See also synthetic rutile.
Titanium dioxide pigment (TiO2) is a white powder with high opacity, brilliant whiteness, excellent covering power and resistance to colour change. These properties have made it a valuable pigment and opacifier for a broad range of applications in paints, plastic goods, inks and paper.
The pigment is manufactured by processing naturally occurring the titanium-containing rutile or ilmenite minerals. Rutile is an impure form of titanium dioxide whereas ilmenite contains titanium combined with iron as a compound oxide. Though common throughout the world, they are most readily exploited in Australia, USA, India and South Africa.
In Australia nearly all titanium dioxide is produced from ilmenite as it naturally occurs in accessible high concentrations and in a form which allows the ready extraction of the rutile. These favourable factors have made ilmenite a competitive raw material for Australia's producers reflected in high export activity.
Low energy cost regions use the slagging process.
Australia supplies about 40 per cent of the world's ilmenite and about 25 per cent of its rutile. In contrast to its dominance in titanium minerals, Australia supplies only about a 3 per cent share of the world's titanium dioxide pigment production of around 4 million tonnes. This imbalance implies significant opportunity for adding further value.
In 1995, Western Australia produced 160 000 tonnes of titanium dioxide pigment valued at around $350 million.
By June 1998, Australia is anticipated to export A$1.1 bn of titanium minerals of which two-thirds is exported to Europe and North America.
Titanium dioxide pigment may be manufactured by either the sulfate or the chlorine process (Australia now only use the chlorine process). The technology for the chloride process is tightly held and Ticor is license by Kerr McGee under which brand name it also markets its pigment.
The sulfate process was the first commercial scale technology used to convert ilmenite to titanium dioxide. Producing large quantities of waste iron sulfate and producing an inferior product for most applications, few sulfate process plants are now being built. In 1996, Tioxide, a sulfate-based plant at Burnie, Tasmania, ceased operation after some forty years in operation using ilmenite shipped from Western Australia and local sulfuric acid from metal smelting operations in Tasmania. The plant produced large volumes of iron sulfate waste product. The sulfate process produces a form of pigment called anatase, which is preferred over chloride-derived pigment for use on papers, ceramics and inks.
In cheap electricity locations such as South Africa (coal power) and Norway (hydro power), the ilmenite may be slagged to produce rutile and iron. In Australia, the Becher process produces iron oxide as waste which is retuned to the mine site.
The newer chloride process avoids the iron sulfate waste problem and, at larger scales, is cheaper to operate. This process requires the ilmenite to be processed to the rutile form (ie. removal of the iron component to yield crude titanium dioxide [synthetic rutile]) for which the Becher process was developed in Western Australia. Typically 1.06 tonnes of synthetic rutile is required for each tonne of pigment.
The chlorine process, as now exclusively used in Australia, reacts chlorine with synthetic rutile to form volatile titanium tetrachloride which is then oxidised leaving behind iron chloride and other impurities with the bulk of the chlorine re-cycled. Consumption of chlorine is therefore related to the amount of iron oxide (and alumina) left in the synthetic rutile which is typically 4 per cent. As iron chloride is environmentally harmful it is treated with lime to convert it to iron oxides and the calcium chloride drained to sea.
About one tonne of chlorine is required to produce 5 to 6 tonnes of titanium dioxide pigment (depending on the iron content of the rutile used consuming the chlorine as ferric chloride and with about one-third of chlorine ending up as hydrogen chloride). Tiwest is now supplying hydrochloric acid to Coogee for conversion to ammonium chloride (for use in synthetic rutile production).By using rutile (and not the iron-containing ilmenite), the chloride plants avoid the production of much larger amounts of iron chloride that has to be disposed off (eg. by deep well disposal as used by Dupont of the USA).After removal of vanadium salts, and further fractional distillation, the pure titanium tetrachloride is reacted with oxygen at high temperature to produce titanium dioxide. The titanium dioxide is ground and coated to different grades. The liberated chlorine is recycled. In other words, chlorine is larely consumed as iron chloride which is converted to iron hydroxide after treating with lime. The resultant calcium chloride and iron oxide can be safely disposed.
Worldwide there is a marked swing to the use of the chloride process with few new sulfate plants being established. The chloride process offers tighter product control, less labour intensive, and environmentally safer. Currently about about 60 per cent of the 4 million tonnes of pigment produced produced world-wide is produced by the chlorine process. Though declining in response to concerns about environmentally unacceptable waste, many sulfate plants have introduced innovative techniques deferring their closure. This status is contributing to depress prices for synthetic rutile.
The chloride plants require a high grade of rutile. The lower grades of ilmenite (52 to 57 per cent titanium dioxide) are exported by West Australian titanium mineral producers to oveseas sulfate-based plants and electric arc furnaces. The producers claim the lower grades of ilmenite could not be economically converted to synthetic rutile in the current world status of cheap slagged ilmenite (with zero nucleide content).The nucleide issue is that the mineral sands contain monazite which typically contains 6 per cent of the radioactive element thorium (and some uranium. In 1990, some 13 000 tonnes of monazite were produced but fell to zero due to competition from nucleide free sources such as China. There is interest in processing monazite by Rhone-Poulenc at Pinjarra.
About 40 per cent of the state's ilmenite production (about $80 per tonne) is converted to synthetic rutile ($470 per tonne) and of that 40 per cent, only about 30 per cent is converted to the pigment (valued at about $2 000 per tonne). In other words, pigment production could increase eight-fold!
There are two manufacturers of titanium dioxide pigment in Western Australia,Millennium International Chemicals (MIC, formerly SCM Chemicals Ltd) at Kemerton, Western Australia andTiwest Joint Venture at Kwinana, Western Australia.
Millennium Inorganic Chemicals (MIC, formerly SCM Chemicals and part of the Millennium Chemicals group) is located near the regional city of Bunbury some 150 kilometres south of the State capital of Perth. It uses the chlorine process in a plant established in 1990 with a capacity of around 80,000 tonnes. Located near high grade ilmenite deposits, it is well placed to expand and profitable.
Synthetic rutile (ie. after the Becher process) is purchased by Millennium Inorganic Chemicals on the open market from West Australian mineral sand mining companies.
In February 2000, MIC purchased Hanwha Ceramics becoming Millennium Performance Chemicals.
In 2001, the company expanded production to 95 000 tpa having signalled intentions to double its production train.
The Tiwest Joint Venture (formerly Cooljarloo Joint Venture) was established in 1990 as a joint venture of Minproc and Kerr McGee. Unlike Millennium Inorganic Chemicals, it owns the mineral deposit (at Cooljarloo). Tiwest operates with a primary processing plant at Chandala producing crude titanium dioxide (synthetic rutile) from ilmenite from their mine near Eneabba. The operation uses the thermal Becher process to convert 220 000 tonnes ilmenite to 130 000 tonnes of synthetic rutile (94 per cent titanium dioxide). The iron oxide waste by-product is returned to the mine site. About one-half, 65 000 tonnes, of the synthetic rutile is used to produce pigment with technology based on the Kerr McGee 100 000 tonne USA plant.
Tiwest titanium pigment plant at Kwinana.
The Kwinana plant processes about half the rutile (produced at Chandala) to the pigment producing about 70 000 tonnes per year of titanium dioxide pigment. About 85 per cent is exported. The balance of the synthetic rutile, and all the natural rutile is sold largely to their part owners (Kerr McGee) in the USA.
Zirconium ortho sulfate & zirconium oxychloride supplied by Hanwha and sodium aluminate provided by Coogee Chemicals are also used to modify the pigment to render it more suitable for specialised applications (varies the surface area). This is an important way for product differentiation into which extensive research has been applied.
Millennium Inorganic Chemicals Chemicals requires chlorine and 45 000 tpa oxygen supplied by BOC and 65 000 tonnes of nitrogen. (Air Liquide supplies oxygen to Tiwest at Kwinana.) Electricity About 1000 kW hours of electricity is required to produce one tonne of pigment from synthetic rutile. At a nominal industry value of A$0.06 per kilowatt hour, electricity would represent 4 to 5 per cent of the finished pigment (a total of around 8 per cent, allowing for around 4 per cent for the production of synthetic rutile).
In Nov 1997, it was announced Tiwest was establishing a cogeneration plant to that the production of 80 000 tpa of titanium dioxide pigment would require 14 megawatts of electricity per hour (and 20 tonnes of steam).
Chlorine is an important input for the pigment industry produced by two chloralkali plants. The two plants operate at small scale using current technology dedicated to the production of the expensive to transport chlorine on take or pay contracts. The scale penalty is however much less than the cost of shipping expensive to transport chlorine, although chlorine is claimed to be at least twice the cost of that produced by overseas plants.
The Australian market for titanium dioxide pigment is estimated to be about 40 000 tonnes per year valued at $80 million supplied by the local manufacturers for all but 1 000 tonnes of imported pigment. About three-quarters of production is exported (Tiwest is 85 per cent exported)..
The large applications for titanium dioxide pigment are for the manufacture of paints (about 60 per cent), plastics (about 25 per cent), and paper and printing inks (about 15 per cent). The Western Australian market is estimated to be less than 1 000 tonnes of pigment.
The domestic price of titanium pigment is determined by imports and in 1987 was about 10 per cent above world traded prices as a consequence of import duties. The removal of tariffs has now eliminated that margin though imports remain at less than 2 per cent of the market (believed to be special specification forms of the pigment).
Turnover has been increasing at 3 per cent per year in recent years with both plants operating near full capacity with some debottlenecking at the Tiwest plant.
Western Australia's two titanium dioxide plants are modern (commissioned 1990 and 1991) of world class standard in technology and scale (70 000 and 65 000 tonne capacity respectively).
Capital cost is a disadvantage for the pigment industry here. For Tiwest the cost is around A$4 500 per tonne of pigment compared with A$3 500 in competitive plants. Whereas competitive plants move their products an average of 500 km, the Australian producers move them an average of 5 000 km. Production to cash too is longer, 60 to 90 days cf 30 days for competitors..
Millennium Inorganic Chemicals and Tiwest are both favourably located with respect to synthetic rutile supplies - Millennium Inorganic Chemicals supplied by the southern suppliers and Tiwest using northern reserves of ilmenite for its plant. The titanium minerals are at internationally competitive prices less international freight costs. Their competitiveness is reflected in the pigment industry exporting about three-quarters of production overseas.
Though showing world competitiveness, access to low cost rutile is claimed to offset the cost of major overseas chlorine and electricity. Chlorine is also claimed to be twice the cost of competing plants (having been ten-times greater and electricity, though acknowledged to be cheap by most world standards, could be cheaper when compared to some Australian states.
Millennium Inorganic Chemicals has also been quite profitable recording an average of 28.5 per cent annual weighted average return on shareholders funds over five years (24 per cent for 1995-96). The figure was calculated as net profit after tax divided by shareholders funds expressed as a percentage. Source Business Review Weekly, February 17, 1997 prepared by IBIS Business Information.) This return places Millennium Inorganic Chemicals as 68th most profitable. For comparison, Australia's 100 biggest firms achieved 10.9 per cent for 1995-96.
Until closing in 1996, the other Australian producer of titanium dioxide, Tioxide at Burnie, Tasmania, had been using ilmenite shipped from Western Australian for use in a sulfate process. Producing large amounts of iron sulfate waste, before closing it responded to environmental concerns by switching to imported rutile slag typically containing 85 per cent titanium dioxide.
Western Australia titanium mineral sands plants typically convert less than one-half the ilmenite to synthetic rutile of which one-third is supplied to Western Australia's two pigments plants with the balance exported. The balance of ilmenite not converted to rutile is often of a lower grade (52 to 57 per cent titanium dioxide) which is exported largely to sulfate-based plants. In other words, some seven-eighths of the state's titanium mineral is exported as raw materials for overseas pigment plants.
Synthetic rutile prices have been declining as the swing from sulfate to chloride plants has been slower than predicted and through competition from South Africa's low cost chloride-grade rutile slag producers. (prices in 1994-98 are 17 per cent lower than in the 1980s in real terms). This pressure is being reflected in declining prices for ilmenite and synthetic rutile but of course, as their raw material, is helping Western Australia's pigment industry. Tiwest, also helped by improving pigment prices, announced plans (June 1994) to double pigment production with an outlay of $168m.
Though to a large extent a commodity product competing on price, research is being extended to producing superior forms of the pigment. Tiwest is producing a new grade of titanium dioxide coated with zirconium sulfate to improve the UV stability of the medium in which the pigment is applied. (Zirconium sulfate is produced at Hanwha). The availability of local zirconium chemicals, may help the pigment industry and create a market niche.
Expectations of rapid world growth (3 per cent, or some 100 000 tonnes per year) has led to investment in chloride plants helped by the closure of sulfate process units. One industry source suggested a world capacity utilisation rate of 79 per cent for sulfate producers and 92 per cent for chloride plants (an average of 86 per cent for all plants). Helped by innovative technology, the closures of sulfate plants have been below expectations sustaining the market for the cheaper, lower grades of ilmenite. As a result, Western Australia's titanium mineral producers find it more profitable to export ilmenite (claimed to be for lower cost sulfate and lower cost iron chloride deep well projects) than to add value to produce synthetic rutile.
Clearly any enlargement (up to eight-fold) of Western Australia's pigment industry will relieve the pressure on the ilmenite and synthetic rutile industry. At present, overseas pigment plants add about $1.6 billion, or about three times the value currently added in Western Australia to the state's titanium minerals. It is worth noting also that while Australia produces around 26 per cent of world production of titanium minerals, it produces just 4 per cent of world production of titanium dioxide pigment!
The titanium dioxide pigment industry has the theoretical potential to approach the turnover value of the alumina industry.
In the Goldfields, a sulfate-derived pigment could be viable in this region where sulfuric acid is available on competitive terms and with fewer environmental issues to preclude the dumping of iron sulfate waste.
|Millennium Inorganic Chemicals Chemicals announced a A$470M plant expansion doubling titanium dioxide pigment production to 190,000 tonnes within two years. The company indicates it did not have contract to underwrite its increased production and was seeking new markets.|
On March 5, 1997, Tiwest announced (West Australian) that because of a fall in the price of pigment from US$2080 to US$1400, the expansion has been deferred. A price of US$1700 is sought. (Ticor also incurred a A423million loss last year). Current production is around 80 000 tonnes.
Titanium metal is produced by the Knoll process, chlorinating rutile to titanium tetrachloride and reduced to titanium sponge using magnesium metal. The sponge is converted to the titanium in the ingot form in an electric arc furnace. Typical power consumption is around 2.5Megawatts per tonne produced equivalent to 10 per cent of final product.
Involving titanium tetrachloride, the process is ideally integrated with the manufacture of titanium dioxide pigment.
Australia presently does not manufacture magnesium metal. The process is moderately energy-intensive. A downturn in world demand has created some current capacity under-utilisation.
Contacts Tiwest Joint Venture
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