JP2004352596A - Manufacturing method of hydraulic material and hydraulic building material - Google Patents
Manufacturing method of hydraulic material and hydraulic building material Download PDFInfo
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- JP2004352596A JP2004352596A JP2003155237A JP2003155237A JP2004352596A JP 2004352596 A JP2004352596 A JP 2004352596A JP 2003155237 A JP2003155237 A JP 2003155237A JP 2003155237 A JP2003155237 A JP 2003155237A JP 2004352596 A JP2004352596 A JP 2004352596A
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- hydraulic
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- lime
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Links
- 239000000463 material Substances 0.000 title claims abstract description 56
- 239000004566 building material Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000010802 sludge Substances 0.000 claims abstract description 33
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 30
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 30
- 239000004571 lime Substances 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000010459 dolomite Substances 0.000 claims abstract description 25
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 25
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000292 calcium oxide Substances 0.000 claims abstract description 18
- 239000002689 soil Substances 0.000 claims abstract description 14
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000004568 cement Substances 0.000 claims abstract description 8
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 4
- 239000008187 granular material Substances 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 21
- 239000000920 calcium hydroxide Substances 0.000 claims description 21
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 21
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- 230000029087 digestion Effects 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000010440 gypsum Substances 0.000 claims description 10
- 229910052602 gypsum Inorganic materials 0.000 claims description 10
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 235000012241 calcium silicate Nutrition 0.000 claims description 6
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 claims description 6
- 239000001506 calcium phosphate Substances 0.000 claims description 5
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 5
- 235000011010 calcium phosphates Nutrition 0.000 claims description 5
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims description 5
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019700 dicalcium phosphate Nutrition 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 238000010276 construction Methods 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 239000000047 product Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 14
- 235000012255 calcium oxide Nutrition 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 13
- 238000010304 firing Methods 0.000 description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000011505 plaster Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 238000005065 mining Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004572 hydraulic lime Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010410 dusting Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- FGZBFIYFJUAETR-UHFFFAOYSA-N calcium;magnesium;silicate Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])([O-])[O-] FGZBFIYFJUAETR-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001678 gehlenite Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 208000008842 sick building syndrome Diseases 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- -1 that is Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 235000019976 tricalcium silicate Nutrition 0.000 description 1
- 229910021534 tricalcium silicate Inorganic materials 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、採掘した鉱石から石灰やドロマイトを製造する精製工程で発生するスラッジを主原料とした、水硬性材料の製造方法に関する。本発明はまた、この水硬性材料を使用した水硬性建築材料にも関する。この明細書においては、「モル」の語を、「グラム原子」に代えて便宜的に用いる。
【０００２】
【従来の技術】
石灰系またはドロマイト系の建築材料として、我が国では古くから、水酸化カルシウムを主成分とする漆喰や、水酸化カルシウムとマグネシウムとを含むドロマイトプラスターが使用されてきた。これらの建築材料は、水と混合してペースト状し、またはさらに骨材を混合してモルタル状にし、内外壁に塗るなどして使用されていれる。
【０００３】
近年、サイディング、石膏ボード、クロス等が建築材料の主流となってきたが、ホルムアルデヒドによるシックハウス症候群や、カビ・ダニ等によるアレルギー問題が指摘され、健康と環境の観点から、水酸化カルシウムを主成分として含む石灰系およびドロマイト系の建築材料が、見直されてきている。水酸化カルシウムは、ホルムアルデヒドを吸着する作用がある上、抗菌性や調湿性を有する材料である。
【０００４】
しかし，石灰系・ドロマイト系の建築材料は、空気中の炭酸ガスと反応して硬化する気硬性材料であるため、施工後の硬化速度が遅く、また、そのために厚塗りが困難であって下塗りと上塗りの２回に分けて施工する必要があり、どうしても工期が長くなってしまう。さらに、このような特殊な工法であるため、石灰系・ドロマイト系建築材料を用いた施工は熟練した左官職人に頼らなければならないが、左官職人の数は年々減少してきている。
【０００５】
従って、石灰系・ドロマイト系の建築材料のもつ特性を失うことなく、すなわち水酸化カルシウムを主成分とする建築材料であって、施工後の硬化が速く、かつ施工に熟練を要しないような建築材料が求められている。
【０００６】
一方、欧米においては、石灰系とセメント系の両方の特性を併せ持つ水硬性石灰が広く使用されている。一般に水硬性石灰は、シリカやアルミナを含む純度の低い石灰石を焼成し、焼成物を水和することにより得られ、気硬性物質である水酸化カルシウムと、水硬性物質であるケイ酸カルシウムおよびアルミン酸カルシウムとを主成分とする。従って、漆喰等と比較して、施工から硬化に至るまでの時間は短いが、原料中の不純分含有量のばらつきが大きいために、製品の硬化時間や強度、色等の特性のばらつきが大きいという問題がある。生成した水硬性物質の結晶を固定化するため、焼成物を急冷する工程が必要となる場合もある。
【０００７】
ところで、石灰やドロマイトの製造工程では、採掘した原石を水洗する過程で、多量のスラッジが発生する。このスラッジは、一般にシックナー等により沈降濃縮された後、フィルタープレスのような濾過手段により脱水される。以下の記述においては、この水洗および脱水をへたスラッジを、「水洗スラッジ」または単に「スラッジ」と呼ぶ。脱水によって得たフィルターケーキは、なお２０％以上の水分を含む。固形分中の１０％程度は、原石に付着した土に由来するシリカ、アルミナ、酸化鉄等の成分からなる。このようなものであるから、スラッジは利用が困難な廃棄物とされ、多くの場合、採掘跡地等に堆積処分されている。
【０００８】
しかし近年、社会的に環境への関心が高まり、ゼロエミッション、省エネルギー、資源の有効活用等の問題にいかに取り組むかが、企業の課題となっている。石灰系のスラッジを利用する手段として、スラッジに顔料など無機着色物質を混合し、混合物を温度９００〜１３００℃の範囲で焼成したのち消化することによって、自然色で色むらのない漆喰用有色消石灰を製造する方法（特開平９−１５６９６８）や、スラッジにアルミニウム含有廃棄物や石炭灰を混合し、１０００〜１４００℃で焼成することにより、石灰系とセメント系の特性を併せ持つ地盤改良材を製造する方法（特開平１０−２６７７７）が提案されている。
【０００９】
これらの先行技術は、石灰系スラッジを利用する手段として有効なものであるが、なにぶん発生するスラッジの量が膨大であるため、処理しきれず、より普遍性のある利用の途が求められている。
【００１０】
【発明が解決しようとする課題】
本発明の第一の目的は、石灰およびドロマイトの製造工程から大量に発生する廃棄物であるスラッジを有効に活用する一つの方策を提案するものであって、スラッジを主原料とし、これに所定の成分組成を有する他の原料を配合して焼成し、ついで消化することにより水硬性材料、とくに建築材料を製造する方法を提供することにある。
【００１１】
本発明の第二の目的は、この水硬性材料を中心とする建築材料であって、従来の石灰系・ドロマイト系建築材料の利点を維持しつつ、特殊な施工技術を要することなく、短時間で施工できるような水硬性建築材料を提供することにある。
【００１２】
【課題を解決するための手段】
上記した第一の目的を達成する本発明の水硬性材料の製造方法は、下記の原料（Ｉ）〜（ＩＩＩ）を、
（Ｉ）石灰系および（または）ドロマイト系の水洗スラッジ
（ＩＩ）ＳｉＯ２、Ａｌ２Ｏ３およびＦｅ２Ｏ３をモル比で１．００：０．２０〜０．５０：０．０５〜０．２０の割合で含有し、非晶質物質を含む土
（ＩＩＩ）炭酸カルシウムを軽度に焼成して得た酸化カルシウム
ＳｉＯ２、Ａｌ２Ｏ３、Ｆｅ２Ｏ３、ＣａＯおよびＭｇＯの含有量に基づいて次式から求められるセメント係数（ＣＩ）
【００１３】
【発明の実施の形態】
上記の方法により製造された本発明の水硬性材料は、水酸化カルシウム１５〜６０重量％およびケイ酸二カルシウム（２ＣａＯ・ＳｉＯ２）１５重量％以上を含有し、水硬性建築材料として使用可能である。
【００１４】
本発明で水硬性材料の製造に使用する原料（Ｉ）は、前記のように、石灰やドロマイト製造工程から発生するスラッジである。スラッジを構成する個々の粒子の大きさが、径１００μｍ以下であることが好ましく、必要によりスラッジの粉砕工程を加えるとよい。
【００１５】
原料（ＩＩ）は、ＳｉＯ２、Ａｌ２Ｏ３およびＦｅ２Ｏ３をモル比で１．００：０．２０〜０．５０：０．５０〜０．２０の割合で含有し、非晶質物質を含む土である。シリカは、焼成工程において原料（Ｉ）中に含まれるカルシウムと反応し、水硬性物質であるケイ酸二カルシウム２ＣａＯ・ＳｉＯ２を生成する。２ＣａＯ・ＳｉＯ２の生成により、本発明の水硬性材料が水和したのち、長期にわたって強度が発現し、建築物の機械的強度を十分に高く得ることができる。
【００１６】
アルミナも同様にカルシウムと反応し、初期強度が大きいカルシウムアルミネートを生成する。アルミナはシリカおよびカルシウムとも反応して、水硬性を有する非晶質化合物を生成する。アルミナ／シリカのモル比が０．２０より小さいと、これらの生成が不十分となり、逆に０．５０より大きいと、水硬性を示さない結晶質ゲーレナイト（２ＣａＯ・Ａｌ２Ｏ３・ＳｉＯ２）が生成し、さらにシリカ分が少なくなるため、２ＣａＯ・ＳｉＯ２の生成が不十分となる。
【００１７】
酸化鉄は、焼成工程における水硬性組成の生成温度を低下させる働きをするが、酸化鉄／シリカのモル比が０．０５より小さいとその効果が不十分であり、逆に０．２０より大きくなると、材料が融着を起こしたりして、焼成工程におけるハンドリングに不都合を生じる。土の中の非晶質物質は、水硬性物質の生成効率を高める。
【００１８】
このような土としては、たとえば関東ローム層のような火山灰質の土が適当である。石灰やドロマイトを採掘する工程で発生する表土を利用できれば、経済面でも環境面でも有利となる。
【００１９】
原料（ＩＩＩ）は、軽度に焼成した酸化カルシウムである。酸化カルシウムは水との反応性が大きいため、スラッジおよび土に含まれている水分を吸収し、それによって混合物のハンドリング性を改善することができる。軽度に焼成した酸化カルシウムは、商業生産されている通常の生石灰で十分である。
【００２０】
これらの原料を、前記した式により定義されるセメント係数が０．３〜１．０の範囲となるよう混合し、造粒する。セメント係数が０．３より小さい配合割合であると、水硬性物質の生成量が少なく、施工後硬化するまでに要する時間が長くなり、硬化後の強度も低くなる。逆に、１．０より大きい配合割合では、焼成工程において融着に起因するハンドリングの悪化が生じるし、その後の消化が困難になる。
【００２１】
造粒は、焼成を容易にするための工程であり、代表的にはパン型の造粒機を使用して行なうが、成型機を用いた成型を行なってもよい。成型機としては、通常のブリケットマシンが使用できる。混合造粒を行なう場合は、適度な水分が残存するように酸化カルシウムの量を調整する。成型機による成型を行なう場合は、事前に廃熱を利用して含水率を低下させるか、酸化カルシウムを多めに配合して、混合物の残留水分が数％以下となるようするとよい。
【００２２】
上記のようにして混合され造粒された原料は、ロータリーキルン等により、温度１１５０〜１３００℃の範囲で焼成する。焼成温度が１１５０℃よりも低いと，水硬性物質の生成が不十分となり、未反応のシリカ等が残存する。焼成温度が１３００℃よりも高いと、融着等により焼成工程におけるハンドリングが悪くなり、後の消化が困難になる。場合によっては、好ましくないケイ酸三カルシウム（３ＣａＯ・ＳｉＯ２）が生成することがある。３ＣａＯ・ＳｉＯ２はポルトランドセメントの主成分であり、水和による強度発現が速いが、そのため、後続の消化工程において水和反応が起こってしまい、製品が水硬性物質としての機能を失ってしまう。
【００２３】
混合原料のＣＩが高く、また焼成温後が高い場合は、焼成物が冷却時に粉化するダスティング現象が起こることがある。これは、焼成品中の２ＣａＯ・ＳｉＯ２結晶が発達し、冷却時にβ型からγ型に転移するためであるが、γ型の２ＣａＯ・ＳｉＯ２は水硬性を有しないから、その生成は好ましくない。
【００２４】
β型の２ＣａＯ・ＳｉＯ２を化学的に安定化させ、γ型への転移を防ぐ手段としては、原料（ＩＶ）として、リン酸カルシウム、リン酸水素カルシウムおよびリン酸から選んだ１種または２種以上を、原料混合時に添加しておけばよい。ただし、過剰のリン分の添加は水硬性の発現に悪影響を及ぼすので、その添加量は、スラッジの固形分１００重量部に対して２重量部以下とすることが好ましい。混合原料のＣＩが小さければ、２ＣａＯ・ＳｉＯ２結晶がそれほど発達せず、土に含まれるアルミナその他の成分により、上記のダスティング現象は抑制される。
【００２５】
焼成された造粒品は、つぎに消化される。消化には、水酸化カルシウムの商業生産のための設備が、好都合に使用できる。消化ののち、必要により、熟成を行なう。消化が不完全であると未反応の酸化カルシウムが残留し、建築材料として使用する際に膨張や亀裂が起こるため、酸化カルシウム分は完全に消化して、水酸化カルシウムとしなければならない。そのためには、焼成物が微細であることが好ましく、消化に先だって、焼成物を粒径１ｍｍ以下に粉砕しておくとよい。
【００２６】
消化に必要な水量は、たとえば昇温試験、すなわち、一定量の焼成物と水とを混合し消化反応が引き起こす温度上昇を測定する試験、の結果から決定することができる。本発明においては、通常、消化水／焼成物の比の適切な値は、重量で、０．１５〜０．４０の範囲内である。
【００２７】
消化し、必要な熟成を受けた水硬性材料は、そのままでも建築材料として使用できるが、粗粒の混入を防ぐため、粉砕および（または）分級を行なって、粒度調整をすることが好ましい。これらの工程には、商用の水酸化カルシウムを製造する設備が使用できる。具体的には、粉砕のめにはボールミル、振動ミルであり、分級のためには振動ふるい、気流式分級機、ローター式分級機である。
【００２８】
このような工程を経て得られた水硬性材料は、前記のように、主成分として水酸化カルシウム１５〜６０重量％，およびケイ酸二カルシウム（２ＣａＯ・ＳｉＯ２）１５重量％以上を含有するほか、その他の成分として、アルミン酸カルシウム、ケイ酸カルシウムマグネシウム、酸化および（または）水酸化マグネシウム、非晶質物質等を含む。
【００２９】
水酸化カルシウム含有量が１５％重量に達しないものは、施工性が低く、共存する非晶質物質とのポゾラン反応性や、水酸化カルシウムが有する機能が低いし、材料の色が黒っぽくなるので、施工した壁面の意匠性が低くなる。水酸化カルシウム含有量が６０重量％を超えると、ペーストやモルタルをつくるときに必要な水の量が増加し、また相対的に水硬性物質の含有量が低下するため、硬化速度や機械的強度の低下をまねく。本発明の水硬性材料および建築材料が長期にわたり強度を発現するためには、水硬性材料が１５重量％以上の２ＣａＯ・ＳｉＯ２を含有していることが好ましい。
【００３０】
本発明の水硬性材料は、その１００重量部に対し、最大１５０重量部の乾燥し、粉砕した石灰系および（または）ドロマイト系のスラッジを混合して、建築材料として使用することができる。スラッジの主成分は炭酸カルシウムであり、水硬性建築材料の骨材としてケイ砂等を用いた場合と比較して、モルタルの流動性が改善され、軽量な硬化体を得ることができる。ただし、スラッジはケイ砂等にくらべて微粉であるため、多量に配合すると、モルタルの調製に必要な水の量が増加し、それによって硬化速度や初期強度発現が影響を受けるから、上記した１５０重量部を配合量の限度とする。
【００３１】
本発明の水硬性材料はまた、これに対し、内割で５重量％以下の石膏（無水ベース）を混合し、水硬性建築材料として使用することもできる。石膏は、水硬性建築材料中のカルシウムおよびアルミナとの反応によりエトリンガイトを生成し、初期強度の増加に寄与する。しかし、石膏を大量に添加すると、体積膨張による剥離や亀裂が生じるおそれがあるから、５重量％を限度とする。
【００３２】
本発明の水硬性物質はまた、上記の石膏に代え、または石膏とともに、内割で２０重量％以下の非晶質物質を含む土を混合し、水硬性建築材料として使用することもできる。非晶質物質を含む土からは、水酸化カルシウムに起因する塩基性により、シリカやアルミナがイオン化して溶出しやすいため、ポゾラン反応性が高くなって、それが材料の強度発現に寄与する。土の添加はまた、水硬性建築材料を茶系の自然色とすることができる。ただし、２０重量％を超える多量の土を添加すると、吸水発熱が起こるなど、モルタルの施工性に悪影響がある。
【００３３】
このほか、漆喰やセメントの施工に当たって用いられている種々の添加材、たとえば繊維、ケイソウ土、軽量骨材、ＡＥ剤、減水剤、セルロース系化合物などを、適量添加することも可能である。
【００３４】
本発明の水硬性建築材料は、内外壁用の塗り材として施工できるほか、非加熱タイルやブロックを製造する原料、ブロックやレンガ工事用のバインダー、建材パネルの原料などに使用することができる。
【００３５】
【実施例】
実施例における各種の測定または評価の方法は、下記のとおりである。
［焼成物の昇温活性］ デュワーフラスコ中で２０℃の水６００ｇに、０．６ｍｍ以下に粉砕した焼成物２００ｇを投入し，３００±５０ｒｐｍで攪拌しながら，１０分間の温度上昇ΔＴ℃を測定する。
［化学組成］
水酸化カルシウムＣａ（ＯＨ）２の含有量：示差熱分析による４００〜５５０℃のデータ
ケイ酸二カルシウム２ＣａＯ・ＳｉＯ２の含有量：Ｘ線回折
アルミン酸カルシウム１２ＣａＯ・７Ａｌ２Ｏ３の含有量：Ｘ線回折
酸化マグネシウムＭｇＯの含有量：ＪＩＳ Ｒ９０１１に定める方法により求められた値から、Ｘ線回折により求めた２ＣａＯ・ＭｇＯ・２ＳｉＯ２によるＭｇＯ分を差し引く
［平均粒径］ レーザー回折式粒度分布計（島津製作所製ＳＡＬＤ−２１００）
［圧縮強度］ とくに記載しない限り、骨材として４号ケイ砂を使用した以外は、ＡＳＴＭ Ｃ１４１に記載の方法で供試体を製作し養生した。材齢７日および２８日の供試体の圧縮強度を測定。
［蒸気膨張性］ ＥＮ ４５９に記載の方法に準じた方法。
［安定性試験］ ＪＩＳ Ａ６９０２ に記載の方法。
［硬度］ ＪＩＳ Ａ６９０２ に記載の方法。
［凝結時間］ ＪＩＳ Ｒ５２０１に記載の方法。
【００３６】
以下の実施例において、化学成分および原料配合比は、乾燥重量基準の値である。
【実施例１】
表１の（１）に示す石灰・ドロマイト混合系のスラッジ、（３）に示す石灰・ドロマイト採掘工程において発生する表土、市販の生石灰およびリン酸カルシウムを、表２に示す配合比で混合して造粒し、造粒物を１２５０℃で焼成した。焼成物の昇温活性は、８．６℃であった。焼成物を粒径０．６ｍｍ以下に粉砕した後、水／焼成物の重量比０．２２の水で消化し、熟成した。その後、ボールミルで粉砕し、０．６ｍｍのふるいでふるい分け、本発明の水硬性材料を製造した。
【００３７】
【実施例２】
表１の（１）に示す化学組成をもつ、石灰・ドロマイト混合系のスラッジ、（３）に示す化学組成をもつ、石灰・ドロマイト採掘工程において発生する表土、市販の生石灰およびリン酸カルシウムを、表２に示す配合比で混合造粒し、造粒物を１２５０℃で焼成した。焼成物の昇温活性は８．２℃であった。焼成物を粒径０．６ｍｍ以下に粉砕した後、水／焼成物＝０．２０の水で消化し、熟成した。その後、ボールミルで粉砕し、０．６ｍｍのふるいでふるい分け、本発明の水硬性材料を製造した。
【００３８】
【実施例３】
表１の（２）に示す化学組成をもつ、石灰・ドロマイト混合系のスラッジ、（４）に示す化学組成をもつ、石灰・ドロマイト採掘工程において発生する表土、市販の生石灰およびリン酸カルシウムを、表２に示す配合比で混合して造粒し、造粒物を１２００℃で焼成した。焼成物の昇温活性は１５．１℃であった。焼成物を粒径０．６ｍｍ以下に粉砕した後、水／焼成物＝０．３０の水で消化し、熟成した。その後、ボールミルで粉砕し、０．６ｍｍのふるいでふるい分け、本発明の水硬性材料を製造した。
【００３９】
【実施例４】
実施例１で得られた水硬性材料９５重量部に石膏５重量部を混合し、本発明の水硬性建築材料を製造した。
【００４０】
【実施例５】
実施例２で得られた水硬性材料８５量部に、石膏５重量部と、表１の（３）に示す化学組成を有する表土を乾燥粉砕したもの１０重量部とを混合し、本発明の水硬性建築材料を製造した。
【００４１】
【実施例６】
実施例１で製造した水硬性材料の硬化体の圧縮強度を測定する際に、骨材として、４号ケイ砂のかわりに、水硬性材料１００重量部に対して表１の（１）に示したスラッジを乾燥粉砕したもの４０重量部を使用し、測定を行なった。
【００４２】
【比較例】
市販のＪＩＳ左官用消石灰を用いて、測定および評価を行った。
【００４３】
実施例１〜３の水硬性材料の化学組成を、ＣＩおよび平均粒径とともに、表３に示す。実施例１〜３の水硬性材料および実施例４〜６で製造した水硬性材料の硬化体の特性を、表４に示す。
【００４４】
表１ 水硬性材料の原料（重量％）
表２ 水硬性建築材料の原料配合比
表３ 分析結果（重量％）
表４ 試験結果
【発明の効果】
本発明の水硬性材料の製造方法は、これまで利用価値が乏しく、廃棄されていた石灰系またはドロマイト系のスラッジを主原料として利用することを可能にし、それから有用な水硬性物質を得ることを可能にした方法であって、原鉱石の利用率の向上をはじめとする資源の有効利用、ゼロエミッション、および環境への負担軽減の観点から、寄与するところが顕著である上に、経済効果が大きい。
【００４９】
原料組成をある範囲内で任意に調整することにより、従来の、不純分の多い石灰石を原料とした水硬性石灰の製造において問題となる、製品特性、とくに硬化時間や強度、色などのバラツキのない、均質な水硬性材料を製造することが可能になった。
【００５０】
この水硬性材料は、従来から利用されている消石灰（水酸化カルシウム）を用いた漆喰と比較して、水と混合し施工した後の硬化が速いため、壁材として使用した場合、工期を大幅に短縮することが可能である。強度の発現も速く、かつ高い強度に到達するから、建築材料として求められる機械的強度も十分に高い。このように本発明の水硬性材料は、建築用材料としてはもちろん、水硬性が有用であるそのほかの用途に、好適に使用することができる。
【００５１】
この水硬性材料をベースとし、それに適量の石灰系・ドロマイト系のスラッジ、石膏または土を配合してなる本発明の水硬性建築材料は、内外壁を形成する材料として、またブロック、タイル等の原料として有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a hydraulic material using sludge generated in a refining step of producing lime and dolomite from mined ore as a main raw material. The present invention also relates to a hydraulic building material using the hydraulic material. In this specification, the term “mol” is used for convenience instead of “gram atom”.
[0002]
[Prior art]
As a lime-based or dolomite-based building material, plaster containing calcium hydroxide as a main component and dolomite plaster containing calcium hydroxide and magnesium have long been used in Japan. These building materials are used by mixing them with water to form a paste, or further mixing an aggregate to form a mortar, and coating the inner and outer walls.
[0003]
In recent years, siding, gypsum board, cloth, etc. have become the mainstream of building materials, but sick house syndrome due to formaldehyde and allergy problems due to mold and mite have been pointed out, and from the viewpoint of health and environment, calcium hydroxide is the main component. Lime-based and dolomite-based building materials have been reviewed. Calcium hydroxide has a function of adsorbing formaldehyde and is a material having antibacterial properties and humidity control properties.
[0004]
However, lime-based and dolomite-based building materials are air-hardening materials that harden by reacting with carbon dioxide in the air. Therefore, the curing speed after construction is slow, and it is difficult to apply thick coatings. It is necessary to carry out the work separately in two times, ie, top coat, and the construction period is inevitably lengthened. Furthermore, because of such a special construction method, construction using lime-based and dolomite-based building materials must rely on skilled plasterers, but the number of plasterers is decreasing year by year.
[0005]
Therefore, building materials that do not lose the characteristics of lime-based and dolomite-based building materials, that is, building materials containing calcium hydroxide as a main component and that harden quickly after construction and do not require skill for construction. Materials are needed.
[0006]
On the other hand, in the United States and Europe, hydraulic lime having both characteristics of lime and cement is widely used. In general, hydraulic lime is obtained by calcining low-purity limestone containing silica and alumina and hydrating the calcined product. The hydraulic material is calcium hydroxide, and the hydraulic materials are calcium silicate and alumina. Main component is calcium acid. Therefore, compared to plaster etc., the time from application to hardening is short, but the variation in the content of impurities in the raw material is large, so the hardening time, strength, color and other characteristics of the product are large. There is a problem. In some cases, a step of rapidly cooling the calcined product is required to fix the generated crystals of the hydraulic substance.
[0007]
By the way, in the process of producing lime and dolomite, a large amount of sludge is generated in the process of washing mined rough. This sludge is generally settled and concentrated by a thickener or the like, and then dewatered by a filtering means such as a filter press. In the following description, the sludge that has been washed and dewatered is referred to as “washed sludge” or simply “sludge”. The filter cake obtained by dehydration still contains more than 20% of water. About 10% of the solid content is composed of components such as silica, alumina, and iron oxide derived from the soil attached to the rough. Because of this, sludge is considered to be a waste that is difficult to use, and is often deposited and disposed on mining sites.
[0008]
In recent years, however, interest in the environment has been increasing in society, and it has become an issue for companies how to tackle issues such as zero emission, energy saving, and effective use of resources. As a means of using lime-based sludge, an inorganic coloring substance such as a pigment is mixed with the sludge, and the mixture is calcined at a temperature in the range of 900 to 1300 ° C. and then digested, so that the colored slaked lime for natural plaster without color unevenness is obtained. (Japanese Unexamined Patent Publication (Kokai) No. 9-156968), or by mixing aluminum-containing waste and coal ash with sludge and firing at 1000 to 1400 ° C to produce a ground improvement material having both lime-based and cement-based properties. (Japanese Patent Laid-Open No. Hei 10-26777) has been proposed.
[0009]
These prior arts are effective as means for using lime-based sludge, but since the amount of generated sludge is enormous, it cannot be completely treated, and a more universal way of use is required. .
[0010]
[Problems to be solved by the invention]
A first object of the present invention is to propose a measure for effectively utilizing sludge, which is a large amount of waste generated from a lime and dolomite manufacturing process, and uses sludge as a main raw material, and It is another object of the present invention to provide a method for producing a hydraulic material, in particular, a building material by blending and firing other raw materials having the above-mentioned component composition, followed by digestion.
[0011]
The second object of the present invention is a building material centered on this hydraulic material, and while maintaining the advantages of conventional lime-based and dolomite-based building materials, without requiring special construction techniques, can be used in a short time. It is an object of the present invention to provide a hydraulic building material that can be constructed in a building.
[0012]
[Means for Solving the Problems]
The method for producing a hydraulic material of the present invention that achieves the first object described above includes the following raw materials (I) to (III):
(I) Lime-based and / or dolomite-based washing sludge (II) SiO 2 , Al 2 O 3 and Fe 2 O 3 in a molar ratio of 1.00: 0.20 to 0.50: 0.05-0. The content of calcium oxide SiO 2 , Al 2 O 3 , Fe 2 O 3 , CaO and MgO obtained by lightly sintering earth (III) calcium carbonate containing amorphous material and containing amorphous material Cement coefficient (CI) obtained from the following equation based on
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
The hydraulic material of the present invention produced by the above method contains 15 to 60% by weight of calcium hydroxide and 15% by weight or more of dicalcium silicate (2CaO.SiO 2 ), and can be used as a hydraulic building material. is there.
[0014]
The raw material (I) used in the production of the hydraulic material in the present invention is, as described above, lime or sludge generated from the dolomite production process. The size of each particle constituting the sludge is preferably 100 μm or less, and a sludge crushing step may be added if necessary.
[0015]
The raw material (II) contains SiO 2 , Al 2 O 3 and Fe 2 O 3 in a molar ratio of 1.00: 0.20 to 0.50: 0.50 to 0.20, and is amorphous. Soil containing substances. Silica reacts with calcium contained in the raw material (I) in the firing step, to produce a dicalcium silicate 2CaO · SiO 2 is a hydraulic substance. After the hydraulic material of the present invention is hydrated by the generation of 2CaO · SiO 2 , strength is exhibited for a long time, and the mechanical strength of the building can be sufficiently high.
[0016]
Alumina also reacts with calcium to produce calcium aluminate with high initial strength. Alumina also reacts with silica and calcium to form an amorphous compound having hydraulic properties. When the molar ratio of alumina / silica is less than 0.20, their formation becomes insufficient. On the other hand, when it is more than 0.50, crystalline gehlenite (2CaO.Al 2 O 3 .SiO 2 ) which does not show hydraulicity Is generated and the silica content is further reduced, so that the generation of 2CaO.SiO 2 becomes insufficient.
[0017]
Iron oxide serves to lower the temperature at which the hydraulic composition is formed in the firing step, but if the molar ratio of iron oxide / silica is less than 0.05, its effect is insufficient, and conversely, it exceeds 0.20. In such a case, the materials may be fused, which causes inconvenience in handling in the firing step. Amorphous substances in the soil increase the efficiency of producing hydraulic substances.
[0018]
As such soil, for example, volcanic ash soil such as the Kanto Loam Formation is suitable. The availability of topsoil from the lime and dolomite mining process is economically and environmentally advantageous.
[0019]
Raw material (III) is lightly calcined calcium oxide. Calcium oxide is highly reactive with water, so that it can absorb the moisture contained in sludge and soil, thereby improving the handling of the mixture. For lightly calcined calcium oxide, ordinary quicklime produced commercially is sufficient.
[0020]
These raw materials are mixed and granulated so that the cement coefficient defined by the above formula is in the range of 0.3 to 1.0. When the cement coefficient is less than 0.3, the amount of the hydraulic substance generated is small, the time required for curing after application is long, and the strength after curing is low. Conversely, if the compounding ratio is larger than 1.0, the handling will be deteriorated due to the fusion in the firing step, and the subsequent digestion will be difficult.
[0021]
Granulation is a process for facilitating firing, and is typically performed using a pan-type granulator, but may be performed using a molding machine. As a molding machine, an ordinary briquette machine can be used. When performing mixed granulation, the amount of calcium oxide is adjusted so that an appropriate amount of water remains. In the case of performing molding by a molding machine, the moisture content may be reduced in advance by using waste heat, or calcium oxide may be blended in a large amount so that the residual water content of the mixture is several percent or less.
[0022]
The raw materials mixed and granulated as described above are fired in a temperature range of 1150 to 1300 ° C. by a rotary kiln or the like. If the firing temperature is lower than 1150 ° C., the formation of hydraulic substances becomes insufficient, and unreacted silica and the like remain. If the firing temperature is higher than 1300 ° C., handling in the firing step becomes poor due to fusion or the like, and subsequent digestion becomes difficult. In some cases, undesirable tricalcium silicate (3CaO.SiO 2 ) may be formed. 3CaO.SiO 2 is a main component of Portland cement, and the strength is rapidly developed by hydration. Therefore, a hydration reaction occurs in a subsequent digestion step, and the product loses its function as a hydraulic substance.
[0023]
When the CI of the mixed raw material is high and after the firing temperature is high, a dusting phenomenon in which the fired material is powdered when cooled may occur. This is because the 2CaO · SiO 2 crystal in the fired product develops and changes from β-type to γ-type during cooling. However, since 2CaO · SiO 2 of γ-type has no hydraulic property, its generation is preferable. Absent.
[0024]
As means for chemically stabilizing β-type 2CaO · SiO 2 and preventing transition to γ-type, one or more kinds selected from calcium phosphate, calcium hydrogen phosphate and phosphoric acid as the raw material (IV) May be added at the time of mixing the raw materials. However, since the addition of an excessive amount of phosphorus adversely affects the development of hydraulic property, the amount of addition is preferably 2 parts by weight or less based on 100 parts by weight of the solid content of sludge. If the CI of the mixed raw material is small, 2CaO · SiO 2 crystals do not develop so much, and the above dusting phenomenon is suppressed by alumina and other components contained in the soil.
[0025]
The fired granulate is then digested. For digestion, equipment for the commercial production of calcium hydroxide can be conveniently used. After digestion, aging is performed if necessary. If digestion is incomplete, unreacted calcium oxide will remain, causing swelling and cracking when used as a building material. Therefore, the calcium oxide must be completely digested into calcium hydroxide. For this purpose, the fired product is preferably fine, and the fired product may be pulverized to a particle size of 1 mm or less prior to digestion.
[0026]
The amount of water required for digestion can be determined, for example, from the results of a temperature rise test, that is, a test in which a fixed amount of a baked product and water are mixed and a temperature rise caused by a digestion reaction is measured. In the present invention, usually, an appropriate value of the ratio of digested water / calcined product is in the range of 0.15 to 0.40 by weight.
[0027]
The hydraulic material that has been digested and has undergone necessary aging can be used as it is as a building material. However, in order to prevent the incorporation of coarse particles, it is preferable to carry out pulverization and / or classification to adjust the particle size. In these steps, commercial facilities for producing calcium hydroxide can be used. Specifically, a ball mill and a vibration mill are used for pulverization, and a vibrating sieve, an airflow classifier, and a rotor classifier are used for classification.
[0028]
As described above, the hydraulic material obtained through such a process contains 15 to 60% by weight of calcium hydroxide and 15% by weight or more of dicalcium silicate (2CaO.SiO 2 ) as main components. And other ingredients include calcium aluminate, calcium magnesium silicate, oxidized and / or magnesium hydroxide, amorphous materials and the like.
[0029]
If the calcium hydroxide content does not reach 15% by weight, the workability is low, the pozzolanic reactivity with the coexisting amorphous substance and the function of calcium hydroxide are low, and the color of the material becomes dark. Thus, the design of the constructed wall surface is reduced. When the content of calcium hydroxide exceeds 60% by weight, the amount of water required for forming pastes and mortars increases, and the content of hydraulic substances relatively decreases, so that the curing speed and mechanical strength are reduced. Leads to a decline. In order for the hydraulic material and the building material of the present invention to exhibit strength over a long period of time, it is preferable that the hydraulic material contains 15% by weight or more of 2CaO · SiO 2 .
[0030]
The hydraulic material of the present invention can be used as a building material by mixing up to 150 parts by weight of dried and pulverized lime-based and / or dolomite-based sludge with respect to 100 parts by weight. The main component of the sludge is calcium carbonate, and the fluidity of the mortar is improved as compared with the case where silica sand or the like is used as an aggregate of a hydraulic building material, so that a lightweight cured body can be obtained. However, since sludge is finer powder than silica sand or the like, if it is blended in a large amount, the amount of water required for preparing the mortar increases, thereby affecting the curing speed and the initial strength development. The parts by weight shall be the limit of the compounding amount.
[0031]
On the other hand, the hydraulic material of the present invention can also be used as a hydraulic building material by mixing gypsum (anhydrous base) in an amount of 5% by weight or less. Gypsum produces ettringite by reaction with calcium and alumina in hydraulic building materials and contributes to an increase in initial strength. However, if a large amount of gypsum is added, peeling or cracking may occur due to volume expansion.
[0032]
The hydraulic material of the present invention can also be used as a hydraulic building material by mixing soil containing an amorphous substance of not more than 20% by weight in place of gypsum instead of or together with gypsum. From soil containing an amorphous substance, silica and alumina are easily ionized and eluted due to basicity caused by calcium hydroxide, so that the pozzolan reactivity is increased, which contributes to the development of strength of the material. The addition of soil can also make the hydraulic building material a natural brown color. However, when a large amount of soil exceeding 20% by weight is added, the workability of the mortar is adversely affected, such as generation of water absorption heat.
[0033]
In addition, it is also possible to add an appropriate amount of various additives, such as fibers, diatomaceous earth, lightweight aggregates, AE agents, water reducing agents, and cellulosic compounds, which are used in the construction of plaster or cement.
[0034]
The hydraulic building material of the present invention can be used as a coating material for inner and outer walls, and can be used as a raw material for producing non-heated tiles and blocks, a binder for block and brick work, a raw material for building material panels, and the like.
[0035]
【Example】
Various methods of measurement or evaluation in the examples are as follows.
[Temperature raising activity of fired product] In a Dewar flask, 200 g of fired product crushed to 0.6 mm or less was put into 600 g of water at 20 ° C, and the temperature rise ΔT ° C for 10 minutes was measured while stirring at 300 ± 50 rpm. I do.
[Chemical composition]
The content of calcium hydroxide Ca (OH) 2: The content of the data dicalcium silicate 2CaO · SiO 2 of 400 to 550 ° C. by differential thermal analysis: content of X-ray diffraction calcium aluminate 12CaO · 7Al 2 O 3: the content of X-ray diffraction of magnesium oxide MgO: from the values determined by the method specified in JIS R9011, subtracting the MgO content by 2CaO · MgO · 2SiO 2 as determined by X-ray diffraction average particle diameter] laser diffraction type particle size distribution meter (Shimadzu SALD-2100)
[Compressive strength] Unless otherwise specified, a specimen was produced and cured according to the method described in ASTM C141 except that No. 4 silica sand was used as the aggregate. The compressive strength of specimens of 7 days and 28 days in age was measured.
[Vapor expandability] A method according to the method described in EN 459.
[Stability test] The method described in JIS A6902.
[Hardness] The method described in JIS A6902.
[Setting time] The method described in JIS R5201.
[0036]
In the following examples, the chemical components and the raw material mixing ratio are values on a dry weight basis.
Embodiment 1
Granulated by mixing lime / dolomite mixed sludge shown in (1) of Table 1; topsoil generated in the lime / dolomite mining process shown in (3); commercially available quicklime and calcium phosphate in the mixing ratio shown in Table 2. Then, the granulated product was fired at 1250 ° C. The heating activity of the fired product was 8.6 ° C. The pulverized product was pulverized to a particle size of 0.6 mm or less, digested with water having a weight ratio of water / calcined substance of 0.22, and aged. Then, it was pulverized with a ball mill and sieved with a 0.6 mm sieve to produce a hydraulic material of the present invention.
[0037]
Embodiment 2
Table 2 shows lime / dolomite mixed sludge having the chemical composition shown in (1) of Table 1; topsoil, commercially available quicklime and calcium phosphate generated in the lime / dolomite mining process having the chemical composition shown in (3). The mixture was granulated at the mixing ratio shown in Table 1 and the granulated product was fired at 1250 ° C. The heating activity of the fired product was 8.2 ° C. The baked product was pulverized to a particle size of 0.6 mm or less, digested with water / water of baked product = 0.20, and aged. Then, it was pulverized with a ball mill and sieved with a 0.6 mm sieve to produce a hydraulic material of the present invention.
[0038]
Embodiment 3
Table 2 shows lime / dolomite mixed sludge having the chemical composition shown in (2) of Table 1; topsoil, commercial quicklime and calcium phosphate generated in the lime / dolomite mining process having the chemical composition shown in (4). And granulated by mixing at the mixing ratio shown in Table 1, and the granulated product was fired at 1200 ° C. The heating activity of the fired product was 15.1 ° C. The baked product was pulverized to a particle size of 0.6 mm or less, digested with water / water of baked product = 0.30, and aged. Then, it was pulverized with a ball mill and sieved with a 0.6 mm sieve to produce a hydraulic material of the present invention.
[0039]
Embodiment 4
Five parts by weight of gypsum were mixed with 95 parts by weight of the hydraulic material obtained in Example 1 to produce a hydraulic building material of the present invention.
[0040]
Embodiment 5
To 85 parts by weight of the hydraulic material obtained in Example 2, 5 parts by weight of gypsum and 10 parts by weight of topsoil obtained by drying and pulverizing topsoil having a chemical composition shown in (3) of Table 1 were mixed. Hydraulic building materials were manufactured.
[0041]
Embodiment 6
When measuring the compressive strength of the cured product of the hydraulic material produced in Example 1, as shown in Table 1 (1) with respect to 100 parts by weight of the hydraulic material instead of No. 4 silica sand as an aggregate The measurement was carried out using 40 parts by weight of dried and pulverized sludge.
[0042]
[Comparative example]
The measurement and evaluation were performed using a commercially available slaked lime for JIS plasterers.
[0043]
Table 3 shows the chemical compositions of the hydraulic materials of Examples 1 to 3, together with CI and average particle size. Table 4 shows the properties of the cured materials of the hydraulic materials of Examples 1 to 3 and the hydraulic materials manufactured in Examples 4 to 6.
[0044]
Table 1 Raw materials for hydraulic materials (% by weight)
Table 2 Raw material mixing ratio of hydraulic building materials
Table 3 Analysis results (% by weight)
Table 4 Test results
【The invention's effect】
The method for producing a hydraulic material of the present invention makes it possible to use lime-based or dolomite-based sludge, which has been poorly used up to now, and has been discarded, as a main raw material, and to obtain a useful hydraulic substance therefrom. It is a method that has been made possible, and from the viewpoint of effective utilization of resources such as improvement of the utilization rate of raw ore, zero emission, and reduction of burden on the environment, the contribution is remarkable and the economic effect is large .
[0049]
By arbitrarily adjusting the raw material composition within a certain range, there is a problem in the production of hydraulic lime using limestone having a large amount of impurities as a conventional material, and there are variations in product characteristics, particularly curing time, strength, color, etc. It is now possible to produce a homogeneous, hydraulic material.
[0050]
Compared with the conventionally used plaster using slaked lime (calcium hydroxide), this hydraulic material cures faster after it is mixed with water and is applied. It is possible to shorten to. Since the strength develops quickly and reaches high strength, the mechanical strength required as a building material is sufficiently high. Thus, the hydraulic material of the present invention can be suitably used not only as an architectural material but also in other applications where hydraulic property is useful.
[0051]
Based on this hydraulic material, a hydraulic building material of the present invention comprising a suitable amount of lime-based and dolomite-based sludge, gypsum or soil, is used as a material for forming the inner and outer walls, and also for blocks, tiles and the like. Useful as a raw material.
Claims (8)
（Ｉ）石灰系および（または）ドロマイト系の水洗スラッジ
（ＩＩ）ＳｉＯ２、Ａｌ２Ｏ３およびＦｅ２Ｏ３をモル比で１．００：０．２０〜０．５０：０．０５〜０．２０の割合で含有し、非晶質物質を含む土
（ＩＩＩ）炭酸カルシウムを軽度に焼成して得た酸化カルシウム
ＳｉＯ２、Ａｌ２Ｏ３、Ｆｅ２Ｏ３、ＣａＯおよびＭｇＯの含有量に基づいて次式から求められるセメント係数（ＣＩ）
(I) Lime-based and / or dolomite-based washing sludge (II) SiO 2 , Al 2 O 3 and Fe 2 O 3 in a molar ratio of 1.00: 0.20 to 0.50: 0.05-0. The content of calcium oxide SiO 2 , Al 2 O 3 , Fe 2 O 3 , CaO and MgO obtained by lightly sintering earth (III) calcium carbonate containing amorphous material and containing amorphous material Cement coefficient (CI) obtained from the following equation based on
（ＩＶ）リン酸カルシウム、リン酸水素カルシウムおよびリン酸から選んだ１種または２種以上The method according to any one of claims 1 to 3, wherein the raw material (IV) is added in an amount of 2 parts by weight or less to 100 parts by weight of the raw material (I) during granulation.
(IV) one or more selected from calcium phosphate, calcium hydrogen phosphate and phosphoric acid
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007204282A (en) * | 2006-01-30 | 2007-08-16 | Yoshizawa Lime Industry | Method of producing hydraulic lime |
| JP2009114029A (en) * | 2007-11-07 | 2009-05-28 | Chichibu Sekkai Kogyo Kk | Lime sludge firing method |
| WO2009098727A3 (en) * | 2008-02-06 | 2009-09-24 | Villaga Calce S.P.A. | Process for production of natural hydraulic lime |
| JP2010126420A (en) * | 2008-11-28 | 2010-06-10 | Kusunoki Sekkai Kk | Method for producing high strength building material using hydraulic lime |
| JP2018002563A (en) * | 2016-07-05 | 2018-01-11 | 鹿児島県 | Hydraulic lime and method for producing same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5429058B2 (en) * | 2010-06-03 | 2014-02-26 | 新日鐵住金株式会社 | Quantitative analysis of ettringite in inorganic oxide materials |
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2003
- 2003-05-30 JP JP2003155237A patent/JP4336793B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007204282A (en) * | 2006-01-30 | 2007-08-16 | Yoshizawa Lime Industry | Method of producing hydraulic lime |
| JP2009114029A (en) * | 2007-11-07 | 2009-05-28 | Chichibu Sekkai Kogyo Kk | Lime sludge firing method |
| WO2009098727A3 (en) * | 2008-02-06 | 2009-09-24 | Villaga Calce S.P.A. | Process for production of natural hydraulic lime |
| JP2010126420A (en) * | 2008-11-28 | 2010-06-10 | Kusunoki Sekkai Kk | Method for producing high strength building material using hydraulic lime |
| JP2018002563A (en) * | 2016-07-05 | 2018-01-11 | 鹿児島県 | Hydraulic lime and method for producing same |
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