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WO2014162322A2 - Procédé d'extraction de soufre et de métaux, sous forme d'oxyde, utilisables dans le procédé de waeltz, à partir de boues contenant du soufre et lesdits métaux - Google Patents

Procédé d'extraction de soufre et de métaux, sous forme d'oxyde, utilisables dans le procédé de waeltz, à partir de boues contenant du soufre et lesdits métaux Download PDF

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Publication number
WO2014162322A2
WO2014162322A2 PCT/IT2014/000088 IT2014000088W WO2014162322A2 WO 2014162322 A2 WO2014162322 A2 WO 2014162322A2 IT 2014000088 W IT2014000088 W IT 2014000088W WO 2014162322 A2 WO2014162322 A2 WO 2014162322A2
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WO
WIPO (PCT)
Prior art keywords
sulphur
metals
sox
reactor
process according
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/IT2014/000088
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English (en)
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WO2014162322A3 (fr
Inventor
Aldo Imerito
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.)
Ecotec Gestione Impianti SRL
Original Assignee
Ecotec Gestione Impianti SRL
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 Ecotec Gestione Impianti SRL filed Critical Ecotec Gestione Impianti SRL
Priority to EP14732422.2A priority Critical patent/EP2959027B1/fr
Publication of WO2014162322A2 publication Critical patent/WO2014162322A2/fr
Publication of WO2014162322A3 publication Critical patent/WO2014162322A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • C22B1/02—Roasting processes

Definitions

  • the present invention refers to the technical field of the recovery of sulphur.
  • the subject of the present invention is the extraction of sulphur and metals, in oxide form, usable in the Waeltz process, from muds containing compounds of sulphur and said metals, for example from muds of substances chemically similar to goethite and jarosite.
  • the industry for the production of zinc and lead due to the extraction yield of the typical processes of these activities, generates wastes still having remarkable contents of compounds containing zinc, lead and various valuable and precious metals (for example copper and silver) , together with significant amounts of compounds containing iron. Resulting from wet extraction/separation cycles, these residues generally are in form of semisolid mud, with content of imbibition water of about 35 - 40% by weight.
  • Such wastes are a blend or a mixture of substances chemically similar to goethite and jarosite, i.e. they are oxy-hydroxides (FeO ⁇ OH) or mixed sulfates- hydroxides, of MeFe 3 (SO 4 ) 2 (OH) 6 type (where Me is a metal) , mainly of iron, zinc, lead and, typically, sodium or potassium. In addition there are also, to a lesser degree, mixed sulfides of these same metals.
  • the Waeltz process is one of the pyrometallurgical processes industrially most applied in the field of recovery, from refuse or waste, of Zinc and other non- ferrous metals.
  • dusts mixed with coal and fluxes, are subjected to a pyrometallurgical processing in rotary drum furnace, under strongly reducing conditions; in this way, the separation of volatile components (zinc, lead, cadmium, etc.) to be recovered like zinc rich ashes is obtained (about 60% ZnO) from furnace exiting smoke.
  • Non-volatile oxides and metals, occurring in the dust are not recovered but remain in the slag exiting from the process.
  • the feed material for Waeltz process must have a content of sulphur compounds (expressed as elemental sulphur) not higher than 0.1% by weight.
  • a process based, as a whole, on the extraction by thermal oxidative route of sulphur compounds occurring in muds, for example in jarosite and/or goethite muds, with contemporary transformation of the occurring metals in recoverable and exploitable oxides, is therefore an object of the present invention.
  • the muds for example jarosite and/or goethite muds, optionally preventively dried at a temperature between 90 and 200°C, are fed in a suitable closed reactor and heated at a temperature higher than 1400°C, under oxidizing and oxygen rich atmosphere.
  • Such temperature can be obtained preferably in a reactor with thermal plasma systems, or EAF type (Electric Arc Furnace) .
  • EAF type Electro Arc Furnace
  • the sulphur compounds in form of SOx
  • the sulphur compounds are extracted by passing in vapor phase and are removed from the reactor along off-gas capture line.
  • the exploitable occurring metals (zinc, lead, copper, silver, but also iron) , thanks to the oxidizing atmosphere, remain in the melt bath, in oxide form; possible vaporized and off-gas transported metals (therefore still in oxidizing atmosphere) are transformed in metal oxide particles, which are recovered by special filters and reunited to the produced metallic oxides in the main reactor, which as a whole will be send as feed to the Waeltz process.
  • the melted metallic oxides are discharged from the reactor and fast cooled, so as to have an easy grindable product. These materials, reunited to oxide dusts recovered from the filters placed on the off-gas line, are ground at a suitable grain size and sent as a feed to a Waeltz plant. Sulphur, extracted from the melt bath by the off-gas line, is initially in form of SOx ( (SO 3 + SO 2 ) . After the elimination of the particulate matter consisting of metallic oxides, the gaseous flow containing SOx and oxygen is sent to a multistep processing system, where it is subjected to various reduction steps, in arc plasma reactors, in the presence of carbon and hydrogen.
  • Such system consists of a number of steps sufficient to maximize the extraction of sulphur from the gas; the number of steps is function of the composition of the incoming gas into the multistep system. Every step carries out the work of sulphur extraction, with a certain extraction yield from the gases being processes.
  • the single step acts on the gas in the following way: the gas is subjected to a plasma generated inside of a reactor under reducing atmosphere, by means of the addition of a carbon and/or hydrogen source.
  • the source of carbon and/or hydrogen consists of a gas (or a gas mixture) selected from the group consisting of H 2 , CH 4 , C 2 H 6 and combinations thereof.
  • the second step of the process acts in perfectly identical way to first one: the fraction of SO x that has not reacted in the first step, is subjected to a plasma generated inside a reactor kept under reducing atmosphere by means of the addition of a source of carbon and/or hydrogen.
  • the source of carbon or hydrogen consists of a gas (or a gas mixture) selected from the group consisting of H 2 , CH 4 , C 2 H 6 and combinations thereof.
  • H 2 S occurring in the gaseous flow is transformed in H 2 and elemental sulphur; the SO x are transformed mainly in elemental sulphur, H 2 S e COS; and the formation of CO/H 2 continues also
  • the third step (if it is necessary to be carried out) will perform the same work exactly as carried out by two previous steps and so on.
  • the residual gas mainly consisting of CO, H 2 , H 2 S, COS, plus a very little fraction of SO x , immediately will be cooled to a temperature lower than 50°C; this in order to allow the condensation and recovery in liquid form of the residual fraction of SO 3 , which is sent upstream to multistep process starting.
  • the residual fraction of SO 2 along with CO, H 2 , H 2 S and COS, is subjected to an arc plasma reducing treatment, without addition of exogenous reducing agents.
  • Such treatment results mainly in syngas (CO, H 2 , plus a minimal part of H 2 O, CO 2 , SO 2 ) , that will be accumulated and used for the production of heat and/or electric power .
  • figure 1 represents a flow-chart of an embodiment of the process according to the invention.
  • the reactor used in the test consists of an external enclosure made of AISI 316 stainless steel. Internally, the reactor is coated with refractory bricks of JM 32 type from ATT S.p.a. According to this configuration, cathode and anode consist of two horizontal, metallic bars positioned in such a way that the terminal tips, where sets off the spark, are located few millimeters to each other and the sample to be treated. Cathode and anode are moved in such a way that, after the electric arc/plasma ignition, the same remains triggered and effectively can run over the sample to be treated. In this test an electric arc is used; about DC 100 Volts are applied with a current value of 500 Ampere. The atmosphere inside of the reactor is oxygen enriched. The mud treatment has been carried for about 15 minutes, in order to assure the complete melting and reaction of all the sample; the melted product successively has been discharged and fast cooled, so as to result in a compact but easy grindable solid.
  • the system displays the loss of oxygen ions and undergoes a reticular rearrangement resulting in the formation of metal oxides at higher oxidation state.
  • all the present metallic elements are retained within the melt deriving solid matrix (with the exception of oxide micro-particulate matter, mechanically dragged within the off-gas flow) , while the sulphur containing compounds escape from the matrix and are collected along the off-gas capture line.
  • a section consisting of a filtering system (electrostatic filters) acting as capture device for the particulate solid matter, mainly consisting of As, Pb, Fe, Al, Zn, Cd, Cu, Mg metal oxides, thus allowing the recovery thereof.
  • particulate matter mainly consisting of As, Pb, Fe, Al, Zn, Cd, Cu, Mg metal oxides.
  • Such particulate matter is reunited to ground material coming from the melt cooling, homogenized and sent to Waeltz process.
  • the residual gases mainly SO x , O 2 , H 2 S (with traces of other gases like H 2 O and CO 2 ) are passed to the multistep treatment for the separation of sulphur.
  • the gas is conveyed into an aspiration system where it is reunited to a stoichiometrically adjusted, methane flow and injected in the first section of the multistep treatment.
  • It consists of a transferred arc plasma torch wherein 10 slms (standard liter per minute) of gaseous mixture consisting of about 150 g of SO 3 mixed with about 75 g of methane are injected. SO 3 present is converted in other compounds with a yield of about 91%. Due to the strongly reducing atmosphere, the main products from the transformation are:
  • the gas that has been subjected to plasma processing and transformed, is conveyed in an expansion room with a cooled wall where sulphur and part of the possibly formed water are condensed.
  • the residual gas mainly consisting of CO, H 2 , H 2 S and COS, plus residual SO 3 , is conveyed in a processing system wherein is subjected to strong electrical discharged.
  • a processing system consists of brass tube acting as channeling device towards two steel electrodes; between the electrodes an electric discharge is triggered thus resulting in molecular bond rupture.
  • the obtained ions pass in an expansion room, wherein there is a wall acting as heat exchanger, in order to allow the formed sulphur to be condensed thus avoiding to react again with hydrogen or carbon monoxide formed due to the passage through the electric discharge of COS e H 2 S.
  • the final result is the production of condensed sulphur, that is added to that obtained in the previous step and sent to be purified, and syngas mainly consisting of CO, H 2 , H 2 O, CO 2 and traces of other molecules, like evidenced by mass spectroscopy analysis.
  • the melt solid obtained from the reactor of sulphur oxidative extraction has the composition (not standardized) as reported in the following table /

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

Abstract

La présente invention concerne un procédé d'extraction de soufre et de métaux, sous forme d'oxyde, utilisables dans le procédé de Waeltz, à partir de boues contenant des composés de soufre et lesdits métaux, par exemple à partir de boues contenant des substances chimiquement similaires à la goéthite et à la jarosite. La figure 1 est un schéma représentant un mode de réalisation du procédé de l'invention.
PCT/IT2014/000088 2013-04-05 2014-03-31 Procédé d'extraction de soufre et de métaux, sous forme d'oxyde, utilisables dans le procédé de waeltz, à partir de boues contenant du soufre et lesdits métaux Ceased WO2014162322A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP14732422.2A EP2959027B1 (fr) 2013-04-05 2014-03-31 Procédé d'extraction de soufre et de métaux, sous forme d'oxyde, utilisables dans le procédé de waeltz, à partir de boues contenant du soufre et lesdits métaux

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITRM2013A000205 2013-04-05
IT000205A ITRM20130205A1 (it) 2013-04-05 2013-04-05 Procedimento per la estrazione di zolfo e di metalli, in forma di ossidi, utilizzabili nel processo waeltz, da fanghi che contengono composti dello zolfo e di detti metalli

Publications (2)

Publication Number Publication Date
WO2014162322A2 true WO2014162322A2 (fr) 2014-10-09
WO2014162322A3 WO2014162322A3 (fr) 2014-11-20

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PCT/IT2014/000088 Ceased WO2014162322A2 (fr) 2013-04-05 2014-03-31 Procédé d'extraction de soufre et de métaux, sous forme d'oxyde, utilisables dans le procédé de waeltz, à partir de boues contenant du soufre et lesdits métaux

Country Status (3)

Country Link
EP (1) EP2959027B1 (fr)
IT (1) ITRM20130205A1 (fr)
WO (1) WO2014162322A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020149777A1 (fr) * 2019-01-14 2020-07-23 Val'eas Recycling Solutions Ab Traitement d'un matériau à base de fer ferrique comprenant du zinc et du soufre

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2743282A1 (de) * 1977-09-27 1979-04-05 Metallgesellschaft Ag Waelzverfahren zur verfluechtigung von zink und blei aus eisenoxydhaltigen materialien
ES2104508B1 (es) * 1995-04-10 1998-07-01 Aser Sa Procedimiento para el tratamiento hidrometalurgico de depuracion de oxido waelz mediante su lixiviacion con carbonato sodico.
EP2082070A1 (fr) * 2006-11-02 2009-07-29 Umicore Récupération de métaux non ferreux à partir de sous-produits de l'industrie de production du zinc et du plomb utilisant la fusion électrique avec plasma immergé
WO2008002114A1 (fr) * 2006-12-20 2008-01-03 State Affiliate 'the Eastern Mining And Metallurgical Research Institute For Non-Ferrous Metals' Republic State Affiliate 'national Enterprise Of Complex Processing For Mineral And Raw Material Of The Procédé de transformation de matériaux contenant du plomb

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020149777A1 (fr) * 2019-01-14 2020-07-23 Val'eas Recycling Solutions Ab Traitement d'un matériau à base de fer ferrique comprenant du zinc et du soufre

Also Published As

Publication number Publication date
WO2014162322A3 (fr) 2014-11-20
ITRM20130205A1 (it) 2014-10-06
EP2959027B1 (fr) 2018-04-11
EP2959027A2 (fr) 2015-12-30

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