JP6853438B2 - Method for Producing Highly Active Copper Slag Fine Powder, Highly Active Copper Slag Fine Powder and Cement Composition - Google Patents
Method for Producing Highly Active Copper Slag Fine Powder, Highly Active Copper Slag Fine Powder and Cement Composition Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 85
- 229910052802 copper Inorganic materials 0.000 title claims description 85
- 239000010949 copper Substances 0.000 title claims description 85
- 239000002893 slag Substances 0.000 title claims description 82
- 239000004568 cement Substances 0.000 title claims description 43
- 239000000203 mixture Substances 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000843 powder Substances 0.000 claims description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 55
- 210000004556 brain Anatomy 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 22
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000000292 calcium oxide Substances 0.000 claims description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 7
- 230000000694 effects Effects 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- -1 ferrous compound Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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- 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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Description
本発明は、高活性銅スラグ微粉末の製造方法、高活性銅スラグ微粉末およびセメント組成物に関する。 The present invention relates to a method for producing highly active copper slag fine powder, a highly active copper slag fine powder, and a cement composition.
銅スラグは銅精錬所において銅地金を精錬する際に副産されるガラス質物質であり、一般に、酸化鉄、二酸化けい素、酸化カルシウム、酸化アルミニウムなどを含む金属酸化物である。銅スラグは、酸化鉄を多く含むためセメント製造の際の鉄原料をして活用されている。また、銅スラグは比較的密度が高く、また化学的に安定であることから、砂粒状にしてモルタルやコンクリートの細骨材として利用されている。さらには、ケーソンの中詰材や防波堤のマウンドを構築する材料としても活用されている。ただし、その一部は産業廃棄物として処分されているのが現状である。
また、セメント業界では低炭素社会の実現のために、セメントクリンカー焼成の際に排出されるＣＯ２を低減することが課題となっており、その対策のひとつとして、セメントの一部を混合材で置き換えることが検討されている。
Copper slag is a vitreous substance produced as a by-product when refining copper base metal in a copper smelter, and is generally a metal oxide containing iron oxide, silica dioxide, calcium oxide, aluminum oxide and the like. Since copper slag contains a large amount of iron oxide, it is used as an iron raw material in cement production. Moreover, since copper slag has a relatively high density and is chemically stable, it is used as a fine aggregate for mortar and concrete by making it into sand granules. It is also used as a caisson filling material and as a material for building breakwater mounds. However, the current situation is that some of them are disposed of as industrial waste.
In addition, in the cement industry, in order to realize a low-carbon society, it is an issue to reduce CO 2 emitted during firing of cement clinker, and as one of the countermeasures, a part of cement is mixed with a mixed material. It is being considered to replace it.
特許文献１には、コンクリートの細骨材として、銅スラグと粗粒率２．７５未満の砂とから構成され、細骨材全体に対する前記砂の比率を、体積比で４３％以上としたコンクリートが記載されている。 Patent Document 1 describes concrete as a fine aggregate of concrete, which is composed of copper slag and sand having a coarse grain ratio of less than 2.75, and the ratio of the sand to the entire fine aggregate is 43% or more in terms of volume. Is described.
また、特許文献２には、土壌を固化して六価クロムの溶出を防止するためのセメント系固化材として、ポルトランドセメントおよび石膏の水硬性成分に対して、第一鉄化合物または高炉スラグ微粉末の一種または二種と、銅スラグ微粉末とを配合したセメント系固化材が記載されている。この特許文献２には、銅スラグ微粉末の比表面積が４０００ｃｍ２／ｇ以下では固化処理後の圧縮強度が十分に向上せず、六価クロムの溶出量をやや抑制できない傾向があるとされている。 Further, in Patent Document 2, as a cement-based solidifying material for solidifying soil and preventing the elution of hexavalent chromium, a ferrous compound or a blast furnace slag fine powder is used with respect to the water-hardening component of Portland cement and gypsum. A cement-based solidifying material containing one or two of the above and fine copper slag powder is described. According to Patent Document 2, when the specific surface area of the copper slag fine powder is 4000 cm 2 / g or less, the compressive strength after the solidification treatment is not sufficiently improved, and the elution amount of hexavalent chromium tends to be slightly suppressed. There is.
銅スラグは銅精錬所において大量に副生する。このため、大量に発生した銅スラグについて、例えば、その活性を高めて、セメント用混合材やコンクリート用混合材として利用できれば好ましい。
本発明は、前述した事情に鑑みてなされたものであって、銅精錬所において副生した銅スラグを用いて、セメント用混合材として用いることができる高活性な銅スラグとして改質できる高活性銅スラグ微粉末の製造方法、セメント用混合材として有用な高活性銅スラグ微粉末およびこれを含むセメント組成物を提供することを目的とする。
Copper slag is produced in large quantities in copper refineries. Therefore, it is preferable that a large amount of generated copper slag can be used as, for example, a mixed material for cement or a mixed material for concrete by increasing its activity.
The present invention has been made in view of the above circumstances, and is highly active and can be modified as a highly active copper slag that can be used as a cement mixture by using copper slag produced as a by-product in a copper smelting plant. It is an object of the present invention to provide a method for producing copper slag fine powder, a highly active copper slag fine powder useful as a mixing material for cement, and a cement composition containing the same.
上記の課題を解決するために、本発明者は鋭意研究を重ねた結果、酸化鉄の含有量が３５質量％以上５５質量％以下の範囲、二酸化けい素の含有量が２８質量％以上３８質量％以下の範囲、酸化カルシウムの含有量が１質量％以上１０質量％以下の範囲、酸化アルミニウムの含有量が２質量％以上８質量％以下の範囲にある組成を有し、平均粒子径が１ｍｍ以上５０ｍｍ以下である塊状銅スラグを、ブレーン比表面積が２０００ｃｍ２／ｇ以上となるまで粉砕して得た銅スラグ微粉末は、溶解シリカ量が１．５ｍｍｏｌ／Ｌ以上と高くなることを見出した。そして、その銅スラグ微粉末は、セメントに対する活性度指数が高く、セメント用混合材として有用であることを確認して本発明を完成させた。 In order to solve the above problems, the present inventor has conducted extensive research, and as a result, the content of iron oxide is in the range of 35% by mass or more and 55% by mass or less, and the content of silicon dioxide is 28% by mass or more and 38% by mass. It has a composition in the range of% or less, the content of calcium oxide in the range of 1% by mass or more and 10% by mass or less, the content of aluminum oxide in the range of 2% by mass or more and 8% by mass or less, and the average particle size is 1 mm. It has been found that the copper slag fine powder obtained by pulverizing a massive copper slag having a brain specific surface area of 50 mm or more until the brain specific surface area becomes 2000 cm 2 / g or more has a high dissolved silica amount of 1.5 mmol / L or more. .. Then, the present invention was completed by confirming that the copper slag fine powder has a high activity index for cement and is useful as a mixed material for cement.
従って、本発明の高活性銅スラグ微粉末の製造方法は、酸化鉄の含有量が３５質量％以上５５質量％以下の範囲、二酸化けい素の含有量が２８質量％以上３８質量％以下の範囲、酸化カルシウムの含有量が１質量％以上１０質量％以下の範囲、酸化アルミニウムの含有量が２質量％以上８質量％以下の範囲にある組成を有し、平均粒径が１ｍｍ〜５０ｍｍの塊状銅スラグを、ブレーン比表面積が２０００ｃｍ２／ｇ以上の微粉末となるまで粉砕することを特徴とする。 Therefore, in the method for producing highly active copper slag fine powder of the present invention, the iron oxide content is in the range of 35% by mass or more and 55% by mass or less, and the silicon dioxide content is in the range of 28% by mass or more and 38% by mass or less. , The composition has a composition in which the content of calcium oxide is in the range of 1% by mass or more and 10% by mass or less, the content of aluminum oxide is in the range of 2% by mass or more and 8% by mass or less, and the average particle size is 1 mm to 50 mm. The copper slag is pulverized until it becomes a fine powder having a specific surface area of 2000 cm 2 / g or more.
ここで、本発明の高活性銅スラグ微粉末の製造方法においては、前記塊状銅スラグを、ブレーン比表面積が５０００ｃｍ２／ｇを超えないように粉砕することが好ましい。
この場合、過剰に微細な銅スラグ微粉末の生成を抑制できるので、得られる銅スラグ微粉末をセメントに混合する際の作業性が向上すると共に、過剰な粉砕動力を低減できる。
Here, in the method for producing highly active copper slag fine powder of the present invention, it is preferable to pulverize the massive copper slag so that the brain specific surface area does not exceed 5000 cm 2 / g.
In this case, since the formation of excessively fine copper slag fine powder can be suppressed, workability when mixing the obtained copper slag fine powder with cement can be improved, and excessive crushing power can be reduced.
本発明の高活性銅スラグ微粉末は、酸化鉄の含有量が３５質量％以上５５質量％以下の範囲、二酸化けい素の含有量が２８質量％以上３８質量％以下の範囲、酸化カルシウムの含有量が１質量％以上１０質量％以下の範囲、酸化アルミニウムの含有量が２質量％以上８質量％以下の範囲にある組成を有し、ブレーン比表面積が２０００ｃｍ２／ｇ以上で、溶解シリカ量が１．５ｍｍｏｌ／Ｌ以上であることを特徴とする。
このような構成の高活性銅スラグ微粉末は、ブレーン比表面積が２０００ｃｍ２／ｇ以上と微細であることに加えて、溶解シリカ量が１．５ｍｍｏｌ／Ｌ以上と高いので、セメントに混合した場合の活性度指数が高く、セメント用混合材として有用となる。
The highly active copper slag fine powder of the present invention has an iron oxide content in the range of 35% by mass or more and 55% by mass or less, a silicon dioxide content in the range of 28% by mass or more and 38% by mass or less, and a calcium oxide content. It has a composition in which the amount is in the range of 1% by mass or more and 10% by mass or less, the content of aluminum oxide is in the range of 2% by mass or more and 8% by mass or less, the specific surface area of the brain is 2000 cm 2 / g or more, and the amount of dissolved silica is. Is 1.5 mmol / L or more.
The highly active copper slag fine powder having such a structure has a fine brain specific surface area of 2000 cm 2 / g or more and a high amount of dissolved silica of 1.5 mmol / L or more. Has a high activity index and is useful as a mixture for cement.
本発明のセメント組成物は、セメントと、酸化鉄の含有量が３５質量％以上５５質量％以下の範囲、二酸化けい素の含有量が２８質量％以上３８質量％以下の範囲、酸化カルシウムの含有量が１質量％以上１０質量％以下の範囲、酸化アルミニウムの含有量が２質量％以上８質量％以下の範囲にある組成を有し、ブレーン比表面積が２０００ｃｍ２／ｇ以上で、溶解シリカ量が１．５ｍｍｏｌ／Ｌ以上である銅スラグ微粉末とを含み、銅スラグ微粉末を、前記セメント１００質量部に対して５質量部以上３５質量部以下の範囲の量にて含むことを特徴としている。
このような構成のセメント組成物は、混合材として、上記の高活性銅スラグ微粉末を含むので、圧縮強度を大幅に低下させることなく、ＣＯ２排出量を抑制できるセメントを提供することができる。
The cement composition of the present invention contains cement, an iron oxide content in the range of 35% by mass or more and 55% by mass or less, a silicon dioxide content in the range of 28% by mass or more and 38% by mass or less, and calcium oxide. It has a composition in which the amount is in the range of 1% by mass or more and 10% by mass or less, the content of aluminum oxide is in the range of 2% by mass or more and 8% by mass or less, the specific surface area of the brain is 2000 cm 2 / g or more, and the amount of dissolved silica is. The copper slag fine powder containing 1.5 mmol / L or more is contained, and the copper slag fine powder is contained in an amount in the range of 5 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the cement. There is.
Since the cement composition having such a structure contains the above-mentioned highly active copper slag fine powder as a mixed material, it is possible to provide a cement capable of suppressing CO 2 emissions without significantly reducing the compressive strength. ..
本発明によれば、銅精錬所において副生した銅スラグを用いて、セメント用混合材として用いることができる高活性な銅スラグと改質できる高活性銅スラグ微粉末の製造方法、セメント混合材用として有用な高活性銅スラグ微粉末およびこれを含むセメント組成物を提供することが可能となる。 According to the present invention, a method for producing highly active copper slag that can be used as a mixture for cement and highly active copper slag fine powder that can be modified, a cement mixture, using copper slag produced as a by-product in a copper smelter. It is possible to provide a highly active copper slag fine powder useful for use and a cement composition containing the same.
以下に、本発明の実施形態である高活性銅スラグ微粉末の製造方法、高活性銅スラグ微粉末およびセメント組成物について説明する。 Hereinafter, a method for producing highly active copper slag fine powder, a highly active copper slag fine powder, and a cement composition according to an embodiment of the present invention will be described.
本実施形態の高活性銅スラグ微粉末の製造方法において、原料となる塊状銅スラグは、銅精錬所において副生した副生物である。塊状銅スラグは、酸化鉄の含有量が３５質量％以上５５質量％以下の範囲、酸化けい素の含有量が２８質量％以上３８質量％以下の範囲、酸化カルシウムの含有量が１質量％以上１０質量％以下の範囲、酸化アルミニウムの含有量が２質量％以上８質量％以下の範囲とされている。このような組成を有する塊状銅スラグを粉砕することによって、活性な酸化ケイ素などが粉体の表面に露出するので、得られる銅スラグ微粉末の表面の活性が増加することによって、銅スラグ微粉末の反応性が向上して、活性度指数が向上すると考えられる。 In the method for producing highly active copper slag fine powder of the present embodiment, the bulk copper slag used as a raw material is a by-product produced in a copper smelter. The bulk copper slag has an iron oxide content of 35% by mass or more and 55% by mass or less, a silicon oxide content of 28% by mass or more and 38% by mass or less, and a calcium oxide content of 1% by mass or more. The range is 10% by mass or less, and the content of aluminum oxide is 2% by mass or more and 8% by mass or less. By crushing the massive copper slag having such a composition, active silicon oxide and the like are exposed on the surface of the powder. Therefore, the activity of the surface of the obtained copper slag fine powder is increased, so that the copper slag fine powder is obtained. It is considered that the reactivity of the slag is improved and the activity index is improved.
本実施形態において用いる高活性銅スラグ微粉末もの原料は、平均粒径が１ｍｍ〜５０ｍｍの塊状銅スラグとされている。この塊状物を粉砕して、微粉末とすることによって、得られ銅スラグ微粉末の表面の活性が確実に増加する。 The raw material of the highly active copper slag fine powder used in the present embodiment is a massive copper slag having an average particle size of 1 mm to 50 mm. By pulverizing this lump to make a fine powder, the activity of the surface of the obtained copper slag fine powder is surely increased.
本実施形態においては、上記の塊状銅スラグを、ブレーン比表面積が２０００ｃｍ２／ｇ以上となるように粉砕する。高活性な銅スラグ微粉末を得るためには、ブレーン比表面積を高くすることが有効である。従って、ブレーン比表面積は３０００ｃｍ２／ｇ以上が好ましく、４０００ｃｍ２／ｇ以上が特に好ましい。一方、銅スラグ微粉末が過剰に微細になると、得られる銅スラグ微粉末をセメントに混合する際の作業性が向上すると共に、過剰な粉砕動力が必要となる。従って、塊状銅スラグを、ブレーン比表面積が５０００ｃｍ２／ｇを超えないように粉砕することが好ましい。 In the present embodiment, the above-mentioned massive copper slag is pulverized so that the brain specific surface area is 2000 cm 2 / g or more. In order to obtain highly active copper slag fine powder, it is effective to increase the specific surface area of the brain. Therefore, the Blaine specific surface area is preferably not less than 3000cm 2 / g, 4000cm 2 / g or more is particularly preferable. On the other hand, when the copper slag fine powder becomes excessively fine, workability when mixing the obtained copper slag fine powder with cement is improved, and excessive crushing power is required. Therefore, it is preferable to grind the massive copper slag so that the specific surface area of the brain does not exceed 5000 cm 2 / g.
塊状銅スラグの粉砕は、乾式で行うことが好ましい。粉砕装置としては、ディスクミル、ボールミル、竪型ミル、チューブミルなど高炉スラグやセメントクリンカーなどの粉砕に利用されている公知の粉砕装置を用いることができる。また、ジョークラッシャー、ハンマークラッシャーなどの破砕機と前記粉砕装置とを併用してもよい。 The pulverization of the massive copper slag is preferably carried out by a dry method. As the crushing device, a known crushing device used for crushing blast furnace slag, cement clinker, etc. such as a disc mill, a ball mill, a vertical mill, and a tube mill can be used. Further, a crusher such as a jaw crusher or a hammer crusher may be used in combination with the crusher.
以上のような構成された本発明の高活性銅スラグ微粉末の製造方法によれば、原料として、酸化鉄の含有量が３５質量％以上５５質量％以下の範囲、二酸化けい素の含有量が２８質量％以上３８質量％以下の範囲、酸化カルシウムの含有量が１質量％以上１０質量％以下の範囲、酸化アルミニウムの含有量が２質量％以上８質量％以下の範囲にある組成を有し、平均粒子径が１ｍｍ〜５０ｍｍの塊状銅スラグを、ブレーン比表面積が２０００ｃｍ２／ｇ以上となるまで粉砕するので、微細でかつ溶解シリカ量が１．５ｍｍｏｌ／Ｌ以上と高く、活性度指数が高くセメント用混合材として有用な高活性銅スラグ微粉末を得ることができる。 According to the method for producing highly active copper slag fine powder of the present invention configured as described above, the content of iron oxide is in the range of 35% by mass or more and 55% by mass or less, and the content of cement dioxide is as a raw material. It has a composition in the range of 28% by mass or more and 38% by mass or less, the content of calcium oxide in the range of 1% by mass or more and 10% by mass or less, and the content of aluminum oxide in the range of 2% by mass or more and 8% by mass or less. Since massive copper slag having an average particle diameter of 1 mm to 50 mm is pulverized until the brain specific surface area is 2000 cm 2 / g or more, it is fine and the amount of dissolved silica is as high as 1.5 mmol / L or more, and the activity index is high. Highly active copper slag fine powder, which is highly useful as a mixture for cement, can be obtained.
また、本実施形態によれば、塊状銅スラグ粉末をブレーン比表面積が５０００ｃｍ２／ｇを超えないように粉砕することによって、過剰に微細な銅スラグ微粉末の生成を抑制でき、得られる高活性銅スラグ微粉末は、セメントに混合する際の作業性が向上すると共に、過剰な粉砕動力を低減できる。 Further, according to the present embodiment, by crushing the massive copper slag powder so that the specific surface area of the brain does not exceed 5000 cm 2 / g, the formation of excessively fine copper slag fine powder can be suppressed, and the obtained high activity can be obtained. The copper slag fine powder can improve workability when mixed with cement and reduce excessive crushing power.
また、本実施形態の高活性銅スラグ微粉末は、ブレーン比表面積が２０００ｃｍ２／ｇ以上で、溶解シリカ量が１．５ｍｍｏｌ／Ｌ以上とされている。本実施形態の高活性銅スラグ微粉末によれば、ブレーン比表面積が２０００ｃｍ２／ｇ以上と微細であることに加えて、溶解シリカ量が１．５ｍｍｏｌ／Ｌ以上と高いので、セメントに混合した場合、活性度指数が高く、セメント用混合材として有用となる。ブレーン比表面積は３０００ｃｍ２／ｇ以上が好ましく、４０００ｃｍ２／ｇ以上が特に好ましい。一方、ブレーン比表面積が大きくなりすぎると、セメントに混合する際の作業性が向上するおそれがある。従って、ブレーン比表面積は５０００ｃｍ２／ｇを超えないことが好ましい。 Further, the highly active copper slag fine powder of the present embodiment has a brain specific surface area of 2000 cm 2 / g or more and a dissolved silica amount of 1.5 mmol / L or more. According to the highly active copper slag fine powder of the present embodiment, the specific surface area of the brain is as fine as 2000 cm 2 / g or more, and the amount of dissolved silica is as high as 1.5 mmol / L or more, so that it is mixed with cement. In this case, the activity index is high and it is useful as a mixed material for cement. Blaine specific surface area is preferably 3000 cm 2 / g or more, 4000 cm 2 / g or more is particularly preferable. On the other hand, if the specific surface area of the brain becomes too large, the workability when mixed with cement may be improved. Therefore, it is preferable that the brain specific surface area does not exceed 5000 cm 2 / g.
本実施形態のセメント組成物は、セメントと、ブレーン比表面積が２０００ｃｍ２／ｇ以上で、溶解シリカ量が１．５ｍｍｏｌ／Ｌ以上である銅スラグ微粉末とを含み、銅スラグ微粉末を、セメント１００質量部に対して５質量部以上３５質量部以下の範囲の量にて含む。本実施形態のセメント組成物によれば、混合材として、上記の高活性銅スラグ微粉末を含むので、圧縮強度を大幅に低下させることがないセメント組成物を提供することができる。 The cement composition of the present embodiment contains cement and copper slag fine powder having a brain specific surface area of 2000 cm 2 / g or more and a dissolved silica amount of 1.5 mmol / L or more, and the copper slag fine powder is cemented. It is contained in an amount in the range of 5 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass. According to the cement composition of the present embodiment, since the above-mentioned highly active copper slag fine powder is contained as a mixing material, it is possible to provide a cement composition that does not significantly reduce the compressive strength.
以下に、本発明を、実施例により説明する。 Hereinafter, the present invention will be described with reference to Examples.
［本発明例１〜４］
銅精錬所において副生した下記の組成を有する塊状銅スラグを用意した。塊状銅スラグの平均粒径は、２４ｍｍ（粒径の範囲は２〜４０ｍｍ）であった。
Ｆｅ２Ｏ３ ：５１．２５質量％
ＳｉＯ２ ：３４．７２質量％
ＣａＯ ：５．４３質量％
Ａｌ２Ｏ３ ：５．４８質量％
ＭｇＯ ：０．７３質量％
ＳＯ３ ：０．１１質量％
Ｎａ２Ｏ ：１．２５質量％
Ｋ２Ｏ ：０．８４質量％
ＴｉＯ２ ：０．５０質量％
ＭｎＯ ：０．１６質量％
Ｐ２Ｏ５ ：０．１８質量％
[Examples 1 to 4 of the present invention]
A massive copper slag having the following composition produced as a by-product in a copper smelter was prepared. The average particle size of the massive copper slag was 24 mm (the particle size range was 2 to 40 mm).
Fe 2 O 3 : 51.25% by mass
SiO 2 : 34.72% by mass
CaO: 5.43% by mass
Al 2 O 3 : 5.48% by mass
MgO: 0.73% by mass
SO 3 : 0.11% by mass
Na 2 O: 1.25% by mass
K 2 O: 0.84% by mass
TiO 2 : 0.50% by mass
MnO: 0.16% by mass
P 2 O 5 : 0.18% by mass
［本発明例１〜４］
上記の塊状銅スラグを、ディスクミルを用いて、ブレーン値が約２０００ｃｍ２／ｇ（本発明例１）、約３０００ｃｍ２／ｇ（本発明例２）、約４０００ｃｍ２／ｇ（本発明例３）、約５０００ｃｍ２／ｇ（本発明例４）になるように粉砕して、銅スラグ微粉末を得た。
[Examples 1 to 4 of the present invention]
The bulk copper slag, by using a disk mill, Blaine value of about 2000 cm 2 / g (Invention Example 1), about 3000 cm 2 / g (Invention Example 2), about 4000 cm 2 / g (Invention Example 3 ), Grinded to about 5000 cm 2 / g (Example 4 of the present invention) to obtain fine powder of copper slag.
得られた銅スラグ微粉末について、ブレーン比表面積、粒度分布、溶解シリカ量、活性度評価を下記の方法により測定した。 The specific surface area of the brain, the particle size distribution, the amount of dissolved silica, and the evaluation of the activity of the obtained fine copper slag powder were measured by the following methods.
（ブレーン比表面積）
ＪＩＳ Ｒ ５２０１「セメントの物理試験方法」に記載のブレーン空気透過装置を用いた比表面積試験に準拠して測定した。
(Brain specific surface area)
The measurement was performed in accordance with the specific surface area test using the brain air permeation device described in JIS R 5201 “Physical test method for cement”.
（粒度分布）
粒度分布は、レーザー回折式粒度分布測定装置（日機装社製マイクロトラック、型式ＭＴ３３００ＥＸII）を用い、銅スラグ微粉末を装置内でエタノール（分散媒屈折率：１.３６０）とともに、超音波（出力３０Ｗ）で１分間分散させ、粒子の屈折率に起因するパラメータを１.７０に設定して測定した。
(Particle size distribution)
For the particle size distribution, a laser diffraction type particle size distribution measuring device (Microtrac manufactured by Nikkiso Co., Ltd., model MT3300EXII) was used, and copper slag fine powder was mixed with ethanol (dispersion medium refractive index: 1.360) in the device and ultrasonic waves (output 30 W). ) For 1 minute, and the parameter due to the refractive index of the particles was set to 1.70 for measurement.
（溶解シリカ）
ＪＩＳ Ａ １１４５「骨材のアルカリシリカ反応性試験方法（化学法）」に準拠して、溶解シリカ量を測定した。
(Dissolved silica)
The amount of dissolved silica was measured in accordance with JIS A 1145 “Alkaline Silica Reactivity Test Method for Aggregate (Chemical Method)”.
（活性度指数）
ＪＩＳ Ａ ６２０６「コンクリート用高炉スラグ微粉末」に準拠して測定した。銅スラグ微粉末の置換率は２０質量％とした。活性度指数は、材齢２８日と材齢９１日で測定した。なお、表１には、参考例１として、基準モルタルの圧縮強度を記載した。
(Activity index)
Measured according to JIS A 6206 "Blast furnace slag fine powder for concrete". The replacement rate of the copper slag fine powder was 20% by mass. The activity index was measured at 28 days of age and 91 days of age. In Table 1, the compressive strength of the reference mortar is shown as Reference Example 1.
表１の結果から、ブレーン比表面積が２０００ｃｍ２／ｇ以上とされた本発明例１の銅スラグ微粉末は、材齢９１日の活性度指数が８８．４と高いことからセメント用混合材として有用であることが確認された。
また、ブレーン比表面積が大きくなるに伴って、指数的に溶解シリカと活性度指数が増加することが確認された。これは、粉砕が進むに伴って、銅スラグ粉末の表面に活性な酸化ケイ素が露出するためであると考えられる。そして、溶解シリカ量が増加することによって、銅スラグ微粉末中のシリカ分とセメント中のカルシウム分との反応性が向上して、活性度指数がさらに向上すると考えられる。
From the results in Table 1, the copper slag fine powder of Example 1 of the present invention having a brain specific surface area of 2000 cm 2 / g or more has a high activity index of 88.4 at 91 days of age, and thus is used as a cement mixture. It was found to be useful.
It was also confirmed that the dissolved silica and the activity index increased exponentially as the specific surface area of the brain increased. It is considered that this is because active silicon oxide is exposed on the surface of the copper slag powder as the pulverization progresses. Then, it is considered that the reactivity of the silica content in the copper slag fine powder and the calcium content in the cement is improved by increasing the amount of dissolved silica, and the activity index is further improved.
Claims (4)
銅スラグ微粉末を、前記セメント１００質量部に対して５質量部以上３５質量部以下の範囲の量にて含むことを特徴とするセメント組成物。 The content of cement and iron oxide is in the range of 35% by mass or more and 55% by mass or less, the content of silicon dioxide is in the range of 28% by mass or more and 38% by mass or less, and the content of calcium oxide is 1% by mass or more and 10% by mass. It has a composition in the range of% or less, the content of aluminum oxide in the range of 2% by mass or more and 8% by mass or less, the specific surface area of the brain is 2000 cm 2 / g or more, and the amount of dissolved silica is 1.5 mmol / L or more. Contains some copper slag fine powder
A cement composition containing fine copper slag powder in an amount in the range of 5 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the cement.
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