WO2016044862A1 - Synthese au four a arc a courant continu d'alliages de ferromanganese et de metal raffines - Google Patents

Synthese au four a arc a courant continu d'alliages de ferromanganese et de metal raffines Download PDF

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Publication number
WO2016044862A1
WO2016044862A1 PCT/ZA2015/000032 ZA2015000032W WO2016044862A1 WO 2016044862 A1 WO2016044862 A1 WO 2016044862A1 ZA 2015000032 W ZA2015000032 W ZA 2015000032W WO 2016044862 A1 WO2016044862 A1 WO 2016044862A1
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WO
WIPO (PCT)
Prior art keywords
manganese
gas
furnace
product
reaction zone
Prior art date
Application number
PCT/ZA2015/000032
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English (en)
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WO2016044862A9 (fr
Inventor
Vernon Harding
Jacques BEYLEFELD
Original Assignee
Vernon Harding
Beylefeld Jacques
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 Vernon Harding, Beylefeld Jacques filed Critical Vernon Harding
Priority to EP15784259.2A priority Critical patent/EP3137636A1/fr
Publication of WO2016044862A1 publication Critical patent/WO2016044862A1/fr
Publication of WO2016044862A9 publication Critical patent/WO2016044862A9/fr

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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
    • C21C5/52—Manufacture of steel in electric furnaces
    • C21C5/5229—Manufacture of steel in electric furnaces in a direct current [DC] electric arc furnace
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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 resent invention is in the technical field of pyaametaliuray and relates te method of producing refined ar nitrated feiromangaoese alloye or metal so o DC are free ace.
  • nlaaganese is usee , principally, in steel and staiatess steel production .
  • the bulk of manganese product produced today consists of low or lewc:" grade high carbonalooaseaaganese tbiC mkTv ⁇ .: of feraesCeoewaioeimse ( eJVlnSi ss ⁇ ; with b n content of between 60 - ⁇ 80%, which principally a produced ' employing carbathernric reduction in an AC moeneetgeo " arc furnace. ⁇ 00 ⁇
  • a high grade manganese product ' means r alloy or metal product. In which manganese Is present In a concentration of at leas! 76% (m/mV arc;; car-ben ;s present In a concentration less than 2% mpop.
  • the Invention provides for a pyrouwtallurglcal method tor producing a first high grape a oca msec product by reducing a manganese oxcie reacts ni . Irs a test, reaction zone within a c. ;o rem vessel DC! arc furn ce, with a reducing agent w an inert or nitrogen rich atrnespnere.
  • the manganese oxide or acta of may be Input io the furnace as pa t of a ⁇ 0 D 121 ] " he reduction may be alumirmthermm wherein the reducing agen s elemloaoe added to t ie furnace as part of the charge in a arse granulated form te ⁇ as chips,
  • the tee ⁇ mi on may be slllcotherrosc, wherein the reducing aga f is slllcao or ferroessocn.
  • the first reaction acne may be a sollu/tlqald phase comprising cf e slag layer and an underlying eietsl/alioy layer, Odl SI
  • the temperature of the horr reaction soee may be In a range l o00 ';': C lo IPeiPC fb ' eferabha the tem e atu e range o? the reacbon aone is 1 700 '::' C to leOCeTT
  • Manganese product may be manganese or a bete or ferroseoo alloy of manganese.
  • the Inert or estrogen rich atmosphere ⁇ may bo achieved- e imtodmrng. ia ao Interior of t e closed vessel DC arc fumaca ; an men. gas or ni ogen respectively.
  • the Introduction of the men gas or nitrogen may purge the vessel of prior gas content.
  • nitrogen Is introduced to mak u at mash 95% of the atmosphere.
  • a second mgh grade niaeganese product may be produced by oxidaean cf a. vapour of the first loon grade manganese product, for usancee -meoriaee mamgaoese, a second reaction zone, veth irogeo,
  • the second high grace rnancanese product may ae a manganese ohrlda.
  • the manganese nitooe may be one or more of the following . nN, Mn$ ;- s dryhT rOr; 3 ⁇ 4 N; ; and naa.
  • the arytjanese nonde so olcoN Preferably : the arytjanese nonde so olcoN.
  • the second reaoaoo zone may occur ithin a gee hase
  • the second, raaouoo zona may be located above the nqeid/soHa phaaa within the furnace and may extend to an off-gas ioaated within an off-gas conduit which removes an off- gas from the furnace.
  • the temperature of the second reaction ser e may be be w l oiTC. preferably ct a range uOCoC to 1 19CTC.
  • the maogunese nitride e pay co extracted from the second reaction cone and separated irorn other off-gas content by mf ration.
  • the tirterea manganese nitbde may be reanad or recycled to tine furnace os part of the charge, ddlSj
  • the first high grade manganese product and niangaaese nitride may be refined by passing a refining can through a aessei (ladley containing rrioifeo product ar ooodo ; and allowing the refining gas to percolate it ; rough the product or i ,0":U;, " > .C)026j
  • the refinrng gas may be oxygen or ao.
  • nt may be an one preferably a oa cinod ore.
  • the ore may be one or more of the following: pyroiuaihe brairnTo haasnweoite, rhodonite * psilonvelane, rnaoganite rtmdooraosi o ana aracanoeakTo [002S]
  • the manganese o ide rescfant may be or manganese nerewa waste stream, for sxacyple a dust or sludge asLo stream or a high grade slag.
  • a fluxing agent may be hit reduced, web the charge, to the brraaee ia control one or mere of the following pararaeiers: the viscosity of the slag layer; are melting point of the st g l er, the capacity of the siag layer to absorb phosphorous and the capacity of the slag layer or absorb sappelcm 00301
  • the dax g agent may da CaO. gO or SdA based.
  • Figure ' i is a process diagram., which Includes the nielloed of the leverblom Illustrating major egyspraent ana process flows; ace
  • Figure 2 is a process flow diagram focussing or; the process steps of the method a? the nvention.
  • Figt.ce 1 of the accompanying drawings illustrates a process a), wlind Includes a method of the invention ltd illustrated in greater ' de il -n figure 2. in which a high grade manganese product 14 Is produced from a nmaganeoe exam
  • Hie manganese oxide input I S can be an ore ; such as. tor example pyrotuslte, braunite, hausraanrria, rhooonPe. gsHomefaae. rnanyar e, rhodoehioshe and mangsnoeakdte.
  • the manganese oxide Inpol can also be manganese bearing waste stream m:cn as oust sludge or a high grade slag.
  • an ore such as pyroluslte (h1rr0;d ;s used in the process 10.
  • [C 0341 Ore mafebal Is temporarily stored In stockpiles 6 before reporting to a separator 18 widen separates an oversize fraction from a sized fraction 20 of the ore rnateriah
  • This si ed fraction Is wran to a calciaer 22, with or wrihonr the addihou of limestone menemtlng upon the ore typed and me::.; oc:! ?o thermally decom ose the oxides, each as pyroieslte : or carbonates, snob as rhodorxte, of the ore., removing volatile Tactions and producing a manganese ore.
  • he calcined ore 24 reports to a batching system 20.. which intdaaes plurality of Iropgers, respectively designated 2BA. 2SB, 28C , . , 2820 each of reach a dedicated to rear. I so a furnace feed mgmde t one of which Is the calosreo ore 2-0
  • the other furnace feed ingredients include a fluxing agent 3D ami a reducing agora. 32, in the form of granules or sized scrap, which ;n das particular embodiment is aluminium , in other enrnw earns of the invention, employing sTe teuTale reduction, the redticing agent 32 can be silicon., metal or.
  • Recycled product froni the smelting process such as manganese ni rides, can be input to the furnace feed at this stage This will be explained below In more
  • each hopper releases Its respective content, of ore 24, fluxing agent 30 or alumlreum 32 at a predefined power to feed rate rape.
  • a mixer 34 which mixes tie:: feed ingredients sen a feed me: 33 before release to a DC mat; or: a or tilt g DC arc ! urease 36.
  • the cuxx.es of the invention 12 employs stationary orbiting DC arc Ouosce 36 which l as a dosed vessel body 33.
  • the roof of tret dosed vessel body a pierced by a plurality of toed chutes 40 ⁇ through which he teed ram 35 Is introduced to an Interior of the furnace 3n and an off-gas duet 42, through, which gas and dust partsoies leave the furnace.
  • h.v electrode 44 (see Figure .2). carryiryg a DC current, penetrates the vessel 38 to termi a e, at an Interior end 43 1 lust above ar ; even bath 48 of furnace s: net content.
  • vassal body is further penetrated, at respective sides, by a metal and slag tapboie ; respectively designa ed 50A and 50B ; (or In the ease of a tlrbng t)Ct furnace, a single pouring spent 301, througb which a metal or elioy product 51 and elan 62A is released from the furnace.
  • the cues bath 43 comprises an upper ' queH d slag layer 62, of flux and elomlnium oxides, at a temperature typically In the range 1700 ⁇ 1800 ::' C aun 3 ⁇ 4 lower metal layer or alloy layer 54, at a vwwomturc typically In the r nge 1600 ⁇ ⁇ 17QCFC.
  • a temperature typically In the range 1700 ⁇ 1800 ::' C aun 3 ⁇ 4 lower metal layer or alloy layer 54 at a vwwomturc typically In the r nge 1600 ⁇ ⁇ 17QCFC.
  • temperatures exceed 20G0 ':' C m the are between electrode 44 and open nap; 48; the fed ' mi iegjefies. reacts and separates between the slag lager 52 and the n etai/ahoy iayer 54.
  • Tfre nitride synthesis process represented ; n equations 8 and 4. can produce one or more of -many possible manganese nitride orooeofs, such as; iVin id . ni;N>- . ; ; ssnsNc : fTire and Pli1 ⁇ 4 .
  • the manganese nitrides are separated from the gaseous (00471 Reaction of the gaseous nzwar om: occam w ere the tem rature e> m a range 800 * 0 to 1 1 OCT;, A crop in temperaiore to wit in this range occurs in off gas found sn the eft-gas mar ⁇ between a furnace ofagas .out et 0? and a dry pas cleaning facility 58 (hereinafter referred to as a "gas reaction zone "' ⁇ .
  • nitride nitride products can produoe one or more of many possible manganese nitride products, .such as: nfT ru & nuzPn. iv3 ⁇ 4N and n.o .
  • the preferable product s efrpTd fOOSO
  • These manganese nitrides ru e sol ds which in the fo rn of dust particles, report to the harm abatement and dry gas cleaning facility 58 as pari of the off -pas stream, in the facility, fire manganese nithces are separated fro -he gaseous components of the off-gas stream, on a series of High temperature ars ⁇ not shown) housed within the facility 58.
  • T ' he nitrogen stream 59 is inns produced by the separatism with this stream channelled back to the gas reaction zone in the of 6 gas duct me some of this streams being released to the atmosphere, dye mount depending upon m ps m a This ;s illustrated in Figaro 1 .
  • O Si ' l The filtered, separated manganese nltnde pardcies 60 tod into collection funnels 82, beneath toe facliity S8. to be channelled aiong ana of two optional processing streams: a recycle stream 64, or a redoing stream 66. These wry streams are Illustrated in F gure 6
  • the recycle stream 64 comprising the manganese nltnde product 66. reports to the batching system 26 to ro i part at the fed mix 35 as reqused hire product 66 of the refining stream 66 reports to e ladle pas refining system 66.
  • the manganese .nitride product 58 can be an important component of toe fed mix 3d to monism the mesons parameters of the smelting process with n the furnace 36.
  • This regulation should higher concentrations yd manganese be required in: d fed mix 36. and ultimately In the end product 64; and should em temperature need to be mo unco within the furnace: manganese nitride can be recycled into the feed mix.
  • T ' he manganese nitride has a temperature quenching effect, an Important function when the temperature within the furnace 36 needs to be optimally regulated.
  • the manganese nitride pmdaet 66 is e high grade manganese product m Itself.
  • T ' he product 66 can he mechanically agglomerated, aided by the use of hinders, and sold as briquettes or pellets.
  • the gas rePrang eastern 68 is interposed between tea furnace 36 ana Pa; enai sizian pracess 55. in the process of gas refining, the moiten raetai aiiay a- tea oca; taphoie 50A into a iaoie ?D (or a series of iaeies) which has a paraas ceramic aiaa at as ease. it is through this porous l g that a refining gas, Poai a gas streaia 72 ; permeates the inane to pewsiale through the sawon rneiai alien content 74 of
  • i OP 5 at he refining gas principally, comprises oxygen .
  • This gas sen aiaa be an.
  • Percoiafing exygee through the isdie content 74 has the effect at oxidising P impacties or contaminants tyeieaPe ' anna in a manganese rnetei / aiiay semi ; , product, Eaarnaies of Phase aaataaiioants include Ca . hasp ha Ai .
  • Sulphur and phosphorous are camaaon nereraelaPc aantaeiinaias ai a ioetai/aiiay araaaat- The reduction of these cantaraiaaats in the matai/aiioy predeel.
  • the refirsaa aaa caa include inert gasses in a aaa oas ta reduce the paces ureas w e of CP aaa CO arid aid in aPrriaa the ceaienis 74 of tea iodic 70.
  • f0666J The com osition of the flexing agent 30 Infroclueed to the freaane 36 as part of one ocs mix Id; ;s an m ortan variable n> the smeihag p oc ss eras consequently., to the efficiency of this process and ultimately the rvmnooshlen of tire product 14 hoed
  • Raxing of a slag is done to reduce the melting point and viscosity of the Day layer 52. This has the enact of improving manganese metal or alley recovery- by rodncing the aianganese oxide content of trie slog layer 62 and, h r r symbolized viscosity of this layer, allowing toe. metal/alloy product 14 p.: separata from tire clap I n nance and settle, by grawly ami the additional forces c e ted by the 130 coupling or current flow ( ' from catnode/eleatrade to anode). Into 6a, metahalloy layer ' 54 tin recovery.
  • SiOD Silicon -oxide

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne un procédé pyrométallurgique pour la production d'un premier produit de manganèse de haute qualité par réduction d'un réactif d'oxyde de manganèse dans une première zone de réaction dans un four à arc à courant continu à cuve fermée, avec un agent de réduction, sous une atmosphère inerte ou riche en azote.
PCT/ZA2015/000032 2014-04-28 2015-04-28 Synthese au four a arc a courant continu d'alliages de ferromanganese et de metal raffines WO2016044862A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP15784259.2A EP3137636A1 (fr) 2014-04-28 2015-04-28 Synthese au four a arc a courant continu d'alliages de ferromanganese et de metal raffines

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ZA201402856 2014-04-28
ZA2014/02856 2014-04-28

Publications (2)

Publication Number Publication Date
WO2016044862A1 true WO2016044862A1 (fr) 2016-03-24
WO2016044862A9 WO2016044862A9 (fr) 2016-07-14

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EP (1) EP3137636A1 (fr)
WO (1) WO2016044862A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE889593A (fr) * 1980-07-18 1981-11-03 Uddeholms Ab Procede de traitement d'alliages
WO2004110104A1 (fr) * 2003-06-04 2004-12-16 Sms Demag Aktiengesellschaft Four a arc a courant continu

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE889593A (fr) * 1980-07-18 1981-11-03 Uddeholms Ab Procede de traitement d'alliages
WO2004110104A1 (fr) * 2003-06-04 2004-12-16 Sms Demag Aktiengesellschaft Four a arc a courant continu

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Publication number Publication date
EP3137636A1 (fr) 2017-03-08
WO2016044862A9 (fr) 2016-07-14

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