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20th European Symposium on Computer Aided Process Engineering – ESCAPE20 115

S. Pierucci and G. Buzzi Ferraris (Editors)


© 2010 Elsevier B.V. All rights reserved.

Energy and Economic Assessment of Soda and


Organosolv Biorefinery Processes
Araceli García, María González, Rodrigo Llano-Ponte, Jalel Labidi*
Chemical and Environmental Engineering Department, University of the Basque
Country, Plaza Europa, 1, 20018, Donostia-San Sebastián, Spain
*E-mail: jalel.labidi@ehu.es

Abstract

The paper industry is facing the necessity of improving process efficiency, especially in
terms of energy and raw materials consumption. In most of the cases, the production of
pulp and paper generates an energy surplus that is often not conveniently used. The
actual trend is to convert traditional pulp and paper processes in biorefineries where all
components of lignocellulosic materials can be converted in added value products such
as bioethanol, lignin, cellulose whiskers and other chemicals than can replace the
common petroleum based products. In the present work, the energetic and economical
efficiencies of two biorefinery processes were studied using the simulation software
Aspen Plus. Soda and organosolv processes were used for raw material delignification.
The simulation design and treatment sequences (reaction, solid fraction washing,
products recovery and liquid fraction processing) are similar for both processes. Mass
and energy balances were established and the processes were compared in terms of
yield, solvents/reactants recovery and energy consumption based on the same amount of
processed raw material. In this way, the development of rigorous simulations allowed to
determine the economical feasibility of both biorefinery models, and to establish the
optimal operation conditions for both processes.

Keywords: biorefinery, organosolv, soda process, energy, economic analysis

1. Introduction
The existing pulp and paper production processes require large consumption of raw
materials, energy and water and huge amounts of effluents are generated (Nurmesniemi
et al., 2007). The analysis and improvement of this technology is being widely studied
applying process simulation, for designing and optimizing the different parts involved
in the process in order to improve energetic and economical efficiencies (Bujak, 2008).
Several methods have been established to simulate pulp and paper processes. Some
authors have developed mathematical models and correlations that represent the process
(Bhargava et al., 2008) and they have subsequently applied them to the simulation
(Mercangöz and Doyle, 2008). Commercial software (Cadsim Plus, Aspen Plus,
Wimgems…), which incorporates mathematic models of different usual equipments,
has been also used to simulate and optimize pulp and paper processes (González et al.,
2009). Biorefinery technology, especially the 'Lignocellulose Feedstock Biorefinery', is
becoming an actual alternative to petroleum based industry to produce energy,
chemicals and products. The conversion of 'nature-dry' raw material (wood, straw,
forest and agricultural lignocellulosic residues) into goods is getting more and more
important due to the abundance and variety of available raw materials, its renewable
116 A. García et al.

nature and the good position of the conversion products on the market (Kamm and
Kamm, 2004). Lignocellulose, the most abundant renewable biomass produced from
photosynthesis, is a complicated natural composite with three main biopolymers
(cellulose, hemicellulose and lignin), whose structures and compositions vary greatly,
depending on plant species, growth conditions and the method used to treat biomass
(Ding and Himmel, 2006). There are several technologies to fractionate lignocellulosic
feedstock components: enzymatic fractionating, hot water or acid chemical hydrolysis,
steam or ammonia fiber explosion, alkaline treatment and organosolv processes (Mosier
et al., 2005). In the present work two different technologies have been studied to
fractionate lignocellulosic material: alkaline treatment (soda) and organosolv-ethanol
processes (based on using organic alcohols and acids as reagents). Experimental data
have been used to develop process simulations in order to establish mass and energy
balances in a large-scale operation. The results obtained by process simulation have
been used to establish the energetic and economic efficiency of both processes.

2. Biorefinery Processes Description


In the present work, soda and organosolv-ethanol processes have been applied to
fractionate lignocellulosic material. Both treatments present different process conditions
and yields, and, therefore, they require different equipment and unit operations.
Nevertheless, the treatment sequence in both studied biorefinery processes present is
similar: raw material fractionation (reaction), cellulosic solid fraction SF treatment
(washing) and liquid fraction LF processing (by-products obtaining, recovery of
chemicals and energy). A brief description of these stages for each process is given in
the following paragraphs.

2.1. Soda Process


The soda process is one of the most commonly applied in the non-wood pulp and paper
industry (Iglesias et al., 1996), since it reaches high yields at low temperature, good
pulp and paper properties and also because of the obtaining of sulfur-free products. In
figure 1, a general diagram of the proposed soda process is shown. The raw material
(biomass) is first treated with a soda solution (NaOH concentration: 15% w/w) in an
atmospheric reactor (T: 90ºC, time: 90 min, liquid/solid ratio: 6/1 w/w) obtaining two
streams: a wet solid fraction, SF, mainly constituted by cellulose, and a liquid fraction,
LF, containing dissolved hemicelluloses, lignin and part of the non reacted inorganic
chemicals. The SF is sent to the washing stage, where water is used for cleaning fibers
and removing most of the dissolved components in the SF. The resulting washing liquor
WL is then mixed with the LF from the reactor and this stream is treated for energy and
chemicals recovery. The first step of this stage consists of the concentration of LF in a
multiple effect evaporator system, where part of the contained water is removed by
using low pressure steam. The concentrated LF is then burned in the recovery boiler,
where the heat released by the organic matter combustion (hemicelluloses and lignin) is
used for high pressure steam generation. This steam, after temperature conditioning, is
then used for heating requirements in the plant. LF combustion generates a smelt,
mainly composed by Na2CO3. For chemicals regeneration and reuse, a causticizing step
is applied, where the majority of the NaOH is regenerated, recovered and sent back to
the biomass fractionation stage. Thus, in this scheme, no by-products are obtained and
lignin and hemicelluloses are burned to recover energy and reactants.
Energy and Economic Assessment of Soda and Organosolv Biorefinery Processes 117

Figure 1. Process diagram of the soda biorefinery process proposed.

2.2. Organosolv-Ethanol Process


Organosolv process diagram is presented in figure 2.

Figure 2. Process diagram of the organosolv-ethanol biorefinery process proposed.

Organosolv processes, based on using mixtures of water and organic alcohols or acids
and particularly, ethanol organosolv process, gained new relevance for biomass pre-
treatment in a biorefinery sense (Lignol process) as it allowed obtaining several high-
value products (cellulose, lignin, hemicelluloses, extractives) under mild reaction
conditions by a cost-effective process in which solvents were recovered and recycled at
the end of the process (Pan et al., 2005). The raw material (biomass) is mixed with the
solvent (ethanol-water, 60/40 w/w) in a pressurized reactor (T: 160ºC, time: 90 min,
liquid/solid ratio: 6/1 w/w). Once reaction time is finished, a flash stream composed by
ethanol and water, is obtained from the reactor, condensed and recycled to the reaction
118 A. García et al.

step. Two other streams are obtained: a wet solid fraction, SF, mainly constituted by
cellulose, a liquid fraction, LF, containing dissolved hemicelluloses, lignin and
remaining solvent. The SF is sent to the washing stage, where a mixture of ethanol-
water with the same concentration used in reaction stage is used for cleaning fibers. The
resulting washing liquor WL is then mixed with the LF from the reactor and this stream
is treated to recover by-products and solvents. Firstly, lignin content in LF is obtained
by precipitation by adding of two volumes of water. Remaining LF after lignin
precipitation is sent to the distillation unit, where a mixture of ethanol-water is obtained
as distillate and recycled to the reaction unit. The residue, composed by water and co-
products, mainly hemicellulosic sugars, is treated by heating in a flash unit to obtain a
clean water stream, which is sent back to the lignin precipitation unit, and a
concentrated stream with the remaining process by-products for subsequent treatment
and use.

3. Simulation Approach of Biorefinery Processes by using Aspen Plus


Aspen Plus was used to design and simulate both processes on the basis of experimental
results. Lignin, cellulose and hemicelluloses were defined by their chemical structure
and physical properties which were obtained from the National Renewable Energy
Laboratory (NREL) database (NREL/MP-425-20685; task number BF521004), whereas
other conventional components were selected from the ASPEN PLUS data bank.
ELECT-NRTL model (Non-Random, Two Liquids for electrolyte systems) was used to
simulate the thermodynamic properties of solutions in the soda process, whereas NRTL-
RK (Non-Random, Two Liquids - Redlich Kwong) model was selected in the case of
organosolv one. These routes include the NRTL equation, obtained by Renon and
Prausnitz, for the liquids activity coefficients calculation, Henry’s law for the dissolved
gases and, in the second case, RKS (Redlich-Kwong-Soave) equation of state for the
vapour phase. The simulation process was developed using the following inlet streams
to the reactor: 1000 kg/h of dry raw material and 6000 kg/h of solvent (soda-water 15%
w/w and ethanol-water 60% w/w respectively) which corresponded to a liquid/solid
ratio (w/w) of 6. Raw material composition was defined as a typical lignocellulosic non-
wood material composition: 45% cellulose, 28% hemicelluloses, 25% lignin, 2%
inorganic compounds (% on a dry weight basis). Reaction conditions for the simulation
were: Soda process temperature: 90ºC, ethanol process temperature: 160ºC.

4. Simulation Results and Comparative Study


Obtained process solid fraction yield was 450 kg/h and 495 kg/h (on a dry weight basis)
for soda and ethanol systems respectively. Furthermore, the latter scheme allowed the
obtaining of 130 kg/h of organosolv lignin, which is a sulfur-free aromatic type
structure with high amount of phenolic hydroxyl groups that favour their incorporation
into polymer formulations and their chemical modification (Kubo and Kadla, 2004).
Hemicellulosic sugars (311 kg/h) were also obtained in an aqueous concentrated
solution that could be subsequently treated for different applications as, for example, by
enzymatic hydrolysis to produce bio-ethanol. Chemicals and water consumption of both
processes is included in Table 1. According to energy requirements, the utilities
consumptions for both processes have been calculated (Table 2 for soda process and
Table 3 for ethanol-organosolv process). To determine the corresponding cost of steam
and cooling water requirements, a factor of 48 €/kW·year (heating) and 4.7 €/kW·year
(cooling) has been applied respectively.
Energy and Economic Assessment of Soda and Organosolv Biorefinery Processes 119

Table 1. Chemicals and water requirements for the two biorefinery processes analyzed (for
1000 kg/h of raw material).
Soda process Organosolv-ethanol process
REQUIREMENTS (kg/h) (kg/h)
Soda Water Na2CO3 Ethanol Water
Reaction stage 900 5100 0 3600 2400
SF washing 0 1275 0 390 260
Lignin precipitation 0 0 0 0 2500
Soda recovery 0 1340 1087 0 0
Total required 900 7715 1087 3990 5160
RECOVERED 820 840 0 3895 4214
FRESH INPUT 80 6875 1087 85 861

Table 2. Utilities requirements and associated costs for the soda process (for 1000 kg/h of raw
material). MPS: Medium pressure steam; LPS: Low pressure steam.
Soda process
Utility requirements Costs
PROCESS STAGE
MPS LPS Cold water Heating Cooling
kg/h k€/year
Reaction stage 776 0 0 20.2 0
Soda recovery
Multiple evaporators 0 5463 0 153.6 0
Fresh vapor 0 1340 0 37.7 0
Vapor condensation 0 0 25341 0 2.76
Recovery boiler 0 495 0 13.9 0
Total 776 7298 25341 225.4 2.76
Energy (MW) 0.42 4.275 0.587
GENERATED 794 7298 0
NET REQUIREMENT 0 0 25341 0 2.76
TOTAL COST 2.76

Table 3. Utilities requirements and associated costs for the organosolv-ethanol process
(for 1000 kg/h of raw material). MPS: Medium pressure steam; LPS: Low pressure steam.
Organosolv-ethanol process
Utility requirements Costs
PROCESS STAGE
MPS LPS Cold water Heating Cooling
kg/h k€/year
Reaction stage 3549 0 0 92.2 0
Solvents recovery
Flash stream condensation 0 0 88500 0 9.6
Distillation condenser 0 0 59144 0 6.4
Distillation reboiler 0 768 0 21.6 0
Water evaporation 0 1571 0 44.2 0
Steam flash condensation 0 0 39717 0 4.3
Total 3549 2339 187361 157.9 20.4
Energy (MW) 1.92 1.37 4.34
GENERATED 0 0 0 0 0
NET REQUIREMENT 3549 2339 187361
TOTAL COST 178.3
120 A. García et al.

As it can be observed, soda process energetic requirements are considerably lower than
organosolv-ethanol ones, as most of the heating utilities are generated within the
process. On the other side no by-products are obtained and only the enriched cellulosic
solid fraction is produced. However, organosolv process allowed the obtaining of high
quality cellulose, lignin and profitable hemicellulosic components.

4. Conclusions
Simulation tools have been successfully applied to compare two biorefinery processes
treating the same raw material, in terms of energy and chemicals consumptions. Soda
process was found to be energy efficient, as energy requirement of the process was
generated by the combustion of the organic fraction of the black liquor in the recovery
boiler. Organosolv-ethanol process allowed an integral use of the raw material and the
obtaining of high added value by-products, as well as the recovery of the solvents.
Process simulation has permitted the study of biorefinery processes and the evaluation
of different alternatives design of the studied processes and also different operation
conditions.

5. Acknowledgements
The authors would like to thank the Spanish Ministry of Science and Innovation
(CTQ2007-65074-C02-02) and the Diputación Foral de Gipuzkoa for their financial
support.

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