JP5474649B2 - Hydraulic composition - Google Patents
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- JP5474649B2 JP5474649B2 JP2010099574A JP2010099574A JP5474649B2 JP 5474649 B2 JP5474649 B2 JP 5474649B2 JP 2010099574 A JP2010099574 A JP 2010099574A JP 2010099574 A JP2010099574 A JP 2010099574A JP 5474649 B2 JP5474649 B2 JP 5474649B2
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- 239000000203 mixture Substances 0.000 title claims description 56
- 239000000843 powder Substances 0.000 claims description 31
- 239000010440 gypsum Substances 0.000 claims description 27
- 229910052602 gypsum Inorganic materials 0.000 claims description 27
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 17
- 235000019738 Limestone Nutrition 0.000 claims description 16
- 239000006028 limestone Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002893 slag Substances 0.000 claims description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 12
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 12
- 239000004571 lime Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 229910004261 CaF 2 Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000010881 fly ash Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 description 31
- 239000002994 raw material Substances 0.000 description 29
- 239000011398 Portland cement Substances 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 20
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 17
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 17
- 238000011161 development Methods 0.000 description 16
- 230000006835 compression Effects 0.000 description 15
- 238000007906 compression Methods 0.000 description 15
- 238000010304 firing Methods 0.000 description 15
- 150000004683 dihydrates Chemical class 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 238000010276 construction Methods 0.000 description 12
- 230000036571 hydration Effects 0.000 description 12
- 238000006703 hydration reaction Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000002689 soil Substances 0.000 description 12
- 239000004568 cement Substances 0.000 description 11
- 239000000292 calcium oxide Substances 0.000 description 9
- 239000004567 concrete Substances 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 9
- 235000012255 calcium oxide Nutrition 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000002440 industrial waste Substances 0.000 description 8
- 239000002956 ash Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 210000004556 brain Anatomy 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 239000010801 sewage sludge Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 for example Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000006072 paste Substances 0.000 description 3
- 238000004056 waste incineration Methods 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000011400 blast furnace cement Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000010920 waste tyre Substances 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000006063 cullet Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000005406 washing Methods 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)
- Processing Of Solid Wastes (AREA)
Description
本発明は、製造時の環境負荷を小さくすることができ、かつ、普通ポルトランドセメントと同等の流動特性および硬化特性を有する水硬性組成物に関するものである。 The present invention relates to a hydraulic composition that can reduce the environmental load during production and has flow characteristics and curing characteristics equivalent to those of ordinary Portland cement.
わが国では、経済成長、人口の都市部への集中に伴い、産業廃棄物や一般廃棄物等が急増している。従来から、前記廃棄物の大半は、焼却によって十分の一程度に減容化し埋め立て処分されているが、最近では埋め立て処分場の残余容量が逼迫していることから、新しい廃棄物処理方法の確立が緊急課題になっている。この課題に対処するために、都市ゴミ焼却灰等を原料としてセメントクリンカーを製造する方法が提案されている（特許文献１）。
また、近年の地球環境問題の深刻化に伴い、セメントの製造の際の炭酸ガスの抑制も大きな課題となってきている。
In Japan, industrial waste, general waste, etc. are rapidly increasing with economic growth and population concentration in urban areas. Conventionally, most of the above waste has been reduced to one-tenth by incineration and landfilled, but recently the remaining capacity of the landfill site has become tight, so a new waste disposal method has been established. Has become an urgent issue. In order to cope with this problem, a method of manufacturing cement clinker using municipal waste incineration ash or the like as a raw material has been proposed (Patent Document 1).
In addition, with the recent global environmental problems becoming serious, the suppression of carbon dioxide gas during the production of cement has become a major issue.
しかし、上記特許文献１に記載されたセメントクリンカーでは、水和反応性が高い3CaO・Al2O3を10質量％以上含むため、該セメントクリンカーを使用したセメントは、普通ポルトランドセメントと比べて流動性が低下することに加え、流動性の経時変化も大きくなり、強度発現性もやや劣るという課題があった。
また、上記特許文献１に記載されたセメントクリンカーは、ポルトランドセメントクリンカーよりも低温(1400℃程度)で焼成可能であり、燃料原単位の低減により製造の際の炭酸ガスの発生量を抑制することは可能ではあるが、近年の地球環境問題の深刻化に伴い、製造の際により炭酸ガス発生量を抑制できる水硬性組成物が求められている。
However, since the cement clinker described in Patent Document 1 contains 10% by mass or more of 3CaO · Al 2 O 3 having high hydration reactivity, the cement using the cement clinker is more fluid than ordinary Portland cement. In addition to the decrease in the property, there is a problem that the change with time of the fluidity increases and the strength development is slightly inferior.
Further, the cement clinker described in Patent Document 1 can be fired at a lower temperature (about 1400 ° C.) than the Portland cement clinker, and suppresses the amount of carbon dioxide generated during production by reducing the fuel unit. However, as the global environmental problems become more serious in recent years, there is a demand for a hydraulic composition that can suppress the amount of carbon dioxide generated during production.
そこで、本発明においては、製造時の環境負荷を小さくすることができ、かつ、普通ポルトランドセメントと同等の流動特性および硬化特性を有する水硬性組成物を提供することを目的とする。 Accordingly, an object of the present invention is to provide a hydraulic composition that can reduce the environmental load during production and has flow characteristics and curing characteristics equivalent to those of ordinary Portland cement.
本発明者らは、斯かる実情に鑑み、鋭意検討した結果、特定の鉱物を特定量含む焼成物の粉砕物と、石膏とを組み合わせることにより、製造時の環境負荷を小さくすることができるうえ、普通ポルトランドセメントと同等の流動特性および硬化特性が得られることを見いだし、本発明を完成させたものである。
すなわち、本発明は、11CaO・7Al2O3・CaF2含有量が0.1〜15質量％、4CaO・Al2O3・Fe2O3含有量が5〜25質量％、3CaO・SiO2含有量が30質量％以下、フリーライム量が1.0質量％以下で、残部が2CaO・SiO2である焼成物Ａの粉砕物と、石膏を含むことを特徴とする水硬性組成物を提供するものである。
As a result of intensive studies in view of such circumstances, the present inventors can reduce the environmental burden during production by combining a pulverized product of a fired product containing a specific amount of a specific mineral with gypsum. The present inventors have found that the fluidity and curing characteristics equivalent to those of ordinary Portland cement can be obtained, and the present invention has been completed.
That is, according to the present invention, 11CaO · 7Al 2 O 3 · CaF 2 content is 0.1 to 15% by mass, 4CaO · Al 2 O 3 · Fe 2 O 3 content is 5 to 25% by mass, 3CaO · SiO 2 content Is provided with a hydraulic composition characterized by containing a pulverized product of calcined product A having a lime content of 30% by mass or less, a free lime content of 1.0% by mass or less and the balance being 2CaO · SiO 2 , and gypsum. .
本発明の水硬性組成物は、産業廃棄物、一般廃棄物及び建設発生土から選ばれる一種以上を原料として使用できるので、廃棄物の有効利用の促進にも貢献することができるうえ、原料としての石灰石の使用量を低減できるので、製造の際の炭酸ガスの発生量を抑制することが可能である。また、本発明で使用する焼成物は、ポルトランドセメントクリンカーよりも低温で焼成することができるので、燃料原単位の低減により炭酸ガスの発生量を抑制することも可能である。このように、本発明の水硬性組成物は、製造時の環境負荷を小さくすることができる。
また、本発明の水硬性組成物は、普通ポルトランドセメントと同等の流動特性および硬化特性を有するものである。よって、本発明の水硬性組成物は、普通ポルトランドセメントの代替品として使用することが可能である。
Since the hydraulic composition of the present invention can use one or more selected from industrial waste, general waste and construction generated soil as a raw material, it can contribute to the promotion of effective use of waste, and as a raw material. Since the amount of limestone used can be reduced, the amount of carbon dioxide generated during production can be suppressed. In addition, since the fired product used in the present invention can be fired at a lower temperature than the Portland cement clinker, it is also possible to suppress the generation amount of carbon dioxide gas by reducing the fuel basic unit. Thus, the hydraulic composition of the present invention can reduce the environmental load during production.
Further, the hydraulic composition of the present invention has flow characteristics and curing characteristics equivalent to those of ordinary Portland cement. Therefore, the hydraulic composition of the present invention can be used as a substitute for ordinary Portland cement.
以下、本発明について詳細に説明する。
本発明で使用する焼成物Ａは、11CaO・7Al2O3・CaF2(以降、C11A7CaF2と称す)含有量が0.1〜15質量％、4CaO・Al2O3・Fe2O3(以降、C4AFと称す)含有量が5〜25質量％、3CaO・SiO2(以降、C3Sと称す)含有量が30質量％以下、フリーライム量が1.0質量％以下で、残部が2CaO・SiO2(以降、C2Sと称す)からなるものである。
焼成物Ａ中のC11A7CaF2含有量が少なくなると、焼成物を製造する際の焼成温度を低減することが困難となるので、製造時の環境負荷を小さくすることが困難となる。一方、焼成物Ａ中のC11A7CaF2含有量が多くなると、普通ポルトランドセメントと同等の流動特性や硬化特性を得ることが困難となる。
よって、焼成物Ａ中のC11A7CaF2含有量は、0.1〜15質量％が好ましく、0.5〜14質量％がより好ましく、1〜13質量％が特に好ましい。
Hereinafter, the present invention will be described in detail.
The calcined product A used in the present invention has a content of 11CaO · 7Al 2 O 3 · CaF 2 (hereinafter referred to as C 11 A 7 CaF 2 ) of 0.1 to 15% by mass, 4CaO · Al 2 O 3 · Fe 2 O. 3 (hereinafter referred to as C 4 AF) content is 5-25% by mass, 3CaO · SiO 2 (hereinafter referred to as C 3 S) content is 30% by mass or less, free lime content is 1.0% by mass or less, The balance is made of 2CaO · SiO 2 (hereinafter referred to as C 2 S).
If the content of C 11 A 7 CaF 2 in the fired product A is reduced, it is difficult to reduce the firing temperature when producing the fired product, and thus it is difficult to reduce the environmental load during production. On the other hand, when the content of C 11 A 7 CaF 2 in the fired product A increases, it becomes difficult to obtain fluidity and curing properties equivalent to those of ordinary Portland cement.
Therefore, the content of C 11 A 7 CaF 2 in the fired product A is preferably 0.1 to 15% by mass, more preferably 0.5 to 14% by mass, and particularly preferably 1 to 13% by mass.
焼成物Ａ中のC4AF含有量が少なくなると、本願の水硬性組成物を使用して得たモルタルやコンクリート等が炭酸化した場合に強度低下を引き起こす場合がある。一方、焼成物Ａ中のC4AF含有量が多くなると、高温時に原料が溶融し易くなり、溶融した原料がキルンに付着するなどして焼成が困難になる。
よって、焼成物Ａ中のC4AF含有量は、5〜25質量％が好ましく、5.5〜20質量％がより好ましく、6〜15質量％が特に好ましい。
When the content of C 4 AF in the fired product A is decreased, strength may be reduced when mortar, concrete, or the like obtained using the hydraulic composition of the present application is carbonized. On the other hand, when the content of C 4 AF in the fired product A increases, the raw material is easily melted at a high temperature, and the melted raw material adheres to the kiln, making firing difficult.
Therefore, the C 4 AF content in the fired product A is preferably 5 to 25% by mass, more preferably 5.5 to 20% by mass, and particularly preferably 6 to 15% by mass.
焼成物Ａ中のC3S含有量が多くなると、石灰石の使用量が増加し石灰石の脱炭酸により、多くの炭酸ガスが排出され、さらに脱炭酸に要する熱量も多くなるので、製造時の環境負荷を小さくすることが困難となる。一方、焼成物Ａ中のC3S含有量が少なくなると、普通ポルトランドセメントと同等の硬化特性を得ることが困難になるので、焼成物Ａ中のC3S含有量は、30質量％以下が好ましく、2〜27質量％がより好ましく、5〜25質量％が特に好ましい。 When the C 3 S content in the fired product A increases, the amount of limestone used increases, and a large amount of carbon dioxide gas is discharged due to the decarboxylation of limestone, and the amount of heat required for decarboxylation also increases. It becomes difficult to reduce the load. On the other hand, if the C 3 S content in the fired product A decreases, it becomes difficult to obtain the same curing characteristics as ordinary Portland cement. Therefore, the C 3 S content in the fired product A is 30% by mass or less. Preferably, 2 to 27 mass% is more preferable, and 5 to 25 mass% is particularly preferable.
焼成物Ａ中のフリーライム量が多くなると、強度発現性が低下する虞があり、普通ポルトランドセメントと同等の硬化特性を得ることが困難となる。一方、焼成物Ａ中のフリーライム量を0質量％とすることは困難であるので、焼成物中のフリーライム量は、1.0質量％以下が好ましく、0.1〜0.9質量％がより好ましく、0.2〜0.8質量％が特に好ましい。 If the amount of free lime in the baked product A is increased, the strength development may be reduced, and it becomes difficult to obtain a curing property equivalent to that of ordinary Portland cement. On the other hand, since it is difficult to make the amount of free lime in the baked product A 0% by mass, the amount of free lime in the baked product is preferably 1.0% by mass or less, more preferably 0.1 to 0.9% by mass, and more preferably 0.2 to 0.8% by mass is particularly preferred.
本発明で使用する焼成物Ａは、上記C11A7CaF2、C4AF、C3S、フリーライム以外に、C2Sを含むものである。
焼成物Ａ中のC2S含有量が少なくなると、普通ポルトランドセメントと同等の流動特性や硬化特性を得ることが困難となる。一方、焼成物Ａ中のC2S含有量が多くなると、相対的にC11A7CaF2含有量等が少なくなるので、セメントの初期強度が低下する。また、焼成物の原料として産業廃棄物等を使用することも困難となるので、製造時の環境負荷を小さくすることが困難となる。
よって、焼成物Ａ中のC2S含有量は、30〜94質量％が好ましく、35〜85質量％がより好ましく、40〜80質量％が特に好ましい。
The calcined product A used in the present invention contains C 2 S in addition to the above C 11 A 7 CaF 2 , C 4 AF, C 3 S, and free lime.
When the C 2 S content in the fired product A decreases, it becomes difficult to obtain flow characteristics and hardening characteristics equivalent to those of ordinary Portland cement. On the other hand, when the C 2 S content in the fired product A is increased, the C 11 A 7 CaF 2 content and the like are relatively decreased, so that the initial strength of the cement is lowered. In addition, since it is difficult to use industrial waste as a raw material for the fired product, it is difficult to reduce the environmental load during production.
Therefore, the C 2 S content in the fired product A is preferably 30 to 94% by mass, more preferably 35 to 85% by mass, and particularly preferably 40 to 80% by mass.
本発明において、焼成物Ａの鉱物組成は、例えば、粉末Ｘ線回折に基づく検量線法や粉末Ｘ線回折に基づくプロファイルフィッティング法(リートベルト解析法等)により測定することができる。
In the present invention, the mineral composition of the fired product A can be measured by, for example, a calibration curve method based on powder X-ray diffraction or a profile fitting method (Rietveld analysis method or the like) based on powder X-ray diffraction.
本発明で使用する焼成物Ａは、産業廃棄物、一般廃棄物及び建設発生土から選ばれる１種以上を原料として使用することができる。産業廃棄物としては、例えば、高炉スラグ；石炭灰；生コンスラッジ、下水汚泥、浄水汚泥、建設汚泥、製鉄汚泥等の各種汚泥；廃石膏ボート等の石膏廃材；ボーリング廃土、各種焼却灰、鋳物砂、ロックウール、廃ガラス、高炉２次灰、建設廃材、コンクリート廃材などが挙げられ；一般廃棄物としては、例えば下水汚泥乾粉、都市ごみ焼却灰、貝殻等が挙げられる。建設発生土としては、建設現場や工事現場等から発生する土壌や残土、さらには廃土壌等が挙げられる。
また、一般のポルトランドセメントクリンカー原料、例えば、石灰石、生石灰、消石灰等のCaO原料、珪石、粘土等のSiO2原料、粘土等のAl2O3原料、鉄滓、鉄ケーキ等のFe2O3原料も使用することができる。なお、フッ素原料としては、蛍石や下水汚泥等を使用することができる。
As the fired product A used in the present invention, one or more selected from industrial waste, general waste, and construction generated soil can be used as a raw material. Industrial waste includes, for example, blast furnace slag; coal ash; ready-made sludge, sewage sludge, purified water sludge, construction sludge, steel sludge, and other sludge; gypsum waste materials such as waste gypsum boats; boring waste soil, various incineration ash, castings Sand, rock wool, waste glass, blast furnace secondary ash, construction waste, concrete waste, and the like; examples of general waste include sewage sludge dry powder, municipal waste incineration ash, and shells. Examples of construction generated soil include soil and residual soil generated from construction sites and construction sites, and waste soil.
Also, general Portland cement clinker raw materials, for example, CaO raw materials such as limestone, quicklime and slaked lime, SiO 2 raw materials such as silica and clay, Al 2 O 3 raw materials such as clay, Fe 2 O 3 such as iron cake and iron cake Raw materials can also be used. In addition, fluorite, sewage sludge, etc. can be used as a fluorine raw material.
上記各原料を、CaO:55〜63質量％、SiO2:26〜30質量％、Al2O3:6〜13質量％、Fe2O3:1.5〜8.5質量％、F:0.004〜0.8質量％となるように混合し、好ましくは1000〜1400℃で焼成することにより、焼成物Ａが製造される。より好ましい焼成温度は1050〜1350℃であり、特に好ましい焼成温度は1100〜1300℃である。
各原料を混合する方法は、特に限定するものではなく、慣用の装置等で行えばよい。
また、焼成に使用する装置も特に限定するものではなく、例えば、ロータリーキルン、電気炉等を使用することができる。ロータリーキルンで焼成する際には、燃料代替廃棄物、例えば、廃油、廃タイヤ、廃プラスチック等を使用することができる。
Each of the above raw materials is CaO: 55 to 63% by mass, SiO 2 : 26 to 30% by mass, Al 2 O 3 : 6 to 13% by mass, Fe 2 O 3 : 1.5 to 8.5% by mass, F: 0.004 to 0.8% by mass %, And preferably fired at 1000 to 1400 ° C. to produce fired product A. A more preferred firing temperature is 1050 to 1350 ° C, and a particularly preferred firing temperature is 1100 to 1300 ° C.
The method of mixing each raw material is not particularly limited, and may be performed with a conventional apparatus or the like.
Moreover, the apparatus used for baking is not specifically limited, For example, a rotary kiln, an electric furnace, etc. can be used. When firing in a rotary kiln, alternative fuel wastes such as waste oil, waste tires, waste plastics, etc. can be used.
本発明の水硬性組成物は、上記焼成物Ａの粉砕物と石膏を含むものである。石膏としては、２水石膏、α型又はβ型半水石膏、無水石膏等を単独又は２種以上組み合わせてを使用することができる。
本発明においては、水硬性組成物中の２水石膏及び半水石膏の合量に対する半水石膏の割合はSO3換算で30質量％以上であることが好ましい。２水石膏及び半水石膏の合量に対する半水石膏の割合がSO3換算で30質量％未満では、水硬性組成物の水和熱が大きくなり、また凝結時間が極端に短くなる、流動性が低下する、硬化体の寸法安定性が低下する等の理由から好ましくない。２水石膏及び半水石膏の合量に対する半水石膏の割合は、水和熱低減や流動性向上の観点から、40〜90質量％が好ましい。
なお、２水石膏・半水石膏の定量は、特開平6-242035号公報に記載される試料容器を使用した熱分析（熱重量測定等）により行うことができる。
The hydraulic composition of the present invention contains the pulverized product of the fired product A and gypsum. As the gypsum, dihydrate gypsum, α-type or β-type hemihydrate gypsum, anhydrous gypsum and the like can be used alone or in combination of two or more.
In the present invention, the ratio of hemihydrate gypsum to the total amount of dihydrate gypsum and hemihydrate gypsum in the hydraulic composition is preferably 30% by mass or more in terms of SO 3 . If the ratio of hemihydrate gypsum to the total amount of dihydrate gypsum and hemihydrate gypsum is less than 30% by mass in terms of SO 3 , the heat of hydration of the hydraulic composition will increase and the setting time will become extremely short. This is not preferable because of a decrease in the dimensional stability of the cured product. The ratio of hemihydrate gypsum to the total amount of 2-hydrate gypsum and hemihydrate gypsum is preferably 40 to 90 mass% from the viewpoint of reducing heat of hydration and improving fluidity.
The quantification of dihydrate gypsum and hemihydrate gypsum can be performed by thermal analysis (thermogravimetric measurement or the like) using a sample container described in JP-A-62-242035.
本発明の水硬性組成物は、高炉スラグ粉末、フライアッシュ、石灰石粉末、珪石粉末から選ばれる１種以上の無機粉末を含むことができる。これらの無機粉末を含むことにより、水和熱の低減や流動性の向上、耐久性の向上等を図ることができる。
水硬性組成物中の無機粉末量は、
(1)高炉スラグ粉末であれば、流動性や強度発現性、さらにはアルカリ骨材反応の抑制効果、耐硫酸塩性等から、60質量％以下であることが好ましく、20〜55質量％であることがより好ましく、30〜50質量％であることが特に好ましい。
(2)フライアッシュ、石灰石粉末や珪石粉末であれば、30質量％以下であることが好ましく、2〜25質量％であることがより好ましく、3〜20質量％であることが特に好ましい。
なお、無機粉末としては、水和熱や、流動性、強度発現性や耐久性等の観点から、ブレーン比表面積2500〜6000cm2/gのものを使用するのが好ましく、3000〜5000cm2/gのものを使用するのがより好ましい。
The hydraulic composition of the present invention can contain one or more inorganic powders selected from blast furnace slag powder, fly ash, limestone powder, and quartzite powder. By including these inorganic powders, it is possible to reduce heat of hydration, improve fluidity, improve durability, and the like.
The amount of inorganic powder in the hydraulic composition is
(1) If it is a blast furnace slag powder, it is preferable that it is 60 mass% or less from fluidity | liquidity and intensity | strength development property, the inhibitory effect of alkali-aggregate reaction, sulfate resistance, etc., and 20-55 mass% More preferably, it is particularly preferably 30 to 50% by mass.
(2) If it is fly ash, limestone powder or silica powder, it is preferably 30% by mass or less, more preferably 2 to 25% by mass, and particularly preferably 3 to 20% by mass.
In addition, as the inorganic powder, it is preferable to use a brane specific surface area of 2500 to 6000 cm 2 / g from the viewpoint of heat of hydration, fluidity, strength development and durability, 3000 to 5000 cm 2 / g. It is more preferable to use those.
本発明の水硬性組成物は、塩素含有物を含むことができる。塩素含有物を含むことにより、初期強度発現性の向上等を図ることができる。
塩素含有物としては、塩素を0.5質量％以上含有するものが好ましい。具体的な塩素含有物としては、塩化カルシウムや塩化カリウム等の塩化物、JIS R 5214に規定される速硬エコセメントや速硬エコセメントクリンカーの粉砕物、塩素バイパスダストや塩素バイパスダストの水洗物等が挙げられる。本発明においては、廃棄物の有効利用の促進や初期強度発現性等の観点から、塩素含有物として、速硬エコセメントや速硬エコセメントクリンカーの粉砕物、塩素バイパスダストや塩素バイパスダストの水洗物を使用することが好ましく、特に塩素バイパスダストや塩素バイパスダストの水洗物を使用することが好ましい。
これらの塩素含有物のブレーン比表面積は、流動性や強度発現性等から、2000〜10000cm2/gであることが好ましく、2500〜7000cm2/gであることがより好ましい。
塩素含有物の添加量は、水硬性組成物中の塩素量が350mg/kg以下、好ましくは50〜330mg/kg、より好ましくは100〜300mg/kgとなる量とすることが好ましい。水硬性組成物中の塩素量が350mg/kgを越えると、流動性が低下する。また、鉄筋コンクリートに使用した場合、鉄筋が発錆する可能性が高くなるので好ましくない。なお、水硬性組成物中の塩素量が少なくなると、初期強度発現性が低下することがあるので、水硬性組成物中の塩素量が50mg/kg以上であることが好ましい。
The hydraulic composition of the present invention can contain a chlorine-containing material. Inclusion of the chlorine-containing material can improve the initial strength development.
As the chlorine-containing material, those containing 0.5% by mass or more of chlorine are preferable. Specific chlorine-containing materials include chlorides such as calcium chloride and potassium chloride, pulverized products of fast-hardening ecocement and fast-hardening ecocement clinker specified in JIS R 5214, and water-washed products of chlorine bypass dust and chlorine bypass dust. Etc. In the present invention, from the viewpoint of promoting the effective use of waste and initial strength development, etc., as a chlorine-containing material, pulverized fast-hardened ecocement or fast-hardened ecocement clinker, chlorine bypass dust and chlorine bypass dust are washed with water. It is preferable to use a thing, and it is especially preferable to use the water washing thing of chlorine bypass dust or chlorine bypass dust.
The chlorine specific surface area of these chlorine-containing materials is preferably 2000 to 10,000 cm 2 / g, more preferably 2500 to 7000 cm 2 / g, from the viewpoint of fluidity and strength development.
The amount of chlorine-containing material added is preferably such that the amount of chlorine in the hydraulic composition is 350 mg / kg or less, preferably 50 to 330 mg / kg, more preferably 100 to 300 mg / kg. When the amount of chlorine in the hydraulic composition exceeds 350 mg / kg, the fluidity decreases. Moreover, when it uses for a reinforced concrete, since possibility that a reinforcing bar rusts will become high, it is not preferable. In addition, when the amount of chlorine in the hydraulic composition decreases, the initial strength development property may be lowered. Therefore, the amount of chlorine in the hydraulic composition is preferably 50 mg / kg or more.
本発明の水硬性組成物は、C2S及び2CaO・Al2O3・SiO2(以降、C2ASと称す)を必須成分とし、C2S100質量部に対して、C2AS＋C4AFを10〜100質量部含有し、かつ、3CaO・Al2O3(以降、C3Aと称す)の含有量が20質量部以下である焼成物Ｂの粉砕物を含有することができる。このような焼成物Ｂの粉砕物を含有することにより、水和熱の低減や流動性の向上等を図ることができる。また、このような焼成物Ｂは、産業廃棄物等を原料とするものであるので、廃棄物の有効利用を促進することができる。
上記焼成物Ｂは、C2S及びC2ASを必須成分とするもので、C2S100質量部に対して、C2ASを10〜100質量部、好ましくは20〜90質量部含有するものである。C2AS含有量が10質量部未満では、流動性が低下する。また、焼成時に焼成温度を上げてもフリーライム量が低下しにくく、焼成が困難になり、また、生成するC2Sも水和活性のないγ型C2Sである可能性が高くなり、強度発現性を大きく低下させることがある。一方、C2AS含有量が100質量部を超えると、強度発現性が低下することがある。
The hydraulic composition of the present invention, C 2 S and 2CaO · Al 2 O 3 · SiO 2 ( hereinafter, referred to as C 2 AS) and the essential components, with respect to C 2 S100 parts by, C 2 AS + C 4 AF 10 to 100 parts by mass, and a pulverized product of the calcined product B having a content of 3CaO · Al 2 O 3 (hereinafter referred to as C 3 A) of 20 parts by mass or less can be contained. By containing such a pulverized product of fired product B, it is possible to reduce heat of hydration and improve fluidity. Moreover, since such a baked product B is made from industrial waste or the like as a raw material, the effective use of waste can be promoted.
The calcined product B is for an essential component C 2 S and C 2 AS, with respect to C 2 S100 parts by 10 to 100 parts by weight of C 2 AS, which preferably contain 20 to 90 parts by weight It is. When the C 2 AS content is less than 10 parts by mass, the fluidity decreases. Also, even if the firing temperature is raised during firing, the amount of free lime is unlikely to decrease, making firing difficult, and the possibility that C 2 S produced is also γ-type C 2 S without hydration activity increases. Strength development may be greatly reduced. On the other hand, when the C 2 AS content exceeds 100 parts by mass, strength development may be reduced.
また、焼成物Ｂは、C2S100質量部に対するC3Aの含有量が20質量部以下、好ましくは10質量部以下のものである。C3Aの含有量が20質量部を超えると、水和熱が大きくなり、流動性も悪くなる。 The calcined product B has a C 3 A content of 20 parts by mass or less, preferably 10 parts by mass or less, relative to 100 parts by mass of C 2 S. When the content of C 3 A exceeds 20 parts by mass, the heat of hydration increases and the fluidity also deteriorates.
さらに、焼成物Ｂは、P2O5を0.2〜8.0質量％（より好ましくは0.5〜6.0質量％）、アルカリ（Na2O+K2O）を0.4〜4.0質量％（より好ましくは0.5〜3.5質量％）含有することが好ましい。P2O5やアルカリをこの範囲で含有する場合、C2Sを活性化させるため、C3Aなどのカルシウムアルミネートがない場合でも、強度発現性が良好になる。そして、カルシウムアルミネートが少なくなるほど、流動性も良好でかつ水和熱も低くなる。
なお、焼成物Ｂ中のフリーライム量は、水和熱や流動性、強度発現性等から、1.5質量％以下、特に1.0質量％以下であるのが好ましい。
Furthermore, calcined product B is the P 2 O 5 0.2~8.0 wt% (more preferably 0.5 to 6.0 wt%), an alkali (Na 2 O + K 2 O ) 0.4~4.0 wt% (more preferably 0.5 to (3.5% by mass) is preferable. When P 2 O 5 and an alkali are contained in this range, C 2 S is activated, so that the strength development is good even in the absence of calcium aluminate such as C 3 A. And the less calcium aluminate, the better the fluidity and the lower the heat of hydration.
The amount of free lime in the fired product B is preferably 1.5% by mass or less, particularly 1.0% by mass or less, from the viewpoint of heat of hydration, fluidity, strength development, and the like.
このような焼成物Ｂは、産業廃棄物、一般廃棄物及び建設発生土から選ばれる１種以上を原料とし、これを焼成することにより製造することができる。
また、一般のポルトランドセメントクリンカー原料、例えば、石灰石、生石灰、消石灰等のCaO原料、珪石、粘土等のSiO2原料、粘土等のAl2O3原料、鉄滓、鉄ケーキ等のFe2O3原料も使用することができる。
Such a fired product B can be produced by firing one or more selected from industrial waste, general waste, and construction generated soil as a raw material.
Also, general Portland cement clinker raw materials, for example, CaO raw materials such as limestone, quicklime and slaked lime, SiO 2 raw materials such as silica and clay, Al 2 O 3 raw materials such as clay, Fe 2 O 3 such as iron cake and iron cake Raw materials can also be used.
なお、焼成物Ｂの原料組成によっては、特に、前記産業廃棄物、一般廃棄物及び建設発生土から選ばれる１種以上（以下、廃棄物原料と称する）を原料として用いた場合、C4AFが生成することがあるが、本発明においては、焼成物ＢのC2ASの一部、好ましくはC2AS質量の70質量％以下がC4AFで置換されても良い。C4AFがこの範囲を超えて置換されると、焼成の温度範囲が狭くなり、製造の管理が難しくなる。 Depending on the raw material composition of the baked product B, in particular, when one or more selected from the industrial waste, general waste and construction generated soil (hereinafter referred to as waste raw material) is used as the raw material, C 4 AF In the present invention, a part of C 2 AS of the baked product B, preferably 70% by mass or less of the C 2 AS mass may be substituted with C 4 AF. If C 4 AF is substituted beyond this range, the temperature range for firing becomes narrow, and manufacturing control becomes difficult.
焼成物Ｂの鉱物組成は、使用原料中のCaO、SiO2、Al2O3、Fe2O3の各含有量（質量％）から、次式により求めることができる。
C4AF＝3.04×Fe2O3
C3A ＝1.61×CaO−3.00×SiO2−2.26×Fe2O3
C2AS＝−1.63×CaO＋3.04×SiO2＋2.69×Al2O3＋0.57×Fe2O3
C2S ＝1.02×CaO＋0.95×SiO2−1.69×Al2O3−0.36×Fe2O3
The mineral composition of the calcined product B can be obtained from the contents (mass%) of CaO, SiO 2 , Al 2 O 3 and Fe 2 O 3 in the raw materials used by the following formula.
C 4 AF = 3.04 × Fe 2 O 3
C 3 A = 1.61 × CaO−3.00 × SiO 2 −2.26 × Fe 2 O 3
C 2 AS = -1.63 x CaO + 3.04 x SiO 2 + 2.69 x Al 2 O 3 + 0.57 x Fe 2 O 3
C 2 S = 1.02 × CaO + 0.95 × SiO 2 −1.69 × Al 2 O 3 −0.36 × Fe 2 O 3
焼成物Ｂの焼成温度は、1000〜1350℃、特に1200〜1330℃であるのが、焼成工程の熔融相の状態が良好であるので好ましい。
用いる装置は特に限定されず、例えばロータリーキルン等を用いることができる。また、ロータリーキルンで焼成する際には、燃料代替廃棄物、例えば廃油、廃タイヤ、廃プラスチック等を使用することができる。
このような焼成により、C2ASが生成し、上記組成の焼成物Ｂを得ることができる。
The firing temperature of the fired product B is preferably 1000 to 1350 ° C., particularly 1200 to 1330 ° C., because the molten phase in the firing process is in good condition.
The apparatus to be used is not specifically limited, For example, a rotary kiln etc. can be used. Moreover, when baking with a rotary kiln, a fuel alternative waste, for example, waste oil, a waste tire, a waste plastic, etc. can be used.
By such firing, C 2 AS is produced, and a fired product B having the above composition can be obtained.
焼成物Ｂの粉砕物の配合量は、水和熱や、流動性、耐久性や強度発現性等の観点から、水硬性組成物中の20質量％以下、特に1〜15質量％であることが好ましい。
焼成物Ｂの粉砕物は、ブレーン比表面積が2500〜5000cm2/gであるのが、水和熱や、流動性、強度発現性等の観点から好ましい。なお、粉砕方法は特に制限されず、例えばボールミル等を用い、通常の方法で粉砕することができる。
The blending amount of the pulverized product of the fired product B is 20% by mass or less, particularly 1 to 15% by mass in the hydraulic composition from the viewpoints of heat of hydration, fluidity, durability and strength development. Is preferred.
The pulverized product of the fired product B preferably has a Blaine specific surface area of 2500 to 5000 cm 2 / g from the viewpoints of heat of hydration, fluidity, strength development, and the like. The pulverization method is not particularly limited, and can be pulverized by an ordinary method using, for example, a ball mill.
なお、本発明において、水硬性組成物中の石膏量は、流動性や強度発現性等から、SO3換算で1〜5質量％であることが好ましく、1.5〜3.5質量％であることがより好ましい。 In the present invention, the amount of gypsum in the hydraulic composition is preferably 1 to 5% by mass, more preferably 1.5 to 3.5% by mass in terms of SO 3 in terms of fluidity and strength development. preferable.
本発明の水硬性組成物の製造方法は特に制限されず、例えば、焼成物Ａの粉砕物と石膏からなる水硬性組成物の製造においては、焼成物Ａと石膏を同時粉砕しても良いし、焼成物Ａの粉砕物と石膏を混合しても良い。塩素含有物、高炉スラグ粉末等の無機粉末や焼成物Ｂの粉砕物を含む水硬性組成物では、塩素含有物粉末、高炉スラグ粉末等の無機粉末や焼成物Ｂの粉砕物を焼成物Ａの粉砕物等に混合しても良いし、焼成物Ａと石膏と高炉スラグ粉末等の無機粉末や焼成物Ｂを同時粉砕しても良い。
なお、本発明において、得られる水硬性組成物は、モルタルやコンクリートのブリーディングの低減や、流動性、強度発現性の観点から、ブレーン比表面積が2500〜4500cm2/gであることが好ましく、3000〜3500cm2/gであることがより好ましい。
The method for producing the hydraulic composition of the present invention is not particularly limited. For example, in the production of a hydraulic composition comprising a pulverized product of calcined product A and gypsum, the calcined product A and gypsum may be pulverized simultaneously. The pulverized product of the fired product A and gypsum may be mixed. In the hydraulic composition containing inorganic powder such as chlorine-containing material, blast furnace slag powder, or pulverized product of baked product B, the pulverized product of inorganic powder such as chlorine-containing material, blast furnace slag powder, or baked product B The pulverized product or the like may be mixed, or the calcined product A, gypsum, blast furnace slag powder or other inorganic powder or the calcined product B may be pulverized simultaneously.
In the present invention, the obtained hydraulic composition preferably has a brane specific surface area of 2500 to 4500 cm 2 / g from the viewpoint of reducing bleeding of mortar and concrete, fluidity, and strength development. More preferably, it is ˜3500 cm 2 / g.
本発明の水硬性組成物は、ペースト、モルタル又はコンクリートの状態で使用される。 減水剤としては、リグニン系、ナフタレンスルホン酸系、メラミン系、ポリカルボン酸系の減水剤（ＡＥ減水剤、高性能減水剤、高性能ＡＥ減水剤も含む）が使用できる。
モルタル又はコンクリートの状態で使用する場合は、通常モルタル、コンクリートの製造に使用されている細骨材・粗骨材、すなわち、川砂、陸砂、砕砂等や、川砂利、山砂利、砕石等を使用することができる。また、都市ゴミ、都市ゴミ焼却灰、下水汚泥焼却灰の一種以上を溶融して製造した溶融スラグ、あるいは高炉スラグ、製鋼スラグ、銅スラグ、碍子屑、ガラスカレット、陶磁器廃材、クリンカーアッシュ、廃レンガ、コンクリート廃材等の廃棄物を細骨材・粗骨材の一部または全部に使用することができる。
なお、必要に応じて、支障のない範囲内で、空気連行剤、消泡剤等の混和剤を使用することは差し支えない。
The hydraulic composition of the present invention is used in the state of paste, mortar or concrete. As the water reducing agent, lignin-based, naphthalenesulfonic acid-based, melamine-based, and polycarboxylic acid-based water reducing agents (including AE water reducing agents, high-performance water reducing agents, and high-performance AE water reducing agents) can be used.
When used in the state of mortar or concrete, fine aggregates and coarse aggregates that are usually used in the production of mortar and concrete, that is, river sand, land sand, crushed sand, river gravel, mountain gravel, crushed stone, etc. Can be used. Also, molten slag produced by melting one or more of municipal waste, municipal waste incineration ash, and sewage sludge incineration ash, or blast furnace slag, steelmaking slag, copper slag, eggplant scrap, glass cullet, ceramic waste, clinker ash, waste brick In addition, waste such as concrete waste can be used for some or all of fine aggregate and coarse aggregate.
If necessary, an admixture such as an air entraining agent or an antifoaming agent may be used within a range that does not hinder the operation.
ペースト、モルタル又はコンクリートの混練方法は、特に限定するものではなく、例えば、(1)各材料を一括してミキサに投入して１分以上混練する方法、(2)水以外の材料をミキサに投入して空練りした後に、水を投入して１分以上混練する方法等で行うことができる。混練に用いるミキサは、特に限定するものではなく、ホバートミキサ、パンタイプミキサ、二軸ミキサ等の慣用のミキサで混練すれば良い。
ペースト、モルタル又はコンクリートの成形方法は、特に限定するものではなく、例えば、振動成形等を行えば良い。
また、養生条件も、特に限定するものではなく、例えば、気中養生、水中養生、蒸気養生等を行えば良い。
The method of kneading paste, mortar, or concrete is not particularly limited. For example, (1) a method in which each material is put into a mixer at once and kneaded for 1 minute or more, and (2) a material other than water is mixed in the mixer. After adding and kneading, water can be added and mixed for 1 minute or longer. The mixer used for kneading is not particularly limited, and may be kneaded with a conventional mixer such as a Hobart mixer, a pan type mixer, or a biaxial mixer.
The method for forming the paste, mortar or concrete is not particularly limited, and for example, vibration molding or the like may be performed.
Further, the curing conditions are not particularly limited, and for example, air curing, underwater curing, steam curing, or the like may be performed.
以下、実施例により本発明を説明する。
１．実施例１
（１）焼成物Ａの製造：
原料として、建設発生土と、一般のポルトランドセメントクリンカー原料である石灰石、珪石、鉄原料と、試薬を使用して、下記の焼成物Ａを電気炉を用いて製造した。
なお、No.2の焼成物は普通ポルトランドセメントクリンカーに相当する。
(1)焼成物Ａ；C11A7CaF2:8質量％、C2S:61質量％、C3S:9質量％、C4AF:16質量％、フリ ーライム量:1.0質量％、焼成温度:1300℃
(2)焼成物(No.2)；C3S:58質量％、C2S:21質量％、C3A:9質量％、C4AF:9質量％、フリー ライム量:1.0質量％、焼成温度:１４７０℃
なお、上記焼成物Ａの製造においては建設発生土を焼成物1ton当たり510kg使用し、No.2の焼成物(普通ポルトランドセメントクリンカー)の製造においては、建設発生土を焼成物1ton当たり300kg使用した。
Hereinafter, the present invention will be described by way of examples.
1. Example 1
(1) Production of fired product A:
The following calcined product A was manufactured using an electric furnace, using construction generated soil, limestone, silica, and iron raw materials, which are general Portland cement clinker raw materials, and reagents.
Note that No. 2 fired product corresponds to ordinary Portland cement clinker.
(1) Baked product A; C 11 A 7 CaF 2 : 8% by mass, C 2 S: 61% by mass, C 3 S: 9% by mass, C 4 AF: 16% by mass, free lime content: 1.0% by mass, Firing temperature: 1300 ° C
(2) Baked product (No. 2); C 3 S: 58% by mass, C 2 S: 21% by mass, C 3 A: 9% by mass, C 4 AF: 9% by mass, free lime content: 1.0% by mass , Firing temperature: 1470 ° C
In the production of the fired product A, 510 kg of construction generated soil was used per 1 ton of fired product, and in the manufacture of No. 2 fired product (ordinary Portland cement clinker), 300 kg of construction generated soil was used per 1 ton of fired product. .
上記の通り、本発明で使用する焼成物Ａは、廃棄物等を原料として大量に使用できることが分かる。また、本発明で使用する焼成物Ａは、低温で製造できることも分かる。このように、本発明で使用する焼成物Ａは、製造時の環境負荷を小さくすることができる。 As above-mentioned, it turns out that the baked product A used by this invention can be used in large quantities by using a waste etc. as a raw material. Moreover, it turns out that the baked product A used by this invention can be manufactured at low temperature. Thus, the fired product A used in the present invention can reduce the environmental load during production.
（２）水硬性組成物の製造
上記焼成物Ａに、排脱ニ水石膏（住友金属社製）及び前記排脱ニ水石膏を140℃で加熱して得た半水石膏を添加し、バッチ式ボールミルでブレーン比表面積が3250±50cm2/gとなるように同時粉砕して、水硬性組成物を製造した。
なお、該水硬性組成物中のニ水石膏量(SO3換算)は焼成物の粉砕物100質量部に対して0.8質量部であり、半水石膏量(SO3換算)は焼成物の粉砕物100質量部に対して0.8質量部である。
(2) Manufacture of hydraulic composition To the calcined product A, drained dihydrate gypsum (manufactured by Sumitomo Metals) and hemihydrate gypsum obtained by heating the drained dihydrate gypsum at 140 ° C are added, and batch A hydraulic composition was produced by simultaneous pulverization with a ball mill so that the specific surface area of the brain was 3250 ± 50 cm 2 / g.
The amount of dihydrate gypsum (in terms of SO 3 ) in the hydraulic composition is 0.8 parts by mass with respect to 100 parts by mass of the pulverized product of the baked product, and the amount of hemihydrate gypsum (in terms of SO 3 ) is pulverized of the baked product. 0.8 parts by mass with respect to 100 parts by mass of the product.
（３）評価
上記水硬性組成物について、以下の方法でフロー値と圧縮強度を測定した。
(A)フロー値
上記水硬性組成物および細骨材（JIS R 5201に定める標準砂）、水およびポリカルボン酸系高性能ＡＥ減水剤(ＢＡＳＦポゾリス社製「レオビルドSP8N」)を使用して、モルタルを調製し、混練直後のモルタルフロー値を測定した。モルタルの配合は、水／水硬性組成物(質量)比＝0.35、細骨材／水硬性組成物(質量)比＝2.0、減水剤／水硬性組成物(質量)比＝0.0065とした。混練は7分間行い、混練直後のモルタルをフローコーン（上面直径5cm、下面直径10cm、高さ15cm）に投入し、フローコーンを上方へ取り去った際のモルタルの広がりを測定し、フロー値とした。
(B)圧縮強度
モルタルの圧縮強度（３日、７日及び28日）を「JIS R 5201(セメントの物理試験方法)」に準じて測定した。なお、モルタルの配合は、水／水硬性組成物(質量)比＝0.5、細骨材／水硬性組成物(質量)比＝3.0とした。
その結果、フロー値は253(mm)、３日の圧縮強度は33.1(N/mm2)、７日の圧縮強度は45.1(N/mm2)、28日の圧縮強度は61.2(N/mm2)であった。
(3) Evaluation About the said hydraulic composition, the flow value and the compressive strength were measured with the following method.
(A) Flow value Using the above hydraulic composition and fine aggregate (standard sand as defined in JIS R 5201), water and polycarboxylic acid-based high-performance AE water reducing agent (BASF Pozzolith "Reobuild SP8N"), Mortar was prepared and the mortar flow value immediately after kneading was measured. The mortar was formulated such that the water / hydraulic composition (mass) ratio = 0.35, the fine aggregate / hydraulic composition (mass) ratio = 2.0, and the water reducing agent / hydraulic composition (mass) ratio = 0.0005. Kneading was carried out for 7 minutes. The mortar immediately after kneading was put into a flow cone (top diameter 5 cm, bottom diameter 10 cm, height 15 cm), and the spread of the mortar when the flow cone was removed upward was measured to obtain a flow value. .
(B) Compressive strength Compressive strength (3 days, 7 days and 28 days) of mortar was measured according to "JIS R 5201 (Cement physical test method)". The mortar was mixed with a water / hydraulic composition (mass) ratio of 0.5 and a fine aggregate / hydraulic composition (mass) ratio of 3.0.
As a result, the flow value is 253 (mm), the compression strength for 3 days is 33.1 (N / mm 2 ), the compression strength for 7 days is 45.1 (N / mm 2 ), and the compression strength for 28 days is 61.2 (N / mm 2 ).
２．比較例１
市販普通ポルトランドセメント（C3S;59質量％、C2S;21質量％、C3A含有量;9質量％、C4AF;9質量％、f-CaO;0.5質量％、ニ水石膏量(SO3換算)は0.8質量％であり、半水石膏量(SO3換算)は0.9質量％）について、フロー値と圧縮強度を実施例１と同様にして測定した。
その結果、フロー値は261(mm)で、３日の圧縮強度は30.8(N/mm2)、７日の圧縮強度は46.1(N/mm2)、28日の圧縮強度は61.0(N/mm2)であった。
2. Comparative Example 1
Commercial ordinary Portland cement (C 3 S; 59% by mass, C 2 S; 21% by mass, C 3 A content; 9% by mass, C 4 AF; 9% by mass, f-CaO; 0.5% by mass, dihydrate gypsum The flow value and compressive strength were measured in the same manner as in Example 1 with respect to the amount (SO 3 conversion) of 0.8% by mass and the hemihydrate gypsum amount (SO 3 conversion) of 0.9% by mass).
As a result, the flow value is 261 (mm), the compression strength for 3 days is 30.8 (N / mm 2 ), the compression strength for 7 days is 46.1 (N / mm 2 ), and the compression strength for 28 days is 61.0 (N / mm 2 ). mm 2 ).
上記のように、本発明の水硬性組成物は、普通ポルトランドセメントと同等の流動特性および硬化特性を有することが分かる。 As described above, it can be seen that the hydraulic composition of the present invention has flow characteristics and curing characteristics equivalent to those of ordinary Portland cement.
３．実施例２
実施例１で製造した水硬性組成物に、高炉スラグ粉末(ブレーン比表面積4000cm2/g)と、二水石膏及び半水石膏を混合して、水硬性組成物を製造した。
なお、該水硬性組成物中の高炉スラグ粉末量は40質量％、ニ水石膏量(SO3換算)は1.0質量％で、半水石膏量(SO3換算)は1.0質量％である。
該水硬性組成物について、フロー値と圧縮強度を実施例１と同様にして測定した。
その結果、フロー値は305(mm)で、３日の圧縮強度は21.8(N/mm2)、７日の圧縮強度は33.8(N/mm2)、28日の圧縮強度は58.2(N/mm2)であった。
3. Example 2
The hydraulic composition prepared in Example 1 was mixed with blast furnace slag powder (Brain specific surface area 4000 cm 2 / g), dihydrate gypsum and hemihydrate gypsum to produce a hydraulic composition.
The amount of blast furnace slag powder in the hydraulic composition is 40% by mass, the amount of dihydrate gypsum (in terms of SO 3 ) is 1.0% by mass, and the amount of hemihydrate gypsum (in terms of SO 3 ) is 1.0% by mass.
With respect to the hydraulic composition, the flow value and the compressive strength were measured in the same manner as in Example 1.
As a result, the flow value is 305 (mm), the compression strength for 3 days is 21.8 (N / mm 2 ), the compression strength for 7 days is 33.8 (N / mm 2 ), and the compression strength for 28 days is 58.2 (N / mm 2 ). mm 2 ).
４．比較例２
市販高炉セメントＢ種(高炉スラグ粉末含有量は40質量％)について、フロー値と圧縮強度を実施例１と同様にして測定した。
その結果、フロー値は310(mm)で、３日の圧縮強度は20.5(N/mm2)、７日の圧縮強度は34.0(N/mm2)、28日の圧縮強度は58.0(N/mm2)であった。
4). Comparative Example 2
The flow value and compressive strength were measured in the same manner as in Example 1 for commercially available blast furnace cement type B (content of blast furnace slag powder was 40% by mass).
As a result, the flow value is 310 (mm), the compression strength for 3 days is 20.5 (N / mm 2 ), the compression strength for 7 days is 34.0 (N / mm 2 ), and the compression strength for 28 days is 58.0 (N / mm 2 ). mm 2 ).
実施例２と比較例２から、本発明の水硬性組成物は、高炉セメントと同等の流動特性および硬化特性を有することが分かる。 From Example 2 and Comparative Example 2, it can be seen that the hydraulic composition of the present invention has flow characteristics and hardening characteristics equivalent to those of blast furnace cement.
５．実施例３
実施例１で製造した水硬性組成物に、石灰石粉末(ブレーン比表面積4000cm2/g)と、二水石膏及び半水石膏を混合して、水硬性組成物を製造した。
なお、該水硬性組成物中の石灰石粉末量は10質量％、ニ水石膏量(SO3換算)は1.0質量％で、半水石膏量(SO3換算)は1.0質量％である。
該水硬性組成物について、フロー値と圧縮強度を実施例１と同様にして測定した。
その結果、フロー値は263(mm)で、３日の圧縮強度は29.0(N/mm2)、７日の圧縮強度は44.3(N/mm2)、28日の圧縮強度は56.6(N/mm2)であった。
5. Example 3
The hydraulic composition produced in Example 1 was mixed with limestone powder (Brain specific surface area 4000 cm 2 / g), dihydrate gypsum and hemihydrate gypsum to produce a hydraulic composition.
The amount of limestone powder in the hydraulic composition is 10% by mass, the amount of dihydrate gypsum (in terms of SO 3 ) is 1.0% by mass, and the amount of hemihydrate gypsum (in terms of SO 3 ) is 1.0% by mass.
With respect to the hydraulic composition, the flow value and the compressive strength were measured in the same manner as in Example 1.
As a result, the flow value is 263 (mm), the compressive strength of 3 days 29.0 (N / mm 2), the compressive strength of 7 days 44.3 (N / mm 2), compressive strength of 28 days 56.6 (N / mm 2 ).
６．比較例３
比較例１で使用した市販普通ポルトランドセメントに、石灰石粉末(ブレーン比表面積4000cm2/g)と、二水石膏及び半水石膏を混合して、石灰石粉末混合セメントを製造した。
なお、該石灰石粉末混合セメント中の石灰石粉末量は10質量％、ニ水石膏量(SO3換算)は1.0質量％で、半水石膏量(SO3換算)は1.0質量％である。
該石灰石粉末混合セメントについて、フロー値と圧縮強度を実施例１と同様にして測定した。
その結果、フロー値は271(mm)で、３日の圧縮強度は28.2(N/mm2)、７日の圧縮強度は43.5(N/mm2)、28日の圧縮強度は56.2(N/mm2)であった。
6). Comparative Example 3
Limestone powder (Brain specific surface area 4000 cm 2 / g), dihydrate gypsum and hemihydrate gypsum were mixed with the commercial ordinary Portland cement used in Comparative Example 1 to produce a limestone powder mixed cement.
The amount of limestone powder in the limestone powder mixed cement is 10% by mass, the amount of dihydrate gypsum (in terms of SO 3 ) is 1.0% by mass, and the amount of hemihydrate gypsum (in terms of SO 3 ) is 1.0% by mass.
About this limestone powder mixed cement, the flow value and the compressive strength were measured in the same manner as in Example 1.
As a result, the flow value is 271 (mm), the compression strength for 3 days is 28.2 (N / mm 2 ), the compression strength for 7 days is 43.5 (N / mm 2 ), and the compression strength for 28 days is 56.2 (N / mm 2 ). mm 2 ).
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