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Abstract−− Fischer-Tropsch synthesis is an im- 2001; Wang et al., 2003), but few investigations have
portant chemical process for the production of liq- been done in order to optimize the production of spe-
uid fuels and olefins. In recent years, the abundant cific products.
availability of natural gas and the increasing de- The Fischer-Tropsch reaction yields predominately
mand of olefins and liquid fuels have led to a high straight chain hydrocarbons (α-olefins and alkanes)
interest to further develop this process. A mathe- where the main reaction products are α-olefins. There
matical model of a tubular reactor used for syngas is general agreement that the reaction may be viewed
polymerization was developed and the carbon as a methylene polymerization reaction where the
monoxide polymerization was studied from a mod- monomer unit (=CH2), is not initially present. The
eling point of view. Simulation results show that products are formed by hydrogenation of CO to gen-
different parameters affect syngas conversion and erate the methylene monomer, in situ. Polymerization
carbon product distribution, such as operating occurs through initiation of chains, competing chain
pressure, gas velocity and syngas composition. Op- propagation and chain termination steps. Theories on
timization of several hydrocarbon products were the CO polymerization mechanism are based in the
done in order to search for the best operating con- superposition of two ASF (Anderson-Schulz-Flory)
ditions for their production. distributions and rely in the dual site theory (Madon
Keywords−− Multitubular Reactor, Fischer- and Taylor, 1981), secondary chain growth of read-
Tropsch Synthesis, Liquid Fuels, Olefins sorbed alkenes theory (Schulz and Claeys, 1990; Igle-
sia et al., 1991), or the dual mechanism of chain
growth theory (Patzlaff et al., 1999, 2002). Iron cata-
I. INTRODUCTION lysts are more likely to obey a dual mechanism of
In recent years, the Fischer-Tropsch Synthesis (FTS) chain growth theory.
became a subject of renewed interest particularly in In this work a mathematical model of a tubular re-
the context of the conversion of remote natural gas actor used for CO polymerization was developed and
into liquid transportation fuels and due to an escala- the carbon monoxide polymerization was studied from
tion in the price of oil. Natural gas, biomass and coal a modeling point of view based on the kinetics of an
can be converted to carbon monoxide and hydrogen iron catalyst obeying a dual mechanism theory.
(synthesis gas) via the existing processes, such as
steam reforming, carbon dioxide reforming, partial II. TUBULAR REACTOR
oxidation and catalytic partial oxidation. The syngas The tubular reactor for Fischer-Tropsch synthesis con-
can be converted into hydrocarbons (paraffins and sists of a multitube reactor where the synthesis gas is
olefins) by the FT synthesis reaction: fed at the top of the reactor and passes through the bed
CO + (1 + m / 2n )H ⎯
1 of catalyst inside the tubes. The synthesis gas passes
2 ⎯→ C H + H O .
n m 2
(1)
n through the reactor in plug-flow regime. Water passes
The FT synthesis can be carried out in iron, cobalt through the shell side of the multitube reactor to re-
and ruthenium based catalysts. Fe-based catalysts are move the heat released by the FTS reaction and to
much less expensive than the Co-based catalysts, control the reactor temperature, ensuring an isothermal
which can be an important economical factor for the condition inside the reactor, in spite of the high heat of
process specially because the catalyst has to be re- reaction (ΔH = - 170 kJ/mol CO).
placed due to deactivation. When iron catalysts are
used, the carbon monoxide polymerization occurs in III. MATHEMATICAL MODEL
combination with the water gas shift reaction (WGS): A. Tubular Reactor Model
CO + H 2 O ←
⎯→ CO 2 + H 2 . (2) The basic assumptions made for the reactor were:
Many researchers have been working on catalyst steady-state operation, isothermal conditions, gas
development (Raje and Davis, 1997; van Steen and passing through the reactor in plug-flow regime due to
Schulz, 1999) and reactor design (Maretto and its velocity, hydrocarbon products in the gas and in the
Krishna, 1999; Krishna and Sie, 2000; Krishna et al., liquid phases are assumed to be in equilibrium at the
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Latin American Applied Research 36:141-148 (2006)
reactor outlet; mass and heat transfer resistances be- Table 1. Kinetic parameters for Fischer-Tropsch synthesis
tween the catalyst and the gas phase is negligible; neg- in iron catalyst and for water gas shift (Raje and Davis,
ligible radial concentration and temperature gradient 1997).
within the tube; negligible concentration and tempera- kFTS 0.1106 [mol/kg.s.MPa]
ture gradient within the catalyst; intrinsic kinetics for a 3.016
Fischer-Tropsch synthesis and water-gas shift reac- kWGS 0.0292 [mol/kg.s]
tions. K1 85.81
The kinetic model for the FTS reaction on an iron K2 3.07
catalyst and for the WGS reaction are given by (Raje * Obtained experimentally at T = 270oC, P = 0.5 – 3.0 MPa
and Davis, 1997): and H2/CO = 0.67 – 1.7.
k ⋅P ⋅P
R FTS = FTS CO H 2 . (3) Table 2. Operating conditions and reactor parameters.
(PCO + a ⋅ PH 2O )
⎛ Temperature [oC] 270
P ⋅P ⎞
k WGS ⋅ ⎜⎜ PCO ⋅ PH 2O − CO 2 H 2 ⎟⎟ Total Pressure [MPa] 1.0 to 4.0
R WGS = ⎝ K1 ⎠. (4) Gas velocity [m/s] 1.0 to 10.0
(PCO + K 2 ⋅ PH 2O )2 Catalyst apparent density [kg/m3] 647
The material balance for component i in the reactor Reactor Length [m] 10.0
as a function of its axial position is given by: Reactor Diameter [m] 0.025
dFCO Fixed Bed Porosity 0.60
= ρ ⋅ A ⋅ (− R FTS − R WGS ) , (5) Catalyst Diameter [m] 70.0 x10-6
dz
dFH 2
= ρ ⋅ A ⋅ (− 2 ⋅ R FTS + R WGS ) ,
B. Kinetic model
(6) The kinetic model used to simulate the CO polymeri-
dz
zation and product distribution assumes that the alkyl
dFH 2O
= ρ ⋅ A ⋅ (+ R FTS − R WGS ) , (7) and alkenyl mechanism acts together in the FTS syn-
dz thesis.
dFCO 2 The alkyl mechanism can be represented by the fol-
= ρ ⋅ A ⋅ (R WGS ) . (8) lowing reactions:
R (1)
dz
• CH 2 + •H ⎯⎯→ ki1
initiation
The partial pressure of the species is given by:
Fi R (n ) + •CH 2 ⎯⎯→ R (n + 1)
kp1
propagation
Pi = ⋅ PT . (9) R (n ) + •H ⎯kpar
⎯ P(n )
⎯→ reduction by surface
∑ Fi hydride giving alkanes
R (n ) ⎯kolef
⎯→ P = (n )
Due to the assumption of isothermal condition in β-hydride elimination
⎯
the reactor, which can be considered based on the aca-
demic and patent reports (Freide et al., 2003, 2004; giving a olefins
Wang et al., 2003), only the mass balances and popu- The alkenyl mechanism can be represented by the
lation balances for the hydrocarbon species were con- following reactions:
sidered in this work. As such, all heat produced by the • CH 2 + •CH ⎯⎯→ ki 2
R (2 ) initiation
reaction is assumed to be removed by the cooling
jacket of the reactor. R" (n ) + •CH 2 ⎯⎯→ R" (n + 1) propagation
kp 2
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L. C. A. MAZZONE, F. A. N. FERNANDES
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Latin American Applied Research 36:141-148 (2006)
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L. C. A. MAZZONE, F. A. N. FERNANDES
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Latin American Applied Research 36:141-148 (2006)
Table 6. Optimal operating conditions for maximum pro- H2:CO ratio is increased, the production of light paraf-
duction of gasoline, light olefins and higher olefins. fins increases, producing a greater quantity of methane
Optimal yield of H2:CO Pressure Gas veloc- and ethane which has to be recycled back to the re-
ratio [MPa] ity [m/s] former to produce syngas.
Gasoline 1.18 4.0 10.0 Decision on which optimum point to choose:
Light Olefins (C2-4) 0.88 4.0 10.0 maximum production or maximum yield may depend
Higher Olefins (C5+) 1.73 4.0 10.0 on economical reasons. Running the system with the
Higher Olefins (C12+) 2.00 4.0 10.0 operating conditions that favors maximum yield will
lead to lower costs on recycling and burning of un-
When the maximization focuses on the mass pro- wanted products (paraffin light gases and LPG) but
duction of the desired product the operating conditions production will be lower for the same reactor size.
are different from the conditions for maximum yields. While running the system with the operating condi-
Pressure and gas velocity are maintained since maxi- tions which favor maximum production will lead to
mum production is also associated to higher gas con- higher recycling costs which may be compensated by
centrations. The H2:CO ratios for maximum produc- the enhanced production rate.
tion are higher than for maximum yield, existing a
trade-off from reducing the average chain length to- V. CONCLUSIONS
wards a higher mass production associated to higher Fischer-Tropsch synthesis can be used to produce
propagation rates. transportation fuels and olefins from natural gas and
As shown in Table 7, when light olefins are the de- the polymerization conditions can be set to maximize
sired product, the production of heavy olefins (C5+) is the production of a certain product generated by the
at 7.4 kg/h per tube, but when the H2:CO ratio is in- FTS reaction, such as light olefins, higher olefins and
creased, the average chain length of paraffins dimin- gasoline.
ishes and the average chain length of olefins increases,
producing 9.0 kg/h per tube of heavy olefins. As
Table 5. Product distribution (weight fraction) of reactor operating at the optimum conditions for maximum yields of gasoline,
light olefins and higher olefins.
Table 7. Product distribution (weight basis) of reactor operating at the optimum conditions for maximum production of gasoline,
light olefins and higher olefins (kg/h per tube).
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L. C. A. MAZZONE, F. A. N. FERNANDES
According to the simulations, the optimum operat- wi weight fraction of hydrocarbon with i carbons
ing condition to maximize heavy olefins production in the product distribution
and yield needs high pressures and high gas velocity XCO carbon monoxide conversion
associated to hydrogen to carbon monoxide ratios be- Y hydrocarbon yield
tween 1.45 and 1.75. The optimum operating condi- z axial position [m]
tion to maximize light olefins production needs high φ porosity
pressures and high gas velocity associated to hydrogen ν stoichiometric coefficient
to carbon monoxide ratios between 0.50 and 0.90. The μ gas mixture viscosity [N.s/m2]
production of gasoline and diesel using this iron-based ρ catalyst density [kg/m3]
catalyst is not economically viable in this kind of reac- ρg gas mixture density [kg/m3]
tor since their yields are lower than 5% in mass weight
while some commercial catalyst presents yields higher
than 15% in mass weight. REFERENCES
Davis, B.H., “Fischer-Tropsch Synthesis: Relationship
between Iron Catalyst Composition and Process
ACKNOWLEDGMENT Variables.” Cat. Today, 84, 83-98 (2003).
The authors gratefully acknowledge the financial sup- Donnelly, T.J. and C.N. Satterfield, “Product distribu-
port of the Brazilian research funding institution tions of the Fischer-Tropsch synthesis on precipi-
CNPq/CTPetro (Conselho Nacional de Desen- tated iron catalysts.” Appl. Catal., 52, 93-114
volvimento Científico). (1989).
Dry, M.E., “Practical and theoretical aspects of the
catalytic Fischer-Tropsch process.” Appl. Catal.,
NOMENCLATURE 138, 319-344 (1996).
A area [m2] Fernandes, F.A.N., “Polymerization Kinetics of
Ci,j concentration of component i Fischer-Tropsch Reaction on Iron Based Catalysts
Fi molar flow rate of component i [mol.h-1] and Product Grade Optimization”. Chem. Eng.
dP catalyst particle diameter [m] Tech., 28, 930-938 (2005).
H reactor height [m] Freide, J.J.H.M.F., T.D. Gamlin, C. Graham, J.R.
ket ethane formation rate constant [MPa-1.h-1] Hensman, B. Nay and C. Sharp, “An adventure in
ki initiation rate constant for the alkyl mecha- catalysis: the story of the BP Fischer-Tropsch cata-
nism [MPa-1] lyst from laboratory to full-scale demonstration in
ki2 initiation rate constant for the alkenyl mecha- Alaska”, Topics Catal., 26, 3-12 (2003).
nism [mol/h] Friede, J.J.H.M.F., J.R. Hensman, N. David, C. Sharp,
kmet methane formation rate constant [MPa-1.h-1] G.B. Smith. “Fischer-Tropsch Process”. European
kO2 ethylene formation rate constant [h/mol] Patent EP1392622 (2004).
kolef termination by b-elimination rate constant for Iglesia, E., S.C. Reyes and R.J. Madon, “Transport-
the alkyl mechanism [h-1] enhanced α-olefin readsorption pathways in Ru-
kolef2 termination rate constant for the alkenyl catalyzed hydrocarbon synthesis.” J. Catal., 129,
mechanism [h-1] 238-256 (1991).
kp propagation rate constant for the alkyl Krishna, R. and S.T. Sie, “Design and Scale Up of the
mechanism [h/mol] Fischer-Tropsch Bubble Column Slurry Reactor.”
kp2 propagation rate constant for the alkenyl Fuel Proc. Tech., 64, 73-105 (2000).
mechanism [h/mol] Krishna, R., J.M. van Baten, M.I. Urseanu, and J.
kpar termination rate constant for the alkyl mecha- Ellenberger, “Design and Scale Up of a Bubble
nism yielding paraffin [MPa-1.h-1] Column Slurry Reactor for Fischer-Tropsch Syn-
Ki equilibrium constant of reaction i or adsorp- thesis.” Chem. Eng. Sci., 56, 537-545 (2001).
tion coefficient of component i Li, S., S. Krishnamoorthy, A. Li, G.D. Meitzner and
Pi partial pressure [MPa] E. Iglesia, “Promoted Iron-Based Catalysts for the
PT total pressure in the reaction zone [MPa] Fischer–Tropsch Synthesis: Design, Synthesis,
P(n) paraffin containing n carbons [mol] Site Densities, and Catalytic Properties.” J. Catal.,
P=(n) olefin containing n carbons [mol] 206, 202-217 (2002).
Ri rate of reaction i [mol/s.kgcat] Madon, R.J. and W.F. Taylor, “Fischer-Tropsch syn-
R(n) alkyl propagating species containing n car- thesis on a precipitated iron catalyst.” J. Catal., 69,
bons [mol] 32-43 (1981).
R”(n) alkenyl propagating species containing n car- Maretto, C. and R. Krishna, “Modelling of a Bubble
bons [mol] Column Slurry Reactor for Fischer-Tropsch Syn-
RFTS overall Fischer-Tropsch reaction rate thesis.” Cat. Today, 52, 279-289 (1999).
T temperature [K] Patzlaff, J., Y. Liu, C. Graffmann and J. Gaube,
UG gas velocity [m/s] “Studies on product distributions of iron and cobalt
147
Latin American Applied Research 36:141-148 (2006)
catalyzed Fischer–Tropsch synthesis.” Appl. van Steen, E. and H. Schulz, “Polymerization Kinetics
Catal., 186, 109-119 (1999). of the Fischer-Tropsch CO Hydrogenation using
Patzlaff, J., Y. Liu, C. Graffmann, and J. Gaube, “In- Iron and Cobalt Based Catalysts.” Appl. Catal.,
terpretation and Kinetic Modeling of Product Dis- 186, 309-320 (1999).
tributions of Cobalt Catalyzed Fischer-Tropsch Wang, Y.N., Y.Y. Xu, Y.W. Li, Y.L. Zhao and B.J.
Synthesis.“ Cat. Today, 71, 381-394 (2002). Zhang, “Heterogeneous Modeling for Fixed Bed
Raje, A.P. and B.H. Davis, “Fischer-Tropsch Synthe- Fischer-Tropsch Synthesis: Reactor Model and its
sis over Iron-Based Catalysts in a Slurry Reactor. Applications.” Chem. Eng. Sci., 58, 867-875
Reaction Rates, Selectivities and Implications for (2003).
Improving Hydrocarbon Productivity.” Cat.Today,
36, 335-345 (1997).
Schulz, H. and M. Claeys, “Kinetic Modelling of
Fischer-Tropsch Product Distributions.” Appl.
Catal., 186, 91-107 (1990).
148