DE2333830A1 - FIREPROOF OBJECTS - Google Patents

Description

PATENT LAWYERS
D R. - IN GH FIMCKE

DIPL-IN GH BOHR
DiPL-INO-S-STAEGER

8MÜNCHEf4 5 Z O J O O O U

MÜLLERSTRASSE 31

Folder 2325 ^ - Dr. K.
Case MD 25 ^ 95

Imperial Chemical Industries Ltd, London, Great Britain

Refractory items

Priority: July 3, 1972 - Great Britain

The invention relates to a refractory article, and more particularly to a refractory article in sheet, paper, board, blanket, felt or cloth form or in the form of combinations thereof, which suitable for thermal insulation and electrical insulation, filtration, chemical treatment and acoustic insulation suitable.

30988 4/1129

According to the invention, a refractory article is proposed, which has a paper, cloth, board, plate, blanket or felt shape and made of fiber from one refractory metal oxide, which is made with a refractory. Oxide binders are bound.

If a cloth is used it can be woven or non-woven. Alumina or zirconia fibers are very suitable for use according to the invention. The refractory .. oxide fiber is preferably made by a Process prepared, which is described in the Dutch patent application 7 ^ 08 399, the content of which as to be included in the present application. In this process, pasers are produced by that one defibrates a composition with a viscosity of more than 1 poise, which is obtained from an aqueous solution or from a sol of a heather compound, such as an oxychloride, a basic acetate, a basic formate: or nitrate of aluminum and / or zirconium and a minor amount of a water-soluble organic polymer contains, the produced Paser dries and heats to convert the metal compound into the oxide and the Decompose polymer. Fibers can also be used which are only partially converted into the oxide, provided that they are not in the binding composition dissolve.

Preferred water-soluble organic polymers are polyethylene oxide, Polyvinyl alcohol and polyvinyl pyrrolidone.

The fiber production is preferably carried out by a blowing process, which consists in that the Composition to be processed into fibers extruded through one or more holes in at least one gas stream, the one component of high speed in the direction of travel

309884/1129

BAD ORIGINAL ^C0PY

of the extruded composition. The dimensions and shape of said hole can vary widely. It is preferred to use a hole in which at least one dimension is greater than 30 / -'- and less than 500 .. *. The gas flow is preferably an air flow, in particular air at room temperature. It is convenient to use two gas streams which converge at or near the point where the composition is extruded from the hole. Preferably the angle between the converging gas streams is 30 to 60 °. At least some of the water in the composition is removed by the gas stream. The speed of removal can conveniently be determined by mixing the gas with water vapor. For example, air with a relative humidity of more than 8C% can be used. The velocity of the gas flow can be varied within wide limits, but it is preferred to use velocities in the range from 60.9 to 457.2 m / sec. The pressure required to extrude "the composition through the holes depends on the viscosity of the composition and the rate of extrusion desired. It has been found that

that · pressures from 1.1 to 70 kg / cm absolute for compositions are expedient that have viscosities up to about 100 poise.

The fibers made by the blown process are generally small in diameter, typically from 0.5 to 5.0 «-" «■, which is a very suitable one Diameter range for 'papermaking techniques trades ·. The fibers are generally discontinuous in length and can have very high length to ratios Have diameters, for example ratios of more than 5000. The fibers can be made as individual fibers

309884/1129

BAD ORIGWAL ^Cop Y

• be collected, or they can be collected in the form of a thread, a mat, a blanket or a felt. Venn they are collected as individual fibers, they can be molded into paper sheets, blankets or felts by any convenient method. If they are collected in the form of a mat, then they can be made into a yarn and that yarn can then be made into a cloth for use in accordance with the invention. Fibers with average diameters of 1 to 3A are particularly useful. The vast absence of shot, that is a material that has a non-fibrous nature, in which fiber is an advantage in the manufacture of papers and other articles according to the invention. The defibration of the aqueous solution of the metal compounds, in particular by the blowing described above Fibers with a greatly reduced shot content compared to other processes for the production of refractory oxide fibers, fibers with a specific surface area of 0.5 to 150 m / g are preferred.

According to the invention there is a precursor for a refractory ' Object made of a paper, cloth, board, plate, blanket or felt made of fire-proof Metal oxide fibers and from a composition - which can be converted into a refractory oxide binder.

The compositions which can be converted into a refractory binder are preferably liquids which contain compounds which can be converted into a refractory oxide, for example by heating. Suitable 'compounds which can form refractory oxides _T are colloidal or dissolved inorganic oxygen compounds, such as, for example, hydrated oxide sols of aluminum oxide, silicon dioxide, titanium oxide, zirconium oxide or mixtures

309884/1129

BAD ORIGINAL ^COp Y

from it. Oxychlorides, basic acetates or basic formates of aluminum and / or zirconium are particularly preferred. Aluminosilicates are also useful. Silica sols with the name "Syton" or the names N 1030 or N 1050 (NaIfloc Ltd.) and alumina and alumina monohydrate brines (Boehmite) with the name "Baymal" or "Cerasol" are very suitable. Alkali metal silicates, organic esters of inorganic acids such as alkyl silicates and alkyl titanates ^ can be used.

Finely divided solid filter materials such as clays, calcined clays and other mineral silicates can be present within the fiber or on the surface of the paper, cloth, plate, board or felt, for example to modify the rheological or refractory properties. Light fillers, such as exfoliated mica, can also be present. Depending on the relative proportions of the fiber _{5 of} the binder and. Other materials present, the objects can have a gas permeability, a density, a strength, an elasticity and a thermal conductivity which lie within a wide range, which is why they can also be used for a wider range of applications than the previously known refractory objects The proportions of binder are expediently between 1 and 50% by weight, based on the refractory oxide fibers present.

The refractory manufactured according to the invention ' stand can be in any shape, depending on its intended use. So boards can hold up to thick structures by lamination or other combination, with or without the use a refractory binder, which is the

3Q9884 / 1129

the same or a different person than he is for Tying the fibers is used.

In one embodiment of the invention, the article exists from a flat board or from a laminated assembly of flat boards. Such an 'object usually must be supported by an external metallic or refractory framework. For example a plurality of panels can be held side by side to create parallel gas passages that form a result in low pressure drop and still have effective contact with the gas due to the open Texture of the panels.

There is a second embodiment of the invention the refractory article made from a ribbed or embossed plate. Such plates can have smooth surfaces have between the ribs or embossments, or the ribs and / or embossments may overflow be. The ribs may, but may not, be parallel and regular, and there may be two or more There may be groups of ribs that intersect one another. Ribs and embossing can both be present, uni them can from 'the general level of the paper either according to. go up or down or go both ways. This list of possibilities, which is not exhaustive, explains an advantage of the invention, namely the, de3 it is possible to manufacture a wide variety of plate-like refractory articles.

In particular, the invention also relates to a laminated assembly of such panels which lie together. The elevations of the ribs and / or embossing of successive Plates can be in contact with each other,

309884/1129

to make passages through, the compilation. The ribbed or embossed panels can alternate with flat panels, an arrangement which the need eliminated ensuring an exact coincidence of the elevations. It is particularly suitable if the plates are to be formed into a spiral roll.

As an alternative, according to the invention, there is also a compilation suggested making a single long plate that is ribbed or embossed at one frequency which is small on one side and becomes higher on the other side, wrapped in a spiral is so that radial passages arise. This grouping may include a flat spiral sandwiched between the corrugated or embossed spiral. In such Compilations must be a piece of paper, a cloth, a sheet, a blackboard, a blanket or a felt with sufficient Extensibility when wet can be used. Invention according to For example, compilations can be 1 to 4 CC

2
Have passageways per area of 6.45 cm. There are advantageously low overall densities, such as from 0.25 g / cm, possible.

In the compilations, the ribbed and / cder embossed panels may be connected to each other or to flat panels, but this is not essential provided that the tablets are held by their ends. The binding of the panels to one another or to supporting end pieces can be done with the help of the same binding material as is used for the mutual adhesion of the fibers used in the tablets.

30988A / 1129

The refractory articles of the invention are in general elastic. Their active surface for contact with sizes can be perforated or incised increased by holes. Some of the serious difficulties encountered while holding ceramic M3trices found in metal containers occur does not arise because of the flexibility of the articles of the invention.

The refractory articles of the invention are suitable suitable for many applications, such as for thermal insulation and electrical insulation, for filtration, chemical Treatment (especially of gases) and for acoustic isolation.

In the field of thermal insulation, these objects are suitable as sheaths or panels that are used as linings or attachments can be used for pouring or for molding. Since such objects after a are often discarded for a single use, they may contain organic modifiers such as e.g. Fibers, for example polyester or viscose fibers, Rubber latices and starches, which can be used to to improve the low temperature elasticity of the objects. Such organic modifiers will be normally destroyed during use as a result of the high temperatures that occur.

The structures are suitable for filtration processes, where high temperature resistance of the filter is required, such as the filtration of molten Metal prior to casting or in the filtration of hot exhaust gases containing particulate solids.

309884/1129

The refractory articles are also suitable as separators in batteries and as diaphragms for electrolytic Cells.

The refractory articles according to the invention are particularly suitable for treating gases for the purpose of calming them or for the purpose of performing chemical reactions »Due to the low pressure drop and high They can be used with or without the addition of further catalytic material as a catalyst for the geometric surface the treatment of exhaust gases can be used to remove atmospheric pollutants, such as nitrogen oxides, Carbon monoxide, hydrocarbons, sulfur dioxide, hydrogen sulfide, ammonia and solvent vapors. In particular, the invention also comprises a method for the catalytic treatment of internal combustion engine exhaust gases with or without added oxygen.

In the manufacture of precursors of refractory articles according to the invention, refractory metal oxide fibers can be impregnated with a composition which is alterable to make it a refractory binder gives away. The composition is then subjected to the necessary transformation to conform to the refractory structure of the invention.

Since the impregnation is usually carried out after the fibers have been wrapped in a paper, cloth, board, a If the plate, blanket or felt has been transferred, it may be desirable to use the organic binder that added during papermaking or felting must be removed or decomposed before the convertible composition is applied, otherwise access of the composition through the fibers is degraded.

30988A / 1129

The precursor of the refractory structure is preferably made of refractory metal oxide fibers, especially aluminum oxide or zirconia fibers made by Defibration of an aqueous composition of compounds of the metal as described above. Particularly preferred are pasers made by what is described above Blow molding processes are made because fibers are of a suitable diameter and free from shot can be obtained.

Conversion of the impregnation composition into a refractory binder is conveniently carried out by heating. The temperature of heating depends on the decomposition temperature or temperatures of the compound or compounds in the composition. For oxychlorides and salts of organic acids of metals, which can be decomposed into refractory oxides, temperatures in the range from 400 to 150O ⁰ G are expedient. The objects can be heated further in order to sinter the refractory binders, for example to temperatures of 1000 to 2000 ⁰ G.

The paper, d ^r -s cloth, the plate, the board, the ceiling or the felt can after impregnation still wet mechanical be subjected to treatments which are suitable for producing the desired shape, in particular by squeezing, pulling apart, Rib formation or embossing. These operations can be carried out in batches or in a continuous web by passing over or passing through appropriately shaped surfaces, which may be rollers. The paper, the cloth, the sheet, the board: .., the blanket or the felt can

309884/1129

also expediently shaped before impregnation be, for example, by rib formation or by embossing.

After impregnation, the impregnation composition preferably becomes a non-flowable state converted by chemical treatment as follows:

For hydrated oxide brine treatment with organic Acids and / or ammonium salts are appropriate, such as c; for example in British patent application 41846/69 " is described. Treatment with an alum solution, in particular having a pH of 3 to 5, is preferred.

A Jiit treatment is suitable for alkali metal silicates Acid. Such treatments are expediently long effective, for example, when a connection that lanpj-'rn Releases acid, is mixed into the fiber and into the silicate. Suitable compounds are silicofluorides and hydrolyzable organic esters such as ethyl acetate. A convenient chemical treatment that runs faster, takes place with carbon dioxide.

For esters of inorganic acids, hydrolysis is extremely useful, especially in the presence a strong acid such as hydrochloric acid in a catalytic a lot.

Normal or elevated temperatures can be used in the chemical treatment.

309884/1129

As an alternative to chemical treatment, paper, cloth, board, plate or felt can be used after the impregnation are partially dried so that they are still flexible before the mechanical Treatment is running. This drying should preferably be some form of uniform heating such as dielectric heating, microwave heating or infrared heating.

A retention aid such as a cationic one Polymer, for example polyacrylomide, can be advantageous Way to impregnation composition or fibers before or after impregnation be admitted. A suitable concentration of the retention aid is 0.01 to 0.20% by weight.

If the refractory article is to be used for the chemical treatment of gases, then can the fiber or the binder itself is an active material for supporting the chemical reaction be. Examples are aluminum oxide and aluminosilicate. Much more often the active material is a separate one Component. Here, such a material can be a component of the fiber which, under certain circumstances, is part of the Liquid is added from which the fiber is originally spun or flaked, as in in Dutch patent application 7 108 399 is. The active material can be used with the binding composition or with the finished refractory article or at several times during the manufacturing process; of the object are added. -

309884/1129

The active material 'can be any active material which is already known for gas treatment, such as transition metals and their oxides, basic compounds of alkali metals and alkaline earth metals and combinations of two or more thereof.

The catalysts are metals and oxides of groups Ib and VIII of the periodic table and oxides of groups Va, VIa and VIIa are particularly useful. The active material can be applied directly to the surface of the refractory Article present, or it can be in a surface layer of the material with a relatively high specific surface area, as is the case with active aluminum oxide or an alkaline earth oxide, for example the EaIl is.

The invention is further illustrated by the following examples explained.

example 1

ο A paper with a basis weight of 200 g / m, which consisted of aluminum oxide fibers (manufactured according to example 6 * of the Dutch patent application 7 108 3.99) and was bound with 10% of an acrylic latex, was coated with a colloidal solution of silicon dioxide (N 1- 030 ex Nalfloc Ltd.) impregnated. The impregnated paper was impregnated with a 0.5% (w / v) solution of alum, followed by treatment with a 0.02% (w / v) solution of polyacrylamide (Magnafloc "., R 292 ex Allied Colloids Ltd.) The paper was drained and made into a corrugated shape, v; o it into a uniformly corrugated

* as described below ■

309 3 84/1129

BAD ORIGINAL ^C0PY '

Mold was allowed to dry. The panel was ^{fired at 800 °} G to remove organics. ■

Example 2

An assembly was made which consisted of a corrugated sheet of alumina fiber attached to a flat sheet of alumina fiber and bonded to it by an acrylic resin. This combination was wound up in a spiral shape in a cylinder and impregnated with colloidal silicon dioxide (IT 1030 ex-UsIfIce Ltd.). The impregnated cylinder was treated with a 0.5% (w / v) alum solution and then with a 0.02% (w / v) solution of polyacrylamide (Magnafloc). The cylinder was ^{dried at 100 °} C. and then "^{burned" at 800 °} C. in order to remove organic substances.

Example '5

A sheet of zirconium oxide fibers made according to Example 20 * of Dutch patent application 7 108 399 was wound onto a cylindrical mold to make a tube and then impregnated with a 5% (w / w) solution of alumina sol. The impregnated drill was treated with a 0.55 # ige.a (w / v) solution of Al ^ un and then 2. ·. - <id, still treated with a 0.02% (w / v) solution of Polyacry L-ftiid (Magnafloc). The tube was then removed from the mold and fired ^{at ICCO 0 C.}

* as described below

309834/1129

BAD ORlGiNAL ^COPY

Example 4

An aluminum oxide fiber paper with the size of 33 x 33 cm was impregnated with a 5% strength (by weight) solution of sodium silic-.t (Q 70 ex ICI Ltd.) and ^{dried at 10O 0} G. The treated paper was further 10 min with Treated 4N hydrochloric acid, whereupon it was washed acid-free. The product was then ^{burned at 800 °} C. in order to produce a fire-resistant panel which was suitable as a heat-insulating panel.

example

Aluminum oxide fiber papers with a thickness of 0.1 mm were immersed in a netrium silicate solution with a relatively low NaoOrSiO ^ ratio, the ratio being in the range from 1: 2.5 to 1: 4.0 (Na ₂ 0: Si0 ₂ ) and the total pesticide content of the solution was 20 μi. Sufficient layers were then placed on top of one another that a finished thickness of 6.3 mm was obtained. The stack was then pressed into a mold at a pressure of 7 atmospheres. Following the removal of the bus form, the product was .24- st dried at 80 to 100 ⁰ C, which is d ^ nn having a large strength. Improved stability to an aqueous environment was obtained by firing at 800-100 ° C for one time

Reached 2 half an hour. Breaking modulus values of 280 kg / cm.

were obtained and the density ranged from C, CA- to 0.96 g / cm ^. The product was ^{heat-resistant, strong and abrasion-resistant up to 10CO 0} C, which is why it could be used as lightweight panels for fire doors, furnace linings and heat-resistant covers.

309884/1129

Example 6

2 A paper with a basis weight of 100 g / m 2, which consisted of zirconium oxide fibers (produced as in Example 3) and which was impregnated with 20% by weight of a fibrous aluminum oxide hydretsol, was placed while still wet between a meshing pair of corrugated rollers passed through, which had a constant combing distance of 0.1 mm. The rolls were heated to 12O ⁰ G, and a stream of air at 140 ⁰ G was directed at the Pepier when it came out of the rollers. Thus, a corrugated paper was obtained, which was cut into plates approximately 10.1 10.1 mm in size. Plates of similarly impregnated and dried flat paper were also cut to the approximate size of 10.1 χ 10.1 mm. A fibrous alumina hydrate sol was applied to the ribs of the corrugated sheets and a stack made up of alternating corrugated and flat sheets was made. The combination was ^{dried at 100 °} C. under slight pressure, ^{fired at 700 °} C. and cooled. It was then impregnated with 10% (weight) colloidal silica (Ii 1030 ex NaIfloc Ltd.). After drying at 1C0 ° C, the assembly was fired at 1000 G ^0, where a strong refractory article was obtained.

Example 7

Corrugated zirconia fiber papers were made as described in Example 6. A long, flat, 1mm wide layer of zirconia fiber paper with a

Basic dish of 1GO g / m was made. The zirconium oxide fiber was made as in Example 3

309884/1129

is written, and the 'paper contained 5 wt .-% as a binder an acrylic resin and 5% by weight of a microfine glass fiber. The flat sheet was folded back and forth several times to form a folded stack 10.1 10.1 cm in size to manufacture. A layer of corrugated paper measuring 10.1 10.1 cm was placed on top of each of the Folded to create a honeycomb structure. The four closed sides of the item were using a cement made of zirconia fibers and alumina sol was made, and the two open sides were coated with a colloidal silica sol splattered. The structure was dried and then fired at 800 ° C.

The manufacture of alumina and zirconia fibers used in this example is described in Dutch patent application 7 ^ 08 399, namely example 6 describes the case of the manufacture of alumina fibers and example 20 the case of the manufacture of zirconia fibers. In Example 6, 50 ml of aluminum oxychloride solution containing 11.2% by weight of Al and 8.1% by weight of Cl were mixed with 30 ml of a 2% strength (by weight) solution of a higher molecular weight polyvinyl alcohol. The mixture was concentrated to a viscosity of 50 poise by evaporation under reduced pressure. The concentrated solution was introduced into a fiber blowing apparatus wherein two high velocity streams of air from each side at an angle of 30 ° impinged on a stream of the solution emerging from a 25 / * wide hole under pressure. The air streams had a temperature of 35 ^° C. and a relative humidity of 40%.

309884/1129

A mat of very fine fibers with lengths up to 10 ce and estimated diameters of 1 μ. was collected on a sieve. The mat was 1 st to 800 ⁰ G heated, with clear glassy parsers are obtained that were silky and flexible.

According to Example 20, a solution which is suitable for the production of high temperature resistant, yttrium stabilized zirconium oxide fibers, which are particularly useful for thermal insulation, is made from: 500 g zirconium acetate solution (22% (w / w) ZrC _n ), 220 ml a 1% (w / w) polyethylene oxide solution, 12.8 g of yttrium chloride hydrate and
2 ml of concentrated hydrochloric acid.

The solution was brought to a vacuum rotary evaporator to a viscosity of 15 poise at 2O ⁰ C and introduced into a container equipped mm with a spinneret hole having a diameter of 0.025.

A high velocity air stream exiting through slots on either side of this hole and in one Converged at an angle of 30 °, was used to pull the jet of liquid downwards from the hole in order to to produce substantially shot-free fibers with an average diameter of 1.5 / t.

The fibers were 1/2 st at 200 ⁰ O dried, to produce fibers having an average diameter of 1yt6.

A preferred example of a refractory article is shown in the accompanying drawings, wherein Figure 1 shows an isometric view of a finished article according to the invention; and

309884/1129

FIG. 2 shows an isometric section through two planes of a detail of the object from FIG.

The article consists of a sandwich of fish panels 10 with a thickness of 0.25 mm, which are embossed with Alternate panels 12 of the same thickness. The embossing is everywhere without any flat surfaces lie in between. Upward embossing alternates with downward embossing in one Distance of 1 cm and at a total amplitude of about 2.5 nm. On top and bottom of the sandwich lie thick plates 14 made of flat paper with a thickness of 0.75 mm. The sandwich is between them Flanges 18 of the side plates 16 are easily printed. the Ends of the thin plates are cemented to the side plates 16 by an alkali silicate layer 20, and in addition, the layer 20 cements the panels 14 on the planches 18 formed on the side plates 16.

30988W1129

Claims (1)

Claims Refractory object, characterized in that it consists of a paper, a cloth, a board, a plate, a blanket or a felt made of refractory metal oxide fibers, which is with a refractory Oxide binders are bound. 2. Refractory article according to claim 1, characterized in that the refractory metal oxide fibers have been prepared by having a composition having a viscosity greater than 1 poise shredded, from an aqueous solution or from watery
one / so! a metal compound which can form a refractory oxide, while also containing a minor amount of a water-soluble organic polymer, and drying and heating the fiber to convert the metal compound to the oxide and to add the polymer. decompose. 3. Refractory article according to claim 2, characterized in that the defibration performed thereby It has been found that the composition to be fiberized is passed through one or more holes extruded in at least one gas stream containing a high velocity component in the direction of travel having extruded composition. 4. Refractory article according to claim 3, characterized in that the gas flows at or in the 309884/1129 Near the point where the composition converge is extruded out of the hole. 5. Refractory article according to claim 3 or 4, characterized in that the gas is mixed with water vapor will. 6. Refractory article according to claim 5, characterized in that the gas consists of air with a relative humidity of more than 80%. 7. Refractory article according to one of claims 2 to 6, characterized in that the metal compound an oxychloride, a basic acetate, a basic formate or a nitrate of aluminum and / or Zircon is and has been decomposed into aluminum oxide and / or zirconium oxide. 8. Refractory article according to one of claims 2 to 7, characterized in that the water-soluble organic polymer is polyethylene oxide, polyvinyl alcohol or polyvinyl pyrrolidone. 9. Refractory article according to one of claims 1 to 8, characterized in that the fiber of the refractory metal oxide has a diameter of 0.5 to 5.0.I ¹ -. 10. Refractory article according to one of the claims 1 to 9, characterized in that it has the? 02 "τ. a flat panel or in the form of a laminated assembly of flat panels. 309884/1129 11. Refractory article according to one of the claims 1 to 9, characterized in that it is in the form of a ribbed or embossed panel or the shape a laminated assembly of corrugated or embossed panels. 12. Refractory article according to one of the claims 1 to 9 »characterized in that it is the In the form of a laminated assembly of flat panels and ribbed or embossed panels. 15. Refractory article according to claim 12, characterized in that the flat panels alternate with ribbed or embossed panels. .14. Refractory article according to one of claims 10 to 13, characterized in that the Panels have the shape of a spiral roll. 15. Refractory article according to one of the Claims 10 to 14, characterized in that the panels are bound in an assembly. 16 «Refractory article according to claim" ^ » characterized in that the panels by the same refractory binder which has been used to bind the fibers into the panels. 17 · Refractory article according to one of the claims 1 to 16, characterized in that it contains a catalytic material. 18. Precursors of a refractory according to one of claims 1 to 17 »thereby geriennseicr.-v. 309884/1129 that he made of a piece of paper, a cloth., a blackboard, a Sheet, blanket or felt made of refractory ketal oxide fibers and a composition, which can be converted into a refractory oxide binder. 19 precursor according to claim 18, characterized in that that the composition, which can be converted into a refractory oxide binder, has a is liquid that contains components that can form a refractory oxide when heated. 20. Precursor according to claim 19, characterized in that that the liquid contains a colloidal or dissolved inorganic oxygen compound. 21. A precursor according to claim 20, characterized in that the colloidal oxygen compound consists of a sol of alumina, silica, titania, zirconia, or mixtures thereof. 22. Precursor according to claim 20, characterized in that the oxygen compound is an oxychloride, ein.basisches acetate or a basic formate of aluminum and / or zirconium is. 23. A method of making a refractory article precursor according to any one of the claims 18 to 22, characterized in that refractory carbon dioxide fibers are impregnated with a liquid composition, which can be converted into a refractory oxide binder. 309884/1129 24. Procedure according to. Claim 25, characterized in that that the refractory metal oxide fibers by defibering a composition with a Viscosity of more than 1 poise can be formed aqueous an aqueous solution or a / Sor of a metal compound which can form a refractory oxide and which is a smaller amount of a water-soluble one organic polymer, and that the fibers formed are dried and heated to form the metal compound to convert to the oxide and to decompose the polymer. 25. The method according to claim 23 or 24, characterized in that 'that the refractory oxide fibers take the form of paper, cloth, plate, board, blanket or felt. 26. The method according to any one of claims 23 to 25, characterized in that the impregnation composition is converted into a non-flowable state. 27. The method according to claim 26, characterized in that the conversion of the composition into a non-flowable state is carried out by chemical treatment or by partial drying. 28. The method according to any one of claims 23 to 27, characterized in that the Pspier, the cloth, the The panel, board, blanket or felt is subjected to a mechanical treatment that is suitable to create the desired shape before:. or after impregnation. 309884/1129 29. The method according to claim 28, characterized in that the mechanical treatment in a squeezing, in a stretching, in a rib formation or in an embossing. 30. The method according to any one of claims 23 to 29, characterized in that a catalyst material or a precursor thereof into the liquid binding composition from which the fibers are made, or to any component of the refractory article is added. 31. Method of making a refractory Article according to one of Claims 1 to 17 »thereby characterized in that a precursor of a refractory article according to one of claims 18 to 22 heated. 32. The method of claim 311 wherein the precursor to a temperature of 4-00 to 1500 ⁰ C is heated. PATENT LAWYERS MtHNA.H.FINCK £, DIPL-INO. H. BOHR . λβΤΑΕββ » 309884/1129 Blank page