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BEYOND PIGMENT: The Growing Benefits of
Titanium Dioxide for Our Society
Jean-François Pasquier Business Director
Specialty Chemicals & Materials
TiO2 World Summit
Cleveland October 2016
TiO2 Beyond Pigment: Ultrafine and Other
Specialties
The Demonstrated Benefits of Ultrafine TiO2
in Catalysts
New Opportunities to Meet Current and
Future Society Challenges
Agenda
2
• Extensively studied
• Oxide support with transition metal
chemistry
• Photoactive
• Established methods for structured
materials
• Tailored properties related to
manufacturing route
• Established manufacturing routes for
economies of scale
TiO2
(001)
(011)
(101)
(a)
(101)
(011)
A material for innovation
3
• Well established manufacturing processes giving economies of scale
• Versatile physical and chemical properties related to the technology
• Numerous modes of introduction into the catalyst or material
system, i.e. powders, gels, sols, chemicals
Cristal Ultrafine TiO2 Technologies
Pigmentary TiO2
Anatase and Rutile
200 - 300 nm,
refractive index
Optimized for light
scattering properties
and dispersion
< 100 nm, surface reactivity
& semi-conductor properties
Ultrafine products from different technologies
Opening a large spectrum of opportunities
4
Global technology leader in
titania-based applications
Major applications include:
• Emissions Control
• Refining Catalysis
• Petrochemical Catalysis
• Energy Storage
• Photovoltaics
• Photocatalysis
• Colored Pigments
• Electronics
• Ceramics
Over 30 years of industry-leading experience
in ultrafine TiO2 for specialty applications
5
DeNOx (stationary)
DeNOx (mobile) DeNOx (off-road)
Oxidation Mobile
Oxidation NO,
HC, CO, PM
DeNOx (marine)
NOx reduction into N2
(with ammonia/urea)
TiO2-based Products
for Environmental
Catalysis
TiO2
A key component of environmental applications
6
0
20 000 000
40 000 000
60 000 000
80 000 000
100 000 000
120 000 000
Cumulative NOx conversion in mt
Ultrafine TiO2 Contribution to Depollution
Cristal Estimate Based on Publically Available Information
More than 110 million MT NOx converted in power plants in the last 35 years
7
Physical
Properties
• Crystallinity
• Porosity
• Thermal Stability
Chemistry
• Active Phase
• Mixed Oxides
• Acidity
Catalysis
• DeNOx
• Petrochem
• Photocat
TiO2
A material of choice for innovation in catalysis
Manufacturing
• Process
• Delivery Systems
• Rheology
8
Thermal stability
• Euro VI and US 2010 – SCR + DPF needed
• 600°C thermal stability generally far
enough with passive regeneration of the
DPF
• More thermal stability is needed with
active regeneration
• The SCRF technology (SCR on DPF)
requires significant thermal stability
Cristal emphasis on improving both
Activity at low temperature
• Regulatory trends towards low NOx
• Necessity to comply with fuel
economy requirements and CO2
emissions limit
• Thermal efficiency results in lower
exhaust temperature
The challenges of China VI regulation
Latest Developments
…to meet the most stringent DeNOx catalyst requirements
9
• New family of stabilized titania has been introduced to the market
• Technology is highly effective for improving thermal stability
• Optimal SCR activity and activity retention can be achieved
0
50
100
150
200
250
300
500 550 600 650 700 750 800 850 900 950
Surf
ace
Are
a [
m2
/g]
Temperature [C]
New Stabilized Titania- Surface Area Stability10 wt% Silica
Standard Technology
New Technology
Calcined 6 h in air Hydrothermally aged 16 h
100% Anatase
0
10
20
30
40
50
60
70
DeN
Ox C
on
vers
ion
, 350C
Ti-Si (10% SiO2) DT-58 DT-S10
Activity of Aged Catalysts
Nominal 10% SiO2, 10% WO3, 2%V2O5
Aged 800C, 16 h, 10% H2O
Latest Developments
…to meet the most stringent DeNOx catalyst requirements
Cristal patented technology allows
for better thermal stability and better NOx conversion
10
Alumina
Supported
Cristal TiO2
Supported
US 8,168,562;
S.M. Augustine
US 6,022,823;
S.M. Augustine,
D.W. Smith,
R.M. Hanes,
M.D. Evans
Cristal TiO2 improves stability of PdAu catalysts
11
Demonstrated Performance of TiO2 for Petrochem Catalysts
Vinyl Acetate Process – Optimum Metal-Support Interaction
Performance of
VAM Catalysts
Performance of
Allyl Acetate
Catalysts
New Opportunities to Meet Current
Society Challenges
Environment: Photocatalysis for Self-
Cleaning and Air Depollution
Water Conservation: TiO2 Uses for Water
Treatment
Energy: TiO2 for Power Generation and
Power Storage
12
• The ultrafine TiO2 can be incorporated into the product (i.e. paint, concrete,
etc.) or post applied to the surface (i.e. sol post treatment)
• There are two mechanisms of ultrafine TiO2 that create the self-cleaning
functionality:
– Hydrophilicity of the surface
– Degradation of organic contaminants
Initial
Application
Performance after
19 months
How does
ultrafine TiO2
impact self
cleaning?
CristalACTiV™ Ultrafine TiO2 Photocatalytic Properties for Self Cleaning
Utilizing ultrafine TiO2 to create self-cleaning surfaces
13
CristalACTiV™ Ultrafine TiO2 Effectiveness
for Depollution
Key Learnings
• Technology shift —
cement to paint to sol
technology
• Trial success correlates
to activity of the system
• Application area is a key
factor — Camden/Sir
John Cass Trial
• Measurement system
failures — Sir John Cass,
High Holborn
• Measured response is
only possible if pollution
source is significant-
Konningstunnel
Field trial evolution and learnings
Picada
High Holborn Milan Tunnel
Photopaq Vinci Car Park
Sir John Cass School
Manilla Trial
Koningstunnel
Yanbu Housing
Camden
0
1
2
3
4
5
6
7
8
9
10
1995 2000 2005 2010 2015 2020
Progression (Years)
Cristal Field Studies
Cement-based
technology
Paint Sol
technology
Perf
orm
ance
14
Active Layer
0
5
10
15
20
Past Technology Intermediate Technology New Technology
Substrate Substrate
PC in Cement Paint - Dispersion of PC Sol-based Treatment
Technology Dispersion Powder Sol
Application >3 micron; 10% PC
effective
>10 micron; 4%PC
effective <1 micron; 100% PC
effective
Surface Area 80-50 m2/g 10-50 m2/g 350+ m2/g
Technology
Improvement
Active Layer
Old Technology
Comments Needs activation Can be deactivated Instantaneous
CristalACTiV™ Ultrafine TiO2 Effectiveness
for Depollution Technology evolution
Photocatalytic Capabilities of Test Materials NOx Removal (g/month/m2)
15
Assumptions
• The typical Euro VI diesel car emits 80 mg/km of
NOx pollutants
• Avg. driver in the UK drives 12,700km per year
• Total pollution approximately 1,000 grams of
NOx per vehicle per annum
Solutions
• A typical forest canopy can remove 1.64 grams
of NOx per square meter per annum
• CristalACTiV photocat application – removes 0.5
grams of NOx per square meter per day (182.5
grams per year), at a cost of £3/m2
• Other options – traffic control, tolls to enter
clean air zones, conversion to cleaner
fuels/electric cars – I\intrusive to people/longer-
term solutions to develop
Cristal Estimate Based on Publically Available Information
http://www.fs.fed.us/ne/newtown_square/publications/
other_publishers/OCR/ne_2006_nowak001.pdf
0
100
200
300
400
500
600
700
0
20
40
60
80
100
120
140
160
180
200
Tree Canopy PhotocatalyticTiO2
Are
a (
in m
2)
NO
x P
olluta
nt
Reducti
on (
in g
/m2)
NOx Emission Reduction of a Single Car Choice of Trees or Photocatalytic TiO2 to Treat Emissions
NOx Removed per sq.meter
No. of sq. metersrequired to treatemissions from 1 car
Treatment
Area =
5.5 m2
Treatment Cost
= $22
Treatment
area=
610 m2
CristalACTiV™ Ultrafine TiO2 Effectiveness
for Depollution Costs to remove pollution
16
Ultrafine TiO2 Offers New Options
for Water Filtration
• Access to safe, pure drinking water is becoming a growing societal concern
• Traditional water treatment techniques include:
o flocculation and filtration methods for solids removal
o chemical disinfection for purification against microorganisms
• Treatment systems can occur at the source, by the municipalities, or at point of use
What role does
ultrafine TiO2
have in water
treatments?
Filtration – The micropore structure of
UF TiO2 can be used to remove
harmful contaminants
Disinfection – The reaction mechanism of
UF TiO2 and UV light can be used for redox
reaction to treat organic pollutants
17
PSC Liquid DSC
Solid Hole Transport Material
Titania
Perovskite Light Absorber
Liquid Electrolyte
Titania
Dye
Nano-Platinum Catalyst
Si Solar Cell Human Hair
500 nanometres
TiO2: A Key Element for the Solar Cells
Next Generation
Novel Architecture of PSC
18
Source: DYESOL Limited
TiO2 in Batteries: Lithium Titanate Oxide
• Lithium Titanate Oxide (LTO) replaces the graphite as anode material
• LTO is compatible with all cathode materials, but is generally used in
combination with manganese-based materials.
• Highest safety of Li-Ion technologies
• Quick recharge rates
• High cycle life- charge/discharge
(>5,000 discharges cycles vs. ~400 of a regular Li-ion)
• Good performance at low temperature
• LTO battery’s can be shipped and stored at zero charge
• Can use aluminum as a battery case – lightweight
LTO
Batt
ery
Chara
cte
rist
ics
19
Samples of LTO
material have been
produced from the HPX
products in the Cristal
labs
Tested for discharge
capacity
Patented technology
LTO produced from HPX-100 LTO produced from HPX-400
TiO2 in batteries: Lithium Titanate Oxide
LTO manufactured using Cristal TiO2 as precursor
20
HPX-400
• 1C = cell full discharged in 1 hour
• C/5 = cell fully discharged in 5 hours
• 10/C = cell fully discharged in 6 minutes
• Higher capacity at a given discharge
rate is preferred
• Test performed by a Cristal partner
• Test at 80% loading
• Discharge capacities vs. charge/
discharge cycles
HPX-100
TiO2 in batteries: Lithium Titanate Oxide
LTO manufactured using Cristal TiO2 as precursor
LTO manufactured from Cristal products demonstrates
higher discharge stability!
21
Beyond Pigment…
• TiO2, and more specifically Ultrafine TiO2, has
demonstrated its ability to dramatically improve the
quality of life and to meet growing societal challenges
• New environmental applications are emerging and novel
TiO2 materials for water conservation and for energy
generation and storage are being developed
• Cristal offers the largest range of Specialty TiO2 and a
robust experience to meet the existing and coming
challenges
22
Thank you!
