POLITECNICO DI MILANO

Industrial Organic Chemistry

Fischer-Tropsch Synthesis (FTS)
 Franz Fischer

www.fischer-tropsch.org
Chemicals from CO/H2
 Fischer – Tropsch synthesis (FTS)

· This name designates the process that converts carbon monoxide

and hydrogen into a mixture consisting mainly of straight chain
hydrocarbons having from 1 to over 100 carbon atoms.

· The reaction was first studied in the early '20s in Germany. It is

catalyzed by Fe, Co (Ru, Ni) at these conditions:
T = 180-250 ° C, P = 10-30 atm.

· 15 FTS plants operated during World War II, with a synthetic oil
production of about 500 000 t/year.
• After WW II, FTS plants were built in South Africa (SASOL),
Russia and Malaysia (Shell).

SASOL I Technology (Sasolburg, 1955)

· Coal gasification with H2O/O2 at 30 atm  syngas: H2/CO = 1.7/1

· Syngas purification with Rectisol (CH3OH ) from H2S, CO2, tars
· System of two reactors: i) fixed bed; ii) circulating fluidized bed
Recent history of the FT process:
• 1993: Shell started in Bintulu Malaysia the first GtL plant but it was partially
destroyed by an explosion in 1997. It was recommissioned in 2000 (14.500 bpd).

• 2004: Coal gasification was replaced by natural gas reforming and SASOL I was
shifted from a CtL to a GtL plant

• 2007: Sasol-QP (Oryx) installed FT plant in Qatar (GtL) (34.000 bpd)

• 2011: Shell (Pearl) installed FT plant in Qatar (GtL) (140.000 bpd)

• 2013: Chevron Sasol installed FT plant in Nigeria (GtL) (34.000 bpd)

• To date: the major oil companies exploiting the FT technology are Sasol, Shell and
Qatar petroleum. However other companies (BP, Amoco, Statoil, ENI, Velocys and
Nippon FtL Technology Research Association) are currently investigating FT
process.
X To Liquid processes: CtL

Natural gas (GtL); coal (CtL);

biomasses (BtL)

Syngas
(CO and H2)

FT synthesis GtL
n CO + 2 nH2  - (CH2)n- + n H2O

Products upgrading
(i.e waxes hydrocracking )

Synfuels and chemicals Advantages:

• Decrease of oil dependency
• Exploitation of remote natural gas (or coal) fields
• Monetization of "biomass"
• Diesel with high performance: high cetane
number (75 vs 50)
• Clean fuels: free of sulfur and aromatics
GtL
Syngas production: (H2/CO)FT ≈ 2

Natural ATR, POX, CPOX

gas (H2/CO)GTL ≈ 2
(GtL)

Exploiting the WGS

Coal Gasification reaction…
(CtL) CO + H2O  CO2 + H2

(H2/CO)CTL/BTL < 2

Gasification
Biomass
(BtL)
FT synthesis: Chemistry
Paraffins:
(2n+1) H2 + n CO  CnH2n+2 + n H2O ∆H0r/n = - 161.5 kJ/mol
CO+ 3 H2  CH4 + H2O ∆H0r/n = - 206 kJ/mol

Olefins:
2n H2 + n CO CnH2n + n H2O ∆H0r/n = - 149 kJ/mol

Oxygenates:
2n H2 + n CO  CnH2n+1OH + (n-1) H2O ∆H0r/n = - 131.1 kJ/mol
CO + H2O  CO2 + H2 ∆H0r = - 9.5 kcal/mol

n CO + 2 nH2  - (CH2)n- + n H2O

∆H0r/n = - 170 kJ/mol

Catalysts and operative conditions strongly affect the product distribution

Other reactions
FT synthesis: Catalysts
• Cheap
• Bulk catalysts
• HTFT (250<T<350°C)
• High selectivity to olefins
and oxygenates
• Active in the WGS
reaction

CtL/BtL
(H2/CO < 2)

• Expensive
• Supported catalysts
(Al2O3/SiO2/TiO2) GtL
• LTFT (T<250°C) (H2/CO ≈ 2 )
• High selectivity to paraffins
• Low activity in the WGS

Active phases: Co°, FeCx

Conventional Fe and Co FT catalysts:
FT synthesis: Catalysts

6 3
9

12
Selectivity [%]

48

36

19
6

24 18
4
4
7 4
FT synthesis: Operating conditions
Temperature

• ↑Xco by increasing T: FT reaction is T

kinetically controlled

• ↑ SHClight ; ↓α; ↓O/P: By increasing

T, hydrogenation reactions increases
FT synthesis: Operating conditions
H2/COIN

H2/CO

H2/CO

• ↑Xco increases by increasing H2/CO

ratio in the feed

• ↑ SHClight ; ↓O/P; ↓ α : hydrogenation

reaction increases by increases the
amount of H2 in the feed
FT synthesis: Operating conditions
Pressure

P
P

• ↑Xco increases with P

• ↑ SHCheavy ; ↑ α; ↑ O/P:
P hydrogenation reaction decreases
with P
FT synthesis: Reactor technologies
In conventional FT processes, four types of reactors are used:
• Fixed-bed multitubular reactors
• Fluidized-bed reactors
• Slurry-bed reactors
• Circulating fluidized bed reactors
FT synthesis: Reactor technologies

MTFBR LTFT
Multi Tubolar Fixed Bed Reactor
Disadvantages:
• Design complexity, which is difficult to
scale up
• High pressure drop and insufficient heat
removal
• Low catalyst utilization
• Occurrence of mass transport limitations
• Need for periodical replacement of
catalyst
• High cost

Sasol I (Arge), South Africa, 1955

 FT - SASOL Technology

Fixed bed

• Operated at 220 °C, 2.7 MPa, with a Fe-based catalyst

promoted with K or Co/Al2O3.
• Multitubolar reactor (shell and tube):
· diameter 3 m, length 13 m,
· 2050 tubes with a diameter of 50 mm, cooled by boiling
water under pressure
· temperature is controlled by adjusting the shell-side
pressure
· catalyst load: 40 m3
· catalyst lifetime: about 6 months
• Downstream: refinery with separation of HC cuts
FT synthesis: Reactor technologies

HTFT
SBCR
Slurry Bubble Column Reactor

Advantages:
• Lower Design complexity than fixed bed
• Cheaper than FTBR
• Fast heat removal (no hot spot)
• No mass transport limitations
Disadvantages:
• Separation of the catalyst from the
waxes
• Catalyst attrition
• Catalyst deactivation

Sasol (Oryx) (2008)

Sasol I, Sud Africa, dal 1993
 FT - SASOL Technology

Circulating fluidized bed

Reactors with catalyst recirculation (Synthol):
· operated at approx. 320 ° C and 2.2 MPa
· catalyst based on molten magnetite, with little K: it must resist the continuous
motion

· Catalyst circulation = 8000 t / h

· Gives products in the range of gasoline
· Conversion and productivity are much higher than in the fixed bed: > 9 times if
referred to cross-sectional area of the reactor
· Deactivation due to the formation of waxes on the catalyst particles.

In the ‘80s ​SASOL II and III were built: much larger units still based on circulating
fluidized bed reactors.
Influence of particle size
FT synthesis: NEW Reactor technology
Compact reactors

Conventional FT reactor Compact FT reactor

Think smaller means…

 Exploiting the most of the available resources
 Converting undervalued gas into higher valuable liquid fuels
 Building plants wherever the opportunity is
 Accessing markets faster - no need for pipelines
 Cutting the time between the concept and being operational
 Reducing cost plants: smaller needs less gas to be profitable
FT synthesis: NEW Reactor technology

Combination of microchannel reactors and SUPER-ACTIVE CATALYSTS

that together, significantly intensify the FT process.

Velocys technology makes possible to build GTL

plants that process 150 – 1500 million m3 per
year of gas producing 1,500 – 15,000 barrels
per day (bpd) of liquid fuels

Microchannel reactor:
 Enhanced heat and mass transfer rate
 Isothermal behavior – thermaly stable
 Close coupling of exothermic reaction with steam generation
FT synthesis: Mechanism
CO + *  CO* • Dissociative absorption of CO (in
the form of C and O atoms) on the
CO* + *  C* + O*
catalytic surface.
C* + H2  CH2*
• C* (Cads) reacts with molecular H2 to
give CH2* (monomeric unit)

Chain growth: α • The monomeric unit (CH2*) is

CH2* + CH2* CH3-CH*
CH3-CH* + CH2*  CH3-CH2-CH*
Desorption: 1-α
added to an other CH2* ..
• This mechanism occurs in the
adsorbed phase giving linear
products

CH3-CH=CH2
• Re-combination: α-olefin
CH3-CH2-CH* • Hydrogenation: paraffin
H2 CH3-CH2-CH3
This theory does not explain the formation of alcohols and oxygenated compounds, which are
found in the product mixture in small amounts.
FT synthesis: Mechanism
• Not dissociative adsorption of CO
CO + *  CO*
• CO* (COads) reacts with molecular
CO* + H2  HCOH*
H2 to give the oxymethilenic specie
HCOH* (monomeric unit).

Chain growth: α
-H2O
HCOH* + HCOH*  HC-COH*
HC-COH* + H2 CH3-COH*
-H2O
CH3-COH* + HCOH  CH3C-COH*
CH3C-COH* +H2  CH3CH2-COH
• The mechanism occurs by
adding HCOH*, and
eliminating a molecule of
H2O and eventually by
hydrogenating

Desorption: 1-α • Alcohol formation after

hydrogenation
H2 CH3-CH2-CH2-OH
• Hydrogenation and removal
CH3-CH2-COH* of H2O: olefin
H2 CH3-CH=CH2 • Olefin hydrogenation:
-H2O paraffin
FT synthesis: ASF distribution
-1
-2
-3
-4
-5
ln(Sn/n) -6
-7
-8
-9 α
-10
-11
-12
0 5 10 15 20 25 30 35 40 45 50
n°C

• It explains the hydrocarbon products distribution. It occurs following a polymerization

mechanism involving the addition of the monomeric unit CH2*

• At each step the chain growth may terminate by addition or removal of one H atom in the
chain, followed by desorption.

• α : chain growth probability and 1-α the probabilty to terminate the chain growth.
FT synthesis: ASF distribution
• The probability to obtain a species with a carbon number «n» is:
(product between the probability to form the species with carbon number from 1 to n-1 and the probability to desorb
the species with carbon number n)

Pn = αn-1 (1-α)

• Pn is equal to the molar fraction of the hydrocarbon with carbon number n in the
product mixture:
Pn = yn

• Corresponding to a mass fraction: Wn

Wn = A n Pn

Where A is a constant to determine with the assumption that the integral of Wn is 1.

∞

∫W
0
N ⋅ dN =
1
1 α ⋅ ln 2 (α )
= A ∞=
(1 − α )
∫ α α
• A: N −1
N ⋅ ⋅ (1 − ) ⋅ d N
0
FT synthesis: ASF distribution
• Then:
α N ⋅ ln 2 (α ) ⋅ N
WN =

• linearized form:
W 
ln  N N ln(α ) + ln ln 2 (α ) 
 =⋅
 N 

ASF theory is based on the following assumptions:

• linear growth, for which no branched products are formed;
• there is no difference in the hydrocarbon products from olefins
and paraffins;
• the products do not give secondary reactions;
• the probability α is constant with the number of carbon atoms
(n).
FT synthesis: Deviations from the ASF distribution
W 
ln  N N ln(α ) + ln ln 2 (α ) 
 =⋅
 N 

• CH4 is understimated
• C2H4 is overstimated
• Change of the slope at C8
• Decreasing of O/P ratio by
increasing n
C1
-2 experimental data
α1
-4
ln(xn/n)

C2
α2
-6

-8

-10

-12
0 10 20 30 40 50
Number of Carbon Atoms (n)
FT synthesis: Deflections from the ASF distribution

CH4 is understimated

• Existence of different active sites able to activate the methanation reaction

• Metals of VIII group are active in the olefins and paraffins hydrogenolysis:

CnH2n+1* + H*  Cn-1H2n+1* + CH3*

• Mass transfer phenomena may increase the H2/CO ratio within the catalysts pores

• Hot-spot phenomena may increase the local temperature of the catalyst bed

C2H4 is overestimated due to its high reactivity

FT synthesis: Deflections from the ASF distribution

α1 Change of the slope at C8

α2

• The bimodality of the distribution may be due to the presence of

different active sites responsible for two different probability of chain
growth: each active site activates a pseudo-polymerization reaction
with its chain growth probability

yn = Pn = αn-1 (1-α) yn= Z(1 - α1) α1n-1 + (1 - Z)(1 – α2) α2n-1

Z is the mole fraction of organic product synthesized on the

site 1. In site 1 dominates the formation of the species C1-C10.
In site 2 dominates the formation of species C10 +.
FT synthesis: Deflections from the ASF distribution

α1 Change of the slope at C8

α2

• The bimodality of the distribution may be due to the presence of different active sites
responsible for two different probability of chain growth: each active site activates a
pseudo-polymerization reaction with its chain growth probability

• The variation of α can be caused by olefins secondary

reactions. These reactions occur after the re-adsorption
of the olefins on the active sites before leaving the
reactor.. increasing “n”, the secondary reactions are
favored.
 Development of a kinetic model for the Fischer-Tropsch synthesis:

Kinetic models

SIMPLIFIED DETAILED
Both the CO conversion and the
The CO conversion is estimated
products distribution are estimated
as a function of the operative
as a function of the operative
conditions
conditions

Simple and flexible tool Comprehensive tool used to

used to evaluate the
performances of the
system from a thermal and
material point of view
evaluate the performances
of the system from the point
of view of the productivity
and selectivity of the
reaction products
 Development of a kinetic model for the Fischer-Tropsch synthesis:

Kinetic models

SIMPLIFIED Hypothesis:

The CO conversion is estimated 1. NO interactions between the

as a function of the operative kinetics of the CO consumption
conditions kinetics and of the products
formation

2. The «lump» hydrocarbon is

representative of the entire FT
products distribution: CnHm
Simple and flexible tool H2 1
used to evaluate the CO + H2 → CnHm + H2O
CO usage n
performances of the
system from a thermal and 3. The stoichiometry of the reaction
material point of view is independent from the operative
conditions
 Development of a kinetic model for the Fischer-Tropsch synthesis:

SIMPLIFIED KINETIC MODEL

H2 1
«Lump» reaction: CO + H2 → CnHm + H2O
CO usage n

Starting from the experimental data, we are able to determine: H2/COusage , olefinicity o, n, m...

H 2 − FH 2
0
H2 def. F def . mololefin
= o=
CO USAGE 0
FCO − FCO mololefin + mol paraffin
out

m = 2n + 2 − 2o
∑ nC ⋅ y +∑ nC ⋅ y
50 17

n= Pn On
nC =1 nC = 2

y Pn Molar fraction of the paraffin with «n» carbon number

yOn Molar fraction of the olefin with «n» carbon number

Development of a kinetic model for the Fischer-Tropsch synthesis:

SIMPLIFIED KINETIC MODEL

H2 1
«Lump» reaction: CO + H2 → CnHm + H2O
CO usage n

rCO = − k (T ) ⋅ (..................)
 Eatt 
k (T ) = k0 ⋅ exp − 
 R ⋅ T 

In order to develop the CO consumption kinetics, empirical (power law) or

mechanistic models (Langmuir Hinshelwood Hougen Watson) have been used
 Development of a kinetic model for the Fischer-Tropsch synthesis:

SIMPLIFIED KINETIC MODEL

H2 1
«Lump» reaction: CO + H2 → CnHm + H2O
CO usage n

It describes the rate of the CO

consumption as a function of the
rCO = − k (T ) ⋅ (..................)
temperature and the partial pressures
of the reactants

− rCO = k (T ) ⋅ p aH 2 ⋅ p CO
b

It is not based on the reaction mechanism

In order to develop the CO consumption kinetics, empirical (power law) or

mechanistic models (Langmuir Hinshelwood Hougen Watson) have been used
 Development of a kinetic model for the Fischer-Tropsch synthesis:

SIMPLIFIED KINETIC MODEL

H2 1
«Lump» reaction: CO + H2 → CnHm + H2O
CO usage n

rCO = − k (T ) ⋅ (..................)
k (T ) ⋅ ∏ p iα i

− rCO = k (T ) ⋅ p aH 2 ⋅ p CO
b − rCO = i
γ
  ( ) 
1 + ∑  A i T ⋅ ∏ p β
k
k

It is not based on the reaction mechanism
i  k 
It is based on the reaction mechanism

In order to develop the CO consumption kinetics, empirical (power law) or

mechanistic models (Langmuir Hinshelwood Hougen Watson) have been used
 Development of a kinetic model for the Fischer-Tropsch synthesis:
Example: Sarup-Wojciechowski model..
PH0.25 ⋅ PCO
0.5
rCO = −k (T ) ⋅
FT: CO + 2H2 → -CH2- + H2O (1 + K ⋅ P )0.5 2
CO

Reaction mechanism by following LHHW model:

1. H2 + 2l ↔ 2H*
2. CO + l ↔ CO*
3. CO* + l ↔ C* + O*
4. C* + H* → CH* + l
5. CH* + H* → CH2* + l
6. O* + H* → OH* + l
7. OH* + H* → H2O + 2l
 Development of a kinetic model for the Fischer-Tropsch synthesis:
Example: Sarup-Wojciechowski model..
PH0.25 ⋅ PCO
0.5
rCO = −k (T ) ⋅
FT: CO + 2H2 → -CH2- + H2O (1 + K ⋅ P ) 0.5 2
CO

Reaction mechanism by following LHHW model:

1. H2 + 2l ↔ 2H* Hypothesis 1: the slow stage is given by the reactions 4 and 6, which
2. CO + l ↔ CO* proceed at the same rate

3. CO* + l ↔ C* + O* (a) rCO = k 4 ⋅ ϑC* ⋅ ϑH*

4. C* + H* → CH* + l
5. CH* + H* → CH2* + l (b) k 4 ⋅ ϑC* ⋅ ϑH* = k 6 ⋅ ϑO* ⋅ ϑH*
6. O* + H* → OH* + l
7. OH* + H* → H2O + 2l
 Development of a kinetic model for the Fischer-Tropsch synthesis:
Example: Sarup-Wojciechowski model..
PH0.25 ⋅ PCO
0.5
rCO = −k (T ) ⋅
FT: CO + 2H2 → -CH2- + H2O (1 + K ⋅ P ) 0.5 2
CO

Reaction mechanism by following LHHW model:

1. H2 + 2l ↔ 2H* Hypothesis 1: the slow stage is given by the reactions 4 and 6, which
2. CO + l ↔ CO* proceed at the same rate

3. CO* + l ↔ C* + O* (a) rCO = k 4 ⋅ ϑC* ⋅ ϑH*

4. C* + H* → CH* + l
5. CH* + H* → CH2* + l (b) k 4 ⋅ ϑC* ⋅ ϑH* = k 6 ⋅ ϑO* ⋅ ϑH*
6. O* + H* → OH* + l
7. OH* + H* → H2O + 2l Hypothesis 2: equilibrium for the reactions 1, 2 and 3

(c) k1 ⋅ PH 2 ⋅ ϑ2 = k1 ⋅ ϑH
2
* ϑH* = K1 ⋅ PH 2 ⋅ ϑ2
(d) k 2 ⋅ PCO ⋅ ϑ = k 2 ⋅ ϑCO* ϑCO* = K 2 ⋅ PCO ⋅ ϑ
(e) k 3 ⋅ ϑCO* ⋅ ϑ = k 3 ⋅ ϑC* ⋅ ϑO* ϑC* ⋅ ϑO* = K 3 ⋅ ϑCO* ⋅ ϑ
 Development of a kinetic model for the Fischer-Tropsch synthesis:
(a) rCO = k 4 ⋅ ϑC* ⋅ ϑH* 1. H2 + 2l ↔ 2H*
2. CO + l ↔ CO*
3. CO* + l ↔ C* + O*
(b) k 4 ⋅ ϑC* ⋅ ϑH* = k 6 ⋅ ϑO* ⋅ ϑH* 4. C* + H* → CH* + l
5. CH* + H* → CH2* + l
6. O* + H* → OH* + l
(c) k1 ⋅ PH 2 ⋅ ϑ = k1 ⋅ ϑH* ϑH* = K1 ⋅ PH 2 ⋅ ϑ2
2 2
7. OH* + H* → H2O + 2l

(d) k 2 ⋅ PCO ⋅ ϑ = k 2 ⋅ ϑCO* ϑCO* = K 2 ⋅ PCO ⋅ ϑ

(e) k 3 ⋅ ϑCO* ⋅ ϑ = k 3 ⋅ ϑC* ⋅ ϑO* ϑC* ⋅ ϑO* = K 3 ⋅ ϑCO* ⋅ ϑ

Balance of the free sites..

1 = ϑ + ϑH* + ϑCO* + ϑC* + ϑO* + ϑCH* + ϑCH 2 * + ϑOH*

Hypothesis 3: the concentration of the surface species CH*, CH2* and OH is negligible

(f) 1 = ϑ + ϑH* + ϑCO* + ϑC* + ϑO*

 Development of a kinetic model for the Fischer-Tropsch synthesis:
(a) rCO = k 4 ⋅ ϑC* ⋅ ϑH* 1. H2 + 2l ↔ 2H*
2. CO + l ↔ CO*
3. CO* + l ↔ C* + O*
(b) k 4 ⋅ ϑC* ⋅ ϑH* = k 6 ⋅ ϑO* ⋅ ϑH* 4. C* + H* → CH* + l
5. CH* + H* → CH2* + l
6. O* + H* → OH* + l
(c) k1 ⋅ PH 2 ⋅ ϑ = k1 ⋅ ϑH* ϑH* = K1 ⋅ PH 2 ⋅ ϑ2
2 2
7. OH* + H* → H2O + 2l

(d) k 2 ⋅ PCO ⋅ ϑ = k 2 ⋅ ϑCO* ϑCO* = K 2 ⋅ PCO ⋅ ϑ

(e) k 3 ⋅ ϑCO* ⋅ ϑ = k 3 ⋅ ϑC* ⋅ ϑO* ϑC* ⋅ ϑO* = K 3 ⋅ ϑCO* ⋅ ϑ

k4
ϑO* = K 2 K 3 ⋅ p CO ⋅ ϑ2 (g)
k6

k6
ϑC* = K 2 K 3 ⋅ pCO ⋅ ϑ 2 (h)
k4
 Development of a kinetic model for the Fischer-Tropsch synthesis:
1. H2 + 2l ↔ 2H*
2. CO + l ↔ CO*
(a) rCO = k 4 ⋅ ϑC* ⋅ ϑH*
3. CO* + l ↔ C* + O*
4. C* + H* → CH* + l
(b) k 4 ⋅ ϑC* ⋅ ϑH* = k 6 ⋅ ϑO* ⋅ ϑH* 5. CH* + H* → CH2* + l
6. O* + H* → OH* + l
7. OH* + H* → H2O + 2l
(c) k1 ⋅ PH 2 ⋅ ϑ = k1 ⋅ ϑH* ϑH* = K1 ⋅ PH 2 ⋅ ϑ2
2 2

(d) k 2 ⋅ PCO ⋅ ϑ = k 2 ⋅ ϑCO* ϑCO* = K 2 ⋅ PCO ⋅ ϑ

(e) k 3 ⋅ ϑCO* ⋅ ϑ = k 3 ⋅ ϑC* ⋅ ϑO* ϑC* ⋅ ϑO* = K 3 ⋅ ϑCO* ⋅ ϑ

(f) 1 = ϑ + ϑH* + ϑCO* + ϑC* + ϑO*

k4 By replacing in the balance of the sites (f)
(g) ϑO* = K 2 K 3 ⋅ p CO ⋅ ϑ2 the equations (c) (d) (e) (g) (h)...
k6

k6
(h) ϑC* = K 2 K 3 ⋅ pCO ⋅ ϑ 2
k4
 Development of a kinetic model for the Fischer-Tropsch synthesis:
1. H2 + 2l ↔ 2H*
2. CO + l ↔ CO*
(a) rCO = k 4 ⋅ ϑC* ⋅ ϑH*
3. CO* + l ↔ C* + O*
4. C* + H* → CH* + l
(b) k 4 ⋅ ϑC* ⋅ ϑH* = k 6 ⋅ ϑO* ⋅ ϑH* 5. CH* + H* → CH2* + l
6. O* + H* → OH* + l
7. OH* + H* → H2O + 2l
(c) k1 ⋅ PH 2 ⋅ ϑ = k1 ⋅ ϑH* ϑH* = K1 ⋅ PH 2 ⋅ ϑ2
2 2

(d) k 2 ⋅ PCO ⋅ ϑ = k 2 ⋅ ϑCO* ϑCO* = K 2 ⋅ PCO ⋅ ϑ

(e) k 3 ⋅ ϑCO* ⋅ ϑ = k 3 ⋅ ϑC* ⋅ ϑO* ϑC* ⋅ ϑO* = K 3 ⋅ ϑCO* ⋅ ϑ

(f) 1 = ϑ + ϑH* + ϑCO* + ϑC* + ϑO*

k4 By replacing in the balance of the sites (f)
(g) ϑO* = K 2 K 3 ⋅ p CO ⋅ ϑ2 the equations (c) (d) (e) (g) (h)...
k6
1
ϑ=
k6 k4 k6
(h) ϑC* = K 2 K 3 ⋅ pCO ⋅ ϑ 2 1 + K1 ⋅ p H 2 + K 2 ⋅ p CO +
k6
⋅ K 2 K 3 ⋅ p CO +
k4
⋅ K 2 K 3 ⋅ p CO
k4
 Development of a kinetic model for the Fischer-Tropsch synthesis:
1
ϑ=
k4 k6
1 + K1 ⋅ p H 2 + K 2 ⋅ p CO + ⋅ K 2 K 3 ⋅ p CO + ⋅ K 2 K 3 ⋅ p CO
k6 k4
rCO = k 4 ⋅ ϑC* ⋅ ϑH*

k’ k6
k⋅ ⋅ K 2 K 3 ⋅ K1 ⋅ p 0CO
.5
⋅ p 0H.5
k4 2
r= 2
 
1 + K1 ⋅ p H + K 2 ⋅ p CO + k 4 ⋅ K 2 K 3 ⋅ p CO + k 6 ⋅ K 2 K 3 ⋅ p CO 
 2
k k 
 6 4 

Kd Ka Kb Kc

k ' ⋅ p 0CO
.5
⋅ p 0H.5 k ' ⋅ p 0CO
.5
⋅ p 0H.5
r= r=
( )
2 2
0.5 0.5 2
1 + K a ⋅ p CO + (K b + K c ) ⋅ p CO + K d ⋅ p H
2
( 0. 5 2
1 + K ' '⋅p CO )
 Development of a kinetic model for the Fischer-Tropsch synthesis:
Power-law (PL)
 E 
rCO = −k0 ⋅ exp − att  ⋅ PHo12 ⋅ PCO
o2

 R ⋅T  Plug-Flow Reactor (PFR)

k0, Eatt, o1, o2  dFCO FCO (Wcat = 0 ) = FCO

0

 dW = rCO
 cat FH 2 (Wcat = 0 ) = FH02
Sarup-Wojciechowski (SW)  dFH 2
FCn H m (Wcat = 0 ) = 0
H2
 = ⋅ rCO
 Eatt  PH 2 ⋅ PCO
0.5 0.5
= − k0 ⋅ exp − ⋅ dW
 cat CO
FH 2O (Wcat = 0 ) = 0
rCO
( )
usage
 R ⋅ T  1 + K ⋅ PCO
2

0.5
 dFCn H m rCO
 = − Finert (Wcat = 0 ) = Finert
0
k0, Eatt, K  dWcat n
 dFH O
 2
= −rCO
Yates-Satterfield (YS)  dW cat
 E  PH 2 ⋅ PCO  dF
rCO = − k0 ⋅ exp − att  ⋅  inert = 0
(
 R ⋅ T  1 + K ⋅ PCO )
2

 dWcat
k0, Eatt, K
Development of a kinetic model for the Fischer-Tropsch synthesis:

Kinetic models

DETAILED
Both the CO conversion and the
products distribution are estimated
as a function of the operative
conditions

Comprehensive tool used to

evaluate the performances
of the system from the point
of view of the productivity
and selectivity of the
reaction products
 Development of a kinetic model for the Fischer-Tropsch synthesis:
Reaction mechanism...
 Development of a kinetic model for the Fischer-Tropsch synthesis:
Reaction mechanism...
 Development of a kinetic model for the Fischer-Tropsch synthesis:
Reaction mechanism...
Plug-Flow Reactor (PFR)

 dFCO FCO (Wcat = 0 ) = FCO

0
 dW = −rCO
 cat FH 2 (Wcat = 0 ) = FH0
 dFH 2
2

 = −rH 2 FPn (Wcat = 0 ) = 0

 dW
FCH 4 (Wcat = 0 ) = 0
cat
 dFP
 = rP ,n FO n (Wcat = 0 ) = 0
n

 cat
dW
 dF FO 2 (Wcat = 0 ) = 0
 CH 4 = rCH
 FH 2O (Wcat = 0 ) = 0
 dWcat
4


 dFOn = r Finert (Wcat = 0 ) = Finert
0

 dWcat On


 dFO2
 dW = rO2
 cat
 dFH 2O
 = rM 1
dW
 cat
 dFinert
 =0

 cat
dW
 Development of a kinetic model for the Fischer-Tropsch synthesis:
Reaction mechanism...
Plug-Flow Reactor (PFR)

 dFCO FCO (Wcat = 0 ) = FCO

0
 dW = −rCO
parameter value unit  cat FH 2 (Wcat = 0 ) = FH0
 dFH 2
2

FPn (Wcat = 0 ) = 0
-4 -1 -1
k H2 3.38 x 10 mmol s g bar  = −rH 2
 dW
FCH 4 (Wcat = 0 ) = 0
-1 cat
E H2 442.42 kJ mol  dFP
 = rP ,n FO n (Wcat = 0 ) = 0
n
-3 -1 -1
k M1 2.76 x 10 mmol s g bar
 cat
dW
E M1 -1  dF FO 2 (Wcat = 0 ) = 0
231.94 kJ mol
 CH 4 = rCH
 FH 2O (Wcat = 0 ) = 0
 dWcat
-1 -1 -1
k IN 1.59 x 10 mmol s g
4


k CH4 7.29 x 10
-2
mmol s g
-1 -1
 dFOn = r Finert (Wcat = 0 ) = Finert
0

-1 -1 -1
 dWcat On
kG 1.91 x 10 mmol s g 
 dFO2
 dW = rO2
-2 -1 -1
k P,n 1.65 x 10 mmol s g
-3 -1 -1  cat
k On,dx 1.99 x 10 mmol s g  dFH 2O
k On,sx -5 -1 -1  = rM 1
3.03 x 10 mmol s g bar dW
 cat
k O2,sx 1.06 x 10
-3 -1
mmol s g bar
-1  dFinert
 =0

 cat
dW
 Conventional FT reactors: advantages and scalability

The FTS is highly exothermal (∆H0R ≅ −167 kJ/molCO) and the selectivity is
strongly temperature dependent (→ ∆Tmax < 10°C)

→ how to manage the heat removal?

Slurry bubble column reactors Ext. cooled multitubular fixed bed reactors

60m 20m

7m

10m
Comparison with current FBR: Shell FT technology
Syngas 2mm
29386 tubes
I.D. 1”

Coolant

Catalyst
packed
bed
20 m 12 m

Coolant
(steam)
Coolant

Products

7m
 Shell FT technology

Problem

Solution 1

51

“Modular Reactor Technology for GasToLiquids Application”, 4 Aprile 2011

 Shell FT technology

Solution 2

52

“Modular Reactor Technology for GasToLiquids Application”, 4 Aprile 2011

 Shell FT technology
Syngas

Coolant

Catalyst
packed
bed
Liquid
phase

Coolant
(steam)

Coolant

Products

53

“Modular Reactor Technology for GasToLiquids Application”, 4 Aprile 2011

 Shell FT technology

The multi-tubular “nature” of Shell reactors makes these units easy to be

scaled (up or down) by changing the number of tubes
BUT

The need of gas and liquid recycles makes the Shell reactors very difficult
to be scaled in terms of tube length (i.e. reactor height)
Heat transfer parameters is governed by “CONVECTION”:
1) Reynolds numbers of the gas phase -> short reactors can be operated only at
high syngas space velocity (i.e. low CO conversion per pass, i.e. high recycle
ratios);
2) The superficial velocity of the liquid phase -> short reactors have to be fed with
amount of liquid similar to long reactors.

Shell reactors CANNOT be “shortened” (tube length = 12 m)

Shell technology is NOT suitable for off-shore applications

54

“Modular Reactor Technology for GasToLiquids Application”, 4 Aprile 2011

 FTS process intensification at Shell

Is it possible to increase the convective heat removal?

Is it possible to decrease the pressure drops across the reactor?
=> Conductive structured catalysts

OCFS CCFS Knitted wire Al foam

ε = 0.84 ε = 0.95 ε = 0.90 ε = 0.90

Such reactors allow the adoption of

reactor tubes 2” I.D. with low ∆P
BUT
Such reactors are effective only in
presence of liquid phase recycle!

55

“Modular Reactor Technology for GasToLiquids Application”, 4 Aprile 2011

 Concept applied to small scale MT-FBR for FTS?
Selection of materials,
washcoating and testing Industrial reactor Improved reactor config.:
DEVELOPMENT

at lab-scale (at PoliMi) modeling «Packed monolith» Lab-scale

concept testing (at PoliMi)
p

Appl. Catal. A 370 (2009) 93

Chem. Eng. J. 171 (2011) 1294
WO/2010/130399
Proof of concept
(and optimization)
DEMONSTRATION

at the pilot scale Design & manufacturing Demonstration

(at eni site) of improved materials at the pilot scale Process analysis
(at eni site) & scenarios

WO/2014/102350

56