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While cyclic molecules are formed (mostly in Fe-HTFT), these form via secondary
reactions
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Fischer-Tropsch Synthesis (FTS) Some basics
Additional reactions that are not formally part of the FT synthesis, but happen in
parallel, include:
Water-gas shift (WGS) + 2 2 + 2
Methanol formation + 22 3
These reactions are considered non-FT as they are direct reactions with CO and do
not go via the FT monomer.
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The Reaction Mechanism
Many reaction mechanisms have been proposed for the FTS
The mechanisms differ depending on the active metal, the promoters that are added
to the catalyst and many other factors
The mechanism given below is a very simplified one, adapted from literature
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Monomer formation
H2 H H
CO CO CO H HCO HC O
CH H CH2 CH4
O H OH OH H H2O
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Monomer formation
H2 H H
CO CO CO H HCO HC O
Monomer
CH H CH2 CH4
O H OH OH H H2O
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Chain growth
CH3 CH2
CH2 CH2 CH CH2
CH3 CH3
CH H H CH3
OR
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Chain growth
CH3 CH2
CH2 CH2 CH CH2
Initiation
CH3 CH3
CH H H CH3
OR
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Chain growth
CH3 CH2
CH2 CH2 CH CH2
Termination
CH3 CH3
CH H H CH3
OR
Termination
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Chain growth
CH3 CH3
CH3 CH2 CH2 R3
CH CH2 CH CH CH2 CH etc.
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Anderson-Schulz-Flory (ASF) Distribution
Assume a fixed growth probability
Fixed here means invariant with regards to carbon number
There are models where is chain length dependent, but they generally add complication without
additional accuracy
The growth probability is the ratio of the growth reaction rate to the sum of the growth
and all termination rates
=
+
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Anderson-Schulz-Flory (ASF) Distribution
1-a
C1* C1 product
a
1-a
C2* C2 product
a
1-a
C3* C3 product
a
.
.
.
* 1-a
Cn Cn product
a
1-a
Cn+1* Cn+1 product
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Anderson-Schulz-Flory (ASF) Distribution
Carbon selectivity (Sn) is the fraction of the total FT product carbon atoms that form
chains of length n
= 1 1
Sn = = n 1 1 2
1
2
1
log = log + log
For non-ideal cases, two growth probabilities are used 1 and 2 with a weight for
the lighter distribution (1) and (1- ) for the heavier distribution (2).
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Anderson-Schulz-Flory (ASF) Distribution
4.5E-02
4.0E-02
3.5E-02
3.0E-02
Carbon Selectivity (Sn)
2.5E-02
Alpha : 0.94
2.0E-02 Alpha : 0.92
Alpha : 0.90
1.5E-02
1.0E-02
5.0E-03
0.0E+00
0 10 20 30 40 50 60 70 80 90 100
Carbon Number
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Anderson-Schulz-Flory (ASF) Distribution
Schulz-Flory plot for an ideal distribution gives a straight line with slope of log()
0.0E+00
0 10 20 30 40 50 60 70 80 90 100
-2.0E+00
-4.0E+00
log(Sn/n)
Alpha : 0.94
-6.0E+00
Alpha : 0.92
Alpha : 0.90
-8.0E+00
-1.0E+01
-1.2E+01
Carbon Number
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Anderson-Schulz-Flory (ASF) Distribution
HTFT LTFT
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2. Your Catalyst
Your Catalyst
You are being supplied with a novel catalyst developed by your companys R&D
department
The FT reaction rate was found to fit the model proposed by Botes (Botes, 2008):
0.5
2
= 2
1 + 0.2
1 1
= 28.5 exp 12000 /.
508
1
2 2 2
=
2
1 + 1.22 + 6.5
0.5
2
1 1
= 8.5 exp 15500 /.
508
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Your Catalyst
The catalyst represents a major breakthrough for Fe-based LTFT, as it produces no
oxygenated products only paraffins and olefins
The ratio of paraffin to olefin at any given carbon number is given according to a model by
Botes (Botes, 2008)
= 7.2 0.185
The catalyst was found to produce a product slate according to an ideal ASF distribution
with an alpha value of 0.945, measured at H2:CO = 1.5 and at a temperature of 245C
It was also found that the growth probability varies with reactant partial pressures
according to
0.5
2
= 0 0.5
1
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Your Catalyst
2.50%
2.00%
Carbon Selectivity
1.50%
1.00%
0.50%
0.00%
0 20 40 60 80 100
Carbon Number
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3. Synthesis gas generation
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Autothermal Reforming Reactions
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Pictures of Synthesis Gas Unit
Fired Heaters
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4. The Design Brief
The Design Brief
You are tasked with designing a plant to produce wax from methane, using the
supplied catalyst
The required production rate will be supplied
The synthesis gas will be produced from natural gas using auto-thermal reforming
(ATR)
A detailed design is not required as this is a package unit supplied by HTAS.
The H2:CO of the synthesis gas may be adjusted by extracting hydrogen via a
membrane system. This hydrogen may be used to hydrogenate the FT products,
should you wish. It is the only source of hydrogen available.
Existing reactors are available to you, but should you decide to use them, you will need to compress
the hydrogen to 55bara and you will need to supply the compressor
The wax products must be fractionated (and optionally hydrogenated) into ten
possible products that your company will sell at prices that will be given to you.
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The Design Brief
The primary objective of the project is to maximise the profits (IRR) for your company
by:
Selecting an optimal product slate
Operating the plant at optimal conditions to produce this slate
Minimizing CAPEX and OPEX
Maximising the efficiency of the unit
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Questions?
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