Centro Nacional de Pesquisa em Energia e Materiais

Laboratório Nacional de Ciência e Tecnologia do Bioetanol

MeT 01/2016

COMPONENTS DATABANK FOR

THE INDUSTRIAL SIMULATIONS IN THE
VIRTUAL SUGARCANE BIOREFINERY (VSB)

Isabelle Sampaio
Edvaldo Morais

Tassia Junqueira
Vera Gouveia

Antonio Bonomi
 ABSTRACT

The simulation of an industrial process, within the Virtual Sugarcane Biorefinery

platform, is based on mass and energy balances carried out through process
simulators, such as Aspen Plus, SuperPro and EMSO.
Considering the process simulation in Aspen Plus, the inclusion of components
present in a sugarcane biorefinery (e.g., first and second generation processes)
is detailed. Some components and additional data were introduced in the
simulator databank due to their absence or the need to complement the
physicochemical properties with information available in literature.

Guidelines for the definition of thermodynamic models in the unit operation

models is also included in this technical memorandum. The appropriate
selection is essential to improve process representativeness, since the
thermodynamic models are the basis for the calculation of phase equilibrium
computation and energy balance.

Keywords: biorefinery; process simulation; properties; thermodynamic models.

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 SUMMARY

1 INTRODUCTION ............................................................................... 4

2 COMPONENT DATABANK .............................................................. 4

3 ASPEN PLUS PROPERTY METHODS .......................................... 10

4 FINAL REMARKS ............................................................................ 12

REFERENCES ....................................................................................... 12

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1 Introduction
The Virtual Sugarcane Biorefinery (VSB) is an innovative framework that
integrates computer simulation platforms with economic, social and
environmental evaluation tools to assess technical and sustainability impacts
of different sugarcane biorefinery alternatives/routes integrating all the stages
of the biomass chain: agricultural production, transport, industrial conversion,
use and final disposal of the products.

The first steps in the process simulation include definition of feedstock

composition components (feedstock, inputs, products, etc.), physicochemical
properties and thermodynamic models. Feedstock composition was previously
described in MeT 22/2015, the other steps are covered in this technical
memorandum.
This technical memorandum presents the current component databank
constructed for the VSB simulations, the properties that were modified or
inserted when necessary, their respective sources and the thermodynamic
property methods selected for the different unit operations of the process.

2 Component databank
Sugarcane composition is comprised of water, fibers, extractives and ashes
(see MeT 22/2015). Different chemical compounds were chosen to represent
these categories of components on the databank as described in Morais et al.
(2016):

 Ashes are assumed to be comprised by:

– Minerals: represented by K2O;

– Salts: represented by KCl, since potassium salts are those present in

greater proportion (approximately 60% of the total salts in the ash);

– Soil: represented by SiO2;

 Extractives are assumed to be comprised by:

– Organic acids: represented by aconitic acid. The concentration of this acid
on sugarcane is around 3 times higher than that of all the other organic acids;
– Sucrose;

– Glucose;

 Phosphoric acid: represents the phosphates present in the sugarcane plant.

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It is important to keep in mind that not only the components present on the
inputs of the process should be inserted (such as sugars from sugarcane), but
all chemical compounds should be considered, whether they are final products
(ethanol), undesired fermentation products (e.g. acetic acid, glycerol) or
reactants (such as lime for juice treatment). Table 1 presents all the
components inserted into the simulations’ databank.

As a general rule, the same databank is used in all simulations constructed

within the VSB, with occasional modifications depending on specific demands
of the simulated process (e. g.: insertion of new chemical compounds,
modification of specific properties of the compounds).

Some components were already available at the Aspen Plus databank and did
not have their properties altered; other compounds were not present at the
databank (identified as “user defined” in Table 1) or needed additional
properties.

Table 1: Current chemical compounds databank of the simulations.

Aspen Plus Complete name Type Alias on Aspen Plus databank

ID
ACET-AC Acetic Acid Conventional ACETIC-ACID
ACETATE Cellulose Acetate Solida ACETIC-ACID
CAL-ACON Calcium Aconitate Solida USER DEFINED
CAL-PHOS Calcium Phosphate Solida CALCIUM-PHOSPHATE
CAO Calcium Oxide Conventional CALCIUM-OXIDE
CAOH2 Lime Conventional CALCIUM-HYDROXIDE
CELLULOS Cellulose Solida USER DEFINED
CO2 Carbon Dioxide Conventional CARBON-DIOXIDE
ENZYME Enzymes Solida USER DEFINED
ETHANOL Ethanol Conventional ETHANOL
FLOCCUL Flocculant Solida POLY(ACRYLAMIDE-STYRENE)
FURFURAL Furfural Conventional FURFURAL
GLUCOLIG Glucose Oligomers Conventional DEXTROSE
GLUCOSE Glucose Conventional DEXTROSE
GLYCEROL Glycerol Conventional GLYCEROL
H2O Water Conventional WATER
H2SO4 Sulfuric Acid Conventional SULFURIC-ACID
H3PO4 Phosphoric Acid Conventional ORTHOPHOSPHORIC-ACID

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 HMF Hydroxymethylfurfural Conventional USER DEFINED
ISOAMIL Isoamyl alcohol Conventional 3-METHYL-1-BUTANOL
ISOBUTOH Isobutanol Conventional ISOBUTANOL
LGNSOLb Soluble lignin Solida USER DEFINED
LIGNIN Lignin Solida USER DEFINED
MINERALS Minerals Conventional POTASSIUM-OXIDE
N2 Nitrogen Conventional NITROGEN
NAOH Caustic Soda Conventional SODIUM-HYDROXIDE
NH4OH Ammonium Hydroxide Conventional AMMONIUM-HYDROXIDE
O2 Oxygen Conventional OXYGEN
ORG-AC Organic Acids Conventional TRANS-ACONITIC-ACID
SALTS Salts Conventional POTASSIUM-CHLORIDE
SOIL Soil Conventional SILICON-DIOXIDE
SUCROSE Sucrose Conventional SUCROSE
XYLAN Xylan Solida USER DEFINED
XYLOLIG Xylose Oligomers Conventional D-XYLOSE
XYLOSE Xylose /Arabinose Conventional D-XYLOSE
YEAST Yeast Solida USER DEFINED
a
Solid components do not take part in phase equilibrium.
b
Solubilization represented by a phase change (solid to mixed).

For most chemical compounds presented on Table 1, Aspen Plus default

physicochemical properties were used. For other components, respective
properties used on the simulations’ databank (Aspen Plus v. 7.3.2) were
defined as explained below:

 ACETATE (acetyl group): represented by acetic acid, having its standard

enthalpy of combustion changed to match the one calculated for the reaction
equation: Acetate(s) + 2O2 → 2H2O + 2 CO2;

 CAL-ACON (calcium aconitate): properties collected from gypsum (CaSO4-

2H2O) available at NREL databank (WOOLEY AND PUTSCHE, 1996),
except by its molecular weight (MW), which was calculated based on the
molecular formula of calcium aconitate;

 CELLULOSE: Cellulose was inserted as a user defined component. The

values for molecular weight, enthalpy of formation of the solid (DHSFRM),
solid heat capacity (CPSPO1) and molar volume of the solid (VSPOLY) were
found on Wooley and Putsche (1996);

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 ENZYME: the enzyme component was inserted as a solid component with
user defined properties. The values for molecular weight (molecular formula:
CH1.59O0.42N0.24S0.01), enthalpy of formation, solid heat capacity and volume
of the solid were retrieved from NREL (2011);

 FLOCCUL (Flocculant polymer): represented on the simulation databank by

polyacrylamide;

 GLUCOLIG (glucose oligomers): inserted as glucose (dextrose), with

recalculated values for molecular weight and standard enthalpy of formation,
using data from cellulose (WOOLEY AND PUTSCHE, 1996);

 H3PO4 (phosphoric acid): the value for the dipole moment (MUP) of the
compound was retrieved from Colby College (2012);

 HMF (hydroxymethylfurfural): this component was not present at the Aspen

Plus databank (version 7.3.2). The molecular structure of HMF was imported
from CHEMSPIDER (2012). Since version 8.6, this component is available in
the Aspen Plus databank (2015);

 LGNSOL (soluble lignin): similar to LIGNIN with same physicochemical

properties. The solubilization of lignin is represented by a phase change
(solid to mixed).

 LIGNIN: some data for lignin were retrieved from Wooley and Putsche (1996)
(solid heat capacity, molar volume of the solid). Other values were modified
to better represent the sugarcane lignin, as the values found on Wooley and
Putsche (1996) represent wood lignin. The lignin structure was also modified
to correctly represent sugarcane lignin (molecular formula:
C9O2.9H8.6(OCH3)). The correct value for the enthalpy of formation of this
compound was estimated using the enthalpy of combustion (27000 kJ/kg)
given by Stanmore (2010);

 NAOH: the dipole moment for the compound was retrieved from Colby
College (2012);

 NH4OH: Molecular weight, critical pressure (Pc), critical temperature (Tc)

and normal boiling point (Tb) were retrieved from SuperPro Designer®
databank. Dipole moment was assumed equal to the dipole moment of
NaOH, found on Colby College (2012). The enthalpy of formation was
retrieved from an older version of the Aspen Plus databank (v. 7.1), since this
property was missing in v. 7.3.2;

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 ORG-AC (organic acids): This compound represents the organic acids
present on the sugarcane and was inserted as trans-aconitic-acid on the
databank. The parameters from the Aspen Databank for acetic acid were
used for the radius of gyration (RGYR), dipole moment and enthalpy of
formation.

 XYLAN: Xylan was inserted as a user defined component. Values for solid
heat capacity were obtained in NREL (2011); values for molar volume of the
solid and enthalpy of formation of the solid were found on Wooley and
Putsche (1996);

 XYLOLIG (xylose olygomers): inserted as xylose (d-xylose), with

recalculated values for molecular weight and standard enthalpy of formation,
using data from xylan (WOOLEY AND PUTSCHE, 1996). The parameters
from the Aspen Plus databank for glucose were used for the radius of
gyration and dipole moment;

 XYLOSE: inserted as xylose (d-xylose). The values for dipole moment and
radius of gyration of glucose were used for xylose;

 YEAST: molecular weight and solid standard enthalpy of formation were

retrieved from SuperPro Designer® databank. Solid molar volume was
calculated based on its density (1180 kg/ m3) from Scherrer et al. (1977) and
molecular weight. The solid heat capacity polynomial function coefficients
were obtained from NREL (2011).

Some components, even those retrieved from one of the Aspen Plus
databases, had a few properties modified or inserted when necessary. The
modifications provided by the users are stored in USERDEF Table (a specific
table for the main properties of user defined compounds); CPSPO1 (Solid heat
capacity) and VSPOLY (Solid molar volume). The inserted values are shown in
Table 2, Table 3 and Table 4, respectively.

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 Table 2: User defined properties.

Component Molecular Solid Standard Pc Dipole Tb Tc Radius of

weight standard enthalpy of moment gyration
enthalpy of formation
formation
Aspen code MW DHSFRM DHFORM PC MUP TB TC RGYR
Unity g/mol J/kmol kcal/mol bar debye °C °C meter
ACETATE -4.56E+08
CAL-ACON 462 -2E+09
CELLULOS 162.1436 -9.8E+08
ENZYME a 24.0156 -7.494E+07
GLUCOLIG 162.1424 -192.87534
H3PO4 3.46106
HMF 4.73674
LGNSOL 194.1968 -3.5E+08
LIGNIN 194.1968 -3.5E+08
NAOH 6.86371
NH4OH 35.046 -86.27114 117.06 6.86371 -2.15 132.39
ORG-AC 1.74 2.61E-10
XYLAN 132.117 -7.6E+08
XYLOLIG 132.11612 -149.41258 2.749101 4.75E-10
XYLOSE 2.749101 4.75E-10
YEAST 30.25542 -9.7E+07
a
Enzyme properties may change according to the cocktail used.

Table 3: Solid molar volume*

VSPOLY CAL-ACON CELLULOS ENZYME LGNSOL LIGNIN XYLAN YEAST

C1 0.0747 0.106 0.0152 0.0817 0.0817 0.0864 0.0256402
C2 0 0 0 0 0 0 0
C3 0 0 0 0 0 0 0
C4 0 0 0 0 0 0 0
C5 0 0 0 0 0 0 0
C6 298.15 298.15 298.15 298.15 298.15 298.15 298.15
C7 - - - - - - -
* Solid Volume Polynomial (VSPOLY/1…) in m3/kmol

V*(T) = C1 + C2T + C3T2 + C4T3 + C5T4 for C6 ≤ T ≤ C7

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Table 4: Solid heat capacity*
CPSPO1 CAL- CELLULOS ENZYME LGNSOL LIGNIN XYLAN YEAST
ACON
C1 72182 -11704 35533 31431.7 31431.7 -9529.9 35910
C2 97.343 672.07 0 394.427 394.427 547.25 0
C3 0 0 0 0 0 0 0
C4 0 0 0 0 0 0 0
C5 0 0 0 0 0 0 0
C6 0 0 0 0 0 0 0
C7 298.15 298.15 298.15 298.15 298.15 298.15 298.15
C8 1000 1000 1000 1000 1000 1000 1000
* Solid Heat Capacity (CPSPO1/1…8) in J/kmol.K

Cp*(T) = C1 + C2T + C3T2 + C4/T+ C5/T2 + C6/√T for C7 ≤ T ≤ C8

It is important to mention that when opening a simulation in a different version

from that in which it was originally built, sometimes loss of properties may occur.
In these cases, it is recommended to open the simulation on the version of the
simulator in which it was constructed and check the “Review” table of properties
to copy and insert the missing data to the new version of the simulation.

3 Aspen Plus Property methods

Alongside with the definition of the chemical compounds, defining the property
methods that will be used is an important step when beginning a new
simulation. Property methods are a collection of methods and models that are
used on Aspen Plus to estimate thermodynamic and transport properties.
(ASPENTECH, 2009)
According to the Aspentech (2009), the thermodynamic properties estimated
by the simulator are:
• Fugacity coefficient (K-values)

• Enthalpy
• Entropy

• Gibbs free energy

• Volume
The transport properties are:

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 • Viscosity

• Thermal conductivity
• Diffusion coefficient

• Surface tension
When selecting property methods for a simulation, it is necessary to take into
account different factors such as the chemical function of the components
(polar, non-polar, electrolyte), process pressure and temperature, physical
state, among others.

Property methods used on VSB simulations

As previously explained for the chemical compounds selected for the
construction of the simulations, property methods may also differ depending on
specific details of the process that is going to be simulated; the following
description of selected methods applies to simulations with standard
configurations for first and second generation ethanol production.

- NRTL-RK: The NRTL (Non-random Two-Liquid) model estimates activity

coefficients for the liquid phase. The Redlich-Kwong (RK) equation of state
is used to estimate the properties of the vapor phase for sections of the
plant with moderate operating pressures (up to 10 bar) and high sugar
concentrations where deviations from the ideal behavior for the vapor
phase may be expected.
- NRTL-HOC: For sections of the plant where short chain organic acids are
present in higher concentrations (fermentation, distillation), Hayden
O'Connell (HOC) was selected for calculation of the properties of the vapor
phase to account for possible dimerization of these acids.

- RKS-BM (Redlich-Kwong-Soave and Boston-Mathias alpha function):

According to Aspentech (2009), this model is suitable for representing
combustion processes. Therefore, this model was selected for the boiler
where biomass is burnt.

- STEAMNBS: This model was selected for processes that involved

expansion or compression of steam. Aspentech (2009) indicates this model
for steam cycles, turbines and compressors. In the VSB, processes
involving steam cycles are found on the cogeneration, heat and power
(CHP) sector of the plant.

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4 Final Remarks
This technical memorandum is useful for those that are beginning to build a
process model for a sugarcane-based biorefinery or similar process, e.g. using
other feedstocks or producing different products. In addition, this organized
information support future publications including process simulations carried
out within the VSB.
The proper definition of feedstock composition, physicochemical properties and
thermodynamic models are essential to obtain reliable mass and energy
balances for different routes and technologies, allowing evaluation of different
biorefinery alternatives.

References

ASPENTECH. Physical Property Methods. 2009.

CHEMSPIDER, 2012, Chemspider Databank. Available at

<http://www.chemspider.com>. Accessed in: March 2016.

COLBY COLLEGE, 2012, Computational Chemistry Lab. Available at:

<http://www.colby.edu/chemistry/webmo/mointro.html>. Accessed in:
March 2016.
MeT 22. Sugarcane biomass composition for the industrial simulations
in the Virtual Sugarcane Biorefinery (VSB). Campinas, CNPEM, 2015.
MORAIS, E. R. et al. Biorefinery alternatives. In: BONOMI, A.; CAVALETT,
O.; CUNHA, M. P.; LIMA, M. A. P. (eds). Virtual Biorefinery: An
Optimization Strategy for Renewable Carbon Valorisation. Springer,
2016.
NREL, 2011, Process Design for Biochemical Conversion of Biomass to
Ethanol – DW1111A Aspen Plus simulation file. Avaiable at:
<http://www.nrel.gov/extranet/biorefinery/aspen_models>. Accessed in:
March, 2012.

SCHERRER, R.; BERLIN, E.; GERHARDT, P. Density, Porosity, and

Structure of Dried Cell Walls Isolated from Bacillus megaterium and
Saccharomyces cerevisiae. J Bacteriol 129(2):1162-4, 1977.

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STANMORE, B. R. Generation of Energy from Sugarcane Bagasse by
Thermal Treatment. Waste Biomass Valorization 1(1):77-89, 2010. doi:
10.1007/s12649-009-9000-3

WOOLEY, R.J.; PUTSCHE, V., 1996, Development of an Aspen Plus

Physical Property Database for Biofuels Components. NREL/MP-425-
20685. National Renewable Energy Laboratory.

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