CN101624267A - Low-temperature ceramic curing agent of red mud from Bayer process - Google Patents
Low-temperature ceramic curing agent of red mud from Bayer process Download PDFInfo
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Abstract
The invention relates to a low-temperature ceramic curing agent of red mud from a Bayer process. The low-temperature ceramic curing agent is prepared by the following raw materials by weight parts: 100 aluminosilicate residues, 20-150 industrial by-product gypsum, 50-200 excited materials, 0-3.0 water-reducing agent, 0-5.0 flocculating agent and 0-5.0 retarder. The production method thereof comprises the following steps: (1) processing main raw materials; (2) preparing additives; and (3) preparing a curing agent. The invention has the beneficial effects that (1) all components of the curing agent can irreversibly react with the red mud; compared with the prior gelled material, the invention does not use cement, base excited materials and expensive high molecular polymers, thereby achieving low cost; (2) the invention uses the industrial residues as the raw materials to cure the red mud so as to achieve the aim of treating a waste with another waste; no secondary waste is exhausted in a production process and an application process so as to benefit environmental protection; and (3) the invention can thoroughly solve the safety problem of a red mud library after curing the red mud.
Description
Technical field
The present invention relates to a kind of low-temp ceramics solidifying agent of Bayer process red mud, belong to material of construction and technical field of alumina production.
Background technology
Red mud is the solid slag that discharges in the aluminum oxide production process, according to the difference of alumina-producing method, is divided into sintering process, Bayer process and mixed combining method red mud.According to measuring and calculating, 1 ton of aluminum oxide of every production produces red mud 1.0-1.5 ton approximately, the also alkali waste of subsidiary 3~4m3 of red mud of giving money as a gift per ton.Along with the reduction of aluminium industrial expansion and aluminum ore grade, the red mud quantity discharged is with increasing, and safety is stored up the great restraining factors that become Sustainable Development of Enterprises.Sintering process and mixed combining method red mud are because of containing the beta-dicalcium silicate similar to cement, in the process of storing up, can produce gel strength by the aquation of himself, realize red mud solidified, therefore, existing most of aluminum oxide enterprise all adopts red mud from sintering process to build a dam, and stores up to be difficult to the solidified Bayer process red mud in the dam.But, sintering process is produced aluminum oxide energy consumption height, under the severe day by day background of energy situation, with atrophy gradually, Bayer process and Liquor of Ore Dressing Bayer process are produced aluminum oxide and are then had flourish trend, but it is different with red mud from sintering process, Bayer process red mud does not contain the gel mineral, self can not solidify with the prolongation of the time of storing up, even the Bayer process red mud of mummification also can liquefy under the rainwater effect in the process of storing up, therefore, simple Bayer process red mud is stored up and is built a dam and has avalanche and stride the dam risk.
Be to solve the technical barrier that Bayer process red mud is stored up, patent 200710077627.7,200520084837.5,200810226872.4,200710010404.9,200610048091.1,200510200170.5,200510200169.2,200310117213.4,200510045082.2 and 200610200463.8 from dam structure, store up aspects such as mode, reinforcing structure, drainage pattern and study.These technology mainly are to adopt physical method to carry out the red mud dam strengthening, do not change the chemistry and the mineralogical character of Bayer process red mud self.
Patent application 200610109277.3 discloses a kind of stacked arrangement of bauxite, it is characterized in that: in the bauxite slurries admixture be equivalent to the base-material (one or more of flyash, coal gangue, red mud, silicon ash, volcanic ash, float stone, blast furnace slag) and 0%~15% gelling exciting agent (cement, lime, gypsum, water glass) of dried mine tailing weight part 10%~70%, its essence is that relying on the gelling exciting agent that the chemi-excitation of base-material is produced the gelling mineral realizes curing to mine tailing.Patent 98113594.3 discloses a kind of production method of soil-solidified-agent, it is characterized in that with slag or slag composition be body material, is equipped with an amount of alkali-activator and the tensio-active agent combined grinding is made to Blain specific surface 400-900m2/kg.The slag composition is that one or more of slag and ferrochrome slag, phosphorus slag, silicon manganese slag, flyash and other industrial residue are compound, alkali-activator is that a kind of among Na2CO3, NaOH, Na2SO4, KA1 (SO4) 2.6H2O, K2NO2, NaF, the K2CO3 or several be who knows with cement and mixed, and tensio-active agent is trolamine, cellulose lye, sodium-acetate, sulfonated lignin etc.Curable sandstone of this solidifying agent and earth (comprise and contain mud stone fragment, sandy soil, silt, clay, mud, municipal wastes, flyash, industrial tailings etc.) are to make material of construction.
Industrial residue prepares that the low-temp ceramics matrix material is existing to be reported: as Chinese patent literature disclosed 200610010688.7,200510010946.7,200710137584.7,03135919.1,200810058211.5 etc.Above-mentioned low-temp ceramics matrix material is characterised in that: the matrix phase composite of matrix material is the industrial residue of low temperature calcination and physics grinding, activator (alkali, water glass, lime are main body), tensio-active agent, polymer emulsion, and the wild phase of matrix material or disperse phase are respectively plant residuum, plastic waste, undisturbed industry waste residue, macromolecular material and pore.Do not relate to undressed Bayer process red mud.
Comprehensive existing document is not difficult to find out, does not see bibliographical information as yet at Bayer process red mud solidified low-temp ceramics solidifying agent production method specially.
Summary of the invention
The low-temp ceramics solidifying agent that the purpose of this invention is to provide a kind of Bayer process red mud is to solve the problem that Bayer process red mud is stored up and built a dam and have avalanche and stride the dam risk.
The objective of the invention is to be achieved through the following technical solutions:
The low-temp ceramics solidifying agent of a kind of Bayer process red mud of the present invention is mixed with by following materials based on weight: 100 parts in aluminosilicate waste residue, industry by-product gypsum 20-150 part, excitation material 50-200 part, water reducer 0-3.0 part, flocculation agent 0-5.0 part, retardant 0-5.0 part.
Described aluminosilicate waste residue comprises one or more in Metal smelting slag, yellow phosphorus slag, flyash, calcining mine tailing, calcining red mud and the calcining coal gangue; Described industry by-product gypsum comprises one or more in desulfurized gesso of flue gas, phosphogypsum, titanium gypsum, fluorgypsum, citric acid gypsum, wet method manganese slag and the plumbous cadmia; Described excitation material comprises one or more in lime, carbide slag and the cement flue Dust;
Described water reducer comprises one or more of calcium lignin sulphonate, sodium lignosulfonate, naphthalenesulfonate, Sodium salts humic acids, poly carboxylic acid; Flocculation agent comprises one or more of polyacrylamide, polyaluminium sulfate, polymkeric substance ferric sulfate, iron trichloride; Retardant comprises one or more of borax, sodium phosphate, Sodium Fluoride, nitrocalcite.
The production method of the low-temp ceramics solidifying agent of above-mentioned Bayer process red mud may further comprise the steps:
1) main raw material is handled: aluminosilicate waste residue, industry by-product gypsum, excitation material are mixed homogenize, ageing 2-5 hour by the said ratio metering.
Compound is dried to water ratio less than 1%.
The exsiccant compound is carried out grinding, and powder fineness is that 0.08mm tails over less than 10%.
2) additive preparation: water reducer, flocculation agent and retardant are mixed by the proportioning metering, be broken into the powder that particle is not more than 1mm.
3) solidifying agent preparation: the weight by proportioning is measured main raw material and additive respectively, add Forced Mixing 2-5min in the powder mixing machine, become product.
Beneficial effect of the present invention is: 1) the present invention is a kind of specially at Bayer process red mud solidified and special gelatin gel material that build a dam, during application, only need directly the Bayer process red mud slurry directly to be mixed with solidifying agent to realize storing up of Bayer process red mud, in the process of storing up, each component of solidifying agent will with red mud generation irreversible reaction, the final gel mineral that form based on hydrated aluminium silicates, this gel mineral are the non-crystal structure of class zeolite mostly, some performance with pyroceramic, but because of there not being high temperature sintering, and under normal temperature condition, finish, so be referred to as low-temp ceramics.Compare with traditional gelling material, the present invention is without cement and alkali excitation material and expensive high molecular polymer, so cost is low; 2) main raw material of the present invention is an industrial residue, solidifies red mud with it, has reached the purpose of the treatment of wastes with processes of wastes against one another, does not have the secondary waste discharge in production and application process, therefore helps environment protection; 3) after red mud is solidified in the present invention, can thoroughly solve the safety problem in red mud storehouse.
Description of drawings
Come the present invention is further elaborated below in conjunction with accompanying drawing.
Fig. 1 is the process flow sheet of the low-temp ceramics solidifying agent production method of a kind of Bayer process red mud of the present invention.
Specific embodiment
A kind of low-temp ceramics solidifying agent of Bayer process red mud is mixed with by following materials based on weight:
Aluminosilicate waste residue: 20 parts of yellow phosphorus slags, 50 parts in flyash, 30 parts of blast furnace slags;
Industry by-product gypsum: 20 parts of phosphogypsums, 130 parts of desulfurated plasters;
Excitation material: 50 parts in lime, 100 parts of carbide slags, 50 parts of kiln ashes;
Water reducer: 2.0 parts of wooden calcium sulfonates, 0.4 part of naphthalenesulfonate, 0.1 part of poly carboxylic acid;
Flocculation agent: 3.0 parts of polyaluminium sulfates, iron(ic) chloride 1.5,0.5 part of polyacrylamide;
Retardant: 1.0 parts of boraxs, 0.5 part of sodium phosphate, 0.5 part of Sodium Fluoride, 3 parts in nitrocalcite.
The production method of the low-temp ceramics solidifying agent of the described Bayer process red mud of the embodiment of the invention may further comprise the steps:
1) main raw material is handled: by said ratio aluminosilicate waste residue, industry by-product gypsum, excitation material are mixed, and ageing 2 hours, dry again, the test water ratio is 0.6%, and putting into ball mill grinding to powder fineness is 0.08mm, and tailing over is 8.0%;
2) additive preparation: by said ratio water reducer, flocculation agent and retardant are mixed, fragmentation, test 1mm tails over less than 2%;
3) after solidifying agent preparation: the main raw material and the step 2 of step 1) processing) additive of preparation mixes 5min in high-speed mixer, become product.
According to GB/T17671-1999 Test method for strength of hydraulic cement mortar (ISO method) test 3 days, performance: ultimate compression strength 13.2MPa, folding strength 3.6MPa; 28 days performance: ultimate compression strength 36.8MPa, folding strength 6.3MPa; Presetting period: 55min, final setting time 1h42min.Adopt this solidifying agent 13%, the Bayer process red mud 87% of giving money as a gift is modulated into the slurry of water ratio 58% after the mixing, and 28 days ultimate compression strength is 2.3MPa, and the cured body coefficient of softening is 0.79.
Embodiment 2:
A kind of low-temp ceramics solidifying agent of Bayer process red mud is mixed with by following materials based on weight:
Aluminosilicate waste residue: 20 parts of calcining mine tailings, 50 parts of calcining coal gangues, 30 parts of calcining red muds;
Industry by-product gypsum: 10 parts of fluorgypsums, 10 parts of citric acid gypsums;
Excitation material: 30 parts in lime, 10 parts of carbide slags, 10 parts of kiln ashes;
The production method of the low-temp ceramics solidifying agent of the described a kind of Bayer process red mud of the embodiment of the invention may further comprise the steps:
By said ratio aluminosilicate waste residue, industry by-product gypsum, excitation material are mixed, ageing 5 hours, dry again, the test water ratio is 0.4%, puts into the ball mill grinding, and the test powder fineness is 0.08mm, and tailing over is 3.0%, directly becomes product.
Test according to GB/T17671-1999 Test method for strength of hydraulic cement mortar (ISO method): 3 days performance: ultimate compression strength 6.2MPa, folding strength 1.6MPa; 28 days performance: ultimate compression strength 22.8MPa, folding strength 3.5MPa; Presetting period: 80min, final setting time 2h36min.Adopt this solidifying agent 15%, the Bayer process red mud 85% of giving money as a gift is modulated into the lotion of water ratio 45% after the mixing, and 28 days ultimate compression strength is 1.6MPa, and the cured body coefficient of softening is 0.72.
Embodiment 3:
A kind of low-temp ceramics solidifying agent of Bayer process red mud is mixed with by following materials based on weight:
Aluminosilicate waste residue: 50 parts of blast furnace slags, 40 parts in slag, 10 parts of hot method manganese slags;
Industry by-product gypsum: 10 parts of wet method manganese slags, 10 parts of plumbous cadmias, 100 parts of desulfurated plasters;
Excitation material: 50 parts in lime, 80 parts of carbide slags, 20 parts of kiln ashes;
Water reducer: 0.2 part of sodium lignosulfonate, 0.8 part of Sodium salts humic acids, 1.0 parts of poly carboxylic acid;
Flocculation agent: 1.3 parts of polyaluminium sulfates, 1.2 parts in polymkeric substance ferric sulfate;
Retardant: 0.5 part of Sodium Fluoride, 2.0 parts in nitrocalcite;
The production method of the low-temp ceramics solidifying agent of the described a kind of Bayer process red mud of the embodiment of the invention may further comprise the steps:
1) main raw material is handled: by said ratio aluminosilicate waste residue, industry by-product gypsum, excitation material are mixed, and ageing 3.5 hours, dry again, the test water ratio is 0.2%, puts into the ball mill grinding, to powder fineness 0.08mm, tailing over is 2.0%;
2) additive preparation: by said ratio water reducer, flocculation agent and retardant are mixed, fragmentation to powder fineness, tails over less than 1.2%;
3) solidifying agent preparation: the main raw material and the step 2 of step 1) processing) additive of preparation mixes 3min in high-speed mixer, becomes product.
According to GB/T17671-1999 Test method for strength of hydraulic cement mortar (ISO method) test, 3 days performance: ultimate compression strength 8.2MPa, folding strength 2.3MPa; 28 days performance: ultimate compression strength 28.9MPa, folding strength 3.8MPa; Presetting period: 70min, final setting time 2h22min.Adopt this solidifying agent 6%, the Bayer process red mud 92% of giving money as a gift is modulated into the lotion of water ratio 60% after the mixing, and 28 days ultimate compression strength is 1.2MPa, and the cured body coefficient of softening is 0.69.
Claims (2)
1, a kind of low-temp ceramics solidifying agent of Bayer process red mud is characterized in that: be mixed with by following materials based on weight: 100 parts in aluminosilicate waste residue, industry by-product gypsum 20-150 part, excitation material 50-200 part, water reducer 0-3.0 part, flocculation agent 0-5.0 part, retardant 0-5.0 part.
Described aluminosilicate waste residue comprises one or more in Metal smelting slag, yellow phosphorus slag, flyash, calcining mine tailing, calcining red mud and the calcining coal gangue; Described industry by-product gypsum comprises one or more in desulfurized gesso of flue gas, phosphogypsum, titanium gypsum, fluorgypsum, citric acid gypsum, wet method manganese slag and the plumbous cadmia; Described excitation material comprises one or more in lime, carbide slag and the cement flue Dust;
Described water reducer comprises one or more of calcium lignin sulphonate, sodium lignosulfonate, naphthalenesulfonate, Sodium salts humic acids, poly carboxylic acid; Flocculation agent comprises one or more of polyacrylamide, polyaluminium sulfate, polymkeric substance ferric sulfate, iron trichloride; Retardant comprises one or more of borax, sodium phosphate, Sodium Fluoride, nitrocalcite.
2, the production method of the low-temp ceramics solidifying agent of the described Bayer process red mud of claim 1 is characterized in that, may further comprise the steps:
1) main raw material is handled: aluminosilicate waste residue, industry by-product gypsum, excitation material are mixed homogenize, ageing 2-5 hour by the said ratio metering;
Compound is dried to water ratio less than 1%;
The exsiccant compound is carried out grinding, and powder fineness is 0.08mm, tails over less than 10%.
2) additive preparation: water reducer, flocculation agent and retardant are mixed by the prescription metering, be broken into the powder that particle is not more than 1mm.
3) solidifying agent preparation: the weight by proportioning is measured main raw material and additive respectively, add Forced Mixing 2-5min in the powder mixing machine, become product.
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