CN102391002B - Magnesia-alumina spinel skinning-resistant non-amorphous refractory material for cement kiln as well as preparation method and application thereof - Google Patents
Magnesia-alumina spinel skinning-resistant non-amorphous refractory material for cement kiln as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a magnesia-alumina spinel skinning-resistant non-amorphous refractory material for a cement kiln as well as a preparation method and application thereof. The refractory material comprises the following raw materials: 74-88 parts by weight of magnesia-alumina spinel which has the grain size below 5mm and is in rough-grade fit, 9-17 parts by weight of cordierite which has the grain size below 3mm and is in fine fit, 1-2 parts by weight of siliceous dust, 1-2 parts by weight of silica sol, 0-6 parts by weight of silicon nitride powder, 2-6 parts by weight of organic binder, and 0.05-0.15 parts by weight of high-efficiency water reducing agent. The refractory material is a duplex structure with the magnesia-alumina spinel as a main crystalline phase and the cordierite as a paracrystalline phase, so that the refractory material has a certain high-temperature resistance and excellent skinning-resistant and thermal-shock resistances, can be matched with a magnesia-alumina spinel skinning-resistant amorphous refractory material to serve as skinning-resistant non-amorphous refractory materials for a novel cement dry-process rotary kiln and a cement pre-sintering production process, and has a wide application prospect.
Description
Technical field
The invention belongs to the cement kiln refractory in building material field, particularly relate to a kind of have certain high temperature resistant and excellent resistive connection skin, thermal shock resistance, can be used as magnesium-aluminium spinel resistive connection skin amorphous refractory of the short flow process pre-fired of cement dry method rotary kiln and energy-saving cement kiln and preparation method thereof and application.
Background technology
Along with the progress of cement industry, new type nonaqueous cement rotary kiln is at home and abroad used widely.Each manufacture of cement producer, according to the national policy of legislations of environmental protection and energy-saving and emission-reduction, is more and more used the solid waste such as building waste, domestic refuse, sewage sludge, industrial residue as raw material and the fuel of producing cement clinker.Thereby various impurity in cement rotary kiln, as the content of heavy metal ion, sulphur, chlorine, alkali rolls up, through the circulation enrichment of preheater, decomposing furnace, clinkering zone in cement rotary kiln, very easily form skinning and stop up at kiln tail system, affect the normal operation of cement rotary kiln.
In order to improve cement output, reduce the net effect that burns till hear rate and grinding pow consumption, raising clinker quality, China Building Material Scientific Research General Institute has been invented a kind of cement presintering production method and system (publication number: CN101139175) thereof in August, 2007.Solve skinning problem particularly important to promoting this Technology, because when kiln tail system temperature is during up to 900-1200 ℃, the skinning of cement slurry, blockage problem become more serious.A kind of solution is to purge by air bubble, and another solution is to use resistive connection skin refractory materials, makes it not react with sulphur chlor-alkali and cement slurry component.Therefore, to there is certain resistance to elevated temperatures and excellent resistive connection skin, thermal shock resistance with the composite refractory material of this complete sets of Techniques.
At present, the temperature of new type nonaqueous cement rotary kiln tail system is 800-1000 ℃, and the resistive connection skin refractory materials of use has the refractory materials such as High-Alumina, silicon carbide.Because material in rotary system is alkaline environment, select the refractory materials of basic refractory or neutral meta-alkalescence.SiC based refractories belongs to amphoteric refractory, and thermal shock resistance is fine, but in cement presintering production technique, in the time rising to 1200 ℃ when kiln end temperature, its resistance of oxidation declines greatly, the SiO of material surface
2film starts the reaction with CaO and occurs liquid phase binding material, and anti-scaling property lost efficacy.Therefore, raise with kiln end temperature, High-Alumina, SiC based refractories will be substituted by other non-chromium alkaline refractory materials.
Magnesia-alumina spinel refractory has excellent resistive connection skin, resistance to elevated temperatures, and the erosion of low basicity kiln material in can resisting well, and its shortcoming is that thermal shock resistance is poor.Ruitai Technology Co., Ltd and China Building Material Scientific Research General Institute have been invented antiskinning castable for magnesium aluminate spinel for cement kiln (publication number: CN101412630) in October, 2008, anti-skinning pouring material for cement kiln (publication number: CN 101987793A) has been invented in October, 2010 by Anhui Ruitai New Material Technology Co., Ltd, has effectively supported the development of cement presintering production technique.But 1200 ℃ of high temperature anti-scaling properties of these two kinds of crusting resistant pouring materials are bad, reason is that these two kinds of crusting resistant pouring materials all need to use silicon ash and pure calcium aluminate cement as bonding agent.The CaO that cement is brought into, the SiO that silicon ash is brought into
2the alkali of enrichment of circulating more than 1200 ℃ and in kiln material reacts and forms eutectic mixture and produce liquid phase, and binding material has had a strong impact on the anti-scaling property of material.
Summary of the invention
The object of this invention is to provide a kind of cement kiln magnesium-aluminium spinel resistive connection skin amorphous refractory.
For solving the problems of the technologies described above, the present invention takes following technical scheme:
Magnesium-aluminium spinel resistive connection skin amorphous refractory for a kind of cement kiln, the magnesium-aluminium spinel 74-88 weight part that its raw material packet coordinates in the following level Four of 5mm containing particle diameter, the trichroite 9-17 weight part that particle diameter coordinates in the following two-stage of 3mm, silicon ash 1-2 weight part, silicon sol 1-2 weight part, silicon nitride powder 0-6 weight part, organic bond 2-6 weight part, high efficiency water reducing agent 0.05-0.15 weight part.
Magnesium-aluminium spinel resistive connection skin amorphous refractory for this cement kiln, the component that its composition of raw materials comprises following ratio of weight and number:
The component that its composition of raw materials comprises following ratio of weight and number: 1-5mm magnesium-aluminium spinel 46-56 part, 0.088-1mm magnesium-aluminium spinel 10-14 part, 0.02-0.088mm magnesium-aluminium spinel 6-15 part, is less than 0.02mm magnesium-aluminium spinel ultrafine powder 9-12 part; 0.088-3mm (refer to be more than or equal to 0.088mm and be less than 3mm) trichroite 0-14 part, is less than 0.088mm trichroite 0-9 part; Silicon ash 1-2 part, silicon sol 1-2 part, silicon nitride powder 0-6 part, organic bond 2-6 part, high efficiency water reducing agent 0.05-0.15 part.
In above-mentioned formula, described magnesium-aluminium spinel is commercially available fireproof magnesia alumina spinel materials; Described magnesium-aluminium spinel ultrafine powder is 0.02mm sieve 95% the magnesium-aluminium spinel ultrafine powder down that commercially available magnesium aluminate spinel refractory raw material obtains after processing.Described trichroite is commercially available cordierite refractory material; Described silicon ash is commercially available silicon ash products; Described silicon sol is commercially available silicon sol product; Described silicon nitride powder is commercially available silicon nitride powder; Described organic bond can be selected from the combination of any one or two kinds of commercial polyethylene alcoholic solution, polyacrylate emulsion product; Described high efficiency water reducing agent can be selected from any one or a few the combination in sulfonate series concrete high-efficiency water reducing agent, polycarboxylic acid series high efficiency water reducing agent, tripoly phosphate sodium STPP high efficiency water reducing agent, Sodium hexametaphosphate 99 high efficiency water reducing agent and the sodium polyacrylate high efficiency water reducing agent of sulfonate series concrete high-efficiency water reducing agent, condensation trimeric cyanamide of commercially available condensation naphthaldehyde.
The preparation method of magnesium-aluminium spinel resistive connection skin amorphous refractory for cement kiln provided by the present invention, can comprise the following steps:
1) take raw material by above-mentioned formula;
2) raw material is mixed, makes base substrate through batching, mixing, ageing mixture, shaping, dry after again after 500-1200 ℃ of thermal treatment, obtain cement kiln magnesium-aluminium spinel resistive connection skin amorphous refractory.
Innovative point of the present invention is:
1) this refractory materials employing magnesium-aluminium spinel is paracrystalline phase as principal crystalline phase, trichroite, under normal temperature using silicon sol as bonding agent, by the coalescent intensity that produces between silicon sol and fire resisting material particle, in the situation of insufficient strength, add organic bond and carry out bonded particulate and produce intensity, avoid using pure calcium aluminate cement and bring eutectic material CaO into;
2) the lower magnesium-aluminium spinel ultrafine powder (MgOAl of temperature (700-1000 ℃) in
2o
3) start with silicon ash, silicon sol in SiO
2reaction generates trichroite (2MgO2Al
2o
35SiO
2) produce Ceramic bond, medium temperature intensity is provided;
3) the lower MgOAl of high temperature (1000-1300 ℃)
2o
3with SiO
2reaction rate accelerates, generate more trichroite (2MgO2Al
2o
35SiO
2), form take magnesium-aluminium spinel as principal crystalline phase, trichroite is the heterogeneous structure of paracrystalline phase.Wherein, the chemical stability of magnesium-aluminium spinel is fine, with cement kiln material and sulphur chlor-alkali, chemical reaction does not occur, and makes developed material have excellent resistive connection skin; Trichroite has very low thermal expansivity, makes developed material have excellent heat-shock resistance;
4) by further adding little trichroite and the good silicon nitride of thermal conductivity of thermal expansivity, reduce better thermal stresses, improve the heat-shock resistance of material.
Below in conjunction with specific embodiment, the present invention is described in further details.
Embodiment
For overcoming the shortcoming of existing cement kiln refractory, solve cement kiln refractory non-refractory (1000-1300 ℃), easy skinning, the poor difficult problem of thermal shock resistance in the market, the invention provides a kind of have certain high thermal resistance, excellent resistive connection skin, the cement kiln magnesium-aluminium spinel resistive connection skin amorphous refractory of heat-shock resistance.
Magnesium-aluminium spinel resistive connection skin amorphous refractory for cement kiln provided by the present invention, for the regular position of kiln end system of cement kiln, by each raw material, through batching, mixing, ageing mixture, become setting product after being shaped, firing, product specification is according to the size design of kiln.The magnesium-aluminium spinel 74-88 weight part that its raw material packet coordinates in the following level Four of 5mm containing particle diameter, the trichroite 9-17 weight part that particle diameter coordinates in the following two-stage of 3mm, silicon ash 1-2 weight part, silicon sol 1-2 part, silicon nitride powder 0-6 weight part, organic bond 2-6 weight part, high efficiency water reducing agent 0.05-0.15 weight part.
Concrete, the component that its composition of raw materials comprises following ratio of weight and number:
1-5mm (refer to be more than or equal to 1mm and be less than 5mm) magnesium-aluminium spinel 46-56 part, 0.088-1mm (refer to be more than or equal to 0.088mm and be less than 1mm) magnesium-aluminium spinel 10-14 part, 0.02-0.088mm (refer to be more than or equal to 0.01mm and be less than 0.088mm) magnesium-aluminium spinel 6-15 part, is less than 0.02mm magnesium-aluminium spinel ultrafine powder 9-12 part; 0.088-3mm (refer to be more than or equal to 0.088mm and be less than 3mm) trichroite 0-14 part, is less than 0.088mm trichroite 0-9 part; Silicon ash 1-2 part, silicon sol 1-2 part, silicon nitride powder 0-6 part, organic bond 2-6 part, high efficiency water reducing agent 0.05-0.15 part.Wherein, when trichroite is different with silicon nitride, be 0.
In the statement of size scope of the present invention, lower value contains, and higher limit does not contain.In literary composition, the similar statement implication of rest part is identical.
Or, the component that its composition of raw materials comprises following ratio of weight and number:
1-5mm magnesium-aluminium spinel 49-56 part, 0.088-1mm magnesium-aluminium spinel 12-14 part, 0.02-0.088mm magnesium-aluminium spinel 9-15 part, be less than 0.02mm magnesium-aluminium spinel ultrafine powder 9-12 part, 0.088-3mm trichroite 0-9 part, is less than 0.088mm trichroite 0-9 part, silicon ash 1-2 part, silicon sol 1-2 part, organic bond 4-6 part, 0.15 part of high efficiency water reducing agent.Wherein, when the trichroite of two grades is different, be 0.
In the present invention, described magnesium-aluminium spinel is commercially available fireproof magnesia alumina spinel materials.Adopt the magnesium-aluminium spinel of different-grain diameter to be used in conjunction with, make to make closestpacking between material granule, improve the alkali resistant aggressiveness of material.
Described magnesium-aluminium spinel ultrafine powder is 0.02mm sieve 95% the magnesium-aluminium spinel ultrafine powder down that commercially available magnesium aluminate spinel refractory raw material obtains after processing.Adopt magnesium-aluminium spinel ultrafine powder under middle temperature with silicon ash, silicon sol in SiO
2reaction generates trichroite (zeopan 2MgO2Al
2o
35SiO
2), produce Ceramic bond, improve the medium temperature intensity of material.
Described trichroite is commercially available cordierite refractory material (natural or artificial).Adopt the trichroite of different-grain diameter, adopt the trichroite of different-grain diameter, better reduce thermal stresses, improve the heat-shock resistance of material.
Described silicon ash is commercially available silicon ash products.At high temperature react with magnesium-aluminium spinel and generate trichroite, produce Ceramic bond, the hot strength of material is provided.
Described silicon sol is commercially available silicon sol product.Silicon sol is a kind of air-setting bonding agent, coalescent and produce intensity at normal temperatures and between fire resisting material particle, finally becomes gel; SiO under middle temperature in silicon sol
2react with magnesium-aluminium spinel ultrafine powder and generate trichroite, produce Ceramic bond, the hot strength of material is provided.
Described silicon nitride powder is commercially available silicon nitride powder.Because the thermal conductivity of silicon nitride is good, can improve the heat-shock resistance of material, be at high temperature oxidized in addition silicon-dioxide, react with magnesium-aluminium spinel and generate trichroite generation Ceramic bond, the hot strength of material is provided.
Described organic bond can be selected from the combination of any one or two kinds of commercial polyethylene alcoholic solution, polyacrylate emulsion product.Its effect is to add the insufficient strength in conjunction with particle at silicon sol, improves the normal temperature strength of material.
Described high efficiency water reducing agent can be selected from any one or a few the combination in sulfonate series concrete high-efficiency water reducing agent (WRA-1), polycarboxylic acid series high efficiency water reducing agent (WRA-2), tripoly phosphate sodium STPP high efficiency water reducing agent, Sodium hexametaphosphate 99 high efficiency water reducing agent and the sodium polyacrylate high efficiency water reducing agent (WRA-3) of sulfonate series concrete high-efficiency water reducing agent, condensation trimeric cyanamide of commercially available condensation naphthaldehyde.Its effect is better dispersing ultrafine powder, micro mist, improves the normal temperature strength of material, reduces the apparent porosity of material.
Embodiment implements under take technical solution of the present invention as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
In following embodiment, method therefor is ordinary method if no special instructions.
Preparation and the detection of magnesium-aluminium spinel resistive connection skin amorphous refractory of embodiment 1-3, cement kiln
One, the preparation of magnesium-aluminium spinel resistive connection skin amorphous refractory for cement kiln
Embodiment of the present invention 1-3 cement kiln is as shown in table 1 with the formula of magnesium-aluminium spinel resistive connection skin amorphous refractory:
The formula of magnesium-aluminium spinel resistive connection skin amorphous refractory for table 1 embodiment 1-3 cement kiln (unit: kilogram)
The preparation method of magnesium-aluminium spinel resistive connection skin amorphous refractory for the cement kiln of embodiment 1-3, comprises the following steps:
1) take raw material by formula shown in table 1;
2) feed proportioning, mixing, ageing mixture, shaping are made to base substrate, dry after again after 500-1200 ℃ of thermal treatment, obtain cement kiln magnesium-aluminium spinel resistive connection skin amorphous refractory.
Two, the Performance Detection of magnesium-aluminium spinel resistive connection skin amorphous refractory for cement kiln
The folding strength (according to refractory materials strength at normal temperature test method (GB/T3001-2007)) of cement kiln magnesium-aluminium spinel resistive connection skin amorphous refractory prepared by detection embodiment 1-3, compressive strength (according to refractory materials cold crushing strength test method (GB/T5072-2008)), with containing the cement slurry of alkali resistive connection skin at high temperature (according to the splitting tensile test proposing in " measuring the research of cement tensile strength with split the law ", between test block of the same race and skinning material resistive connection skin represent with tensile splitting strength, the low explanation resistive connection of intensity level skin is good, vice versa), burning line changes (changing test method (GB/T5988-2007) according to refractory materials heating permanent line) and the remaining folding strength conservation rate (the thermal shock fatigue test proposing according to " research that the fatigue behaviour of refractory materials anti-thermal shock is evaluated ") after thermal shock fatigue test 10 times is air-cooled, make with amorphous refractory and contrast (the high-strength Alkali resistant castable refractory of 13NL with the test specimen of equal-specification with unshape refractory with commercially available cement kiln simultaneously, 50S crusting resistant pouring material).
Detected result is as shown in table 2, detected result show product of the present invention contrast and there is good manufacturing property (raw material through batching, mixing, ageing mixture postforming is functional, is convenient to the demoulding, not losing fangle.After maintenance 24h, 110 ℃ of folding strengths reach 8MPa, and 110 ℃ of compressive strengths arrive 40MPa, are convenient to transportation and fire.) and excellent high temperature resistant, anti-scaling property (1100 ℃ of compressive strengths more than 100MPa, burning line changes and is less than 0.3%, illustrates that high-temperature physical property is good; But the tensile splitting strength of 1200 ℃ of skinning test blocks of 13NL and 50S is higher, be the more than 4 times of this product average, illustrate that the anti-scaling property of contrast is not as the anti-scaling property of this product.), by adding the mineral such as trichroite, silicon nitride, greatly improve the thermal shock resistance of magnesia-aluminum spinel composite fire-resistant material goods (in 1100 ℃ of thermal shock fatigue tests, 10 air-cooled remaining folding strength conservation rate averages of this material reach 85%, exceed 13NL nearly 30%, a little less than 50S).Consider property indices, illustrate that product of the present invention is better than contrast.
The performance test results of magnesium-aluminium spinel resistive connection skin unshape refractory for table 2 embodiment 1-3 cement kiln
Comprehensive, refractory materials of the present invention be take magnesium-aluminium spinel as principal crystalline phase, trichroite is paracrystalline phase, using the combination of silicon sol and polyvinyl alcohol solution, polyacrylate emulsion any one or two kinds as bonding agent, by the coalescent intensity that produces between silicon sol and fire resisting material particle, in the situation of insufficient strength, add organic bond and carry out bonded particulate generation intensity at normal temperatures; The lower magnesium-aluminium spinel ultrafine powder (MgOAl of middle temperature (700-1000 ℃)
2o
3) start with silicon ash, silicon sol in SiO
2reaction generates trichroite (2MgO2Al
2o
35SiO
2) generation Ceramic bond; The lower MgOAl of high temperature (1000-1300 ℃)
2o
3with SiO
2reaction rate accelerates, generate more trichroite (2MgO2Al
2o
35SiO
2), form take magnesium-aluminium spinel as principal crystalline phase, trichroite is the heterogeneous structure of paracrystalline phase.Thereby make this kind of refractory materials there is certain high temperature resistant and excellent resistive connection skin, thermal shock resistance, can support the use the resistive connection skin amorphous refractory as novel concrete dry-process rotory kiln and cement presintering production technique with magnesium-aluminium spinel resistive connection skin unshape refractory.
Claims (7)
1. magnesium-aluminium spinel resistive connection skin amorphous refractory for cement kiln, is characterized in that: its raw material is made up of the component of following ratio of weight and number:
1-5mm magnesium-aluminium spinel 49-56 part,
0.088-1mm magnesium-aluminium spinel 12-14 part,
0.02-0.088mm magnesium-aluminium spinel 9-15 part,
Be less than 0.02mm magnesium-aluminium spinel ultrafine powder 9-12 part,
0.088-3mm trichroite 0-9 part,
Be less than 0.088mm trichroite 0-9 part,
Silicon ash 1-2 part,
Silicon sol 1-2 part,
Organic bond 4-6 part,
0.15 part of high efficiency water reducing agent;
Wherein, when the trichroite of two grades is different, be 0.
2. magnesium-aluminium spinel resistive connection skin amorphous refractory for cement kiln according to claim 1, is characterized in that: its raw material is made up of the component of following ratio of weight and number:
56 parts of 1-5mm magnesium-aluminium spinels,
14 parts of 0.088-1mm magnesium-aluminium spinels,
9 parts of 0.02-0.088mm magnesium-aluminium spinels,
Be less than 9 parts of 0.02mm magnesium-aluminium spinel ultrafine powders,
Be less than 9 parts of 0.088mm trichroites,
2 parts of silicon ashes,
1 part of silicon sol,
6 parts of organic bonds,
0.15 part of high efficiency water reducing agent.
3. magnesium-aluminium spinel resistive connection skin amorphous refractory for cement kiln according to claim 1, is characterized in that: its raw material is made up of the component of following ratio of weight and number:
49 parts of 1-5mm magnesium-aluminium spinels,
12 parts of 0.088-1mm magnesium-aluminium spinels,
15 parts of 0.02-0.088mm magnesium-aluminium spinels,
Be less than 12 parts of 0.02mm magnesium-aluminium spinel ultrafine powders,
9 parts of 0.088-3mm trichroites,
1 part of silicon ash,
2 parts of silicon sol,
4 parts of organic bonds,
0.15 part of high efficiency water reducing agent.
4. according to magnesium-aluminium spinel resistive connection skin amorphous refractory for the arbitrary described cement kiln of claims 1 to 3, it is characterized in that: described magnesium-aluminium spinel is commercially available fireproof magnesia alumina spinel materials;
Described magnesium-aluminium spinel ultrafine powder is 0.02mm sieve 95% the magnesium-aluminium spinel ultrafine powder down that commercially available magnesium aluminate spinel refractory raw material obtains after processing;
Described trichroite is commercially available cordierite refractory material;
Described silicon ash is commercially available silicon ash products;
Described silicon sol is commercially available silicon sol product;
Described organic bond is selected from the combination of any one or two kinds of commercial polyethylene alcoholic solution, polyacrylate emulsion product;
Described high efficiency water reducing agent is selected from any one or a few the combination in sulfonate series concrete high-efficiency water reducing agent, polycarboxylic acid series high efficiency water reducing agent, tripoly phosphate sodium STPP high efficiency water reducing agent, Sodium hexametaphosphate 99 high efficiency water reducing agent and the sodium polyacrylate high efficiency water reducing agent of sulfonate series concrete high-efficiency water reducing agent, condensation trimeric cyanamide of commercially available condensation naphthaldehyde.
5. according to magnesium-aluminium spinel resistive connection skin amorphous refractory for the cement kiln described in claim 1 or 2 or 3, it is characterized in that: described cement kiln magnesium-aluminium spinel resistive connection skin amorphous refractory is setting product, and its specification is according to the size design at the each position of kiln tail system in cement presintering production technique and cement dry method rotary kiln.
6. magnesium-aluminium spinel resistive connection skin amorphous refractory for cement kiln, is characterized in that: its raw material is made up of the component of following ratio of weight and number:
46 parts of 1-5mm magnesium-aluminium spinels,
10 parts of 0.088-1mm magnesium-aluminium spinels,
6 parts of 0.02-0.088mm magnesium-aluminium spinels,
Be less than 12 parts of 0.02mm magnesium-aluminium spinel ultrafine powders,
14 parts of 0.088-3mm trichroites,
Be less than 3 parts of 0.088mm trichroites,
1 part of silicon ash,
2 parts of silicon sol,
6 parts of silicon nitride powders,
2 parts of organic bonds,
0.05 part of high efficiency water reducing agent.
7. a method of preparing the arbitrary described cement kiln of claim 1 to 6 magnesium-aluminium spinel resistive connection skin amorphous refractory, comprises the following steps:
1) take raw material by formula;
2) feed proportioning, mixing, ageing mixture, shaping are made to base substrate, dry after again after 500-1200 ℃ of thermal treatment, obtain cement kiln magnesium-aluminium spinel resistive connection skin amorphous refractory.
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