CN1208279C - Light refractory bricks - Google Patents
Light refractory bricks Download PDFInfo
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- CN1208279C CN1208279C CN 03100439 CN03100439A CN1208279C CN 1208279 C CN1208279 C CN 1208279C CN 03100439 CN03100439 CN 03100439 CN 03100439 A CN03100439 A CN 03100439A CN 1208279 C CN1208279 C CN 1208279C
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Abstract
The present invention relates to a fire-resistant material with high quality, low thermal coefficient and long service life for an inner lining of a high-temperature kiln, which belongs to the field of fire-resistant materials. The present invention is characterized in that mullite is used as a main crystal phase, and anorthite is used as a coupling phase; the fire-resistant material has the main chemical components of 54.0 to 57.0 wt% of Al2O3, 40.0 to 43.0 wt% of SiO2, 1.0 to 2.0 wt% of CaO, 0.1 to 1.0 wt% of Fe2O3 and 0.1 to 0.7 wt% of other impurities, wherein the fineness degree of the raw materials totally conforms to the requirement that the surplus of a screen with square holes of 0.088mm is at most 5.0%. The present invention maintains the advantages of low thermal coefficient and low volume density of a light fire-resistant brick made from anorthite, and improves the strength and the usage temperature of the light fire-resistant brick made from anorthite obviously. The present invention replaces a fire-resistant lining made form aluminium-silicate fire-resistant fibers which may cause cancer, and the present invention can be used for the fire-resistant lining which comes into contact with the flame directly. Large numbers of sapphires which are abundantly stored in China can be used as the raw material of the present invention, and the consumption of the sapphires can reach 70 wt%. In addition, the present invention can also use calcining coal slack (low iron content) of which the weight ratio is as high as 40%.
Description
Technical field
The invention belongs to fire resisting material field, the high-quality refractory material that particularly a kind of low thermal conductivity, long-life high temperature furnace lining are used.
Background technology
Because energy-conservation needs, the lighting of various inner lining of kiln is more and more paid attention to by industry member.Though the aluminosilicate-type refractory fibre of large usage quantity is confirmed aspect saving energy in kiln fully at present, has the deadly defect of three aspects.At first be that price is too expensive, up to 5～60,000 yuan, contain the zirconium fiber and contain 2～30,000 yuan per ton of chromium fiber as polycrystalline mullite fibre price per ton; The secondth, the heat-resistant limit of refractory fibre life-time service is many below 1200 ℃.Though polycrystalline mullite fibre can be 1300～1400 ℃ of uses, too Ang Gui cost is hung back most of users.When refractory fibre uses under ultimate temperature in addition work-ing life very short, generally have only 1/2～1/5 of refractory brick; The 3rd, the aluminosilicate-type refractory fibre has carcinogenic possibility to respiratory system, and the European Community has classified aluminosilicate refractory fiber as two class carcinogenic substances.Therefore be that more external big refractory materials manufacturers and domestic many refractory factories of representative have all been developed the refractory lining of various light fire bricks as kiln with Britain J. P. Morgan ﹠ Co..The light fire brick of Britain J. P. Morgan ﹠ Co. can be divided into three series by the composition of principal crystalline phase:
(1) corundum-mullite light fire brick
Principal crystalline phase is a mullite, and paracrystalline phase is a corundum, and maximum operation (service) temperature is from 1650 ℃ to 1760 ℃, and volume density is minimum to be 1.02g/cm
3～1.25g/cm
3, thermal conductivity (800 ℃) is 0.44～0.51W/mK.
(2) mullite light fire brick
Principal crystalline phase is a mullite, and other crystalline phase almost can not detect with instrument.Maximum operation (service) temperature is from 1430 ℃ to 1540 ℃, and volume density is minimum to be 0.78g/cm
3～0.88g/cm
3, thermal conductivity (800 ℃) is 0.31～0.36W/mK.
(3) lime feldspar series light fire brick
Principal crystalline phase is a lime feldspar, and other crystalline phase almost can not detect with instrument.Maximum operation (service) temperature is from 1100 ℃ to 1260 ℃, and volume density is minimum to be 0.45g/cm
3～0.48g/cm
3, thermal conductivity (800 ℃) is 0.17～0.18W/mK.
Wherein (1), (2) though two serial light fire bricks have higher use temperature, thermal conductivity is higher than aluminum silicate fiber liner (0.14～0.16W/mK, 800 ℃) far away.Though the 3rd serial light fire brick thermal conductivity be near aluminum silicate fiber, because intensity is lower, use temperature is lower, is 1200 ℃～1350 ℃ inner lining of kiln and can not be used for the long term operation temperature.And its use temperature of most of kilns of using in industry is all in this scope.In fact low volume density, low thermal conductivity, low cost and the eco-friendly kiln refractory lining material that therefore can be applied to this temperature are in the vacancy state.
Summary of the invention
The present invention seeks to keep the refractory fibre thermal conductivity to hang down and the two-fold advantage of light fire brick long service life, overcome the harmful shortcoming of refractory fibre, overcome the shortcoming that the lime feldspar fire brick series can not directly use as inner lining of kiln simultaneously.
A kind of light fire brick is characterized in that wherein mullite is as principal crystalline phase, and the lime feldspar conduct is in conjunction with phase, and its main chemical compositions is: Al
2O
354.0～57.0wt.%, SiO
240.0～43.0wt.%, CaO 1.0～2.0wt.%, Fe
2O
30.1～1.0wt.%, foreign matter content are 0.1～0.7wt.%.
Core concept:
Lime feldspar has that thermal conductivity is low, thermal expansivity is little, density is little and the characteristics of easy-sintering, but its fusing point lower (1550 ℃).When foreign ion existed, the fusing point of lime feldspar goods was just lower, therefore was that the light fire brick of principal crystalline phase has that volume density is little, thermal conductivity is low, specific heat capacity is low and the good thermal shock characteristics with the lime feldspar.But because the lime feldspar non-refractory, thereby its maximum operation (service) temperature has only 1260 ℃.All there is this product output in the Britain BNZ company that root (Morgen) company, German Gauss rein in (Gossler) company and the U.S. that rubs.This product is because use temperature and intensity are all lower, can only be as the thermofin of kiln, and can not use as direct refractory lining.
The fusing point of mullite is 1850 ℃～1910 ℃, therefore is that the refractory materials of principal crystalline phase all has higher use temperature with the mullite.But owing to be subjected to the restriction of existing material choice collocation and traditional processing technology, be that the light fire brick of principal crystalline phase all can not be made the very low product of volume density with the mullite, its thermal conductivity is also higher.Its lowest volume density of JM26 product as domestic and international large usage quantity is 0.78g/cm
3, minimum thermal conductivity (800 ℃) is 0.31W/mK.Be applied to inner lining of kiln and can not obtain the ideal energy-saving effect, can not replace the carcinogenic refractory fibre of possibility fully.
Being of core concept of the present invention combines the two premium properties of lime feldspar and mullite, promptly keep the low thermal conductivity of lime feldspar light fire brick and the advantage of low volume density, its intensity and use temperature are significantly improved, thereby can be used for the direct refractory lining that contacts with flame, reach the purpose of the carcinogenic aluminosilicate refractory fiber class refractory lining of replacement possibility.
Lime feldspar in conjunction with mullite light fire brick production technique as shown in Figure 1.
In raw material shown in Figure 1, the fineness of all raw materials all will meet the requirement of 0.088mm square hole sieve surplus≤5.0%.The add-on of each raw material and specification of quality are as follows during batching: the calcining coal gangue add-on is 1～40wt.%, requires Al
2O
3Content is 43.0～48.0wt.%, Fe
2O
3Content is 0.1～1.0wt.%; Remove bauxite add-on 1～30wt.%, require Al
2O
3Content is 70.0～80.0wt.%, Fe
2O
3Content is 0.1～1.0wt.%; Kyanite add-on 20～80wt.% requires Al
2O
3Content is 52.0～57.0wt.%, Fe
2O
3Content is 0.1～0.8wt.%; Kaolinite clay add-on 3.0～7.0wt.% requires Al
2O
3Content is 35.0～38.0wt.%, Fe
2O
3Content is 0.1～1.0wt.%, and CaO+MgO content is 0.1～0.4wt.%, Na
2O+K
2O content is 0.1～0.8wt.%; Montmorillonitic clay add-on 3.0～7.0wt.% requires Al
2O
3Content is 18.0～24.0wt.%, Fe
2O
3Content is 0.1～1.0wt.%, and CaO+MgO content is 0.1～2.5wt.%, Na
2O+K
2O content is 0.1～1.5wt.%; Pure calcium aluminate cement add-on 5.0～15.0wt.% requires Al
2O
3Content is 68.0～76.0wt.%, Fe
2O
3Content is 0.1～0.7wt.%, and CaO content is 23.0～33.0wt.%; White cement can replace pure calcium aluminate cement, but the two can not use with, and white cement add-on 5.0～10.0wt.% requires SiO
2Content is 18.0～25.0wt.%, Fe
2O
3Content is 0.1～0.7wt.%, and CaO content is 72.0～77.0wt.%.
Preparation process shown in Figure 1 is above-mentioned raw materials to be made mud and foams mix, casting, maintenance, oven dry and calcining obtain finished product after cut mill processing, and wherein maintaining process is to leave standstill 12～24 hours in 10 ℃～40 ℃ air.The temperature of oven dry is controlled at below 150 ℃, and wherein preceding 10 hours temperature is controlled at below 100 ℃, and at the uniform velocity heats up.It is 5～15 hours that base substrate remains on time of 100 ℃～150 ℃.Temperature-fall period can be lowered the temperature naturally with the structure and the operating method of drying kiln, does not need to carry out cooling rate control.Hong Gan base substrate water ratio is controlled at below the 3.0wt.% at last.Calcining process can adopt any combustion gas, fuel oil kiln or electric heating kiln.The time that is raised to 1400 ℃ from room temperature is 8～20 hours, can at the uniform velocity heat up, and adobe needs 1400 ℃ of insulations 5～15 hours, and the large size adobe should be adopted the lower limit of heat-up rate and the upper limit of soaking time.Temperature-fall period can be lowered the temperature naturally with kiln, but should not be less than 10 hours, and the local temperature difference of piling up adobe in the kiln should be less than ± 10 ℃.
Shown in Fig. 1, be to prepare rosined soap earlier among the foamy preparation technology, the preparation of rosined soap should be according to the discrepancy adjustment NaOH/ rosiny ratio of the different places of production and different batches rosin character.Optimum value should be 0.12～0.14 generally speaking.Use water rinse after the made rosin liquid drying, remove unnecessary NaOH.
After rosined soap after the rinsing dried again, add in the entry and be heated to 20～80 ℃ with gelatine, it is standby to be prepared into dense whipping agent.Wherein the weight ratio of gelatine/rosined soap is 1.00～1.05.Institute's water consumption is 5～10 times of rosined soap+gelatine weight.Zhi Bei dense whipping agent also needs the water with 5～10 times to dilute before the whisking machine of packing into is got blisters as stated above.Prepared dense whipping agent is no more than 24 hours in the shelf-time in summer, in winter, spring, be no more than 48 hours when deposit autumn.
Beneficial effect of the present invention:
Product of the present invention is with close product J M20 in world market and JM23 performance comparison are as shown in table 1 at present.
Two kinds of product performance contrasts of table 1 product of the present invention (AM) and JM series
| Product, | Maximum operation (service) temperature (℃) | Volume density (g/cm 3) | Strength at normal temperature (MPa) | Normal temperature ultimate compression strength (MPa) | Reheating linear change rate on reheating (%) (maximum operation (service) temperature-30 ℃ insulation 24 hours) |
| AM24A | 1350 | ≤0.40 | ≥1.20 | ≥0.90 | ≤0.20 |
| AM24B | 1350 | ≤0.50 | ≥1.50 | ≥1.10 | ≤0.20 |
| JM20 | 1100 | ≤0.45 | ≥0.80 | ≥0.70 | ≤0.20 |
| JM23 | 1260 | ≤0.48 | ≥1.10 | ≥0.90 | ≤0.20 |
From the correlation data of table 1 as can be seen, the use temperature of product of the present invention exceeds 250 ℃ and 90 ℃ respectively than JM20 and JM23, and intensity improves about 30%.From principal crystalline phase, JM20 and JM23 are to be principal crystalline phase with the lime feldspar, and the present invention then is to be principal crystalline phase with the mullite, so use temperature and intensity all increases, thereby can be directly used in the liner of kiln.The present invention can also prepare more high-intensity goods.As the volume density when goods is 1.0g/cm
3The time its ultimate compression strength can reach 10.0～15.0Mpa, folding strength can reach 3.5～5.0Mpa, the thermal conductivity during 800 ℃ in this goods is 0.30W/mK, maximum operation (service) temperature is 1400 ℃.
Beneficial effect of the present invention also is to use in a large number the abundant kyanite of China's reserves.Generally speaking, the kyanite volume in the refractory materials is not more than 20wt.%, and the present invention can use the kyanite up to 70wt.%, thereby opens up a new way for the high value added utilization of these mineral products.
In addition, the present invention can also use the calcining coal gangue (low iron) up to 40wt.%, and comprehensive utilization and Sustainable development are had certain meaning.
Starting material of the present invention can have bigger alternative according to the practical situation of China different areas, therefore help reducing production costs.
Description of drawings
Fig. 1 is that lime feldspar is in conjunction with mullite light fire brick technological process of production figure
Embodiment
Embodiment 1
By shown in Figure 1, get calcining and levigate after colliery powder 31wt.%, kyanite 30wt.%, pure calcium aluminate cement 10wt.% removes red bauxite 19wt.%, kaolinite clay 5wt.%, montmorillonitic clay 5wt.%, the back that is mixed in mixer adds the sodium citrate aqueous solution that accounts for amount of solid 35%.The concentration of sodium citrate aqueous solution is 0.5wt.%.And blend together uniform mud.Be that to prepare rosined soap and rosined soap/gelatine be that 1.2 ratio prepares foaming liquid for 0.13 ratio in NaOH/ rosin before this.In stirred slurry, foaming liquid packed into and get blisters in the whisking machine.Need to grasp when mud stirs, whisking machine can be supplied the foam of capacity.Then mud is mixed with foam.How many lime feldspars is in conjunction with volume density the controlling by the adding foam volume of mullite light fire brick.The volume density of goods is 0.48g/cm in the present embodiment
3, the foamy add-on is 18 times of mud volume.
Above-mentioned mud and foams mix evenly after maintenance, oven dry, the calcining, are obtained finished product through cutting mill processing by the goods desired shape corresponding mould of packing in the back.The main performance index of resulting product is as follows:
Maximum operation (service) temperature (℃) 1350
Volume density (g/cm
3) 0.48
Cold conditions ultimate compression strength (MPa) 2.6
Cold conditions folding strength (MPa) 1.3
Heavily burn line and change 1320 ℃ * 24hrs (%)-0.14
Thermal conductivity (W/mK)
400℃ 0.135
600℃ 0.146
800℃ 0.168
1000℃ 0.192
Embodiment 2
By shown in Figure 1, get kyanite 70wt.%, pure calcium aluminate cement 12wt.% removes red bauxite 3wt.%, kaolinite clay 4wt.%, montmorillonitic clay 6wt.%, the back that is mixed in mixer adds the sodium citrate aqueous solution that accounts for amount of solid 37wt.%.The concentration of sodium citrate aqueous solution is 0.5wt.%.Then solution is become uniform mud with the solid powder mixed together.Be that to prepare rosined soap and rosined soap/gelatine be that 1.2 ratio prepares foaming liquid for 0.13 ratio in NaOH/ rosin before this.In stirred slurry, foaming liquid packed into and get blisters in the whisking machine.Need to grasp when mud stirs, whisking machine can be supplied the foam of capacity.Then mud is mixed with foam.How many lime feldspars is in conjunction with volume density the controlling by the adding foam volume of mullite light fire brick.The volume density of goods is 0.4g/cm in the present embodiment
3, the foamy add-on is 23 times of mud volume.
Above-mentioned mud and foams mix evenly after maintenance, oven dry and the calcining, are obtained finished product through cutting mill processing by the goods desired shape corresponding mould of packing in the back.The main performance index of resulting product is as follows:
Maximum operation (service) temperature (℃) 1350
Volume density (g/cm
3) 0.40
Cold conditions ultimate compression strength (MPa) 1.25
Cold conditions folding strength (MPa) 0.90
Heavily burn line and change 1320 ℃ * 24hrs (%)-0.18
Thermal conductivity (W/mK)
400℃ 0.092
600℃ 0.128
800℃ 0.165
1000℃ 0.193
Claims (4)
1, a kind of light fire brick is characterized in that wherein mullite is as principal crystalline phase, and the lime feldspar conduct is in conjunction with phase, and its main chemical compositions is: Al
2O
354.0～57.0wt.%, SiO
240.0～43.0wt.%, CaO 1.0～2.0wt.%, Fe
2O
30.1～1.0wt.%, foreign matter content are 0.1～0.7wt.%.
2, light fire brick as claimed in claim 1, it is characterized in that the fineness of all raw materials all will meet the requirement of 0.088mm square hole sieve surplus≤5.0%, the add-on of each raw material and specification of quality are as follows during batching: the calcining coal gangue add-on is 1～40wt.%, requires Al
2O
3Content is 43.0～48.0wt.%, Fe
2O
3Content is 0.1～1.0wt.%; Remove bauxite add-on 1～30wt.%, require Al
2O
3Content is 70.0～80.0wt.%, Fe
2O
3Content is 0.1～1.0wt.%; Kyanite add-on 20～80wt.% requires Al
2O
3Content is 52.0～57.0wt.%, Fe
2O
3Content is 0.1～0.8wt.%; Kaolinite clay add-on 3.0～7.0wt.% requires Al
2O
3Content is 35.0～38.0wt.%, Fe
2O
3Content is 0.1～1.0wt.%, and CaO+MgO content is 0.1～0.4wt.%, Na
2O+K
2O content is 0.1～0.8wt.%; Montmorillonitic clay add-on 3.0～7.0wt.% requires Al
2O
3Content is 18.0～24.0wt.%, Fe
2O
3Content is 0.1～1.0wt.%, and CaO+MgO content is 0.1～2.5wt.%, Na
2O+K
2O content is 0.1～1.5wt.%; Pure calcium aluminate cement add-on 5.0～15.0wt.% requires Al
2O
3Content is 68.0～76.0wt.%, Fe
2O
3Content is 0.1～0.7wt.%, and CaO content is 23.0～33.0wt.%; Or replace pure calcium aluminate cement with white cement, but the two can not use with, and white cement add-on 5.0～10.0wt.% requires SiO
2Content is 18.0～25.0wt.%, Fe
2O
3Content is 0.1～0.7wt.%, and CaO content is 72.0～77.0wt.%.
3, light fire brick as claimed in claim 2, it is characterized in that raw material is made mud and foams mix, casting, maintenance, oven dry and calcining obtains light fire brick after cut mill processing, wherein maintenance is to leave standstill 12～24 hours in 10 ℃～40 ℃ air; The temperature of oven dry is controlled at below 150 ℃, and wherein preceding 10 hours temperature is controlled at below 100 ℃, and at the uniform velocity heats up; It is 5～15 hours that base substrate remains on time of 100 ℃～150 ℃, Hong Gan base substrate water ratio is controlled at below the 3.0wt.% at last, the time that is raised to 1400 ℃ from room temperature is 8～20 hours, at the uniform velocity heat up, adobe needs 1400 ℃ of insulations 5～15 hours, and the lower limit of heat-up rate and the upper limit of soaking time are adopted in the large size adobe, and temperature-fall period is lowered the temperature naturally with kiln, but be no less than 10 hours, the local temperature difference of piling up adobe in the kiln is less than ± 10 ℃.
4, light fire brick as claimed in claim 3 is characterized in that wherein among the foamy preparation technology it being preparation rosined soap earlier, and NaOH/ rosiny ratio is 0.12～0.14, uses water rinse after the made rosin liquid drying, removes unnecessary NaOH; After the rosined soap that obtains after the rinsing is dried again, add in the entry and be heated to 20～80 ℃ with gelatine, be prepared into dense whipping agent, wherein the weight ratio of gelatine/rosined soap is 1.00～1.05, institute's water consumption is 5～10 times of rosined soap+gelatine weight, and the dense whipping agent of preparation also needs the water with 5～10 times to dilute before the whisking machine of packing into is got blisters.
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|---|---|---|---|
| CN 03100439 CN1208279C (en) | 2003-01-14 | 2003-01-14 | Light refractory bricks |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03100439 CN1208279C (en) | 2003-01-14 | 2003-01-14 | Light refractory bricks |
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| CN1424280A CN1424280A (en) | 2003-06-18 |
| CN1208279C true CN1208279C (en) | 2005-06-29 |
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2003
- 2003-01-14 CN CN 03100439 patent/CN1208279C/en not_active Expired - Fee Related
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