CN103342465A - Method for preparing glass ceramics by utilizing composite red mud and coal ash - Google Patents
Method for preparing glass ceramics by utilizing composite red mud and coal ash Download PDFInfo
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- CN103342465A CN103342465A CN2013102647702A CN201310264770A CN103342465A CN 103342465 A CN103342465 A CN 103342465A CN 2013102647702 A CN2013102647702 A CN 2013102647702A CN 201310264770 A CN201310264770 A CN 201310264770A CN 103342465 A CN103342465 A CN 103342465A
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Abstract
The invention relates to a method for preparing high-performance glass ceramics by utilizing composite red mud and coal ash and is applicable to the fields of architectural ornament and artware. The method comprises the following steps of: uniformly mixing 10-70 mass percent of red mud, 20-70 mass percent of coal ash and 5-25 mass percent of additive, preparing base glass by employing a high-temperature melting temperature, and performing heat treatment on the base glass to obtain the glass ceramics. According to the method, solid wastes can be consumed to the greatest degree, the wastes are changed into valuable materials, the energy is saved, the consumption is reduced, the production cost is greatly reduced, green environment-friendly production can be realized, the problem of environmental pollution of the red mud and coal ash is solved, the wastes are changed into valuable materials, and the method has good social benefits and economic benefits.
Description
Technical field
The present invention relates to utilize solid waste to prepare the method for pottery, relate in particular to and utilize red mud and the compound method for preparing glass-ceramic of flyash, be applicable to building decoration field and artwork field.
Background technology
Red mud is the solid waste that produces with bauxite into alumina, and mineral composition and chemical ingredients are very complicated, and 1 ton of aluminum oxide of every production is approximately produced 1.0-1.3 ton red mud.As the waste residue of quantity discharged maximum in the alumina producing, main component has SiO
2, CaO, Fe
2O
3, Al
2O
3With a spot of TiO
2, MgO, Na
2O, K
2O and tens kinds of micro-rare and scatter elements.Though red mud is having certain utilization ratio aspect some engineering utilizations, consumption still is limited, consumption red mud that can't be a large amount of.
Power Plant in China is based on fire coal, it is reported statistics, and China's thermoelectricity industry in 2010 is 1,300,000,000 tons in consumption mark coal approximately, nearly 400,000,000 tons of the flyash amounts of generation.Be example with the Shandong Province, coal consumption has reached 2.5 hundred million tons, nearly 8,000 ten thousand tons of flyash quantity discharged, in fact in recent years be many coal gangues of save energy foundation and the operation in low combustion value coal slime power station, the quantity discharged of flyash is increased, estimate that total amount surpasses 8,000 ten thousand tons, enormous amount.The stacking of flyash not only will take a large amount of soils, and flyash light weight, particle are little very easily causes environmental pollution.The discharging of a large amount of flyash has brought very big pressure for waste treatment and environment protection.The handling problem of flyash receives very big concern.
Up to the present, utilization of coal ash is except the producing building building block, and brickmaking is made beyond the low-grade concrete, still is used for greatly filling out the hole, paving the way, and its comprehensive utilization ratio is no more than 40%, some economically less developed region even be lower than 30%.Therefore, utilize flyash to become a current social very difficult task how efficiently, in a large number.The discharging of a large amount of flyash has brought very big pressure for waste treatment and environment protection.How improving red mud and utilization of coal ash rate is the problem that the present invention need solve.
Summary of the invention
Purpose of the present invention is exactly to provide red mud and the compound method for preparing glass ceramic material of flyash utilized at the defective of above-mentioned existence, be to solve the problem of environmental pollution of red mud and flyash, turn waste into wealth, the present invention adopts high-temperature melting method to prepare high value added product red-mud coal ash glass-ceramic, the overall utilization of the two reaches as high as 95%, and the red-mud coal ash glass-ceramic that makes can be used as building and ornament materials, industrial anti-abrasive material and artwork.
The method and technology scheme of red mud and the compound preparation glass-ceramic of flyash of utilizing of the present invention is, utilize the compound method for preparing glass-ceramic of red mud and flyash, being 10 ~ 70% red mud, 20 ~ 70% flyash with the quality percentage composition evenly mixes with 5 ~ 25% additive, adopt high-temperature melting method to prepare parent glass, heat-treated by parent glass again and obtain glass-ceramic.
Further, being 30 ~ 40% red mud, 40 ~ 55% flyash with the quality percentage composition evenly mixes with 15 ~ 20% additive, adopts high-temperature melting method to prepare parent glass, is heat-treated by parent glass and obtains glass-ceramic.
Described additive is by Na
2CO
3, H
3BO
3, Na
2B
4O
7In at least a and ZrO
2, TiO
2In at least a composition.
Additive is by 0 ~ 15 weight part Na
2CO
3, 0 ~ 10 weight part H
3BO
3, 0 ~ 5 weight part Na
2B
4O
7, 0 ~ 3 weight part ZrO
2, 0 ~ 5 weight part TiO
2Form; Na wherein
2CO
3, boric acid H
3BO
3With borax Na
2B
4O
7In have at least a kind of parts by weight can not be 0, ZrO
2And TiO
2In have at least a kind of parts by weight not to be 0.
Preferably, each set of dispense ratio of preparation glass-ceramic is the flyash of the red mud of 40 weight parts, 40 weight parts, the Na of 10 weight parts
2CO
3, the H of 5 weight parts
3BO
3, the TiO of 3 weight parts
2, the ZrO of 2 weight parts
2
The preparation glass-ceramic each set of dispense ratio can also for, with the red mud of 50 weight parts, the flyash of 45 weight parts, the Na of 2 weight parts
2CO
3, the TiO of 3 weight parts
2
Adopt high-temperature melting method to prepare being operating as of parent glass: red mud, flyash evenly to be mixed with additive, in High Temperature Furnaces Heating Apparatus, keep 1400 ℃ ~ 1600 ℃ temperature 1 ~ 4h, carry out melt processed; Vitreum is cooled to room temperature 550 ℃ ~ 750 ℃ annealing behind 0.5 ~ 10h, obtain parent glass.
Parent glass is heat-treated and is obtained being operating as of glass-ceramic: parent glass is placed heat treatment furnace, temperature rise rate with 5 ~ 20 ℃/min is warming up to 750 ℃ ~ 1100 ℃, insulation 0.5 ~ 5h, room temperature is down to the rate of temperature fall of 5 ~ 50 ℃/min in the back, obtains glass-ceramic.
Beneficial effect of the present invention is: the present invention utilizes solid waste red mud and flyash as main raw material, has prepared high performance glass ceramic material, obtains high economic benefit when solving environmental issue.Red mud and the powdered coal ash ratio in product is up to 95%, and does not have secondary and can pollute the waste residue generation.Not only can farthest consume solid waste, turn waste into wealth, turn harm into good, and energy-saving and cost-reducing, reduce production costs significantly and simultaneously can realize environmental protection production, have good social benefit and economic benefit.And have wear-resisting, acid-and base-resisting by the glass-ceramic that this invention is produced and corrode, good stability, "dead", premium properties such as be difficult for fading can be used as high-abrasive material, chemical resistant material and building and ornament materials and use.Following table is that the performance contrast of the glass-ceramic prepared and common building material product is as shown in table 1:
Table 1: the glass-ceramic that the present invention prepares and the contrast of the performance of other building material product
Performance | Natural marble | Grouan | Commercially available certain glass-ceramic | Glass-ceramic of the present invention |
Density (g/cm 3) | 2.6~2.7 | 2.6~2.8 | 2.6~2.7 | 2.5~3.0 |
Folding strength (MPa) | 7~17 | 8~15 | 30~60 | 150~235 |
Mohs' hardness | 3~5 | 5.5~6 | 5~6 | 7~8 |
Water-intake rate (%) | 0.3 | 0.35 | 0~0.06 | <0.04 |
Chemical stability | UC | UB | UA- | UA+ |
Radioactivity | Have | Have | Do not have | Do not have |
Embodiment:
In order to understand the present invention better, describe technical scheme of the present invention in detail with specific examples below, but the present invention is not limited thereto.
Embodiment 1:
With the red mud of 40 weight parts, the flyash of 40 weight parts, the Na of 10 weight parts
2CO
3, the H of 5 weight parts
3BO
3, the TiO of 3 weight parts
2, the ZrO of 2 weight parts
2Evenly mix.In High Temperature Furnaces Heating Apparatus, keep 1400 ℃ of temperature 4h to carry out melt processed, anneal in the 750 ℃ of annealing furnaces of packing into then, behind 10h, be cooled to room temperature, obtain parent glass.With after the moulding of parent glass sample in heat treatment furnace, be warming up to 750 ℃ with the temperature rise rate of 20 ℃/min, insulation 5h, room temperature is down to the rate of temperature fall of 50 ℃/min in the back, it is as shown in table 4 to obtain the glass-ceramic performance:
The performance of table 2: embodiment 1 preparation glass-ceramic
Performance | Glass-ceramic of the present invention |
Density (g/cm 3) | 2.6 |
Folding strength (MPa) | 235 |
Mohs' hardness | 7 |
Water-intake rate (%) | <0.03 |
Chemical stability | UA+ |
Radioactivity | Do not have |
Embodiment 2:
With the red mud of 40 weight parts, the flyash of 40 weight parts, the Na of 15 weight parts
2CO
3, the ZrO of 5 weight parts
2Evenly mix.In High Temperature Furnaces Heating Apparatus, keep 1500 ℃ of temperature 2h to carry out melt processed, anneal in the 550 ℃ of annealing furnaces of packing into then, behind 2h, be cooled to room temperature, obtain parent glass.With after the moulding of parent glass sample in heat treatment furnace, be warming up to 850 ℃ with the temperature rise rate of 10 ℃/min, insulation 1h, room temperature is down to the rate of temperature fall of 20 ℃/min in the back, it is as shown in table 2 to obtain the glass-ceramic performance:
The performance of table 3: embodiment 2 preparation glass-ceramic
Performance | Glass-ceramic of the present invention |
Density (g/cm 3) | 2.5 |
Folding strength (MPa) | 196 |
Mohs' hardness | 8 |
Water-intake rate (%) | <0.03 |
Chemical stability | UA+ |
Radioactivity | Do not have |
Embodiment 3:
With the red mud of 40 weight parts, the flyash of 45 weight parts, the Na of 5 weight parts
2CO
3, the H of 5 weight parts
3BO
3, the TiO of 5 weight parts
2Evenly mix.In High Temperature Furnaces Heating Apparatus, keep 1500 ℃ of temperature 2h to carry out melt processed, anneal in the 600 ℃ of annealing furnaces of packing into then, behind 3h, be cooled to room temperature, obtain parent glass.With after the moulding of parent glass sample in heat treatment furnace, be warming up to 900 ℃ with the temperature rise rate of 5 ℃/min, insulation 0.5h, room temperature is down to the rate of temperature fall of 10 ℃/min in the back, it is as shown in table 3 to obtain the glass-ceramic performance:
The performance of table 4: embodiment 3 preparation glass-ceramic
Performance | Glass-ceramic of the present invention |
Density (g/cm 3) | 2.6 |
Folding strength (MPa) | 189 |
Mohs' hardness | 8 |
Water-intake rate (%) | <0.03 |
Chemical stability | UA+ |
Radioactivity | Do not have |
Embodiment 4:
With the red mud of 30 weight parts, the flyash of 50 weight parts, the Na of 10 weight parts
2CO
3, the Na of 5 weight parts
2B
4O
7, the TiO of 5 weight parts
2Evenly mix.In High Temperature Furnaces Heating Apparatus, keep 1550 ℃ of temperature 3h to carry out melt processed, anneal in the 600 ℃ of annealing furnaces of packing into then, behind 3h, be cooled to room temperature, obtain parent glass.With after the moulding of parent glass sample in heat treatment furnace, be warming up to 900 ℃ with the temperature rise rate of 20 ℃/min, insulation 4h, room temperature is down to the rate of temperature fall of 35 ℃/min in the back, it is as shown in table 5 to obtain the glass-ceramic performance:
The performance of table 5: embodiment 4 preparation glass-ceramic
Performance | Glass-ceramic of the present invention |
Density (g/cm 3) | 2.6 |
Folding strength (MPa) | 154 |
Mohs' hardness | 7 |
Water-intake rate (%) | <0.04 |
Chemical stability | UA+ |
Radioactivity | Do not have |
Embodiment 5:
With the red mud of 30 weight parts, the flyash of 55 weight parts, the Na of 10 weight parts
2CO
3, the Na of 2 weight parts
2B
4O
7, the ZrO of 3 weight parts
2Evenly mix.In High Temperature Furnaces Heating Apparatus, keep 1550 ℃ of temperature 3h to carry out melt processed, anneal in the 550 ℃ of annealing furnaces of packing into then, behind 4h, be cooled to room temperature, obtain parent glass.With after the moulding of parent glass sample in heat treatment furnace, be warming up to 900 ℃ with the temperature rise rate of 10 ℃/min, insulation 2.5h, room temperature is down to the rate of temperature fall of 10 ℃/min in the back, it is as shown in table 6 to obtain the glass-ceramic performance:
The performance of table 6: embodiment 5 preparation glass-ceramic
Performance | Glass-ceramic of the present invention |
Density (g/cm 3) | 2.6 |
Folding strength (MPa) | 176 |
Mohs' hardness | 8 |
Water-intake rate (%) | <0.04 |
Chemical stability | UA+ |
Radioactivity | Do not have |
Embodiment 6:
With the red mud of 50 weight parts, the flyash of 45 weight parts, the Na of 2 weight parts
2CO
3, the TiO of 3 weight parts
2Evenly mix.In High Temperature Furnaces Heating Apparatus, keep 1500 ℃ of temperature 3h to carry out melt processed, anneal in the 600 ℃ of annealing furnaces of packing into then, behind 1.5h, be cooled to room temperature, obtain parent glass.With after the moulding of parent glass sample in heat treatment furnace, be warming up to 1100 ℃ with the temperature rise rate of 15 ℃/min, insulation 0.5h, room temperature is down to the rate of temperature fall of 20 ℃/min in the back, it is as shown in table 7 to obtain the glass-ceramic performance:
The performance of table 7: embodiment 6 preparation glass-ceramic
Performance | Glass-ceramic of the present invention |
Density (g/cm 3) | 3.0 |
Folding strength (MPa) | 210 |
Mohs' hardness | 8 |
Water-intake rate (%) | <0.03 |
Chemical stability | UA+ |
Radioactivity | Do not have |
Embodiment 7:
With the red mud of 40 weight parts, the flyash of 40 weight parts, the Na of 10 weight parts
2CO
3, the H of 2 weight parts
3BO
3, the Na of 3 weight parts
2B
4O
7, the TiO of 3 weight parts
2, the ZrO of 2 weight parts
2Evenly mix.In High Temperature Furnaces Heating Apparatus, keep 1400 ℃ of temperature 4h to carry out melt processed, anneal in the 650 ℃ of annealing furnaces of packing into then, behind 2h, be cooled to room temperature, obtain parent glass.With after the moulding of parent glass sample in heat treatment furnace, be warming up to 950 ℃ with the temperature rise rate of 20 ℃/min, insulation 1.5h, room temperature is down to the rate of temperature fall of 30 ℃/min in the back, it is as shown in table 8 to obtain the glass-ceramic performance:
The performance of table 8: embodiment 7 preparation glass-ceramic
Performance | Glass-ceramic of the present invention |
Density (g/cm 3) | 2.5 |
Folding strength (MPa) | 163 |
Mohs' hardness | 8 |
Water-intake rate (%) | <0.04 |
Chemical stability | UA+ |
Radioactivity | Do not have |
The glass-ceramic that above-described embodiment obtains is tested folding strength according to the GB6569-2006 testing method, and microhardness is according to the testing method test of GB/T16534-1996.
Claims (8)
1. utilize the compound method for preparing glass-ceramic of red mud and flyash, it is characterized in that, being 10 ~ 70% red mud, 20 ~ 70% flyash with the quality percentage composition evenly mixes with 5 ~ 25% additive, adopt high-temperature melting method to prepare parent glass, heat-treated by parent glass again and obtain glass-ceramic.
2. red mud and the compound method for preparing glass-ceramic of flyash utilized as claimed in claim 1, it is characterized in that, being 30 ~ 40% red mud, 40 ~ 55% flyash with the quality percentage composition evenly mixes with 15 ~ 20% additive, adopt high-temperature melting method to prepare parent glass, heat-treated by parent glass again and obtain glass-ceramic.
3. red mud and the compound method for preparing glass-ceramic of flyash utilized as claimed in claim 1 or 2 is characterized in that described additive is by Na
2CO
3, H
3BO
3, Na
2B
4O
7In at least a and ZrO
2, TiO
2In at least a composition.
4. red mud and the compound method for preparing glass-ceramic of flyash utilized as claimed in claim 3 is characterized in that additive is by 0 ~ 15 weight part Na
2CO
3, 0 ~ 10 weight part H
3BO
3, 0 ~ 5 weight part Na
2B
4O
7, 0 ~ 3 weight part ZrO
2, 0 ~ 5 weight part TiO
2Form; Na wherein
2CO
3, boric acid H
3BO
3With borax Na
2B
4O
7In have at least a kind of parts by weight can not be 0, ZrO
2And TiO
2In have at least a kind of parts by weight not to be 0.
5. utilize red mud and the compound method for preparing glass-ceramic of flyash as described in claim 3, it is characterized in that, each set of dispense ratio of preparation glass-ceramic is the flyash of the red mud of 40 weight parts, 40 weight parts, the Na of 10 weight parts
2CO
3, the H of 5 weight parts
3BO
3, the TiO of 3 weight parts
2, the ZrO of 2 weight parts
2
6. utilize red mud and the compound method for preparing glass-ceramic of flyash as described in claim 3, it is characterized in that, each set of dispense ratio of preparation glass-ceramic is, with the red mud of 50 weight parts, the flyash of 45 weight parts, the Na of 2 weight parts
2CO
3, the TiO of 3 weight parts
2
7. utilize the compound method for preparing glass-ceramic of red mud and flyash as claimed in claim 1 or 2, it is characterized in that, adopt high-temperature melting method to prepare being operating as of parent glass: red mud, flyash are evenly mixed with additive, in High Temperature Furnaces Heating Apparatus, keep 1400 ℃ ~ 1600 ℃ temperature 1 ~ 4h, carry out melt processed; Vitreum is cooled to room temperature 550 ℃ ~ 750 ℃ annealing behind 0.5 ~ 10h, obtain parent glass.
8. red mud and the compound method for preparing glass-ceramic of flyash utilized as claimed in claim 1 or 2, it is characterized in that, parent glass is heat-treated and is obtained being operating as of glass-ceramic: parent glass is placed heat treatment furnace, temperature rise rate with 5 ~ 20 ℃/min is warming up to 750 ℃ ~ 1100 ℃, insulation 0.5 ~ 5h, room temperature is down to the rate of temperature fall of 5 ~ 50 ℃/min in the back, obtains glass-ceramic.
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CN103922792A (en) * | 2014-04-23 | 2014-07-16 | 袁利民 | Method of producing light honeycomb material by melting and foaming red mud at high temperature |
CN103922598A (en) * | 2014-03-10 | 2014-07-16 | 刘立强 | All-solid waste black glass ceramic and preparation method and application thereof |
CN103922599A (en) * | 2014-03-06 | 2014-07-16 | 贵州大学 | Method for preparing microcrystalline glass by utilization of red mud-fly ash-titanium slag |
CN106633191A (en) * | 2016-11-23 | 2017-05-10 | 贵州省过程工业技术研究中心 | Method for producing flame-retardant ceramic rubber and plastic filler by using red mud |
CN106892565A (en) * | 2017-02-27 | 2017-06-27 | 江苏省冶金设计院有限公司 | It is a kind of by red mud and coal ash for manufacturing for foam pyroceram method |
CN108164149A (en) * | 2018-01-16 | 2018-06-15 | 王明国 | A kind of glass ceramics for adulterating graphene oxide and preparation method thereof |
CN109020231A (en) * | 2018-10-11 | 2018-12-18 | 清华大学 | A method of preparing alloyed iron and devitrified glass |
CN113087398A (en) * | 2021-04-13 | 2021-07-09 | 山东建筑大学 | Microcrystalline glass prepared from coal gasification furnace slag and preparation method thereof |
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CN103922599B (en) * | 2014-03-06 | 2016-02-10 | 贵州大学 | A kind of method utilizing red mud-flyash-titanium slag to prepare devitrified glass |
CN103922598A (en) * | 2014-03-10 | 2014-07-16 | 刘立强 | All-solid waste black glass ceramic and preparation method and application thereof |
CN103922792A (en) * | 2014-04-23 | 2014-07-16 | 袁利民 | Method of producing light honeycomb material by melting and foaming red mud at high temperature |
CN103922792B (en) * | 2014-04-23 | 2016-03-16 | 袁利民 | A kind of method utilizing red mud high-temperature fusion foam production light weight cellular material |
CN106633191B (en) * | 2016-11-23 | 2019-01-08 | 贵州省过程工业技术研究中心 | A method of Flame-retardant ceramic rubber filling is produced using red mud |
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CN106892565A (en) * | 2017-02-27 | 2017-06-27 | 江苏省冶金设计院有限公司 | It is a kind of by red mud and coal ash for manufacturing for foam pyroceram method |
CN108164149A (en) * | 2018-01-16 | 2018-06-15 | 王明国 | A kind of glass ceramics for adulterating graphene oxide and preparation method thereof |
CN108164149B (en) * | 2018-01-16 | 2021-09-14 | 盐城汇达玻璃仪器有限公司 | Graphene oxide doped glass ceramic and preparation method thereof |
CN109020231A (en) * | 2018-10-11 | 2018-12-18 | 清华大学 | A method of preparing alloyed iron and devitrified glass |
CN109020231B (en) * | 2018-10-11 | 2020-05-05 | 清华大学 | Method for preparing alloy iron and microcrystalline glass |
CN113087398A (en) * | 2021-04-13 | 2021-07-09 | 山东建筑大学 | Microcrystalline glass prepared from coal gasification furnace slag and preparation method thereof |
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