WO2018007630A1 - Composition sous forme de briquettes comprenant des composes calco-magnesiens vifs, son procede d'obtention et leur utilisation - Google Patents
Composition sous forme de briquettes comprenant des composes calco-magnesiens vifs, son procede d'obtention et leur utilisation Download PDFInfo
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- WO2018007630A1 WO2018007630A1 PCT/EP2017/067167 EP2017067167W WO2018007630A1 WO 2018007630 A1 WO2018007630 A1 WO 2018007630A1 EP 2017067167 W EP2017067167 W EP 2017067167W WO 2018007630 A1 WO2018007630 A1 WO 2018007630A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/02—Oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/30—Oxides other than silica
- C04B14/308—Iron oxide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/021—Agglomerated materials, e.g. artificial aggregates agglomerated by a mineral binder, e.g. cement
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
- C04B22/062—Oxides, Hydroxides of the alkali or alkaline-earth metals
- C04B22/064—Oxides, Hydroxides of the alkali or alkaline-earth metals of the alkaline-earth metals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/06—Oxides, Hydroxides
- C04B22/066—Magnesia; Magnesium hydroxide
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/244—Binding; Briquetting ; Granulating with binders organic
- C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00732—Uses not provided for elsewhere in C04B2111/00 for soil stabilisation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00758—Uses not provided for elsewhere in C04B2111/00 for agri-, sylvi- or piscicultural or cattle-breeding applications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0087—Uses not provided for elsewhere in C04B2111/00 for metallurgical applications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0087—Uses not provided for elsewhere in C04B2111/00 for metallurgical applications
- C04B2111/00887—Ferrous metallurgy
Definitions
- the present invention relates to a composition in the form of briquettes comprising at least one bright calco-magnesium compound, said composition having from 40% to 100% by weight of equivalent CaO + MgO, preferably 60% to 100% by weight of equivalent CaO + MgO, relative to the weight of said composition.
- the term " bright calco-magnesium compound" is intended to mean a solid mineral material whose chemical composition is mainly calcium oxide and / or magnesium oxide.
- the living calco-magnesium compounds within the meaning of the present invention therefore comprise quicklime (calcium lime), bright magnesium lime, dolomitic quicklime or bright calcined dolomite, also known as cooked dolomite.
- the living calcium-magnesium compounds contain impurities, that is, compounds such as silica, SiO 2, or alumina, Al 2 O 3 , etc., up to a few percent. It is understood that these impurities are expressed in the aforementioned forms but may actually appear in different phases. It also generally contains a few percent residual CaCO 3 or MgCO 3 , called incuits, and some residual Ca (OH) 2 or Mg (OH) 2 , due to partial hydration of the live products during cooling, handling and / or storage phases.
- Lime means a mineral solid whose chemical composition is mainly calcium oxide, CaO.
- Quicklime is commonly obtained by calcination of limestone, mainly consisting of CaCO 3 .
- Quicklime contains impurities, that is, compounds such as magnesium oxide, gO, silica, SiO 2 or alumina, Al 2 O 3 , etc., up to a few percent . It is understood that these impurities are expressed in the aforementioned forms but may actually appear in different phases. It also generally contains a few percent of residual CaCO 3 , called incuits, and a few percent of residual Ca (OH) 2 , due to the partial hydration of calcium oxide CaO during the cooling phases. handling and / or storage. According to the present invention, the term
- “Briquette” a compact having an oblong shape, having a mass of about 5 to 100 g per briquette, inscribed in an ellipsoid of flattened or elongated revolution (in English oblate ellipsoid of revolution or prolate ellipsoid of revolution).
- the briquettes are in the form of soap or are called briquettes “egg” (in English “egg briquettes”)
- tablets that are typically in the form of pellets as produced by the presses "Titan” of the company “Eu rota b”.
- tablets for industrial use are of regular shape, more particularly in the form of low cylinder height.
- Briquettes are known from the state of the art, see for example WO2015007661. According to this document, compacts (namely briquettes or tablets) are described comprising particles of calco-magnesium compound comprising at least 50% of bright calco-magnesium compound.
- the mechanical resistance to the fall is measured by means of a test shatter.
- the compacts described generally have a test Shatter index of less than 10%.
- Stress test number is meant the mass percentage of fines less than 10 mm generated after 4 drops of 2 m from 10 kg of product. These fines are quantified by sieving through a 10 mm square screen at the end of the 4 drops of 2 m.
- US5186742 discloses lime briquettes containing from 55 to 85% by weight of lime, from 10 to 40% by weight of ash and from 0.1 to 10% by weight of paper fibers as well as optionally a lubricant.
- the briquettes disclosed in US 5186742 are tested for their resistance to falling, which test is not comparable to the test for measuring the Shatter test index and has a compressive strength between 150 and 300 pounds, which corresponds to a Shatter test index well above 10%.
- Calco-Magnesium compounds are used in many industries, such as iron and steel, gas processing, water and sludge treatment, agriculture, building industry, public works and others. They can be used either in the form of pebbles or pieces, or in the form of fines (generally less than 7 mm in size). In some industries, the shape of pebble is nevertheless preferred.
- the heaters always maintain an equilibrium of the materials between the calco-magroidiens compounds in roller and the fines generated before and during the calcination as well as during the manipulations and subsequent operations. Nevertheless, in some cases, an excess of fines is produced. These fines can then be agglomerated to one another in the form of briquettes or the like, which not only gives the possibility of removing excess fines but also artificially increasing the production of calcium and magnesium compounds by adding pebbles. these briquettes or the like with pebbles.
- Barnett et al Roll-press briquetting: Compacting fines to reduce waste-handling costs, powder and bulk engineering, vol.24, No. 10, October 2010, 1-6 discloses a method of manufacturing raw briquettes of lime.
- this document is silent as to the production conditions as well as the mechanical properties of briquettes obtained.
- Briquettes of excess fines or the like generally have lower mechanical strength than Calcium and magnesium (calc-magnesium) compounds in a pebble. They also have aging resistance during storage or handling which is significantly lower than that of calcium and magnesium compounds in a pebble.
- Lubricants and binders are additives often used in agglomeration processes in the form of briquettes or the like.
- Lubricants can be of two types, internal or external. Internal lubricants are intimately mixed with briquetting materials. They favor on the one hand the flowability of the mixture during the feeding of the briqueteuse and on the other hand the rearrangement of the particles within the mixture during the compression. External lubricants are applied to the surfaces of the briquetting rollers and primarily assist in the demolding. In both cases, they reduce the friction on the surface and thus the wear. Lubricants can be liquids such as mineral oils, silicones, etc. or solids such as talc, graphite, paraffins, stearates, etc. In the case of compositions based on living calco-magnesium compounds, stearates are preferred and more particularly calcium stearate or magnesium stearate.
- Binders are substances having the property of agglomerating the particles together, either by adhesion forces or by a chemical reaction. They can be of mineral origin (cements, clays, silicates %), of vegetable or animal origin (celluloses, starches, gums, alginates, pectin, glues, %), of synthetic origin (polymers, waxes ). In many cases, they are used and implemented with water that activates their agglomeration properties.
- Briquettes or the like based on caico-magnesian compounds can also be consolidated by means of a very high temperature heat treatment which leads to the sintering of said briquettes or the like.
- a very high temperature heat treatment which leads to the sintering of said briquettes or the like.
- a heat treatment of one to several hours at a temperature above 1200 T, and even ideally above 1300 ° C leads to an increase in the mechanical properties of said briquettes.
- This heat treatment at very high temperature nevertheless leads to a chronological evolution of the texture characteristics of the aforementioned briquettes, it leads in particular to a sharp decrease in both the specific surface area and the pore volume. This is also accompanied by a sharp decrease in water reactivity, as explained in EN 459-2: 2010 E, which has many drawbacks for certain applications.
- the object of the invention is to overcome the disadvantages of the state of the art by providing a composition as mentioned at the beginning, characterized in that said bright calco-magnesium compound comprises quicklime in the form of crushed particles at a concentration at least 10% by weight and at most 100% by weight relative to the total weight of said composition, said composition in the form of briquettes having a test Shatter number of less than 10%.
- Quicklime in the form of crushed particles is called lime fines from the grinding of quicklime and therefore corresponds to a dimensional reduction of the rock lime.
- the grinding can be indifferently made from the all-comer at the exit of the oven (out of the oven) and / or at the outlet of the silo (taken out silo) or from the all-coming at the exit of the oven and / or at the output of the silo previously screened.
- the grinding can be carried out using different types of mills (hammer mill, impact mill ...), either in open circuit (no recirculation loop), or in closed circuit (recirculation loop).
- Quicklime in the form of crushed particles is distinguished from lime screen.
- Screen lime is called lime fines from lime screen.
- the particle size is defined by the size of the screen. For example, a lime screened at 3 mm results in a 0-3 mm screening lime. Thus the screening on the all-out oven led to a "primary” screening lime. Screening on the all-out storage silo leads to a "secondary" screening lime.
- quicklime in the form of crushed particles lime fines generally containing more than very fine lime fines screening.
- quicklime fines in the form of crushed particles will typically contain at least 30% by weight, most often at least 40% by weight, or even at least 50% by weight. by weight of very fine less than 100 ⁇ , while the screening lime fines often contain at most 25% by weight, or even at most 15% by weight of very fine less than 100 ⁇ .
- the chemical composition of crushing lime fines is generally more homogeneous than that of lime fines.
- a lime in rock 10-50 mm cooked with a fuel which generates ashes such as coal (lignite, coal, anthracite ...) or petroleum coke
- coal lignite, coal, anthracite
- petroleum coke a fuel which generates ashes
- the 0-3 mm fines resulting from the grinding or the screening of this rock lime are characterized, it will be noted that the fraction 0-200 ⁇ of the fines ⁇
- 0-3 mm from grinding has a chemistry similar to that of the fraction 200 ⁇ -3 mm " whereas the 0-200 ⁇ fraction of the fine 0-3 mm from the screen contains more impurities than that of the fraction 200 ⁇ -3 mm.
- Crushing lime fines are generally more reactive than lime fines.
- the grinding fines typically have t 6 o values of less than 5 min where the primary screening fines often have t 60 values greater than 5 min.
- the briquettes according to the present invention have a particularly advantageous Shatter test number of less than 10%, thereby conferring on the briquettes sufficient mechanical strength to permit industrial use in most processes using the compounds.
- said bright calco-magnesium compound comprises one or more bright calco-magnesium compound (s).
- the bright calco-magnesium compound is selected from the group consisting of quicklime (calcium), magnesium lime, bright dolomite lime, calcined dolomite and mixtures thereof, preferably in the form of particles, such as particles from screening, grinding, filter dust and mixing.
- Said bright calco-magnesium compound can therefore be considered as a calco-magnesian component of the composition in the form of briquettes, which may contain other compounds.
- the calco-magnesium compound is present in the composition at a concentration of at least 50% by weight, preferably at least 60% by weight, more preferably at least 70% by weight. more particularly at least 80% by weight, or even at least 90% by weight relative to the total weight of said composition.
- the term "Shatter test number” means the mass percentage of fines less than 10 mm generated after 4 drops of 2 m from 10 kg of product (briquettes). These fines are quantified by sieving through a 10 mm square screen at the end of the 4 drops of 2 m.
- the determination of the% by weight of CaO + MgO equivalent is carried out by X-ray fluorescence spectrometry (XRF) as described in the EN 15309 standard.
- XRF X-ray fluorescence spectrometry
- Chemical, semi-quantitative analysis by XRF to determine the relative mass concentration of elements whose atomic mass is between 16 (oxygen) and 228 (uranium) is carried out at the start of the samples milled at 80 ⁇ and shaped in the form of pellet.
- the samples are introduced into a PANalytical / MagiX PRO PW2540 apparatus, operating in wavelength dispersion.
- the measurement is carried out with a power of 50kV and 80 mA, with a Duplex detector.
- said bright calco-magnesium compound is soft cooking or medium cooking, preferably soft cooking.
- Live calco-magnesium compounds are industrially produced by cooking natural limestones in different types of furnaces such as straight furnaces (regenerative furnaces with double flow, ring furnaces, standard straight furnaces, etc.). rotary kilns.
- the quality of the calco-magnesium compound, such as for example quicklime, especially its reactivity to water, and the consistency of this quality, are partly related to the type of oven used, the conditions of use of the oven, to the nature of the limestone from which the living calco-magnesium compound originates, or even to the nature and quantity of the fuel used.
- the quick lime obtained by gentle firing generally have specific surfaces measured by nitrogen adsorption manometry after degassing under vacuum at 190 ° C. for at least 2 hours and calculated according to the multi-point BET method as described in the standard ISO 9277: 2010E greater than 1 m 7g whereas over-cooked quicklime usually has surfaces well below 1 m 2 / g
- the reactivity of quicklime is measured using the water reactivity test of the European standard EN 459 ⁇ 2: 2010 E.
- 150g of quicklime are added with stirring in a Dewar cylindrical of 1.7 dm 3 capacity containing 600 cm 3 of permutated water at 20 ° C.
- the quicklime is brought in the form of fines of size between 0 and 1 mm.
- the stirring at 250 rpm is carried out by means of a specific pale.
- the evolution of the temperature is measured as a function of time, which makes it possible to draw a curve of reactivity. We can deduce from this curve the value t 60 which is the time required to reach 60 ° C.
- the reactivity of the cooked dolomite is measured using this same reactivity test, in this case 120 g of dolomite
- the fired dolomite is added in the form of fines of between 0 and 1 mm in size.
- the fired dolomite is added with stirring in a cylindrical Dewar having a capacity of 1.7 dm 3 and containing 400 cm 3 of deionized water at 40 ° C. stirring at 250 rpm is carried out by means of a specific pale.
- the evolution of the temperature is measured as a function of time, which makes it possible to draw a curve of reactivity.
- the value t 70 can be deduced from this curve. is the time needed to reach 70 ° C.
- composition according to the present invention advantageously comprises a calco-magnesium compound with soft or medium cooking, 1Q preferably soft which is therefore necessarily relatively reactive, thus providing reactive briquettes.
- a bright calco-magnesian compound with a soft or medium, preferably soft, cooking is characterized by a value t 60 of less than 10 min, preferably 8 min, preferentially 6 min, and still more preferably 4 min when the calco compound -Magnesian alive is a quicklime and a value of t 70 less than 10 min, preferably 8 min, preferably 6 min, and more preferably 4 min when the bright calco-magroidien compound is a cooked dolomite.
- said quicklime in the form of crushed particles is a quick-cooking quicklime or medium-bake, preferably soft cooking.
- said quicklime in the form of crushed particles according to the present invention has a high water reactivity characterized by a value of t 50 less than 10 min, preferably less than 8 min, preferentially less than 6 min and still preferably lower at 4 min.
- said briquettes have a largest dimension of at most 50 mm, preferably at most 40 mm, more preferably at most 30 mm.
- briquettes of the composition in the form of briquettes pass through a sieve with square mesh of 50 mm, preferably 40 mm, and in particular 30 mm, side respectively.
- said briquettes have an uppermost dimension of at least 10 mm, preferably at least 15 mm, more preferably at least 20 mm.
- highest dimension is meant a characteristic dimension of the briquette which is the largest, namely the diameter, the length, the width, the thickness, preferably in the longitudinal direction of the oblong briquette.
- said briquettes are raw briquettes and have a BET specific surface area greater than or equal to 1 m 2 / g, preferably greater than or equal to 1.2 m 2 / g, more preferably greater than or equal to 1.4 mVg.
- said briquettes are cooked briquettes and have a BET specific surface area greater than or equal to 0.4 m 2 / g, preferably greater than or equal to 0, 6 m 2 / g, more preferably greater than or equal to 0.8 m 2 / g.
- BET specific surface area is meant within the meaning of the present invention, the specific surface area measured by nitrogen adsorption at 190 manometry after vacuum degassing ° C for at least 2 hours and calculated according to the BET multi-point method such that described in ISO 9277: 2010E and expressed in m 7g
- said briquettes are raw briquettes or cooked briquettes, and have a porosity greater than or equal to 20%, preferably greater than or equal to 22%, more preferably greater than or equal to 24%.
- porosity is understood to mean the total pore volume determined by mercury intrusion porosimetry according to Part 1 of ISO 15901-1; 2005E, which consists in dividing the difference between the measured skeletal density. at 30000 psia, and apparent density, measured at 0.51 psia, by skeletal density.
- the measurement of porosity can also be measured by oil intrusion porosimetry.
- the density and the porosity of the briquettes are determined by intrusion of kerosene, according to a measuring protocol resulting from the EN ISO 5017 standard. The measurements are carried out on 5 briquettes.
- the density of the briquettes is calculated according to the formula ml / (m3 - m2) x Dp and the porosity in percent according to the formula (m3 - ml) / (m3 - m2) x 100.
- the composition is in the form of raw briquettes and the briquettes have a high water reactivity defined by a value of t 60 of less than 10 min, preferentially less than 8 min, preferably less than 10 min. at 6 min, and still preferably less than 4 min.
- the composition is in the form of cooked briquettes and the briquettes have a high water reactivity defined by a value of t 60 less than 10 min, preferentially less than 8 mm, preferably lower than at 6 min, and still preferably less than 4 min.
- the composition when the composition is in the form of raw briquettes and the calco-magnesium compound is mainly quicklime, said composition has a reactivity value t 60 less than 10 min, preferably less than 8. min, preferably less than 6 ml and even more preferably less than 4 min. If fluxes are present or for example an iron oxide, to take account of the flux content, such as for example an iron-based compound in the composition, a little more than 150 g of said composition is added in the test. reactivity to have the equivalent of 150g of quicklime added.
- the composition when the composition is in the form of raw briquettes and the calco-magnesium compound is mainly of the cooked method, said composition has a reactivity value t 70 less than 10 min, preferably less than 8 ml. preferably less than 6 minutes and even more preferably less than 4 minutes. If fluxes are present or for example an iron oxide, to take into account the melting content such as, for example, the iron compound in the composition, a little more than 120 g of said composition is added to the reactivity test for have the equivalent of 120g of cooked cooking added.
- the composition when the composition is in the form of cooked briquettes and the calco-magnesian compound is mainly quicklime, said composition has a value t 60 of less than 10 min, preferably less than 8 min, preferably less than 6 minutes and even more preferably less than 4 minutes.
- fluxes are present or for example an iron oxide, to take account of the content of melts, such as for example iron-based compound in the composition, a little more than 150 g of said composition is added in the reactivity test to have the equivalent of 150 g of "free" quicklime added.
- quicklime "free” is meant quicklime that has not reacted with iron oxide to lead to calcium ferrites CaFe 2 0 4 and / or Ca 2 Fe 2 0 5 .
- said quicklime in the form of crushed particles is present at a concentration of at least 15% by weight, preferably at least 20% and more preferably at least 20% by weight. at least 30%, in particular at least 40% by weight relative to the total weight of said composition.
- said quicklime in the form of crushed particles is present at a concentration of at most 90% by weight, preferably at most 80%, preferably at most 70%, more preferably at most 50% by weight relative to the total weight of said composition.
- the composition based on bromine compounds in the form of briquettes also comprises a binder or a lubricant, preferably in the form of a powder or concentrated aqueous suspension, more particularly chosen from the group consisting of binders of mineral origin such as cements, clays, silicates, binders of vegetable or animal origin, such as celluloses, starches, gums, alginates, pectin, glues, binders synthetic origin, such as polymers, waxes, liquid lubricants such as mineral oils or silicones, solid lubricants such as talc, graphite, paraffins, stearates, in particular calcium stearate, stearate magnesium, and mixtures thereof, preferably calcium stearate and / or magnesium stearate, at a content of between 0.10 and 1% by weight, preferably between 0.15 and 0.15% by weight. and 0.6% by weight, more preferably between 0.20 and 0.50% by weight relative to the total weight
- said briquettes have a mean weight per briquette of at least 5 g, preferably at least 10 g, more preferably at least 12 g, and in particular at least 15 g. boy Wut.
- said briquettes have a mean weight per briquette less than or equal to 100 g, preferably less than or equal to "
- 60 g more preferably less than or equal to 40 g and in particular less than or equal to 30 g.
- said briquettes have an apparent density of between 2 g / cm 3 and 3.0 g / cm 3 , preferably between 2.2 g / cm 3 and 2.8 g / cm 3 .
- said bright calco-magnesium compound further comprises fine particles of calco-magnesium compound chosen from fine particles rejected in the screening of the cobalt production of said bright calco-magnesium compound, dust calc-magnesian filters and their mixture, at a concentration of at least 10% by weight and at most 90% by weight relative to the total weight of said composition.
- said fine particles rejected in the production screen of calco-magnesian compound rollers are fine particles of live dolomite.
- said fine particles rejected in the calco-magnesian compound pebble production screen are fine particles of quicklime.
- said fine particles rejected on screening are fine particles rejected on screening at 7 mm during said production of rolls of said calco-magnesium compound.
- said fine particles rejected on screening are fine particles rejected on screening at 5 mm during said production of rolls of said calco-magnesian compound.
- said fine particles rejected on screening are fine particles rejected on screening at 3 mm during said production of rolls of said calco-magnesium compound.
- said fine particles rejected on screening are a mixture of fine particles rejected on screening at 7 mm during said production of rolls of said calco-magnesium compound and / or fine particles rejected on the screen. mm during said pebble production of said calco-magnesium compound and / or fine particles rejected at 3 mm during the production of pebbles of said calco-magnesium compound.
- the fine particles rejected on screening therefore advantageously have a particle size d 100 of less than or equal to 7 mm, in particular less than or equal to 5 mm, more particularly less than or equal to 3 mm; a d 90 less than or equal to 3 mm and a d 50 less than or equal to 1 mm.
- the notation x represents a diameter expressed as ⁇ , measured by laser granulometry in methanol without sonication, relative to which x% by volume of the particles measured are less than or equal.
- said composition in the form of briquettes further comprises one or more compounds based on iron at a concentration of at least 3% by weight and at most 60%. by weight expressed as Fe 2 O 3 equivalent relative to the total weight of said composition.
- At least one of the iron-based compound (s) is a compound based on iron oxide, preferably active iron, present at a concentration of at least 3% by weight. weight and at most 60% by weight expressed in Fe 2 0 3 equivalent relative to the total weight of said composition.
- said composition in the form of briquettes comprises at least 50% by weight of calcium expressed as CaO equivalent, relative to the total weight of said composition.
- said composition in the form of briquettes comprises a molar ratio Ca / Mg greater than or equal to 1, preferably greater than or equal to 2, more preferably greater than or equal to 3
- the green briquettes contain an iron-based compound which is an iron oxide compound
- said green briquettes can be advantageously subjected to heat treatment at a temperature between 700 ° C and 1200, preferably between 90O ° C, or 1050T and 1200X, particularly around HOO'C, for a predetermined time for example between 5 and 20 minutes, preferably greater than or equal to 7 minutes and less than or equal to 15 minutes, with training and i C
- said iron-based compound may be formed from one or more iron-based compounds, together totaling in the composition a content of 3 to 50% by weight relative to the total weight of said composition.
- the composition according to the present invention is packaged in container types having a content volume greater than 1 m 3 such as large bags, containers, silos and the like, preferably sealed.
- the composition in the form of briquettes consists of raw briquettes having a test Shatter number of less than 8%, preferably less than 6%, and even more preferably less than 5%, in particular less than 4%.
- the composition in the form of briquettes consists of cooked briquettes having a test Shatter number of less than 6%, preferably less than 4%, and more preferably less than 3%, particular less than 2%, or even less than 1.5%.
- the invention also relates to a method of manufacturing a composition in the form of briquettes.
- the process is characterized in that it comprises the following steps: a) supplying a powder mixture comprising at least 40% by weight of CaO + MgO equivalent relative to the weight of said powder mixture, and comprising at least one calco compound vivid magnesium, said at least one bright calco-magnesium compound comprising quicklime in the form of crushed particles at a concentration of at least 10% by weight and at most 100% by weight relative to the total weight of said mixture powder,
- said powder mixture comprises at most 100% by weight, preferably at most 90% by weight, more preferably at most 88%, in some embodiment at most 80% by weight. more preferably, at most 60% by weight of CaO + MgO equivalent relative to the weight of said composition.
- step a) is carried out in the presence of a binder or a lubricant, preferably in the form of a concentrated aqueous powder or suspension, more particularly chosen from the group consisting of binders of mineral origin such as cements, clays, silicates, binders of vegetable or animal origin, such as celluloses, starches, gums, alginates, pectin, glues, binders of origin synthetic, such as polymers, waxes, liquid lubricants such as mineral oils or silicones, solid lubricants such as talc, graphite, paraffins, stearates, in particular calcium stearate, magnesium stearate and mixtures thereof, preferably calcium stearate and / or magnesium stearate, at a content of between 0.1 and 1% by weight, preferably between 0.15 and 0.6% by weight, more preferably e 0.2 and 0.5% by weight relative to the total weight of said briquettes.
- binders of mineral origin such as cements, clays,
- the method according to the present invention further comprises a heat treatment of said collected raw briquettes at a temperature of between 700 ° C. and 1200 ° C., preferably around 900 ° C. for a predetermined duration of between 5 and 20 minutes. , preferably greater than or equal to 7 minutes and less than or equal to 15 minutes, with formation and obtaining of cooked briquettes.
- said homogeneous mixture brought into the process according to the invention comprises a bright calco-magnesium compound with soft or medium cooking, preferably soft cooking.
- said quicklime in the form of crushed particles, of said substantially homogeneous mixture brought into the process according to lg the invention is a quicklime soft cooking or medium cooking, preferably soft cooking.
- said bright calco-magnesium compound is quicklime.
- said quicklime in the form of crushed particles, of said substantially homogeneous mixture brought into the process according to the invention has a high water reactivity characterized by a Tg value of less than 10 min, preferentially less than 8 min, preferably less than 6 min and more preferably less than 4 min.
- said quicklime in the form of crushed particles, of said substantially homogeneous mixture brought into the process according to the invention is obtained by grinding starting from quicklime rock whose size is greater than 3 mm. , preferably greater than 5 mm, preferably greater than 7 mm, and even more preferably greater than 10 mm, and less than 120 mm, preferably 100 mm, preferably less than 80 mm, and still more preferably less than 60 mm.
- said at least one bright calco-magnesium compound comprises quicklime in the form of crushed particles at a concentration of at least 15% by weight, in particular at least 20% by weight, more preferably preferably at least 30% by weight, particularly preferably at least 40% by weight relative to the total weight of said substantially homogeneous powder mixture.
- said substantially homogeneous mixture based on bright calco-magnesium compounds brought into the process according to the invention comprises quicklime in the form of crushed particles at a concentration of at most 90% by weight, in preferably at most 80% by weight, more preferably at most 70% by weight, particularly preferably at most 50% by weight relative to the total weight of said substantially homogeneous powder mixture.
- said bright calco-magnesium compound further comprises fine particles of calco-magnesium compound chosen from fine particles rejected in the screening of the cobalt production of said bright calco-magnesium compound, dust calc 1 g magnesian filter and their mixture, at a concentration of at least 10% by weight and at most 90% by weight relative to the total weight of said substantially homogeneous powder mixture.
- said fine particles rejected in the production screen of calco-magnesian compound rollers are fine particles of live dolomite.
- said fine particles rejected in the calco-magnesian compound pebble production screen are fine particles of quicklime.
- said fine particles rejected on screening are fine particles rejected on screening at 7 mm during said production of rolls of said calco-magnesium compound.
- said fine particles rejected on screening are fine particles rejected on screening at 5 mm during said production of rolls of said calco-magnesium compound.
- said fine particles rejected on screening are fine particles rejected on screening at 3 mm during said production of rolls of said calco-magnesium compound.
- said fine particles rejected on screening are a mixture of fine particles rejected on screening at 7 mm during said production of rolls of said calco-magnesium compound and / or fine particles rejected on the screen. during said production of rolls of said calco-magnesium compound and / or fine particles rejected at 3 mm screening during the production of rolls of said calco-magnesium compound.
- the fine particles rejected on screening therefore advantageously have a particle size d 1 ⁇ of less than or equal to 7 mm, in particular less than or equal to 5 mm, more particularly less than or equal to 3 mm; a d 90 less than or equal to 3 mm and a d 50 less than or equal to 1 mm.
- the notation d represents a diameter expressed in ⁇ m, measured by laser granulometry in methanol without sonication, with respect to which x% by volume of the particles measured are less than or equal.
- said substantially homogeneous pulverulent mixture further comprises one or more compounds based on iron, at a concentration of at least 3% by weight and at most 60%. by weight expressed as Fe 2 O 3 equivalent relative to the weight of said mixture.
- At least one of the iron-based compound (s) is an iron oxide compound present at a concentration of at least 3% by weight and at most 60% by weight. % by weight expressed as Fe 2 O 3 equivalent relative to the weight of said substantially homogeneous mixture, preferably of active iron.
- said substantially homogeneous mixture based on bright calco-magnesium compounds comprises at least 50% by weight of calcium expressed as CaO equivalent, relative to the total weight of said mixture.
- said substantially homogeneous mixture based on living calco-magnesium compounds comprises a molar ratio Ca / g greater than or equal to 1, preferably greater than or equal to 2, more preferably greater than or equal to 3
- the method further comprises a heat treatment of said collected raw briquettes, a temperature of between 700 ° C. and 1200 ° C., preferably between 900 ° C. and even 1050 ° C. and 1200 ° C., more particularly around 1100 ° C., for a predetermined duration, for example between 5 and 20 minutes, preferably greater than or equal to 7 minutes and less than or equal to 15 minutes, with formation and production of cooked briquettes in which the iron oxide-based compound is converted, at least partially, into calcium ferrites.
- the method further comprises, before said feeding of a substantially homogeneous powder mixture,
- the present invention also relates to the use of raw or cooked briquettes according to the present invention, in the iron and steel industry, in particular in the manufacture of steel in elementary oxygen converters, in electric arc furnaces, or in the secondary metallurgy, in the treatment of flue gases, in water treatment, in the treatment of sludge and waste water, in agriculture, in the construction industry and in public works, as for example for stabilization soil.
- the invention also relates to a use of a composition in the form of raw briquettes or in the form of briquettes cooked according to the present invention in the iron and steel industry, in particular in oxygen converters or in electric arc furnaces.
- the raw or cooked briquettes according to the present invention are used in oxygen converters or in electric arc furnaces, mixed with briquettes of bright calco-magnesium compounds or with rolls of bright calco-magnesium compounds.
- composition according to the present invention thus doped with fluxing agents, is found to melt faster than lime rock, and helps to form a liquid slurry earlier in the process, in comparison with conventional processes, because of homogeneous mixing and shaping of this homogenized mixture which further accelerates the slag forming process and minimizes the formation of high melting slag components such as calcium silicates which usually form during the aforementioned method of the state of the art.
- the process further comprises pretreatment of the modified atmosphere briquettes containing at least 2% by volume of C0 2 and at most 30% by volume of C0 2 , preferably at most 25% by volume of C0 2 , preferably at most 20% by volume of C0 2 , more preferably at most 15% by volume of C0 2 , more preferably still not more than 10% by volume of
- the invention also relates to the use of a composition in the form of raw briquettes or in the form of briquettes cooked in a process for refining molten metal, in particular dephosphorizing molten metal and / or desulphurizing molten metal and / or reduction of loss of refined metal in the slag.
- compositions in the form of raw briquettes or in the form of briquettes cooked according to the present invention in a process for refining molten metal comprises
- At least one step of introducing hot metal and possibly iron-based waste into a tank at least one step of introducing a composition in the form of raw briquettes or in the form of cooked briquettes according to the present invention, preferably in the form of briquettes cooked according to the present invention, at least one oxygen blowing step in said tank, at least one step of forming a slag with said briquette composition in said tank, at least one step of obtaining refined metal having a reduced content of phosphorus and / or sulfur compounds and / or an increased content of refined metal from the hot metal by dephosphorization and / or desulfurization, and at least one step of unloading said refined metal having a reduced content in phosphorus and / or sulfur compounds and / or increased in refined metal.
- the use according to the present invention further comprises a step of adding quicklime, preferably quicklime rock or compacts of quicklime, in particular tablets or briquettes of quicklime.
- quicklime preferably quicklime rock or compacts of quicklime, in particular tablets or briquettes of quicklime.
- Fig. 1 shows the correlation between the test Shatter index and the compressive force on different samples of calco-magnesium compound briquettes and optionally iron-based compound.
- FIG. 2 is a plot of BET specific surface area and oil intrusion porosity (%) versus Fe 2 0 3 equivalent content in briquettes according to the present invention.
- Figure 3 is a graph of Shatter Test Index (STI) versus Fe 2 0 3 equivalent content in cooked and raw briquettes according to the present invention.
- STI Shatter Test Index
- Figure 4 is a graph of% Fe 2 t3 ⁇ 4 converted to calcium ferrites as a function of Fe 2 0 3 equivalent content in cooked briquettes according to the present invention.
- FIG. 5 is a graph of the evolution of the calcium ferrite content expressed in Fe 2 O 3 equivalent in the briquettes fired as a function of the iron oxide content expressed in Fe 2 O 3 equivalent in the raw briquettes before treatment. thermal.
- the present invention relates to a method of briquetting a composition
- a composition comprising at least one bright calco-magnesium compound comprising quicklime in the form of crushed particles at a concentration of at least 10% by weight and at most 100% by weight. weight relative to the total weight of said composition.
- the briquetting process according to the invention comprises a feed of a substantially homogeneous powder mixture comprising at least one bright calco-magnesium compound.
- fluxes such as B 2 0 3 , a0 3 , aluminate calcium, calcium silicate, calcium ferrite such as Ca 2 Fe 2 O 5 or CaFe 2 O 4 , Al metal, g metal, Fe metal, Mn metal, Mo metal, Zn metal, Cu metal, Si elemental, CaF 2 > C, Cac 2 , alloys such as CaSi, CaMg, CaFe, FeMn, FeSi, FeSiMn, FeMo; Ti0 2 , a ⁇
- Molybdenum oxide a copper oxide, a zinc oxide, a molybdenum hydroxide, a copper hydroxide, a zinc hydroxide, and mixtures thereof.
- the substantially homogeneous powder mixture is fed to a roller press of a briqueter, also sometimes referred to as a tangential press, for example a Komarek press, Sahut Konreur, Hosokawa Bepex, Koppern.
- a roller press of a briqueter also sometimes referred to as a tangential press, for example a Komarek press, Sahut Konreur, Hosokawa Bepex, Koppern.
- the substantially homogeneous powder mixture is compressed, optionally in the presence of a binder or a lubricant, preferably in the form of a concentrated aqueous powder or suspension, more particularly chosen from the group consisting of binders of mineral origin such as cements, clays, silicates, binders of vegetable or animal origin, such as celluloses, starches, gums, aiginates, pectin, glues, binders of synthetic origin, such as polymers, waxes, liquid lubricants such as mineral oils or silicones, solid lubricants such as talc, graphite, paraffins, stearates, in particular calcium stearate, magnesium stearate, and their mixtures, preferably calcium stearate and / or magnesium stearate, at a content of between 0.1 and 1% by weight, preferably between 0.15 and 0.6% by weight, preferentially between 0.2 and 0.5% by weight relative to the total weight of said mixture.
- the rollers of the roller press develop linear speeds at the periphery of the rolls of between 10 and 100 cm / s, preferably between 20 and 80 cm / s, and linear pressures of between 60 and 160 kN / cm, preferably between 80 and 140 kN / cm, and even more preferably between 80 and 120 kN / cm.
- the surface pressure is between 300 and 500 MPa, preferably between 300 and 450 MPa, and more preferably between 350 and 450 MPa.
- the calco-magnesian composition in the form of raw briquettes is obtained and these are collected.
- the collected raw briquettes are heat treated at a temperature of 3 ⁇ 4 temperature between 700 ° C and 1200 ° C, preferably between 700T and 1000T, preferably between 800 ° C and 1000 ° C, for a predetermined period of time.
- the raw briquettes are thus brought into a high temperature furnace where they undergo a heat treatment of these briquettes at a temperature of less than or equal to 1200 ° C., preferably less than or equal to 100 ° C. They are then cooled and collected in the form of cooked briquettes for, among other things, improving their resistance to aging as well as their resistance to falling.
- the heat treatment time is related to the temperature of the heat treatment (the time is shorter as the temperature is high) and the thickness of the briquette bed (the time increases with the thickness of the bed to leave the time to heat to diffuse inside the bed).
- the heat treatment is preferably carried out at around 9 OCTC for example for a predetermined duration of between 3 and 20 minutes, preferably greater than or equal to 5 minutes and less than or equal to 15 minutes, more particularly greater than or equal to 7 minutes and less than or equal to 13 minutes, with formation and obtaining of cooked briquettes.
- each reduction in the heat treatment temperature of 50 ° C leads to double the heat treatment time.
- the heat treatment is preferably carried out at about 900 ° C. for a predetermined period of between 6 and 40 minutes, preferably greater than or equal to 10 minutes and less than or equal to 30 minutes, more particularly greater than or equal to 14 minutes and less than or equal to 26 minutes.
- heat treatment for a period of 10 to 20 minutes at 900 ° C is sufficient for a layer of briquettes up to 100 to 150 mm thick in the oven. Typically it is necessary to double the heat treatment time for a 50 ° C drop in temperature. _.
- the bright calco-magnesium compound is advantageously a calco-magnesian compound with soft or medium cooking, preferably soft cooking.
- the method further comprises a heat treatment of said collected raw briquettes, a temperature between 900 ° C and 1200X, preferably between 1050X and 1200 ° C, in particular around 1100X, for a predetermined time with formation and obtaining cooked briquettes in which the compound based on iron oxide is converted, at least partially, into calcium ferrites.
- the raw briquettes are thus brought into a high temperature oven where they undergo a heat treatment of these briquettes at a temperature of less than or equal to 1200 ° C. They are then cooled and collected in the form of briquettes cooked to, among other things, promote the formation of calcium ferrites, which are sought after in iron and steel applications, and improve their resistance to aging as well as their resistance to falling.
- the heat treatment time is related to the temperature of the heat treatment (the time is shorter as the temperature is high) and the thickness of the briquette bed (the time increases with the thickness of the bed to leave the time to heat to diffuse inside the bed).
- the heat treatment is preferably carried out at about 1100 ° C. for a predetermined duration of between 3 and 20 minutes, preferably greater than or equal to 5 minutes and less than or equal to 15 minutes, more particularly greater than or equal to 7 minutes and less than or equal to 13 minutes, to obtain cooked briquettes, in which said active iron oxide is converted into calcium ferrite.
- each reduction in the heat treatment temperature of 50 ° C leads to double the heat treatment time.
- the heat treatment is preferably carried out at around 1100 ° C. for a period of 2? predetermined duration of between 6 and 40 minutes, preferably greater than or equal to 10 minutes and less than or equal to 30 minutes, more particularly greater than or equal to 14 minutes and less than or equal to 26 minutes.
- a horizontal oven such as for example a tunnel oven, a passage oven, a trolley furnace, a roller kiln or even a mesh belt furnace can be used.
- any other type of conventional oven but not leading to the alteration of the integrity of the compacts, for example due to too much attrition, can be used.
- Cooling can either be carried out conventionally in the downstream part of the furnace or outside the furnace, for example in a countercurrent vertical cooler for the cooling air or in a fluidized bed cooler. cooling air in case of quenching.
- the cooling after the heat treatment is carried out rapidly in less than 15 min, preferably in less than 10 min, in a fluidized bed by cooling air.
- the process comprises, before said feeding of a substantially homogeneous powdery mixture, a) feeding a mixer with said at least one bright calco-magnesium compound and
- the substantially homogeneous mixture based on calco-magnesium compound comprises at least 10% by weight of crushed quicklime particles, preferably at least 20% by weight, more particularly at least 30% by weight. and at most 100% by weight relative to the total weight of said mixture.
- the "raw” briquettes are advantageously based on quick lime (possibly dolomitic) in the form of particles rejected on screening during the production of pebbles and quicklime in the form of crushed particles.
- the determination of the% by weight of CaO + MgO and Fe 2 O 3 equivalents is carried out by X-ray fluorescence spectrometry (RFX) as described in the EN 15309 standard.
- Chemical, semi-quantitative, RFX analysis for determining the relative mass concentration of the elements whose atomic mass is between 16 (oxygen) and 228 (uranium) is carried out at the start of the samples milled at 80 ⁇ and shaped in the form of pellet.
- the samples are introduced into a PANalytical / agiX PRO PW2540 apparatus, operating in wavelength dispersion.
- the measurement is carried out with a power of 50kV and 80 mA, with a Duplex detector.
- lubricant for example stearate such as calcium or magnesium stearate, preferably 0.2 to 0.5% by weight.
- briquettes typically soap shapes, balls, platelets ... known to those skilled in the art and issued from tangential roller presses
- a size of at least 10 mm preferably from minus 15mm and at most 50mm, preferably at most 40mm, preferably at most 30mm, an sense of their passage through a square mesh screen.
- the green briquettes of the composition have good mechanical strength characterized by a Shatter Test Index ("STI", the percentage by weight of fines less than 10 mm after 4 drops of 2 m) of less than 8%, preferably less than 6%, %, 4%.
- STI Shatter Test Index
- the porosity of the raw briquettes is greater than or equal to 20%, preferably greater than or equal to 22%, more preferably greater than or equal to 24%.
- the green briquettes have a bulk density of between 2.0 and 3.0, preferably between 2.2 and 2.8. 2g
- Raw briquettes have good resistance to aging. Thus, when they are exposed to a humic atmosphere containing, for example, 5 to 15 g / m 3 of absolute humidity, the degradation of their mechanical properties (STI) only occurs above 1.5% mass, preferably 2% of weight gain, and even more preferably 2.5% of weight gain, following the hydration reaction of CaO quicklime Ca (OH) 2 .
- STI mechanical properties
- the baked briquettes of the present invention have a Shatter Test Index ("STI", i.e. mass percentage of fines less than 10mm after 4 drops of 2m) of less than 6%, preferably less than 4%, 3%, 2%. Indeed, in certain embodiments of the process according to the present invention, the cooked briquettes have a test Shatter index of less than 8%, sometimes less than 6%, less than 4%, less than 3%, or even around 2%. %.
- STI Shatter Test Index
- BET specific surface area greater than or equal to 0.4 m 2 / g, preferably greater than or equal to 0.6 m 7 g, more preferably greater than or equal to 0.8 m 2 / g
- the porosity is greater than or equal to 20%, preferably greater than or equal to 22%, more preferably greater than or equal to 24%.
- the baked briquettes have an apparent density of between 2.0 and 3.0, preferably between 2.2 and 2.8.
- Cooked briquettes have good resistance to aging. Thus, when they are exposed to a humic atmosphere containing, for example, 5 to 15 g / m 3 of absolute humidity, the degradation of their mechanical properties (STI) occurs only above 4% of mass preferably 4.5% of weight gain, and more preferably 5% of weight gain, following the hydration reaction of CaO quicklime Ca (OH) 2 .
- STI mechanical properties
- Example 1 Briquettes of quicklime, derived from crushed quick lime fines
- Crushed quick lime fines were prepared from a soft-baked rock lime produced in a parallel-flow regenerative furnace.
- the grinding is carried out in a hammer mill equipped with a 2 mm screen and a 3Q recirculation loop for sizes larger than 2 mm.
- These grinding quicklime fines contain 71% of particles greater than 90 ⁇ , 37% of particles greater than 500 ⁇ m, 21% of particles greater than 1 mm and 1% of particles of between 2 and 3 mm.
- the t 60 value of the water reactivity test is 0.9 min.
- the BET specific surface area (measured by nitrogen adsorption manometry after degassing under vacuum at 190 ° C.
- crushed quicklime fines contain 95.7% CaO and 0.8% MgO by weight.
- a Gericke GCM450 powder mixer is used, with a capacity of
- the total flow rate of the powder is 300 kg / h and the residence time is 3.5 s.
- the mixture obtained is very substantially homogeneous.
- a tangential press equipped with frets with a diameter of 604 mm and a width of 145 mm is used for the production of briquettes with a theoretical volume of 7.2 cm 3 with a soap form (4 rows of 67 bags per fret, or 268 pockets per ring) and can develop a linear pressure up to 120 kN / cm.
- the tangential press is fed and compacted at a speed of 12 revolutions per minute (ie a linear velocity of 38 cm / s) at a linear pressure of 120 kN / cm (ie a calculated surface pressure). 455 MPa for 0.5 degree angle).
- briquettes with an average volume of 8.2 cm 3 , an average weight of 19 g and an average density of 2.3 are obtained. These briquettes have a length of about 36 mm, a width of about 26 mm and a thickness of about 15.5 mm. These briquettes develop a BET surface area of 1.6 m 2 / g and have a total pore volume of mercury (determined by mercury intrusion porosimetry according to part 1 of ISO 15901-1: 2005E which consists in dividing the difference between skeletal density, measured at 30000 psia, and apparent density, measured at 0.51 psia, by skeletal density) of 26%.
- the water reactivity of the briquettes is determined by adding 150 g of these briquettes, previously crushed in the form of fines of size between 0 and 1 mm, to 600 cm 3 of water at 20 ° C.
- the value t 60 is 1.1 min.
- Example 2 Briquettes of quicklime, derived from a mixture of fines of quick-grinding quick-grinding lime and fines of quicklime of screening
- the grinding quicklime fines are those of Example 1.
- the quick lime screen fines were recovered at the end of the screening through a screen at 3 mm of the all-comer at the outlet of a furnace. rotary equipped with a preheater.
- These quick lime screen fines contain 74% of particles greater than 90 ⁇ , 60% of particles greater than 500 ⁇ , 47% of particles greater than 1 mm and 18% of particles between 2 and 3 mm.
- the value t 60 of the water reactivity test is 4 min.
- the BET specific surface area is 1.2 m 2 / g.
- These quick lime screen fines contain 97.1% CaO and 0.7% MgO by weight.
- the mixture, produced according to the method of Example 1, consists of: 0.25% by weight of calcium stearate powder,
- the briquettes are produced starting from this mixture according to the method of Example 1. This gives about 10 tons of briquettes having an average volume of 8.3 cm 3 , an average weight of 19.2 g and a mean density of 2.3. These briquettes have a length of about 36 mm, a width of about 26 mm and a thickness of about 15.6 mm. These briquettes develop a BET surface area of 1.4 m 2 / g and have a total pore volume of mercury of 26%.
- the water reactivity of the briquettes is determined by adding 150 g of these briquettes, previously crushed in the form of fines of size between 0 and 1 mm, to 600 cm 3 of water at 20 ° C.
- the value t 60 is 1.8 min.
- the grinding quick lime fines are those of Example 1.
- the comminuted firing fines were prepared from a baked rock digestion produced in a parallel flow regenerative furnace. The grinding was carried out in a hammer mill. These fired milling fines contain 91% of particles greater than 90 ⁇ , 44% of particles greater than 500 ⁇ , 31% of particles greater than 1 mm and 17% of particles greater than 2 mm and 8% of particles between 3 and 5 mm.
- the value t 70 of the water reactivity test is 3.1 min.
- the BET specific surface area is 2.8 m 2 / g.
- These fired milling fines contain 58.5% CaO and 38.4% wt%.
- the mixture, produced according to the method of Example 1, consists of: 0.25% by weight of calcium stearate powder,
- the briquettes are produced starting from this mixture according to the method of Example 1. This gives about 10 tons of briquettes having an average volume of 8.1 cm 3 , an average weight of 19.1 g and a mean density of 2.3. These briquettes have a length of about 36 mm, a width of about 26 mm and a thickness of about 15.5 mm. These briquettes develop a BET surface area of 2.2 m 2 / g and have a total pore volume of mercury of 27%.
- Example 4 Briquettes of quicklime, derived from a mixture of fines of quick-grinding quick-grinding lime and iron oxide fines
- the grinding quick lime fines are those of Example 1.
- the iron oxide fines are obtained by grinding a Fe 2 O 3 type iron ore passing through a sieve at 150 ⁇ and characterized in particle size.
- Coulter laser (based on the diffraction of light and according to the theories of Fraunhofer and Mie) by a d 10 of 0.5 ⁇ , a d 50 of 12.3 ⁇ and a d 90 of 35.7 ⁇ .
- These iron oxide fines contain 64.6% Fe.
- the mixture, produced according to the method of Example 1, consists of:
- the briquettes are produced starting from this mixture according to the method of Example 1. This gives about 10 tons of briquettes having an average volume of 8.5 cm 3 , an average weight of 22.3 g and a mean density of 2.6. These briquettes have a length of about 36 mm, a width of about 26 mm and a thickness of about 16.1 mm. These briquettes develop a BET surface area of 1.6 m 2 / g and have a total pore volume of mercury of 25%.
- the water reactivity of the briquettes is determined by adding 166.7 g of these briquettes, previously crushed in the form of fines of size between 0 and 1 mm, to 600 cm 3 of water at 20 ° C.
- the 166.7 g of briquettes correspond to 150 g of quicklime.
- the value t 60 is 1.2 min.
- Example 5 Briquettes of quicklime, derived from crushed quick lime fines, heat-treated
- Briquettes with an average volume of 8.2 cm 3 , an average weight of 19 g and an average density of 2.3 are obtained. These briquettes have a length of about 36 mm, a width of about 26 mm and a thickness of about 15.5 mm. These briquettes develop a BET surface area of 1.3 m 2 / g and have a total pore volume of mercury of 27%.
- the water reactivity of the briquettes is determined by adding 150 g of these briquettes, previously crushed in the form of fines of size between 0 and 1 mm, to 600 cm 3 of water at 20 ° C.
- the value t 60 is 1.0 min.
- Example 6 Briquettes of quicklime, derived from a mixture of fines of quick-grinding quick-grinding and iron-oxide fines, heat-treated
- Briquettes with an average volume of 8.5 cm 3 , an average weight of 22.2 g and an average density of 2.6 are obtained. These briquettes have a length of about 36 mm, a width of about 26 mm and a thickness of about 16.1 mm. These briquettes develop a BET surface area of 0.9 m 2 / g and have a total pore volume of mercury of 27%.
- the water reactivity of the briquettes is determined by adding 178.2 g of these briquettes, previously crushed in the form of fines of size between 0 and 1 mm, to 600 cm 3 of water at 20 ° C.
- the 178.2 grams of briquettes correspond to 150 grams of quicklime (i.e., not in the form of calcium ferrites).
- the value t 60 is 1.5 min.
- the fines of quicklime of screening are those of Example 2.
- the mixture, produced according to the method of Example 1, consists of:
- the briquettes are produced starting from this mixture according to the method of Example 1. There are obtained nearly 10 tons of briquettes having an average volume of 8.3 cm 3 , an average weight of 19.4 g and a mean density of 2.3. These briquettes have a length of about 36 mm, a width of about 26 mm and 3 ⁇ 4 a thickness of about 15.6 mm. These briquettes develop a BET specific surface area of 1.2 m 2 / g and have a total pore volume of mercury of 26%.
- Comparative Example 2 Briquettes of cooked dolomite, obtained from fines of cooked grinding
- the comminuted firing fines are those of Example 3.
- the mixture, produced according to the method of Example 1, consists of:
- the briquettes are produced starting from this mixture according to the method of Example 1. This gives about 10 tons of briquettes having an average volume of 8.4 cm 3 , an average weight of 19.9 g and a mean density of 2.3. These briquettes have a length of about 36 mm, a width of about 26 mm and a thickness of about 16.0 mm. These briquettes develop a BET specific surface area of 2.6 m 2 / g and have a total pore volume of mercury of 26%.
- Raw briquettes are produced according to the invention with crushing quicklime containing particles of sizes between 0 and 2 mm, but having different grain size profiles and iron oxide contents of sizes less than 100 ⁇ expressed in Fe equivalent. 2 0 3 ranging from 10% to 60%.
- the iron oxide used in these examples is characterized by a d 10 of 0.5 ⁇ , d so 12.3 ⁇ and 90 d of 35.7 ⁇ .
- the grinding quicklime particles of size between 0 and 2 mm have at least 30% of particles that are less than 90 ⁇ .
- Raw briquettes of the same composition were heat-treated at 1100 ° C or 1200 ° C for 20 minutes to obtain cooked briquettes with different contents of quicklime and base compounds.
- _ V iron The composition of the briquettes and the heat treatments carried out are shown in Table 1. For these raw and cooked briquettes, several tests were carried out and described below using FIGS. 2 to 5.
- Figure 2 presents a graph showing:
- Figure 3 presents a graph showing:
- the Shatter test indices are less than 20% for raw briquettes with iron compound contents expressed 3? in Fe 2 0 3 equivalent less than 40%, whereas for cooked briquettes, all Shatter tests are less than 10%, or even 6%,
- FIG. 4 presents a graph showing the evolution of the yield of iron-based compound (iron oxide) converted to calcium ferrite
- FIG. 5 shows the evolution of the calcium ferrite content expressed in Fe 2 0 3 equivalent in the briquettes baked as a function of the iron oxide content expressed in Fe 2 0 3 equivalent in the raw briquettes before heat treatment.
- the Shatter test scores were compared to the compressive strength on several raw briquette samples to establish the correlation between the test Shatter index and the compressive force.
- the raw briquettes tested included quicklime with a particle size ranging from 0 to 3 mm with different iron oxide contents, from 0 to 60% by weight and different lubricant contents ranging from 0.125 to 0.5% by weight, based on the total weight of the briquettes.
- the parameters of the briquetting process were also modified to ensure that the population for correlation was sufficiently wide. 3g
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16/309,373 US10718034B2 (en) | 2016-07-08 | 2017-07-07 | Composition in the form of briquettes comprising burnt calcium-magnesium compounds, method for obtaining same, and use thereof |
BR112018075614-8A BR112018075614A2 (pt) | 2016-07-08 | 2017-07-07 | composição na forma de briquetes que compreende compostos de cálcio-magnésio que contêm cal, mé-todo de obtenção desta e uso da mesma |
EP17740707.9A EP3481773A1 (fr) | 2016-07-08 | 2017-07-07 | Composition sous forme de briquettes comprenant des composes calco-magnesiens vifs, son procede d'obtention et leur utilisation |
JP2018566576A JP6696007B2 (ja) | 2016-07-08 | 2017-07-07 | 生のカルシウム−マグネシウム化合物を含むブリケット形態の組成物、その製造方法およびその使用 |
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BE2016/5572A BE1023887B1 (fr) | 2016-07-08 | 2016-07-08 | Composition sous forme de briquettes comprenant des composes calco-magnesiens vifs, son procede d'obtention et leur utilisation |
BE2016/5572 | 2016-07-08 |
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WO2018007630A1 true WO2018007630A1 (fr) | 2018-01-11 |
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PCT/EP2017/067167 WO2018007630A1 (fr) | 2016-07-08 | 2017-07-07 | Composition sous forme de briquettes comprenant des composes calco-magnesiens vifs, son procede d'obtention et leur utilisation |
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US (1) | US10718034B2 (fr) |
EP (1) | EP3481773A1 (fr) |
JP (1) | JP6696007B2 (fr) |
BE (1) | BE1023887B1 (fr) |
BR (1) | BR112018075614A2 (fr) |
FR (1) | FR3053674A1 (fr) |
TW (1) | TW201834969A (fr) |
WO (1) | WO2018007630A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP3812475A1 (fr) | 2019-10-23 | 2021-04-28 | Carmeuse Research And Technology | Granulés compactés à base de calcium |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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BE1023884B1 (fr) * | 2016-07-08 | 2017-09-04 | Lhoist Rech Et Developpement Sa | Procédé de fabricatrion de briquettes contenant de l'oxyde de fer actif, et briquettes ainsi obtenues |
US20230027137A1 (en) * | 2021-07-21 | 2023-01-26 | Steve Kohn | Hemp paper cardboard cartons and corrugated boxes |
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US5186742A (en) | 1991-11-27 | 1993-02-16 | Chemical Lime Company | Method and composition for use in recycling metal containing furnace dust |
US7105114B2 (en) | 2004-08-10 | 2006-09-12 | Chemical Lime Company | Briquetting of lime based products with carbon based additives |
EP2199417A1 (fr) * | 2007-09-18 | 2010-06-23 | Kabushiki Kaisha Kobe Seiko Sho | Procédé de fabrication d'une briquette dans laquelle est incorporée une matière carbonée à l'aide de poussières d'installation de fabrication de fer contenant de l'huile |
WO2015007661A1 (fr) | 2013-07-15 | 2015-01-22 | S.A. Lhoist Recherche Et Developpement | Composition comprenant un ou des composes calco-magnesiens sous forme de compacts |
EP3042965A1 (fr) * | 2015-01-09 | 2016-07-13 | S.A. Lhoist Recherche Et Developpement | Procédé de déphosphorisation de métal fondu pendant un processus de raffinage |
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JP2001348609A (ja) | 2000-06-07 | 2001-12-18 | Nippon Steel Corp | フォーミング抑制剤 |
US10307766B1 (en) * | 2015-05-01 | 2019-06-04 | Mississippi Lime Company | Systems and methods for separating soft burned and hard burned calcium oxide |
-
2016
- 2016-07-08 BE BE2016/5572A patent/BE1023887B1/fr not_active IP Right Cessation
-
2017
- 2017-07-07 TW TW106122928A patent/TW201834969A/zh unknown
- 2017-07-07 US US16/309,373 patent/US10718034B2/en not_active Expired - Fee Related
- 2017-07-07 BR BR112018075614-8A patent/BR112018075614A2/pt not_active Application Discontinuation
- 2017-07-07 JP JP2018566576A patent/JP6696007B2/ja not_active Expired - Fee Related
- 2017-07-07 FR FR1756456A patent/FR3053674A1/fr not_active Withdrawn
- 2017-07-07 EP EP17740707.9A patent/EP3481773A1/fr not_active Withdrawn
- 2017-07-07 WO PCT/EP2017/067167 patent/WO2018007630A1/fr active Search and Examination
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US5186742A (en) | 1991-11-27 | 1993-02-16 | Chemical Lime Company | Method and composition for use in recycling metal containing furnace dust |
US7105114B2 (en) | 2004-08-10 | 2006-09-12 | Chemical Lime Company | Briquetting of lime based products with carbon based additives |
EP2199417A1 (fr) * | 2007-09-18 | 2010-06-23 | Kabushiki Kaisha Kobe Seiko Sho | Procédé de fabrication d'une briquette dans laquelle est incorporée une matière carbonée à l'aide de poussières d'installation de fabrication de fer contenant de l'huile |
WO2015007661A1 (fr) | 2013-07-15 | 2015-01-22 | S.A. Lhoist Recherche Et Developpement | Composition comprenant un ou des composes calco-magnesiens sous forme de compacts |
EP3042965A1 (fr) * | 2015-01-09 | 2016-07-13 | S.A. Lhoist Recherche Et Developpement | Procédé de déphosphorisation de métal fondu pendant un processus de raffinage |
WO2016110574A1 (fr) | 2015-01-09 | 2016-07-14 | S.A. Lhoist Recherche Et Developpement | Procédé de déphosphorisation de métal en fusion lors d'un procédé de raffinage |
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BARNETT THOMAS P: "Roll-press briquetting: Compacting fines to reduce waste-handling costs", vol. 24, no. 10, October 2010 (2010-10-01), pages 1 - 6, XP002742275, ISSN: 1938-9140, Retrieved from the Internet <URL:http://www.powderbulk.com/wp-content/uploads/pdf/pbe_201010_058.pdf> [retrieved on 20150715] * |
E A S GARICA ET AL: "PELOTIZAÇÃO DE FINOS DE CALCÁRIO UTILIZANDO ÁGUA E CAL VIRGEM COMO AGENTES AGLOMERANTES AGLOMERANTES", XXVI ENCONTRO NACIONAL DE TRATAMENTO DE MINÉRIOS E METALURGIA EXTRATIVA, vol. 1, January 2015 (2015-01-01), Poços de Caldas, pages 59 - 67, XP055349510 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3812475A1 (fr) | 2019-10-23 | 2021-04-28 | Carmeuse Research And Technology | Granulés compactés à base de calcium |
WO2021078878A1 (fr) | 2019-10-23 | 2021-04-29 | Carmeuse Research And Technology | Granulés compactés à base de calcium |
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JP2019521252A (ja) | 2019-07-25 |
US20190256946A1 (en) | 2019-08-22 |
US10718034B2 (en) | 2020-07-21 |
FR3053674A1 (fr) | 2018-01-12 |
BR112018075614A2 (pt) | 2019-04-09 |
BE1023887B1 (fr) | 2017-09-04 |
EP3481773A1 (fr) | 2019-05-15 |
JP6696007B2 (ja) | 2020-05-20 |
TW201834969A (zh) | 2018-10-01 |
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