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!