SE545037C2 - A method for utilizing metal oxide containing side streams in ferrochrome smelting processes - Google Patents

A method for utilizing metal oxide containing side streams in ferrochrome smelting processes

Info

Publication number
SE545037C2
SE545037C2 SE2150308A SE2150308A SE545037C2 SE 545037 C2 SE545037 C2 SE 545037C2 SE 2150308 A SE2150308 A SE 2150308A SE 2150308 A SE2150308 A SE 2150308A SE 545037 C2 SE545037 C2 SE 545037C2
Authority
SE
Sweden
Prior art keywords
briquettes
ferrochrome
side streams
cement
furnace
Prior art date
Application number
SE2150308A
Other languages
Swedish (sv)
Other versions
SE2150308A1 (en
Inventor
Kimmo Vallo
Petteri Linja
Original Assignee
Outokumpu Oy
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 Outokumpu Oy filed Critical Outokumpu Oy
Publication of SE2150308A1 publication Critical patent/SE2150308A1/en
Publication of SE545037C2 publication Critical patent/SE545037C2/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/12—Making spongy iron or liquid steel, by direct processes in electric 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
    • C21C5/52—Manufacture of steel in electric furnaces
    • C21C5/54—Processes yielding slags of special composition
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/12—Making spongy iron or liquid steel, by direct processes in electric furnaces
    • C21B13/125—By using plasma
    • 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
    • C21C5/52—Manufacture of steel in electric furnaces
    • C21C5/527—Charging of the electric furnace
    • 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
    • C21C7/0006—Adding metallic additives
    • 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
    • C21C7/0087—Treatment of slags covering the steel bath, e.g. for separating slag from the molten metal
    • 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
    • C21C7/068—Decarburising
    • 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
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/32—Obtaining chromium
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • C21B3/04—Recovery of by-products, e.g. slag
    • C21B3/06—Treatment of liquid slag
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B3/00—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces
    • F27B3/08—Hearth-type furnaces, e.g. of reverberatory type; Tank furnaces heated electrically, with or without any other source of heat
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

Abstract

The invention is directed to briquetting metal oxide dusts and fine material with cement-based binders. After this the briquettes can be fed into arc furnaces for ferrochrome production through already existing inlet systems.

Description

A method for utilizing metal oxide containing side streams in ferrochrome smelting processes Technical Field The invention relates to recycling of metal oxides by using cement based briquettes in submerged arc furnace for ferrochrome production to recover metals. ln the method side streams from ferrochrome and fine steel production are formed into briquettes with cement, which briquettes can be fed into the submerged arc furnace through the standard inlet system and through the pre-heating furnace. ln the submerged arc furnace the metal oxides are reduced to metals mainly with carbon and the metals are recovered in the ferrochrome product.
Background ln the ferrochrome furnace, material having a small particle size cannot be used as it will not reach the reaction area, but is stopped because of the gas stream present on the charge layer. Metal oxide dusts created in ferrochrome and stainless steel production are typically very fine and they cannot be fed as such into the submerged arc furnace. Additionally, fine metal oxides increase the electrical conductivity of the charge layer inside the furnace, which reduces the production capacity. Because of these above-mentioned reasons all fine material must be agglomerated before feeding into the submerged arc furnace for ferrochrome production.
The material(s) to be formed into briquettes is typically mixed in a Concrete mixer with cement and water. The mixture is used to form briquettes ofthe desired size in a briquetting machine and allowed to dry for a desired period to reach the required strength. The production method here is the same used to produce cement-based slab stones.
Metal oxides from ferrochrome production that can be reduced in the submerged arc furnace under selected conditions can be used to form briquettes. ln fine steel production suitable fractions are, for example, dust from filter plants, flakes from casting and rolling machines, slurries from water treatment, shot blasting dust from cold rollers and metal sediment formed by acid treatment in annealing - pickling processes. ln ferrochrome production, suitable fractions are, for example, fine materials formed in pelleting and furnace feeding. To improve the metal yield a suitable reduction material, such as carbon, can be added into the briquettes to speed up the reaction kinetics.
The potential of the invention in ferrochrome production is in improving chromium yield, reducing waste, better use of raw material and avoiding landfill charges. By altering the composition ofthe briquette the composition ofthe ferrochrome can be altered to suit the customer. ln fine steel production advantages would be in improving the present recycling ofthe side streams and in making recycling cheaper.
Previous solutions to problems relating to recycling side streams have been based on separate dust smelters, forming briquettes with organic binders, and direct reduction processes. Dust smelters and direct reduction processes are challenging due to the big investments required and possible high running costs. Using organic binders, such as molasses, can lead to briquettes falling apart before reaching the reaction area in the submerged arc furnace for ferrochrome production. ln fine steel production using these briquettes in arc furnaces reduces energy efficiency and therefore reduces yield.
US patent US8409320 B2 discloses briquetting steel production side streams containing oxides with molasses and feeding these into the arc furnace of a smelting plant, where metals are reduced and slag is boiled. The patent does not deal with briquetting oxide material with cement and feeding the briquettes into the submerged arc furnace for ferrochrome production or into the arc furnaces for steel production.
US patent publications US2014/0352496 and US 2013192422 disclose preparation and use of cement and molasses based briquettes in arc furnaces for fine steel production. The patent concentrates on slag boiling with briquettes in an arc furnace. The patent does not deal with using briquettes in a submerged arc furnace used in ferrochrome production.
Description of the lnvention Nowhere in the publications of the prior art is presented using a submerged arc furnace used in ferrochrome production. Submerged arc furnaces cannot create conditions where slag boils, and is otherwise not suitable for reducing material from boiling slag because of reactions at the reduction zone and disturbed gas streams.
The solution according to the present invention is based on feeding into the ferrochrome furnace material from side streams of ferrochrome and fine steel production that would be difficult to use with any other technology. Additionally, it is possible, and rational to feed other side streams from the metal industry and the mining industry containing metal oxides that can be reduced with carbon into the ferrochrome arc furnace.
The chemical composition ofthe main components ofthe feed material is presented in Table Table 1. Typical compositions of briquettes.
CrzOg FezOg NiO IV|oO3 SiOZ CaO C (coke) 0-30% 20-70% 0-10% 0-5% 0-20% 0-15% 0-20% Using the material according to Table 1 a mixture is formed with cement and water. ln addition to cement as a reinforcer, blast furnace slag, for example can be used as desired. The mixture is cast as briquettes, for example, as a 6 pointed 60 x 60 x 60 mm sized briquette. Typically a finished briquette contains 2 - 30% cement, ofwhich a part (10 - 70%) can be replaced with for example blast furnace slag. The size of the briquette depends on or is influenced by the feeding or inlet system in the used submerged arc furnace. Briquettes are allowed to dry for about 4 weeks in outdoor conditions to reach the final strength before feeding into the furnace. lt is also possible to use accelerators and heating to adjust hardness. lf desired 0 - 25% of reducing agent (coke, ferrosilicon, aluminium, silicon carbide) can be added into the briquette, whereby reduction is better because the reducing agent itself is physically closer to the metal oxides.
Briquettes are preferably fed into the submerged arc furnace via a preheating furnace in which the briquette dries and heats up to approximately 500 °C in a C02 atmosphere. This breaks silicate bonds and replaces them with carbonate bonds, while the briquette maintains it strength. The briquette flows as plug flow through an inlet tube into the pot of the submerged arc furnace and simultaneously starts to heat because ofthe furnace gases. When the briquette reaches the melting zone, the metal oxides within start reducing, first the iron oxide reduces partly by pot gases, and finally chrome oxide reduces. ln the submerged arc furnace for ferrochrome production the cement contained in the briquettes increases the pH of slag and thus reduces the chromium content of slag by approximately 0.5 - 5%. Reduced metals melt and dissolve into metal in the furnace and the melt is melted out ofthe furnace as a castable alloy, the composition of which depends on the metal content of the feeds. ln practice, for example all Ni, I\/|o and Fe fractions in feeds are reduced into metal. The composition of metal and slag is presented in Table Table 2. I\/|etal and slag composition obtained from a submerged arc furnace Typical analysis of metal Cr Si Ni l\/lo C 40-55% 3-10% 0-5% 0-2% 5-8% Typical analysis of slag Cr Fe SiOg A|2O3 l\/lgO CaO 0.5-10% 0-4% 25-30% 22-28% 20-25% 2-5% ln one embodiment, various secondary raw-materials, such as catalysts are used as a briquette raw-material, allowing metals in metal oxides to be recovered into the ferrochrome. These raw-materials can be metal oxides that contain nickel, molybdenium, titanium, copper, manganese, or cobolt.
Next the invention is explained in more detail with reference to the attached Figures Figure 1 shows an Ellingham diagram, which illustrates the order of reduction of metal oxides.
Figure 2 shows how the levels of nickel and manganese change in the ferrochrome product during the feed experiment.
Figure 3 shows changes in chromium content ofthe ferrochrome product during the experiment.
Figure 4 shows carbon and si|icon content of the ferrochrome product during the experiment.
The order of reduction of metal oxides is defined by the Ellingham diagram of Figure 1. Different metals that can be reduced by carbon in the arc furnace under selected conditions can be seen. Carbon is able to reduce metals that are above the line presenting the reaction of carbon. This reduction reaction itself is dependent on temperature and pressure. ln practice, noble elements reduce first, so the reduction order is Ni, I\/|o, Fe, Cr. The diagram also shows reaction equations for reduction, varying according to oxidation stage, for example, individual equations for different oxidation stages of iron.
According to the invention cement is the only binding material that can hold the briquette together in the pre-heating furnace temperature of 400-600 degrees. Additionally, it gives the briquette adequate mechanical strength so that briquettes can be fed into the furnace through the inlet system. Chemical bonds ofthe cement change to carbonate bonds in the heat of pre-heating oven, whereby the original strength of the briquette is almost completely maintained. Using cement-based briquettes also provides the submerged arc furnace with lime that increases the pH ofthe slag leading to a higher degree of reduction and a higher yield of chromium.
The particle size distribution in briquettes depends on the raw materials used in the formation of briquettes. The particle size distribution should follow the Fuller curve as closely as possible because this allows minimising the amount of cement used and provides savings in raw materials. The amount of briquettes added can be up to 20 w-%, preferably 3-10 w-% of the total material feed dependent on the current obtained slag material analysis The invention is not limited to the raw materials presented above. By means ofthe method other side streams containing metal oxides can also be used economically. For example, oxides from the nickel industry would blend nickel into ferrochrome and the thus formed ferrochrome would be better suited for the manufacture of austenitic steel grades.
Figures 2-4 show results of an experiment in which cement-based briquettes containing flakes from fine steel production were fed into a submerged arc furnace used in ferrochrome production.
Figure 2 shows changes in nickel and manganese content ofthe ferrochrome product during the feed experiment, i.e. metal oxides reduce to end-product.
Figure 3 shows change in chromium concentration ofthe ferrochrome product in the end-product during the experiment. The chromium concentration dropped as expected as the proportion of other metals increased.Figure 4 shows that carbon and silicon concentrations remain at a normal level in the end product during the briquette experiment.

Claims (6)

1. ing industrial metal oxides,
2. in
3. ising side streams conta
4. _jc__.______A method for util characterised in that material c
5. S
6.Am X O M t 6 m g .m in Ofita tted with cement e m O rl h C O rl rl e r.| rl æm .Mæ a n rl U r.| C rl a d e g rl e m b U S asißatâ is br into a and the briquettes are fed production. m m f es hm ..La mf, .å .mm dm Ga s .%m g am at fS aa |mC m O r f S 6 k a ...ll .ß S 6 .im X O ala t 6 m g .m m a t n O C ala .H 6 t a m .iim method according to cla 25 rolling machines, dust from filtering works, side streams from water treatment or metal slurries from annealing - pickling lines. ^~ ' , characterised in method according to ~ that briquettes are fed through a pre -heating furnace characterised in that the in the pre-heating furnace is between 400 andim h C o t.m d rl o C C a d o h t e m e h T tempefatufe °C. The method according to any of the previous claims, characterised in that briquettes are added to comprise a maximum of. . . . . . . . . . . . . . . . . . . % of the total feed. The method according to any of the previous claims, characterised in that the metal oxides conta c c c c c c c c c c c in oxides of metals selected ining material conta from the group consisting of chromium, iron, nickel, titanium, cobalt, manganese, and copper.
SE2150308A 2018-09-26 2019-09-25 A method for utilizing metal oxide containing side streams in ferrochrome smelting processes SE545037C2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20185805A FI130393B (en) 2018-09-26 2018-09-26 Method for using sidestreams containing metal oxides in ferrochrome smelting processes
PCT/FI2019/050687 WO2020065134A1 (en) 2018-09-26 2019-09-25 A method for utilizing metal oxide containing side streams in ferrochrome smelting processes

Publications (2)

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SE2150308A1 SE2150308A1 (en) 2021-03-18
SE545037C2 true SE545037C2 (en) 2023-03-07

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SE2150308A SE545037C2 (en) 2018-09-26 2019-09-25 A method for utilizing metal oxide containing side streams in ferrochrome smelting processes

Country Status (8)

Country Link
JP (1) JP7322141B2 (en)
KR (1) KR20210065943A (en)
CN (1) CN112689683A (en)
FI (1) FI130393B (en)
SE (1) SE545037C2 (en)
TW (1) TWI820222B (en)
WO (1) WO2020065134A1 (en)
ZA (1) ZA202101409B (en)

Citations (4)

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Publication number Priority date Publication date Assignee Title
JPS50130615A (en) * 1974-04-02 1975-10-16
US3947267A (en) * 1973-07-23 1976-03-30 Armco Steel Corporation Process for making stainless steel
US5654976A (en) * 1995-04-18 1997-08-05 Elkem Technology A/S Method for melting ferrous scrap metal and chromite in a submerged arc furnace to produce a chromium containing iron
WO2010103343A1 (en) * 2009-03-10 2010-09-16 Tata Steel (Kzn) (Pty) Limited An improved process for production of high carbon ferrochrome (hcfecr) and charge chrome with the use of a new type of chromite ore agglomerates

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Publication number Priority date Publication date Assignee Title
JPS5288520A (en) * 1976-01-21 1977-07-25 Nisshin Steel Co Ltd Treatment of waste generated in manufacturing alloy steel
JPS531103A (en) * 1976-06-25 1978-01-07 Nisshin Steel Co Ltd Treatment of plating sludge
JPS5848642A (en) * 1981-09-18 1983-03-22 Nippon Kokan Kk <Nkk> Manufacture of unfired agglomerated ore
JPH0660359B2 (en) * 1985-01-14 1994-08-10 新日本製鐵株式会社 Method for producing unfired agglomerated ore
CN1158903A (en) * 1996-12-03 1997-09-10 吕美竺 Industrial production method of cold-cured pellet used directly for iron and steel smelting
US7896963B2 (en) * 2003-09-23 2011-03-01 Hanqing Liu Self-reducing, cold-bonded pellets
KR101368541B1 (en) * 2010-12-28 2014-02-27 주식회사 포스코 Smelting reductant for the use of molten stainless steel and a smelting reduction method using the same
CN103436694A (en) * 2013-09-04 2013-12-11 宁夏天元锰业有限公司 Method for preparing chrome ore pellets
CN104962763B (en) * 2015-05-25 2016-11-30 北京科技大学 A kind of crystalline silicon cutting waste material produces the method for chromium system ferroalloy

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947267A (en) * 1973-07-23 1976-03-30 Armco Steel Corporation Process for making stainless steel
JPS50130615A (en) * 1974-04-02 1975-10-16
US5654976A (en) * 1995-04-18 1997-08-05 Elkem Technology A/S Method for melting ferrous scrap metal and chromite in a submerged arc furnace to produce a chromium containing iron
WO2010103343A1 (en) * 2009-03-10 2010-09-16 Tata Steel (Kzn) (Pty) Limited An improved process for production of high carbon ferrochrome (hcfecr) and charge chrome with the use of a new type of chromite ore agglomerates

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Publication number Publication date
ZA202101409B (en) 2023-10-25
JP2022501497A (en) 2022-01-06
TWI820222B (en) 2023-11-01
KR20210065943A (en) 2021-06-04
CN112689683A (en) 2021-04-20
SE2150308A1 (en) 2021-03-18
WO2020065134A1 (en) 2020-04-02
FI20185805A1 (en) 2020-03-27
JP7322141B2 (en) 2023-08-07
FI130393B (en) 2023-08-09
TW202024343A (en) 2020-07-01

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