Development of Fisher‐Tropsch synthesis in KokkolaHenrik Romar
Riikka Lahti
Ylivieska 3.11.2009
HighBio
Aim
of the work
The different compounds can be prepared by catalytic conversion
Why Co and Fe based catalysts?
Fischer‐Tropsch synthesis
(FTS), some
parameters
• Pressure 5 ‐
60 bar
• Temperature~ 200 ‐
400 °C
• Catalyst: Co or Fe on a carrier, traces of Ru
• Reaction products: aliphatic hydrocarbons (C1‐C30)
The H2/CO‐ratio affects the chain lengths
[19] Vessia, Øyvind, Biofuels from lignocellustic material, project report, Norwegian University of Science technology, 2005,
Deugd et al., Trends in Fischer-Tropsch reactor tegnology-opportunities for structured reactors, Topics in Catalysis, vol.26, 2003, p.29-39
Particle size of the carrier affects catalytical activity and selectivity
Reactor Configuration for the Conversion of Syngas
Temperature Sensor
To Ventilation
H2
Furnace
Gas analysis
Pressure sensor
Pressurereducer
Gases
Hot trap(Waxes)
Cold trapHydrocarbons, water
CO
Inert gase.g. 5 % N2(internal standard)
Mass Flow Controllers
Pressure controller
Catalysts
used
in our
research
• Metals
Co
and Ru
(mass%) Fe
and Ru
• Carrier
Al2
O3
pelleted Al2
O3
100 µm
• Precursors Co(NO3
)2
* 6H2
O Fe(NO3
)2 Ru(NO)(NO3
)3 Co(Ac)2
Catalyst
preparation
1(2)
2 step
impregnation1.
Drying
of carrier
2.
Precursor
dissolved
in a small
volume
of H2
03.
Mixing
12h
4.
Filtration5.
Drying
at 102 °C 12 hours
6.
Repeat
steps
1‐5, impregnation
with
the filtrate7.
If
Ru
is used, steps
1‐5 are
repeated
Catalyst
preparation
2(2)
• Calcination: Temperature
Rt600°C/6 h, 7 h hold Precursors
are
modified
to MeO
on the surface
of
the carrier
• Reduction, performed
in reactor Temperature
Rt450‐550 °C/6 h,16 h hold.
H2
flow 25 ml/min Metallic
catalyst
• Reactor
is cooled
down
to about
170 °C
FTS reaction
• Pressure
9 bar
• Temperature
220‐330 °C– Rise
from
170 °C reaction
temperature
1°C/min
• Gas
flows
– H2
50 ml/min
– CO
25 ml/min
– N2
0‐75 ml/min
Reactions
1.
CO (ad)
C(ad)
+ O (ad)2.
H2 (ad) 2 H (ad)
3.
C (ad)
+ 2 H (ad)
‐CH2‐
(ad)
(‐CH2‐)n
4.
O (ad)
+ 2 H (ad)
H2
O (ad)
H2
O
Hr
= ‐165 kJ/mol exothermic
Adsorbtion and bond cleavage
Synthesis reactions
Results
Co/Al2 O3 IR spectra
Commercial diesel
FTS-diesel
GC-analysis of commercial diesel
C9C22
C22
C11
C20 13%
GC-analysis of FTS products Fe/ Al2 O3 (pelletts)
C7
C22
C11: 10,3%
GC-analysis of FTS products Co /Al2 O3 (pelletts)
Sasol
Puralox
SCCa‐5/200 as carrier
• Smaller
particles
than
pelleted
alumina
• Same
surface
area/ g as pellets
(220 m2/g)
• With
a Co
catalyst
prepared
from
Co(NO3
)2
we succeeded
to keep
the reactor
active
(exotermic)
and productive
for 72 hours
• Reaction
was
active
when
it
was
stopped
for weekend
(safety
reasons)
• Products
were
collected
and analysed
every
24 hour
Recent
tests
• With a ratio of H2
/CO = 2 main component was C7 (C6 to C25 was produced)
• A lower ratio (1,25/1) shifted main component to C9
• A ratio of 1/1 has been tested but not analyzed
Future
experiments
• New equipment for gas analysis (CO, H2
, N2
and C1‐ C5) after reactor in order to measure conversion rate
is needed
• Analysis of tar‐content in real syngas
will be performed
• FTS on real syngas
in the near future
Thank You!