JP6831197B2 - Insulated amorphous refractory - Google Patents
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- 239000011819 refractory material Substances 0.000 claims description 27
- 239000004094 surface-active agent Substances 0.000 claims description 19
- 229920005610 lignin Polymers 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000005484 gravity Effects 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 11
- 238000009472 formulation Methods 0.000 claims description 3
- 238000005452 bending Methods 0.000 description 7
- 239000004088 foaming agent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- -1 for example Substances 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 244000205754 Colocasia esculenta Species 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- 240000004270 Colocasia esculenta var. antiquorum Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 229920000569 Gum karaya Polymers 0.000 description 1
- 229920000161 Locust bean gum Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000934878 Sterculia Species 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 229920002310 Welan gum Polymers 0.000 description 1
- 206010000496 acne Diseases 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 229920000591 gum Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 235000010494 karaya gum Nutrition 0.000 description 1
- 239000000231 karaya gum Substances 0.000 description 1
- 229940039371 karaya gum Drugs 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910001562 pearlite Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052851 sillimanite Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 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
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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- Ceramic Products (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
- Furnace Charging Or Discharging (AREA)
Description
本発明は、断熱不定形耐火物に関する。 The present invention relates to a heat insulating amorphous refractory.
従前より、例えば鋼片加熱炉や均熱炉のスキッドパイプのように、耐火性のみならず断熱性も要求される部位に断熱不定形耐火物が用いられている。 Conventionally, heat-insulating amorphous refractories have been used in parts where not only fire resistance but also heat insulation is required, such as skid pipes of steel piece heating furnaces and soaking furnaces.
不定形耐火物に断熱性を付与する技術としては、オガクズ等の可燃性物質を燃焼（焼失）させることにより、耐火物内部に空隙（気孔）を形成する技術が知られている。例えば、特許文献１には断熱性骨材としてオガクズを用いることが記載されており（第２頁左欄）、特許文献２には気孔付与剤としてオガクズを用いることが記載されている（段落００３８）。また、特許文献３には、発泡剤として過酸化物の水溶液を用いるとともに気孔形成材としておがくずを用いることが記載されている（段落００３５）。 As a technique for imparting heat insulation to an amorphous refractory, a technique for forming voids (pores) inside the refractory by burning (burning) a flammable substance such as sawdust is known. For example, Patent Document 1 describes the use of sawdust as a heat insulating aggregate (left column on page 2), and Patent Document 2 describes the use of sawdust as a pore-imparting agent (paragraph 0038). ). Further, Patent Document 3 describes that an aqueous solution of a peroxide is used as a foaming agent and sawdust is used as a pore-forming material (paragraph 0035).
しかし、オガクズを添加してこれを燃焼（焼失）させることにより耐火物内部に空隙（気孔）を形成する技術では、オガクズと耐火材料との比重差などによりオガクズが耐火材料中に均一に分散しにくく、結果として耐火物内部に空隙（気孔）を均一に分散させることが困難である。 However, in the technology of forming voids (pores) inside the refractory by adding sawdust and burning (burning) it, the sawdust is uniformly dispersed in the refractory material due to the difference in specific gravity between the sawdust and the refractory material. It is difficult, and as a result, it is difficult to uniformly disperse voids (pores) inside the refractory.
一方、特許文献３のように発泡剤を用いれば耐火物内部に空隙（気孔）を均一に分散させることは可能であるが、発泡剤はガスを発生するので、そのガスの種類によっては爆発等のおそれがある。例えば、特許文献３に例示されている過酸化物の水溶液からは助燃性ガスである酸素が発生するので、周囲に火種があると爆発を招くおそれがある。また、水素を発生する発泡剤もあり、このような発泡剤を用いると爆発の危険性が高くなる。 On the other hand, if a foaming agent is used as in Patent Document 3, it is possible to uniformly disperse voids (pores) inside the refractory, but since the foaming agent generates gas, it may explode depending on the type of gas. There is a risk of. For example, since oxygen, which is a flammable gas, is generated from the aqueous solution of peroxide exemplified in Patent Document 3, there is a risk of explosion if there is a fire in the surroundings. There are also foaming agents that generate hydrogen, and the use of such foaming agents increases the risk of explosion.
本発明が解決しようとする課題は、発泡剤を用いることなく耐火物内部に空隙（気孔）を均一に分散させることができる断熱不定形耐火物を提供することある。 An object to be solved by the present invention is to provide a heat-insulating amorphous refractory capable of uniformly dispersing voids (pores) inside the refractory without using a foaming agent.
本発明者らが前記課題を解決するために、従前より断熱不定形耐火物に用いられているオガクズの作用について検討を重ねた結果、オガクズから溶出するリグニンが界面活性剤と共存すると、その相互作用により優れた起泡効果が得られ、しかもその泡を安定化させる効果も得られることがわかった。 As a result of repeated studies by the present inventors on the action of sawdust, which has been used in heat-insulating amorphous refractories in order to solve the above-mentioned problems, when lignin eluted from sawdust coexists with a surfactant, the mutual It was found that an excellent foaming effect was obtained by the action, and also an effect of stabilizing the foam was obtained.
すなわち、本発明の一観点によれば次の断熱不定形耐火物が提供される。
「耐火材料と添加剤との配合物に水を添加してなる断熱不定形耐火物であって、
前記添加剤として、リグニンを溶出する材料と界面活性剤とを含有し、
前記リグニンを溶出する材料として針葉樹のオガクズを前記耐火材料に対して０．３質量％以上５質量％以下、前記界面活性剤を前記耐火材料に対して０．００１質量％以上０.２質量％以下含有し、
水の添加量は、前記配合物に対して３５質量％以上６０質量％以下であり、
常温で２４時間養生して１１０℃で２４時間乾燥させたときのかさ比重が１．６以下である断熱不定形耐火物。」
That is, according to one aspect of the present invention, the following heat-insulating amorphous refractory is provided.
"A heat-insulating amorphous refractory made by adding water to a combination of a refractory material and an additive.
As the additive, a material for eluting lignin and a surfactant are contained, and
As a material for eluting the lignin, sawdust of coniferous tree is 0.3% by mass or more and 5% by mass or less with respect to the refractory material, and the surfactant is 0.001% by mass or more and 0.2% by mass with respect to the refractory material. Contains the following,
The amount of water added is 35% by mass or more and 60% by mass or less with respect to the formulation.
A heat-insulating amorphous refractory having a bulk specific gravity of 1.6 or less when cured at room temperature for 24 hours and dried at 110 ° C for 24 hours. "
本発明の断熱不定形耐火物は、添加剤としてリグニンを溶出する材料と界面活性剤とを含有するので、耐火材料と添加剤との配合物に水を添加して混練する際に、溶出したリグニン及び界面活性剤が相互作用により優れた起泡効果を発揮するとともに、その泡を安定化させる。これにより、発泡剤を用いることなく耐火物内部に空隙（気孔）を均一に分散させて、常温で２４時間養生して１１０℃で２４時間乾燥させたときのかさ比重が１．６以下という低かさ比重で断熱性の高い断熱不定形耐火物を得ることができる。 Since the heat-insulating amorphous refractory of the present invention contains a material that elutes lignin and a surfactant as additives, it elutes when water is added to the mixture of the refractory material and the additive and kneaded. The lignin and the surfactant exert an excellent foaming effect by the interaction and stabilize the foam. As a result, the voids (pores) are uniformly dispersed inside the refractory without using a foaming agent, and the bulk specific gravity is as low as 1.6 or less when cured at room temperature for 24 hours and dried at 110 ° C. for 24 hours. A heat-insulating amorphous refractory with a bulky specific gravity and high heat-insulating properties can be obtained.
本発明の断熱不定形耐火物は、通常の不定形耐火物（キャスタブル耐火物）と同様に、耐火材料と添加剤との配合物に水を添加し混練することで得られる。 The heat-insulating amorphous refractory of the present invention can be obtained by adding water to a mixture of a refractory material and an additive and kneading the mixture in the same manner as a normal amorphous refractory (castable refractory).
耐火材料としては、例えば、ＣａＯ・６Ａｌ２Ｏ３（カルシウムヘキサアルミネート、以下「ＣＡ６」という。）を主たる鉱物組成とする断熱性骨材、アルミナ、マグネシア、シャモット、シリカ、チタニア、ジルコン、スピネル、バーミキュライト、パーライト、軽石、断熱れんが屑、カイヤナイト等のシリマナイト族鉱物、ムライト等から選択される一種以上を用いることができる。なお、耐火材料としては、ＣＡ６を主たる鉱物組成とする断熱性骨材を用いることが好ましい。ＣＡ６は軽量でかつ熱伝導率が低く、耐スケール溶損性に優れるという特徴を有しており、断熱不定形耐火物の断熱性をさらに向上させることができる。 The refractory material, for example, CaO · 6Al 2 O 3 (calcium hexaaluminate, hereinafter referred to as "CA6".) The heat-insulating aggregate whose main mineral composition, alumina, magnesia, chamotte, silica, titania, zircon, spinel , Vermiculite, pearlite, pimples, adiabatic brick scraps, sillimanite minerals such as kayanite, and one or more selected from mullite and the like can be used. As the refractory material, it is preferable to use a heat insulating aggregate having CA6 as a main mineral composition. CA6 is lightweight, has low thermal conductivity, and has excellent scale melting resistance, and can further improve the heat insulating property of a heat insulating amorphous refractory.
添加剤としては、リグニンを溶出する材料と界面活性剤とを用いる。リグニンを溶出する材料としては、オガクズ、モミガラ、小麦粉、蕎麦殻などの植物繊維を含むもの全般が挙げられるが、入手が容易で低コストなオガクズが好ましく、なかでも本発明者らの試験の結果によると針葉樹のオガクズが好ましい。リグニンを溶出する材料は、耐火材料１００質量％に対して外掛けで０．３質量％以上５質量％以下添加する。すなわち、本発明の断熱不定形耐火物は、リグニンを溶出する材料を耐火材料に対して０．３質量％以上５質量％以下含有する。その含有量が０．３質量％未満では十分な起泡効果が得られず、断熱性が不十分となる。一方、その含有量が５質量％を超えると、不定形耐火物として必要な流動性が得られず、強度も不足する。リグニンを溶出する材料の含有量は、耐火材料に対して１質量％以上３質量％以下であることが好ましい。 As the additive, a material that elutes lignin and a surfactant are used. Examples of the material for eluting lignin include all materials containing plant fibers such as sawdust, rice husk, wheat flour, and soybean husk, but sawdust, which is easily available and low in cost, is preferable, and among them, the results of the tests conducted by the present inventors. According to, coniferous sawdust is preferred. The material for eluting lignin is added in an amount of 0.3% by mass or more and 5% by mass or less with respect to 100% by mass of the refractory material. That is, the heat-insulating amorphous refractory of the present invention contains a material that elutes lignin in an amount of 0.3% by mass or more and 5% by mass or less with respect to the refractory material. If the content is less than 0.3% by mass, a sufficient foaming effect cannot be obtained, and the heat insulating property becomes insufficient. On the other hand, if the content exceeds 5% by mass, the fluidity required for an amorphous refractory cannot be obtained, and the strength is also insufficient. The content of the material that elutes lignin is preferably 1% by mass or more and 3% by mass or less with respect to the refractory material.
界面活性剤としては、アルキルベンゼンスルホン酸、ナフタレンスルホン酸ソーダ類脂肪酸塩、アルキル硫酸エステル塩、ポリカルボン酸塩、及び洗剤等から選択される一種以上が挙げられる。界面活性剤は、耐火材料１００質量％に対して外掛けで０．００１質量％以上０．２質量％以下添加する。すなわち、本発明の断熱不定形耐火物は、界面活性剤を耐火材料に対して０．００１質量％以上０．２質量％以下含有する。その含有量が０．００１質量％未満では十分な起泡効果が得られず、断熱性が不十分となる。一方、その含有量が０．２質量％を超えると、不定形耐火物として必要な流動性が得られず、強度も不足する。界面活性剤の含有量は、耐火材料に対して０．００５質量％以上０．１質量％以下であることが好ましい。 Examples of the surfactant include one or more selected from alkylbenzene sulfonic acid, sodium naphthalene sulfonic acid fatty acid salt, alkyl sulfate ester salt, polycarboxylic acid salt, detergent and the like. The surfactant is added in an amount of 0.001% by mass or more and 0.2% by mass or less on the outside with respect to 100% by mass of the refractory material. That is, the heat-insulating amorphous refractory of the present invention contains 0.001% by mass or more and 0.2% by mass or less of the surfactant with respect to the refractory material. If the content is less than 0.001% by mass, a sufficient foaming effect cannot be obtained, and the heat insulating property becomes insufficient. On the other hand, if the content exceeds 0.2% by mass, the fluidity required for an amorphous refractory cannot be obtained, and the strength is also insufficient. The content of the surfactant is preferably 0.005% by mass or more and 0.1% by mass or less with respect to the refractory material.
添加剤としては、リグニンを溶出する材料と界面活性剤以外に、結合剤、分散剤、増粘剤、硬化時間調整剤、爆裂防止剤等を適宜含んでもよい。 As the additive, in addition to the material for eluting lignin and the surfactant, a binder, a dispersant, a thickener, a curing time adjusting agent, an explosion inhibitor and the like may be appropriately contained.
結合剤としては、アルミナセメント、ポルトランドセメント、リン酸塩、珪酸塩、水硬性遷移アルミナ等を使用することができるが、耐火原料のなかで微粉のマグネシアと蒸発シリカの組み合わせのように凝集性の結合部を形成する原料で代用することも可能である。 As the binder, alumina cement, Portland cement, phosphate, silicate, hydraulic transition alumina and the like can be used, but among the fireproof raw materials, coagulant like a combination of fine powder magnesia and evaporated silica. It is also possible to substitute the raw material forming the joint portion.
分散剤としてはアルカリ金属リン酸塩、アルカリ金属ポリリン酸塩、ポリカルボン酸塩、アルキルスルホン酸塩、及び芳香族スルホン酸塩等から選択される一種以上を用いることができる。 As the dispersant, one or more selected from alkali metal phosphates, alkali metal polyphosphates, polycarboxylic acid salts, alkyl sulfonates, aromatic sulfonates and the like can be used.
増粘剤としては、山芋澱粉、タロ芋澱粉、カルボキシメチルセルロース、メチルセルロース、サンザンガム、カラヤガム、ローカストビーンガム、ウェランガム、アラビヤゴム、及びアルギン酸ソーダ等から選択される一種以上を用いることができる。 As the thickener, one or more selected from yam starch, taro starch, carboxymethyl cellulose, methyl cellulose, Sanzan gum, Karaya gum, locust bean gum, welan gum, arabia gum, sodium alginate and the like can be used.
硬化時間調整剤には、硬化促進剤と硬化遅延剤とがあり、硬化促進剤としては、消石灰、塩化カルシウム、アルミン酸ソーダ、及び炭酸リチウム等から選択される一種以上を用いることができ、硬化遅延剤としては、例えば、ホウ酸、クエン酸、炭酸ソーダ、及び砂糖等から選択される一種以上を用いることができる。 The curing time adjusting agent includes a curing accelerator and a curing retarder, and as the curing accelerator, one or more selected from slaked lime, calcium chloride, sodium aluminate, lithium carbonate and the like can be used, and curing can be performed. As the retarder, for example, one or more selected from boric acid, citric acid, sodium carbonate, sugar and the like can be used.
爆裂防止剤としては、スサやビニロン繊維等の有機繊維、及び金属粉から選択される一種以上を用いることができる。 As the explosion inhibitor, one or more selected from organic fibers such as susa and vinylon fibers and metal powder can be used.
本発明の断熱不定形耐火物において水の添加量は、耐火材料と添加剤との配合物（耐火材料と添加剤との合量）に対して３５質量％以上６０質量％以下とする。水の添加量が３５質量％未満であると、粘性が高くなって不定形耐火物として必要な流動性が得られない。一方、水の添加量が６０質量％を超えると、前述したリグニンを溶出する材料（溶出したリグニン）と界面活性剤との相互作用により起泡した泡が抜けて安定しない。 In the heat-insulating amorphous refractory of the present invention, the amount of water added is 35% by mass or more and 60% by mass or less with respect to the mixture of the refractory material and the additive (the total amount of the refractory material and the additive). If the amount of water added is less than 35% by mass, the viscosity becomes high and the fluidity required for an amorphous refractory cannot be obtained. On the other hand, when the amount of water added exceeds 60% by mass, the foamed bubbles due to the interaction between the above-mentioned lignin-eluting material (eluted lignin) and the surfactant are removed and unstable.
以上のとおり、リグニンを溶出する材料及び界面活性剤の含有量、並びに水の添加量の要件を全て満たすことにより、常温で２４時間養生して１１０℃で２４時間乾燥させたときのかさ比重が１．６以下という低かさ比重で断熱性の高い断熱不定形耐火物を得ることができる。 As described above, by satisfying all the requirements for the content of the material for eluting lignin and the surfactant, and the amount of water added, the bulk specific gravity when cured at room temperature for 24 hours and dried at 110 ° C. for 24 hours can be obtained. It is possible to obtain a heat-insulating amorphous refractory with a low specific gravity of 1.6 or less and high heat-insulating properties.
表１に示す各例の不定形耐火物について、かさ比重、熱伝導率、養生後の常温曲げ強度及び流動性を評価した。なお、表１に示す耐火材料としては、ＣＡ６を主たる鉱物組成とする断熱性骨材を用いた。また、表１には示していないが結合剤としてアルミナセメントを用いた。 The bulk specific gravity, thermal conductivity, normal temperature bending strength and fluidity after curing were evaluated for the amorphous refractories of each example shown in Table 1. As the refractory material shown in Table 1, a heat insulating aggregate having CA6 as a main mineral composition was used. Although not shown in Table 1, alumina cement was used as a binder.
かさ比重は、耐火材料と添加剤との配合物に水を添加して混練後、４０×４０×１６０ｍｍ形状の型枠に流し込んで成形し、常温で２４時間養生し、その後脱枠し１１０℃で２４時間乾燥して得た試験片について、ＪＩＳ Ｒ ２２０５に基づいて測定した。表１では、かさ比重が１．０以下を◎、１．０超１．６以下を○、１．６超を×で表記した。 The bulk specific gravity is determined by adding water to a mixture of a refractory material and an additive, kneading it, pouring it into a mold having a shape of 40 × 40 × 160 mm, molding it, curing it at room temperature for 24 hours, and then removing the frame at 110 ° C. The test piece obtained by drying in 24 hours was measured based on JIS R 2205. In Table 1, a bulk specific gravity of 1.0 or less is indicated by ⊚, more than 1.0 and 1.6 or less is indicated by ◯, and more than 1.6 is indicated by ×.
熱伝導率は、前述と同様に混練、成形、養生、乾燥して得た試験片について、８００℃の温度下での熱伝導率を熱線法により測定した。表１では、熱伝導率（Ｗ／ｍ・Ｋ）が０．３５以下を◎、０．３５超０．６以下を○、０．６超を×で表記した。 The thermal conductivity of the test pieces obtained by kneading, molding, curing, and drying in the same manner as described above was measured by the hot wire method at a temperature of 800 ° C. In Table 1, a thermal conductivity (W / m · K) of 0.35 or less is indicated by ⊚, more than 0.35 and 0.6 or less is indicated by ◯, and more than 0.6 is indicated by ×.
養生後の常温曲げ強度は、前述と同様に混練、成形、養生して得た試験片について、ＪＩＳ Ｒ ２５１１に基づいて測定した。表１では、養生後の常温曲げ強度（ＭＰａ）が０．６以上を◎、０．３以上０．６未満を○、０．３未満を×で表記した。 The room temperature bending strength after curing was measured based on JIS R 2511 for the test pieces obtained by kneading, molding, and curing in the same manner as described above. In Table 1, the normal temperature bending strength (MPa) after curing is indicated by ⊚, 0.3 or more and less than 0.6 is indicated by ◯, and less than 0.3 is indicated by ×.
流動性はフリーフロー値により評価した。フリーフロー値とは、ＪＩＳ Ｒ ２５２１に規定するフローコーンに坏土（前記配合物と水との混練物）を流し込んで満たし、フローコーンを上方に抜き取って６０秒静置したときの坏土の広がり直径をいう。具体的には、表１に示す各例の配合物と水との混練直後のフリーフロー値を測定した。表１では、フリーフロー値（ｍｍ）が１３０以上を◎、１１０以上１３０未満を○、１１０未満を×で表記した。 Liquidity was evaluated by the free flow value. The free flow value is the value of the clay when the flow cone specified in JIS R 2521 is filled with clay (a kneaded mixture of the above-mentioned compound and water), the flow cone is pulled out upward, and the mixture is allowed to stand for 60 seconds. Spread diameter. Specifically, the free flow value immediately after kneading the formulations of each example shown in Table 1 with water was measured. In Table 1, a free flow value (mm) of 130 or more is indicated by ⊚, 110 or more and less than 130 is indicated by ◯, and less than 110 is indicated by ×.
表１中、実施例１、３〜６は本発明の要件を満たす本発明の実施例であり、かさ比重、熱伝導率、養生後の常温曲げ強度及び流動性のいずれの評価も良好であった。
In Table 1, Examples 1 , 3 to 6 are examples of the present invention satisfying the requirements of the present invention, and all of the evaluations of bulk specific gravity, thermal conductivity, normal temperature bending strength after curing and fluidity are good. It was.
これに対して比較例１は、リグニンを溶出する材料の含有量が本発明の下限値を下回る例であり、かさ比重が高くなり熱伝導率も高くなった。比較例２は、リグニンを溶出する材料の含有量が本発明の上限値を上回る例であり、養生後の常温曲げ強度が低くなり流動性も低くなった。 On the other hand, Comparative Example 1 is an example in which the content of the material for eluting lignin is lower than the lower limit of the present invention, and the bulk specific gravity is increased and the thermal conductivity is also increased. Comparative Example 2 is an example in which the content of the material for eluting lignin exceeds the upper limit of the present invention, and the bending strength at room temperature after curing is lowered and the fluidity is also lowered.
比較例３は、界面活性剤の含有量が本発明の下限値を下回る例（界面活性剤を含有しない例）であり、かさ比重が高くなり熱伝導率も高くなった。比較例４は、界面活性剤の含有量が本発明の上限値を上回る例であり、養生後の常温曲げ強度が低くなり流動性も低くなった。 Comparative Example 3 is an example in which the content of the surfactant is lower than the lower limit of the present invention (an example in which the surfactant is not contained), and the bulk specific gravity is increased and the thermal conductivity is also increased. Comparative Example 4 is an example in which the content of the surfactant exceeds the upper limit of the present invention, and the bending strength at room temperature after curing is lowered and the fluidity is also lowered.
比較例５は、水の添加量が本発明の下限値を下回る例であり、流動性が低くなった。比較例６は、水の添加量が本発明の上限値を上回る例であり、養生後の常温曲げ強度が低くなるとともに、かさ比重及び熱伝導率が高くなった。 Comparative Example 5 is an example in which the amount of water added is less than the lower limit of the present invention, and the fluidity is low. Comparative Example 6 is an example in which the amount of water added exceeds the upper limit of the present invention, and the bending strength at room temperature after curing is lowered, and the bulk specific gravity and thermal conductivity are increased.
Claims (2)
前記添加剤として、リグニンを溶出する材料と界面活性剤とを含有し、
前記リグニンを溶出する材料として針葉樹のオガクズを前記耐火材料に対して０．３質量％以上５質量％以下、前記界面活性剤を前記耐火材料に対して０．００１質量％以上０.２質量％以下含有し、
水の添加量は、前記配合物に対して３５質量％以上６０質量％以下であり、
常温で２４時間養生して１１０℃で２４時間乾燥させたときのかさ比重が１．６以下である断熱不定形耐火物。 A heat-insulating amorphous refractory made by adding water to a mixture of a refractory material and an additive.
As the additive, a material for eluting lignin and a surfactant are contained, and
As a material for eluting the lignin, sawdust of coniferous tree is 0.3% by mass or more and 5% by mass or less with respect to the refractory material, and the surfactant is 0.001% by mass or more and 0.2% by mass with respect to the refractory material. Contains the following,
The amount of water added is 35% by mass or more and 60% by mass or less with respect to the formulation.
A heat-insulating amorphous refractory having a bulk specific gravity of 1.6 or less when cured at room temperature for 24 hours and dried at 110 ° C for 24 hours.
前記界面活性剤を前記耐火材料に対して０．００５質量％以上０．１質量％以下含有する請求項１に記載の断熱不定形耐火物。 Coniferous sawdust as a material for eluting the lignin is 1% by mass or more and 3% by mass or less with respect to the refractory material.
The heat-insulating amorphous refractory according to claim 1, which contains 0.005% by mass or more and 0.1% by mass or less of the surfactant with respect to the refractory material.
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