US20150082944A1 - Granules Containing Agglomerated Bulk Material - Google Patents

Granules Containing Agglomerated Bulk Material Download PDF

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Publication number
US20150082944A1
US20150082944A1 US14/346,244 US201214346244A US2015082944A1 US 20150082944 A1 US20150082944 A1 US 20150082944A1 US 201214346244 A US201214346244 A US 201214346244A US 2015082944 A1 US2015082944 A1 US 2015082944A1
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binder
bulk material
granules
granules according
reactive
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Wolfgang Rückert
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Rheinkalk GmbH
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Rheinkalk GmbH
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    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/076—Use of slags or fluxes as treating agents
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    • 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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    • 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
    • C04B18/023—Fired or melted materials
    • C04B18/026—Melted materials
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    • C04B32/00—Artificial stone not provided for in other groups of this subclass
    • C04B32/005—Artificial stone obtained by melting at least part of the composition, e.g. metal
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/04—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
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    • C04B35/03—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
    • C04B35/057—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on calcium oxide
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    • C04B35/06—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on oxide mixtures derived from dolomite
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62695—Granulation or pelletising
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    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
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    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0067—Function or property of ingredients for mortars, concrete or artificial stone the ingredients being formed in situ by chemical reactions or conversion of one or more of the compounds of the composition
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
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    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
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    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/443—Nitrates or nitrites
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    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
    • C04B2235/445—Fluoride containing anions, e.g. fluosilicate
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    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
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    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0037—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 by injecting powdered material
    • C21C7/0043—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 by injecting powdered material into the falling stream of molten metal
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    • C21—METALLURGY OF IRON
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    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/0068—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 by introducing material into a current of streaming metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Definitions

  • the invention relates to granules containing at least one agglomerated bulk material and a binder matrix.
  • the invention also relates to a method for producing such granules and their use as an input material in the steel and refractory industry.
  • Production of granules from bulk material by means of agglomeration is essentially known. Through agglomeration the individual particles of the bulk material can be enlarged whereby the particle size distribution is shifted into a coarser size range.
  • a common granulation method is wet granulation, also known as pelletisation.
  • the boundary layer forces which hold the granule particles together, are normally hardened binders, capillary forces, molecular attraction and/or interlocking bonds of a jagged or fibrous surface.
  • the handling and storage in particular of bulk material can be made easier by agglomeration.
  • various material properties such as for example flowability can be improved.
  • materials in powder form a reduction in dust can be brought about.
  • Agglomeration of reactive bulk material such as quicklime or dolomite is particularly advantageous.
  • Quicklime reacts violently with water making its handling and storage difficult.
  • the particle surface area of the lime can be reduced thereby lowering its reactivity and making it easier to handle and store.
  • Quicklime for example, reacts with water to form hydrated lime.
  • the chemical and physical properties of hydrated lime, Ca(OH) 2 differ from those of quicklime, CaO, making it unsuitable for various application areas, such for example as steel production, since in the hot molten steel the hydrated lime, Ca(OH) 2 , with the addition of heat, is split into lime and water. This results in a significant temperature loss of the melt, which becomes unacceptable, inter alia, for further processing in continuous casting and, due to the higher energy expended, in steel production. In addition, considerable amounts of water vapour are released, which can be decomposed into its elements on the hot steel surface. Due to its low hydrogen partial pressure the molten metal absorbs hydrogen, which could lead to serious quality issues in the finished product (in particular hydrogen embrittlement).
  • organic binders are used for agglomeration methods.
  • Organic binders are unsuitable for agglomeration of reactive bulk material, however, since they have an adverse effect on the further application of the agglomerate.
  • organic binders can decompose upon contact with lime.
  • the gases given off by organic binders are also harmful to the health of persons coming into contact with the agglomerate.
  • a further advantage of the granules according to the invention is that even at high temperatures their stability is preserved.
  • salts have only low volatility.
  • the use of salts can prevent the reactive bulk material forming undesired mixed phases with the binder thereby losing properties that are important for its respective application.
  • the object of the invention was to provide granules of the kind mentioned at the beginning, with which the disadvantages of the state of the art can be avoided.
  • To date only hot agglomeration of lime has been successfully investigated in practice, although in so doing high temperatures of up to 900° C. were required. Agglomeration using water as the binder is not possible for lime-based reactive bulk materials if the chemical properties are to be retained. Due to the major advantages of liquid binders, including due to the strong bond-forming effect of capillary forces, agglomeration with other liquids was envisaged.
  • This object is met according to the invention by granules containing at least one agglomerated reactive bulk material and a binder matrix, wherein the binder matrix contains at least one organic or inorganic salt as the binder.
  • organic and inorganic salts are exceptionally well-suited as binders for the agglomeration of reactive bulk material.
  • organic or inorganic salts as binders the fine-grained fractions of the reactive bulk materials can be bound securely and stably in the binder matrix.
  • the binders behave quite differently in the finished product. Thus when using anhydrous diboron trioxide (B 2 O 3 ) both mixed crystal phases and also pure binder phases may result.
  • anhydrous calcium nitrate, Ca(NO 3 ) 2 the particles can be become included in a binder matrix or, with sustained addition of heat, the binder can ultimately be decomposed to solid lime, CaO, with the separation of nitrogen oxides, NOx.
  • CaO solid lime
  • the salt provides the reactive bulk material with excellent atmospheric protection, meaning that the granules have high stability and outstanding handling and storage properties.
  • a further advantage of the granules according to the invention is their thermal stability.
  • salts have only a low volatility.
  • the reactive bulk material can be prevented from reacting with the binder and thereby losing properties that are important for its application.
  • the melting point of the binder is lower than the melting point of the reactive bulk material.
  • the granules can also be created by melting the salt and distributing the molten material in a bulk material bed.
  • Advantages of this technique are the multiple possibilities for applying the molten salt in this approach, for example thermal spraying or atomisation of a molten material on a moved bulk material bed.
  • the bulk material bed can serve for heat insulation from the environment, in particular from machine parts. The energy costs of this approach are particularly favourable.
  • the proportion of binder can increase significantly if the bulk material temperature is set too low.
  • a further advantage of low-melting salts in the production of the granules according to the invention is their favourable thermodynamic properties.
  • the melting point of the binder is preferably below 600° C., in particular in the range from 100° C. to 600° C.
  • Binders which, with regard to the application of the agglomerated bulk material, provide added value are particularly suitable.
  • a chemical reaction between binder and bulk material during the agglomeration process can provide added value in that the agglomerate has a particular strength and/or chemical properties with particular added value to, or low effect on, the application.
  • binders are used which during the agglomeration process form covalent bonds and/or ionic mixed crystals with the reactive bulk material.
  • the formation of mixed crystal phases is possible.
  • the low-melting mixed phases (CaO.2B 2 O 3 ) can make an important contribution to the additional consolidation. Particularly good bonds can also be achieved with ionic liquids.
  • Ionic liquids contain exclusively ions. Thus liquid salts are involved without the salt being dissolved in a medium such as water. Previously hot molten salts (for sodium chloride over 800° C.) were the only known examples of such liquids.
  • Today ionic liquids are understood to be salts which are liquid at temperatures of below 100° C. Examples of cations used, which can in particular be alkylated, are: imidazolium, pyridinium, pyrrolidinium, guanidinium, uronium, thiouronium, piperidinium, morpholinium, ammonium and phosphonium.
  • Organic ions such as for example imides and amides, can also be anions.
  • the size and symmetry of the ions involved prevents the formation of a strong crystal lattice. Low thermal energy is therefore all that is required to overcome the lattice energy and break open the solid crystal structure.
  • the ionic liquids contain no water, the reactive bulk material is not hydrated. By heating the ionic liquid and using it as a liquid binder in the bulk material a capillary force-induced bond is created. Upon cooling and hardening of the ionic liquid it becomes permanently solid. The process operates in the same way for molten salts, but the temperature level is higher. The melting temperature for ionic liquids is considerably below the melting temperature of salts. The use of ionic liquids would thus lead to significant energy savings.
  • Reactive bulk material within the meaning of the invention shall be understood to be a bulk material which undergoes a chemical and/or physical reaction with common agglomeration agents, in particular water and/or organic solvents, in particular molasses or mineral or vegetable oil. Binders exist in particular which are catalytically decomposed by the reactive bulk material, such as for example mineral and vegetable oils.
  • a particularly suitable bulk material according to the invention is a reactive lime-based material, preferably quicklime, CaO, calcined dolomite, MgO.CaO or calcined magnesite, MgO, or mixtures of these substances, or mixtures with the respective carbonates or other input materials.
  • Quicklime granules are of particular technical value, for example in steel production or the refractory industry, since they have better handling and storage properties than powdered quicklime.
  • Quicklime is a highly reactive bulk material, which reacts violently with water thereby losing its advantageous properties, for example in steel production. Through the use according to the invention of salt in the agglomeration of quicklime this can be prevented and a stable agglomerate obtained.
  • the binder consists of chemical elements which have no or a positive effect on the steel production process.
  • the binder contains one or more of the following elements: sodium, boron, aluminium, iron, fluorine, nitrogen, carbon, oxygen.
  • Particularly suited according to the invention is the use of one or more of the following salts as binders: calcium nitrate, iron fluoride, sodium fluoride, cryolite, boron trioxide.
  • Boron trioxide in particular, due to its low melting temperature of approximately 450° C. and its high resistance to temperature, has particularly advantageous properties.
  • a further advantageous property of boron trioxide as a binder in view of steel production is that it lowers the viscosity of the slag in the desired manner.
  • the grain size of the bulk material in the granules according to the invention can have wide ranges of variation. Practical tests have shown that granules with particularly good properties are obtained if the bulk material in the granules has an average grain size of 0-100 ⁇ m and/or a D50 value of 40 to 60 ⁇ m.
  • the grain size of the granules can also have wide ranges of variation.
  • An appropriate variation in the granule grain size is within the range 1 to 6 mm or above.
  • the proportion of bulk material in the granules is preferably in the range from 85 to 99%.
  • the apparent density of the granules varies as a function of the type of bulk material, the type of binder and the respective proportions of the individual components of the granules.
  • a further object of the invention is a method for producing granules comprising the following steps (process variant A):
  • process variant B is that energy consumption can be reduced compared with variant A, since the bulk material can have a temperature below the temperature of the binder.
  • a suitable mixing unit for example an air mixer or horizontal axis or vertical axis bulk material mixer
  • the homogenised starting mixture can be briquetted and then heated.
  • the mixture is introduced into a suitable furnace, for example a chamber furnace, in either briquette or loose form.
  • the furnace is brought to the required operating temperature with a suitable fuel or inductively or the temperature is maintained in the furnace during the possibly discontinuous process.
  • a suitable dwell time the loose finished product is removed from the furnace and cooled and broken or moved while still in the hot state such that agglomerates form, for example using a stirrer.
  • the briquetted mixture can be directly cooled.
  • the use of an indirectly heated rotary furnace is particularly advantageous, in which the loose or briquetted mixture can be continuously added and heated whilst in motion. As a result of the rotation of the furnace agglomerates form which are then cooled.
  • Heating the binder to a temperature of at least the melting temperature of the binder in process variant B is advantageously carried out as follows: feeding of the binder in a refractory container, for example a graphite crucible or one in high temperature-resistant metal, and then direct heating of the binder in a suitable furnace.
  • a refractory container for example a graphite crucible or one in high temperature-resistant metal
  • Cooling of the mixture with the formation of the granules in process variant A/B takes place at its simplest naturally.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Civil Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Ceramic Products (AREA)
  • Glanulating (AREA)
  • Treatment Of Steel In Its Molten State (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Detergent Compositions (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Oxide Ceramics (AREA)
US14/346,244 2011-09-21 2012-09-20 Granules Containing Agglomerated Bulk Material Abandoned US20150082944A1 (en)

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EP11182167.4A EP2573058B1 (de) 2011-09-21 2011-09-21 Granulat enthaltend agglomeriertes Schüttgut
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PCT/EP2012/068505 WO2013053576A1 (de) 2011-09-21 2012-09-20 Granulat enthaltend agglomerisiertes schüttgut

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BR112014006739A2 (pt) 2017-03-28
PL2573058T3 (pl) 2017-09-29
US10781500B2 (en) 2020-09-22
US20180363078A1 (en) 2018-12-20
MX2014003439A (es) 2014-07-28
JP2014531975A (ja) 2014-12-04
EP2573058A1 (de) 2013-03-27
EP2573058B1 (de) 2016-12-21
WO2013053576A1 (de) 2013-04-18

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