JP4302120B2 - Method for preventing consolidation of granulated blast furnace slag or its grain size adjusted blast furnace granulated slag fine aggregate for concrete - Google Patents
Method for preventing consolidation of granulated blast furnace slag or its grain size adjusted blast furnace granulated slag fine aggregate for concrete Download PDFInfo
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- JP4302120B2 JP4302120B2 JP2006119171A JP2006119171A JP4302120B2 JP 4302120 B2 JP4302120 B2 JP 4302120B2 JP 2006119171 A JP2006119171 A JP 2006119171A JP 2006119171 A JP2006119171 A JP 2006119171A JP 4302120 B2 JP4302120 B2 JP 4302120B2
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- 239000002893 slag Substances 0.000 title claims description 53
- 238000000034 method Methods 0.000 title claims description 37
- 238000007596 consolidation process Methods 0.000 title claims description 8
- 229920002125 Sokalan® Polymers 0.000 claims description 34
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 23
- -1 alkali metal salts Chemical class 0.000 claims description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 230000002265 prevention Effects 0.000 claims description 11
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 235000011008 sodium phosphates Nutrition 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 159000000000 sodium salts Chemical group 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000001692 EU approved anti-caking agent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229940064004 antiseptic throat preparations Drugs 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 229940042400 direct acting antivirals phosphonic acid derivative Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 150000003007 phosphonic acid derivatives Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage 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
- 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
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
本発明は高炉水砕スラグ又はその粒度調整物の固結防止方法及びこの固結防止方法によって得られるコンクリート用高炉水砕スラグ細骨材に関する。近年、天然砂が枯渇しつつあるなかで自然保護の観点から、天然砂の代替として高炉水砕スラグやこれを粉砕して粒度調整した粒度調整物（以下、これらを単に高炉水砕スラグ等という）がコンクリート用細骨材に使用される機会が増えている。高炉水砕スラグ等は、出荷待ちや使用待ちのために野積み状態で長期間貯蔵されたり、また船舶等で長期間輸送されることが多いが、これをそのまま長期間に亘って貯蔵したり輸送したりすると、固結して遂には岩塊のようになってしまい、前記したような天然砂の代替として使えなくなってしまうので、高炉水砕スラグ等を天然砂の代替として使用する場合には、それを長期間に亘り貯蔵や輸送してもそれが固結しないようにすることが強く要求される。本発明はかかる要求に応える高炉水砕スラグ等の固結防止方法及びこの固結防止方法によって得られるコンクリート用高炉水砕スラグ細骨材に関する。 TECHNICAL FIELD The present invention relates to a method for preventing caking of granulated blast furnace slag or a particle size adjusted product thereof, and a blast furnace granulated slag fine aggregate for concrete obtained by the caking prevention method. In recent years, natural sand has been depleted, and from the viewpoint of nature conservation, ground granulated blast furnace slag as an alternative to natural sand, and a particle size adjusted product obtained by pulverizing this to adjust the particle size (hereinafter simply referred to as granulated blast furnace slag, etc.) ) Is increasingly used for fine aggregates for concrete. Granulated blast furnace slag, etc. is stored for a long period of time in a piled state for waiting for shipment or use, and is often transported for a long period of time by ship etc. When transported, it will solidify and eventually become a rock mass, and it can no longer be used as a substitute for natural sand as described above, so when using granulated blast furnace slag as a substitute for natural sand, etc. Is strongly required to prevent it from consolidating even if it is stored or transported over a long period of time. The present invention relates to a method for preventing consolidation of blast furnace granulated slag and the like that meets such requirements, and a blast furnace granulated slag fine aggregate for concrete obtained by the method for preventing consolidation.
従来、高炉水砕スラグ等の固結防止方法として、１）脂肪族オキシカルボン酸やその塩のアルキレンオキサイド付加物（例えば特許文献１及び２参照）、２）アクリル酸系重合体（例えば特許文献３及び４参照）、３）ホスホン酸誘導体（例えば特許文献５参照）等を固結防止剤として用い、これらの固結防止剤を水で希釈した水溶液を高炉水砕スラグ等へスプレーすることが行なわれている。ところが、これら従来の固結防止方法には、相応の効果が認められるものの、長期間に亘る安定した固結防止性の要求に対して効果の発現が不充分という問題がある。高炉水砕スラグ等の品質乃至性状はその製造時の条件によって変動するが、前記のような従来法ではかかる品質乃至性状の変動によって固結防止性が影響を受け、例えば高炉水砕スラグ等からカルシウムイオン等が溶出して粒子相互間に存在する間隙水のｐＨが上昇し、固結性が高くなると、そのような高炉水砕スラグ等に従来法を適用しても固結防止性は充分に発揮されないのである。
本発明が解決しようとする課題は、高炉水砕スラグ等の品質乃至性状の変動に影響されることなく、長期間に亘り安定して高炉水砕スラグ等の固結を充分に防止できる固結防止方法を提供する処にあり、またかかる固結防止方法によって得られるコンクリート用高炉水砕スラグ細骨材を提供する処にある。 The problem to be solved by the present invention is a consolidation that can sufficiently prevent consolidation of blast furnace granulated slag and the like stably over a long period of time without being affected by variations in quality or properties of blast furnace granulated slag or the like. It is in the place which provides the prevention method, and is in the place which provides the blast furnace granulated slag fine aggregate for concrete obtained by this consolidation prevention method.
しかして本発明者らは、前記の課題を解決するべく研究した結果、高炉水砕スラグ等に特定の２成分系から成る固結防止剤を所定量となるよう用いることが正しく好適であることを見出した。 Therefore, as a result of researches to solve the above-mentioned problems, the present inventors correctly use a specific two-component anti-caking agent for blast furnace granulated slag and the like so as to have a predetermined amount. I found.
すなわち本発明は、高炉水砕スラグ等の固結防止方法であって、高炉水砕スラグ等１００質量部当たり、下記のＡ成分を３０〜９９質量％及び下記のＢ成分を７０〜１質量％含有しており且つ双方を合計で１００質量％となるよう含有して成る固結防止剤を０．００２〜０．５質量部の割合となるよう用いることを特徴とする固結防止方法に係る。また本発明は、かかる固結防止方法によって得られるコンクリート用高炉水砕スラグ細骨材に係る。 That is, the present invention is a method for preventing caking of blast furnace granulated slag and the like, and per 100 parts by mass of blast furnace granulated slag, etc. The anti-caking method characterized by using the anti-caking agent which contains and contains both so that it may become 100 mass% in total in the ratio of 0.002-0.5 mass part . Moreover, this invention relates to the blast furnace granulated slag fine aggregate for concrete obtained by this caking prevention method.
Ａ成分：質量平均分子量１０００〜１０００００のアクリル酸系重合体及びそのアルカリ金属塩から選ばれる少なくとも一つ Component A: at least one selected from an acrylic acid polymer having a mass average molecular weight of 1,000 to 100,000 and an alkali metal salt thereof
Ｂ成分：リン酸、リン酸ナトリウム、リン酸一水素ナトリウム、リン酸二水素ナトリウム、トリポリリン酸及びトリポリリン酸ナトリウムから選ばれる少なくとも一つ Component B: at least one selected from phosphoric acid, sodium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, tripolyphosphoric acid and sodium tripolyphosphate
本発明の固結防止方法で用いる固結防止剤に供するＡ成分は、質量平均分子量が１０００〜１０００００、好ましくは３０００〜５００００のアクリル酸系重合体及びそのアルカリ金属塩から選ばれる少なくとも一つである。アクリル酸系重合体のアルカリ金属塩としては、アクリル酸系重合体のナトリウム塩、カリウム塩、リチウム塩等が挙げられるが、工業的見地からナトリウム塩が好ましい。本発明において、質量平均分子量はＧＰＣ法によるポリエチレングリコール換算の質量平均分子量を意味し、またアクリル酸系重合体のアルカリ金属塩はアクリル酸系重合体を例えばアルカリ金属水酸化物を用いて完全中和したものだけではなく、部分中和したものも含むことを意味する。 The component A used in the anti-caking agent used in the anti-caking method of the present invention is at least one selected from acrylic acid polymers having a mass average molecular weight of 1,000 to 100,000, preferably 3000 to 50,000, and alkali metal salts thereof. is there. Examples of the alkali metal salt of the acrylic acid polymer include sodium salt, potassium salt, lithium salt and the like of the acrylic acid polymer, and sodium salt is preferable from an industrial viewpoint. In the present invention, the weight average molecular weight means the weight average molecular weight in terms of polyethylene glycol according to the GPC method, and the alkali metal salt of the acrylic acid polymer is completely contained in the acrylic acid polymer using, for example, an alkali metal hydroxide. It means that not only the sum but also the partially neutralized one is included.
またアクリル酸系重合体は、アクリル酸を単独重合して得られるポリアクリル酸の他に、アクリル酸と共重合可能な他のビニル単量体を１０モル％未満の範囲でアクリル酸と共重合して得られる共重合体をも含むことを意味する。ここで共重合可能なビニル単量体の具体例としては、メタクリル酸又はその塩、アクリルアミド、メタクリル酸ヒドロキシエチルエステル、アクリル酸メチルエステル、（メタ）アリルスルホン酸塩等の水溶性のビニル単量体が挙げられる。以上説明したアクリル酸系重合体やそのアルカリ金属塩は、いずれも公知の方法で合成できる。 In addition to polyacrylic acid obtained by homopolymerizing acrylic acid, acrylic acid polymer is copolymerized with acrylic acid in a range of less than 10 mol% of other vinyl monomers copolymerizable with acrylic acid. It means that the copolymer obtained by doing is also included. Specific examples of the copolymerizable vinyl monomer include methacrylic acid or a salt thereof, acrylamide, methacrylic acid hydroxyethyl ester, acrylic acid methyl ester, (meth) allyl sulfonate, and the like. The body is mentioned. Any of the acrylic acid polymers and alkali metal salts thereof described above can be synthesized by known methods.
本発明の固結防止方法で用いる固結防止剤に供するＢ成分は、リン酸、リン酸ナトリウム、リン酸一水素ナトリウム、リン酸二水素ナトリウム、トリポリリン酸及びトリポリリン酸ナトリウムから選ばれる少なくとも一つであるが、工業的見地からリン酸及びトリポリリン酸ナトリウムが好ましい。なかでも、Ａ成分としてアクリル酸系重合体を用いる場合にはＢ成分としてトリポリリン酸ナトリウムを用いるのが好ましく、またＡ成分としてアクリル酸系重合体のアルカリ金属塩を用いる場合にはＢ成分としてリン酸を用いるのが好ましい。 The component B used for the anti-caking agent used in the anti-caking method of the present invention is at least one selected from phosphoric acid, sodium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, tripolyphosphoric acid and sodium tripolyphosphate. However, phosphoric acid and sodium tripolyphosphate are preferred from an industrial standpoint. In particular, when an acrylic acid polymer is used as the A component, sodium tripolyphosphate is preferably used as the B component, and when an alkali metal salt of an acrylic acid polymer is used as the A component, phosphorus is used as the B component. It is preferable to use an acid.
本発明の固結防止方法で用いる固結防止剤は、前記したＡ成分を３０〜９９質量％及びＢ成分を７０〜１質量％、好ましくは前記したＡ成分を４０〜９７質量％及びＢ成分を６０〜３質量％含有しており、且つ双方を合計で１００質量％となるよう含有して成るものである。Ａ成分及びＢ成分の含有割合は、以上のような含有割合の範囲内にて、高炉水砕スラグ等の品質乃至性状との関係で適宜に選択するのが好ましい。 The anti-caking agent used in the anti-caking method of the present invention comprises 30 to 99% by mass of the A component and 70 to 1% by mass of the B component, preferably 40 to 97% by mass of the A component and B component. In an amount of 60 to 3 mass%, and the total content of both is 100 mass%. The content ratios of the A component and the B component are preferably selected as appropriate in relation to the quality and properties of the blast furnace granulated slag and the like within the range of the content ratio as described above.
本発明の固結防止方法で用いる固結防止剤としては、濃度１質量％の水溶液のｐＨが４〜１０となるものが好ましく、５〜９となるものがより好ましい。濃度１質量％の水溶液のｐＨがかかる数値範囲となるものが、高炉水砕スラグ等の品質乃至性状の変動に影響されることなく、より優れた固結防止効果を発揮する。 As the anti-caking agent used in the anti-caking method of the present invention, an aqueous solution having a concentration of 1% by mass is preferably 4 to 10, more preferably 5 to 9. Those having a numerical value range in which the pH of an aqueous solution having a concentration of 1% by mass exhibits a more excellent anti-caking effect without being affected by variations in quality or properties such as granulated blast furnace slag.
本発明の固結防止方法は、高炉水砕スラグ等１００質量部当たり、以上説明したような固結防止剤を０．００２〜０．５質量部の割合、好ましくは０．００５〜０．１質量部の割合となるように用いる。 In the anti-caking method of the present invention, the anti-caking agent as described above is in a proportion of 0.002 to 0.5 parts by mass, preferably 0.005 to 0.1 per 100 parts by mass of blast furnace granulated slag and the like. It uses so that it may become a ratio of mass part.
高炉水砕スラグ等に固結防止剤を用いる方法それ自体は特に制限されないが、通常は固結防止剤を水で希釈して水溶液となし、好ましくは濃度１．５〜１５質量％の水溶液となし、かかる水溶液を、高炉水砕スラグ等１００質量部当たり、固結防止剤として０．００２〜０．５質量部の割合、好ましくは０．００５〜０．１質量部の割合となるようスプレーして用いる。 The method of using an anti-caking agent in blast furnace granulated slag itself is not particularly limited, but usually an anti-caking agent is diluted with water to form an aqueous solution, preferably an aqueous solution having a concentration of 1.5 to 15% by mass. None, such an aqueous solution is sprayed at a rate of 0.002 to 0.5 parts by mass, preferably 0.005 to 0.1 parts by mass as an anti-caking agent per 100 parts by mass of granulated blast furnace slag, etc. And use.
また本発明の固結防止方法の対象となる高炉水砕スラグ等それ自体も、例えばその品質や性状等が特に制限されるというものではないが、本発明の固結防止方法は、粒子相互間に存在する間隙水のｐＨが１１以上となるようなｐＨの高いすなわち固結性の高い高炉水砕スラグ等に対しても、長期間に亘り安定してその固結を充分に防止する。 Further, the granulated blast furnace slag as a target of the anti-caking method of the present invention itself is not particularly limited, for example, in quality or properties, but the anti-caking method of the present invention is used between particles. Even in the case of blast furnace granulated slag having a high pH such that the pH of interstitial water is 11 or more, that is, a highly solidified blast furnace granulated slag, the solidification is sufficiently prevented for a long period of time.
本発明の固結防止方法を実施するに際しては合目的的に他の添加剤を併用することができる。かかる他の添加剤としては、防腐剤、防錆剤、酸化防止剤等が挙げられる。 In carrying out the anti-caking method of the present invention, other additives can be used in combination for the purpose. Examples of such other additives include antiseptics, rust inhibitors, and antioxidants.
本発明のコンクリート用高炉水砕スラグ細骨材は、以上説明したような本発明の固結防止方法によって得られるものであり、言い替えれば高炉水砕スラグ等に前記したような特定の２成分系から成る固結防止剤を所定量となるよう用いたものである。 The blast furnace granulated slag fine aggregate for concrete of the present invention is obtained by the caking prevention method of the present invention as described above. In other words, a specific two-component system as described above for blast furnace granulated slag and the like. The anti-caking agent consisting of is used in a predetermined amount.
以上説明した本発明の固結防止方法によると、高炉水砕スラグ等の品質乃至性状の変動に影響されることなく、長期間に亘り安定して高炉水砕スラグ等の固結を充分に防止できる。またかくして固結を防止した高炉水砕スラグ等をコンクリート用細骨材の一部として用いたとき、コンクリートの諸物性に何ら悪影響を与えることがない。 According to the anti-caking method of the present invention described above, the caking of granulated blast furnace slag and the like can be sufficiently prevented stably for a long period of time without being affected by variations in quality and properties of the blast furnace granulated slag and the like. it can. Moreover, when blast furnace granulated slag or the like thus prevented from being consolidated is used as a part of the fine aggregate for concrete, there is no adverse effect on the physical properties of the concrete.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明が該実施例に限定されるというものではない。尚、以下の実施例等において、別に記載しない限り、部は質量部を、また％は質量％を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to the examples. In the following examples and the like, unless otherwise indicated, “part” means “part by mass” and “%” means “% by mass”.
試験区分１（Ａ成分として用いるアクリル酸系重合体及びそのアルカリ金属塩の合成）
・アクリル酸系重合体（ａ−１）の合成
反応容器にアクリル酸７２ｇ、３−メルカプトプロピオン酸３．５ｇ及び水６８７．５ｇを仕込んで混合し、雰囲気を窒素置換した後、窒素雰囲気下に、反応系の温度を温水浴にて６０℃に保ち、濃度２０％の過硫酸ナトリウム水溶液８ｇを滴下して重合を開始し、４時間重合反応を行なって、アクリル酸系重合体（ａ−１）の１０％水溶液を得た。このアクリル酸系重合体（ａ−１）の質量平均分子量は７３００であった。
Test Category 1 (Synthesis of acrylic acid polymer and alkali metal salt used as component A)
Synthesis of acrylic acid polymer (a-1) 72 g of acrylic acid, 3.5 g of 3-mercaptopropionic acid and 687.5 g of water were charged and mixed in a reaction vessel, and the atmosphere was replaced with nitrogen, and then the atmosphere was changed to nitrogen. The temperature of the reaction system is kept at 60 ° C. in a warm water bath, 8 g of 20% sodium persulfate aqueous solution is added dropwise to initiate the polymerization, the polymerization reaction is carried out for 4 hours, and the acrylic acid polymer (a-1 ) Was obtained. The acrylic acid polymer (a-1) had a mass average molecular weight of 7,300.
・アクリル酸系重合体（ａ−２）の合成
アクリル酸系重合体（ａ−１）と同様にして、表１に記載したアクリル酸系重合体（ａ−２）の１０％水溶液を得た。
Synthesis of acrylic acid polymer (a-2) A 10% aqueous solution of acrylic acid polymer (a-2) described in Table 1 was obtained in the same manner as acrylic acid polymer (a-1). .
アクリル酸系重合体のアルカリ金属塩（ａ−３）の合成
反応容器にアクリル酸７２ｇ、３−メルカプトプロピオン酸３．５ｇ及び水７４２ｇを仕込んで混合し、濃度３０％の水酸化ナトリウム水溶液６６ｇをかき混ぜながら加えて中和した。雰囲気を窒素置換した後、窒素雰囲気下に、反応系の温度を温水浴にて６０℃に保ち、濃度２０％の過硫酸ナトリウム水溶液１０ｇを滴下して重合を開始し、４時間重合反応を行なってアクリル酸系重合体のアルカリ金属塩（ａ−３）の１０％水溶液を得た。このアクリル酸系重合体のアルカリ金属塩（ａ−３）の中和度は０．５、質量平均分子量は４２００であった。
Synthesis of alkali metal salt of acrylic acid polymer (a-3) A reaction vessel was charged with 72 g of acrylic acid, 3.5 g of 3-mercaptopropionic acid and 742 g of water and mixed, and 66 g of 30% aqueous sodium hydroxide solution was added. The mixture was neutralized by stirring. After substituting the atmosphere with nitrogen, the temperature of the reaction system was kept at 60 ° C. in a warm water bath under a nitrogen atmosphere, and 10 g of 20% sodium persulfate aqueous solution was added dropwise to initiate polymerization, and the polymerization reaction was carried out for 4 hours. Thus, a 10% aqueous solution of an alkali metal salt of an acrylic acid polymer (a-3) was obtained. The degree of neutralization of the alkali metal salt (a-3) of this acrylic acid polymer was 0.5, and the mass average molecular weight was 4,200.
・アクリル酸系重合体のアルカリ金属塩（ａ−４）〜（ａ−６）の合成
アクリル酸系重合体のアルカリ金属塩（ａ−３）と同様にして、表１に記載したアクリル酸系重合体のアルカリ金属塩（ａ−４）〜（ａ−６）の１０％水溶液を得た。
Synthesis of alkali metal salts (a-4) to (a-6) of acrylic acid polymer The acrylic acid system described in Table 1 in the same manner as the alkali metal salt (a-3) of acrylic acid polymer A 10% aqueous solution of polymer alkali metal salts (a-4) to (a-6) was obtained.
表１において、
中和度：化学量論的にアルカリ金属水酸化物により中和されているアクリル酸系重合体のカルボキシル基のモル数／アクリル酸系重合体の全カルボキシル基のモル数
In Table 1,
Degree of neutralization: moles of carboxyl groups of acrylic acid polymer stoichiometrically neutralized with alkali metal hydroxide / moles of all carboxyl groups of acrylic acid polymer
試験区分２（固結防止剤の調製）
・固結防止剤（Ｐ−１）の１０％水溶液の調製
Ａ成分として試験区分１で合成したアクリル酸系重合体（ａ−１）の１０％水溶液８０部、Ｂ成分としてトリポリリン酸ナトリウムの１０％水溶液２０部を混合して固結防止剤（Ｐ−１）の１０％水溶液を調製した。固結防止剤（Ｐ−１）を水で希釈した固形分濃度１％の水溶液のｐＨを測定したところ、４．３であった。
Test Category 2 (Preparation of anti-caking agent)
Preparation of 10% aqueous solution of anti-caking agent (P-1) 80 parts of 10% aqueous solution of acrylic acid polymer (a-1) synthesized in test category 1 as component A, 10 of sodium tripolyphosphate as component B A 20% aqueous solution was mixed to prepare a 10% aqueous solution of an anti-caking agent (P-1). The pH of the aqueous solution having a solid content concentration of 1% obtained by diluting the anti-caking agent (P-1) with water was 4.3.
・固結防止剤（Ｐ−２）〜（Ｐ−１３）及び（Ｒ−１）〜（Ｒ−１９）の１０％水溶液の調製
固結防止剤（Ｐ−１）と同様にして、固結防止剤（Ｐ−２）〜（Ｐ−１３）及び（Ｒ−１）〜（Ｒ−１９）の１０％水溶液を調製した。以上で調製した各固結防止剤の内容を表２にまとめて示した。
-Preparation of 10% aqueous solution of anti-caking agents (P-2) to (P-13) and (R-1) to (R-19), caking in the same manner as the anti-caking agent (P-1) 10% aqueous solutions of inhibitors (P-2) to (P-13) and (R-1) to (R-19) were prepared. Table 2 summarizes the contents of the anti-caking agents prepared above.
表２において、
ｐＨ：固形分濃度１％の水溶液のｐＨ
ａ−１〜ａ−６：表１記載のアクリル酸系重合体又はそのアルカリ金属塩
ｂ−１：トリポリリン酸ナトリウム
ｂ−２：リン酸
ｂ−３：リン酸ナトリウム
ｂ−４：トリポリリン酸
ｂ−５：リン酸二水素ナトリウム
ｂ−６：リン酸一水素ナトリウム
ｃ−１：硫酸ナトリウム
ｃ−２：塩化ナトリウム
ｃ−３：硝酸ナトリウム
ｄ−１：硫酸
In Table 2,
pH: pH of an aqueous solution having a solid content concentration of 1%
a-1 to a-6: Acrylic acid polymer or alkali metal salt thereof listed in Table 1 b-1: sodium tripolyphosphate b-2: phosphoric acid b-3: sodium phosphate b-4: tripolyphosphoric acid b- 5: Sodium dihydrogen phosphate b-6: Sodium monohydrogen phosphate c-1: Sodium sulfate c-2: Sodium chloride c-3: Sodium nitrate d-1: Sulfuric acid
試験区分３
実施例１〜１５及び比較例１〜２４（固結防止方法及びその評価）
バットに高炉水砕スラグ細骨材｛ＪＦＥミネラル社製の福山産高炉水砕スラグをＪＩＳ−Ａ５０１１（コンクリート用スラグ骨材）に準じて５mm高炉水砕スラグ細骨材の粒度分布に調整したもので、間隙水のｐＨ値が標準（ｐＨ値９．５〜１１未満のもの）よりも高いもの（ｐＨ値１１．７のもの）｝を広げ、試験区分２で調製した固結防止剤の１０％水溶液を表３記載の添加量となるようスプレーし、ハンドスコップで混合した。更に可傾式ミキサーで５分間混合した後、含水率１０％となるように水を加え、再び可傾式ミキサーで５分間混合して、高炉水砕スラグ細骨材に固結防止剤を付着させた。このようにして固結防止剤を付着させた高炉水砕スラグ細骨材を内径１００mmの円筒状容器に高さ１２５mmまで充填し、これに高炉水砕スラグの貯蔵高さ１０ｍに相当する０．１５ＭＰａの圧力を載荷して供試体とした。供試体は、水分の蒸発を防ぐため容器を密封し、８０℃の恒温室で最長１６週間まで促進養生した。所定期間養生後、供試体を脱枠し、粒度測定を行なった。粒度測定は、目開き５mm篩を用いて行ない、篩を通過しないで篩上に残存したものの質量を測定し、供試体中におけるその割合を求めた（表３中の５mm篩上割合）。結果を表３にまとめて示した。表３において、５mm篩上割合（％）の数値が低いほど、高炉水砕スラグ細骨材の固結が防止されていることを意味する。
Test category 3
Examples 1 to 15 and Comparative Examples 1 to 24 (caking prevention method and evaluation thereof)
Blast furnace granulated slag fine aggregate {Fukuyama blast furnace granulated slag made by JFE Mineral Co., Ltd. adjusted to the particle size distribution of 5mm blast furnace granulated slag fine aggregate according to JIS-A5011 (concrete slag aggregate) The pH value of the pore water is higher than that of the standard (having a pH value of less than 9.5 to 11) (having a pH value of 11.7)}. % Aqueous solution was sprayed so as to have the addition amount shown in Table 3, and mixed with a hand scoop. Further, after mixing for 5 minutes with a tilting mixer, add water so that the water content becomes 10%, and again mix with a tilting mixer for 5 minutes to attach an anti-caking agent to the granulated blast furnace slag fine aggregate. I let you. The blast furnace granulated slag fine aggregate to which the anti-caking agent is adhered in this way is filled in a cylindrical container having an inner diameter of 100 mm to a height of 125 mm, which corresponds to a storage height of 10 m for the blast furnace granulated slag. A specimen was loaded with a pressure of 15 MPa. The specimen was sealed in a container in order to prevent evaporation of moisture, and was accelerated and cured for up to 16 weeks in a constant temperature room at 80 ° C. After curing for a predetermined period, the specimen was removed and the particle size was measured. The particle size was measured using a sieve having a mesh opening of 5 mm, the mass of the material remaining on the sieve without passing through the sieve was measured, and the ratio in the specimen was obtained (the ratio of 5 mm sieve in Table 3). The results are summarized in Table 3. In Table 3, it means that the consolidation of a blast-furnace granulated slag fine aggregate is prevented, so that the numerical value (%) on a 5 mm sieve is low.
表３において、
添加量：高炉水砕スラグ細骨材１００質量部当たりの固結防止剤（固形分）の添加質量部
Ｒ−２０：グルコン酸ナトリウム
In Table 3,
Addition amount: part by mass of anti-caking agent (solid content) per 100 parts by mass of granulated blast furnace slag fine aggregate R-20: sodium gluconate
試験区分４
実施例１６〜２８及び比較例２５〜３６（コンクリート用高炉水砕スラグ細骨材の製造及びその評価）
表４に記載の配合番号１の条件で、各例のコンクリートを次のように調製した。５０Ｌのパン型強制練りミキサーに、普通ポルトランドセメント（密度３．１６、ブレーン値３３００）、細骨材として大井川水系砂（密度２．６３）及び試験区分３と同様に固結防止剤をその添加量が０．０３となるようにスプレーして混合した高炉水砕スラグ（ＪＦＥミネラル社製の福山産高炉水砕スラグ、密度２．７４）の２種類並びに粗骨材（岡崎産砕石、密度２．６８）を順次投入して１５秒間空練りした。次いで各例いずれも目標スランプが１８±１cmの範囲内となるよう、セメントに対し０．８％量の高性能ＡＥ減水剤（竹本油脂社製の商品名チューポールＨＰ−１１）を練り混ぜ水と共に投入して２分間練り混ぜた。この際、目標空気量が４〜５％となるようにＡＥ剤（竹本油脂社製の商品名ＡＥ−３００）を加えた。かくして調製した各例のコンクリートについて次の方法で評価した。結果を表５にまとめて示した。
Test category 4
Examples 16 to 28 and Comparative Examples 25 to 36 (Manufacture and evaluation of blast furnace granulated slag fine aggregate for concrete)
The concrete of each example was prepared as follows on the conditions of the mixing | blending number 1 of Table 4. Add 50L pan-type forced kneading mixer with normal Portland cement (density 3.16, brane value 3300), Oikawa water sand (density 2.63) as fine aggregate and anti-caking agent as in test category 3 Two types of blast furnace granulated slag (Fukuyama blast furnace granulated slag manufactured by JFE Mineral Co., Ltd., density 2.74) and coarse aggregate (Okazaki crushed stone, density 2) mixed by spraying so that the amount is 0.03 .68) were sequentially added and kneaded for 15 seconds. Then, in each example, 0.8% amount of high-performance AE water reducing agent (trade name Tupol HP-11 manufactured by Takemoto Yushi Co., Ltd.) is mixed with the cement so that the target slump is within the range of 18 ± 1 cm. And kneaded for 2 minutes. At this time, an AE agent (trade name AE-300 manufactured by Takemoto Yushi Co., Ltd.) was added so that the target air amount was 4 to 5%. The concrete of each example thus prepared was evaluated by the following method. The results are summarized in Table 5.
スランプ：ＪＩＳ−Ａ１１０１に準拠して測定した。
空気量：ＪＩＳ−Ａ１１２８に準拠して測定した。
圧縮強度：ＪＩＳ−Ａ１１０８に準拠して測定した。
凝結時間：ＪＩＳ−Ａ６２０４に準拠して測定した。
Slump: Measured according to JIS-A1101.
Air amount: Measured according to JIS-A1128.
Compressive strength: measured in accordance with JIS-A1108.
Setting time: Measured according to JIS-A6204.
表４において、
＊１：固結防止剤をスプレーして混合したコンクリート用高炉水砕スラグ細骨材
In Table 4,
* 1: Blast furnace granulated slag fine aggregate for concrete mixed by spraying anti-caking agent
表５において、
固結防止剤の種類：表２に記載の固結防止剤
＊２：固結防止剤を添加しないもの
＊３：表４の配合番号２で練り混ぜたコンクリートであって、高炉水砕スラグを混入していないコンクリート
In Table 5,
Type of anti-caking agent: Anti-caking agent listed in Table 2 * 2: No anti-caking agent added * 3: Concrete kneaded with compound No. 2 in Table 4, and granulated blast furnace slag Unmixed concrete
Claims (9)
Ａ成分：質量平均分子量１０００〜１０００００のアクリル酸系重合体及びそのアルカリ金属塩から選ばれる少なくとも一つ
Ｂ成分：リン酸、リン酸ナトリウム、リン酸一水素ナトリウム、リン酸二水素ナトリウム、トリポリリン酸及びトリポリリン酸ナトリウムから選ばれる少なくとも一つ A method for preventing caking of granulated blast furnace slag or its particle size-adjusted product, comprising 30 to 99% by mass of the following A component and 70 to 70% of the following B component per 100 parts by mass of granulated blast furnace slag or its granulated product: An anti-caking agent comprising 1% by mass of an anti-caking agent containing 100% by mass of both in a total amount of 0.002 to 0.5 parts by mass Method.
Component A: at least one selected from acrylic acid polymers having a mass average molecular weight of 1000 to 100,000 and alkali metal salts thereof Component B: phosphoric acid, sodium phosphate, sodium monohydrogen phosphate, sodium dihydrogen phosphate, tripolyphosphoric acid And at least one selected from sodium tripolyphosphate
A blast furnace granulated slag fine aggregate for concrete obtained by the consolidation prevention method according to any one of claims 1 to 8.
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