Scribd Logo
Загрузить

Добро пожаловать в Scribd!

  • US7951282B2Hydrometallurgical Processing of Manganese Containing Materials

    Загружено:

    trinh xuan hiep
    12 просмотров7 страниц
    chế biến quặng măngan

    Авторское право

    © © All Rights Reserved

    Доступные форматы

    PDF или читайте онлайн в Scribd

    Этот документ был вам полезен?

    Это неприемлемый материал?

    Пожаловаться на этот документ
    chế biến quặng măngan

    Авторское право:

    © All Rights Reserved
    Скачайте в формате PDF или читайте онлайн в Scribd
    Отметить как неприемлемый контент
    12 просмотров7 страниц

    US7951282B2Hydrometallurgical Processing of Manganese Containing Materials

    Загружено:

    trinh xuan hiep
    chế biến quặng măngan

    Авторское право:

    © All Rights Reserved
    Скачайте в формате PDF или читайте онлайн в Scribd
    Отметить как неприемлемый контент
    из 7
    2) United States Patent oy os) 03) wo ep @y 66) n 6s) G0) Ward Inventor Christopher Brett Ward, Attadale (AU) Assignee: Mesa Minerals Limited, Applecross au Notice: Subject to any disclaimer, the term ofthis, pateat is extended or adjusted under 38 USC. 154(b) by 1212 days Appl.Nos — 100801,277 PCT Filed: Oct. 1, 2008, PCTNo: — PETLAUaS/01298 $371 (0M), (2),(4)Date: Sep. 3, 2004 PCT Pub, Nos WO2004/033738 PCT Pub, Date: Ape: 22, 2004 Prior Publication Data S 2005)0103163A1 May 19, 2008 Foreign Application Priority Data ‘USO07951282B2 (10) Patent No. 4s) Date of Patent: US 7,951,282 B2 May 31, 2011 (32) US.CL 205/539; 205/540; 205/541; 205/542 '58) Flld of Classification Search, 205/539. 542 See application file for comple search history 66) References Cited US. PATENT DOCUMENTS 3301777 A 1967 Leonand 209290.11 MAME A$ 4196) Browne 20st FOREIGN PATENT DOCUMENTS be BUGS AL 10/1989 Wo woos i463" "41998 * cited by examiner Primary Examiner — Arua S Phase (74) Attornes, Agent, or Firm —Gottlied, Rockman & Reisman, Pc on ABSTRACT A proces forthe hydrometallurgical processing of manga ese containing materials, the process characterized by the ‘combination of a manganese dioxide containing feedstock Andanaeiie satutionto form an eile soutionto be leeches, fn passing a volume of sulphur dioxide gns through that Jeach solution as the leaching agent, whereby no sintering or roasting pretreatment step of the feedstock is underiaken and the levels of dthionate fon generated in the leach solution are 10,2002 (Av) 2ou2ss2042 shan shouts le cue a poe. forte produon of cleave mange inte, 3) mee Gein (200601) 22 Clans, Drawing Sheets 10 Ce ? Linens eae a ee a - wet ing] subbing Limestone.) Urestone ‘Sulphur, Leiter] a Lint Lime} Sweats Sine eo [tn | LK mening ae Manganese Jarosie _ Geothite venga surnie | hens pica poate aa eonereaae o 1 aes aan cupnse sendin eon Cen | EME lle chew A | testes fol be} 2s : Prat (sisting 9" cece EOIN Fg So 22 siege * Noutalsaton Sormge a Frvation 3H 1_f EMO Maing EMD EMD & Sizing Washing Screening aThlekening US 7,951,282 B2 Sheet 1 of 3 May 31, 2011 U.S, Patent ebei01S e Suipuaig yonpold Buluee.0g Buzis 9 Buyueyoiut 2 Bujuasiog Guiysem awa awa onenits z uonesiesnen Buyysru; te TD suuonoeyg PMCHE Yo fy, OM! mine) le “BBBIOIS % be Bi |e fT Wa, ne eae == —“rarem pesyeyouluida Esuobeoy id weg eBei0jg enpisou, apiyding rae Gun ie Nyse M or Onpisey wonenid | Segre yn Areno204 vensidesid voneiea cet Sern eens pola Coury Fotos, TH ‘2UO}SOUU/ 2u0}S0U] Su UHV YONA ne gj ~— Sulggnuos ean I id <-auoseuiry %) 5 GS ; zl U.S. Patent May 31, 2011 Sheet 2 of 3 US 7,951,282 B2 oo eo oc ee nN peat ee U.S. Patent May 31, 2011 Sheet 3 of 3 US 7,951,282 B2 eee eee Paelspet celled eee Se aes US 7,951,282 B2 1 HYDROME-TALLURGICAL PROCESSING OF "MANGANESE CONTAINING MATERIALS. FIELD OF THE INVENTION ‘The present invention relates to the hydrometallurgical processing of manganese containing materials. More paricu- Jay, the process ofthe present invention is intends to allow ‘efficient hydrometallugical processing of low-grade manga nese dioxide feedstock to produce manganese products, including electrolytic manganese dioxide. BACKGROUND ART Its generally known that manganese may be leached fom manganese dioxide containing ores using sulphur dioxide. However, the sulphur dioxide leaching of manganese dioxide ‘containing materials is also known to produce by-product 5 gl levels of dithionate fons in solution, With dthionate fon levels ofthis magnitude itis generally necessary 0 incorporate into any flow sheet a high capital cost stage, boing “oxidation” or “aging” The long residence times required to “oxidise” the dlithionste ion fom the >S gi levels dawn to lower than 1g are highly capital intensive. Tailure to contol dithionate levels in the production of 3 ‘manganese sulphate erysta prot has previously led othe ‘manganese dithionate contaminant in that product slowly reting o release sulphur dioxide gs. Ti. would prove advantageous io provide process wherchy low-grade manganese dioxide containing materials or feed- stock could provide manganese sulphate leach solutions with ‘level of dithionae on less than about 5 g/l, and preferably Jess than | gi The ability o recover manganese dioxide from low-grade Jeedstocks will avoid oat leat reduce the nced for further ‘manganese oe mining and andlsturbanee, bringing various ‘eaviroamental henelis, For example, the ulisation of man- _ganese tailings allows for conservation of existing resources Punter, theuse of hydnometalurgcal route forthe reduc tion of Ma(1¥} nogates the nee forthe use of gas fred kilns ‘oF hid bed reactors, feed stocks no longer need to be heated to about 1000" C.and then cooled prior to leaching, and there js lesser nee for carbon input, which in tm results i loser jreenhouse gas emissions. Sill further, the use of the relatively easily controlled hyctometallurgieal route allows monitoring ofthe soliton potential ofthe leach solution or siury thereby indicating ‘complete dissoltion of Mn(1V), The use ofthe sulphur dion ‘de leach provides complete conversion of Ma(IV) 1 Ma), thereby avoiding the prciction of leachable manganese spe- ‘ies in Solid residues. 0 o 2 In particular itis deste to produce clectoltic nose dione" EMD"), solionsconsiing elevated dition. ‘eton levels result in chemical reaction oscuring that elect shen and port ofthe PMD prc nthe clst= ‘witht serain occupational health and eevironmentl ise "Thepreceding dvetion othe Background et tended to focbate an understanding ofthe present invention only. 1 should be appreciated tht the discussion snot an ackaavs- egement or imisson that any of the material referred to ‘was pt of the common general knowledge in Australias the prot date of the application. TTvughout the specification, unless the context requires cherie, the Word “comprise” of variations sch a "Come pines” or “comprising”, will be understood to mp the Inclusion of a sated integer or group of integers but not the exclusion of any oer integer or group of integers DISCLOSURE OF THE INVENTION In accordance wih the present vention theres provided a poe or the hymen rea of mag Combination eo manganese done consiing aoock Sinan aide sotaionto form an acide solution tobeleschisd, apne volume of up oxide gn ugh a ‘easingpre-tenen' spol tock Gunderaken and thelevel ofithionate ion genertedin the leach soltion are Jes than about 5 Preferably He levels of dithionate ion generated ia the Jeach solution are lees than about 12 ‘Sil preferably the pi ofthe eich sfuton is msinained aes an bout 1. none form th aventio the leach sofution comprises a stury of manganese dioxide conning materia t# siry densky of ew than aout 10% wi less than about 120 gi manganese sulphate, 2 terpenture of grester than aboot 55° Cand ata pt of ess han about 1 1 athe form ofthe invention the manganese dioxide containing Fedstock contains les than about 0% manga Preferably, the leach solton has an ial soluble ion concentation of greater tan 4g. The ron is preferably in the for of eric sulphate (Py{80,),), The eros concen tration preferably msintsined at level below about 0 by providing an exces or residual amouut of manganese donde the sur” The ratio of ferric to ferrous may be monitored through the leach o enstre an oxidation redution potential (ORP) of $80mV, or above (vs Ag/AgCl reference electrode) “The sup oni ga s preferably posse through the Jeachsoluton overapestod ofa ess IO hours where) upto about 95% of manganese dioxide is disolved. Preferably the deach is condicte over period of between about 10 fo 1S our Preferably ones stoichiometrt amount of sulphur diox- fe has hoon added othe Teach soon to achieve 4 98% jon of the manganere dioxide presen, the reaction i ‘In accordance with present invention there is further pro vided a proces for the proluction of electrolytic manganese oxide, the process characterised by a leach of a manganese ‘ioxide containing feedstock, without a sintering or roasting pre-ireatment step of that feedstock, in which a volume of ulpurdiowie gos asthe leaching agents passed though an ‘acidic solution containing manganese dioxide, the dithionate jon levels in sad solotion being maintained at ess than about 5 w/the resulting leach solution being processed to provide an appropriate electrolyte that is passed To an electrowinning ‘lage during which electrolytic manganese dioxide is depos- ited. US 7,951,282 B2 3 Preferably, the levels of dithionate ion generated in the leach solution aze less than about 1 Sill preferably, the pH of the leach Solution is maintained at less than about 1.5, none form ofthe invention the leach solution comprises slurry of manganese dioxide containing material ata slurry density of less than about 10% wi less than about 120 gl ‘manganese sulphate, a temperature of greater than about 95° (C.,and at a pH of less than about 15. ‘In another form ofthe invention the manganese dioxide ‘containing feedstock contains less than 40% mangance, Preferably; the leach solution has an inital soluble iron ‘concentration of greater than 4 y/. The iron is preferably ia the form of ferric sulphate (Fe-(S0,),). The ferous eoncen- tration is preferably maintained ata level below about 05 pi by providing an excess of residual amount of manganese dioxide inthe slury The rato of ferric to Ferrous may be monitored throughout the leach to ensure an oxidation reduction potential (ORP) of 550 mV; or above (vs Ag/AgCl reference electra). "The sulphur dioxide gas is preferably passed through the Jeach solution over period ofa least 10 hours whereby up t0 about 95% of manganese dioxide is dissolved. Preferably, the Jeach is conducted over a period of between about 10 0 1S hours, Preferably, once a stoichiometric amount of sulphur diox- ide has beet added tothe leach solution to achieve a 95% 95°C. The leach solution is maintained aa pH of ess than about 1.5 The leach solution within the leach 16has an initial soluble ‘ro concentration of >4 gl. The ioa is in the form of feric sulphate (Fe,(SO,),). The ferrous concentration is main- ‘ainedat lessthan 0.3 p/ by ensuring there isla an excess ‘residual amount of manganese dioxide in the leach. ‘The leach is conducted over a period of 10 to 1S hours by passing a volume of sulphur dioxide gos through the lech Solution, The rate at which the sulphur dioside is passed throughtbe lech solutions governed by the requirement that Lup to 95% of the manganese dioxide inthe slurry fed to the leach 16 is dissolwed/solbilized over the period of 10 10 1S ‘hours. Is envisaged that longer time perils may be tlse ‘he ratioofferieto ferrous in the leach 16 is monitored by ‘an Oxidation Reduction Potential (ORP) probe. minimum value of 550 mV is roqured (vs Ag/AgCl reference elee- {mde}. Ifthe ORD vale falls below $50 mV more Feedstock sum is added to the leach 16. Is believed thatthe predominant leaching reaction pro coeds 28 flows: However, itis understood that whilst the process of the present invention ensures thatthe production of manganese sulphate isthe predominant reaetion, trae of dthionate is stil generated. The production of ditionate is believed 10 proceed as. free radial combination resetion as follows High pH values favour the production of dithionate. As seh the pH ofthe leach 16 is maintained at Fess than about 15,88 noted hereinabove. Once a stoichiometric quantity of sulphur dioxide 20 has ‘ben fed throngh the lel solution, wherchy a maxiniim of 95% ofthe manganese dioxide present is dissolved solu lized, dhe reaction is halted by withdrawing the sulphur diox- {de20 feed tothe leach 16. The stoichiometic aldition of SO, is represented griphically in PIG. 2 relative othe % mung nese leached and the Fh, showing that the Fh or solution potential provides an accurate indication of eompletion ofthe ‘manganese (IV) dissolution reaction, whit FIG, 3 demon- strats the effect of sulphur dioxide addition on the % man- saanese leached over time. Its envisaged tht the sulphur dioxide 20 might also be provided as a waste gas from a smelting or an industrial be added t the phite solution (S02), ‘The remainder ofthe process 10 forthe production of EMD involves the passing of pregnant leach solution oa jarsiting step 22 to reduce potassium and sodium levels as desired. A oethiting step 24 is thon used to reduce iron levels to sub- ‘pm levels though the addition of ground limestone, A solid Jiguid separation step is thon use, involving both thickening 2 aad filtation 28 ‘Solids from the filtration 28 are washed to relaim any resiual manganese sulphate solution, this being. fed back to the loach 16 to make up any volume lost from the return electrolyte 17 to a manganese sulphate bleed stream 30. This bleed sircam 30 allows manganese sulphate to be conc rently produced for use in fertilisers, for example US 7,951,282 B2 5 Ovetow from the thickening 26is pase t a sulpiding step 2 forthe removal of heavy metals, including ick ‘obaltand molybdenum, Following the sulphiingstep 32 the heavy metal sulphides are removed by presareilaion 34 an he eleetolye from the eecrownning step 18 held in orage take 36 The electowinning stp 18 then proceeds using sub- merged titanium anodes, tubular copper cathodes and totally wax free envionment. Fully laden apdes are are tested ons two-weekly cycle with rming EMD chip being pesado dee ces peck operations specifically at ites inthe leaching of manganese com. tSning fe stocks to prodice leach solution wih dihonate fone ofa than Sp andthe wy applied othe proceso ypes oF manganese dion ning oes Ginloing bot igh and ow te), ine lings, fies, fumes ad talings of manganese feralloy prodietion facilities, ocean Moor manganese ns, eo fanganesenodites, wastes fom zine refinery cells and man- ‘Emcee diode contained in used or paralysed alkaline or ‘arbor zinc bates. The leach solution generedby repro ‘essing such materials in aeordanoe with the present inven thoean then be purified and used inthe production of EMD, EMM and othr manganese chemieal products Modifications and varias ch a would be apparett to the skilled adresse are considered oil within the scope of the present invention “the invention eaimed i 1.A proces forthe iydrometallungiealprocesing of man- ance containing materials, the process characterised by combining manganese dioxide containing feedstock hav- ing Tos than 40% Mn with an ace solution wo form a leach solution; and leaching he each solution by passing vokume of sulphur inde pasos the leaching agen through sid Teach sclition fo produce a manganese compen, ‘wife mating the lvel of dinate on generated in the leach soliton ars than about 5 g/ by maintaining annexcessoftmanganese dioxin elec sluionand indiataning the oxidation reduction potential of the leach solution at a fevel of at last sbout 550 mV (vs [ABIAgCT reference elecrod),whervin the leah sli tion frther contains levels of sable fon ant the fer ‘os concenration is maintained ata feve blow about O05 pi by the exces of manganese donde 2.A process acconlng io claim 1, wherein the level of hist on generate inthe fac solutions mainsined at des than about Tg 3A process according to claim 1, wherein the pH ofthe dea sluton is mained at les han about 1.5 “4A proces according to claim 1, wherein the leach solt- sion comprises a slur of manganese dioxide contiing imate ata sry density of les than aboot 10% wy ess than sbout 120 gf manganese sulphate, a temperature of seater tan sbout 95°C and ata po ess han about 1.5 3. A proces according to elatt 1, wherein the inital soluble ion concentration nthe leach slain greater than al “A process aoconingto claim §, wherein the ions inthe form of ferric sulphate (Fe,(SO,)s). "7A process acconiing to cain 1, wherein the ratio of {eri to ferrous is monitored atleast intervals thoughout the leach A process according to claim 1, wherein the sulphur Aion asin posse tough the each solution over period ‘fat ess 10 hous, whereby up o about 95% of manganese Aone is dissolved 0 o 6 9. A process according to claim 1, wherein the leach is conducted ever a period of between about 10 0 about 1S hours. 10. A process according to clam 1, whercin the reaction is halted once a stoichiometric amount of sulphur dioxide has ‘been added to the leach solution so as 10 achieve a 95% issolution of the manganese dioxide present 11.A process forthe production of electrolytic manganese ioxide, the process characterised by: «leach of manganese dioxide containing feedstock hav ing les than 40% Ma, ia which a volume of sulphur dioxide gas as the leaching ayent is passed through sid feedstock combined with an acidic solution, the dithion- stein levels in the resulting leach solution being main- tained at less than about 5 g/Iby maintaininganexcessof manganese dioxide in the leach solution and maintain- ing the oxidation reduction potential of the leach sok tion at a level of at least about 550 mV’ (vs AMARC] reference electtode, wherein the leah solution further ‘contains levels of soluble ion and the ferous concen ‘ation is maintained st a level below about 0.5 g/l by the ‘excess of manganese dioxide; and processing the resuling leach solution to provide an appeo- priate electrolyte that is passed to an electrowinning Stage during which electrolytic manganese dioxide is deposited, 12, A process according to claim 11, wherein the levels of

    Вам также может понравиться