WO1996010653A1 - Traitement des mineraux pour l'extraction du zirconium - Google Patents

Traitement des mineraux pour l'extraction du zirconium Download PDF

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Publication number
WO1996010653A1
WO1996010653A1 PCT/AU1995/000654 AU9500654W WO9610653A1 WO 1996010653 A1 WO1996010653 A1 WO 1996010653A1 AU 9500654 W AU9500654 W AU 9500654W WO 9610653 A1 WO9610653 A1 WO 9610653A1
Authority
WO
WIPO (PCT)
Prior art keywords
zircon
milled
leaching
alumina
milling
Prior art date
Application number
PCT/AU1995/000654
Other languages
English (en)
Inventor
Wieslaw Alexander Kaczmarek
Barry William Ninham
James Stanislaus Williams
Tony Puclin
Original Assignee
The Australian National University
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
Priority claimed from AUPM8574A external-priority patent/AUPM857494A0/en
Priority claimed from AUPN2680A external-priority patent/AUPN268095A0/en
Application filed by The Australian National University filed Critical The Australian National University
Priority to AU36005/95A priority Critical patent/AU3600595A/en
Publication of WO1996010653A1 publication Critical patent/WO1996010653A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
    • 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
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • 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 present invention relates to the treatment of minerals, and particularly for the treatment of zircon mineral (ZrSiO.) for the extraction of zirconium. More particularly, the present invention relates to the cold milling of particulate zircon mineral to form nanostructured products, from which the silica (SiO 2 ) and various minerals can be separated by a leaching process.
  • zircon mineral ZrSiO.
  • the present invention relates to the cold milling of particulate zircon mineral to form nanostructured products, from which the silica (SiO 2 ) and various minerals can be separated by a leaching process.
  • Zirconium is an important material in the nuclear industry, where it is used as cladding for fuel rods. While this accounts for more than 90% of Zr metal consumption, the metal also finds many other chemical and industrial uses.
  • the mineral zircon (ZrSiO 4 ) would seem to hold great potential as a source of zirconium. However its highly refractory nature makes separation a costly process.
  • the traditional methods that are used to decompose zircon are either thermal or chemical. The thermal route involves dissociation using a plasma torch followed by rapid cooling, which causes zirconia and silica to crystallise individually. Zircon can be decomposed chemically but only by the use of aggressive reagents and elevated temperatures the two major process routes employed being alkali fusion and carbochlorination.
  • Ball milling of ores, with and without additives, to facilitate the comminution process is not new.
  • the early potential of ball milling for the reduction and extraction of ores has generally not been fulfilled, and interest in such ore processing technology has waned.
  • the development of a new form of high energy ball mill at The Australian National University, and the success that has been achieved in mechanical alloying work with that ball mill (see, for example, the specifications of International Patent Application Nos. PCT/AU91/00248, PCT/AU92/00073 and PCT/AU94/00057, have stimulated new interest in the cold milling of ores. That new ball mill, which is described in the specification of International Patent Application No.
  • PCT/AU90/00471 (WIPO Publication No. WO91/04810), enables controlled energy milling of a charge to be effected.
  • the present inventors have now discovered that under certain milling conditions, minerals containing silica, such as zircon, can be reduced while being converted into a nanostructural form, and that silica and other minerals can be removed from this product (for example, using hydrochloric acid).
  • the basic requirements of the cold milling process are: (i) that high energy milling is carried out at room temperature for a sufficient time period (up to 300 hours) to produce a powder having nanostructural form, and (ii) that the milling is effected in the presence of suitable additives to the ball mill charge.
  • the present invention seeks to provide a method of treating minerals containing silica, such as zircon mineral, to convert such minerals into a form where the silica content and the various other minerals can be removed by a simple leaching process.
  • silica such as zircon mineral
  • the present invention seeks to provide a method of treating minerals containing silica, utilising a cold milling process.
  • the present invention provides a method of treatment of silica containing minerals to facilitate the removal of silica and various minerals, the method comprising high energy milling of the silica containing mineral in particulate form in the presence of a suitable additive for a period sufficient to form a nanostructural product.
  • said silica containing mineral is zircon (ZrSiO-).
  • said additive is a chemical activator.
  • said chemical activator is alumina (Al 2 O 3 ).
  • said nanostructural product is zirconia (ZrO-,).
  • the high energy milling is effected in a ball mill of the type described and claimed in the specification of International Patent Application No. PCT/AU90/00471.
  • the method includes the additional step of leaching the nanostructural product of the milling to remove at least a major proportion of the zirconia (ZrO : ) therein.
  • said leaching is effected using acid, such as hydrochloric acid.
  • Fig. 1 is a schematic diagram of ball mill used in experiments, the mill being shown with magnets in a high energy grinding and impacting configuration;
  • Fig. 2 shows XRD patterns of dry milled zircon: a) premilled material b) 170 h. c) 340 h, and d) 500 h;
  • Fig. 3 shows XRD patterns of dry milled zircon with alumina a) premilled material b) 170 h, and c) 340 h;
  • Fig. 4 shows EDXA spectra of milled zircon with alumina: a) 170 h, and b) 340 h;
  • Fig. 5 shows EDXA spectra of milled zircon with alumina after leaching: a) milled 170 h and b) milled 340 h;
  • Fig. 6 shows EDXA spectra of solids obtained from filtrates after drying: a) sample milled 170 h, and b) milled 340 h.
  • the milling process was conducted in a vertical stainless steel ASI lini-Ball mill operating in high energy mode at room temperature under vacuum (-100 Pa). See Fig.l for a schematic diagram of the milling process.
  • Four ferromagnetic balls ( ⁇ -Fe with Cr hardened surface) with a weight of -70 g each were used.
  • the effective ball mass was increased to -5 kg.
  • Use of the magnets, designed to control the ball movement, has been described in earlier literature.
  • the mill was charged with 4.36g of zircon (Westralian Sands Ltd, premilled to 0.5-1.0 mm) and 3.64g of alumina ( ⁇ -alumina, l .ORm. Leco Corp), ie. a 3:2 molar ratio of Al 2 O 3 :ZrSiO 4 .
  • This composition was shown by Di Rupo et al to be optimal for
  • reaction sintering The air was then removed from the mill. Milling was carried out at a rotation speed of -160 rpm. and samples taken at 170 and 340 hours . A control ⁇ - sample, containing 8g of zircon, was also milled.
  • Leaching of milled materials was carried out as follows: Concentrated HCI (36%) was added to 0.2-0.3g of sample (accurately weighed) in a ratio of 50ml acid ⁇ er gram of sample, and allowed to leach at room temperature for a) 1 day with dilution to 3 times initial volume using deionized water and leaching for a further 3 days, or b) 4 days with no dilution. Both methods produced identical results. Samples were agitated several times per day. The leached solutions were then filtered through pre-weighed 0.2 ⁇ m Nucleopore polycarbonate filters (after a dilution for method b), dried at 105 ° C for 24 hours, and the solids weighed. The filtrates were made up to 100ml with water for chemical analysis.
  • XRD X-ray powder diffraction
  • Philips diffractometer with CoK ⁇ radiation.
  • XRD patterns were identified using the PDF CD-ROM Retrieval/Display System V2.13a 1987-1992 (International Centre for Diffraction Data).
  • Solid state elemental analysis was carried out using the Rutherford backscattering technique (RBS); liquid state analysis for Fe, Si, and Al using Flame Atomic Absorption Spectrometry (varian Spectra AA-30).
  • Qualitative elemental analysis was carried out using Energy-Dispersive S-ray Analysis (EDXA) on a Jeol 6400 scanning electron microscope Gravimetric analysis of solutions for Zr was carried out using mandelic acid precipitation.
  • EDXA Energy-Dispersive S-ray Analysis
  • the milling of zircon with alumina appears to result in a rapid disordering of both initially crystalline materials under the conditions examined.
  • the X-ray diffraction (XRD) patterns of milled zircon (as a control) is shown in Fig. 2.
  • the milled zircon shows significant line broadening and decrease in peak intensities when compared with the premilled material.
  • the process of formation of the disordered phase is milling time dependent and for the 340 h and 500 h milled samples is clearl) visible.
  • Milled AI 2 O 3 /ZrSiO 4 powders examined by EDXA showed significant amounts of Al, Si, Zr, Fe, and traces of Cr (a component of the steel from the mill and balls), as expected (Fig. 4). Leached Materials
  • control solution (acid only) which went through the same leaching and filtration process contained no detectable amounts of Al or Fe, but did contain SiO 2 in an amount equal to the lowest detected in a sample, equivalent to around 0.1 wt% of the starting material.
  • the leaching process i) removes little or no SiO 2 , ii) removes a significant proportion of the A1 2 0 3 , and, iii) removes almost all of the zirconium.
  • the ball milling of zircon mineral with alumina results in a disordered mixture which is highly amenable to leaching with hydrochloric acid in order to remove the zirconium.
  • Zircon milled alone in similar conditions also results in a disordered phase.
  • the milling process also introduces a significant contamination of iron from the ball mill (much higher than is usually observed in mechanical milling) due to the hard abrasive nature of the oxides used; however the iron can be completely removed by the HCI leaching process. After the leaching process, all of the zirconium was found to be in solution (within experimental accuracy). This is the most significant result of this work.
  • the milling and leaching process will be understood by persons skilled in the art, to have significant potential as a low energy, low cost method for extracting zirconium from zircon.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Un mélange d'alumine (Al2O3) et de zircon (ZrSiO4) a été soumis à un broyage mécanique. On a découvert que la présence d'alumine favorise considérablement la transition ordre-désordre du zircon. Le lessivage par acide des mélanges oxydés broyés permet de dissoudre complètement le zirconium et une certaine proportion de l'alumine ainsi que des traces seulement de silice. Le lessivage du zirconium était impossible tant que le zircon était broyé seul. Les résultats quantitatifs de ce procédé de lessivage sont présentés.
PCT/AU1995/000654 1994-10-04 1995-10-04 Traitement des mineraux pour l'extraction du zirconium WO1996010653A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU36005/95A AU3600595A (en) 1994-10-04 1995-10-04 Treatment of minerals for extraction of zirconium

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AUPM8574A AUPM857494A0 (en) 1994-10-04 1994-10-04 Decomposition of silica containing minerals by room temperature reaction sintering
AUPM8574 1994-10-04
AUPN2680 1995-04-28
AUPN2680A AUPN268095A0 (en) 1995-04-28 1995-04-28 Treatment of minerals for extraction of zirconium

Publications (1)

Publication Number Publication Date
WO1996010653A1 true WO1996010653A1 (fr) 1996-04-11

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Application Number Title Priority Date Filing Date
PCT/AU1995/000654 WO1996010653A1 (fr) 1994-10-04 1995-10-04 Traitement des mineraux pour l'extraction du zirconium

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6203768B1 (en) 1995-08-28 2001-03-20 Advanced Nano Technologies Pty Ltd Process for the production of ultrafine particles
CN113337706A (zh) * 2021-05-25 2021-09-03 中国冶金地质总局昆明地质勘查院 一种红柱石原矿的纯化方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU570650A1 (ru) * 1976-04-12 1977-08-30 Институт геологии и геофизики СО АН СССР Способ переработки концентратов и полупродуктов, содержащих цветные и редкие металлы
AU5547980A (en) * 1979-02-13 1980-08-21 Elkem A/S Acid leaching of silicate ores
FR2469462A1 (fr) * 1979-11-09 1981-05-22 Rhone Poulenc Ind Procede de traitement d'un minerai complexe de titane, zirconium et terres rares
FR2533587A1 (fr) * 1982-09-27 1984-03-30 Commissariat Energie Atomique Procede de traitement de minerais complexes de manganese, en particulier de nodules manganiferes
AU4505885A (en) * 1984-07-27 1986-01-30 Cookson Group Plc Extracting zirconia from dissociated zircon
FR2593193A1 (fr) * 1986-01-20 1987-07-24 Cogema Procede de lixiviation acceleree de minerai d'uranium
JPH03191029A (ja) * 1989-12-20 1991-08-21 Nisshin Steel Co Ltd ケイ酸苦土ニッケル鉱石の処理方法
WO1995008004A1 (fr) * 1993-09-13 1995-03-23 The Australian National University Traitement de l'ilmenite par broyage a froid

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU570650A1 (ru) * 1976-04-12 1977-08-30 Институт геологии и геофизики СО АН СССР Способ переработки концентратов и полупродуктов, содержащих цветные и редкие металлы
AU5547980A (en) * 1979-02-13 1980-08-21 Elkem A/S Acid leaching of silicate ores
FR2469462A1 (fr) * 1979-11-09 1981-05-22 Rhone Poulenc Ind Procede de traitement d'un minerai complexe de titane, zirconium et terres rares
FR2533587A1 (fr) * 1982-09-27 1984-03-30 Commissariat Energie Atomique Procede de traitement de minerais complexes de manganese, en particulier de nodules manganiferes
AU4505885A (en) * 1984-07-27 1986-01-30 Cookson Group Plc Extracting zirconia from dissociated zircon
FR2593193A1 (fr) * 1986-01-20 1987-07-24 Cogema Procede de lixiviation acceleree de minerai d'uranium
JPH03191029A (ja) * 1989-12-20 1991-08-21 Nisshin Steel Co Ltd ケイ酸苦土ニッケル鉱石の処理方法
WO1995008004A1 (fr) * 1993-09-13 1995-03-23 The Australian National University Traitement de l'ilmenite par broyage a froid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DERWENT ABSTRACT, Accession No. 51167A/28, Class M25; & SU,A,570 650 (AS SIBE GEOL GEOPHY), 29 September 1977. *
PATENT ABSTRACTS OF JAPAN, C-884, page 158; & JP,A,03 191 029 (NISSHIN STEEL CO LTD), 21 August 1991. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6203768B1 (en) 1995-08-28 2001-03-20 Advanced Nano Technologies Pty Ltd Process for the production of ultrafine particles
CN113337706A (zh) * 2021-05-25 2021-09-03 中国冶金地质总局昆明地质勘查院 一种红柱石原矿的纯化方法

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