JP2001220128A - Method for manufacturing hydrogrossular using coal- gasification slag - Google Patents
Method for manufacturing hydrogrossular using coal- gasification slagInfo
- Publication number
- JP2001220128A JP2001220128A JP2000028812A JP2000028812A JP2001220128A JP 2001220128 A JP2001220128 A JP 2001220128A JP 2000028812 A JP2000028812 A JP 2000028812A JP 2000028812 A JP2000028812 A JP 2000028812A JP 2001220128 A JP2001220128 A JP 2001220128A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogrossular
- raw material
- acidic gas
- coal gasification
- gasification slag
- 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.)
- Granted
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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
- Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
Landscapes
- Treating Waste Gases (AREA)
- Processing Of Solid Wastes (AREA)
- Gas Separation By Absorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、石炭ガス化炉等か
ら排出されるスラグ（以下「石炭ガス化スラグ」とい
う）を有効に利用したハイドログロシュラーの製造方法
に関する。また、本発明は、上記ハイドログロシュラー
を用いた酸性ガスの吸収除去技術に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrogrossular slag effectively utilizing slag discharged from a coal gasifier or the like (hereinafter referred to as "coal gasification slag"). Further, the present invention relates to a technology for absorbing and removing an acidic gas using the above-mentioned hydrogrossular.
【０００２】[0002]
【従来技術】石炭ガス化複合発電等の石炭ガス化炉では
灰分が排出される。その灰分は、灰分の抜き出し形態に
よって、１）通常の微粉炭焚ボイラと同様な灰の形態で
抜き出す乾灰式と、２）灰分を溶融してガラス状に固化
した形態で抜き出すスラグ式に大別される。スラグ式で
は、その容積を小さくできるとともに、非溶出性であ
り、その取扱いが容易であるため、スラグ式で排出され
たスラグ（すなわち、石炭ガス化スラグ）の排出量も多
い。2. Description of the Related Art Ash is discharged from a coal gasifier such as an integrated coal gasification combined cycle power plant. The ash content is largely divided into 1) a dry ash type, which is extracted in the form of ash similar to a normal pulverized coal-fired boiler, and 2) a slag type, in which the ash is melted and solidified into a glass. Separated. In the slag type, the volume can be reduced, the slag is non-elutable, and the handling thereof is easy. Therefore, the amount of slag (ie, coal gasification slag) discharged in the slag type is large.
【０００３】[0003]
【発明が解決しようとする課題】近年、環境保全又は資
源活用に対する要請が高まる中で、産業廃棄物のリサイ
クル化に関する技術開発の要請も高くなっている。産業
廃棄物の一つである石炭ガス化スラグも例外でなく、こ
れを工業的規模で活用することは重要な課題である。In recent years, as the demand for environmental conservation or resource utilization has increased, the demand for technical development relating to the recycling of industrial waste has also increased. Coal gasification slag, one of the industrial wastes, is no exception, and its use on an industrial scale is an important issue.
【０００４】しかしながら、石炭ガス化スラグの有効利
用を図るための技術は、廃棄プラスチックの粉砕媒体と
しての利用（特開平１１−２０９７６７号）が提案され
ている程度であって、工業的に有効利用できる方法は未
だ開発されるに至っていないのが現状である。[0004] However, the technology for effectively utilizing coal gasification slag has only been proposed to use waste plastic as a grinding medium (Japanese Patent Laid-Open No. 11-209767), and is industrially effectively used. At present, a method that can be used has not yet been developed.
【０００５】従って、本発明の主目的は、石炭ガス化ス
ラグを工業的規模で利用するための技術を提供すること
にある。Accordingly, it is a primary object of the present invention to provide a technique for utilizing coal gasification slag on an industrial scale.
【０００６】[0006]
【課題を解決するための手段】本発明者は、かかる現状
に鑑み、鋭意研究を重ねた結果、石炭ガス化スラグが酸
性ガス吸収除去のための原料として有効であることを見
出し、ついに本発明を完成するに至った。Means for Solving the Problems In view of the present situation, the present inventors have conducted intensive studies and found that coal gasification slag is effective as a raw material for absorbing and removing acidic gas. Was completed.
【０００７】すなわち、本発明は、石炭ガス化スラグを
含む原料スラリーを水熱処理することによりハイドログ
ロシュラーを製造する方法に係るものである。[0007] That is, the present invention relates to a method for producing a hydrogrossular by hydrothermally treating a raw material slurry containing coal gasification slag.
【０００８】また、本発明は、Ｓｉ欠損型カトアイト、
カトアイト及びヒブシャイトの少なくとも１種を含むハ
イドログロシュラーからなる酸性ガス吸収材に係るもの
である。[0008] The present invention also provides a Si-deficient cathoito,
The present invention relates to an acidic gas absorbent made of a hydrogrossular containing at least one of katoite and hibbsite.
【０００９】さらに、本発明は、上記酸性ガス吸収材を
４００℃を超える温度で酸性ガスと接触させることを特
徴とする酸性ガスの吸収除去方法に係るものである。Further, the present invention relates to a method for absorbing and removing an acidic gas, which comprises contacting the acidic gas absorbing material with an acidic gas at a temperature exceeding 400 ° C.
【００１０】[0010]
【発明の実施の形態】１．ハイドログロシュラーの製造
方法 本発明の製造方法は、石炭ガス化スラグを含む原料スラ
リーを水熱処理することによりハイドログロシュラーを
製造する方法である。BEST MODE FOR CARRYING OUT THE INVENTION The manufacturing method of the present invention is a method of manufacturing a hydrogrossler by hydrothermally treating a raw material slurry containing coal gasification slag.
【００１１】石炭ガス化スラグは、石炭ガス化炉で排出
されるものであって、灰分を溶融してガラス状に固化し
たものである。石炭ガス化炉が用いられるプラントの種
類は特に制限されず、石炭ガス化複合発電等のプラント
に設置されている石炭ガス化炉が挙げられる。[0011] Coal gasification slag is discharged from a coal gasification furnace, and is obtained by melting ash and solidifying it into a glass. The type of plant in which the coal gasifier is used is not particularly limited, and examples thereof include a coal gasifier installed in a plant such as an integrated coal gasification combined cycle.
【００１２】石炭ガス化スラグの組成は、ハイドログロ
シュラーの原料として使用できる限り特に制限されな
い。例えば、少なくともＳｉＯ2、Ａｌ2Ｏ3及びＣａＯ
を含むスラグ、あるいはこれらに加えてＭｇＯ、Ｆｅ2
Ｏ3、Ｎａ2Ｏ、Ｋ2Ｏ、ＴｉＯ2等のいずかを含むスラグ
が使用できる。本発明では、例えばＳｉＯ2含有量が４
５重量％未満、特に４４重量％以下の石炭ガス化スラグ
も用いることができる。また、一般に、石炭ガス化スラ
グは、溶融物が固化したものであることから実質的に非
晶質からなるものを用いることが望ましい。[0012] The composition of the coal gasification slag is not particularly limited as long as it can be used as a raw material for hydrogrossular. For example, at least SiO 2 , Al 2 O 3 and CaO
Containing slag, or additionally MgO, Fe 2
A slag containing any of O 3 , Na 2 O, K 2 O, TiO 2 and the like can be used. In the present invention, for example, when the SiO 2 content is 4
Less than 5% by weight, especially less than 44% by weight, of coal gasification slag can also be used. In general, coal gasification slag is desirably substantially amorphous because it is a solidified melt.
【００１３】本発明においては、所望のハイドログロシ
ュラーの組成、用途等に応じてケイ酸質原料、アルミナ
質原料及び石灰質原料の少なくとも１種を適宜加えるこ
ともできる。In the present invention, at least one of a siliceous raw material, an alumina raw material, and a calcareous raw material can be appropriately added according to the desired composition, use, and the like of the hydrogrossular.
【００１４】ケイ酸質原料としては、ＳｉＯ2を供給で
きるものであれば限定されず、例えばシリカ、珪藻土、
カオリン、ケイ砂、石英等を挙げることができる。アル
ミナ質原料としては、Ａｌ2Ｏ3を供給できるものであれ
ば限定されず、例えば酸化アルミニウム、水酸化アルミ
ニウム、カオリン、ベーマイト、シラス、パーライト等
が挙げられる。石灰質原料としては、ＣａＯを供給でき
るものであれば限定されず、例えば生石灰、消石灰、半
水石膏、無水石膏、二水石膏等を挙げることができる。The siliceous raw material is not limited as long as it can supply SiO 2. For example, silica, diatomaceous earth,
Kaolin, quartz sand, quartz and the like can be mentioned. The alumina raw material is not limited as long as it can supply Al 2 O 3, and examples thereof include aluminum oxide, aluminum hydroxide, kaolin, boehmite, shirasu, and pearlite. The calcareous raw material is not limited as long as it can supply CaO, and examples thereof include quick lime, slaked lime, hemihydrate gypsum, anhydrous gypsum, gypsum and the like.
【００１５】これらの原料は、単独で添加しても良い
し、また混合物又は化合物の形態で添加しても良い。例
えば、本発明では、カオリンをケイ酸質原料及びアルミ
ナ質原料として添加することができる。These raw materials may be added alone or in the form of a mixture or a compound. For example, in the present invention, kaolin can be added as a siliceous raw material and an alumina raw material.
【００１６】これら原料の配合割合は、所望のハイドロ
グロシュラーの組成（特にＳｉＯ2、Ａｌ2Ｏ3及びＣａ
Ｏ）となるように秤量して配合すれば良い。用いる石炭
ガス化スラグをそのまま単独で原料スラリーとすること
により所望のハイドログロシュラーが得られる場合に
は、ケイ酸質原料等を添加せずにハイドログロシュラー
を製造することができる。これに対し、用いる石炭ガス
化スラグ単独では所望のハイドログロシュラーが得られ
ない場合には、そのハイドログロシュラーの組成となる
ようにケイ酸質原料等を適宜添加すれば良い。The mixing ratio of these raw materials depends on the composition of the desired hydrogrossular (particularly SiO 2 , Al 2 O 3 and Ca
O) may be weighed and blended. When a desired hydrogloss slag can be obtained by using the coal gasification slag alone as a raw material slurry as it is, the hydrogloss slag can be produced without adding a siliceous raw material or the like. On the other hand, in the case where the desired hydrogrossular cannot be obtained by using the coal gasification slag alone, a siliceous raw material or the like may be appropriately added so that the composition of the hydroglosular is obtained.
【００１７】これらの原料は、混合前及び／又は混合後
に必要に応じて粉砕、分級等により粒度調整を行うこと
もできる。原料スラリーに用いる際の原料粉末の平均粒
径は通常０．１〜１００μｍ程度とすれば良い。These raw materials can be subjected to particle size adjustment by pulverization, classification and the like as necessary before and / or after mixing. The average particle size of the raw material powder when used in the raw material slurry may be generally about 0.1 to 100 μm.
【００１８】次いで、これら原料から原料スラリーを調
製する。原料スラリー中の固形分の割合は原料スラリー
組成、粒度等に応じて適宜設定すれば良いが、通常は固
形分：水＝１：６〜２０（好ましくは１：６〜１２）
（重量比）とする。Next, a raw material slurry is prepared from these raw materials. The ratio of the solid content in the raw material slurry may be appropriately set according to the raw material slurry composition, the particle size, etc., but usually, the solid content: water = 1: 6 to 20 (preferably 1: 6 to 12).
(Weight ratio).
【００１９】原料スラリーの水熱合成の条件は、原料ス
ラリーの種類等に応じて適宜決定することができるが、
通常は温度１３０〜３００℃（好ましくは１５０〜２０
０℃）及び圧力０．３〜８．６ＭＰａ（好ましくは０．
５〜１．６ＭＰａ）とすれば良い。水熱合成の時間は、
温度、圧力、原料スラリーの量等に応じて適宜変更でき
る。水熱合成のための反応装置としては、例えば市販の
オートクレーブ等を用いることができる。The conditions for hydrothermal synthesis of the raw material slurry can be appropriately determined according to the type of the raw material slurry, etc.
Usually, the temperature is 130 to 300 ° C. (preferably 150 to 20 ° C.)
0 ° C.) and a pressure of 0.3 to 8.6 MPa (preferably 0.1 MPa).
5 to 1.6 MPa). The time for hydrothermal synthesis is
It can be appropriately changed according to the temperature, the pressure, the amount of the raw slurry, and the like. As a reactor for hydrothermal synthesis, for example, a commercially available autoclave or the like can be used.
【００２０】水熱合成した後、公知の固液分離法に従っ
て固形分を回収し、必要に応じて乾燥すれば良い。さら
に必要に応じて成形、造粒、粉砕、分級等の処理を施す
こともできる。これによって、最終的にハイドログロシ
ュラーを得ることができる。本発明の製造方法では、例
えばＳｉ欠損型カトアイト（Ｃａ3Ａｌ2（ＯＨ）12）、
ヒブシャイト（Ｃａ3Ａｌ2（ＳｉＯ4）2（ＯＨ）4）、
カトアイト（Ｃａ3Ａｌ 2（ＳｉＯ4）（ＯＨ）8）等を含
むハイドログロシュラーが得られる。２．酸性ガス吸収
材本発明の酸性ガス吸収材は、Ｓｉ欠損型カトアイト、
カトアイト及びヒブシャイトの少なくとも１種を含むハ
イドログロシュラーからなる。After hydrothermal synthesis, according to a known solid-liquid separation method.
Solids may be collected and dried if necessary. Further
Subject to molding, granulation, pulverization, classification, etc. as necessary
You can also. This ultimately results in a hydrogloss
Can be obtained. In the manufacturing method of the present invention, an example
For example, Si-deficient catatoite (CaThreeAlTwo(OH)12),
Hibscheid (CaThreeAlTwo(SiOFour)Two(OH)Four),
Katoite (CaThreeAl Two(SiOFour) (OH)8) Etc.
The resulting hydrogrossular product is obtained. 2. Acid gas absorption
Material The acid gas absorbing material of the present invention is a Si-deficient katoite,
C containing at least one of katoite and hibbsite
Consists of Idroglossrer.
【００２１】一般式Ｃａ3Ａｌ2（ＳｉＯ4）3-x（Ｈ
4Ｏ4）x（但し、０＜ｘ≦３）で示されるハイドログロ
シュラーの中で、Ｓｉ欠損型カトアイトはｘ＝３、カト
アイトはｘ＝２、ヒブシャイトはｘ＝１で示される化合
物である。なお、本発明の酸性ガス吸収材では、その効
果を妨げない範囲内でＳｉ欠損型カトアイト、カトアイ
ト及びヒブシャイト以外の成分が含まれていても良い。The general formula Ca 3 Al 2 (SiO 4 ) 3-x (H
4 O 4 ) x (where 0 <x ≦ 3), where Si-deficient katite is a compound represented by x = 3, katite is represented by x = 2, and hybsite is represented by x = 1. . The acidic gas absorbent of the present invention may contain components other than Si-deficient katite, katite and hibbsite as long as the effect is not impaired.
【００２２】また、酸性ガス吸収材は、通常は粉末状の
形態とすれば良い。その場合の平均粒径は、用途等に応
じて適宜設定できるが、通常１〜２００μｍ程度とすれ
ば良い。また、必要に応じて造粒又は成形することによ
り、造粒物又は成形体として用いることもできる。The acidic gas absorbent may be usually in the form of a powder. In this case, the average particle size can be appropriately set according to the application and the like, but is usually set to about 1 to 200 μm. Also, by granulating or molding as necessary, it can be used as a granulated product or molded product.
【００２３】本発明の酸性ガス吸収材は、特に本発明の
製造方法によって得られたハイドログロシュラーを好適
に用いることができる。すなわち、石炭ガス化スラグを
含む原料スラリーを水熱合成することによって得られた
ハイドログロシュラーが好ましい。As the acidic gas absorbing material of the present invention, particularly, a hydrogrossular obtained by the production method of the present invention can be suitably used. That is, a hydrogrossular obtained by hydrothermally synthesizing a raw material slurry containing coal gasification slag is preferable.
【００２４】酸性ガスの種類としては、本発明に係るハ
イドログロシュラーに吸収される限り制限されず、例え
ば塩化水素（ＨＣｌ）ガス、フッ化水素（ＨＦ）ガス、
塩素ガス（Ｃｌ2）あるいはこれらの混合ガスが挙げら
れる。この中でも、特に塩化水素ガスに好適に用いるこ
とができる。３．酸性ガスの吸収除去方法本発明の酸性
ガスの吸収除去方法は、Ｓｉ欠損型カトアイト、カトア
イト及びヒブシャイトの少なくとも１種を含むハイドロ
グロシュラー（すなわち、本発明吸収材）を４００℃を
超える温度で酸性ガスと接触させることを特徴とする。The type of the acidic gas is not limited as long as it is absorbed by the hydrogrossler according to the present invention. For example, hydrogen chloride (HCl) gas, hydrogen fluoride (HF) gas,
Chlorine gas (Cl 2 ) or a mixed gas thereof may be used. Among them, particularly, hydrogen chloride gas can be suitably used. 3. Method for Absorbing and Removing Acidic Gas The method for absorbing and removing acid gas of the present invention is a method for absorbing and removing a hydrogrossular (that is, the absorbent of the present invention) containing at least one of Si-deficient katite, katite, and hibbsite at a temperature exceeding 400 ° C. It is characterized by being brought into contact with a gas.
【００２５】Ｓｉ欠損型カトアイト、カトアイト及びヒ
ブシャイトの少なくとも１種を含むハイドログロシュラ
ーは、本発明の製造方法によって得られるものが好適に
使用することができる。As the hydrogrossular containing at least one of Si-deficient catatoite, cathoite and hibbsite, those obtained by the production method of the present invention can be suitably used.
【００２６】酸性ガスとの接触方法は、本発明吸収材と
の接触が確実に行える限りはいずれの方法でも良い。例
えば、空気流入口及び流出口を有する容器中に吸収材を
充填し、この容器に酸性ガスを流通させることによって
接触させることができる。また例えば、本発明吸収材を
網目ケース等に収納し、これを酸性ガスを吹き込むこと
により接触させることもできる。これらの場合の酸性ガ
ス流通量及び酸性ガス吸収材の充填量は、酸性ガスの種
類等によって適宜変更することができる。As a method for contacting with the acidic gas, any method may be used as long as the contact with the absorbent of the present invention can be surely performed. For example, a container having an air inlet and an outlet can be filled with an absorbent, and the container can be brought into contact by flowing an acidic gas through the container. Further, for example, the absorbent material of the present invention can be housed in a mesh case or the like, and can be brought into contact by blowing an acidic gas. In these cases, the flow rate of the acidic gas and the filling amount of the acidic gas absorbent can be appropriately changed depending on the type of the acidic gas and the like.
【００２７】また、ゴミ焼却炉、燃焼装置、溶融炉等又
はこれら各種施設の煙道・配管に、本発明の吸収材を設
置したり、あるいは本発明吸収材の粉末を排ガス等の被
処理ガスに直接散布することによっても接触させること
が可能である。Further, the absorbent of the present invention may be installed in the flue / pipe of a garbage incinerator, a combustion apparatus, a melting furnace, etc. or these various facilities, or the powder of the absorbent of the present invention may be treated with a gas to be treated such as exhaust gas. It can also be brought into contact by spraying directly on the surface.
【００２８】本発明吸収材は、用いるハイドログロシュ
ラーの作動温度にもよるが、通常は４００℃を超える温
度で使用し、特に８００〜１０００℃の高温でも有効に
酸性ガスの吸収除去が可能である。本発明では、このよ
うな高温でも酸性ガスを吸収除去することができるの
で、ダイオキシン等の有毒物質の発生をより効果的に抑
制ないし防止することができる。また、本発明方法によ
り吸収された酸性ガス（又はその成分）は、通常の環境
下では吸収材から溶出することはないので、安全性にお
いても優れた効果を発揮できる。さらに、酸性ガスを吸
収した使用済みのハイドログロシュラーは、石灰及び水
とともに混合し、１１０〜２００℃で水熱処理を施すこ
とにより再生することも可能である。The absorbent of the present invention is usually used at a temperature exceeding 400 ° C., although it depends on the operating temperature of the hydrogrossler used. Particularly, it is possible to effectively absorb and remove acidic gas even at a high temperature of 800 to 1000 ° C. is there. In the present invention, the acidic gas can be absorbed and removed even at such a high temperature, so that the generation of toxic substances such as dioxin can be more effectively suppressed or prevented. Further, the acidic gas (or a component thereof) absorbed by the method of the present invention does not elute from the absorbent under a normal environment, and therefore can exhibit excellent effects in safety. Further, the used hydrogrossular which has absorbed the acidic gas can be regenerated by mixing it with lime and water and performing a hydrothermal treatment at 110 to 200 ° C.
【００２９】[0029]
【発明の効果】本発明の製造方法によれば、廃棄物であ
る石炭ガス化スラグをハイドログロシュラーという工業
的に利用可能な材料に変えることができ、環境保全又は
資源の有効利用に大いに貢献することができる。According to the production method of the present invention, coal gasification slag as waste can be changed to an industrially usable material called hydrogrossular, which greatly contributes to environmental conservation or effective use of resources. can do.
【００３０】また、本発明の製造方法により得られるハ
イドログロシュラーは、さまざまな用途への適用が期待
でき、例えば酸性ガス吸収材、骨材、路盤材、埋め戻し
材、土木用充填材、農地造成材、造園材、鋳型及び中子
製造用の硬化剤等の使用が可能である。この中でも、特
に、酸性ガス吸収材として、塩化水素等の吸収除去に有
用である。The hydrogrossular obtained by the production method of the present invention can be expected to be applied to various uses, for example, an acid gas absorbent, an aggregate, a roadbed material, a backfill material, a civil engineering filler, an agricultural land. It is possible to use a curing material for producing a building material, a landscaping material, a mold and a core. Among them, it is particularly useful as an acidic gas absorbent for absorbing and removing hydrogen chloride and the like.
【００３１】[0031]
【実施例】以下に実施例を示し、本発明の特徴をより具
体的に説明する。但し、本発明は、実施例に限定される
ものではない。The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the examples.
【００３２】実施例１ 石炭ガス化スラグを用いてハイドログロシュラーを製造
した。Example 1 A hydrogrossular was produced using coal gasification slag.
【００３３】石炭ガス化スラグのほか、生石灰及び水酸
化アルミニウムを用い、組成がモル比でＣａＯ：Ａｌ2
Ｏ3：ＳｉＯ2＝３：１：１となるように秤量して混合
し、これに水を加えて原料スラリーを調製した。原料ス
ラリーは固形分：水＝１：１２とした。次いで、上記ス
ラリーをオートクレーブに投入し、１００ｒｐｍで攪拌
しながら温度２００℃、圧力１．６ＭＰａで１０時間の
水熱処理を施した。In addition to coal gasification slag, lime and aluminum hydroxide are used, and the composition is CaO: Al 2
The materials were weighed and mixed so that O 3 : SiO 2 = 3: 1: 1, and water was added thereto to prepare a raw material slurry. The raw material slurry was solid content: water = 1: 12. Next, the slurry was put into an autoclave and subjected to a hydrothermal treatment at a temperature of 200 ° C. and a pressure of 1.6 MPa for 10 hours while stirring at 100 rpm.
【００３４】なお、石炭ガス化スラグは、表１に示す物
性・組成をもつスラグを１０５℃で乾燥後、ボールミル
で粉砕し、これを分級して平均粒径３１μｍとしたもの
を用いた。As the coal gasification slag, slag having the physical properties and composition shown in Table 1 was dried at 105 ° C., pulverized by a ball mill, and classified to have an average particle diameter of 31 μm.
【００３５】[0035]
【表１】 [Table 1]
【００３６】反応後、得られた固形分を乾燥後、粉末Ｘ
線回折分析により反応生成物の同定を行った。その結
果、反応生成物は、Ｓｉ欠損型カトアイトのほか、ヒブ
シャイトとほぼ同じ組成を有する生成物から構成されて
いることが確認された。さらに、この反応生成物を走査
型電子顕微鏡により観察したところ、反応生成物は直径
２〜３μｍ程度の不定形粒子表面を粒径０．１μｍ程度
の帯状、針状又は花弁状粒子に覆われた凝集体であるこ
とが確認された。After the reaction, the obtained solid was dried, and the powder X was dried.
The reaction product was identified by line diffraction analysis. As a result, it was confirmed that the reaction product was composed of a product having substantially the same composition as hibbsite, in addition to the Si-deficient cathoite. Further, when the reaction product was observed with a scanning electron microscope, the surface of the reaction product was covered with band-like, needle-like or petal-like particles having a diameter of about 0.1 μm on the surface of irregular particles having a diameter of about 2 to 3 μm. It was confirmed that it was an aggregate.
【００３７】試験例１ 実施例１で得られた反応生成物を試料として用い、酸性
ガス吸収試験を実施し、その吸収能力を調べた。 （１）実験方法 試料１ｇを充填した耐熱管を円筒状電気炉中に装着後、
内部空間温度を８００℃に保持し、窒素ガスで希釈した
塩化水素ガス（濃度１０００ｐｐｍ）を流量５００ｍｌ
／分で耐熱管内に３時間流通させた。 （２）実験結果 酸性ガス流通後の試料について、その化学成分を蛍光Ｘ
線分析装置により調べ、そのＣｌ吸収量を求めた。その
結果を表２に示す。また、走査型電子顕微鏡による観察
を行った。Test Example 1 Using the reaction product obtained in Example 1 as a sample, an acid gas absorption test was carried out to examine its absorption capacity. (1) Experimental method After mounting a heat-resistant tube filled with 1 g of a sample in a cylindrical electric furnace,
The internal space temperature was maintained at 800 ° C., and hydrogen chloride gas (concentration: 1000 ppm) diluted with nitrogen gas was flowed at 500 ml.
Per minute in a heat-resistant tube for 3 hours. (2) Experimental results The chemical composition of the sample after acid gas flow was measured using fluorescent X
It was examined with a line analyzer, and its Cl absorption was determined. Table 2 shows the results. In addition, observation with a scanning electron microscope was performed.
【００３８】[0038]
【表２】 [Table 2]
【００３９】表２の結果より、本発明品は８００℃とい
う高温でＣｌ吸収を効果的に行えることがわかる。な
お、Ｃｌ以外の成分としてＣａ、Ａｌ及びＳｉが確認さ
れた。From the results shown in Table 2, it can be seen that the product of the present invention can effectively absorb Cl at a high temperature of 800 ° C. In addition, Ca, Al, and Si were confirmed as components other than Cl.
【００４０】また、Ｃｌが吸収された反応生成物は、吸
収前に比べて不定形粒子表面の帯状、針状又は花弁状粒
子が減少した。不定形粒子自体の大きさには変化は認め
られず、粒径２〜３μｍ程度を維持していた。In the reaction product in which Cl was absorbed, the number of band-like, needle-like, or petal-like particles on the surface of the irregular-shaped particles was smaller than before the absorption. No change was observed in the size of the irregular shaped particles themselves, and the particle diameter was maintained at about 2 to 3 μm.
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） Ｂ０９Ｂ 3/00 Ｂ０１Ｄ 53/34 １１８Ｚ Ｃ１０Ｊ 3/02 Ｂ０９Ｂ 3/00 ＺＡＢ // Ｃ０９Ｋ 3/00 ３０４Ａ Ｆターム(参考） 4D002 AA18 AA19 AA23 AB01 AC01 AC04 AC10 BA14 CA07 CA11 DA05 DA11 DA46 DA47 DA66 EA06 EA14 GA01 GA02 GB01 GB02 GB03 GB08 GB12 4D004 AA36 AA43 BA02 BA10 CA29 CA39 CA45 DA03 DA06 4D020 AA10 BA02 BA08 BA30 BB01 CA05 DB06 4G066 AA17A AA17B AA20A AA20B AA22B AA66B AA76A BA20 CA07 CA31 FA14 FA18 FA20 4G073 BA11 BA57 BA63 BD13 CE06 FB01 FB02 FB10 FB18 FC03 GA08 UA06 Continuation of the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (reference) B09B 3/00 B01D 53/34 118Z C10J 3/02 B09B 3/00 ZAB // C09K 3/00 304A F term (reference) 4D002 AA18 AA19 AA23 AB01 AC01 AC04 AC10 BA14 CA07 CA11 DA05 DA11 DA46 DA47 DA66 EA06 EA14 GA01 GA02 GB01 GB02 GB03 GB08 GB12 4D004 AA36 AA43 BA02 BA10 CA29 CA39 CA45 DA03 DA06 4D020 AA10 BA02 BA08 A30 A06 AB AA DBA AA76A BA20 CA07 CA31 FA14 FA18 FA20 4G073 BA11 BA57 BA63 BD13 CE06 FB01 FB02 FB10 FB18 FC03 GA08 UA06
Claims (8)
熱処理することによりハイドログロシュラーを製造する
方法。1. A method for producing a hydrogrossular material by hydrothermally treating a raw material slurry containing coal gasification slag.
ミナ質原料及び石灰質原料の少なくとも１種を加えてな
る原料スラリーを水熱処理することによりハイドログロ
シュラーを製造する方法。2. A method for producing hydrogrossular material by hydrothermally treating a raw material slurry obtained by adding at least one of a siliceous raw material, an alumina raw material and a calcareous raw material to coal gasification slag.
びＣａＯを含む請求項１又は２に記載の製造方法。3. The method according to claim 1, wherein the coal gasification slag contains SiO 2 , Al 2 O 3 and CaO.
る請求項１〜３のいずれかに記載の製造方法。4. The production method according to claim 1, wherein the coal gasification slag is substantially amorphous.
アイト、カトアイト及びヒブシャイトの少なくとも１種
を含む請求項１〜４のいずれかに記載の製造方法。5. The production method according to claim 1, wherein the hydrogrossular contains at least one of Si-deficient katoite, katoite and hibbscheite.
ブシャイトの少なくとも１種を含むハイドログロシュラ
ーからなる酸性ガス吸収材。6. An acidic gas absorbing material comprising a hydrogrossular material containing at least one of Si-deficient cathoite, cathoite and hibbsite.
て得られる、Ｓｉ欠損型カトアイト、カトアイト及びヒ
ブシャイトの少なくとも１種を含むハイドログロシュラ
ーからなる酸性ガス吸収材。7. An acidic gas absorbing material obtained by the production method according to any one of claims 1 to 5, comprising a hydrogrossular material containing at least one of Si-deficient katite, katite and hibbsite.
４００℃を超える温度で酸性ガスと接触させることを特
徴とする酸性ガスの吸収除去方法。8. A method for absorbing and removing an acidic gas, comprising contacting the acidic gas absorbent according to claim 6 with an acidic gas at a temperature exceeding 400 ° C.
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| JP3692443B2 JP3692443B2 (en) | 2005-09-07 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010084958A1 (en) | 2009-01-23 | 2010-07-29 | 国立大学法人秋田大学 | Hydro composite with iron and steel slag as starting material, and manufacturing method therefor |
| JP2013158727A (en) * | 2012-02-07 | 2013-08-19 | Tottori Univ | Fluorine remover and treatment method for fluorine-containing liquid |
| CN112604655A (en) * | 2020-11-27 | 2021-04-06 | 天津市城市新海绵环保科技有限公司 | Application of coal-based gasified slag, composite porous adsorption base material and preparation method thereof |
| CN112718250A (en) * | 2020-12-15 | 2021-04-30 | 湖北工业大学 | Method for removing carbon from gasified slag |
| CN113390909A (en) * | 2021-06-11 | 2021-09-14 | 安徽理工大学 | Coal and gangue identification method based on X-ray diffraction technology |
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2000
- 2000-02-07 JP JP2000028812A patent/JP3692443B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010084958A1 (en) | 2009-01-23 | 2010-07-29 | 国立大学法人秋田大学 | Hydro composite with iron and steel slag as starting material, and manufacturing method therefor |
| JP2015038022A (en) * | 2009-01-23 | 2015-02-26 | 国立大学法人 千葉大学 | Hydro composite material with steel slag as raw material and production method thereof |
| JP2013158727A (en) * | 2012-02-07 | 2013-08-19 | Tottori Univ | Fluorine remover and treatment method for fluorine-containing liquid |
| CN112604655A (en) * | 2020-11-27 | 2021-04-06 | 天津市城市新海绵环保科技有限公司 | Application of coal-based gasified slag, composite porous adsorption base material and preparation method thereof |
| CN112604655B (en) * | 2020-11-27 | 2022-06-14 | 天津市城市新海绵环保科技有限公司 | Application of coal-based gasified slag, composite porous adsorption base material and preparation method thereof |
| CN112718250A (en) * | 2020-12-15 | 2021-04-30 | 湖北工业大学 | Method for removing carbon from gasified slag |
| CN112718250B (en) * | 2020-12-15 | 2022-04-26 | 湖北工业大学 | Method for removing carbon from gasified slag |
| CN113390909A (en) * | 2021-06-11 | 2021-09-14 | 安徽理工大学 | Coal and gangue identification method based on X-ray diffraction technology |
| CN114985435A (en) * | 2022-08-05 | 2022-09-02 | 中国科学院过程工程研究所 | Method for comprehensively utilizing waste salt and various solid wastes |
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|---|---|
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