Composite material of silicon carbide mullite heat accumulator and preparation method thereof
One, technical field:
The present invention relates to a kind of heat-storage type burner parts, particularly relate to a kind of composite material of silicon carbide mullite heat accumulator and preparation method thereof.
Two, background technology:
Heat accumulating type high-temperature air burning (being called for short HTAC) is one and has energy-conservation and the novel combustion technology environmental protection double effects; Heat storage is the key part of heat-storage type burner, is widely used in the kilns such as various process furnace, hotblast stove, heat treatment furnace, pyrolyzer, roaster, thawing furnace, homogenizing furnace and oil gas boiler of industries such as iron and steel, machinery, building materials, petrochemical industry and non-ferrous metal metallurgy, and this technology is passed through reversing system; Make the heat release of alternately absorbing heat of two regenerator; Low-calorie inferior fuel (like blast furnace gas) reclaims the heat in the flue gas to greatest extent, combustion air and coal gas is heated to more than 1000 ℃ again, even also can be realized stable ignition and efficient burning; But fuel saving 40-70%; Output improves more than 15%, and billet oxidization burning loss descends more than 40%, oxynitride (NO
X) quantity discharged is less than 100ppm, smog discharge temperature is lower than 160 ℃, helps reducing the Greenhouse effect of the earth greatly.If national most of Industrial Stoves all adopt the HTAC technology, its economic benefit and social benefit are inestimable, will greatly alleviate the energy scarcity situation, effectively improve existent environment of people.
The HTAC technology needs the main the following aspects of considering: the heat storage capacity of heat storage, heat transfer rate, thermal shock resistance, oxidation-resistance, corrodibility, the pressure-losses and economy etc.The work-ing life of present domestic honeycomb is lower, and the honeycomb of process furnace was generally 3~6 months work-ing life, even occurs using once a large amount of cracked situation of week, and the heat storage that is used on the ladle baking facility increases because of flue-gas temperature low work-ing life to some extent.The problem that heat storage in use often occurs mainly contains: melt, soften, break, obstruction and corrosion etc., wherein the anti-thermal shock poor stability of heat storage material is the most normal problem of appearance.Cause the reason of above problem to mainly contain following 3 points:
(1) problem of materials: the honeycomb long term operation be at rapid heat cycle, also possibly have in the severe environment of corrosive gases, often bears high temperature and inside and outside difference variation and the stress that causes.This Working environment has proposed harsh requirement to the heat storage material.In order to increase heat storage capacity, reduce the volume of regenerator, need to increase the density of heat storage.But anti-thermal shock stability is mutually exclusive to a certain extent with density, and promptly density is high more, and anti-thermal shock stability is poor more.In use, heat storage and air-flow carry out heat exchange, and some have corrosive gas and particle has a negative impact to honeycomb.Such as, ferric oxide particles can reduce the reflowing temperature of aluminium silicon material, makes honeycomb fusing and blocks pore; Sour gas is known from experience honeycomb generation corrosive nature; Molecule can stop up gas passage etc. attached to the honeycomb surface.
(2) bias current problem: heat exchanging process is roughly following in the regenerator: in the smoke evacuation stage, flue gas flow is stored in sensible heat in the honeycomb when honeycomb, the heating honeycomb; At combustionphase, air (or coal gas) is heated when flowing through honeycomb, and waste heat is taken back in the stove again.In above arbitrary stage,, after several times switching-overs, cause honeycomb localized hyperthermia easily and produce thermal stresses if bias current appears in gas in regenerator.When the thermal stress that produces exceeded it and bears the limit, honeycomb will break.
(3) " secondary combustion " problem: the air jet of regenerative combustion system and gas port generally all are separate; Help forming hypoxic atmosphere in the stove like this; Expand flame edge, form the homogeneous temp field, improve heating quality and the discharging that reduces oxynitride.But the optimum value of air and coal gas two bursts of effusive speed, the angle of cut and distances be difficult to be held, and deal with improperly and then cause in the stove local gas-fired insufficient easily, and other local oxygen also has residue.These flue gases are when being inhaled into regenerator, and air can contact generation " secondary combustion " again with coal gas, and liberated heat can be absorbed by honeycomb fully, although do not cause power loss, localized hyperthermia is easy to make the honeycomb fusing and lost efficacy.
Three, summary of the invention:
The technical problem that the present invention will solve: the composite material of silicon carbide mullite heat accumulator that a kind of heat storage capacity is high, intensity is high, thermal shock resistance is high, resistance to chemical corrosion is good is provided;
The preparation method of this composite material of silicon carbide mullite heat accumulator also is provided.
Technical scheme of the present invention:
A kind of composite material of silicon carbide mullite heat accumulator, form by following weight percentages: black silicon carbide powder 75-85%, mullite powder 14-20%, metallic silicon power 1-3%, andaluzite powder 1-4%, kaolin 1-4%, the above-mentioned raw materials total amount is 100%; Add the hydroxypropylcellulose that accounts for above-mentioned raw materials 3-5%, the tung oil of 4-6%, the glycerine 1-3% of 1-3% and the water of 15-18%.
Said black silicon carbide powder comprises 150 purpose black silicon carbide powder 22-27%, 250 purpose black silicon carbide powder 37-42%, 325 purpose black silicon carbide powder 12-17%; Said mullite powder is 14-18%, granularity 180-240 order; Said metallic silicon power is 1-1.5%, granularity 250 orders; Said andaluzite powder is 1-2%, granularity 180 orders; Said kaolin is 1-2%, granularity 200-220 order.
Said hydroxypropylcellulose is 3-4%, tung oil 4-5%, glycerine 1-1.5%, water 15-16%.
Said metallic silicon power requires: silicone content>=97%, calcium contents≤0.30%, iron level≤0.70%.
Said black silicon carbide is a refinery coke silit, wherein contains SiC 95-97%, and density is 3.2-3.25g/cm
3
The preparation method of described composite material of silicon carbide mullite heat accumulator may further comprise the steps,
Take by weighing raw material by prescription,, add auxiliary material mullite powder, metallic silicon power, andaluzite powder and kaolin major ingredient black silicon carbide sphere of powder mill 2-3h; Do and mix 30-60min, add hydroxypropylcellulose, tung oil, G & W, wet mixing 1-1.5h; Old 8-10h slightly refines mud at vacuum deairing machine; The mud bar that slightly refines behind the mud is cut into sheet, and old 4-5h carries out refining mud, and extrusion moulding dries blank to water cut≤2%, and shove charge is burnt till at 1350 ℃.
Pressure is 14-16MPa during said moulding.
Said blank is dried carried out at twice, and elder generation with microwave drying to water cut≤10%, dries blank to water cut≤2% under 300-350 ℃ with baking oven again.
Said firing temperature is designed to: be warming up to 400 ℃ by room temperature through 1h, be warming up to 600 ℃ through 1.5h, be warming up to 950 ℃ through 3h, be warming up to 1200 ℃ through 5h, be warming up to 1350 ℃ through 3h again, at 1350 ℃ of insulation 2h; Naturally cool to 200 ℃ then.
Positive beneficial effect of the present invention:
(1) products material compatibility of the present invention is reasonable, and consumption is fastidious, and product performance are good.Product material density is big, unit weight is little, can increase heat storage capacity, reduces the regenerator volume; Product strength is high, can adapt to the carriage requirement of big regenerator under the high temperature; Even, the good thermal shock stability of expansion when product is heated, load softening point is high; Product high temperature creep value is little, rate≤0.5% behind 1450 ℃, loading 0.2MPa, 48h; Product hardness is big, and resistance to chemical corrosion is good, and thermal conductivity is high, has good antioxygenation simultaneously, is specially adapted to that environment is abominable, the comparatively serious occasion of regenerator oxidation corrosion, and its long service life is than long 2~4 times of common mullite heat accumulator.
Performance of products of the present invention detects index, like following table 1.
(2) the inventive method adopts secondary drying technology, and microwave is adopted in oven dry for the first time, and baking oven is adopted in oven dry for the second time, can prevent the product distortion, helps again reducing cost; Adopt special firing temperature curve to burn till product, can effectively guarantee the quality and the stable performance of product.
(3) product of the present invention can effectively solve fusing that existing honeycomb heat accumulation body in use often occurs, soften, breaks and problem such as corrosion; Product anti-thermal shock stability improves greatly; Help the application of HTAC technology in Industrial Stoves; With the situation of alleviating energy scarcity greatly, help improving environment for human survival, will produce better economic and social benefit.
Four, embodiment:
Embodiment 1: a kind of composite material of silicon carbide mullite heat accumulator; Form by following weight percentages: 150 order black silicon carbide powder 22%, 250 order black silicon carbide powder 42%, 325 order black silicon carbide powder 12%; 180-240 order mullite powder 15%, 250 order metallic silicon power 1%, 180 order andaluzite powder 4%; 200-220 order kaolin 4%, above-mentioned raw materials gross weight are 100%; Add the hydroxypropylcellulose that accounts for above-mentioned raw materials 3%, 4% tung oil, 3% glycerine, 15% water.
Wherein metallic silicon power requires: silicone content>=97%, calcium contents≤0.30%, iron level≤0.70%; Black silicon carbide is a refinery coke silit, wherein contains SiC 95-97%, Fe
2O
31-1.2%, density is 3.2-3.25g/cm
3
The preparation method of described composite material of silicon carbide mullite heat accumulator may further comprise the steps:
Take by weighing raw material by prescription and granularity requirements; With major ingredient black silicon carbide sphere of powder mill 2-3h, add auxiliary material mullite powder, metallic silicon power, andaluzite powder and kaolin, do and mix 30-60min; Add hydroxypropylcellulose, tung oil, G & W; Wet mixing 1-1.5h, old 8-10h slightly refines mud at vacuum deairing machine; Then the mud bar is cut into the old again 4-5h of sheet, carry out refining mud, extrusion moulding; Forming pressure 14-16MPa uses diameter to cut into blank as the steel wire of 0.2-0.3mm, with blank with microwave drying to moisture mass content below 7%; Dry to moisture mass content below 2% at 300-350 ℃ with baking oven again, with the diamond saw blade cutting, the floating powder of cleaning; Shove charge is burnt till at 1350 ℃.
Temperature design is when burning till: be warming up to 400 ℃ by room temperature through 1h, be warming up to 600 ℃ through 1.5h again, be warming up to 950 ℃ through 3h again; Be warming up to 1200 ℃ through 5h, be warming up to 1350 ℃ through 3h, at 1350 ℃ of insulation 2h, naturally cool to 200 ℃ then, kiln discharge obtains product.
Embodiment 2: the composite material of silicon carbide mullite heat accumulator raw material is formed: 150 purpose black silicon carbide powder 27%, 250 purpose black silicon carbide powder 37%, 325 purpose black silicon carbide powder 17%; 180-240 purpose mullite powder 14%; 250 purpose metallic silicon powers 3%; 180 purpose andaluzite powder 1%, 200-220 purpose kaolin 1%, the above-mentioned raw materials gross weight is 100%; Add the hydroxypropylcellulose that accounts for above-mentioned raw materials 5%, 4% tung oil, 2% glycerine, 16% water.The performance requriements of said metallic silicon power and refinery coke silit is with embodiment 1.
Preparing method: take by weighing raw material by prescription and granularity requirements,, add mullite powder, metallic silicon power, andaluzite powder and kaolin with black silicon carbide sphere of powder mill 2h; Do and mix 40min, add hydroxypropylcellulose, tung oil, G & W, wet mixing 1h; Old 10h slightly refines mud at vacuum deairing machine; After thick white silk finishes the mud bar is cut into the old again 4-5h of sheet, carry out refining mud, extrusion moulding then; Forming pressure 13-16MPa uses diameter to cut into blank as the steel wire of 0.2-0.3mm, with blank microwave drying to water cut below 9%; Under 300 ℃, dry to water cut below 2% with baking oven again, with the diamond saw blade cutting, the floating powder of cleaning; Shove charge is burnt till at 1350 ℃.Temperature design is with embodiment 1 when burning till.
Embodiment 3: the composite material of silicon carbide mullite heat accumulator raw material is formed: 150 purpose black silicon carbide powder 25%, 250 purpose black silicon carbide powder 37%, 325 purpose black silicon carbide powder 13%; 180-240 purpose mullite powder 18%; 250 purpose metallic silicon powers 2%; 180 purpose andaluzite powder 3%, 200-220 purpose kaolin 2%, the above-mentioned raw materials gross weight is 100%; Add the hydroxypropylcellulose that accounts for above-mentioned raw materials 4%, 5% tung oil, 2% glycerine, 16% water.The performance requriements of said metallic silicon power and refinery coke silit is with embodiment 1.
Preparing method: take by weighing raw material by prescription and granularity requirements; With black silicon carbide sphere of powder mill 2.5h, add mullite powder, metallic silicon power, andaluzite powder and kaolin, do and mix 30min; Add hydroxypropylcellulose, tung oil, G & W; Wet mixing 1.5h, old 8h slightly refines mud at vacuum deairing machine; After thick white silk finishes the mud bar is cut into the old again 4-5h of sheet, carry out refining mud, extrusion moulding then; Forming pressure 12-15MPa uses diameter to cut into blank as the steel wire of 0.2-0.3mm, with blank microwave drying to water cut below 8%; Under 320 ℃, dry to water cut below 2% with baking oven again, with the diamond saw blade cutting, the floating powder of cleaning; Shove charge is burnt till at 1350 ℃.Temperature design is with embodiment 1 when burning till.
Embodiment 4: the composite material of silicon carbide mullite heat accumulator raw material is formed: 150 purpose black silicon carbide powder 23%, 250 purpose black silicon carbide powder 39%, 325 purpose black silicon carbide powder 13%; 180-240 purpose mullite powder 20%; 250 purpose metallic silicon powers 1%; 180 purpose andaluzite powder 2%, 200-220 purpose kaolin 2%, the above-mentioned raw materials gross weight is 100%; Add the hydroxypropylcellulose that accounts for above-mentioned raw materials 4%, 4% tung oil, 1% glycerine, 18% water.The performance requriements of said metallic silicon power and refinery coke silit is with embodiment 1.
Preparing method: take by weighing raw material by prescription and granularity requirements,, add mullite powder, metallic silicon power, andaluzite powder and kaolin with black silicon carbide sphere of powder mill 3h; Do and mix 40min, add hydroxypropylcellulose, tung oil, G & W, wet mixing 1.2h; Old 9h slightly refines mud at vacuum deairing machine; After thick white silk finishes the mud bar is cut into the old again 4-5h of sheet, carry out refining mud, extrusion moulding then; Forming pressure 15-17MPa uses diameter to cut into blank as the steel wire of 0.2-0.3mm, with blank microwave drying to water cut below 8%; Under 350 ℃, dry to water cut below 2% with baking oven again, with the diamond saw blade cutting, the floating powder of cleaning; Shove charge is burnt till at 1350 ℃.Temperature design is with embodiment 1 when burning till.
Embodiment 5: the composite material of silicon carbide mullite heat accumulator raw material is formed: 150 purpose black silicon carbide powder 26%, 250 purpose black silicon carbide powder 40%, 325 purpose black silicon carbide powder 15%; 180-240 purpose mullite powder 16%; 250 purpose metallic silicon powers 1%; 180 purpose andaluzite powder 1%, 200-220 purpose kaolin 1%, the above-mentioned raw materials gross weight is 100%; Add the hydroxypropylcellulose that accounts for above-mentioned raw materials 3%, 4% tung oil, 3% glycerine, 17% water.The performance requriements of said metallic silicon power and refinery coke silit is with embodiment 1.
Preparing method: take by weighing raw material by prescription and granularity requirements; With major ingredient black silicon carbide sphere of powder mill 2h, add auxiliary material mullite powder, metallic silicon power, andaluzite powder and kaolin, do and mix 50min; Add hydroxypropylcellulose, tung oil, G & W; Wet mixing 1h, old 9h slightly refines mud at vacuum deairing machine; After thick white silk finishes the mud bar is cut into the old again 4-5h of sheet, carry out refining mud, extrusion moulding then; Forming pressure 15-16MPa uses diameter to cut into blank as the steel wire of 0.2-0.3mm, with blank microwave drying to water cut below 10%; Under 340 ℃, dry to water cut below 2% with baking oven again, with the diamond saw blade cutting, the floating powder of cleaning; Shove charge is burnt till at 1350 ℃.Temperature design is with embodiment 1 when burning till.
Embodiment 6: the raw material of composite material of silicon carbide mullite heat accumulator is formed: 150 purpose black silicon carbide powder 24%, 250 purpose black silicon carbide powder 38%, 325 purpose black silicon carbide powder 14%; 180-240 purpose mullite powder 19%; 250 purpose metallic silicon powers 2%; 180 purpose andaluzite powder 1%, 200-220 purpose kaolin 2%, the above-mentioned raw materials gross weight is 100%; Add the hydroxypropylcellulose that accounts for above-mentioned raw materials 4%, 4% tung oil, 3% glycerine, 15% water.The performance requriements of said metallic silicon power and refinery coke silit is with embodiment 1.
Preparing method: take by weighing raw material by prescription and granularity requirements; With major ingredient black silicon carbide sphere of powder mill 3h, add auxiliary material mullite powder, metallic silicon power, andaluzite powder and kaolin, do and mix 60min; Add hydroxypropylcellulose, tung oil, G & W; Wet mixing 1h, old 8.5h slightly refines mud at vacuum deairing machine; After thick white silk finishes the mud bar is cut into the old again 4-5h of sheet, carry out refining mud, extrusion moulding then; Forming pressure 14-16MPa uses diameter to cut into blank as the steel wire of 0.2-0.3mm, with blank microwave drying to water cut below 7%; Under 300-350 ℃, dry to water cut below 2% with baking oven again, with the diamond saw blade cutting, the floating powder of cleaning; Shove charge is burnt till at 1350 ℃.Temperature design is with embodiment 1 when burning till.
Product in the foregoing description is through detecting, and performance index all meet the parameter in the table 1.