JP2007099545A - Alumina cement composition and monolithic refractory using the same - Google Patents
Alumina cement composition and monolithic refractory using the same Download PDFInfo
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- JP2007099545A JP2007099545A JP2005289521A JP2005289521A JP2007099545A JP 2007099545 A JP2007099545 A JP 2007099545A JP 2005289521 A JP2005289521 A JP 2005289521A JP 2005289521 A JP2005289521 A JP 2005289521A JP 2007099545 A JP2007099545 A JP 2007099545A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000004568 cement Substances 0.000 title claims abstract description 78
- 239000000203 mixture Substances 0.000 title claims abstract description 50
- 239000011823 monolithic refractory Substances 0.000 title abstract 2
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 239000000654 additive Substances 0.000 claims abstract description 23
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 15
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000000292 calcium oxide Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 15
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 7
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 28
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 25
- 238000000034 method Methods 0.000 description 16
- 235000012255 calcium oxide Nutrition 0.000 description 13
- 239000000395 magnesium oxide Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 235000010755 mineral Nutrition 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- -1 alkali metal salts Chemical class 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 235000015165 citric acid Nutrition 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 5
- 150000008041 alkali metal carbonates Chemical class 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000001509 sodium citrate Substances 0.000 description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002978 Vinylon Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910001570 bauxite Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000011819 refractory material Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 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 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229910052845 zircon Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910052849 andalusite Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011044 quartzite Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
Abstract
Description
本発明は、従来のアルミナセメント組成物に比べて、30℃以上の高温雰囲気での施工において、流動性を長時間保持し、かつ高強度を発現することが可能なアルミナセメント組成物に関する。 The present invention relates to an alumina cement composition capable of maintaining fluidity for a long time and exhibiting high strength in construction in a high temperature atmosphere of 30 ° C. or higher as compared with a conventional alumina cement composition.
従来、アルミナセメント又はアルミナセメント組成物は、耐火性に優れていることから、不定形耐火物用バインダーとして広く使用されている。不定形耐火物の施工方法の一つに、アルミナセメント、耐火骨材、及び水を混合した不定形耐火物を型枠へ流し込む、所謂、流し込み施工が挙げられるが、流し込み時の施工温度の影響を受ける場合があった。特に30℃以上での高温雰囲気での施工においては、充填や鋳込み不良が発生し、乾燥後の施工体の強度が低下する等の課題があった。 Conventionally, alumina cement or an alumina cement composition is widely used as a binder for amorphous refractories because of its excellent fire resistance. One of the construction methods for amorphous refractories is so-called casting construction, in which an amorphous refractory mixed with alumina cement, refractory aggregate, and water is poured into the formwork, but the influence of construction temperature during casting. There was a case. In particular, in construction in a high temperature atmosphere at 30 ° C. or higher, there were problems such as filling and casting failure, and the strength of the construction body after drying was reduced.
その為、充填や鋳込み時間を充分に確保する為に、様々な添加剤が使用されている。アルミナセメントの鉱物組成と添加剤の種類に関する基本特性を述べた文献として、非特許文献１が挙げられる。
しかしながら、夏場に使用するために硬化遅延剤を添加して、硬化時間を調整した不定形耐火物を、例えば、秋頃のように、想定より低い気温の時に施工すると、硬化時間が長くなり、強度発現性が低下して、脱枠や乾燥等、養生後のスケジュールが遅れる等の課題があった。 However, when using a non-standard refractory with a curing retarder added for use in the summer and adjusting the curing time, such as in the fall, when the temperature is lower than expected, the curing time will be longer, There was a problem that the strength development was reduced and the schedule after curing was delayed such as unframed and dried.
これらの課題を解決するため、アルミナセメントにヒドロオキシカルボン酸塩等を配合してなるアルミナセメント組成物、無機炭酸塩等を配合してなるアルミナセメント組成物、及びポリメタクリル酸等を含有してなるアルミナセメント組成物等の、種々の添加剤を添加したアルミナセメント組成物が提案されている。
これらの添加剤は、添加剤の組み合わせや使用量、水硬成分の鉱物組成によりその作用が大きく異なり、耐火物分野、製銑設備や製鋼設備を始めとする鉄鋼分野において、特に高い温度で施工される場合には、十分ではなかった。 These additives vary greatly in action depending on the combination and amount of additives used and the mineral composition of the hydraulic component, and are applied at particularly high temperatures in the refractory field, steelmaking and other steel industries. If so, it was not enough.
本発明者は種々検討を重ねた結果、特定の鉱物組成のクリンカーと特定の添加剤を組み合せることにより、前記課題が解決できるとの知見を得て、本発明を完成するに至った。 As a result of various studies, the present inventor has obtained knowledge that the above problem can be solved by combining a clinker having a specific mineral composition and a specific additive, and has completed the present invention.
即ち、本発明は、CaO・Al2O3、CaO・2Al2O3、12CaO・7Al2O3、並びに、非晶質を含むアルミナセメントと、添加剤としてアルミナ、カルボン酸及び／又はその塩、炭酸塩、並びに、ポリアクリル酸及び／又はその塩を含むことを特徴とするアルミナセメント組成物であり、アルミナセメントの化学成分がCaO22〜32質量％、Al2O368〜78質量％で、アルミナセメントセメント70〜50質量部に対してアルミナを30〜50質量部含有することを特徴とする前記アルミナセメント組成物である。 That is, the present invention, CaO · Al 2 O 3, CaO · 2Al 2 O 3, 12CaO · 7Al 2 O 3, as well, the alumina cement containing amorphous alumina as an additive, the carboxylic acid and / or salts thereof , Carbonate, and polyacrylic acid and / or a salt thereof, an alumina cement composition characterized in that the chemical component of the alumina cement is CaO 22-32 mass%, Al 2 O 3 68-78 mass% The alumina cement composition is characterized by containing 30 to 50 parts by mass of alumina with respect to 70 to 50 parts by mass of alumina cement cement.
さらに、カルボン酸及び／又はその塩を1.0〜2.0質量％、炭酸塩を0.2〜1.0質量％、並びに、ポリアクリル酸及び／又はその塩を0.5〜1.5質量％含むことを特徴とする前記アルミナセメント組成物であり、カルボン酸及び／又はその塩がクエン酸及び／又はクエン酸塩、炭酸塩が炭酸ナトリウム、ポリアクリル酸塩がポリアクリル酸ナトリウムであることを特徴とする前記アルミナセメント組成物であり、前記アルミナセメント組成物と耐火骨材を含有してなる不定形耐火物である。 The alumina cement further comprising 1.0 to 2.0% by mass of carboxylic acid and / or salt thereof, 0.2 to 1.0% by mass of carbonate, and 0.5 to 1.5% by mass of polyacrylic acid and / or salt thereof. The alumina cement composition, wherein the carboxylic acid and / or salt thereof is citric acid and / or citrate, the carbonate is sodium carbonate, and the polyacrylate is sodium polyacrylate. Yes, it is an amorphous refractory containing the alumina cement composition and a refractory aggregate.
本発明のアルミナセメント組成物を用いた不定形耐火物は、30℃以上の高温雰囲気での施工においても高流動性並びに高強度発現性を有している。本発明のアルミナセメント組成物は、耐火物分野のみならず、高温下での高流動性、耐食性、耐摩耗性が要求される化学プラントのライニング材料や耐食材料としても好適である。 The amorphous refractory using the alumina cement composition of the present invention has high fluidity and high strength even in construction in a high temperature atmosphere of 30 ° C. or higher. The alumina cement composition of the present invention is suitable not only for the refractory field, but also as a lining material and corrosion resistant material for chemical plants that require high fluidity, corrosion resistance, and wear resistance at high temperatures.
本発明に係るアルミナセメントは、CaO・Al2O3（セメントの鉱物組成の記載方法に従い、以下「CA」という。）、CaO・2Al2O3（以下「CA2」という。）、12CaO・7Al2O3（以下「C12A7」という。）、並びに、非晶質を含むものであり、さらに、化学成分がCaO22〜32質量％、Al2O368〜78質量％であるものが好ましい。 The alumina cement according to the present invention includes CaO · Al 2 O 3 (hereinafter referred to as “CA” according to the description method of the mineral composition of the cement), CaO · 2Al 2 O 3 (hereinafter referred to as “CA 2 ”) , 12CaO · 7Al 2 O 3 (hereinafter referred to as “C 12 A 7 ”) as well as amorphous material, and chemical components of CaO 22 to 32 mass% and Al 2 O 3 68 to 78 mass% Is preferred.
本発明に係るアルミナセメントクリンカーは、赤ボーキサイト等の天然原料をバイヤープロセス等の精製法により精製して得られた高純度アルミナや、ボーキサイトなどのAl2O3源と、石灰石や生石灰などのCaO源を、所定の成分割合になるように配合し、電気炉、反射炉、縦型炉、平炉、シャフトキルン、及びロータリーキルン等の設備で溶融又は焼成して得られるものである。 The alumina cement clinker according to the present invention is a high-purity alumina obtained by refining a natural raw material such as red bauxite by a purification method such as a buyer process, an Al 2 O 3 source such as bauxite, and a CaO such as limestone or quicklime. The source is blended so as to have a predetermined component ratio, and is obtained by melting or firing in equipment such as an electric furnace, a reflection furnace, a vertical furnace, a flat furnace, a shaft kiln, and a rotary kiln.
目的とするアルミナセメントの鉱物組成を得る方法としては、CA―CA２―C12Ａ7組成物を一時に合成する方法、CA、CA２とC12Ａ7を所定の割合に配合する方法、CA―CA２組成物を一時に合成し、C12Ａ7を所定の割合で配合する方法などが挙げられる。 As a method of obtaining the target mineral composition of alumina cement, a method of synthesizing CA-CA 2 -C 12 A 7 composition at a time, a method of blending CA, CA 2 and C 12 A 7 in a predetermined ratio, Examples thereof include a method of synthesizing a CA-CA 2 composition at a time and blending C 12 A 7 at a predetermined ratio.
アルミナセメントの混合は、クリンカー同士を混合後、粉砕しても良く、あるいはまた、各々粉砕したものを混合しても良く、目的の鉱物組成比にする手段は特に制限されるものではない。 The mixing of the alumina cement may be performed after mixing the clinker and may be pulverized, or each pulverized product may be mixed, and the means for obtaining the target mineral composition ratio is not particularly limited.
本発明に係るアルミナセメントは、目的とするCA、CA２やC12Ａ7の他に、原料中の不可避的な不純物から生成する２CaO・Al2O3・SiO2（以下「C2AS」という。）、CaO・TiO2（以下「CT」という。）、及び４CaO・Al2O3・Fe2O3（以下「C4AF」という。）等を含む場合があるが、本発明の効果を阻害しない範囲であれば問題ない。アルミナセメント中の不純物の量は少ない方が好ましく、２．５質量％以下であることが好ましい。不純物の量が多いと、本発明のアルミナセメント組成物を用いた不定形耐火物の高温施工時の体積変化が大きくなり、充填や鋳込み不良が発生、或いは、スラグへの耐食性が低下する場合がある。 The alumina cement according to the present invention includes 2CaO.Al 2 O 3 .SiO 2 (hereinafter referred to as “C 2 AS”) produced from unavoidable impurities in the raw material in addition to the target CA, CA 2 and C 12 A 7. ), CaO.TiO 2 (hereinafter referred to as “CT”), 4CaO.Al 2 O 3 .Fe 2 O 3 (hereinafter referred to as “C 4 AF”), and the like. There is no problem as long as the effect is not disturbed. The amount of impurities in the alumina cement is preferably small, and is preferably 2.5% by mass or less. If the amount of impurities is large, the volume change during high-temperature construction of the amorphous refractory using the alumina cement composition of the present invention increases, filling or casting failure may occur, or corrosion resistance to slag may be reduced. is there.
本発明に係るアルミナセメントは、CA、CA２、C12Ａ7、並びに、非晶質を含む。そうでないと、例えば、マグネシア等の塩基性骨材を配合した不定形耐火物において、特に高温下で流動性や可使時間の確保が困難となり、充填や鋳込み不良が発生し、乾燥後の施工体の強度が低下する等、好ましくない場合がある。 Alumina cement according to the present invention include CA, CA 2, C 12 A 7, and an amorphous. Otherwise, for example, in an irregular refractory compounded with basic aggregates such as magnesia, it will be difficult to secure fluidity and pot life, especially at high temperatures, and filling and casting defects will occur. In some cases, the strength of the body decreases, and so on.
焼成法で本発明のアルミナセメントを製造する場合、Al2O3源とCaO源を所定の割合で混合又は混合粉砕し、ロータリーキルンにて1300℃以上の温度で焼成する。焼成温度は、一般に1400〜1600℃が好ましい。 When the alumina cement of the present invention is produced by a firing method, an Al 2 O 3 source and a CaO source are mixed or mixed and ground at a predetermined ratio, and fired at a temperature of 1300 ° C. or higher in a rotary kiln. The firing temperature is generally preferably 1400-1600 ° C.
溶融法で本発明のアルミナセメントを製造する場合、Al2O3源とCaO源を所定の割合で混合又は混合粉砕し、電気炉や平炉等の溶融装置によって、1500℃以上、好ましくは1600〜1800℃の温度で溶融後、高圧空気等に接触させて冷却するのが一般的である。 When the alumina cement of the present invention is produced by a melting method, the Al 2 O 3 source and the CaO source are mixed or mixed and pulverized at a predetermined ratio, and the melting device such as an electric furnace or a flat furnace is 1500 ° C. or higher, preferably 1600 to After melting at a temperature of 1800 ° C., it is generally cooled by contacting with high-pressure air or the like.
本発明のアルミナセメント中の非晶質は、18〜28質量％が好ましい。非晶質が28%を超えると、高温での流動性が低下したり、可使時間が短くなったりする場合がある。一方、非晶質が18質量%未満であると、硬化遅延が生じ作業効率が低下する場合がある。非晶質量は、例えば、試料に標準物質としてクォーツを添加してX線回折測定し、Rietveld法を用いて定量することが可能である。 The amorphous content in the alumina cement of the present invention is preferably 18 to 28% by mass. If the amorphous content exceeds 28%, the fluidity at high temperatures may decrease, or the pot life may be shortened. On the other hand, if the amorphous content is less than 18% by mass, there may be a delay in curing and work efficiency may be reduced. The amorphous amount can be quantified using, for example, the Rietveld method by adding quartz to a sample as a standard substance, measuring X-ray diffraction.
本発明に係るアルミナセメントクリンカーの粉砕は特に限定されるものではなく、通常、粉塊物の微粉砕に使用される、例えばローラーミル、ジエットミル、チューブミル、ボールミル、振動ミル等の粉砕機が使用可能である。 The pulverization of the alumina cement clinker according to the present invention is not particularly limited, and is usually used for fine pulverization of a lump, for example, a pulverizer such as a roller mill, a jet mill, a tube mill, a ball mill, or a vibration mill is used. Is possible.
粉砕したアルミナセメントのブレーン比表面積は、3000〜12000ｃｍ２／ｇが好ましく、4000cm２／g〜10000cm２／gがより好ましい。3000cm２／g未満では強度発現性が低下し、一方、12000cm２／gを超えると、流動性が低下する場合がある。 Blaine specific surface area of the milled alumina cement is preferably 3000~12000cm 2 / g, 4000cm 2 / g~10000cm 2 / g is more preferable. 3000 cm 2 / is less than g reduces the strength development, whereas exceeding 12000 2 / g, there is a case where the flowability is decreased.
本発明に係る添加剤としてのアルミナは、バイヤープロセス等によって高純度化処理された水酸化アルミニウムをロータリーキルンで焼成して得られる精製アルミナであって、Al2O3を９５質量％以上含有する高純度アルミナである。一般に、高純度アルミナ、バイヤーアルミナ、易焼結アルミナ、又は軽焼アルミナと呼ばれるものである。 Alumina as an additive according to the present invention is purified alumina obtained by firing aluminum hydroxide that has been highly purified by a buyer process or the like in a rotary kiln, and contains 95% by mass or more of Al 2 O 3. It is a pure alumina. In general, it is called high-purity alumina, buyer alumina, easily sintered alumina, or light-burned alumina.
本発明に係る添加剤としてのアルミナは、特に、不純物としてのNa2O含有量が重要である。Na2O量が多いと、本発明のアルミナセメント組成物を用いた不定形耐火物の流動性、耐火性が低下、又は高温下での収縮量が大きくなる場合がある。Na2O量は0.5質量％以下が好ましく、0.35質量％以下がより好ましい。 The content of Na 2 O as an impurity is particularly important for alumina as an additive according to the present invention. When the amount of Na 2 O is large, the flowability and fire resistance of the amorphous refractory using the alumina cement composition of the present invention may be lowered, or the amount of shrinkage at high temperatures may be increased. The amount of Na 2 O is preferably 0.5% by mass or less, and more preferably 0.35% by mass or less.
本発明においては、アルミナセメントクリンカーと添加剤としてのアルミナを配合し、粉砕機で混合粉砕することも、添加剤としてのアルミナを単独でアルミナセメントクリンカーと同程度の粒度まで粉砕後、クリンカー粉砕物と混合することも可能である。 In the present invention, an alumina cement clinker and alumina as an additive are blended and mixed and pulverized by a pulverizer. Alternatively, the alumina as an additive is pulverized to the same particle size as the alumina cement clinker alone, and then the clinker pulverized product. It is also possible to mix with.
アルミナセメントとアルミナの配合割合は、アルミナセメント70〜50質量部に対し、アルミナ30〜50質量部が好ましい。アルミナの配合量が50質量部を超えると、耐火性は増加するが、養生強度や乾燥後の強度が低下し、流動性も低下する場合がある。一方、30質量部未満では、耐火性が向上しない場合がある。 The mixing ratio of alumina cement and alumina is preferably 30 to 50 parts by mass of alumina with respect to 70 to 50 parts by mass of alumina cement. When the amount of alumina exceeds 50 parts by mass, fire resistance increases, but curing strength and strength after drying may decrease, and fluidity may also decrease. On the other hand, if it is less than 30 parts by mass, the fire resistance may not be improved.
本発明では、添加剤として、カルボン酸及び／又はその塩、炭酸塩、並びに、ポリアクリル酸及び／又はその塩を使用する。 In this invention, carboxylic acid and / or its salt, carbonate, and polyacrylic acid and / or its salt are used as an additive.
本発明に係るカルボン酸及び／又はその塩は、クエン酸、酒石酸、コハク酸、乳酸及びグルコン酸等のオキシカルボン酸、及び／又はその塩が挙げられる。これらのうち、クエン酸及び／又はそのアルカリ金属塩が好ましく、中でもクエン酸及び／又はクエン酸ナトリウムの使用が好ましい。カルボン酸又はその塩の粒度は、セメントと混和した際、水に溶解しやすいように、細かいほど好ましく、100メッシュ以下、特に200メッシュ以下が好ましい。カルボン酸又はその塩の純度は、特に限定されるものではないが、現在、工業的に精製されているカルボン酸又はその塩の使用が可能で、純度が80質量％程度以上のものが好ましい。中でも、不純物として硫酸塩が0.05質量％以下のクエン酸及び／又はそのアルカリ金属塩や、20℃における1質量％水溶液のpHが7〜10の範囲のクエン酸及び／又はそのアルカリ金属塩を使用することは、可使時間が長くとれ、作業性に優れる点から好ましい。本発明のカルボン酸及び／又はその塩の含有量は、アルミナセメント組成物中1.0〜2.0質量％が好ましい。カルボン酸及び／又はその塩の含有量が1.0質量％未満では、減水効果が低い、又は可使時間が短くなる傾向があり、一方、2.0質量％を超えると、温度が低下した場合に硬化が遅延し、強度発現性が低下する傾向がある。 Examples of the carboxylic acid and / or salt thereof according to the present invention include oxycarboxylic acid such as citric acid, tartaric acid, succinic acid, lactic acid and gluconic acid, and / or a salt thereof. Of these, citric acid and / or alkali metal salts thereof are preferred, and among these, use of citric acid and / or sodium citrate is preferred. The particle size of the carboxylic acid or a salt thereof is preferably as fine as possible so that it can be easily dissolved in water when mixed with cement, and is preferably 100 mesh or less, particularly preferably 200 mesh or less. The purity of the carboxylic acid or a salt thereof is not particularly limited, but currently industrially purified carboxylic acid or a salt thereof can be used, and a purity of about 80% by mass or more is preferable. Among them, citric acid and / or its alkali metal salt whose sulfate is 0.05 mass% or less as an impurity, citric acid and / or its alkali metal salt whose pH of 1 mass% aqueous solution at 20 ° C. is in the range of 7 to 10 are used. It is preferable that the pot life is long and the workability is excellent. The content of the carboxylic acid and / or salt thereof of the present invention is preferably 1.0 to 2.0% by mass in the alumina cement composition. If the content of the carboxylic acid and / or salt thereof is less than 1.0% by mass, the water reducing effect tends to be low, or the pot life tends to be short. On the other hand, if the content exceeds 2.0% by mass, curing occurs when the temperature decreases. There is a tendency to delay and decrease the strength development.
本発明に係る炭酸塩としては、炭酸ナトリウム、炭酸カリウム、炭酸カルシウム、炭酸水素カリウム、及び炭酸水素ナトリウム等が挙げられる。これらのうち、炭酸ナトリウムを使用することが好ましく、JISK1201、JISK8624、及びJISK8625で規定される炭酸ナトリウムを使用することが可能である。炭酸塩の粒度は、セメントと混和した際、水に溶解しやすいように、細かいほど好ましく、100メッシュ以下が好ましく、200メッシュ以下がより好ましい。アルカリ金属炭酸塩の純度は、特に限定されるものではないが、現在、工業的に製造されているアルカリ金属炭酸塩の使用が可能であり、純度が80質量％程度以上のものが好ましい。本発明のアルカリ金属炭酸塩の含有量は、アルミナセメント組成物中0.2〜1.0質量％が好ましい。アルカリ金属炭酸塩の量が0.2質量％未満では、可使時間が短くなる傾向があり、一方、1.0質量％を超えると、温度が低下した場合に硬化が遅延し、強度発現性が低下する傾向がある。 Examples of the carbonate according to the present invention include sodium carbonate, potassium carbonate, calcium carbonate, potassium bicarbonate, and sodium bicarbonate. Of these, sodium carbonate is preferably used, and sodium carbonate defined by JISK1201, JISK8624, and JISK8625 can be used. The particle size of the carbonate is preferably as fine as possible so as to be easily dissolved in water when mixed with cement, preferably 100 mesh or less, and more preferably 200 mesh or less. The purity of the alkali metal carbonate is not particularly limited, but it is possible to use an industrially produced alkali metal carbonate, and a purity of about 80% by mass or more is preferable. The content of the alkali metal carbonate of the present invention is preferably 0.2 to 1.0% by mass in the alumina cement composition. When the amount of the alkali metal carbonate is less than 0.2% by mass, the pot life tends to be shortened. On the other hand, when it exceeds 1.0% by mass, the curing is delayed when the temperature is lowered, and the strength development tends to be lowered. There is.
本発明では、ポリアクリル酸及び／又はその塩を使用する。ポリアクリル酸の塩としては、ナトリウム塩、カリウム塩、及びカルシウム塩等が使用可能であるが、入手のしやすさからナトリウム塩の使用が好ましい。特に、ポリアクリル酸ナトリウム及び／又はその塩の数平均分子量が15,000以下の水に可溶なもので、40質量％水溶液の25℃における粘度が1000mPa・s以下のものの使用が、流動性向上の面から好ましく、100〜500mPa・sの粘度のものがより好ましい。ポリアクリル酸及び／又はその塩の水溶液の粘度は、例えば、Ｂ型粘度計により測定できるが、ポリアクリル酸及び／又はその塩の重合度が高い程、粘度が大きくなる傾向がある。 In the present invention, polyacrylic acid and / or a salt thereof is used. As the salt of polyacrylic acid, sodium salt, potassium salt, calcium salt and the like can be used, but use of sodium salt is preferable from the viewpoint of availability. In particular, the use of sodium polyacrylate and / or its salt that is soluble in water having a number average molecular weight of 15,000 or less and whose 40% by weight aqueous solution has a viscosity at 25 ° C. of 1000 mPa · s or less improves fluidity. From the aspect, a viscosity of 100 to 500 mPa · s is more preferable. The viscosity of the aqueous solution of polyacrylic acid and / or a salt thereof can be measured by, for example, a B-type viscometer, but the viscosity tends to increase as the degree of polymerization of polyacrylic acid and / or a salt thereof increases.
本発明において、ポリアクリル酸及び／又はその塩を水溶液の状態で添加する場合、イオンの解離状態やpHは、特に限定されるものではないが、流動性向上の面から、ポリアクリル酸及び／又はその塩がアニオン性で、且つ、２５℃における１質量％スラリーのpHが中性からアルカリ性であることが好ましく、pHが7.5〜11であることがより好ましい。酸性であると、流動性が低下する傾向がある。 In the present invention, when polyacrylic acid and / or a salt thereof is added in the form of an aqueous solution, the dissociation state and pH of the ions are not particularly limited, but from the viewpoint of improving fluidity, polyacrylic acid and / or Alternatively, the salt thereof is anionic, and the pH of the 1% by mass slurry at 25 ° C. is preferably neutral to alkaline, and more preferably 7.5 to 11. If it is acidic, the fluidity tends to decrease.
本発明のポリアクリル酸及び／又はその塩の含有量は、アルミナセメント組成物中0.5〜1.5質量％が好ましい。ポリアクリル酸及び／又はその塩の含有量が0.5質量％未満では、可使時間が短くなる傾向があり、一方、1.5質量％を超えると、温度が低下した場合に硬化が遅延し、強度発現性が低下する傾向がある。 The content of the polyacrylic acid and / or salt thereof of the present invention is preferably 0.5 to 1.5% by mass in the alumina cement composition. When the content of polyacrylic acid and / or its salt is less than 0.5% by mass, the pot life tends to be shortened. On the other hand, when it exceeds 1.5% by mass, curing is delayed when the temperature is lowered, and strength is developed. Tend to decrease.
本発明においては、カルボン酸及び／又はその塩、炭酸塩、ポリアクリル酸及び／又はその塩の添加方法は、特に限定されるものではなく、各添加剤を所定の配合になるように混合し、あらかじめ粉砕したアルミナセメントクリンカーと、V型ブレンダー、コーンブレンダー、ナウターミキサー、パン型ミキサー、及びオムニミキサー等の混合機を用いて混合するか、あるいは、所定の配合でアルミナセメントクリンカーに添加後、振動ミル、チューブミル、ボールミル、及びローラーミル等の粉砕機で混合粉砕することが可能である。混合粉砕の方が、生産効率が良好で安価な生産が可能であり、好ましい。 In the present invention, the method of adding carboxylic acid and / or salt thereof, carbonate, polyacrylic acid and / or salt thereof is not particularly limited, and the respective additives are mixed so as to have a predetermined composition. Mix with pre-ground alumina cement clinker and blender such as V blender, cone blender, nauter mixer, pan mixer, omni mixer, etc. It can be mixed and pulverized by a pulverizer such as a vibration mill, a tube mill, a ball mill, and a roller mill. Mixed pulverization is preferable because production efficiency is good and inexpensive production is possible.
本発明に係る耐火骨材としては、溶融アルミナ、焼結アルミナ、仮焼アルミナ、及び易焼結アルミナ等のアルミナ、溶融マグネシア、焼結マグネシア、天然マグネシア、及び仮焼マグネシア等のマグネシア、溶融マグネシアスピネルや焼結マグネシアスピネル等のマグネシアスピネル、並びに、シリカヒューム、コロイダルシリカ、仮焼アルミナ、及び易焼結アルミナ等の超微粉、その他溶融シリカ、焼成ムライト、酸化クロム、ボーキサイト、アンダルサイト、シリマナイト、シャモット、ケイ石、ロー石、粘土、ジルコン、ジルコニア、ドロマイト、パーライト、バーミキシュライト、煉瓦屑、陶器屑、窒化珪素、窒化硼素、炭化珪素、及び窒化珪素鉄等が挙げられる。また、アルミナとジルコニアを溶融することで得られる、耐熱スポーリング性を向上させたアルミナ・ジルコニアクリンカー等の使用も可能である。 Examples of the refractory aggregate according to the present invention include alumina such as fused alumina, sintered alumina, calcined alumina, and easily sintered alumina, magnesia such as fused magnesia, sintered magnesia, natural magnesia, and calcined magnesia, and fused magnesia. Magnesia spinel such as spinel and sintered magnesia spinel, and ultrafine powder such as silica fume, colloidal silica, calcined alumina, and easily sintered alumina, other fused silica, calcined mullite, chromium oxide, bauxite, andalusite, sillimanite, Examples thereof include chamotte, quartzite, rholite, clay, zircon, zirconia, dolomite, pearlite, vermiculite, brick scrap, ceramic scrap, silicon nitride, boron nitride, silicon carbide, and silicon nitride iron. In addition, it is possible to use alumina / zirconia clinker or the like obtained by melting alumina and zirconia and having improved heat spalling properties.
中でも、本発明に係る不定形耐火物においては、耐火性、耐用性、及び耐食性の面から、アルミナ、マグネシア及び超微粉の中から選ばれる一種又は二種以上の耐火骨材を使用することが好ましい。 Among them, in the amorphous refractory according to the present invention, from the viewpoint of fire resistance, durability, and corrosion resistance, it is possible to use one or two or more kinds of refractory aggregates selected from alumina, magnesia and ultrafine powder. preferable.
マグネシアとしては、水酸化マグネシウムや炭酸マグネシウムを溶融又は焼成した溶融マグネシア又は焼結マグネシアや、軽焼マグネシア、仮焼マグネシアなどを所定のサイズに粉砕し、篩い分けしたものなどが挙げられる。 Examples of magnesia include molten magnesia or sintered magnesia obtained by melting or firing magnesium hydroxide and magnesium carbonate, light-burned magnesia, calcined magnesia, and the like, which are crushed to a predetermined size and sieved.
さらに、超微粉とは、粒子径10μｍ以下の粒子が80質量％以上占める耐火性微粉末であって、平均粒子径が1μｍ以下で、ＢＥＴ法による比表面積が10m2/g以上のものが、不定形耐火物に配合した際、流動性が確保でき、高強度を発現するため好ましい。具体的には、シリカヒューム、コロイダルシリカ、易焼結アルミナ、非晶質シリカ、ジルコン、炭化珪素、窒化珪素、酸化クロム、及び酸化チタン等の無機微粉が使用可能であり、このうち、シリカヒューム、コロイダルシリカ、及び易焼結アルミナの使用が好ましい。 Furthermore, the ultra fine powder is a refractory fine powder in which particles having a particle size of 10 μm or less occupy 80% by mass or more, an average particle size of 1 μm or less, and a specific surface area by the BET method of 10 m 2 / g or more, When blended with an amorphous refractory, fluidity can be secured and high strength is manifested. Specifically, inorganic fine powders such as silica fume, colloidal silica, easily sintered alumina, amorphous silica, zircon, silicon carbide, silicon nitride, chromium oxide, and titanium oxide can be used. , Colloidal silica, and easily sintered alumina are preferred.
耐火骨材は、通常、5〜3mm、3〜1mm、1mm下、200メッシュ下、及び325メッシュ下等のサイズのものを、使用目的に応じて配合するのが一般的である。 In general, refractory aggregates having a size of 5 to 3 mm, 3 to 1 mm, 1 mm, 200 mesh, 325 mesh, and the like are blended according to the purpose of use.
本発明に係る不定形耐火物中のアルミナセメント組成物と耐火骨材の配合割合は、施工場所に応じて適宜決定され、特に限定されるものではない。通常の不定形耐火物の製造方法に準じ、各材料を所定の配合になるように配合し、V型ブレンダー、コーンブレンダー、ナウターミキサー、パン型ミキサー、及びオムニミキサー等の混合機を用いて予め均一混合するか、あるいは、混練り機に直接秤込む事も可能である。 The mixing ratio of the alumina cement composition and the refractory aggregate in the amorphous refractory according to the present invention is appropriately determined according to the construction site and is not particularly limited. In accordance with the usual manufacturing method for irregular refractories, each material is blended to a prescribed blend, using a blender such as a V-type blender, cone blender, nauter mixer, pan-type mixer, and omni mixer. It is possible to carry out uniform mixing in advance or to directly weigh into a kneader.
更に本発明では、硬化調節を行う目的で、通常、不定形耐火物に配合される硬化遅延剤や硬化促進剤、流動化剤等の添加剤を流動性、強度等が低下しない範囲で併用することが可能である。 Furthermore, in the present invention, for the purpose of adjusting the curing, additives such as a retarder, a curing accelerator, a fluidizing agent, etc., which are usually blended in an amorphous refractory, are used in combination as long as fluidity, strength, etc. are not reduced. It is possible.
硬化促進剤としては、例えば、Li2CO3、Ca(OH)2、 NaOH、KOH等のリチウム塩や水酸化物が挙げられ、中でも、リチウム塩は硬化促進作用が強い。また、硬化遅延剤としては、例えば、カルボン酸類、アルカリ金属炭酸塩、硼酸類、ポリアクリル酸類、ポリメタクリル酸類及びヘキサメタ燐酸、トリポリ燐酸、ピロ燐酸等のアルカリ塩類、ポリカルボン酸系、ポリエーテル系減水剤等が挙げられる。 Examples of the curing accelerator include lithium salts and hydroxides such as Li 2 CO 3, Ca (OH) 2, NaOH, KOH, etc. Among them, the lithium salt has a strong curing promoting action. Examples of the curing retarder include, for example, carboxylic acids, alkali metal carbonates, boric acids, polyacrylic acids, polymethacrylic acids and alkali salts such as hexametaphosphoric acid, tripolyphosphoric acid, pyrophosphoric acid, polycarboxylic acid-based, polyether-based Examples include water reducing agents.
アルミナ原料とカルシウム原料を所定の割合で配合し、ロータリーキルンで1400〜1800℃で焼成して、表1に示す鉱物組成と化学成分のアルミナセメントクリンカーを製造した。製造したアルミナセメントクリンカーとアルミナを、アルミナセメント組成物のＣａＯ含有量が１６質量％になるよう混合し、ボールミルで同時粉砕してブレーン値6500cm2／gになるよう調整した。次に、添加剤ａ、添加剤ｂ及び添加剤ｃを、表１に示す量混合してアルミナセメント組成物を作製した。このアルミナセメント組成物７．３質量部に対して、耐火骨材92.7質量部を混合し、さらに、アルミナセメント組成物と耐火骨材の合計100質量部に対してシリカフラワー０．５質量部、ビニロン繊維０．１５質量部を添加して、混練直後のフロー値が180±10mmになるように加水、モルタルミキサーで4分間混練りして、不定形耐火物を得た。材料の混練りから養生は、35℃の恒温室内で行い、フロー値の経時変化と圧縮強度を測定した。結果を表１に示す。 Alumina raw material and calcium raw material were blended at a predetermined ratio and fired at 1400-1800 ° C. in a rotary kiln to produce an alumina cement clinker having the mineral composition and chemical components shown in Table 1. The produced alumina cement clinker and alumina were mixed so that the CaO content of the alumina cement composition was 16% by mass, and pulverized simultaneously with a ball mill to adjust the brane value to 6500 cm 2 / g. Next, additive a, additive b, and additive c were mixed in the amounts shown in Table 1 to prepare an alumina cement composition. 97.3 parts by mass of refractory aggregate is mixed with 7.3 parts by mass of this alumina cement composition, and further 0.5 parts by mass of silica flour with respect to 100 parts by mass in total of the alumina cement composition and the refractory aggregate, 0.15 parts by mass of vinylon fiber was added, and water was added so that the flow value immediately after kneading was 180 ± 10 mm, followed by kneading for 4 minutes with a mortar mixer to obtain an amorphous refractory. The materials were kneaded and cured in a constant temperature room at 35 ° C., and the flow value with time and the compressive strength were measured. The results are shown in Table 1.
〈使用材料〉
アルミナ原料：焼結アルミナ粉、純度98.0質量%
カルシア原料：炭酸カルシウム、純度96.0質量%
アルミナ：市販品、純度99.0質量%
添加剤ａ：クエン酸ナトリウム、石津製薬社製試薬1級
添加剤ｂ：炭酸ナトリウム、石津製薬社製試薬1級
添加剤ｃ：ポリアクリル酸ナトリウム、日本純薬社製試薬1級
耐火骨材：次に示す各骨材の混合物。
日本軽金属社製WAG5―3ｍｍ：17.0質量部
日本軽金属社製WAG3―1ｍｍ：24.5質量部
日本軽金属社製WAG1―0ｍｍ：24.5質量部
昭和電工社製Al―170：2.5質量部
日本軽金属社製MM―22B：2.5質量部
日本軽金属社製NR200F―T：12.0質量部
アルマティス社製T―60(―45MY)：3.7質量部
宇部化学社製U99S：6.0質量部
シリカフラワー：エルケム社製商品名「９７１Ｕ」
ビニロン繊維：クラレ社製商品名「ビニロン」
水：上水道水
<Materials used>
Alumina raw material: sintered alumina powder, purity 98.0% by mass
Calcia raw material: Calcium carbonate, purity 96.0% by mass
Alumina: Commercial product, purity 99.0% by mass
Additive a: Sodium citrate, reagent grade 1 additive made by Ishizu Pharmaceutical Co., Ltd. b: Sodium carbonate, reagent grade 1 additive made by Ishizu Pharmaceutical Co., Ltd. c: Sodium polyacrylate, reagent grade 1 fireproof aggregate made by Nippon Pure Chemical Co., Ltd .: A mixture of the following aggregates:
Nippon Light Metal Co., Ltd. WAG5-3mm: 17.0 parts by mass Nippon Light Metal Co., Ltd. WAG3-1mm: 24.5 parts by mass Nippon Light Metal Co., Ltd. WAG1-0mm: 24.5 parts by mass Showa Denko Co., Ltd. Al-170: 2.5 parts by mass MM by Nippon Light Metal Co., Ltd. 22B: 2.5 parts by mass Nippon Light Metal Co., Ltd. NR200F-T: 12.0 parts by mass Almatis T-60 (-45MY): 3.7 parts by mass Ube Chemical Co., Ltd. U99S: 6.0 parts by mass Silica Flower: Product name “971U by Elchem” "
Vinylon fiber: Kuraray brand name “Vinylon”
Water: tap water
〈測定方法〉
(1)フロー値：作製した不定形耐火物をJISR2521記載の方法に準じて、混練直後のフロー値を測定した。
(2)養生圧縮強度：JIS R 2521に準じて測定。40×40×160mmの型枠に混練物を詰め、35℃恒温室内で24時間養生した後、試験片の圧縮強度を測定した。
(3)乾燥圧縮強度：JIS R 2521に準じて測定。40×40×160mmの型枠に混練物を入れ、35℃恒温室内で24時間養生した後、更に110℃にて24時間乾燥して、試験片の圧縮強度を測定した。
<Measuring method>
(1) Flow value: The flow value immediately after kneading of the produced amorphous refractory was measured according to the method described in JISR2521.
(2) Curing compressive strength: Measured according to JIS R 2521. The kneaded material was packed in a 40 × 40 × 160 mm mold and cured for 24 hours in a 35 ° C. constant temperature room, and then the compressive strength of the test piece was measured.
(3) Dry compression strength: Measured according to JIS R 2521. The kneaded material was put into a 40 × 40 × 160 mm mold, cured in a constant temperature room at 35 ° C. for 24 hours, and further dried at 110 ° C. for 24 hours, and the compressive strength of the test piece was measured.
表１に示すように、本発明のアルミナセメント組成物は、流動性が良好で可使時間が長く、高い強度が得られる。 As shown in Table 1, the alumina cement composition of the present invention has good fluidity, long pot life, and high strength.
実験Ｎｏ．１−２のアルミナセメントクリンカーとアルミナの配合割合を表２に示すような割合に変更したこと以外は、実施例１と同様に行った。結果を表２に示す。 Experiment No. The same procedure as in Example 1 was conducted except that the mixing ratio of the alumina cement clinker of 1-2 and the alumina was changed to the ratio shown in Table 2. The results are shown in Table 2.
アルミナセメント70〜50質量部と、アルミナ30〜50質量部からなるアルミナセメント組成物は、流動性が良好で可使時間が長く、高い強度が得られる。 An alumina cement composition composed of 70-50 parts by mass of alumina cement and 30-50 parts by mass of alumina has good fluidity, long pot life, and high strength.
実験Ｎｏ．１−２のアルミナセメントクリンカーを用い、表３に示すように添加剤の添加量を変えたこと以外は、実施例１と同様に行った。結果を表３に示す。 Experiment No. The same procedure as in Example 1 was conducted, except that 1-2 alumina cement clinker was used and the additive amount was changed as shown in Table 3. The results are shown in Table 3.
表３に示すように、クエン酸ナトリウムを1.0〜2.0質量％、炭酸ナトリウムを0.2〜1.0質量％、並びに、ポリアクリル酸ナトリウムを0.5〜1.5質量％含むアルミナセメント組成物は、流動性が良好で可使時間が長く、高い強度が得られる。 As shown in Table 3, the alumina cement composition containing 1.0 to 2.0% by mass of sodium citrate, 0.2 to 1.0% by mass of sodium carbonate, and 0.5 to 1.5% by mass of sodium polyacrylate has good fluidity. Long pot life and high strength.
材料の混練りから養生を20℃の恒温室内で行ったこと以外は、実施例３と同様に行った。結果を表４に示す。 The same procedure as in Example 3 was performed except that the materials were kneaded and cured in a constant temperature room at 20 ° C. The results are shown in Table 4.
表４に示すように、クエン酸ナトリウムを1.0〜2.0質量％、炭酸ナトリウムを0.2〜1.0質量％、並びに、ポリアクリル酸ナトリウムを0.5〜1.5質量％含むアルミナセメント組成物は、室温でも流動性が良好で可使時間が長く、高い強度が得られる。
As shown in Table 4, the alumina cement composition containing 1.0 to 2.0 mass% sodium citrate, 0.2 to 1.0 mass% sodium carbonate, and 0.5 to 1.5 mass% sodium polyacrylate has fluidity even at room temperature. Good, long pot life and high strength.
Claims (5)
An amorphous refractory comprising the alumina cement composition according to any one of claims 1 to 4 and a refractory aggregate.
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| JP2009096658A (en) * | 2007-10-16 | 2009-05-07 | Denki Kagaku Kogyo Kk | Alumina cement composition, and monolithic refractory using the same |
| JP2013520392A (en) * | 2010-02-24 | 2013-06-06 | フラテッリ ビガラン ディ ビガラン ダリオ エ マリオ アンド セ エセ ア エセ | Reinforced composite material, method of preparing it, method of using it to prepare a product, and product formed by such a method and method of using the product |
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| JP2009096658A (en) * | 2007-10-16 | 2009-05-07 | Denki Kagaku Kogyo Kk | Alumina cement composition, and monolithic refractory using the same |
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