JP2015199661A - Anti-solidifying agent and anti-solidifying method of blast furnace water-granulated slag - Google Patents
Anti-solidifying agent and anti-solidifying method of blast furnace water-granulated slag Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims abstract description 163
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 148
- 238000000034 method Methods 0.000 title claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- -1 aluminum compound Chemical class 0.000 claims abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 24
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 18
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims abstract description 18
- 239000000600 sorbitol Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims abstract description 10
- 229940050410 gluconate Drugs 0.000 claims abstract description 10
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims abstract description 9
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000174 gluconic acid Substances 0.000 claims abstract description 9
- 235000012208 gluconic acid Nutrition 0.000 claims abstract description 9
- 230000002708 enhancing effect Effects 0.000 claims description 44
- 238000007596 consolidation process Methods 0.000 claims description 29
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 23
- 239000000470 constituent Substances 0.000 claims description 9
- 230000003014 reinforcing effect Effects 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 30
- 230000002787 reinforcement Effects 0.000 abstract description 5
- 230000008023 solidification Effects 0.000 abstract 2
- 238000007711 solidification Methods 0.000 abstract 2
- 230000002265 prevention Effects 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 238000005728 strengthening Methods 0.000 description 15
- 230000003449 preventive effect Effects 0.000 description 13
- 239000011734 sodium Substances 0.000 description 12
- 230000007774 longterm Effects 0.000 description 11
- 150000004645 aluminates Chemical class 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000035515 penetration Effects 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002671 adjuvant Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000001692 EU approved anti-caking agent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000002552 dosage form Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910001388 sodium aluminate Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CZNVSLGYWMSMKE-OPDGVEILSA-K Ferric gluconate Chemical compound [Fe+3].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O CZNVSLGYWMSMKE-OPDGVEILSA-K 0.000 description 1
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XKGUZGHMWUIYDR-UHFFFAOYSA-N benzyl n-(3-fluoro-4-morpholin-4-ylphenyl)carbamate Chemical compound C=1C=C(N2CCOCC2)C(F)=CC=1NC(=O)OCC1=CC=CC=C1 XKGUZGHMWUIYDR-UHFFFAOYSA-N 0.000 description 1
- 239000004227 calcium gluconate Substances 0.000 description 1
- 235000013927 calcium gluconate Nutrition 0.000 description 1
- 229960004494 calcium gluconate Drugs 0.000 description 1
- NEEHYRZPVYRGPP-UHFFFAOYSA-L calcium;2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(O)C([O-])=O.OCC(O)C(O)C(O)C(O)C([O-])=O NEEHYRZPVYRGPP-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004222 ferrous gluconate Substances 0.000 description 1
- 235000013924 ferrous gluconate Nutrition 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000007589 penetration resistance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004224 potassium gluconate Substances 0.000 description 1
- 235000013926 potassium gluconate Nutrition 0.000 description 1
- 229960003189 potassium gluconate Drugs 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007873 sieving Methods 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
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Manufacture Of Iron (AREA)
Abstract
Description
本発明は、高炉水砕スラグの固結防止剤及び固結防止剤セット、並びに高炉水砕スラグの固結防止方法に関する。 The present invention relates to an anti-caking agent and an anti-caking agent set for granulated blast furnace slag, and a method for preventing caking of blast furnace granulated slag.
高炉水砕スラグは、ボールミルでの微粉砕を経てセメント混和材に、また、ロッドミルでの磨砕や天然砂との混合による粒度調整を経てコンクリート用細骨材として用いられている。この時、水砕スラグは、セメント混和材やコンクリート用細骨材の用途として出荷されるまでに、製鉄所で長期間ストックされることが多く、固結現象の発生が大きな課題となっている。特に、コンクリート用細骨材として磨砕した高炉水砕スラグは、細粒分が多くなって保管時に固結現象が発生しやすく、以後の運搬や用途利用に不都合が生じることがあった。 Blast furnace granulated slag is used as a cement admixture after being finely pulverized in a ball mill, and as fine aggregate for concrete after being adjusted in particle size by grinding with a rod mill or mixing with natural sand. At this time, granulated slag is often stocked for a long time in steelworks before being shipped as cement admixture or fine aggregate for concrete, and the occurrence of consolidation phenomenon is a major issue. . In particular, blast furnace granulated slag that has been ground as fine aggregate for concrete has a large amount of fine particles and is liable to cause a consolidation phenomenon during storage, resulting in inconvenience in subsequent transportation and use.
従来、高炉水砕スラグの固結防止方法としては、高炉水砕スラグに、各種化合物を含有する固結防止剤を添加することが行われている。例えば、オキシカルボン酸（特許文献１）、糖アルコール類（特許文献２）、ソルビトール（特許文献３）、アクリル酸系重合体（特許文献４）を含有する固結防止剤を添加することが開示されており、また、単独の化合物ではなく複数の化合物を含有する、例えば、カルボキシル基含有ポリマー及びソルビトール（特許文献５）を含有する固結防止剤を添加することも開示されている。 Conventionally, as a method for preventing consolidation of blast furnace granulated slag, an anti-caking agent containing various compounds has been added to blast furnace granulated slag. For example, adding an anti-caking agent containing an oxycarboxylic acid (Patent Document 1), a sugar alcohol (Patent Document 2), a sorbitol (Patent Document 3), and an acrylic acid polymer (Patent Document 4) is disclosed. It is also disclosed that an anti-caking agent containing a plurality of compounds, for example, a carboxyl group-containing polymer and sorbitol (Patent Document 5) is added instead of a single compound.
上述の特許文献１〜５に開示された固結防止剤は、降雨等による水との接触の無い条件下においては、長期の固結防止効果を得ることができる。しかしながら、これらの固結防止剤は、ガラス質のスラグ表面への付着性については、必ずしも十分であるということはできない。高炉水砕スラグは、固結防止剤と混合され、その後保管されるが、この付着性の不十分さによって、固結防止剤がスラグ表面に十分に付着しないことにより、未付着の固結防止剤が固結防止に寄与できないことや、付着した固結防止剤の水への抵抗性が低下することが問題となる。 The anti-caking agent disclosed in Patent Documents 1 to 5 described above can obtain a long-term anti-caking effect under conditions where there is no contact with water due to rainfall or the like. However, it cannot be said that these anti-caking agents are necessarily sufficient for adhesion to the glassy slag surface. Blast furnace granulated slag is mixed with anti-caking agent and then stored, but due to this lack of adhesion, the anti-caking agent does not adhere sufficiently to the slag surface, thereby preventing non-caking caking. The problem is that the agent cannot contribute to prevention of caking and that the resistance of the adhering anticaking agent to water is lowered.
水への抵抗性については、例えば、固結防止剤と混合された水砕スラグを屋外で保管した場合、降雨等水との接触によって、高炉水砕スラグから固結防止剤が流失し、これによって期待するほど長期の固結防止効果が得られないという問題があった。そのため、高炉水砕スラグのストック時における固結トラブルは後を絶たず、水砕スラグ資源化の大きなネックになっている。 Regarding water resistance, for example, when granulated slag mixed with an anti-caking agent is stored outdoors, the anti-caking agent is washed away from the blast furnace granulated slag due to contact with water such as rainfall. There is a problem that the anti-caking effect for a long time cannot be obtained as expected. For this reason, consolidation problems during the stocking of blast furnace granulated slag are continually becoming a major bottleneck in the utilization of granulated slag resources.
水への抵抗性の問題を避けるためには、固結防止剤で処理したスラグを屋内で保管することが考えられるが、保管のための屋内スペースの確保や、搬出・搬入に手間等の解決すべき課題があった。また、予め固結防止剤を大量に添加しておく、又は、固結防止剤を定期的に添加する等の方法も考えられるが、このためには大量の固結防止剤が必要となり、大きなコストの上昇が課題であった。 In order to avoid water resistance problems, it is conceivable to store slag treated with anti-caking agents indoors. However, it is necessary to secure indoor space for storage and to solve the trouble of carrying out and carrying in. There were issues to be addressed. In addition, a method of adding a large amount of an anti-caking agent in advance or adding an anti-caking agent regularly can be considered, but this requires a large amount of an anti-caking agent, which is large. The increase in cost was an issue.
さらに、高炉水砕スラグへの付着性が高く、水との接触によっても流失し難いポリカルボン酸等の高分子化合物の固結防止剤としての適用も検討されているが、発明者等の検討によると、必ずしも十分な固結防止効果を得ることができるとはいい難かった。 In addition, the application to high blast furnace granulated slag as an anti-caking agent for high molecular weight compounds such as polycarboxylic acids, which have high adhesion to blast furnace granulated slag and are difficult to be washed away by contact with water, has also been investigated. According to the above, it was difficult to say that a sufficient anti-caking effect could be obtained.
本発明は、上述の課題を解決するためになされたものであり、高炉水砕スラグに添加されて使用された場合、降雨等の水と接触する機会のある屋外での保管時においても、高炉水砕スラグの固結を防止する成分の流失が抑制され、長期の固結防止効果を実現することが可能な高炉水砕スラグの固結防止剤及び固結防止剤セット、並びに高炉水砕スラグの固結防止方法を提供することを目的とする。 The present invention has been made to solve the above-mentioned problems, and when added to a granulated blast furnace slag, the blast furnace is used even when stored outdoors where there is an opportunity to come into contact with water such as rainfall. Anti-caking agent and anti-caking agent set of granulated blast furnace slag capable of achieving long-term anti-caking effect, and the blast furnace granulated slag An object of the present invention is to provide an anti-caking method.
換言すれば、本発明は、長期間固結し難い高炉水砕スラグの生産を可能とし、水砕スラグの品質トラブルの低減及び取扱性の向上をもたらし、水砕スラグのさらなる有効利用の促進に寄与することが可能な高炉水砕スラグの固結防止剤及び固結防止剤セット、並びに高炉水砕スラグの固結防止方法を提供することを目的とする。 In other words, the present invention enables the production of granulated blast furnace slag that is difficult to consolidate for a long period of time, reduces the quality troubles of the granulated slag and improves the handleability, and promotes more effective use of the granulated slag. An object of the present invention is to provide an anti-caking agent and an anti-caking agent set for blast furnace granulated slag that can contribute, and a method for preventing caking of blast furnace granulated slag.
本発明によって、以下の高炉水砕スラグの固結防止剤、高炉水砕スラグの固結防止剤セット、及び高炉水砕スラグの固結防止方法が提供される。 The present invention provides the following anti-caking agent for blast furnace granulated slag, an anti-caking agent set for granulated blast furnace slag, and a method for preventing caking of blast furnace granulated slag.
［１］高炉水砕スラグに添加されて、前記高炉水砕スラグの固結を防止する高炉水砕スラグの固結防止剤であって、固結防止主剤及び付着性強化助剤を含有してなることを特徴とする高炉水砕スラグの固結防止剤。
［２］前記固結防止主剤は、ソルビトール、グルコン酸及びグルコン酸塩からなる群から選択される１以上の化合物であり、かつ前記付着性強化助剤は、アルミニウム化合物である前記［１］に記載の高炉水砕スラグの固結防止剤。
［３］前記固結防止主剤１質量部に対して、前記付着性強化助剤を、前記アルミニウム化合物中の構成元素のＡｌをＡｌ2Ｏ3に換算して得られるＡｌ2Ｏ3量として、０．０１〜５０質量部の割合で含有してなる前記［２］に記載の高炉水砕スラグの固結防止剤。
[1] An anti-caking agent for blast furnace granulated slag which is added to blast furnace granulated slag to prevent caking of the blast furnace granulated slag, and includes an anti-caking main agent and an adhesion strengthening auxiliary agent. An anti-caking agent for granulated blast furnace slag, characterized in that.
[2] In the above [1], the anti-caking main agent is one or more compounds selected from the group consisting of sorbitol, gluconic acid and gluconate, and the adhesion enhancing aid is an aluminum compound. The anti-caking agent for granulated blast furnace slag as described.
[3] With respect to 1 part by mass of the anti-caking agent, the adhesion enhancing aid is used as the amount of Al 2 O 3 obtained by converting Al of the constituent element in the aluminum compound into Al 2 O 3 , The anti-caking agent for granulated blast furnace slag as described in [2], which is contained at a ratio of 0.01 to 50 parts by mass.
［４］高炉水砕スラグに添加されて、前記高炉水砕スラグの固結を防止する高炉水砕スラグの固結防止剤セットであって、固結防止主剤及び付着性強化助剤の組み合わせを含むことを特徴とする高炉水砕スラグの固結防止剤セット。
［５］前記固結防止主剤は、ソルビトール、グルコン酸及びグルコン酸塩からなる群から選択される１以上の化合物であり、かつ前記付着性強化助剤は、アルミニウム化合物である前記［４］に記載の高炉水砕スラグの固結防止剤セット。
[4] An anti-caking agent set for granulated blast furnace slag that is added to blast furnace granulated slag to prevent caking of the blast furnace granulated slag, and includes a combination of an anti-caking main agent and an adhesion enhancing auxiliary. An anti-caking agent set for granulated blast furnace slag characterized by containing.
[5] In the above [4], the anti-caking main agent is one or more compounds selected from the group consisting of sorbitol, gluconic acid and gluconate, and the adhesion enhancing aid is an aluminum compound. Anti-caking agent set of granulated blast furnace slag as described.
［６］高炉水砕スラグに固結防止剤を添加して、前記高炉水砕スラグの固結を防止する高炉水砕スラグの固結防止方法であって、前記固結防止剤として、前記［１］〜［３］のいずれかに記載の固結防止剤を添加することを特徴とする高炉水砕スラグの固結防止方法（以下、「第１の高炉水砕スラグの固結防止方法」とも記す）。 [6] A method for preventing caking of blast furnace granulated slag by adding an anti-caking agent to blast furnace granulated slag to prevent caking of the blast furnace water granulated slag, 1] to [3], wherein the anti-caking agent for blast furnace granulated slag is added (hereinafter referred to as “first anti-caking method for granulated blast furnace slag”). Also noted).
［７］高炉水砕スラグの固結を防止する高炉水砕スラグの固結防止方法であって、固結防止主剤及び付着性強化助剤を高炉水砕スラグに添加することを特徴とする高炉水砕スラグの固結防止方法（以下、「第２の高炉水砕スラグの固結防止方法」とも記す）。
［８］前記固結防止主剤は、ソルビトール、グルコン酸及びグルコン酸塩からなる群から選択される１以上の化合物であり、かつ前記付着性強化助剤は、アルミニウム化合物である前記［７］に記載の高炉水砕スラグの固結防止方法。
［９］前記固結防止主剤１質量部に対して、前記付着性強化助剤を、前記アルミニウム化合物中の構成元素のＡｌをＡｌ2Ｏ3に換算して得られるＡｌ2Ｏ3量として、０．０１〜５０質量部の割合で添加する前記［８］に記載の高炉水砕スラグの固結防止方法。
［１０］前記固結防止主剤及び前記付着性強化助剤を、同時に又は時間差を設けて添加する前記［７］〜［９］のいずれかに記載の高炉水砕スラグの固結防止方法。
[7] A method of preventing consolidation of blast furnace granulated slag to prevent consolidation of blast furnace granulated slag, wherein a flocculation preventive main agent and an adhesion strengthening auxiliary agent are added to the blast furnace granulated slag. Method for preventing consolidation of granulated slag (hereinafter, also referred to as “second method for preventing consolidation of granulated blast furnace slag”).
[8] In the above [7], the caking preventive main agent is one or more compounds selected from the group consisting of sorbitol, gluconic acid and gluconate, and the adhesion enhancing aid is an aluminum compound. The method for preventing caking of granulated blast furnace slag as described.
[9] With respect to 1 part by mass of the anti-caking agent, the adhesion enhancing aid is used as the amount of Al 2 O 3 obtained by converting Al of the constituent element in the aluminum compound into Al 2 O 3 , The method for preventing consolidation of granulated blast furnace slag according to [8], which is added at a ratio of 0.01 to 50 parts by mass.
[10] The method for preventing caking of granulated blast furnace slag according to any one of [7] to [9], wherein the caking prevention main agent and the adhesion enhancing auxiliary are added simultaneously or with a time difference.
本発明によって、高炉水砕スラグに添加されて使用された場合、降雨等の水と接触する機会のある屋外での保管時においても、高炉水砕スラグの固結を防止する成分の流失が抑制され、長期の固結防止効果を実現することが可能な高炉水砕スラグの固結防止剤、高炉水砕スラグの固結防止剤セット、及び高炉水砕スラグの固結防止方法が提供される。 In accordance with the present invention, when added to blast furnace granulated slag, the loss of components that prevent consolidation of blast furnace granulated slag is suppressed even during outdoor storage where there is an opportunity to come in contact with water such as rainfall. There are provided an anti-caking agent for blast furnace granulated slag, an anti-caking agent set for granulated blast furnace slag, and a method for preventing caking of blast furnace water granulated slag that can achieve a long-term anti-caking effect. .
以下、本実施の形態の高炉水砕スラグの固結防止剤、高炉水砕スラグの固結防止剤セット、及び高炉水砕スラグの固結防止方法を具体的に説明する。 Hereinafter, the anti-caking agent for granulated blast furnace slag, the anti-caking agent set for granulated blast furnace slag, and the anti-caking method for granulated blast furnace slag according to the present embodiment will be specifically described.
本実施の形態の高炉水砕スラグの固結防止剤は、高炉水砕スラグに添加されて、高炉水砕スラグの固結を防止するために用いられる剤であり、固結防止主剤及び付着性強化助剤を含有してなることを特徴とするものである。また、本実施の形態の高炉水砕スラグの固結防止剤セットは、高炉水砕スラグに添加されて、高炉水砕スラグの固結を防止するために用いられる剤のセットであり、固結防止主剤及び付着性強化助剤の組み合わせを含むことを特徴とするものである。 The anti-caking agent for granulated blast furnace slag according to the present embodiment is an agent that is added to the granulated blast furnace slag and used to prevent caking of the granulated blast furnace slag. It is characterized by containing a reinforcing aid. Moreover, the anti-caking agent set for blast furnace granulated slag according to the present embodiment is a set of agents that are added to the blast furnace granulated slag and used for preventing caking of the blast furnace granulated slag. It is characterized by including a combination of a preventive main agent and an adhesion enhancing aid.
本実施の形態の高炉水砕スラグの固結防止剤及び固結防止剤セットは、それぞれ上述のように構成されることによって、高炉水砕スラグに添加された場合、高炉水砕スラグの固結を防止する成分である固結防止主剤を高炉水砕スラグの表面に多量かつ強固に付着させて付着歩留まりを高めることができるとともに、保管時の水との接触による固結防止主剤の流失を防止し、低コストで長期の固結防止効果を実現することができる。 The anti-caking agent and anti-caking agent set of blast furnace granulated slag according to the present embodiment are configured as described above, and when added to the blast furnace granulated slag, the caking of the blast furnace granulated slag is consolidated. It is possible to increase the adhesion yield by attaching a large amount and strong adhesion of the anti-caking agent, which is a component to prevent slag, to the surface of the granulated blast furnace slag, and to prevent the caking-resistant main agent from being lost due to contact with water during storage. In addition, a long-term caking prevention effect can be realized at low cost.
固結防止主剤は、ソルビトール、グルコン酸及びグルコン酸塩からなる群から選択される１以上の化合物であることが好ましい。グルコン酸塩としては、例えば、グルコン酸ナトリウム、グルコン酸カルシウム、グルコン酸アンモニウム、グルコン酸鉄（II）、グルコン酸鉄（III）、グルコン酸カリウムを好適例として挙げることができる。 The caking preventive main agent is preferably one or more compounds selected from the group consisting of sorbitol, gluconic acid and gluconate. Preferred examples of gluconate include sodium gluconate, calcium gluconate, ammonium gluconate, iron (II) gluconate, iron (III) gluconate, and potassium gluconate.
また、付着性強化助剤は、アルミニウム化合物であることが好ましい。アルミニウム化合物としては、特に制限はないが、例えば、硫酸アルミニウム、塩化アルミニウム、アルミン酸ソーダ、ポリ塩化アルミニウム等を好適例として挙げることができる。 The adhesion enhancing aid is preferably an aluminum compound. Although there is no restriction | limiting in particular as an aluminum compound, For example, aluminum sulfate, aluminum chloride, sodium aluminate, a polyaluminum chloride etc. can be mentioned as a suitable example.
上述のように、固結防止効果には優れるが長期効果に難があるソルビトール、グルコン酸等を固結防止主剤として用い、これと付着性強化助剤を併用することによって、ソルビトール等の固結防止主剤のスラグ表面への付着が飛躍的に改善されて、長期の固結防止効果を確保することができる。 As described above, sorbitol, gluconic acid, etc., which are excellent in anti-caking effect but difficult in long-term effect, are used as an anti-caking agent, and by using this together with an adhesion enhancing aid, caking of sorbitol, etc. The adhesion of the preventive main agent to the slag surface is dramatically improved, and a long-term caking prevention effect can be ensured.
また、固結防止剤は、固結防止主剤１質量部に対して、付着性強化助剤を、アルミニウム化合物中の構成元素のＡｌをＡｌ2Ｏ3に換算して得られるＡｌ2Ｏ3量として、０．０１〜５０質量部の割合で含有してなることが好ましく、０．０２〜５質量部の割合で含有してなることがさらに好ましい。 Further, the anti-caking agent is an amount of Al 2 O 3 obtained by converting an adhesion strengthening auxiliary to Al 2 O 3 as the constituent element in the aluminum compound with respect to 1 part by mass of the anti-caking agent. It is preferable to contain in the ratio of 0.01-50 mass parts, and it is still more preferable to contain in the ratio of 0.02-5 mass parts.
このように構成することによって、高炉水砕スラグへの一度の添加だけで、長期的な固結防止効果を実現することができる。０．０１質量部未満であると、十分な付着性改善効果が得られないことがあり、また、５０質量部を超えると、所定の固結防止効果を実現するために必要な固結防止剤量に対して付着性強化助剤の添加量が過大となり、コストが増大するとともに、添加による手間が増加することがある。 By comprising in this way, a long-term caking prevention effect is realizable only by the addition to granulated blast furnace slag once. When the amount is less than 0.01 parts by mass, a sufficient adhesion improving effect may not be obtained. When the amount exceeds 50 parts by mass, the anti-caking agent necessary for realizing a predetermined anti-caking effect is obtained. The addition amount of the adhesion enhancing aid may be excessive with respect to the amount, which may increase the cost and labor of addition.
本実施の形態の固結防止剤の剤型としては、特に制限はないが、例えば、固体（錠剤、粉末）、液体等を挙げることができる。また、本実施の形態の固結防止剤セットは、固結防止主剤及び付着性強化助剤が別々の容器に収容された、いわゆる２剤タイプであることが好ましい。なお、各容器に収容される固結防止主剤及び付着性強化助剤の剤型についても特に制限はなく、例えば、固体（錠剤、粉末）、液体等を挙げることができる。 The dosage form of the anti-caking agent of the present embodiment is not particularly limited, and examples thereof include solids (tablets and powders) and liquids. Moreover, it is preferable that the anti-caking agent set of this Embodiment is what is called a 2 agent type by which the caking prevention main agent and the adhesion reinforcement | strengthening adjuvant were accommodated in the separate container. In addition, there is no restriction | limiting in particular about the dosage form of the caking prevention main agent and adhesive reinforcement | strengthening adjuvant accommodated in each container, For example, solid (tablet, powder), a liquid, etc. can be mentioned.
本実施の形態の第１の高炉水砕スラグの固結防止方法は、高炉水砕スラグに固結防止剤を添加して、前記高炉水砕スラグの固結を防止する方法であり、本発明の実施形態である前述の固結防止剤を添加することを特徴とするものである。 The first blast furnace granulated slag anti-caking method of the present embodiment is a method for preventing caking of the blast furnace granulated slag by adding an anti-caking agent to the blast furnace granulated slag. The above-described anti-caking agent as an embodiment of the present invention is added.
また、本実施の形態の第２の高炉水砕スラグの固結防止方法は、高炉水砕スラグの固結を防止する方法であり、固結防止主剤及び付着性強化助剤を高炉水砕スラグに添加することを特徴とするものである。 The second blast furnace granulated slag consolidation preventing method of the present embodiment is a method for preventing consolidation of the blast furnace granulated slag, and the anti-caking main agent and the adhesion enhancing aid are used as the blast furnace granulated slag. It is characterized by adding to the above.
このように、（ｉ）固結防止主剤及び付着性強化助剤を含有してなる固結防止剤を高炉水砕スラグに添加する（第１の高炉水砕スラグの固結防止方法）、或いは（ii）固結防止主剤及び付着性強化助剤を高炉水砕スラグにそれぞれ添加する（第２の高炉水砕スラグの固結防止方法）ことによって、固結防止主剤を高炉水砕スラグの表面に多量かつ強固に付着させて付着歩留まりを高めることができるとともに、保管時の水との接触による固結防止主剤の流失を防止し、低コストで長期の固結防止効果を実現することができる。 Thus, (i) an anti-caking agent containing an anti-caking main agent and an adhesion enhancing auxiliary is added to the blast furnace granulated slag (first method for preventing caking of the granulated blast furnace slag), or (Ii) The anti-caking agent and the adhesion-strengthening aid are added to the blast furnace granulated slag, respectively (second anti-caking method of blast furnace granulated slag), whereby the anti-caking agent is added to the surface of the granulated blast furnace slag. In addition to increasing the adhesion yield, it is possible to increase the adhesion yield and to prevent the caking preventive agent from flowing away due to contact with water during storage, and to realize a long-term caking prevention effect at low cost. .
付着性強化助剤の形態としては、液体でも固体でもよいが、例えば、液体のものを用い、固結防止主剤と混合後の固結防止剤の剤型を液体状にすることも可能である。この場合、液体状の固結防止剤を水砕スラグに一度添加して混合するだけの簡単な作業によって、また、薬剤貯留タンクや薬剤供給設備の追加の設置を要することなく、長期的な固結防止効果を実現することができる。 The form of the adhesion enhancing aid may be liquid or solid, but for example, it is possible to use a liquid and form the anti-caking agent and the anti-caking agent after mixing. . In this case, the liquid anti-caking agent can be added to the granulated slag once and mixed, and there is no need to install a drug storage tank or drug supply equipment for a long time. It is possible to achieve an anti-settling effect.
第２の高炉水砕スラグの固結防止方法においては、固結防止主剤１質量部に対して、付着性強化助剤を、アルミニウム化合物中の構成元素のＡｌをＡｌ2Ｏ3に換算して得られるＡｌ2Ｏ3量として、０．０１〜５０質量部の割合で高炉水砕スラグに添加することが好ましく、０．０２〜５質量部の割合で高炉水砕スラグに添加することがさらに好ましい。これにより、高炉水砕スラグへの一度の添加だけで、長期的な固結防止効果を実現することができる。 In the second blast furnace granulated slag consolidation prevention method, the adhesion strengthening aid is converted into Al 2 O 3 as the constituent element in the aluminum compound for 1 part by mass of the anti-caking main agent. The amount of Al 2 O 3 obtained is preferably added to the granulated blast furnace slag at a rate of 0.01 to 50 parts by mass, and further added to the granulated blast furnace slag at a rate of 0.02 to 5 parts by mass. preferable. Thereby, a long-term caking prevention effect is realizable only by one time addition to granulated blast furnace slag.
第２の高炉水砕スラグの固結防止方法においては、固結防止主剤及び付着性強化助剤を、同時に又は時間差を設けて添加することができる。同時に添加してもよいが、時間差を設けて添加する場合、例えば、固結防止主剤を高炉水砕スラグに一次添加した後に付着性強化助剤を二次添加すると、固結防止主剤が高炉水砕スラグに強固に付着し、高炉水砕スラグの長期的な固結防止効果を維持することができる。このような添加方法は、例えば、高炉水砕スラグの運搬から貯蔵までのプロセスで簡易に行うことが可能であり、具体的には、一次添加はベルトコンベア乗り継ぎ部での散布、二次添加はベルトコンベア切り出し部での散布で効率的に行うことができる。 In the second method for preventing caking of granulated blast furnace slag, the caking preventive main agent and the adhesion enhancing aid can be added simultaneously or with a time difference. Although it may be added at the same time, for example, when adding with a time difference, for example, when the anti-caking main agent is first added to the blast furnace granulated slag and then the adhesion enhancing aid is added secondarily, the anti-caking main agent is added to the blast furnace water. It adheres firmly to the crushed slag and can maintain the long-term caking prevention effect of the blast furnace granulated slag. Such an addition method can be easily performed, for example, in the process from transportation to storage of granulated blast furnace slag. Specifically, the primary addition is spraying at the belt conveyor connecting portion, and the secondary addition is It can be carried out efficiently by spreading at the belt conveyor cutout section.
以下、本発明を実施例によってさらに具体的に説明するが、本発明はこれらの実施例によっていかなる制限を受けるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
（実施例１）
５ｍｍ以下の粒度に調製した水砕スラグに、固結防止主剤としてソルビトールを、水砕スラグ１ｔあたり０．２ｋｇ、及び付着性強化助剤としてアルミン酸Ｎａを０．０１４ｋｇ−Ａｌ2Ｏ3／ｔ（固結防止主剤１質量部に対してアルミニウム化合物中の構成元素のＡｌをＡｌ2Ｏ3に換算して得られるＡｌ2Ｏ3量として０．０７質量部の含有（添加）割合に相当）を添加した。さらに、水砕スラグの含水比が１０質量％となる量のイオン交換水を添加し、ハンドシャベルを用いてよく混合し、混合スラグを得た。
(Example 1)
To granulated slag prepared to a particle size of 5 mm or less, sorbitol as an anti-caking agent, 0.2 kg per ton of granulated slag, and Na aluminate as an adhesion strengthening aid 0.014 kg-Al 2 O 3 / t (Equivalent to a content (addition) of 0.07 parts by mass as the amount of Al 2 O 3 obtained by converting Al as a constituent element in an aluminum compound to Al 2 O 3 with respect to 1 part by mass of the anti-caking agent) Was added. Further, ion-exchanged water was added in such an amount that the water content of the granulated slag was 10% by mass, and the mixture was thoroughly mixed using a hand shovel to obtain mixed slag.
（実施例２〜４及び比較例１〜６）
実施例１において、固結防止主剤の種類及び添加率並びに付着性強化助剤の種類及び添加量を表１に示すものに変えたこと以外は、実施例１と同様にした。また、表１中のポリアクリル酸Ｎａには、和光純薬工業社製のポリアクリル酸Ｎａ（重量平均分子量３，０００以下）を用いた。
(Examples 2 to 4 and Comparative Examples 1 to 6)
In Example 1, it carried out similarly to Example 1 except having changed the kind and addition rate of a caking prevention main ingredient, and the kind and addition amount of the adhesion reinforcement auxiliary agent into what was shown in Table 1. Moreover, polyacrylic acid Na (weight average molecular weight 3,000 or less) manufactured by Wako Pure Chemical Industries, Ltd. was used as polyacrylic acid Na in Table 1.
［固結防止効果の評価１（水砕スラグへの通水なしの場合）］
上述の実施例１〜４及び比較例１〜６で得られた混合スラグを直径１００ｍｍ×高さ２００ｍｍのサミットモールド内に１．５ｋｇ入れたのち、圧力を加えて０．１５Ｎ／ｍｍ2の圧力で３分間載荷した。これを除荷したのち、密封し、４０℃で所定の期間養生した。養生開始から２８、５６、９１日間経過後の各試料を取出し、５ｍｍ篩でふるった後、篩上に残った水砕スラグの質量を測定し、これをサミットモールドに入れた水砕スラグの総質量で除した値を固結割合（質量％）とし、固結防止効果を評価した。結果を表２に示す。
[Evaluation of anti-caking effect 1 (no water flow through granulated slag)]
After putting 1.5 kg of the mixed slag obtained in Examples 1 to 4 and Comparative Examples 1 to 6 into a summit mold having a diameter of 100 mm and a height of 200 mm, a pressure is applied and a pressure of 0.15 N / mm 2 is applied. And loaded for 3 minutes. After unloading, it was sealed and cured at 40 ° C. for a predetermined period. Each sample after 28, 56, and 91 days after the start of curing was taken out, sieved with a 5 mm sieve, the mass of the granulated slag remaining on the sieve was measured, and the total of the granulated slag put in the summit mold The value divided by mass was set as a consolidation ratio (mass%), and the anti-caking effect was evaluated. The results are shown in Table 2.
表２の結果より、固結防止主剤であるソルビトールを単独で用いた場合（比較例２）と比較して、固結防止主剤のソルビトールに付着性強化助剤であるアルミン酸Ｎａ又は硫酸アルミニウムを併用した場合（実施例１、２）は、特に、９１日目の固結割合において顕著に低い固結割合を示した。また、固結防止主剤にグルコン酸Ｎａを用いた場合についても、付着性強化助剤を用いない場合（比較例３）と比較して、付着性強化助剤にアルミン酸Ｎａ又は硫酸アルミニウムを併用した場合（実施例３、４）は、より低い固結割合を示した。一方、固結防止主剤を添加せず、付着性強化助剤であるアルミニウム化合物のみを用いた場合（比較例５、６）には、顕著な固結防止効果は得られなかった。以上のことから、固結防止主剤に付着性強化助剤を併用することにより、より長期の固結防止効果を得られることが分かる。これは、付着性強化助剤が、固結防止主剤の水砕スラグへの付着性を強化したことによると考えられる。 From the results of Table 2, compared to the case where sorbitol, which is a caking prevention main agent, is used alone (Comparative Example 2), the adhesion strengthening aid, Na aluminate or aluminum sulfate, is added to the sorbitol, the caking prevention main agent. When used in combination (Examples 1 and 2), a conspicuously low consolidation ratio was exhibited particularly in the consolidation ratio on the 91st day. Moreover, also when Na gluconate is used for the anti-caking agent, Na aluminate or aluminum sulfate is used in combination with the adhesion enhancing aid as compared with the case where the adhesion enhancing aid is not used (Comparative Example 3). In the cases (Examples 3 and 4), a lower consolidation ratio was shown. On the other hand, when the caking prevention main agent was not added and only the aluminum compound as the adhesion strengthening aid was used (Comparative Examples 5 and 6), no significant caking prevention effect was obtained. From the above, it can be seen that a long-term anti-caking effect can be obtained by using an adhesion enhancing auxiliary together with the anti-caking agent. This is considered to be because the adhesion enhancing auxiliary agent enhanced the adhesion of the caking preventive main agent to the granulated slag.
また、水砕スラグへの付着性の高いポリアクリル酸Ｎａを固結防止主剤に用いた場合（比較例４）では、固結防止剤を添加していない場合（比較例１）と比較してわずかに固結防止効果を示したものの、顕著な固結防止効果は得られなかった。 Moreover, when polyacrylic acid Na with high adhesiveness to granulated slag is used as the anti-caking agent (Comparative Example 4), compared with the case where no anti-caking agent is added (Comparative Example 1). Although a slight anti-caking effect was exhibited, a remarkable anti-caking effect was not obtained.
（実施例５）
５ｍｍ以下の粒度に調製した水砕スラグに、固結防止主剤としてソルビトールを、水砕スラグ１ｔあたり０．２ｋｇ、及び付着性強化助剤としてアルミン酸Ｎａを０．００２ｋｇ−Ａｌ2Ｏ3／ｔ（固結防止主剤１質量部に対してアルミニウム化合物中の構成元素のＡｌをＡｌ2Ｏ3に換算して得られるＡｌ2Ｏ3量として０．０１質量部の含有（添加）割合に相当）を添加した。さらに、水砕スラグの含水比が１０質量％となる量のイオン交換水を添加し、ハンドシャベルを用いてよく混合し、混合スラグを得た。
(Example 5)
0.002 kg-Al 2 O 3 / t of granulated slag prepared to have a particle size of 5 mm or less, sorbitol as an anti-caking agent, 0.2 kg per ton of granulated slag, and Na aluminate as an adhesion strengthening aid (Equivalent to a content (addition) ratio of 0.01 part by mass of Al 2 O 3 obtained by converting Al of the constituent element in the aluminum compound into Al 2 O 3 with respect to 1 part by mass of the anti-caking agent) Was added. Further, ion-exchanged water was added in such an amount that the water content of the granulated slag was 10% by mass, and the mixture was thoroughly mixed using a hand shovel to obtain mixed slag.
（実施例６〜１１及び比較例７〜８）
実施例５において、固結防止主剤及び付着性強化助剤の種類及び添加量を表３に示すものに変えたこと以外は、実施例５と同様にした。なお、付着性強化助剤にアルミン酸Ｎａ又は硫酸アルミニウムを用いた場合の添加量は、Ａｌ2Ｏ3としての添加量（ｋｇ−Ａｌ2Ｏ3／ｔ）である。また、表３中の実施例１１における「ポリＤＡＤＭＡＣ」とは、「ポリジアリルジメチルアンモニウムクロライド」を意味する。
(Examples 6-11 and Comparative Examples 7-8)
In Example 5, it carried out similarly to Example 5 except having changed into the thing shown in Table 3, and the kind and addition amount of the caking prevention main agent and adhesion reinforcement adjuvant. The addition amount in the case of using the aluminate Na or aluminum sulfate to the adhesion reinforcing aids are added amount of the Al 2 O 3 (kg-Al 2 O 3 / t). “PolyDADMAC” in Example 11 in Table 3 means “polydiallyldimethylammonium chloride”.
［固結防止効果の評価２（水砕スラグへの通水（雨水）ありの場合）］
ここでは、雨水による水砕スラグからの固結防止主剤の流失を想定し、固結防止主剤と混合された水砕スラグを水と接触させ、流出した水中の固結防止主剤量を測定することで、固結防止主剤のスラグへの付着性を評価するとともに、水と接触させた水砕スラグを養生し、養生後の水砕スラグの固結割合を算出し、固結防止効果（雨水に対する抵抗性）を評価した。
[Evaluation of anti-caking effect 2 (when water (rain water) flows through granulated slag)]
Here, assuming the loss of the caking preventive main agent from the granulated slag due to rain water, contact the water granulated slag mixed with the caking preventive main agent with water, and measure the amount of caking preventive main agent in the outflowed water In addition to evaluating the adhesion of the anti-caking agent to the slag, curing the granulated slag in contact with water, calculating the caking rate of the granulated slag after curing, Resistance) was evaluated.
まず、排水コック付きサミットモールドを作製した。その手順は以下のとおりである。直径１００ｍｍ×高さ２００ｍｍのサミットモールドの側面に、底面からの高さが１５ｍｍとなる位置に穴を開け、ここに内径３ｍｍのステンレスパイプを通し、固定した。次いで、サミットモールド内に２００ｍＬの砂利を入れ、その上に５Ａろ紙を置いた。さらに、ステンレスパイプに、コックを取り付けたビニールホースを接続し、これを排水コック付きサミットモールドとした。 First, a summit mold with a drain cock was prepared. The procedure is as follows. A hole was made in a side surface of a summit mold having a diameter of 100 mm and a height of 200 mm at a position where the height from the bottom surface was 15 mm, and a stainless steel pipe having an inner diameter of 3 mm was passed through and fixed. Next, 200 mL of gravel was placed in the summit mold, and 5A filter paper was placed thereon. Furthermore, the vinyl hose which attached the cock to the stainless steel pipe was connected, and this was made into the summit mold with a drain cock.
以下に、水と接触させた後の固結防止主剤の流出率の評価方法及び固結割合の算出方法を示す。実施例５〜１１及び比較例７〜８で得られた混合スラグを排水コック付きサミットモールド内に９００ｇ入れたのち、圧力を加えて０．１５Ｎ／ｍｍ2の圧力で３分間載荷した。これを除荷したのち、排水コックを閉じた状態で７００ｍＬのイオン交換水を約５分間かけてゆっくりと滴下した。これを１５分間静置したのち、排水コックを開け、流出水を回収した。回収した流出水の全有機炭素量を測定し、添加した固結防止主剤の全有機炭素量に対する比率を固結防止主剤流出率（単位：質量％）とした。 Below, the evaluation method of the outflow rate of the caking prevention main agent after making it contact with water, and the calculation method of a caking ratio are shown. After 900 g of the mixed slag obtained in Examples 5 to 11 and Comparative Examples 7 to 8 was placed in a summit mold with a drain cock, pressure was applied and loaded at a pressure of 0.15 N / mm 2 for 3 minutes. After unloading this, 700 mL of ion-exchanged water was slowly dropped over about 5 minutes with the drain cock closed. After standing for 15 minutes, the drain cock was opened and the effluent was collected. The total amount of organic carbon in the recovered effluent was measured, and the ratio of the added anti-caking main agent to the total organic carbon amount was defined as the anti-caking main agent outflow rate (unit: mass%).
さらに、水を流出させた後の排水コック付きサミットモールドのコックを閉じ、密封したのち、４０℃で所定の期間養生した。養生開始から２８日間経過後の各試料を取出し、５ｍｍ篩でふるった後、篩上に残った水砕スラグの質量を測定し、これをサミットモールドに入れた水砕スラグの質量で除した値を固結割合（単位：質量％）とした。結果を、固結防止主剤流出率の測定結果と併せて表３に示す。 Further, the cock of the summit mold with drain cock after draining water was closed and sealed, and then cured at 40 ° C. for a predetermined period. Each sample after 28 days from the start of curing was taken out, sieved with a 5 mm sieve, the mass of granulated slag remaining on the sieve was measured, and this was divided by the mass of granulated slag placed in the summit mold Was a consolidation ratio (unit: mass%). The results are shown in Table 3 together with the measurement results of the caking prevention main agent outflow rate.
表３に示すように、付着性強化助剤を添加した場合（実施例５〜１１）、これらを添加していない場合（比較例７、８）と比較して、固結防止主剤であるソルビトールの流出が抑制されていることが分かる。特にアルミニウム化合物であるアルミン酸ナトリウム又は硫酸アルミニウムを用いた場合に、顕著な流出の抑制効果が得られることがわかる。従って、付着性強化助剤、特にアルミニウム化合物を固結防止主剤と併せて添加することは、水砕スラグへの固結防止主剤の付着性を強化する上で有効であることが分かる。 As shown in Table 3, sorbitol, which is an anti-caking agent, was added when adhesion enhancing aids were added (Examples 5 to 11) and when these were not added (Comparative Examples 7 and 8). It can be seen that the outflow is suppressed. In particular, it can be seen that when aluminum aluminate or aluminum sulfate, which is an aluminum compound, is used, a remarkable effect of suppressing outflow is obtained. Therefore, it can be seen that the addition of an adhesion enhancing aid, particularly an aluminum compound, together with the anti-caking agent is effective in enhancing the adhesion of the caking preventing agent to the granulated slag.
また、表３に示すように、付着性強化助剤、特にアルミニウム化合物であるアルミン酸ナトリウム又は硫酸アルミニウムを添加した場合（実施例５〜９）、これらを添加していない場合（比較例７、８）と比較して、２８日目の固結割合が有意に低く、より長期の固結防止効果を与えていることが分かる。これは、付着性強化助剤であるアルミニウム化合物が、水砕スラグへの固結防止主剤の付着を強化して流出を抑制したことに起因するものと考えられる。 Moreover, as shown in Table 3, when an adhesion enhancing aid, particularly sodium aluminate or aluminum sulfate, which is an aluminum compound, was added (Examples 5 to 9), when these were not added (Comparative Example 7, Compared with 8), it can be seen that the consolidation ratio on day 28 is significantly lower, giving a longer-term consolidation prevention effect. This is considered to be due to the fact that the aluminum compound, which is an adhesion enhancing aid, strengthens the adhesion of the caking preventive main agent to the granulated slag and suppresses the outflow.
（実施例１２）
５ｍｍ以下の粒度に調製した水砕スラグに、固結防止主剤としてソルビトールを、水砕スラグ１ｔあたり０．２ｋｇ、及び水砕スラグの含水比が１０質量％となる量のイオン交換水を添加し、ハンドシャベルを用いてよく混合し、５分間放置した。次いで、付着性強化助剤として１０質量％濃度に調製したアルミン酸Ｎａを、０．００７ｋｇ−Ａｌ2Ｏ3／ｔとなる量（固結防止主剤１質量部に対してアルミニウム化合物中の構成元素のＡｌをＡｌ2Ｏ3に換算して得られるＡｌ2Ｏ3量として０．０３５質量部の含有（添加）割合に相当）添加し、ハンドシャベルを用いて混合した。
(Example 12)
To the granulated slag prepared to a particle size of 5 mm or less, add sorbitol as an anti-caking main agent, 0.2 kg per 1 ton of granulated slag, and ion-exchanged water in such an amount that the water content of the granulated slag is 10% by mass. Mix well using a hand shovel and let stand for 5 minutes. Next, Na aluminate prepared to a concentration of 10% by mass as an adhesion strengthening aid is used in an amount of 0.007 kg-Al 2 O 3 / t (a constituent element in the aluminum compound with respect to 1 part by mass of the anti-caking agent). of Al Al 2 O content of 0.035 parts by weight 3 as the amount of Al 2 O 3 obtained in terms of (added) corresponds to the ratio) was added and mixed using a hand shovel.
［固結防止効果の評価３（付着性強化助剤を後から添加した場合）］
前述の「固結防止効果の評価２（水砕スラグへの通水（雨水）ありの場合）」と同様の方法によって、実施例１２の混合スラグからの固結防止主剤流出率及び２８日間経過後の固結割合を評価した。
[Evaluation 3 of anti-caking effect (when adhesion enhancing aid is added later)]
By the same method as the above-mentioned “Evaluation 2 of anti-caking effect 2 (when water (rain water) is passed through granulated slag)”, the outflow rate of main caking prevention agent from the mixed slag of Example 12 and 28 days elapsed The subsequent consolidation rate was evaluated.
その結果、付着性強化助剤を後から添加した実施例１２では、固結防止主剤流出率が３５質量％、固結割合が３４質量％と、付着性強化助剤を固結防止主剤と同時に添加した場合（実施例６）と同等の値となった。このことから、付着性強化助剤は、固結防止主剤と同時に添加した場合でも、固結防止主剤が水砕スラグに添加・混合された後に添加した場合でも同様の効果を得られることがわかる。 As a result, in Example 12 in which the adhesion enhancing aid was added later, the outflow rate of the caking prevention main agent was 35% by mass and the caking rate was 34% by mass. When it was added (Example 6), the value was equivalent. From this, it can be seen that the adhesion enhancing aid can obtain the same effect even when it is added at the same time as the anti-caking agent, or when it is added after the anti-caking agent is added to and mixed with the granulated slag. .
（実施例１３）
特開２００３−３０６３５７号公報に記載された方法に準拠して、屋外フィールド試験用高炉水砕スラグ細骨材を得た。すなわち、高炉水砕スラグ細骨材をクラッシャーで破砕し、その破砕物に、固結防止主剤と付着性強化助剤とからなる固結防止剤（表４にその組成を示す）を水で希釈した希釈液を、固結防止主剤の破砕物に対する添加率が０．２５ｋｇ／ｔとなるように（このときの付着性強化助剤の添加率は０．００７１ｋｇ−Ａｌ2Ｏ3／ｔ）スプレーした後、スクリーンでふるい分けして５ｍｍ高炉スラグ細骨材粒度に調整した高炉水砕スラグを得、これを屋外フィールド試験用高炉スラグ細骨材とした。
(Example 13)
Based on the method described in JP-A-2003-306357, a blast furnace granulated slag fine aggregate for outdoor field test was obtained. That is, blast furnace granulated slag fine aggregate is crushed with a crusher, and the crushed material is diluted with water with an anti-caking agent (the composition of which is shown in Table 4) consisting of an anti-caking main agent and an adhesion enhancing auxiliary. Spray the diluted solution so that the addition rate of the anti-caking main agent to the crushed material is 0.25 kg / t (the addition rate of the adhesion enhancing aid at this time is 0.0071 kg-Al 2 O 3 / t). After that, blast furnace slag fine slag adjusted to 5 mm blast furnace slag fine aggregate particle size was obtained by sieving with a screen, and this was used as a blast furnace slag fine aggregate for outdoor field test.
（比較例９、１０）
固結防止主剤及び付着性強化助剤のいずれをも添加しなかった（比較例９）、又は固結防止主剤のみを実施例１３と同一の添加率で添加し、付着性強化助剤を添加しなかった（比較例１０）こと以外は実施例１３と同様の方法により、屋外フィールド試験用高炉スラグ細骨材を得た。
(Comparative Examples 9 and 10)
Neither the anti-caking agent or the adhesion strengthening aid was added (Comparative Example 9), or only the anti-caking agent was added at the same rate as in Example 13, and the adhesion enhancing aid was added. A blast furnace slag fine aggregate for outdoor field test was obtained in the same manner as in Example 13 except that it was not performed (Comparative Example 10).
［固結防止効果の評価４（屋外フィールド試験）］
屋外フィールド試験用高炉スラグ細骨材を、ショベルカーを用いて屋外に高さ３ｍの山として野積みした。野積みされた山について、野積み開始から１、２、４、６、８及び１２週のそれぞれの経過時点で、山内部の固結の程度を評価した（明らかな固結が認められた場合は、その週の次回の評価は行っていない）。固結の程度の評価は、ＡＳＴＭ Ｃ ４０３のプロクター貫入抵抗試験により求めたプロクター貫入抵抗値を指標とし、この抵抗値（単位：（Ｎ／ｍｍ2）が大きい程固結の程度が大きいと評価した。表５にその結果を示す。
[Evaluation of anti-caking effect 4 (outdoor field test)]
Blast furnace slag fine aggregate for outdoor field tests was piled up as a 3 m high mountain outdoors using a shovel car. For the piles piled up, the degree of consolidation inside the piles was evaluated at the time points of 1, 2, 4, 6, 8, and 12 weeks from the start of piled up (when clear consolidation was observed) Does not perform the next evaluation of the week). Evaluation of the degree of consolidation is based on the Procter penetration resistance value obtained by the ASTM C 403 Procter penetration resistance test, and the greater the resistance value (unit: (N / mm 2 )), the greater the degree of consolidation. Table 5 shows the results.
表５より、固結防止主剤及び付着性強化助剤のいずれをも含有する固結防止剤を使用した場合は、１２週経過時点でも１週目よりわずかに大きいプロクター貫入抵抗値を示したのみであり、１２週の試験期間中において、ほぼ固結が認められなかった。一方、固結防止主剤及び付着性強化助剤のいずれをも添加していない比較例９については、１週目から高いプロクター貫入抵抗値を示し、固結の進行の速さは他の２例と比べて明らかであった。また、固結防止主剤のみを添加し、付着性強化助剤を添加していない比較例１０においては、４週目までは実施例１３と同等のプロクター貫入抵抗値で推移したが、６週目から実施例１３と比較して高いプロクター貫入抵抗値を示し、１０週目には明らかな固結が認められた。比較例１０と実施例１３では、固結防止主剤の高炉スラグ細骨材に対する添加率は同じであり、両者における固結防止性能の違いは、付着性強化助剤によるものであると考えられる。また、上述の比較例５で示したように、付着性強化助剤であるアルミン酸Ｎａ単独では、固結防止効果はない、又は非常に小さいため、実施例１３で得られた高い固結防止性能は、付着性強化助剤であるアルミン酸Ｎａの固結防止主剤の単純な相加効果ではないといえる。これは、付着性強化助剤が、固結防止主剤の高炉スラグへの付着性を強化したことにより得られたものであると推定される。 From Table 5, when using the anti-caking agent containing both the anti-caking main agent and the adhesion enhancing aid, only a slightly larger Procter penetration resistance value than the first week was shown even after 12 weeks. In the test period of 12 weeks, almost no caking was observed. On the other hand, Comparative Example 9 to which neither the anti-caking agent nor the adhesion enhancing auxiliary agent was added showed a high Procter penetration resistance value from the first week, and the speed of the progress of caking was the other two cases. It was clear compared with. Further, in Comparative Example 10 in which only the caking preventive main agent was added and no adhesion strengthening aid was added, the same Procter penetration resistance value as in Example 13 was maintained until the 4th week, but the 6th week. Thus, a higher proctor penetration resistance value was exhibited as compared with Example 13, and clear consolidation was observed at 10 weeks. In Comparative Example 10 and Example 13, the addition rate of the anti-caking agent to the blast furnace slag fine aggregate is the same, and the difference in anti-caking performance between the two is considered to be due to the adhesion enhancing aid. Further, as shown in Comparative Example 5 above, Na aluminate, which is an adhesion enhancing aid, has no or very small anti-caking effect, so the high anti-caking obtained in Example 13 was obtained. It can be said that the performance is not a simple additive effect of the anti-caking main agent of Na aluminate which is an adhesion enhancing aid. This is presumed that the adhesion enhancing aid was obtained by strengthening the adhesion of the anti-caking agent to the blast furnace slag.
本発明は、高炉水砕スラグを用いる土木・建築等の産業分野において有効に利用される。 The present invention is effectively used in industrial fields such as civil engineering and construction using blast furnace granulated slag.
Claims (10)
固結防止主剤及び付着性強化助剤を含有してなることを特徴とする高炉水砕スラグの固結防止剤。 A blast furnace granulated slag anti-caking agent added to the blast furnace granulated slag to prevent caking of the blast furnace granulated slag,
An anti-caking agent for granulated blast furnace slag, comprising an anti-caking main agent and an adhesion enhancing auxiliary.
固結防止主剤及び付着性強化助剤の組み合わせを含むことを特徴とする高炉水砕スラグの固結防止剤セット。 An anti-caking agent set for granulated blast furnace slag that is added to the granulated blast furnace slag to prevent caking of the granulated blast furnace slag,
An anti-caking agent set for granulated blast furnace slag, comprising a combination of an anti-caking main agent and an adhesion enhancing auxiliary.
前記固結防止剤として、請求項１〜３のいずれか１項に記載の固結防止剤を添加することを特徴とする高炉水砕スラグの固結防止方法。 A method for preventing caking of blast furnace granulated slag by adding an anti-caking agent to blast furnace granulated slag and preventing caking of the blast furnace granulated slag,
The anti-caking method for granulated blast furnace slag, wherein the anti-caking agent according to any one of claims 1 to 3 is added as the anti-caking agent.
固結防止主剤及び付着性強化助剤を高炉水砕スラグに添加することを特徴とする高炉水砕スラグの固結防止方法。 A method of preventing consolidation of blast furnace granulated slag to prevent consolidation of granulated blast furnace slag,
A method for preventing consolidation of blast furnace granulated slag, comprising adding an anti-caking main agent and an adhesion enhancing auxiliary to blast furnace granulated slag.
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| JP2011201749A (en) * | 2010-03-26 | 2011-10-13 | Katayama Chem Works Co Ltd | Solidification preventing agent and solidification preventing method of granulated blast furnace slag |
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