EP3551772B1 - Verfahren zur handhabung eines schlacketopfes und verwendung von kalziumpartikel-schlamme zum auskleben einer innenwand eines schlacketopfes - Google Patents

Verfahren zur handhabung eines schlacketopfes und verwendung von kalziumpartikel-schlamme zum auskleben einer innenwand eines schlacketopfes Download PDF

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Publication number
EP3551772B1
EP3551772B1 EP17828850.2A EP17828850A EP3551772B1 EP 3551772 B1 EP3551772 B1 EP 3551772B1 EP 17828850 A EP17828850 A EP 17828850A EP 3551772 B1 EP3551772 B1 EP 3551772B1
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Prior art keywords
calcic
milk
weight
slag
equal
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English (en)
French (fr)
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EP3551772A1 (de
EP3551772C0 (de
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Guillaume DENOLLIN
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Lhoist Recherche et Developpement SA
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Lhoist Recherche et Developpement SA
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Classifications

    • 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
    • F27D3/00—Charging; Discharging; Manipulation of charge
    • F27D3/15—Tapping equipment; Equipment for removing or retaining slag
    • F27D3/1545—Equipment for removing or retaining slag
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • C21B3/04—Recovery of by-products, e.g. slag
    • C21B3/06—Treatment of liquid slag
    • C21B3/10—Slag pots; Slag cars
    • 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
    • F27D1/16—Making or repairing linings ; Increasing the durability of linings; Breaking away linings
    • F27D1/1636—Repairing linings by projecting or spraying refractory materials on the lining

Definitions

  • the present invention relates to the field of handling slag tanks and ladles used in ferrous or non-ferrous metallurgy.
  • slag slag
  • a first technique lies in tilting the tank in which it floats above the bath of molten metal. Slag can also be collected by scraping or overflowing during tipping.
  • tanks or slag ladles in English “slag pot” or “slag laddle”), which are typically made of refractories, cast iron or steel (in English cast iron or steel).
  • Blast furnace slag is a co-product resulting from the manufacture of cast iron in a blast furnace, where it corresponds to the sterile gangue of iron ore to which are added mineral additions and fuel ashes, in particular coke, coal and/or alternative fuels. It therefore separates from the liquid cast iron by difference in density.
  • the amount of slag produced corresponds directly to the richness of the iron ore used. For a blast furnace operating with iron-rich ores, a proportion of 180 to 350 kg of slag is generally reached for one tonne of cast iron produced.
  • Steelmaking slag comes from pyro-metallurgical tools, such as various refining tools like pig iron desulfurization tools, converters turning pig iron into steel (BOF- Basic Oxygen Furnace), electric furnaces (EAF-Electric Arc Furnace), stainless steel refining converters (AOD-Argon Oxygen Decarburization) and various secondary metallurgy grader tools.
  • various refining tools like pig iron desulfurization tools, converters turning pig iron into steel (BOF- Basic Oxygen Furnace), electric furnaces (EAF-Electric Arc Furnace), stainless steel refining converters (AOD-Argon Oxygen Decarburization) and various secondary metallurgy grader tools.
  • various refining tools like pig iron desulfurization tools, converters turning pig iron into steel (BOF- Basic Oxygen Furnace), electric furnaces (EAF-Electric Arc Furnace), stainless steel refining converters (AOD-Argon Oxygen
  • steel mill slag The function of steel mill slag is to collect impurities and unwanted chemical elements. The latter are in the vast majority of cases in the form of oxides. They are generally generated during the use of the pyro-metallurgical tool concerned.
  • a high lime content will, for example, make the slag capable of capturing phosphorus oxides in the converter, which makes its use as a fertilizer possible.
  • a high lime content makes the slag basic, which is favorable to the capture of alumina inclusions.
  • this slag must also spare the refractory bricks.
  • the present invention relates more particularly to the field of handling slag tanks and ladles but also crucibles and shells, made of steel or cast iron, used in metal preparation workshops in ferrous or non-ferrous metallurgy.
  • the slag concerned in the context of the present invention is slag from steelmaking or non-ferrous metallurgy.
  • slag tanks the tanks, ladles, crucibles, shells and the like made of steel or cast iron intended to collect slag from the steelworks or the metallurgical industry.
  • the slag vats should be kept above 150°C in order to avoid any accumulation of water. Indeed, this would generate explosions during the pouring of the slag itself at a temperature of more than 1200°C. It is therefore common practice to heat slag tanks prior to commissioning.
  • wolf or “clinker” also depends on the steelmaking tool that generated the slag. Some being by physical and chemical nature more prone than others to the formation of wolves.
  • the slag tanks cool significantly following the exposure to climatic conditions and to the duration of the “deloupage” process (“deskulling” in English or “ontbering” in Dutch). They must then be reheated later.
  • this reheating represents significant calorific energy that is too expensive to return to the optimum temperature ranges around 250°C.
  • the tanks are reheated to around 150°C for the safety reasons mentioned above.
  • this layer deposited mineral may involve the formation of an intermediate slag phase by means of an endothermic reaction which provides a cooling effect, or on the contrary, the formation of an intermediate phase with a higher melting point, or even play on other effects related to a phase transformation, such as playing on the dilation or on the shrinkage.
  • suspensions include mixed compounds whose composition has an impact on the composition of the slag, the chemical properties of which are thus modified, such as for example the basicity (determined by the ratio of the quantity of basic elements to the quantity of acid elements in the solid fraction), basicity which is modified by adapting the basicity of the suspension according to the basicity of the slag poured into the tank or slag ladle.
  • US5437890 discloses a pretreatment of the walls of slag tanks made of refractory materials with an essentially mineral mixture comprising lime, slag fines and water in order to prevent the adhesion of the slag to the refractory walls, which destroy the walls of the tank.
  • JP2015094020 , JPH085260 and the document JPS63295458 refer, for example, to treatment with lime suspensions.
  • the document JP2015094020 discloses a treatment of the inner surface of the slag tanks by spraying a lime suspension to be used in the hot slag recycling process during the realization of the desulfurization treatment.
  • the lime slurry spray nozzle is connected to a lime slurry tank, wherein the lime slurry has a lime concentration of 13.5 to 15% by weight based on the total lime slurry weight. Excess lime slurry and wash water both sprayed on the inner surface of the slag vats returns to the lime slurry tank.
  • JPS63295458 also discloses that slaked lime is fed to the wall of the slag vats to facilitate the draining of slag from the vat when the slag is cooled and solidified.
  • this document does not disclose any characteristic of the lime, nor how, nor even at what content it is applied to the inner wall of the slag tanks.
  • it does not describe anything regarding the removal of slag by pouring.
  • the solidification of the slag is expected in order to be able to remove it from the tank or the slag ladle.
  • the object of the invention is to overcome the drawbacks of the state of the art by providing a process providing optimized pre-treatment of steel or cast iron slag tanks and ladles in order to facilitate handling thereof on pyro steelmaking sites. -metallurgical between the slag collection point at the iron and steel or pyro-metallurgical tool and the dumping of the slag into a deposit site, typically a landfill site.
  • a method for handling a slag tank or ladle comprising an inner wall and an outer wall, according to claim 1.
  • the method according to the present invention is characterized in that said slag tank or ladle is a steel or cast iron tank or ladle and in that said mineral suspension comprises calcium particles in suspension in an aqueous phase forming a milk of calcium particles , and additives, said calcium particles being chosen from the group consisting of slaked lime, decarbonated dolomite at least partially slaked, limestone and mixtures thereof and having a content of calcium particles of between 20 and 60% by weight relative to the weight of said milk of calcium particles, said mineral layer being a thin layer.
  • the term “commissioning” means the circulation of the slag tank or ladle for the role expected of a slag tank or ladle, namely the collection of dairy.
  • the method according to the present invention focuses on steel or cast iron tanks.
  • the choice concerning ladles or slag tanks made of steel or cast iron (and not of refractory), makes it possible to make the most of the difference in coefficient of expansion between the materials.
  • milk of calcium particles chosen exclusively from the restricted group consisting of slaked lime, at least partially slaked decarbonated dolomite, limestone and mixtures thereof has a content of calcium particles of between 20 and 60% by weight, relative to the total weight of the milk of calcium particles is lined on the inside wall of the slag tanks or pockets, a fine and homogeneous mineral layer is produced and it has been surprisingly noticed that the slag poured into it does not adhere or very little at the time of dumping in landfill.
  • the layer thus formed acts as a mold release agent forming a layer that significantly reduces the formation of clinker by significantly reducing the adhesion between the slag tank or ladle and the slag that is poured into it.
  • the specific concentration of between 20 and 60% of calcium particles in the milk of calcium particles allows, when milk of calcium particles is sprayed, that the water contained in the suspension evaporates almost instantaneously on contact with the hot wall and that a layer of calcium particles is applied and thus forms a thin and homogeneous layer, which does not affect the concentration of calcium particles in the slag, but also avoids bringing residual water into the slag, which is dangerous for handling the tank or slag ladle.
  • the temperature of the tank or the bag is higher than 100°C, which leads to the evaporation of the water contained in the milk of calcium particles and thus leaves a thin and homogeneous layer of calcium particles.
  • the terms "tank or slag ladle lined with a mineral layer on one surface” means that approximately 70%, for example more than 80%, in particular more than 85%, or even more 90% of the surface is lined with a fine mineral layer.
  • Calcium oxide, CaO is often called “quicklime”, while calcium hydroxide, Ca(OH) 2 , is called “hydrated lime” or “slaked lime”, the two compounds sometimes being informally called “lime”.
  • lime is an industrial product based on calcium oxide or hydroxide respectively.
  • Quicklime means a solid mineral material whose chemical composition is mainly calcium oxide, CaO. Quicklime is generally obtained by calcining limestone (mainly composed of CaCO 3 ).
  • Quicklime can also contain impurities such as magnesium oxide, MgO, sulfur oxide, SO 3 , silica, SiO 2 , or even alumina, Al 2 O 3 , .. ., the sum of which is at a rate of a few% by weight. Impurities are expressed here in their oxide form, but of course they can appear in different phases. Quicklime generally also contains a few % by weight of residual limestone, called unfired residues.
  • Suitable quicklime according to the present invention may comprise MgO, expressed as MgO, in an amount ranging from 0.5 to 10% by weight, preferably less than or equal to 5% by weight, more preferably less than or equal to 3% by weight, most preferably less than or equal to 1% by weight relative to the total weight of the quicklime.
  • quicklime is used in the presence of water.
  • Calcium oxide in quicklime reacts rapidly with water to form calcium dihydroxide Ca(OH) 2 , in the form of slaked lime or hydrated lime, in a reaction called the hydration or slaking reaction which is very exothermic.
  • calcium dihydroxide will be referred to simply as calcium hydroxide.
  • Hydrated lime can therefore contain the same impurities as those of the quicklime from which it is produced.
  • the slaked lime can also comprise Mg(OH) 2 in an amount ranging from 0.5 to 10% by weight, preferably less than or equal to 5% by weight, more preferably less than or equal to 3% by weight. weight, most preferably less than or equal to 1% by weight relative to the total weight of the slaked lime.
  • the slaked lime may also include calcium oxide, which may not have been fully hydrated during the slaking step, or calcium carbonate CaCO 3 .
  • the calcium carbonate can come from the initial limestone (incuit) from which the said slaked lime is obtained (via calcium oxide), or come from a partial carbonation reaction of the slaked lime by contact with a atmosphere containing CO 2 .
  • the amount of calcium oxide in the slaked lime according to the present invention is generally less than or equal to 3% by weight, preferably less than or equal to 2% by weight and more preferably less than or equal to 1% by weight with respect to the total weight of slaked lime.
  • the amount of CO 2 in the slaked lime (mainly in the form of CaCO 3 ) according to the present invention is less than or equal to 5% by weight, preferably less than or equal to 3% by weight, plus preferably less than or equal to 2% by weight, relative to the total weight of the slaked lime according to the present invention.
  • milk of lime is understood to mean a suspension of solid particles of slaked lime in an aqueous phase at a concentration greater than or equal to 200 g/kg.
  • the solid particles can obviously contain impurities, namely phases derived from SiO 2 , Al 2 O 3 , Fe 2 O 3 , MnO, P 2 O 5 and/or SO 3 , globally representing a few tens of grams per kilogram.
  • These solid particles may also contain calcium oxide which would not have been hydrated during extinction, just as they may contain calcium carbonate CaCO 3 and/or magnesium carbonate MgCO 3 , optionally combined in the form of dolomite.
  • milk of calcium particles means a suspension of solid calcium particles in an aqueous phase at a concentration greater than or equal to 200 g/kg.
  • Dolomite includes both calcium carbonate and magnesium carbonate in varying proportions as well as various impurities.
  • the cooking of the dolomite causes the release of CO 2 (decarbonation) and a lively dolomitic product is obtained, namely composed mainly of CaO and MgO, although carbonates, especially CaCO 3 , can remain in more or less significant quantity. .
  • a lively dolomitic product is obtained, namely composed mainly of CaO and MgO, although carbonates, especially CaCO 3 , can remain in more or less significant quantity.
  • water is added to hydrate the live part of the decarbonated dolomite.
  • the avidity of CaO for water being much higher than that of MgO for water, it is often necessary to hydrate under pressure, for example in an autoclave, resulting in a product that is at least partially hydrated. It is indeed common for a part of the MgO to remain in the form of MgO.
  • the Ca/Mg proportions between the oxide, carbonate and hydrate part are
  • limestone is understood to mean, within the meaning of the present invention, a natural mineral material derived from limestone ore or, when the properties must be controlled, derived from the carbonation of quicklime. Limestone responds to the general formula CaCO 3 and can obviously contain impurities.
  • the milk of calcium particles is a milk of lime and said calcium particles are particles of slaked lime.
  • the mold release effect of the mineral layer allows the slag to be discharged, carrying the mineral layer with it and thus leaving the tank or slag pocket perfectly clean for the following operations.
  • the slaked lime is transformed anyway into quicklime because of the temperature of the slag which is higher than 1200°C. This transformation releases water vapor which detaches the spilled slag from the many attachment points formed between the slag and the inner wall of the tank or slag ladle. This significantly reduces the total surface area of slag adhering to the mineral layer formed of lime particles.
  • the mineral layer comprising calcium hydrate carbonates and thus transforms into a layer of calcium carbonate.
  • the calcium carbonate decarbonates and forms quicklime by releasing CO 2 and no longer water vapor (although the two phenomena can occur simultaneously).
  • Said calcium particles in the milk of calcium particles of said mineral suspension have an average particle size d 50 of between 1.5 ⁇ m and 10 ⁇ m.
  • said calcium particles in the milk of calcium particles of said mineral suspension have an average particle size d 50 less than or equal to 8 ⁇ m, in particular less than or equal to 6 ⁇ m, more particularly less than or equal to 5 ⁇ m, particularly less than 4 ⁇ m.
  • said calcium particles in the milk of calcium particles of said mineral suspension have an average particle size d 50 greater than or equal to 2 ⁇ m, in particular greater than or equal to 2.5 ⁇ m.
  • the notation d X represents a diameter, expressed in ⁇ m, compared to which X % of the particles or grains measured are smaller.
  • the reactivity of a milk of lime is therefore evaluated by the evolution over time of the measurement of the conductivity of a solution prepared by diluting a small quantity of milk of lime in a large volume of demineralised water.
  • the corresponding dissolution time , t(x%) in s is then obtained from the graph conductivity vs. time (see Figure 2 of EN12485(2010)).
  • said mineral suspension contains or is a milk of lime
  • the latter has a reactivity expressed in the form of a dissolution time t (90%) greater than 0.1 s in particular greater than 0.2 s and less than 10 s, in particular less than 5 s.
  • the particles of slaked lime have a sufficiently fine particle size to also contribute to the formation of a fine mineral layer, in particular homogeneous, contributing to the simplification of the demoulding of the slag.
  • said milk of calcium particles has a stability characterized by the bottle test as described in the document WO 2001/096240 .
  • Said additives of said mineral suspension are chosen from the group consisting of carbohydrates as well as dispersants and plasticizing additives, such as polycarbonates or polyacrylates, or polyphosphonates, in particular DTPMP.
  • said dispersing or thinning additives of said mineral suspension are present at a mass content of between 0.2 and 5% relative to the weight of said mineral suspension.
  • the content of the aforementioned additives is less than or equal to 3%, in particular less than or equal to 2%, more particularly less than or equal to 1.5% relative to the weight of the said mineral suspension.
  • the content of the aforementioned additives is greater than or equal to 0.5%, relative to the weight of the said mineral suspension.
  • the mineral suspension is coated on the inner wall of the slag tanks or ladles.
  • additives may be present in said mineral suspension, in particular one or more carbohydrates with one or more dispersing or thinning agents.
  • the water contained in the suspension evaporates almost instantaneously on contact with the hot wall. If the mineral suspension contains a carbohydrate, the evaporation of the water contained in the mineral suspension causes a rapid increase in the concentration of carbohydrate until it forms a weak glue favoring the adhesion of the calcium particles to the walls. of the slag tank, also due to the temperature of the slag tank or ladle, which is above 100°C.
  • the temperature of the slag produces a reaction of calcination of the carbohydrate, possibly simultaneously with the dehydration of the calcium hydroxide when the calcium particles are particles of slaked lime or decarbonated dolomite at least partially hydrated, which facilitates the demolding of the slag, these phenomena occurring from 500°C.
  • the fine mineral layer formed by spraying allows, when the slag is poured into the tank or slag ladle, to produce a shear plane behind the mineral layer (at the interface between the inner wall of the tank or slag ladle and the mineral layer).
  • the shear plane can be produced a priori because the presence of the carbohydrate acts as a weak glue, compared to the potential adhesion of the slag to the inner wall of the slag vessel or ladle.
  • the mineral layer "stuck" on the inner wall of the slag tank or ladle is composed of fine mineral particles.
  • the temperature of the tank or slag ladle, just before the pouring of the slag typically has a temperature of 100° C. to 350° C., the temperature at which the mineral particles are stable.
  • the mineral layer can therefore be applied to the slag tank or ladle well before it is used.
  • the slag tanks or ladles thus coated can even be stored
  • the dispersants or the thinning agents can be, for example, polymer or mineral additives such as, for example, anionic polymers or acidic polymers, boric acid and water-soluble salts of boric acid, such as alkali metal borates, aluminum borates, C 2 -C 10 carboxylic acids , for example containing at least 2 acid groups and the salts thereof, such as for example alkali metal salts or ammonium salts; hydroxides, carbonates, sulphates, nitrates, phosphates, of alkali metals or of ammonium.
  • polymer or mineral additives such as, for example, anionic polymers or acidic polymers, boric acid and water-soluble salts of boric acid, such as alkali metal borates, aluminum borates, C 2 -C 10 carboxylic acids , for example containing at least 2 acid groups and the salts thereof, such as for example alkali metal salts or ammonium salts; hydroxides, carbonates, sulphates
  • anionic polymer used in the context of the present invention describes all polymers containing acid groups, in free, neutralized or partially neutralized form.
  • polymers can be in the form of free acid, alkali metal salts, partially or entirely, of mixed salts, soluble in water.
  • the preferred anionic polymers are formed from acrylic acid with one or other of the monomers chosen from acrylamide, dimethylacrylamide, methacrylic acid, maleic acid or AMPS (2-acrylamido-2-acid). sulfonic methylpropane) in a preferred composition of 100:0 to 50:50 (by weight) and completely neutralized in the form of a sodium salt.
  • said dispersant or plasticizing agent is a phosphonate or a phosphonic acid chosen from organophosphonic acids, nitrogenous or not, or their salts, more particularly from the group consisting of aminoalkylene polyphosphonic acids, where the alkylene radical contains from 1 to 20 carbon atoms, hydroxyalkylidene polyphosphonic acids, where the alkylidene radical contains from 2 to 50 carbon atoms, phosphono- alkanepolycarboxylics, where the alkane group contains from 3 to 12 carbon atoms and where the molar ratio of the alkylphosphonic acid radical to the carboxylic acid radical is in the range from 1:2 to 1:4, their derivatives, such as their salts, and their mixtures.
  • said phosphonate or phosphonic acid comprises, in acid form, from 2 to 8, preferably from 2 to 6 “phosphonic acid” characteristic groups.
  • said phosphonate or phosphonic acid is chosen from the group consisting of aminotris(methylenephosphonic) acid (ATMP), 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), ethylenediamine tetrakis( methylenephosphonic acid) (EDTMP), hexamethylenediamine tetrakis(methylenephosphonic) acid (HDTMP), diethylenetriamine pentakis(methylenephosphonic) acid (DTPMP), (2-hydroxy)ethylamino-N,N-bis(methylenephosphonic ) (HEMPA), 2-phosphono-1,2,4-butanetricarboxylic acid (PBTC), 6-amino-1-hydroxyhexylene-N,N-diphosphonic acid (neridronic acid), N,N'-bis(3-aminopropyl)ethylenediamine hexakis(methylenephosphonic), bis(hexamethylenetriamine)pentakis(methylenephosphonic acid),
  • said carbohydrate is chosen from the group consisting of disaccharides, such as sucrose or sucrose, sorbitol, monosaccharides, oligosaccharides, xylose, glucose, galactose, fructose, mannose, lactose, maltose, glucuronic acid, gluconic acid, erythritol, xylitol, lactitol, maltitol, dextrins, cyclodextrins, inulin, glucitol, uronic acid, rhamnose, arabinose, erythrose, threose, ribose, allose, trehalose, galacturonic acid, and mixtures thereof.
  • disaccharides such as sucrose or sucrose, sorbitol, monosaccharides, oligosaccharides, xylose, glucose, galactose, fructose, mannose, lactose, maltos
  • said carbohydrate is chosen from the group consisting of disaccharides, such as sucrose or sucrose, sorbitol and mixtures thereof.
  • these carbohydrates are known to reduce the viscosity of milk of lime and keep it low over time, thus facilitating the storage conditions of the milk of lime.
  • said milk of calcium particles has a viscosity of between 0.1 Pa.s and 2 Pa.s, ie between 100 cps and 2000 cps.
  • the viscosity is greater than 0.15 Pa.s and less than 1 Pa.s, preferably less than 0.6 Pa.s, more preferably less than 0.5 Pa.s, even more preferably less than 0 .3 Pa.s.
  • the viscosity of a milk of lime is a determining property with regard to the implementation and handling (pumping, transport by pipe, etc.) of the suspension. To this end, experience has established that the dynamic viscosity of the suspension must be less than 2 Pa.s ( US 5616283 ) and that it is desirable not to exceed a dynamic viscosity of 1.5 Pa.s ( WO 2007110401 ).
  • the viscosity in the context of the present invention is measured by means of a Brookfield viscometer (rheometer) of the DV-III type at 100 rotations/min (rpm) using a No. 3 LV needle.
  • said calcium particles of the milk of calcium particles have a particle size d 97 of between 7 and 100 ⁇ m.
  • said calcium particles of the milk calcium particles have a particle size d 97 greater than or equal to 10 ⁇ m and less than or equal to 20 ⁇ m, in particular less than or equal to 15 ⁇ m.
  • said milk of calcium particles has a content of calcium particles greater than or equal to 25% by weight, preferably greater than or equal to 27% by weight, preferably greater than or equal to 30 % by weight, preferably greater than or equal to 35% by weight, relative to the total weight of the milk of calcium particles and a content of calcium particles less than or equal to 55% by weight, preferably less than or equal to 50% by weight, preferably less than or equal to 48% by weight, relative to the total weight of the milk of calcium particles.
  • said mineral layer, carpeted on the inner wall has a layer thickness of between 0.1 and 0.5 mm.
  • a subject of the invention is also a use of a milk of calcium particles according to claim 8.
  • Said milk mineral layer of calcium particles has a layer thickness between 0.1 and 0.5 mm.
  • the milk of calcium particles is a milk of lime and said calcium particles are particles of slaked lime.
  • Said calcium particles of said mineral suspension have an average particle size d 50 of between 1.5 ⁇ m and 10 ⁇ m.
  • said calcium particles in the milk of calcium particles of said mineral suspension have an average particle size d 50 less than or equal to 8 ⁇ m, in particular less than or equal to 6 ⁇ m, more particularly less than or equal to 5 ⁇ m, particularly less than 4 ⁇ m.
  • said calcium particles in the milk of calcium particles of said mineral suspension have an average particle size d 50 greater than or equal to 2 ⁇ m, in particular greater than or equal to 2.5 ⁇ m.
  • Said additives of said mineral suspension are chosen from the group consisting of carbohydrates, dispersants, plasticizing additives, such as polycarbonates or polyacrylates, or polyphosphonates, in particular DTPMP.
  • said carbohydrate is chosen from the group consisting of disaccharides, such as sucrose or sucrose, sorbitol, monosaccharides, oligosaccharides, xylose, glucose, galactose, fructose, mannose, lactose, maltose, glucuronic acid, gluconic acid, erythritol, xylitol, lactitol, maltitol, dextrins, cyclodextrins, inulin, glucitol , uronic acid, rhamnose, arabinose, erythrose, threose, ribose, allose, trehalose, galacturonic acid, and mixtures thereof.
  • disaccharides such as sucrose or sucrose, sorbitol, monosaccharides, oligosaccharides, xylose, glucose, galactose, fructose, mannose, lactose, malto
  • said carbohydrate is chosen from the group consisting of disaccharides, such as sucrose or sucrose, sorbitol and mixtures thereof.
  • said milk of calcium particles has a viscosity of between 0.1 Pa.s and 2 Pa.s.
  • said calcium particles of the milk of calcium particles have a particle size d 97 of between 7 and 100 ⁇ m.
  • said milk of calcium particles has a content of calcium particles greater than or equal to 25% by weight, preferably greater than or equal to 27% by weight, preferably greater than or equal to 30% by weight, preferably greater than or equal to 35% by weight, relative to the total weight of the milk, of calcium particles and a content of calcium particles less than or equal to 55% by weight, preferably, less than or equal to 50% by weight, preferably less than or equal to 48% by weight, relative to the total weight of the milk, of calcium particles
  • Said outer wall is sometimes also called boilerwork (“shell” in English or “pantser” in Dutch).
  • this method is characterized in that said pyro-metallurgical tool is a tool made of steel or cast iron and in that said mineral suspension comprises calcium particles in suspension in an aqueous phase forming a milk of calcium particles, and optionally additives, said calcium particles being chosen from the group consisting of slaked lime, at least partially slaked decarbonated dolomite, limestone and of their mixtures and having a content of calcium particles of between 20 and 60% by weight relative to the weight of said milk of calcium particles, said mineral layer being a thin layer.
  • the method according to the present invention focuses on steel or cast iron tanks.
  • the choice concerning ladles or slag tanks made of steel or cast iron (and not of refractory), makes it possible to make the most of the difference in coefficient of expansion between the materials. of metallic type forming the slag tanks or ladles and the slag oxides.
  • milk of calcium particles chosen exclusively from the restricted group consisting of slaked lime, at least partially slaked decarbonated dolomite, limestone and mixtures thereof has a content of calcium particles of between 20 and 60% by weight, relative to the total weight of the milk of calcium particles is lined on the inner wall or the outer wall of the pyro-metallurgical tools, a fine and homogeneous mineral layer is formed, and it has been surprisingly noticed that the frequency of maintenance of these tools pyro-metallurgy was significantly reduced and easier.
  • the milk of calcium particles is a milk of lime and said calcium particles are particles of slaked lime.
  • said calcium particles in the milk of calcium particles of said mineral suspension have an average particle size d 50 of between 1.5 ⁇ m and 10 ⁇ m.
  • said calcium particles in the milk of calcium particles of said mineral suspension have a size mean of particles d 50 less than or equal to 8 ⁇ m, in particular less than or equal to 6 ⁇ m, more particularly less than or equal to 5 ⁇ m, very particularly less than 4 ⁇ m.
  • said calcium particles in the milk of calcium particles of said mineral suspension have an average particle size d 50 greater than or equal to 2 ⁇ m, in particular greater than or equal to 2.5 ⁇ m.
  • the notation d X represents a diameter, expressed in ⁇ m, compared to which X % of the particles or grains measured are smaller.
  • the reactivity of a milk of lime is therefore evaluated by the evolution over time of the measurement of the conductivity of a solution prepared by diluting a small quantity of milk of lime in a large volume of demineralised water.
  • the corresponding dissolution time , t(x%) in s is then obtained from the graph conductivity vs. time (see Figure 2 of EN12485(2010)).
  • said mineral suspension contains or is a milk of lime
  • the latter has a reactivity expressed in the form of a dissolution time t (90%) greater than 0.1 s in in particular greater than 0.2 s and less than 10 s, in particular less than 5 s.
  • the particles of slaked lime have a sufficiently fine particle size to also contribute to the formation of a fine mineral layer, in particular homogeneous, contributing to the simplification of the demoulding of the slag.
  • the stability of calcium particle milk or mineral suspension can be determined using the stability method called the bottle test as described in the document WO 2001/096240 .
  • said additives of said mineral suspension are chosen from the group consisting of carbohydrates as well as dispersants and plasticizing additives and their mixture, such as polycarbonates or polyacrylates, or polyphosphonates, in particular of the DTPMP.
  • additives may be present in said mineral suspension, in particular one or more carbohydrates with one or more dispersing or thinning agents.
  • said carbohydrate is selected from the group consisting of disaccharides, such as sucrose or sucrose, sorbitol, monosaccharides, oligosaccharides, xylose, glucose, galactose , fructose, mannose, lactose, maltose, glucuronic acid, gluconic acid, erythritol, xylitol, lactitol, maltitol, dextrins, cyclodextrins, inulin, glucitol, uronic acid, rhamnose, arabinose, erythrose, threose, ribose, allose, trehalose, galacturonic acid, and mixtures thereof.
  • disaccharides such as sucrose or sucrose, sorbitol, monosaccharides, oligosaccharides, xylose, glucose, galactose , fructose, mannose, lactose, mal
  • said carbohydrate is selected from the group consisting of disaccharides, such as sucrose or sucrose, sorbitol and mixtures thereof.
  • these carbohydrates are known to reduce the viscosity of milk of lime and keep it low over time, thus facilitating the storage conditions of the milk of lime.
  • said milk of calcium particles has a viscosity of between 0.1 Pa.s and 2 Pa.s, ie between 100 cps and 2000 cps.
  • the viscosity of a milk of lime is a determining property with regard to the implementation and handling (pumping, transport by pipe, etc.) of the suspension. To this end, experience has established that the dynamic viscosity of the suspension must be less than 2 Pa.s ( US 5616283 ) and that it is desirable not to exceed a dynamic viscosity of 1.5 Pa.s ( WO 2007110401 ).
  • the viscosity in the context of the present invention is measured by means of a Brookfield viscometer (rheometer) of the DV-III type at 100 rotations/min (rpm) using a No. 3 LV needle.
  • said calcium particles of the milk of calcium particles have a particle size d 97 of between 7 and 100 ⁇ m.
  • said milk of calcium particles has a content of calcium particles greater than or equal to 25% by weight, preferably greater than or equal to 27% by weight, preferably greater than or equal to 30% by weight, of preferably greater than or equal to 35% by weight, relative to the total weight of the milk, of calcium particles and a content of calcium particles less than or equal to 55% by weight, preferably less than or equal to 50% by weight, preferably less or equal to 48% by weight, relative to the total weight of the milk of calcium particles.
  • said mineral layer, carpeted on the inner wall has a layer thickness of between 0.1 and 5 mm, preferably between 0.15 and 3 mm, more preferably between 0 .2 and 2 mm, in particular between 0.5 and 1 mm.
  • the present invention finally relates to a use of a milk of calcium particles chosen from the restricted group consisting of slaked lime, at least partially slaked decarbonated dolomite, limestone and their mixtures for lining an inner wall and/or an outer wall with a mineral layer of a pyro-metallurgical tool made of steel or cast iron to reduce the frequency of handling of said pyro-metallurgical tool, in which said milk of calcium particles is sprayed and has a content of calcium particles of between 20 and 60% by weight, relative to the total weight of the milk of calcium particles.
  • the mineral layer of milk of lime has a layer thickness of between 0.1 and 5 mm, preferably between 0.15 and 3 mm, more preferably between 0.2 and 2 mm. , in particular between 0.5 and 1 mm.
  • the milk of calcium particles is a milk of lime and said calcium particles are particles of slaked lime.
  • said calcium particles of said mineral suspension have an average particle size d 50 of between 1.5 ⁇ m and 10 ⁇ m.
  • said calcium particles in the milk of calcium particles of said mineral suspension have an average particle size d 50 less than or equal to 8 ⁇ m, in particular less than or equal to 6 ⁇ m, more particularly less than or equal to 5 ⁇ m, very particularly less than 4 ⁇ m.
  • said calcium particles in the milk of calcium particles of said mineral suspension have an average particle size d 50 greater than or equal to 2 ⁇ m, in particular greater than or equal to 2.5 ⁇ m.
  • said additives of said mineral suspension are chosen from the group consisting of carbohydrates as well as dispersants and plasticizing additives, such as polycarbonates or polyacrylates, or polyphosphonates, in particular DTPMP.
  • additives may be present in said mineral suspension, in particular one or more carbohydrates with one or more dispersing or thinning agents.
  • said carbohydrate is chosen from the group consisting of disaccharides, such as sucrose or sucrose, sorbitol, monosaccharides, oligosaccharides, xylose, glucose , galactose, fructose, mannose, lactose, maltose, glucuronic acid, gluconic acid, erythritol, xylitol, lactitol, maltitol, dextrins, cyclodextrins, inulin, glucitol, uronic acid, rhamnose, arabinose, erythrose, threose, ribose, allose, trehalose, galacturonic acid, and mixtures thereof.
  • disaccharides such as sucrose or sucrose, sorbitol, monosaccharides, oligosaccharides, xylose, glucose , galactose, fructose, mannose, lactose, mal
  • said carbohydrate is chosen from the group consisting of disaccharides, such as sucrose or sucrose, sorbitol and mixtures thereof.
  • said milk of calcium particles has a viscosity of between 0.1 Pa.s and 2 Pa.s.
  • said calcium particles of the milk of calcium particles have a particle size d 97 of between 7 and 100 ⁇ m.
  • said milk of calcium particles has a content of calcium particles greater than or equal to 25% by weight, preferably greater than or equal to 27% by weight, preferably greater than or equal to 30% by weight, preferably greater than or equal to 35% by weight, relative to the total weight of the milk of calcium particles and a content of calcium particles less than or equal to 55% by weight, preferably less than or equal to 50% by weight, preferably less than or equal to 48% by weight, relative to the total weight of the milk, of calcium particles

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Engineering & Computer Science (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Carbon Steel Or Casting Steel Manufacturing (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Furnace Charging Or Discharging (AREA)
  • Furnace Details (AREA)

Claims (13)

  1. Verfahren zur Handhabung eines Schlackenkubels oder einer Schlackenpfanne aus Stahl oder aus Gusseisen, eine Innenwand und eine Außenwand umfassend, wobei das Verfahren die Schritte umfasst der
    a) Sammlung einer Schlacke in dem Schlackenkubel oder der Schlackenpfanne eines pyrometallurgischen Werkzeugs,
    b) Transportieren des Schlackenkubels oder der Schlackenpfanne des pyrometallurgischen Werkzeugs bis zu einer Schlackenabladestelle, typischerweise einer Deponie,
    c) Entleerung des Kubels oder der Pfanne an der Schlackenabladestelle, typischerweise an der Deponie, um die darin enthaltene Schlacke zu entfernen,
    d) Aussprühen einer Mineralsuspension an der Innenwand des Schlackenkubels oder der Schlackenpfanne, vor zumindest einem Schritt des Sammelns der Schlacke, um die Innenwand mit einer Mineralschicht zu beschichten , und
    e) Verwendung des mit der Mineralschicht überzogenen Schlackenkubels oder Schlackenpfanne mit dem Ziel der Sammlung von Schlacke a),
    dadurch gekennzeichnet, dass die Mineralsuspension kalkhaltige Partikel in Suspension in einer wässrigen Phase, die eine kalkhaltige Partikelmilch bildet, und Zusatzstoffe, die aus der Kohlenhydrat-Gruppe sowie Dispergiermittel und Fluidizierungsmittel bestehen, wie Polycarbonate oder Polyacrylate oder Polyphosphonate, umfasst, wobei die kalkhaltigen Partikel aus der Gruppe ausgewählt sind, die aus gelöschtem Kalk, zumindest teilweise gelöschtem dekarbonisiertem Dolomit, Kalkstein und deren Mischungen besteht und einen Gehalt von kalkhaltigen Partikeln von zwischen 20 und 60 Gew.-% in Bezug auf das Gewicht der kalkhaltigen Partikelmilch aufweist, wobei die kalkhaltigen Partikel in der kalkhaltigen Partikelmilch der Mineralsuspension eine durchschnittliche Partikelgröße d50 von zwischen 1,5 µm und 10 µm aufweisen, und dadurch, dass die Mineralschicht eine dünne Schicht ist, die auf der Innenwand überzieht und eine Schichtdicke von zwischen 0,1 und 0,5 mm aufweist.
  2. Verfahren nach Anspruch 1, wobei die Kohlenhydrat-Gruppe aus Verbindungen von Dissacchariden, wie Sucrose oder Saccharose, Sorbitol, Monosacchariden, Oligosacchariden, Xylose, Glucose, Galactose, Fructose, Mannose, Lactose, Maltose, Glucuronsäure, Gluconsäure, Erythritol, Xylitol, Lactitol, Maltitol, Dextrinen, Cyclodextrinen, Inulin, Glucitol, Uronsäure, Rhamnose, Arabinose, Erythrose, Threose, Ribose, Allose, Trehalose, Galacturonsäure und deren Mischungen besteht.
  3. Verfahren nach Anspruch 1 oder 2, wobei die Kohlenhydrat-Gruppe aus Verbindungen von Dissacchariden, wie Sucrose oder Saccharose, Sorbitol und deren Mischungen besteht.
  4. Verfahren nach einem der vorstehenden Ansprüche, wobei der kalkhaltige Partikelschlamm eine Viskosität von zwischen 0,1 Pa.s und 2 Pa.s aufweist.
  5. Verfahren nach einem der vorstehenden Ansprüche, wobei die kalkhaltigen Partikel des kalkhaltige Partikelmilch eine Partikelgröße d97 von zwischen 7 und 100 µm aufweisen.
  6. Verfahren nach einem der vorstehenden Ansprüche, wobei die kalkhaltige Partikelmilch eine Kalkmilch ist und die kalkhaltigen Partikel Partikel aus gelöschtem Kalk sind, und wobei die Kalkmilch eine Reaktivität, in Form einer Auflösungszeit t(90%) ausgedrückt, von größer als 0,1 s, insbesondere größer als 0,2 s und kleiner als 10 s, insbesondere kleiner als 5 s aufweist.
  7. Verfahren nach einem der vorstehenden Ansprüche, wobei die kalkhaltige Partikelmilch einen Gehalt an kalkhaltigen Partikeln größer als oder gleich 25 Gew.-%, vorzugsweise größer als oder gleich 27 Gew.-%, vorzugsweise größer als oder gleich 30 Gew.-%, vorzugsweise größer als oder gleich 35 Gew.-% in Bezug auf das Gesamtgewicht der kalkhaltigen Partikelmilch, und einen Gehalt an kalkhaltigen Partikeln kleiner als oder gleich 55 Gew.-%, vorzugsweise kleiner als oder gleich 50 Gew.-%, vorzugsweise kleiner als oder gleich 48 Gew.-% in Bezug auf das Gesamtgewicht der kalkhaltigen Partikelmilch aufweist.
  8. Verwendung einer kalkhaltigen Partikelmilch, ausgewählt aus der Gruppe, die aus dem gelöschten Kalk besteht, zumindest teilweise gelöschtem dekarbonisiertem Dolomit, Kalkstein und deren Mischungen besteht, um eine Innenwand eines Schlackenkubels oder einer Schlackenpfanne aus Stahl oder aus Gusseisen mit einer Mineralschicht aus kalkhaltigen Partikeln auszukleiden, wobei die kalkhaltige Partikelmilch besprüht wird und einen Gehalt an kalkhaltigen Partikeln zwischen 20 und 60 Gew.-% in Bezug auf das Gesamtgewicht der kalkhaltigen Partikelmilch aufweist, wobei die dünne Mineralschicht aus kalkhaltigen Partikeln eine Schichtdicke von zwischen 0,1 und 0,5 mm aufweist, wobei die kalkhaltigen Partikel der Mineralsuspension eine durchschnittliche Partikelgröße d50 von zwischen 1,5 µm und 10 µm aufweisen, wobei die Suspension Zusatzstoffe aus der Gruppe der Kohlenhydrate sowie Dispergiermitteln und fluidisierende Zusatzstoffe, wie Polycarbonate oder Polyacrylate oder Polyphosphonate, umfasst.
  9. Verwendung einer kalkhaltigen Partikelmilch nach Anspruch 8, wobei die Kohlenhydrat-Gruppe aus Verbindungen von Dissacchariden, wie Sucrose oder Saccharose, Sorbitol, Monosacchariden, Oligosacchariden, Xylose, Glucose, Galactose, Fructose, Mannose, Lactose, Maltose, Glucuronsäure, Gluconsäure, Erythritol, Xylitol, Lactitol, Maltitol, Dextrinen, Cyclodextrinen, Inulin, Glucitol, Uronsäure, Rhamnose, Arabinose, Erythrose, Threose, Ribose, Allose, Trehalose, Galacturonsäure und deren Mischungen besteht.
  10. Verwendung einer kalkhaltigen Partikelmilchnach Anspruch 8 oder Anspruch 9, wobei die Kohlenhydrat-Gruppe aus Verbindungen von Dissacchariden, wie Sucrose oder Saccharose, Sorbitol und deren Mischungen besteht.
  11. Verwendung einer kalkhaltigen Partikelmilch nach einem der Ansprüche 8 bis 10, wobei die kalkhaltige Partikelmilch eine Viskosität von zwischen 0,1 Pa.s und 2 Pa.s aufweist.
  12. Verwendung einer kalkhaltigen Partikelmilch nach einem der Ansprüche 8 bis 11, wobei die kalkhaltigen Partikel der kalkhaltigen Partikelmilch eine Partikelgröße d97 von zwischen 7 und 100 µm aufweisen.
  13. Verwendung einer kalkhaltigen Partikelmilch nach einem der Ansprüche 8 bis 12, wobei die kalkhaltige Partikelmilch einen Gehalt an kalkhaltigen Partikeln größer als oder gleich 25 Gew.-%, vorzugsweise größer als oder gleich 27 Gew.-%, vorzugsweise größer als oder gleich 30 Gew.-%, vorzugsweise größer als oder gleich 35 Gew.-% in Bezug auf das Gesamtgewicht der kalkhaltigen Partikelmilch, und einen Gehalt an kalkhaltigen Partikeln kleiner als oder gleich 55 Gew.-%, vorzugsweise kleiner als oder gleich 50 Gew.- %, vorzugsweise kleiner als oder gleich 48 Gew.-% in Bezug auf das Gesamtgewicht der kalkhaltigen Partikelmilch aufweist.
EP17828850.2A 2016-12-08 2017-12-07 Verfahren zur handhabung eines schlacketopfes und verwendung von kalziumpartikel-schlamme zum auskleben einer innenwand eines schlacketopfes Active EP3551772B1 (de)

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CN112695142A (zh) * 2020-12-09 2021-04-23 钢城集团凉山瑞海实业有限公司 一种防止冶金渣罐粘结的方法
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BE794158A (fr) 1972-01-17 1973-05-16 Foseco Int Enduits refractaires
GB1593397A (en) * 1976-10-12 1981-07-15 Foseco Trading Ag Slag pots
JPS63295458A (ja) 1987-05-26 1988-12-01 Kazuhisa Hoshino 電気炉製鋼で発生する熔融スラグの分割回収方法及びその再生処理方法
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US5437890A (en) 1994-04-18 1995-08-01 Edw. C. Levy Co. Coatings for receptacles
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US5616283A (en) 1995-08-25 1997-04-01 Chemical Lime Company High solids lime as a caustic replacement
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EP1840097A1 (de) 2006-03-27 2007-10-03 Carmeuse S.A. Stabilisierung von Kalkmilch-Suspensionen
JP5994764B2 (ja) 2013-11-13 2016-09-21 Ｊｆｅスチール株式会社 スラグポット内面に石灰スラリーを散布する装置及び方法
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EP3551772C0 (de) 2023-06-07
BR112019011470B1 (pt) 2022-07-19
TWI750276B (zh) 2021-12-21
FR3060019A1 (fr) 2018-06-15
WO2018104447A1 (fr) 2018-06-14
ES2951208T3 (es) 2023-10-18
BR112019011470A2 (pt) 2019-10-22
MX2019006313A (es) 2019-07-12
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US11221181B2 (en) 2022-01-11
AU2017373747A1 (en) 2019-06-20
PL3551772T3 (pl) 2023-10-09
US20190376746A1 (en) 2019-12-12
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AU2017373747B2 (en) 2023-07-13
ZA201903542B (en) 2020-12-23

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