WO2012149635A1 - Procédé de production et de raffinage de frd (fer de réduction directe) à faible teneur en carbone - Google Patents

Procédé de production et de raffinage de frd (fer de réduction directe) à faible teneur en carbone Download PDF

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Publication number
WO2012149635A1
WO2012149635A1 PCT/CA2012/000387 CA2012000387W WO2012149635A1 WO 2012149635 A1 WO2012149635 A1 WO 2012149635A1 CA 2012000387 W CA2012000387 W CA 2012000387W WO 2012149635 A1 WO2012149635 A1 WO 2012149635A1
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WO
WIPO (PCT)
Prior art keywords
carbon
reduction
metal oxides
oxides
iron
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Ceased
Application number
PCT/CA2012/000387
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English (en)
Inventor
Wei-Kao Lu
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Individual
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Individual
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Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US14/113,304 priority Critical patent/US20140060251A1/en
Publication of WO2012149635A1 publication Critical patent/WO2012149635A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0046—Making spongy iron or liquid steel, by direct processes making metallised agglomerates or iron oxide
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/006—Starting from ores containing non ferrous metallic oxides
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/008—Use of special additives or fluxing agents
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/10—Making spongy iron or liquid steel, by direct processes in hearth-type furnaces
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
    • 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
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/56—Manufacture of steel by other methods
    • 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

Definitions

  • This invention relates to metallization of metal oxides in ores and subsequent refining to commercial products such as steels and ferroalloys.
  • This invention particularly relates to carbon levels in solid products of reduction and the subsequent de-carburization of liquid iron and iron alloys in converters.
  • DRI made according to existing commercial "Direct Reduction" processes of ironmaking may be divided into two groups: (1) DRI made in a shaft furnace and rotary kiln which is limited in carbon by chemical reactions, not by supplies, and varies with operating conditions. (2) DRI made in Rotary Hearth Furnaces which has both residual carbon as well as iron oxides with uncertain amounts due to re-oxidation of sponge iron and incomplete reduction.
  • my invention is the design of ore-coal composite pellets and the use of a PSH Furnace, so as to take advantage of (1) carbon as the most powerful reducing agent and (2) the introduction of a mechanism to cut-off all reduction reactions at the exhaustion of carbon.
  • Figure 1 is a binary phase diagram for the system AL2O3-B2O3;
  • Figure 2 is a binary phase diagram for the system B2O 3 -MgO;
  • Figure 3 is a binary phase diagram for the system SiO 2 - B 2 O 3 ;
  • Figure 4 is a binary phase diagram for the system CaO- B2O3;
  • Figure 5 is a photomicrograph of direct reduction iron from green balls without flux additions
  • Figure 6 is a photomicrograph of direct reduction iron from green balls with a flux addition of 4 g silica per 100 g of ore;
  • Figure 7 is a photomicrograph of direct reduction iron from green balls with a flux addition of 5 g of silica and 1.1. g boron oxide in borax.
  • Hot metal from a BF containing 4.5% C and "carbon ferrochrome" from a SAF containing over 6% C are raw materials for making of steels of much less than 1% C and medium carbon ferrochrome of around 2% C, respectively. Therefore, de-carburization is a necessary refining step in the current industrial setting.
  • Composite pellets also referred to as "green pellets" made of typical iron ore and medium or high volatile coal with a C/O ratio (where C stands for total carbon in carbonaceous reductants and O stands for combined oxygen in reducible oxides in ore, both in atomic-grams) in the range of 0.95 to 1.05 may be reduced to DRI of 95% metallization in a laboratory under PSH Furnace operating conditions. Subsequently, the melting of the resultant DRI under a controlled atmosphere, without any flux additions to control S & P, may be carried out in an induction furnace to achieve the separation of liquid metal from slag.
  • C/O ratio where C stands for total carbon in carbonaceous reductants and O stands for combined oxygen in reducible oxides in ore, both in atomic-grams
  • the composition ranges are comparable to liquid steel tapped from a BOF.
  • the impurity sulfur (S) is removed partly inside the BF and partly at a de-sulfurizing station between the BF and the BOF.
  • Phosphorus (P) is removed externally first (not in North America because domestic raw materials have low P content), then, in the BOF.
  • the removal of S and P from liquid iron can be effectively done, because the operating conditions can be controlled to have a very high temperature and slags of high basicity (in comparison to the BF) under a neutral or slightly reducing or oxidizing atmosphere.
  • semi liquid steel from a melter of DRI from a PSH Furnace may be used directly in a LF, i.e., bypassing the BOF for most grades of steel using typical North American raw materials.
  • Ferroalloys are made in a submerged arc furnace (SAF). This is similar to a BF because both are coke based shaft furnaces, although differing in heat source. In the smelting of chromite ore to produce carbon ferrochrome, a higher temperature is required. With electric heating, a SAF can be operated around 1700°C to satisfy such a requirement. [0014] The most important industrial mineral as a source of chromium is chromite
  • FeO.Cr 2 0 3 with some of the Fe replaced with Mg and some of the Cr replaced with Al.
  • the composition of one of many types of spinels may be written as (Mg,Fe)(Cr,AI) 2 0 4 .
  • Thermodynamically, pure chromium oxide is not much more difficult to reduce than iron oxide.
  • the difficulty in making ferrchrome is due to the fact that chromium oxide in the ore is in the form of spinel minerals.
  • My invention involves: (1) The making of properly designed composite pellets of chromite ore and coal to produce DRI with a high degree of metallization and controlled and lower residual carbon in PSH type furnaces as explained above. (2) Using a flux added to composite pellets to initiate the making of slag and to promote the growth of metallic particles at a temperature of 1500°C or lower. (3) Melting hot DRI under a controlled atmosphere in a melter (electric heated furnace or a converter heated by oxy-fuel burner) to produce medium carbon ferrochrome of around 2% Carbon, or lower.
  • a melter electric heated furnace or a converter heated by oxy-fuel burner
  • Figure 6 illustrates the results using a flux addition of 4 g of silica per 100 g of ore.
  • Figure 7 illustrates the results from pellets or green balls having a flux addition of 5 g of silica and 1.1 g boron oxide in borax.
  • the bright white phase is metallic and the orange phase is slag.
  • Priority for control of this end of furnace shifts from the "intensity" of supplying of heat energy to maintain a less oxidizing atmosphere and high temperature to achieve complete metallization and sintering.
  • the last one or two burners near the discharging end may be replaced by a plasma torch for this purpose.
  • the roof height may be lowered in this section to reflect less gas flow above the bed of DRI.

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

Abstract

L'invention porte sur un procédé pour la réduction directe d'oxydes métalliques avec du carbone. Selon le procédé, on forme des boulettes contenant un mélange d'oxydes métalliques ayant des potentiels de réduction qui se suivent lorsqu'ils sont chauffés en présence de carbone et une quantité de carbone suffisante pour réduire les oxydes métalliques plus facilement réduits mais cependant insuffisante pour réduire la totalité des oxydes métalliques. Les boulettes sont chauffées à une température au moins suffisante pour réduire les oxydes métalliques plus facilement réduits pour produire du métal de réduction directe tout en enlevant suffisamment du carbone sous la forme d'oxydes de carbone pendant la réduction pour éviter une étape de décarburation subséquente dans le traitement ultérieur du métal de réduction directe.
PCT/CA2012/000387 2011-05-04 2012-04-30 Procédé de production et de raffinage de frd (fer de réduction directe) à faible teneur en carbone Ceased WO2012149635A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/113,304 US20140060251A1 (en) 2011-05-04 2012-04-30 Process of the production and refining of low-carbon dri (direct reduced iron)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161457638P 2011-05-04 2011-05-04
US61/457,638 2011-05-04

Publications (1)

Publication Number Publication Date
WO2012149635A1 true WO2012149635A1 (fr) 2012-11-08

Family

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Family Applications (1)

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PCT/CA2012/000387 Ceased WO2012149635A1 (fr) 2011-05-04 2012-04-30 Procédé de production et de raffinage de frd (fer de réduction directe) à faible teneur en carbone

Country Status (2)

Country Link
US (1) US20140060251A1 (fr)
WO (1) WO2012149635A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018201218A1 (fr) 2017-05-02 2018-11-08 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Réduction carbothermique directe de chromite au moyen d'un catalyseur pour la production d'alliage de ferrochrome
US10358693B2 (en) 2017-10-20 2019-07-23 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources Method of direct reduction of chromite with cryolite additive

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115786739B (zh) * 2022-11-23 2024-01-23 北京科技大学 一种提高铬矿合金化率的方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB929201A (en) * 1959-08-24 1963-06-19 Tohoku Denki Seitetsu Kabushik Method of recovering nickel and iron from laterite ore by preferential reduction
US5567224A (en) * 1995-06-06 1996-10-22 Armco Inc. Method of reducing metal oxide in a rotary hearth furnace heated by an oxidizing flame
US20040154436A1 (en) * 2001-06-18 2004-08-12 Shuzo Ito Method for producing granular metal
US20060096420A1 (en) * 2003-01-07 2006-05-11 Hiroshi Sugitatsu Method for reducing chromium containing raw material
US20080069763A1 (en) * 2002-10-08 2008-03-20 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd) Method for manufacturing titanium oxide-containing slag
WO2010023691A1 (fr) * 2008-08-30 2010-03-04 Tata Steel Limited Procédé de séparation de zinc et d'extraction de fer dans des minerais de fer à haute teneur en zinc
CN102051482A (zh) * 2010-12-17 2011-05-11 兰州三普电力有限公司 微波直接还原铬铁粉矿的工艺及其专用坩埚

Family Cites Families (7)

* Cited by examiner, † Cited by third party
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GB191128829A (en) * 1911-12-21 1912-12-23 George Otis Gridley Improvements in and relating to Machine Tools.
GB1397200A (en) * 1972-04-04 1975-06-11 Ici Australia Ltd Process of producing metallic iron from iron oxides
JPS6023182B2 (ja) * 1979-12-01 1985-06-06 新日本製鐵株式会社 中炭素高クロム溶湯の溶製方法
JPS61111947A (ja) * 1984-11-01 1986-05-30 川崎製鉄株式会社 製鋼スラグの改質方法
CA2299109C (fr) * 1999-02-26 2010-08-24 Wei-Kao Lu Fours a soles droits apparies pour la reduction d'oxyde metallique
US20120285295A1 (en) * 2004-12-07 2012-11-15 Nu-Iron Technology, Llc Method for producing metallic iron nuggets
CN100507013C (zh) * 2006-09-13 2009-07-01 宝山钢铁股份有限公司 利用铬矿粉和煤直接生产铬铁合金的方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB929201A (en) * 1959-08-24 1963-06-19 Tohoku Denki Seitetsu Kabushik Method of recovering nickel and iron from laterite ore by preferential reduction
US5567224A (en) * 1995-06-06 1996-10-22 Armco Inc. Method of reducing metal oxide in a rotary hearth furnace heated by an oxidizing flame
US20040154436A1 (en) * 2001-06-18 2004-08-12 Shuzo Ito Method for producing granular metal
US20080069763A1 (en) * 2002-10-08 2008-03-20 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd) Method for manufacturing titanium oxide-containing slag
US20060096420A1 (en) * 2003-01-07 2006-05-11 Hiroshi Sugitatsu Method for reducing chromium containing raw material
WO2010023691A1 (fr) * 2008-08-30 2010-03-04 Tata Steel Limited Procédé de séparation de zinc et d'extraction de fer dans des minerais de fer à haute teneur en zinc
CN102051482A (zh) * 2010-12-17 2011-05-11 兰州三普电力有限公司 微波直接还原铬铁粉矿的工艺及其专用坩埚

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018201218A1 (fr) 2017-05-02 2018-11-08 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Réduction carbothermique directe de chromite au moyen d'un catalyseur pour la production d'alliage de ferrochrome
US10358693B2 (en) 2017-10-20 2019-07-23 Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of Natural Resources Method of direct reduction of chromite with cryolite additive

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US20140060251A1 (en) 2014-03-06

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