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NANOTITANIUMDIOXIDE –

A BRIEF DISCUSSION

The Kerala Minerals and Metals Limited(A Government of Kerala undertaking)

Kollam, Kerala

RAJENDRA PRASAD

Deputy General Manager

(Technical Service& R&D/Marketing)

The Kerala Minerals and Metals Limited

INDIA’S ONLY RUTILE GRADE

TITANIUM DIOXIDE

MANUFACTURING FACILITY

(THROUGH CHLORIDE ROUTE)

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KMML – AN INTRODUCTION

HISTORY

In 1932, M/s F.X.Periera & Sons (Travancore) Pvt. Ltd., established the first full fledged Mineral Industry in Chavara

Taken over by the Govt. of Kerala in 1956

Converted as a limited company in 1972 in the name “THE KERALA MINERALS & METALS LTD”

Commercial production of Titanium Dioxide started in 1985 with an installed capacity of 22,000 tones per year

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KMML – AN INTRODUCTION

KMML is the only integrated plant in the world of Titanium Chemicals and Metals that undertakes

MINING – MINERAL SEPARATION – TITANIUM DIOXIDE PIGMENT

MANUFACTURE at one complex

The company has two units:

1)Mineral Separation Unit (MS Unit)

2)Titanium Dioxide Pigment Unit (TP Unit)

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KMML – AN INTRODUCTION

MINING AREA

22 KM LONG BEACH FROM NEENDAKARA TO KAYAMKULAM

Mining Rights - 50% TO KMML and 50 % TO IRE

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KMML – AN INTRODUCTION

MINING AREA

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KMML – AN INTRODUCTION

M.S. UNIT

ILMENITE

NATURAL RUTILE

LEUCOXENE

ZIRCON

TP UNIT

TITANIUM DIOXIDE (RUTILE) – Various Grades

TITANIUM TETRA CHLORIDE

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UNITS & PRODUCTS

KMML – AN INTRODUCTION

KMML– PROCESS CHART

INDEX

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OUR PRODUCTS INCLUDE

• TITANIUM DIOXIDE PIGMENT (DIFFERENT GRADES) CAPACITY - 40,000T/annum

• TITANIUM TETRACHLORIDE CAPACITY - 90,000T/annum

• TITANIUM METAL SPONGE CAPACITY 500/annum (to be commissioned in Feb,2010)

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KMML – AN INTRODUCTION

TITANIUM DIOXIDE PIGMENT GRADES

• KMML presently offers a wide range of titanium dioxide grades as shown below

– KEMOX – RC 800– KEMOX – RC 800 PG– KEMOX – RC 813 – KEMOX – RC 822– KEMOX – RC 808

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APPLICATIONS

• PAINTS – Architectural, Outdoor, Indoor, Industrial, Glossy, Matty….

• POWDER COATINGS• PRINTING INKS• PAPERS• RUBBER• TEXTILES and many more…..

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PACKING AND PALLETING

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KMML – AN INTRODUCTION

TITANIUM SPONGE• KMML has taken a big leap into aerospace working

towards value addition of its Titanium Tetra Chloride with the launch of Titanium Sponge Plant

• Titanium Metal derived from Titanium Sponge finds use in a variety of fields like aerospace industry, atomic energy, defence etc

• Due to its lightweight, higher strength, non-corrosive and non-reactive quality, it finds use in surgical and orthopaedic transplants

• KMML’s foray into the production of Titanium Sponge makes it the first and only company in India, and the 7th country in the world, to produce Titanium Sponge

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KMML – AN INTRODUCTION

NANOTITANIUM DIOXIDE• Nanomaterials - Particles with Dimension in the

range of 1-100 Nm

• The Average Density and Coordination between the neighbors changes as Crystal Size is reduced, hence properties of Nanomaterials differ from Parent Material

• As Size Decreases the following properties increases

- Hardness & Strength of Metals and Alloys - Electrical Conductivity in Ceramics and Magnetic

Nanocomposites

• Nanomaterials finds application mainly in Nanoelectronics, Catalysis, Semiconductors, Coatings, Ceramics Etc

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NANOTITANIUM DIOXIDE – GLOBAL OVERVIEW

• Recently there has been a surge in Nano TiO2 products in the international arena

• The Global Production of Nanotitanium Dioxide is Approximately 5000 Tonnes/Annum

• In India Currently 10-20 tonnes of Nanotitanium Dioxide is Imported Annually for Various Applications

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NANOTITANIUM DIOXIDE – GLOBAL OVERVIEW

IMPORT DETAILS

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S.N Year Quantity (MT) Rate / Kg

1 2004 9.1 1150

2 2005 2.8 939.4

3 2006 11.6 1161.7

4 2007 10.5 859.1

5 2008 4 1095

6 2009 10 1028

The leading Global Manufacturers of Nanotitanium Dioxide are:

- Kemira - Tayca - Sachtleben - Millenium and numerous Chinese Companies

• At present two types of TiO2 are commercially available

- NANORUTILE TITANIUM DIOXIDE & - NANOANATASE TITANIUM DIOXIDE

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NANOTITANIUM DIOXIDE – GLOBAL OVERVIEW

SACHTLEBEN

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NANOTITANIUM DIOXIDE – GLOBAL OVERVIEW

Grade Applications

Hombitec RM300 Paints & Coaings

Hombitec RM400 Wood Coating

Hombitec RM230L Plastics

Hombitec RM220 Automobile Coatings

Hombitec RM200 Electronics

Hombitec RM130F Food Packing

TAYCA

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NANOTITANIUM DIOXIDE – GLOBAL OVERVIEW

Grade Applications

MT-100S, MT-100HD, MT-500HD, MT-500B, MT-500SA, MT-600SA, MT-700HD

Automotive Coatings

MT-100T, MT-100TV, MT-100Z, MT-100F, MT-150W, MT-100SA, MT-100SAS, MT-500H, MT-500H, MT-500SA

Cosmetics

MT-100S Plastics

KEMIRA

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NANOTITANIUM DIOXIDE – GLOBAL OVERVIEW

Grade Applications

L-181, L-230, L-530, L-531, L-830

Coatings

M170, M160, M212, M262, M263, M610, M111

Cosmetics

P160, P170, P190, P580

Plastics

• Particle Size - Pigmentary TiO2: 250 - 350 NM - Nano TiO2: 20 – 50 NM

• Pigmentary TiO2 - Scatter visible Light and absorb UV light

Nano TiO2 - Scatter and reflect UV light effectively and transmit Visible light through the crystal

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• Nanotitanium Dioxide have higher Surface Area and high Photocatalytic Activity,

• Heavy Surface Coatings are required to suppress the Photocatalytic Activity

• For Coating applications, Nanorutile is surface coated with Silica, Alumina and Zirconia

• Nanoanatase has higher Photocatalytic Activity, hence used in Self Cleaning Paints Etc

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NANOTITANIUM DIOXIDE – PROPERTIES

NANOTITANIUM DIOXIDE

APPLICATIONS OF NANORUTILES

• Paint Industry: Nano particles provide better UV protection against chalking and fading when used in coatings

• Metallic Coatings: Nanorutile mixed with Aluminium flakes is used to impart Metallic Look in the Automobile industry This is based on scattering of visible light by nano TiO2 particles and Aluminum flakes

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NANOTITANIUM DIOXIDE

APPLICATIONS OF NANORUTILES

• Plastics: Nano titanium dioxide particles in combination with polymers provide better UV stability

• Cosmetic Industry: The UV scattering ability finds extensive application in Sunscreen Cosmetics

• Wood Coatings: Nanorutiles provide better UV shielding and hence lower wood yellowing when used in wood coatings

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NANOTITANIUM DIOXIDE

SYNTHETIC ROUTES

The main commercial routes for manufacture of nano titanium dioxide are

• Vapor phase synthesis from Titanium Tetrachloride and Oxygen

• Thermal Hydrolysis From Titanium Oxy Chloride And Titanyl Sulphate

• Hydrothermal Synthesis

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NANOTITANIUM DIOXIDENANO TIO2 AT KMML

• KMML R&D has developed a process for making Nanotitanium Dioxide from Titanium Tetrachloride

• Indian Patent has been filed for the process developed (application Number: 5789/Che/2010 Dated 5/3/10)

• The Process involves scrubbing of Titanium Tetrachloride with water to make Titanium Oxy Chloride and then precipitating Nano Tio2 from Oxy chloride Solution at low temperature by Water addition

• Thus precipitated Nano TiO2 is washed, filtered, calcined and fluid jet milled to obtain the final product

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NANOTITANIUM DIOXIDENANO TIO2 AT KMML

• Currently KMML is setting up a pilot plant for making nanotitanium dioxide of capacity 10MT/annum and is expected to be commissioned soon

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Nano Titanium dioxide developed at KMML

NANOTITANIUM DIOXIDENANO TIO2 AT KMML

H2O Titanium OxychlorideTiCl4 Vapors

Nano Particles

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Filtration

CalcinationMicronizingSurface Treatment

Filtration

Drying inCalciner

Micronising

Scrubber Precipitation of Pigment

NANOTITANIUM DIOXIDE

SPECIFICATION OF TITANIUM TETRACHLORIDE (STARTING RAW MATERIAL)

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TiCl4 (%) > 99.5

Vanadium 10ppm (max)

Silicon 50 ppm (max)

Aluminum 20 ppm (max)

Iron 5 ppm

Residue remaining at 150 oC

0.1%

NANOTITANIUM DIOXIDE

TITANIUM OXYCHLORIDE DATA COMPARISON

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COMPOSITION

KRONOS KERMCGEE

DUPONT MILLENIUM

KMML

HCl (%) 12 19 19 – 21 19 – 20

TiOCl2 (%) 43 36 35 – 39 35 – 38 35 – 39

H2O Balance Balance 40 – 46 Balance

Sp. Gravity 1.55 1.45 - 1.50

1.49

KMML WORLDS RICHEST SOURCE OF MINERAL SANDS

THANK YOU

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