WO2015131266A1 - The production of high-grade synthetic rutile from low-grade titanium-bearing ores - Google Patents
The production of high-grade synthetic rutile from low-grade titanium-bearing ores Download PDFInfo
- Publication number
- WO2015131266A1 WO2015131266A1 PCT/CA2015/000128 CA2015000128W WO2015131266A1 WO 2015131266 A1 WO2015131266 A1 WO 2015131266A1 CA 2015000128 W CA2015000128 W CA 2015000128W WO 2015131266 A1 WO2015131266 A1 WO 2015131266A1
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- WO
- WIPO (PCT)
- Prior art keywords
- grade
- process according
- titanium
- hydrochloric acid
- acid
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/36—Azeotropic distillation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/03—Preparation from chlorides
- C01B7/035—Preparation of hydrogen chloride from chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
- C01B7/0712—Purification ; Separation of hydrogen chloride by distillation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide (Fe2O3)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- 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
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- 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
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- 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 generally relates to a two- stage leaching process using concentrated hydrochloric acid that upgrades a variety of inferior quality titanium-iron ores into premium titanium concentrate and iron oxide products.
- High-grade synthetic rutile is an excellent feed material for fluid bed chlorination, and is also a good feedstock for making either pigment or titanium sponge.
- Pigment is defined as a powdered substance that is mixed with a liquid in which it is relatively insoluble and used especially to impart color to coating materials (as paints) or to inks, plastics, and rubber.
- T1O 2 pigment is the most important white pigment used in the coatings industry. It is widely used due to the unigue combination of its superior properties, including high refractive index, low specific gravity, high hiding power and opacity, and non-toxicity .
- Patent No. 7,803,336, and U.S. Patent No. 2,167,628 describe hydrometallurgical processes that involve digestion of the ore in a mineral acid, such as hydrochloric acid or sulphuric acid, to extract value metals, including titanium dioxide from the ore.
- a mineral acid such as hydrochloric acid or sulphuric acid
- Another notable drawback of each of the previously noted processes is that they require a purification step of the leach solution prior to T1O2 recovery, either by reduction of the existing ferric iron to its ferrous state, or by a separate solvent extraction step to recover the titanium in a more pure form.
- the present invention has been made in order to solve one or more of the above problems. It is an object of the present invention to provide a method that produces a high-grade synthetic rutile from ilmenite, particularly from low-grade ore, that is widely available.
- the high-grade synthetic rutile produced in the present invention preferably contains 95-98% T1O2 , with 98% T1O2 being the most preferable amount.
- any low-grade ore containing under 20% T1O2 can be used.
- the low-grade ore contains 10-20% T1O2 , with 20% T1O2 being the most preferable amount.
- the present invention is not limited to Magpie deposits containing 11% T1O2, and could encompass any deposit, including in Canada Lac Lablache and Lac Brule (Quebec), Pipestone Lake (Manitoba), and others.
- the process can be naturally applied advantageously to higher grade titanium bearing ores and concentrates.
- Another object of the present invention is to provide a method of extraction that has the advantage of being applicable to many iron-titanium ores, regardless of the percentage of gangue minerals, provided that these are not carbonates or other high acid consumers .
- Iron-titanium ores used in the present invention can be obtained from deposits like Balla Balla (Australia) , Panzhua (China) , Abu Ghalaga (Egypt) , Itaituba (Brazil) , along with many other newly discovered deposits in Russia.
- the process for the recovery of high-grade synthetic rutile involves leaching ground ore with two separate quantities of hydrochloric acid after which the dissolved titanium is precipitated from the filtered liquor by hydrolysis.
- the soluble iron chlorides are either hydrolyzed in turn, or reduced to metal and hydrochloric acid.
- the present invention is not limited to hydrochloric acid, and may include other hydrogen halides (where halide by definition refers to flourine, chlorine, bromine, or iodine) .
- unreacted hydrochloric acid is recovered and iron or iron oxide is produced following the process for the recovery of high-grade synthetic rutile.
- FIG. 1 is an illustration of the process flow sheet with a two-step leaching process.
- FIG. 2 is an illustration of the process flow sheet with a one-step leaching process.
- the present invention provides a two-step leaching process for the recovery of high-grade synthetic rutile from low-grade ores, which include but are not limited to the following steps :
- step (b) filtering (110) a filter cake (115) from the slurry obtained in step (a) ;
- step (c) performing a second leaching reaction (120) by contacting the solid (115) obtained in step (b) with fresh 35- 40% hydrochloric acid (200) at an acid to solid ratio of 2- 2.5, and at a temperature of 75 - 80 °C; and
- the recovery of the free unreacted acid is made by mixing the two filtered solution (174) from the first leaching process (105) and (176) from the second leaching process (120), and distilling off hydrochloric acid (194) and water until the titanium is hydrolyzed (135) and substantial part of the iron chlorides precipitate as hydrates (178) . Filtering removes the residual saturated liquor (140) .
- the product contains 98% Ti0 2 (155), less than 1.5% Fe 2 0 3 , 0.06% CaO and 0.02% Mgo, 0.1% Si0 2 , and 0.07% Al 2 0 3 .
- the calcining process is a thermal decomposition of a material (see Fathi Habashi, Textbook of Pyrometallurgy. Quebec City, Canada: etallurgie Extractive Quebec, 2002) .
- the calcining process involves the decomposition of titanyl-hydroxide (TiO(OH) 2 ) to titanium dioxide (Ti0 2 ) and water vapor.
- the high-grade synthetic rutile produced from the two-step leaching process has an amount of titanium oxide in the range of 95-98% Ti02.
- the high-grade synthetic rutile produced preferably contains 95-98% T1O2, with over 98% T1O2 being the most preferable.
- the high-grade synthetic rutile produced in the present invention may further include a pre-leaching step by contacting a low-grade ilmenite with dilute hydrochloric acid to remove a substantial amount of the phosphorus content therefrom.
- the initial amount of phosphate (P2O5) in the ore (feed) is in the range of 0.12-0.15%.
- the amount of phosphate in the final T1O2 product is in the range of 1.8-2.1%.
- Preferred phosphate content in the product is under 0.05%.
- Conducting the pre-leaching step results in a product with a P2O5 content under 0.05%.
- the low-grade ilmenite ore deposits are not limited.
- the low-grade ore deposits may include any amount of T1O2. Any ore having under 20% T1O2 is considered low-grade ilmenite, with the range 10-12% T1O2 being preferable, and over 12% T1O 2 being the most preferable. Further, the deposits may be obtained anywhere in which low-grade ores are found, and thus, the invention is not limited thereto.
- a titanium dioxide precipitator may be used.
- a titanium dioxide precipitator comprises a heater for boiling the leach solution to liberate free hydrochloride via the hydrochloride acid outlet and a means of collecting and discharging the precipitated titanium dioxide slurry.
- a T1O2 free filtrate solution (180) may be further treated to recover vanadium and chromium (184) .
- Recovery of vanadium and chromium ( 184 ) involves either solvent extraction or selective precipitation .
- the chloride solution free of titanium, vanadium, and chromium, may be fed to a spray-type reactor where high temperature hydrolysis in a slightly oxidizing atmosphere (188) produces iron oxide (190) and hydrochloric acid (196).
- the present invention provides a one-step leaching process (105) for the recovery of high-grade synthetic rutile from low-grade ores (100), which includes but is not limited to the following steps :
- an agitated tank at 75°C may be used at an ambient pressure with concentrated 37% hydrochloric acid (242) that has an acid to ore ratio of 6.1. These conditions dissolve all of the iron and titanium. After filtration (110) to remove the silicate gangue minerals, the solution is subjected to distillation (200) to expel excess hydrochloric acid (202) .
- titanyl-hydroxide and TiO(OH)2 precipitate, but not iron.
- vanadium and chromium can be extracted (250) by organic solvents, while ferrous chloride solution (270) is then subjected to oxyhydrolysis (280) to recover Fe203 (290) and hydrochloric acid (292)
- the low-grade ore is finely ground to 200 mesh with preferable and more preferable ranges of 50% and 80% passing minus 200 mesh, respectively.
- a first leaching reaction is made by contacting the low-grade ore with hydrochloric acid that has a concentration in the range of 35-40%, and using an ore to acid ratio of between 2 to 2.5. Due to the pulp density and the fine granulometry, only slight stirring is required to prevent sedimentation. This first leaching reaction dissolves the magnetite in approximately one hour. The temperature is held at 60 - 70 °C.
- the pregnant liquor, now containing only 2-4% HC1 is preferably replaced with fresh concentrated acid to dissolve ilmenite and the titanium present in the ore to obtain a slurry.
- the slurry is then filtered, and the solid, without washing, is sent to a second leaching reaction.
- a second leaching reaction is conducted by adding fresh acid, which has a concentration in the range of 35-40%, to a filter cake at a ratio of between 2 to 2.5, respectively.
- the reaction lasts another hour, and the temperature is held at 75 - 80 °C.
- the residue is removed by a second filtration process, and washed.
- an optional step is to dry this waste at high temperatures to remove all of the acid.
- the losses in free HC1 amount to about 0.1 ton per ton or ore leached.
- Non-recoverable losses, due to the solution which cannot be removed, amount to 1.4-1.6% of the total iron and 4-4.5% of total Ti02. If the non-soluble iron and titanium are taken into account, the total recovery is about 95% for iron and 90% for titanium.
- the sequential steps of leaching-filtrating-leaching enhance the dissolution of the ilmenite.
- the iron oxide minerals respond much more rapidly to the HC1 leach than the titanium minerals.
- the solution from the first leach contains much more iron and only a small quantity of titanium.
- 70% of the total iron and 30% of the titanium oxide are leached into solution after the first stage.
- the small quantity of titanium is attributed to the dissolution of titanium minerals at the beginning of the leach when the hydrochloric acid concentration is high, but as the acid concentration diminishes, the dissolution of the titanium minerals slows down, and may undergo hydrolyzation.
- Controlling the temperature during the first leach has a double purpose: (1) it reduces the dissolution of titanium, and (2) it reduces the hydrolysis of what little titanium is dissolved.
- the two leaching reactions discussed in Example 1 consume more than one-half of the available acid.
- the recovery of the free unreacted acid is performed by mixing the two filtered solutions obtained from the first and second leaching reactions discussed in Example 1, and distilling off hydrochloric acid and water until the titanium is hydrolyzed and a substantial part of the titanium chlorides precipitate as hydrates. About 90% of the titanium chlorides precipitate as hydrates. Another filtering step removes the residual saturated liquor.
- the chloride crystals are dissolved with a minimum amount of dilute acid leaving behind an insoluble TiO(OH)2 in the form of a finely divided granular solid, which filters easily.
- the high-grade synthetic rutile contains an amount of T1O2 in the range of 95-98% T1O2, which meets the requirements of synthetic rutile concentrates.
- ferric chloride is reduced with iron and the solution is partly evaporated to crystallize hydrated ferrous chloride, which can then be reduced to metal by hydrogen to produce iron powder.
- the chloride solution is fed to a spray-type reactor in an atmosphere of hydrogen at high temperature.
- Iron powder is produced, along with the simultaneous regeneration of hydrochloric acid and the evaporation of water.
- the iron produced contains 0.4% T1O2 and 1 - 3.5% Cr 2 0 3 .
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- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR112016020502A BR112016020502A2 (en) | 2014-03-05 | 2015-02-27 | the production of high grade synthetic rutile from ore containing low grade titanium |
CA2941424A CA2941424A1 (en) | 2014-03-05 | 2015-02-27 | The production of high-grade synthetic rutile from low-grade titanium-bearing ores |
CN201580021130.6A CN106232840A (en) | 2014-03-05 | 2015-02-27 | Senior titania is produced from rudimentary titaniferous ore |
AU2015226786A AU2015226786A1 (en) | 2014-03-05 | 2015-02-27 | The production of high-grade synthetic rutile from low-grade titanium-bearing ores |
EP15757750.3A EP3114244A4 (en) | 2014-03-05 | 2015-02-27 | The production of high-grade synthetic rutile from low-grade titanium-bearing ores |
ZA2016/06799A ZA201606799B (en) | 2014-03-05 | 2016-10-03 | The production of high-grade synthetic rutile from low-grade titanium-bearing ores |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201461948319P | 2014-03-05 | 2014-03-05 | |
US61/948,319 | 2014-03-05 |
Publications (1)
Publication Number | Publication Date |
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WO2015131266A1 true WO2015131266A1 (en) | 2015-09-11 |
Family
ID=54016790
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CA2015/000128 WO2015131266A1 (en) | 2014-03-05 | 2015-02-27 | The production of high-grade synthetic rutile from low-grade titanium-bearing ores |
Country Status (8)
Country | Link |
---|---|
US (1) | US20150252448A1 (en) |
EP (1) | EP3114244A4 (en) |
CN (1) | CN106232840A (en) |
AU (1) | AU2015226786A1 (en) |
BR (1) | BR112016020502A2 (en) |
CA (1) | CA2941424A1 (en) |
WO (1) | WO2015131266A1 (en) |
ZA (1) | ZA201606799B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EA037945B1 (en) * | 2017-03-02 | 2021-06-10 | Метсо Ототек Финланд Ой | Method for treating titanium-containing slag |
CN107188127B (en) * | 2017-06-30 | 2020-05-05 | 安徽金星钛白(集团)有限公司 | Method for preparing titanium dioxide seed crystal by using chlorination waste acid |
CN109179496B (en) * | 2018-09-18 | 2021-02-02 | 攀枝花中达钛业科技有限公司 | High grade titanium dioxide and preparation method thereof |
JPWO2021002332A1 (en) * | 2019-07-02 | 2021-01-07 | ||
CN110468285B (en) * | 2019-09-11 | 2020-09-08 | 中南大学 | Method for preparing TiO from titanium-containing furnace slag2Method for producing powder |
WO2021072534A1 (en) * | 2019-10-15 | 2021-04-22 | 9203-5468 Quebec Inc. Dba Nmr360 | Process for the recovery of titanium dioxide, vanadium and iron compounds from various materials |
CN114293031A (en) * | 2022-01-10 | 2022-04-08 | 广东粤桥新材料科技有限公司 | Multistage-type rusting method applied to iron-containing minerals |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2527257A (en) * | 1948-09-01 | 1950-10-24 | Edwin G Judd | Process of separating titanium from its ores |
US3236596A (en) * | 1961-08-05 | 1966-02-22 | Bayer Ag | Process for the decomposition of titanium dioxide-containing minerals with hydrochloric acid |
US3407033A (en) * | 1966-01-21 | 1968-10-22 | Giulini Gmbh Geb | Method of treating titanium ores with hydrochloric acid to produce titanium tetrachloride therefrom |
EP0186370A2 (en) * | 1984-12-10 | 1986-07-02 | Grampian Mining Company Limited | Titanium dioxide pigment production from ilmenite |
RU2149908C1 (en) * | 1998-11-03 | 2000-05-27 | Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук | Method of breaking down of mineral and technogenic materials |
US6375923B1 (en) * | 1999-06-24 | 2002-04-23 | Altair Nanomaterials Inc. | Processing titaniferous ore to titanium dioxide pigment |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3428427A (en) * | 1965-06-24 | 1969-02-18 | Quebec Iron & Titanium Corp | Process for producing a product high in titanium dioxide content |
WO1996024555A1 (en) * | 1995-02-10 | 1996-08-15 | Bhp Minerals International Inc. | PROCESSING ILMENITE ORE TO TiO2 PIGMENT |
CN1244498C (en) * | 2003-05-29 | 2006-03-08 | 北京有色金属研究总院 | Manufacture of high grade artificial rutile from low grade primary greporite |
CN101638719A (en) * | 2009-09-08 | 2010-02-03 | 北京矿冶研究总院 | Method for producing synthetic rutile by wet process |
WO2011094858A1 (en) * | 2010-02-04 | 2011-08-11 | Neomet Technologies Inc. | Process for the recovery of titanium dioxide and value metals by reducing the concentration of hydrochloric acid in leach solution and system for same |
WO2013029119A1 (en) * | 2011-09-02 | 2013-03-07 | Iluka Resources Limited | Production of ferrotitanium by aluminothermic reduction |
-
2015
- 2015-02-27 WO PCT/CA2015/000128 patent/WO2015131266A1/en active Application Filing
- 2015-02-27 US US14/634,434 patent/US20150252448A1/en not_active Abandoned
- 2015-02-27 CN CN201580021130.6A patent/CN106232840A/en active Pending
- 2015-02-27 CA CA2941424A patent/CA2941424A1/en not_active Abandoned
- 2015-02-27 AU AU2015226786A patent/AU2015226786A1/en not_active Abandoned
- 2015-02-27 BR BR112016020502A patent/BR112016020502A2/en not_active Application Discontinuation
- 2015-02-27 EP EP15757750.3A patent/EP3114244A4/en not_active Withdrawn
-
2016
- 2016-10-03 ZA ZA2016/06799A patent/ZA201606799B/en unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2527257A (en) * | 1948-09-01 | 1950-10-24 | Edwin G Judd | Process of separating titanium from its ores |
US3236596A (en) * | 1961-08-05 | 1966-02-22 | Bayer Ag | Process for the decomposition of titanium dioxide-containing minerals with hydrochloric acid |
US3407033A (en) * | 1966-01-21 | 1968-10-22 | Giulini Gmbh Geb | Method of treating titanium ores with hydrochloric acid to produce titanium tetrachloride therefrom |
EP0186370A2 (en) * | 1984-12-10 | 1986-07-02 | Grampian Mining Company Limited | Titanium dioxide pigment production from ilmenite |
RU2149908C1 (en) * | 1998-11-03 | 2000-05-27 | Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра Российской академии наук | Method of breaking down of mineral and technogenic materials |
US6375923B1 (en) * | 1999-06-24 | 2002-04-23 | Altair Nanomaterials Inc. | Processing titaniferous ore to titanium dioxide pigment |
Non-Patent Citations (1)
Title |
---|
See also references of EP3114244A4 * |
Also Published As
Publication number | Publication date |
---|---|
AU2015226786A1 (en) | 2016-10-20 |
EP3114244A1 (en) | 2017-01-11 |
ZA201606799B (en) | 2022-08-31 |
BR112016020502A2 (en) | 2018-12-11 |
US20150252448A1 (en) | 2015-09-10 |
CN106232840A (en) | 2016-12-14 |
EP3114244A4 (en) | 2017-11-08 |
CA2941424A1 (en) | 2015-09-11 |
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