Ilmenite | |
---|---|
General | |
Category | Oxide mineral |
Formula (repeating unit) | Iron titanium oxide, FeTiO 3 |
IMA symbol | Ilm [1] |
Strunz classification | 4.CB.05 |
Dana classification | 04.03.05.01 |
Crystal system | Trigonal |
Crystal class | Rhombohedral (3) H-M symbol: (3) |
Space group | R3 (no. 148) |
Unit cell | a = 5.08854(7) c = 14.0924(3) [Å]: Z = 6 |
Identification | |
Color | Iron-black; gray with a brownish tint in reflected light |
Crystal habit | Granular to massive and lamellar exsolutions in hematite or magnetite |
Twinning | {0001} simple, {1011} lamellar |
Cleavage | Absent; parting on {0001} and {1011} |
Fracture | Conchoidal to subconchoidal |
Tenacity | Brittle |
Mohs scale hardness | 5–6 |
Luster | Metallic to submetallic |
Streak | Black |
Diaphaneity | Opaque |
Specific gravity | 4.70–4.79 |
Optical properties | Uniaxial (–) |
Birefringence | Strong; O: pinkish brown, E: dark brown (bireflectance) |
Other characteristics | Weakly magnetic |
References | [2] [3] [4] |
Ilmenite is a titanium-iron oxide mineral with the idealized formula FeTiO
3. It is a weakly magnetic black or steel-gray solid. Ilmenite is the most important ore of titanium [5] and the main source of titanium dioxide, which is used in paints, printing inks, [6] fabrics, plastics, paper, sunscreen, food and cosmetics. [7]
Ilmenite is a heavy (specific gravity 4.7), moderately hard (Mohs hardness 5.6 to 6), opaque black mineral with a submetallic luster. [8] It is almost always massive, with thick tabular crystals being quite rare. It shows no discernible cleavage, breaking instead with a conchoidal to uneven fracture. [9]
Ilmenite crystallizes in the trigonal system with space group R3. [10] [3] The ilmenite crystal structure consists of an ordered derivative of the corundum structure; in corundum all cations are identical but in ilmenite Fe2+ and Ti4+ ions occupy alternating layers perpendicular to the trigonal c axis.
Pure ilmenite is paramagnetic (showing only very weak attraction to a magnet), but ilmenite forms solid solutions with hematite that are weakly ferromagnetic and so are noticeably attracted to a magnet. Natural deposits of ilmenite usually contain intergrown or exsolved magnetite that also contribute to its ferromagnetism. [8]
Ilmenite is distinguished from hematite by its less intensely black color and duller appearance and its black streak, and from magnetite by its weaker magnetism. [9] [8]
In 1791 William Gregor discovered a deposit of black sand in a stream that runs through the valley just south of the village of Manaccan (Cornwall), and identified for the first time titanium as one of the constituents of the main mineral in the sand. [11] [12] [13] Gregor named this mineral manaccanite. [14] The same mineral was found in the Ilmensky Mountains, near Miass, Russia, and named ilmenite. [9]
Pure ilmenite has the composition FeTiO3. However, ilmenite most often contains appreciable quantities of magnesium and manganese and up to 6 wt% of hematite, Fe2O3, substituting for FeTiO3 in the crystal structure. Thus the full chemical formula can be expressed as (Fe,Mg,Mn,Ti)O3. [8] Ilmenite forms a solid solution with geikielite (MgTiO
3) and pyrophanite (MnTiO
3) which are magnesian and manganiferous end-members of the solid solution series. [3]
Although ilmenite is typically close to the ideal FeTiO
3 composition, with minor mole percentages of Mn and Mg, [3] the ilmenites of kimberlites usually contain substantial amounts of geikielite molecules, [15] and in some highly differentiated felsic rocks ilmenites may contain significant amounts of pyrophanite molecules. [16]
At temperatures above 950 °C (1,740 °F), there is a complete solid solution between ilmenite and hematite. There is a miscibility gap at lower temperatures, resulting in a coexistence of these two minerals in rocks but no solid solution. [8] This coexistence may result in exsolution lamellae in cooled ilmenites with more iron in the system than can be homogeneously accommodated in the crystal lattice. [17] Ilmenite containing 6 to 13 percent Fe2O3 is sometimes described as ferrian ilmenite. [18] [19]
Ilmenite alters or weathers to form the pseudo-mineral leucoxene, a fine-grained yellowish to grayish or brownish material [8] [20] enriched to 70% or more of TiO2. [19] Leucoxene is an important source of titanium in heavy mineral sands ore deposits. [21]
Ilmenite is a common accessory mineral found in metamorphic and igneous rocks. [3] It is found in large concentrations in layered intrusions where it forms as part of a cumulate layer within the intrusion. Ilmenite generally occurs in these cumulates together with orthopyroxene [22] or in combination with plagioclase and apatite ( nelsonite ). [23]
Magnesian ilmenite is formed in kimberlites as part of the MARID association of minerals (mica-amphibole-rutile-ilmenite-diopside) assemblage of glimmerite xenoliths. [24] Manganiferous ilmenite is found in granitic rocks [16] and also in carbonatite intrusions where it may also contain anomalously high amounts of niobium. [25]
Many mafic igneous rocks contain grains of intergrown magnetite and ilmenite, formed by the oxidation of ulvospinel. [18]
Most ilmenite is mined for titanium dioxide production. [26] Ilmenite and titanium dioxide are used in the production of titanium metal. [27] [28]
Titanium dioxide is most used as a white pigment and the major consuming industries for TiO2 pigments are paints and surface coatings, plastics, and paper and paperboard. Per capita consumption of TiO2 in China is about 1.1 kilograms per year, compared with 2.7 kilograms for Western Europe and the United States. [29]
Titanium is the ninth most abundant element on Earth and represents about 0.6 percent of the Earth's crust. Ilmenite is commonly processed to obtain a titanium concentrate, which is called "synthetic rutile" if it contains more than 90 percent TiO2, or more generally "titaniferous slags" if it has a lower TiO2 content. More than 80 percent of the estimated global production of titanium concentrate is obtained from the processing of ilmenite, while 13 percent is obtained from titaniferous slags and 5 percent from rutile. [30]
Ilmenite can be converted into pigment grade titanium dioxide via either the sulfate process or the chloride process. [31] Ilmenite can also be improved and purified to titanium dioxide in the form of rutile using the Becher process. [32]
Ilmenite ores can also be converted to liquid iron and a titanium-rich slag using a smelting process. [33]
Ilmenite ore is used as a flux by steelmakers to line blast furnace hearth refractory. [34]
Ilmenite can be used to produce ferrotitanium via an aluminothermic reduction. [35]
Feedstock | TiO 2 Content | Process |
---|---|---|
(%) | ||
Ore | <55 | Sulfate |
Ore | >55 | Chloride |
Ore | <50 | Smelting (slag) |
Synthetic rutile | 88–95 | Chloride |
Chloride slag | 85–95 | Chloride |
Sulfate slag | 80 | Sulfate |
Year | 2011 | 2012–13 |
---|---|---|
Country | USGS | Projected |
Australia | 1,300 | 247 |
South Africa | 1,161 | 190 |
Mozambique | 516 | 250 |
Canada | 700 | |
India | 574 | |
China | 500 | |
Vietnam | 490 | |
Ukraine | 357 | |
Senegal | - | 330 |
Norway | 300 | |
United States | 300 | |
Madagascar | 288 | |
Kenya | - | 246 |
Sri Lanka | 62 | |
Sierra Leone | 60 | |
Brazil | 48 | |
Other countries | 37 | |
Total world | ~6,700 | ~1,250 |
Most ilmenite is recovered from heavy mineral sands ore deposits, where the mineral is concentrated as a placer deposit and weathering reduces its iron content, increasing the percentage of titanium. However, ilmenite can also be recovered from "hard rock" titanium ore sources, such as ultramafic to mafic layered intrusions or anorthosite massifs. The ilmenite in layered intrusions is sometimes abundant, but it contains considerable intergrowths of magnetite that reduce its ore grade. Ilmenite from anorthosite massifs often contain large amounts of calcium or magnesium that render it unsuitable for the chloride process. [39]
The proven reserves of ilmenite and rutile ore are estimated at between 423 and 600 million tonnes titanium dioxide. The largest ilmenite deposits are in South Africa, India, the United States, Canada, Norway, Australia, Ukraine, Russia and Kazakhstan. Additional deposits are found in Bangladesh, Chile, Mexico and New Zealand. [40]
Australia was the world's largest ilmenite ore producer in 2011, with about 1.3 million tonnes of production, followed by South Africa, Canada, Mozambique, India, China, Vietnam, Ukraine, Norway, Madagascar and United States.
The top four ilmenite and rutile feedstock producers in 2010 were Rio Tinto Group, Iluka Resources, Exxaro and Kenmare Resources, which collectively accounted for more than 60% of world's supplies. [41]
The world's two largest open cast ilmenite mines are:
Major mineral sands based ilmenite mining operations include:
Attractive major potential ilmenite deposits include:
In 2020, China has by far the highest titanium mining activity. About 35 percent of the world’s ilmenite is mined in China, representing 33 percent of total titanium mineral mining (including ilmenite and rutile). South Africa and Mozambique are also important contributors, representing 13 percent and 12 percent of worldwide ilmenite mining, respectively. Australia represents 6 percent of the total ilmenite mining and 31 percent of rutile mining. Sierra Leone and Ukraine are also big contributors to rutile mining. [30]
China is the biggest producer of titanium dioxide, followed by the United States and Germany. China is also the leader in the production of titanium metal, but Japan, the Russian Federation and Kazakhstan have emerged as important contributors to this field.
Patenting activity related to titanium dioxide production from ilmenite is rapidly increasing. [30] Between 2002 and 2022, there have been 459 patent families that describe the production of titanium dioxide from ilmenite, and this number is growing rapidly. The majority of these patents describe pre-treatment processes, such as using smelting and magnetic separation to increase titanium concentration in low-grade ores, leading to titanium concentrates or slags. Other patents describe processes to obtain titanium dioxide, either by a direct hydrometallurgical process or through two industrially exploited processes, the sulfate process and the chloride process. Acid leaching might be used either as a pre-treatment or as part of a hydrometallurgical process to directly obtain titanium dioxide or synthetic rutile (>90 percent titanium dioxide, TiO2). The sulfate process represents 40 percent of the world’s titanium dioxide production and is protected in 23 percent of patent families. The chloride process is only mentioned in 8 percent of patent families, although it provides 60 percent of the worldwide industrial production of titanium dioxide. [30]
Key contributors to patents on the production of titanium dioxide are companies from China, Australia and the United States, reflecting the major contribution of these countries to industrial production. Chinese companies Pangang and Lomon Billions Groups are the main contributors and hold diversified patent portfolios covering both pre-treatment and the processes leading to a final product.
In comparison, patenting activity related to titanium metal production from ilmenite remains stable. [30] Between 2002 and 2022, there have been 92 patent families that describe the production of titanium metal from ilmenite, and this number has remained quite steady. These patents describe the production of titanium metal starting from mineral ores, such as ilmenite, and from titanium dioxide (TiO2) and titanium tetrachloride (TiCl4), a chemical obtained as an intermediate in the chloride process. The starting materials are purified if needed, and then converted to titanium metal by a chemical reduction process using a reducing agent. Processes mainly differ in regard to the reducing agent used to transform the starting material into titanium metal: magnesium is the most frequently cited reducing agent and the most exploited in industrial production.
Key players in the field are Japanese companies, in particular Toho Titanium and Osaka Titanium Technologies, both focusing on reduction using magnesium. Pangang also contributes to titanium metal production and holds patents describing reduction by molten salt electrolysis. [30]
Ilmenite has been found in lunar samples, particularly in high-Ti lunar mare basalts common from Apollo 11 and Apollo 17 sites, and on average, constitutes up to 5% of lunar meteorites. [46] Ilmenite has been targeted for ISRU water and oxygen extraction due to a simplistic reduction reaction which occurs with CO and H2 buffers. [47] [48] [49]
This article incorporates text from a free content work. Licensed under CC-BY. Text taken from Production of titanium and titanium dioxide from ilmenite and related applications , WIPO.
Hematite, also spelled as haematite, is a common iron oxide compound with the formula, Fe2O3 and is widely found in rocks and soils. Hematite crystals belong to the rhombohedral lattice system which is designated the alpha polymorph of Fe
2O
3. It has the same crystal structure as corundum (Al
2O
3) and ilmenite (FeTiO
3). With this it forms a complete solid solution at temperatures above 950 °C (1,740 °F).
Titanium is a chemical element; it has symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in sea water, aqua regia, and chlorine.
Rutile is an oxide mineral composed of titanium dioxide (TiO2), the most common natural form of TiO2. Rarer polymorphs of TiO2 are known, including anatase, akaogiite, and brookite.
Limonite is an iron ore consisting of a mixture of hydrated iron(III) oxide-hydroxides in varying composition. The generic formula is frequently written as FeO(OH)·nH2O, although this is not entirely accurate as the ratio of oxide to hydroxide can vary quite widely. Limonite is one of the three principal iron ores, the others being hematite and magnetite, and has been mined for the production of iron since at least 400 BC.
Iron ores are rocks and minerals from which metallic iron can be economically extracted. The ores are usually rich in iron oxides and vary in color from dark grey, bright yellow, or deep purple to rusty red. The iron is usually found in the form of magnetite (Fe
3O
4, 72.4% Fe), hematite (Fe
2O
3, 69.9% Fe), goethite (FeO(OH), 62.9% Fe), limonite (FeO(OH)·n(H2O), 55% Fe), or siderite (FeCO3, 48.2% Fe).
In geology, a placer deposit or placer is an accumulation of valuable minerals formed by gravity separation from a specific source rock during sedimentary processes. The name is from the Spanish word placer, meaning "alluvial sand". Placer mining is an important source of gold, and was the main technique used in the early years of many gold rushes, including the California Gold Rush. Types of placer deposits include alluvium, eluvium, beach placers, aeolian placers and paleo-placers.
Titanium dioxide, also known as titanium(IV) oxide or titania, is the inorganic compound derived from titanium with the chemical formula TiO
2. When used as a pigment, it is called titanium white, Pigment White 6 (PW6), or CI 77891. It is a white solid that is insoluble in water, although mineral forms can appear black. As a pigment, it has a wide range of applications, including paint, sunscreen, and food coloring. When used as a food coloring, it has E number E171. World production in 2014 exceeded 9 million tonnes. It has been estimated that titanium dioxide is used in two-thirds of all pigments, and pigments based on the oxide have been valued at a price of $13.2 billion.
Armalcolite is a titanium-rich mineral with the chemical formula (Mg,Fe2+)Ti2O5. It was first found at Tranquility Base on the Moon in 1969 during the Apollo 11 mission, and is named for Armstrong, Aldrin and Collins, the three Apollo 11 astronauts. Together with tranquillityite and pyroxferroite, it is one of three new minerals that were discovered on the Moon. Armalcolite was later identified at various locations on Earth and has been synthesized in the laboratory. (Tranquillityite and pyroxferroite were also later found at various locations on Earth). The synthesis requires low pressures, high temperatures and rapid quenching from about 1,000 °C to the ambient temperature. Armalcolite breaks down to a mixture of magnesium-rich ilmenite and rutile at temperatures below 1,000 °C, but the conversion slows down with cooling. Because of this quenching requirement, armalcolite is relatively rare and is usually found in association with ilmenite and rutile, among other minerals.
Skarns or tactites are coarse-grained metamorphic rocks that form by replacement of carbonate-bearing rocks during regional or contact metamorphism and metasomatism. Skarns may form by metamorphic recrystallization of impure carbonate protoliths, bimetasomatic reaction of different lithologies, and infiltration metasomatism by magmatic-hydrothermal fluids. Skarns tend to be rich in calcium-magnesium-iron-manganese-aluminium silicate minerals, which are also referred to as calc-silicate minerals. These minerals form as a result of alteration which occurs when hydrothermal fluids interact with a protolith of either igneous or sedimentary origin. In many cases, skarns are associated with the intrusion of a granitic pluton found in and around faults or shear zones that commonly intrude into a carbonate layer composed of either dolomite or limestone. Skarns can form by regional or contact metamorphism and therefore form in relatively high temperature environments. The hydrothermal fluids associated with the metasomatic processes can originate from a variety of sources; magmatic, metamorphic, meteoric, marine, or even a mix of these. The resulting skarn may consist of a variety of different minerals which are highly dependent on both the original composition of the hydrothermal fluid and the original composition of the protolith.
Chromite is a crystalline mineral composed primarily of iron(II) oxide and chromium(III) oxide compounds. It can be represented by the chemical formula of FeCr2O4. It is an oxide mineral belonging to the spinel group. The element magnesium can substitute for iron in variable amounts as it forms a solid solution with magnesiochromite (MgCr2O4). A substitution of the element aluminium can also occur, leading to hercynite (FeAl2O4). Chromite today is mined particularly to make stainless steel through the production of ferrochrome (FeCr), which is an iron-chromium alloy.
A layered intrusion is a large sill-like body of igneous rock which exhibits vertical layering or differences in composition and texture. These intrusions can be many kilometres in area covering from around 100 km2 (39 sq mi) to over 50,000 km2 (19,000 sq mi) and several hundred metres to over one kilometre (3,300 ft) in thickness. While most layered intrusions are Archean to Proterozoic in age, they may be any age such as the Cenozoic Skaergaard intrusion of east Greenland or the Rum layered intrusion in Scotland. Although most are ultramafic to mafic in composition, the Ilimaussaq intrusive complex of Greenland is an alkalic intrusion.
The Tiwest Joint Venture was a joint venture between Tronox Western Australia Pty Ltd and subsidiaries of Exxaro Australia Sands Pty Ltd. The Tiwest Joint Venture was a mining and processing company, established in 1988, to extract ilmenite, rutile, leucoxene and zircon from a mineral sands deposit at Cooljarloo, 14 km north of Cataby, Western Australia. As of June 2012, the joint venture was formally dissolved, when Tronox acquired the mineral-sands-related divisions of Exxaro outright.
Ulvöspinel or ulvite is an iron titanium oxide mineral with formula: Fe2TiO4 or TiFe2+2O4. It forms brown to black metallic isometric crystals with a Mohs hardness of 5.5 to 6. It belongs to the spinel group of minerals, as does magnetite, Fe3O4.
In geology, a redox buffer is an assemblage of minerals or compounds that constrains oxygen fugacity as a function of temperature. Knowledge of the redox conditions (or equivalently, oxygen fugacities) at which a rock forms and evolves can be important for interpreting the rock history. Iron, sulfur, and manganese are three of the relatively abundant elements in the Earth's crust that occur in more than one oxidation state. For instance, iron, the fourth most abundant element in the crust, exists as native iron, ferrous iron (Fe2+), and ferric iron (Fe3+). The redox state of a rock affects the relative proportions of the oxidation states of these elements and hence may determine both the minerals present and their compositions. If a rock contains pure minerals that constitute a redox buffer, then the oxygen fugacity of equilibration is defined by one of the curves in the accompanying fugacity-temperature diagram.
Kenmare Resources plc is a publicly traded mining company headquartered in Dublin, Republic of Ireland. Its primary listing is on the London Stock Exchange and it has a secondary listing on Euronext Dublin. Kenmare is one of the world's largest mineral sands producers and the Company owns and operates the Moma Titanium Minerals Mine. Moma is one of the world's largest titanium minerals deposits, located 160 km from the city of Nampula in Mozambique.
The chloride process is used to separate titanium from its ores. The goal of the process is to win high purity titanium dioxide from ores such as ilmenite (FeTiO3) and rutile (TiO2). The strategy exploits the volatility of TiCl4, which is readily purified and converted to the dioxide. Millions of tons of TiO2 are produced annually by this process, mainly for use as white pigments. The chloride process has largely displaced the older sulfate process, which relies on hot sulfuric acid to extract iron and other impurities from ores.
The Becher process is an industrial process used to produce synthetic rutile, a form of titanium dioxide, from the ore ilmenite. It is competitive with the chloride process and the sulfate process, which achieve similar net conversions.
QIT-Fer et Titane is a Canadian mining company located in Quebec. The company operates an ilmenite mine at Lac Allard in northern Quebec, and in the southern Quebec municipality of Sorel-Tracy operates refining facilities that produce titanium dioxide, pig iron, steel, and other metal products.
Richards Bay Minerals (RBM) is a South African mining company. RBM's principal product is titanium dioxide in the form of an 85% pure titanium dioxide slag; the company also produces the higher-purity 95% titanium dioxide product rutile as well as pig iron and zircon.
Nelsonite is an igneous rock primarily constituted of ilmenite and apatite, with anatase, chlorite, phosphosiderite, talc and/or wavellite appearing as minor components. Rocks are equigranular with a grain size around 2 – 3 mm. The black ilmenite is slightly magnetic while the whitish apatite is not.