗｔ％添加した実施例４の溶融スラグは結晶性を有しており、Ｔｉ２Ｏ３を５ｗｔ％添加したゲーレナイトのピーク強度は１０５０であった。 To the raw material for the molten slag of Example 4, 5 wt% of Ti 2 O 3 was added. The other conditions were the same as in Example 1. Reagent TiO 2 (titanium (IV) oxide, anatase type) was used as a raw material for Ti 2 O 3 contained in the molten slag. From the XRD measurement, the molten slag of Example 4 to which 5 wt% of Ti 2 O 3 was added had crystallinity, and the peak intensity of gehlenite to which 5 wt% of Ti 2 O 3 was added was 1050.

実施例５の溶融スラグの原料には、ＭｇＯを５ｗｔ％添加した。これ以外の条件は実施例１と同様にした。溶融スラグ中に含まれるＭｇＯの原料としては、試薬ＭｇＯ（酸化マグネシウム（重質）、特級）を用いた。ＸＲＤの測定から、ＭｇＯを５ｗｔ％添加した実施例５の溶融スラグは結晶性を有しており、ＭｇＯを５ｗｔ％添加したゲーレナイトのピーク強度は１７０１であった。   To the raw material for the molten slag of Example 5, 5 wt% of MgO was added. The other conditions were the same as in Example 1. A reagent MgO (magnesium oxide (heavy), special grade) was used as a raw material for MgO contained in the molten slag. From the XRD measurement, the molten slag of Example 5 to which 5 wt% of MgO was added had crystallinity, and the peak intensity of gehlenite to which 5 wt% of MgO was added was 1701.

実施例６の溶融スラグの原料には、Ｎａ２Ｏを３．５ｗｔ％添加した。これ以外の条件は実施例１と同様にした。溶融スラグ中に含まれるＮａ２Ｏの原料としては、試薬ＮａＨＣＯ３（炭酸水素ナトリウム、特級）を用いた。ＸＲＤの測定から、Ｎａ２Ｏを３．５ｗｔ％添加した実施例６の溶融スラグは結晶性を有しており、Ｎａ２Ｏを３．５ｗｔ％添加したゲーレナイトのピーク強度は２５１５であった。 To the raw material for the molten slag of Example 6, 3.5 wt% of Na 2 O was added. The other conditions were the same as in Example 1. As a raw material for Na 2 O contained in the molten slag, a reagent NaHCO 3 (sodium bicarbonate, special grade) was used. From the XRD measurement, the molten slag of Example 6 to which 3.5 wt% of Na 2 O was added had crystallinity, and the peak intensity of gehlenite to which 3.5 wt% of Na 2 O was added was 2515.

（比較例１）
比較例１の溶融スラグの溶融においては、実施例１の還元溶融ではなく、還元剤を添加せず酸化溶融を行った。ＸＲＤの測定から、比較例１の溶融スラグはガラスが主成分であり、比較例１のゲーレナイトのピーク強度は４２８であった。
図５は、比較例１の酸化溶融した場合における溶融スラグのＸＲＤの測定結果を示すもので、図の横軸及び縦軸は、図４と同じである。図４に示した実施例１で還元溶融した溶融スラグのＸＲＤの測定結果と比較すると、結晶化の度合いが著しく弱いことが分かる。 (Comparative Example 1)
In the melting of the molten slag of Comparative Example 1, not the reduction melting of Example 1, but the oxidation melting was performed without adding a reducing agent. From the XRD measurement, the molten slag of Comparative Example 1 was mainly composed of glass, and the peak intensity of the gehlenite of Comparative Example 1 was 428.
FIG. 5 shows the XRD measurement result of the molten slag in the case of oxidation melting in Comparative Example 1, and the horizontal and vertical axes in the figure are the same as those in FIG. Compared with the XRD measurement result of the molten slag reduced and melted in Example 1 shown in FIG. 4, it can be seen that the degree of crystallization is remarkably weak.

（比較例２）
比較例２の溶融スラグの原料にはＦｅ２Ｏ３を５ｗｔ％添加した。これ以外の条件は比較例１と同様にした。ＸＲＤの測定から、比較例２の溶融スラグはガラス質であった。 (Comparative Example 2)
5 wt% of Fe 2 O 3 was added to the raw material for the molten slag of Comparative Example 2. The other conditions were the same as in Comparative Example 1. From the measurement of XRD, the molten slag of Comparative Example 2 was glassy.

（参考例１）
参考例１の溶融スラグの原料には、Ｆｅ２Ｏ３を１５ｗｔ％添加した。これ以外の条件は実施例１と同様にした。ＸＲＤの測定から、参考例１の溶融スラグはガラス質であった。 (Reference Example 1)
15% by weight of Fe 2 O 3 was added to the raw material for the molten slag of Reference Example 1. The other conditions were the same as in Example 1. From the measurement of XRD, the molten slag of Reference Example 1 was glassy.

（比較例３）
比較例３の溶融スラグの原料には、ＴｉＯ２を５ｗｔ％添加した。これ以外の条件は比較例１と同様にした。ＸＲＤの測定から、比較例３の溶融スラグはガラス質であった。 (Comparative Example 3)
5 wt% of TiO 2 was added to the raw material of the molten slag of Comparative Example 3. The other conditions were the same as in Comparative Example 1. From the XRD measurement, the molten slag of Comparative Example 3 was glassy.

（参考例２）
参考例２の溶融スラグの原料には、ＭｇＯを１０ｗｔ％添加した。これ以外の条件は実施例１と同様にした。ＸＲＤの測定から、参考例２の溶融スラグはガラス質であった。 (Reference Example 2)
10 wt% of MgO was added to the raw material for the molten slag of Reference Example 2. The other conditions were the same as in Example 1. From the measurement of XRD, the molten slag of Reference Example 2 was glassy.

表１に、実施例１〜６、比較例１〜３及び参考例１，２で得たゲーレナイトのピーク強度等の結果を纏めて示す。
Table 1 summarizes the results of peak strength and the like of gehlenite obtained in Examples 1 to 6, Comparative Examples 1 to 3, and Reference Examples 1 and 2.

実施例７では、溶融スラグの原料の基本組成比（ｗｔ％）を、ＳｉＯ２：Ａｌ２Ｏ３：ＣａＯ＝４２．５：１５：４２．５とした。ＣａＯ／ＳｉＯ２の重量比である塩基度は１である。ＸＲＤ測定から、添加剤を添加しない場合の溶融スラグは結晶性を有しており、ゲーレナイトのピーク強度は２１７１であった。 In Example 7, the basic composition ratio (wt%) of the raw material for molten slag was SiO 2 : Al 2 O 3 : CaO = 42.5: 15: 42.5. The basicity which is the weight ratio of CaO / SiO 2 is 1. From the XRD measurement, the molten slag in the case where no additive was added had crystallinity, and the peak intensity of gehlenite was 2171.

実施例８の溶融スラグの原料には、Ｆｅ２Ｏ３を１０ｗｔ％添加した。これ以外の条件は実施例７と同様にした。ＸＲＤ測定から、Ｆｅ２Ｏ３を１０ｗｔ％添加した実施例８の溶融スラグは結晶性を有しており、Ｆｅ２Ｏ３を１０ｗｔ％添加したゲーレナイトのピーク強度は２１４２であった。 10 wt% of Fe 2 O 3 was added to the raw material for the molten slag of Example 8. The other conditions were the same as in Example 7. From the XRD measurement, the molten slag of Example 8 to which 10 wt% of Fe 2 O 3 was added had crystallinity, and the peak intensity of gehlenite to which 10 wt% of Fe 2 O 3 was added was 2142.

実施例９の溶融スラグの原料には、ＴｉＯ２を５ｗｔ％添加した。これ以外の条件は実施例７と同様にした。ＸＲＤ測定から、ＴｉＯ２を５ｗｔ％添加した実施例９の溶融スラグは結晶性を有しており、ＴｉＯ２を５ｗｔ％添加したゲーレナイトのピーク強度は３６１であった。 5 wt% of TiO 2 was added to the raw material for the molten slag of Example 9. The other conditions were the same as in Example 7. From the XRD measurement, the molten slag of Example 9 to which 5 wt% of TiO 2 was added had crystallinity, and the peak intensity of gehlenite to which 5 wt% of TiO 2 was added was 361.

実施例１０の溶融スラグの原料には、Ｐ２Ｏ５を３ｗｔ％添加した。溶融スラグ中に含まれるＰ２Ｏ５の原料としては、試薬Ｐ２Ｏ５（酸化リン（V） 無水リン酸 １級）を用いた。これ以外の条件は実施例７と同様にした。ＸＲＤ測定から、Ｐ２Ｏ５を３ｗｔ％添加した実施例１０の溶融スラグは結晶性を有しており、Ｐ２Ｏ５を３ｗｔ％添加したゲーレナイトのピーク強度は２０６１であった。 3 wt% of P 2 O 5 was added to the raw material for the molten slag of Example 10. As a raw material of P 2 O 5 contained in the molten slag, a reagent P 2 O 5 (phosphorus oxide (V) anhydrous phosphoric acid first grade) was used. The other conditions were the same as in Example 7. From the XRD measurement, the molten slag of Example 10 to which 3 wt% of P 2 O 5 was added had crystallinity, and the peak intensity of gehlenite to which 3 wt% of P 2 O 5 was added was 2061.

実施例１１の溶融スラグの原料には、Ｎａ２Ｏを３.５ｗｔ％添加した。これ以外の条件は実施例７と同様にした。ＸＲＤ測定から、Ｎａ２Ｏを３.５ｗｔ％添加した実施例１１の溶融スラグは結晶性を有しており、Ｎａ２Ｏを３.５ｗｔ％添加したゲーレナイトのピーク強度は２６５３であった。 To the raw material for the molten slag of Example 11, 3.5 wt% of Na 2 O was added. The other conditions were the same as in Example 7. From the XRD measurement, the molten slag of Example 11 to which Na 2 O was added by 3.5 wt% had crystallinity, and the peak intensity of gehlenite to which Na 2 O was added by 3.5 wt% was 2653.

（比較例４）
比較例４の溶融スラグの溶融においては、実施例７の還元溶融ではなく、還元剤を添加せず酸化溶融を行った。これ以外の条件は実施例７と同様にした。ＸＲＤ測定から、比較例４の溶融スラグはガラス質であった。 (Comparative Example 4)
In the melting of the molten slag of Comparative Example 4, not the reducing melting of Example 7, but the oxidizing melting was performed without adding a reducing agent. The other conditions were the same as in Example 7. From the XRD measurement, the molten slag of Comparative Example 4 was glassy.

（参考例３）
参考例３の溶融スラグの原料には、Ｆｅ２Ｏ３を１５ｗｔ％添加した。これ以外の条件は実施例７と同様にした。ＸＲＤ測定から、参考例３の溶融スラグはガラス質であった。 (Reference Example 3)
15% by weight of Fe 2 O 3 was added to the raw material for the molten slag of Reference Example 3. The other conditions were the same as in Example 7. From the XRD measurement, the molten slag of Reference Example 3 was glassy.

（参考例４）
参考例４の溶融スラグの原料には、Ｐ２Ｏ５を５ｗｔ％添加した。これ以外の条件は実施例７と同様にした。ＸＲＤ測定から、参考例４の溶融スラグはガラス質であった。 (Reference Example 4)
5 wt% of P 2 O 5 was added to the raw material for the molten slag of Reference Example 4. The other conditions were the same as in Example 7. From the XRD measurement, the molten slag of Reference Example 4 was glassy.

表２に、実施例７〜１１、比較例４及び参考例３，４で得たゲーレナイトのピーク強度等の結果を纏めて示す。
Table 2 summarizes the results of peak intensity and the like of gehlenite obtained in Examples 7 to 11, Comparative Example 4 and Reference Examples 3 and 4.

実施例１２では、溶融スラグの原料の基本組成比（ｗｔ％）を、ＳｉＯ２：Ａｌ２Ｏ３：ＣａＯ＝４４．３：２０：３５．７とした。ＣａＯ／ＳｉＯ２の重量比である塩基度は０．８である。さらに溶融スラグの原料には、Ｎａ２Ｏを８ｗｔ％添加した。ＸＲＤ測定から、実施例１２の溶融スラグは結晶性を有しており、Ｎａ２Ｏを８ｗｔ％添加したゲーレナイトのピーク強度は２４９１であった。 In Example 12, the basic composition ratio (wt%) of the raw material for molten slag was SiO 2 : Al 2 O 3 : CaO = 44.3: 20: 35.7. Basicity in a weight ratio of CaO / SiO 2 is 0.8. Further, 8 wt% of Na 2 O was added to the raw material for the molten slag. From the XRD measurement, the molten slag of Example 12 had crystallinity, and the peak intensity of gehlenite to which 8 wt% of Na 2 O was added was 2491.

表３に、実施例１２のゲーレナイトで得たピーク強度等の結果を纏めて示す。
Table 3 summarizes the results of peak intensity and the like obtained with the gehlenite of Example 12.

実施例１３では、溶融スラグの原料の基本組成比（ｗｔ％）を、ＳｉＯ２：Ａｌ２Ｏ３：ＣａＯ＝４１．９：２０：３８．１とした。ＣａＯ／ＳｉＯ２の重量比である塩基度は０．９である。さらに溶融スラグの原料にはＴｉＯ２を５ｗｔ％添加した。ＸＲＤ測定から、実施例１３の溶融スラグは結晶性を有しており、ＴｉＯ２を５ｗｔ％添加したゲーレナイトのピーク強度は７７６であった。 In Example 13, the basic composition ratio (wt%) of the raw material for molten slag was SiO 2 : Al 2 O 3 : CaO = 41.9: 20: 38.1. The basicity which is the weight ratio of CaO / SiO 2 is 0.9. Furthermore, 5 wt% of TiO 2 was added to the raw material of the molten slag. From the XRD measurement, the molten slag of Example 13 had crystallinity, and the peak intensity of gehlenite to which 5 wt% of TiO 2 was added was 776.

実施例１４の溶融スラグの原料には実施例１３のＴｉＯ２ではなく、Ｎａ２Ｏを８ｗｔ％添加した。これ以外の条件は実施例１３と同様にした。ＸＲＤ測定から、Ｎａ２Ｏを８ｗｔ％添加した実施例１４の溶融スラグは結晶性を有しており、Ｎａ２Ｏを８ｗｔ％添加したゲーレナイトのピーク強度は１６１１であった。 Instead of the TiO 2 of Example 13, 8 wt% of Na 2 O was added to the raw material for the molten slag of Example 14. The other conditions were the same as in Example 13. From the XRD measurement, the molten slag of Example 14 to which 8 wt% of Na 2 O was added had crystallinity, and the peak intensity of gehlenite to which 8 wt% of Na 2 O was added was 1611.

表４に、実施例１３及び１４で得たゲーレナイトのピーク強度等の結果を纏めて示す。
Table 4 summarizes the results of peak intensity and the like of gehlenite obtained in Examples 13 and 14.

実施例１５では、溶融スラグの原料の基本組成比（ｗｔ％）を、ＳｉＯ２：Ａｌ２Ｏ３：ＣａＯ＝５０：１５：３５とした。ＣａＯ／ＳｉＯ２の重量比である塩基度は０．７である。ＸＲＤ測定から、添加剤を添加しない場合の溶融スラグは結晶性を有しており、ゲーレナイトのピーク強度は２４８０であった。 In Example 15, the basic composition ratio (wt%) of the raw material for molten slag was SiO 2 : Al 2 O 3 : CaO = 50: 15: 35. Basicity in a weight ratio of CaO / SiO 2 is 0.7. From the XRD measurement, the molten slag in the case where no additive was added had crystallinity, and the peak intensity of gehlenite was 2480.

実施例１６の溶融スラグの原料には、Ｆｅ２Ｏ３を１０ｗｔ％添加した。これ以外の条件は実施例１５と同様にした。ＸＲＤ測定から、Ｆｅ２Ｏ３を１０ｗｔ％添加した実施例１６の溶融スラグは結晶性を有しており、Ｆｅ２Ｏ３を１０ｗｔ％添加したゲーレナイトのピーク強度は３１１２であった。 10 wt% of Fe 2 O 3 was added to the raw material for the molten slag of Example 16. The other conditions were the same as in Example 15. From the XRD measurement, the molten slag of Example 16 to which 10 wt% of Fe 2 O 3 was added had crystallinity, and the peak intensity of gehlenite to which 10 wt% of Fe 2 O 3 was added was 3112.

（参考例５）
参考例５の溶融スラグの原料には、Ｆｅ２Ｏ３を１５ｗｔ％添加した。これ以外の条件は実施例１５と同様にした。ＸＲＤ測定から、参考例５の溶融スラグはガラス質であった。 (Reference Example 5)
15% by weight of Fe 2 O 3 was added to the raw material for the molten slag of Reference Example 5. The other conditions were the same as in Example 15. From the XRD measurement, the molten slag of Reference Example 5 was glassy.

表５に、実施例１５，１６及び参考例５で得たゲーレナイトのピーク強度等の結果を纏めて示す。
Table 5 summarizes the results of peak intensity and the like of gehlenite obtained in Examples 15 and 16 and Reference Example 5.

実施例１７では、溶融スラグの原料の基本組成比（ｗｔ％）を、ＳｉＯ２：Ａｌ２Ｏ３：ＣａＯ＝４５．６：２２．５：３１．９とした。ＣａＯ／ＳｉＯ２の重量比である塩基度は０．７である。原料には、Ｆｅ２Ｏ３を１０ｗｔ％添加した。ＸＲＤ測定から、Ｆｅ２Ｏ３を１０ｗｔ％添加した実施例１７の溶融スラグは結晶性を有しており、Ｆｅ２Ｏ３を１０ｗｔ％添加したゲーレナイトのピーク強度は３２０２であった。 In Example 17, the basic composition ratio (wt%) of the raw material for molten slag was SiO 2 : Al 2 O 3 : CaO = 45.6: 22.5: 31.9. Basicity in a weight ratio of CaO / SiO 2 is 0.7. As a raw material, 10 wt% of Fe 2 O 3 was added. From the XRD measurement, the molten slag of Example 17 to which 10 wt% of Fe 2 O 3 was added had crystallinity, and the peak intensity of gehlenite to which 10 wt% of Fe 2 O 3 was added was 3202.

（参考例６）
参考例６の溶融スラグの原料には、Ｆｅ２Ｏ３を１５ｗｔ％添加した。これ以外の条件は実施例１７と同様にした。ＸＲＤ測定から、参考例６の溶融スラグはガラス質であった。 (Reference Example 6)
15% by weight of Fe 2 O 3 was added to the raw material for the molten slag of Reference Example 6. The other conditions were the same as in Example 17. From the XRD measurement, the molten slag of Reference Example 6 was glassy.

表６に、実施例１７及び参考例６で得たゲーレナイトのピーク強度等の結果を纏めて示す。
Table 6 summarizes the results of peak strength and the like of gehlenite obtained in Example 17 and Reference Example 6.

実施例１８では、溶融スラグの原料の基本組成比（ｗｔ％）を、ＳｉＯ２：Ａｌ２Ｏ３：ＣａＯ＝３８．５：１５：４６．５とした。ＣａＯ／ＳｉＯ２の重量比である塩基度は１．２である。ＸＲＤ測定から、添加剤を添加しない場合の溶融スラグは結晶性を有しており、ゲーレナイトのピーク強度は１６４０であった。 In Example 18, the basic composition ratio (wt%) of the raw material for molten slag was set to SiO 2 : Al 2 O 3 : CaO = 38.5: 15: 46.5. Basicity in a weight ratio of CaO / SiO 2 is 1.2. From the XRD measurement, the molten slag in the case where no additive was added had crystallinity, and the peak intensity of gehlenite was 1640.

実施例１９の溶融スラグの原料には、Ｆｅ２Ｏ３を１０ｗｔ％添加した。これ以外の条件は実施例１８と同様にした。ＸＲＤの測定から、Ｆｅ２Ｏ３を１０ｗｔ％添加した実施例１９の溶融スラグは結晶性を有しており、Ｆｅ２Ｏ３を１０ｗｔ％添加したゲーレナイトのピーク強度は２４０３であった。 10 wt% of Fe 2 O 3 was added to the raw material for the molten slag of Example 19. The other conditions were the same as in Example 18. From the XRD measurement, the molten slag of Example 19 to which 10 wt% of Fe 2 O 3 was added had crystallinity, and the peak intensity of gehlenite to which 10 wt% of Fe 2 O 3 was added was 2403.

実施例２０の溶融スラグの原料には、ＴｉＯ２を５ｗｔ％添加した。これ以外の条件は実施例１８と同様にした。ＸＲＤの測定から、ＴｉＯ２を５ｗｔ％添加した実施例２０の溶融スラグは結晶性を有しており、ＴｉＯ２を５ｗｔ％添加したゲーレナイトのピーク強度は２５７８であった。 5 wt% of TiO 2 was added to the raw material for the molten slag of Example 20. The other conditions were the same as in Example 18. From the XRD measurement, the molten slag of Example 20 to which 5 wt% of TiO 2 was added had crystallinity, and the peak intensity of gorenite to which 5 wt% of TiO 2 was added was 2578.

実施例２１の溶融スラグの原料には、ＭｇＯを５ｗｔ％添加した。これ以外の条件は実施例１８と同様にした。ＸＲＤの測定から、ＭｇＯを５ｗｔ％添加した実施例２１の溶融スラグは結晶性を有しており、ＭｇＯを５ｗｔ％添加したゲーレナイトのピーク強度は３３５３であった。   5 wt% of MgO was added to the raw material for the molten slag of Example 21. The other conditions were the same as in Example 18. From the XRD measurement, the molten slag of Example 21 to which 5 wt% of MgO was added had crystallinity, and the peak intensity of gehlenite to which 5 wt% of MgO was added was 3353.

実施例２２の溶融スラグの原料には、Ｐ２Ｏ５を３ｗｔ％添加した。これ以外の条件は実施例１８と同様にした。ＸＲＤの測定から、Ｐ２Ｏ５を３ｗｔ％添加した実施例２２の溶融スラグは結晶性を有しており、Ｐ２Ｏ５を３ｗｔ％添加したゲーレナイトのピーク強度は２４３８であった。 3 wt% of P 2 O 5 was added to the raw material for the molten slag of Example 22. The other conditions were the same as in Example 18. From the XRD measurement, the molten slag of Example 22 to which 3 wt% of P 2 O 5 was added had crystallinity, and the peak intensity of gehlenite to which 3 wt% of P 2 O 5 was added was 2438.

実施例２３の溶融スラグの原料には、Ｎａ２Ｏを８ｗｔ％添加した。これ以外の条件は実施例１８と同様にした。ＸＲＤの測定から、Ｎａ２Ｏを８ｗｔ％添加した実施例２３の溶融スラグは結晶性を有しており、Ｎａ２Ｏを８ｗｔ％添加したゲーレナイトのピーク強度は２４７３であった。 8 wt% of Na 2 O was added to the raw material for the molten slag of Example 23. The other conditions were the same as in Example 18. From the XRD measurement, the molten slag of Example 23 to which 8 wt% of Na 2 O was added had crystallinity, and the peak intensity of gehlenite to which 8 wt% of Na 2 O was added was 2473.

表７に、実施例１８〜２３で得たゲーレナイトのピーク強度等の結果を纏めて示す。
Table 7 summarizes the results of peak strength and the like of gehlenite obtained in Examples 18-23.

以上説明した実施例、比較例及び参考例では、人工骨材が結晶性の溶融スラグとなる条件を正確に求めるためにゲーレナイトを主成分とする人工骨材の原料としてはＳｉＯ２、Ｃａ（ＯＨ）２、Ａｌ２Ｏ３、Ｎａ２Ｏ、ＭｇＯ等の試薬を使用した。実際に溶融スラグを製造する場合には上述したように、原料となる焼却灰の組成は、本発明の人工骨材の組成が得られるように調製すればよい。原料の組成は蛍光Ｘ線分析装置によって測定することができる。このように調製した原料を、図２で説明した温度プログラムで還元溶融を行い、所定時間保持した後で冷却することによって本発明の人工骨材となる溶融スラグを製造できる。 In the examples, comparative examples, and reference examples described above, SiO 2 , Ca (OH) are used as raw materials for artificial aggregates containing gehlenite as a main component in order to accurately determine the conditions under which the artificial aggregates become crystalline molten slag. ) 2 , Al 2 O 3 , Na 2 O, MgO and other reagents were used. When actually manufacturing molten slag, as described above, the composition of the incinerated ash used as a raw material may be prepared so as to obtain the composition of the artificial aggregate of the present invention. The composition of the raw material can be measured by a fluorescent X-ray analyzer. The raw material prepared in this way is reduced and melted by the temperature program described in FIG. 2, held for a predetermined time, and then cooled, whereby a molten slag serving as the artificial aggregate of the present invention can be manufactured.

本発明は、上記実施の形態に限定されるものではなく、特許請求の範囲に記載した発明の範囲内で種々の変形が可能であり、それらも本発明の範囲内に含まれることはいうまでもない。例えば、人工骨材に含有されるＦｅ２Ｏ３、Ｐ２Ｏ５、ＴｉＯ２の何れかの割合は上記範囲で得られる人工骨材の強度等を考慮して適宜に調整できる。 The present invention is not limited to the above embodiment, and various modifications are possible within the scope of the invention described in the claims, and it goes without saying that these are also included in the scope of the present invention. Nor. For example, the proportion of any of Fe 2 O 3 , P 2 O 5 , and TiO 2 contained in the artificial aggregate can be appropriately adjusted in consideration of the strength of the artificial aggregate obtained in the above range.

Claims (10)

２ＣａＯ・Ａｌ２Ｏ３・ＳｉＯ２で表されるゲーレナイトを含み、Ａｌはアルミナ換算で１０〜２２質量％であり、ＣａＯ／ＳｉＯ２が１．２以下であることを特徴とする、人工骨材。 Artificial bone material comprising galenite represented by 2CaO · Al 2 O 3 · SiO 2 , wherein Al is 10 to 22% by mass in terms of alumina, and CaO / SiO 2 is 1.2 or less. . Ｎａ２Ｏ及び／又はＭｇＯが含有され、Ｎａ２Ｏは８質量％以下であり、ＭｇＯは５質量％以下であることを特徴とする、請求項１に記載の人工骨材。 The artificial bone material according to claim 1, wherein Na 2 O and / or MgO is contained, Na 2 O is 8% by mass or less, and MgO is 5% by mass or less. さらに、Ｆｅ２Ｏ３、Ｐ２Ｏ５及びＴｉＯ２から成る群より選ばれた少なくとも１種が含有されることを特徴とする、請求項１又は２に記載の人工骨材。 Additionally, Fe 2 O 3, P 2 O 5 and at least one selected from the group consisting of TiO 2 is characterized in that it is contained, artificial bone material according to claim 1 or 2. 前記Ｆｅ２Ｏ３が、１０質量％以下含有されていることを特徴とする、請求項３に記載の人工骨材。 The artificial bone material according to claim 3, wherein the Fe 2 O 3 is contained in an amount of 10% by mass or less. 前記Ｐ２Ｏ５が、３質量％以下含有されていることを特徴とする、請求項３に記載の人工骨材。 The artificial bone according to claim 3, wherein the P 2 O 5 is contained in an amount of 3% by mass or less. 前記ＴｉＯ２が、５質量％以下含有されていることを特徴とする、請求項３に記載の人工骨材。 The artificial bone material according to claim 3, wherein the TiO 2 is contained in an amount of 5 mass% or less. 請求項１ないし６の何れかに記載の人工骨材の製造方法であって、
人工骨材の原料及び還元剤を、所定の溶融温度まで昇温して溶融液とする還元溶融工程と、
該溶融液を溶融温度で所定時間保持する工程と、
所定時間保持した後上記溶融液を徐冷して、溶融液を結晶化する工程と、
を備えていることを特徴とする、人工骨材の製造方法。 A method for producing an artificial aggregate according to any one of claims 1 to 6,
A reducing and melting step in which the raw material for the artificial aggregate and the reducing agent are heated to a predetermined melting temperature to form a melt,
Holding the melt at a melting temperature for a predetermined time;
A step of slowly cooling the melt after holding for a predetermined time to crystallize the melt;
A method for producing an artificial aggregate, comprising: 前記原料は、一般廃棄物の焼却灰、又は一般廃棄物及び産業廃棄物の焼却灰からなることを特徴とする、請求項７に記載の人工骨材の製造方法。   The said raw material consists of incineration ash of general waste, or incineration ash of general waste and industrial waste, The manufacturing method of the artificial aggregate of Claim 7 characterized by the above-mentioned. 前記還元剤は、コークスであることを特徴とする、請求項７に記載の人工骨材の製造方法。   The method for producing an artificial aggregate according to claim 7, wherein the reducing agent is coke. 前記原料にさらにＣａ化合物を添加することを特徴とする、請求項７ないし９の何れかに記載の人工骨材の製造方法。   The method for producing an artificial bone material according to any one of claims 7 to 9, wherein a Ca compound is further added to the raw material.
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