CN109790073A - 耐火陶瓷制品、用于制备这种制品的配料以及用于制备这种制品的方法 - Google Patents
耐火陶瓷制品、用于制备这种制品的配料以及用于制备这种制品的方法 Download PDFInfo
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- CN109790073A CN109790073A CN201780060697.3A CN201780060697A CN109790073A CN 109790073 A CN109790073 A CN 109790073A CN 201780060697 A CN201780060697 A CN 201780060697A CN 109790073 A CN109790073 A CN 109790073A
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- 239000004615 ingredient Substances 0.000 title claims abstract description 104
- 239000011214 refractory ceramic Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 162
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 114
- 239000000395 magnesium oxide Substances 0.000 claims description 81
- 229910052717 sulfur Inorganic materials 0.000 claims description 78
- 239000011593 sulfur Substances 0.000 claims description 78
- 239000002994 raw material Substances 0.000 claims description 19
- 229910052596 spinel Inorganic materials 0.000 claims description 14
- 239000011029 spinel Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004568 cement Substances 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910000514 dolomite Inorganic materials 0.000 claims description 4
- 239000010459 dolomite Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- 229910001677 galaxite Inorganic materials 0.000 claims description 2
- 229910001691 hercynite Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 235000012245 magnesium oxide Nutrition 0.000 description 72
- 239000005864 Sulphur Substances 0.000 description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 11
- 229910052906 cristobalite Inorganic materials 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 229910052682 stishovite Inorganic materials 0.000 description 11
- 229910052905 tridymite Inorganic materials 0.000 description 11
- 238000010304 firing Methods 0.000 description 9
- 238000005245 sintering Methods 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- 239000011734 sodium Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920001732 Lignosulfonate Polymers 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- -1 A12O3 Chemical compound 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229920005610 lignin Polymers 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及耐火陶瓷制品，用于制备这种制品的配料以及用于制备这种制品的方法。
Description
本发明涉及耐火陶瓷制品，用于制备这种制品的配料以及用于制备这种制品的方法。
在本发明的意义上，术语“耐火陶瓷制品”尤其是指具有600℃以上的使用温度的耐火制品且优选根据DIN 51060：2000-6的耐火材料，即具有大于SK 17的示温锥当量的材料。示温锥当量的确定可以特别是根据DIN EN 993 - 12 : 1997-06进行。
已知用“耐火陶瓷配料”来表示由一种或多种组分或原料制成的组合物，可以通过该组合物借助温度处理，即特别是借助陶瓷烧制来制备耐火陶瓷制品。
本发明涉及一种碱性耐火陶瓷制品，确切地是一种基于MgO（氧化镁，矿物学“方镁石”）的碱性耐火陶瓷制品。
这种基于MgO的碱性耐火陶瓷制品基本上已被证明是用于高温应用的耐火陶瓷制品。特别地，这种MgO制品用于金属工业中机组(Aggregaten)的耐火内衬，例如，在连续浇铸设备中，以及在玻璃熔炉中或在非金属工业的焙烧炉中，例如在隧道式炉中或回转炉中用于耐火内衬。
虽然这种基于MgO的制品被证明在高温使用时是高度耐火的，但是在这种制品的储存和运输过程中它们可能会被损坏。因为这种制品中的MgO倾向于水化并且可以与湿气反应生成氢氧化镁Mg(OH)2，由此这种制品破裂并且在较长的湿气作用下甚至会崩解。
因此，已知的是保护基于MgO的耐火陶瓷制品免受这种水化，例如通过用沥青或石蜡浸渍制品。然而这样的浸渍一方面伴随有显著的成本，且另一方面导致在其应用时在所述浸渍制品的加热过程中浸渍成分的挥发，这伴随有显著的生烟和臭气污染和因此通常是非期望的。
然而，由于这种浸渍仅在表面上保护制品，因此不能确保持久保护制品免受水化。因此，由于湿气渗入制品体积，制品中的氧化镁水化可能继续发生。
此外，制品的耐火性能可以通过浸渍改变，特别是其耐火性甚至会劣化。
本发明的目的在于提供一种基于MgO的耐火陶瓷制品，该制品被保护免受水化。本发明的另一个目的在于提供这样一种基于MgO的耐火陶瓷制品，该制品被保护免受水化，并且同时相对未受水化保护的制品不具有劣化的性能，特别是不具有劣化的耐火性能。特别地，本发明的目的还在于提供这样一种制品，在其加热过程中不会发生生烟和臭气污染。另一个目的在于提供一种用于制备这种制品的配料。最后，本发明的目的在于提供一种用于制备这种制品的方法。
根据本发明，提供一种耐火陶瓷制品用于实现该目的，包括以下特征：
该制品具有陶瓷粘结(Bindung)；
该制品具有至少为75质量％的MgO份额；
该制品具有在0.01至0.20质量％范围内的硫份额。
以质量％示范的数据分别表示以质量％计的相关组分的份额，基于制品的总质量。
本发明是基于意料之外的基本认识，即基于MgO的耐火陶瓷制品被有效地保护免受制品中MgO水化，只要制品中的总硫含量以非常特定的质量存在。根据本发明，已发现制品中总硫的该特定质量份额在0.01至0.20质量％的范围内。根据本发明，已发现硫不能抑制制品中MgO水化，只要硫以低于0.01质量％的份额存在于制品中。此外，已经发现，如果制品中的硫份额超过0.20质量％，则制品的耐火性能可能劣化。例如，硫与制品的其它成分在其应用时可形成低熔点相，其可以显著降低耐热性、特别是其热强度，只要硫以超过0.20质量％的份额存在于制品中。
根据本发明，已经发现，水化保护通过硫仍可进一步改善且硫对制品可能产生的不利影响仍可更好阻止，只要硫在制品中的份额接近0.01至0.05质量％的还更特定的范围。在这方面，例如，还可以规定，硫以至多0.20质量％、0.15质量％、0.10质量％或0.05质量％的份额存在于制品中。在这方面，优选地可以例如规定，该制品具有在0.01至0.15质量％范围内的硫份额，进一步优选在0.01至0.10质量％范围内，且更优选在0.01至0.05质量％范围内。
关于制品中硫份额的示范数据分别基于制品的总质量。
在此给出的关于本发明制品或配料中的硫份额的数据分别为在所述制品或配料中的总硫含量，其根据按照DIN 51085：2015-01的方法B（燃烧后IR检测）来测定。该测定方法基于待分析材料在感应加热坩埚中与氧反应并随后红外检测载气体积中的SO2浓度。同本发明范围内与本发明制品和本发明配料相关地一样，硫含量以元素硫（S）给出。
此外在这方面，在本发明的意义上，硫不一定是游离硫，而且还是例如结合形式的硫。
根据本发明规定，硫以在制品体积上分布的方式存在于其中，特别是以在制品的整个体积上分布的方式存在。由此确保了制品在整个体积上有效地被保护免受MgO水化。为了可以实现硫在制品体积上这样的分布，规定在制备制品时向配料中引入含硫组分且与配料的其它组分或原料混合，使得硫在配料体积上且在由该配料制成的耐火陶瓷制品上分布。
可以规定，硫以非均匀地在制品体积上分布的方式地存在于其中。特别地，就硫份额而言，制品中可能存在梯度。例如，硫份额可以从制品的边缘区域，例如从制品的外表面向制品的内部区域增加。这可能是例如由以下所致，即在制品的陶瓷烧制期间，由其制成制品的配料的含硫组分的硫份额，在边缘区域中比在制品的内部区域中挥发得更强烈。因此，本发明制品中硫的本发明份额代表平均值，其中优选规定，在本发明制品中不存在区域、特别是不存在宏观区域，其中硫份额超出本发明份额，特别地不显著超出本发明份额。
由于不需要浸渍制品以保护免受制品中的MgO水化，因此在制品的应用时由于这种浸渍的挥发而不发生生烟或臭气污染。
本发明制品具有至少75质量％的MgO份额，即例如，MgO份额还为至少80质量％。此外，该制品可以例如具有至多97质量％的MgO份额，即例如，还至多95或92质量％。在这方面，该制品可具有例如在75至97质量％范围内的MgO份额，即例如还在80至95质量％范围内或者在80至92质量％范围内。
关于制品中MgO质量份额的示范数据分别基于制品的总质量。
只要在本文中给出关于制品中氧化物份额的数据，特别是关于氧化物MgO、A12O3、CaO、SiO2、Fe2O3、K2O或Na2O的份额的数据，这些氧化物不必以纯的形式存在于制品中。相反，这些氧化物可以以纯的形式和/或以结合形式存在于制品中。
例如，MgO可以作为纯MgO（方镁石）和/或镁尖晶石（MgO · A12O3）存在于制品中。此外，例如，氧化物A12O3可以作为纯A12O3（刚玉）或作为镁尖晶石存在于制品中。
根据本发明的耐火制品是陶瓷制品，即具有陶瓷粘结的制品。已知这种陶瓷化合物是在制品烧制过程中通过烧结制备的。因此，本发明制品是陶瓷、即烧结的耐火制品。
该制品可具有1至20质量％范围内的A12O3份额。在这方面，制品可以例如具有至少1、2、3、4或5质量％的A12O3份额。此外，制品可以例如具有至多20、19、18、17或16质量％的A12O3份额。在这方面，例如，制品还可以具有在3至18质量％或在5至16质量％范围内的A12O3份额。
该制品可以具有在0.5至3.0质量％范围内的CaO份额，即例如还具有至少0.6或0.7质量％的CaO份额，和例如，还具有至多3.0质量％、2.9质量％、2.8质量％、2.7质量％、2.6质量％或2.5质量％的CaO份额。在这方面，制品还可以例如具有在0.6至2.8质量％范围内或0.7至2.5质量％范围内的CaO份额。
制品可具有低于1.5质量％的SiO2份额，即例如还低于1.0质量％。在这方面，制品可以例如具有0.1至1.5质量％范围内或0.3至1.5质量％范围内的SiO2份额。
制品可具有低于10质量％的Fe2O3份额，即例如，Fe2O3的份额还低于5或低于3质量％。在这方面，该制品可以例如具有0.1至10质量％范围内、0.1至5质量％范围内或0.1至3质量％范围内的Fe2O3份额。
制品可具有低于0.5质量％的Na2O份额，即例如，Na2O的份额还低于0.1或低于0.05质量％。例如，制品可以具有0.01至0.5质量％范围内或0.01至0.1质量％范围内的Na2O份额。
制品可具有低于0.2质量％的K2O份额，即例如，K2O份额还低于0.1质量％。
例如，制品可具有0.01至0.1质量％范围内的K2O份额。
该制品可具有低于0.5质量％的Na2O和K2O总质量的份额，即例如还低于0.2或0.1质量％的份额。例如，制品中Na2O和K2O总质量的份额可以在0.01至0.5质量％的范围内。
关于制品中MgO、A12O3、CaO、SiO2、Fe2O3、Na2O和K2O的质量份额的示范数据分别基于制品的总质量。
除了上述物质，即MgO、A12O3、CaO、SiO2、Fe2O3、Na2O、K2O和硫，本发明制品可具有另外的物质，例如以低于5质量％的份额，即例如还以低于4、3、2或低于1质量％的份额，分别基于所述制品的总质量。
根据一个实施方案规定，Cr2O3在制品中的份额低于5质量％，即例如还低于4、3、2或1质量％，分别基于所述制品的总质量。
根据一个实施方案规定，游离碳在制品中的份额低于3质量％，即例如还低于2或低于1质量％，分别基于所述制品的总质量。
本发明还涉及用于制备本发明制品的配料，其包括以下特征：包含一种或多种基于氧化镁的原料的基础组分；
包含一种或多种含硫原料的含硫组分；
配料具有至少75质量％的MgO份额；配料具有这样的硫份额，使得可由配料烧制的耐火陶瓷制品具有根据本发明耐火陶瓷制品的硫份额。
配料的基础组分可以包含一种或多种基于氧化镁的以下原料：烧结氧化镁、熔融氧化镁、烧结白云石或熔融白云石。基础组分优选包含烧结氧化镁形式的基于氧化镁的原料。
除了基于氧化镁的原料外，基础组分可包含一种或多种另外的原料、特别是一种或多种含氧化铝（A12O3）原料、特别是一种或多种以下含氧化铝原料：
镁尖晶石、烧结刚玉、熔融刚玉、煅烧粘土、锰尖晶石、铁尖晶石或镁铁尖晶石。基础组分可以优选包含镁尖晶石形式的含氧化铝原料。
基础组分优选包含原料烧结氧化镁或镁尖晶石中的至少一种。更优选地，基础组分由原料烧结氧化镁或镁尖晶石中的至少一种组成。最优选地，基础组分由原料烧结氧化镁和镁尖晶石组成。
本发明配料可具有MgO、另外的氧化物A12O3、CaO、SiO2、Fe2O3和Na2O和根据本发明制品可能存在的另外的物质的份额。
在这方面，先前对本发明制品中这些物质的份额所作出的说明相应地对本发明配料中这些物质的份额适用。所述配料可具有K2O份额，其超过制品中的K2O份额，因为K2O份额可能在配料的烧制期间挥发。在这方面，可以规定，所述配料具有低于2.5质量％的K2O份额，即例如K2O份额还低于2.0质量％、低于1.0质量％或低于0.4质量％。例如，配料可具有0.01至2.5质量％范围内的K2O份额，即例如K2O份额还在0.01至1.0质量％范围内。
配料的基础组分以这样的方式存在于配料中，或者以这样的方式组成(zusammengestellt)，以致该配料总共具有上述氧化物的本发明份额。由于特别是基于氧化镁和氧化铝的原料，特别是烧结氧化镁和镁尖晶石，除了主要氧化物MgO和Al2O3外通常还具有氧化物CaO、SiO2、Fe2O3、K2O和Na2O中一种或多种的份额，本领域技术人员能够容易地将原料以这样的方式组成本发明配料，使得该配料总共具有这些氧化物的本发明份额。然而，基于氧化镁和氧化铝的原料、特别是烧结氧化镁和镁尖晶石通常不具有硫份额，这将使得有可能调配(konfektionieren)的配料具有这样的硫份额，使得耐火陶瓷制品可由该配料烧制，该耐火陶瓷制品具有本发明的硫份额。因此，本发明规定，本发明配料具有含硫组分，其包含一种或多种含硫原料。该含硫组分允许实现配料中这样的硫份额，使得由本发明配料可烧制耐火陶瓷制品，其具有本发明的硫份额。为此目的，含硫组分 - 取决于该组分中硫的浓度 - 以相应的份额加入配料中。
在本发明配料被烧制成耐火陶瓷制品期间，配料中的硫份额转移到气相中并且挥发，从而使这些份额随后不再用于提供具有本发明的硫份额的经烧制的耐火陶瓷制品。根据本发明，已经发现，至最多超过80质量％、特别是超过90质量％、特别是90至98质量％的存在于配料中的硫可在烧制期间挥发，基于硫在配料中的总质量。在这方面，根据本发明规定，配料具有这样的硫份额，使得可由该配料烧制的耐火陶瓷制品具有如本文所公开的本发明耐火陶瓷制品的硫份额，即在最一般的实施方案中，在0.01至0.20质量％范围内的硫份额。配料必须具有何种确切的硫份额，用以由该配料烧制具有如在此公开的本发明耐火陶瓷制品所具有的硫份额的耐火陶瓷制品，可由本领域技术人员通过计算或实验容易确定。根据一个实施方案规定，配料 - 为了实现在耐火陶瓷制品中这样的硫份额 - 具有在0.02至0.9质量％范围内的硫份额，基于所述配料的总质量。特别有利地，可由本发明配料烧制具有本发明的硫份额的本发明制品，当配料具有在0.03至0.5质量％范围内的硫份额，并且最有利地，当该配料具有在0.06至0.3质量％范围内的硫份额。在这方面还可以例如规定，所述配料具有至多0.9质量％、0.7质量％、0.5质量％、0.4质量％或0.3质量％的硫份额并具有例如至少0.02质量％、0.03质量％、0.04质量％、0.05质量％或0.06质量％的硫份额。
根据一个更优选的实施方案规定，所述含硫组分包含至少一种以废耐火陶瓷制品形式的含硫原料。这样的废耐火陶瓷制品可以特别是以下废耐火陶瓷制品中的一种或多种：水泥回转炉的废炉衬或玻璃槽的再生器的废炉衬。
如已知地，在用于烧制水泥熟料的回转炉（“水泥回转炉”）中的烧制工艺期间或在用于熔化和处理玻璃的炉（“玻璃槽”）中产生气态物质，其渗入水泥回转炉或玻璃槽的再生器的耐火炉衬并冷凝成含硫物质，尤其是碱金属硫酸盐，例如硫酸钾（K2SO4）或硫酸钠（Na2SO4）。根据本发明，现在已经意料之外地发现，这样的废含硫炉衬可以用作原料，用以调节用于制备本发明制品的本发明配料中硫份额。已发现水泥回转炉的耐火炉衬是特别有利的。根据一个优选的实施方案，含硫组分因此包含以水泥回转炉的废炉衬形式的含硫原料。根据一个实施方案规定，含硫组分由水泥回转炉的废炉衬组成。水泥回转炉的废炉衬尤其可以是基于MgO的这种，特别地MgO份额为至少75质量％或至少80质量％。此外，废炉衬可例如具有至多97质量％的MgO份额，即例如还至多95或92质量％。此外，废炉衬可例如具有75至97质量％范围内的MgO份额，即例如还在80至95质量％范围内或者在80至92质量％范围内。关于废炉衬中MgO质量份额的示范数据分别基于炉衬的质量。
基础组分可以例如以至少50质量％的份额存在于本发明配料中，即例如还以至少60、70、80、90、95或99质量％的份额。此外可以例如规定，该基础组分以至多99质量％的份额存在于配料中，即例如，还以至多95、90、80、70或60质量％的份额。在这方面，基础组分可以例如以50至99质量％范围内的份额存在于配料中，优选例如还以60至90质量％范围内的份额，且更优选以60至80质量％范围内的份额。
基础组分优选以最大5mm的粒度存在配料中。例如可规定，基础组分的至少90质量％，基于所述基础组分的总质量，以至多5mm的粒度存在于该配料中，根据DIN EN 933-1:2012-03测定。
含硫组分，例如以水泥回转炉的废炉衬形式，可以例如以至少1质量％的份额存在于配料中，即例如还以至少5、10、20、30或40质量％的份额。此外，可以规定，含硫组分以至多60质量％的份额存在于配料中，即例如还以至多50质量％或40质量％的份额。特别地，含硫组分可以1至60质量％范围内的份额存在于配料中，更优选地以10至40质量％范围内的份额且最优选以20至40质量%范围内的份额。
含硫组分优选以最大5mm的粒度存在配料中。例如可规定，含硫组分的至少90质量％，基于基础组分的总质量，以至多5mm的粒度存在于该配料中，根据DIN EN 933-1:2012-03测定。
除了基础组分和含硫组分外，配料还可具有一种或多种另外的组分，优选以低于10质量％的份额，即例如还以低于5质量％或低于1质量％的份额。
先前给出的关于配料的数据、特别地还有关于配料中硫份额的数据涉及不含可能存在的可加入配料的粘合剂的配料。优选地可规定，向配料添加至少一种常用粘合剂，以改善配料的可加工性或赋予由配料成型的生坯足够的生坯强度。在这方面，可向配料添加例如常用的临时粘合剂，例如木质素磺酸盐，例如以至最多5质量％的份额，特别是以1至5质量％范围内的份额，分别基于不含粘合剂的配料的总质量。只要这样的粘合剂，像例如还有木质素磺酸盐，具有硫份额，这些都是对本发明制品的制备无任何意义的，因为根据本发明已发现，在该制品烧制成烧结的耐火陶瓷制品的过程中，粘合剂中这样的硫份额几乎完全挥发。在这方面，已经发现，这样的粘合剂在烧制制品中所留下的可能存在的硫份额低于平均0.01质量％的硫份额，基于这样的制品。然而根据本发明已经发现，在这样少的硫份额的情况下，制品的水化保护由于这些硫份额没有产生。
本发明还涉及一种制备本发明制品的方法，包括以下特征：提供本发明配料；将配料烧制成耐火陶瓷制品。
以这样的方式进行配料的烧制，使得配料的组分、特别是基础组分彼此烧结，从而形成陶瓷粘结。因此，在烧制后，存在烧结的、即陶瓷耐火制品。
为了使含硫组分的硫分布在所述配料的整个体积上，可以特别地规定，配料在其烧制之前混合，特别是紧密混合。例如，配料可以在浆式混合器中混合。由此，可实现的是含硫组分的硫在所述配料的整个体积上，和因此也在由该配料制备的制品的整个体积上分布。
配料可在其烧制前成型，例如通过压制，或者也可以未成型烧制，即用作未成型耐火制品或用作所谓的坯料(Masse)。
烧制在配料的组分烧结的温度下实施。例如，配料的烧制可在1400至1800℃范围内的温度下、特别是在约1480℃的温度下进行。
例如，烧制可以持续3至12小时的范围内的时间进行，特别是进行约6小时。
此外，以这样的方式、特别是在这样的温度下并持续这样的时间进行烧制，使得由配料烧制的耐火陶瓷制品具有本发明制品的硫份额。
由本发明的权利要求以及以下实施例得出本发明的其它特征。
本发明的所有特征可以单独地或组合地彼此任意组合。
下面将更详细地阐释本发明的实施例。
根据实施例，首先，提供具有以下质量份额的以下组分的配料：由烧结氧化镁和镁尖晶石组成的基础组分：70质量％；和以水泥回转炉的废炉衬形式的含硫组分：30质量％。
基于配料的总质量，所述烧结氧化镁以59质量％的份额和镁尖晶石以11质量％的份额存在于基础组分中。基础组分完全以至最大5mm的粒度存在。基于烧结氧化镁的总质量，烧结氧化镁具有96.80质量％的MgO份额和如下其它氧化物的份额：Al2O3：0.04质量％，SiO2：0.77质量％；CaO：2.21质量％；Fe2O3：0.18质量％；Na2O：0.00质量％；K2O：0.00质量％；硫（根据DIN 51085：2015-01根据方法B作为元素硫测定）：0.00质量％。
基于镁尖晶石的总质量，镁尖晶石具有32.70质量％的MgO份额、66.73质量％的Al2O3份额和如下其它氧化物的份额：SiO2：0.08质量％；CaO：0.28质量％；Fe2O3：0.21质量％；Na2O：0.00质量％；K2O：0.00质量％；硫（根据DIN 51085：2015-01根据方法B作为元素硫测定）：0.00质量％。
构成含硫组分的水泥回转炉的废炉衬以破碎至低于5mm粒度的氧化镁砖的形式存在。基于含硫组分的总质量，除了84.03质量％份额的MgO和除了0.57质量％份额的硫（根据DIN 51085：2015-01根据方法B作为元素硫测定），该组分具有如下其它氧化物的份额：A12O3：10.35质量％，SiO2：0.56质量％；CaO：2.50质量％；Fe2O3：0.75质量％；Na2O：0.08质量％；K2O：1.16质量％。
总的来说，由此得出配料的以下组成，基于配料的总质量：
MgO: 85.92质量%
A12O3: 10.47质量%
SiO2: 0.63质量%
CaO: 2.09质量%
Fe2O3: 0.35质量%
Na2O: 0.02质量%
K2O: 0.35质量%
S: 0.17质量%。
配料已配有3.1质量％份额的木质素磺酸盐形式的粘合剂，基于不含粘合剂的配料，和随后在浆式混合器中紧密混合，使得特别地含硫组分的硫均匀地分布在配料上。随后，将配料压制成生坯、干燥且最后在1480℃的温度下烧制持续6小时的时间，以便使配料的组分彼此烧结。在烧制期间，木质素磺酸盐的硫份额完全挥发，并且配料的其余组分的硫份额挥发约88％，从配料中的0.17质量％硫至制品中的0.02质量％硫。冷却后，耐火陶瓷制品以本发明耐火陶瓷制品的形式存在。制品的组成如下：
MgO : 86.62质量%
A12O3 : 10.31质量%
SiO2 : 0.60质量%
CaO : 2.01质量%
Fe2O3 : 0.38质量%
Na2O : 0.03质量%
K2O : 0.03质量%
S : 0.02质量%。
由于配料的组分的紧密混合，硫以在该制品的整个体积上分布的方式存在于其中。由此产生制品在其整个体积上的非常好的水化保护。
为了定量测定由制品中硫引起的水化保护程度，进行了常用的 Angenot试验，该试验经常用于评价碱性耐火陶瓷制品的耐水化性。在Angenot试验中，将制品暴露于饱和水蒸气气氛中，并且测定直至光学可辨别的制品破损的时间。
在本发明的情况下，Angenot试验如下进行：
根据上述实施例制备的制品以圆柱形样品的形式提供，该样品的直径和高度分别为50mm。将该样品置于圆柱形容器中，在其中形成有加热至95℃的水浴。在此样品位于设置在水浴上方的金属格栅上。然后用圆锥形盖子封闭容器，该盖子具有直径约2cm的圆形开口。由此，在样品周围形成饱和水蒸气气氛。随后，测量直至光学可辨别的样品破损的时间。
在这方面，直至本发明制品的样品破损的时间测定为142小时。
为了比较根据实施例的本发明制品与根据现有技术的基于MgO的耐火陶瓷制品的耐水化性，由这种制品根据现有技术制备对比样品并进行相应的Angenot试验。
根据现有技术的制品由仅具有上述基础组分的配料制成，且基于配料的总质量，烧结氧化镁的份额为83质量％和镁尖晶石的份额为17质量％。
总的来说，由此得出根据现有技术的该配料的以下组成，基于配料的总质量：
MgO : 86.8质量%
A12O3 : 10.5质量%
SiO2 : 0.8质量%
CaO : 1.7质量%
Fe2O3 : 0.2质量%
Na2O : 0.0质量%
K2O : 0.0质量%
S : < 0.01质量%
根据本发明的实施例，如以上所实施地，进一步处理该配料并烧结成耐火陶瓷制品。从该制品中获得样品，以相同的方式对其进行如上述所实施的Angenot试验。
在此，直至样品破损的时间测定为39小时。
因此，通过本发明，直至制品破损的时间可以变为超过三倍。
Claims (15)
1.耐火陶瓷制品，其包括以下特征：
所述制品具有陶瓷粘结；
所述制品具有至少75质量％的MgO份额；
所述制品具有在0.01至0.20质量％范围内的硫份额。
2.根据权利要求1的制品，其具有在0.01至0.05质量％范围内的硫份额。
3.根据前述权利要求中至少一项的制品，其中所述制品具有在75至97质量％范围内的MgO份额。
4.根据前述权利要求中至少一项的制品，其中所述制品具有在1至20质量％范围内的Al2O3份额。
5.根据前述权利要求中至少一项的制品，其中所述制品具有在0.5至3.0质量％范围内的CaO份额。
6.根据前述权利要求中至少一项的制品，其中所述制品具有低于1.5质量％的SiO2份额。
7.根据前述权利要求中至少一项的制品，其中所述制品具有低于10质量％的Fe2O3份额。
8.根据前述权利要求中至少一项的制品，其中所述制品具有低于0.5质量％的Na2O份额。
9.根据前述权利要求中至少一项的制品，其中所述制品具有低于0.2质量％的K2O份额。
10.根据前述权利要求中至少一项的制品，其中所述制品具有低于0.5质量％的来自Na2O和K2O的总质量的份额。
11.用于制备根据前述权利要求中至少一项的制品的配料，其包括以下特征：
包含一种或多种基于氧化镁的原料的基础组分；
包含一种或多种含硫原料的含硫组分；
所述配料具有至少75质量％的MgO份额；
所述配料具有这样的硫份额，使得可由所述配料烧制的耐火陶瓷制品具有按照根据权利要求1的制品的硫份额。
12.根据权利要求11的配料，其中所述基础组分包含一种或多种基于氧化镁的以下原料：烧结氧化镁、熔融氧化镁、烧结白云石或熔融白云石。
13.根据权利要求11或12中至少一项的配料，其中除了一种或多种基于氧化镁的原料外，所述基础组分包含一种或多种以下含氧化铝原料：镁尖晶石、烧结刚玉、熔融刚玉、煅烧粘土、锰尖晶石、铁尖晶石或镁铁尖晶石。
14.根据权利要求11至13中至少一项的配料，其中所述含硫组分包含以水泥回转炉的废炉衬形式的含硫原料。
15.用于制备根据权利要求1至10中至少一项的制品的方法，其包括以下特征：提供根据权利要求11至14中至少一项的配料；将配料烧制成耐火陶瓷制品。
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| EP16199243.3 | 2016-11-17 | ||
| EP16199243.3A EP3323794B1 (de) | 2016-11-17 | 2016-11-17 | Feuerfestes keramisches erzeugnis, versatz zur herstellung eines solchen erzeugnisses sowie verfahren zur herstellung eines solchen erzeugnisses |
| PCT/EP2017/071200 WO2018091156A1 (de) | 2016-11-17 | 2017-08-23 | Feuerfestes keramisches erzeugnis, versatz zur herstellung eines solchen erzeugnisses sowie verfahren zur herstellung eines solchen erzeugnisses |
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| CN109790073A true CN109790073A (zh) | 2019-05-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780060697.3A Active CN109790073B (zh) | 2016-11-17 | 2017-08-23 | 耐火陶瓷制品、用于制备这种制品的配料以及用于制备这种制品的方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US11053165B2 (zh) |
| EP (1) | EP3323794B1 (zh) |
| CN (1) | CN109790073B (zh) |
| ES (1) | ES2908291T3 (zh) |
| PL (1) | PL3323794T3 (zh) |
| RU (1) | RU2754151C2 (zh) |
| WO (1) | WO2018091156A1 (zh) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA686668A (en) * | 1964-05-19 | Basic Incorporated | Hydration resistant refractory magnesia | |
| GB1213256A (en) * | 1969-07-01 | 1970-11-25 | Basic Inc | Dolomitic refractories |
| DE1571601B1 (de) * | 1966-03-23 | 1971-04-15 | Kaiser Aluminum & Chemicals Co | Magnesiahaltige feuerfeste Produkte |
| US3879208A (en) * | 1974-02-19 | 1975-04-22 | Kaiser Aluminium Chem Corp | Refractory composition |
| EP2995596A1 (de) * | 2014-09-11 | 2016-03-16 | Refractory Intellectual Property GmbH & Co. KG | Versatz zur Herstellung eines feuerfesten keramischen Erzeugnisses, Verfahren zum Aufbringen einer Spritz- oder Gießmasse auf eine Oberfläche, Verfahren zur Herstellung eines feuerfesten keramischen Erzeugnisses, ein feuerfestes keramisches Erzeugnis sowie die Verwendung eines Versatzes |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE968586C (de) | 1951-07-19 | 1958-03-06 | Oesterr Amerikan Magnesit | Verfahren zur Erhoehung der Widerstandsfaehigkeit von feuerfesten, gebrannten, basischen Steinen auf der Grundlage von Magnesia gegen Hydratation |
| DE961697C (de) | 1951-11-06 | 1957-04-11 | Oesterr Amerikan Magnesit | Verfahren zur Herstellung von hydratationsbestaendigen, feuerfesten, gebrannten magnesiahaltigen Steinen und Massen |
| US3199995A (en) * | 1963-04-10 | 1965-08-10 | Harbison Walker Refractories | Hydration prevention |
| AT250849B (de) * | 1963-05-31 | 1966-11-25 | Russell Pearce Heuer | Feuerfeste Steine, Blöcke und Massen aus gebrannter Magnesia |
| US3468683A (en) | 1966-11-03 | 1969-09-23 | Basic Inc | Dolomitic containing refractories and process of producing the same |
| DE1927750A1 (de) * | 1969-05-30 | 1970-12-10 | Basic Inc | Feuerfeste Produkte auf Dolomit-Basis und Verfahren zu ihrer Herstellung |
| US3786129A (en) * | 1971-05-04 | 1974-01-15 | Tateho Kagakukogyo K K | Method of manufacturing fused magnesia |
| SU530014A1 (ru) * | 1975-08-29 | 1976-09-30 | Ленинградский Ордена Трудового Красного Знамени Технологический Институт Им.Ленсовета | Огнеупорна набивна масса дл футеровки тепловых агрегатов |
| CA1083184A (en) * | 1976-03-11 | 1980-08-05 | James A. Crookston | High density low porosity refractory product and process for making the same |
| SU1038321A1 (ru) * | 1982-02-04 | 1983-08-30 | Саткинский Ордена Ленина Комбинат "Магнезит" | Способ получени огнеупорного порошка из каустической магнезитовой пыли |
| US4383045A (en) | 1982-04-27 | 1983-05-10 | Martin Marietta Corp. | Magnesia refractories bonded with sulfamic acid |
| JPS60112666A (ja) * | 1983-11-24 | 1985-06-19 | 宇部化学工業株式会社 | 高密度マグネシア・カルシアクリンカ−およびその製造法 |
| DE3532228A1 (de) * | 1984-10-02 | 1986-04-17 | Toshiba Ceramics Co., Ltd., Tokio/Tokyo | Feuerfeste zusammensetzung |
| SU1320189A1 (ru) * | 1985-02-12 | 1987-06-30 | Восточный научно-исследовательский и проектный институт огнеупорной промышленности | Кальцинированный периклаз |
| US5001092A (en) * | 1988-12-02 | 1991-03-19 | Quigley Company Inc. | Sodium sulfate containing refractory composition |
| WO2008091041A1 (en) * | 2007-01-26 | 2008-07-31 | Wonjin Worldwide Co., Ltd. | Carbon-containing refractory composition containing no resinous binder |
| FR2915195B1 (fr) * | 2007-04-23 | 2009-06-26 | Saint Gobain Ct Recherches | Produit refractaire pour element d'empilage d'un regenerateur d'un four verrier |
| RU2443657C1 (ru) * | 2010-09-08 | 2012-02-27 | Общество С Ограниченной Ответственностью "Группа "Магнезит" | Шихта для изготовления периклазошпинельных изделий |
| FR2999566B1 (fr) * | 2012-12-19 | 2015-04-10 | Saint Gobain Ct Recherches | Produit alumine-magnesie pour gazeificateur ou pour four metallurgique |
-
2016
- 2016-11-17 EP EP16199243.3A patent/EP3323794B1/de active Active
- 2016-11-17 PL PL16199243T patent/PL3323794T3/pl unknown
- 2016-11-17 ES ES16199243T patent/ES2908291T3/es active Active
-
2017
- 2017-08-23 WO PCT/EP2017/071200 patent/WO2018091156A1/de active Application Filing
- 2017-08-23 US US16/338,490 patent/US11053165B2/en active Active
- 2017-08-23 RU RU2019107504A patent/RU2754151C2/ru active
- 2017-08-23 CN CN201780060697.3A patent/CN109790073B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA686668A (en) * | 1964-05-19 | Basic Incorporated | Hydration resistant refractory magnesia | |
| DE1571601B1 (de) * | 1966-03-23 | 1971-04-15 | Kaiser Aluminum & Chemicals Co | Magnesiahaltige feuerfeste Produkte |
| GB1213256A (en) * | 1969-07-01 | 1970-11-25 | Basic Inc | Dolomitic refractories |
| US3879208A (en) * | 1974-02-19 | 1975-04-22 | Kaiser Aluminium Chem Corp | Refractory composition |
| EP2995596A1 (de) * | 2014-09-11 | 2016-03-16 | Refractory Intellectual Property GmbH & Co. KG | Versatz zur Herstellung eines feuerfesten keramischen Erzeugnisses, Verfahren zum Aufbringen einer Spritz- oder Gießmasse auf eine Oberfläche, Verfahren zur Herstellung eines feuerfesten keramischen Erzeugnisses, ein feuerfestes keramisches Erzeugnis sowie die Verwendung eines Versatzes |
Non-Patent Citations (1)
| Title |
|---|
| S.M.SIADATI ET AL.: "Acidic and basic binders for magnesite based aggregate in plaster of tundish", 《CERAMICS INTERNATIONAL》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3323794A1 (de) | 2018-05-23 |
| RU2019107504A (ru) | 2020-12-17 |
| RU2754151C2 (ru) | 2021-08-30 |
| PL3323794T3 (pl) | 2022-04-19 |
| ES2908291T3 (es) | 2022-04-28 |
| EP3323794B1 (de) | 2021-12-29 |
| CN109790073B (zh) | 2022-02-01 |
| RU2019107504A3 (zh) | 2020-12-17 |
| US20200039885A1 (en) | 2020-02-06 |
| WO2018091156A1 (de) | 2018-05-24 |
| US11053165B2 (en) | 2021-07-06 |
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