CN1657485A - Sintered magnesing complex-phase refractory - Google Patents

Sintered magnesing complex-phase refractory Download PDF

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Publication number
CN1657485A
CN1657485A CN 200510055648 CN200510055648A CN1657485A CN 1657485 A CN1657485 A CN 1657485A CN 200510055648 CN200510055648 CN 200510055648 CN 200510055648 A CN200510055648 A CN 200510055648A CN 1657485 A CN1657485 A CN 1657485A
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magnesium
magnesia
raw material
magnesing
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CN1283584C (en
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袁林
王杰曾
陈雪峰
曹变梅
赵洪亮
杨瑞莲
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Ruitai Technology Co., Ltd.
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BEIJING RUITAI HIGH-TEMP MATERIAL SCIENCE AND TECHNOLOGY Co Ltd
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Abstract

A sintered magnesium type composite refractory for cement kiln is proportionally prepared from MgFe sand, magnesite, MgAl spinel, desiliconized Zr and lanthanum oxide, all of which have different granularities.

Description

A kind of sintered magnesing complex-phase refractory
Technical field
The present invention relates to a kind of refractory materials.
Background technology
Cement rotary kiln life-time service magnesia chrome brick is as thermal zone kiln lining.In the use, the portion C r in the brick can be from Cr 3+Change severe toxicity and carcinogenic Cr into 6+Thereby, the health of destroying environment and threatening the people.Over year, making extensive work aspect the equivalent material of seeking magnesia chrome brick both at home and abroad, but effect is all undesirable surplus in the of 10.Its reason is: Cr 2O 3In magnesite refractory, play and improve directly combination, reduce erosion rate, improve heat-shock resistance and strengthen the adherent effect of kliner coating.These beneficial effects can only substitute for other material parts.Therefore, can not obtain satisfied result with one matter substitute chromium iron ore.
Chinese patent 1378997A uses Fe 2O 3/ Al 2O 3=3: 7-2: 6, MgO content is the magnesium iron composite spinelle sandy plain material brickmaking of 20-60%.The R of this kind spinel 2O 3Content is very high, only should add with particle form.After weathering, generate solution cavity near the composite spinelle easily.After kiln atmosphere changed, spinel particle was easy to produce bigger volume change, thereby reduced the work-ing life of material.
Chinese patent 1378992A uses or Fe 2O 3/ Al 2O 3=0: 10-6: 4, MgO content is the single equal raw material brickmaking of ≈ 100-85%.All the physical properties of raw material is identical, and the direction in case crackle produces to the consumed energy minimum is expanded, and is difficult to meet unrelieved stress compression, crack deflection or bifurcated in the expansion, splits obstruction such as sharp passivation.Therefore, need very high R 2O 3Content could obtain desired heat-shock resistance, thereby the resistance to fouling of material is affected.
Chinese patent 03111675.2 uses magnesium iron sand and contains Cr 2O 3With contain ZrO 2Raw material brickmaking.Because this material has used the raw material that contains chromium, can not avoid the chromium public hazards.
Periclasite in the magnesite refractory has good heat-resistance and resistance to fouling.But thermal expansivity is very high, thereby heat-shock resistance is very poor.Magnesia chrome spinel, magnesium-aluminium spinel and pleonast(e) all have lower thermal expansivity, add in the magnesian to form unrelieved stress or tiny crack, thereby make the crackle in the expansion obtain deflection, bifurcated or passivation, improve the heat-shock resistance of material.The magnesia chrome spinel fusing point is very high, is of value to hanging kliner coating and improving resistance to fouling, but serious environment pollution.The magnesium-aluminium spinel fusing point is very high, but not anti-erosion is unfavorable for hanging kliner coating.The pleonast(e) fusing point is very low, and not anti-erosion helps kliner coating and adheres to but be unfavorable for keeping lastingly kliner coating, also kiln atmosphere is changed responsive.So, be to use the above-mentioned spinel of single still only compound use all can not reach the purpose of protecting environment and guaranteed performance simultaneously.
Therefore, the design of novel refractory at first should manage to jump out this performance magic triangle of resistance to fouling, heat-shock resistance and physical strength.
The material that resistance to fouling requires to be easy to be etched is wrapped in erosion resistant material inside, and the not erosion-resistant work of institute isolates phase, the erosion-resistant external phase of doing in other words.Like this, the magnalium of anti-erosion difference, pleonast(e) just should not be as body materials.
Heterogeneous, different in nature material place in the matrix material will produce unrelieved stress.In case low bulk material material is made particle, high dilatant is made matrix, particle is relative expansion in the cooling after the burning, is the radial tiny crack at center or unrelieved stress correspondingly thereby be easy to produce with the particle.At this moment, though material can have higher heat-shock resistance and resistance to fouling.But loss of strength is bigger.Otherwise high dilatant makes particle, when the low bulk material is made matrix, and particle is relative contraction in the process of cooling after the burning, thereby is easy to produce ring-type tiny crack or unrelieved stress correspondingly at granule boundary.At this moment, material can have higher heat-shock resistance, and loss of strength is also little, but relatively poor magnalium, the pleonast(e) of anti-erosion made external phase, and the resistance to fouling of material is bad naturally.
Summary of the invention
The objective of the invention is to invent a kind of magnesing complex-phase refractory, make it have excellent mechanical intensity, refractoriness under load, heat-shock resistance and extension kliner coating.
This patent is found: the zirconic acid lanthanum is a kind ofly to have high-melting-point, be easy to stick kliner coating, help improving the mineral of thermal shock resistance again.Like this, just found the way that solves resistance to fouling, heat-shock resistance and physical strength contradiction.Solution is: mainly do thick, middle aggregate by magnesium iron sand, with resistance to fouling magnesia-zirconic acid lanthanum matrix parcel magnesium iron sand preferably, fill the highest magnesia fine aggregate of the coefficient of expansion between thick, middle aggregate.Very high as the heat-shock resistance requirement, can also in material, add particle in zirconium white fine particle and the small amount of magnesium aluminate.
Prescription of the present invention is (weight percent):
6-1mm???????????1-0.088mm??????<0.088mm
Magnesium iron sand 100-50% 00
Magnesia 0-50% 100-40% 98-80%
Magnesium-aluminium spinel 0-20% 0-20% 0
Desilicated zirconia 0 0-40% 1-13%
Lanthanum trioxide 00 1-7%
Wherein the content of ferric oxide is 5-15% in the magnesium iron sand.Raw meal particle size is the 50-60% that accounts for the gross weight ratio of 6-1mm in the described various raw material, the 10-20% that accounts for the gross weight ratio of 1-0.088mm, and the gross weight that accounts for of<0.088mm compares 25-38%.
The raw material that meets above-mentioned granularity and composition requirement after weighing, cooperating, again through add spent pulping liquor, mix, moulding, drying, burn till at 1600-1750 ℃ and to make refractory brick.
Embodiment
Embodiment 1: granularity 6-1mm, Fe 2O 3Content is 12% magnesium iron sand 50%, 1-0.088mm magnesia 17%,<0.088mm magnesia powder 30%,<0.088mm desiliconization zirconium powder 1%,<after 0.088mm lanthanum trioxide powder 2% cooperates, add 3% spent pulping liquor, through mixing, after the moulding, drying, burning till at 1700 ℃ and to make refractory brick.The performance of material is:
??MgO% ????Fe 2O 3 Volume density g/cm 3 Apparent porosity % Compressive strength MPa The soft T0.6 of lotus ℃ 1100 ℃ of water-cooleds of anti-thermal shock/time Hang the kliner coating grade
??≥85 ????6 3.1 17 ??60 1650 ??>=4 Good
Embodiment 2: granularity 6-1mm, Fe 2O 3Content is 8% magnesium iron sand 45%, magnesium-aluminium spinel 5%, magnesia 10%; 1-0.088mm magnesia 8%, desilicated zirconia 2%;<0.088mm magnesia powder 28%,<0.088mm desiliconization zirconium powder 1%,<after 0.088mm lanthanum trioxide powder 1% cooperates, add 3% spent pulping liquor, through mixing, after the moulding, drying, burning till at 1700 ℃ and to make refractory brick.The performance of material is:
MgO% Fe 2O 3 Volume density g/cm Apparent porosity % Compressive strength MPa The soft T0.6 of lotus ℃ 1100 ℃ of water-cooleds of anti-thermal shock/time Hang the kliner coating grade
≥85 5 ??3.2 18 ??53 1670 >=7 Well
From the above: novel material has excellent mechanical intensity, refractoriness under load, heat-shock resistance and extension kliner coating Journal of Sex Research simultaneously and has reached purpose substantially.This composite diphase material have resistivity against fire height, resistance to fouling strong, atmosphere is changed advantages such as very responsive, good thermal shock and kliner coating easy to hang, can be used for cement kiln to substitute existing magnesium chrome refractory, to avoid Cr in the magnesia chrome brick 6+The problem of environmental pollution that produces.

Claims (1)

1. sintered magnesing complex-phase refractory, it is characterized in that: the prescription of described refractory materials is by magnesium iron sand, magnesia, magnesium-aluminium spinel, desilicated zirconia, lanthanum trioxide is made into, raw meal particle size is the 50-60% that accounts for the gross weight ratio of 6-1mm in the described various raw material, 1-0.088mm the 10-20% that accounts for the gross weight ratio, the 25-38% that accounts for the gross weight ratio of<0.088mm, wherein magnesium iron sand accounts for 100-50% in the 6-1mm particulate raw material, magnesia accounts for 0-50%, magnesium-aluminium spinel accounts for 0-20%, 1-0.088mm magnesia accounts for 100-40% in the particulate raw material, magnesium-aluminium spinel accounts for 0-20%, desilicated zirconia accounts for 0-40%, magnesia accounts for 98-80% in the<0.088mm particulate raw material, desilicated zirconia accounts for 1-13%, lanthanum trioxide accounts for 1-7%, and the content of ferric oxide is 5-15% in the aforementioned magnesium iron sand.
CN 200510055648 2005-03-22 2005-03-22 Sintered magnesing complex-phase refractory Active CN1283584C (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100372808C (en) * 2006-04-18 2008-03-05 中国建筑材料科学研究院大石桥镁砖厂 Making process of zirconium-containing magnesia brick
CN102093063A (en) * 2010-12-10 2011-06-15 河南瑞泰耐火材料科技有限公司 Magnesium-aluminum-zirconium composite spinel refractory material
CN101550016B (en) * 2009-04-28 2011-08-03 莱芜钢铁集团有限公司 Magnesia chrome carbon coating and preparation method thereof
CN101486580B (en) * 2008-04-16 2011-08-24 中钢集团耐火材料有限公司 Ferro-magnesium-aluminum spinelle fire-resistant material
CN101423401B (en) * 2008-12-01 2011-11-09 瑞泰科技股份有限公司 Composite combining corundum based refractory materials
CN103030410A (en) * 2012-12-14 2013-04-10 河南瑞泰耐火材料科技有限公司 Aluminum magnesium chromium composited spinel brick
CN104591756A (en) * 2015-01-29 2015-05-06 濮阳濮耐高温材料(集团)股份有限公司 Magnesium-iron brick preparation raw material capable of increasing high temperature bending strength of magnesium-iron brick and magnesium-iron brick preparation process
CN101412629B (en) * 2008-08-29 2016-12-14 瑞泰科技股份有限公司 Periclase-magnesium aluminate spinel composite refractory brick and production technology thereof
CN106278301A (en) * 2016-07-22 2017-01-04 武汉科技大学 A kind of cement kiln spinel fireproof coating and preparation method thereof
CN108191439A (en) * 2018-02-28 2018-06-22 攀钢冶金材料有限责任公司 A kind of blast furnace slag high temperature cabonization electric furnace refractory brick and preparation method thereof
CN110066182A (en) * 2019-05-28 2019-07-30 江苏诺明高温材料股份有限公司 Utilize the method for pyrite cinder preparation magnesium-ferrum-aluminum composite material

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100372808C (en) * 2006-04-18 2008-03-05 中国建筑材料科学研究院大石桥镁砖厂 Making process of zirconium-containing magnesia brick
CN101486580B (en) * 2008-04-16 2011-08-24 中钢集团耐火材料有限公司 Ferro-magnesium-aluminum spinelle fire-resistant material
CN101412629B (en) * 2008-08-29 2016-12-14 瑞泰科技股份有限公司 Periclase-magnesium aluminate spinel composite refractory brick and production technology thereof
CN101423401B (en) * 2008-12-01 2011-11-09 瑞泰科技股份有限公司 Composite combining corundum based refractory materials
CN101550016B (en) * 2009-04-28 2011-08-03 莱芜钢铁集团有限公司 Magnesia chrome carbon coating and preparation method thereof
CN102093063B (en) * 2010-12-10 2013-09-18 河南瑞泰耐火材料科技有限公司 Magnesium-aluminum-zirconium composite spinel refractory material
CN102093063A (en) * 2010-12-10 2011-06-15 河南瑞泰耐火材料科技有限公司 Magnesium-aluminum-zirconium composite spinel refractory material
CN103030410A (en) * 2012-12-14 2013-04-10 河南瑞泰耐火材料科技有限公司 Aluminum magnesium chromium composited spinel brick
CN104591756A (en) * 2015-01-29 2015-05-06 濮阳濮耐高温材料(集团)股份有限公司 Magnesium-iron brick preparation raw material capable of increasing high temperature bending strength of magnesium-iron brick and magnesium-iron brick preparation process
CN106278301A (en) * 2016-07-22 2017-01-04 武汉科技大学 A kind of cement kiln spinel fireproof coating and preparation method thereof
CN106278301B (en) * 2016-07-22 2018-11-13 武汉科技大学 A kind of cement kiln spinel fireproof coating and preparation method thereof
CN108191439A (en) * 2018-02-28 2018-06-22 攀钢冶金材料有限责任公司 A kind of blast furnace slag high temperature cabonization electric furnace refractory brick and preparation method thereof
CN108191439B (en) * 2018-02-28 2021-04-27 攀钢冶金材料有限责任公司 Refractory brick for blast furnace slag high-temperature carbonization electric furnace and preparation method thereof
CN110066182A (en) * 2019-05-28 2019-07-30 江苏诺明高温材料股份有限公司 Utilize the method for pyrite cinder preparation magnesium-ferrum-aluminum composite material

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Owner name: RUITAI TECHNOLOGY CO., LTD.

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Address after: No. 1 East Lane, Chaoyang District, Beijing, Guanzhuang

Patentee after: Ruitai Technology Co., Ltd.

Address before: No. 1 East Lane, Chaoyang District, Beijing, Guanzhuang

Patentee before: Beijing Ruitai High-Temp Material Science and Technology Co., Ltd.

EE01 Entry into force of recordation of patent licensing contract

Assignee: Henan Ruitai Refractory Technology Co., Ltd.

Assignor: Ruitai Technology Co., Ltd.

Contract fulfillment period: 2009.4.21 to 2019.4.20 contract change

Contract record no.: 2009410000082

Denomination of invention: Sintered magnesing complex-phase refractory

Granted publication date: 20061108

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Record date: 2009.5.5

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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.4.21 TO 2019.4.20; CHANGE OF CONTRACT

Name of requester: HENAN RUITAI REFRACTORY MATERIAL SCIENCE CO., LTD.

Effective date: 20090505