WO2019076619A1 - USE OF AN OFF-SPRING AND / OR OF A FORMED OR UNFORMED FIRE-RESISTANT PRODUCT FOR A REFRACTORY DELIVERY OF A COAL GASING MACHINE, SUCH DELIVERY AND COAL GASING MACHINE WITH SUCH A DELIVERY - Google Patents

Abstract

The present invention relates to the use of an offset and / or the use of a shaped or unshaped refractory product for a refractory lining, in particular for a working liner or a security liner, a coal gasification plant, such delivery and a coal gasification plant with such delivery.

Description

The present invention relates to the use of an offset and / or the use of a shaped or unshaped refractory product for a refractory product of a coal gasification plant, such delivery and coal gasification plant with such delivery refractory lining, in particular for a working feed or a security feed, a coal gasification plant, such a delivery and a coal gasification plant with such a delivery. The term "refractory" should not be limited in the context of the invention to the definition according to ISO 836 or DIN 51060, which define a cone drop point of> 1500 ° C. Refractory products according to the invention have a printer softening point T ₀ , s according to DIN EN ISO 1893: 2009-09 of To, 5 ° to 600 ° C., preferably To, 5 ° to 800 ° C. Accordingly, refractory or refractory granular materials or granulations in the sense of the invention are materials or grains suitable for a refractory product are suitable with the above-mentioned printer softening point To, 5. The refractory products according to the invention are used to protect aggregate constructions in aggregates in which temperatures between 600 and 2000 ° C., in particular between 1000 and 1800 ° C. prevail.

As is well known, heavy clay products are products that are produced from grain sizes with grain sizes up to 6 mm, in special cases also up to 25 mm (see "Gerald Routschka / Hartmut Wuthnow, Practical Guide" Refractory Materials ", 5th edition, Vulkan-Verlag, (hereinafter only referred to as "practical manual"), chapter 2).

The term "grain" or "granular material" in the context of the invention comprises a pourable solid which consists of many small, solid grains. If the grains have a grain size <200 μm, the grain size is a flour or powder. The grains are usually produced by mechanical comminution, eg breaking and / or grinding. It but may also be granules, which are produced by granulation without mechanical comminution. Grain size distribution is usually adjusted by sieving.

In the dissertation of Dipl.-Ing. Patrick Gehre, "Corrosion and Thermal Resistant Refractories for A Os-based Residual Aeration Systems - Materials Development and Corrosion Testing", September 23, 2013, the state of the art regarding coal gasification plants is described in detail:

In a coal gasification plant, coal, especially lignite or hard coal, reacts during gasification with oxygen and water vapor under reducing conditions. In this case, temperatures up to 1600 ° C and pressures up to 50 bar arise. The coal reacts during a partial oxidation with free (O2) or bound (H2O, CO2) oxygen as gasification agent, the oxygen being used substoichiometrically with respect to the gasification medium (coal), which leads to reducing conditions in the gasification plants. As a by-product ash or slag (liquid ash) is deposited. The resulting gasification gas has typical components C0 ₂ , CO, CH ₄ , H ₂ , H ₂ O, H ₂ S and NH ₃ .

Depending on the gasification conditions, the composition of the gasification gas is different. In the production of synthesis gas (CO + H2), the main focus is on the production of CO and H2, for the use as fuel gas, however, on a high methane value. Typically, as the gasification temperature increases, the gas composition shifts toward CO and H2 to produce syngas. Increasing the pressure reduces the CO and H2 contents in the gas and increases the proportion of hydrocarbons.

In the known gasification processes and principles, a distinction is made depending on the type of gasification agent between autothermal, allothermal and hydrogenating gasification. In the autothermal gasification, a partial oxidation takes place by the use of an oxygen-containing gasification agent, wherein the provision of the required process heat takes place directly through the exothermic oxidation reaction. In contrast, in the allothermal gasification, water vapor is used as the gasifying agent. Heterogeneous water gas reactions dominate. The supply of the required heat takes place externally, without this materially or energetically connected to the gasification. Hydrogenating gasification uses hydrogen instead. Here, methane-rich gasification gas is obtained under elevated pressure.

Furthermore, depending on the type of gas-solid contacting, a distinction is made between fixed-bed or moving-bed, fluidized bed and entrained flow processes. Due to the different upper process temperatures, the ash is either dry (fixed bed process with T <1300 ° C) or liquid (entrained flow and slag bath process with T> 1300 ° C). Depending on the temperature, a distinction is also made in high-temperature gasification processes (T> 1300 ° C) and low-temperature gasification processes (T <1300 ° C). Coal gasification plants typically have a metallic plant jacket that must be protected from overheating and corrosion by slag attack. This purpose is a lining or delivery of refractory material. The lining or delivery can z. B. multilayer structure and a fire-side or hot-side work chuck, which is in direct contact with the slag, and have a security lining arranged behind it. The safety lining still offers a certain degree of corrosion protection if the slag penetrates the working lining after a long service life. The protective lining may be followed by further layers, in particular for thermal insulation and thus for the protection of the metallic plant jacket against overheating.

The different gasification plants can also be divided into different zones. An entrainment gasifier with head burner has z. B. an upper area, which includes the dome and the upper portion of the side wall. In the upper area are the burner and the inlet for the gasification agents and substances. The ones below Sidewalls experience the highest stress in the flow gasifier by slag infiltration, corrosion and temperature fluctuations. In the lower area is the slag outlet, where also high corrosive and additionally abrasive stresses occur due to the high flow speed of the slag.

During gasification, different process parameters affect the lining materials.

Depending on the type of process (high or low-temperature gasification process), the lining materials are exposed to different temperatures, for example. Furthermore, during the gasification it can always come back to fluctuations in temperature z. B. by changing the promotion of the gasification agent or the startup and shutdown of the gasification plant. This results in thermal stresses. When a protective layer is formed by reaction of the lining materials with slag constituents, the different thermal expansion coefficients can lead to spalling of this layer.

The pressure prevailing in gasification plants must also be taken into account. Usually, pressures of up to 40 bar are achieved. However, recent developments foresee a process pressure of up to 100 bar. This too can have an influence on the corrosion.

As already explained, there is a reducing atmosphere in the gasification plants. However, it can in operation again and again, for. B. due to process stops, come to oxidizing conditions, which is why the lining should resist a constant change between oxidizing and reducing atmosphere. Oxidizing materials such. As carbonaceous materials (MgO-C) are therefore only partially in question.

Mainly the gasifier atmosphere consists of H2 and CO. In addition, there is water vapor H2O (g) and CO2. In addition, due to Impurities in the coal small amounts of H2S, Nhh or other components may be present.

Furthermore, the coal and ash particles have an abrasive effect on the working liner. However, the greatest importance in terms of corrosion has the slag. The slag is produced from the ash introduced with the coal, which melts at the high temperatures of the gasification, is thrown on the carburetor wall and flows as slag at this. The interaction of the slag with the refractory lining usually causes the greatest damage. As a rule, the coal slag consists of the main components S1O2, Al2O3, FeO and CaO. As minor constituents, among others, Na 2 O, MgO, K 2 O, SO 3 and C may be contained. Depending on the ratio of the components with each other, the slag is basic or acidic. As a rule, coal slags contain a relatively high proportion of S1O2, Al2O3 and alkalies with a low CaO content. They are thus significantly more acidic than slags from the iron and steel industry. Depending on the deposit, the coal slags can also have iron contents of 5 to 20 wt .-% and high sulfur contents. Especially lignite slags are very aggressive.

The known lining materials are usually infiltrated by slag and react with it to new phases to form a protective layer, which protects the material from further attacks against coal slag.

Particularly suitable refractory products for the lining are chro m oxide-containing bricks, for example MgCr204, Cr203-Al203 bricks O- of the bricks made of CrO 2, Al 2 O 3 and OO 2 or bricks based on SiC. Disadvantage of Cr203-containing materials is mainly their disposal. In addition, they are relatively expensive. Because of this, there is a desire to develop Cr203-free materials that are produced with low energy and CO2 emissions and can be easily disposed of or recycled after use. Patrick Gehre has therefore dealt with such materials based on alumina in his above-mentioned dissertation. An aluminum spinel casting compound was investigated. This was added to improve the corrosion resistance of Al2O3 to coal slag in a second step ΤΊΟ2 and OO2. In a next step, the microstructure of an AbOs casting material was optimized by adding intermediate lignite coal ash to increase the sintering effect.

Also known in the art are refractory bricks made of carbon for the lining of blast furnaces or for the lining of the electrolytic sump in the production of primary aluminum (see Practical Guide, Chapter 4.4.4). These can be divided into two groups: amorphous and graphite. By adding aggregates, further varieties have been developed in recent years which, depending on the type of aggregates, e.g. in metallic silicon, be termed "microporous" or "supermicroporous". According to the Practical Guide, page 57 / Table 4.9 A, carbon and graphite stones are subdivided according to their carbon content and their Al2O3, S1O2 and SiC content.

As raw materials for the production of carbon and graphite bricks gas calcined or electrically calcined anthracite, graphite, petroleum or pitch coke are used as driers. The binders used are coal tar pitch, petrol pitch or resins, which form a coke-binder matrix in the finished block. These are coke-binders. The preparation is carried out in a conventional manner by shaping a green mass. After shaping, the "green body" is subjected to a firing process up to about 1200 ° C., whereby the binder is converted into coke and impregnated with impregnating agents which are similar to the binders, which can be recompressed Impregnating agent is also converted into coke by another firing cycle. Furthermore, as additives, for example, Si, Al2O3, Ti, T1O2 may be present.

The object of the present invention is to provide a molded article of unshaped refractory product for use in feed, preferably for the working liner or for the safety chuck, a coal gasification plant which drastically reduces the rate of wear of the infeed while at the same time increasing its thermal conductivity. The product should also ensure a cost-effective and environmentally friendly delivery concept. Furthermore, an offset for the production of such a product is to be provided.

Another object of the invention is to provide a refractory lining of a coal gasification plant with at least one such refractory product. The working lining and / or the safety lining of the delivery preferably has the product.

Furthermore, a coal gasification plant is to be provided with such a delivery.

These objects are achieved by the features of claims 1, 15, 16, 32 and 35. Advantageous developments of the invention are characterized in the appended subclaims.

In the following the invention will be explained in more detail by way of example with reference to a drawing.

Show it:

Figure 1: A sawed crucible, prepared according to Embodiment 1, after the test

Figure 2: A sawed crucible, prepared according to Embodiment 2, after the test Figure 3: A sawed crucible, prepared according to a comparative example

Within the scope of the invention, it has surprisingly been found that refractory, unshaped or shaped, highly carbonaceous products which, based on their dry matter, amount to at least 70% by weight, preferably to at least 80% by weight, preferably to at least 90% by weight. , Particularly preferably at least 95 wt .-% consist of carbon, can be used for the refractory lining of a coal gasification plant.

Or. the products consist, based on their dry matter, of 70-99% by weight, preferably 80-99%, preferably 90-99%, particularly preferably 95-99% by weight of carbon.

In particular, it has been found in the context of the invention that the high-carbon products according to the invention are not wetted by the coal slag and therefore are not infiltrated. Thus, the wear rate is significantly reduced compared to the known products.

The use of the high-carbon products according to the invention was actually remote because carbon material is known to be used for the gasification of carbon. It was therefore actually to be expected that the products according to the invention would wear out very quickly in the atmosphere prevailing in coal gasification plants.

The products according to the invention preferably have the carbon in amorphous form and / or in graphitic modification.

The products according to the invention preferably have an amorphous carbon content of at least 60% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight, very particularly preferably at least 90% by weight, based on their dry matter. %, on. Or. the products according to the invention preferably have, based on their dry mass, an amorphous carbon content of 60-99% by weight, preferably 70-99% by weight, more preferably 80-99% by weight, most preferably from 90-99 wt .-%, on. The total carbon content is determined in a manner known per se using elementary carbon analysis according to DIN 19539: 2016-12. Preferably, the multiphase carbon and hydrogen / moisture analyzer LECO RC 612 is used.

The content of amorphous carbon is also determined according to DIN19539: 2016-12.

The shaped, heavy ceramic products according to the invention are ceramic unfired or fired, in particular pressed, preferably produced in a ceramic factory, products, in particular stones or plates. The shaped products, in particular the stones, are bricked up to form the lining, with mortar or mortar-free ("crunchy").

The unshaped products according to the invention are products which, for the most part by the user, are produced from an unshaped mass, for example by casting or spraying. Unformed products are usually placed at the place of use behind formwork in larger fields and form after hardening part of the delivery. The unshaped products according to the invention are preferably injection molding compounds, ramming compounds, casting compounds, vibrating compounds or casting compounds. Both the shaped and unshaped products according to the invention are produced in a manner known per se from a coarse ceramic offset. According to an independent aspect of the invention, an offset of at least 90% by weight, preferably at least 95% by weight, preferably 100% by weight, based on the total mass, is used for the production of the molded or unshaped products according to the invention of the batch, consists of a) a dry mixture or a dry substance mixture, based on the total dry matter of the dry substance mixture, at least 80 wt .-%, preferably at least 90 wt .-%, preferably at least 95 wt.%, particularly preferably 100 Wt .-% of at least one grain of carbon material, and

 b) at least one cokeable liquid and / or dry, pulverulent binder,

 c) optionally water,

 d) optionally at least one liquid additive (additive).

An inventive offset thus preferably consists of a dry material mixture of granular dry substances or grains and binder and optionally water and liquid additive. That is, the amount of binder, water and liquid additive is added additively to the dry mix and refers to the total dry mass of the dry mix (not the total mass of the mix). The offset preferably has from 0.5 to 20% by weight, preferably from 1 to 15% by weight, of liquid and / or dry, cokeable binder, based on the dry total mass of the dry substance mixture. In the case of unshaped products, the liquid and / or solid or dry, powdery binder is preferably included in a separate container from the other dry components of the offset.

The addition of water is usually only necessary if only a dry cokeable binder is used. The liquid or dry cokeable binder is an organic binder.

Preferably, the liquid chargeable binder is a binder of the following group: synthetic resin, preferably phenolic resin, pitch or pitch derivative.

The synthetic resin is in particular liquid as resol or in alcoholic solution with novolaks and / or hexamethylenetetramine as hardener.

The dry cokeable binder is preferably a binder of the following group: synthetic resin, preferably phenolic resin.

Carbon material in the context of the invention means a material which has a total carbon content of at least 70% by weight, based on the dry mass of the carbon material. The carbon material preferably has at least 80% by weight, particularly preferably at least 90% by weight, very particularly preferably at least 95% by weight, of carbon, based on the dry matter of the carbon material.

Or. Carbon material in the context of the invention means a material which has a total carbon content of 70-99% by weight. The carbon material preferably has 80-99% by weight, particularly preferably 90-99% by weight, very particularly preferably 95-99% by weight, of carbon, based on the dry mass of the carbon material.

The carbon is present in the carbon material in amorphous form and / or in graphitic modification.

The carbon material, based on its dry mass, preferably has an amorphous carbon content of at least 60% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight, very particularly preferably at least 90% by weight. -% on. Preferably, the Offset as a carbon material exclusively on such carbon material.

Or. The carbon material, based on its dry mass, preferably has an amorphous carbon content of 60-99% by weight, preferably 70-99% by weight, particularly preferably 80-99% by weight, very particularly preferably from 90-99% by weight. Preferably, the offset as the carbon material exclusively on such carbon material.

Preferably, the dry substance mixture, based on its total dry matter, at least 70 wt .-%, preferably at least 80 wt .-%, preferably at least 90 wt .-%, particularly preferably 95 wt .-% of carbon material, which exclusively amorphous Contains carbon.

In particular, the offset has as carbon material only grains of carbon material containing exclusively amorphous carbon.

The total carbon content and the amorphous carbon content of the carbon material are also determined as indicated above.

Preferably, the carbon material is a material from the following group: anthracite, preferably gas-calcined or electrically calcined anthracite, graphite, petroleum or pitch coke, thermal black. Particularly preferably it is anthracite and thermal black.

According to an advantageous aspect of the invention, the dry matter mixture comprises the following constituents, in each case based on the total dry matter of the dry substance mixture, or consists of these constituents (the quantities indicate in each case the total sum of the respective components, eg the total proportion of coarse grain size, the total proportion on flour grain or on further grain size): a) at least one coarse grain of carbon material with a particle size> 200 μιτι, preferably in an amount of 50 to 90 wt .-%, preferably from 60 to 90 wt .-% b) at least one flour grain of carbon material, with a grain size <200 μιτι, preferably in an amount of 10 to 50 wt .-%, preferably from 10 to 40 wt .-% c) at least one further grain of another refractory material, in an amount of 0 to 15 wt .-%, preferably from 0 to 10 wt .-% d) at least one additive having a particle size <200 μιτι, in an amount of 0 to 3 wt .-% e) optionally at least one additive for refractory materials, preferably in a total amount of <2 wt .-%

The components may be included in the dry matter mixture in any combination. Also, the same carbon material may be present both as a flour grain and as a coarse grain. The coarse component serves as supporting grain in a manner known per se.

The coarse grain carbon material is preferably a material from the following group: anthracite, preferably gas-calcined or electrically calcined anthracite, graphite, petroleum or pitch coke. Most preferably, it is exclusively anthracite.

Preferably, the dry substance mixture thus generally, based on its total dry matter, at least 50 wt .-%, preferably at least 60 wt .-%, preferably at least 70 wt .-%, anthracite on. Furthermore, the coarse grain can also consist of a recylated carbon material, preferably of a recycled magnesia carbon material. For example, the grain size can be chen and processing a carbon stone, in particular a magnesia carbon stone, or produced by electrode breakage.

As already explained above, the coarse grain can also consist of granules, ie grains which have been produced by granulating a flour-shaped carbon material. In this case, it is preferably granules of granulated thermal black.

Furthermore, the coarse grain size of the carbon material preferably has a grain size up to a maximum of 8 mm, preferably up to a maximum of 6 mm, particularly preferably up to a maximum of 4 mm. The grain distribution of the coarse grains from the at least one carbon material and / or the dry material mixture according to the invention is preferably continuous, preferably according to a Litzow, Furnas or Fuller curve or has a Gaussian distribution.

Preferably, the carbon material of the flour grain is a material from the following group: thermal black, anthracite, preferably calcined or calcined anthracite, graphite. Especially preferred are exclusively thermal black and anthracite.

The grain distribution of the flour grain of the at least one carbon material is preferably also continuous, preferably according to a Litzow, Furnas or Fuller curve or it has a Gaussian distribution.

The further granulation is, for example, a material from the following group:

SiC, magnesia, alumina

The dry additive is an additive suitable for refractory products. These additives are given for example in the Practical Guide, page 28 / point 3.3. They are used to improve the processability or deformability or to modify the structure of the products and thus to achieve special properties. The additive is, for example, an additive from the following group:

Metal powders, powders of non-oxidic substances, powders of oxidic substances The admixture is, for example, an admixture from the following group:

Pressing aids, condenser

According to a preferred embodiment of the invention, the dry matter mixture, based on its total dry matter, consists of the following materials (in% by weight) with the specified particle fractions or particle size classes:

According to a further preferred embodiment of the invention, the dry substance mixture, based on its total dry matter, consists of the following materials (in% by weight) with the specified particle fractions or particle size classes:

The specified particle fractions or grain classes each have grain sizes between the two specified test grain sizes. The term grain fraction or grain class means that no grains on stay in the upper sieve and do not fall through the lower sieve. So there is no oversize and no undersize.

In contrast, the term "grain group" implies that some grains remain on the upper sieve (oversize) and some fall through the lower sieve (undersize).

The grain fractions preferably each have a continuous particle size distribution.

The preparation of the products according to the invention from the offset according to the invention is as follows: For the production of shaped articles, in particular stones, a mixture or molding material from the dry mixture of the inventive offset with the at least one liquid binder and optionally the dry binder and / or optionally prepared liquid additive and / or optionally water. For optimum distribution of the binder (s) and / or water, e.g. Mixed for 3 to 10 minutes.

The mixture is poured into molds and pressed so that moldings are formed. The pressing pressures are in customary ranges, for example 60-180 MPa, preferably 100-150 MPa. Preferably, a drying is carried out after pressing, for example between 100 and 200 ° C, in particular between 120 and 180 ° C. The drying is preferably carried out to a residual moisture content of between 0.1 and 2.5% by weight, in particular between 0.2 and 2.0% by weight, determined in accordance with DIN 51078: 2002-12. The shaped bodies according to the invention, in particular the stones, can be used unfired or tempered or fired. Preferably, however, they are used unfired. The unfired shaped bodies, in particular the bricks, preferably have a bulk density of 1.3 to 2.0 g / cm ³ , in particular from 1.3 to 1.8 g / cm ³ , determined in accordance with DIN EN 993-1: 1995-04 on.

The cold compressive strength according to DIN EN 993-5: 1998-12 of the unfired, shaped articles according to the invention, in particular of the stones, is preferably from 15 to 100 MPa, in particular from 45 to 90 MPa.

The cold bending strength according to DIN EN 993-6: 1995-04 of the unfired, shaped products according to the invention, in particular of the stones, is preferably 0.5 to 15 MPa, in particular 0.5 to 10 MPa. In addition, the unfired shaped bodies, in particular the bricks, preferably have an E-modulus according to DIN EN ISO 12680-1: 2007-05 of 5 to 30 GPa, preferably 10 to 20 GPa.

The green pressed stones are tempered in a ceramic kiln, e.g. a tunnel kiln, between 200 and 800 ° C, in particular between 300 and 700 ° C.

For firing, the pressed, preferably dried, pressed stones in a ceramic kiln, for example a tunnel kiln, are fired by a ceramic, preferably between 1000 and 2500 ° C., in particular between 1400 and 2000 ° C. It is fired in a reducing atmosphere. During firing, the binder cokens in a manner known per se, so that it forms a coke bond matrix after firing, in which the dry substances of the offset are embedded. In the case of the preferred use of the green bricks, the coke binder matrix is formed in situ during use of the products. Furthermore, it is preferably carried out by impregnation with at least one coking impregnating agent, which is similar to the binders, a densification. As already explained, during impregnation, the Ren penetrated impregnating agent by another firing cycle also converted into coke. It can also be impregnated several times.

Impregnation further increases the density of the products, further improves the strength and infiltration resistance. The coking impregnating agent is an organic impregnating agent. The impregnating agent used is preferably an impregnating agent from the following group:

Resin, preferably phenolic resin, pitch, pitch derivative

Preferably, the fired molded products, in particular stones, a bulk density of 1, 1 to 1, 9 g / cm ^3, in particular 1, 2 to 1, 7 g / cm ^3, determined according to DIN 993-1: 1995- 04 on.

The cold compressive strength according to DIN EN 993-5: 1998-12 of the fired, shaped products according to the invention, in particular the stones, is preferably from 15 to 90 MPa, in particular from 35 to 80 MPa. The cold bending strength according to DIN EN 993-6: 1995-04 of the fired, shaped products according to the invention, in particular the stones, is preferably 0.5 to 15 MPa.

In addition, the green bodies, in particular the bricks, preferably have an modulus of elasticity according to DIN EN ISO 12680-1: 2007-05 of 3 to 30 GPa, preferably 5 to 20 GPa.

For the production of unshaped products, a mixture of the dry matter mixture according to the invention with the at least one liquid binder and optionally the at least one dry binder and / or optionally liquid additive and / or, if appropriate, water is produced. The unshaped products, after tempering or firing (especially in situ), also exhibit the strength properties and bulk densities given above for the molded products.

As already explained and recognizable from the above-mentioned properties, the products according to the invention are outstandingly suitable for use in infeeds, in particular in the working lining (= wear lining) and / or in the safety lining. In particular, it has been shown that the products according to the invention are not wetted by the coal slag and therefore are not infiltrated. The infiltration resistance could i.a. also result from the high purity of the raw materials and their low porosity and the resulting low surface areas. Essential for the infiltration resistance is the non-wettability of carbon.

The infiltration resistance significantly reduces the wear rate compared to the known products. In addition, the thermal conductivity of the delivery could be increased.

The advantages of the invention over the prior art are thus in particular the high corrosion resistance in connection with low material costs.

Also, the products of the invention have a low bulk density. Furthermore, the lack of infiltration with the coal slag and the absence of chromium allow a cost-effective disposal of the material after use or even a recycle of the used material.

The use of the highly carbon-containing products according to the invention was, as already explained, remote for the person skilled in the art, because it had to be assumed that the products according to the invention wear very quickly in the atmosphere prevailing in coal gasification plants. The superiority of the coarse ceramic products according to the invention is clarified on the basis of the following examples:

 Examples:

 In the examples, crucibles were produced from the following lots: TABLE 1 Composition of the offset for the embodiment 1 (the grain groups are given)

Table 2: composition of the offset for the embodiment 2

Es wurden Rohstoffe mit folgenden Rohstoffdaten verwendet:

Raw materials with the following raw material data were used:

Table 3: Raw material data of the raw materials used

For the comparative example, an offset was used for the Applicant's standard product "Almag AF." This is a chromium-free product based on magnesia and melt spinel.

Crucibles were produced from the offsets as follows:

The raw materials were premixed dry in a compulsory mixer for three minutes. Thereafter, the binder (synthetic resin) was added and mixed for another four minutes. The finished mixture was then pressed using a uniaxial press into prismatic test specimens (220 x 80 x 100 mm ³ ). For this purpose, first three pre-strokes of 10, 20 and 40 MPa specific pressing pressure were given up for pre-compression and deaeration of the molding compound. For final pressing three final strokes of 80 MPa were finally abandoned. The molding thus obtained was cured after pressing at a temperature of 180 ° C for 12 h. During thermal curing, the binder contained was polymerized. After the material had hardened, the crucible was produced for the corrosion test. To this end, the specimens were sawed to a size of 80 × 80 × 80 mm ³ and provided with an internal bore 0 40 mm × 40 mm.

 The crucibles were filled with intermediate brown coal ash. The ash composition is shown in the following tables:

Table 4: Chemical composition [% by weight] of the intermediate lignite ash slag

Table 5: Mineralogical composition [% by weight] of the intermediate lignite ash (slag)

The crucibles were then removed under the following conditions:

Heating rate: 10 K / min, while purging with argon (150 l / h)

Temperature: 1500 ° C

Atmosphere: 150 l / h H ₂ + 300 l / h CO Holding time: 6 h

 Cooling: free, while rinsing with argon (150 l / h)

The following table shows the measured strength properties before the test for the two embodiments according to the invention: TABLE 6 Properties of the crucibles of Examples 1 and 2 before the test

In FIGS. 1 to 3, the diagonally sawed crucibles after the test are also shown. It can be seen in both embodiments of the invention (Figures 1 and 2) no discernible interaction of the crucible materials with the atmosphere or the slag. The materials were not even wetted.

In contrast, it can be seen clearly in the comparative example (FIG. 3) that the microstructure is completely infiltrated with the slag. In addition, thermochemical corrosion occurred.

Claims

claims Use of a coarse ceramic offset for the production of a shaped or unshaped, heavy ceramic refractory product for refractory lining, preferably for the working liner or the safety liner, a coal gasification plant, characterized in that the heavy clay offset has or consists of the following components: a) a dry substance mixture, based on the total dry matter of the dry substance mixture, at least 80 wt .-%, preferably at least 90 wt .-%, preferably at least 95 wt.%, Particularly preferably 100 wt .-% of carbon material, and b) at least one chargeable liquid binder and / or a cokeable dry binder. Use according to claim 1, characterized in that the offset 0.5 to 20 wt .-%, preferably 1 to 15 wt .-%, cokeable binder, based on the dry total mass of the dry substance mixture having. Use according to claim 1 or 2, characterized in that the liquid chargeable binder is a binder from the following group: Synthetic resin, preferably phenol formaldehyde resin, preferably in the form of a resol or in alcoholic solution, pitch, tar, pitch derivative Use according to one of the preceding claims, characterized in that the dry cokeable binder is synthetic resin, preferably phenolic resin. Use according to one of the preceding claims, characterized in that the carbon material has a total carbon content of at least 70% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight, based on the dry mass of the carbon material, determined in accordance with DIN19539: 2016-12. Use according to one of the preceding claims, characterized in that the carbon material has a total carbon content of 70-99 wt .-%, preferably from 80 to 99 wt .-%, preferably from 90 to 99 wt .-%, particularly preferably from 95 to 99 wt .-%, based on the dry mass of the carbon material , determined according to DIN19539: 2016-12. Use according to one of the preceding claims, characterized in that the carbon material comprises the carbon in amorphous form and / or in graphitic modification, wherein preferably the carbon material contains exclusively amorphous carbon. Use according to one of the preceding claims, characterized in that the carbon material has an amorphous carbon content of at least 60% by weight, preferably at least 70% by weight, preferably at least 80% by weight, particularly preferably at least 90% by weight, based on the dry mass of the carbon material, determined in accordance with DIN 19539: 2016-12. Use according to one of the preceding claims, characterized in that  the carbon material has a total carbon content of 60-99 wt .-%, preferably from 70 to 99 wt .-%, preferably from 80 to 99 wt .-%, particularly preferably from 90 to 99 wt .-%, based on the dry mass of the carbon material , determined according to DIN19539: 2016-12. 10. Use according to one of the preceding claims,  characterized in that  the dry substance mixture, based on its total dry matter, at least 70 wt .-%, preferably at least 80 wt .-%, preferably at least 90 wt .-%, more preferably 95 wt .-%, most preferably 100 wt. -%, consists of carbon material containing only amorphous carbon. Use according to one of the preceding claims,  characterized in that  the carbon material is a material from the following group: Anthracite, preferably gas-calcined or electrically calcined anthracite, graphite, petroleum or pitch coke, thermal black, recycled carbon material, in particular recycled magnesia-carbon material Use according to one of the preceding claims,  characterized in that the dry substance mixture, based on its total dry matter, contains at least 50% by weight, preferably at least 60% by weight, preferably at least 70% by weight, of anthracite. 13. Use according to one of the preceding claims, characterized in that  the dry matter mixture consists of anthracite and thermal black. Use according to one of the preceding claims,  characterized in that  the dry substance mixture, based on its total dry matter, comprises or consists of the following constituents: a) at least one coarse grain of carbon material having a particle size> 200 μιτι, preferably in an amount of 50 to 90 wt .-%, preferably from 60 to 90 Wt .-% b) at least one flour grain of carbon material, with a grain size <200 μιτι, preferably in an amount of 10 to 50 wt .-%, preferably from 10 to 40 wt .-% c) at least one further grain from another refractory material, in an amount of 0 to 15 wt .-%, preferably from 0 to 10 wt .-% d) at least one additive having a particle size <200 μιτι, in an amount of 0 to 3 wt .-% e) optionally at least one additive for refractory materials, preferably in a total amount of <2 wt .-%. Use of a shaped or unshaped, heavy clay fireproof product, in particular of a product made from an offset according to one of the preceding claims, for the refractory lining, preferably for the working lining or the security lining, of a coal gasification plant, characterized in that the product, based on its dry mass, a total carbon content determined according to DIN19539: 2016-12 of at least 70 wt .-%, preferably of at least 80 wt .-%, preferably of at least 90 wt.%, particularly preferably of at least 95 wt. %, having. Use of a shaped or unshaped, heavy ceramic refractory product, in particular a product made from an offset according to one of the preceding claims, for the refractory lining, preferably for the working food or the safety food, a coal gasification plant,  characterized in that  the product, based on its dry matter, a total carbon content determined according to DIN19539: 2016-12 of 70-99 wt .-%, preferably from 80-99 wt .-%, preferably from 90-99 wt.%, Particularly preferably of at least 95 -99% by weight. 17. Use according to claim 15 or 16,  characterized in that  the product comprises the carbon in amorphous form and / or graphitic modification, preferably the product contains exclusively amorphous carbon. 18. Use according to one of claims 15 to 17,  characterized in that  the product, based on its dry matter, a content of amorphous carbon determined according to DIN19539: 2016-12 of at least 60 wt .-%, preferably of at least 70 wt .-%, preferably of at least 80 wt.%, Particularly preferably of at least 90 % By weight. 19. Use according to one of claims 15 to 18, characterized in that  the product, based on its dry mass, a content of amorphous carbon determined according to DIN 19539: 2016-12 of 60- 99 wt .-%, preferably from 70-99 wt .-%, preferably from 80-99 wt.%, Especially preferably from 90 to 99% by weight. Use according to one of claims 15 to 19,  characterized in that  the molded product is a green, in particular pressed, shaped body, preferably a stone. 21. Use according to one of claims 15 to 20,  characterized in that the unfired shaped body, in particular the stone, has a bulk density of 1.3 to 2.0 g / cm ³ , in particular from 1.3 to 1.8 g / cm ³ , determined in accordance with DIN EN 993-1: 1995-04. Use according to one of the preceding claims 15 to 21, characterized in that  the unfired shaped body, in particular the stone, has a cold compressive strength according to DIN EN 993-5: 1998-12 of 15 to 100 MPa, in particular of 45 to 90 MPa. Use according to one of the preceding claims 15 to 22, characterized in that the unfired shaped body, in particular the stone, has a cold bending strength according to DIN EN 993-5: 1998-12 of 0.5 to 15 MPa, in particular from 0.5 to 10 MPa. 24. Use according to one of the preceding claims 15 to 23, characterized in that the unfired shaped body, in particular the stone, has an E-modulus according to DIN EN ISO 12680-1: 2007-05 of 5 to 30 GPa, preferably of 10 to 20 GPa. 25. Use according to one of claims 15 to 19,  characterized in that  the molded product is a tempered shaped body, preferably a stone. Use according to one of claims 15 to 19,  characterized in that  the molded product is a fired shaped body, preferably a stone. 27. Use according to claim 26,  characterized in that the fired shaped body, in particular the stone, a bulk density of 1, 1 to 1, 9 g / cm ³ , in particular from 1, 2 to 1, 7 g / cm ³ , determined according to DIN EN 993-1: 1995-04. 28. Use according to claim 26 or 27,  characterized in that  the fired shaped body, in particular the stone, has a cold compressive strength according to DIN EN 993-5: 1998-12 of 15 to 90 MPa, in particular of 35 to 80 MPa. Use according to one of the preceding claims,  characterized in that  the fired shaped body, in particular the stone, has a cold bending strength according to DIN EN 993-5: 1998-12 of 0.5 to 15 MPa. 30. Use according to one of claims 26 to 29, characterized in that  the fired molding, in particular the stone, has an modulus of elasticity according to DIN EN ISO 12680-1: 2007-05 of 3 to 30 GPa, preferably of 5 to 20 GPa. 31. Use according to one of claims 15 to 19,  characterized in that  the unshaped product is a spray mass, ramming mass, casting compound, vibration mass or potting compound. 32. Delivery of a coal gasification plant,  characterized in that  the delivery comprises at least one refractory product according to one of the preceding claims. 33. Delivery according to claim 32,  characterized in that  the delivery has a working lining which has the at least one refractory product. 34. Delivery according to claim 32 or 33,  characterized in that  the delivery comprises a security food having the at least one refractory product. 35. coal gasification plant,  characterized in that  the coal gasification plant has a delivery according to one of claims 32 to 34.