WO2011095018A1 - 镁铁铝尖晶石砖及其制备方法 - Google Patents
镁铁铝尖晶石砖及其制备方法 Download PDFInfo
- Publication number
- WO2011095018A1 WO2011095018A1 PCT/CN2010/078472 CN2010078472W WO2011095018A1 WO 2011095018 A1 WO2011095018 A1 WO 2011095018A1 CN 2010078472 W CN2010078472 W CN 2010078472W WO 2011095018 A1 WO2011095018 A1 WO 2011095018A1
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- WIPO (PCT)
- Prior art keywords
- magnesia
- ferrous
- spinel
- aluminum spinel
- spinel brick
- Prior art date
Links
- 239000011449 brick Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 229910001691 hercynite Inorganic materials 0.000 title abstract 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 43
- 239000000203 mixture Substances 0.000 claims abstract description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 229910052596 spinel Inorganic materials 0.000 claims description 69
- 239000011029 spinel Substances 0.000 claims description 69
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 43
- 229910052782 aluminium Inorganic materials 0.000 claims description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- -1 magnesium iron aluminum Chemical compound 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 10
- 229920002472 Starch Polymers 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 235000010981 methylcellulose Nutrition 0.000 claims description 7
- 229920001353 Dextrin Polymers 0.000 claims description 5
- 239000004375 Dextrin Substances 0.000 claims description 5
- 235000019425 dextrin Nutrition 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims description 2
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 7
- 239000004568 cement Substances 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 7
- 239000011651 chromium Substances 0.000 description 4
- 239000011819 refractory material Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 244000000188 Vaccinium ovalifolium Species 0.000 description 1
- NACUKFIFISCLOQ-UHFFFAOYSA-N [Mg].[Cr] Chemical compound [Mg].[Cr] NACUKFIFISCLOQ-UHFFFAOYSA-N 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
- C04B35/043—Refractories from grain sized mixtures
- C04B35/0435—Refractories from grain sized mixtures containing refractory metal compounds other than chromium oxide or chrome ore
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D1/00—Casings; Linings; Walls; Roofs
- F27D1/0003—Linings or walls
- F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5463—Particle size distributions
- C04B2235/5472—Bimodal, multi-modal or multi-fraction
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/72—Products characterised by the absence or the low content of specific components, e.g. alkali metal free alumina ceramics
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
Definitions
- the invention relates to a magnesium iron aluminum spinel brick and a preparation method thereof, and belongs to the technical field of refractory materials. Background technique
- magnesia-chrome bricks have become the main material used in the cement rotary kiln firing zone in the new dry-process cement production line. As magnesia-chrome bricks are in use, some of the chromium in the bricks will change from Cr 3+ to highly toxic and carcinogenic Cr 6+ , destroying the environment and affecting people's lives.
- chromium-free is the trend and development direction of alkaline materials for cement kiln.
- the alternative material is mainly white marble refractory material.
- the dolomitic refractory material has good thermal shock resistance and erosion resistance, it is very easy to hydrate.
- Ogilvy &Mather's magnesium-iron-aluminum spinel bricks are truly entering the commercial application at home and abroad.
- the company's magnesia-aluminum bricks are prepared from synthetic ferrous aluminum spinel and magnesia (particle size less than 4 mm), and Fe 2 0 in the composition of ferrous aluminum spinel. 3: A1 2 0 3 ratio is 30: 70 to 60: 40, and contains 20-60% of MgO measured by Fe 2 0 3 + Al 2 0 3 . Since the MgO content in the ferrous aluminum spinel is high, the sintering activity is low, and the sintering temperature of the entire ferrous aluminum spinel brick needs to be correspondingly increased.
- the patent 200810049559.8 is based on sintered magnesia with a limit particle size of 8mm. Prepared by ferrous aluminum spinel; the amount of spinel added is 3-40% by mass, and the composition thereof is A1 2 0 3 45-65 mass%, FeO 20-55 mass%, and MgO 0-15 mass%.
- the material may contain excess FeO or A1 2 0 3 , which may cause the ferrous aluminum spinel brick to appear larger during firing or use. The volume effect is not conducive to volume stability.
- the object of the present invention is to provide a magnesium iron aluminum spinel brick and a preparation method thereof.
- the magnesium iron aluminum spinel brick of the present invention has a chemical weight percentage composition of Fe 2 0 3 2.5 ⁇ 9.6%, A1 2 0 3 2.9 ⁇ 12% and MgO 76 ⁇ 93%.
- the XRD line of the ferrous aluminum spinel material of the magnesia-alumina spinel brick shows that the main crystal phase is Fe Al 2 0 3 .
- the preparation method of the magnesium iron aluminum spinel brick is prepared by using magnesia and ferrous aluminum spinel as raw materials, adding a binder, pressing and forming, drying and drying at a high temperature, and the firing temperature is 1400 ⁇ 1700. °C.
- the ferrous aluminum spinel is introduced in the form of FeOAl 2 0 3 , and the chemical weight composition of the ferrous aluminum spinel is in the ratio of Fe 2 0 3 :Al 2 0 3 (40 to 45): (55 to 60), And the total mass of Fe 2 0 3 + Al 2 0 3 is 0 to 20%.
- the ferrous aluminum spinel material is a pellet having a particle size of ⁇ 3111111.
- the ferrous aluminum spinel material is a powder having a particle size of ⁇ 0.088111111.
- the binder is one of a dextrin, a pulp waste liquid, a starch, a methyl cellulose, a resin, or a combination of any of several.
- the chemical composition is calculated by converting FeO into Fe 2 0 3 .
- the invention adopts the magnesia sand with the limit particle size of 5 mm which is relatively convenient to be implemented in the field of refractory materials in China, and introduces the pre-synthesized ferrous aluminum spinel with high activity, thereby obtaining the high-performance magnesium-aluminum alloy for the rotary kiln firing zone.
- the magnesia-alumina spinel brick of the present invention comprises magnesia and a pre-synthesized ferrous aluminum spinel.
- Magnesia sand can be selected from fused magnesia, sintered magnesia and medium-grade magnesia, and the ultimate particle size is 5mm; the matrix portion contains two parts of particle size of 0.088mm and 0.045mm.
- the pre-synthesized ferrous aluminum spinel has a limit particle size of 3 mm.
- the pre-synthesized ferrous aluminum spinel is the key, in order to maintain the high sintering activity of the ferrous aluminum spinel material, a volume-stable magnesium iron-aluminum spinel brick is obtained, and the ferrous aluminum tip of the present invention
- the composition of the spar is
- Fe 2 0 3 A1 2 0 3 ratio is close to the theoretical composition of ferrous aluminum spinel, which is (40 ⁇ 45): (55 ⁇ 60), and contains Fe 2 0 3 +Al 2 0 3 total mass 0 ⁇ 20 % of MgO. Since the MgO content in the ferrous spinel is low, the driving force for diffusion of Fe 2+ into the magnesia is strong, and therefore, the ferrous spinel maintains a high sintering activity.
- the magnesia-alumina spinel brick of the present invention is obtained by mixing, molding and firing magnesia and ferrous aluminum spinel raw materials in proportion. Since the FeO and A1 2 3 3 contents in the ferrous aluminum spinel are close to the theoretical ratio of FeOAl 2 0 3 , the iron in the pre-synthesized ferrous aluminum spinel is basically in the form of FeOAl 2 0 3
- the present invention can not only maintain the sintering activity of the ferrous aluminum spinel, but also ensure the stability of the valence state of the iron during sintering and use of the material, and also ensure the volume stability and goodness of the magnesium iron aluminum spinel brick of the invention. Hanging kiln skin performance.
- the magnesium iron aluminum spinel brick of the invention can be used in a suitable high temperature field, especially the firing zone of the new dry normal rotary kiln, and solves the problem of Cr 6+ pollution of the magnesia chrome brick for the firing zone.
- magnesia and the pre-synthesized ferrous aluminum spinel are added to the mixer in a chemical composition ratio, and then 2-4% of the binder of the above mixture is added, and the binder is dextrin, pulp waste liquid, starch
- 2-4% of the binder of the above mixture is added, and the binder is dextrin, pulp waste liquid, starch
- One or a combination of any one of methyl cellulose and resin, after being uniformly mixed, is press-formed on a 600-1200 ton press. After drying at 110 ° C and firing in a high temperature kiln at 1400-1700 ° C, a chrome-free magnesia-alumina spinel brick can be obtained.
- the brick can be directly used in the cement rotary kiln firing zone.
- magnesia particles have a maximum of 5 mm; the ferrous aluminum spinel particles have a maximum of 3 mm.
- the chemical weight composition of the product is Fe 2 0 3 2.5-9.6%, A1 2 0 3 2.9-12%, and MgO 76-93%.
- Magnesia includes semi-mixed fused magnesia, sintered magnesia, mid-range magnesia, fused magnesia and sintered magnesia.
- the binder was a mixture of 4% methylcellulose, 3% starch, 2% dextrin and 1% starch, 2% starch and 2% methylcellulose, respectively.
- the ratio of Fe 2 O 3 : Al 2 0 3 in the chemical composition of the ferrous aluminum spinel is close to the theoretical composition of the ferrous aluminum spinel, which are respectively:
- the XD line of the ferrous aluminum spinel shows mainly FeOAl 2 0 3 .
- the scheme of the embodiment and the indicators of the performance of related products can also be seen in Table 2.
- the limit particle of magnesia is 5mm; the limit particle of ferrous aluminum spinel is 3mm, including two parts of particles (3-0.088mm) and fine powder (0.088mm).
- the chemical weight composition of the brick is Fe 2 0 3 2.5-9.6%, A1 2 0 3 2.9-12%, MgO 76-93%.
- magnesia includes fused magnesia, sintered magnesia, mid-range magnesia, fused magnesia, and sintered magnesia.
- the binder was a mixture of 2% methylcellulose, 3% starch, 2% dextrin and 1% starch, 2% starch and 2% methylcellulose, respectively.
- the ratio of Fe 2 O 3 : Al 2 0 3 in the chemical composition of the ferrous aluminum spinel is close to the theoretical composition of the ferrous aluminum spinel, and ? 6 2 0 3 : 1 2 0 3 is 40:60-45:55, and contains 0-20% by mass of MgO measured by Fe 2 0 3 + Al 2 0 3 .
- the XD line of the ferrous aluminum spinel shows mainly FeOAl 2 0 3 .
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Description
镁铁铝尖晶石砖及其制备方法 技术领域
本发明涉及一种镁铁铝尖晶石砖及其制备方法, 属于耐火材料技术领域。 背景技术
因镁铬材料具有良好的高温性能和出色的挂窑皮性能, 所以, 镁铬砖成为 新型干法水泥生产线中的水泥回转窑烧成带用的主要材料。 由于镁铬砖在使用 中, 砖中的部分铬会从 Cr3+转变为剧毒和致癌的 Cr6+, 破坏环境和影响人民的 生活健康。
因此, 无铬化是水泥窑用碱性材料的趋势及发展方向。 近年国内外在寻找 镁铬砖的替代材料方面作了大量工作, 但效果均不理想。 其替代材料主要为白 云石质耐火材料, 白云石质耐火材料尽管抗热震性、耐侵蚀性好,挂窑皮性强, 但十分容易水化。
奥镁公司 (RHI)在研究中发现将预先合成的亚铁铝尖晶石引入到氧化镁 材料中, 能够显著提高碱性砖的挂窑皮性能, 因此, 添加亚铁铝尖晶石的镁砖 也就成为最有希望替代镁铬砖的一种无铬化材料。
铁铝尖品石在自然界中存在极少, 主要依靠人工合成。
目前, 国内外真正进入商业应用的是奥美公司的镁铁铝尖晶石砖。 正如专 利 CN02106242.0所讲,该公司的镁铁铝砖是以合成的亚铁铝尖晶石和镁砂(粒 度小于 4mm) 为原料制备的, 且亚铁铝尖晶石的成分中 Fe203 : A1203比例为 30: 70至 60: 40, 并且含有以 Fe203+Al203计量质量的 20-60 %的 MgO。 由于 该亚铁铝尖晶石中的 MgO含量较高, 烧结活性较低, 整个亚铁铝尖晶石砖的 烧结温度需要相应地提高。
而专利 200810049559.8是以极限粒度 8mm的烧结镁砂为主, 加入预合成
的亚铁铝尖晶石制备的;尖晶石加入量为质量的 3-40 %,其成分为 A1203 45-65 质量%、 FeO 20-55质量%、 MgO 0-15质量%。该专利中, 由于亚铁铝尖晶石中 的铁含量范围宽, 材料中可能含有过剩的 FeO或 A1203, 导致亚铁铝尖晶石砖 在烧成或使用中可能出现较大的体积效应而不利于体积稳定。
发明内容
本发明的目的在于提供一种镁铁铝尖晶石砖及其制备方法。
本发明所述的镁铁铝尖晶石砖, 其化学重量百分组成为: Fe203 2.5〜9.6%、 A1203 2.9〜12%和 MgO 76〜93%。所述镁铁铝尖晶石砖的亚铁铝尖晶石原料的 XRD谱线显示主要晶相为 Fe Al203。
一种镁铁铝尖晶石砖的制备方法是以镁砂和亚铁铝尖晶石为原料, 外加结 合剂, 经压制成型、 干燥后高温烧成而制得, 烧成温度为 1400〜1700°C。
¾φ:
所述亚铁铝尖晶石以 FeOAl203形式引入, 亚铁铝尖晶石的化学重量组成 中 Fe203:Al203比例为 (40〜45) : (55〜60), 并且含有 Fe203+Al203合计质量 0〜20%。
所述亚铁铝尖晶石原料为粒径≤3111111的颗粒料。
所述亚铁铝尖晶石原料为粒径≤0.088111111的粉料。
所述结合剂为糊精、 纸浆废液、 淀粉、 甲基纤维素、 树脂中的一种或任意 几种的组合。
所述的化学成分都是将 FeO换算为 Fe203来计算。
本发明采用我国耐火材料领域比较方便实施的极限粒度为 5mm的镁砂, 同时引入活性较高的预合成亚铁铝尖晶石, 从而制得了高性能的水泥回转窑烧 成带用镁铁铝尖晶石砖。
本发明的镁铁铝尖晶石砖包括镁砂和预先合成的亚铁铝尖晶石。 镁砂可选 电熔镁砂、烧结镁砂以及中档镁砂等, 极限粒度为 5mm; 基质部分包含粒度为 0.088mm和 0.045mm以下两部分。预合成的亚铁铝尖晶石的极限粒度为 3mm。
本发明中, 预合成的亚铁铝尖晶石是关键, 为保持亚铁铝尖晶石原料的高 烧结活性, 制得体积稳定的镁铁铝尖晶石砖, 本发明的亚铁铝尖晶石的成分为
Fe203: A1203比例接近亚铁铝尖晶石的理论组成, 为 (40〜45) : (55〜60), 并且含有 Fe203+Al203合计质量 0〜20%的 MgO。 由于该亚铁尖晶石中的 MgO 含量低, Fe2+向镁砂中扩散的驱动力较强, 因此, 该亚铁尖晶石保持着较高的 烧结活性。
将镁砂、 亚铁铝尖晶石原料按比例混合、 成型、 烧成, 制得了本发明的镁 铁铝尖晶石砖。 由于亚铁铝尖晶石中的 FeO和 A1203含量接近于 FeOAl203的 理论比例, 使得预合成的亚铁铝尖晶石中的铁基本上都是以 FeOAl203的形式 存在, 既能保持亚铁铝尖晶石的烧结活性, 又保证了铁在材料烧结和使用过程 中价态的稳定, 也保障了本发明镁铁铝尖晶石砖的体积稳定性和良好的挂窑皮 性能。
本发明的镁铁铝尖晶石砖可用于适宜的高温领域, 尤其是新型干法线回转 窑的烧成带, 解决了烧成带用镁铬砖的 Cr6+污染问题。
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例
将镁砂和预合成的亚铁铝尖晶石按化学组成的比例加入到混炼机内, 再加 入上述混合物质量的 2-4%的结合剂, 结合剂为糊精、纸浆废液、淀粉、 甲基纤 维素、树脂中的一种或任意几种的组合, 混合均匀后, 在 600-1200吨压力机上 压制成型。经 110°C干燥后再在 1400-1700°C的高温窑内烧成, 可得到无铬型的 镁铁铝尖晶石砖。 该砖可直接用于水泥回转窑烧成带。
实施例及产品性能指标情况见表 1。 其中, 镁砂的颗粒最大 5mm; 亚铁铝 尖晶石的颗粒最大 3mm。 产品的化学重量组成为 Fe203 2.5-9.6%、 A1203 2.9-12%、 MgO 76-93%。
四个实施例中:
镁砂包括电熔镁砂、烧结镁砂、 中档镁砂、 电熔镁砂和烧结镁砂对半混合。 结合剂分别为 4%的甲基纤维素、 3%的淀粉、 2%的糊精和 1%淀粉的混合、 2%的淀粉和 2%的甲基纤维素的混合。
实施例中,亚铁铝尖晶石化学成分中的 Fe203:Al203比例接近亚铁铝尖晶石 的理论组成, 四个实施例中分别为:
40 : 60-45 : 55并且含有以 Fe203+Al203计量的 0-20质量%的 MgO, 分别为 0%、 5%、 10%和 15%。 亚铁铝尖晶石的 X D谱线显示主要为 FeOAl203。 实施例的方案及相关产品性能的指标情况还可见表 2。 其中, 镁砂的极限颗粒 为 5mm;亚铁铝尖晶石的极限颗粒为 3mm,包括颗粒(3-0.088mm)和细粉( 0.088mm) 两部分。 该砖的化学重量组成为 Fe203 2.5-9.6%、 A1203 2.9-12%、
MgO 76-93%。
结合剂分别为 2%的甲基纤维素、 3%的淀粉、 2%的糊精和 1%淀粉的混合、 2%的淀粉和 2%的甲基纤维素的混合。
实施例中,亚铁铝尖晶石化学成分中的 Fe203:Al203比例接近亚铁铝尖晶石 的理论组成, 且?6203: 1203为 40:60-45:55, 并且含有以 Fe203+Al203计量的 0-20质量%的 MgO。 亚铁铝尖晶石的 X D谱线显示主要为 FeOAl203。
Claims
1、 一种镁铁铝尖晶石砖,其特征在于,所述的镁铁铝尖晶石砖化学重量百 分组成为: Fe203 2.5〜9.6%、 A1203 2.9〜12%和 MgO 76〜93%。
2、根据权利要求 1所述的镁铁铝尖晶石砖,其特征在于,所述镁铁铝尖晶 石砖的亚铁铝尖晶石原料的 X D谱线显示主要晶相为 FeOAl203。
3、根据权利要求 1所述的镁铁铝尖晶石砖的制备方法,其特征在于,所述 的镁铁铝尖晶石砖是以镁砂和亚铁铝尖晶石为原料,外加结合剂,经压制成型、 干燥后高温烧成而制得, 烧成温度为 1400〜1700°C。
4、 根据权利要求 3所述的镁铁铝尖晶石砖的制备方法, 其特征在于,所述 亚铁铝尖晶石以 FeOAl203形式引入。
5、根据权利要求 4所述的镁铁铝尖晶石砖的制备方法,其特征在于亚铁铝 尖晶石的化学重量组成中 Fe203:Al203比例为 (40〜45) : (55〜60), 并且含有 Fe203+Al203合计质量 0〜20%的 MgO。
6、根据权利要求 5所述的镁铁铝尖晶石砖的制备方法,其特征在于,所述亚 铁铝尖晶石原料为粒 ≤3mm的颗粒料。
7、根据权利要求 5所述的镁铁铝尖晶石砖的制备方法,其特征在于,所述亚 铁铝尖晶石原料为粒 ≤0.088mm的粉料。 ,
8、 根据权利要求 3或 5所述的镁铁铝尖晶石砖的制备方法, 其特征在于, 所述结合剂为糊精、 纸浆废液、 淀粉、 甲基纤维素、 树脂中的一种或任意几种 的组合。
9根据权利要求 1或 5所述的镁铁铝尖晶石砖,其特征在于所述的化学成分 都是将 FeO换算为 Fe203来计算。
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