CN1514810A - 煅烧的耐火陶瓷模制体,其应用以及制备模制件的配料 - Google Patents
煅烧的耐火陶瓷模制体,其应用以及制备模制件的配料 Download PDFInfo
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Abstract
本发明涉及一种具有基于(Mg)2+(Al,Cr)2 3+O4的尖晶石基体的煅烧耐火陶瓷模制件,其中存在基于铬刚玉和/或刚玉的较粗颗粒以及基于ZrO2的较粗颗粒。
Description
本发明涉及一种煅烧的耐火陶瓷模制件,其可能的应用以及制备该模制件的配料(Versatz)。
从Schulle的“耐火材料”,第一版,1990(ISBN 3-342-00306-5),第288,289页已知一种基于铬刚玉的耐火材料,它含约10重量%的Cr2O3和约90重量%的Al2O3。其中也提到基于Cr2O3/ZrO2的耐火材料。同时也提到,几乎不知道这种材料作为耐火陶瓷的应用。
在DE 19727917 C1中描述了一种用于制备煅烧的耐火陶瓷模制件的配料,它得自粒度<0.1mm的5-35重量%的Cr2O3、粒度为0.5-4mm的1-10重量%的ZrO2和粒度为0.2-4.0mm的55-94重量%的Al2O3,该模制件可用于具有高的耐温度变化性能和高的运行温度的导渣炉,例如焚烧废物的旋转管式炉。还提到这类砖的高结构弹性和优良的耐腐蚀性。
但是,例如在特殊废物的焚烧装置中总是存在对耐火材料基体的强腐蚀。特别是在强碱性渣或氧化铁含量高的渣或在工艺过程中其C/S-比(碱性)变化的渣的情况下就是这样。由DE 19727917 C1的配料烧制的砖也遇到局限性,即其不满意的耐磨行为。
本发明的目的是提供一种模制件,它与DE 19727917 C1的产品相比具有改进的耐腐蚀性,特别是对呈交变/变化的碱性的渣具有改进的耐受性。
这类模制件的应用范围可以是:废物焚烧炉装置和其它炉/熔化设备或气化装置的内衬,在这些装置中均会遇到腐蚀性的熔体和/或渣。
本发明的基本思路是形成耐渣腐蚀的模制件基体。
本发明的煅烧的耐火陶瓷模制件在其最一般的实施方案中的特征是其混合尖晶石基体,其中存在较粗的基于刚玉和/或铬刚玉以及ZrO2的颗粒。所需产品的特性例如在同时存在铬刚玉和锆钢玉或同时存在刚玉和锆富铝红柱石时达到。
混合尖晶石基体可由相应的配料组分如Cr2O3、MgO或Al2O3作为各个组分和/或以预合成的尖晶石,特别是MA-尖晶石(MgO-Al2O3)或MCA-尖晶石(MgO-Cr2O3-Al2O3)的形式或以其它方法来制备。
铬刚玉颗粒源于配料中铬和铝的氧化物,并在煅烧过程中形成。它也可至少部分以预反应的组分加入。
含ZrO2的颗粒可来自含斜锆石的材料(原料),但例如也可来自烧结-锆富铝红柱石、熔融-锆富铝红柱石、烧结-锆刚玉、熔融-锆刚玉,或来自ZAC材料(由SiO2、ZrO2和Al2O3预反应的材料),可单独使用或混合使用。
基于MA-尖晶石[(MgO、Al2O3)-尖晶石]的配料组分可以级分<0.5或<0.3或<0.1mm使用。这种尖晶石,优选的非化学计算量存在例如MgO过量的尖晶石与配料中的氧化铬反应产生混合尖晶石形式(Mg)2+(Al,Cr)2 3+O4和形成煅烧产物基体的基础材料的主要成分。这种混合尖晶石具有优异的耐上述危险渣的特性。
氧化铝,特别是作为粒度为0.5-10mm的组分可与(细颗粒的)氧化铬反应和形成上述铬刚玉-颗粒,其在基体中的分布,与含ZrO2颗粒一样。
当然,根据原料的杂质程度,在配料组分中可存在其它组分,因此变成该模制件的次要成分。
在煅烧产物中,所述粗粒的平均直径(d50)为0.5-10mm。
根据煅烧温度和炉气氛以及氧化铬或刚玉(Al2O3)的含量,在铬刚玉颗粒内的氧化铬浓度会有波动,这时煅过程可如下进行:在铬刚玉颗粒内,保留至少一个不含氧化铬的区,特别是芯区(Kernzone)。
因此煅烧过程可如此进行,以使铬刚玉颗粒在其表面附近区域有最高的氧化铬浓度。
附图1-4给出煅烧产物磨光片的所给比例的显微照片。其中1:铬刚玉颗粒,2:铝刚玉颗粒,3:混合尖晶石基体,4:孔。在细粒的尖晶石基体中清楚看到基于铬刚玉和锆刚玉的粗颗粒。
基体组分,即主要由所述混合尖晶石组成的组分可为总重量的10-70重量%,通常为15-50重量%。
由于特别对腐蚀性渣,如含碱渣或含高氧化铁量的渣的优异稳定性,该煅烧的耐火陶瓷模制件适合作为废物焚烧炉,如出现这类渣的特殊废物焚烧炉的内衬。
制备所述模制件的配料在其最一般的实施方案中包括下列组分(其单独或与另外的组分一起总计为100重量%):
-2-35重量%的<0.5mm的氧化铬,
-1-15重量%的>0.2mm的氧化锆,
-1-12重量%的<0.5mm的氧化镁,
-38-96重量%的<10mm的氧化铝。
该配料的组分可以纯氧化物或物质使用,以所述比例将所述氧化物引入配料中。
该配料的特别特征在于,可用带特有的暂时粘合剂,如亚硫酸盐废碱液的配料加工成模制件,并接着进行煅烧,其中亚硫酸盐废碱液基本上可完全烧掉。
由此,本发明可不应用例如含磷酸盐的粘合剂,这是另一个比现有技术好的主要优点。
与此相反,DE 19727917 C1中的配料不能应用带特有的暂时粘合剂,如亚硫酸盐废碱液进行加工。在已知的配料情况下,用暂时粘合剂不可能达到足够的坯件强度。
该配料可在下列的准则范围内变化:
-Al2O3组分的颗粒级分可为<6mm或<4mm,
-含ZrO2组分的颗粒级分可为1-4mm,
-Cr2O3和MgO的颗粒级分可为<0.2mm,<0.1mm或>0.05mm,
-Al2O3、Cr2O3和/或MgO可至少部分以尖晶石,特别是MA尖晶石或MCA尖晶石引入,例如为5-25重量%,
-MgO至少部分以尖晶石存在,Al2O3-组分或Cr2O3-组分按比例被减少(reduzieren),
-Cr2O3的引入量可为5-25重量%,
-ZrO2在配料中的量为1-6重量%,
-Al2O3-配料组分可占总配料的64-87重量%,一部分可呈细粒度(<0.1mm)存在,
-SiO2含量应限制为<3.0重量%,或更好为<0.1重量%。在这种情况下,建议应用含ZrO2的组分,其尽量是不含SiO2的,
-Fe2O3的含量可为<0.5重量%,
-MgO在配料中的含量可为3-8重量%,
-Al2O3组分可以至少部分以铬刚玉引入,
-MA-尖晶石例如可有下列组成(所有数据均以重量%表示):
MgO: 31-35
Al2O3: 64-67
CaO: 0.3-0.6
Fe2O3: 0.1-0.3
此外,其它组分如Na2O、SiO2,其含量各自<0.2重量%。
该配料,包括其暂时粘合剂,以通常的方法加工,并制成模制件,特别是压制成模制件。接着在1200-1700℃下煅烧。
由下列物质的配料:
-8重量%的<0.1mm的氧化铬
-5重量%的0.5-4mm的锆刚玉
-15重量%非化学计算量的<0.1mm的尖晶石(前述的类型)
-<4mm的其余刚玉和加入3重量%的亚硫酸盐废碱液(按配料组分总量计)开始,经100MPa的压力压制和经1550℃煅烧。该砖有下列参数:
粗密度(按DIN EN 993-1): 3.35g/cm3
开的孔隙度(按DIN EN 993-1): 15.1%
冷压强度(按DIN 51067): 170N/mm2
压力下软化(按DIN 51053 T1): To>1700℃
耐温度交变性能(按DIN EN 993,
11部分,相对于水) >30循环
这些值在按DE 19727917 C1的砖的范围内。但本发明的砖其耐腐蚀性性能有明显超越,特别是对所述危险性的渣。实验室试验(在感应坩埚炉中的渣化试验)中的其耐用性>30%。
Claims (21)
1.具有基于(Mg)2+(Al,Cr)2 3+O4的尖晶石基体的煅烧耐火陶瓷模制件,其中存在基于铬刚玉和/或刚玉的较粗颗粒以及基于ZrO2的较粗颗粒。
2.权利要求1的模制件,其中,与尖晶体基体的颗粒相对的较粗颗粒由组分铬刚玉和锆刚玉组成。
3.权利要求1的模制件,其中刚玉颗粒和/或铬刚玉颗粒的平均直径(d50)为0.5-10mm。
4.权利要求1的模制件,其中含ZrO2的颗粒的平均直径(d50)为0.5-10mm。
5.权利要求1的模制件,其中尖晶石基体占总重量的10-70重量%。
6.权利要求1-5之一的模制件用作废物焚烧炉,特别是特殊废物焚烧炉的内衬的应用。
7.用于制备权利要求1-5之一的模制件的配料,其含
7.1 2-35重量%的颗粒级分<0.5mm的Cr2O3,
7.2 1-15重量%的颗粒级分大于或等于0.2mm的ZrO2,
7.3 1-12重量%的颗粒级分<0.5mm的MgO,
7.4 38-96重量%的颗粒级分<10mm的Al2O3。
8.权利要求7的配料,其中至少部分组分MgO、Al2O3或Cr2O3是以尖晶石存在。
9.权利要求8的配料,其中至少部分组分是以MA-尖晶石或MCA-尖晶石存在。
10.权利要求7的配料,其中Cr2O3的含量为5-25重量%。
11.权利要求7的配料,其中ZrO2含量为1-6重量%。
12.权利要求11的配料,其中Al2O3含量为64-87重量%。
13.权利要求7的配料,其中Fe2O3含量为<0.5重量%。
14.权利要求7的配料,其中ZrO2组分由含斜锆石的原料形成。
15.权利要求7的配料,其中ZrO2组分由烧结-锆富铝红柱石、熔融-锆富铝红柱石、烧结-锆刚玉、熔融-锆刚玉或ZAC材料形成,这些材料可单独或混合使用。
16.权利要求7的配料,其中ZrO2组分以粒度为1-4mm存在。
17.权利要求7的配料,其中MA-尖晶石的含量为5-25重量%。
18.权利要求7的配料,其中Cr2O3和含MgO的组分中的至少一种以颗粒级分<0.2mm存在。
19.权利要求7的配料,其中Cr2O3和含MgO的组分中的至少一种以颗粒级分<0.1mm存在。
20.权利要求7的配料,其中最大30重量%是以级分<0.1mm的Al2O3存在。
21.权利要求7的配料,其中Al2O3以粒度>0.2mm存在。
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Application Number | Priority Date | Filing Date | Title |
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DE10160366A DE10160366C2 (de) | 2001-12-08 | 2001-12-08 | Gebranntes feuerfestes keramisches Formteil, seine Verwendung und Versatz zur Herstellung des Formteils |
DE10160366.5 | 2001-12-08 |
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CN1514810A true CN1514810A (zh) | 2004-07-21 |
CN1272278C CN1272278C (zh) | 2006-08-30 |
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US (1) | US6982233B2 (zh) |
EP (1) | EP1451127B1 (zh) |
JP (1) | JP2005512934A (zh) |
KR (1) | KR100704283B1 (zh) |
CN (1) | CN1272278C (zh) |
AT (1) | ATE307099T1 (zh) |
AU (1) | AU2002349028A1 (zh) |
DE (2) | DE10160366C2 (zh) |
DK (1) | DK1451127T3 (zh) |
ES (1) | ES2248623T3 (zh) |
HU (1) | HUP0401016A2 (zh) |
PL (1) | PL373169A1 (zh) |
WO (1) | WO2003053879A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102937291A (zh) * | 2012-11-20 | 2013-02-20 | 南京创能电力科技开发有限公司 | 一种具有多层结构的等离子燃烧器 |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005520407A (ja) * | 2002-03-11 | 2005-07-07 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | 情報を表示するシステム及び方法 |
DE102004007062B4 (de) * | 2004-02-13 | 2007-08-02 | Refractory Intellectual Property Gmbh & Co. Kg | Versatz zur Herstellung eines feuerfesten keramischen Erzeugnisses und Verfahren zu dessen Herstellung |
EP1710216B8 (de) * | 2005-04-07 | 2016-03-02 | Oerlikon Metco AG, Wohlen | Kompressor mit einer oberflächenschicht eines keramischen werkstoffs und das verfahren seiner herstellung |
US8197566B2 (en) * | 2008-12-08 | 2012-06-12 | General Electric Company | Gasifier additives for improved refractory life |
US20100212359A1 (en) * | 2009-02-23 | 2010-08-26 | Hilary Tony Godard | Spinel isopipe for fusion forming alkali containing glass sheets |
JP6427456B2 (ja) * | 2015-04-14 | 2018-11-21 | Dowaエコシステム株式会社 | 不定形耐火組成物、及び不定形耐火物 |
DE102016224443A1 (de) * | 2016-12-08 | 2018-06-14 | Siemens Aktiengesellschaft | Erosionsbeständiger keramischer Werkstoff, Pulver, Schlicker und Bauteil |
CN108101561B (zh) * | 2017-12-29 | 2020-12-01 | 武汉科技大学 | 一种不锈钢冶炼用钢包浇注料及其制备方法 |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS56134569A (en) * | 1980-03-25 | 1981-10-21 | Asahi Glass Co Ltd | Spinel structure heat-melt refractories |
DE3527790A1 (de) | 1985-08-02 | 1987-02-05 | Refratechnik Gmbh | Spinellbildende zusammensetzung sowie ihre verwendung |
JP2975849B2 (ja) * | 1994-07-25 | 1999-11-10 | 住友金属工業株式会社 | 製鋼用耐火物 |
DE19727917C1 (de) | 1997-07-01 | 1999-02-25 | Didier Werke Ag | Feuerfester Versatz auf Basis Chromoxid/Aluminiumoxid und dessen Verwendung |
DE19803327C2 (de) * | 1998-01-29 | 1999-12-09 | Schott Glas | Verfahren zur Herstellung von keramischen hochtemperaturbeständigen Werkstoffen mit einem einstellbaren thermischen Ausdehnungskoeffizienten und deren Verwendung |
US6261983B1 (en) * | 2000-01-12 | 2001-07-17 | Baker Refractories | Magnesia spinel refractory brick |
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2001
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2002
- 2002-11-08 HU HU0401016A patent/HUP0401016A2/hu unknown
- 2002-11-08 AU AU2002349028A patent/AU2002349028A1/en not_active Abandoned
- 2002-11-08 ES ES02781312T patent/ES2248623T3/es not_active Expired - Lifetime
- 2002-11-08 JP JP2003554597A patent/JP2005512934A/ja active Pending
- 2002-11-08 PL PL02373169A patent/PL373169A1/xx not_active Application Discontinuation
- 2002-11-08 DE DE50204633T patent/DE50204633D1/de not_active Expired - Fee Related
- 2002-11-08 US US10/477,869 patent/US6982233B2/en not_active Expired - Fee Related
- 2002-11-08 EP EP02781312A patent/EP1451127B1/de not_active Expired - Lifetime
- 2002-11-08 CN CNB028114582A patent/CN1272278C/zh not_active Expired - Fee Related
- 2002-11-08 WO PCT/EP2002/012489 patent/WO2003053879A1/de active IP Right Grant
- 2002-11-08 KR KR1020047000013A patent/KR100704283B1/ko not_active IP Right Cessation
- 2002-11-08 DK DK02781312T patent/DK1451127T3/da active
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102937291A (zh) * | 2012-11-20 | 2013-02-20 | 南京创能电力科技开发有限公司 | 一种具有多层结构的等离子燃烧器 |
CN102937291B (zh) * | 2012-11-20 | 2015-08-12 | 南京创能电力科技开发有限公司 | 一种宽煤种等离子点火燃烧器 |
Also Published As
Publication number | Publication date |
---|---|
US6982233B2 (en) | 2006-01-03 |
EP1451127A1 (de) | 2004-09-01 |
ES2248623T3 (es) | 2006-03-16 |
DE50204633D1 (de) | 2006-03-02 |
HUP0401016A2 (hu) | 2004-09-28 |
DE10160366C2 (de) | 2003-10-02 |
EP1451127B1 (de) | 2005-10-19 |
ATE307099T1 (de) | 2005-11-15 |
KR20040068096A (ko) | 2004-07-30 |
KR100704283B1 (ko) | 2007-04-10 |
DK1451127T3 (da) | 2006-03-06 |
US20040142812A1 (en) | 2004-07-22 |
PL373169A1 (en) | 2005-08-22 |
JP2005512934A (ja) | 2005-05-12 |
CN1272278C (zh) | 2006-08-30 |
DE10160366A1 (de) | 2003-06-26 |
WO2003053879A1 (de) | 2003-07-03 |
AU2002349028A1 (en) | 2003-07-09 |
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