CN103420684A - Calcium hexaluminate CA6/anorthite CAS2 composite light heat-insulation refractory material and preparation method thereof - Google Patents
Calcium hexaluminate CA6/anorthite CAS2 composite light heat-insulation refractory material and preparation method thereof Download PDFInfo
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- CN103420684A CN103420684A CN2012102588324A CN201210258832A CN103420684A CN 103420684 A CN103420684 A CN 103420684A CN 2012102588324 A CN2012102588324 A CN 2012102588324A CN 201210258832 A CN201210258832 A CN 201210258832A CN 103420684 A CN103420684 A CN 103420684A
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Abstract
The invention relates to a calcium hexaluminate CA6/anorthite CAS2 composite light heat-insulation refractory material and a preparation method thereof, and belongs to the technical field of refractory materials. The preparation method realizes preparation of the CA6/CAS2 composite light heat-insulation refractory material from magnesium slag. The preparation method utilizes industrial waste magnesium slag obtained by a Pidgeon process-based magnesium manufacturing technology, kaolin and industrial alumina as raw materials, wherein the raw materials comprise 10-25wt% of the magnesium slag, 7-25wt% of the kaolin and 55-80wt% of the industrial alumina. The raw materials are mixed uniformly according to a certain ratio, the mixture is added with a certain amount of a binder and a pore forming agent, and then the mixture is molded and then is sintered into the CA6/CAS2 composite light heat-insulation refractory material having principal crystalline phases of CA6 and CAS2 at a high temperature in air. The CA6/CAS2 composite light heat-insulation refractory material mainly comprises CaO, Al2O3 and SiO2. The preparation method of the CA6/CAS2 composite light heat-insulation refractory material has the simple processes and low magnesium slag raw material requirement, does not need other processes, reduces a cost and magnesium slag pollution, and realizes magnesium slag comprehensive utilization.
Description
Technical field:
The present invention establishes and a kind of calcium hexaluminate that utilizes the magnesium slag to prepare/lime feldspar complex phase light heat insulating refractory materials and preparation method thereof, belongs to technical field of refractory materials.
Background technology:
A kind of industrial residue of discharging when the magnesium slag is MAGNESIUM METAL factory employing production of magnesium by pidgeonprocess, main chemical compositions is CaO, SiO
2, Al
2O
3.Research shows that the magnesium slag has certain pozzolanic activity.The processing of most of magnesium slags mainly be take stacking and is buried as main, utilizes approach seldom, and utilization ratio is extremely low, though indivedual magnesium factory has, the magnesium slag is filled for plant area's shoofly and terrace, because the very low result of use of intensity is not good, has so both wasted resource, contaminate environment again.
In recent years, calcium hexaluminate, as a kind of novel refractory material aggregate, has unique en plaque crystalline structure, is conducive to improve the heat-proof quality of material, performances such as its good high volume stability, heat-shock resistance, anti-slag in addition, success be applied to steel-making and ceramic industry kiln.Calcium hexaluminate (CaAl
12O
19, be called for short CA
6) be CaO-Al
2O
3Al in system
2O
3The calcium aluminate phase that middle content is the highest, belong to six side's strains, has the characteristic of preferential formation sheet or tabular crystal perpendicular to the C direction of principal axis.Its theoretical density is 3.79gcm
-3, fusing point is 1875 ℃, thermal expansivity is 8.0 * 10
-6℃
-1.
Lime feldspar (CaAl
2Si
2O
8, be called for short CAS
2) belonging to triclinic(crystalline)system, its crystal generally is tabular or sheet-pile shape, in aggregate, is that subhedral is to xenomorphic granular.Its theoretical density is 2.75gcm
-3, fusing point is 1550 ℃, thermal expansivity is 4.82 * 10
-6℃
-1, thermal conductivity is low.
Prior art adopts the pure chemistry raw material to synthesize CA more
6, cost is higher, complex process, and production efficiency is not high, is difficult to be used widely.It is starting material that industrial residue magnesium slag, kaolin and the commercial alumina that Pidgeon process industry refining magnesium produces take in the present invention, prepared calcium hexaluminate/lime feldspar complex phase light heat insulating refractory materials by the pyroreaction sintering process, this preparation method both can prepare with low cost the refractory materials of calcium hexaluminate/lime feldspar complex phase light heat insulating, can reduce to a certain extent again the pollution of magnesium slag and realize the comprehensive utilization of magnesium slag, and that this material has is high temperature resistant, lightweight, characteristics that heat insulation and preservation effect is good, applicable to the liner high-temperature material of elevated temperature vessel and kiln.
Summary of the invention:
The object of the invention is to utilize the magnesium slag to prepare calcium hexaluminate CA
6/ lime feldspar CAS
2The complex phase light heat insulating refractory materials, the preparation method of a kind of calcium hexaluminate/lime feldspar complex phase light heat insulating refractory materials is provided, adopting magnesium slag, kaolin and commercial alumina is that raw material prepares calcium hexaluminate/lime feldspar complex phase light heat insulating refractory materials, both can prepare the refractory materials of calcium hexaluminate/lime feldspar complex phase light heat insulating with low cost, and can reduce to a certain extent again the pollution of magnesium slag and realize the comprehensive utilization of magnesium slag.
Technical solution of the present invention is as follows:
A kind of complex phase light heat insulating refractory materials, the main phase of this light thermal insulation fire-resistant material is calcium hexaluminate CA
6/ lime feldspar CAS
2Complex phase; The main chemical of this complex phase is: Al
2O
3Content 60～85wt.%, CaO content 6～18wt.%, SiO
2Content 4～15wt.%, three's sum is 100%.
A kind of method of utilizing the magnesium slag to prepare calcium hexaluminate/lime feldspar complex phase light heat insulating refractory materials, comprising the steps: 1) the magnesium slag, kaolin, aluminum oxide that will cross 100 mesh sieves are according to the stoichiometric batching and take water as the grinding medium ball mill mixing, Ball-milling Time is 30min, rotating speed is 300r/min, obtains mud; 2) above-mentioned mud is dried and added the PVA fluidizer of 4wt.%, then granulation, form granular powder; 3) by granular powder at 20MPa～40MPa forming under the pressure to form base substrate; 4) by the base substrate of forming sintering in stove, sintering schedule is: the temperature rise rate in room temperature to 1200 ℃ stage is 5～8 ℃/min, 1200 ℃ of temperature rise rates to final firing temperature are 2～5 ℃/min, final firing temperature is 1400～1500 ℃, soaking time 0.5～4h under final firing temperature, then be chilled to room temperature with stove, obtain calcium hexaluminate/lime feldspar complex phase light heat insulating refractory materials.
Described magnesium slag major ingredient is: CaO content 40～55wt.%, SiO
2Content 20～30wt.%, Al
2O
3Content 2～5wt.%, Fe
2O
3The about 9wt.% of content, MgO content 6～10wt.%, its addition is 10～25wt.%; The kaolin major ingredient is: CaO content 0～3wt.%, SiO
2Content 40～50wt.%, Al
2O
3Content 35～60wt.%, its addition is 7～25wt.%; Commercial alumina is commercially available industrial raw material, and its specification of quality is Al
2O
3Purity>=94.0wt.%, the particle size size of raw material is 1.00mm, its addition is 55～80wt.%.
The magnesium slag that utilizes of the present invention prepares calcium hexaluminate/lime feldspar complex phase light heat insulating refractory materials, both can reduce the cost for preparing calcium hexaluminate/lime feldspar complex phase light heat insulating refractory materials, can realize again the comprehensive utilization of magnesium slag.
Embodiment:
Below in conjunction with embodiment, the present invention is elaborated: the present embodiment is implemented take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Raw material of the present invention is: smelt industrial residue magnesium slag, kaolin and commercial alumina that magnesium produces.Described magnesium slag major ingredient is: CaO content 40～55wt.%, SiO
2Content 20～30wt.%, Al
2O
3Content 2～5wt.%, Fe
2O
3The about 9wt.% of content, MgO content 6～10wt.%, its addition is 10～25wt.%; The kaolin major ingredient is: CaO content 0～3wt.%, SiO
2Content 40～50wt.%, Al
2O
3Content 35～60wt.%, its addition is 7～25wt.%; Commercial alumina is commercially available industrial raw material, and its specification of quality is Al
2O
3Purity>=94.0wt.%, the particle size size of raw material is 1.00mm, its addition is 55～80wt.%.
Embodiment 1:
Batching point: magnesium slag 19.80wt.%, kaolin 19.60wt.%, commercial alumina 60.60wt.%.
After magnesium slag, kaolin, the aluminum oxide of 100 mesh sieves are put proportion ingredient according to batching excessively, take water as the grinding medium ball mill mixing, and Ball-milling Time is 30min, and rotating speed is 300r/min, then the raw material after drying is added to the PVA fluidizer granulation of 4wt.%, and in the 20MPa compacted under.After moulding, base substrate is placed in stove and carries out sintering under air atmosphere, the temperature rise rate in room temperature to 1200 ℃ stage adopts 8 ℃/min, 1200 ℃ of temperature rise rates to the final firing temperature stage adopt 2 ℃/min, final firing temperature is 1400 ℃, insulation 0.5h, after be chilled to room temperature with stove, obtain calcium hexaluminate/lime feldspar composite diphase material.
The calcium hexaluminate of preparation/lime feldspar composite diphase material, main phase is CaAl
12O
19And CaAl
2Si
2O
8, Al wherein
2O
3Content 70wt.%, CaO content 15wt.%, SiO
2Content 15wt.%.
Embodiment 2:
Batching point: magnesium slag 18.43wt.%, kaolin 16.39wt.%, commercial alumina 65.18wt.%.
After magnesium slag, kaolin, the aluminum oxide of 100 mesh sieves are put proportion ingredient according to batching excessively, take water as the grinding medium ball mill mixing, and Ball-milling Time is 30min, and rotating speed is 300r/min, then the raw material after drying is added to the PVA fluidizer granulation of 4wt.%, and in the 30MPa compacted under.After moulding, base substrate is placed in stove and carries out sintering under air atmosphere, the temperature rise rate in room temperature to 1200 ℃ stage adopts 6 ℃/min, 1200 ℃ of temperature rise rates to the final firing temperature stage adopt 3 ℃/min, final firing temperature is 1420 ℃, insulation 2h, after be chilled to room temperature with stove, obtain calcium hexaluminate/lime feldspar composite diphase material.
The calcium hexaluminate of preparation/lime feldspar composite diphase material, main phase is CaAl
12O
19And CaAl
2Si
2O
8, Al wherein
2O
3Content 73.18wt.%, CaO content 13.86wt.%, SiO
2Content 12.96wt.%.
Embodiment 3:
Batching point: magnesium slag 13.53wt.%, kaolin 9.21wt.%, commercial alumina 77.26wt.%.
After magnesium slag, kaolin, the aluminum oxide of 100 mesh sieves are put proportion ingredient according to batching excessively, take water as the grinding medium ball mill mixing, and Ball-milling Time is 30min, and rotating speed is 300r/min, then the raw material after drying is added to the PVA fluidizer granulation of 4wt.%, and in the 40MPa compacted under.After moulding, base substrate is placed in stove and carries out sintering under air atmosphere, the temperature rise rate in room temperature to 1200 ℃ stage adopts 5 ℃/min, 1200 ℃ of temperature rise rates to the final firing temperature stage adopt 5 ℃/min, final firing temperature is 1500 ℃, soaking time adopts 4h, after be chilled to room temperature with stove, obtain calcium hexaluminate/lime feldspar composite diphase material.
The calcium hexaluminate of preparation/lime feldspar composite diphase material, main phase is CaAl
12O
19And CaAl
2Si
2O
8, Al wherein
2O
3Content 82wt.%, CaO content 10wt.%, SiO
2Content 8wt.%.
Claims (3)
1. a complex phase light heat insulating refractory materials, it is characterized in that: the main phase of this light thermal insulation fire-resistant material is calcium hexaluminate CA
6/ lime feldspar CAS
2Complex phase; The main chemical of this complex phase is: Al
2O
3Content 60～85wt.%, CaO content 6～18wt.%, SiO
2Content 4～15wt.%, three's sum is 100%.
2. a method of utilizing the magnesium slag to prepare calcium hexaluminate/lime feldspar complex phase light heat insulating refractory materials, is characterized in that, the method comprises the steps:
1) magnesium slag, kaolin, the aluminum oxide that will cross 100 mesh sieves are prepared burden and take water as the grinding medium ball mill mixing according to stoichiometric, and Ball-milling Time is 30min, and rotating speed is 300r/min, obtains mud;
2) above-mentioned mud is dried and added the PVA fluidizer of 4wt.%, then granulation, form granular powder;
3) by granular powder at 20MPa～40MPa forming under the pressure to form base substrate;
4) by the base substrate of forming sintering in stove, sintering schedule is: the temperature rise rate in room temperature to 1200 ℃ stage is 5～8 ℃/min, 1200 ℃ of temperature rise rates to final firing temperature are 2～5 ℃/min, final firing temperature is 1400～1500 ℃, soaking time 0.5～4h under final firing temperature, then be chilled to room temperature with stove, obtain calcium hexaluminate/lime feldspar complex phase light heat insulating refractory materials.
3. prepare according to claim 2 the method for calcium hexaluminate/lime feldspar complex phase light heat insulating refractory materials, it is characterized in that:
The major ingredient of described magnesium slag is: CaO content 40～55wt.%, SiO
2Content 20～30wt.%, Al
2O
3Content 2～5wt.%, Fe
2O
3The about 9wt.% of content, MgO content 6～10wt.%, its addition is 10～25wt.%;
The kaolin major ingredient is: CaO content 0～3wt.%, SiO
2Content 40～50wt.%, Al
2O
3Content 35～60wt.%, its addition is 7～25wt.%;
Commercial alumina is commercially available industrial raw material, and its specification of quality is Al
2O
3Purity>=94.0wt.%, the particle size size of raw material is 1.00mm, its addition is 55～80wt.%.
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|---|---|---|---|
| CN201210258832.4A CN103420684B (en) | 2012-07-25 | 2012-07-25 | Calcium hexaluminate CA6/anorthite CAS2 composite light heat-insulation refractory material and preparation method thereof |
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|---|---|---|---|
| CN201210258832.4A CN103420684B (en) | 2012-07-25 | 2012-07-25 | Calcium hexaluminate CA6/anorthite CAS2 composite light heat-insulation refractory material and preparation method thereof |
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| CN103420684B CN103420684B (en) | 2014-07-30 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402470A (en) * | 2014-11-14 | 2015-03-11 | 钢铁研究总院 | Composite high-temperature refractory material and making method thereof |
| CN107056313A (en) * | 2017-06-30 | 2017-08-18 | 张静芬 | A kind of cement rotary kiln stove castable refractory |
| CN107500788A (en) * | 2017-08-24 | 2017-12-22 | 浙江科屹耐火材料有限公司 | A kind of insulating fire brick and preparation method thereof |
| CN111925222A (en) * | 2020-08-05 | 2020-11-13 | 辽宁科技大学 | Method for preparing refractory ball for hot blast furnace by using aluminum titanium slag |
| CN113636835A (en) * | 2021-08-30 | 2021-11-12 | 武汉理工大学 | Anorthite heat storage ceramic prepared from magnesium slag and preparation method thereof |
| CN114133257A (en) * | 2020-12-31 | 2022-03-04 | 郑州轻工业大学 | Micro-nano hole heat insulation refractory material containing calcium hexaluminate and preparation method thereof |
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| CN101456575A (en) * | 2009-01-08 | 2009-06-17 | 上海交通大学 | Method for preparing calcium-hexaluminate ceramic powder by calcium slag |
| CN101928153A (en) * | 2010-09-01 | 2010-12-29 | 中国地质大学（北京） | Calcium hexaluminate and corundum composite porous light heat insulation refractory material and preparation method thereof |
| CN102491770A (en) * | 2011-12-06 | 2012-06-13 | 安徽瑞泰新材料科技有限公司 | Wear-resisting castable refractory |
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Patent Citations (4)
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402470A (en) * | 2014-11-14 | 2015-03-11 | 钢铁研究总院 | Composite high-temperature refractory material and making method thereof |
| CN104402470B (en) * | 2014-11-14 | 2016-03-30 | 钢铁研究总院 | A kind of combined high temperature refractory materials and manufacture method thereof |
| CN107056313A (en) * | 2017-06-30 | 2017-08-18 | 张静芬 | A kind of cement rotary kiln stove castable refractory |
| CN107500788A (en) * | 2017-08-24 | 2017-12-22 | 浙江科屹耐火材料有限公司 | A kind of insulating fire brick and preparation method thereof |
| CN111925222A (en) * | 2020-08-05 | 2020-11-13 | 辽宁科技大学 | Method for preparing refractory ball for hot blast furnace by using aluminum titanium slag |
| CN114133257A (en) * | 2020-12-31 | 2022-03-04 | 郑州轻工业大学 | Micro-nano hole heat insulation refractory material containing calcium hexaluminate and preparation method thereof |
| CN113636835A (en) * | 2021-08-30 | 2021-11-12 | 武汉理工大学 | Anorthite heat storage ceramic prepared from magnesium slag and preparation method thereof |
| CN113636835B (en) * | 2021-08-30 | 2022-11-18 | 武汉理工大学 | Anorthite heat storage ceramic prepared from magnesium slag and preparation method thereof |
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