SYNGAS TO ETHANOL: A SIMULATION APPROACH

Jlio C. C. Miranda (1)*, Gustavo H.S.F. Ponce (1), Moiss Alves (1), Maria.R.W.
Maciel (1) Rubens Maciel F (1)

(1) University of Campinas. School of Chemical Engineering.

ABSTRACT

The chemical route to directly produce higher alcohols, among them ethanol, from
syngas (CO + H2) is gaining space in the last decade as a possible route to produce
synthetic fuels and additives. Here we simulated a case of study using the kinetic data
of K-Co-MoS2/C catalyst to produce ethanol and propanol from syngas. The process
was divided in three parts: reaction section, separation section and recycle, recycling
only pure syngas in order to make possible optimize downstream processes. After
sensitivity analysis and optimization, the results showed that from 100 kmol/h (1069.8
kg/h) of syngas input are generated 435 kg/h (99.3 %) of ethanol and 92.5 kg/h (99.9
%) of propanol. The process showed itself favorable presenting, due the exothermic
reaction, a net energy consumption of -1047.04 kWh (cooling).

Keywords: syngas, ethanol, simulation, energy

Introduction

The growing demand for energy-based comforts and mobility as the great energy
consumption of processing industry added to pollution and the perspective of worlds
petroleum reserves depletion have increased, in the last decade, the search for
alternative and sustainable energy sources. Among these energy sources, liquid fuels
are the focus of policies regarding the current search for sustainability and energy
security. In this scenario, ethanol is gaining space due its low associated cost and low
pollutant emissions, being a possible alternative in case of a future energy crisis (Gao,
2012).
Nowadays ethanol is produced in commercial scale by two ways, from
fermentation of sugars obtained from vegetal sources in a process known as first-
generation and by ethylene hydration. Besides these, two other processes are
intensively investigated: second-generation ethanol, in which lignocellulosic feedstock
is processed generating cellulose that is transformed into ethanol; and third generation
ethanol, in which starting from synthesis gas originated by biomass or petroleum coke
gasification is possible to produce a great variety of alcohols with a carbonic chain
varying from C1 to C7.
Biomass and coal gasification generates the synthesis gas (syngas), a mixture
of, mostly, carbon monoxide (CO) and Hydrogen gas (H2) known by its use on
ammonia and hydrocarbon (Fischer-Tropsch) production processes. However, the
direct catalytic conversion of syngas, investigated during the last 90 years, is drawing
attention in the last decade as a possible route to produce synthetic fuels and
additives. (Subramani and Gangwal, 2008; Christensen et al., 2011).

*
Author for correspondence: julioccmiranda@gmail.com
 In this route, the initial feedstock is gasified to syngas, then it is reformed,
cleaned, compressed, heated and finally catalytically converted to a mixture of
alcohols with high molecular weight, among them ethanol. This process presents
advantages as low reaction time, abundant and cheap feedstocks, the use of lignin
(hardly used component of biomass) and the almost complete conversion of synthesis
gas, having the potential to, in a near future, exceed the production of ethanol through
fermentative route (Saga et al., 2010; Phillips. 2007; He and Zhang, 2011).
Considering the chemical route to produce ethanol, this paper proposes a
simulation layout using the catalyst K-Co-MoS2/C (Gunturu et al. 1998). This catalyst
is a modified Fischer-Tropsch catalyst (MoS2), thus, follows the Anderson-Schulz-
Flory (ASF) distribution and with addition of Co as a reaction promoter, can promote
methanol homologation reaction, which improves ethanol production.
The main goal of this paper is to propose and optimize a novel process layout for
the chemical route using K-Co-MoS2/C catalyst in order to obtain an energy profile of
the entire process, establishing a comparison basis to produce ethanol from syngas.

Simulation

The simulation, schematically showed in Figure 1, was divided in three parts:

Reaction section: the gas is compressed and introduced in the reactor.
Separation section: the exit stream from the reactor is directed to a flash
drum and them passes through dehydration (SEP-1) and alcohols separation
(SEP-2)
Recycle Section: the effluent streams are directed to two reactors that
emulate the gasification and RGWS reactions, calculating the amount of
syngas that can be produced and reinserted into the process.

Reaction Section. Compressor and a PFR reactor compose the reaction section.
Gunturu et al. (1998) obtained the kinetic data used for the simulation, considering the
following reactions:

CO + 2H2 CH3 OH + H2 O (1)

CH3 OH + H2 CH4 + H2 O (2)
CH3 OH + CO + 2H2 C2 H5 OH + H2 O (3)
C2 H5 OH + CO + 2H2 C3 H7 OH + H2 O (4)

The catalyst was K-Co-MoS2/CO, a Fischer-Tropsch catalyst (MoS2) with cobalt

(Co) as a promoter to increase the rate of homologation reaction (Eq. 3). Being a
Fischer-Tropsch catalyst, we assume that the reaction yields follow the Anderson-
Schulz-Flory (ASF) product distribution:

Wn
= (1 )2 n1 (4)
n

where:
Wn component mass fraction
carbon number in the chain
chain growth factor
FIGURE 1. Flowsheet of Ethanol/Propanol process production using syngas as feedstock, K-CO-MoS2/C catalyst
 The reaction system and its kinetic data, provided in LHHW kinetic model was
then, remodeled, considering the production of hydrocarbons and alcohols (until C 5).
To introduce the WGS (water gas shift reaction) (Eq. 5) we considered that the reaction
reaches its equilibrium.

CO + H2 O CO2 + H2 (5)

We followed this procedure to analyze the impact of this other products in

downstream processes variables as final product composition, waste streams and
energy used on separation. The catalyst mass in this step was set as 2000 kg. The
stream leaving the reactor goes then to the separation section

Separation Section. Separation section is composed by four parts. Firstly, a gross

separation is carried out in a flash drum, which separates CO, H2, most of CO2 and
some residual hydrocarbons in the top stream. Such stream is directed to the recycle
section, where is reprocessed generating clean syngas.
The second part of separation is made in a distillation column, where the bottom
stream carries the alcohols plus water and the top stream the rest of hydrocarbons,
CO and CO2.
Sequentially, the dehydration step is the third part of the process. As observed
in Eq. 1-4, the reaction system generates water which remains in the process after the
first distillation column (C-1001). Water forms azeotropes with ethanol (95.5 % w/w)
and propanol (71.1 % w/w), which energetically hinders the separation. Thus, in order
to separate water, an extractive distillation layout similarly used first-generation
ethanol production was adopted (Dias et al. 2009).
Basically, the extractive distillation is carried out using two Columns. In the first
one is added the solvent (MEG - Mono Ehtylene Glycol) to break the azeotropes. In
the second one, the solvent is separated from the water resulting into two purified
streams. Lastly, the regenerated solvent is recycled to the first column (Figure 2).
The stream of interest, that leaves SEP-1 contains of ethanol, propanol and a
small amount of methanol. It goes to SEP-2, where the two major products are
separated to their specifications by a distillation column, shown in Figure 3.

FIGURE 2. Dehydration Process Layout (SEP-1)

 FIGURE 3. Alcohols Purification (SEP2)

Recycle Section. Recycle section represents synthesis gas reforming and cleaning.
The reactions generate small amounts of hydrocarbons and methanol. These
components pass through the recycle section in order to reintroduce clean syngas to
the system. This operation assumes RWGS reaction (reverse water-gas shift reaction)
in equilibrium and the gasification of the products to only CO an H2. The two reactors
are considered adiabatic to not influence energy calculations.

Results and Discussion

After defining the unit operations necessary to obtain the desired products, we
started an analysis to find the best operation points that optimize the entire process.
Such analysis focused the energy consumption minimization at a minimum products
purity for selling. The optimization ranges were narrowed by successive simulations
until the improvements on energy consumption become the lowest as possible.
We used as thermodynamic model UNIQUAC package because of its
robustness when treating with polar compounds. For the unit operations using high
pressures (>10bar) the SRK thermodynamic package was linked (UNIQUAC-SRK
package).

Unit Operations and Streams

Reactor. The reactors entrance was fixed in 100kmol/h, with a ratio CO : H2 of 1 : 2,

this value was obtained after performing a sensitivity analysis as shown in Figure 4.
Temperature and catalyst load were fixed, respectively 350 C and 2000 kg. As we
observed, in Figure 4, the selectivity of ethanol attain its maximum value, promoting a
selectivity of more than 70 % (Catom basis). Other factors that can influence the
reactors operation were also analyzed, as the catalyst load and temperature.
 FIGURE 4. Influence of CO:H2 ratio on Selectivity

In Figure 5 it is shown that in 300-350 C range, the conversion of synthesis gas

only increase with temperature, from 20 to 80%. However, analyzing selectivity
regarding temperature, what is shown on Figure 6, there is a small decrease of 6 % in
ethanol selectivity, from 78 to 72 %.

FIGURE 5. Conversion (%) vs. Temperature (C)

FIGURE 6. Selectivity vs. Temperature (C)

 The catalyst load analysis is shown on Figures 7 and 8. From them we see that
increasing the catalyst load (0-3500 kg) increases conversion but has a negative
impact on selectivity, from 80 % to 65 %.

FIGURE 7. Conversion (%) vs. Catalyst load (kg)

FIGURE 8. Selectivity vs. Catalyst load (kg)

Based on this analysis, the reactor operates as Table 1 shows:

TABLE 1. Reactor Results

Temperature 350 C
Pressure 68.95 bar
Catalyst load 2000 kg
Bed Voidage 0.40
Conversion 78.47 % CObasis
Ethanol Selectivity 72.28 % w/w
Residence time 44.65 sec
Duty (-) 1008.8 kW

Flash Drum. The flash drum is the first step on purification; here we tried to attain the
best operation condition to recover most of the light components as CO, CO2 and H2.
The optimization problem was set in a way to achieve 99 % of CO recovery in the top
and 99 % of ethanol in the bottom stream using less energy as possible. The best
results reached are presented in Table 2.
 TABLE 2. Flash Drum Results
Temperature 40 C
Pressure 35 bar
Duty (-) 500 kW
w% (top) 26.19 %
Recovery (top)
CO 99.78 %
H2 99.87 %
CO2 86.06 %
w% (bottom) 73.81 %
Recovery (bottom)
Methane 1.06 %
Ethane 5.71 %
Propane 10.14 %
Butane 16.60 %
Pentane 21.18 %
Methanol 98.88 %
Ethanol 99.11 %
Propanol 99.38 %
Butanol 99.50 %
Pentanol 99.58 %

Distillation Column. The bottom stream of the flash drum (S-1008) contains small
fractions of hydrocarbons CO, H2 and CO2. These light components need to be
withdrawn and recycled and the stream with alcohols and water directed to the
dehydration step. The optimization problem fixed 99.9% of ethanol recovery in the
columns bottom and 99.9% purity of alcohols-water mixture (S-1011) in the top. The
variables were: NSTAGE (number of stages, 10-25), FSTAGE (feed stage, 2-10) and MRR
(mass reflux ratio, 0.1-1.0).
The optimized results for the distillation column are in Table 3.

TABLE 3. Distillation Column (C-1001) Results

Temperature (top) 32.15 C
Temperature (bottom) 80.75 C
Pressure 1 bar
Duty (reboiler) 38.40 kW
Duty (condenser)(-) -0.30 kW
NSTAGE 25
FSTAGE 2
MASSRR 0.1
Mass Flow (top) 7.97 kg
w% (top) 1%
Recovery (top)
Methane 100 %
Ethane 100 %
Propane 79.75 %
Butane 2.97 %
Pentane 100 %
Mass Flow (bottom) 781.60 kg
w% (bottom) 98.99 %
Recovery (bottom)
Methanol 99.82 %
Ethanol 99.88 %
H2O 99.96 %
Pentanol 99.99 %

Dehydration (SEP-1). The dehydration step, as can be seen in Figure 3 is composed

by two distillation columns. The first column has two feed streams; one is the stream
containing alcohols-water mixture (S-103) and the other containing the solvent
monoethylene glycol (S-104).
The column was optimized regarding the recovery of both alcohols, ethanol and
propanol. Setting the recovery of these two compounds as 99% w/w and minimizing
the energy consumption in the reboiler, the variables for the optimization problem
were: NSTAGE (number of stages. 50-55), F1STAGE (alcohols-water feed stage, 35-45).
F2STAGE (solvent feed stage, 5-15), MRR (mass reflux ratio, 0.1-1-0) and MS (solvent
mass flow, 1400-1800). Table 4 shows the results for the first distillation column (C-
101) of SEP-1.

TABLE 4. C-101 (SEP-1) Results

Temperature (top) 25.00 C
Temperature (bottom) 130.23 C
Pressure 1 bar
w% (top) 2.05
Duty (reboiler) 273.76 kW
Duty (condenser)(-) 142.57 kW
NSTAGE 55
F1STAGE 41
F2STAGE 6
MRR 0.2
MS 1600 kg
Mass Flow(top) 527.50
w% (top) 22.15%
Recovery (top)
Alcohols 99.73%
Mass Flow(bottom) 1854.10
w% (bottom) 77.85%
Recovery (bottom)
H2O 99.93%

Different from dehydration of a first generation ethanol plant, wich receives a

stream with concentration around 8% w/w of ethanol (Dias, 2008), this plant generates
a stream with 68% of ethanol and propanol mixed with water. For this reason, we
eliminate the column that increases concentration ethanol from 8% to 93% (hydrated
ethanol). Such decision affected mostly the solvent stream once in a typical process,
the relation between mass inlet of hydrated ethanol and solvent (MEG) is 2:1, here the
ratio obtained through optimization is higher (1:2).
Other impacts are related with the column sizing. The number of stages that, in
the normal process commonly reaches 35-40 stages and here attained 55 stages
(Junqueira 2011). However, this layout reduced dramatically the reflux ratio, from 1
(conventional) for 0.2.
The second column (regeneration columns) is responsible for the solvent
recovery. It receives a stream composed by MEG (~86.3 % w/w) and water (~13.7%
w/w) (S-108) and then splits this mixture it in two other streams, with purified
components. We set that the solvent stream (S-110) concentration, which returns back
to C-101 column, must have 99.9 % w/w of MEG and the rest of columns entrance
water and the other products. The top stream leaving regeneration the column has
99.3 % w/w of water and is contaminated by pentanol (0.55 %), propanol (0.1 %) and
butanol (0.05 %).
We optimize the column concerning the energy consumption, varying NSTAGE (10-20).
FSTAGE (2-10) and MRR (0.1-1). Table 5 shows the optimized results for C-102 of SEP-
1.

Alcohols Purification (SEP-2). The unit for alcohols purification (SEP-2) receives a
feed stream composed by the alcohols ethanol and propanol, with small amounts of
methanol, water, butane and traces of MEG. In this block occurs a simple distillation,
where, in the top stage is produced ethanol (99.3 %) and in the bottom stage propanol
(99.9 %).
This column was optimized trying to achieve the minimum concentration of ethanol
and propanol for selling, recovering 99.9% of ethanol in the top stream We searched
for the lowest energy duty as well, varying NSTAGE (number of stages, 55-60), FSTAGE
(feed stage, 40-50) and MRR (mass reflux ratio, 1-2).
Table 6 shows the results for SEP-2.

TABLE 5. C-102 (SEP-1) Results

Temperature (top) 98.69 C
Temperature (bottom) 196.64 C
Pressure 1 bar
Duty (reboiler) 303.59 kW
Duty (condenser) (-) 223.44 kW
NSTAGE 11
FSTAGE 5
MRR 0.4
Mass Flow (top) 254.20
w% (top) 13.71 %
Recovery (top)
H2O 100.00 %
Mass Flow (bottom)
w% (bottom) 86.29 %
Recovery (bottom)
MEG 99.99 %

TABLE 6. Results Alcohol Separation (SEP-2)

Temperature (top) 77.5 C
Temperature (bottom) 96.8 C
Pressure 1 bar
Duty (Condenser) (-) 297.12 kW
Duty (Reboiler) 295.74 kW
Recovery (top)
NSTAGE 60
FSTAGE 47
MRR 1.9
Mass Flow (top) 435.00 kg
w% (top) 82.46 %
Recovery (top)
Ethanol 99.99 %
Ethanol (conc.) 99.30 %
Methanol 100.00 %
Methanol (conc.) 0.49 %
Mass Flow (bottom) 92.50 kg
w% (bottom) 17.54 %
Recovery (bottom)
Propanol 99.99 %
Propanol (conc.) 99.90 %

RWGS and Gasification. In order to measure how much of syngas can be

reprocessed and reintroduced to the process we assumed two units where RGWS and
Gasification take place, the first is a stoichiometric reactor set with 100 % of conversion
of CO2, according to Eq. 5. The second one is a Gibbs reactor, which assumes that
only syngas leaves the reactor. This recycle can be turned on and off not affecting the
overall process and serving just as a matter of calculation. To make possible this
operation, the stream S-1025 introduced 23.54 kg/h of oxygen in the system.
With the recirculation of syngas produced by these units to the process entrance.
a lower amount of syngas is required on the feedstream. The results showed that if
the wastes of the process are reconditioned the amount of syngas can be reduced
approximately 31 % (mass), reintroducing 311.74 kg of syngas into the system. This
enhances the importance of optimization on separation steps, reducing the need of
reprocessing syngas.
Energy and Production

After the sensitivity analysis and optimization of the process, we analyzed the
energy spent by the unit operations in order to observe the most consuming units as
well as how the process can be better integrated.
Table 7 shows the utilities results for the process units.

TABLE 7. Energy requirements

Cold Utilities Hot Utilities
Equipment Energy (kW) Equipment Energy (kW)
Reactor (R-100) -1008.85 Reboiler (C-1001) 38.40
Flash (F-1001) -500.40 SEP-1 (Reboiler. C-101) 273.76
Condenser (C-1001) -0.30 SEP-1 (Reboiler. C-102) 303.59
SEP-1 (Condenser. C-101) -142.57 SEP-2 (Reboiler. C-201) 295.74
SEP-1 (Condenser. C-102) -223.44 Compressor (CO-1001) 785.43
SEP-2 (Condenser. C-201) -297.12
Heat Exchanger (K-1001) -520.40
Heat Exchanger (K-1002) -50.88
Total -2743.96 Total 1696.92
Total Net Energy Consumption -1047.04

The process is energetically feasible and can help to diminish the carbon footprint
of ethanol production, mostly because of the exothermic reactions. We observed a
consumption of cold utilities in overall process. Therefore, if energy integration is
correctly carried out, it can generate usable energy for other units or as the example
of first generation process produce energy.
Besides energy issues, we obtained two products with adequate purity for selling
as well a water stream that requires treatment. Considering the reprocessing of wastes
and syngas cleaning 311.74 kg/h (1 : 1.83) of syngas can be spared. Correcting the
process entrance, we have for 758.06 kg/h (1 : 2.06) of syngas the products shown in
Table 8. If we did not consider the gas and wastes recovering and cleaning besides
the products considered in Table 8, we have a stream S-1012:

TABLE 8. Products Flows and Purity

Product Stream Mass Flow (kg/h) % mass
Ethanol S-1017 435.00 99.30
Propanol S-1016 92.50 99.90
Water S-1014 254.21 99.40

Waste Stream
CO S-1012 201.40 69.88%
H2 S-1012 30.34 10.53%
CO2 S-1012 21.74 7.54%
Water S-1012 1.43 0.49%
Methane S-1012 1.50 0.52%
Ethane S-1012 4.75 1.65%
Propane S-1012 3.86 1.34%
Butane S-1012 3.21 1.11%
Pentane S-1012 14.94 5.18%
Methanol S-1012 0.03 0.01%
Ethanol S-1012 4.39 1.52%
Propanol S-1012 0.61 0.21%

Converted Syngas S-1023 311.74 100%

Conclusion

Third generation ethanol through chemical route using the catalyst K-Co-MoS2/C
showed itself a favorable process regarding energy and effective use of syngas as
feedstock. However, it generates products as hydrocarbons and CO2 that must be in
some way used or recovered. The exothermic reaction is one of the key factors of the
process, making the energy balance favorable, what through proper energy integration
can make the process more sustainable and attractive.
Generation of water is problematic to the system as well, a stream containing
water and pentane is withdrawn in dehydration, requiring probably an unit of water
treatment or the use of a pre-existing unit. Was proposed that in the dehydration unit
the stream containing alcohols went directly to the extractive column, without a
previous concentration, this can be reconsidered, since the solvent usage increased
approximately 4 times.
Considering the factors above, one interesting step would be the integration of
this kind of process with a first generation ethanol plant, sharing its utilities, products
and energy through bagasse burning. Economic factors should also be taken into
account as catalyst price and its deactivation as the costs and types of energy used.

References

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7963.
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 Appendix Stream Sumary

S-1001 S-1002 S-1003 S-1004 S-1005 S-1006 S-1007 S-1008 S-1009 S-1010 S-1011 S-1012 S-1013

Temperature (C) 25.00 25.00 25.00 956.00 349.90 349.90 349.90 40.00 42.50 42.50 80.70 80.70 25.00
Pressure (bar) 1.01 1.00 1.00 69.96 68.95 68.95 65.45 35.00 1.50 1.50 1.00 1.00 1.01
Vapor Fraction 1.00 1.00 1.00 1.00 1.00 1.00 1.00 0.00 0.00 0.00 0.00 0.00 1.00
Mole Flow (kmol/h) 72.18 100.00 100.00 100.00 100.00 48.57 48.57 25.23 25.23 25.23 25.05 25.05 72.18
Mass Flow (kg/h) 758.06 1069.81 1069.81 1069.81 1069.81 1069.81 1069.81 789.58 789.58 789.58 781.60 781.60 758.06
Volume Flow (m3/h) 1765.85 2478.92 2478.92 146.07 75.12 36.49 38.44 0.93 0.94 0.94 0.99 0.99 1765.85
Enthalpy (Gcal/h) -0.62 -0.88 -0.88 -0.21 -0.65 -1.52 -1.52 -1.70 -1.70 -1.70 -1.66 -1.66 -0.62
Mass Flow (kg/h)

CO 660.06 935.55 935.55 935.55 935.55 201.40 201.40 0.45 0.45 0.45 0.00 0.00 660.06
H2 98.00 134.26 134.26 134.26 134.26 30.34 30.34 0.04 0.04 0.04 0.00 0.00 98.00
CO2 0.00 0.00 0.00 0.00 0.00 21.74 21.74 3.03 3.03 3.03 0.00 0.00 0.00
WATER 0.00 0.00 0.00 0.00 0.00 254.31 254.31 253.01 253.01 253.01 252.89 252.89 0.00
METHANE 0.00 0.00 0.00 0.00 0.00 1.50 1.50 0.02 0.02 0.02 0.00 0.00 0.00
ETHANE 0.00 0.00 0.00 0.00 0.00 4.75 4.75 0.27 0.27 0.27 0.00 0.00 0.00
PROPANE 0.00 0.00 0.00 0.00 0.00 3.94 3.94 0.40 0.40 0.40 0.08 0.08 0.00
BUTANE 0.00 0.00 0.00 0.00 0.00 3.83 3.83 0.64 0.64 0.64 0.62 0.62 0.00
PENTANE 0.00 0.00 0.00 0.00 0.00 14.94 14.94 3.17 3.17 3.17 0.00 0.00 0.00
METHANOL 0.00 0.00 0.00 0.00 0.00 2.16 2.16 2.14 2.14 2.14 2.13 2.13 0.00
ETHANOL 0.00 0.00 0.00 0.00 0.00 436.41 436.41 432.52 432.52 432.52 432.01 432.01 0.00
PROPANOL 0.00 0.00 0.00 0.00 0.00 93.11 93.11 92.53 92.53 92.53 92.50 92.50 0.00
BUTANOL 0.00 0.00 0.00 0.00 0.00 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.00
PENTANOL 0.00 0.00 0.00 0.00 0.00 1.33 1.33 1.32 1.32 1.32 1.32 1.32 0.00
EG 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
O2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
 S-1014 S-1016 S-1017 S-1018 S-1019 S-1020 S-1021 S-1022 S-1023 S-1025 S-1026 S-1027 S-1028

Temperature (C) 98.70 96.80 77.50 32.20 32.20 38.60 38.60 250.00 250.00 25.00 25.00 40.00 38.70
Pressure (bar) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 35.00 1.50
Vapor Fraction 0.00 0.00 0.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Mole Flow (kmol/h) 14.05 1.54 9.47 0.19 0.19 23.52 23.52 23.52 27.82 0.74 27.82 23.34 23.34
Mass Flow (kg/h) 254.21 92.50 435.00 7.98 7.98 288.21 288.21 288.21 311.74 23.54 311.74 280.23 280.23
Volume Flow (m3/h) 0.28 0.13 0.59 4.70 4.70 609.55 609.55 1023.02 1210.14 18.24 689.68 43.07 403.30
Enthalpy (Gcal/h) -0.94 -0.11 -0.61 -0.01 -0.01 -0.26 -0.26 -0.22 -0.22 0.00 -0.26 -0.25 -0.25
Mass Flow (kg/h)

CO 0.00 0.00 0.00 0.45 0.45 201.40 201.40 215.24 275.49 0.00 275.49 200.95 200.95
H2 0.00 0.00 0.00 0.04 0.04 30.34 30.34 29.34 36.26 0.00 36.26 30.30 30.30
CO2 0.00 0.00 0.00 3.03 3.03 21.74 21.74 0.00 0.00 0.00 0.00 18.71 18.71
WATER 252.69 0.00 0.19 0.12 0.12 1.43 1.43 10.33 0.00 0.00 0.00 1.31 1.31
METHANE 0.00 0.00 0.00 0.02 0.02 1.50 1.50 1.50 0.00 0.00 0.00 1.48 1.48
ETHANE 0.00 0.00 0.00 0.27 0.27 4.75 4.75 4.75 0.00 0.00 0.00 4.48 4.48
PROPANE 0.00 0.00 0.08 0.32 0.32 3.86 3.86 3.86 0.00 0.00 0.00 3.54 3.54
BUTANE 0.00 0.00 0.62 0.02 0.02 3.21 3.21 3.21 0.00 0.00 0.00 3.20 3.20
PENTANE 0.00 0.00 0.00 3.17 3.17 14.94 14.94 14.94 0.00 0.00 0.00 11.78 11.78
METHANOL 0.00 0.00 2.13 0.00 0.00 0.03 0.03 0.03 0.00 0.00 0.00 0.02 0.02
ETHANOL 0.00 0.04 431.97 0.51 0.51 4.39 4.39 4.39 0.00 0.00 0.00 3.89 3.89
PROPANOL 0.08 92.41 0.01 0.03 0.03 0.61 0.61 0.61 0.00 0.00 0.00 0.58 0.58
BUTANOL 0.02 0.04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
PENTANOL 1.32 0.00 0.00 0.00 0.00 0.01 0.01 0.01 0.00 0.00 0.00 0.01 0.01
EG 0.10 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
O2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 23.54 0.00 0.00 0.00
 S-101 S-102 S-103 S-104 S-105 S-106 S-107 S-108 S-109 S-110 S-111 S-112

Temperature (C) 80.70 25.00 80.70 25.00 79.20 130.20 130.20 130.20 98.70 196.60 25.00 25.00
Pressure (bar) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00
Vapor Fraction 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Mole Flow (kmol/h) 25.05 0.00 25.05 25.78 11.01 39.82 39.82 39.82 14.05 25.78 25.78 25.78
Mass Flow (kg/h) 781.60 0.11 781.60 1600.01 527.50 1854.11 1854.11 1854.11 254.21 1599.90 1599.90 1600.01
Volume Flow (m3/h) 0.99 0.00 0.99 1.43 0.72 1.85 1.87 1.85 0.28 1.69 1.43 1.43
Enthalpy (Gcal/h) -1.66 0.00 -1.66 -2.82 -0.72 -3.65 -3.65 -3.65 -0.94 -2.65 -2.82 -2.82
Mass Flow (kg/h)

CO 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
H2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
CO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
WATER 252.89 0.00 252.89 0.01 0.19 252.70 252.70 252.70 252.69 0.01 0.01 0.01
METHANE 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
ETHANE 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
PROPANE 0.08 0.00 0.08 0.00 0.08 0.00 0.00 0.00 0.00 0.00 0.00 0.00
BUTANE 0.62 0.00 0.62 0.00 0.62 0.00 0.00 0.00 0.00 0.00 0.00 0.00
PENTANE 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
METHANOL 2.13 0.00 2.13 0.00 2.13 0.00 0.00 0.00 0.00 0.00 0.00 0.00
ETHANOL 432.01 0.00 432.01 0.00 432.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00
PROPANOL 92.50 0.00 92.50 0.00 92.42 0.08 0.08 0.08 0.08 0.00 0.00 0.00
BUTANOL 0.05 0.00 0.05 0.00 0.04 0.02 0.02 0.02 0.02 0.00 0.00 0.00
PENTANOL 1.32 0.00 1.32 0.00 0.00 1.32 1.32 1.32 1.32 0.00 0.00 0.00
EG 0.00 0.11 0.00 1600.00 0.01 1599.99 1599.99 1599.99 0.10 1599.90 1599.90 1600.00
O2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
 S-201 S-202 S-203 S-204 S-206

Temperature (C) 79.19 79.19 79.19 77.48 96.84

Pressure (bar) 1.00 1.00 1.00 1.00 1.00
Vapor Fraction 0.00 0.00 0.00 0.00 0.00
Mole Flow (kmol/h) 11.01 11.01 11.01 9.47 1.54
Mass Flow (kg/h) 527.50 527.50 527.50 435.00 92.50
Volume Flow (m3/h) 0.72 0.72 0.72 0.59 0.13
Enthalpy (Gcal/h) -0.72 -0.72 -0.72 -0.61 -0.11
Mass Flow (kg/h)

CO 0.00 0.00 0.00 0.00 0.00

H2 0.00 0.00 0.00 0.00 0.00
CO2 0.00 0.00 0.00 0.00 0.00
WATER 0.19 0.19 0.19 0.19 0.00
METHANE 0.00 0.00 0.00 0.00 0.00
ETHANE 0.00 0.00 0.00 0.00 0.00
PROPANE 0.08 0.08 0.08 0.08 0.00
BUTANE 0.62 0.62 0.62 0.62 0.00
PENTANE 0.00 0.00 0.00 0.00 0.00
METHANOL 2.13 2.13 2.13 2.13 0.00
ETHANOL 432.01 432.01 432.01 431.97 0.04
PROPANOL 92.42 92.42 92.42 0.01 92.41
BUTANOL 0.04 0.04 0.04 0.00 0.04
PENTANOL 0.00 0.00 0.00 0.00 0.00
EG 0.01 0.01 0.01 0.00 0.01
O2 0.00 0.00 0.00 0.00 0.00
TYPE OF PRESENTATION RECOMMENDED BY THE SYMPOSIUM: Oral

LIST OF COAUTHORS:

M.Sc. Jlio Csar de Carvalho Miranda,Ph.D. Candidate, presenting author.

e-mail: julioccmiranda@gmail.com
State University of Campinas Unicamp
LOPCA Laboratory of Optimization, Project and Process Control
Av. Albert Einstein, 500 CEP 13083-852 Campinas SP Brasil

M. Sc. Gustavo Henrique Santos Flores Ponce, Ph.D. Candidate

e-mail: gustavo_ponce_182@hotmail.com
State University of Campinas Unicamp
LOPCA Laboratory of Optimization, Project and Process Control
Av. Albert Einstein, 500 CEP 13083-852 Campinas SP Brasil

Ph. D. Moiss Alves,

e-mail:moavesp@gmail.com
State University of Campinas Unicamp
LOPCA Laboratory of Optimization, Project and Process Control
Av. Albert Einstein, 500 CEP 13083-852 Campinas SP Brasil

Prof. Dr. Rubens Maciel Filho, Full Professor

e-mail:maciel@feq.unicamp.br
State University of Campinas Unicamp
LOPCA Laboratory of Optimization, Project and Process Control
Av. Albert Einstein, 500 CEP 13083-852 Campinas SP Brasil

Prof. Dra. Maria Regina Wolf Maciel, Full Professor

e-mail: wolf@feq.unicamp.br
State University of Campinas Unicamp
LOPCA Laboratory of Optimization, Project and Process Control
Av. Albert Einstein, 500 CEP 13083-852 Campinas SP Brasil

Author for all correspondence