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Final Year Design Project 2017

Wax from Methane via Fe-LTFT


1. The Fischer-Tropsch Synthesis
Fischer-Tropsch Synthesis (FTS) Some basics
Conversion of synthesis gas (CO + H2) to organic molecules
Polymerization reaction where the monomer is made in-situ
Mostly paraffins and olefins
Some oxygenates (aldehydes, ketones, alcohols, acids)
Some branching (mostly methyl branches)

The relative amount of olefins/oxygenates depends on the catalyst and operating


conditions
Co-LTFT makes significantly less olefins and oxygenates than Fe-LTFT

While cyclic molecules are formed (mostly in Fe-HTFT), these form via secondary
reactions

The products produced follow an Anderson-Shultz-Flory distribution with a fixed


probability of a chain growing by one carbon number at every step - ,.
High long chains
Low short chains

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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

Formic acid can also form as an intermediate of the WGS reaction


+ 2 2 + 2

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

There are four basic steps:


Monomer formation
Chain Initiation
Chain Growth
Chain Termination

The products, like for many polymerisation reactions, follow a Schultz-Flory


distribution

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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.

The chain can desorb after monomer insertion Terminates as olefin

Two hydrogenations in a row Terminates as paraffin

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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

Paraffin Olefin Total

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3. Synthesis gas generation

Haldor-Topse Autothermal Reforming


Auto-Thermal Reforming (ATR)

Ref: Haldor Topsoe Brochures

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Autothermal Reforming Reactions

Internal Combustion Zone


Cold Tip Swirl Burner

CH4 + 3/2O2 CO + 2H2O (CTS)

Endothermic Reforming Reaction


CH4 + H2O CO + 3H2

Water Gas Shift Reaction Nickel type


reforming
CO + H2O CO2 + H2 catalysts

Boudouard Reaction (Soot formation)


- Limit is 650C

2CO CO2 + C (soot)

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Pictures of Synthesis Gas Unit

3-D drawing of ATR with Waste Heat Boiler &


Fluid Dynamic modelling of an ATR burner HTAS Heat Exchanger Reforming unit
Steam Superheater

Ref: Haldor Topsoe Brochures

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

As per your companys preference, the reactor will be an isothermal, multi-tubular,


fixed-bed reactor, operating at 245C

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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