EP0656072B1 - Composition de liant et procede d'agglomeration de matiere particulaire - Google Patents

Composition de liant et procede d'agglomeration de matiere particulaire Download PDF

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Publication number
EP0656072B1
EP0656072B1 EP92917701A EP92917701A EP0656072B1 EP 0656072 B1 EP0656072 B1 EP 0656072B1 EP 92917701 A EP92917701 A EP 92917701A EP 92917701 A EP92917701 A EP 92917701A EP 0656072 B1 EP0656072 B1 EP 0656072B1
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EP
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Prior art keywords
cellulose
water
mixture
particulate material
weight
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EP92917701A
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German (de)
English (en)
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EP0656072A4 (fr
EP0656072A1 (fr
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James Schmitt
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Akzo Nobel NV
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Akzo Nobel NV
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Classifications

    • 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
    • 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

Definitions

  • the present invention relates to a novel process for agglomerating particulate materials containing iron.
  • Agglomeration is commercially used in industries where materials are encountered in a form which is too finely divided for convenient processing or handling. Thus, there is a need to upgrade the size, density and/or uniformity of finely divided particles for more efficient handling, processing or recovery. Agglomeration is particularly useful in the metal refining industry, where the concentrate ore encountered is typically finely divided.
  • a binding agent is added to the wetted mineral ore concentrate and the binder/mineral ore composite is conveyed to a balling drum or other means for pelletizing the ore.
  • the binding agent serves to bold or bind the mineral ore together until after firing.
  • the pellets are formed, but they are still wet. These wet pellets are commonly referred to as “green pellets” or “green balls”. These green pellets are thereafter transported to a kiln and heated in stages to an end temperature of about 1316°C (2400°F).
  • bentonite clay was the binding agent of choice in the pelletizing operations for mineral ore concentrates.
  • Use of bentonite as a binding agent produces balls or pellets having a very good wet and dry strength and also provides a desired degree of moisture control.
  • Use of bentonite does, however, have several disadvantages. Initially, bentonite adds to the silica content of the pellets when the ore pellets are fired at a temperature of 1316°C (2400°F) or higher. Higher amounts of silica are not desirable because silica decreases the efficiency of blast furnace operations used in smelting the ore.
  • alkalis are oxides of, for example, sodium and potassium.
  • alkalis oxides of, for example, sodium and potassium.
  • the presence of alkalis in the blast furnace causes both the pellets and coke to deteriorate and to form scabs on the furnace wall, which increases fuel consumption and decreases the productivity of the smelting operation.
  • Organic binders have proven to be an attractive alternative to bentonite because organic binders do not increase the silica content of the ore and they impart physical and mechanical properties to the pellets comparable with those of bentonite. Organic binders also burn out during ball firing operations thus causing an increase in the microporosity of the pellets. Accordingly, the pore volume and surface/mass ratio of the formed pellets produced using organic binders is larger than that of pellets produced using bentonite. Due to the larger surface area and increased permeability of the pellets produced using organic binders, the reduction of metallic oxides such as iron oxide is more efficient than with pellets prepared with bentonite.
  • organic binders examples include polyacrylate, polyacrylamide and copolymers thereof, methacrylamide, polymethacrylamide, cellulose derivatives such as alkali metal salts of carboxymethyl cellulose and carboxymethylhydroxyethyl cellulose, poly (ethylene oxide), guar gum, dairy wastes, starches, dextrins, wood related products, alginates, pectins, and the like.
  • compositions for iron ore agglomeration which comprise 10-45% by weight of a water-in-oil emulsion of a water soluble vinyl addition polymer, 55-90% by weight of a polysaccharide, 0.001 - 10% by weight of a water soluble surfactant and 0-15 weight % of Borax.
  • U. S. Patent No. 4,948,430 discloses a binder for the agglomeration of ore in the presence of water, which comprises 10% - 90% of a water soluble sodium carboxymethylhydroxyethyl cellulose and 10% to 90% of sodium carbonate.
  • U. S. Patent No. 4,288,245 discloses pelletization of metallic ores, especially iron ore, with carboxymethyl cellulose and the salt of a weak acid.
  • U. S. Patent No. 4,863,512 relates to a binder for metallic containing ores which comprises an alkali metal salt of carboxymethyl cellulose and sodium tripolyphosphate.
  • European Patent Application Publication No. 0 376 713 discloses a process for making pellets of particulate metal ore, particularly iron ore.
  • the process comprises mixing a water-soluble polymer with the particular metal ore and water and pelletizing the mixture.
  • the water-soluble polymer may be of any typical type, e.g., natural, modified natural or synthetic.
  • the mixture may optionally comprise a pelletizing aid which may be sodium carbonate, sodium bicarbonate, sodium silicate, sodium phosphate, sodium stearate, sodium benzoate, sodium tartrate, sodium oxylate, sodium citrate, sodium acetate, the corresponding ammonium, potassium, calcium, and magnesium salts of the preceding sodium salts, urea, and calcium oxide.
  • Organic binder compositions such as those mentioned above, are not, however, without their own disadvantages. While they are effective hinders, they generally do not impart adequate dry strength to the pellets at economical use levels. Thus, there is an ongoing need for economical binders with improved properties.
  • the present invention relates to a process of agglomerating particulate material containing iron in the presence of water which comprises mixing said particulate material with a binding effective amount of at least one water-soluble polymer selected from the group of modified natural polymers and synthetic polymers, and a binder enhancing effective amount of a source of hydroxide ions selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, and mixtures thereof, to produce a mixture, forming said mixture into agglomerates, and drying and firing said agglomerates.
  • the present inventors have found that the addition of caustic, in either liquid or powdered form, to the mineral ore, as an integral part of the organic binder or as a separate entity, unexpectedly provides a synergistic effect in the pelletization process, giving the resultant pellets superior wet drop numbers and dry crush strength compared to pellets formed without the use of caustic.
  • This increase in performance obtained by the addition of caustic allows the user to effectively reduce the amount of organic binder required thus significantly reducing total binder cost.
  • agglomerated or "agglomeration” as used in the context of the present invention shall mean the processing of finely divided materials, whether in powder, dust, chip, or other particulate form, to form pellets, granules, briquettes, and the like.
  • the iron-containing particulate material which may be agglomerated in accordance with this present invention includes iron ore deposits, ore tailings, cold and hot fines from a sinter process or aqueous iron ore concentrates from natural sources or recovered from various processes.
  • Iron ore or any of a wide variety of the following minerals may form a part of the material to be agglomerated: taconite, magnetite, hematite, limonite, goethite, siderite, franklinite, pyrite, chalcopyrite, chromite, ilmenite and the like.
  • the water-soluble polymer(s) useful in the present invention include
  • Preferred polymers for use in the present invention are alkali metal salts of carboxymethyl cellulose. Any substantially water-soluble alkali metal salt of carboxymethyl cellulose may be used in this invention.
  • the sodium salt is, however, preferred.
  • Alkali metal salts of carboxymethyl cellulose, more particularly sodium carboxymethyl cellulose are generally prepared from alkali cellulose and the respective alkali metal salt of monochloroacetic acid.
  • Cellulose which is used in the manufacture of sodium carboxymethyl cellulose is generally derived from wood pulp or cotton linters, but may be derived from other sources such as sugar beet pulp, bagasse, rice hulls, bran, microbially-derived cellulose, and waste cellulose e.g. shredded paper).
  • the sodium carboxymethyl cellulose used in the present invention generally has a degree of substitution (the average number of carboxymethyl ether groups per repeating anhydroglucose chain unit of the cellulose molecule) of from about 0.4 to about 1.5, more preferably about 0.6 to about 0.9, and most preferably about 0.7.
  • the average degree of polymerization of the cellulose furnish is from about 50 to about 4000. Polymers having a degree of polymerization on the higher end of the range are preferred. It is more preferred to use sodium carboxymethyl cellulose having a Brookfield viscosity in a 1% aqueous solution of more than 2000 mPa.s (cps) at 30 rpm, spindle #4. Still more preferred is sodium carboxymethyl cellulose having a Brookfield viscosity in a 1% aqueous solution of more than about 4,000 mPa.s (cps) at 30 rpm, spindle #4.
  • a series of commercially available binders containing sodium carboxymethyl cellulose especially useful in the present invention is marketed by the Dreeland, Inc. of Virginia, MN, Denver, CO, and Akzo Chemicals of Amersfoort, the Netherlands, under the trademark Peridur®.
  • binding effective amount of polymer will vary depending upon numerous factors known to the skilled artisan. Such factors include, but are not limited to, the type of iron-containing particulate material to be agglomerated or pelletized, the moisture content of the particulate material, particle size, the agglomeration equipment utilized, and the desired properties of the final product, e.g. dry strength (crush), drop number, pellet size and smoothness.
  • a binding effective amount of polymer will typically be in the range of between about 0.01% to 1% by weight based on the dry weight of the mixture of particulate material, polymer and caustic.
  • the polymer is present in a range of between about 0.01 to 0.4% by weight, and most preferred, about 0.04%.
  • austic shall mean a source of hydroxide ions (OH - ) selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, and mixtures thereof.
  • Sodium hydroxide commonly known as caustic soda, is the most preferred caustic.
  • a "binder enhancing effective amount of caustic” depends on the same factors as does the binding effective amount of polymer.
  • a binding effective amount of caustic will typically be in the range of between about 0.004% to 0.15% by weight based on the dry mixture of particulate material, polymer and caustic.
  • caustic is present in the range of between about 0.01% to 0.04% by weight, and most preferred at about 0.03% by weight.
  • the present invention contemplates a process of agglomerating particulate material containing iron in the presence of water which comprises mixing said particulate material with between about 0.01% to 1% by weight of at least one water soluble polymer selected from hydroxyethyl cellulose, alkali metal salts of carboxymethyl cellulose, methyl cellulose, methylhydroxyethyl cellulose and mixtures thereof, and 0.004% to 0.15% by weight of sodium hydroxide to produce a mixture, and forming said mixture into agglomerates.
  • at least one water soluble polymer selected from hydroxyethyl cellulose, alkali metal salts of carboxymethyl cellulose, methyl cellulose, methylhydroxyethyl cellulose and mixtures thereof, and 0.004% to 0.15% by weight of sodium hydroxide to produce a mixture, and forming said mixture into agglomerates.
  • the present invention contemplates a process of agglomerating iron ore wherein said ore is mixed with between about 0.01 to 0.4% by weight of an alkali metal salt of carboxymethyl cellulose, from about 0.01 to 0.04% by weight sodium hydroxide, and from about 0.02-0.5 wt% (based on dry ore) of soda ash, to produce a mixture, and forming said mixture into agglomerates.
  • the binder composition used in the process of the present invention may also contain other substances, for instance, those that are formed as by-products in the preparation of the alkali metal salt of carboxymethyl cellulose, such as sodium chloride and sodium glycolate, as well as other polysaccharides or synthetic water-soluble polymers and other "inorganic salts" (for want of a better term sodium carbonate, sodium citrate, and the like are referred to as "inorganic salts" herein).
  • Exemplary polysaccharides include, e.g., hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethylhydroxyethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, guar, hydroxpropyl guar and sugar beet pulp, and the like.
  • Exemplary synthetic water-soluble polymers include partially hydrated polyacrylamide, polyvinyl alcohol, styrene/maleic anhydride copolymers, and polyacrylate and copolymers thereof, etc.
  • Exemplary inorganic salts include, e. g. the salts described by Roorda in U. S. Patent Nos. 4,288,245 and 4,597,797 such as sodium citrate, soda ash, and the like.
  • the ratios of polymer, e.g. alkali metal salt of carboxymethyl cellulose, caustic and water to particulate material, e.g. concentrated ore are dependent on various factors including the agglomeration method used, the material to be agglomerated and the desired properties of the agglomerates to be prepared. A person of ordinary skill in the art can readily determine the specific amounts that will be most suitable for individual circumstances. Pelletization is generally carried out using the binder composition in an amount of from about 0.0044% to about 0.44%, preferably from about 0.022% to about 0.22% (by weight of the total dry mixture), of the binder composition and about 2% to about 20%, preferably about 5% to about 15%, water, by weight of the total dry mixture. In addition to the binder composition, clays such as bentonite clay may be used in pelletization. The total amount of these clays will depend on the user's objectives, but will generally be less than 0.22%, based on the weight of the total dry mixture.
  • the concentrated ore may be agglomerated into particles or agglomerates by rotating the concentrated ore powder in a drum or disc with a binder and water, followed by drying and firing.
  • Agglomerates can also be formed by briquetting, nodulizing, or spray drying.
  • binder composition constituents may be carried out in any manner commonly applied in the art.
  • the binder constituents may be mixed as solid matter with the concentrated ore in a dry or liquid form or as an emulsion or dispersion. Further, they may be simultaneously, successively or alternatively added to the concentrated ore before or during the pelletizing treatment.
  • liquid caustic is sprayed on moist concentrated ore resulting from the aforementioned separation process, which has all but about 10 wt% of the water removed by, e.g. rotating disc filter.
  • the polymeric binder composition is applied so that the binder components and concentrated ore are well mixed and adequately hydrated prior to being formed into green pellets.
  • the water content should generally be in the range of about 4 to 30 wt% based on the weight of dry particulate matter and most preferably between about 7 and 12 wt%.
  • Other substances may also be optionally added to the binder composition.
  • small amounts of flux e. g., limestone or dolomite may also be added to enhance mechanical properties of the pellets.
  • the flux also helps to reduce the dust level in the indurating furnace when the pellets are fired.
  • Olivine, serpentine, magnesium and similar minerals may be used to improve metallurgical properties of the pellets.
  • Drying the wet balls and firing the resultant dry balls may be carried out as one continuous or two separate steps. The important factors are that the balls must be dry prior to firing as the balls will degrade or spall if fired without first drying them. It is therefore preferred that the balls be heated slowly to a temperature of at least about 1204°C (2200°F), preferably to at least about 1316°C (2400°F) and then fired at that temperature. In another embodiment, they are dried at low temperatures, preferably by heating, or alternatively, under ambient conditions, and then fired at a temperature of at least about 1204°C (2200°F), more preferably at about 1316°C (2400°F). Firing is carried out for a sufficient period of time to bond the small particles into pellets with enough strength to enable transportation and/or further handling, generally about 15 minutes to about 3 hours.
  • pellets resulting from this process are dry, hard agglomerates having sizes that are suitable for, e. g. shipping, handling, sintering, etc.
  • Pellets generally have an average diameter of about 0.6 to about 2.5 cm (1/4 to about 1 inch), preferably about 1.3 cm (1/2 inch).
  • Pellet size is generally a function of the user and operator's preference, more than of binding ability of the compositions of this invention and virtually any size pellet desired by blast furnace operations and mine operations can be prepared.
  • the process was begun by placing 2500 grams (calculated as dry weight) of iron ore concentrate (moisture content approximately 9 to 10 wt. %) into a Mullen Mixer (Model No. 1 Cincinnati Muller, manufactured by National Engineering Co.).
  • polymer is then added to the mixer and spread evenly over the iron ore concentrate. If a mixture of polymers was used, the mixture was premixed by hand prior to addition to the muller mixer. The loaded mixer was run for three (3) minutes to evenly distribute the polymer. The resulting concentrate mixture was screened to remove particles smaller than those retained on a 2.36 mm (an 8 mesh) wire screen.
  • a balling disc fabricated from an airplane tire (approx. 40.6 (16") diameter) driven by a motor having a 60 RPM rotational speed was employed to produce green balls of the concentrate mixture.
  • Pellet "seeds" were formed by placing a small portion of the screened concentrate mixture in the rotating balling tire and adding atomized water to initiate seed growth. As the size of the seed pellets approached 4.75 mm (4 mesh), they were removed from the balling disc and screened. The seed pellets with a size between 4.75 mm and 3.35 mm (4 and 6 mesh) were retained. This process was repeated if necessary until 34 grams of seed pellets were collected.
  • Finished green balls were produced by placing the 34 grams of seed pellets of size between 4.75 mm and 3.35 mm (4 and 6 mesh) into the rotating tire of the balling disc and adding portion of the remaining concentrate mixture from the muller mixer over a 4 minute growth period. Atomized water was added if necessary. When the proper size was achieved (-13.2 mm, +12.5 mm) ((-0.530 inch, +0.500 inch)) concentrate mixture addition ceased and the pellets were allowed a 30 second finishing roll. The agglomerated pellets were removed from the disc, screened to -13.2 mm, +12.5 mm (-0.530, +0.500 inch) size and stored in an air-tight container until they were tested.
  • Net Drop Number was determined by repeatedly dropping two groups of ten (10) pellets each from 45.7 cm (an 18 inch) height to a steel plate until a crack appeared on the surface of each pellet. The number of drops required to produce a crack on the surface of each pellet was recorded. The average of all 20 pellets was taken to determine the drop number of each agglomerated mixture.
  • Dry Crush Strength was determined by drying twenty (20) pellets of each agglomerated mixture to measure the moisture content. The dry pellets were then individually subjected to a Chatillon Spring Compression Tester, Model LTCM (11.35 kg range) ((25 pound range)) at a loading rate of 0.254 cm/s (0.1 inch/second). The dry strength report for each agglomerate mixture is the average cracking pressure of the twenty pellets.
  • CMC carboxymethyl cellulose
  • a CMC/soda ash combination was employed with and without the addition of NaOH.
  • the CMC/soda ash combination consists of about 70 to 85% technical grade CMC and 15-30% soda ash.
  • the data obtained is compiled in Table 3, below.
  • CM Starch a carboxymethyl starch
  • the polyacrylamide (PL1400® ), the polyacrylate (FP100® ), CMDHPC, CMHPC, and CM- Starch showed benefits throughout the addition of caustic. This was not the case with the CM-Guar. Small additions of caustic significantly improved performance, however when the dosage of caustic was increased beyond optimum levels, both the wet and dry strengths were destroyed.
  • Non-ionic polymers have also been considered for use as binders. These polymers include, but are not limited to hydroxyethyl cellulose (HEC), methyl hydroxyethyl cellulose (Meth. HEC), hydroxypropyl cellulose (HPC), dextrin, and hydroxypropyl guar (HPG). Caustic addition to these binders was also investigated and the data is tabulated in Table 5, below.
  • the dextrin binder tested showed no improvement in wet drop number and dry strength.

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Claims (8)

  1. Procédé d'agglomération d'un matériau particulaire contenant du fer en présence d'eau, qui comprend le mélange dudit matériau particulaire avec une quantité liante efficace d'au moins un polymère soluble dans l'eau choisi dans le groupe constitué par les polymères naturels modifiés et les polymères synthétiques, et une quantité efficace pour améliorer le liant d'une source d'ions hydroxyde choisie dans le groupe constitué par l'hydroxyde de sodium, l'hydroxyde de potassium, l'hydroxyde d'ammonium et leurs mélanges, pour produire un mélange, la formation dudit mélange en agglomérats, et le séchage et la cuisson desdits agglomérats.
  2. Procédé selon la revendication 1, caractérisé en ce que ledit matériau particulaire est du minerai de fer.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que ledit polymère soluble dans l'eau est choisi dans le groupe constitués par les dérivés de guar, le carboxyméthylguar, l'hydroxypropylguar, le carboxyméthylhydroxypropylguar, l'amidon modifié, les dérivés d'amidon, le carboxyméthylamidon, l'amidon prégélatinisé, les polyacrylamides et leurs dérivés, les polyacrylates et leurs copolymères, les poly(oxydes d'éthylène), les dérivés de cellulose, la carboxyméthylcellulose, l'hydroxyéthylcellylose, la carboxyméthylhydroxyéthylcellulose, la méthylhydroxyéthylcellulose, la carboxyméthyldihydroxypropylcellulose et leurs mélanges.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que ledit polymère soluble dans l'eau est un sel de métal alcalin de carboxyméthylcellulose et ladite source d'ions hydroxyde est l'hydroxyde de sodium.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que ledit polymère soluble dans l'eau comprend en plus un sel d'un acide faible choisi dans le groupe constitué par la cendre de soude, le citrate de sodium et leurs mélanges.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la quantité de polymère soluble dans l'eau est de 0,01% à 1% en poids, par rapport au poids sec du mélange du matériau particulaire, du polymère et de la source d'ions hydroxyde.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la quantité de source d'ions hydroxyde est de 0,004% à 0,15% en poids, par rapport au poids sec du mélange du matériau particulaire, du polymère et de la source d'ions hydroxyde.
  8. Procédé selon la revendication 5, caractérisé en ce que le minerai de fer est mélangé avec 0,01 à 0,4% en poids d'un sel de métal alcalin de carboxyméthylcellulose, de 0,01 à 0,04% en poids d'hydroxyde de sodium et de 0,02 à 0,5% en poids de cendre de soude, pour produire un mélange, et par la formation dudit mélange en agglomérats.
EP92917701A 1992-08-06 1992-08-06 Composition de liant et procede d'agglomeration de matiere particulaire Expired - Lifetime EP0656072B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CA002141787A CA2141787C (fr) 1992-08-06 1992-08-06 Composition liante et procede pour agglomerer des substances particulaires
PCT/US1992/006551 WO1994003648A1 (fr) 1992-08-06 1992-08-06 Composition de liant et procede d'agglomeration de matiere particulaire
BR9207150A BR9207150A (pt) 1992-08-06 1992-08-06 Processo e composição aglutinante para aglomeração de material particulade e minério de ferro na presença de água

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EP0656072A1 EP0656072A1 (fr) 1995-06-07
EP0656072A4 EP0656072A4 (fr) 1996-06-26
EP0656072B1 true EP0656072B1 (fr) 2000-03-15

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AT (1) ATE190671T1 (fr)
AU (1) AU685385B2 (fr)
BR (1) BR9207150A (fr)
CA (1) CA2141787C (fr)
DE (1) DE69230806T2 (fr)
ES (1) ES2144422T3 (fr)
NO (1) NO311227B1 (fr)
WO (1) WO1994003648A1 (fr)

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US20040221426A1 (en) 1997-10-30 2004-11-11 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) Method of producing iron oxide pellets
CA2251339A1 (fr) 1997-10-30 1999-04-30 Hidetoshi Tanaka Methode de production de granules d'oxyde de fer
GB9724032D0 (en) * 1997-11-13 1998-01-14 Allied Colloids Ltd Ore pelletisation
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RU2605328C2 (ru) * 2011-02-16 2016-12-20 Соликс Алгредиентс, Инк. Композиция, набор и способ извлечения целевых соединений из биомассы
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RU2590034C1 (ru) * 2015-01-12 2016-07-10 Общество с ограниченной ответственностью "Научно-производственное внедренческое предприятие ТОРЭКС" Способ интенсификации процессов окускования железорудных материалов
IT201800006815A1 (it) * 2018-06-29 2019-12-29 An organic-inorganic hybrid material comprising a metal and lignin, processes for preparing the same and uses thereof / materiale ibrido organico-inorganico comprendente metallo e lignina, processi per la sua preparazione e suoi usi
CN109112297B (zh) * 2018-10-19 2020-08-28 攀钢集团攀枝花钢铁研究院有限公司 转炉富集污泥成型用粘结剂及转炉富集污泥成型方法
KR20220134012A (ko) * 2020-05-18 2022-10-05 닛폰세이테츠 가부시키가이샤 괴성물의 제조 방법 및 괴성물

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DE69230806T2 (de) 2000-11-16
ATE190671T1 (de) 2000-04-15
ES2144422T3 (es) 2000-06-16
DE69230806D1 (de) 2000-04-20
EP0656072A4 (fr) 1996-06-26
CA2141787C (fr) 2006-10-10
NO950401L (no) 1995-02-03
CA2141787A1 (fr) 1994-02-17
NO950401D0 (no) 1995-02-03
NO311227B1 (no) 2001-10-29
AU2406792A (en) 1994-03-03
EP0656072A1 (fr) 1995-06-07
BR9207150A (pt) 1995-12-12
AU685385B2 (en) 1998-01-22
WO1994003648A1 (fr) 1994-02-17

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