CA2169947A1 - Ilmenite processing using cold milling - Google Patents
Ilmenite processing using cold millingInfo
- Publication number
- CA2169947A1 CA2169947A1 CA002169947A CA2169947A CA2169947A1 CA 2169947 A1 CA2169947 A1 CA 2169947A1 CA 002169947 A CA002169947 A CA 002169947A CA 2169947 A CA2169947 A CA 2169947A CA 2169947 A1 CA2169947 A1 CA 2169947A1
- Authority
- CA
- Canada
- Prior art keywords
- dimethyl ammonium
- ilmenite
- milling
- additive
- didodecyl
- 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.)
- Abandoned
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
Abstract
High energy ball milling of particulate ilmenite (or other titaniferous ore) at room temperature, for periods of up to 300 hours, in the presence of a suitable additive, produces a nanostructural powder from which at least a major proportion of the iron in the titaniferous ore can be leached. The additive may be a reducing agent (for example, amorphous boron), a long chained hydrocarbon (for example, dodecane) or a surfactant (preferably dihexadecyl dimethyl ammonium acetate, or didodecyl dimethyl ammonium bromide, or didodecyl dimethyl ammonium acetate, or didodecyl dimethyl ammonium hydroxide, or sodium didodecyl sulphate). The leaching is preferably effected using 4M hydrochloric acid at a temperature of from 80 .degree.C to 100 .degree.C.
Description
WO 95/08004 PCT/AU~ ce~
~169947 TITLE: "ILMENITE PROCESSING USING COLD MILLING"
Technical Field This invention concerns the treatment of minerals contA; ni ng 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 Lc...oved by a leaching process.
r-.-L.J.G~.d to the Invention Ilmenite, FeTiO3, and titaniferous minerals generally, are relatively inert minerals that have long been a major source of titanium dioxide, TiO2, 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.
Most of the currently used metallurgical processing of ilmenite includes hot acid l~ch;ng of the particulate mineral, with associated environmental problems. For example, the "sulphate route" for the extraction of titanium dioxide from ilmenite involves the steps of (a) mixing dry milled ilmenite with 85 to 92 per cent sulphuric acid;
(b) heating the mixture of ground ilmenite and sulphuric acid to a temperature of about 160C, at which temperature an exothermic reaction is initiated, the W095/08004 21 6 9 9 ~ 7 - PCT/AU94/00550 product of this reaction being a mixture of ferrous, ferric and titanium sulphates;
(c) forming an aqueous (or weakly acid) solution of the mixture of sulphates, then reducing the ferric sulphate to ferrous sulphate with scrap iron;
(d) clarifying the solution by sedimentation;
(e) removing the iron in the solution by crystA~lisation (as FeSO4.7HzO); and (f) extracting the titanium dioxide using hydrolysis.
Another technique that is used to process ilmenite is the so-called "chloride route", which involves the chlorination of impure rutile using gaseous chlorine at a temperature in the range of from 650C to 1,150C to form titanium tetrachloride (TiCl~). The TiCl~ is then oxidised to produce pure titanium dioxide.
The "Rech~r" process is also used to upgrade ilmenite - to remove iron and provide a feedstock for the "chloride route". In the RPrhPr process, ilmenite is reacted with coal and sulphur in an iron reduction kiln at 1100C. This reaction reduces the iron in the ilmenite to the metallic form. After cooling the products of the reaction, the iron is rusted out in slurry form with ammonium chloride acting as a catalyst for the rusting. The remai ni ~g iron compounds are removed by 1P~.h; ng with sulphuric acid.
One of the more promising alternative ilmenite processing methods, developed jointly by Commonwealth Scientific and Industrial Research Organisation and Murphyores Pty Limited, known as the "Murso process", is described in the W095t08004 21 ~ ~ ~ 4 7 PCT/AU94/00550 specification of Australian patent No 416,143. 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 e~Ance~ reactivity, from which the iron can be leached with dilute hydrochloric acid. The cost of using hydrogen as the reducing agent and the cost of regeneration of the hydrochloric acid used for l~Ach;ng have made the adoption of the Murso process commercially unattractive. Several attempts have been made to modify the Murso process to improve its economics, but at the time of writing this specification, it has not been adopted commercially.
The search for other improved methods of producing rutile from ilmenite has continued.
Disclosure of the Present Invention 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 ob;ective is achieved by a cold milling process.
Ball milling of ores, with and without additives to facilitate the comminution process (the reduction of particle size) is not new. The early potential of ball milling for the reduction and extraction of ores, however, 216~9~!~
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 mec~nical alloying work with that ball mill (see, for example, the specifications of International Patent Applications 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 (WIP0 Publication No W0 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 100C).
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.
Thus, according to the present invention, there is provided a method of treatment of a titaniferous ore to facilitate the removal of iron from the ore to produce rutile, the method 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.
~1699~7 ~
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). Among the surfactants which may constitute the additive of the present invention are:
(a) ~ heYa~ecyl dimethyl ammonium acetate (DHDAA);
(b) didodecyl dimethyl ammonium bromide (DDAB);
(c) didodecyl dimethyl ammonium acetate (DDAA);
(d) didodecyl dimethyl ammonium hydroxide (DDAOH); and (e) sodium didodecyl sulphate (SDDS) - an anionic double ~.h~; ne~ surfactant.
noAec~ne is a preferred long chained hydrocarbon which can be used as the additive of this invention.
To extend this method to include the production of rutile, the milled ore must subsequently be l~che~ to extract the iron from it (for example, using hydrochloric acid at a temperature of about 100C).
Preferably 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.
A better understanding of the present invention will be obtained from the following description and discussion of experimental work in connection with the cold milling of - 25 ilmenite, which has been undertaken by the present inventors.
~169947 Description of Cold Milling Work The present inventors hypothesised that subjecting a particulate titaniferous material to prolonged milling should change the mineral into a reactive nanostructural form, from which it should be possible to remove a-Fe by acid leaching or by magnetic separation. When this hypothesis was tested, simple milling of ilmenite did not produce a reactive nanostructural form of the mineral.
However, milling ilmenite with an additive to the ball mill charge, surprisingly, did yield a reactive nanostructural product.
A series of experiments were then performed with ilmenite (in its mineral sand form) to investigate this phenomenon further. In each experiment, the particulate ilmenite was subjected to prolonged high-energy milling in a ball mill of the type described in the specification of International patent application No PCT/AU90/00471. (It will be appreciated that milling in other types of high energy ball mill for an appropriate period of time should have the same effect.) The milling was effected for a period sufficient - to convert the particulate ilmenite charge of the ball mill into a nanostructural material. This required high energy ball milling for a period of time which depended upon the milling conditions and the additive(s) to the ball mill charge.
The milled samples were then le~heA with no further treatment.
W095/08004 ~ PCT/AU94/OOS50 2169~9~7 ;-At different stages of the experiments, 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. In particular, structural development of the as-milled samples was monitored by x-ray diffraction of cobalt Ka radiation using a Phillips diffractometer, and Rutherford backscattering spectrometry was used to analyse the presence of iron in chemically leached samples.
A range of additives were used with the initial charge of the ball mill. In each experiment, the additive remained in the charge of the ball mill for the duration of the milling. Although there was some variation of the concentration of some of the additives, no attempt was made to optimise their concentrations or their reducing properties. One control experiment was carried out using ilmenite alone (that is, with no additive to the charge of the ball mill).
Particular additives used in the experiments were as follows:
1. DDAA (didodecyl dimethyl ammonium acetate);
~169947 TITLE: "ILMENITE PROCESSING USING COLD MILLING"
Technical Field This invention concerns the treatment of minerals contA; ni ng 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 Lc...oved by a leaching process.
r-.-L.J.G~.d to the Invention Ilmenite, FeTiO3, and titaniferous minerals generally, are relatively inert minerals that have long been a major source of titanium dioxide, TiO2, 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.
Most of the currently used metallurgical processing of ilmenite includes hot acid l~ch;ng of the particulate mineral, with associated environmental problems. For example, the "sulphate route" for the extraction of titanium dioxide from ilmenite involves the steps of (a) mixing dry milled ilmenite with 85 to 92 per cent sulphuric acid;
(b) heating the mixture of ground ilmenite and sulphuric acid to a temperature of about 160C, at which temperature an exothermic reaction is initiated, the W095/08004 21 6 9 9 ~ 7 - PCT/AU94/00550 product of this reaction being a mixture of ferrous, ferric and titanium sulphates;
(c) forming an aqueous (or weakly acid) solution of the mixture of sulphates, then reducing the ferric sulphate to ferrous sulphate with scrap iron;
(d) clarifying the solution by sedimentation;
(e) removing the iron in the solution by crystA~lisation (as FeSO4.7HzO); and (f) extracting the titanium dioxide using hydrolysis.
Another technique that is used to process ilmenite is the so-called "chloride route", which involves the chlorination of impure rutile using gaseous chlorine at a temperature in the range of from 650C to 1,150C to form titanium tetrachloride (TiCl~). The TiCl~ is then oxidised to produce pure titanium dioxide.
The "Rech~r" process is also used to upgrade ilmenite - to remove iron and provide a feedstock for the "chloride route". In the RPrhPr process, ilmenite is reacted with coal and sulphur in an iron reduction kiln at 1100C. This reaction reduces the iron in the ilmenite to the metallic form. After cooling the products of the reaction, the iron is rusted out in slurry form with ammonium chloride acting as a catalyst for the rusting. The remai ni ~g iron compounds are removed by 1P~.h; ng with sulphuric acid.
One of the more promising alternative ilmenite processing methods, developed jointly by Commonwealth Scientific and Industrial Research Organisation and Murphyores Pty Limited, known as the "Murso process", is described in the W095t08004 21 ~ ~ ~ 4 7 PCT/AU94/00550 specification of Australian patent No 416,143. 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 e~Ance~ reactivity, from which the iron can be leached with dilute hydrochloric acid. The cost of using hydrogen as the reducing agent and the cost of regeneration of the hydrochloric acid used for l~Ach;ng have made the adoption of the Murso process commercially unattractive. Several attempts have been made to modify the Murso process to improve its economics, but at the time of writing this specification, it has not been adopted commercially.
The search for other improved methods of producing rutile from ilmenite has continued.
Disclosure of the Present Invention 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 ob;ective is achieved by a cold milling process.
Ball milling of ores, with and without additives to facilitate the comminution process (the reduction of particle size) is not new. The early potential of ball milling for the reduction and extraction of ores, however, 216~9~!~
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 mec~nical alloying work with that ball mill (see, for example, the specifications of International Patent Applications 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 (WIP0 Publication No W0 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 100C).
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.
Thus, according to the present invention, there is provided a method of treatment of a titaniferous ore to facilitate the removal of iron from the ore to produce rutile, the method 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.
~1699~7 ~
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). Among the surfactants which may constitute the additive of the present invention are:
(a) ~ heYa~ecyl dimethyl ammonium acetate (DHDAA);
(b) didodecyl dimethyl ammonium bromide (DDAB);
(c) didodecyl dimethyl ammonium acetate (DDAA);
(d) didodecyl dimethyl ammonium hydroxide (DDAOH); and (e) sodium didodecyl sulphate (SDDS) - an anionic double ~.h~; ne~ surfactant.
noAec~ne is a preferred long chained hydrocarbon which can be used as the additive of this invention.
To extend this method to include the production of rutile, the milled ore must subsequently be l~che~ to extract the iron from it (for example, using hydrochloric acid at a temperature of about 100C).
Preferably 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.
A better understanding of the present invention will be obtained from the following description and discussion of experimental work in connection with the cold milling of - 25 ilmenite, which has been undertaken by the present inventors.
~169947 Description of Cold Milling Work The present inventors hypothesised that subjecting a particulate titaniferous material to prolonged milling should change the mineral into a reactive nanostructural form, from which it should be possible to remove a-Fe by acid leaching or by magnetic separation. When this hypothesis was tested, simple milling of ilmenite did not produce a reactive nanostructural form of the mineral.
However, milling ilmenite with an additive to the ball mill charge, surprisingly, did yield a reactive nanostructural product.
A series of experiments were then performed with ilmenite (in its mineral sand form) to investigate this phenomenon further. In each experiment, the particulate ilmenite was subjected to prolonged high-energy milling in a ball mill of the type described in the specification of International patent application No PCT/AU90/00471. (It will be appreciated that milling in other types of high energy ball mill for an appropriate period of time should have the same effect.) The milling was effected for a period sufficient - to convert the particulate ilmenite charge of the ball mill into a nanostructural material. This required high energy ball milling for a period of time which depended upon the milling conditions and the additive(s) to the ball mill charge.
The milled samples were then le~heA with no further treatment.
W095/08004 ~ PCT/AU94/OOS50 2169~9~7 ;-At different stages of the experiments, 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. In particular, structural development of the as-milled samples was monitored by x-ray diffraction of cobalt Ka radiation using a Phillips diffractometer, and Rutherford backscattering spectrometry was used to analyse the presence of iron in chemically leached samples.
A range of additives were used with the initial charge of the ball mill. In each experiment, the additive remained in the charge of the ball mill for the duration of the milling. Although there was some variation of the concentration of some of the additives, no attempt was made to optimise their concentrations or their reducing properties. One control experiment was carried out using ilmenite alone (that is, with no additive to the charge of the ball mill).
Particular additives used in the experiments were as follows:
1. DDAA (didodecyl dimethyl ammonium acetate);
2. DDAB (didodecyl dimethyl ammonium bromide);
3. DHDAA (dihexadecyl dimethyl ammonium acetate);
4. DDAOH (didodecyl dimethyl ammonium hydroxide);
5. SDDS (sodium didodecyl sulphate);
6. Do~e~An~-; and 7. Amorphous boron.
During the milling - which lasted for up to 300 hours - the charge of the ball mill was held at room temperature (about 25C). For experiments using the additives 1 to 5 above, the milling was performed in aqueous solution. Considering the point of zero charge of the ilmenite particle, it was necec~Ary to ad;ust the pH of the aqueous solution of the additives DDAA, DDAB and DHDAA so that it had a value of 10, which corresponds to negatively charged ilmenite particles, in order to get adsorption of the cationic species. For the experiments with the additive SDDS, 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 obtAin~ 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 80C to 100C. The Rutherford backscattering spectroscopy spectra of the leAche~ materials showed (a) that less than 5 atomic per cent of the iron in the sample milled with DDAOH remained after leaching; and (b) there had been a significant reduction of the iron content of the ilmenite samples that had been milled with SDDS and with amorphous boron.
WOg5/08004 PCTIAU94/00550 ~1~99~7 The x-ray diffraction pattern of the material milled with DDAOH and then le~c~e~ with hydrochloric acid showed only peaks corresponA~ng to rutile.
Thus the experiments showed that prolonged milling of ilmenite with an appropriate additive produces a nanostructural powder that is amenable to lP~h~ng with hot hydrochloric acid to remove the iron component of the ilmenite and leave rutile (TiO2).
During the milling - which lasted for up to 300 hours - the charge of the ball mill was held at room temperature (about 25C). For experiments using the additives 1 to 5 above, the milling was performed in aqueous solution. Considering the point of zero charge of the ilmenite particle, it was necec~Ary to ad;ust the pH of the aqueous solution of the additives DDAA, DDAB and DHDAA so that it had a value of 10, which corresponds to negatively charged ilmenite particles, in order to get adsorption of the cationic species. For the experiments with the additive SDDS, 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 obtAin~ 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 80C to 100C. The Rutherford backscattering spectroscopy spectra of the leAche~ materials showed (a) that less than 5 atomic per cent of the iron in the sample milled with DDAOH remained after leaching; and (b) there had been a significant reduction of the iron content of the ilmenite samples that had been milled with SDDS and with amorphous boron.
WOg5/08004 PCTIAU94/00550 ~1~99~7 The x-ray diffraction pattern of the material milled with DDAOH and then le~c~e~ with hydrochloric acid showed only peaks corresponA~ng to rutile.
Thus the experiments showed that prolonged milling of ilmenite with an appropriate additive produces a nanostructural powder that is amenable to lP~h~ng with hot hydrochloric acid to remove the iron component of the ilmenite and leave rutile (TiO2).
Claims (16)
1. A method of treatment of a titaniferous ore to facilitate the removal of iron from the ore to produce rutile, the method 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.
2. A method as defined in claim 1, in which said additive is a reducing agent.
3. A method as defined in claim 2, in which said reducing agent is amorphous boron.
4. A method as defined in claim 1, in which said additive is a long chained hydrocarbon.
5. A method as defined in claim 4, in which said hydrocarbon is dodecane.
6. A method as defined in claim 1, in which said additive is a surfactant.
7. A method as defined in claim 6, in which said surfactant is a surfactant selected from the group consisting of:
(a) dihexadecyl dimethyl ammonium acetate;
(b) didodecyl dimethyl ammonium bromide;
(c) didodecyl dimethyl ammonium acetate;
(d) didodecyl dimethyl ammonium hydroxide; and (e) sodium didodecyl sulphate.
(a) dihexadecyl dimethyl ammonium acetate;
(b) didodecyl dimethyl ammonium bromide;
(c) didodecyl dimethyl ammonium acetate;
(d) didodecyl dimethyl ammonium hydroxide; and (e) sodium didodecyl sulphate.
8. A method as defined in claim 6 or claim 7, in which said surfactant is in aqueous solution and the pH of the aqueous solution is adjusted to ensure adsorption of the surfactant by the titaniferous ore.
9. A method as defined in any preceding claim, in which the high energy milling is effected at a temperature of about 25°C.
10. A method as defined in any preceding claim, in which the high energy milling is effected for a period of about 300 hours.
11. A method as defined in any preceding claim in which 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.
12. A method as defined in any preceding claim, in which the titaniferous ore is ilmenite.
13. A method as defined in any preceding claim, including the additional step of leaching the nanostructural titaniferous product of the milling to remove at least a major proportion of the iron therein.
14. A method as defined in claim 13, in which said leaching is effected using hydrochloric acid.
15. A method as defined in claim 14, in which said leaching is effected using 4M hydrochloric acid at a temperature in the range of from 80°C to 100°C.
16. A method of treatment of a titaniferous ore as defined in claim 1, substantially as hereinbefore described.
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 |
|---|---|
| CA2169947A1 true CA2169947A1 (en) | 1995-03-23 |
Family
ID=3777190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002169947A Abandoned CA2169947A1 (en) | 1993-09-13 | 1994-09-13 | Ilmenite processing using cold milling |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0719346A4 (en) |
| JP (1) | JPH09504829A (en) |
| CA (1) | CA2169947A1 (en) |
| NZ (1) | NZ273552A (en) |
| WO (1) | WO1995008004A1 (en) |
| ZA (1) | ZA947050B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996010653A1 (en) * | 1994-10-04 | 1996-04-11 | The Australian National University | Treatment of minerals for extraction of zirconium |
| DE69612390T2 (en) | 1995-08-28 | 2001-10-31 | Advanced Nano Technologies Pty | METHOD FOR PRODUCING ULTRAFINE PARTICLES |
| US6440383B1 (en) | 1999-06-24 | 2002-08-27 | Altair Nanomaterials Inc. | Processing aqueous titanium chloride solutions to ultrafine titanium dioxide |
| US6375923B1 (en) | 1999-06-24 | 2002-04-23 | Altair Nanomaterials Inc. | Processing titaniferous ore to titanium dioxide pigment |
| US6548039B1 (en) | 1999-06-24 | 2003-04-15 | Altair Nanomaterials Inc. | Processing aqueous titanium solutions to titanium dioxide pigment |
| DE10124523A1 (en) * | 2001-05-19 | 2002-11-21 | Deutsche Telekom Ag | Method for presenting several electronically stored pages of a publication on an electronic display that allows a reader to have a feel for its thickness and allows leafing through in a manner analogous to a real publication |
| DE10249163A1 (en) * | 2002-10-22 | 2004-05-06 | Plath, Peter Jörg, Prof.Dr. | Method and device for using Faraday instabilities to carry out tribochemical reactions |
Family Cites Families (8)
| 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 |
| JPS6036818B2 (en) * | 1976-05-19 | 1985-08-22 | ザ ダウ ケミカル カンパニ− | Method for crushing ore or coal containing metal components |
| BR7800585A (en) * | 1978-01-31 | 1979-08-21 | Vale Do Rio Doce Co | PROCESS OF OBTAINING MECHANICAL CONCENTRATES FROM ANATASIO |
| 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 |
| DE3721509A1 (en) * | 1987-06-30 | 1989-01-12 | Kloeckner Humboldt Deutz Ag | Process and apparatus for leaching metal-containing, non-predried raw materials |
| US5383615A (en) * | 1989-10-03 | 1995-01-24 | The Australian National University | Ball milling apparatus |
-
1994
- 1994-09-13 JP JP7508867A patent/JPH09504829A/en active Pending
- 1994-09-13 ZA ZA947050A patent/ZA947050B/en unknown
- 1994-09-13 NZ NZ273552A patent/NZ273552A/en unknown
- 1994-09-13 WO PCT/AU1994/000550 patent/WO1995008004A1/en not_active Application Discontinuation
- 1994-09-13 CA CA002169947A patent/CA2169947A1/en not_active Abandoned
- 1994-09-13 EP EP94927454A patent/EP0719346A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| NZ273552A (en) | 1996-12-20 |
| ZA947050B (en) | 1995-08-07 |
| WO1995008004A1 (en) | 1995-03-23 |
| EP0719346A1 (en) | 1996-07-03 |
| EP0719346A4 (en) | 1997-05-07 |
| JPH09504829A (en) | 1997-05-13 |
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