21st European Symposium on Computer Aided Process Engineering – ESCAPE 21

E.N. Pistikopoulos, M.C. Georgiadis and A.C. Kokossis (Editors)

© 2011 Elsevier B.V. All rights reserved.


Optimization of lignocellulosic based diesel

Mariano Martín, Ignacio E. Grossmann*

Center for Advanced Process Decision-Making, Department of Chemical Engineering,
Carnegie Mellon University, Pittsburgh, PA, 15213, USA

Abstract

In this paper we present the superstructure optimization for the production of FT-diesel
via gasification of lignocellulosic material, switchgrass. We propose a superstructure of
alternatives including two types of gasification, two reforming technologies and
different gas clean-up processes. The reactors involved in the process, WGSR, FT-
reactor and hydrocracking are modelled using reduced order models. We optimize the
superstructure using a special decomposition technique. The results indicate that the
optimal process involves the use of indirect low pressure gasifier, followed by steam
reforming without need for further H2:CO composition adjustment. The process
produces diesel at $0.72/gal ($0.19/L).

Keywords: FT-diesel, switchgrass, mathematical optimization

1. Introduction.

The Fischer-Tropsch technology has been extensively developed and

commercialized during shortage of supply of crude-based liquid fuels. It typically uses
coal as raw material because the FT products can be refined to gasoline, diesel fuel, and
aviation fuel depending upon the process conditions (Brown and Wright 2009). Among
the renewable sources of energy, a promising option is to produce biofuels from
switchgrass in which the FT technology can be used for the sustainable production of
green gasoline and FT-diesel. However, a number of challenges still need to be
addressed since the FT-process design has only focused on the reactor analysis and
optimization in isolation from the rest of the process (Wang et al. 2008, Teles and
Fernandes 2008, Swanson et al 2010). In this paper mathematical programming
techniques are used to optimize the process flowsheet and its operating conditions for
the production of FT-diesel by optimizing a superstructure that has embedded a number
of alternative technologies. The objective function considered is the gross profit given
by sales of the FT-diesel minus the energy consumption, and the cost of hydrogen used
in hydrocracking. Reduced order models for the main reactors have been developed
based on experimental data from the literature to integrate reactor operating conditions
with raw material preparation and product purification.
Energy optimization of lignocellulosic based diesel 1699

2. Description of superstructure.

We consider a process superstructure that consists of four different parts. The

first one is the gasification of the raw material. Two different technologies have been
considered: (1) Indirect low pressure gasification where the combustion of char
provides the energy for the gasification of the biomass by heating sand, which is
transferred back to the gasifier, and (2) Direct high pressure gasification of the raw
material with steam and oxygen to avoid the dilution of the gas.
The gas generated must be cleaned from solids as well as other compounds like
hydrocarbons, NH3, CO2 or H2S that are generated in the gasification. The hydrocarbons
are partially removed in the tar where they are reformed with steam or are partially
oxidized. In the case of gasification at high pressure, solids are removed in a ceramic
filter, and next the gas is expanded generating energy. If the indirect lower pressure
method of gasification is used, the solids are removed together with NH3 in a wet
scrubber. In both cases, the last traces of hydrocarbons are removed in a PSA system
with a bed of silica gel.
At this point the ratio of H2:CO may have to be adjusted for the optimal
operation of the FT reactor (Wang et al., 2008). Three technologies are proposed to
either increase the H2:CO ratio, maintain the one obtained after the reforming stage, or
reduce the amount of H2 in the stream. A Water Gas Shift Reactor (WGSR) model
based on the results by Choi et al. (2003), a bypass, and a hybrid membrane-PSA
system for H2 removal are considered for each option. The split fraction among the
alternatives determines the ratio between H2 and CO that is fed to the reactor.
The second part corresponds to the removal of sour gases, CO2 and H2S.
According to the study by Martín and Grossmann (2011a), two technologies operating
in sequence are considered for this task: the absorption of the sour gases in monoethanol
amine (MEA), possibly followed by a PSA system with a bed of Zeolite 5A.
Once the gas is purified, the syngas consisting of H2 and CO is fed to the
Fischer-Tropsch reactor to produce liquid hydrocarbons using a catalyst of iron or
cobalt. The optimal conditions (ratio of H2 and CO and operating temperature at the
reactor) are to be optimized, while the optimal operating pressure is assumed to be 30
atm according to experimental results Wang et al. (2008). The synthetic biodiesel is
produced in addition to gasoline, gas products and heavy fuels, (Opdal and Skreiberg
2006).
Finally, the gas products are separated from the FT-liquids which are refined to
green gasoline and FT-diesel using atmospheric distillation. The heavy products can be
hydrotreated to increase the yield to diesel, (Dry, 2008). The results from Bezergianni et
al. (2009) are used to provide a model for the hydrocracking of the heavy oil. Figure 1
shows the superstructure embedding the different alternatives.
1700 Martín et al.

Figure 1.- Superstructure of alternatives

3. Solution procedure

A partial decomposition technique is used. The original MINLP problem is

decomposed into 4 NLP’s subproblems: whether the biomass gasification is direct or
indirect, and whether the reforming is partial oxidation or steam reforming. Each of the
resulting subproblems is solved as an NLP, which optimizes the operating conditions
based on the ratio H2:CO to be used at the reactor, the operating temperature at the
WGSR and the Fischer-Tropsch reactor, and the operating conditions at the
hydrocracking unit. The objective function to be maximized is given by the profit from
selling the FT-diesel minus the use of energy to prepare the feed for the FT-reactor, as
well as the cost of hydrogen used in hydrocracking Thus, the main decision variables
are the split fraction for the composition adjustment, the water gas shift operating
conditions (temperature and steam needed), the operating conditions at the Fischer-
Tropsch reactor (temperature and H2:CO ratio) and the hydrocracking reactor. Next,
heat integration within the process is performed by designing a heat exchanger network,
Yee and Grossmann (1990). Finally, a detailed economic evaluation accounting for
labour, maintenance, utilities, administration, raw material and annualized equipment
cost is carried out to select the best solution among the four subproblems.

4.- Results and discussion

For a production plant of 60 MGal/y (227ML/y) of biofuel (including green

gasoline and FT-diesel) from lignocellulosic switchgrass, we optimize the production of
FT-diesel. As seen in Table 1, between the two gasifier technologies, the direct
gasification shows lower yield towards biofuels and higher consumption of utilities
(pure oxygen and large amount of steam). On the other hand, for the processes that use
of indirect gasification, the steam reforming has higher yield towards biofuels and does
not require pure oxygen, resulting in a more profitable alternative in spite of the fact that
partial oxidation generates an excess of energy.
Energy optimization of lignocellulosic based diesel 1701

Table 1.-Summary of results

Indirect Gasification Direct Gasification
P.O. S. R. P.O. S. R.
Raw material contribution (%) 51.3 51.4 53.4 48.5
Annualized Equipment (%) 38.2 36.3 37.2 36.1
Utilities & Chemicals (%) 2.8 4.0 3.3 8.8
Labor (%) 4.1 4.4 3.2 3.5
Management (%) 3.7 3.9 2.8 3.1
Biofuel yield (kg/kgwet) 0.23 0.24 0.17 0.20
Selectivity to Diesel 0.83 0.79 0.65 0.88
Production cost ($/gal)/($/L) 0.77(0.20) 0.72(0.19) 0.98(0.26) 0.90(0.24)

P.O.: partial Oxidation; S.R.: Steam reforming

Figure 2 shows the optimal flowsheet and the main operating conditions. As a
result, the optimal process consists of the pretreatment of the switchgrass, followed by
indirect gasification and steam reforming so that the ratio H2:CO is 1.4, appropriate for
the FT-reactor avoiding further composition adjustment. Next, the syngas is fed to the
FT-reactor. The optimal operating conditions for the production of diesel are 30 bar,
212ºC. The optimal process has a yield from switchgrass to biofuels (green gasoline and
diesel) of 0.24 kg Biofuel/kg biomass and selectivity to diesel (fraction of diesel out of the
liquid fuels obtained, green gasoline and diesel) of 0.79. The manufacturing cost is
$0.72 /gallon ($0.19/L) of either FT-diesel or FT-gasoline where 50% corresponds to
raw material, making the price rather sensitive to the volatility of the price of raw
material as is the case in fuels absed on crude oil.

Figure 2.- Optimal flowsheet for the production of FT-diesel.

5. Conclusions.

The optimization of a superstructure for the production of FT-diesel from

switchgrass has been formulated as a MINLP model. The problem is solved by
decomposing the MINLP into four NLP’s, one for each gasifier and reforming
alternative. Each subproblem is optimized to determine the operating conditions. No
further adjustment of the H2:CO ratio in needed due to the fact that after the reforming
1702 Martín et al.

the ratio is already within the required operating conditions. However, the working
temperature of the FT reactor is adjusted to improve the yield towards diesel. Therefore,
it is shown that the operation conditions at the reactor should not be optimized
independently of the process (Wang et al., 2008, Swanson et al., 2010, Kim et al., 2009)
in order to obtain better results for the operation of the whole plant.
A very promising manufacturing cost of $0.72/galbiofuel ($0.19/L) is obtained,
making the production of green gasoline and FT diesel from switchgrass competitive vs.
ethanol via hydrolysis of switchgrass whose manufacturing price is $0.8/gal ($0.21/L)
(Martín and Grossmann, 2011b). Nevertheless, it is clear that the optimal conceptual
design has to be validated with pilot plant scale experiments and detailed simulations.

Acknowledgments

The authors gratefully acknowledge financial support from the NSF grant
CBET0966524, the Center for Advanced Process Decision-making at Carnegie Mellon
University, and from the Ministry of Education and Science of Spain and Fulbright commission
providing Dr. M. Martín a MICINN – Fulbright Postdoctoral fellowship.

References

S. Bezergianni, Kalogianni, A., Vasalos, I. A. (2009) Hydrocracking of vacuum gas oil-vegetable oil mixtures
for biofuels production Bioresource Technology 100 (2009) 3036–3042
R.C., Brown, Wright, M., (2009) Biomass conversion to fuels and electric power. Pages 53-64 Proceedings
(SCOPE) Cornell University, Ithaca NY, USA
Y., Choi, Stenger, H. G. (2003) Water gas shift reaction kinetics and reactor modeling for fuel cell grade
hydrogen J Power Sources 124, 432–439
M.E., Dry, (2002) The Fischer–Tropsch process : 1950–2000 Catalysis Today 71, 227–241
Y.H ., Kim, Jun, K.-W., Joo, H., Han, C., Song, I.K. (2009) A simulation study on gas-to-liquid (natural gas to
Fischer-Tropsch synthetic fuel) process optimization, Chemical Engineering Journal, 155, 1-2, 427-432
M., Martín, Grossmann, I.E. (2011a) Enegy optimization of bioethanol production from switchgrass via
Gasification. AIChE J. DOI: 10.1002/aic.12544
M., Martín,; Grossmann, I.E. (2011b) Energy optimization of bioethanol production from switchgrass via
Hydrolysis. To be submitted AIChE J.
O., Opdal, Skreiberg O. (2006) Production of synthetic biodiesel via Fischer-Tropsch synthesis Biomass-To-
Liquids in Namdalen, Norway Project report by Olav A. Opdal Department of Energy & Process engineering
Faculty of Engineering Science and Technology Norwegian University of Science and Technology
R.M., Swanson, Platon, A., Satrio, J.A:, Brown, R.C. (2010) Techno-economic analysis of biomass-to-liquids
production based on gasification. Fuel. doi:10.1016/j.fuel.2010.07.027
U.M., Teles, Fernandes, F.A.N. (2008) Hydrocracking of Fisher – Tropsh Products. Optimization of Diesel
and Nafta Cuts. Chem. Biochem Eng. Q. 22, 227-231
Y. Wang, Fan, W., Liu, Y., Zeng, Z., Hao, X., Chang, M., Zhang, C., Xu, Y., Xiang, H., Li, Y. (2008)
Modeling of the Fischer–Tropsch synthesis in slurry bubble column reactors Chemical Engineering and
Processing, 222–228
T.F. Yee, Grossmann, I.E. (1990) Simultaneous optimization models for heat integration – II. Heat exchanger
networks synthesis. Comput. Chem. Eng., 28, 1165-1184.