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WO2016049465A1 - Particule composite pour la production d'acier et le raffinage de minerai - Google Patents

Particule composite pour la production d'acier et le raffinage de minerai Download PDF

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Publication number
WO2016049465A1
WO2016049465A1 PCT/US2015/052240 US2015052240W WO2016049465A1 WO 2016049465 A1 WO2016049465 A1 WO 2016049465A1 US 2015052240 W US2015052240 W US 2015052240W WO 2016049465 A1 WO2016049465 A1 WO 2016049465A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite particle
iron
dust
metal
core
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2015/052240
Other languages
English (en)
Inventor
John H. Hull
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aquablok Ltd
Original Assignee
Aquablok Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aquablok Ltd filed Critical Aquablok Ltd
Priority to US15/509,928 priority Critical patent/US20170247772A1/en
Publication of WO2016049465A1 publication Critical patent/WO2016049465A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • C21B3/02—General features in the manufacture of pig-iron by applying additives, e.g. fluxing agents
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B5/00—Making pig-iron in the blast furnace
    • C21B5/02—Making special pig-iron, e.g. by applying additives, e.g. oxides of other metals
    • C21B5/023—Injection of the additives into the melting part
    • 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
    • C21C7/0025—Adding carbon material
    • 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
    • C21C7/0037—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00 by injecting powdered material
    • 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
    • C22B1/248—Binding; Briquetting ; Granulating of metal scrap or alloys
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2200/00—Recycling of non-gaseous waste material
    • 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
    • C21C2200/00—Recycling of waste material
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to improved methods of making steel or other metals using recycled/recovered waste products to make composite particles that can be re-used in the metal-making and ore refining processes.
  • Suitably-sized waste products may be employed as cores and waste fines or dusts may be employed in coatings of the composite particle.
  • Steel is an alloy of iron and carbon that is typically produced in a two-stage process.
  • iron ore is reduced or smelted with coke and limestone in a blast furnace, producing molten iron which may be cast into pig iron or earned to the next stage as molten iron.
  • molten iron which may be cast into pig iron or earned to the next stage as molten iron.
  • steelmaking impurities such as sulfur, phosphorus, and excess carbon are removed and alloying elements such as manganese, nickel, chromium and vanadium are added to produce the exact steel formulation required.
  • Steel mills then turn molten steel into blooms, ingots, slabs and sheets through casting, hot rolling and/or cold rolling.
  • iron oxide dust is a hazardous substance when inhaled, and therefore somewhat dangerous to handle in large quantities.
  • MSDS for iron oxides states: "May cause irritation to the respiratory tract. Symptoms may include coughing and shortness of breath. Long term inhalation exposure to iron has resulted in mottling of the lungs, a condition referred to siderosis.”
  • OHSA has set a legal airborne permissible exposure limit (PEL) of 10 mg/m 3 averaged over an 8-hour workshift for iron oxide fumes, and 5 mg in 3 for iron oxide dust or particulates.
  • PEL legal airborne permissible exposure limit
  • iron oxides are sold as waste or byproducts, they generally must be treated as a hazardous substance and special precautions are required for transport and storage, adding to disposai costs.
  • iron fines not suitable for direct use in the blast furnace are recycled in various ways.
  • WO1992/007964 a process for recycling ore fines is described wherein the dust and sludge from the blast furnace and converters is mixed and the mixture is added to the stream of converter slag when the molten slag is poured into a ladle. The stream force draws the mixture down into the molten slag. The resultant slag is solidified, crushed and reintroduced to the blast furnace.
  • Bluescope steel has described a recycle process in which ore fines are mixed with lime fines and coke to agglomerate the fines, followed by sintering in a flame chamber to fuse the fines and coke agglomerate. See, for example : hiips: . ⁇ , ⁇ . b fu e$cope3 ⁇ 4t ee L ⁇ re/rae i w l 0 38/ Reus! n g1 ⁇ 220 he ⁇ OB y - :
  • the invention relates to composite particles useful for making metal alloys such as iron and steel, the composite particle comprising a core of an aggregate material and a coating surrounding the core, the coating comprising a metal dust such as a iron oxide dust, and a binder, Composite particles so formed may be used like any ordinary ore particle in an ore refining process.
  • a composite particle comprising:
  • an aggregate core a coating around the aggregate core, the coating comprising metal dust and a binder.
  • the metal dust is iron oxide dust and the aggregate core is a limestone or dolomite particle, or a taconite particle, which are often used in steelmaking anyway, so they is prevalent in steel mills.
  • the cores may be sized to a standard size number of about 7-10, for example 8 to 9.
  • the binder may comprise mineral clay such as the kaolinite, montmorillonite/ smectite/ bentomte, palygorskite / attapulgite, vermiculite, and minnesotaite groups.
  • the binder may comprise from about 2% to about 10% by weight of the composite particle, for example about 5%,
  • the bulk of the composite particle e.g.
  • the aggregate and iron dust which are already components used in steelmaking
  • the metal (e.g. iron oxide) dust may comprise about 20% to about 60% by weight of the composite particle, such as from about 30% to about 50% by weight.
  • the coating is relatively thin, so that the final composite particle may have standard size number from 6-9 or 6- 8, only slightly larger than the aggregate core.
  • the composite particles may be formed in a batch roiling process as is known in the art.
  • the core may comprise any other ore particle of suitable size
  • the metal dust may comprise fines or dusts of any metal useful in making a desired alloy.
  • the invention relates a process for making metals or alloys by (1) smelting composite particles described above with other metal ores; (2) cooling the molten ore-melt; and (3) optionally further processing the metal with carbon or other elements and to remove further impurities, and optionally alloying it with other metals.
  • the Invention relates a process for making iron and/or steel by (1) smelting composite particles described above having dolomite or limestone cores and iron oxide dust with other iron ore; (2) cooling the molten pig iron; and (3) optionally further processing the steel with carbon and to remove further impurities, and optionally alloying it. with other metals, [0011]
  • Other features and advantages of the invention will be apparent from the detailed description that follows.
  • the invention relates to composite particles useful for making iron and steel, the composite particle comprising a core of an aggregate material and a coating surrounding the core, the coating comprising iron oxide dust and a binder.
  • Composite particles so formed may be used like any ordinary ore particle. They also area means to recycle iron oxide dust ⁇ normally a waste byproduct - within in a steel mill.
  • the size of the composite particle can range from a small pebble to a large size rock or even larger,
  • the composite particle is generally spherical in form, but it can also be other shapes such as oval, egg, oblong, or irregular giving rise to at least one major axis and at least, one minor axis.
  • Particles may be sized by reference to their major dimension, which generally gives rise to an average size.
  • particles may be sized by reference to the sieve or mesh size which allows them to pass through, thus generating a maximum size parameter.
  • the AASHTO uses this latter method and attributes a standard "size number" to aggregate or particles that have a particular size distribution as set forth in their Table 1, partially reproduced below.
  • aggregate particles of standard size number 8 will have a size distribution such that all will pass a 12.5 mm sieve, most (85-100%) will pass a 9.5mm sieve, only 10-30% will pass a 4.75 mm sieve, etc,
  • Composite particles of the invention generally have a major axis dimension of from about 1/4 inch to 1 inch or more; more typically from about 3/8 inch to about 1/2 inch.
  • composite particles of the invention may be sized as are aggregates by the AASHTO standard sizes, and particles having a standard size number from 6 to 9, or from 6 to 8 should be suitable.
  • the core of the composite particle may he formed of nearly any material. It may comprise from about 10 to about 80% of the major axis dimension and from about 30 to 80% of the total weight of the composite particle. Cores may also be sized as are aggregates by the AASHTO standard sizes, and size numbers 7 to 10 or from 8 to 9 may be used, corresponding generally to major dimensions of about 3/16 to about 1/2 inch, or from 1/4 to about 3/8 inch. Cores may comprise a solid stone or rock core such as a fine aggregate and/or coarse aggregate. Fine aggregate includes small particles such as sand and other sand-sized materials. Coarse aggregate includes larger particles such as gravel, crushed stone, recycled aggregates (from construction, demolition and excavation waste), and manufactured aggregates (for example, furnace slag and bottom ash).
  • a particularly useful core material in steel making plants is appropriately sized limestone or dolomite aggregates.
  • Other useful core materials - particularly for steel-making - include iron ore or taconite nuggets or pellets, Taconite is a form of low-grade iron ore and it may be rained from various locations including the Mesabi Iron Range, near Ribbing, MN. To make these pellets, the hard taconite ore is blasted and then ground down with water to a fine powder. The fine iron-rich particles, mostly of magnetite are extracted from the powder by use of magnetism. The wet. taconite powder is roiled with clay inside large rotating cylinders. The cylinders cause the powder to roll into marble-sized bails.
  • the balls are then dried and heated until they are white hot, The halls become hard as they cool.
  • the finished product is taconite pellets.
  • Other iron-related minerals that may also be suitable as cores include, for example, Grunerite/ Cummingtonite (Mg 5 Fe)7Sig022(OU)2; Actinolite
  • any "steel slag" pellets or fines as that term is used in the industry.
  • the addition of limestone or dolomite (calcium compounds) forms complexes with aluminum, silicon and phosphorus to form "slag" - a waste product of steelmaking.
  • Slag floats to the top of the melt, is poured off and placed in piles for disposal.
  • the slag cools so quickly, in fact, that it solidifies as an amorphous, glass-like solid ranging from fine sand particles to large blocks, both of which can be extremely hard.
  • Much of the metallic fraction (the discarded steel products in the pile) is remo ved with large magnets and sold as steel scrap.
  • the resulting nonmetaliic grades have applications in construction and in the present invention.
  • the finest fractions (about No. 8 or smaller) are referred to as "slag fines". But properly sized slag may serve as cores for the invention.
  • Cores useful for making other metals or alloys include the cores mentioned above, and also ore particles of any ore used in making the desired metal or alloy.
  • the core may be more dense, less dense or equally as dense as the coating layer.
  • the core has a relatively greater density as compared to that of the coating layer.
  • the coating layer of the composite particles may partially or completely encapsulate the core.
  • the coating is made of at least two components: metal dust and a binder,
  • the metal dust is preferably the dust of a metal to be incorporated into the metal or alloy, such as iron oxide dust cars be incorporated into the making of steel or iron,
  • the binder material is a clay mineral or a mixture of clay minerals that, while not hardening, does generate cohesive strength by the hydration process.
  • Clay is common name for a wide variety of weathered mineral or igneous rock.
  • Suitable clays may be found in the kaolinite group, the smectite or montmoriilonite group, the attapulgite group and the zeolite group.
  • these groups contain sheets or layers formed of specific tetrahedral and/or octahedral structures of aluminum and silicon oxides. The layers or platelets are held together by ionic bonds with charged ions (usually cations) located between the layers.
  • the Nickel-Strunz classification (version 10) divides silicates (group 9) into nine different subcategories, the most useful being Phyllosiiicates (group 9E) and the Tektosilicates with and without Zeolitic HjO (groups 9G and GF. respectively).
  • Phyllosiiicates (group 9E) are divided into nine subcategories, the most useful being group 9EC (with mica sheets), group 9ED (with kaolin layers), and group 9EE (single tetrahedral nets of six- membered rings).
  • Exemplary clays from these groups include kaolinite.
  • montmoriilonite also called smectite and bentonite
  • tale mondorite
  • nontronite palygorskite or attapulgite
  • muscovite vemiicuHte
  • saponite hectorite
  • rectorite and minnesotaite.
  • Bentonite is a useful impure clay largely containing montmoriilonite.
  • the layers or "platelets” of phyllosiiicates that give them many of their properties, including the plasticity for use as pottery.
  • the layers are of thickness dimensions in the few nanometer range, they are often referred to as nanoclays.
  • An example is the NANOLIN D series of nanociays available from Zhejiang Fenghong Clay Chemicals Co., LTD., which are made from highly purified smeciiie thai exhibits ultra-fine phase dimensions.
  • the size of these nanociays is typically in the range of 1- 100 nm; the average fully dispersed thickness of platelets is around 25 nm; the aspect ratio ranges from 100 to 1000,
  • Modified clays are formed when various processes are used to separate and expand the layers or platelets, intercalation, exfoliation, and fuming are processes that modify the layered structure. Intercalation inserts a polymer or other molecule between the platelet layers to isolate them, but without much physical separation. Exfoliation, on the other hand, inserts a polymer or molecule and expands the space between layers by 10-20 fold. Fuming is a flaming process that introduces hydroxy! groups onto the surface of the silica structures,
  • a clay-sized material can also be used, such as gypsum, fiyash, cement, or other materials, having an average particle size of less than about 10 microns
  • the binder material may also include other clay-sized or quasi clay-sized materials such as organophilie bentonite, zeolites, and inorganic oxides of aluminum, iron, and/or manganese,
  • the binder may be present in the composite particle in amounts from about 2% to about 10% by weight, for example, from about 3% to about 7%, or about 5% by- weight.
  • the second component of the coating layer is the metal dust, of which one embodiment is iron oxide dust.
  • iron ore is typically crushed to a size of about 7 mm to about 25 mm for use in the blast furnaces, corresponding roughly to a size number of about 5 to about 8.
  • Particulates smaller than about 6 or 7 mm in size are considered “fines” and are either not used or are re cycled as described in the background.
  • dust refers to particles that are smaller still, having a particle size in the range of about no more than about a hundred microns: or a size such that essentially 100% passes through a standard No, 150 mesh.
  • Collection of iron oxide dust generally already takes place in steel making plants to avoid dispersing the hazardous dust. Collection bags or filters may be used, as well as certain types of scrubbers and separators to isolate the iron oxide dust from other useful components that might be in the process stream (e.g. gases and other particulates).
  • Collection bags or filters may be used, as well as certain types of scrubbers and separators to isolate the iron oxide dust from other useful components that might be in the process stream (e.g. gases and other particulates).
  • the metal particle dust may be included in the composite particles in amounts from about 20% to about 60% by weight of the particle, for example from about 30% to about 50% by weight.
  • the composite particles of the invention can be manufactured by a batch rolling process, using a roller such as a concrete mixer or pugmill.
  • a roller such as a concrete mixer or pugmill.
  • the binder and iron oxide dust will be combined into a mixture that is applied as a coating to the core which has been prewetted with a water-based emulsified binder.
  • the pfewetted cores and coating materials are added to the mixer, and rotation causes the cores to become coated, and compacting of the coating layer on the core may occur as the aggregates fall and collide against the wall of the roller.
  • the composite particles can be manufacture using processes analogous to those described in the patent literature cited and Incorporated herein in connection with composite particles for sedimentation capping systems.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Les particules composites sont utilisées en combinaison avec des particules de minerai dans le cadre d'un processus de raffinage ou de purification de minerai, comme un processus de fabrication d'acier ou de fer. Les particules composites comprennent un noyau, qui peut être un agrégat de calcaire, de dolomite, ou de toute autre particule de minerai. Le noyau est entouré par une couche de revêtement comprenant de la poussière métallique et un liant. La poussière métallique peut être de la poussière d'oxyde de fer qui, avec le calcaire, est fréquente dans le cadre du processus de fusion du fer. Ainsi, les particules composites contribuent à recycler la poussière de fer gaspillée et dangereuse. Le liant peut être de l'argile minérale, comme de la bentonite, de la montmorillonite ou de la kaolinite, et peut représenter environ 2-10 % en poids de la particule.
PCT/US2015/052240 2014-09-25 2015-09-25 Particule composite pour la production d'acier et le raffinage de minerai Ceased WO2016049465A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/509,928 US20170247772A1 (en) 2014-09-25 2015-09-25 Composite Particle For Steel Making and Ore Refining

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201462055300P 2014-09-25 2014-09-25
US62/055,300 2014-09-25

Publications (1)

Publication Number Publication Date
WO2016049465A1 true WO2016049465A1 (fr) 2016-03-31

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3502284A1 (fr) * 2017-12-22 2019-06-26 Imertech Sas Procédé de traitement de minéraux
CN111154971A (zh) * 2020-01-17 2020-05-15 山东泰山钢铁集团有限公司 一种用于烧结配料的球团窑皮颗粒及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112020015541B1 (pt) 2018-02-15 2023-11-14 Praxair Technology, Inc Adsorvente compósito de núcleo-cápsula para uso na separação de gases de batelada, e processo de separação de gás cíclico
US20230090940A1 (en) * 2020-03-04 2023-03-23 Jessica H. CUI Heat and fire resistant geopolymer materials

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4126453A (en) * 1976-05-17 1978-11-21 Esm, Inc. Composition for a fluidizing flux in the production of iron and steel
WO2005103307A1 (fr) * 2004-04-23 2005-11-03 Corem Granules et boulettes de minerai de fer agglomerees en couches
US20110179910A1 (en) * 2008-09-11 2011-07-28 Christian Boehm Process for producing agglomerates of finely particulate iron carriers
CN103484665A (zh) * 2013-10-14 2014-01-01 北京科技大学 采用不同粘结剂和两次成球方式制作冶金复合球团的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4126453A (en) * 1976-05-17 1978-11-21 Esm, Inc. Composition for a fluidizing flux in the production of iron and steel
WO2005103307A1 (fr) * 2004-04-23 2005-11-03 Corem Granules et boulettes de minerai de fer agglomerees en couches
US20110179910A1 (en) * 2008-09-11 2011-07-28 Christian Boehm Process for producing agglomerates of finely particulate iron carriers
CN103484665A (zh) * 2013-10-14 2014-01-01 北京科技大学 采用不同粘结剂和两次成球方式制作冶金复合球团的方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3502284A1 (fr) * 2017-12-22 2019-06-26 Imertech Sas Procédé de traitement de minéraux
WO2019120951A1 (fr) * 2017-12-22 2019-06-27 Imertech Sas Procédé de traitement minéral
CN111511938A (zh) * 2017-12-22 2020-08-07 伊梅斯切公司 矿物处理方法
US20200318216A1 (en) * 2017-12-22 2020-10-08 Imertech Sas Mineral treatment process
US12031193B2 (en) 2017-12-22 2024-07-09 Imertech Sas Mineral treatment process
CN111154971A (zh) * 2020-01-17 2020-05-15 山东泰山钢铁集团有限公司 一种用于烧结配料的球团窑皮颗粒及其制备方法

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