CN1315755C - Chromium-free monothilic refractory for melting furnace for waste and melting furnace for waste lined with the same - Google Patents

Chromium-free monothilic refractory for melting furnace for waste and melting furnace for waste lined with the same Download PDF

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CN1315755C
CN1315755C CNB2004800072610A CN200480007261A CN1315755C CN 1315755 C CN1315755 C CN 1315755C CN B2004800072610 A CNB2004800072610 A CN B2004800072610A CN 200480007261 A CN200480007261 A CN 200480007261A CN 1315755 C CN1315755 C CN 1315755C
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melting furnace
refractory
raw material
quality
oxide
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CN1761634A (en
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津田秀行
北泽浩
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Krosaki Harima Corp
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
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    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
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Abstract

A chromium-free monothilic refractory for a melting furnace for a waste, which comprises a yttria based raw material as a refractory raw material component and an alumina based material as a main material and has a composition: Y2O3: 0.3 to 15 mass %, Al2O3: 85 mass % or more, as measured by the chemical analysis; and a melting furnace lined with the chromium-free monothilic refractory. The refractory exhibits the durability comparable to that of a conventional chromium-containing refractory.

Description

Waste melting furnace is the waste melting furnace of liner with the unshape refractory that does not contain chromium and with it
Technical field
The present invention relates to a kind of unshape refractory that does not contain chromium that is used for gasification and melting stove, ash fusion stove the like waste melting furnace liner and be the waste melting furnace of liner with it.
Background technology
As to the subtracting appearanceization and suppress the very useful offal treatment stove of generation of two   of discarded object, in recent years, occurred directly with the melting furnace of castoff fusing or with the ash fusion stove of the burning ash fusion of discarded object.
These waste melting furnaces are (hereinafter referred to as melting furnace.) slag composition contain much alkali from the waste composition, and because the operation of melting furnace is under the harsh working conditions of ultrahigh-temperature more than 1300 ℃, so the loss of the refractory materials of liner is very obvious.
The refractory materials that is used for melting furnace is broadly divided into amorphous refractory and unshape refractory.The construction of amorphous refractory is attended by piling up of brick, needs the technology of heavy physical labour and height.Therefore, in recent years, with unshape refractory as liner by general.
In the past, the unshape refractory that always is used for melting furnace be aluminum oxide-chromic oxide material (opening flat 10-324562 communique) representative with reference to the spy contain the chromic oxide product.This material is followed the slag resistance of resistivity against fire, volume stability and the chromic oxide of aluminum oxide, has shown good resistance to fouling.But, be converted into harmful Cr VI as the chromium oxide of a refractory material composition part, so that the refractory material after the slag of discharging and the use brings the problem of environmental pollution from stove.
Therefore, as the melting furnace unshape refractory, proposed not conform in fact the Chrome-free material of chromic oxide raw material.As aluminium oxide-zirconium oxide material (opening the 2000-281455 communique) with reference to the spy, aluminum oxide-magnesium material (opening the 2001-153321 communique), aluminum oxide-silicon carbide-material (opening the 2000-203952 communique) with reference to the spy with reference to the spy.
But when above Chrome-free material was used as melting furnace, its wearing quality can not show a candle to and contains the chromic oxide product.The slag of melting furnace is a high alkalinity, and aluminium oxide-zirconium oxide material or the aluminum oxide-zirconium composition of magnesium oxide material, magnesium component are dissolved in the slag, cause the resistance to fouling variation.As for the siliceous material of aluminum oxide-titanium carbide-because melting furnace be operating as oxidizing atmosphere, so the oxidized decomposition of silicon carbide composition makes the reduction highly significant of resistance to fouling.
Summary of the invention
The present invention to be to provide the liner as melting furnace, has with the unshape refractory that does not contain chromium that contains the same outstanding wearing quality of chromic oxide product and is that the melting furnace of liner is a problem with it.
Waste melting furnace of the present invention is characterized in that with the unshape refractory that does not conform to chromium, as the fire resistance raw material, contains the yttria raw material and as the aluminum oxide raw material of main material, the chemical analysis value is Y 2O 3: 0.3～15 quality %, Al 2O 3: 85 quality % or higher.
Chrome-free material before above-mentioned is to combine with zirconium white, magnesium oxide or the silicon carbide of aluminum oxide a great deal of.Relative therewith, Chrome-free material of the present invention is the yttrium oxide raw material that contains specified quantitative in the aluminum oxide main material.Therefore, although be the Chrome-free material, brought into play outstanding durability as melting furnace with liner.Its reason is considered as follows.
Waste melting furnace contains alkali (Na in operation 2O+K 2O): the slag of 1.5～15 quality % can pass through in stove.The melting furnace slag is that the service temperature of high alkalinity and smelting furnace is a ultrahigh-temperature as previously mentioned, so the viscosity during fusion is very little.Moreover alkali has very strong erosion action for refractory materials.The unshape refractory that does not contain chromium in the past is because the slag viscosity of melting furnace is low, and the alkali composition can deeply be penetrated in the refractory materials tissue and go, and the wearing quality of refractory materials is greatly reduced.
Therewith relative, refractory material of the present invention, the combination of yttria raw material and aluminum oxide raw material by specified quantitative, the Y of yttria raw material under the high temperature in refractory material uses 2O 3The Al of composition and aluminum oxide raw material 2O 3Composition reacts, and has generated the YAG (yttrium-aluminium-garnet: Y of macromolecule 3Al 5O 12), make the matrix of refractory material become densified.
Have, refractory material of the present invention is because the Y of yttria raw material again 2O 3The reaction of composition and melting furnace slag, the viscosity of the slag that contacts with the refractory material working face increases, and has prevented soaking into of slag, and the reaction speed of slag and refractory material is slack-off in addition, has suppressed the erosion of refractory material.
The key element that improves the refractory materials wearing quality also has anti-bursting apart property except resistance to fouling.Because the operating temperature of melting furnace is 1300 ℃ or higher superhigh temperature, and the furnace wall generally adopts water-cooling structure, so refractory material becomes very big in furnace wall thickness direction thermograde in use, bursts apart easily.
Refractory material of the present invention is because Al 2O 3Content is 85 quality % or higher nearly, Al 2O 3The volume stability excellence that composition self has.And because the generation of above-mentioned YAG makes the matrix densification that becomes, the void content of refractory materials tissue is low, the thermal conductivity height.Thus, refractory materials of the present invention thermograde on the furnace wall thickness direction in use diminishes, and bursting apart property of antagonism has produced good effect.
And, contained Y from the yttria raw material in the refractory material of the present invention 2O 3Composition has the low character of overbasic melting furnace slag solubility.So, do not have the Y from refractory material matrix 2O 3The excessive stripping of composition is so that Y 2O 3It is big that the slag viscosity that composition causes becomes, and the effect of corrosion resistance raising is continued thus.
Slag viscosity becomes the big effect that slag soaks into of preventing that produces and becomes the same of branch generation with the chromic oxide of former aluminum oxide-chromic oxide fire resistant materials, but, the chromic oxide composition is different with the yttrium oxide raw material, environmental pollution problems is arranged, can not obtain the antipollution effect of Chrome-free material of the present invention.
The present invention uses rich yttrium mixed rare earth oxide also passable as the yttria raw material.When the chemical composition value of this rich yttrium mixed rare earth oxide is removed principal component Y 2O 3Comprise from Gd outward, 2O 3, Er 2O 3, Dy 2O 3, Yb 2O 3In when selecting more than one 5～35 quality %, can be further enhanced to corrosion resistance and the anti-slag impregnability of the distinctive high alkalinity slag of melting furnace.This thinks what following reason caused.
Under the high temperature during refractory material uses, the Gd in the rich yttrium mixed rare earth oxide 2O 3, Er 2O 3, Dy 2O 3, Yb 2O 3Composition and Y 2O 3Equally with the Al of aluminum oxide raw material 2O 3React, generated the Y with garnet structure of macromolecule 3Al 5O 12, Er 3Al 5O 12, Dy 3Al 5O 12, Yb 3Al 5O 12In addition, Gd 2O 3And Al 2O 3Reaction becomes the Gd with perovskite structure 2Al 2O 6Like this, the garnet structure of this macromolecule or perovskite structure make refractory material dense structure, and, because Gd 2O 3, Er 2O 3, Dy 2O 3, Yb 2O 3Self have outstanding alkali resistance, corrosion resistance also is improved.
Moreover, except principal component Y 2O 3Contain Gd outward, 2O 3, Er 2O 3, Dy 2O 3, Yb 2O 3In this richness yttrium mixed rare earth oxide and Y of one or more 5～35 quality % 2O 3The yttria that purity is high is compared and the Al of aluminum oxide raw material 2O 3The composition reaction wants fast, and the lower working face organization in the rear of its temperature also can be fully densified when refractory material used, and the anti-slag impregnability can further improve.
The object lesson of yttria raw material used in the present invention can from above yttria, be selected one or more in the middle of the rich yttrium mixed rare earth oxide etc.Y 2O 3Purity without limits, such as, although Y 2O 3Purity only be 70 quality % degree, also can use as not containing special harmful components.But the preferred stable high-purity raw of service property (quality).Contain Gd 2O 3, Er 2O 3, Dy 2O 3, Yb 2O 3In in the rich yttrium mixed rare earth oxide of one or more 5～35 quality %, Y 2O 3The purity lower limit for example also can be 50 quality %.
Y when the use amount of yttria raw material is adjusted into and forms all chemical composition value representations with unshape refractory 2O 3: 0.3～15 quality %.More preferably 0.5～10 quality %.Y 2O 3Ratio as being lower than this scope, then can not obtain corrosion resistance of the present invention, the effect of anti-slag impregnability and anti-bursting apart property is such as too high then Y 2O 3And Al 2O 3Reaction product increase, densified too much, anti-bursting apart property variation.
For making the Y with the chemical composition value representation 2O 3Ratio in this scope, can be by adjusting use amount and the Y of yttria raw material 2O 3Purity carry out.When using high-purity yttria raw material, the use amount of yttria raw material is exactly the Y with the chemical composition value representation basically 2O 3Ratio.
Rich yttrium mixed rare earth oxide is except Y 2O 3Comprise and be selected from Gd outward, 2O 3, Er 2O 3, Dy 2O 3, Yb 2O 3In one or more raw material.Though can obtain from sintetics and thick smart rare-earth oxide, from considering preferred thick smart rare-earth oxide economically.
Thick smart rare-earth oxide is to carry out the refining raw material of process midway of rare earth element from rare earth ore.As to xenotime [Y (PO 4)] etc. with Y 2O 3Processing what obtain for the rare earth ore of principal component with acid, alkali is exactly to remove dephosphorization, the thick smart rare-earth oxide of alkaline-earth metal etc.
For rich yttrium mixed rare earth oxide, be preferably to contain with the chemical composition value representation and be selected from Gd 2O 3, Er 2O 3, Dy 2O 3, Yb 2O 3In one or more, content is 5～35 quality %, more preferably content is 10～30 quality %.Be selected from Gd 2O 3, Er 2O 3, Dy 2O 3, Yb 2O 3During one or more less thaies 5 quality %, corrosion resistance and anti-slag impregnability special variation not the when using the high-purity yttria.As surpassing 35 quality %, then because Y 2O 3Ratio descend the corrosion resistance variation.
For rich yttrium mixed rare earth oxide, Y 2O 3Ratio be preferably 50 quality % or higher, more preferably 60 quality % or higher.Y 2O 3Upper limit ratio according to Gd 2O 3, Er 2O 3, Dy 2O 3, Yb 2O 3Proportion is naturally determined, is had no particular limits, such as being 95 quality % or 90 quality %.
In addition, thick smart rare earth oxide contains the Nd from ore inevitably 2O 3, La 2O 3, CeO 2Composition.Construction water when these compositions and unshape refractory construction reacts, and is accompanied by the reason of the fragility that digests the caused refractory material of expansion that produces when becoming the construction drying.On the other hand, because CeO 2Be soluble in the overbasic slag.Therefore, preferred thick smart rare earth oxide Nd 2O 3, La 2O 3, CeO 2One or more content is 15 quality % or lower.
In order to improve the reactivity with aluminum oxide, the granularity of yttrium oxide raw material is particulate preferably.Such as 100 μ m or littler, average preferred 1～45 μ m.Form the aluminum oxide raw material of major ingredient as the resistivity against fire raw material, no matter be electricity melt aluminum oxide, sintered alumina, red bauxite or with these regenerant as the refractory materials of main raw material is any can.These raw materials will suitably be adjusted into coarse grain, and middle grain and particulate use.The micro mist part also can be used facile calcined alumina as Ultramicro-powder.
The use amount of aluminum oxide raw material preferably is adjusted into and accounts for all Al with the chemical analysis value representation of unshape refractory composition 2O 3: 85 quality % or higher.Such as Al 2O 3Ratio be lower than this scope and then can not obtain corrosion resistance of the present invention and anti-bursting apart property.Al 2O 3Ratio 90～99.7 quality % more preferably.
For making the Al of aluminum oxide raw material 2O 3Composition reaches above-mentioned ratio, mainly is the Al by the aluminum oxide raw material 2O 3Purity and its usage ratio decide.For example, when using high-purity alpha-alumina, in fact the use amount of aluminum oxide raw material is exactly the Al with the chemical composition value representation 2O 3Ratio.
When in adhesive described later, using the aluminium oxide concrete, although amount seldom, also provide Al from the aluminium oxide concrete 2O 3Composition.The aluminium oxide concrete generally contains the Al of 55～80 quality % 2O 3Al given to this invention 2O 3Ratio refer to account for the total ratio that forms of unshape refractory, come the concrete Al of self-alumina 2O 3Amount also should be included in.
Tackiness agent and the dispersion agent that adds in case of necessity with in the past in material employed there is no special different.Except that above-mentioned aluminum oxide concrete, phosphoric acid salt, silicate etc. in addition that tackiness agent can be enumerated.Consider preferential oxidation aluminium concrete from the intensity aspect of construction body.As for the usage quantity of tackiness agent, the resistivity against fire raw material is formed and the total amount of tackiness agent is that 100 quality % ratios are represented to account for, and is preferably 1～10 quality %.
Dispersion agent has makes unshape refractory have mobile effect when construction.Various scheme about the dispersion agent material was proposed up to now.The kind of dispersion agent is also unrestricted, as inorganic salt such as tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, super sodium polyphosphate, acidic sodium hexametaphosphate, Sodium Tetraborate, yellow soda ash, poly-metaphosphites, Trisodium Citrate, sodium tartrate, sodium polyacrylate, sodium sulfonate, polycarboxylate, the beta-naphthalenesulfonic-acid salt, naphthene sulfonic acid contains the polyethers dispersion agent of carboxyl etc.The total of relative resistivity against fire raw material of the usage quantity of dispersion agent and tackiness agent is measured 100 mass parts, preferred 0.01～1 mass parts.
In the scope of not damaging effect of the present invention, also can add the resistivity against fire raw material beyond the aluminum oxide, fire-resistant big particle, metal powder, glass, sclerosis conditioning agent, Aluctyl, organic fibre, dry promotor etc.Resistivity against fire raw material as beyond the aluminum oxide has magnesium oxide, spinel, volatile silica, silica, silicon-dioxide, titanium oxide, molybdenum oxide, Tungsten oxide 99.999, Columbium pentoxide, tantalum pentoxide etc.As metal powder Pure Silicon Metal, nickel, aluminium etc. are arranged.
In the construction, the water that forms about 100 mass parts adding, 3～7 mass parts with respect to above-mentioned unshape refractory mixes, and waters construction with model.To apply vibration during pouring so that fill.Want health, drying after the construction.Except directly pouring was constructed in stove, this construction also can be to construct at the prefabrication of stove inner lining at the products formed that other places pouring constructions obtain.In addition, also can make up pouring construction and prefabricated construction.
Have, the alleged Chrome-free of the present invention refers to be substantially devoid of chromic oxide again.General in the past contain the chromic oxide that the chromic oxide product contains 5～60 quality %.Even chromium oxide is at 1 quality % or lowlyer also can produce problem of environmental pollution.For obtaining the effect of Chrome-free, except inevitable, preferably do not contain chromium oxide.
Melting furnace generally is provided with refrigerating unit.Refrigerating unit for example is auxiliary facilities such as cold water pipe, cold water jacket, cooling air jacket, sprinkling filter.Unshape refractory of the present invention is specially adapted to the liner as the melting furnace of this this refrigerating unit of equipment because it has the effect of anti-bursting apart property.
The simple declaration of accompanying drawing
Fig. 1 represents Y 2O 3Account for the content of unshape refractory in forming and the graph of a relation of the corrosion resistance of unshape refractory.
Embodiment
Below be illustrated with regard to embodiments of the invention and comparative example thereof.Provided each routine test-results simultaneously.Table 1 is the chemical composition of each routine employed fire resistance raw material, and table 2 is embodiments of the invention, and table 3 is comparative example.
Table 1
Chemical ingredients (quality %)
SiO 2 Al 2O 3 Fe 2O 3 ZrO 2 Cr 2O 3 MgO SiC Y 2O 3 Gd 2O 3 Er 2O 3 Dy 2O 3 Yb 2O 3
Sintered alumina 0.1 99.7
Electricity melts aluminum oxide 0.1 99.4 0.1
Electricity melts zirconium white 0.1 0.3 0.1 98.6
Calcined polishing aluminum oxide 99.9
Sintered magnesia 1.0 0.1 0.1 97.2
Yttrium oxide 99.9
Rich yttrium mixed rare earth oxide compound A 72.2 4.8 3.8 6.3 2.9
Rich yttrium mixed rare earth oxide compound B 70.7 29.3
Silicon carbide 0.3 0.1 97.2
Chromic oxide 0.1 99.7
Chemical constitution is empty hurdle less than 0.1 quality %
Table 2
The embodiment of the invention
1 2 3 4 5 6 7 8 9
Unshape refractory forms The resistivity against fire raw material Electricity melts aluminum oxide 8～1mm 20 20 20 20 20 20 20 20 20
" 1mm or littler 23 23 23 23 23 23 23 23 23
Sintered alumina 8～1mm 20 20 20 20 20 20 20 20 20
" 1mm or littler 21.9 21.1 19.7 14.8 21 13 21 13 16.8
The average 1 μ m of Calcined polishing aluminum oxide 10 10 10 10 10 10 10 10 10
Sintered magnesia 1mm or littler 2
Yttrium oxide 45 μ m or littler 1.1 1.9 3.3 8.2 4.2
Rich yttrium mixed rare earth oxide compound A45 μ m or littler 2 10
Rich yttrium mixed rare earth oxide compound B45 μ m or littler 2 10
Wedding agent: aluminum oxide concrete 4 4 4 4 4 4 4 4 4
Dispersion agent: the polyethers that contains carboxyl (0.2) (0.2) (0.2) (0.2) (0.2) (0.2) (0.2) (0.2) (0.2)
The chemical constitution of unshape refractory (quality %) Al 2O 3 96.8 96 94.9 90.1 96 92.8 96 92.8 91.8
Y 2O 3 1.1 1.8 3.3 8.2 1.4 7.2 1.4 7.1 1.2
Amount of water (mass parts) 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5
Test Resistance to fouling (corroding size mm) 14 13 12 12 11 10 11 10 14
Bursting apart property of heat resistanceheat resistant ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎
The wearing quality of real machine test (the loss size mm/ month) 13 12
The ratio of dispersant is the mass parts of total amount 100 mass parts of relative fire resistance raw material and bond.
The water addition ratio example forms the mass parts of 100 mass parts for relative unshape refractory.
In the hurdle of result of the test, empty hurdle is not for doing experiment.
Table 3
Comparative example
1 2 3 4 5 6 7 8
Unshape refractory forms The resistivity against fire raw material Electricity melts aluminum oxide 8～1mm 20 20 20 20 20 10 10 40
" 1mm or littler 23 23 23 18 23 13 13 41
Sintered alumina 8～1mm 20 20 20 20 20 10 10
" 1mm or littler 23 3 6 3 5 13 13
Electricity melts zirconium white 8～1mm 20
" 1mm or littler 20
Silicon carbide 8～1mm 20
" 1mm or littler 20
The average 1 μ m of Calcined polishing aluminum oxide 10 10 10 10 10 10 10 5
Sintered magnesia 1mm or littler 15 18
The average 1 μ m or littler of chromic oxide 10
Yttrium oxide 45 μ m or littler 20 2
Rich yttrium mixed rare earth oxide compound A45 μ m or littler 25
Wedding agent: aluminum oxide concrete 4 4 4 4 4 4 4 4
Dispersion agent: the polyethers that contains carboxyl (0.2) (0.2) (0.2) (0.2) (0.2) (0.2) (0.2) (0.2)
The chemical constitution of unshape refractory (quality %) Al 2O 3 97.9 78.1 81 73.1 80 58.5 58.5 88.5
Y 20 3 19.9 1.9 18.1
Amount of water (mass parts) 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5
Test Resistance to fouling (corroding size mm) 23 18 19 18 35 45 42 12
Bursting apart property of heat resistanceheat resistant ◎ × × × × △ ◎ ×
The wearing quality of real machine test (the loss size mm/ month) 50 46 15
The ratio of dispersant is the mass parts of total amount 100 mass parts of relative fire resistance raw material and bond.
The water addition ratio example forms the mass parts of 100 mass parts for relative unshape refractory.
In the hurdle of result of the test, empty hurdle is not for doing experiment.
For unshape refractory shown in each routine table 2, the table 3 form mix with mixer after, pour in the metal pattern, to apply vibration to promote the filling of construction object to model during pouring.Carry out 24 hours health subsequently, carry out 110 ℃ * 24 hours drying after the demoulding again.
Resistance to fouling will have been carried out the rotation erosion test by the standard square size of the 230mm * 114mm * 65mm resulting moulding product of constructing as sample with above-mentioned condition.Etchant has used the chemical ingredients value to be SiO 2: 42.8 quality %, CaO:31.7 quality %, Al 2O 3: 12.4 quality %, Fe 2O 3: 4.8 quality %, Na 2O:3.7 quality %, K 2O:1.1 quality %, Cl:0.9 quality %, (CaO/SiO 2: gasification and melting stove slag 0.74).After corroding in 1600 ℃ * 30 hours, measured the erosion size.
Bursting apart property of heat resistanceheat resistant, same as described above, the moulding product that obtain to construct by the standard square size are as sample, in electric furnace, carry out 1400 ℃ * 15 minutes heating with the one side of relative length direction after, force air cooling, after repeating 10 such heating-coolings, estimate by following 4 grades according to the be full of cracks situation of sample.◎ ... almost not be full of cracks.Zero ... have trickle be full of cracks to take place.△ ... it is very big to chap.* ... be full of cracks is greatly or peel off.
As real machine test, in be lining in average every day and handling 100t rubbish and be equipped with in the gasification and melting stove of chilled water unit at sidewall.Use after 12 months, measured loss rate (the mm/ month).About 1400 ℃ of service temperature.
Shown in test-results, the unshape refractory of making according to embodiments of the invention all has outstanding resistance to fouling and resists bursting apart property regardless of any.Although not expression in the table, the slag of working face soaks into little, and this also can think has contribution to the effect that improves corrosion resistance.Have, with the embodiment that rich yttrium mixed rare earth oxide compound uses as the yttrium oxide raw material, its resistance to fouling is outstanding again.
Relative therewith, comparative example 1 its slag of trioxygen-containingization two yttrium raw materials does not soak into greatly, and resistance to fouling is poor.Y 2O 3Composition surpasses comparative example 2 and comparative example 4 its corrosion resistances of limited range of the present invention and resists bursting apart property all poor.Comparative example 3 and Al that alumina content is few 2O 3Content be less than limited range of the present invention and also do not contain comparative example 5 its corrosion resistances of yttria raw material, anti-bursting apart property is all poor.
Contain zirconia, Al 2O 3Content is less than the comparative example 6 of limited range of the present invention, and silicon carbide-containing, Al 2O 3It is all very poor that content is less than comparative example 7 its corrosion resistances of limited range of the present invention.
Though there is chromic generation problem in comparative example 8 because of the high resistance to fouling of its chromic oxide content is good.Because the problem on the environment can not obtain as the effect of the present invention that does not contain chromium.In addition, poor because of its anti-bursting apart property, when for sidewall the melting furnace of chilled water unit being housed, probably can there be the damage of bursting apart.
About real machine test, the embodiment of the invention 1,5 is compared with the aluminium oxide-zirconium oxide material of comparative example 6, the aluminum oxide-silicon carbide-material of comparative example 7, and wearing quality is far better.
The embodiment of the invention 1,5 is compared with the aluminium oxide-zirconium oxide material of comparative example 8, though its resistance to fouling is slightly poor, perhaps because anti-bursting apart property is good, so the wearing quality of real machine test there is no big difference.
Fig. 1 represents to consist of the basis with the unshape refractory of embodiment 1, changes the Y of formed body 2O 3Group component is (with Y 2O 3Amount is as the criterion, increase and decrease Al 2O 3), Y 2O 3The figure of the relation between amount and the refractory material corrosion resistance.From then on figure result can confirm Y 2O 3Ratio is within the scope of the invention favourable to corrosion resistance.
The offal treatment stove is different with incinerator, is high-temperature operation, and the loss mechanism of its refractory materials is to be that the offal treatment stove of cause is peculiar with the high-alkali slag from the waste composition.Unshape refractory of the present invention as offal treatment stove unshape refractory, although be the Chrome-free material, brought into play and has been contained the wearing quality that the chromic oxide product is equal to mutually shown in the test-results of above-mentioned embodiment.
Industrial applicibility
Waste melting furnace is with melting furnace or ash fusion stove and known. The unshape refractory that does not contain chromium involved in the present invention is used as the inner lining material of such waste melting furnace.

Claims (4)

1. waste melting furnace is characterized in that with not containing the unshape refractory of chromium, forms as the fire resistance raw material, contains the yttria raw material and as the aluminum oxide raw material of main material, this unshape refractory has the Y with the chemical analysis value representation 2O 3: 0.3～15 quality %, Al 2O 3: 85 quality % or higher composition.
2. according to the waste melting furnace unshape refractory that does not contain chromium of claim 1 record, wherein, the yttrium oxide raw material is one or more that select from yttrium oxide and rich yttrium mixed rare earth oxide compound.
3. according to the castoff fusing inner lining of furnace unshape refractory that does not contain chromium of claim 1 or 2 records, wherein, waste melting furnace is for making the Na that contains as alkali in the operation 2O and K 2The content of O is the waste melting furnace that the slag of 1.5～1 5 quality % passes through in stove.
4. waste melting furnace, it is that the unshape refractory that does not contain chromium with each record of claim 1 to 3 carries out liner by pouring construction and/or prefabricated construction and forms.
CNB2004800072610A 2003-03-31 2004-03-30 Chromium-free monothilic refractory for melting furnace for waste and melting furnace for waste lined with the same Expired - Fee Related CN1315755C (en)

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US8278231B2 (en) 2008-11-24 2012-10-02 Exxonmobil Chemical Patents Inc. Heat stable formed ceramic, apparatus and method of using the same
US8512663B2 (en) 2009-05-18 2013-08-20 Exxonmobile Chemical Patents Inc. Pyrolysis reactor materials and methods
US8450552B2 (en) 2009-05-18 2013-05-28 Exxonmobil Chemical Patents Inc. Pyrolysis reactor materials and methods
JP5271239B2 (en) * 2009-11-24 2013-08-21 黒崎播磨株式会社 Furnace
CN105503241B (en) * 2015-12-21 2018-04-17 四川欣意迈科技有限公司 A kind of manganese mud foaming rare-earth ceramic section bar and preparation method thereof
EP3453689B1 (en) * 2017-09-08 2020-08-26 AGC Ceramics Co., Ltd. High-zirconia electrocast refractory and method for manufacturing the same
CN110041087B (en) * 2019-05-16 2022-09-20 鞍山市和丰耐火材料有限公司 Chromium-free brick for vacuum treatment of silicon steel and production method thereof
WO2023094437A1 (en) * 2021-11-26 2023-06-01 Topsoe A/S Refractory product and its use
CN115286405B (en) * 2022-08-25 2023-03-24 宜兴瑞泰耐火材料有限公司 Low-aluminum mullite brick with high molybdenum waste liquid corrosion resistance and preparation method thereof
CN115745636A (en) * 2022-12-07 2023-03-07 无锡远能耐火材料有限公司 Acid-resistant salt-resistant modified corundum brick for rotary kiln of hazardous waste incineration system and preparation method thereof

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