Charles SkidmoreMinchem Limited

(United Kingdom)

TZMI CONGRESS 7-9th Nov 2016

Zirconium Chemicals – Looking Back and Looking Forward

Disclaimer

This presentation includes certain information that is based on projected and/or estimated expectations and assumptions. These forward looking statements include, but are not limited to, statements regarding estimates, intentions and beliefs, as well as anticipated future productions, reserves, cost and market conditions. While Minchem Ltd has prepared this information using the best of its experience and judgement, in all good faith, there are risks and uncertainties involved which could cause results to differ from projections. Minchem Ltd shall not be liable for the correctness and/or accuracy of the information nor for any differences between the information herein and actual figures or information, and furthermore reserves the right to change its projections from time to time.

Zirconium (Zr) Chemicals – Looking Back and Looking Forward

• What are Zr Chemicals?• History of Zr Chemicals• Where/how made?• Pressures on production• Markets and Pressures on markets• Looking Forward

This presentation will focus on the following areas:-

What are Zr Chemicals?Any compound based on the Group IVB element, Zirconium (Zr), Atomic #40.

Zr not rare – 20th most abundant element, more plentiful than Cu.

Main Zirconium Chemicals

– Silicate (Zircon – ZrO2.SiO2) – main feedstock material used for Zr chemicals.– Oxides (Zirconia, ZrO2) – in unstabilised (monoclinic)/stabilised forms.– Chlorides – Tetrachloride, Oxychloride (ZOC)– Sulphates – Orthosulphate (ZOS), Basic Sulphate (ZBS)– Carbonates – Basic Carbonate (ZBC), Ammonium/Potassium Carbonates

(AZC/KZC)– Acetate – (ZAC)– Phosphate – (ZP)– Hydroxide – (ZOH)– Metal – (Zr) – with/without HfO2

What are Reactive Zr Chemicals?– Easy solubility in acids/alkalis/water.– Not Zircon or ZrO2

What are Zr Chemicals? Monoclinic/Stabilised/Chemical ZrO2

On cooling – volume change cracks structure.

Avoid by adding Cubic Oxide dopant - CaO, Y2O3, MgO or CeO2.Fully stabilised - C phase.Partially stabilised – T phase held by C grain. Crack causes T → M expansion – stops cracking. Form of transformation toughening.

Chemical ZrO2 – made from Reactive Zr Chemical e.g. ZOC

ZrO2 – 3 phases• Monoclinic (M) − up to 1170°C • Tetragonal (T) − 1170 to 2370°C • Cubic (C) − over 2370°C.

→ 3 – 5% volume change

History of Zr Chemicals

• 1789 – Zr discovered by German chemist Martin Heinrich Klaproth using Sri Lankan Zircon (NaOH/HCl)

• Late 1800’s/early 1900’s – Many studies on Zr chemicals resulting in patents

– 1909 Gustrow (German Patent) ZrO2 opacifier in enamels

– 1917 Glazebrook, Rosenheim and Rodd (British Patent ) ZOC/ZBS preparations

– 1918 Norton (British Patent) Al2O3-ZrO2 abrasive

Main driver: Zr metal for Pyrophoric devices - fuses/fireworks/explosives.

• 1922 – First book – ‘Zirconium and its Compounds’ by Francis Preston Venable.

• 1924 – Philips lamp factory. Dutch chemists Anton van Arkel/J H de Boer. Thermal Iodide route, Crystal Bar process.

• pre-1930 – No production of Reactive Zr chemical, despite research/patents.

History of Zr Chemicals• 1930’s – Quest was for pure Zr metal.

– More knowledge of extraction technology.

– 1937 - IG Farben Waterproofing textiles with ZOC.

– 1938 - Invention of Kroll Process. William Justin Kroll. Luxemburg laboratory. Reduced ZrCl4 to Zr using Mg. Cheaper than Iodide process. Became main method.

• 1940’s

– Use of Zircon as Opacifier to replace Tin Oxide.

– Use of crude ZrO2 in refractories to withstand corrosion.

– 1948 - C A Seabright, Harshaw Chemical, Zircon ceramic pigments. This did most to promote Zr chemicals.

• 1950’s − Magnesium Elektron Limited (MEL). Zr chemical pioneers – only producer?

– 1950 - ZrO2 for ceramic colours (Harshaw patent).

– 1951 - Zr (0.5%) to Mg alloy as grain size controller.

– 1956 - ZBC for textile/paint.

• 1960’s

– 1961 – Milestone – invention of Vibro Energy Mill. Henry Podmore – improved Zircon Opacifiers

New ZrO2 late 1950’s/early 1960’s. Phalaborwa, South Africa

• Rare mineral. Baddeleyite. Palabora Mining Co (PMC) and Foskor Ltd.

• Unusual - ZrO2 not reacted with SiO2 - 96 to 99% ZrO2

• Between 1960 – 1980 Phalaborwa was major source ZrO2

• Only other mine is Kovdor, Russia. Now 8000 tpa.

• Phalaborwa, S.Africa - Black, Kovdor, Russia - Pinky-red.

• PMC made ZOS, later planned ZBC/ZBS. Ended Zr interests in 2000.

Courtesy of Palabora Europe Ltd

History of Zr Chemicals

History of Zr Chemicals

• 1990’s Demand for ZrO2/Reactive Zr Chemicals grew.

• Phalaborwa Baddeleyite running out.

• Fused monoclinic ZrO2 replaced Baddeleyite –pioneered by AFM Australia, Alister MacDonald – in Ceramic Colours - and by Foskor S.Africa in Refractories – Kim Hodierne/Mark Jackson.

• Few Reactive Zr Chemicals made.

• MEL leading the way with JV in USA and Japan.

History of Zr ChemicalsThe Emergence of China and Japan

• 1960’s ZOC started in China. Driver – Military, Zr metal.

• 1969/1970 First plants Shang Wuyi/Jiaozuo Chemical Factory.• 1974 First ZrO2 exported.• 1976 First modern industrial scale plant - Yixing Chemical (Xinxing).

More producers followed e.g. Jiangxi Kingan.

• Japan Increased demand for ZOC.• China Increasing Zr metal interest.

All ZrO2/Reactive Zr Chemicals supply increased – low production costs - prices fell.Reactive Zr Chemicals mainly Chinese made.

• ROW Focus on added value Zr Chemicals products.

• 1990’s Shenyang Astron Mining Co Ltd – Alex Brown/Kang Rong. Much of PMC’s business transferred to Astron.

History of Zr ChemicalsThe Emergence of China and Japan

• 1962 Ron Garvie, US Bureau of Mines/CSIRO Australia. Transformation toughening mechanism of ZrO2. New PSZ ceramics - Ken Jack, Richard Brook, Ron Stevens in UK.

• 1970/80’s Japan led field in new Partially Stabilised ZrO2 (PSZ) for Advanced Ceramics and Reactive Zr Chemical. All made largely from Chinese ZOC.- TOSOH (Toya Soda Manufacturing est. 1935) - DKK (Daichi Kigenso Kagaku Kogyo est. 1956)

- Saint Gobain (Sepr) Patent – new way to split Zircon to make a superior ZrO2 using Plasma.

• 2016 China has 80% of world supply of Fused Monoclinic, Stabilised ZrO2, Chemical ZrO2, Reactive Zr Chemicals.

Where/How made? Production Processes – Fused Monoclinic ZrO2

Dry Process

50% of all worldwide ZrO2 produced using Dry Process

• Feed Zircon to electric arc furnace (Carbon electrodes).• 2800°C Zircon → ZrO2 + SiO2 fume• More Zircon added – semi-continuous batch process• Molten ZrO2 quenched → ingot moulds or granulation in air

or water. Resultant Fused Monoclinic ZrO2 crushed/sized. • Add Cubic Oxide – CaO, MgO, Y2O3 – to mix – make

stabilised ZrO2 (fully or partially stabilised).

Many plants e.g. Shenyang Astron, now Imerys.

Where/How made?Production Processes – Plasma ZrO2

Wet/Dry Process

• Variation of ‘Dry’ process using plasma. Individual Zircon particles split to ZrO2+ SiO2 then ‘Wet’ chemical method –NaOH – used to remove SiO2 e.g. Sepr/ZTech.

• Dry method needs high purity Zircon since Fe, U+Th tracks with ZrO2

• Fused Monoclinic ZrO2 (Dry process) - Hard ZrO2 with low surface area 1 – 2 m2/g. Lower reactivity.

• Plasma ZrO2 (Wet method) - finer particles – higher surface area 6-8 m2/g – more reactive – but more costly.

Where/How made? Production Processes – Reactive Zr Chemicals

• All use ZOC as starting materials (solution chemistry)

• ZOC production

• ZOC with 35 – 36% ZrO2 contained

• ZOH, ZBS, ZBC etc made from ZOC

Source: TCMS

Where/How made? Production Processes – Chemical ZrO2

Chemical ZrO2 made mainly from ZOC

Source: TCMS

Where/How made?Comparison Fused/Chemical ZrO2

Chemical Zr has:

• Higher purity

• Fine particle size

• Low U+Th

Chemical analysis (wt %) Fused zirconia Chemical zirconia

ZrO2 (+HfO2) 99.3 99.9

SiO2 0.1 0.01

Al2O3 0.3 0.005

Fe2O3 0.18 0.002

TiO2 0.13 0.002

U+Th 400-1,000 ppm 20 ppm

Physical properties

Sintered colour Brown/gold Cream/white

Particle size 5-10 µm 0.1-20 µm

Surface area 1-3 m2/g 1-30 m2/g

Source: TCMS

Other Production Processes – Zr metalFused Monoclinic ZrO2/ZOC (Zircon) used. Scott Coffin, ATI, will explain.

Pressures on ProductionThese include:

• Falling quality of Zircon feedstocks – low U+Th contained grades less plentiful

• Increasing costs – Transport/Electricity/Chemicals/Labour/Environmental

• Falling worldwide demand

• Meeting national/international regulations, e.g. REACH

Zr Chemicals capacity/output (2016)Capacity (t) Output (t)

Zircon 1,500,000 1,100,000

Fused ZrO2 110,000 73,000

Chemical ZrO2 90,000 30,000

ZOC 280,000 200,000

Other Zr chemicals (from ZOC) 50,000

Markets and Pressures on MarketsWhere is Zircon used?

47%

21%

17%

12%3%

Ceramics

Chemicals

Refractories

Foundry

Other

Markets and Pressures on MarketsWhere are ZrO2 and Reactive Zr Chemicals used?

Markets and Pressures on MarketsFused Monoclinic/Chemical ZrO2

Ceramic Pigments

• Slower markets due to building/construction/real estate decline.

• New ceramic printing by ink jet uses less colour hence less ZrO2.

• ZrO2 prices below 50% of 2011 leading to suppliers opting out.

Markets and Pressures on MarketsReactive Zr Chemicals

TiO2 coating

• Coating on TiO2 for hardness/uv control. Mainly ZOC and ZOS.

• ZOC has replaced ZOS to some extent.

• TiO2 business has been slow – so less coating being done.

• Alternative coatings used –SiO2, Al2O3.

• ZOC/ZOS Class 8 Corrosive chemical.

Markets and Pressures on MarketsReactive Zr Chemicals

Paint Driers

• Used to crosslink the polymer binder leading to a faster cure.

• Mainly Zr driers substituting Pb driers.

• ZBC usage should grow.

• Some replacement by Sr driers.

• Growth of Alkyl Emulsions –different drying chemistry.

Looking ForwardZirconium – Bright Future?

Zr Chemicals Supply - Zircon• ~230,000 tpa Zircon used in Zr Chemicals.• Current surplus of Zircon with Africa adding 200,000 tpa output.• Zircon prices will increase with some possible further loss of markets.• Should be enough in future but lower gradings. Leading to increased cost to make Zr

Chemicals.

Other Zr bearing ores• Kovdor Baddeleyite will continue – is there another Phalaborwa?

• Need to produce Zr compound alongside other valuable products – RE, minor metals –that cover cost of manufacture of Zr Chemicals.

e.g. Eudialyte• Polymetallic mineral (Ca,Na2)6(Zr,Fe)(Si3O9)2(OHCl)2

• Found in: Australia, Brazil, Greenland, Mexico, Norway, Russia, S.Africa.• Rich in Na – readily soluble in acid.• Deposits contain ‘difficult elements’ – Zr, Nb, RE’s, Be.

Looking Forward AZL Dubbo Project (DZP)

Alkane Resources Ltd.

• Gold mining company.

• 400 km NW Sydney.

• Final stages of ~$1bn plant.

Key points

• An alternative feedstock for all Zr chemical production.

• Not based on Zircon. Independent of Zircon supply constraints.

• Not Chinese – not subject to possible Chinese export tariff increases.

• ZrO2 output will be Chemical ZrO2, not made through the Zircon-ZOC route.

• It will have low U+Th levels (<50ppm – around 1/10 of fused monoclinic ZrO2).

• Orebody with long mine life, 80 years. 35 years at 1 million tonnes ore/annum.

• Dubbo has RE which could be incorporated in the ZrO2 to produce stabilised feedstocks.

• Produce a Hf-free ZrO2 independent of Zr metal production (recovering the valuable HfO2).

Looking ForwardD

ZP P

roce

ss P

lan

t

Rare earth chemical concentrate 95% REO 6,664 tpa (REO units)

Niobium as ferro-niobium 65% Nb 1,967(Nb units)

Zirconia and zirconium chemicals 95% ZrO2 16,374 tpa (ZrO2 units)

Hafnium as HfO2 concentrate HfO2 con 50 tpa *(Hf units)

Product Output

* Start up output. 200 tpa potential depending on market demand

Tonnage based upon recoveries developed from mass balances of the demonstration pilot plant. Total output approximately 25,200 tpa of all products

Source: Alkane Resources

Looking Forward

Zircon/Fused Monoclinic ZrO2/Stabilised ZrO2

• Usage continue unless higher price causes substitution

Chemical ZrO2/Reactive Zr Chemicals• Usage will increase• Largely high tech areas such as:

- Biomedical- Advanced ceramics- Nano materials

Biomedical• Wearable miniaturised dialysis system – replacing Hospital units• Use Reactive Zr Chemical in disposable cartridge• Acceptance in living tissues major driving point here.• Dental implants market growing fast. Pressure from plastics

long term.• Joint replacement – hips, knees.• Reconstructive surgery.

Zircon Industry Association (ZIA) handbook shows emerging R&D in Zr Chemicals

Looking ForwardResearch & Development

Looking ForwardResearch and Development

World needs to find answers to many questions such as:• More food?• Better housing?• Cure for cancer?• Reduce energy cost?• Reduce pollution?

Answer could be a Zirconium Compound.

Zirconium Chemicals – Looking Back and Looking Forward

Minchem Challenge

New lower cost ways to split the ZrO2-SiO2 bond?Or

Other Sources?

Many Thanks

Presented by Charles Skidmore