JP4864806B2 - Anti-caking method and anti-caking agent for granulated blast furnace slag - Google Patents
Anti-caking method and anti-caking agent for granulated blast furnace slag Download PDFInfo
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- 239000002893 slag Substances 0.000 title claims description 82
- 239000003795 chemical substances by application Substances 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 24
- 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 description 99
- 239000007864 aqueous solution Substances 0.000 claims description 82
- 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 description 70
- 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 description 70
- 239000000174 gluconic acid Substances 0.000 claims description 70
- 235000012208 gluconic acid Nutrition 0.000 claims description 70
- 239000000600 sorbitol Substances 0.000 claims description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 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 description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000007596 consolidation process Methods 0.000 claims description 16
- 230000000694 effects Effects 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 17
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 12
- 230000002265 prevention Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000003139 buffering effect Effects 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000001692 EU approved anti-caking agent Substances 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
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229940050410 gluconate Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B5/00—Treatment of metallurgical slag ; Artificial stone from molten metallurgical slag
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
本発明は、高炉水砕スラグの固結防止方法および固結防止剤に関する。 The present invention relates to an anti-caking method and an anti-caking agent for granulated blast furnace slag.
高炉水砕スラグは、高炉から出滓した溶融スラグに高圧水を噴射し急冷凝固して、直接砂状に製造される。高炉水砕スラグの用途としては、微粉砕してセメント原料にしたり、製造されたままの粒度で土木工事用材や、また粒度・粒形調整をしてコンクリート用細骨材に利用される。粒度・粒形調整は、製造された砂粒を磨砕するなどによって行われる。 Granulated blast furnace slag is produced directly into sand by injecting high-pressure water into molten slag discharged from the blast furnace and rapidly solidifying it. Blast furnace granulated slag can be used as a raw material for cement by finely pulverizing, as well as for civil engineering materials with as-manufactured granularity, and fine aggregate for concrete by adjusting the particle size and particle shape. The particle size and particle shape are adjusted by grinding the produced sand particles.
ところで、高炉水砕スラグは、例えばコンクリート用細骨材に利用されるまでに、長期間野積みされることがあり、その際に固結するという問題がある。特に磨砕などを行って、粒度が細かくなった高炉水砕スラグは固結し易い。 By the way, there is a problem that blast furnace granulated slag is piled up for a long time before being used for fine aggregate for concrete, for example, and solidifies at that time. In particular, ground granulated blast furnace slag is easily consolidated by grinding.
固結防止技術については、従来から多数提案されてきたが、最も広く利用されているのは固結防止剤を添加する方法である。固結防止剤としては、脂肪族オキシカルボン酸やその塩（例えば、特許文献１参照）、糖アルコール類（例えば、特許文献２参照）、ソルビトール（特許文献３参照）、アクリル酸系重合体（例えば、特許文献５参照）、カルボキシル基含有ポリマーとソルビトール（特許文献６参照）、などが開示されている。 Many anti-caking techniques have been proposed in the past, but the most widely used is a method of adding an anti-caking agent. Examples of the anti-caking agent include aliphatic oxycarboxylic acids and salts thereof (see, for example, Patent Document 1), sugar alcohols (see, for example, Patent Document 2), sorbitol (see, Patent Document 3), acrylic acid polymers ( For example, Patent Document 5), carboxyl group-containing polymers and sorbitol (see Patent Document 6), and the like are disclosed.
従来の固結防止剤には、オキシカルボン酸やアクリル酸系重合体など、カルボキシル基をもつ物質が多く用いられている。しかしながらカルボキシル基をもつ物質単独や、これら同類物質を２種類以上含んだ場合でも長期的には必ずしも十分な効果が得られてはいなかった。近年では、長期固結防止のためにカルボキシル基をもつ高分子が開示されているが、高分子を主成分とする固結防止剤は、従来の低分子量成分からなる固結防止剤と比較して、同等質量添加した場合のスラグ粒子当たりに付着する分子数が少ないので、十分な効果が得られない。そのために多量に添加する必要があり、費用対効果に劣る。 As the conventional anti-caking agent, many substances having a carboxyl group such as oxycarboxylic acid and acrylic polymer are used. However, even when a substance having a carboxyl group alone or two or more of these similar substances are contained, a sufficient effect has not always been obtained in the long term. In recent years, polymers having carboxyl groups have been disclosed for the purpose of preventing long-term caking, but anti-caking agents composed mainly of polymers are compared with conventional anti-caking agents composed of low molecular weight components. In addition, since the number of molecules attached per slag particle when the same mass is added is small, a sufficient effect cannot be obtained. Therefore, it is necessary to add a large amount, which is inferior in cost effectiveness.
そこで本発明は、従来より長期固結防止が可能で、高分子系固結防止剤よりスラグ粒子当たりに付着する分子数を顕著に増加させることで少ない添加量でも固結防止効果が得られ、費用対効果にも優れる、高炉水砕スラグの固結防止剤及び固結防止方法を提供する。 Therefore, the present invention can prevent caking for a long period of time than before, and the caking prevention effect can be obtained even with a small addition amount by remarkably increasing the number of molecules attached per slag particle than the polymeric anti-caking agent, Provided are an anti-caking agent and an anti-caking method for granulated blast furnace slag, which are excellent in cost effectiveness.
本発明による高炉水砕スラグの固結防止剤は、ソルビトールとグルコン酸を含有する。ソルビトールまたはグルコン酸を単独で固結防止剤に用いる技術は既に知られているが、発明者等は、ソルビトール及びグルコン酸の固結防止効果を詳細に調査した結果、両物質を併用することで、著しい固結防止効果が発現できることを見いだした。 The anti-caking agent for granulated blast furnace slag according to the present invention contains sorbitol and gluconic acid. Although the technology of using sorbitol or gluconic acid alone as an anti-caking agent is already known, the inventors have investigated in detail the anti-caking effect of sorbitol and gluconic acid. It was found that a significant anti-caking effect can be exhibited.
高炉水砕スラグの固結は、高炉水砕スラグからＣａが溶出しｐＨが上昇することによって起こることが知られている。そこでソルビトール水溶液、グルコン酸水溶液、グルコン酸と水酸化ナトリウムを混合した水溶液のそれぞれに、水酸化カルシウム水溶液を添加することによって固結の模擬試験を行ったところ、図１の模式図に示すようなｐＨ変化を観察した。なお、図１において、「Ｓ」はソルビトール水溶液の場合、「Ｇ」はグルコン酸水溶液の場合、「ＧＮ」はグルコン酸と水酸化ナトリウムの混合水溶液の場合を示している。その結果、グルコン酸にはｐＨ緩衝効果のあることが分かったが、ソルビトールには同様な効果は全く見られなかった。また、グルコン酸と水酸化ナトリウムを混合した水溶液では、グルコン酸水溶液には劣るものの、ソルビトール水溶液よりはｐＨ緩衝効果があった。一方、両物質とも固結防止効果のあることを確認したが、ソルビトールは効果のバラツキが大きかった。 It is known that consolidation of granulated blast furnace slag occurs when Ca is eluted from the granulated blast furnace slag and pH is increased. Therefore, a simulation test of caking was performed by adding a calcium hydroxide aqueous solution to each of an aqueous solution of sorbitol, an aqueous solution of gluconic acid, and an aqueous solution in which gluconic acid and sodium hydroxide were mixed. As shown in the schematic diagram of FIG. A change in pH was observed. In FIG. 1, “S” indicates a sorbitol aqueous solution, “G” indicates a gluconic acid aqueous solution, and “GN” indicates a mixed aqueous solution of gluconic acid and sodium hydroxide. As a result, gluconic acid was found to have a pH buffering effect, but sorbitol did not show any similar effect. In addition, the aqueous solution in which gluconic acid and sodium hydroxide are mixed is inferior to the aqueous gluconic acid solution, but has a pH buffering effect than the aqueous sorbitol solution. On the other hand, both substances were confirmed to have an anti-caking effect, but sorbitol had a large variation in effects.
そこで、ソルビトールにグルコン酸を所定の比率で加えたところ、効果のバラツキが小さくなると共に、ソルビトール又はグルコン酸単独以上の固結防止効果があることを知見し、本発明を成すに至った。 Therefore, when gluconic acid was added to sorbitol at a predetermined ratio, the effect variation was reduced, and it was found that there was an anti-caking effect more than sorbitol or gluconic acid alone, and the present invention was achieved.
即ち、本発明の課題解決手段は以下の通りである。
（１） 高炉水砕スラグに、ソルビトールとグルコン酸の両方を水溶液として添加する固結防止方法であって、前記ソルビトールと前記グルコン酸の合計の添加量に対するソルビトールの添加量が５０〜９５質量％であることを特徴とする、高炉水砕スラグの固結防止方法。
（２） 前記ソルビトールと前記グルコン酸の合計の添加量が、前記高炉水砕スラグ１００質量部に対して、０．０１〜０．１質量部であることを特徴とする、（１）に記載の高炉水砕スラグの固結防止方法。
（３） 前記高炉水砕スラグに、前記ソルビトールと前記グルコン酸の両方を含む水溶液を添加する、又は、前記ソルビトールと前記グルコン酸と水酸化ナトリウム若しくは水酸化カリウムの少なくともいずれか一方とが混合された水溶液を添加することを特徴とする、（１）又は（２）に記載の高炉水砕スラグの固結防止方法。
（４） 前記高炉水砕スラグに、前記ソルビトールの水溶液を添加した後に、前記グルコン酸の水溶液又は前記グルコン酸と前記水酸化ナトリウム若しくは水酸化カリウムとが混合された水溶液を添加することを特徴とする、（１）〜（３）のいずれか１項に記載の高炉水砕スラグの固結防止方法。
（５） ソルビトールとグルコン酸の合計量に対するソルビトールの量が５０〜９５質量％の水溶液であることを特徴とする、高炉水砕スラグの固結防止剤。
（６） 前記水溶液中に、更に水酸化ナトリウム又は水酸化カリウムが含まれていることを特徴とする、（５）に記載の高炉水砕スラグの固結防止剤。
That is, the problem solving means of the present invention is as follows.
(1) An anti-caking method of adding both sorbitol and gluconic acid as an aqueous solution to granulated blast furnace slag, wherein the amount of sorbitol added relative to the total amount of sorbitol and gluconic acid is 50 to 95% by mass A method for preventing caking of granulated blast furnace slag, characterized in that
(2) The total addition amount of the sorbitol and the gluconic acid is 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the granulated blast furnace slag. To prevent caking of granulated blast furnace slag.
(3) An aqueous solution containing both the sorbitol and the gluconic acid is added to the granulated blast furnace slag, or the sorbitol, the gluconic acid, and at least one of sodium hydroxide or potassium hydroxide are mixed. A method for preventing caking of granulated blast furnace slag according to (1) or (2), wherein an aqueous solution is added.
(4) After adding the aqueous solution of sorbitol to the granulated blast furnace slag, an aqueous solution of the gluconic acid or an aqueous solution in which the gluconic acid and the sodium hydroxide or potassium hydroxide are mixed is added. The method of preventing consolidation of blast furnace granulated slag according to any one of (1) to (3).
(5) An anti-caking agent for granulated blast furnace slag, characterized in that the amount of sorbitol relative to the total amount of sorbitol and gluconic acid is an aqueous solution of 50 to 95% by mass.
(6) The anti-caking agent for granulated blast furnace slag according to (5), wherein the aqueous solution further contains sodium hydroxide or potassium hydroxide.
本発明の固結防止方法及び固結防止剤の適用により、固結防止期間を従来より延長することができ、長期間保管しておいても問題なく高炉水砕スラグを利用できる。 By applying the anti-caking method and anti-caking agent of the present invention, the anti-caking period can be extended compared to the prior art, and blast furnace granulated slag can be used without problems even if stored for a long time.
また、本発明の固結防止方法及び固結防止剤は、従来のカルボキシル基を有する高分子のみを主成分とする固結防止方法や固結防止剤と比較して、同等質量添加した場合のスラグ粒子当たりに付着する分子数を顕著に増加させることで少ない添加量でも十分な固結防止効果を得ることができる。従って、固結防止剤を多量に添加する必要がなく、費用対効果に優れる。 Further, the anti-caking method and anti-caking agent of the present invention are compared with the conventional anti-caking method and anti-caking agent mainly composed of a polymer having a carboxyl group, and when the same mass is added. By significantly increasing the number of molecules attached per slag particle, a sufficient anti-caking effect can be obtained even with a small addition amount. Therefore, it is not necessary to add a large amount of anti-caking agent, and it is excellent in cost effectiveness.
以下に添付図面を参照しながら、本発明の好適な実施の形態について詳細に説明する。 Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings.
本発明の高炉水砕スラグの固結防止方法及び固結防止剤は、ソルビトールとグルコン酸の両方を水溶液として高炉水砕スラグに添加し、且つ、両者の比率を所定の範囲にすることで、顕著な効果を発揮するものである。本発明の固結防止剤とは、溶質としてソルビトールとグルコン酸の両方を含有し、溶質のソルビトールと溶質のグルコン酸の合計量に対して溶質のソルビトールを所定の割合で含んでいる水溶液である。ソルビトール水溶液とグルコン酸水溶液を別々に添加する固結防止方法に用いる場合には、それぞれの水溶液を、固結防止用水溶液と呼ぶこととする。 The anti-caking method and anti-caking agent of the blast furnace granulated slag of the present invention are added to the blast furnace granulated slag as an aqueous solution of both sorbitol and gluconic acid, and by making the ratio of both within a predetermined range, It shows a remarkable effect. The anti-caking agent of the present invention is an aqueous solution containing both sorbitol and gluconic acid as solutes, and containing solute sorbitol in a predetermined ratio with respect to the total amount of solute sorbitol and solute gluconic acid. . When used in the anti-caking method in which an aqueous sorbitol solution and an aqueous gluconic acid solution are added separately, each aqueous solution will be referred to as an anti-caking aqueous solution.
本発明において高炉水砕スラグの固結防止に用いるソルビトールやグルコン酸には、例えば、製造用原料グルコースの未反応物などが少量残留している場合でも、本発明の方法に用いる固結防止用水溶液や本発明の固結防止剤中にソルビトールとグルコン酸とアルカリ金属水酸化物以外の成分が少量であれば（条件にもよるが、例えば、５質量％未満）本発明の効果は得られる。 In the present invention, the sorbitol and gluconic acid used for preventing consolidation of granulated blast furnace slag, for example, for the prevention of consolidation used in the method of the present invention, even when a small amount of unreacted material such as glucose for production remains. If there are a small amount of components other than sorbitol, gluconic acid and alkali metal hydroxide in the aqueous solution or the anti-caking agent of the present invention (depending on conditions, for example, less than 5% by mass), the effects of the present invention can be obtained. .
ソルビトールやグルコン酸の含有量は、例えば高速液体クロマトグラフ法で分析できる。 The content of sorbitol and gluconic acid can be analyzed by, for example, high performance liquid chromatography.
本発明の固結防止に用いるグルコン酸の水溶液は酸性を示す（５０質量％水溶液でｐＨは１．２程度）。高炉水砕スラグの固結は徐々にｐＨが上昇して起こることから、固結防止用水溶液や固結防止剤が酸性であることは、固結防止に対して好ましい。固結防止用水溶液や固結防止剤を添加する時の高炉水砕スラグのｐＨが既に高いものほど、例えば製造後経過時間の長いものほど、酸性の固結防止用水溶液や固結防止剤を用いるとより効果的である。しかし高炉水砕スラグのｐＨが１０．５程度未満である場合は、必ずしも固結防止用水溶液や固結防止剤が酸性でなくてもよい。 The aqueous solution of gluconic acid used for the anti-caking of the present invention is acidic (50% by mass aqueous solution and pH is about 1.2). Since consolidation of blast furnace granulated slag occurs with a gradual increase in pH, it is preferable for the prevention of consolidation that the aqueous solution for anti-caking and the anti-caking agent are acidic. The higher the pH of the granulated blast furnace slag when adding the anti-caking aqueous solution or anti-caking agent, for example, the longer the post-production elapsed time, the more the acidic anti-caking aqueous solution or anti-caking agent is added. It is more effective when used. However, when the pH of the granulated blast furnace slag is less than about 10.5, the anti-caking aqueous solution or anti-caking agent may not necessarily be acidic.
また、固結防止用水溶液や固結防止剤が中性に近いほど、取り扱い上の問題は少ない。 In addition, the closer the neutralization aqueous solution and anti-caking agent are to neutrality, the fewer the handling problems.
そこで本発明では、アルカリ金属水酸化物を加えて、ｐＨを調整したものを用いることも可能である。アルカリ金属水酸化物としては、例えば、水酸化ナトリウムや水酸化カリウムがあるが、コストの点において水酸化ナトリウムが好ましい。 Therefore, in the present invention, it is also possible to use a material whose pH is adjusted by adding an alkali metal hydroxide. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and sodium hydroxide is preferable in terms of cost.
アルカリ金属水酸化物の添加量は、高炉水砕スラグに添加する、グルコン酸とアルカリ金属化合物との混合水溶液、又はソルビトールとグルコン酸とアルカリ金属化合物との混合水溶液において、ｐＨが８．５程度まで可能である。 The addition amount of the alkali metal hydroxide has a pH of about 8.5 in a mixed aqueous solution of gluconic acid and an alkali metal compound or a mixed aqueous solution of sorbitol, gluconic acid and an alkali metal compound, which is added to the granulated blast furnace slag. Is possible.
本発明でスラグに添加する固結防止成分中のソルビトール含有量は、５０〜９５質量％である。この場合の含有量は、ソルビトールとグルコン酸の合計を１００質量％と定義する。原料中の不可避的残留成分や、グルコン酸の中和に用いるアルカリ金属水酸化物を含有量に含めないとする。本発明においては、ソルビトールの含有量が５０質量％未満であると、防止効果が急速に低下する。また、ソルビトールの含有量が９５質量％を越えると、ソルビトール単独と同様に効果のバラツキが大きく固結防止効果が安定しない。 The sorbitol content in the anti-caking component added to the slag in the present invention is 50 to 95% by mass. Content in this case defines the sum total of sorbitol and gluconic acid as 100 mass%. Suppose that unavoidable residual components in the raw material and alkali metal hydroxide used for neutralization of gluconic acid are not included in the content. In the present invention, when the sorbitol content is less than 50% by mass, the prevention effect is rapidly reduced. On the other hand, when the content of sorbitol exceeds 95% by mass, the effect variation is large as in the case of sorbitol alone, and the anti-caking effect is not stable.
本発明では固結防止用水溶液や固結防止剤を、水溶液中の溶質であるソルビトールとグルコン酸の正味質量として、高炉水砕スラグ（乾燥質量換算）１００質量部に対して０．０１〜０．１質量部添加する。この場合の０．０１〜０．１質量部は、溶質のソルビトールと溶質のグルコン酸の合計量とする。原料製造中の不可避的残留成分や、グルコン酸の中和に用いるアルカリ金属水酸化物、及び水溶液の水分は添加量に含めない。本発明に用いる合計添加量が０．０１質量部未満であると、十分な固結防止効果が得られない。一方、添加量の上限は特に規定しないが、ソルビトールとグルコン酸を添加した高炉水砕スラグをコンクリート用細骨材に利用する場合などは、ソルビトールとグルコン酸の合計添加量が０．１質量部を越えると、コンクリート品質に影響する場合があるため、０．１質量部以下であることが好ましい。 In the present invention, an anti-caking aqueous solution or an anti-caking agent is used in an amount of 0.01 to 0 with respect to 100 parts by mass of granulated blast furnace slag (in terms of dry mass) as the net mass of sorbitol and gluconic acid as solutes in the aqueous solution. Add 1 part by weight. In this case, 0.01 to 0.1 part by mass is the total amount of solute sorbitol and solute gluconic acid. Inevitable residual components during raw material production, alkali metal hydroxides used for neutralization of gluconic acid, and water in aqueous solutions are not included in the added amount. When the total addition amount used in the present invention is less than 0.01 parts by mass, a sufficient anti-caking effect cannot be obtained. On the other hand, the upper limit of the addition amount is not particularly specified, but when using blast furnace granulated slag added with sorbitol and gluconic acid for fine aggregate for concrete, the total addition amount of sorbitol and gluconic acid is 0.1 parts by mass. If it exceeds 1, it may affect the concrete quality, so it is preferably 0.1 parts by mass or less.
本発明における固結防止剤の高炉水砕スラグへの添加方法は、ソルビトールとグルコン酸を混合、又は更にアルカリ金属水酸化物を混合して水溶液とし、例えば０．５〜１０質量％の濃度に希釈して、スラグに散布する。希釈濃度は、固結防止剤がスラグに均一にかつ上記含有量添加できれば、０．５〜１０質量％に特定されるものではない。 In the present invention, the anti-caking agent is added to granulated blast furnace slag by mixing sorbitol and gluconic acid, or further mixing an alkali metal hydroxide to form an aqueous solution, for example, at a concentration of 0.5 to 10% by mass. Dilute and apply to slag. The dilution concentration is not limited to 0.5 to 10% by mass as long as the anti-caking agent can be added to the slag uniformly and the above content.
本発明ではまた、高炉水砕スラグにソルビトール水溶液を添加した後、グルコン酸水溶液、又はグルコン酸とアルカリ金属水酸化物を混合した水溶液を添加することも可能である。 Moreover, in this invention, after adding sorbitol aqueous solution to blast furnace granulated slag, it is also possible to add gluconic acid aqueous solution or the aqueous solution which mixed gluconic acid and the alkali metal hydroxide.
ソルビトールとグルコン酸を予め混合、又は更にアルカリ金属水酸化物を予め混合した水溶液（本発明の固結防止剤）を添加する方法が、最も確実に固結防止効果を得る方法であるが、これらの成分を別々に固結防止用水溶液として添加しても、両方共にほぼ均一に分散して添加できれば、ほぼ同等の効果が得られる。別々に添加する場合は、ソルビトール水溶液を添加した後、グルコン酸水溶液、又はグルコン酸とアルカリ金属水酸化物を混合した水溶液を添加することが好ましい。 A method of adding an aqueous solution (an anti-caking agent of the present invention) in which sorbitol and gluconic acid are mixed in advance, or further mixed with an alkali metal hydroxide in advance (the anti-caking agent of the present invention) is the method for obtaining the most effective anti-caking effect. Even if these components are separately added as an anti-caking aqueous solution, if both can be dispersed almost uniformly, substantially the same effect can be obtained. When adding separately, after adding sorbitol aqueous solution, it is preferable to add gluconic acid aqueous solution or the aqueous solution which mixed gluconic acid and the alkali metal hydroxide.
ソルビトールはスラグ表面に十分付着することで固結防止効果を発現するが、グルコン酸はｐＨ緩衝効果も発揮して固結を防止するので、必ずしもスラグ表面に直接付着している必要はなくスラグ表面に存在する水分中に含有されていれば良い。そこで、最初にソルビトール水溶液を添加してソルビトールをスラグに付着させた後、グルコン酸水溶液、又はグルコン酸とアルカリ金属水酸化物を混合した水溶液を添加しても、予め混合した場合とほぼ同等の固結防止効果が得られる。 Sorbitol exhibits sufficient anti-caking effect by adhering to the slag surface, but gluconic acid also exerts a pH buffering effect to prevent caking, so it is not always necessary to adhere directly to the slag surface. As long as it is contained in the water present in the water. Therefore, after first adding an aqueous sorbitol solution to adhere sorbitol to the slag, adding an aqueous gluconic acid solution or an aqueous solution in which gluconic acid and an alkali metal hydroxide are mixed is almost equivalent to the case of mixing in advance. A caking prevention effect is obtained.
固結防止用水溶液や固結防止剤を高炉スラグにできるだけ均一に分散させるために、本発明では固結防止用水溶液や固結防止剤における溶質成分濃度を調整する。すなわち、高炉スラグに添加した水溶液が流出してしまうと、必用な添加量が確保できないので、流出しない程度に、本発明では高炉スラグに対して水溶液を１〜１０質量部添加する。従って、添加する水溶液は、ソルビトールとグルコン酸の合計の濃度が０．１〜１０質量％になるよう調製した水溶液とすれば良い。 In order to disperse the anti-caking aqueous solution and the anti-caking agent as uniformly as possible in the blast furnace slag, in the present invention, the concentration of solute components in the anti-caking aqueous solution and the anti-caking agent is adjusted. That is, if the aqueous solution added to the blast furnace slag flows out, a necessary addition amount cannot be secured. Therefore, in the present invention, 1 to 10 parts by mass of the aqueous solution is added to the blast furnace slag to such an extent that the aqueous solution does not flow out. Therefore, the aqueous solution to be added may be an aqueous solution prepared so that the total concentration of sorbitol and gluconic acid is 0.1 to 10% by mass.
以下に、本発明の実施例及び比較例を示し、その結果を表１に示す。表１で「固結防止成分含有量（質量％）」として記載されている数値は、固結防止剤や固結防止用水溶液の溶質として添加する成分の合計含有量を１００としたときの各溶質成分の質量割合である。 Below, the Example and comparative example of this invention are shown, and the result is shown in Table 1. In Table 1, the numerical values described as “anti-caking component content (mass%)” are the values when the total content of the components added as the solute of the caking preventing agent and the caking preventing aqueous solution is 100. It is the mass ratio of the solute component.
実施例（実施例８を除く）及び比較例に使用したソルビトールは市販の含有量５０〜７０質量％の水溶液を用い、グルコン酸は市販の含有量４８〜５２質量％の水溶液を用いて、両水溶液を適正量混合して、各固結防止成分が所定の割合となるように混合してから使用した。また、ＮａＯＨを添加した固結防止用水溶液又は固結防止剤を用いる場合は、固結防止用水溶液又は固結防止剤を調整する時に、グルコン酸と当量のＮａＯＨを加えて所定の含有量になるようにした。この場合、表１にはグルコン酸Ｎａと記載する。 The sorbitol used in the examples (excluding Example 8) and the comparative example uses a commercially available aqueous solution with a content of 50 to 70% by mass, and gluconic acid uses a commercially available aqueous solution with a content of 48 to 52% by mass. A proper amount of the aqueous solution was mixed, and each anti-caking component was mixed at a predetermined ratio before use. In addition, when using an anti-caking aqueous solution or an anti-caking agent to which NaOH has been added, when adjusting the aqueous caking preventing solution or anti-caking agent, NaOH equivalent to gluconic acid is added to a predetermined content. It was made to become. In this case, Table 1 describes it as Na gluconate.
比較例として単独使用したソルビトールおよびグルコン酸は、実施例で用いたものと同じである。また、比較例では、固結防止成分として、カルボン酸を有する高分子であるポリアクリル酸Ｎａを使用し、質量平均分子量が約８０００で含有量が約４５質量％の水溶液を原液として、正味成分量が表１の成分に示す質量％になるよう混合して、固結防止用の水溶液を調製した。 The sorbitol and gluconic acid used alone as comparative examples are the same as those used in the examples. In the comparative example, polyacrylic acid Na, which is a polymer having a carboxylic acid, is used as an anti-caking component, and an aqueous solution having a mass average molecular weight of about 8000 and a content of about 45% by mass is used as a stock solution. An aqueous solution for preventing caking was prepared by mixing so that the amount was mass% shown in the components of Table 1.
本発明を適用する高炉水砕スラグは、製造時点で含水しており、製造後にヤードに移しても、少なくとも数質量％前後、多くは１０質量％程度の水分を含んだものである。このスラグに直接固結防止用水溶液や固結防止剤を適用する試験が好ましいが、固結を確認するまでに長時間を必要とすることから、本実施例では、固結を促進させるため硫酸カルシウムを添加した高炉水砕スラグ微粉末を用いて固結加速試験を行った。より固結し易いスラグを用いているので、実際に適用するスラグに対しても十分効果はある。 The granulated blast furnace slag to which the present invention is applied is water-containing at the time of production, and even if it is transferred to the yard after production, it contains water of at least about several mass%, most of which is about 10 mass%. A test in which an aqueous solution or an anti-caking agent is directly applied to the slag is preferable, but since it takes a long time to confirm caking, in this embodiment, sulfuric acid is used to promote caking. A consolidation acceleration test was performed using ground granulated blast furnace slag powder with added calcium. Since slag that is more easily consolidated is used, there is a sufficient effect on the slag that is actually applied.
そこで、本実施例では以下の方法で固結防止効果を評価した。先ず高炉水砕スラグ微粉末１００質量部に対し１４質量部の水を添加して、スラグと水を十分馴染ませた。これは、前記のように実際に適用するスラグが最初から含水していることを模擬するためである。 Therefore, in this example, the anti-caking effect was evaluated by the following method. First, 14 parts by mass of water was added to 100 parts by mass of ground granulated blast furnace slag, and the slag and water were sufficiently mixed. This is for simulating that the slag actually applied contains water from the beginning as described above.
その後、表１の固結防止成分の組成（質量％）となるように、固結防止剤または固結防止用水溶液のそれぞれを、スラグに対して溶質成分の合計質量が表に記載のスラグへの添加量（スラグ１００質量部に対する）になるように希釈して、スラグ（乾燥質量換算）に対して６質量部添加して、スラグと固結防止成分を十分馴染ませた。例えば含有量が約５０質量％のグルコン酸水溶液を用い、グルコン酸をスラグに対して０．０３質量部添加する場合は、該グルコン酸水溶液を１００倍希釈した固結防止用水溶液をスラグ１００質量部に対して６質量部添加する。また、ソルビトール：グルコン酸＝５０：５０質量％の固結防止剤をスラグに０．０３質量部添加する場合は、ソルビトール含有量が５０質量％の水溶液とグルコン酸含有量が５０質量％の水溶液を当量混合して２００倍希釈した水溶液を、スラグ１００質量部に対して６質量部添加する。 Thereafter, the anti-caking agent or the caking-preventing aqueous solution is added to the slag with the total mass of the solute component relative to the slag so that the composition (mass%) of the anti-caking component shown in Table 1 is obtained. It was diluted so that it would be an added amount (based on 100 parts by mass of slag), and 6 parts by mass was added to the slag (in terms of dry mass), so that the slag and the anti-caking component were sufficiently acclimated. For example, when using a gluconic acid aqueous solution having a content of about 50% by mass and adding 0.03 parts by mass of gluconic acid to slag, 100% by mass of the anti-caking aqueous solution obtained by diluting the gluconic acid aqueous solution 100 times 6 parts by mass is added to parts. When 0.03 parts by mass of a sorbitol: gluconic acid = 50: 50 mass% anti-caking agent is added to the slag, an aqueous solution having a sorbitol content of 50 mass% and an aqueous solution having a gluconic acid content of 50 mass% 6 parts by mass of an aqueous solution diluted 200 times by equivalent mixing with respect to 100 parts by mass of slag.
また固結防止成分を含まない水を同様な方法で添加した比較材も調製した（比較例８）。 Moreover, the comparative material which added the water which does not contain a caking prevention component by the same method was also prepared (Comparative Example 8).
従って、スラグに対する水分量は、実施例と比較例全てにおいて合計約２０質量部とした。固結防止用水溶液や固結防止剤を希釈した水溶液を添加する場合、厳密な水分添加量は６質量部未満となるが、水溶液中の固結防止成分濃度は約１質量％程度としたので、全水分量は何れの例も約２０質量％でほぼ同一と考えて差し支えない。 Therefore, the total amount of water relative to the slag was about 20 parts by mass in all of the examples and comparative examples. When adding an aqueous solution for anti-caking or an aqueous solution diluted with an anti-caking agent, the exact amount of water added is less than 6 parts by mass, but the concentration of the anti-caking component in the aqueous solution is about 1% by mass. In all cases, the total water content is about 20% by mass and can be considered to be almost the same.
次いで、固結防止用水溶液や固結防止剤を添加したスラグ微粉末を金型に充填し、φ２０×２０ｍｍ程度に圧縮成形して固結評価試験体を作成した。試験体が乾燥しないよう密封した後、常温で養生し、５日毎に試験体の圧縮強度を測定した。固結防止用水溶液や固結防止剤を含まない比較材の１０日強度を１００とした強度比を活性度指数として、各固結防止用水溶液や固結防止剤の各養生期間における強度を表１に示す。比較材の養生１０日以降の強度は、殆ど変化がなく、本固結評価試験条件における最大強度であり、活性度指数１００とした。また強度比が４程度以下、即ち圧縮強度が成形直後強度と殆ど同等であった場合は、固結していないとして、活性度指数を０として表した。 Next, a slag fine powder to which an aqueous solution for anti-caking or an anti-caking agent was added was filled in a mold, and compression molded to about φ20 × 20 mm to prepare a caking test specimen. After sealing the specimen so that it did not dry, it was cured at room temperature and the compressive strength of the specimen was measured every 5 days. The strength ratio of each anti-caking solution and anti-caking agent in the curing period is expressed as an activity index, with the strength ratio of the comparison material containing no anti-caking agent and anti-caking agent as 10 days. It is shown in 1. The strength of the comparative material after 10 days was almost unchanged, and was the maximum strength under the consolidation evaluation test conditions. Further, when the strength ratio was about 4 or less, that is, when the compressive strength was almost equal to the strength immediately after molding, the activity index was expressed as 0 because it was not consolidated.
実施例１は、ソルビトールとグルコン酸が５０質量％となる固結防止剤を、スラグ１００質量部に対し０．０１７質量部添加した。養生１０日目までは成形時の強度と変わりなく、まだ固結していなかった。１５日目では、最大強度の約３０％程度の強度を示し、１０〜１５日の間に顕著な固結が始まったと推定した。２０日目にはほぼ最大強度に達し、完全に固結した。 In Example 1, 0.017 parts by mass of an anti-caking agent containing 50% by mass of sorbitol and gluconic acid was added to 100 parts by mass of slag. Up to the 10th day of curing, the strength was not different from that at the time of molding and was not yet consolidated. On the 15th day, it showed an intensity of about 30% of the maximum intensity, and it was estimated that remarkable consolidation started within 10 to 15 days. On day 20, the maximum strength was reached and it was completely consolidated.
実施例２は、ソルビトール／グルコン酸が質量比８０／２０となる固結防止剤を、スラグ１００質量部に対し０．０１７質量部添加した。実施例１と同様、養生１０日目では成形時の強度と変わりなく、まだ固結していなかった。１５日目では、最大強度の約２１％程度の強度を示し、１０〜１５日の間に顕著な固結が始まったと推定した。しかし２０日目の強度は、最大強度の約９３％程度でまだ完全な固結には至っておらず、顕著な固結の開始時期は、実施例１よりは遅く、より固結防止効果に優れていると判断した。 In Example 2, 0.017 parts by mass of an anti-caking agent having a mass ratio of sorbitol / gluconic acid of 80/20 was added to 100 parts by mass of slag. As in Example 1, on the 10th day of curing, the strength at the time of molding was not changed, and it was not yet consolidated. On the 15th day, it showed an intensity of about 21% of the maximum intensity, and it was estimated that remarkable consolidation started within 10 to 15 days. However, the strength on the 20th day is about 93% of the maximum strength and has not yet been fully consolidated, and the start time of significant consolidation is later than in Example 1 and is more effective in preventing consolidation. It was judged that.
実施例３は、ソルビトール含有量が９５質量％であり、実施例１、２に比較してソルビトールの含有量が高いほど固結防止効果に優れていた。実施例４は、実施例３のグルコン酸に当量のＮａＯＨを添加した固結防止剤を用いた。実施例３よりは若干固結防止効果が低下したものの、実施例２相当の性能が発現していた。 In Example 3, the sorbitol content was 95% by mass, and the higher the sorbitol content compared to Examples 1 and 2, the better the anti-caking effect. In Example 4, an anti-caking agent obtained by adding an equivalent amount of NaOH to the gluconic acid of Example 3 was used. Although the anti-caking effect was slightly lower than in Example 3, the performance corresponding to Example 2 was exhibited.
実施例５は、実施例３と同一の固結防止剤を、スラグ１００質量部に対して０．０１質量部添加した例である。実施例３より固結防止期間は若干短くなったが、問題ない固結防止性能を示した。実施例６は、実施例３と同一の固結防止剤を、スラグ１００質量部に対して０．０９質量部添加した。２０日間の試験期間内では固結は観察されなかった。一方で固結防止剤コストは、実施例３の数倍である。 Example 5 is an example in which 0.01 parts by mass of the same anti-caking agent as Example 3 was added to 100 parts by mass of slag. Although the anti-caking period was slightly shorter than that in Example 3, the anti-caking performance was satisfactory. In Example 6, 0.09 parts by mass of the same anti-caking agent as in Example 3 was added to 100 parts by mass of slag. No consolidation was observed within the 20 day test period. On the other hand, the anti-caking agent cost is several times that of Example 3.
実施例７は、実施例３と同一の固結防止剤を、スラグ１００質量部に対して０．００５質量部添加した例である。添加量が実施例５の０．０１質量部より少ないと十分な固結防止ができない場合があった。この時の試料は、高炉水砕スラグ微粉末１００質量部に対し１４質量部の水を添加した後、固結防止剤を添加するまでの時間が長かった。高炉水砕スラグは、水と接触した製造直後からＣａが溶出しｐＨの上昇は始まり、ある時間経過した後に固結に至る。従って水と接触してからの経過時間の長いスラグほど固結し易い状態にある。実施例７は固結性の高まっているスラグを模擬した例である。 Example 7 is an example in which 0.005 parts by mass of the same anti-caking agent as Example 3 was added to 100 parts by mass of slag. When the amount added was less than 0.01 parts by mass of Example 5, there was a case where sufficient caking prevention could not be performed. The sample at this time took a long time to add an anti-caking agent after adding 14 parts by mass of water to 100 parts by mass of ground granulated blast furnace slag powder. In granulated blast furnace slag, Ca elutes immediately after production when it comes into contact with water, the pH starts to rise, and solidifies after a certain period of time. Therefore, the longer the slag has elapsed since contact with water, the easier it is to consolidate. Example 7 is an example simulating slag having increased caking properties.
実施例８は、実施例１と同じ固結成分添加量において、ソルビトール水溶液を添加した後、グルコン酸とアルカリ金属水酸化物を混合した水溶液を添加した例である。実施例１とほぼ同じ固結防止効果が得られ、この場合は事前の成分混合調整が不要となった。 Example 8 is an example in which an aqueous solution obtained by mixing gluconic acid and an alkali metal hydroxide was added after adding an aqueous sorbitol solution in the same amount of addition of the solidified component as in Example 1. Almost the same anti-caking effect as in Example 1 was obtained, and in this case, prior component mixing adjustment became unnecessary.
比較例１〜５は、実施例で用いた固結防止剤の成分を単独で用いた例である。いずれも養生１０日目までには固結が始まっていると推定され、実施例に劣った。 Comparative Examples 1 to 5 are examples in which the components of the anti-caking agent used in the examples were used alone. In any case, it was estimated that consolidation had started by the 10th day of curing, which was inferior to the examples.
比較例１、２はソルビトール単独使用例で実験条件は同じである。比較例１は最も効果があった場合で、比較例２は最も効果がなかった場合であり、固結防止効果が安定していなかった。比較例５はポリアクリル酸Ｎａを単独で用いたが、本発明の試験の中では最も固結防止効果が低かった。更に固結防止剤コストは、概ね実施例の２倍である。比較例６は比較例５においてポリアクリル酸Ｎａの２０％をソルビトールに置換した場合であり、比較例５よりは若干固結開始時間が遅くなったと思われるが、実施例ほどの固結防止効果は得られなかった。 Comparative Examples 1 and 2 are examples in which sorbitol is used alone, and the experimental conditions are the same. The comparative example 1 was the case where the effect was the most effective, and the comparative example 2 was the case where the effect was the least effective, and the caking prevention effect was not stable. In Comparative Example 5, polyacrylic acid Na was used alone, but the anti-caking effect was the lowest among the tests of the present invention. Furthermore, the cost of the anti-caking agent is approximately twice that of the example. Comparative Example 6 is a case where 20% of polyacrylic acid Na was replaced with sorbitol in Comparative Example 5, and it seems that the solidification start time was slightly delayed as compared with Comparative Example 5. Was not obtained.
比較例７は、ソルビトール／グルコン酸が質量比４０／６０の固結防止剤である。養生１０日目までには固結が始まらなかったが、１５日目までの間に固結防止効果が急激に低下した。ソルビトールの含有量が５０質量％未満であると、実施例１〜３ほどの効果が得られなかった。 Comparative Example 7 is an anti-caking agent having a sorbitol / gluconic acid mass ratio of 40/60. Although the caking did not start by the 10th day of curing, the caking prevention effect decreased sharply by the 15th day. When the content of sorbitol was less than 50% by mass, the effects as in Examples 1 to 3 were not obtained.
以上、添付図面を参照しながら本発明の好適な実施形態について説明したが、本発明はかかる例に限定されないことは言うまでもない。当業者であれば、特許請求の範囲に記載された範疇内において、各種の変更例または修正例に想到し得ることは明らかであり、それらについても当然に本発明の技術的範囲に属するものと了解される。 As mentioned above, although preferred embodiment of this invention was described referring an accompanying drawing, it cannot be overemphasized that this invention is not limited to this example. It will be apparent to those skilled in the art that various changes and modifications can be made within the scope of the claims, and these are naturally within the technical scope of the present invention. Understood.
Claims (6)
前記ソルビトールと前記グルコン酸の合計の添加量に対するソルビトールの添加量が５０〜９５質量％であることを特徴とする、高炉水砕スラグの固結防止方法。 An anti-caking method of adding both sorbitol and gluconic acid as an aqueous solution to granulated blast furnace slag,
The method for preventing consolidation of granulated blast furnace slag, wherein the amount of sorbitol added relative to the total amount of sorbitol and gluconic acid is 50 to 95% by mass.
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