JP3042962B2 - Method for producing coal ash solidified material - Google Patents
Method for producing coal ash solidified materialInfo
- Publication number
- JP3042962B2 JP3042962B2 JP6136065A JP13606594A JP3042962B2 JP 3042962 B2 JP3042962 B2 JP 3042962B2 JP 6136065 A JP6136065 A JP 6136065A JP 13606594 A JP13606594 A JP 13606594A JP 3042962 B2 JP3042962 B2 JP 3042962B2
- Authority
- JP
- Japan
- Prior art keywords
- coal ash
- solidified
- calcium
- hydrothermal treatment
- coal
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Processing Of Solid Wastes (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、石炭灰を主要成分とす
る石炭灰質固化物の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a coal ash solidified product containing coal ash as a main component.
【０００２】[0002]
【従来の技術】エネルギー源として石炭を利用している
火力発電所や各種の工場では、フライアッシュ等の石炭
灰が大量に産出されている（約４００万トン／年）。こ
のうち、有効利用されるものは約４０％にすぎず、残り
の約６０％は埋め立て処分されているのが現状である。
しかしながら、石炭灰の埋め立て処分場を確保すること
はかならずしも容易ではなく、漁業権の保証やリサイク
ル法の制定により埋め立て処分場の確保がますます困難
になってきている。従って、今後さらに増大するであろ
う石炭灰の有効利用が緊急の課題となっている。2. Description of the Related Art A large amount of coal ash such as fly ash is produced in thermal power plants and various factories utilizing coal as an energy source (about 4 million tons / year). Of these, only about 40% are effectively used, and the remaining 60% are currently landfilled.
However, it is not always easy to secure a landfill site for coal ash, and it has become increasingly difficult to secure a landfill site due to the guarantee of fishing rights and the establishment of the Recycling Law. Therefore, effective utilization of coal ash, which is expected to further increase in the future, is an urgent issue.
【０００３】現在のところでは、石炭灰は特開昭６３−
１７２４７号公報および特開平４−３０５０４４号公報
に示されているように無機質系の建設材料の一原料とし
て提案され、または特開平３−１６１７６号公報に示さ
れているように多孔質の濾過助剤の一原料として提案さ
れている。また、特殊な例としては刊行物「日本工業新
聞：人工海底山脈を石炭灰で構築（平成５年２月２６日
発行）」に示されているように、人工漁礁の一原料とし
ても提案されている。これらの提案のうち建設材料、人
工漁礁の一原料として利用する場合には、石炭灰の大量
の利用が期待できる。At present, coal ash is disclosed in
As disclosed in JP-A-17247 and JP-A-4-305044, it has been proposed as a raw material of an inorganic construction material, or as disclosed in JP-A-3-16176. It has been proposed as a raw material of the agent. As a special example, as shown in the publication "Nippon Kogyo Shimbun: Constructing artificial seabed mountains with coal ash (issued on February 26, 1993)", it is also proposed as a raw material for artificial reefs. ing. If these proposals are used as construction materials or as a raw material for artificial reefs, a large amount of coal ash can be expected.
【０００４】[0004]
【発明が解決しようとする課題】ところで、上記した石
炭灰を建設材料、人工漁礁の原料として利用する場合に
は、石炭灰をいずれもセメントと混合して蒸気養生また
はオートクレーブ処理して使用されるが、石炭灰を主要
原料とするとはいうもののその混合比率は必ずしも高く
なく、また石炭灰の混合比率を高めようとする場合に
は、固化物の強度が低下するという問題があった。ま
た、この場合にはセメントを多く使用しているため水に
対する耐久性が悪く、寸法安定性も悪いという問題もあ
った。これを解決する手段として、本発明者等は石炭灰
に酸化カルシウム、水酸化カルシウム等のカルシウム化
合物を混合して、高温および高圧下で水熱処理して固化
する方法を提案し、すでに特許出願済みである。When the above-mentioned coal ash is used as a construction material or a raw material for an artificial reef, both of the coal ash are mixed with cement and used after steam curing or autoclaving. However, although coal ash is used as a main raw material, its mixing ratio is not always high, and when trying to increase the mixing ratio of coal ash, there is a problem that the strength of the solidified product is reduced. Further, in this case, since a large amount of cement is used, there is a problem that durability against water is poor and dimensional stability is poor. As a means to solve this, the present inventors have proposed a method in which calcium compounds such as calcium oxide and calcium hydroxide are mixed with coal ash and subjected to hydrothermal treatment under high temperature and high pressure to solidify, and a patent application has already been filed. It is.
【０００５】しかしながら、これらのカルシウム化合物
と石炭灰との混合物を石炭灰質固化物の製造原料とする
場合には、高強度で、水に対する耐久性および寸法安定
性に優れた固化物を得ることができるが耐凍結融解性に
劣り、この固化物を寒冷地の屋外で使用した場合には固
化物にクラック等の傷が発生して破損するおそれがあ
る。従って、本発明の目的は、かかる問題に対処するこ
とにある。[0005] However, when a mixture of these calcium compounds and coal ash is used as a raw material for producing a solidified coal ash, it is necessary to obtain a solidified material having high strength and excellent in durability against water and dimensional stability. Although it is possible, it has poor freeze-thaw resistance, and when the solidified product is used outdoors in a cold region, the solidified product may be damaged due to cracks or other damage. Accordingly, it is an object of the present invention to address such a problem.
【０００６】[0006]
【課題を解決するための手段】本発明は、石炭灰と、酸
化カルシウムおよび水酸化カルシウムの少なくとも１種
類のカルシウム化合物との混合物からなる石炭灰質原料
を所定の形状に成形し、同成形物を高温および高圧下で
水熱処理する石炭灰質固化物の製造方法であり、前記石
炭灰質原料における前記石炭灰と前記カルシウム化合物
との重量比を６０：４０〜９７：３に調製するととも
に、前記成形物をアルカリを包含させた状態で水熱処理
すること、および、同水熱処理に先立って室温〜１００
℃の範囲の温度でで養生することを特徴とするものであ
る。According to the present invention, a coal ash raw material comprising a mixture of coal ash and at least one calcium compound of calcium oxide and calcium hydroxide is formed into a predetermined shape, and the formed product is formed. A method for producing a coal ash solid which is subjected to hydrothermal treatment at a high temperature and a high pressure, wherein a weight ratio of the coal ash to the calcium compound in the coal ash raw material is adjusted to 60:40 to 97: 3, and the molded product is formed. Is subjected to hydrothermal treatment in a state in which alkali is contained , and room temperature to 100 prior to the hydrothermal treatment.
Curing at a temperature in the range of ° C.
【０００７】本発明の石炭灰質固化物の製造方法におい
ては、前記成形物に同成形物中の石炭灰に対して重量比
で０．００１〜２０％のアルカリを包含させた状態で水
熱処理すること、前記成形物を２５０℃以下の温度で水
熱処理すること、前記成形物をオートクレーブにて高温
および高圧下で水熱処理すること、等の各手段を採用す
ることができる。In the method for producing a solidified coal ash according to the present invention, hydrothermal treatment is performed in a state where the above-mentioned molded article contains 0.001 to 20% by weight of alkali with respect to the coal ash in the molded article. Each means such as hydrothermal treatment of the molded article at a temperature of 250 ° C. or lower, and hydrothermal treatment of the molded article in an autoclave at high temperature and high pressure can be employed.
【０００８】[0008]
【発明の作用・効果】本発明に係る製造方法によれば、
固化物は高温、高圧下での水熱処理以前の成形物の状態
では、原料成分の各微粒子が互いに密に充填した状態を
呈しており、その後の高温、高圧下での水熱処理により
各微粒子間にて石炭灰中のＳｉＯ2、Ａｌ2Ｏ3、Ｆｅ2Ｏ
3等と、ＣａＯ等のカルシウム化合物の各成分が反応し
て、主としてトバモライト等のＣ−Ｓ−Ｈ（カルシウム
シリケート ハイドレート）、ハイドロガーネット等が
生成される。この結果、固化物を構成する各微粒子は互
いに強固に固着した状態でかつ微粒子自身硬化して、石
炭灰を主要成分とする硬化体となって、高強度で、水に
対する耐久性および寸法安定性に優れた固化物を得るこ
とができる。この場合、成形物にアルカリを包含させた
状態で高温高圧下で水熱処理を行うと、耐凍結溶解性が
良好になることが判明した。この理由は定かではない
が、アルカリの存在により上記した反応が助長され、固
化物中の気孔が一層減少するとともに、反応生成物が強
固に固着した状態になることによるものと推測される。According to the manufacturing method of the present invention,
In the state of the molded product before the hydrothermal treatment at high temperature and high pressure, the fine particles of the raw material components are in a state of being densely packed with each other. SiO 2 , Al 2 O 3 , Fe 2 O in coal ash
3 and other components of the calcium compound such as CaO react to produce mainly CSH (calcium silicate hydrate) such as tobermorite, hydrogarnet and the like. As a result, the fine particles constituting the solidified material are firmly fixed to each other and harden themselves, forming a hardened material containing coal ash as a main component, having high strength, durability to water and dimensional stability. An excellent solidified product can be obtained. In this case, it was found that when hydrothermal treatment was performed under a high temperature and a high pressure in a state where an alkali was included in the molded product, the freeze-thaw resistance was improved. The reason for this is not clear, but it is presumed that the presence of the alkali promotes the above-mentioned reaction, the pores in the solidified material are further reduced, and the reaction product is firmly fixed.
【０００９】従って、得られる石炭灰質固化物は、圧縮
強度が例えば４００ｋｇ／ｃｍ2以上という高強度のも
のとなり、コンクリートパネル、コンクリート杭等の高
強度のコンクリート製品への適用が可能であるととも
に、水に対する耐久性が良好なため水場での使用が可能
であり、かつ耐凍結溶解性が良好なため寒冷地での使用
が可能である。このため、本発明の製造方法で製造され
た石炭灰質固化物は消波ブロック等の港湾用ブロック、
人工漁礁、人工藻場基盤、コンクリートパネル、コンク
リート杭等の建築、土木用材として広い分野で大量に利
用することができるとともに、当該石炭灰質固化物の原
料中の石炭灰の混合比が高いことから、石炭灰の大量の
利用が可能となる。Therefore, the obtained coal ash solidified product has a high compressive strength of, for example, 400 kg / cm 2 or more, and can be applied to high-strength concrete products such as concrete panels and concrete piles. Since it has good durability against water, it can be used in water places, and because it has good freeze-thaw resistance, it can be used in cold regions. For this reason, coal ash solidified produced by the production method of the present invention is used for harbor blocks such as wave-dissipating blocks,
Because it can be used in large quantities in a wide range of fields such as artificial reefs, artificial seaweed bed bases, concrete panels, concrete piles and other construction and civil engineering materials, and because of the high mixing ratio of coal ash in the raw material of the coal ash solidified material Thus, a large amount of coal ash can be used.
【００１０】しかして、本発明において採用できるカル
シウム化合物としては、酸化カルシウム、水酸化カルシ
ウム等を挙げることができ、使用に際してはこれら各化
合物を単独でまたは２種のものを併用することができ
る。これら各化合物は、作用効果の点からいえば同等で
ある。なお、炭酸カルシウムについては上記反応が遅
く、また石膏等の硫酸カルシウムについては未反応の硫
酸カルシウムが残存し易いため、いずれの場合にも水熱
処理を長くする必要がある。これは、以下の理由による
ものと推測される。The calcium compounds that can be employed in the present invention include calcium oxide and calcium hydroxide. These compounds can be used alone or in combination of two or more. These compounds are equivalent from the viewpoint of action and effect. The above reaction is slow for calcium carbonate, and unreacted calcium sulfate tends to remain for calcium sulfate such as gypsum. Therefore, in any case, it is necessary to lengthen the hydrothermal treatment. This is presumed to be due to the following reasons.
【００１１】すなわち、Ｃ−Ｓ−Ｈの生成反応は、石炭
灰中のシリカ成分と主にカルシウム化合物中のカルシウ
ム成分との反応によるものと考えられるが、アルカリを
添加した場合にはこの反応が促進されるものと考えられ
る。また、カルシウム成分が酸化カルシウムおよび水酸
化カルシウムでは、これらのカルシウム成分が容易にイ
オン化されるため、Ｃ−Ｓ−Ｈの生成反応に必要なカル
シウム成分が容易に供給され、その結果アルカリの関与
により上記生成反応は一層促進されるものと考えられ
る。これに対して、炭酸カルシウムおよび硫酸カルシウ
ムでは、これらのカルシウム成分（通常水に不溶）はア
ルカリの関与によりわずかにイオン化するものと考えら
れるが、Ｃ−Ｓ−Ｈの生成反応に必要なカルシウム成分
が充分には供給されないため、この生成反応はたとえア
ルカリが関与した場合でも酸化カルシウムおよび水酸化
カルシウムに比較して不充分になるものと考えられる。
特に、硫酸カルシウムは炭酸カルシウムに比較して、ア
ルカリの関与によってもカルシウム成分のイオン化が一
層し難いため、未反応の硫酸カルシウムが残存し易くな
るものと考えられる。That is, it is considered that the reaction of producing C—S—H is due to the reaction between the silica component in the coal ash and the calcium component mainly in the calcium compound. It is expected to be promoted. In addition, when the calcium component is calcium oxide or calcium hydroxide, these calcium components are easily ionized, so that the calcium component necessary for the C—S—H production reaction is easily supplied, and as a result, alkali is involved. It is considered that the above formation reaction is further accelerated. On the other hand, in calcium carbonate and calcium sulfate, these calcium components (usually insoluble in water) are considered to be slightly ionized due to the involvement of alkali, but the calcium components required for the C—S—H generation reaction Is not supplied sufficiently, it is considered that this production reaction becomes insufficient compared to calcium oxide and calcium hydroxide even when alkali is involved.
In particular, it is considered that unreacted calcium sulfate is more likely to remain in calcium sulfate because calcium components are more difficult to ionize than calcium carbonate even with the participation of alkali.
【００１２】石炭灰質原料において、石炭灰とカルシウ
ム化合物の重量比は６０：４０〜９７：３の範囲が好ま
しく、石炭灰の混合比が６０重量％未満の場合には石炭
灰質固化物の強度および耐久性が低く、９７重量％を越
えると固化し得ず石炭灰質固化物としての強固な形態を
保持し得ない。In the coal ash raw material, the weight ratio of the coal ash to the calcium compound is preferably in the range of 60:40 to 97: 3. When the mixing ratio of the coal ash is less than 60% by weight, the strength and the strength of the coal ash solidified product are reduced. The durability is low, and if it exceeds 97% by weight, it cannot be solidified and cannot maintain a strong form as a coal ash solidified product.
【００１３】また、本発明の製造方法において採用でき
るアルカリとしては、アルカリ金属の水酸化物（ＮａＯ
Ｈ，ＫＯＨ等）、アルカリ金属炭酸塩（Ｎａ2ＣＯ
3等）、およびアンモニア等を挙げることができる。こ
れらの各化合物のうちでは、作用効果の点からいえばア
ルカリ金属の水酸化物、アンモニア、アルカリ金属の炭
酸塩の順であり、これらのうちアルカリ金属の水酸化物
が好ましく、中でも水酸化ナトリウムがより好ましい。
成形物中のアルカリの含有量については、成形物中の石
炭灰に対して重量比で０．００１〜２０％の範囲が好ま
しく、より好ましくは０．１〜１０％であって、この範
囲においては、強度および耐久性とともに耐凍結融解性
の良好な固化物を得ることができる。アルカリを成形物
中に包含させる手段としては、アルカリを石炭灰および
カルシウム化合物の混合物である石炭灰質原料中に粉末
または水溶液の状態で添加する手段、成形物に水溶液の
状態で含浸させる手段等があり、特にアルカリを水溶液
の状態で包含させる手段が好ましい。さらにまた、高
温、高圧下での水熱処理は石炭灰の含有量が多い成形物
を高強度化するために必要であってオートクレーブ中で
行うことが好ましく、処理温度は好ましくは２５０℃以
下、より好ましくは２５０℃〜１２０℃である。また、
処理圧力は４０気圧以下が好ましい。The alkali that can be employed in the production method of the present invention is an alkali metal hydroxide (NaO).
H, KOH, etc.), alkali metal carbonates (Na 2 CO
3 ), and ammonia. Among these compounds, alkali metal hydroxide, ammonia, and alkali metal carbonate are in the order of action and effect. Of these, alkali metal hydroxide is preferable, and sodium hydroxide is particularly preferable. Is more preferred.
The alkali content in the molded product is preferably in the range of 0.001 to 20%, more preferably 0.1 to 10% by weight, based on the weight of the coal ash in the molded product. Can obtain a solidified product having good freeze-thaw resistance as well as strength and durability. Means for incorporating the alkali into the molded article include means for adding the alkali to the coal ash raw material which is a mixture of coal ash and a calcium compound in the form of a powder or an aqueous solution, means for impregnating the molded article in the form of an aqueous solution, and the like. In particular, a means for incorporating an alkali in the form of an aqueous solution is preferable. Furthermore, high-temperature, hydrothermal treatment under high pressure is necessary to increase the strength of a molded product having a high content of coal ash, and is preferably performed in an autoclave, and the processing temperature is preferably 250 ° C or less, more preferably Preferably it is 250-120 degreeC. Also,
The processing pressure is preferably 40 atm or less.
【００１４】石炭灰の組成に関しては、ＳｉＯ2：４０
〜８０重量％、Ａｌ2Ｏ3：１０〜３０重量％、Ｆｅ
2Ｏ3：１〜１５重量％、ＣａＯ：１重量％以上が好まし
く、未燃炭素量が５重量％以上であっても何等問題はな
い。また、石炭灰の粒径に関しては５〜１００μｍのも
ので、フライアッシュが好ましい。石炭灰質原料を所定
の形状に成形する際には、同原料に水を１〜３５重量％
添加することが好ましく、より好ましくは１〜１５重量
％である。このように調製された原料を使用して、プレ
ス成形、押出成形、鋳込成形等により所定の形状の成形
物を得る。この場合、減水剤、保水剤、混和剤等を添加
してもよく、また石炭灰質固化物の強度の向上、比重の
調整、コストの低減等のために、珪砂、火成岩、高炉ス
ラグ、パーライト、ＡＬＣのグス、グラスファイバー等
を添加することもできる。また、得られた固化物素地
（成形物）を、高温高圧下での水熱処理に先立って室温
〜１００℃以下の温度で養生することが好ましく、これ
により固化物の強度の向上が期待できる。Regarding the composition of coal ash, SiO 2 : 40
80 wt%, Al 2 O 3: 10~30 wt%, Fe
2 O 3 : 1 to 15% by weight and CaO: 1% by weight or more are preferable, and there is no problem even if the unburned carbon amount is 5% by weight or more. The particle size of the coal ash is 5 to 100 μm, and fly ash is preferred. When the coal ash raw material is formed into a predetermined shape, water is added to the raw material in an amount of 1 to 35% by weight.
It is preferably added, more preferably 1 to 15% by weight. Using the raw materials thus prepared, a molded product having a predetermined shape is obtained by press molding, extrusion molding, casting molding, or the like. In this case, a water reducing agent, a water retention agent, an admixture, etc. may be added.Also, in order to improve the strength of the coal ash solidified, adjust the specific gravity, reduce costs, etc., silica sand, igneous rock, blast furnace slag, perlite, ALC grease, glass fiber or the like may be added. In addition, the obtained solidified matrix
It is preferable to cure the (molded product) at a temperature of room temperature to 100 ° C. or lower prior to the hydrothermal treatment under a high temperature and a high pressure, so that an improvement in the strength of the solidified product can be expected.
【００１５】なお、大型の石炭灰質固化物、複雑な形状
の石炭灰質固化物を作製するには保型性が必要であり、
この場合には耐久性が若干低下するものの少量のセメン
トを添加することもよく、添加量はカルシウム化合物の
半分以下、好ましくは２０重量％以下とする。また、セ
メントを添加する場合には、高温、高圧下での水熱処理
に先立って室温〜１００℃以下の温度の下、湿潤状態で
養生することが必要である。[0015] In order to produce a large-sized solidified coal ash or a complex-shaped solidified coal ash, it is necessary to have a shape-retaining property.
In this case, although the durability is slightly lowered, a small amount of cement may be added, and the addition amount is set to not more than half of the calcium compound, preferably not more than 20% by weight. In addition, when adding cement, it is necessary to cure in a wet state at a temperature of room temperature to 100 ° C. or lower prior to hydrothermal treatment under high temperature and high pressure.
【００１６】[0016]
（石炭灰質固化物の製造）本製造実験では、石炭灰とし
て平均粒子径２０μｍのフライアッシュ（成分：ＳｉＯ
2…５１重量％、Ａｌ2Ｏ3…２３重量％、Ｆｅ2Ｏ3…５
重量％、ＣａＯ…７重量％）を使用するとともに、カル
シウム化合物としてＣａＯ、Ｃａ（ＯＨ）2、ポルトラ
ンドセメントの３種類を使用し、かつアルカリとして試
薬の水酸化ナトリウム、水酸化カリウム、炭酸ナトリウ
ム、アンモニアを使用した。これらの試薬を水に溶解し
て０．１〜５規定の水溶液を調製し、これらを石炭灰と
各種のカルシウム化合物を適宜の重量混合してなる混合
物にそれぞれ０〜２０重量％の範囲で適宜の重量添加す
るとともに水を５〜２０重量％添加して混練し、各種の
石炭灰質原料を調製した。これらの石炭灰質原料をプレ
ス圧４０ｋｇ／ｃｍ２でプレス成形して円板状の固化物
素地（直径１００ｍｍ、厚み３０ｍｍ）を得た。次い
で、各固化物素地を温度６０℃で１日間養生した後、オ
ートクレーブ内にて１２０〜２５０℃の温度条件で２４
時間高温処理を行った。得られた各石炭灰質固化物につ
いて外観を観察するとともに、圧縮強度、水に対する耐
久性、および耐凍結融解性を測定して、これらの結果を
表１に示す。(Production of coal ash solidified material) In this production experiment, fly ash (component: SiO
2 ... 51 wt%, Al 2 O 3 ... 23 wt%, Fe 2 O 3 ... 5
7% by weight of CaO, CaO, Ca (OH) 2 and Portland cement as calcium compounds, and sodium hydroxide, potassium hydroxide, sodium carbonate as reagents as alkalis. Ammonia was used. These reagents are dissolved in water to prepare a 0.1 to 5N aqueous solution, and these are added to a mixture of coal ash and various calcium compounds at an appropriate weight in the range of 0 to 20% by weight. And 5 to 20% by weight of water were added and kneaded to prepare various coal ash raw materials. These coal ash raw materials were press-formed at a pressing pressure of 40 kg / cm 2 to obtain a disc-shaped solidified body (diameter 100 mm, thickness 30 mm). Next, after each solidified body was cured at a temperature of 60 ° C. for one day, it was cured in an autoclave at a temperature of 120 to 250 ° C. for 24 hours.
High-temperature treatment was performed for hours. The appearance of each obtained coal ash solidified product was observed, and the compressive strength, durability to water, and freeze-thaw resistance were measured. The results are shown in Table 1.
【００１７】但し、石炭灰質固化物の外観の観察では固
化物における亀裂等の損傷の有無、形態保持性の強弱を
判定し、良好なものを○印、不良なものを×印で表示し
ている。また、圧縮強度の測定についてはオートグラフ
により行っている。耐久性の評価については、固化物を
屋外に３カ月放置後亀裂等の損傷の有無、形態保持性の
強弱を判定し、変色等もなく特に良好なものを◎印、良
好なものを○印、不良なものを×印で表示している。ま
た、耐凍結融解性については、固化物の保持温度を２０
℃〜−２０℃の温度範囲で変化させて行い、固化物を２
０℃の温度で８時間、−２０℃の温度で１６時間保持す
る実験を１００回繰り返し行い、固化物での亀裂の発生
の有無を判定し、亀裂の全くないもを◎印、痕跡程度の
ものを○印、明らかに亀裂を認められるものを×印とし
て表示した。なお、表１の比較例中最後の欄（＊印）の
ものは、蒸気養生のみを行ったものである。However, in the observation of the appearance of the solidified coal ash, the presence or absence of damage such as cracks in the solidified coal and the strength of the shape retention were judged. I have. The measurement of the compressive strength is performed by an autograph. Regarding the evaluation of durability, the solidified product was left outdoors for 3 months, and the presence or absence of damage such as cracks and the strength of form retention were judged. , Defective ones are indicated by crosses. Regarding the freeze-thaw resistance, the holding temperature of the solidified product was set at 20.
C. to -20.degree. C., and the solidified
An experiment of holding at a temperature of 0 ° C. for 8 hours and at a temperature of −20 ° C. for 16 hours was repeated 100 times, and it was determined whether or not cracks had occurred in the solidified product. The samples were marked with a circle, and those with obvious cracks were marked with a cross. The last column (*) of the comparative examples in Table 1 is obtained by performing only steam curing.
【００１８】[0018]
【表１】 [Table 1]
【００１９】（注）：Ｃａ化合物の欄における（ａ），
（ｂ），（ｃ）はＣａＯ，Ｃａ（ＯＨ）２，ポルトラン
ドセメントを、アルカリの欄におけるＮａ，Ｋ，Ｎａ
Ｃ，ＮＨはＮａＯＨ，ＫＯＨ，ＮａＣＯ3，ＮＨ
3を、（）内の数値はこれらアルカリの石炭灰に対する
添加量（重量％）を、圧縮強度は(kg/cm2)を意味する。(Note): (a),
(B) and (c) show CaO, Ca (OH) 2 , Portland cement, Na, K, Na in the column of alkali.
C and NH are NaOH, KOH, NaCO 3 , NH
3 , the value in parentheses means the amount (% by weight) of these alkalis added to coal ash, and the compressive strength means (kg / cm 2 ).
【００２０】（考察）表１を参照すると、原料成分であ
る石炭灰とカルシウム化合物との重量比が６０：４０〜
９７：３の範囲において良好な結果が得られており、特
に好ましい範囲は８０：２０〜９５：５である。また、
カルシウム化合物としてはＣａＯおよびＣａ（ＯＨ）2
が同等であり、ポルトランドセメントは良好とはいえ
ず、アルカリの添加の有無にかかわらず固化物の外周に
亀裂の発生が認められた。また、アルカリとしては水酸
化ナトリウムが最も効果があり、次いで水酸化カリウ
ム、アンモニア、炭酸ナトリウムの順である。アルカリ
の添加量は０．００１〜２０重量％が好ましい。なお、
アルカリを添加したものでも成形物素地を蒸気養生だけ
したものでは、良好な結果が得られない。これらの結果
から、本発明の方法により製造される石炭灰質固化物
は、４００ｋｇ／ｃｍ2以上の圧縮強度が要求されるコ
ンクリートパネル、コンクリート杭等各種建設材、消波
ブロック、人工漁礁、人工藻場基盤等として広い分野で
利用することができ、これらに利用する場合寒冷地での
使用も可能である。(Consideration) Referring to Table 1, the weight ratio of coal ash as a raw material component to a calcium compound is 60:40 to 40:40.
Good results have been obtained in the range of 97: 3, and a particularly preferred range is 80:20 to 95: 5. Also,
CaO and Ca (OH) 2 as calcium compounds
Thus, Portland cement was not good, and cracks were observed on the outer periphery of the solidified matter regardless of the presence or absence of alkali. As the alkali, sodium hydroxide is most effective, followed by potassium hydroxide, ammonia, and sodium carbonate. The addition amount of the alkali is preferably 0.001 to 20% by weight. In addition,
Even if an alkali is added, good results cannot be obtained if only the molded body is steam-cured. From these results, the solidified coal ash produced by the method of the present invention can be used for various construction materials, such as concrete panels and concrete piles, which require a compressive strength of 400 kg / cm 2 or more, wave-dissipating blocks, artificial reefs, and artificial algae. It can be used in a wide range of fields as a field base, etc., and when used in these fields, it can be used in cold regions.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ //(Ｃ０４Ｂ 28/18 22:06） (58)調査した分野(Int.Cl.7，ＤＢ名) B09B 3/00 C04B 28/22 Continuation of the front page (51) Int.Cl. 7 identification code FI // (C04B 28/18 22:06) (58) Investigated field (Int.Cl. 7 , DB name) B09B 3/00 C04B 28/22
Claims (4)
ルシウムの少なくとも１種類のカルシウム化合物との混
合物からなる石炭灰質原料を所定の形状に成形し、同成
形物を高温および高圧下で水熱処理する石炭灰質固化物
の製造方法であり、前記石炭灰質原料における前記石炭
灰と前記カルシウム化合物の重量比を６０：４０〜９
７：３に調製するとともに、前記成形物をアルカリを包
含させた状態で水熱処理すること、および、同水熱処理
に先立って室温〜１００℃の範囲の温度で養生すること
を特徴とする石炭灰質固化物の製造方法。1. A coal ash raw material comprising a mixture of coal ash and at least one calcium compound of calcium oxide and calcium hydroxide is formed into a predetermined shape, and the formed product is subjected to hydrothermal treatment at high temperature and high pressure. A method for producing a coal ash solidified product, wherein a weight ratio of the coal ash to the calcium compound in the coal ash raw material is 60:40 to 9
7: 3 and hydrothermal treatment of the molded article in a state of containing alkali , and the hydrothermal treatment
A method for producing a solidified coal ash, which comprises curing at a temperature in the range of room temperature to 100 ° C. prior to heating.
法において、前記成形物に同成形物中の石炭灰に対して
重量比で０．００１〜２０％のアルカリを包含させた状
態で水熱処理することを特徴とする石炭灰質固化物の製
造方法。2. The method for producing a solidified coal ash according to claim 1, wherein said molded article contains 0.001 to 20% by weight of alkali relative to coal ash in said molded article. A method for producing a coal ash solidified product, comprising: performing a hydrothermal treatment at a temperature.
の製造方法において、前記成形物を２５０℃以下の温度
で水熱処理することを特徴とする石炭灰質固化物の製造
方法。3. The method for producing a solidified coal coal according to claim 1, wherein the molded article is subjected to a hydrothermal treatment at a temperature of 250 ° C. or lower.
化物の製造方法において、前記成形物をオートクレーブ
にて高温および高圧下で水熱処理することを特徴とする
石炭灰質固化物の製造方法。4. The method for producing a solidified coal coal according to claim 1, wherein the molded article is subjected to hydrothermal treatment at a high temperature and a high pressure in an autoclave. Method.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6136065A JP3042962B2 (en) | 1994-06-17 | 1994-06-17 | Method for producing coal ash solidified material |
| US08/400,972 US5584895A (en) | 1994-04-18 | 1995-03-08 | Process for preparing solidified material containing coal ash |
| EP19950301626 EP0678488B1 (en) | 1994-04-18 | 1995-03-13 | Process for preparing solidified material containing coal ash |
| DE69504562T DE69504562T2 (en) | 1994-04-18 | 1995-03-13 | Process for the preparation of a solid containing coal ash |
| TW84102347A TW394753B (en) | 1994-04-18 | 1995-03-13 | Process for preparing solidified material containing coal ash |
| KR1019950005952A KR0132739B1 (en) | 1994-04-18 | 1995-03-21 | Process for preparing solidified material containing coal ash |
| CN95104373A CN1117032A (en) | 1994-04-18 | 1995-04-10 | Process for preparing solidified material containing coal ash |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6136065A JP3042962B2 (en) | 1994-06-17 | 1994-06-17 | Method for producing coal ash solidified material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH081126A JPH081126A (en) | 1996-01-09 |
| JP3042962B2 true JP3042962B2 (en) | 2000-05-22 |
Family
ID=15166395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6136065A Expired - Fee Related JP3042962B2 (en) | 1994-04-18 | 1994-06-17 | Method for producing coal ash solidified material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3042962B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08310842A (en) * | 1995-05-11 | 1996-11-26 | Denpatsu Koole Tec:Kk | Vitreous cement |
| AU3595297A (en) * | 1996-07-09 | 1998-02-02 | Pittsburgh Mineral And Environmental Technology, Inc. | Method of making building blocks from coal combustion waste and related products |
| JP2006117478A (en) * | 2004-10-22 | 2006-05-11 | Kagawa Industry Support Foundation | Method of solidifying coal ash and solidified body |
| WO2007032412A1 (en) * | 2005-09-13 | 2007-03-22 | The Institute For Eco & Economy System Corporation | Hydrothermally solidified material by zero emission-type thermal power system, and process for producing the same |
| JP6381397B2 (en) * | 2014-10-03 | 2018-08-29 | 一般財団法人電力中央研究所 | Method for determining production conditions for zeolite-containing cured body and method for producing zeolite-containing cured body |
| JP2018158888A (en) * | 2018-07-19 | 2018-10-11 | 一般財団法人電力中央研究所 | Method for producing zeolite-containing cured body |
-
1994
- 1994-06-17 JP JP6136065A patent/JP3042962B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH081126A (en) | 1996-01-09 |
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