CN103172388A - Magnesium spinel lithoidal refractory body - Google Patents
Magnesium spinel lithoidal refractory body Download PDFInfo
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- CN103172388A CN103172388A CN 201110430304 CN201110430304A CN103172388A CN 103172388 A CN103172388 A CN 103172388A CN 201110430304 CN201110430304 CN 201110430304 CN 201110430304 A CN201110430304 A CN 201110430304A CN 103172388 A CN103172388 A CN 103172388A
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- refractory body
- magnesia
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- grog
- spinel matter
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- Muffle Furnaces And Rotary Kilns (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
Abstract
The invention provides an alkalescence refractory body adapted to an inner liner of a cement rotary kiln. Being as an aggregate, the magnesium spinel lithoidal refractory body comprises 5-30mass% of magnesium aluminate spinel clinker and 10-50mass% of fused magnesium oxide clinker, 0.5-10mass% of zirconia which is partially stabilized by CaO and the like at a joint part, and the balance of sintered magnesium oxide clinker.
Description
Technical field
The present invention relates to the magnesia spinel matter refractory body of a kind of liner that is suitable for cement rotary kiln etc.
Background technology
In alkaline refractory body, the liner refractory body that the magnesium chrome refractory is used as cement rotary kiln is durable good, is widely used all the time.But, have following problem: generate a small amount of but chromium of leachable 6 valencys to water in the refractory body after use and consider from the viewpoint that prevents public hazards, need to pay special attention to, process trouble, and spend expense when discarded.
Countermeasure as reply the problems referred to above, disclose a kind of refractory body that does not contain chromium in Japanese Patent Publication 60-34513, United States Patent (USP) 4849383, the former discloses a kind of refractory body that contains the appropriate amount ferric oxide in magnesia spinel matter refractory body, and the latter discloses a kind of calcium zirconate (CaZrO that coordinated
3) the magnesia refractory body of grog of matter.
But the former refractory body contains ferrous components, thus, shortcoming is slightly arranged on thermotolerance, the combustion zone that the temperature in the clinkering zone of rotary kiln is high can't obtain durable fully while using as liner, and the latter comprises ZrO in a large number
2composition, correspondingly the proportion of refractory body is just large, has in addition the shortcoming of the insufficient grade of resistance to sudden heating.
In the refractory body of using at these cement rotary kilns; for protect that refractory body avoids the flame of high temperature to cause overheated and guarantee weather resistance; importantly on the surface of the refractory body of liner, form the coating that the cement clinker composition by the semi-melting state forms, the formation difficulty of coating is considered to the durable essential characteristic of refractory body.
Summary of the invention
the problem that invention will solve
The invention provides a kind ofly as the cement rotary kiln purposes and preferred refractory body, described refractory body has solved the above-mentioned shortcoming that the refractory body of prior art has.
for the scheme of dealing with problems
The present invention carries out in order to solve above-mentioned problem, and magnesia spinel matter refractory body of the present invention is characterised in that, the magnesium-aluminium spinel grog (MgAl that comprises 5～30 quality % as aggregate
2o
4) and the electrically molten magnesia grog of 10～50 quality %, comprise the partially stabilized zirconium white of 0.5～10 quality % in joint portion, and remainder mainly consists of the sintered magnesia grog.
The excellent heat resistance of electrically molten magnesia grog needless to say, crystalline particle is large and fine and close, therefore, for the refractory body that forms excellent corrosion resistance especially and make these characteristics effective, need to contain the above electrically molten magnesia of 10 quality %, contrary, too much containing sometimes, the problem that exists resistance to sudden heating to reduce, therefore, be made as below 50 quality %.
By contain the partially stabilized zirconium white of 0.5～10 quality % in the combination of this grog, can make wettability to the cement composition of semi-melting, be that the coating tack is good, promote the crystalline particle of the magnesium oxide particle of the joint portion in the formation refractory body to grow up, improve the erosion resistance of refractory body, and the bonding strength of joint portion is improved, the thermostability of giving refractory body.
In order to give these effects, need at least contain the partially stabilized zirconium white of 0.5 quality %, contain while surpassing 10 quality %, the large and tendency that diminish with respect to the erosion resistance of the cement composition of molten state of the proportion phase strain of refractory body is arranged.This partially stabilized zirconic content further preferably is made as 1～3 quality %, thereby can obtain the refractory body that air permeability is little and the coating tack is good.
In the optimal way of magnesia spinel matter refractory body of the present invention, the electrically molten magnesia grog comprises respectively CaO and the SiO of 1～3 quality %
2, in this case, refractory body further improves with respect to the wettability of the cement composition of semi-melting state, in addition, also can use the magnesium oxide of the cheapness of having omitted purifying or the more cheap natural magnesite raw material as the electrically molten magnesia grog, therefore preferably.
In this case, CaO and SiO
2all have pair refractory body to give the effect with respect to the wettability of the cement composition of semi-melting state, and both contain usually with coexisting state, it is unpractical only removing a side.
But, too much contain CaO and SiO
2the time, the refractoriness of refractory body is reduced, therefore, be preferably below 3 quality %.As the sintered magnesia grog, the sintered magnesia grog more than the purity 97 quality % that magnisite burnt till and obtain is for example arranged or the sintered magnesia grog below the purity 99.5 quality % that formed by the seawater purifying.In addition, the electrically molten magnesia grog comprises CaO, SiO
2deng as fusing assistant, can use the electrically molten magnesia grog of purity 94～98 quality % that the magnisite electric smelting is obtained.
In magnesia spinel matter refractory body of the present invention, when the content of magnesium-aluminium spinel grog is less than 5 quality %, young modulus becomes large and resistance to sudden heating reduction, in addition, while being greater than 30 quality %, the tendency of reacting with CaO in semi-melting state cement clinker and making the erosion resistance reduction is arranged easily.
Magnesia spinel matter refractory body of the present invention is particularly preferably as the liner refractory body of cement rotary kiln.As contained partially stabilized zirconium white in magnesia spinel matter refractory body of the present invention, can enumerate with MgO or Y
2o
3partially stabilized zirconium white is as candidate, but it is slightly little to carry out partially stabilized zirconium white stability at high temperature with these, and easy destabilization, therefore, be particularly preferably with CaO and carry out partially stabilized zirconium white in use.
By containing zirconium white that partially stabilized degree is 75～95%, particularly containing the zirconium white that partially stabilized degree is 80～90%, thereby can obtain the refractory body of high-temperature stability and resistance to sudden heating excellence, in this case, the content of the CaO in partially stabilized zirconium white is about 3～6 quality %.
Embodiment
Below, utilize embodiment that the present invention is described in further detail, but the present invention is not subject to any restriction of these embodiment.Study the refractory body of the raw material composition amounted to shown in 8 kinds of tables 1, table 2 and tested, comparing test.
That is, by sintered magnesia grog (content of MgO is 99 quality % and the sintered magnesia grog below particle diameter 5mm), the electrically molten magnesia grog (SiO that the content of MgO is 97 quality % and the C aO that comprises 1.2 quality % and 1.5 quality %
2, particle diameter 1～5mm the electrically molten magnesia grog) and magnalium synthetic spinel grog (Al
2o
3content be the following magnalium synthetic spinel grog of 50 quality % and particle diameter 5mm) etc. coordinate not the zirconic powder of stabilization (median size is 30 μ m approximately), the partially stabilized zirconium white of CaO (CaO content 4.3 quality %, stabilization degree approximately 89%, the about 40 μ m of median size) powder and the partially stabilized zirconium white of MgO (MgO content 3 quality %, stabilization degree approximately 40%, the about 40 μ m of median size) powder etc. in the combination of aggregate of formation, after the tret meter mixes the magnesium sulfate solution of 20 ° of Be as bond material (15 quality %) of 3 quality % in addition, with 1000kg/cm
2carry out press forming, burn till under 1780 ℃ 10 hours after drying and JIS standard straight shape brick that manufactured size is 230mm * 114mm * 65mm.
The straight shape brick of making is cut and investigates characteristic, result and compounding condition are shown in to table 1 and table 2 in the lump.
In table, air penetrability is the test film that uses 50mm * 50mm * 50mm size the value of trying to achieve by following calculating formula (JIS-R2115 of Japanese Industrial Standards).
μ≒η×(V/t)×(L/S)/(P1-P2)
T: test period
V: under absolute pressure P, the volume of the gas seen through in t between at the trial
S: the cross-sectional area of the test film of gas permeation
L: the thickness of the cross section of test film
P
1: absolute pressure when gas is invaded test film
P
2: absolute pressure when gas breaks away from from test film
η: the kinetic viscosity of the gas under test temperature
The kinetic viscosity η ≒ 18 * 10 of air
-6pasec (15～25 ℃)
μ: the air penetrability of test film
Resistance to sudden heating is investigated straight shape brick as follows according to the DIN method: by an end of straight shape brick, in being heated to the electric furnace of 1400 ℃ after heating, with the method let cool in air, investigation is until the number of times of the head of test body while at least lacking 50%.
In addition, the coating tack is estimated by the button method (button method) be commonly called as together with metamorphic layer thickness and size changing rate, described button method is given birth to grog by cement and is placed on the test film of 40mm * 25mm * 15mm and is warming up to 1530 ℃ and keep 10 hours, by the grog fusing, the state of investigation material.
The thermal cycling volume stability is following investigation and obtaining: the test film of 40mm * 40mm * 110mm is put into to electric furnace, raise and reduce the temperature of electric furnace, repeat 300 heating and cooling between 700 ℃ and 1300 ℃, then the volume change of test film is investigated.
[table 1]
[table 2]
Then, make wedge brick (230mm * 114mm * 65～75mm) with the formula of No.1, No.4 and No.7.Install to these as liner in drum rotating formula test furnace, drop into the livings grog of 300g cement every 1 hour inside to test furnace, will be heated to approximately 1530 ℃ and keep 12 hours in stove with burner simultaneously, during dropped into the cement life grog that amounts to 3600g.
Its result, the brick of No.4 and No.7 is compared with the brick of No.1, since the initial stage coating, adheres to well.
In observation after off-test, the coating of No.1 brick is adhered to thickness and is about 1mm, and on the other hand, the No.7 brick is about 10mm, and the No.4 brick is about 6mm.
In addition, investigation be take liquid composition that calcium oxide and silicon oxide be main component to the depth of penetration in brick in cement clinker, and the known No.1 brick of result is about 30mm, and on the other hand, No.7 brick depth of penetration is little, be about 15mm.
By above result, can be said, the refractory body of No.6, No.7, No.8 possesses the refractory body excellence by refractory body preferred condition, particularly No.7 as the cement rotary kiln liner substantially.
the effect of invention
Magnesia spinel matter refractory body of the present invention possesses the desired characteristic of refractory body of using in the clinkering zone that comprises combustion zone as cement rotary kiln, be all characteristicss such as good coating tack, erosion resistance, resistance to sudden heating, anti-structure spalling, with the alkaline refractory body that contained chromium in the past, compare, performance is variation not, and likely become the refractory body of the chromium component of public hazards reason for not containing, do not need special site of storage or processing when use is discarded refractory body afterwards, can obtain the effect that discarded trouble is little and cost is less.Therefore, magnesia spinel matter refractory body of the present invention is particularly preferably as the cement rotary kiln refractory body.
Claims (7)
1. a magnesia spinel matter refractory body, is characterized in that, as aggregate, and the magnesium-aluminium spinel grog (MgAl that comprises 5～30 quality %
2o
4) and the electrically molten magnesia grog of 10～50 quality %, comprise the partially stabilized zirconium white of 0.5～10 quality % in joint portion, and remainder mainly consists of the sintered magnesia grog.
2. magnesia spinel matter refractory body according to claim 1, wherein, partially stabilized zirconic content is 1～3 quality %.
3. magnesia spinel matter refractory body according to claim 1 and 2, wherein, partially stabilized zirconic stabilization composition is C aO.
4. according to claim 1,2 or 3 described magnesia spinel matter refractory bodies, wherein, the magnesium oxide purity of sintered magnesia grog is 97～99.5 quality %.
5. according to the described magnesia spinel matter of any one in claim 1～4 refractory body, wherein, described electrically molten magnesia grog comprises respectively CaO and the SiO of 1～3 quality %
2.
6. a magnesia spinel matter refractory body for cement rotary kiln, is characterized in that, right to use requires the described magnesia spinel matter of any one refractory body in 1～5.
7. a cement rotary kiln, is characterized in that, right to use requires 6 described cement rotary kilns to use magnesia spinel matter refractory body as the liner refractory body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110430304 CN103172388A (en) | 2011-12-20 | 2011-12-20 | Magnesium spinel lithoidal refractory body |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110430304 CN103172388A (en) | 2011-12-20 | 2011-12-20 | Magnesium spinel lithoidal refractory body |
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| CN103172388A true CN103172388A (en) | 2013-06-26 |
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ID=48632664
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|---|---|---|---|
| CN 201110430304 Pending CN103172388A (en) | 2011-12-20 | 2011-12-20 | Magnesium spinel lithoidal refractory body |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105917186A (en) * | 2014-01-23 | 2016-08-31 | 杰富意钢铁株式会社 | Process for producing lining structure of vessel for molten metal, and lining structure of vessel for molten metal |
-
2011
- 2011-12-20 CN CN 201110430304 patent/CN103172388A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105917186A (en) * | 2014-01-23 | 2016-08-31 | 杰富意钢铁株式会社 | Process for producing lining structure of vessel for molten metal, and lining structure of vessel for molten metal |
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Application publication date: 20130626 |