FI126061B - Autoclave for pressure oxidation - Google Patents

Autoclave for pressure oxidation Download PDF

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Publication number
FI126061B
FI126061B FI20136261A FI20136261A FI126061B FI 126061 B FI126061 B FI 126061B FI 20136261 A FI20136261 A FI 20136261A FI 20136261 A FI20136261 A FI 20136261A FI 126061 B FI126061 B FI 126061B
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Finland
Prior art keywords
titanium
layer
autoclave
tin
tin layer
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FI20136261A
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Finnish (fi)
Swedish (sv)
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FI20136261A (en
Inventor
Mari Lindgren
John O'callaghan
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Outotec Finland Oy
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Publication date
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Priority to FI20136261A priority Critical patent/FI126061B/en
Priority to PCT/FI2014/050986 priority patent/WO2015086909A1/en
Publication of FI20136261A publication Critical patent/FI20136261A/en
Application granted granted Critical
Publication of FI126061B publication Critical patent/FI126061B/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J3/00—Processes of utilising sub-atmospheric or super-atmospheric pressure to effect chemical or physical change of matter; Apparatus therefor
    • B01J3/04—Pressure vessels, e.g. autoclaves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/365—Selection of non-metallic compositions of coating materials either alone or conjoint with selection of soldering or welding materials
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/02—Apparatus therefor
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00743—Feeding or discharging of solids
    • B01J2208/00769—Details of feeding or discharging
    • B01J2208/00787—Bringing the solid in the form of a slurry before feeding it to the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
    • B01J2219/0236—Metal based
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
    • B01J2219/0277—Metal based
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Description

Autoclave for Pressure Oxidation
FIELD OF THE INVENTION
The invention relates to autoclaves for pressure oxidation (POX) of slurried ores and concentrates, in particular to brickless POX autoclaves.
BACKGROUND OF THE INVENTION
Autoclaves utilized in leaching operations of slurried ores and concentrates requiring elevated temperatures and pressures are subject to highly corrosive and erosive environment. Examples of such processes include pressure oxidation (POX) of sulfide ores and concentrates and high pressure acid leaching (HPAL) of nickel laterites. In many processes, maintenance and downtime associated with autoclave wear and failure can be substantial.
In pressure oxidation (POX) of sulphide ores and concentrates silicate based bricks are used to provide wear protection in the autoclave while lead, furan or alloys like Inconel provide corrosion resistance between the carbon steel shell and the bricks. However, failure of bricks is common and the wear-course of the bricks need frequent replacement at high cost. For gold POX autoclave the top-course of the vapour phase bricks require replacement every 2 to 5 years and with the slurry phase every 5 to 7 years.
In addition to regular replacement the bricks are also very sensitive to pressure induced failure and it is not uncommon for whole sections of brick work to be lost during an accidental de-pressurization of an autoclave. Hence accidental brick failure and planned brick repairs are major causes of autoclave downtime.
In high pressure acid leaching (HPAL) of nickel laterites, the use of bricks has been successfully substituted by constructing the autoclaves using plates of titanium-clad steel. The titanium and steel plates are positioned one adjacent to another and welded together. However, in the POX autoclaves the use of titanium is limited mainly to the slurry phase. Bricks are still used for the main shell lining due to the risk of titanium fire which would lead to serious failure of the shell if ignited.
BRIEF DESCRIPTION OF THE INVENTION
It is thus an object of the present invention to provide a brickless autoclave for pressure oxidation of slurried ores and concentration having a TiN layer on the interior surface of the shell so as to overcome the above prob- lems. The objects of the invention are achieved by an autoclave which is characterized by what is stated in the relevant independent claims. The preferred embodiments of the invention are disclosed in the dependent claims.
The invention is based on the realization that autoclaves composed of plates of titanium-clad steel can be utilized in leaching operations of slurried ores and concentrates requiring elevated temperatures and pressures if the titanium surface which comes to contact with the slurried ores and/or concentrates and oxygen is converted into a thick, tenacious and hard titanium nitride (TiN) layer. This will provide a POX autoclave with enhanced wear resistance without the risks associated with non-coated titanium. A TiN layer on the interior surface of the autoclave provides enhanced wear-resistance and hardness while TiN does not ignite and burn like titanium. In order to ignite titanium fire a fresh surface of titanium is required. When the inner surface of an autoclave is coated with a thick layer of TiN, there is no pure titanium that could become exposed and ignite as all titanium is converted into titanium nitrides.
Furthermore, TiN is chemically inert under the leaching conditions of slurried ores and concentrates requiring elevated temperatures and pressures. TiN layer formed by diffusion process from existing titanium material is 100% dense and defect free and metallurgical^ bonded to the substrate. This is a significant advantage over e.g. spray coatings that always contain porosity and are only mechanically anchored to the substrate preventing their use in protecting load-bearing structures. TiN layer is metallurgical^ bonded to the substrate meaning that it is not possible for the layer to be detached from the surface under any conditions.
BRIEF DESCRIPTION OF THE DRAWINGS
In the following the invention will be described in greater detail by means of preferred embodiments with reference to the attached [accompanying] drawings, in which
Figure 1 shows a cross section of an autoclave of the present invention;
Figure 2 shows a TiN layer etched with Kroll’s reagent to reveal the extension of the diffusion layer;
Figure 3 shows hardness value (HV) measured from the cross-section of TiN coated titanium sheet;
Figure 4 shows wear test results of a TiN layer as compared to titanium and conventional autoclave coatings.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to an autoclave for pressure oxidation of slurried ores and/or concentrates comprising a main shell having an outer layer and an interior layer. The inner side of the autoclave, i.e. the interior layer, which is exposed to the slurried ores and/or concentrates and oxygen, is composed of titanium or titanium alloy and a titanium nitride (TiN) layer, whereby the TiN layer is formed on the surface of the titanium or titanium alloy so that the TiN layer covers the surface of the titanium or titanium alloy and only the TiN layer comes into contact with the slurried ores and/or concentrates and oxygen. Thus the TiN layer prevents the exposure of metallic titanium to oxygen while the TiN layer itself comes into contact with the slurried ores and/or concentrates and oxygen.
The present invention accordingly provides an autoclave for pressure oxidation of slurried ores and/or concentrates, wherein the interior layer of the autoclave is composed of titanium or titanium alloy having a TiN layer on its surface, the TiN layer coming into contact with the slurried ores and/or concentrates and oxygen and preventing exposure of titanium to oxygen.
Figure 1 shows an example of an autoclave of the present invention. 1a illustrates a cross-section of the autoclave and 1b shows a detail of the different layers of the main shell of the autoclave. The outer layer of the main shell of the autoclave is in this example composed of steel. The thickness of the steel layer is typically from 50 to 100 mm. The steel layer is covered by a titanium layer which is bonded through the use of chemical explosives, i.e. explosion welded, to the steel layer. The titanium layer is further covered by a TiN layer formed on the surface of the titanium or titanium alloy so that the TiN layer covers the surface of the titanium layer and only the TiN layer comes into contact with the slurried ores and/or concentrates and oxygen. The thickness of the titanium layer is typically from 8 to 10 mm. The thickness of the TiN layer is from 3 to 5 mm.
The TiN layer may be formed by nitriding the surface of the titanium or titanium alloy. The TiN layer may be formed e.g. by welding. Nitrogen absorbed on the surface of the interior layer during the nitriding process diffuses into the titanium or titanium alloy. It forms a TiN compound layer and a so called diffusion zone where nitrogen exists as an interstitial solution in the titanium phase. The resulting TiN layer is thus metallurgical^ bonded to the substrate and will not be detached. This is an advantage over spray coatings that rely on mechanical anchoring and can be detached from the surface under some conditions.
The TiN layer prevents exposure of titanium to oxygen and thus ignition of titanium fire. Exposure of metallic titanium by abrasion or scratching of the protective layer is possible when spray coatings are utilized or in applications where the thickness of the coating layer is small e.g. T1O2 coatings. This can be avoided with the TiN layer.
Preferably the TiN layer has a thickness of 1 to 5 mm, more preferably from 3 to 4 mm. A thickness of at least 1 mm is sufficient for providing protection against scratching. The thickness of the TiN layer may be determined for example by optical microscopy of a cross-section of the treated material. Herein the thickness refers to the total thickness of the TiN compound layer and the diffusion zone. Figure 2 shows a TiN layer on a titanium sheet etched with a Kroll’s reagent to reveal the extension of the diffusion layer. Black arrow shows the metallurgical bond between the TiN/diffusion layer and titanium substrate.
Furthermore, the TiN layer has high wear resistance under high temperature erosion-corrosion conditions owning to its hardness. Hardness measurements of Figure 3 show that the hardness of the surface of a TiN coating is about 600 HV, which is almost double compared to the hardness of a super duplex stainless steel. Hardness was measured according to the Vickers hardness test (ASTM E384-11e1). The initial hardness of titanium and titanium alloys varies usually between 100 and 250 HV depending on the chemical composition of the material. Various techniques known in the art can be utilized for measuring the wear resistance of the TiN layer.
In accordance with the present invention the hardness value (HV) of the TiN layer is preferably at least 300 HV, more preferably from 450 to 1800 HV, most preferably from 550 to 800 HV. The hardness of the TiN layer can be controlled by changing the different processing parameters depending on the type of nitriding.
In accordance with an aspect of the present invention the outer layer of the main shell of the autoclave is preferably composed of carbon steel. The interior layer composed of titanium or titanium alloy is preferably bonded to the outer layer by explosion welding. Alternatively it can be bonded by any other similar technique giving sufficiently high quality metallurgical bond. In an further example of the present invention the main shell of the autoclave com prises: an outer layer composed of steel; a titanium layer explosion welded to the steel layer; and a TiN layer formed on the surface of the titanium layer so that the TiN layer covers the surface of the titanium layer and only the TiN layer comes into contact with the slurried ores and/or concentrates.
An autoclave for pressure oxidation of slurried ores and/or concentrates comprising a main shell having an interior surface composed of titanium or titanium alloy having a TiN layer on its surface, the TiN layer coming into contact with the slurried ores and/or concentrates and oxygen and preventing exposure of titanium to oxygen can be provided by the steps of: providing a plate of carbon steel; providing a thin sheet of titanium or titanium alloy; explosion welding the plate of carbon steel to the thin sheet of titanium or titanium alloy to obtain a titanium carbon steel plate; forming a TiN layer on the surface of the titanium or titanium alloy layer of the titanium carbon steel plate using a nitriding method to obtain a TiN coated titanium steel plate; and fabricating the autoclave form a plurality of obtained TiN coated titanium steel plates. The obtained TiN coated titanium steel plates can be fabricated into a final autoclave assembly by for example welding the plates together by the welding methods especially developed for welding TiN coated titanium.
EXAMPLES
Erosion resistance of several interior surfaces (Ti Gr. 2, Ti Gr. 12 T1O2 and TiN) was tested by exposing the interior surface of a slurry port testing devise to quartz sand slurry (125 to 180 microns). The weight loss of the surface was measured after 40 min exposure by weighing the samples before and after the test and calculating the weight change. Results of the test are shown in Figure 4. TiN surface demonstrated best wear properties as only minor weight loss was observed.
It will be obvious to a person skilled in the art that, as the technology advances, the inventive concept can be implemented in various ways. The invention and its embodiments are not limited to the examples described above but may vary within the scope of the claims.

Claims (11)

1. Autoklaavi lietettyjen malmien ja/tai rikasteiden painehapetukseen käsittäen pääkuoren, jossa on sisäkerros, joka on koostettu titaanista tai ti-taanimetalliseoksesta, jonka pinnalla on TiN-kerros, jolloin TiN-kerros tulee kosketuksiin lietettyjen malmien ja/tai rikasteiden ja hapen kanssa ja estää titaanin altistumisen hapelle.An autoclave for pressure oxidation of slurried ores and / or concentrates comprising a main shell having an inner layer composed of titanium or a titanium alloy having a TiN layer on its surface, wherein the TiN layer comes into contact with the slurried ores and / or concentrates and oxygen exposure of titanium to oxygen. 2. Patenttivaatimuksen 1 mukainen autoklaavi, jolloin sisäkerros on korroosiota ja eroosiota kestävä.The autoclave of claim 1, wherein the inner layer is resistant to corrosion and erosion. 3. Patenttivaatimuksen 1 tai 2 mukainen autoklaavi, jolloin TiN-kerroksen paksuus on 1 - 5 mm, edullisesti 3-4 mm.The autoclave according to claim 1 or 2, wherein the TiN layer has a thickness of 1 to 5 mm, preferably 3 to 4 mm. 4. Minkä tahansa patenttivaatimuksen 1 - 3 mukainen autoklaavi, jolloin TiN-kerros on metallurgisesti liitetty titaaniin tai titaanimetalliseokseen.The autoclave according to any one of claims 1 to 3, wherein the TiN layer is metallurgically bonded to titanium or a titanium alloy. 5. Minkä tahansa patenttivaatimuksen 1 - 4 mukainen autoklaavi, jolloin sisäkerros titaania tai titaanimetalliseosta on liitetty pääkuoren ulkokerrokseen räjähdyshitsauksella.An autoclave according to any one of claims 1 to 4, wherein the inner layer of titanium or titanium alloy is bonded to the outer layer of the main shell by explosion welding. 6. Minkä tahansa patenttivaatimuksen 1 - 5 mukainen autoklaavi, jolloin TiN-kerros saadaan aikaan typettämällä titaanin tai titaanimetalliseoksen pinta.The autoclave according to any one of claims 1 to 5, wherein the TiN layer is obtained by nitrogenizing the surface of titanium or a titanium alloy. 7. Minkä tahansa patenttivaatimuksen 1 - 6 mukainen autoklaavi, jolloin TiN-kerroksen kovuusarvo (HV) on edullisesti ainakin 300 HV, edullisemmin 450 - 1800 HV, edullisimmin 550 - 800 HV.The autoclave according to any one of claims 1 to 6, wherein the hardness value (HV) of the TiN layer is preferably at least 300 HV, more preferably 450 to 1800 HV, most preferably 550 to 800 HV. 8. Minkä tahansa patenttivaatimuksen 1 - 7 mukainen autoklaavi, jolloin autoklaavin pääkuori käsittää: ulkokerroksen, joka on koostettu teräksestä; titaanikerroksen, joka on räjähdyshitsattu teräskerrokseen ja jonka paksuus on 8 - 10 mm; ja TiN-kerroksen, joka on muodostettu titaanikerroksen pinnalle siten, että TiN-kerros peittää titaanikerroksen pinnan ja vain TiN-kerros tulee kosketuksiin lietettyjen malmien ja/tai rikasteiden ja hapen kanssa ja jolloin TiN-kerroksen paksuus on 3 - 5 mm.The autoclave according to any one of claims 1 to 7, wherein the main body of the autoclave comprises: an outer layer made of steel; an explosion-welded titanium layer having a thickness of 8 to 10 mm; and a TiN layer formed on the surface of the titanium layer such that the TiN layer covers the surface of the titanium layer and only the TiN layer comes into contact with the slurried ores and / or concentrates and oxygen and wherein the TiN layer is 3-5 mm thick. 9. Minkä tahansa patenttivaatimuksen 1 - 8 mukainen autoklaavi, jolloin pääkuoren ulkokerros on hiiliterästä.The autoclave according to any one of claims 1 to 8, wherein the outer shell of the main shell is carbon steel. 10. Minkä tahansa patenttivaatimuksen 1 - 9 mukainen autoklaavi, jolloin ulkokerroksen paksuus on 50-100 mm.The autoclave according to any one of claims 1 to 9, wherein the outer layer has a thickness of 50 to 100 mm. 11. Minkä tahansa patenttivaatimuksen 1-10 mukainen autoklaavi, jolloin titaanikerroksen paksuus on 8 -10 mm.An autoclave according to any one of claims 1 to 10, wherein the titanium layer has a thickness of 8 to 10 mm.
FI20136261A 2013-12-13 2013-12-13 Autoclave for pressure oxidation FI126061B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
FI20136261A FI126061B (en) 2013-12-13 2013-12-13 Autoclave for pressure oxidation
PCT/FI2014/050986 WO2015086909A1 (en) 2013-12-13 2014-12-11 Autoclave for pressure oxidation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FI20136261A FI126061B (en) 2013-12-13 2013-12-13 Autoclave for pressure oxidation

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FI20136261A FI20136261A (en) 2015-06-14
FI126061B true FI126061B (en) 2016-06-15

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US10358710B2 (en) 2016-07-29 2019-07-23 Brenco Surface Engineering Pty Ltd. Wear resistant coating
JP6402761B2 (en) * 2016-09-29 2018-10-10 住友金属鉱山株式会社 Oxygen blowing pipe and method for leaching metal material

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US4627900A (en) * 1982-08-27 1986-12-09 Amax Inc. Electrochemical dissolution and control of nickel sulfide scale
US5535992A (en) * 1995-03-07 1996-07-16 Goro Nickel S.A. Apparatus and method for acidic leaching of lateritic ores
AUPQ717000A0 (en) * 2000-04-28 2000-05-18 Westerland Pty Ltd Titanium alloy and method of manufacture
JP4852716B2 (en) * 2001-09-13 2012-01-11 Ｄｏｗａメタルマイン株式会社 Zinc concentrate leaching method and leaching equipment
US8025859B2 (en) * 2007-05-18 2011-09-27 Cesl Limited Process for gold and silver recovery from a sulphide concentrate

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