Welcome to the Presentation Of

Titanium Dioxide
Prepared By: Ashraful Kabir(corporate engineer)
 Introduction
Titanium dioxide, also called titania, (TiO2), a white, opaque, naturally
occurring mineral existing in a number of crystalline forms, the most
important of which are rutile and anatase. These naturally occurring
oxide forms can be mined and serve as a source for commercial
titanium. Titanium oxide is odorless and absorbent. Its most
important function in powder form is as a widely used pigment for
lending whiteness and opacity.
Titanium dioxide has been used as a bleaching and opacifying agent
in porcelain enamels, giving them brightness, hardness, and acid
resistance. In modern times it is used in cosmetics, such as in skin
care products and sunscreen lotions, with claims that titanium
dioxide protects the skin from ultraviolet radiation because of its
property to absorb ultraviolet light.
Titanium dioxide
 Forms of Titanium dioxide
• TiO2 possesses different qualities depending on whether it
is produced as pigment-grade or nanomaterial-grade. Both
forms are tasteless, odourless and insoluble.
• Pigment-grade TiO2 particles are approximately 200-350nm
in dimension and this form accounts for 98 percent of total
production. It is used mainly for light scattering and surface
opacity applications, such as paint – this includes its use as
a base for various colour paints or as a standalone ‘brilliant’
white.
• Nano, or ultrafine TiO2 comprises of primary particles sized
less than 100nm. In this grade, titanium dioxide is
transparent (colourless) and boasts improved UV scattering
and absorbing properties compared with larger particle-
size, pigment-grade TiO2.
 Physical Properties Of TiO2
 Solubility: It is insoluble in dilute alkali, dilute acid, but soluble in hot
concentrated sulfuric acid, hydrochloric acid, nitric acid. The solubility of
titanium dioxide is related to solutes.
 The relative density: In the commonly used white pigment, the relative
density of titanium dioxide is minimum. Of the same quality white
pigment, titanium dioxide surface area is the largest and pigment
volume is the highest.
 Permittivity: Because of high dielectric constant of titanium dioxide, it
has excellent electrical properties. Anatase titanium dioxide's
permittivity is lower, only 48.
 Conductivity: Titanium dioxide with the performance of the
semiconductor, its conductivity increased rapidly with increasing
temperature, but also is very sensitive to hypoxia.
 Physical Properties Of TiO2
 Melting and Boiling points: It can be transformed into rutile when
anatase and plate titanium dioxide are at high temperatures, so melting
and boiling points of the board of Rutile and anatase titanium dioxide
actually does not exist. Only rutile titanium dioxide has a melting point
and boiling point, rutile titanium dioxide, a melting point of 1850℃, the
melting point in oxygen-rich is 1879℃. The melting point of titanium
dioxide is related to the purity of the titanium dioxide.

 Hydroscopicity: Although titanium dioxide has hydroscopicity, but not

too strong. The hydrophilic is related to surface area.The surface area is
more large, the moisture absorption is higher.The moisture absorption
of titanium dioxide is relevant to the surface treatment and the nature
too.
 Thermal Stability: Titanium dioxide has a good thermal stability, the
general amount of 0.01% to 0.12%.
 Chemical Properties Of TiO2
Titanium dioxide is non-toxic and chemical
properties are stable. It almost has no reaction
with other material produce under normal
temperature. It has no reaction with oxygen,
hydrogen sulfide, sulfur dioxide, carbon dioxide
and ammonia and is not soluble in water, fatty
acids, other organic acid and weak inorganic
acid except for alkali and hot nitric acid.
 Chemical Properties Of TiO2
But, in some specific conditions, titanium dioxide can get reaction with
some substance. For example, these reactions as follows:

 Only in the circumstance of long time boiling can it be totally soluble in

strong sulfuric acid and hydrofluoric acid. The reaction equation is as
follows:
TiO2+ 2H2SO4 = Ti(SO4)2 + 2H2O
TiO2+ H2SO4 = TiOSO4 + H2O
TiO2 + 6HF = H2TiF6 + 2H2O
 Titanium dioxide can melt in the alkali (sodium hydroxide, potassium
hydroxide) or alkali metal carbonate (sodium carbonate, potassium
carbonate). Any one of which i have mentioned with Titanium dioxide can
be transformed into soluble acid titanate.
TiO2 + 4NaOH = Na4TiO4 + 2H2O
 Chemical Properties Of TiO2
 At high temperature, if a reductant (carbon, starch, petroleum coke) exists,
titanium dioxide can be chlorinated into titanium tetrachloride by chlorine.The
response equation is as follows:
TiO2 +2C +2Cl2 = TiCl4 + 2CO

 Titanium dioxide under high temperature can be restored into Low-valent titanium
compounds by hydrogen, Na, Mg, aluminum, zinc, calcium, and some elements of
the constant. If we put the dry hydrogen into red titanium dioxide, it can get Ti2O3;
In 2000℃ and 15.2 MPa of hydrogen, it also can get TiO. If the rutile titanium
dioxide is injected into the plasma chamber, it will be reduced to titanium metal
through hydrogen. Three reaction equations are as follows:
2TiO2 + H2 = Ti2O3 + H2O
TiO2 + H2 = TiO+ H2O
TiO2 + 2H2 = Ti + 2H2O
 Occurrence in nature
Titanium is a very common element. It is the ninth
most abundant element in the Earth's crust. Its
abundance is estimated to be about 0.63 percent.
That places titanium just above hydrogen and just
below potassium among elements present in the
earth. Titanium metal is brittle when cold and can
break apart easily at room temperature. The most
common mineral sources of titanium are illmenite,
rutile, and anatase. Titanium is also obtained
from iron ore slags.
 Manufacture of titanium dioxide

 There are two main processes, the Sulfate Process and the Chloride
Process which use the two principal ores, ilmenite and rutile,
respectively. Ilmenite contains 45-60% TiO2 and rutile contains up
to 99% TiO2. The ores are mined worldwide but most production is
in Australia and South Africa.
 Each large producer of titanium dioxide balances its production
between the two processes. Each produces the oxide in the rutile
crystal form but the Sulfate Process can also produce another form
of the oxide, anatase, which is softer and which is used for a small
number of specialist applications.
 The Sulfate Process is run as a batch proces and the Chloride
Process is run as a continuous process. It is estimated that about
65% of the world's production is based on the Chloride Process.
 Manufacture of titanium dioxide
The Sulfate Process

The chemistry of the process involves three

main stages:
a) dissolving the ore
b) formation of hydrated titanium dioxide
c) formation of anhydrous titanium dioxide
 Manufacture of titanium dioxide
 (a) Dissolving the ore
The ore is usually ilmenite, FeTiO3. It is ground finely and dissolved in
sulfuric acid to form a mixture of sulfates:

Before the titanium dioxide is extracted, the iron ions must be removed
from the solution so that the colour of the final product is not spoiled. The
solution is therefore reacted with recycled iron sources to convert any
iron(lll) ions that may be present to iron(ll) ions:

The solution is allowed to stand so that the unreacted solid settles, and the
clear liquid is poured off before being concentrated by evaporation. Cooling
then allows light green crystals of iron(ll) sulfate to form and to be filtered
off. These are sold separately. The remaining solution contains titanyl
sulfate, TiOSO4.
 Manufacture of titanium dioxide
 (b) Formation of hydrated titanium dioxide
The next stage involves the hydrolysis of the titanyl sulfate in solution to give insoluble,
hydrated titanium dioxide:

This is a critical stage and the conditions must be controlled to ensure that the precipitate
is suitable for filtering and roasting.
 (c) Formation of anhydrous titanium dioxide
The final stage of the process is the heating of the solid in a furnace, known as a
calciner. This is a rotating cylinder which is typically heated by gas flames. As the cylinder
turns, the titanium dioxide passes along it and its temperature rises from 313 K, as it
enters, to over 1000 K as it leaves:

Heating evaporates the water and decomposes any remaining sulfuric acid in the solid.
After cooling, the product is 'milled' to form crystals of the size needed. Crystals may also
be coated with another substance, such as aluminium oxide or silica, to make the titanium
dioxide mix more easily with liquids or to make the water-based paints made from it last
longer.
 Manufacture of titanium dioxide
This coating is achieved by dispersing the dry product from the
calciner in water containing the dissolved coating chemicals
which precipitate from solution onto the TiO2 crystals. The
coating is usually between 3 and 8% by weight in the final dried
pigment. This coating is achieved by changing the temperature
and pH of the solution. Each TiO2 crystal needs to be coated
uniformly to maximize the effectiveness of the coating. The
coated TiO2 crystals are filtered from the water and dried
before being packed for dispatch to the final customer.
 Manufacture of titanium dioxide
The Chloride Process
There are two main stages:
a) the conversion of rutile to titanium(IV)
chloride
b) the oxidation of titanium(IV) chloride
 Manufacture of titanium dioxide
(a) The conversion of rutile to titanium(IV)
chloride
The rutile is fed into a heated bed together with a source of carbon, usually
coke. Chlorine is fed into the bed and the reaction takes place to form
titanium(IV) chloride in the vapour form which is removed from the
bed. Iron and other metals in the ore are chlorinated and also leave the bed
in the vapour state. The oxygen in the ores is combined with the carbon to
form carbon monoxide and dioxide. The vapour stream is cooled and the
metal chlorides other than titanium(IV) chloride are condensed and
solidified. The titanium(IV) chloride vapour, which contains almost pure
titanium(IV) chloride and has a lower boiling point, is then condensed and
stored as liquid. It is then reboiled and distilled to give a purer product to
feed to the next stage.
 Manufacture of titanium dioxide
 (b) The oxidation of titanium(IV) chloride
Liquid titanium(IV) chloride is vapourised and burnt in oxygen, together with
a hydrocarbon fuel source (for example, methane) to a high temperature to
initiate the reaction and keep the temperature high enough for the reaction
to proceed:

The titanium dioxide is formed (by adding seed crystals) as a fine solid in the
gas stream and is filtered out of the waste gases using cyclones or
filters. Once again control of crystal growth is important to give particles of
the correct size for pigments. This is done by adding nucleating agents to
the gas stream (e.g. water or aluminium chloride) and by cooling the
products. The chlorine in titanium(IV) chloride is released and recycled to
the chlorination stage of the process above.
The product contains small amounts of absorbed chlorine gas which are
removed. The product is washed and dried before milling and surface
treatment in an identical manner to that used in the Sulfate Process
described .
 Comparison of the two processes for the
manufacture of titanium dioxide.
Sulfate Process Chloride Process
 long established and simple  new technology
technology  needs high grade ore
 uses lower grade, cheaper  continuous process
ores  small amounts of waste
 batch process formed with toxicity
 large amounts of waste problems: Cl2and TiCl4
materials  recovery and recycling of
 pollution control expensive chlorine possible
 produces anatase and rutile  only produces rutile
pigments pigments
Process flow diagram
Process flow diagram
 Annual production of titanium dioxide

World 5.7 million tonnes

China 2.7 million tonnes
USA 1.3 million tonnes
Europe 1.3 million tonnes
 Uses of titanium dioxide

 Paints and Coatings: Titanium dioxide provides opacity and durability, while
helping to ensure the longevity of the paint and protection of the painted
surface.
 Plastics, Adhesives and Rubber: Titanium dioxide can help minimize the
brittleness, fading and cracking that can occur as a result of light exposure. This
can enhance the useful life of many plastic and rubber components used in
vehicles, building materials and other exterior applications.
 Cosmetics: Pigment-grade titanium dioxide is use in some cosmetics to aid in
hiding blemishes and brightening the skin. Titanium dioxide allows for the use of
thinner coatings of make-up material for the same desired effect.
 Paper: Titanium dioxide is used to coat paper, making it whiter, brighter and more
opaque.
 Food Contact Materials and Ingredients: The opacity to visible and ultraviolet light
offered by titanium dioxide protects food, beverages, supplements and
pharmaceuticals from premature degradation, enhancing the longevity of the
product. Specific classes of high purity pigment-grade titanium dioxide are also
used in drug tablets, capsule coatings and as a decorative aid in some foods.
Uses of titanium dioxide
Top five vendors in the global titanium
dioxide market
• Chemours
Chemours manufactures performance chemicals under the titanium
technologies (mainly titanium dioxide), fluoroproducts (refrigerants,
industrial fluoropolymer resins, and derivatives), and chemical solutions
(reactive metals, aniline, methylamines, sulfuric acid, and cyanide)
segments.
• CRISTAL
CRISTAL is involved in the production of titanium dioxide using chloride and
sulfate processes. It also manufactures ultrafine and specialty titanium
products and titanium chemicals. The company also serves the plastic bags,
paper, aerospace parts and other industries worldwide.
• Huntsman International
Huntsman International designs, manufactures, and markets differentiated
organic and inorganic chemical products, globally. The company serves
industries such as chemicals, plastics, automotive, furniture, and packaging.
Top five vendors in the global titanium
dioxide market
• KRONOS Worldwide
KRONOS Worldwide is a producer and marketer of value-added
titanium dioxide pigments. It is a white inorganic pigment used in a
wide range of applications such as coatings, plastics, and paper, as
well as many specialty products such as inks, food, and cosmetics.
• Tronox
Tronox is one of the world's leading producers of titanium feedstock,
zircon, and pig iron. Its products are used to manufacture ceramics,
television screen glass, wrought iron, cast iron, and a range of other
industrial and chemical products.
 Titanium dioxide company list
• Gustav Grolman GmbH & Co.KG
• S&B Industrial Minerals GmbH
• KERAMIK-KRAFT e.K.
• HOPEWANG
• TER Chemicals Distribution Group
• Qingdao Shenghua Chemical Co.Ltd
• IMEX Chemicals
• Taiyuan Tengruida Chemical Co.,Ltd
• Sun Chemical LLC
 Titanium dioxide company list
• https://www.industrystock.com/html/titaniu
m-dioxide/product-result-uk-27511-0.html
• https://www.company-
list.org/products/titanium_dioxide.html
 Titanium dioxide plant supplier
Chemours: In our quest to meet the ever-growing global demand for Ti-Pure™
TiO2 pigments, we expanded our Altamira, Mexico, plant in 2016. The increased scale
of our facility, along with our proprietary production technology and our ability to
use a variety of ore feed stocks, helps Chemours provide sustainable, high-quality
TiO2, which adds value to our customers and the community. It will also allow us to
ramp up production steadily over the next few years to an annual capacity of
200,000 tonnes.

Tronox Limited: Tronox Limited operates three titanium dioxide (TiO2) pigment
plants in the USA, Netherlands and Australia; it also operates mines in South Africa
and Australia.
Euphrates International:Euphrates International, LLC is a process engineering and
project management firm that answers the need for focused, knowledgeable experts
to oversee and direct industrial projects with exclusive emphasis in the titanium
dioxide arena. As a respected leader for TiO2 process engineering, they retain highly
skilled individuals with over 70 years TiO2 experience and a demonstrated history of
project management.
 International market Price
(Price from different suppliers)
• Titanium dioxide, Anatase type, $2380/mt CFR
Chattogram based on 100mt
• Titanium dioxide, Rutile type, $2705/mt CFR
Chattogram based on 100mt
• The unit price for #R-900 is at US$ 3,400/Mt,
Container Base ( 20Mt ), FOB/Taiwan ( Tio2 is
made by Taiwan DuPont and will be shipped
out from Taiwan as well )
Thank You