WO2019076619A1 - Utilisation d'un mélange et/ou d'un produit réfractaire moulé ou non moulé pour le revêtement réfractaire d'une installation de gazéification de charbon, un tel revêtement ainsi qu'une installation de gazéification de charbon comprenant un tel revêtement - Google Patents

Utilisation d'un mélange et/ou d'un produit réfractaire moulé ou non moulé pour le revêtement réfractaire d'une installation de gazéification de charbon, un tel revêtement ainsi qu'une installation de gazéification de charbon comprenant un tel revêtement Download PDF

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WO2019076619A1
WO2019076619A1 PCT/EP2018/076693 EP2018076693W WO2019076619A1 WO 2019076619 A1 WO2019076619 A1 WO 2019076619A1 EP 2018076693 W EP2018076693 W EP 2018076693W WO 2019076619 A1 WO2019076619 A1 WO 2019076619A1
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use according
carbon material
dry
weight
product
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PCT/EP2018/076693
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German (de)
English (en)
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Bernd SCHEUBEL
Helge Jansen
Volker Stein
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Refratechnik Holding Gmbh
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Publication of WO2019076619A1 publication Critical patent/WO2019076619A1/fr

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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/521—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained by impregnation of carbon products with a carbonisable material
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    • C04B35/528—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components
    • C04B35/532—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from carbonaceous particles with or without other non-organic components containing a carbonisable binder
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K23/00—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids
    • F01K23/02—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled
    • F01K23/06—Plants characterised by more than one engine delivering power external to the plant, the engines being driven by different fluids the engine cycles being thermally coupled combustion heat from one cycle heating the fluid in another cycle
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/0003—Linings or walls
    • F27D1/0006—Linings or walls formed from bricks or layers with a particular composition or specific characteristics
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D1/00—Casings; Linings; Walls; Roofs
    • F27D1/10—Monolithic linings; Supports therefor
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/424—Carbon black
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/422—Carbon
    • C04B2235/425—Graphite
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
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    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
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Definitions

  • 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.
  • 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.
  • 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).
  • 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 ⁇ m, 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.
  • coal 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.
  • the resulting gasification gas has typical components C0 2 , CO, CH 4 , H 2 , H 2 O, H 2 S and NH 3 .
  • the composition of the gasification gas is different.
  • the main focus is on the production of CO and H2, for the use as fuel gas, however, on a high methane value.
  • 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.
  • 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.
  • 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.
  • 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 gasifier atmosphere consists of H2 and CO.
  • H2S water vapor
  • Nhh or other components due to Impurities in the coal small amounts of H2S, Nhh or other components may be present.
  • the coal and ash particles have an abrasive effect on the working liner.
  • 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.
  • the coal slag consists of the main components S1O2, Al2O3, FeO and CaO.
  • minor constituents among others, Na 2 O, MgO, K 2 O, SO 3 and C may be contained.
  • the slag is basic or acidic.
  • 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.
  • Cr203-containing materials are 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 thesis. An aluminum spinel casting compound was investigated.
  • 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.
  • 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.
  • a coal gasification plant is to be provided with such a delivery.
  • 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
  • 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.
  • 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.
  • the high-carbon products according to the invention are not wetted by the coal slag and therefore are not infiltrated.
  • the wear rate is significantly reduced compared to the known products.
  • 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.
  • 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.
  • 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.
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • the Offset as a carbon material exclusively on such carbon material.
  • 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.
  • the offset as the carbon material exclusively on such carbon material.
  • 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.
  • 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.
  • 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.
  • 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 ⁇ , 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 ⁇ , 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 ⁇ , in an amount of 0
  • 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.
  • 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.
  • the coarse grain can also consist of a recylated carbon material, preferably of a recycled magnesia carbon material.
  • the grain size can be chen and processing a carbon stone, in particular a magnesia carbon stone, or produced by electrode breakage.
  • the coarse grain can also consist of granules, ie grains which have been produced by granulating a flour-shaped carbon material.
  • it is preferably granules of granulated thermal black.
  • 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.
  • 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:
  • 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:
  • the admixture is, for example, an admixture from the following group:
  • 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:
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • a ceramic kiln e.g. a tunnel kiln
  • the pressed, preferably dried, pressed stones in a ceramic 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.
  • 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.
  • the coke binder matrix is formed in situ during use of the products.
  • it is preferably carried out by impregnation with at least one coking impregnating agent, which is similar to the binders, a densification.
  • 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
  • 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.
  • 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.
  • 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 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.
  • the thermal conductivity of the delivery could be increased.
  • 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.
  • Almag AF chromium-free product based on magnesia and melt spinel.
  • 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:
  • Heating rate 10 K / min, while purging with argon (150 l / h)
  • Atmosphere 150 l / h H 2 + 300 l / h CO Holding time: 6 h
  • Cooling free, while rinsing with argon (150 l / h)
  • 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.

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  • Manufacturing & Machinery (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention concerne l'utilisation d'un mélange et/ou l'utilisation d'un produit réfractaire moulé ou non moulé pour un revêtement réfractaire, en particulier pour un revêtement de travail ou un revêtement de sécurité, d'une installation de gazéification de charbon, un tel revêtement ainsi qu'une installation de gazéification de charbon comprenant un tel revêtement.
PCT/EP2018/076693 2017-10-18 2018-10-01 Utilisation d'un mélange et/ou d'un produit réfractaire moulé ou non moulé pour le revêtement réfractaire d'une installation de gazéification de charbon, un tel revêtement ainsi qu'une installation de gazéification de charbon comprenant un tel revêtement WO2019076619A1 (fr)

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DE102017124358.5A DE102017124358B4 (de) 2017-10-18 2017-10-18 Verwendung eines Versatzes und/oder eines geformten oder ungeformten feuerfesten Erzeugnisses für eine feuerfeste Zustellung einer Kohlevergasungsanlage, derartige Zustellung sowie Kohlevergasungsanlage mit einer derartigen Zustellung
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2832564A1 (de) * 1978-07-25 1980-02-07 Sigri Elektrographit Gmbh Verfahren zur waermerueckgewinnung bei einem graphitierungsofen

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1931395B2 (de) * 1969-06-20 1973-09-27 Sigri Elektrographit Gmbh Verwendung von Halbgraphitsteinen zur Auskleidung der Rast von Hochofen

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2832564A1 (de) * 1978-07-25 1980-02-07 Sigri Elektrographit Gmbh Verfahren zur waermerueckgewinnung bei einem graphitierungsofen

Non-Patent Citations (4)

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Title
P. GEHRE; C.G. ANEZIRIS: "Ressourcenschonende, feuerfeste Auskleidungsmaterilalien für Verbrennungs- und Vergassungsanlagen.", ACAMONTA -ZEITSCHRIFT FÜR FREUNDE UND FÖRDERER DER TU BERGAKADEMIE FREIBERG, 1 January 2015 (2015-01-01), pages 11 - 19, XP002786721, DOI: http://www.qucosa.de/fileadmin/data/qucosa/documents/21121/gehre_aneziris_ressourcenschonendeFeuerfetseAuskleidungsmaterialien.pdf *
PATRICK GEHRE: "Korrosions- und thermoschockbeständige Feuerfestmaterialien für Flugstromvergasungsanlagen auf A120 -Basis - Werkstoffentwicklung und Korrosionsuntersuchungen", DISSERTATION, 23 September 2013 (2013-09-23)
WILKENING ET AL: "Untersuchungen zum Verhalten von Kohlenstoff- Hochofensteinen gegenuber chemischen Angriffen", TONINDUSTRIE-ZEITUNG UND KERAMISCHE RUNDS, SPRECHSAAL PUBLISHING, DE, vol. 96, no. 7, 1 January 1972 (1972-01-01), pages 198 - 205, XP009160583, ISSN: 0040-9200 *
WOLFGANG SCHULLE: "Feuerfeste Werkstoffe", 1 January 1990, DEUTSCHER VERLAG FÜR GRUNDSTOFFINDUSTRIE, Leipzig, ISBN: 3-342-00306-5, article 3.1.10.4: "Kohlenstofferzeugnisse", pages: Deckblatt; Seite I und 301 - 303, XP002786720 *

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