JPH10218644A - Acid resistant cement composition - Google Patents
Acid resistant cement compositionInfo
- Publication number
- JPH10218644A JPH10218644A JP9022668A JP2266897A JPH10218644A JP H10218644 A JPH10218644 A JP H10218644A JP 9022668 A JP9022668 A JP 9022668A JP 2266897 A JP2266897 A JP 2266897A JP H10218644 A JPH10218644 A JP H10218644A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- water glass
- cement composition
- slag
- slag powder
- 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
- 239000002253 acid Substances 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 239000004568 cement Substances 0.000 title claims abstract description 24
- 239000002893 slag Substances 0.000 claims abstract description 56
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 33
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004567 concrete Substances 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000002699 waste material Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000378 calcium silicate Substances 0.000 claims abstract description 11
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 11
- -1 calcium silicate aluminate Chemical class 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- 239000002440 industrial waste Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000035515 penetration Effects 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract description 3
- 235000019738 Limestone Nutrition 0.000 abstract description 2
- 239000004927 clay Substances 0.000 abstract description 2
- 239000006028 limestone Substances 0.000 abstract description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000010801 sewage sludge Substances 0.000 description 15
- 239000003513 alkali Substances 0.000 description 9
- 238000001723 curing Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000011383 glass concrete Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000004056 waste incineration Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910017976 MgO 4 Inorganic materials 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
- C04B7/147—Metallurgical slag
- C04B7/153—Mixtures thereof with other inorganic cementitious materials or other activators
- C04B7/1535—Mixtures thereof with other inorganic cementitious materials or other activators with alkali metal containing activators, e.g. sodium hydroxide or waterglass
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/23—Acid resistance, e.g. against acid air or rain
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、廃棄物溶融スラグ
等を利用でき、耐酸性に優れたセメント組成物及びコン
クリート製品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cement composition and a concrete product which can utilize waste molten slag and have excellent acid resistance.
【0002】[0002]
【従来の技術】従来、耐酸コンクリートとしては、アル
カリスラグコンクリート及び水ガラスコンクリートが知
られている。このうち、アルカリスラグコンクリートは
普通セメントを全く用いず、高炉水滓スラグ粉末にアル
カリ金属塩等を刺激剤として加えて硬化させた水硬性コ
ンクリートである。このアルカリスラグコンクリートに
用いるスラグは、銑鉄製造工程で得られた高炉水滓スラ
グであり、通常、化学成分としてCaO38〜45重量
%、SiO233〜35重量%、Al2O314〜18重
量%、MgO4〜8重量%、Fe2O30.5〜2重量%
を有し、CaO/SiO2のモル比が1.3以上である
といわれている。このCaO/SiO2のモル比が1.
3以上の高炉水滓スラグ粉末と水ガラスを用いたコンク
リートは、硬化体中酸に弱い遊離のCa(OH)2が全
く生成されないために、普通セメントコンクリートに比
べて耐酸性が強いと言われている。2. Description of the Related Art Conventionally, alkaline slag concrete and water glass concrete are known as acid-resistant concrete. Among them, alkali slag concrete is a hydraulic concrete obtained by adding an alkali metal salt or the like as a stimulant to blast furnace slag slag powder and hardening without using any cement at all. Slag used in this alkali slag concrete is blast furnace water slag slag obtained in pig iron production process, usually, CaO38~45 wt% as chemical components, SiO 2 33 to 35 wt%, Al 2 O 3 14 to 18 weight %, MgO 4 to 8% by weight, Fe 2 O 3 0.5 to 2% by weight
It is said that the molar ratio of CaO / SiO 2 is 1.3 or more. When the molar ratio of this CaO / SiO 2 is 1.
It is said that concrete using 3 or more blast furnace slag slag powder and water glass has stronger acid resistance than ordinary cement concrete because free Ca (OH) 2, which is weak to acid in the cured product, is not generated at all. ing.
【0003】一方、水ガラスコンクリートは、結合材と
する水ガラスにケイフッ化ナトリウムや縮合リン酸アル
ミニウム等を硬化剤として加えて硬化させたコンクリー
トである。ケイフッ化ナトリウムや縮合リン酸アルミニ
ウム等の硬化剤を用いた水ガラスコンクリートはシリカ
ゲルが生成し硬化する。On the other hand, water glass concrete is concrete obtained by adding sodium silicate or condensed aluminum phosphate as a hardening agent to water glass as a binder. Silica gel is formed and hardened in water glass concrete using a hardening agent such as sodium silicofluoride or condensed aluminum phosphate.
【0004】このシリカゲルは耐酸性に優れていること
から水ガラスコンクリートも耐酸性に優れている。[0004] Since this silica gel has excellent acid resistance, water glass concrete also has excellent acid resistance.
【0005】[0005]
【発明が解決しようとする課題】しかしながら、耐酸セ
メント用として水ガラスと高炉スラグを用いると、高炉
スラグはCaOの含有量が多いため硬化体中にはシリカ
ゲルの他にC−S−H(CaO−SiO2−H2O)ゲル
も多量に生成する。このC−S−Hゲルは、酸には弱い
ため結果とし耐酸性は小さくなる。また、硫酸はC−S
−Hゲルと反応し、石膏のような膨張性物質を生成する
ため、硬化体が膨張応力によって破壊されることがあ
る。従って、CaO分の多い通常の高炉スラグと水ガラ
スを用いたスラグコンクリートは、普通セメントコンク
リートに比べれば耐酸性は強いが、耐酸コンクリート構
造物や耐酸コンクリート製品等の特殊用途に用いるには
耐酸性は十分とはいえない。However, when water glass and blast furnace slag are used for acid-resistant cement, since the blast furnace slag has a large CaO content, the hardened body contains CSH (CaO) in addition to silica gel. —SiO 2 —H 2 O) gels are also produced in large amounts. This C—S—H gel is weak to acids, resulting in low acid resistance. The sulfuric acid is C-S
The cured product may be destroyed by expansion stress because it reacts with the -H gel to generate an expandable substance such as gypsum. Therefore, ordinary blast furnace slag containing a large amount of CaO and slag concrete using water glass are more acid-resistant than ordinary cement concrete, but are not acid-resistant for use in special applications such as acid-resistant concrete structures and acid-resistant concrete products. Is not enough.
【0006】また、水ガラスコンクリートにおいて、シ
リカゲルは耐酸性が強いが、耐水性に劣り、また脱水に
伴う収縮が大きいという問題点を有している。また、上
記反応式に示した反応が完全に最後まで進行することは
難しい。そのため未反応の水ガラスと可溶性の金属塩が
生じたままとなり、これらが水や希酸に溶ける結果、硬
化体がポーラスとなり、耐浸透性が悪くなるという問題
点も有している。従って、水ガラスコンクリートは、耐
水性及び耐浸透性に劣るという欠点を有している。[0006] In water glass concrete, silica gel has a problem in that although it has strong acid resistance, it is inferior in water resistance and shrinks greatly upon dehydration. Also, it is difficult for the reaction shown in the above reaction formula to completely progress to the end. For this reason, unreacted water glass and soluble metal salts remain generated, and as a result of dissolving them in water or dilute acid, the cured product becomes porous and has poor penetration resistance. Therefore, water glass concrete has a drawback of being inferior in water resistance and penetration resistance.
【0007】一方、特に大都市においては、下水汚泥や
都市ゴミの処理をはじめ、建設廃材等の各種産業廃棄物
は、その最終処分場の確保など種々の問題があり、その
リサイクルを含めた再資源化に関する調査研究が盛んに
行われている。また、下水汚泥や都市ゴミを減容化のた
め焼却した下水汚泥焼却灰や都市ゴミ焼却灰、更にはそ
れらのいっそうの減容化のため溶融処理したスラグ等に
ついても、各自治体や装置メーカーは有効利用技術の開
発を行っている。しかし、その用途は、路盤材やブロッ
クの骨材やタイルや煉瓦等の原料として利用され始めて
いるが、その量は微々たるものであり、技術的、価格的
な制約、流通の問題等から、未だに有効活用はまだまだ
少なく、かつ、積極的に有効活用されている段階でもな
く、その処理に悩んでいるのが実状である。On the other hand, especially in large cities, various industrial wastes such as construction waste materials, including treatment of sewage sludge and municipal waste, have various problems such as securing a final disposal site. Investigation research on resource utilization is being actively conducted. Also, municipalities and equipment manufacturers are in charge of sewage sludge incineration ash and municipal waste incineration ash incinerated to reduce the volume of sewage sludge and municipal waste, and slag that has been melt-processed to further reduce the volume. We are developing effective utilization technology. However, its use has begun to be used as a raw material for roadbed materials, aggregates of blocks, blocks, tiles, bricks, etc., but the amount is insignificant, and technical, price restrictions, distribution problems, etc. There is still little effective utilization, and it is not at the stage where it is being actively utilized.
【0008】例えば、下水汚泥に関しては、建設省は、
昭和50年度以降、下水汚泥の資源化に関する調査研究
を行っている。又、下水汚泥の有効利用を促進する為、
汚泥の有効利用施設を補助対象にしている。更に、昭和
63年度より、下水道の建設事業に汚泥製品(路盤材や
土質改良材等)を積極的に用いることを内容とする下水
汚泥資源利用モデル事業を実施している。しかし、この
ように長年その有効利用について検討しているにもかか
わらず、未だに下水汚泥焼却灰やゴミ焼却灰はもちろ
ん、それらを溶融スラグ化した溶融スラグも含めて大き
な有効活用は図られていない。For example, regarding sewage sludge, the Ministry of Construction
Since 1975, we have been conducting research on the recycling of sewage sludge. Also, to promote the effective use of sewage sludge,
Effective sludge utilization facilities are subsidized. Furthermore, since 1988, a sewage sludge resource utilization model project has been implemented, which includes the use of sludge products (roadbed materials, soil improvement materials, etc.) in sewerage construction projects. However, despite the long years of studying its effective use, significant effective use has not yet been achieved, including sewage sludge incineration ash and garbage incineration ash, as well as molten slag that has been made into molten slag. .
【0009】従って本発明の目的は、廃棄物溶融スラグ
も有効利用でき、上記の如き欠点のない、耐酸性に優れ
たセメント組成物及びコンクリート製品を提供すること
にある。Accordingly, an object of the present invention is to provide a cement composition and a concrete product which can effectively utilize waste molten slag and have the above-mentioned drawbacks and have excellent acid resistance.
【0010】[0010]
【課題を解決するための手段】斯かる実情に鑑み本発明
者らは鋭意研究を行った結果、下水汚泥や都市ゴミを溶
融スラグ化した廃棄物溶融スラグ等のCaO/SiO2
のモル比が0.1〜1.2である非晶質カルシウムシリ
ケートアルミネート系スラグ粉末と水ガラス及び必要な
骨材を特定量含有するセメント組成物が優れた耐酸性を
有するコンクリート製品となり得ることを見出し、本発
明を完成した。Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies and found that CaO / SiO 2 such as sewage sludge or waste molten slag obtained by converting municipal waste into molten slag.
Amorphous calcium silicate aluminate slag powder having a molar ratio of 0.1 to 1.2, water glass and a cement composition containing a specific amount of required aggregate can be a concrete product having excellent acid resistance. Thus, the present invention has been completed.
【0011】すなわち本発明は、(A)CaO/SiO
2のモル比が0.1〜1.2の非晶質カルシウムシリケ
ートアルミネート系スラグ粉末10〜95重量%、
(B)水ガラスを固形分で1〜20重量%及び(C)骨
材0〜85重量%を含有する耐酸セメント組成物を提供
するものである。That is, the present invention relates to (A) CaO / SiO
2 to 10 to 95% by weight of amorphous calcium silicate aluminate slag powder having a molar ratio of 0.1 to 1.2,
The present invention provides an acid-resistant cement composition containing (B) 1 to 20% by weight of water glass in solid content and (C) 0 to 85% by weight of aggregate.
【0012】また本発明は、この耐酸セメント組成物と
水とを混合し、成形することにより得られる耐酸コンク
リート製品を提供するものである。The present invention also provides an acid-resistant concrete product obtained by mixing and molding the acid-resistant cement composition and water.
【0013】[0013]
【発明の実施の形態】本発明で用いる非晶質カルシウム
シリケートアルミネート系スラグ粉末はCaO、SiO
2及びAl2O3を主成分とするものであり、粘土、石灰
石、下水汚泥焼却物、ゴミ焼却物、産業廃棄物等の種々
の原料を上記の化学成分となるように調整したものを高
温で溶融し、急冷して得られるスラグを粉砕したもので
ある。ここで、各種の原料は、市販の材料を混合して用
いてもよいが、下水汚泥焼却物、ゴミ焼却物及び産業廃
棄物は、これを直接用いても化学組成が上記の範囲にあ
るものがほとんどであり、経済性及び未利用資源の有効
利用の点からこれを用いるのがより好ましい。すなわち
下水汚泥焼却溶融スラグ、ゴミ焼却溶融スラグ及び産業
廃棄物焼却溶融スラグ等の廃棄物溶融スラグを用いるこ
とが好ましい。因に下水汚泥や都市ゴミを溶融した廃棄
物溶融スラグの化学成分はCaOが5〜35%、SiO
2 が30〜70重量%、Al2O3が5〜25重量%、F
e2O3が2〜20重量%、アルカリ分が1〜15重量
%、リン分が0.5〜23重量%、MgOが2〜6重量
%等であり、ほとんどの場合CaO/SiO2のモル比
が1.2以下である。BEST MODE FOR CARRYING OUT THE INVENTION Amorphous calcium silicate aluminate slag powder used in the present invention is CaO, SiO
2 and Al 2 O 3 as main components, and various raw materials such as clay, limestone, incineration of sewage sludge, incineration of garbage, and industrial waste are adjusted to have the above-mentioned chemical components. And crushed slag obtained by rapid cooling. Here, various raw materials may be used by mixing commercially available materials, but sewage sludge incineration, garbage incineration, and industrial waste have a chemical composition within the above range even when used directly. Most of them are used from the viewpoint of economic efficiency and effective use of unused resources. That is, it is preferable to use waste melting slag such as sewage sludge incineration melting slag, refuse incineration melting slag, and industrial waste incineration melting slag. The chemical composition of waste slag that melts sewage sludge and municipal waste is 5-35% CaO and SiO
2 30-70 wt%, Al 2 O 3 5 to 25 wt%, F
e 2 O 3 is 2-20 wt%, the alkali content of 1-15 wt%, phosphorus content of 0.5 to 23 wt%, a MgO is such as 2-6 wt%, most cases CaO / SiO 2 The molar ratio is 1.2 or less.
【0014】本発明に用いるスラグ粉末(A)のCaO
/SiO2のモル比は、0.1〜1.2であるが、好ま
しくは0.2〜1.0であり、特に好ましくは0.3〜
0.8である。このCaO/SiO2のモル比が0.1
未満であるとスラグの水和活性が極端に小さくなり、水
ガラスを多量に使用しても、実用化できる程の強度を持
つ硬化体が得られないことがある。一方、このモル比が
1.2を超えるとCaOの含有量が相対的に高くなるた
めアルカリスラグコンクリートと同様な問題点を生じる
ことがある。すなわち耐酸性が弱くなり、硫酸存在下で
は、石膏の生成にともなう膨張によりクラックや表面剥
離が発生しやすくなる。CaO of slag powder (A) used in the present invention
The molar ratio of / SiO 2 is 0.1 to 1.2, preferably 0.2 to 1.0, and particularly preferably 0.3 to 1.0.
0.8. When the molar ratio of CaO / SiO 2 is 0.1
If the amount is less than the above, the hydration activity of the slag becomes extremely small, and even if a large amount of water glass is used, a cured product having a strength that can be practically used may not be obtained. On the other hand, if the molar ratio exceeds 1.2, the content of CaO becomes relatively high, so that a problem similar to that of alkaline slag concrete may occur. That is, the acid resistance is weakened, and in the presence of sulfuric acid, cracks and surface peeling are liable to occur due to expansion accompanying the formation of gypsum.
【0015】また、スラグ粉末(A)は、上記成分以外
に、酸化鉄、アルカリ分、リン分、酸化チタン、酸化マ
ンガン、酸化マグネシウム及びハロゲン分から選ばれる
1種又は2種以上が含まれていることが好ましい。これ
ら成分の含有量は、酸化鉄(Fe2O3換算)、アルカリ
分(Na2O及びK2Oの合計換算)、リン分(P2O5換
算)、酸化チタン(TiO2換算)、酸化マンガン(M
nO換算)及び酸化マグネシウム(MgO換算)から選
ばれる1種又は2種以上が合計量で0.1〜50重量
%、又は/及びハロゲン分0.1〜10重量%程度であ
ることが好ましい。The slag powder (A) contains, in addition to the above components, one or more selected from iron oxide, alkali, phosphorus, titanium oxide, manganese oxide, magnesium oxide and halogen. Is preferred. The contents of these components are as follows: iron oxide (in terms of Fe 2 O 3 ), alkali (in terms of total of Na 2 O and K 2 O), phosphorus (in terms of P 2 O 5 ), titanium oxide (in terms of TiO 2 ), Manganese oxide (M
One or more selected from nO) and magnesium oxide (MgO) are preferably about 0.1 to 50% by weight in total and / or about 0.1 to 10% by weight of halogen content.
【0016】スラグ粉末(A)の粉末度は細かいほど粉
末の比表面積が大きくなるため水和反応が速く進行し、
コンクリートの強度が高まり好ましいが、比表面積が1
5000cm2 /gを超えるものとすると、粉砕にかかる
エネルギーや時間が膨大となり経済性に欠ける。一方、
比表面積が1000cm2 /g未満のものでは、水和活性
が乏しく脱型強度が得られず、また耐酸性にも乏しくな
ることがあり好ましくない。従って、スラグ粉末(A)
の比表面積は1000〜15000cm2 /g、特に20
00〜8000cm2 /gが好ましい。The finer the slag powder (A), the greater the specific surface area of the powder, the faster the hydration reaction proceeds,
Concrete with high strength is preferable, but specific surface area is 1
If it exceeds 5,000 cm 2 / g, the energy and time required for pulverization become enormous, resulting in lack of economy. on the other hand,
When the specific surface area is less than 1000 cm 2 / g, the hydration activity is poor and the demolding strength cannot be obtained, and the acid resistance is also poor, which is not preferable. Therefore, slag powder (A)
Has a specific surface area of 1000 to 15000 cm 2 / g, particularly 20
It is preferably from 00 to 8000 cm 2 / g.
【0017】本発明で使用される水ガラス(B)として
は、一般に市販されているものすなわち、無水水ガラ
ス、液体水ガラス、K2Oを含んだ水ガラス等であれば
いずれも使用できるが、刺激剤としての効果を考えると
アルカリ量の多いもの、すなわちSiO2/Na2Oのモ
ル比が小さいものが好ましい。具体的には市販の水ガラ
ス1〜3号のうち1号水ガラスが好ましい。水ガラスの
使用量は、耐酸セメント組成物中1〜20重量%、好ま
しくは2〜15重量%(固形分換算)である。この量が
2重量%未満であるとアルカリ刺激剤としての量が少な
すぎるため、十分な強度が得られず、20重量%を超え
るとフレッシュ状態の混合物の粘性が大きくなりすぎ、
成形又は作業が困難となることがある。また水ガラス
(B)/スラグ粉末(A)の重量比は0.05〜0.4
0、特に0.10〜0.30とすることが好ましい。As the water glass (B) used in the present invention, any commercially available water glass, that is, anhydrous water glass, liquid water glass, water glass containing K 2 O, etc. can be used. Considering the effect as a stimulant, those having a large amount of alkali, that is, those having a small SiO 2 / Na 2 O molar ratio are preferable. Specifically, among commercially available water glasses 1 to 3, water glass 1 is preferable. The amount of water glass to be used is 1 to 20% by weight, preferably 2 to 15% by weight (in terms of solid content) in the acid-resistant cement composition. When the amount is less than 2% by weight, the amount as the alkali stimulant is too small, so that sufficient strength cannot be obtained. When the amount exceeds 20% by weight, the viscosity of the mixture in a fresh state becomes too large,
Molding or work may be difficult. The weight ratio of water glass (B) / slag powder (A) is 0.05 to 0.4.
0, particularly preferably 0.10 to 0.30.
【0018】本発明において使用される骨材(C)とし
ては耐酸性を有する骨材であれば何れでもよく、石英質
岩石、安山岩、玄武岩、陶磁器破砕物等が挙げられる。
また、粒状又は塊状の上記廃棄物溶融スラグも骨材とし
て用いることができる。骨材の使用量は用途に応じて耐
酸セメント組成物中0〜85重量%、好ましくは0〜8
0重量%とすることが好ましい。この量が85重量%を
超えると他の結合材の量が少なくなりすぎ、フレッシュ
状態の混合物の粘性が不足し、パサパサして成形ができ
なくなることがある。As the aggregate (C) used in the present invention, any aggregate having acid resistance may be used, and examples thereof include quartz rock, andesite, basalt, and crushed ceramics.
Further, the above-mentioned waste molten slag in a granular or massive form can also be used as an aggregate. The amount of the aggregate used is 0 to 85% by weight, preferably 0 to 8% by weight in the acid-resistant cement composition depending on the use.
It is preferably 0% by weight. If this amount exceeds 85% by weight, the amount of the other binder may be too small, the viscosity of the mixture in a fresh state may be insufficient, and molding may not be possible due to a dryness.
【0019】本発明の耐酸セメント組成物と水とを混合
し、成形すれば耐酸性に優れたコンクリート製品が得ら
れる。ここで、セメント組成物と水との混合比は、通常
のコンクリート製造時と同様であり、所望のコンクリー
ト製品の成形手段によって適宜決定される。If the acid-resistant cement composition of the present invention and water are mixed and molded, a concrete product having excellent acid resistance can be obtained. Here, the mixing ratio between the cement composition and water is the same as in the case of ordinary concrete production, and is appropriately determined by a desired concrete product molding means.
【0020】この混合物の成形方法としては、流し込み
法、押し出し法、遠心力法、加圧法等の何れを用いても
よい。また、養生方法としては、常温養生、蒸気養生、
オートクレーブ養生等の何れを用いてもよい。本発明の
コンクリート製品としては、耐酸性構造物、例えば酸類
を使用する工場、酸性水温泉地区の槽、床面、壁等の組
成材料、耐酸性裏込め材、耐酸性コンクリート製品、例
えば化学工場排水管、下水道管等が挙げられる。As a molding method of this mixture, any of a casting method, an extrusion method, a centrifugal force method, a pressurizing method and the like may be used. The curing method includes room temperature curing, steam curing,
Any method such as autoclave curing may be used. Examples of the concrete product of the present invention include acid-resistant structures, for example, factories using acids, tanks in an acidic hot spring area, floors, walls, etc., acid-resistant backfill materials, acid-resistant concrete products, for example, chemical factories. Drainage pipes, sewer pipes and the like are mentioned.
【0021】本発明においては、CaO/SiO2のモ
ル比が0.1〜1.2の非晶質カルシウムシリケートア
ルミネート系スラグ粉末を用いることによって、硬化体
中に生成されるC−S−Hゲルの量を減らすことにより
耐酸性を向上させている。また、水ガラスの水和により
生成されたNaOH等のアルカリが本発明のスラグ粉末
の刺激剤となり消費され、このNaOHの消費により、
更に水ガラスの硬化は促進されることになる。換言すれ
ば、水ガラスは本発明の非晶質カルシウムシリケートア
ルミネート系スラグ粉末の刺激剤となり、非晶質カルシ
ウムシリケートアルミネート系スラグ粉末は水ガラスの
硬化剤となる。よって、CaO/SiO2のモル比が
0.1〜1.2の非晶質カルシウムシリケートアルミネ
ート系スラグ粉末を用いることにより、従来のアルカリ
スラグコンクリートでもなく、水ガラスコンクリートで
もなく、両者の長所を兼ねそなえ、耐酸性、耐水性、耐
浸透性が強く、かつ収縮が小さい耐酸セメント組成物が
得られる。In the present invention, by using an amorphous calcium silicate aluminate slag powder having a CaO / SiO 2 molar ratio of 0.1 to 1.2, the C—S— Acid resistance is improved by reducing the amount of H gel. In addition, alkali such as NaOH generated by hydration of water glass becomes a stimulant of the slag powder of the present invention and is consumed. By the consumption of NaOH,
Furthermore, the hardening of the water glass will be accelerated. In other words, the water glass serves as a stimulant for the amorphous calcium silicate aluminate slag powder of the present invention, and the amorphous calcium silicate aluminate slag powder serves as a hardener for the water glass. Therefore, by using the amorphous calcium silicate aluminate-based slag powder having a molar ratio of CaO / SiO 2 of 0.1 to 1.2, neither conventional alkali slag concrete nor water glass concrete is used. Thus, an acid-resistant cement composition having strong acid resistance, water resistance and penetration resistance and small shrinkage can be obtained.
【0022】[0022]
【実施例】次に実施例を挙げて本発明を更に詳細に説明
するが、本発明はこれに何ら限定されるものではない。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.
【0023】実施例1 CaO/SiO2のモル比が1.11の大阪市の下水汚
泥溶融スラグ(表1)を用いて内径が150mm、厚みが
26mmの無筋コンクリート管を作製し、その外圧強さ及
び圧縮強度を測定した。その場合の配合組成、成形方式
及び養生条件は以下の通りである。すなわち、配合組成
は、粉末度が4500cm2 /gの溶融スラグ粉末を34
3kg/m3、1号水ガラスを86kg/m3、砂を781kg/
m3、砂利を1059kg/m3、水を150kg/m3とした。
成形方式は、遠心力成形とし、重力加速度が3gの低速
で3分間、12gの中速で2分間、30gの高速で6分
間回した。養生条件は蒸気養生を用いて、80℃まで2
0℃/時間の昇温速度で昇温し、その後80℃で8時間
保持した後、自然放冷とした。その結果、外圧強さは3
0.2kN/mであり、圧縮強度は366kgf/cm2 であっ
た。その数値は、呼び径が150の無筋コンクリート管
の外圧強さのJIS基準値25kN/mと比べて十分に高
くなっており、実用化に支障のない値であった。Example 1 A straight concrete pipe having an inner diameter of 150 mm and a thickness of 26 mm was prepared using sewage sludge molten slag of Osaka City having a molar ratio of CaO / SiO 2 of 1.11 (Table 1). The strength and compressive strength were measured. The composition, molding method and curing conditions in that case are as follows. That is, the composition was such that the molten slag powder having a fineness of 4500 cm 2 / g was
3 kg / m 3 , No. 1 water glass 86 kg / m 3 , sand 781 kg /
m 3, gravel 1059kg / m 3, and water and 150 kg / m 3.
The molding method was centrifugal force molding, and the gravitational acceleration was 3 minutes at a low speed of 3 g, 2 minutes at a medium speed of 12 g, and 6 minutes at a high speed of 30 g. Curing conditions are up to 80 ° C using steam curing.
The temperature was raised at a rate of 0 ° C./hour, and then maintained at 80 ° C. for 8 hours, followed by natural cooling. As a result, the external pressure strength is 3
It was 0.2 kN / m, and the compressive strength was 366 kgf / cm 2 . The numerical value was sufficiently higher than the JIS standard value of 25 kN / m of the external pressure strength of a plain concrete pipe having a nominal diameter of 150, and was a value that would not hinder practical application.
【0024】実施例2〜18 試験方法について 表2及び表3(表1)に示すような配合の耐酸セメント
組成物(配合No1〜18は本発明品、A〜Cは比較
品)をISOセメントモルタルの作製方法に準じ、寸法
2×2×8cmに成型し、次に示すような条件の蒸気養生
を行った後、脱型し、曲げ、圧縮強度、耐酸性試験用の
試験体とした。耐酸性試験は試験体体積の10倍に相当
する20℃の10%硫酸中に10日間浸漬した後、その
重量測定と外観観察を行った。なお、酸液の交換は2日
ごとに行うこととした。結果を表4〜8に示す。Examples 2 to 18 Test Methods Acid-resistant cement compositions (Formulation Nos. 1 to 18 are products of the present invention, and A to C are comparative products) having the compositions shown in Tables 2 and 3 (Table 1) were used as ISO cements. According to the method of preparing the mortar, it was molded into a size of 2 × 2 × 8 cm, and after steam curing under the following conditions, it was removed from the mold to obtain a test specimen for bending, compressive strength, and acid resistance test. In the acid resistance test, the sample was immersed in 10% sulfuric acid at 20 ° C. corresponding to 10 times the volume of the test sample for 10 days, and then its weight was measured and its appearance was observed. The acid solution was replaced every two days. The results are shown in Tables 4 to 8.
【0025】 [0025]
【0026】[0026]
【表1】 [Table 1]
【0027】[0027]
【表2】 [Table 2]
【0028】[0028]
【表3】 [Table 3]
【0029】[0029]
【表4】 [Table 4]
【0030】[0030]
【表5】 [Table 5]
【0031】[0031]
【表6】 [Table 6]
【0032】[0032]
【表7】 [Table 7]
【0033】[0033]
【表8】 [Table 8]
【0034】[0034]
【発明の効果】本発明の耐酸セメント組成物から得られ
る耐酸コンクリート製品は、耐酸性に優れることはもち
ろん、耐水性・耐浸透性にも優れ、かつ収縮が少ない。
また下水汚泥や都市ゴミを溶融した廃棄物溶融スラグを
原料とすることができるので、これらの有効利用を図る
ことができる。The acid-resistant concrete product obtained from the acid-resistant cement composition of the present invention is excellent not only in acid resistance but also in water resistance and permeation resistance and has little shrinkage.
Further, since waste molten slag obtained by melting sewage sludge or municipal waste can be used as a raw material, it is possible to effectively utilize these.
Claims (4)
1〜1.2の非晶質カルシウムシリケートアルミネート
系スラグ粉末10〜95重量%、(B)水ガラスを固形
分で1〜20重量%及び(C)骨材0〜85重量%を含
有する耐酸セメント組成物。(A) The molar ratio of (A) CaO / SiO 2 is 0.1.
10 to 95% by weight of amorphous calcium silicate aluminate slag powder of 1 to 1.2, (B) 1 to 20% by weight of water glass in solid content and (C) 0 to 85% by weight of aggregate Acid resistant cement composition.
ト系スラグ粉末(A)の一部又は全部が廃棄物溶融スラ
グである請求項1記載の耐酸セメント組成物。2. The acid-resistant cement composition according to claim 1, wherein a part or all of the amorphous calcium silicate aluminate slag powder (A) is a waste molten slag.
スラグであることを特徴とする請求項1又は2記載の耐
酸セメント組成物。3. The acid-resistant cement composition according to claim 1, wherein the aggregate (C) is granular or massive waste molten slag.
組成物と水とを混合し、成形することにより得られる耐
酸コンクリート製品。4. An acid-resistant concrete product obtained by mixing and molding the acid-resistant cement composition according to claim 1, 2 or 3, and water.
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JP2000018438A (en) * | 1998-07-03 | 2000-01-18 | Taiheiyo Cement Corp | Acidproof hume pipe and manufacture thereof |
JP2000053459A (en) * | 1998-08-04 | 2000-02-22 | Taiheiyo Cement Corp | Acid resistant manhole and its production |
JP2000053458A (en) * | 1998-08-04 | 2000-02-22 | Taiheiyo Cement Corp | Acid resistant box culvert and its production |
JP2001088114A (en) * | 1999-09-27 | 2001-04-03 | Taiheiyo Cement Corp | Acid resistant concrete product |
JP2001106562A (en) * | 1999-10-07 | 2001-04-17 | Taiheiyo Cement Corp | Acid-resistant concrete article |
JP2001163660A (en) * | 1999-09-29 | 2001-06-19 | Taiheiyo Cement Corp | Hardenable composition and hardened body |
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JP2002154862A (en) * | 2000-11-15 | 2002-05-28 | Central Res Inst Of Electric Power Ind | Hardenable composition and hardened body |
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KR102305160B1 (en) * | 2020-03-13 | 2021-09-27 | 주식회사 한나눔산업 | Concrete composition and the manufacturing method thereof |
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