CN101134676A - Fire resistive material for coke oven door - Google Patents
Fire resistive material for coke oven door Download PDFInfo
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- CN101134676A CN101134676A CNA2006100305950A CN200610030595A CN101134676A CN 101134676 A CN101134676 A CN 101134676A CN A2006100305950 A CNA2006100305950 A CN A2006100305950A CN 200610030595 A CN200610030595 A CN 200610030595A CN 101134676 A CN101134676 A CN 101134676A
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Abstract
The refractory material for coke oven door consists of mullite 42-63 wt%, cordierite 20-30 wt%, micro silica powder 5-10 wt%, micro active alumina powder 4-8 wt%, kyanite 3-7 wt%, high alumina cement 3-5 wt%, and composite polyphosphate 0.2-0.5 wt%. The mullite is M60 mullite containing Al2O3 not less than 60 wt%, the cordierite contains Al2O3 33-35 wt% and MgO 13-15 wt%, the micro silica powder contains SiO2 not less than 92 wt%, the micro active alumina powder contains Al2O3 more than 98 wt%, the high alumina cement contains Al2O3 not less than 46 wt%, CaO not more than 40 wt% and SiO2 not more than 10 wt%. The refractory material may be produced into coke oven door through low temperature roasting without need of backing, and the coke oven door has service life over 4 years.
Description
Technical field
The present invention relates to a kind of refractory materials, relate in particular to a kind of coke oven door refractory materials.
Background technology
Coke oven is the main equipment of coking, and its purposes is coking coal to be carried out destructive distillation obtain coke and other byproducts in coking chamber.Coke oven is in use operated the effects such as thermal stress, mechanical stress and chemical corrosion that cause continuously owing to coalingging, pluck door, coke pushing etc., makes the fire door material often impaired.
Domestic existing coke oven door material is generally clay brick, trichroite brick, poly-light insulating brick, hollow float bead brick.But the thermal shock resistance performance of clay brick, poly-light cinder brick, hollow float bead brick is general; Though the heat retaining property of poly-light cinder brick and hollow float bead brick is good, apparent porosity is too high, and its inner lining surface is easy to infiltration knot carbon, and the intensity of poly-light cinder brick and hollow float bead brick is too low, is easy to during the dismounting fire door damage.And simple trichroite brick can not satisfy needs of production aspect intensity, because fire door clashes into fire door sometimes in frequent unlatching, especially the refractory materials well damage of fire door bottom often will be repaired.
Domestic coke oven door all adopts the form of fritter burnt brick, and the brickwork joint of fire door is on the high side, and the life-span is low, and maintenance capacity is also big.General about about 2 years of the clay fire door life-span, as occurring the phenomenon of unfilled corner, fracture midway, then to repair with the method for mould material teeming, the fire door after the repairing is also kept about half a year at most work-ing life.
Chinese patent 1562893A has introduced a kind of manufacture method of coke oven door brick, and it adopts mullite and trichroite is main raw material, is mixed with unsetting mould material, pours into furnace door brick, through 1300 ℃ burn till, makes finished product and is used on the fire door again.This patented technology is not introduced the technical performance index of any this finished product, and proportioning also is single ratio: mullite 51%, trichroite 35%, alundum cement 7% (Al
2O
375%), alumina powder 3%, silicon powder 4%.And what adopt in this patent is the high aluminous cement of alumina content, it has preferable performance when 1400 ℃ of high temperature use, but intensity is not high when low temperature, middle temperature, (1000 ℃) do not have too big advantage under the coke oven use temperature, intensity forms slowly during construction, and increases material cost.
Summary of the invention
The object of the present invention is to provide the good refractory materials of a kind of heat-insulating property and thermal shock resistance, can keep fire door work-ing life, double work-ing life than existing coke oven door more than 4 years.
For reaching above-mentioned purpose, the invention provides a kind of coke oven door refractory materials, its weight percentages of components is:
Mullite 42～63;
Trichroite 20～30;
Silicon powder 5～10;
Activated alumina micro mist 4～8;
Kyanite 3～7;
High-alumina cement 3～5;
Compound poly-phosphate+0.2～0.5.
Wherein, mullite is the M60 mullite, and its chemical ingredients is: Al
2O
3〉=60%; The trichroite chemical ingredients is: Al
2O
333～35%, MgO13～15%; The silicon powder chemical ingredients is: SiO
2〉=92%; Activated alumina micro mist chemical ingredients is: Al
2O
398%; The high-alumina cement chemical ingredients is: Al
2O
3〉=46%, CaO≤40%, SiO
2≤ 10%.
Preferably, silicon powder median size＜0.50 micron; Activated alumina micro mist median size＜5.0 microns; The fineness of kyanite is 0.045～0mm.
More preferably, compound poly-phosphate is tripoly phosphate sodium STPP and Sodium hexametaphosphate 99.
Below be the effect and the qualification explanation thereof of main raw material of the present invention:
Mullite 42～63 (wt%, below each raw material identical)
It is main raw material that the present invention selects mullite for use, and mullite is divided into electrofused mullite and fused mullite, in order to make material better thermal shock performance is arranged, and what the present invention selected for use is fused mullite.Moiety by mullite is divided, and M75 (Al is arranged
2O
3〉=75%) M70 (Al,
2O
3〉=70%) M60 (Al,
2O
3〉=60%) M45 (Al,
2O
343～45%) four kinds.The present invention selects the M60 fused mullite for use.Because the use temperature of fire door generally is no more than 1000 ℃, do not need with the very high raw material of fire performance, and high resistivity against fire raw materials cost is also very high; Mullite and trichroite raw material are used in addition, if it is too big that both volume densities differ, can cause segregation in the casting and constructing process of material, the mullite that volume density is big can sink to the bottom, the trichroite particle that volume density is little floats over prefabricated section top easily, even outstanding material surface, cause whole prefabricated section inhomogeneous.In addition, on mullite is selected, guarantee that the mullite mineral facies are many as far as possible in the raw material, mullite is 75～80% mutually in the M60 mullite raw material, is corundum phase and glassy phase on a small quantity.And M45 class mullite has only mullite phase 55% usually, and all the other are non-crystalline state SiO
2Reach 45% mutually.Non-crystalline state SiO
2Glassy phase causes the thermal shock resistance of material to worsen at 1000 ℃ of following life-time service meeting crystallizatioies.So take all factors into consideration the M60 mullite, wherein contain Al
2O
3〉=60%, be comparatively reasonably to select.In mould material, add with 8～3mm, 3～0mm and three granularity ranks of 0.088～0mm.
Trichroite 20～30wt%
Trichroite (2MgO2Al
2O
35SiO
2) have a good thermal property; Low thermal expansivity (25～1000 ℃ of average out to 1.5 * 10
-6℃); Higher decomposition temperature (1460 ℃).Because fire door material requirements thermal shock performance is very high, and use temperature is the application characteristic that is well suited for trichroite about 1000 ℃.It is Al that the raw material specification that adopts requires
2O
3: 33～35%, MgO:13～15%.Add-on is 20～30%, with the granularity adding of 3～0mm.Because trichroite is a porous class light material, suction especially easily during construction, if add-on is too many, then the needed amount of water of material is a lot, the intensity of material just reduces greatly like this, and thermal shock resistance also reduces on the contrary also not because the trichroite amount is improved more.
High-alumina cement 3～5wt%
It is wedding agent that the present invention adopts high-alumina cement, and high-alumina cement is to be the cement of essential mineral with calcium aluminate (CA), and CA has very high hydraulically active, and sclerosis is the early strong important mineralogical composition of cement rapidly.Granularity with 0.088～0mm adds.Fire door material of the present invention does not need to burn till in advance, and through just can directly using behind the low-temperature bake, sintering gradually under use temperature can form higher intensity.So at first require material early strength height.Require employed high-alumina cement Al
2O
3〉=46%, CaO≤40%, SiO
2≤ 10%; Drawing the high-alumina cement weight percent by test is 3%～5% o'clock, and mould material has optimum properties.As the cement add-on very little, the normal temperature strength of fire door refractory materials is not enough; Add-on is too many, and the CaO that brings in the material is too many, can influence the work-ing life of fire door.
Silicon powder 5～10wt%
SiO
2After the micro mist aquation is solidified, form the Si-OH base (silanol) of larger amt on the surface, the dehydration post polymerization forms the network-like micro mist chain of Si-O-Si bonded, makes mould material have higher intensity, and this structure can not improve with temperature and weaken.In order further to improve the construction flowing property of Castable on Gate, the silicon powder amount of adding has good flowing property in 5～10% scopes, during material also has preferably simultaneously, low temperature intensity.Silicon powder requires SiO2 〉=92%, micro mist median size＜0.50 micron.
Activated alumina micro mist 4～8wt%
For further strengthening matrix, improve coking property, the high-temperature behavior of mould material, in matrix, added the activated alumina micro mist.In use, the very high SiO of reactive behavior
2Micro mist and active A l
2O
3Micro mist can react and generate the mullite crystalline phase, helps improving thermal shock resistance and hot strength, adds the reactive sintering effect of micro mist, further promotes dense structureization, thereby has improved the wearing quality of material.The activated alumina micro mist requires Al
2O
398%, micro mist median size＜5.0 micron.Add-on 4～8%.The effect that add-on is brought into play less is not obvious, and add-on is too many, not only can increase the cost of material, and the amount of water that when construction needs can increase, and influences its physicals.
Kyanite 3～7wt%
Because the required construction water yield of refractory castable of the present invention is more than general dense form refractory castable, so void content is more.Again because the activated alumina micro mist amount that adds is many, shrinkage crack can appear in life-time service under temperature variation repeatedly, therefore, add kyanite 3～7% among the present invention as swelling agent, it is at a certain temperature in the life-time service process, can change into the mullite crystalline phase, and volumetric expansion takes place, can reduce the contraction of fire door material.The kyanite fineness that adds is 0.045～0mm, can just take place to transform and expand under lower temperature.If add-on is too many, then the expansion of material is too big, influences its physicals on the contrary.
Compound poly-phosphate+0.2～0.5wt%
Add compound poly-phosphate among the present invention as water reducer, the results showed, adopt single phosphatic water-reducing effect to differ from more than 30% than compound poly-phosphate.Compound poly-phosphate of the present invention is tripoly phosphate sodium STPP and Sodium hexametaphosphate 99, adds composite phosphate 0.2～0.5%, and water-reducing effect is obvious.Compared with prior art, the invention has the advantages that: can pour into the prefabricated section of different shapes and size according to the needs of door structure, not need to burn till in advance, use through being installed on the fire door behind the low-temperature bake.When adding high-alumina cement 3～5wt%, mould material has optimum properties, prepared Castable on Gate intensity height, heat-shock resistance excellence, excellent thermal insulation performance.Door lining work-ing life is more than 2 times of clay brick life-span, and do not damage in use more than 4 years work-ing life, does not need to repair, and has excellent cost performance.
Embodiment
Describe the present invention with embodiment 1～3 below.
Wherein, table 1 is the chemical group submeter of embodiment 1～3 and comparative example, and table 2 is the performance perameter table of embodiment 1～3 and comparative example.
Table 1
| Raw material | Embodiment (wt%) | Comparative example | |||
| 1 | 2 | 3 | 1 1 | ||
| The M60 mullite | 8～3mm | 30 | 25 | 20 | 25 |
| 3～0mm | 10 | 10 | 10 | 10 | |
| 0.088～0mm | 23 | 17 | 12 | 14 | |
| Trichroite 3～0mm | 20 | 25 | 30 | 35 | |
| High-alumina cement 0.088～0mm | 5 | 4 | 3 | -- | |
| Aluminous cement | -- | -- | -- | 7 | |
| Silicon powder＜0.5 μ m | 5 | 8 | 10 | 5 | |
| Activated alumina micro mist＜5 μ m | 4 | 6 | 8 | 4 | |
| Kyanite 0.045～0mm | 3 | 5 | 7 | -- | |
| Tripoly phosphate sodium STPP | +0.1 | +0.15 | +0.25 | +0.15 | |
| Sodium hexametaphosphate 99 | +0.1 | +0.15 | +0.25 | +0.15 | |
Table 2
| Project | Embodiment | Comparative example | |||
| 1 | 2 | 3 | 1 | ||
| Volume density (g/cm 3) | 110℃×24h | 2.22 | 2.19 | 2.17 | 2.13 |
| 1100℃×3h | 2.18 | 2.16 | 2.15 | 1.98 | |
| Compressive strength MPa | 110℃×24h | 68.8 | 67.4 | 70.4 | 40.1 |
| 1100℃×3h | 106.0 | 98.5 | 113.1 | 43.7 | |
| The line velocity of variation, % % | 1100℃×3h | 0 | -0.1 | -0.1 | -0.5 |
| Thermal conductivity w/mk | 350℃×3h | 0.783 | 0.734 | 0.728 | 0.724 |
| Thermal shock resistance (inferior) | 1100 ℃-water-cooled | >80 | >80 | >80 | >45 |
Embodiment 1
As shown in table 1, the proportioning of embodiment 1 is as follows:
Mullite: 63wt%; Mullite is with 8～3mm; 3～0mm; 0.088 three kinds of particle size fractions of～0mm add, wherein: 8～3mm granularity be 30wt%; 3～0mm granularity be 10%; 0.088 that～0mm granularity is 23wt%.
Trichroite: 20%, granularity is 3～0mm;
High-alumina cement: 5%, granularity is 0.088～0mm;
Silicon powder: 5%, granularity is less than 0.5 micron;
The activated alumina micro mist: 4%, granularity is less than 5.0 microns;
Kyanite: 3%, granularity is between 0.045～0mm;
In addition, add tripoly phosphate sodium STPP 0.1% and Sodium hexametaphosphate 99 0.1%.Add water 7% in said components, pour into the test that standard test specimen carries out physicals, its technical indicator sees Table 2, and wherein: 110 ℃ * 24h is meant that sample has passed through 24 hours heat treatment process of drying under 110 ℃; 1100 ℃ * 3h is meant that sample has passed through and burns till 3 hours heat treatment process of insulation under 1110 ℃; 1100 ℃～water-cooled is meant that sample carries out the test conditions of thermal shock resistance test, and sample is put into water again and cooled off after burning till under 1100 ℃, burn 1100 ℃ again then after, put into water and cool off, so constantly recirculation is seen the number of times that sample can experience.Thermal conductivity is measured down at 350 ℃.
The volume density of embodiment 1, compressive strength and line velocity of variation see Table 2 under above-mentioned test conditions, through the thermal shock round-robin test under the 1100 ℃～water-cooled condition, passed through the thermal shock round-robin test more than 80 times, material does not damage, and has shown good heat-shock resistance.The embodiment material is below the 0.783w/mk 350 ℃ thermal conductivity after measured, illustrates that embodiment 1 has good heat-insulating property.
Embodiment 2
As shown in table 1, the proportioning of embodiment 2 following (wt% of unit):
Mullite: 52%; Wherein: 8～3mm granularity be 25%; 3～0mm granularity be 10%; 0.088～0mm granularity is 17%.
Trichroite: 25%, granularity is 3～0mm;
High-alumina cement: 4%, granularity is 0.088～0mm;
Silicon powder: 8%, granularity is less than 0.5 micron;
The activated alumina micro mist: 6%, granularity is less than 5.0 microns;
Kyanite: 5%, granularity is between 0.045～0mm;
In addition, add tripoly phosphate sodium STPP 0.15% and Sodium hexametaphosphate 99 0.15%.
In said components, add water 8%.Test conditions is with embodiment 1.
The volume density of embodiment 2, compressive strength and line velocity of variation see Table 2.Through the thermal shock round-robin test under the 1100 ℃～water-cooled condition, passed through the thermal shock round-robin test more than 80 times, material does not damage, and has shown good heat-shock resistance.The embodiment material is below the 0.734w/mk 350 ℃ thermal conductivity after measured, illustrates that embodiment 2 has good heat-insulating property too.
Embodiment 3
As shown in table 1, the proportioning of embodiment 3 following (wt% of unit):
Mullite: 42%; Wherein: 8～3mm granularity be 20%; 3～0mm granularity be 10%; 0.088～0mm granularity is 12%.
Trichroite: 30%, granularity is 3～0mm;
High-alumina cement: 3%, granularity is 0.088～0mm;
Silicon powder: 10%, granularity is less than 0.5 micron;
The activated alumina micro mist: 8%, granularity is less than 5.0 microns;
Kyanite: 7%, granularity is between 0.045～0mm;
In addition, add tripoly phosphate sodium STPP 0.25% and Sodium hexametaphosphate 99 0.25%.
In said components, add water 9%.Test conditions is with embodiment 1 and 2.
The volume density of embodiment 3, compressive strength and line velocity of variation see Table 2.Through the thermal shock round-robin test under the 1100 ℃～water-cooled condition, passed through the thermal shock round-robin test more than 80 times, material does not damage, and has shown good heat-shock resistance.The embodiment material is below the 0.728w/mk 350 ℃ thermal conductivity after measured, illustrates that embodiment 2 has good heat-insulating property too.
Below, the description and the Comparative Examples 1 of synopsis 1 and table 2 and the embodiment of the invention 1～3 compare:
Comparative example 1 has adopted aluminum oxide〉70% aluminous cement, added more cordierite, do not add kyanite with expansion.After the comparative example 1 material process thermal shock 45 times, sample has occurred than multiple cracks, and the particulate of coming off phenomenon is arranged.
Because comparative example 1 does not add the swelling agent kyanite, so the linear shrinkage after material burns is also bigger, door lining shrinks greatly during application, causes the fire door resistance to air loss bad easily.Comparative example 1 is Duoed more than 2% than embodiment material amount of water during construction, has influenced the physicals of material.Although the low cement coupling system of embodiment because the reasonably combined application of it and micro mist, still have very high in, low temperature intensity.Added kyanite again and used, made the bulk temperature of material also very good as swelling agent.Embodiment uses by various raw material scientific combination, has embodied the excellent comprehensive performance, and cost is also lower, is more suitable for using under the coke oven condition.
Claims (10)
1. a coke oven door refractory materials is characterized in that, its weight percentages of components is:
Mullite 42～63;
Trichroite 20～30;
Silicon powder 5～10;
Activated alumina micro mist 4～8;
Kyanite 3～7;
High-alumina cement 3～5;
Compound poly-phosphate+0.2～0.5.
2. coke oven door refractory materials as claimed in claim 1 is characterized in that, described mullite is the M60 mullite, and its chemical ingredients is: Al
2O
3〉=60%.
3. coke oven door refractory materials as claimed in claim 1 is characterized in that, described trichroite chemical ingredients is: Al
2O
333～35%, MgO 13～15%.
4. coke oven door refractory materials as claimed in claim 1 is characterized in that, described silicon powder chemical ingredients is: SiO
2〉=92%.
5. coke oven door refractory materials as claimed in claim 1 is characterized in that, described activated alumina micro mist chemical ingredients is: Al
2O
3＞98%.
6. coke oven door refractory materials as claimed in claim 1 is characterized in that, described high-alumina cement chemical ingredients is: Al
2O
3〉=46%, CaO≤40%, SiO
2≤ 10%.
7. as claim 1 or 4 described coke oven door refractory materialss, it is characterized in that described silicon powder median size＜0.5 micron.
8. as claim 1 or 5 described coke oven door refractory materialss, it is characterized in that described activated alumina micro mist median size＜5.0 microns.
9. coke oven door refractory materials as claimed in claim 1 is characterized in that, described compound poly-phosphate is tripoly phosphate sodium STPP and Sodium hexametaphosphate 99.
10. coke oven door refractory materials as claimed in claim 1 is characterized in that: the fineness of described kyanite is 0.045～0mm.
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|---|---|---|---|
| CNB2006100305950A CN100482612C (en) | 2006-08-30 | 2006-08-30 | Fire resistive material for coke oven door |
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|---|---|---|---|
| CNB2006100305950A CN100482612C (en) | 2006-08-30 | 2006-08-30 | Fire resistive material for coke oven door |
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| CN101134676A true CN101134676A (en) | 2008-03-05 |
| CN100482612C CN100482612C (en) | 2009-04-29 |
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ID=39159035
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