WO1995008004A1 - Traitement de l'ilmenite par broyage a froid - Google Patents

Traitement de l'ilmenite par broyage a froid Download PDF

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Publication number
WO1995008004A1
WO1995008004A1 PCT/AU1994/000550 AU9400550W WO9508004A1 WO 1995008004 A1 WO1995008004 A1 WO 1995008004A1 AU 9400550 W AU9400550 W AU 9400550W WO 9508004 A1 WO9508004 A1 WO 9508004A1
Authority
WO
WIPO (PCT)
Prior art keywords
dimethyl ammonium
ilmenite
milling
additive
titaniferous
Prior art date
Application number
PCT/AU1994/000550
Other languages
English (en)
Inventor
Andrzej Calka
Patrice Millet
Barry William Ninham
James Stanislaus Williams
Original Assignee
The Australian National University
Westralian Sands Limited
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 The Australian National University, Westralian Sands Limited filed Critical The Australian National University
Priority to AU76892/94A priority Critical patent/AU7689294A/en
Priority to JP7508867A priority patent/JPH09504829A/ja
Priority to EP94927454A priority patent/EP0719346A4/fr
Publication of WO1995008004A1 publication Critical patent/WO1995008004A1/fr

Links

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
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
    • C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
    • C22B34/1245—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a halogen ion as active agent
    • 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
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
    • C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
    • 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
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching

Definitions

  • This invention concerns the treatment of minerals containing titanium dioxide and iron, which are generally called titaniferous minerals.
  • the most common of these minerals is ilmenite. More particularly, this invention concerns cold milling of particulate titaniferous minerals to form nanostructured products from which the iron content (or a significant amount of the iron content) of the mineral can be removed by a leaching process.
  • Ilmenite, FeTi0 3 , and titaniferous minerals generally, are relatively inert minerals that have long been a major source of titanium dioxide, Ti0 2 , which is used as a white pigment in paints, to produce welding rods, and in the cosmetic and ceramics industries. Extraction of the iron from the ilmenite and other titaniferous minerals has been, and still is, an expensive undertaking.
  • chloride route involves the chlorination of impure rutile using gaseous chlorine at a temperature in the range of from 650°C to 1,150°C to form titanium tetrachloride (TiCl 4 ).
  • TiCl 4 is then oxidised to produce pure titanium dioxide.
  • the "Becher” process is also used to upgrade ilmenite - to remove iron and provide a feedstock for the "chloride route".
  • ilmenite is reacted with coal and sulphur in an iron reduction kiln at 1100°C. This reaction reduces the iron in the ilmenite to the metallic form.
  • the iron is rusted out in slurry form with ammonium chloride acting as a catalyst for the rusting.
  • the remaining iron compounds are removed by leaching with sulphuric acid.
  • the Murso process uses an oxidation of the ilmenite to convert substantially all the iron to the ferric state, then reduction of the oxidised material to convert substantially all the ferric iron to the ferrous state. These steps, of oxidation of the ilmenite followed by its reduction, produce a material which has an enhanced reactivity, from which the iron can be leached with dilute hydrochloric acid.
  • the prime object of the present invention is to provide a method of treating ilmenite and other titaniferous minerals to convert such minerals into a form from which the iron content can be removed by a simple leaching process.
  • This objective is achieved by a cold milling process.
  • 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 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 WO 91/04810), enables controlled-energy milling of a charge to be effected.
  • the present inventors have now discovered that under certain milling conditions, ilmenite can be reduced while being converted into a nanostructural form, and that iron can be removed from this product (for example, using hydrochloric acid at a temperature of about 100 C C).
  • 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 a nanostructural form, and (ii) that the milling is effected in the presence of suitable additives to the ball mill charge.
  • a method of treatment of a titaniferous ore to facilitate the removal of iron from the ore to produce rutile comprising high energy milling of the ore in particulate form in the presence of a suitable additive for a period sufficient to form a nanostructural titaniferous product.
  • the additives include both solid and liquid reducing agents.
  • Amorphous boron has been found to be a useful additive, as have a range of surfactants and organic materials (particularly long chained hydrocarbons).
  • surfactants which may constitute the additive of the present invention are:
  • DHDAA dihexadecyl dimethyl ammonium acetate
  • SDDS didodecyl sulphate
  • Dodecane is a preferred long chained hydrocarbon which can be used as the additive of this invention.
  • the milled ore must subsequently be leached to extract the iron from it (for example, using hydrochloric acid at a temperature of about 100°C).
  • the milling is carried out in a ball mill of the type described and claimed in the specification of International patent application No PCT/AU90/00471.
  • simple milling of ilmenite did not produce a reactive nanostructural form of the mineral.
  • milling ilmenite with an additive to the ball mill charge did yield a reactive nanostructural product.
  • the milled samples were then leached with no further treatment.
  • the composition of each sample was assessed using one or more of the following techniques: x-ray diffraction; Mossbauer spectroscopy; transmission and scanning electron microscopy; atomic absorption spectrometry; Rutherford backscattering spectrometry.
  • structural development of the as-milled samples was monitored by x-ray diffraction of cobalt K ⁇ radiation using a Phillips diffractometer, and Rutherford backscattering spectrometry was used to analyse the presence of iron in chemically leached samples.
  • DDAA idodecyl dimethyl ammonium acetate
  • DDAB didodecyl dimethyl ammonium bromide
  • DHDAA dihexadecyl dimethyl ammonium acetate
  • DDAOH didodecyl dimethyl ammonium hydroxide
  • SDDS sodium didodecyl sulphate
  • the pH was adjusted to a value of 5, which corresponds to positively charged ilmenite particles, in order to get adsorption of the anionic surfactant SDDS.
  • Potassium hydroxide and potassium chloride were used for pH adjustment.
  • No adjustment of the pH of the aqueous solution was necessary for experiments with the additive DDAOH.
  • the nanostructural ilmenite products obtained by milling the ilmenite with the additives (i) DDAOH, (ii) SDDS and (iii) amorphous boron, were leached with 4M hydrochloric acid at temperatures ranging from 80°C to 100°C.
  • the Rutherford backscattering spectroscopy spectra of the leached materials showed

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

Abstract

Le broyage à billes très énergique de particules d'ilménite (ou d'autres minerais titanifères) à température ambiante, pendant des périodes allant jusqu'à 300 heures et en présence d'un additif approprié, donne une poudre nanostructuelle dont peut être lessivée au moins une proportion majeure du fer contenu dans le minerai titanifère. L'additif peut être un agent réducteur (du bore amorphe par exemple), un hydrocarbure à chaîne longue (du dodécane par exemple) ou un agent tensio-actif (de préférence acétate de dihexadecy 1 diméthyle ammonium, ou bromure de didodécyle diméthyle ammonium, ou acétate de didodécyle diméthyle ammonium, ou hydroxyde de didodécyle diméthyle ammonium, ou sulfate de sodium didodécyle). Le lessivage s'effectue de préférence en utilisant un acide chlorhydrique de 4M porté à une température allant de 80 à 100 °C.
PCT/AU1994/000550 1993-09-13 1994-09-13 Traitement de l'ilmenite par broyage a froid WO1995008004A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU76892/94A AU7689294A (en) 1993-09-13 1994-09-13 Ilmenite processing using cold milling
JP7508867A JPH09504829A (ja) 1993-09-13 1994-09-13 冷間ミリングを用いたイルメナイト処理
EP94927454A EP0719346A4 (fr) 1993-09-13 1994-09-13 Traitement de l'ilmenite par broyage a froid

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPM117793 1993-09-13
AUPM1177 1993-09-13

Publications (1)

Publication Number Publication Date
WO1995008004A1 true WO1995008004A1 (fr) 1995-03-23

Family

ID=3777190

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1994/000550 WO1995008004A1 (fr) 1993-09-13 1994-09-13 Traitement de l'ilmenite par broyage a froid

Country Status (6)

Country Link
EP (1) EP0719346A4 (fr)
JP (1) JPH09504829A (fr)
CA (1) CA2169947A1 (fr)
NZ (1) NZ273552A (fr)
WO (1) WO1995008004A1 (fr)
ZA (1) ZA947050B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996010653A1 (fr) * 1994-10-04 1996-04-11 The Australian National University Traitement des mineraux pour l'extraction du zirconium
US6203768B1 (en) 1995-08-28 2001-03-20 Advanced Nano Technologies Pty Ltd Process for the production of ultrafine particles
US6375923B1 (en) 1999-06-24 2002-04-23 Altair Nanomaterials Inc. Processing titaniferous ore to titanium dioxide pigment
US6440383B1 (en) 1999-06-24 2002-08-27 Altair Nanomaterials Inc. Processing aqueous titanium chloride solutions to ultrafine titanium dioxide
US6548039B1 (en) 1999-06-24 2003-04-15 Altair Nanomaterials Inc. Processing aqueous titanium solutions to titanium dioxide pigment
WO2004038048A1 (fr) * 2002-10-22 2004-05-06 Plath Peter Joerg Procede et dispositif pour effectuer une reaction tribochimique

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10124523A1 (de) * 2001-05-19 2002-11-21 Deutsche Telekom Ag Verfahren zur Darstellung mehrerer elektronisch gespeicherter Seiten

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2351706A1 (fr) * 1976-05-19 1977-12-16 Dow Chemical Co Procede pour le broyage par voie humide de mineraux ou de produits miniers non organiques ou organiques fossilises
US4175110A (en) * 1978-08-22 1979-11-20 Uop Inc. Recovery of titanium metal values
US4175952A (en) * 1978-07-19 1979-11-27 Uop Inc. Recovery of iron and titanium metal values
US4197276A (en) * 1978-07-31 1980-04-08 Uop Inc. Recovery of titanium metal values
US4256266A (en) * 1978-01-31 1981-03-17 Gustavo Magalhaes Process to obtain anathase concentrates from an anathase ore

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB714857A (en) * 1951-08-30 1954-09-01 British Titan Products Improvements in or relating to the manufacture of titanium dioxide pigments from mineral rutile ores
DE3721509A1 (de) * 1987-06-30 1989-01-12 Kloeckner Humboldt Deutz Ag Verfahren und vorrichtung zur laugung von metallhaltigen, nicht vorgetrockneten rohstoffen
US5383615A (en) * 1989-10-03 1995-01-24 The Australian National University Ball milling apparatus

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2351706A1 (fr) * 1976-05-19 1977-12-16 Dow Chemical Co Procede pour le broyage par voie humide de mineraux ou de produits miniers non organiques ou organiques fossilises
US4256266A (en) * 1978-01-31 1981-03-17 Gustavo Magalhaes Process to obtain anathase concentrates from an anathase ore
US4175952A (en) * 1978-07-19 1979-11-27 Uop Inc. Recovery of iron and titanium metal values
US4197276A (en) * 1978-07-31 1980-04-08 Uop Inc. Recovery of titanium metal values
US4175110A (en) * 1978-08-22 1979-11-20 Uop Inc. Recovery of titanium metal values

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF MINERALS, METALS AND MATERIAL SOCIETY, April 1994, THOMAS S MACKEY, "Upgrading Ilmenite into a High-Grade Synthetic Rutile", pages 59-64. *
See also references of EP0719346A4 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996010653A1 (fr) * 1994-10-04 1996-04-11 The Australian National University Traitement des mineraux pour l'extraction du zirconium
US6203768B1 (en) 1995-08-28 2001-03-20 Advanced Nano Technologies Pty Ltd Process for the production of ultrafine particles
US6375923B1 (en) 1999-06-24 2002-04-23 Altair Nanomaterials Inc. Processing titaniferous ore to titanium dioxide pigment
US6440383B1 (en) 1999-06-24 2002-08-27 Altair Nanomaterials Inc. Processing aqueous titanium chloride solutions to ultrafine titanium dioxide
US6548039B1 (en) 1999-06-24 2003-04-15 Altair Nanomaterials Inc. Processing aqueous titanium solutions to titanium dioxide pigment
WO2004038048A1 (fr) * 2002-10-22 2004-05-06 Plath Peter Joerg Procede et dispositif pour effectuer une reaction tribochimique

Also Published As

Publication number Publication date
NZ273552A (en) 1996-12-20
CA2169947A1 (fr) 1995-03-23
EP0719346A4 (fr) 1997-05-07
ZA947050B (en) 1995-08-07
JPH09504829A (ja) 1997-05-13
EP0719346A1 (fr) 1996-07-03

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