CN1283584C - Sintered magnesing complex-phase refractory - Google Patents
Sintered magnesing complex-phase refractory Download PDFInfo
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- CN1283584C CN1283584C CN 200510055648 CN200510055648A CN1283584C CN 1283584 C CN1283584 C CN 1283584C CN 200510055648 CN200510055648 CN 200510055648 CN 200510055648 A CN200510055648 A CN 200510055648A CN 1283584 C CN1283584 C CN 1283584C
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Abstract
The present invention relates to a formula of a refractory material, which is prepared from magnoferrite sand, magnesite, magnesia alumina spinel, desilication zirconium and lanthanum oxide. The weight of the raw materials whose grain size is from 6mm to 1mm accounts for 50 to 60% of the total weight ratio of all the raw materials. The weight of the raw materials whose grain size is from 1mm to 0.088mm accounts for 10 to 20% of the total weight ratio, and the weight of the raw materials whose grain size is less than 0.088mm accounts for 25 to 38% of the total weight ratio. In the raw materials whose grain size is from 6mm to 1mm, the magnoferrite sand accounts for 100 to 50%, the magnesite accounts for 0 to 50%, and the magnesia alumina spinel accounts for 0 to 20%. In the raw materials whose grain size is from 1mm to 0.088mm, the magnesite accounts for 100 to 40%, the magnesia alumina spinel accounts for 0 to 20%, and the desilication zirconium accounts for 0 to 40%. In the raw materials whose grain size is less than 0.088mm, the magnesite accounts for 98 to 80%, the desilication zirconium accounts for 1 to 13%, the lanthanum oxide accounts for 1 to 7%, and the content of ferric oxide in the magnoferrite sand is from 5% to 15%. The complex phase material has the advantages of high fireproof performance, high corrosion resisting performance, low sensitivity to the change of atmosphere, high heat shock resistance and easy coating adhesion, and can be used for cement kilns to replace the existing magnesium chromium refractory material so as to avoid the problem of environmental pollution generated by Cr<6+> in magnesium chromium bricks.
Description
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
This research group finds: 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 make 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.
The prescription of refractory materials of the present invention is (weight percent):
Raw meal particle size is the 50-60% that accounts for the gross weight ratio of 6-1mm in the various raw materials, 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 that 100-50%, magnesia account for 0-50%, magnesium-aluminium spinel accounts for 0-20% in the 6-1mm particulate raw material; 1-0.088mm magnesia accounts for that 100-40%, magnesium-aluminium spinel account for 0-20%, desilicated zirconia accounts for 0-40% in the particulate raw material; Magnesia accounts for that 98-80%, desilicated zirconia account for 1-13%, lanthanum trioxide accounts for 1-7% in the＜0.088mm particulate raw material, and the content of ferric oxide is 5-15% in the aforementioned magnesium iron sand.
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 6-1m, 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 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 | 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.
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|---|---|---|---|
| CN 200510055648 CN1283584C (en) | 2005-03-22 | 2005-03-22 | Sintered magnesing complex-phase refractory |
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|---|---|---|---|
| CN 200510055648 CN1283584C (en) | 2005-03-22 | 2005-03-22 | Sintered magnesing complex-phase refractory |
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| CN1283584C true CN1283584C (en) | 2006-11-08 |
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Families Citing this family (10)
| 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 |
| 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 |
| CN103030410B (en) * | 2012-12-14 | 2014-10-01 | 河南瑞泰耐火材料科技有限公司 | Aluminum magnesium chromium composited spinel brick |
| CN104591756B (en) * | 2015-01-29 | 2017-04-12 | 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 |
| 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 |
| 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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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. |
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| 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 License type: Exclusive license 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 |