Presentation at Kokkola Material Week. Kokkola University Chydenius, University of Oulu.

1. University of Oulu
BIOECONOMY RESEARCH
COMMUNITY (BRC-OULU)
Biomass to chemicals-New Applications
Davide Bergna 2-11-2016

2. University of Oulu
INTRODUCTION Biomass to Chemicals in Kokkola Chydenius
Carbon
Biomass
Activated Carbon
Support for catalysts
and metals
Water cleaning
Wood saw dust, Peat, Carbon containing wastes from industrial
processes..
Anode coating for batteries
Mechanocatalytical pretreatment
(Sugars)

3. University of Oulu
OUR TEAM – Applied chemistry
Researchers contributed to this
research and presentation:
• M.Sc. Davide Bergna
• Ph.D. Henrik Romar
• M.Sc. Riikka Lahti
• M.Sc. Toni Varila
• M.Sc. Pekka Myllymäki
• M.Sc. Henna Lempiäinen
• Ph.D Sari Tuomikoski
• M.Sc. Laura Schneider
• Lab.Tech. Sini Kivioja
• Lab.Tech. Jaakko Pulkkinen
• Professor Ulla Lassi

4. University of Oulu
“The global market for activated carbon totaled $1.9 billion, in 2013, driven
primarily by Asia-Pacific and North American region for applications in water
treatment and air purification. As per Ceskaa Research, the global market for
activated carbon reached $2.1 billion, in 2014, reflecting a YOY growth rate of
10.2% from 2013. Further, the market is expected to grow at a five-year CAGR of
11.3%, to reach $3.7 billion, by 2019. Stricter government regulations across regions
for air purification and water treatment will drive the market for powdered and
granular activated carbon.
Asia-Pacific was the largest market for activated carbon, accounting for $751.8
million in 2013. Further, it is expected to grow at a five-year CAGR of 14.5% to
reach $1.6 billion in 2019. The other two major markets, North America and Europe
accounted for $510.7 million and $446.8 million, respectively in 2013.”
Activated Carbon
Global Activated Carbon Market: 2014-2019 Report Overview Code: AM-15-01
https://www.ceskaa.com/shop/advanced-materials/global-activated-carbon-market/

5. University of Oulu
Highly porous solids :
- Large internal surface area;
- Well defined pore distribution;
AC are prepared from carbon rich biomass, in principle any carbon containing raw material can be used
Biomass can be converted into AC in a two step process including:
- Carbonization: at 600-900⁰C in inert atmosphere;
- Activation: chemical, physical, combination of the two;
- These steps can be performed sequentially as one single procedure;
The properties of the AC depend on the BIOMASS USED and the CONDITIONS for carbonization
and activation.
Activated Carbon
BERGNA, D., TUOMIKOSKI, S, ROMAR, H., LASSI, U. (2016) Activated carbon from
renewable sources: Thermochemical conversion and activation of biomass and
carbon residues from biomass gasification, submitted

6. University of Oulu
Activated Carbon

7. University of Oulu
Pores are creating the internal surface making pore distribution an important property
2 nm < d < 50 nm
transport pores
d < 2 nm
highest adsorption energy
d > 50 nm
access pores
Activated Carbon
BERGNA, D., TUOMIKOSKI, S, ROMAR, H., LASSI, U. (2016) Activated carbon from
renewable sources: Thermochemical conversion and activation of biomass and
carbon residues from biomass gasification, submitted

8. University of Oulu
3 different units for carbonization and activation:
- Screening unit, fixed bed reactor, SS314, loads 1-5 g of raw material
- Testing unit, fixed bed rector, SS314, loads 5-100 g of raw material
- Semi production unit, rotating fixed bed reactor, quartz, loads 50-800 g (200-1500 ml) of raw material
With all units It is possibile to do:
- Carbonization in the range of 300-1100 ⁰C, inert atmosphere
- Steam and/or CO2 activation in same temperature range, inert atmosphere
- Chemical activations, inert atmosphere
All units are equipped with:
- Gas cleaning units
- Separate MFCs for gas control
- Possibility to control steam feed/steam temperature (semi unit)
Activated Carbon

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Activated Carbon
AC production layout:

10. University of Oulu
CHARACTERIZATION::
- Process yields, % of initial mass;
- Carbon content, % of mass;
- Surface areas, m2/g, isothermal N2 adsorption, BET analysis, DFT analysis;
- Pore sizes, pore volumes, pore size distributions: Micro-, meso-, macropores, BET, BJH, DFT;
- Ash content;
- Adsorptive properties:
- Methylene blue adsorption (liquid phase)
- Iodine number (liquid phase)
- Gas adsorption (gas phase)
- Customer specific compounds (liquid/gas phase)
Activated Carbon
POSSIBILITY TO ”DESIGN” and ”TEST” AC WITH DIFFERENT
CHARACTERISTICS

11. University of Oulu
Examples ”MADE IN” Kokkola:
Raw material used: a number of biomass and industrial waste fractions
Surface areas SBET:
- from 800 to 2300 m2/g;
- Commercial ACs have SBET = 700-1100;
Pore distributions
- High micropore carbons;
- Micro-mesoporous carbons;
- Mesoporous carbons;
Adsorptive properties
- Equal to commercial carbons.
Activated Carbon

12. University of Oulu
Support for catalysts
• Sustainable catalytic conversion of renewable resources to chemicals and fuels is a rapidly
growing field in research.
• 100% fuels and over 85% of the chemicals catalytic conversion
• Conventional metal oxides
• Activated carbon (AC)
 high surface area
 proper pore size distribution
 surface functional groups
LAHTI, R., ROMAR, H., BERGNA, D., HU, T., LASSI, U., COMAZZI, A., PIROLA, C., BIANCHI,
L. (2016) Characterization and properties of biomass-derived carbon-supported metal
catalysts active in the Fischer-Tropsch process (submitted)
Low sustainability (e.g. Alumina-Red Mud)

13. University of Oulu
Support for catalysts
Raw
material
Carbonization and
steam activation under
N2 at 800°C
Activated
carbon
Fe or Co/AC
catalyst
Treatment with
acid
Incipient-wetness
impregnation
of Fe or Co FT synthesis
Co  alkanes  biofuels
Fe  olefines  bioplastics

14. University of Oulu
Support for catalysts
alloyed nanoparticles on sawdust and lignin based AC support:
GLYCEROL OXIDATION:
LEVULINIC ACID HYDROGENATION:
Chemicals Fuels
Fine chemicals Renewable fuels
Platform
Chemical
Platform
Chemical
L. Prati, R. Lahti, A. Villa, D. Bergna,
H. Romar, U. Lassi, C. Bianchi (2016),
Catalysis Today (manuscript)

15. University of Oulu
Au3+
NaBH4
Immobilization
(PVA)
Au
Pt2+ H2+
Au3+
Au3+
Au3+
Au3+
Au
AuPt
Support for catalysts
L. Prati, R. Lahti, A. Villa, D. Bergna,
H. Romar, U. Lassi, C. Bianchi (2016),
Catalysis Today (manuscript)

16. University of Oulu
Support for catalysts
0
10
20
30
40
50
60
0 1 2 3 4 5
conversionmol%
time (h)
1% AuPt Spruce
1% AuPt Lignin
1% AuPt Birch
1% AuPt Pine
0
5
10
15
20
25
30
35
0 2 4 6 8
c
o
n
v
e
r
s
i
o
n
%
time (h)
AuPt/birch
AuPt/lignin
AuPt/pine
AuPt/spruce2
Glycerol oxidation results:
Levulinic acid hydrogenation
results:
 Birch AC high N-groups
on surface
 Spruce AC low carboxylic
and high aromatic groups
on surface
L. Prati, R. Lahti, A. Villa, D. Bergna,
H. Romar, U. Lassi, C. Bianchi (2016),
Catalysis Today (manuscript)

17. University of Oulu
Anode coating for batteries
Carbon from biomass
Active metal impregnation
Material characterization
Anode coating
Battery Testing
Thermal/Chemical
reduction

18. University of Oulu
Water cleaning
Removal of bisphenol-A over
Fe/C catalysts (CWAO)
HEPONIEMI, A., JUHOLA, R., VIELMA, T., TUOMIKOSKI, S., HU, T. & LASSI, U. (2016) Industrial
by-product as a novel catalyst for water purification, submitted
RUNTTI, H. (2016) PhD thesis, University of Oulu
LUUKKONEN, T. (2016) PhD thesis, University of Oulu
Biomass-derived carbon adsorbents (AC) in the removal of metals
and anions from industrial wastewaters

19. University of Oulu
Mechanocatalytical pretreatment of biomass
LEMPIÄINEN, H. et al. (2016) unpublished data.
SCHNEIDER, L., HAVERINEN, J., JAAKKOLA, M. & LASSI, U. (2016) Potassium pyrosulfate catalyst for the mechanocatalytical conversion of
lignocellulosic barley straw, Green Chemistry (submitted)
SCHNEIDER, L., DONG, Y., HAVERINEN, J., JAAKKOLA, M. & LASSI, U. (2016) Efficiency of acetic acid and formic acid as a catalyst in catalytical
and mechanocatalytical pretreatment of barley straw, Bioresource Technology, doi: http://dx.doi.org/10.1016/j.biortech.2016.01.095
DONG, Y., HOLM, J., NOWICKI, J., KÄRKKÄINEN, J. & LASSI, U. (2014) Dissolution and hydrolysis of fibre sludge using ionic liquids containing
sulfonic group, Biomass and Bioenergy 70, 461-467.
SCHNEIDER, L., DONG, Y., HAVERINEN, J., JAAKKOLA, M. & LASSI, U. (2016) Efficiency of acetic acid and formic acid as a catalyst in catalytical
and mechanocatalytical pretreatment of barley straw, Biomass and Bioenergy 91, 134-142.

20. University of Oulu
Conclusions
Right now…
• A solid know-how in biomass to chemicals conversion was built-up in
Kokkola Chydenius;
• Facilities and testing instruments;
• Many projects and ideas in developing phase with our national and
international partners;
• Opportunities for companies and investors.
“..fortuna est momentum quo occasionem convenit talentum..”
“Luck is what happens when preparation meets opportunity” Lucius Annaeus Seneca
Thanks for your attention!