Background technology
Flyash is the waste of a large amount of dischargings of big-and-middle-sized fuel-burning power plant fluidized-bed combustion boiler.It is by the coal dust of wearing into certain fineness thin ash through being collected by dust-precipitator behind the high-temp combustion in fluidized-bed combustion boiler, is called waft ash or flying dust abroad.It is a kind of active material that has, and its main chemical compositions is silicon-dioxide (SiO
2), aluminium sesquioxide (Al
2O
3), small amounts iron (Fe
2O
3) and calcium oxide (CaO) when sweetening agent (do not add during coal combustion calcareous).SiO wherein
2And Al
2O
3Content is the highest, and both sums generally account for more than 60%, is the main active ingredient and the high temperature resistant composition of flyash.Every the kilowatt-hour in coal-burning power plant, need standard coal 300 grams approximately, promptly produce about 100 grams of flyash, one ton of raw coal of every burning can produce 250~300 kilograms in flyash, every kilowatt of installed capacity of coal fired power generation, about one ton of year ash discharge amount, that is to say that installed capacity is 1,000,000 kilowatts a coal-fired power plant, a year ash discharge amount can reach 1,000,000 tons.
Quantity is huge flyash so, and what have is discharged into ash, occupies a large amount of farmlands, and what have is discharged into rivers, and environment is polluted.During winter, Coal-fired capacity rises, and causes flying dust increase in the air, influences people's breathing, is detrimental to health.How to solve so a large amount of lime-ash dischargings, eliminate harm,, become an important topic of electric power, environmental protection and materials industry obtaining increment utilization after the reprocessing of flyash process.
The most of power plant of China all are used for flyash producing directly or indirectly, so not only can reduce land seizure, alleviate environmental pollution, and can economize on resources, and create certain economic benefits.Flyash can be used as cement, mortar, concrete adulterant, and become cement, concrete component, and can make vitrified brick, steam-pressing aero-concrete, foamed concrete, hollow block, sintering ceramsite, the making road as the raw material of producing cement; Construct dam body, build the harbour, the backfill of hollow lowland, farmland, subsidence area, colliery and mine; Produce fertilizer, improve the soil etc. all seen report.Present stage, flyash also had some purposes to be in the research and development, for example: from flyash, select iron, extract aluminium, flyash be used for rubber, plastics are made coating, are used for paint, filler or coating are made in papermaking, dispose of sewage with flyash; Produce multicellular glass with flyash, replace building board etc. with powdered coal ash product.
At present, domestic utilization of coal ash is mainly based on building material industries such as cement and concrete, and the increment effect of its utilization is not high, and utilization ratio is still lower, and it is discarded to still have most of flyash to be piled up, and has not only taken a large amount of soils but also serious environment pollution.
Along with the development of fluidized-bed electricity generation boiler technology and the anxiety of supply of electric power and coal resources, taken fire coal and coal gangue mixture of fluidized-bed electricity generation boiler is used for generating.Burning gangue generating produces and the flyash that do not add the calcic sweetening agent is characterized in that alumina content is higher, alumina content greater than 30%, calcium oxide content less than 5%, iron oxide content be less than 1.0% (can pass through magnetic deironing).This by fluidized-bed electricity generation boiler coal combustion and coal gangue mixture and the aluminous fly-ash of output accounts at present that the flyash total emission volumn is or else disconnected to rise, if the above-mentioned high temperature resistant thing flyash mutually such as high alumina content and silicon-dioxide that contain are used to produce the significant wastage that material of construction such as materials for wall will cause the aluminum oxide resource.So the comprehensive utilization of research invention aluminous fly-ash has important practical significance.
China is world steel output big country, consumes a large amount of refractory materialss.Domestic big-and-middle-sized Rafractory for molten iron discharge channel of blast furnace general requirement is: high temperature resistant, anti-erosion, anti-ly wash away, impermeabilisation, high thermal conductivity.Big-and-middle-sized Rafractory for molten iron discharge channel of blast furnace mainly is Al
2O
3-SiC-C matter mould material, based on corundum and silicon carbide, price is higher in its raw material, such as general corundum price at about 4000~7000 yuan per ton, about 6000 yuan per ton of silicon carbide.And the wastes of flyash a large amount of dischargings that are big-and-middle-sized fuel-burning power plant fluidized-bed combustion boiler, its price is only for dozens of yuan or only spend the short distance freight charges and get final product.Increasingly competitive under the present market economy condition raised labour productivity, and research and the big-and-middle-sized Rafractory for molten iron discharge channel of blast furnace of producing low-cost and high-performance are the basic goals that enterprise development is pursued.
Summary of the invention
The objective of the invention is at the comprehensive increment utilization and the raw materials used price of Refractory Castables for BF Troughs and Runners of existing aluminous fly-ash higher, and cause the cost problem of higher, it is good to propose a kind of anti-blast furnace slag performance and use properties, the blast furnace iron outlet groove refractory material casting material that cost is low.
A kind of blast furnace iron outlet groove refractory material casting material that the present invention proposes, it is characterized in that: this mould material is with technical grade corundum powder, SiC powder, hard pitch powder, alundum cement or aluminous cement, α-Al
2O
3Ultrafine powder, SiO
2Ultra-fine micropowder, metallic silicon power are main raw material,, are additive with the metallic aluminium powder, and add an amount of explosion-proof organic fibre and aluminous fly-ash as dispersion agent with tripoly phosphate sodium STPP or Sodium hexametaphosphate 99; Described technical grade corundum powder is according to accounting for 10~90% of total batching mass percent; Sic powder is according to accounting for 5~35% of total batching mass percent; Hard pitch is according to accounting for 0.3~8% of total batching mass percent; Alundum cement or aluminous cement are according to accounting for 0.1~7% of total batching mass percent; α-Al
2O
3Ultrafine powder is according to accounting for 0.5~10% of total batching mass percent; SiO
2Ultra-fine micropowder is according to accounting for 0.5%~7% of total batching mass percent; Metallic silicon power is according to accounting for 0.1~5% of total batching mass percent; Tripoly phosphate sodium STPP or Sodium hexametaphosphate 99 are according to accounting for 0.001~1% of total batching mass percent; Metallic aluminium powder is according to accounting for 0.001~1% of total batching mass percent; Explosion-proof organic fibre is according to accounting for 0.001~1% of total batching mass percent; Aluminous fly-ash is according to accounting for 1~30% of total batching mass percent; In the described aluminous fly-ash alumina content greater than 30%, calcium oxide content less than 5%, ferric oxide is less than 1.0%.
In above-mentioned refractory material casting material, it is characterized in that: Al in the described technical grade corundum powder
2O
3Content is greater than 88%, and granular size is≤40mm; SiC content is greater than 90% in the sic powder, and granular size is≤3.5mm; The hard pitch powder is a technical grade hard pitch product, and its particle is less than being 1mm, and alundum cement or aluminous cement are technical grade high temperature resistant cement product, α-Al
2O
3Ultrafine powder requires Al
2O
3Content is greater than 98%, and granular size is≤10um; SiO
2SiO in the ultra-fine micropowder
2Content is greater than 88%, and granular size is≤1um; Si content is greater than 88% in the metallic silicon power, and granular size is≤30um; Tripoly phosphate sodium STPP or Sodium hexametaphosphate 99 are the technical grade Chemicals; Al content is greater than 95% in the metallic aluminium powder, and granular size is≤50um; The fusing point of explosion-proof organic fibre is 115~160 ℃, and diameter is 30~120um, and length is 3~5um.
In above-mentioned refractory material casting material, it is characterized in that: described aluminous fly-ash is fluidized-bed electricity generation boiler coal combustion and coal gangue mixture and aluminous fly-ash of output when not adding the calcic sweetening agent.
The preparation method of a kind of blast furnace iron outlet groove refractory material casting material that the present invention proposes, it is characterized in that: described method is at first prepared burden above-mentioned various raw materials in described ratio, stirs the back packing then in stirrer.
Above-mentioned blast furnace iron outlet groove refractory material casting material adds water again and stirs when using, amount of water accounts for 3~7% of total stirring material quality; The material that mixes is packed in the mould of casting house, apply vibration to mould material by vibrating head or oscillating plate; Mould material is the blast furnace iron outlet groove refractory material casting material behind the moisture through 80 ℃~700 ℃ oven dry eliminating mould material again after the dry also demoulding of air-set
Because the present invention adds different mass fractional aluminous fly-ash in iron runner castable, prepared fire-proof pouring material of iron tap channel of blast-furnace stable performance, can satisfy the industrial production requirement, and can reduce the cost of iron runner castable, also opened up new application approach for the comprehensive utilization of flyash.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further:
Composition of raw materials and proportioning that the present invention adopts are respectively: the particle and the fine powder (Al of technical grade corundum raw material (also can be electric smelting compact alumina, fused white corundum, fused brown corundum or compact high-alumina bauxite clinker)
2O
3Content generally is greater than 88%, granular size for≤40mm) account for 50~90% of total batching massfraction: wherein the corundum feed particles of 40~8mm accounts for 2%~25% of total batching massfraction, 8~5mm corundum feed particles accounts for 2%~25% of total batching massfraction, 5~3mm corundum feed particles accounts for 2%~20% of total batching massfraction, 3~1mm corundum feed particles accounts for total batching massfraction 2%~25%, accounts for 2.0%~18% of total batching massfraction less than 1mm corundum feed particles; Silicon-carbide particle and fine powder (SiC content generally is greater than 90%, granular size for≤5mm) account for 5~35% of total batching massfraction; Hard pitch (less than 1mm) accounts for 0.3~8% of total batching massfraction; Alundum cement or aluminous cement (less than 0.1mm) account for 0.1~7% of total batching massfraction, α-Al
2O
3Micro mist (Al
2O
3Content generally is greater than 98%, granular size for≤10um) account for 0.5~10% of total batching massfraction; SiO
2Ultra-fine micropowder (SiO
2Content generally is greater than 88%, granular size for≤1um) account for 0.5%~7% of total batching massfraction; Metallic silicon power accounts for 0.1~5% of total batching massfraction; Tripoly phosphate sodium STPP or Sodium hexametaphosphate 99 account for 0.001~1% of total batching massfraction; Metallic aluminium powder accounts for 0.001~1% of total batching massfraction; Explosion-proof organic fibre 0.001~1%.Aluminous fly-ash (requirement be alumina content greater than 30% and calcium oxide content less than the flyash that does not add the calcic sweetening agent of 5% fluidized-bed electricity generation boiler output) account for 1~30% of total batching massfraction.
Above-mentioned various raw materials are prepared burden earlier in ratio of the present invention, in the stirrer admixtion stirring was packed shipping after 2~30 minutes then.Add water in use again and stir 20 seconds~5 minutes (amount of water account for total stirring material quality 3~7%), make it to reach certain fluidity after the stirring, the material that mixes is packed in the mould of casting house, apply the purpose that vibration reaches flowing forming by vibrating head or oscillating plate to mould material, can come into operation behind the moisture through get rid of mould material after the dry also demoulding of air-set again through 80 ℃ to 700 ℃ oven dry.The mould material refractory materials that adopts above-mentioned raw material and Technology to produce is a kind of blast furnace iron outlet groove refractory material casting material that adds flyash of the present invention.
The technical process of adding the preparation of flyash Refractory Castables for BF Troughs and Runners is:
Raw material → batching → stirrer stirring → packing → shipping → use is on-the-spot → stir → add water → stirring → vibratory compaction → drying → thermal treatment → use
(the main chemical constitution of flyash is the aluminous fly-ash that uses among the present invention: SiO
2: 40%~60%Al
2O
3: 30%~50%) high temperature resistant things such as the aluminum oxide that contains larger proportion and silicon-dioxide add different mass fractional flyash mutually in iron runner castable, can effectively reduce blast furnace iron outlet groove refractory material casting material cost, and the mould material excellent property.
Embodiment 1
Raw material:
The particle of technical grade corundum raw material and the specification of quality of fine powder are Al
2O
3Content generally is greater than 98%, and volume density is greater than 3.4g/cm
3, granular size is≤40mm.Wherein the corundum feed particles of 40~8mm accounts for 12% of total batching massfraction, 8~5mm corundum feed particles accounts for 20% of total batching massfraction, 5~3mm corundum feed particles accounts for 18% of total batching massfraction, 3~1mm corundum feed particles accounts for total batching massfraction 10%, accounts for 10% of total batching massfraction less than 1mm corundum feed particles.Technical grade corundum add-on accounts for 70% of total batching massfraction;
The specification of quality of silicon-carbide particle and fine powder is, the SiC content requirement is greater than 97%, and granular size is≤3mm that add-on accounts for 13% of total batching massfraction;
The hard pitch add-on accounts for 2% of total batching massfraction;
The alundum cement add-on accounts for 3% of total batching massfraction,
α-Al
2O
3The specification of quality of micro mist is Al
2O
3Content generally is greater than 98%, and granular size is≤10um that add-on accounts for 5% of total batching massfraction;
SiO
2The specification of quality of ultra-fine micropowder is SiO
2Content generally is greater than 88%, and granular size is≤1um that add-on accounts for 1% of total batching massfraction;
The metallic silicon power add-on accounts for 1.0% of total batching massfraction;
The tripoly phosphate sodium STPP add-on accounts for 0.05% (adding) of total batching massfraction;
The metallic aluminium powder add-on accounts for 0.2% (adding) of total batching massfraction;
Explosion-proof organic fibre add-on accounts for 0.05% (adding) of total batching massfraction.
The specification of quality of aluminous fly-ash is, alumina content greater than 30% and calcium oxide content less than the flyash that does not add the calcic sweetening agent of 5% fluidized-bed electricity generation boiler output, add-on accounts for 5% of total batching massfraction.
Batching:
Above-mentioned various raw materials are prepared burden earlier in ratio of the present invention, in the stirrer admixtion stirring was packed shipping after 6 minutes then.Add water in use again and stir 190 seconds (amount of water account for total stirring material quality 4.5%).
Moulding:
The material that mixes is packed in the mould of casting house, applies vibration by vibrating head or oscillating plate to mould material and reaches and flow into
Purpose.
Drying and thermal treatment:
After the dry also demoulding of air-set, dried 24 hours through 100 ℃ again, under 10 hours, 500 ℃ insulations of 10 hours, 300 ℃ insulations of 200 ℃ of insulations 10 hours and 8 hours heat-treat condition of 650 ℃ of insulations, mould material is dried and thermal treatment again, make the moisture of mould material to be controlled at less than 0.1%.The mould material that obtains after drying and the thermal treatment is a kind of Refractory Castables for BF Troughs and Runners refractory materials that adds aluminous fly-ash that the present invention relates to.
The physicochemical property of sample is: 110 ℃ of volume densities are greater than 2.76g/cm
3Compressive strength is greater than 18.8Mpa after 110 ℃ of oven dry, and the compressive strength of 1400 ℃ of insulations mould material after 4 hours is greater than 46.2Mpa, and the compressive strength of 1480 ℃ of insulations mould material after 4 hours is greater than 51.2Mpa; Folding strength is greater than 2.39Mpa after 110 ℃ of oven dry, the folding strength 5.19Mpa of 1400 ℃ of insulations mould material after 4 hours, the folding strength 7.51Mpa of 1480 ℃ of insulations mould material after 4 hours.
Embodiment 2
Raw material:
The particle of technical grade palm fibre corundum raw material and the specification of quality of fine powder are Al
2O
3Content generally is greater than 90%, and volume density is greater than 3.4g/cm
3, granular size is≤40mm.Wherein the corundum feed particles of 40~8mm accounts for 5% of total batching massfraction, 8~5mm corundum feed particles accounts for 20% of total batching massfraction, 5~3mm corundum feed particles accounts for 15% of total batching massfraction, 3~1mm corundum feed particles accounts for total batching massfraction 10%, accounts for 5% of total batching massfraction less than 1mm corundum feed particles.The fused brown corundum add-on accounts for 55% of total batching massfraction;
The specification of quality of silicon-carbide particle and fine powder is, SiC content generally is greater than 90%, and granular size is≤3mm that add-on accounts for 15% of total batching massfraction;
The hard pitch add-on accounts for 2% of total batching massfraction;
The alundum cement add-on accounts for 2.5% of total batching massfraction,
α-Al
2O
3The specification of quality of micro mist is Al
2O
3Content generally is greater than 98%, and granular size is≤10um that add-on accounts for 2% of total batching massfraction;
SiO
2The specification of quality of ultra-fine micropowder is SiO
2Content generally is greater than 88%, and granular size is≤1um that add-on accounts for 3.5% of total batching massfraction;
The metallic silicon power add-on accounts for 2% of total batching massfraction;
The tripoly phosphate sodium STPP add-on accounts for 0.06% (adding) of total batching massfraction;
The metallic aluminium powder add-on accounts for 0.3% (adding) of total batching massfraction;
Explosion-proof organic fibre add-on accounts for 0.07% (adding) of total batching massfraction;
The specification of quality of aluminous fly-ash is, alumina content greater than 38% and calcium oxide content less than the flyash that does not add the calcic sweetening agent of 5% fluidized-bed electricity generation boiler output, add-on accounts for 18% of total batching massfraction.
Batching:
Above-mentioned various raw materials are prepared burden earlier in ratio of the present invention, in the stirrer admixtion stirring was wrapped after 7 minutes then
Shipping.Add water in use again and stir 200 seconds (amount of water account for total stirring material quality 5.0%).
Moulding:
The material that mixes is packed in the mould of casting house, applies vibration by vibrating head or oscillating plate to mould material and reaches and flow into
Purpose.
Drying and thermal treatment:
After the dry also demoulding of air-set, dried 24 hours through 100 ℃ again, under 12 hours, 500 ℃ insulations of 10 hours, 300 ℃ insulations of 200 ℃ of insulations 11 hours and 10 hours heat-treat condition of 650 ℃ of insulations, mould material is dried and thermal treatment again, make the moisture of mould material to be controlled at less than 0.1%.The mould material that obtains after drying and the thermal treatment is a kind of Refractory Castables for BF Troughs and Runners refractory materials that adds aluminous fly-ash that the present invention relates to.
The physicochemical property of sample is: 110 ℃ of volume densities are greater than 2.75g/cm
3Compressive strength is greater than 16.4Mpa after 110 ℃ of oven dry, and the compressive strength of 1400 ℃ of insulations mould material after 4 hours is greater than 38.5Mpa, and the compressive strength of 1480 ℃ of insulations mould material after 4 hours is greater than 48.2Mpa; Folding strength is greater than 2.01Mpa after 110 ℃ of oven dry, the folding strength 4.2Mpa of 1400 ℃ of insulations mould material after 4 hours, the folding strength 6.57Mpa of 1480 ℃ of insulations mould material after 4 hours.
Embodiment 3
Raw material:
The particle of compact high-alumina bauxite clinker raw material and the specification of quality of fine powder are Al
2O
3Content generally is greater than 86%, and volume density is greater than 3.2g/cm
3, granular size is≤40mm.Wherein the corundum feed particles of 40~8mm accounts for 11% of total batching massfraction, 8~5mm corundum feed particles accounts for 10% of total batching massfraction, 5~3mm corundum feed particles accounts for 10% of total batching massfraction, 3~1mm corundum feed particles accounts for total batching massfraction 5%, accounts for 4% of total batching massfraction less than 1mm corundum feed particles.The add-on of compact high-alumina bauxite clinker raw material accounts for 40% of total batching massfraction;
The specification of quality of silicon-carbide particle and fine powder is, SiC content generally is greater than 90%, and granular size is≤3mm that add-on accounts for 24% of total batching massfraction;
The hard pitch add-on accounts for 3% of total batching massfraction;
The aluminous cement add-on accounts for 4.5% of total batching massfraction,
α-Al
2O
3The specification of quality of micro mist is Al
2O
3Content generally is greater than 98%, and granular size is≤10um that add-on accounts for 3% of total batching massfraction;
SiO
2The specification of quality of ultra-fine micropowder is SiO
2Content generally is greater than 88%, and granular size is≤1um that add-on accounts for 2.8% of total batching massfraction;
The metallic silicon power add-on accounts for 0.7% of total batching massfraction;
The tripoly phosphate sodium STPP add-on accounts for 0.06% (adding) of total batching massfraction;
The metallic aluminium powder add-on accounts for 0.28% (adding) of total batching massfraction;
Explosion-proof organic fibre add-on accounts for 0.1% (adding) of total batching massfraction;
The specification of quality of aluminous fly-ash is, alumina content greater than 40% and calcium oxide content less than the flyash that does not add the calcic sweetening agent of 5% fluidized-bed electricity generation boiler output, add-on accounts for 22% of total batching massfraction.
Batching: above-mentioned various raw materials are prepared burden earlier in ratio of the present invention, in stirrer, admixtion was stirred 12 fens then
Back packing shipping.Add water in use again and stir 3 minutes (amount of water account for total stirring material quality 4.7%).
Moulding:
The material that mixes is packed in the mould of casting house, applies vibration by vibrating head or oscillating plate to mould material and reaches and flow into
Purpose.
Drying and thermal treatment:
After the dry also demoulding of air-set, dried 26 hours through 100 ℃ again, under 8 hours, 500 ℃ insulations of 12 hours, 300 ℃ insulations of 200 ℃ of insulations 9 hours and 16 hours heat-treat condition of 650 ℃ of insulations, mould material is dried and thermal treatment again, make the moisture of mould material to be controlled at less than 0.1%.The mould material that obtains after drying and the thermal treatment is a kind of Refractory Castables for BF Troughs and Runners refractory materials that adds aluminous fly-ash that the present invention relates to.
The physicochemical property of sample is: 110 ℃ of volume densities are greater than 2.72g/cm
3Compressive strength is greater than 17.4Mpa after 110 ℃ of oven dry, and the compressive strength of 1400 ℃ of insulations mould material after 4 hours is greater than 32.6Mpa, and the compressive strength of 1480 ℃ of insulations mould material after 4 hours is greater than 43.2Mpa; Folding strength is greater than 1.91Mpa after 110 ℃ of oven dry, the folding strength 4.6Mpa of 1400 ℃ of insulations mould material after 4 hours, the folding strength 6.48Mpa of 1480 ℃ of insulations mould material after 4 hours.