JP2002028607A - Regenerating material and regenerating method of water treating material using coal ash as essential raw material - Google Patents
Regenerating material and regenerating method of water treating material using coal ash as essential raw materialInfo
- Publication number
- JP2002028607A JP2002028607A JP2000213312A JP2000213312A JP2002028607A JP 2002028607 A JP2002028607 A JP 2002028607A JP 2000213312 A JP2000213312 A JP 2000213312A JP 2000213312 A JP2000213312 A JP 2000213312A JP 2002028607 A JP2002028607 A JP 2002028607A
- Authority
- JP
- Japan
- Prior art keywords
- coal ash
- water treatment
- particles
- fine
- regenerating
- 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
-
- 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
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Apparatus Associated With Microorganisms And Enzymes (AREA)
- Biological Treatment Of Waste Water (AREA)
- Processing Of Solid Wastes (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、火力発電所等から
排出される石炭灰(特にフライアッシュ)を有効利用すべ
く、この石炭灰を成形・焼成した水処理材の再生材に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reclaimed water treatment material obtained by forming and firing coal ash (particularly fly ash) discharged from a thermal power plant or the like in order to make effective use of the coal ash. .
【０００２】[0002]
【従来の技術】火力発電所等から排出される石炭灰(特
にフライアッシュ)は、石炭、特に粉末状の瀝青炭の燃
焼によって生成される微粒子状の副産物であり、全国各
地の石炭燃焼動力プラント等から極めて大量のフライア
ッシュが排出されている。この大量のフライアッシュを
いかにして処分するかが問題である。現在、フライアッ
シュの処理方法は、主として陸上処理(埋立て等)であ
る。一方、最近はコンクリート用の骨材等の形でも一部
処理されているが、大量のフライアッシュを処理できる
方法はない。このように、フライアッシユについては有
効な処理方法が確立されていないのが現状である。2. Description of the Related Art Coal ash (especially fly ash) discharged from thermal power plants and the like is a particulate by-product produced by the combustion of coal, particularly powdered bituminous coal, and is used in coal-fired power plants around the country. A very large amount of fly ash is discharged from. The problem is how to dispose of this large amount of fly ash. At present, fly ash is mainly treated on land (such as landfill). On the other hand, recently, some forms such as aggregates for concrete have been treated, but there is no method capable of treating a large amount of fly ash. As described above, at present, no effective processing method has been established for fly ashes.
【０００３】近年、このフライアッシユを有効利用しよ
うとする提案がいくつかなされてきた。例えば、特開昭
５２−７８６８７号公報及び特開昭５５−１３４６４０
号公報では、石炭火力発電所等から排出されたフライア
ッシユに対して１０重量％程度のベントナイト粘土を混
ぜて水練りしたものを焼結及び粉砕させることで重金属
捕集剤を得ることが提案されている。[0003] In recent years, several proposals have been made to make effective use of this fly assembly. For example, JP-A-52-78687 and JP-A-55-134640.
Japanese Patent Laid-Open Publication No. HEI 9-216, proposes that a heavy metal scavenger is obtained by mixing and mixing about 10% by weight of bentonite clay with fly ashes discharged from a coal-fired power plant or the like, kneading and sintering and pulverizing the mixture. I have.
【０００４】一方、他の提案として、特開平９−１５６
９９８号公報には、石炭灰微細粒子を成形焼結したセラ
ミックス成形体に関する技術が開示されている。しかし
ながら、そこで使用されている石炭灰微細粒子はその粒
子径が１〜１０μｍと非常に小さく、ベントナイトのよ
うな無機質増粘材の使用量は１０重量％以下と非常に少
ないものである。On the other hand, as another proposal, Japanese Patent Application Laid-Open No. 9-156
Japanese Patent Application Publication No. 998 discloses a technique relating to a ceramic molded body obtained by molding and sintering fine coal ash particles. However, the coal ash fine particles used therein have a very small particle diameter of 1 to 10 μm, and the amount of an inorganic thickener such as bentonite used is very small at 10% by weight or less.
【０００５】[0005]
【発明が解決しようとする課題】しかし、近年の石炭は
そのほとんどが外国炭であり、外国炭の燃焼よって発生
するフライアッシュは粒径が比較的大きい。したがっ
て、上記公報記載の方法では原料としての石炭灰微細粒
子の粒子径が小さいものに限定されるため、粒径の比較
的大きいフライアッシユを処理する場合には必要に応じ
て粉砕等の工程を設けなければならず、結果として工程
が煩雑になったり、製造コストが上昇する等の問題があ
る。従って、この技術は、多くの発電所から排出されて
いる大きな石炭灰微粒子の有効利用を達成することがで
きず、依然として石炭灰を大量に実用的な形で、かつ、
環境上許容できる処理方法が切望されている。また、仮
に再利用されたものの、一度の使用で廃棄し、前述した
陸上処理等の方法により処分するのでは石炭灰の有効利
用率が必ずしも高いとは云えない。However, most of recent coal is foreign coal, and fly ash generated by burning foreign coal has a relatively large particle size. Therefore, in the method described in the above publication, since the particle size of the coal ash fine particles as the raw material is limited to a small particle size, when processing fly ashes having a relatively large particle size, a process such as pulverization is provided as necessary. As a result, there are problems that the process becomes complicated and the manufacturing cost increases. Therefore, this technology cannot achieve the effective utilization of large coal ash fine particles discharged from many power plants, and still produces large quantities of coal ash in a practical form, and
There is a long-felt need for environmentally acceptable processing methods. In addition, although it is supposed to be reused, if it is discarded by one use and disposed by the above-mentioned land treatment or the like, the effective utilization rate of coal ash is not necessarily high.
【０００６】本発明は前記課題を解決するためになされ
たもので、火力発電所等から排出される石炭灰、特にフ
ライアッシュ、しかも、その平均粒子径が大きい石炭灰
を大量に実用的な形で、かつ、環境上許容できる方法で
処理し、きわめて高く有効利用し、石炭灰の有効利用に
より有価な製品として利用した後、無価な製品として廃
棄することなく、再度再生して有効利用に供することを
目的とするものである。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and a large amount of coal ash discharged from a thermal power plant or the like, particularly fly ash having a large average particle diameter, is produced in a practical form. And use it in an environmentally acceptable way, use it very effectively and use it as a valuable product through the effective use of coal ash, and then recycle it again without discarding it as an inexpensive product. It is intended to provide.
【０００７】[0007]
【課題を解決するための手段】本発明者らは前述のごと
く外国炭を主に燃焼する際に発生するフライアッシュで
あって、従来のものより平均粒径が１０〜４０μｍと大
きい石炭灰の有効利用について鋭意検討した結果、水処
理材に好適であることを見い出し、しかもそれがさらな
るリサイクル性に富むことを見い出し、本発明に到達し
た。即ち、本発明の再生材は、平均粒子径が１０〜４０
μｍの石炭灰微細粒子と無機質増粘材を含む原料を焼成
したセラミックス成形体からなり、該セラミックス成形
体は前記石炭灰微細粒子が相互に結合し、該結合した粒
子間に多数の微細な空隙が形成された多孔質構造を有
し、その空隙の平均細孔半径が０.１〜５.０μｍ、且つ
細孔の全容積が０.０１〜０.５ｃｃ／ｇである水処理材
を空気流通下３５０〜１１００℃で熱処理したことを特
徴とするものである。この再生材は、水処理材として、
または、土壌改質材として特に好適である。本発明の水
処理材の再生方法は、平均粒子径が１０〜４０μｍの範
囲にある石炭灰微細粒子と無機質増粘材を含む原料を焼
成したセラミックス成形体からなり、該セラミックス成
形体は前記石炭灰が相互に結合し、該結合した粒子間に
多数の微細な空隙が形成された多孔質構造を有し、その
空隙の平均細孔半径が０.１〜５.０μｍ、且つ細孔の全
容積が０.０１〜０.５ｃｃ／ｇである水処理材を使用に
供した後、これを空気流通下３５０〜１１００℃で熱処
理することを特徴とするものである。Means for Solving the Problems As described above, the present inventors have found that fly ash, which is generated when mainly burning foreign coal and has a larger average particle size of 10 to 40 μm than conventional coal ash. As a result of intensive studies on effective use, they found that they were suitable for water treatment materials, and found that they were even more recyclable, and reached the present invention. That is, the recycled material of the present invention has an average particle diameter of 10 to 40.
μm coal ash fine particles and a ceramic molded body obtained by firing a raw material containing an inorganic thickener, wherein the ceramic molded body has the fine coal ash particles bonded to each other, and a large number of fine voids between the bonded particles. The water treatment material having a porous structure having pores formed therein, the average pore radius of the pores being 0.1 to 5.0 μm, and the total volume of the pores being 0.01 to 0.5 cc / g is removed by air. It is characterized by being heat-treated at 350 to 1100 ° C. under circulation. This recycled material is used as a water treatment material.
Or, it is particularly suitable as a soil modifying material. The method for regenerating a water treatment material of the present invention comprises a ceramic molded body obtained by firing a raw material containing fine coal ash particles having an average particle diameter in the range of 10 to 40 μm and an inorganic thickener. Ash has a porous structure in which a number of fine voids are formed between the bonded particles, and the average pore radius of the voids is 0.1 to 5.0 μm, and After a water treatment material having a volume of 0.01 to 0.5 cc / g is used, it is subjected to a heat treatment at 350 to 1100 ° C. in an air flow.
【０００８】[0008]
【発明の実施の形態】本発明の再生材おいて、その再生
対象である水処理材を説明する。かかる水処理材となる
セラミックス成形体の製造原料は、主として石炭燃焼動
力プラント等から極めて大量に排出される石炭灰微細粒
子、特にフライアッシュであって平均粒子径が１０〜４
０μｍのものである。平均粒子径が４０μｍを越える石
炭灰微粒子を使用した場合には、セラミックス成形体の
強度が不十分となるので好ましくない。平均粒子径が１
０μｍ未満の場合、石炭微粒子を粉砕及び篩い分け等の
工程が必要となり工業的でない。なお本発明では、平均
粒子径とはレーザー回折式粒度分布測定法で測定した体
積基準の累積分布曲線の５０％に相当する粒子径であ
る。水処理材は、この石炭灰微細粒子に無機質増粘材、
またはさらに有機質増粘材、更に水を添加した後、混合
及び混練を行なったものを焼成したものである。石炭灰
微細粒子と無機質増粘材との比率は、乾燥重量として石
炭灰微細粒子６０〜８８重量％、好ましくは７０〜８５
重量％に対して、無機質増粘材は１２〜４０重量％、好
ましくは１５〜３０重量％である。原料とされる石炭灰
微細粒子の平均粒子径が１０〜４０μｍと比較的大きい
ため、無機質増粘材の配合量が従来用いられている１０
重量％以下の場合には増粘作用が不十分で成形が困難と
なり、また、得られたセラミックス成形体の機械的強度
も十分ではなくなる。一方、無機質増粘材の量が４０重
量％を越えると石炭灰混合物の粘性が高くなりすぎ、安
定した成形体に賦型するのが困難となる。BEST MODE FOR CARRYING OUT THE INVENTION In the recycled material of the present invention, a water treatment material to be recycled will be described. The raw material for producing the ceramic molded body as the water treatment material is mainly coal ash fine particles, particularly fly ash, discharged from a coal combustion power plant or the like in a very large amount, and has an average particle diameter of 10 to 4
It is 0 μm. Use of coal ash fine particles having an average particle size of more than 40 μm is not preferred because the strength of the ceramic molded body becomes insufficient. Average particle size is 1
If it is less than 0 μm, steps such as crushing and sieving the coal fine particles are required, which is not industrial. In the present invention, the average particle size is a particle size corresponding to 50% of a volume-based cumulative distribution curve measured by a laser diffraction type particle size distribution measuring method. The water treatment material is an inorganic thickener,
Alternatively, after adding an organic thickener and further water, mixing and kneading are performed, and the resultant is baked. The ratio of the coal ash fine particles to the inorganic thickener is 60 to 88% by weight, preferably 70 to 85% by weight, as a dry weight.
The amount of the inorganic thickener is 12 to 40% by weight, preferably 15 to 30% by weight based on% by weight. Since the average particle diameter of the coal ash fine particles used as a raw material is relatively large, that is, 10 to 40 μm, the amount of the inorganic thickener used is conventionally 10
When the content is less than 10% by weight, the thickening action is insufficient and molding becomes difficult, and the mechanical strength of the obtained ceramic molded body is also insufficient. On the other hand, if the amount of the inorganic thickener exceeds 40% by weight, the viscosity of the coal ash mixture becomes too high, and it is difficult to form a stable molded body.
【０００９】無機質増粘材としては粘土鉱物、好ましく
はベントナイトが使用される。特に１００メッシュパス
より小さい粒子径（０.２５６ｍｍ以下）のベントナイ
トが好ましい。無機質増粘材は、石炭灰微細粒子同士の
結合を助け、粘性を高める一方、乾燥後の機械的強度を
向上させる作用を有するため、成形性及び操作性が良好
となり、かつ、製造工程を簡素化することができる。有
機質増粘材としては、メチルセルロース、ヒドロキシセ
ルロースなどの水溶性高分子が好ましく用いられるが、
これらの有機質増粘材は焼成段階で分解して除去される
ため、環境負荷を考えるとその使用はできるだけ少ない
方が好ましい。石炭灰微細粒子と無機質増粘材との混合
物１００重量部に対して添加される水は２７〜３７重量
部、好ましくは２９〜３５重量部である。添加される水
量が２７重量％未満の場合は混合又は混練が困難となり
均質な混合物を得にくい。一方、３７重量部より多い場
合は、乾燥に長時間を要し製造効率が低下する。石炭灰
微細粒子、無機質増粘材及び水の配合物を十分に混合又
は混練することによって、粘土状のセラミックス成形前
駆体（石炭灰微細粒子、無機質増粘材及び水の混合物）
が得られる。この際に０.１〜１００ｋＰａの条件にて
混練を行い、粘土状のセラミックス成形前駆体中に含ま
れる空気の脱気を行う。脱気することによりセラミック
ス成形前駆体中の各種成分の均一性が向上し、かつ、緻
密な構造となるため、結果として成形及び焼結後のセラ
ミックス成形体の機械的強度が向上する。Clay minerals, preferably bentonite, are used as the inorganic thickener. In particular, bentonite having a particle size (0.256 mm or less) smaller than 100 mesh pass is preferable. The inorganic thickener has the effect of improving the mechanical strength after drying while helping to bond the coal ash fine particles to each other and increasing the viscosity, thus improving the moldability and operability and simplifying the manufacturing process. Can be Water-soluble polymers such as methylcellulose and hydroxycellulose are preferably used as the organic thickener,
Since these organic thickeners are decomposed and removed in the firing step, their use is preferably as small as possible in view of the environmental burden. Water added to 100 parts by weight of the mixture of the coal ash fine particles and the inorganic thickener is 27 to 37 parts by weight, preferably 29 to 35 parts by weight. If the amount of water added is less than 27% by weight, mixing or kneading becomes difficult, and it is difficult to obtain a homogeneous mixture. On the other hand, when the amount is more than 37 parts by weight, a long time is required for drying, and the production efficiency is reduced. By thoroughly mixing or kneading the blend of coal ash fine particles, inorganic thickener and water, a clay-like ceramic molding precursor (mixture of coal ash fine particles, inorganic thickener and water)
Is obtained. At this time, kneading is performed under a condition of 0.1 to 100 kPa, and air contained in the clay-like ceramics molding precursor is deaerated. By degassing, the uniformity of various components in the ceramic molding precursor is improved and a dense structure is obtained. As a result, the mechanical strength of the ceramic molded body after molding and sintering is improved.
【００１０】本発明においては、次いでセラミックス成
形前駆体を目的とする形状に成形又は造粒することによ
りセラミックス未乾燥成形体を得る。成形又は造粒する
方法としては、特に限定されるものではないが、一般的
に知られているストランドカット、シートカット等の押
出造粒法を含む押出成形法、圧縮成形法、加圧成形造粒
法、転動造粒法及び製丸法等任意の成形法が用いられ
る。この際に０.１〜１００ｋＰａの圧力条件下におい
てセラミックス成形前駆体を混練しつつ成形又は造粒す
る方法が好ましく、具体的にはベント部を備えた混練押
出機等を用いることができる。また、成形する形状とし
ては特に限定されるものではないが、円筒状、円柱状、
多角筒状、多角柱状、クローバー状、球状等の任意形状
が用いられる。このようにして得られたセラミックス未
乾燥成形体は次いで乾燥されてセラミックス未焼成成形
体とされる。乾燥方法としては、一般的に知られている
熱風乾燥法等を使用することができるが、特に、成形体
の外表面及び内部の乾燥速度が一致させるような乾燥方
法が好ましい。このような乾燥方法としては自然乾燥法
又は湿度乾燥法等が挙げられる。In the present invention, an undried ceramic molded body is obtained by molding or granulating a ceramic molding precursor into a desired shape. The method of molding or granulation is not particularly limited, but includes extrusion molding methods including generally known extrusion granulation methods such as strand cut and sheet cut, compression molding methods, and pressure molding methods. Any molding method such as a granulation method, a tumbling granulation method, and a rounding method is used. At this time, a method of molding or granulating while kneading the ceramic molding precursor under a pressure condition of 0.1 to 100 kPa is preferable. Specifically, a kneading extruder having a vent portion can be used. Further, the shape to be molded is not particularly limited, but is cylindrical, cylindrical,
An arbitrary shape such as a polygonal cylindrical shape, a polygonal column shape, a clover shape, and a spherical shape is used. The thus-obtained ceramic green compact is then dried to form a ceramic green compact. As a drying method, a generally known hot-air drying method or the like can be used, and particularly, a drying method that makes the drying speeds of the outer surface and the inner part of the molded body coincide with each other is preferable. Examples of such a drying method include a natural drying method and a humidity drying method.
【００１１】このセラミックス未焼成成形体を熱処理す
ることで石炭灰微細粒子及び無機質造粘材を焼結させた
セラミックス成形体が得られる。また、有機質増粘材が
使用されている場合はこの段階で分解除去される。この
熱処理は、１,０００〜１,３００℃の温度範囲で、０.
５〜５時間実施される。このようにして得られるセラミ
ックス成形体は、先に実施した脱気により、石炭灰の成
分及び無機質造粘材の成分からなる緻密な構造を有して
いる。本発明では１０〜４０μｍの比較的大きな石炭灰
微細粒子を原料としているにもかかわらず、上記の製造
法によって粒子が相互に焼結し、結合した粒子間に連通
した微細な空隙を無数に含むミクロ構造を有するセラミ
ックス成形体が生成する。なお、熱処理温度が１,００
０℃未満では焼結後のセラミックス成形体の強度が劣
る。一方、石炭灰の溶融温度は一般に１,１００〜１,２
５０℃の温度範囲であるため、熱処理温度が１,３００
℃を越えると石炭灰微細粒子が溶融して前記ミクロ構造
中の微細な空隙が閉塞されてしまう。具体的な熱処理温
度は上記の温度範囲内で目的とするセラミックス成形体
の性状に合わせて適宜調節することができる。例えば、
緻密、かつ、機械的強度を重要視する場合は１,２００
℃付近の温度にて熱処理することが好ましく、逆に多孔
性を重要視する場合は１,１００℃付近にて熱処理する
ことが好ましい。また、本発明においては、上記熱処理
に必要な温度までの昇温速度を適宜変更することによっ
ても、得られるセラミックス成形体の性状を適宜調節す
ることができる。By subjecting the ceramic green compact to heat treatment, a ceramic compact obtained by sintering fine coal ash particles and an inorganic viscous material is obtained. If an organic thickener is used, it is decomposed and removed at this stage. This heat treatment is performed at a temperature in the range of 1,000 to 1,300 ° C. and a temperature of 0.1 to 1.3 ° C.
Performed for 5-5 hours. The ceramic molded body thus obtained has a dense structure composed of the components of the coal ash and the components of the inorganic viscous material due to the degassing performed earlier. In the present invention, despite the fact that relatively large coal ash fine particles of 10 to 40 μm are used as raw materials, the particles are mutually sintered by the above-described production method, and include a myriad of fine voids connected between the bonded particles. A ceramic compact having a microstructure is formed. Note that the heat treatment temperature is 1,000
If the temperature is lower than 0 ° C., the strength of the ceramic molded body after sintering is poor. On the other hand, the melting temperature of coal ash is generally 1,100 to 1,2.
Since the temperature range is 50 ° C., the heat treatment temperature is 1,300.
When the temperature exceeds ℃, the fine particles of coal ash are melted and fine voids in the microstructure are closed. The specific heat treatment temperature can be appropriately adjusted within the above temperature range according to the intended properties of the ceramic molded body. For example,
1,200 when precise and mechanical strength is important
Heat treatment is preferably carried out at a temperature around ℃, and when porosity is regarded as important, heat treatment is preferably carried out at around 1,100 ℃. Further, in the present invention, the properties of the obtained ceramic molded body can be appropriately adjusted by appropriately changing the rate of temperature increase to a temperature required for the heat treatment.
【００１２】熱処理により得られたセラミックス成形体
は、石炭灰微細粒子が相互に結合し、結合した粒子間に
多数の微細な空隙が形成され、空隙はセラミックス成形
体の表面から内部まで互いに連通しているため、通気性
を有しており、また、毛細管現象により液体を速やかに
吸水し、保水性が良い。そして、原料の石炭灰は溶出試
験ではｐＨ１１〜１２であるのに対して、熱処理後はｐ
Ｈ７〜８となり、有害物の溶出も全く認められない。従
って、水処理材として好適に用いられる。本発明の水処
理材としてのセラミックス成形体は上述した方法で得ら
れるが、その細孔容積が０.０１〜０.５ｃｃ／ｇ、平均
細孔半径が０.１〜５.０μｍであることが必要である。
なお、細孔容積、平均細孔半径及び比表面積は通常の水
銀圧入法等により測定することができる。この水処理材
は特に活性汚泥等の微生物処理に於ける微生物担体とし
て好ましく用いられる。その場合、微生物がセラミック
ス成形体上に付着することが必要であり、担体としての
機械的強度を強くする必要から、上記細孔半径並びに細
孔容積が必要である。即ち細孔半径や細孔容積が上記範
囲よりも小さいと、微生物の付着が十分でなく微生物担
体としての機能が損なわれる。また、細孔半径や容積が
上記範囲よりも大きいと、成形体の機械的強度が弱く、
濾過筒へ充填したりする作業時に破壊して好ましくな
い。また、本発明の水処理材はその形態を円筒状とする
ことで、濾過筒などに充填した場合、汚水の通過させる
ときの圧力損失が小さく、またそれ自身で汚水に含まれ
る固形物の濾過材の役目も果たすことができる。[0012] In the ceramics compact obtained by the heat treatment, fine coal ash particles are bonded to each other, and a large number of fine voids are formed between the bonded particles, and the voids communicate with each other from the surface to the inside of the ceramics compact. Therefore, it has air permeability, absorbs liquid quickly by capillary action, and has good water retention. The raw material coal ash has a pH of 11 to 12 in the dissolution test, whereas the pH after heat treatment is p.
H7-8, and no harmful substances were eluted. Therefore, it is suitably used as a water treatment material. The ceramic molded body as the water treatment material of the present invention is obtained by the above-mentioned method, and has a pore volume of 0.01 to 0.5 cc / g and an average pore radius of 0.1 to 5.0 μm. is necessary.
The pore volume, average pore radius and specific surface area can be measured by a usual mercury intrusion method or the like. This water treatment material is particularly preferably used as a microorganism carrier in the treatment of microorganisms such as activated sludge. In such a case, the microorganisms need to adhere to the ceramic molded body, and the mechanical strength as a carrier needs to be increased. Therefore, the above-described pore radius and pore volume are required. That is, when the pore radius and the pore volume are smaller than the above ranges, adhesion of microorganisms is not sufficient, and the function as a microorganism carrier is impaired. Further, if the pore radius or volume is larger than the above range, the mechanical strength of the molded body is weak,
Undesirably, it breaks during the work of filling the filter tube. Further, the water treatment material of the present invention has a cylindrical shape, so that when filled in a filter tube or the like, the pressure loss when passing the sewage is small, and the filtration of solids contained in the sewage by itself is performed. It can also serve as a material.
【００１３】本発明の再生材は、上述した使用に供した
水処理材に熱処理することで再生したものである。再生
熱処理方法としては、水処理材に含まれている数々の微
生物、藻類を始めとする有機化合物やリン、窒素含有化
合物を始めとする無機化合物を炭化燃焼による除去或い
は酸化物として無害化するために必要な酸素を十分供給
できるだけの空気を流通させながら、３５０〜１１００
℃の温度範囲で、少なくとも５分間以上熱処理すること
が重要である。熱処理温度が３５０℃未満の場合、水処
理材に含まれている有機化合物の炭化燃焼が不十分、か
つ、無機化合物の酸化が進まず、水処理材として再利用
することができない。また熱処理温度が１１００℃を超
えた場合、水処理材が有している微細な細孔が焼結によ
り閉塞され目的とする水処理効果が低下するため好まし
くない。また、熱処理時間が５分間未満の場合、水処理
材自体の温度が十分に上がらず、目的とする有機化合物
の炭化燃焼、無機化合物の酸化が進まず好ましくない。The reclaimed material of the present invention is regenerated by heat-treating the water treatment material used for use as described above. As a regeneration heat treatment method, many microorganisms contained in the water treatment material, organic compounds such as algae and phosphorus, inorganic compounds such as nitrogen-containing compounds are removed by carbonization combustion or made harmless as oxides. 350 to 1100 while allowing enough air to supply sufficient oxygen
It is important to heat-treat at least 5 minutes or more in a temperature range of ° C. When the heat treatment temperature is lower than 350 ° C., the carbonization and combustion of the organic compound contained in the water treatment material is insufficient, and the oxidation of the inorganic compound does not proceed, so that it cannot be reused as the water treatment material. On the other hand, when the heat treatment temperature exceeds 1100 ° C., the fine pores of the water treatment material are blocked by sintering, and the intended water treatment effect is undesirably reduced. Further, when the heat treatment time is less than 5 minutes, the temperature of the water treatment material itself does not sufficiently rise, and carbonization and combustion of the target organic compound and oxidation of the inorganic compound do not proceed, which is not preferable.
【００１４】この熱処理された再生材は、上記水処理材
と同様に、多孔質構造であるので、微生物の担体能が高
く、優れた水処理材として再度用いることができる。ま
た、この再生材は、微細な細孔を有するため、保水性及
び通気性に優れ、土壌改質材、特に園芸用土壌改質材と
して用いることができる。即ち、この再生材も、石炭灰
微細粒子が相互に結合し、結合した粒子間に多数の微細
な空隙が形成され、空隙はセラミックス成形体の表面か
ら内部まで互いに連通しているものであるので、通気性
を有しており、また、毛細管現象により液体を速やかに
吸水し、保水性が良い。従って、植物の発芽率の向上、
根腐れの防止等に多大な効果があるので、土壌改質材と
して好適なものである。しかも、その細孔容積が０.０
１〜０.５ｃｃ／ｇ、平均細孔半径が０.１〜５.０μｍ
であるので、一般の園芸用の土と物理的に混合でき、土
壌改質材としての機械的強度を強い。Since the heat-treated regenerated material has a porous structure like the above-mentioned water treatment material, it has a high ability to support microorganisms and can be reused as an excellent water treatment material. In addition, since this regenerated material has fine pores, it is excellent in water retention and air permeability, and can be used as a soil modifying material, particularly a horticultural soil modifying material. That is, also in this reclaimed material, the coal ash fine particles are bonded to each other, a large number of fine voids are formed between the bonded particles, and the voids communicate with each other from the surface to the inside of the ceramic molded body. It has good breathability, absorbs liquid quickly by capillary action, and has good water retention. Therefore, the improvement of the germination rate of the plant,
Since it has a great effect on prevention of root rot, it is suitable as a soil modifying material. Moreover, the pore volume is 0.0
1-0.5 cc / g, average pore radius 0.1-5.0 μm
Therefore, it can be physically mixed with general horticultural soil, and has high mechanical strength as a soil modifying material.
【００１５】土壌改質材として用いる場合、その形状、
大きさは任意であるが、一般の園芸用の土と物理的に混
合可能で、本発明の効果を最大限に引き出すために、最
大長が０.５〜１５.０ｍｍの範囲が好ましい。特に好ま
しくは０.６〜１０.０ｍｍの範囲である。ここで最大長
とは、その土壌改質材の１つ当たりの占める空間の占有
体積を支配する長さのことで、例えば、図１に示す各立
体形状での長さＬである。大きい場合には、破砕処理し
ておくことが望ましい。尚、園芸用に用いる場合の土と
しては、限られるものではなく、一般に市販されている
各種のものを適用できる。When used as a soil modifying material, its shape,
Although the size is arbitrary, the maximum length is preferably in the range of 0.5 to 15.0 mm, which can be physically mixed with general horticultural soil and maximizes the effects of the present invention. Particularly preferably, it is in the range of 0.6 to 10.0 mm. Here, the maximum length is a length that governs the occupied volume of the space occupied by one soil modifying material, and is, for example, the length L in each three-dimensional shape shown in FIG. If it is large, it is desirable to crush it. The soil used for horticulture is not limited, and various types of commercially available soil can be used.
【００１６】また、土壌改質材と一般の園芸用の土との
混合割合（容量％）は、３.０対９７.０〜５０.０対５
０.０の範囲であることが望ましい。土壌改質材と土と
の混合割合が、３.０対９７.０未満の場合、保水性及び
通気性に優れている効果を有する土壌改質材の容量が少
なく本発明による効果が少ない。また、土壌改質材と土
との混合割合が、５０.０対５０.０を超えた場合、富化
栄養効果のある成分の固定効果が低下するため、逆に植
物の生育が低下するため好ましくない。ここで、土の量
とは、改質対象とする土の量を云い、例えば、園芸の為
に改質するのであれば、その園芸の栽培において影響を
及ぼす有効量を云う。例えば、鉢植えであれば、その鉢
の中に入れる土の量である。また、園芸土として袋詰め
するのであれば、その袋中における割合になる。The mixing ratio (volume%) of the soil modifying material and general horticultural soil is 3.0 to 97.0 to 50.0 to 5
It is desirable to be in the range of 0.0. When the mixing ratio of the soil modifying material and the soil is less than 3.0 to 97.0, the capacity of the soil modifying material having the effect of excellent water retention and air permeability is small, and the effect of the present invention is small. In addition, when the mixing ratio of the soil modifying material and the soil exceeds 50.0 to 50.0, the effect of fixing the component having the enriched nutrient effect decreases, and conversely, the growth of the plant decreases. Not preferred. Here, the amount of soil refers to the amount of soil to be reformed. For example, if the soil is reformed for horticulture, it refers to the effective amount that affects cultivation of the horticulture. For example, in the case of a potted plant, it is the amount of soil put in the pot. If horticultural soil is packed in a bag, the ratio is the ratio in the bag.
【００１７】尚、上記説明では、水処理材を使用に供し
たものを水処理材又は土壌改質材として再生している
が、これに限られず、例えば、石炭灰を原料として上記
水処理材の製造方法と同様の方法により土壌改質材を製
造し、この土壌改質材を使用に供したものを水処理材又
は土壌改質材に再生することも可能である。また、水処
理材又は土壌改質材として使用に供した再生材に対し
て、さらに、上述した再生処理を施すことにより、再び
再生することも可能で、複数回の再生処理により、複数
回の再生使用が可能である。In the above description, the water treatment material is recycled as a water treatment material or a soil modifying material. However, the present invention is not limited to this. It is also possible to produce a soil modifying material by the same method as the method described in the above, and to regenerate a soil treatment material that has been used for use as a water treatment material or a soil modifying material. In addition, it is also possible to regenerate the recycled material used as a water treatment material or a soil modifying material by performing the above-mentioned regeneration process, and by performing the regeneration process a plurality of times, Recyclable use is possible.
【００１８】[0018]
【実施例】［実施例１］平均粒子径が２４μｍの球状の
フライアッシュ８５重量部、群馬県産のベントナイト
（日本タルク（株）社扱）２００メッシュパス品１５重
量部を双腕式ニーダーにて均一になるまで混合し、その
後、水を３２重量部添加して粘土状になるまで混練りし
た。得られたセラミックス成形前駆体を、混練部を有す
る土練式押出成形機を用いて、外径１.５ｍｍ、平均長
さ２ｍｍの円柱状成形体となるように押出成形及び切断
を行った。その後１日間日陰で乾燥を行った後、１,１
８０℃で３時間熱処理を行った。得られたセラミックス
成形体をカルロエルバ社製ポロシメーター２０００型を
用いて水銀圧入法により測定したところ、細孔容積が
０.４８ｃｃ／ｇ、平均細孔半径が１.４μｍ及び比表面
積が０.６４ｍ2／ｇであり、機械的強度に優れたセラミ
ックス成形体であった。また、前記セラミックス成形体
を走査型電子顕微鏡にて形態観察したところ、材料を構
成する粒子が相互に圧着され、圧着された粒子間に多数
の微細な空隙が形成され、更にその空隙が成形体粒子間
の表面から内部まで連結した細孔が発現していることを
確認した。Example 1 85 parts by weight of spherical fly ash having an average particle diameter of 24 μm and 15 parts by weight of a 200 mesh pass product of bentonite from Gunma Prefecture (manufactured by Nippon Talc Co., Ltd.) were used in a double-arm kneader. Then, 32 parts by weight of water was added and kneaded until the mixture became clay-like. The obtained ceramic molding precursor was extruded and cut into a columnar molded body having an outer diameter of 1.5 mm and an average length of 2 mm using a clay extruder having a kneading portion. After drying in the shade for one day, 1.1
Heat treatment was performed at 80 ° C. for 3 hours. The obtained ceramic molded body was measured by a mercury intrusion method using a porosimeter 2000 manufactured by Carlo Elba to find that the pore volume was 0.48 cc / g, the average pore radius was 1.4 μm, and the specific surface area was 0.64 m 2. / G, and was a ceramic molded body having excellent mechanical strength. When the morphology of the ceramic molded body was observed with a scanning electron microscope, the particles constituting the material were pressed together, and a large number of fine voids were formed between the pressed particles. It was confirmed that pores connected from the surface to the interior between the particles were developed.
【００１９】このセラミックス成形体を水処理材として
用いて、好気性水処理を行った。好気性水処理に用いた
水処理装置は図２に示すようなもので、幅６００ｍｍ、
奥行き３００ｍｍ、高さ３００ｍｍの水槽２０と、水槽
２０内を曝気するためのブロアー２２と、水処理材２４
を充填した濾過筒２６と、水槽と２０と濾過筒２６を接
続する第１配管２８及び第２配管３０と、第１配管２８
を通じて水槽２０内の水を濾過筒２６に送給するポンプ
３２とで概略構成されている。濾過筒２６内には汚水処
理量に対して単位時間当たりの容量が１０容量％となる
ように水処理材２４を充填した。水処理材には好気性菌
を担持させておいた。この水処理装置において、水槽２
０内に汚水（水道水）を４０リットル入れ、ポンプ３２
を駆動して、水槽内の水を濾過筒２６に送給しつつ、オ
ーバーフローさせて第２配管３０により水槽２０に戻し
た。また、水槽２２内にはブロアー２２により空気を供
給した。この状態で１４日間、水処理材２４の好気性菌
の繁殖を促す目的で水だけを循環させた。その後、２０
匹の金魚を水中に放流した。６ヶ月間、金魚の生存率を
調べた。実験開始から６ヶ月後の金魚の生存率は９５％
であり、水処理材２４が物理的及び生物的に循環する水
を濾過していたことが明らかとされた。Aerobic water treatment was performed using this ceramic molded body as a water treatment material. The water treatment apparatus used for the aerobic water treatment is as shown in FIG.
A water tank 20 having a depth of 300 mm and a height of 300 mm, a blower 22 for aerating the inside of the water tank 20, and a water treatment material 24
, A first pipe 28 and a second pipe 30 connecting the water tank 20 and the filter cylinder 26, and a first pipe 28
And a pump 32 for feeding the water in the water tank 20 to the filter cylinder 26 through the filter. The filtration tube 26 was filled with a water treatment material 24 so that the volume per unit time with respect to the amount of sewage treatment was 10% by volume. Aerobic bacteria were carried on the water treatment material. In this water treatment apparatus, the water tank 2
40 liters of sewage (tap water) in the pump 0
Was driven to overflow the water in the water tank to the filter tank 26, and returned to the water tank 20 by the second pipe 30. Air was supplied into the water tank 22 by the blower 22. In this state, only water was circulated for 14 days in order to promote the propagation of aerobic bacteria in the water treatment material 24. Then, 20
The goldfish were released into the water. The survival rate of the goldfish was examined for 6 months. Six months after the start of the experiment, the survival rate of the goldfish is 95%
It was found that the water treatment material 24 was filtering water circulating physically and biologically.
【００２０】その後、水処理材を取り出し、２日間放置
して乾燥させた。次いでバッチ式熱処理炉に空気を流通
させて８５０℃で１時間熱処理した。熱処理された水処
理材について、上記同様に水銀圧入法により測定したと
ころ、細孔容積が０.４６ｃｃ／ｇ、平均細孔半径が１.
３μｍ及び比表面積が０.６２ｍ2／ｇであり、走査型電
子顕微鏡にて形態観察したところ、材料を構成する粒子
が相互に圧着され、圧着された粒子間に多数の微細な空
隙が形成され、更にその空隙が成形体粒子間の表面から
内部まで連結した細孔が発現していることを確認した。Thereafter, the water treatment material was taken out and left to dry for 2 days. Next, air was passed through a batch type heat treatment furnace to perform heat treatment at 850 ° C. for 1 hour. When the water treatment material subjected to the heat treatment was measured by the mercury intrusion method in the same manner as described above, the pore volume was 0.46 cc / g, and the average pore radius was 1.
3 μm and a specific surface area of 0.62 m 2 / g. When the morphology was observed with a scanning electron microscope, the particles constituting the material were pressed together, and many fine voids were formed between the pressed particles. Further, it was confirmed that pores in which the voids were connected from the surface to the interior between the molded article particles were developed.
【００２１】［実施例２］実施例１で熱処理して再生し
た水処理材を実施例１での一次の水処理材と同様に水処
理材として用い、金魚の飼育を行った。その結果、６ヶ
月間飼育後の金魚の生存率は９５％であった。この結果
より、新品の水処理材と変わらない効果が得られること
を確認した。[Example 2] The water treatment material regenerated by heat treatment in Example 1 was used as a water treatment material in the same manner as the primary water treatment material in Example 1, and goldfish were bred. As a result, the survival rate of the goldfish after breeding for 6 months was 95%. From this result, it was confirmed that the same effect as a new water treatment material was obtained.
【００２２】［実施例３］実施例１で熱処理した再生材
を破砕して、７.５メッシュパスしたものを土壌改質材
として、園芸用の鉢に対して容量で１０容量％、残りの
９０容量％は一般の園芸土となるように、物理的に混合
し、十分かき混ぜたものを鉢に入れたものを３０鉢用意
した。この鉢にひまわりの種を入れたところ、平均７日
目に発芽した。また、発芽率は１００％であった。下記
比較例２と比較して十分に土壌が改質されていたことが
明らかとされた。[Example 3] The regenerated material heat-treated in Example 1 was crushed and subjected to a 7.5 mesh pass as a soil modifying material. 90 vol% was physically mixed so that it would become a general horticultural soil, and thirty well-stirred ones were placed in a pot to prepare 30 pots. When sunflower seeds were placed in these pots, they germinated on average 7 days. The germination rate was 100%. It was clarified that the soil was sufficiently modified as compared with Comparative Example 2 below.
【００２３】［比較例１］実施例１において、再生する
にあたっての熱処理温度を２００℃とした点以外は実施
例１と同様にし、得られた熱処理品を用いて実施例２と
同様に金魚の飼育を行った。その結果６ヵ月後の金魚の
生存率は４０％であり、水処理材として十分に再生して
いなかった。［比較例２］実施例３において、園芸用の
鉢に対して一般の園芸土のみを用いた点以外は実施例４
と同様にしてひまわりの発芽実験を行った。その結果、
平均９日目に発芽し、かつ、発芽率は８６.７％であっ
た。Comparative Example 1 The procedure of Example 1 was repeated, except that the heat treatment temperature for regeneration was set to 200 ° C., and the obtained heat-treated product was used to produce goldfish in the same manner as in Example 2. Reared. As a result, the survival rate of the goldfish after 6 months was 40%, and the goldfish was not sufficiently regenerated as a water treatment material. Comparative Example 2 Example 4 was the same as Example 3 except that only general horticultural soil was used for horticultural pots.
A germination experiment of sunflower was performed in the same manner as described above. as a result,
It germinated on average 9 days, and the germination rate was 86.7%.
【００２４】[0024]
【発明の効果】本発明は石炭灰という産業廃棄物を有効
利用する技術であり、石炭灰を成形・焼成して得られる
処理効果に優れた付加価値の高い水処理材を複数回再生
して使用することを可能ならしめたものであり、資源の
有効利用性に富み、環境上等から極めて優れたものであ
る。Industrial Applicability The present invention is a technology for effectively utilizing industrial waste called coal ash, and is a method of regenerating a high value-added water treatment material excellent in processing effect obtained by forming and firing coal ash a plurality of times. It is made possible to use it, is rich in effective use of resources, and is extremely excellent from an environmental point of view.
【図１】 土壌改質材における最大長Ｌを説明するため
の斜視図で、図１（ａ）は円筒状、図１（ｂ）は多角柱
状、図１（ｃ）はクローバー状、図１（ｄ）は球状を示
すものである。FIG. 1 is a perspective view for explaining a maximum length L of a soil modifying material. FIG. 1 (a) is a cylindrical shape, FIG. 1 (b) is a polygonal column shape, FIG. 1 (c) is a clover shape, FIG. (D) shows a spherical shape.
【図２】 実施例で使用した好気性水処理装置を示す斜
視図である。FIG. 2 is a perspective view showing an aerobic water treatment device used in Examples.
２４ 水処理材 24 Water treatment materials
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０４Ｂ 38/00 ３０４ Ｂ０９Ｂ 3/00 ＺＡＢ Ｃ１２Ｍ 1/00 Ｃ０４Ｂ 35/00 ＺＡＢＶ Ｆターム(参考） 4B029 AA02 BB01 CC10 4D003 AA01 AB13 BA02 CA02 EA14 EA15 EA24 FA02 4D004 AA37 AA50 BA10 CA14 CA15 CA30 CA42 CB02 CB16 CB21 CB34 CC11 DA03 DA06 DA10 DA20 4G019 FA02 FA13 GA01 4G030 BA32 CA09 GA25 GA27 HA05 HA20 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C04B 38/00 304 B09B 3/00 ZAB C12M 1/00 C04B 35/00 ZABV F-term (Reference) 4B029 AA02 BB01 CC10 4D003 AA01 AB13 BA02 CA02 EA14 EA15 EA24 FA02 4D004 AA37 AA50 BA10 CA14 CA15 CA30 CA42 CB02 CB16 CB21 CB34 CC11 DA03 DA06 DA10 DA20 4G019 FA02 FA13 GA01 4G030 BA32 CA09 GA25 GA27 HA05 HA20
Claims (4)
細粒子と無機質増粘材を含む原料を焼成したセラミック
ス成形体からなり、該セラミックス成形体は前記石炭灰
微細粒子が相互に結合し、該結合した粒子間に多数の微
細な空隙が形成された多孔質構造を有し、その空隙の平
均細孔半径が０.１〜５.０μｍ、且つ細孔の全容積が
０.０１〜０.５ｃｃ／ｇである水処理材を空気流通下３
５０〜１１００℃で熱処理したことを特徴とする再生
材。1. A ceramic formed body obtained by firing a raw material containing coal ash fine particles having an average particle diameter of 10 to 40 μm and an inorganic thickener, wherein the ceramic formed body has the coal ash fine particles bonded to each other, It has a porous structure in which a number of fine voids are formed between the bonded particles, the average pore radius of the voids is 0.1 to 5.0 μm, and the total volume of the pores is 0.01 to 0. 2.5cc / g of water treatment material under air circulation
A reclaimed material characterized by being heat-treated at 50 to 1100 ° C.
請求項１記載の再生材。2. The recycled material according to claim 1, which is used as a water treatment material.
る請求項１記載の再生材。3. The recycled material according to claim 1, which is used as a soil modifying material.
る石炭灰微細粒子と無機質増粘材を含む原料を焼成した
セラミックス成形体からなり、該セラミックス成形体は
前記石炭灰が相互に結合し、該結合した粒子間に多数の
微細な空隙が形成された多孔質構造を有し、その空隙の
平均細孔半径が０.１〜５.０μｍ、且つ細孔の全容積が
０.０１〜０.５ｃｃ／ｇである水処理材を使用に供した
後、これを空気流通下３５０〜１１００℃で熱処理する
ことを特徴とする水処理材の再生方法。4. A ceramic formed body obtained by firing a raw material containing coal ash fine particles having an average particle diameter in a range of 10 to 40 μm and an inorganic thickener, and the ceramic formed body is formed by binding the coal ash to each other. Having a porous structure in which a number of fine voids are formed between the bonded particles, the average pore radius of the voids is 0.1 to 5.0 μm, and the total volume of the pores is 0.01 to 5.0 μm. A method for regenerating a water treatment material, which comprises subjecting a water treatment material having a flow rate of 0.5 cc / g to use and heat-treating it at 350 to 1100 ° C. in an air flow.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000213312A JP2002028607A (en) | 2000-07-13 | 2000-07-13 | Regenerating material and regenerating method of water treating material using coal ash as essential raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000213312A JP2002028607A (en) | 2000-07-13 | 2000-07-13 | Regenerating material and regenerating method of water treating material using coal ash as essential raw material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002028607A true JP2002028607A (en) | 2002-01-29 |
Family
ID=18709084
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
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| JP (1) | JP2002028607A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS637814A (en) * | 1986-06-30 | 1988-01-13 | Ibiden Co Ltd | Ceramic filter |
| JPS6362594A (en) * | 1986-08-06 | 1988-03-18 | Nippon Steel Corp | Fixed bed type continuous activated sludge treatment of waste water by using ceramics as carrier for immobilizing activated sludge |
| JPH0615258A (en) * | 1992-07-06 | 1994-01-25 | Ngk Insulators Ltd | Water purifier and cartridge therefor |
| JP2000154068A (en) * | 1998-11-17 | 2000-06-06 | Mitsubishi Rayon Co Ltd | Ceramic molding using coal ash as principal starting material, its production and material using same |
-
2000
- 2000-07-13 JP JP2000213312A patent/JP2002028607A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS637814A (en) * | 1986-06-30 | 1988-01-13 | Ibiden Co Ltd | Ceramic filter |
| JPS6362594A (en) * | 1986-08-06 | 1988-03-18 | Nippon Steel Corp | Fixed bed type continuous activated sludge treatment of waste water by using ceramics as carrier for immobilizing activated sludge |
| JPH0615258A (en) * | 1992-07-06 | 1994-01-25 | Ngk Insulators Ltd | Water purifier and cartridge therefor |
| JP2000154068A (en) * | 1998-11-17 | 2000-06-06 | Mitsubishi Rayon Co Ltd | Ceramic molding using coal ash as principal starting material, its production and material using same |
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