CA1316183C - Shape or unshaped refractory compounds based on magnesite and their use for lining furnaces - Google Patents

Shape or unshaped refractory compounds based on magnesite and their use for lining furnaces

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Publication number
CA1316183C
CA1316183C CA000583977A CA583977A CA1316183C CA 1316183 C CA1316183 C CA 1316183C CA 000583977 A CA000583977 A CA 000583977A CA 583977 A CA583977 A CA 583977A CA 1316183 C CA1316183 C CA 1316183C
Authority
CA
Canada
Prior art keywords
refractory
weight
magnesite
burnt
shaped
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CA000583977A
Other languages
French (fr)
Inventor
Morteza Nazirizadeh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Didier Werke AG
Original Assignee
Didier Werke AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Didier Werke AG filed Critical Didier Werke AG
Application granted granted Critical
Publication of CA1316183C publication Critical patent/CA1316183C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/03Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/04Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
    • C04B35/043Refractories from grain sized mixtures
    • C04B35/0435Refractories from grain sized mixtures containing refractory metal compounds other than chromium oxide or chrome ore

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE
Disclosed are shaped or unshaped refractory compounds based on extremely pure, low-iron magnesite material in admixture with a zirconium compound, particularly zirconium dioxide, and their use, particularly in the form of burnt moulded bodies or refractory bricks, for lining furnaces or high temperature zones of furnaces for the manufacture of burnt dolomite, burnt lime or burnt magnesite. The refractory compounds according to the inven-tion are characterized by the fact that they contain as magnesite sintered or fused magnesite with a purity of at least 97% by weight of MgO and as admixture 10 to 25% by weight of a zirconium compound with a ZrO2 content of at least 98% by weight, based on MgO. The advantage of the refractory compounds according to the invention lies therein that they can be readily used in furnaces at burning temperatures above 1900°C, whereby they exhibit excellent stability of volume, chemical resistance to the charging material and structural flexibility, and furthermore, make lining with bricks without joint grouting possible.

Description

131~183 l 23843--20 The inventlon relates to magneslte-based refractory material, whlch may be shaped or unshaped. It is understood that shaped or unshaped refractory compoun~s of the kind named lnclude both shaped articles, such as refractory brlcks, as well as un-shaped substances. The shaped articles can be elther ln the drled state, ln the annealed state, ~,.e. followlng treatment at a tem-perature between 400 and 800C, or ln a burnt state, i.e. follow-lng ~irlng usually at temperatures between 1600 and 1800C.
A burnt, refractory moulded body made of magnesla as the main constituent wlth admixture of a zlrconlum oxlde-rlch materlal ls dlsclosed ln German Auslegschrlft No. (GE-AS) 22 49 814. The content of ZrO2 in the moulded body is between 1 and 5% by weight.
Furthermore, ln G~-AS 2Z 49 814, lt ls lndlcated that the zlrconl-um oxlde-rlch admlxture should have a graln slze of 0.3 to 5 mm, or the portlon below 1 mm grain slze should not be more than 50%
by welght of the ~lrconlum oxlde quantlty, preferably, however, 0%
b~ welght. The sinterlng propertles are to be lmproved by thls, - l.e. better compresslon and lower poroslty of the magnesla or the moulded bodles manufactured therefrom should already be achleved at low burnlng ternperatures.
Refractory burnt or unburnt brlcks and substances based on magnesla and contalnlng a ZrO2 admixture of 0.5 to 6% by welght are dlsclosed ln German Offenlegungsschrift No. (GE-AS) 25 07 556.
However, the brlcks or substances described in GE-OS 25 07 556 contaln not less than 3'~ by welght of an oxlde of R2O3 (wherein R
ls Ee, Al or Cr) and not less than 2% by weight of Fe203, each based on the quantity of the magnesia constltuents; moreover, they can contaln admlxtures of . .
h 1316~83 - 2 - 23843-2~2 chrome ore or magnesite chrome sinter in quantities up to 50% by weight, based on the entire mixture. The refractoriness of sintered magnesia products is to be increased by the admixtures, i.e. the formation of low-melting reaction products is to be avoided.
Furthermore, a method for the manufacture of burnt re-fractory magnesia bricks is disclosed in German Patent No.
26 46 430. In this method, a zirconium compound is added to the starting mixture so that the ZrO2 content amounts to up to 5.5% by weight. However, in this previously known method an A12O3 carrier, such as fused corundum or calcined alumina, is added in a quantity of 2 to 10% by weight so that in this case also, as in GE-OS 25 07 556, spinel is formed.
In addition, a refractory compound based on magnesia spinel with a content of 10 to 50% by weight of spinel clinker is described in German Patent No. 36 14 604. This compound also contains 0.5 to 4% by weight of zirconium oxide. This should promote incrustation even at high temperatures, particularly dur-ing overheating in the sintering zone of rotary kilns for the cement industry. The incrustation from the clinker melt is desired in the cement industry in order to protect in this way the actual refractory bricks from thermochemical attacks by the cement clinker melt and to improve the thermal insulation to the out-side.
It is the object of the present invention ts provide shaped or unshaped refractory compounds based on extremely pure, low-iron magnesite material which has a high temperature stability at temperatures above 1900C, a high stability of volume, i.e. no shrinkage, good chemical resistance to the charging material dur-ing operating conditions, high structural flexibility and with which, for example furnaces, particularly rotary kilns, can be lined with bricks without joint grouting. High temperatures occur particularly with use in rotary kilns for manufacturing burnt dolomite or burnt magnesite, and also in shaft kilns during the manufacture of burnt lime. The temperatures occurring there are substantially higher than the temperatures in rotary kilns for manufacturing cement (approx. 1500C).
It was surprisingly found that refractory compositions of the kind named have the aforenamed properties when the magnes-ite starting material used for the manufacture is sintered or fused magnesite having a purity of at least 97% by weight of MgO
and when the refractory compositions contain as admixture 10 to 25% by weight based on MgO of a zirconium compound having a ZrO2 content of at least 98~ by weight.
With the refractory compositions according to the inven-tion there is no spinel binding as with refractory compositions or refractory bricks containing spinels.
In the main burning zones of furnaces for manufacturing burnt dolomite, magnesite or lime, temperatures above 2000C pre-vail in the main burning zone of modern installations so that mag-nesia spinel bricks or magnesia chromite bricks no longer have the desired durability and cannot be used. For example, magnesia chromite bricks and also chrome magnesia bricks undergo consider-able shrinkage of volume; moreover, calcium chromate is formed at these high temperatures, which may result in contamination of the environment. Low-melting calcium aluminate is formed during the manufacture of burnt dolomite where magnesia spinel bricks are used.
According to one preferred embodiment, the amount of zirconium compound in the starting material is 12 to 17% by weight, based on MgO. Refractory bricks with excellent resistance to sudden changes of temperature are obtained hereby.
According to a further preferred embodiment, the total amount of MgO and ZrO2 is at least 97~ by weight of the en tire composition in the starting material. By using starting materials which meet these purity requirements, the formation of spinels is almost entirely avoided so that the occurrence of interfering reactions is further reduced.
According to a further preferred embodiment baddeleyite is used as the zirconium compound in the starting materials of the refractory compositions according to the invention. The baddeley-ite usually have a particle size of less than 0.5 mm. Refractory compositions with excellent stability of volume or substances which are particularly well suited for lining without joint grouting are obtained herewith.
According to a further preferred embodiment, sulfite liquor is used as a temporary binding agent. The use of this binding agent is particularly suitable in the refractory composi-tions according to the invention since no interfering oxidative constituents can be introduced through this into the starting material and thus also not into the shaped or unshaped product 1~16183 manufactured from this starting material.
According to a further preferred embodiment, the sintered or fused magnesite in the starting material has the following particle size distribution:
3.5 to 6.0 mm 5 to 10%
1.0 to 3.5 mm 25 to 40%
0.09 to 1.0 mm 5 to 20%
~ 0.09 mm 25 to 40%
A particularly compact structure of the products manufactured from such starting material is achieved -through this, in particular an excellent stability of volume.
According to a further preferred embodiment, the propor-tion of refractory material in the starting material having a grain size of < 0.09 mm amounts to at least 30% by weight, prefer-ably between 35 and 45~ by weight. A particularly compact and flexible structure of the finished product is achieved through this, the chemical resistance to the charging material, i.e. the dolomite, magnesite or lime to be burnt being improved.
As was already described above, the refractory composi-tions according to the invention can be used particularly in theform of burnt moulded bodies or refractory bricks to line furnaces or high temperature zones or main burning zones of furnaces to manufacture burnt dolomite, burnt lime or burnt magnesite.
The shaped or unshaped refractory compositions according to the invention are manufactured by simply mixing together the starting materials, whereby a suitable temporary binding agent, particularly sulfite liquor, is added. If the product is supplied 131~183 to the consumer in the form of dry matter, a solid temporary binding agent, for example synthetic resins, polyester resins, phenolic resins, etc., can be used, possibly also magnesium sul-fate. If the refractory composition according to the invention is manufactured in the form of shaped parts, a preferably temporary binding agent is likewise added to the starting mixture, and also the required quantity of water. The shaped parts are manufactured from this material in suitable moulds, preferably by pressing, particularly isostatic pressing, and following removal from the mould the shaped parts are dried, usually at temperatures between 100C and 180C, possibly annealed, usually at tempera-tures between 400C and 800C, and possibly also fired usually at temperatures between 1600C and 1800C.
The invention will be explained in greater detail on the basis of the following example.
Example A starting material was prepared from 85 parts by weight of sintered magnesia with an MgO content of 97.5~ by weight and 15 parts by weight of baddeleyite with a minimum content of 98.5~ by weight of ZrO2.
The 85 parts by weight of sintered magnesia had the fol-lowing particle size distribution:
3.5 to 5.0 mm 10 parts by weight 1.0 to 3.5 mm 35 parts by weight 0.09 to 1.0 mm 10 parts by weight not more than 0.09 mm 30 parts by weight The baddeleyite has a particle size of 0 to 0.5 mm.
Following thorough mixing with a sufficient quantity of sulfite liquor, this starting material was mixed and subsequently pressed with a pressing power of 113 to 118 N/mm2 into bricks.
Following removal from the mould, the bricks were dried at 120C
and subsequently subjected to firing between 1740 and 1760C.
The burnt bricks had a bulk density of 3.12 g/cm3, a porosity of 17%, a cold compressive strength, KDF, of 60 N/mm2 and a V-module of 6000 N/mm2.
The burnt bricks were subjected to a corrosion test dur-ing heating in contact with dolomite powder at 2000C, whereby nocorrosion could be ascertained.
Their resistance to sudden changes of temperature, TWB, had a value of >30. The bricks had excellent deformation proper-ties so that they could be used in the main burning zone of a rotary kiln.

Claims (18)

1. A refractory composition which may be shaped or unshaped and is based on extremely pure low-iron magnesite material, the said composition comprising (a) sintered or fused magnesite having an MgO content of at least 97% by weight and (b) 10 to 25% by weight based on MgO of a zirconium compound having a ZrO2 content of at least 98% by weight.
2. A refractory composition according to claim 1, wherein the amount of the zirconium compound is 12 to 17% by weight.
3. A refactory composition according to claim 1, wherein the total amount of MgO and ZrO2 is at least 97% by weight of the entire composition.
4. A refactory composition according to claim 2, wherein the total amount of MgO and ZrO2 is at least 97% by weight of the entire composition.
5. A refractory composition according to any one of claims 1 to 4, wherein the zirconium compound is baddeleyite.
6. A refractory composition according to claim 5, wherein the baddeleyite has a particle size of less than 0.5 mm.
7. A refractory compound according to any one of claims 1 to 4 and 6, wherein the sintered or fused magnesite in the start-ing material has the following grain size distribution:
3.5 to 6.0 mm 5 to 10%
1.0 to 3.5 mm 25 to 40%
0.09 to 1.0 mm 5 to 20%
not more than 0.09 mm 25 to 40%
8. A refractory compound according to any one of claims 1 to 4 and 6, wherein the proportion of refractory material in the starting material having a grain size of not more than 0.09 mm is at least 30% by weight.
9. A refractory compound according to claim 8, wherein the proportion of refractory material in the starting material having a grain size of not more than 0.09 mm is to 35 to 45% by weight.
10. A refractory composition according to any one of claims 1 to 4 and 6, which is in a burnt molded body or refractory brick form.
11. A process which comprises mixing (a) a sintered or fused extremely pure low-iron magnesite having an MgO content of at least 97% by weight, (b) 10 to 25% by weight based on MgO of a zirconium compound having a ZrO2 content of at least 98% by weight and (c) a temporary binding agent, thereby obtaining an unshaped starting refractory composition.
12. A process according to claim 11, wherein a sulfite liquor is used as the temporary binding agent.
13. A process according to claim 11 or 12, wherein the un-shaped composition is shaped and dried at a temperature of 100 to 180°C, thereby obtaining a shaped dry article.
14. A process according to claim 13, which further comprises annealing the shaped article at a temperature of 400 to 800°C, thereby obtaining a shaped annealed article.
15. A process according to claim 13, which further comprises burning the shaped article at a temperature of 1600 to 1800°C, thereby obtaining a shaped burnt article.
16. A method which comprises lining, with a refractory material, furnaces or high temperature zones of furnaces for the manufacture of burnt dolomite, lime or magnesia, wherein the said refractory material is a molded body or refractory brick made of the refractory composition as defined in any one of claims 1 to 4, 6 and 9.
17. A method for manufacturing burnt dolomite, magnesite or lime, which comprises burning dolomite, magnesite or lime in a furnace in which a main burning zone is lined with a molded body or refractory brick made of the refractory composition as defined in any one of claims 1 to 4, 6 and 9.
18. Use of the refractory compound according to any one of claims 1 to 4, 6 and 9, in the form of burnt moulded bodies or refractory bricks, for lining furnaces or high temperature zones of furnaces for the manufacture of burnt dolomite, lime or magnesite.
CA000583977A 1987-11-25 1988-11-24 Shape or unshaped refractory compounds based on magnesite and their use for lining furnaces Expired - Fee Related CA1316183C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3739900.4 1987-11-25
DE19873739900 DE3739900A1 (en) 1987-11-25 1987-11-25 Shaped or unshaped refractory compositions based on magnesite and their use for lining kilns (furnaces)

Publications (1)

Publication Number Publication Date
CA1316183C true CA1316183C (en) 1993-04-13

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ID=6341213

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000583977A Expired - Fee Related CA1316183C (en) 1987-11-25 1988-11-24 Shape or unshaped refractory compounds based on magnesite and their use for lining furnaces

Country Status (4)

Country Link
AT (1) AT393832B (en)
CA (1) CA1316183C (en)
DE (1) DE3739900A1 (en)
FR (1) FR2623493A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4040458A1 (en) * 1990-12-18 1992-06-25 Aken Magnesitwerk Gmbh POROESES, FIRE-RESISTANT SPOOL ELEMENT
DE4337916A1 (en) * 1993-11-06 1995-05-11 Aken Magnesitwerk Gmbh Shaped and unshaped refractory compositions based on magnesia
DE10216879B4 (en) * 2002-04-17 2004-05-06 Refractory Intellectual Property Gmbh & Co.Kg Use of a magnesia zirconia stone

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT316400B (en) * 1971-10-27 1974-07-10 Veitscher Magnesitwerke Ag Fired refractory shaped body
DE2347909A1 (en) * 1973-09-24 1975-04-03 Orissa Cement Ltd Refractory bricks contg. graphite and a binder - esp. for linings in oxygen converters for steel mfr. and similar uses
US4696455A (en) * 1984-10-30 1987-09-29 Consolidated Ceramic Products, Inc. Zircon and MgO preheatable insulating refractory liners and methods of use thereof

Also Published As

Publication number Publication date
DE3739900C2 (en) 1989-12-14
DE3739900A1 (en) 1989-06-08
AT393832B (en) 1991-12-27
FR2623493A1 (en) 1989-05-26
ATA255188A (en) 1991-06-15

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