Exergoenvironmental analysis of methanol production

through the thermochemical route as a co-product of an

ethanol plant
Maria L. G. Renóa, Electo E. S. Loraa, José C.P. Escobara, Osvaldo J. Venturinia, José J.
C. S. Santosb
a
Federal University of Itajubá, Itajubá, Brazil
b
Federal University of Espírito Santo, Vitória-ES, Brazil

Abstract: Biomass is a promising alternative for the reduction of environmental impacts, as well as
long-term a possibility of ensuring energy security and an introduction the socio-economic development
of rural regions. Among the technologies under development that uses the biomass detach the
thermochemical process of biofuel production from biomass, through gasification route.
In this work is done an exergoenvironmental evaluation of the methanol production process from
sugarcane bagasse, considering a methanol plant with a production capacity of 50,000 ton/year. The
thermoeconomics and life cycle assessment (applying the Eco-Indicator 99 method) are used. The
results allowed determining which stages of methanol production process present the greatest
environmental impacts, and the possibilities to minimize these impacts.

Keywords: Methanol, Bagasse, Life Cycle Assessment, Exergoenvironmental.

1. Introduction exergy analysis yields efficiencies which provide a

1.1. Methanol production
The Methanol can be produced chemically from
biomass and fossil fuels. Methanol is suitable as
transportation fuel, chemical building block, or as
solvent. Another common application of methanol
is as a raw material for biodiesel production.
Methanol synthesis via biomass gasification has
already been suggested as an environmentally
friendly method of biomass utilization. Several
biomass-to-methanol demonstration projects have
been developed recently, such as the Hynol project
in United States, the BioMeet and Bio-Fuels
projects in Sweden [1]. In Brazil, there is the
Raudi-Methanol project that proposes the
methanol production from sugarcane bagasse [2].
true measure of how nearly actual performance
approaches the ideal, and identifies more clearly
than energy analysis the causes and locations of
thermodynamic losses and the impact of the built
environment on the natural environment.
Consequently, exergy analysis can assist in
improving and optimizing designs [4].
The exergy measures are traditionally applied to
assess energy efficiency, regarding the exergy
losses in a process system. The exergy loss or
destroyed exergy (irreversibility) is a positive
quantity for all the actual process and for a steady-
state system can be compute by the Equation (1)
[5]:
⎛ ⎞
E d = ∑ ⎜⎝1 − T T ⎟⎠Q
o
j
j − Wvc + ∑ m e
i fi

The processing steps of methanol from biomass j i (1)

are pretreatment, gasification, gas cleaning, gas − ∑ m ee fe
conditioning and methanol synthesis that occurs at e

temperatures of 200 – 300°C and pressures of 5 – Where:

10 MPa [3].
1.2. Exergy analysis and life cycle
assessment
Exergy analysis is a thermodynamic analysis
technique based on the second law of
thermodynamic which provides an alternative and
illuminating means of assessing and comparing
processes and system rationally. In particular,
⎛ To ⎞ 
⎜1 − T j ⎟ Q j = It represents the time rate of exergy
⎝ ⎠
transfer accompanying heat transfer at the rate
Q j occurring at the location on the boundary where
the instantaneous temperature is T j .
Wvc = This term represents the time rate of energy
transfer rate by work
m i e fi = It accounts for the time rate of exergy
transfer accompanying mass flow and flow work
at inlet i.
m e e f e = It accounts for the time rate of exergy
transfer accompanying mass flow and flow work
at exit e.
The irreversibility can be viewed as the wasted
work potential or the lost opportunity to do useful
work. So this measure manifests itself in
environmental degradation and emissions [5] [6].
Decreasing the destroyed exergy of a process
means lower primary fuel consumption, thus
reducing the operating cost and increasing the
process efficiency. This, in turn, will reduce
emissions and wasted heat to the environment.
Another tool that can be used for measuring
environmental performance is the Life Cycle
Assessment (LCA) that is an internationally
renowned methodology for evaluating the
environmental performance of a product, process
or pathway along its partial or whole life cycle,
quantifying the potential environmental impacts of
them.
In relation the Life Cycle Impact Assessment,
many methodologies of human health and
environmental risk have been developed. One of
these methodologies applied in many LCA works
is the Eco-Indicator 99. This method analyzes
environmental burden under three impact areas
(human health, ecosystem, resources), computing
eleven different impact categories like
carcinogens, respiratory organics, respiratory
inorganic, climate change, radiation, ozone layer,
eco-toxicity, acidification, eutrophication, land
use, minerals and fossil fuels.
In the inventory, impacts are analyzed by different
effect categories then damage assessment has been
measured by human health, ecosystem and
resource categories. The human health is
computed in DALY (Disability Adjusted Life
Years) unit, this means that different disabilities
caused by diseases are weighted [8]
Ecosystem Quality is measured in PDF*m2yr,
where PDF is potentially disappeared fraction of
plant species. Finally the resources are measured
in MJ surplus energy additional energy
requirement to compensate lower future ore grade.
The last step is the weighting that refers to using
numerical factors for facility the comparison
across impact category indicators. But the
weighting remains a controversial element of
LCA, mainly because the weighting involves
social, political and ethical value choices.
Different works have been applied the exergy
analysis and LCA, mainly in energy conversion
system [9],[10],[11],[12] . The combination of
LCA and exergy analysis is based on the
methodological approach of exergoeconomic
analysis. But in this case the environmental
impacts are assigned to exergy streams of the
system. So the method generates information on
environmental impacts associated with
thermodynamic efficiency (exergy destruction)
and environmental impacts related to construction,
operation, and maintenance of plant components.
The present work uses this methodology, applying
in methanol production from biomass. The
methanol plant is annexed to an ethanol
autonomous distillery. The thermal and electrical
demand of the whole plant is supply by a
cogeneration system based in
condensing/extraction steam turbines.
The goal of this analysis is appoint which stages
from methanol production system present more
environmental impacts and which are the
possibilities for minimizing them.
2. Methodology and assumptions
This section provides some general information
about the case study of the work and the
description of the methodology applied.
Some of the definitions used in [9] and [10] are
used for the exergoenvironmental analysis.
2.1. Case study parameters
The main parameters of all system analyzed are in
Table 1.
Table 1. Main parameters of case study.
COGENERATION SYSTEM
Equipment performance
Boiler efficiency (%) 88
Isentropic efficiency of steam turbine (%) 90
Power installed (MW) 78
Steam production (t/h) 600
Fuel (bagasse)
Sugarcane bagasse – LHV (kJ/kg) 7560
Moisture (%) 50
Milling system
Steam inlet pressure (MPa) 2 B D , K = bF , K E D , K ,
Steam inlet temperature (°C) 320
Steam pressure exhaustion (MPa) 0.17
Percentage of bagasse from sugarcane 28
Milling capacity of sugarcane (t/h) 1351
Environmental conditions
Atmospheric temperature (°C) 25
Atmospheric pressure (MPa) 0.1013
DISTILLERY AND METHANOL PLANT
Total consumption of steam (kg/tc) 369
Methanol production (m3/h)
Ethanol production (m3/h)
328
2594
Electrical energy demand of distillery 12
(kWh/tc)
Electrical energy demand of methanol plant 0.25
(kWh/kg methanol)
2.2. Exergoenvironmental analysis
The exergoenvironmental analysis of this work
consists mainly of three steps. The first is an
exergy analysis of the energy conversion process
that contains a methanol plant, an ethanol plant
and its cogeneration system for supplying thermal
and electrical demand of these plants. Second, it
computes the environmental impacts by applying
the Eco-Indicator 99 life cycle assessment method.
In last step the environmental impact are assigned
to the exergy streams in the process, using
thermoeconomics tool.
One of results from exergoenvironmental analysis
calls specific environmental impact bj. This
represents environmental impact associated with
the production of the j stream per exergy unit
(mPts/kJ) [9]. Similarly, it computes the
environmental impact rate B j (mPts/s) of stream j.
This impact is the product of its exergy rate
E j and the specific environmental impact bj, as
Equation (2):
B j = b j .E j , (2)
Another important variable calculated is the
environmental impact of exergy destruction. As
work [10], it assumed that exergy destruction is
compensated for by higher consumption of fuel to
obtain the given amount of product. So, in this
case the exergy destruction ( E D ,k ) is multiplied
with specific environmental impact bF,k. associated
with the fuel of component. The result is the
environmental impact of exergy destruction
(Equation (3)).
(3)
For getting the results, it was necessary formulate
mathematical equations, applying the
thermoeconomics concept. So, computing the
specific environmental impact of all internal flows
of exergy (j) through environmental impact
balance of the each equipment or sub-system k
from thermal system, as it is in Equation (4).
∑ (b E ) = Y
j j K , (4)
Where YK is the environmental impacts that occur
during the life cycle phases of equipment or sub-
system k, as example: construction (including
manufacturing, transport and installation),
operation and maintenance.
These environmental impacts use the Eco-
Indicator 99 method for calculation, after it divides
the results by lifespan of equipment.
In this study assumed the lifespan of all
equipments at 100,000 hours. Only the methanol
plant and autonomous distillery it assumed 20
years. The databases (inventory) of equipments
and sub-system (Methanol and distillery plants)
are from data of SimaPro software version 7 [13]
and bibliography references [14], [15], [16], [17].
The thermoeconomic model is a set of cost
equations describing all the process of cost
formation in the plant, it describes the distribution
of the resources in the plant through the
components to obtain the final products. To obtain
the set of equations, this paper considers the
mathematical formalism used in work [18] and
[19]. In the exergoenvironmental evaluation the
approach of thermoeconomic analysis is modified
to deal with an evaluation of the ecological impact
instead of an economic problem .The equations are
shown in Table 2.
The Fig. 1 represents the physical structure,
According to Figure 1 the global plant is compost
by a cogeneration system based on
condensing/extraction steam turbines, operating
with high steam parameters that supplies all the
steam and electricity for the autonomous distillery
and methanol plant that are included in global
plant. The sugarcane bagasse obtained in the
milling section is used as fuel for the cogeneration
system, as well as raw material for the methanol
production, while the sugarcane juice is used for
the hydrated ethanol production. In this way the
three systems are integrated producing surplus T3 + C3 bP 3 ⋅ E P 3 − b16:8 a ,b ⋅ E16:8 a ,b
electricity, hydrated ethanol and methanol.
−b ⋅ E
VI :V = Y
VI :V T 3+ C 3
The Fig. 2 is the productive structure of the case
study of this work. The rectangles in Figure 2 are G1 bP 4 ⋅ E P 4 − bP1 ⋅ E P1 = YG1
the actual productive units that represent the plant G2 b ⋅ E − b ⋅ E = Y
P5 P5 P2 P2 G2
components. The rhombuses and the circles are G3 bP 6 ⋅ E P 6 − bP 3 ⋅ E P 3 = YG 3
fictitious productive units called junctions and
bifurcation, respectively. The inlet and outlet Water b ⋅ E
VI :V +b
VI :V ⋅ E
IV :III+b IV :III II :I ⋅ E II :I
arrows are productive unit fuels (or resources) and Cooler
−bPJ ⋅ E PJ = YWC
products, respectively. When a productive unit has
more than one type of fuel it necessarily
J2 + B2 b ⋅ E + b ⋅ E
PA PA PB PB + bPC ⋅ E PC
incorporates a small junction (e.g., T1+C1, +bPD ⋅ E PD + bPE PE PF ⋅ E + b ⋅ E
PF
Ethanol plant.). The productive flows are all
+bPG ⋅ E PG + bPH ⋅ E PH + bPI ⋅ E PI
exergy flows representing: electrical power (EP),
mechanical power (PM) or exergy of sugarcane +b ⋅ E + b ⋅ E + b ⋅ E
PJ PJ PK PK EX EX
(Esugarcane), bagasse (Ebag), juice (Ejuice) and −bP 4 ⋅ E P 4 − bP 5 ⋅ E P 5 − bP 6 ⋅ E P 6 = 0
water/steam (Ej:k and Ej:k`).For convention it
assumed that the exergy of input flow is the
J1 + B1 b ⋅ E
20 b:5 a ,b ,c , d 20 b:5 a ,b ,c , d

negative value, unlike for output flow. +b20 a:7 a ,b ⋅ E 20 a:7 a ,b + b16:8 a ,b ⋅ E16:8 a ,b
Table 2. Mathematical equations of system +b ⋅ E
6,7 a ,8 a:10 a ,b 6,7 a ,8 a:10 a ,b

Productive Equation +b5 d :6 ⋅ E 5 d :6 + b5c , d :9 a ,b ⋅ E 5c ,d :9 a ,b

structure
B3 bbag ⋅ E bag + b juice ⋅ E juice −b16:15 ⋅ E16:15 − b2:1 ⋅ E 2:1 − b4:3 ⋅ E 4:3
−b ⋅ E − b ⋅ E
−bcane ⋅ E cane = 0 15:18 15:18 1:19 a 1:19 a

−b3:19b ⋅ E3:19b − b11:10 a ⋅ E11:10 a

Boiler 1 b16:15 ⋅ E16:15 − bbag ⋅ E bag1 = Yboiler1
−b12:5 a ⋅ E12:5 a − b14:10b ⋅ E14:10b
B4 bbag ⋅ E bag1 + bbag ⋅ E bag 2 + bbag ⋅ E bag 3
−b ⋅ E +b ⋅ E =0
+bbag ⋅ Ebag 4 − bbag ⋅ E bag = 0
13:7 b 13:7 b 17:8b 17:8b
Ethanol bethanol ⋅ E ethanol − bPK ⋅ E PK
Boiler 2 b2:1 ⋅ E 2:1 − bbag ⋅ E bag 2 = Yboiler 2 plant
−b ⋅ E
6,7 a ,8 a:10 a ,b 6,7 a ,8 a:10 a ,b
Boiler 3 b4:3 ⋅ E 4:3 − bbag ⋅ E bag 3 = Yboiler 3
−b juice ⋅ E juice = Yethanol
Pump 1 b15:18 ⋅ E15:18 − bPA ⋅ E PA = Ypump1
Milling bPM ⋅ E PM − b5 d :6 ⋅ E 5 d :6 = Ymilling
Pump 2 b1:19 a ⋅ E1:19 a − bPB ⋅ E PB = Ypump 2
Methanol bmethanol ⋅ E methanol − bPI ⋅ E PI
Pump 3 b3:19b ⋅ E 3:19b − bPC ⋅ E PC = Ypump 3 plant
−b ⋅ E
5 c ,b:9 a ,b 5 c ,b:9 a ,b
Pump 4 b11:10 a ⋅ E11:10 a − bPD ⋅ E PD = Ypump 4
−bbag ⋅ E bag 4 = Ymethanol
Pump 5 b12:5 a ⋅ E12:5 a − bPE ⋅ E PE = Ypump 5
2.3. Limitations and advantages of
Pump 6 b14:10b ⋅ E14:10b − bPF ⋅ E PF = Ypump 6
exergoenvironmental analysis
Pump 7 b13:7 b ⋅ E13:7 b − bPG ⋅ E PG = Ypump 7 The restriction of exergoenvironmental analysis is
Pump 8 b17:8b ⋅ E17:8b − bPH ⋅ E PH = Ypump 8 referred to the LCA method that presents the
following typical limitations [11]:
T1 + C1 bP1 ⋅ E P1 − b20b:5 a ,b ,c ,d ⋅ E 20b:5 a ,b ,c ,d
▪ The nature of choices and assumptions made in
−b ⋅ E = Y
II :I II :I T 1+ C1 LCA (e.g. system boundary setting, selection of
T2 + C2 bP 2 ⋅ E P 2 − b20 a:7 a ,b ⋅ E 20 a:7 a ,b data sources and impact categories) may be
subjective;
−b IV :III⋅E = Y
IV :III T 2+C 2 ▪ Models used for inventory analysis or the
assess environmental impacts are limited by
 their assumptions, and it may not be available
for all potential impacts or applications;
▪ The results of LCA studies focused on global
and regional issues, so for local applications it
might not be adequately represented;
▪ The accuracy of LCA studies is limited by
accessibility or availability of relevant data, or
by data quality;
▪ The lack of spatial and temporal dimensions in
the inventory data used for impact assessment
introduces uncertainty in impact results.
According the International Stand on LCA the
allocation should be avoided where possible by
sub-division or system boundary expansion [20].
However, when the allocation is inevitable, the
ISO 14041 recommends that the allocation should
reflect the physical relationships between the
environmental loads and the functions. Thus,
allocation can consider the physical properties of
the products, such as mass, volume, energy,
because data on the properties are generally
available and easily interpreted. The choice and
justification of allocation procedures is a major
issue for life cycle assessment, especially since it
can have a significant influence on subsequent
results.
In this way the exergoenvironmental analysis
allows to allocate the main environmental loads
takes into account the quality of the different kinds
of energy.

Fig. 1. Physical structure of thermal system

EP1 EP4
E20b:5a,b,c,d T1 + C1 G1
E16:15
B4 Ebag1 E20a:7a,b EP5
Boiler 1
E2:1 T2 + C2 EP2 G2
Ebag2 J1 B1 J2 B2
Boiler 2 Eex
Ebag3 E4:3 E16:8a,b
Boiler 3 T3 + C3 EP3 G3 EP6
EPA E15:18 EPI
Pump 1 EIV:III
EPB E1:19a EII:I
Ebag Pump 2 EVI:V
EPC E3:19b
Pump 3 wc EPJ
EPD E11:10a
Pump 4 EPK
EPE E12:5a E5d:6
Pump 5 M. drives Milling Ethanol Ethanol
EPF E14:10b plant
Pump 6 E6,7a,8a:10a,b
EPG E13:7b E5c,d:9a,b
Pump 7 Methanol Methanol
EPH E17:8b plant
Pump 8
Ebag4
B3 Ejuice
sugarcane Fig.2.
Fig. Productivestructure
2. Productive structure
of of thermal
thermal system
3. Results environmental impacts (Points/ 100 m3 methanol),
while the Figure 4 presents the environmental
Life Cycle Analysis impacts divided by impact categories
In Figure 3 and 4 are presented the environmental (carcinogens, ecotoxicity, land use, climate
impacts of all system related the production of 100 change, others).
m3 methanol, which is the functional unit of this
work. The Figure 3 presents the total
3
Eco-Indicator 99 Points [Points/100m
600 517
500
400
300 228
methanol)

200 142
100 80.6
50.9 22.1
0.0263 8.59 1.95
0
electricity generation

boiler system

pump system
thermal energy

turbines system

water cooler system

sugarcane production

ethanol plant
methanol plant
Fig. 3.Total environmental impacts of the system

Fig. 4. Environmental impacts of all system by impact categories

The Figure 4 shows that the sugarcane production actually do because of direct and indirect oil
presents a favorable impact for climate change consumption: this system uses external inputs,
mitigation, the reason is related the carbon dioxide such as fertilizers, pesticides, transport
absorption by the sugarcane during its growth. infrastructure and so on, that demand petroleum in
However, the popular belief is that ethanol their production, operation and maintenance.
production systems release no net CO2, they
With respect to the system equipments The solution of linear equations of the Table 2
construction, the results from Figure 3 and Figure provides all values of the environmental impact
4 shows that the environmental impacts from them rates within the process (bj). With this value it is
is relatively low when they are compared with possible compute environmental impact of exergy
methanol synthesis, sugarcane production, destruction ( B D , K ), as well as, the environmental
electricity generation and thermal energy.
impact of life cycle phases of system components
The life cycle energy efficiency and the fossil ( YK ).The main results are presented in Table 3.
energy ratio for this system were determined in
[21]. The first ratio refers to the quantity of energy Table 3. Environmental impact of exergy destruction
primary necessary to produce 1 kg methanol, the and from system components
result gotten was 0.20, while the second ratio
refers to the fossil energy demand for producing 1
Equipment YK B D , K
kg of methanol, and the value gotten was 9.4. (mPts/s) (mPts/s)
Boiler 1 7.44 10-5 0.0008767
Exergy Analysis Boiler 2 7.44 10-5 0.0020797
The available exergy of sugarcane for the ethanol Boiler 3 7.44 10-5 0.0020797
distillery without and with a methanol plant Pump system 2.35 10-5 7.74 10-6
annexed is presented in the Figures 4 and 5. Water cooler 8.45 10-8 2.13 10-5
Milling 2.13 10-7 0.000120
UNAVAILABLE AVAILABLE EXERGY ST1 + C1 4.71 10-5 0.0002243
EXERGY 45% ST2 + C2 4.71 10-5 0.0001009
55%
UNAVAILABLE ST3 + C3 4.71 10-5 0.0001352
41%
EXERGY
G system 0 4.038 10-5
ETHANOL (kW)
Ethanol plant 7.10 10-5 0.02282
SURPLUS
Methanol plant 6.26 10-6 0.00686
4% ELECTRICITY (kW)

Table 3 shows that the major environmental

Fig. 4. System without methanol plant annexed
impacts associated with exergy destruction occur
in the components associated to the cogeneration
UNAVAILABLE
EXERGY AVAILABLE EXERGY systems (boilers, steam turbines, pumps) and
UNAVAILABLE EXERGY
52% 48% ethanol, the second environmental impacts
4% METHANOL associated to the exergy destruction occurs in the
41% ethanol plant and the third correspond to the
ETHANOL
3% methanol plant. It also shows that the
SURPLUS environmental impact caused by exergy
destruction ( B D , K ) is the main source of
ELECTRICITY

Fig. 5. System with methanol plant annexed

Comparing the Figures 4 and 5, the Figure 5
shows that available exergy of sugarcane is 3%
more high in a system that has the methanol plant
annexed. So in terms of global exergetic utilization
and resources use, the system that produces
methanol is more attractiveness and therefore
more sustainable.
For the overall energy conversion system, the
exergetic efficiency is
E Ethanol +E Metanol +E E.exc
ηexer = = 48%
ESugarcane
Exergoenvironmental Analysis
environmental impacts when compared with the
component-related environmental impact of the
system ( YK ) that were very low.
Some technological alternatives that contributes
for decreasing the environmental impacts
associated with exergy destruction in the whole
systems are: mills electrification, steam
consumption reduction in the different process
stages of ethanol production through thermal
integration or more efficiency technology such as:
multipressure-distillation, instead of, atmospheric
one, regenerative heat exchangers for juice x
stillage, juice x juice and juice x condensate;.
Finally in the methanol production process these
impacts can be reduced through an adequate
controle of the (H2 – CO2/CO+CO2) ratio in the
syngas produced by bagasse gasification, having in
mind that the necessity of remove more CO2 away
and adopt s shift process (CO + H2O = CO2 + H2)
to adjust H/C, which will cause material and
exergy destruction.
4. Conclusion
The exergoenvironmental method shows whether
reducing the thermodynamic inefficiencies or
reducing consumption of materials during
construction or operation of the component can
permit to improve the environmental performance
of energy conversion system for biofuel
production.
The results also prove that the sugarcane exergy is
more available and therefore sustainable when
increase the quantity of products from sugarcane,
in this case: electricity, ethanol and methanol.
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on Efficiency, Cost, Optimization, Foz de
Iguaçu, Brazil.
Acknowledgments: The authors would like to
acknowledge Mr. Jeans Buchgeister (Institute of
Technology Assessment and System Analysis),
FAPEMIG, CNPq and CAPES for the financial
support to perform this study.