Summary of the invention
At the above-mentioned deficiency of existing in prior technology, technical problem to be solved by this invention provides a kind of preparation raw material and preparation method of anti-corrosion mullite brick, it is low that it makes that not only anti-corrosion mullite brick has thermal conductivity, heat-insulating property is excellent, and can block the erosion of harmful corrosive gases to the heat insulating layer effectively.
In order to solve the problems of the technologies described above, a kind of anti-corrosion mullite brick of the present invention prepares raw material, and this preparation raw material is 10~17wt% calcium hexaluminate, 12~20wt% andaluzite, 4~10wt% sillimanite, 3~8wt% aluminum oxide, 8~16wt% trichroite, 20~30wt% agalmatolite, 10~15wt% kaolin, 3~10wt% refractory oxide, 1~3wt% whipping agent, 1~4wt% wedding agent; Described refractory oxide is ZrO
2Or MgO or Cr
2O
3Or CaO; Described whipping agent is EPS expanded plastic particle and wood sawdust.
In order to make anti-corrosion mullite brick with above-mentioned raw materials, the preparation method of anti-corrosion mullite brick of the present invention may further comprise the steps:
(a) get the raw materials ready by the material component proportioning;
(b) sillimanite, aluminum oxide, trichroite, agalmatolite, kaolin, refractory oxide and wedding agent are put in the lump carried out dry grinding in the shredder 2~4 hours, and make the matrix material;
(c) calcium hexaluminate and andaluzite are fed in the lump mixed grind added water to surface wettability after 5~10 minutes in the mixing pan, and make granulated aggregate;
(d) the matrix material is joined in the mixing pan and to continue mixed grind in the lump with granulated aggregate and stir, form the compound that granulated aggregate and matrix material mix parcel;
(e) in compound, add whipping agent and inject water, stirred formation mud shape compound 15~20 minutes;
(f) mud shape compound was left standstill 6~12 hours;
(g) the mud shape compound after will leaving standstill is made the mullite brick adobe, demoulding after drying;
(h) this exsiccant mullite brick adobe is packed into sintering oven sinters the anti-corrosion mullite brick finished product into.
Described calcium hexaluminate is to be mixed with aluminum oxide powder by lime carbonate, and forms nano level pore particle under 1400 ℃~1500 ℃ temperature.
The weight ratio of described EPS expanded plastic particle and wood sawdust is 1: (4~10), EPS expanded plastic granularity is 0.5mm~3mm.
Described calcium hexaluminate particulate granularity is 1mm~2mm; The andaluzite granularity is 0.2mm~1mm, and the sillimanite granularity is 0.062~0.088mm; Aluminum oxide is Al
2O
3Micro mist granularity 3~5um; The trichroite granularity is 0.044~0.074mm, and the agalmatolite granularity is 0.074~0.175mm, kaolin granularity 0.038~0.044mm.
The present invention compared with prior art has following significant advantage:
At first, the present invention is because with the principal constituent of granulated aggregates such as calcium hexaluminate and andaluzite as the thermal insulation fire-resistant material, and wherein calcium hexaluminate has the great quantity of micron pore, so its thermal conductivity ℃ is all keeping lower level from room temperature to 1500; And andaluzite has many advantages such as higher refractoriness, resist chemical, heat shock resistance and expanded by heating are little, both are thorough mixing and through high temperature action in proportion, make the thermal insulation fire-resistant brick have better heat-shock resistance, high volume stability, not only have superior heat preservation energy-saving characteristic, and have the high temperature corrosion of resisting obnoxious flavour erosive effect.
Second, the present invention adopt with calcium hexaluminate and andaluzite as aggregate in, be the matrix material with sillimanite, aluminum oxide, trichroite, agalmatolite, kaolin and refractory oxide again, wherein sillimanite at high temperature (1500 ℃) irreversibly become mullite and silicon-dioxide, have volume stability, low creep and slag resistance; Aluminum oxide then is the excellent high-temperature refractory materials, high temperature lower volume and stable chemical performance, and corrosion resistance is strong; The trichroite coefficient of expansion is little, has excellent thermal shock resistance, and in conjunction with mullite good high-temperature performance, both interactions make anti-erosion mullite material performance be greatly improved; Agalmatolite has good thermostability, and agalmatolite also has fabulous unreactiveness, does not act on the therefore fine erosion of resisting corrosives of energy with strong acid-base; Kaolin has good plasticity-and higher cohesiveness, good antiacid dissolubility and resistivity against fire; Wedding agent then helps respectively preparing integral body combination, moulding and the sintering of raw material.
Three, the present invention has also added refractory oxide and whipping agent in the preparation raw material.Refractory oxide has improved the high-temperature behavior and the antiacid caustic corrosion ability of anti-erosion mullite.Whipping agent evenly is mixed in the preparation raw material, and it is burnt mistake and form the small sealed porosity that is evenly distributed in the mullite fragment of brick in sintering process, and the existence of sealed porosity then strengthens the thermal and insulating performance of mullite brick greatly.
The 4th, the present invention is preferred preparation raw material and component ratio thereof, and adopt specific preparation method, each constitutive material not only to bring into play its high-temperature behavior and thermal insulation fire-resistant advantage, and also mutual coordinative role produces the technique effect outside the anticipation.A large amount of practices show with the present invention and prepare the glassy anti-erosion layer that raw material and preparation method's agglomerating anti-corrosion mullite brick surface can form the fine and close sealing of one deck, this layer sealing anti-erosion layer has been blocked harmful corrosives in mullite brick brick body and the infiltration and the erosion of crystal depths fully, thereby has promoted the tolerance of brick body to aggressive gas and high temperature etc. greatly.While brick formed sealed porosity of body sintering and the micron order pore that feed particles had make the present invention have fabulous thermal insulation fire-resistant performance again, and reach the advantage of lightweight, material-saving, saving cost.Therefore, the present invention not only has extremely strong corrosion resistance, and has that thermal conductivity is low, the advantage of good effect of heat insulation.
Embodiment
Embodiment 1
In a sintering batch, the preparation raw material gross weight of its mullite is 25T, wherein calcium hexaluminate account for the raw material gross weight 15%, andaluzite 18%, sillimanite 5%, aluminium oxide powder 5%, trichroite 10%, agalmatolite 22%, kaolin 11%, chromium sesquioxide 8%, whipping agent 3%, wedding agent 3%.Wherein refractory oxide is a chromium sesquioxide; EPS expanded plastic particle in the whipping agent account for preparation raw material gross weight 0.5%, wood sawdust 2.5%; Wedding agent adopts calcium lignin sulphonate, can certainly adopt other general organic bond or inorganic bonding agents.
The calcium hexaluminate granularity that above-mentioned preparation raw material is selected for use is 1.5mm; The andaluzite granularity is 0.55mm; The sillimanite granularity is 0.088mm; The aluminium oxide powder granularity is 4um; The trichroite granularity is 0.074mm; Agalmatolite granularity≤0.09mm; The kaolin granularity is 0.044mm; Chromium sesquioxide granularity 0.044mm; The EPS expanded plastic is surmised 1.5mm.
After above-mentioned preparation raw material is got the raw materials ready by its proportioning and granularity requirements, earlier sillimanite, alchlor micro mist, trichroite, agalmatolite, kaolin, chromium sesquioxide and calcium lignin sulphonate are put in the lump and carried out dry grinding in the shredder 2 hours, above-mentioned raw materials is fully ground stir, and make the matrix material.
Again calcium hexaluminate and andaluzite are fed in the mixing pan in the lump and mix after 5-10 minute, add a spot of water, make it surface wettability, and make granulated aggregate.To grind the matrix prepared material joins and proceeds mixed grind in the lump with granulated aggregate in the mixing pan and stir, and formation granulated aggregate and matrix material mix the compound of parcel, in this compound, add the whipping agent that is mixed by EPS expanded plastic particle and wood sawdust again and add quantitative water, this gauge water is the 23%-27% of compound gross weight, evenly stirred 15-20 minute, can be used for making the mud shape compound of adobe with formation.This mud shape compound was left standstill after the discharging from mixing pan 6 hours, moisture content is penetrated in the raw material full and uniformly.
Raw material after leaving standstill is carried out base.Prepare the mould of required geometrical shape, this geometrical shape is Common Shape structure such as hexahedron both, also other polymorphic structure, and its structure depends on mould.The mud shape compound that adds half in mould uses the wooden mallet ramming process with half storey blank under forming in mould earlier.Its ramming is around the first ramming and four jiaos again in the middle of the ramming in proper order, and ramming finishes the back with the surface that instrument scratches this time half storey blank, the engagement about being beneficial between two blanks.Reinforced by above-mentioned steps again, half storey blank on the ramming, finish whole blank even closely knit after, the refacing and the demoulding.
Drying is carried out in mullite brick adobe after the demoulding, and the temperature of bake drying is controlled at 40 ℃-60 ℃, so that the thorough volatilization of moisture content.Hyperthermia tunnel Kiln is sent in dried adobe sintered into the anti-corrosion mullite brick finished product.The high temp tunnel sintering oven is divided into three zones, total length 80m, and wherein the preheating head of district is 32m, and the high temperature sintering head of district is 20m, and the cooling head of district is 28m.Adobe is 75 hours from advancing kiln to the kiln discharge firing period.
The preheating zone progressively preheats dried anti-corrosion mullite brick base to 1250 ℃ from bake out temperature, the time of preheating is 30 hours, it is longer that this time accounts for total sintering time, wherein temperature rises to 800 ℃ preheating between temperature raising period, has got rid of the water of constitution in intravital free water of adobe and the each component raw material mineral substance; 800 ℃ of-1250 ℃ of whipping agents are burnt loses volatilization, and the base substrate equilibrium is heated, and the intravital pore of base forms, and apparent porosity is the highest.
The high-temperature zone sintering time is 18 hours, wherein from 1250 ℃ be warming up to 1450 ℃ 8 hours consuming time, each feed composition mineral solid state reaction begins during this period, the base substrate apparent porosity descends, volume density raises, high temperature break resistant intensity and compressive strength begin to improve.Continuation with the adobe material from 1450 ℃ of heat temperature raisings to 1500 ℃, heating-up time is 6 hours, the spread coefficient of each component raw material increases in this process, the carrying out that helps the mullite building-up reactions, acceleration of sintering, amount of liquid phase under the high temperature increases simultaneously, the generation that helps mullite crystal grain with grow up, promoted combining closely of matrix and crystal grain, especially the brick surface has formed the very big glaze shape material of viscosity in this process, this glaze shape material is wrapped in the glassy anti-erosion layer that does not come the brick outside surface with formation after cooling, make mullite brick have the ability that extremely strong anti-objectionable impurities is invaded.
After mullite brick was finished sintering, goods were cooled to 1350 ℃, and the cooling soaking time is 4 hours; Last mullite brick enters the cooling zone, makes mullite brick progressively reduce to normal temperature from 1350 ℃, and this temperature fall time is 27 hours, to the slow cooling of mullite brick finished product, avoids the generation of brick body and brick surface crack.This anti-corrosion mullite brick is not only applicable to the heat recovery coke oven of various types, can also be widely used in industrial furnaces such as hotblast stove, pyrolyzer.
Embodiment 2
In a sintering batch, the preparation raw material gross weight of its mullite is 25T, wherein calcium hexaluminate account for the raw material gross weight 10%, andaluzite 15%, sillimanite 8%, aluminium oxide powder 8%, trichroite 16%, agalmatolite 24%, kaolin 13%, zirconium white 3%, whipping agent 2%, wedding agent 1%.Wherein refractory oxide is a zirconium white; EPS expanded plastic particle in the whipping agent account for preparation raw material gross weight 0.2%, wood sawdust 1.8%; Wedding agent adopts yellow starch gum.
The calcium hexaluminate granularity that above-mentioned preparation raw material is selected for use is 1mm; The andaluzite granularity is 0.2mm; The sillimanite granularity is 0.075mm; The aluminium oxide powder granularity is 3um; The trichroite granularity is 0.064mm; Agalmatolite granularity 0.175mm; The kaolin granularity is 0.043mm; Zirconium white granularity 0.043mm; The EPS expanded plastic is surmised 0.5mm.
After above-mentioned preparation raw material is got the raw materials ready by its proportioning and granularity requirements, earlier sillimanite, alchlor, trichroite, agalmatolite, kaolin, zirconium white and yellow starch gum are put in the lump and carried out dry grinding in the shredder 2 hours, above-mentioned raw materials is fully ground stir, and make the matrix material.
Again calcium hexaluminate and andaluzite are fed in the mixing pan in the lump and mix after 5-10 minute, add a spot of water, make it surface wettability, and make granulated aggregate.To grind the matrix prepared material joins and proceeds mixed grind in the lump with granulated aggregate in the mixing pan and stir, and formation granulated aggregate and matrix material mix the compound of parcel, in this compound, add the whipping agent that is mixed by EPS expanded plastic particle and wood sawdust again and add quantitative water, this gauge water is the 23%-27% of compound gross weight, evenly stirred 15-20 minute, can be used for making the mud shape compound of adobe with formation.This mud shape compound was left standstill after the discharging from mixing pan 10 hours, moisture content is penetrated in the raw material full and uniformly.
Raw material after leaving standstill is carried out base.Prepare the mould of required geometrical shape, in mould, add the mud shape compound of half, use the wooden mallet ramming process earlier with half storey blank under in mould, forming.Its ramming is around the first ramming and four jiaos again in the middle of the ramming in proper order, and ramming finishes the back with the surface that instrument scratches this time half storey blank, the engagement about being beneficial between two blanks.Reinforced by above-mentioned steps again, half storey blank on the ramming, finish whole blank even closely knit after, the refacing and the demoulding.
Drying is carried out in mullite brick adobe after the demoulding, and the temperature of bake drying is controlled at 40 ℃-60 ℃, so that the thorough volatilization of moisture content.Hyperthermia tunnel Kiln is sent in dried adobe sintered into the anti-corrosion mullite brick finished product.The high temp tunnel sintering oven is divided into three heating regions, total length 80m, and wherein the preheating head of district is 32m, and the high temperature sintering head of district is 20m, and the cooling head of district is 28m.Adobe is 75 hours from advancing kiln to the kiln discharge firing period.
The preheating zone progressively preheats dried mullite adobe to 1250 ℃ from bake out temperature, the time of preheating is 30 hours, it is longer that this time accounts for total sintering time, wherein temperature rises to 800 ℃ preheating between temperature raising period, has got rid of the water of constitution in intravital free water of adobe and the each component raw material mineral substance; 800 ℃ of-1250 ℃ of whipping agents are burnt loses volatilization, and the base substrate equilibrium is heated, and the intravital pore of base forms, and apparent porosity is the highest.
The high-temperature zone sintering time is 18 hours, wherein from 1250 ℃ be warming up to 1450 ℃ 8 hours consuming time, each feed composition mineral solid state reaction begins during this period, the base substrate apparent porosity descends, volume density raises, high temperature break resistant intensity and compressive strength begin to improve.Continuation with the adobe material from 1450 ℃ of heat temperature raisings to 1500 ℃, heating-up time is 6 hours, the spread coefficient of each component raw material increases in this process, the carrying out that helps the mullite building-up reactions, acceleration of sintering, amount of liquid phase under the high temperature increases simultaneously, the generation that helps mullite crystal grain with grow up, promoted combining closely of matrix and crystal grain, especially the brick surface has formed the very big glaze shape material of viscosity in this process, this glaze shape material is wrapped in the glassy anti-erosion layer that does not come the brick outside surface with formation after cooling, make mullite brick have the ability that extremely strong anti-objectionable impurities is invaded.
After mullite brick was finished sintering, goods were cooled to 1350 ℃, and the cooling soaking time is 4 hours; Last mullite brick enters the cooling zone, makes mullite brick progressively reduce to normal temperature from 1350 ℃, and this temperature fall time is 27 hours, to the slow cooling of mullite brick finished product, avoids the generation of brick body and brick surface crack.
Embodiment 3
In a sintering batch, the preparation raw material gross weight of its mullite is 25T, wherein calcium hexaluminate account for the raw material gross weight 15%, andaluzite 15%, sillimanite 8%, aluminium oxide powder 5%, trichroite 12%, agalmatolite 27%, kaolin 10%, magnesium oxide 5%, whipping agent 1%, wedding agent 2%.Wherein refractory oxide is a magnesium oxide, also can be calcium oxide; EPS expanded plastic particle in the whipping agent account for preparation raw material gross weight 1%, wood sawdust 4%; Wedding agent adopts calcium lignin sulphonate.
The calcium hexaluminate granularity that above-mentioned preparation raw material is selected for use is 2mm; The andaluzite granularity is 1mm; The sillimanite granularity is 0.062mm; The aluminium oxide powder granularity is 5um; The trichroite granularity is 0.044mm; Agalmatolite granularity 0.074mm; The kaolin granularity is 0.038mm; Magnesium oxide granularity 0.038mm; The EPS expanded plastic is surmised 3mm.
After above-mentioned preparation raw material is got the raw materials ready by its proportioning and granularity requirements, earlier sillimanite, alchlor, trichroite, agalmatolite, kaolin, magnesium oxide and calcium lignin sulphonate are put in the lump and carried out dry grinding in the shredder 2 hours, above-mentioned raw materials is fully ground stir, and make the matrix material.
Again calcium hexaluminate and andaluzite are fed in the mixing pan in the lump and mix after 5-10 minute, add a spot of water, make it surface wettability, and make granulated aggregate.To grind the matrix prepared material joins and proceeds mixed grind in the lump with granulated aggregate in the mixing pan and stir, and formation granulated aggregate and matrix material mix the compound of parcel, in this compound, add the whipping agent that is mixed by EPS expanded plastic particle and wood sawdust again and add quantitative water, this gauge water is the 23%-27% of compound gross weight, evenly stirred 15-20 minute, can be used for making the mud shape compound of adobe with formation.This mud shape compound was left standstill after the discharging from mixing pan 12 hours, moisture content is penetrated in the raw material full and uniformly.
Raw material after leaving standstill is carried out base.Prepare the mould of required geometrical shape, in mould, add the mud shape compound of half, use the wooden mallet ramming process earlier with half storey blank under in mould, forming.Its ramming is around the first ramming and four jiaos again in the middle of the ramming in proper order, and ramming finishes the back with the surface that instrument scratches this time half storey blank, the engagement about being beneficial between two blanks.Reinforced by above-mentioned steps again, half storey blank on the ramming, finish whole blank even closely knit after, the refacing and the demoulding.
Drying is carried out in anti-corrosion mullite brick adobe after the demoulding, and the temperature of bake drying is controlled at 40 ℃-60 ℃, so that the thorough volatilization of moisture content.Hyperthermia tunnel Kiln is sent in dried adobe sintered into the anti-corrosion mullite brick finished product.The high temp tunnel sintering oven is divided into three zones, total length 80m, and wherein the preheating head of district is 32m, and the high temperature sintering head of district is 20m, and the cooling head of district is 28m.Adobe is 75 hours from advancing kiln to the kiln discharge firing period.
The preheating zone progressively preheats dried mullite adobe to 1250 ℃ from bake out temperature, the time of preheating is 30 hours, it is longer that this time accounts for total sintering time, wherein temperature rises to 800 ℃ preheating between temperature raising period, has got rid of the water of constitution in intravital free water of adobe and the each component raw material mineral substance; 800 ℃ of-1250 ℃ of whipping agents are burnt loses volatilization, and the base substrate equilibrium is heated, and the intravital pore of base forms, and apparent porosity is the highest.
The high-temperature zone sintering time is 18 hours, wherein from 1250 ℃ be warming up to 1450 ℃ 8 hours consuming time, each feed composition mineral solid state reaction begins during this period, the base substrate apparent porosity descends, volume density raises, high temperature break resistant intensity and compressive strength begin to improve.Continuation with the adobe material from 1450 ℃ of heat temperature raisings to 1500 ℃, heating-up time is 6 hours, the spread coefficient of each component raw material increases in this process, the carrying out that helps the mullite building-up reactions, acceleration of sintering, amount of liquid phase under the high temperature increases simultaneously, the generation that helps mullite crystal grain with grow up, promoted combining closely of matrix and crystal grain, especially the brick surface has formed the very big glaze shape material of viscosity in this process, this glaze shape material is wrapped in the glassy anti-erosion layer that does not come the brick outside surface with formation after cooling, make mullite brick have the ability that extremely strong anti-objectionable impurities is invaded.
After mullite brick was finished sintering, goods were cooled to 1350 ℃, and the cooling soaking time is 4 hours; Last mullite brick enters the cooling zone, makes mullite brick progressively reduce to normal temperature from 1350 ℃, and this temperature fall time is 27 hours, to the slow cooling of mullite brick finished product, avoids the generation of brick body and brick surface crack.