Bioresource Technology 208 (2016) 100109

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Life cycle assessment of advanced bioethanol production from pulp and

paper sludge
Diogo Sebastio, Margarida S. Gonalves, Susana Marques, Csar Fonseca 1, Francisco Grio, Ana C. Oliveira,
Cristina T. Matos
Unidade de Bioenergia, Laboratrio Nacional de Energia e Geologia, I.P., Estrada do Pao do Lumiar, 1649-038 Lisboa, Portugal

h i g h l i g h t s
 LCA was used to evaluate an ethanol plant converting pulp and paper sludge.
 Enzymatic hydrolysis and neutralisation of the CaCO3 are the environmental hotspots.
 Neutralisation and subsequent CO2 emissions is specific to this raw material.
 Two optimisation scenarios were developed (reduced HCl usage and co-fermentation).

a r t i c l e

i n f o

Article history:
Received 21 December 2015
Received in revised form 10 February 2016
Accepted 11 February 2016
Available online 22 February 2016
Keywords:
Life cycle assessment
Bioethanol
Waste valorisation
Pulp and paper sludge

a b s t r a c t
This work evaluates the environmental performance of using pulp and paper sludge as feedstock for the
production of second generation ethanol. An ethanol plant for converting 5400 tons of dry sludge/year
was modelled and evaluated using a cradle-to-gate life cycle assessment approach. The sludge is a burden
for pulp and paper mills that is mainly disposed in landfilling. The studied system allows for the valorisation of the waste, which due to its high polysaccharide content is a valuable feedstock for bioethanol
production. Eleven impact categories were analysed and the results showed that enzymatic hydrolysis
and neutralisation of the CaCO3 are the environmental hotspots of the system contributing up to 85%
to the overall impacts. Two optimisation scenarios were evaluated: (1) using a reduced HCl amount in
the neutralisation stage and (2) co-fermentation of xylose and glucose, for maximal ethanol yield. Both
scenarios displayed significant environmental impact improvements.
2016 Elsevier Ltd. All rights reserved.

1. Introduction
Bioethanol is currently used in commercial gasoline blends,
mainly produced through conventional first generation technology,
which relies on dedicated energy crops competing with arable land
for food and feed. The EU directive 2009/28/EC (European
Commission, 2009) stipulates a mandatory target of 10% incorporation of renewable energy in the transport sector by 2020 and
second-generation (advanced) biofuels produced from lignocellulosic
wastes will count double towards this target. A revision of 2009/28/EC
directive was recently approved by EU and shall soon enforce a cap of
7% on first generation biofuels as well as a non-binding reference

Corresponding author. Current address: European Commission, Joint Research

Centre (JRC), Institute for Environment and Sustainability (IES), Sustainability
Assessment Unit, Via Fermi, 21021, Ispra, VA, Italy.
E-mail address: cst.matos@gmail.com (C.T. Matos).
1
Current address: Section for Sustainable Biotechnology, Aalborg University
Copenhagen, A. C. Meyers Vnge 15, 2450 Copenhagen SV, Denmark
http://dx.doi.org/10.1016/j.biortech.2016.02.049
0960-8524/ 2016 Elsevier Ltd. All rights reserved.

target of 0.5% for biofuels produced from lignocellulosic materials.

In Europe, some demo and flagship plants are already deployed for
advanced bioethanol production from lignocellulosic materials,
namely Beta-Renewables flagship plant in Crescentino (Italy),
Inbicons demo plant in Kalundborg (Denmark), Clariants demo plant
in StraubingMunich (Germany), among others.
Pulp and paper sludge might also be an interesting feedstock for
advanced bioethanol production due to its high polysaccharide
content. Moreover, its usage for bioethanol production has the
advantage of avoiding its disposal in landfill, thereby reducing
the corresponding environmental and economic impact (Monte
et al., 2009). Polysaccharides present in this sludge are highly
accessible to enzymatic hydrolysis due to the physical and chemical processing undertook during pulp and paper manufacturing
(Marques et al., 2008a). This characteristic avoids the costly pretreatment step usually required with unprocessed lignocellulosic
feedstocks. In 2013, the Portuguese pulp and paper industry
generated 350 000 tons of dry sludge (2013 data from CELPA the
Portuguese pulp and paper association). The feasibility of using

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D. Sebastio et al. / Bioresource Technology 208 (2016) 100109

recycled paper sludge to produce ethanol or other bio-based products has been previously reported (Marques et al., 2008a,b; Chen
et al., 2014a). Chen et al. studied the economic feasibility of paper
sludge conversion into ethanol for different scenarios and concluded that the process is economically feasible, reaching a calculated net present value of US$ 3.35 million from virgin wood kraft
pulping sludge (the same sludge source of the current study), and a
maximum of US$ 11.4 million if a fractionation step is performed
(ash and fibre removal before conversion).
Life cycle assessment (LCA) is a technique used to assess the
potential environmental impacts of products, processes and services throughout their entire life-cycle or of one value-added process. This tool has been used for the evaluation of both first
generation and second generation biofuels. The most reported
impact category is climate change and the results for the first generation bioethanol range from 0.027 to 0.080 kg CO2eq/MJ bioethanol using sugarcane as feedstock (California EPA, 2009; Muoz
et al., 2014; Renouf et al., 2008; Wang et al., 2012) and from
0.038 to 0.071 kg CO2eq/MJ bioethanol using corn (Dunn et al.,
2012; Muoz et al., 2014; Wang et al., 2012). Values of 0.026 and
0.056 kg CO2eq/MJ bioethanol have been reported using sugar beet
and wheat, respectively (Muoz et al., 2014). With respect to second generation bioethanol, 0.007 to 0.157 kg CO2eq/MJ bioethanol has been reported when using wheat straw (Borrion et al.,
2012a; Janssen et al., 2014; Mu et al., 2010; Wang et al., 2013),
0.0050.025 kg CO2eq/MJ bioethanol with corn stover (Muoz
et al., 2014; Wang et al., 2012) and 0.0110.020 kg CO2eq/MJ
bioethanol with switchgrass (Dunn et al., 2012; Wang et al.,
2012). With Miscanthus, a value of 0.005 kg CO2eq/MJ bioethanol
has been reported (Wang et al., 2012). The variability of the results
is explained by the use of different process configurations and/or
different methodological assumptions mainly regarding allocation
of impacts between products and by-products (multifunctional
systems) and inclusion or exclusion of land use change (Muoz
et al., 2014). As an example, the use of substitution to deal with
multifunctionality has significant impact on the outcome of a biofuel LCA, which is the case of biofuels systems with simultaneous
electricity production using the non-hydrolysed cellulose fibres
and/or the lignin. Several reviews regarding this topic have also
been published (Borrion et al., 2012b; Morales et al., 2015; von
Blottnitz and Curran, 2007; Wiloso et al., 2012), however no LCA
study regarding the production of bioethanol using pulp and paper
sludge has been reported so far.
The objective of this study was to evaluate the environmental
performance of bioethanol production using sludge resulting from
the wastewater treatment (WWT) of pulp and paper mills through
SHF. Several process optimisation options were analysed through
cradle-to-gate LCA to identify the system environmental hotspots
and the best environmentally efficient options. All the bioethanol
production processes were modelled in SuperPro Designer using
experimental data to obtain all the energy and material balances
(inputs/outputs necessary in each production step). These inputs/
outputs were used in the construction of the LCA case study, which
was then evaluated using the SimaPro software and the CML-IA
method. The three scenarios under study included a base case scenario and two optimisation scenarios: (1) an improved neutralisation stage assuming reduced amount of HCl usage and (2)
considering the use of a recombinant yeast capable of xylose and
glucose co-fermentation.

to landfill. The composition of the sludge used in this paper was in

dry weight basis: 51% cellulose, 12.8% hemicellulose, 1.9% lignin,
29.9% CaCO3, 0.8% other organics and 3.6% sands and a moisture
content of 58.7% (Table 1). This represents an averaged sludge that
was tested for ethanol production during the research project BIIPP
(Biorefinaria Integrada na Indstria da Pasta e Papel, Contract
FCOMP-01-0202-FEDER-011551). The sludge composition is
dependent on the mill products (pulp or pulp and paper), process
and operational variations. Taking this into account, sludge composition significantly varies and the one reported in this work was
chosen as reference for the analysis of the proposed system.

2.2. Ethanol plant model description

According with the findings of the BIIPP project a plant for converting 5400 dry tons of pulp and paper sludge/year to produce
ethanol was modelled using SuperPro Designer 8.5 (Intelligen,
Inc.) (Fig. 1). This sludge is generated in a pulp and paper mill with
a production capacity of 550 000 ton/year. The bioethanol production was designed as a separate hydrolysis and fermentation process (SHF), consisting of four main sections: (1) neutralisation
and enzymatic hydrolysis; (2) concentration; (3) fermentation;
and (4) downstream processing (DSP). DSP consisted of anhydrous
ethanol recovery using two unit operations: distillation and molecular sieving. The SHF scenario was chosen as the base case scenario
of this study in order to develop a model that allowed the assessment of all unit operations individually and depict their contributions to the overall environmental impacts. Additionally, the
separation of the hydrolysis and fermentation processes allows
for process flexibility (within a biorefinery concept), because the
sugars produced may be directed towards the production of other
products in addition to ethanol.
This detailed process model includes all unit operations from
biomass handling till ethanol dehydration and was developed to
calculate energy, water and utilities consumption used as inputs

Table 1
Inputs used in the mass and energy balance.

2. Methods
2.1. Biomass
a

The WWT facilities of pulp and paper mills generate large

amounts of solid waste stream, sludge, which is nowadays diverted

b
c

Parameter

Value

Unit

Sludge available (in a mill)a

HCl 37%
CaCO3 neutralised
Enzyme

5400.00
0.46
55
25

ton sludge/year
kg/kg sludge
%
kg/ton sludge

Sludge compositiona
Cellulose
Hemicellulose
Lignin
CaCO3
Other organics
Sands

51.0
12.8
1.9
29.9
0.8
3.6

%
%
%
%
%
%

Sludge moisture content

Agitation of the hydrolysis tanks
Agitation of the fermentation tanks

58.7
0.43
0.07

%
kW/m3
kW/m3

Enzyme productionb
NH3
Glucose
CSL
Steam
Electricity

0.21
4.20
0.14
1.80
4.00

kg/kg enzyme
kg/kg enzyme
kg/kg enzyme
MJ/kg enzyme
MJ/kg enzyme

Fermentation medium nutrientsc

Corn steep liquor
MgSO4
7H2O
CuSO4
5H2O
Urea

14.6
1.3
0.01
0.8

g/L
g/L
g/L
g/L

BIIPP project.
Dunn et al. (2012).
Adapted from Pereira et al. (2010).

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D. Sebastio et al. / Bioresource Technology 208 (2016) 100109

Fig. 1. SuperPro Designer ethanol plant flowsheet.

of the life cycle inventory. The following sections include a detailed

technological description of the modelled process, the majority of
the required process inputs were tested within the BIIPP project
(see Table 1) and/or obtained from previous published and unpublished work (Marques et al., 2008a,b).

2.2.1. Neutralisation and enzymatic hydrolysis

Belt conveyors (Fig. 1) were used to feed the pulp and paper
sludge into the enzymatic hydrolysis tanks. Due to a high percentage of CaCO3 in the sludge, HCl was added for neutralisation. This
step is a specificity of this raw material and it is not necessary in
other processes using lignocellulosic materials. The enzymatic
hydrolysis and the neutralisation of 55% of the CaCO3 present in
the sludge (using commercial fuming 37% w/w-HCl, corresponding
to 78% of the stoichiometrically required amount) were modelled
to occur in 3 tanks working in parallel (Fig. 1), under the following
conditions: 13% (w/v) solids loading, temperature of 50 C and
using 20 FPU/g carbohydrates of a commercial enzyme preparation
(dosage which showed enzymatic hydrolysis yields above 80%,
independently of neutralization, corresponding to 25 kg enzyme/
dry ton of biomass). The hydrolysis duration was modelled for
36 h (value optimised according with previous laboratory
experiments and including 1 h for loading and 1 h for unloading).
The cellulose and hemicellulose hydrolysis efficiencies were set
to 90% and 70%, respectively, of maximal theoretical yields (based

on experimental data). In order to simplify the model, all the

hydrolysed hemicellulose was considered to be xylose.
2.2.2. Concentration
After the hydrolysis a belt filter press (Fig. 1) was used to
remove the unconverted solids. The remaining solids composition
was calculated to be 47% CaCO3, 18% cellulose, 13% hemicellulose,
7% lignin and 15% other solids. This filtration cake had 70% moisture content and was recycled to the WWT of the pulp and paper
mill. This is further explained in Section 2.3.1.
The hydrolysate was then evaporated considering a multipleeffect evaporator (Fig. 1) to achieve a concentration of 130 g sugars/L before fermentation. The hydrolysate leaved the evaporator
with a temperature of 40 C and it was mixed with the other input
streams in the fermentation and hydration steps.
2.2.3. Fermentation
Fermentation occurred in 3 fermenters working in parallel
(Fig. 1) at a temperature of 35 C and during 36 h (including 1 h
for loading and 1 h for unloading). Active dry yeast (Ethanol Red,
Fermentis) was assumed to be bought according to the production
needs, rehydrated in the factory using the hydrolysate wort and
used as fermentation inoculum. A rehydration tank (Fig. 1) was
modelled to obtain a yeast inoculum with an initial concentration
of 0.5 g dwb/L. The fermentation media used was assumed to have

D. Sebastio et al. / Bioresource Technology 208 (2016) 100109

a composition similar to the work of Pereira et al. (2010) and

adjusted proportionally to the concentration of carbon source in
this work (see Table 1). A 100% carbon conversion was assumed
for glucose (ethanol yield 90%, biomass yield 5% and maintenance
using 5% of carbon) and in the base case scenario xylose was not
used.
Yeast purchase from outside suppliers is the current practise in
most of the ethanol production facilities and was adopted in this
work.
2.2.4. Downstream processing
After fermentation, a belt filter press (Fig. 1) was used to separate the yeast biomass from the fermentation broth. A final moisture content of 65% was assumed for the rejected biomass.
Purification of ethanol was modelled in two distillation columns and a molecular sieves unit (Fig. 1). The distillation design
was based on a National Renewable Energy Laboratory (NREL)
2011 report (Humbird et al., 2011). The molecular sieves unit separates the azeotropic mixture of water and ethanol, leaving the
second distillation column, achieving in the end 99.5%-bioethanol.
2.2.5. Optimisation scenarios
Additionally to the base case scenario described in the previous
section, two different optimisation scenarios were developed. The
scenarios were: (i) reduced HCl usage in the neutralisation; and
(ii) co-fermentation of glucose and xylose. Table 2 depicts the main
ethanol process model parameters of the different scenarios under
consideration in this study.
2.2.5.1. Reduced HCl usage. To construct this optimisation scenario,
the commercial 37%-w/w HCl fed to the hydrolysis tanks was
reduced to half (from 78% to 39% of the stoichiometric proportion).
This reduction diminished both cellulose and hemicellulose
hydrolysis yield by 5% (assumption based on enzymatic hydrolysis
experiments performed with pulp and paper sludge from different
industries and with neutralised and non-neutralised paper sludge)
and the amount of CaCO3 neutralised, in proportion with the base
case scenario (see Table 2).
2.2.5.2. Co-fermentation. The other optimisation scenario focused
on an efficient co-fermentation of glucose and xylose. In this scenario, it was assumed the usage of a recombinant yeast (cV-40,
Terranol (Olofsson, 2014)) able to ferment C5 sugars. The initial
inoculum concentration was increased to 1 g dwb/L (according
with (Olofsson, 2014)) and the fermentation time kept at 36 h.
The xylose consumption was assumed as 100% (ethanol yield of
90% and maintenance using 10% of carbon).

Table 2
Main parameters of the three modelled cases for ethanol production from pulp and
paper sludge.
Base
case
Hydrolysis time (h)
Solids loading (%)
Cellulose hydrolysis yield (%)
Hemicellulose hydrolysis yield
(%)
Hydrolysis temperature (C)
Enzyme Dosage (FPU/
g carbohydrates)
HCl loading (stoichiometric %)
Fermentation time (h)
Yeast inoculum (g dwb/L)
Glucose fermentation yield (%)
Xylose fermentation yield (%)
Fermentation temperature (C)

Reduced HCl
usage

Cofermentation

36
13
90
70

36
13
85
65

36
13
90
70

50
20

50
20

50
20

78
36
0.5
100
0
35

39
36
0.5
100
0
35

78
36
1
100
100
35

103

2.3. Life cycle assessment

2.3.1. Goal and scope
The purpose of this study was to identify and assess the potential environmental impacts associated with the production of
bioethanol from pulp and paper sludge in order to obtain a complete picture of the environmental performance of the proposed
system, identify the environmental hotspots and propose improvements. The hotspots were determined by evaluating the contribution of the different raw materials, process phases and emissions to
the overall environmental performance of the system. Two
improvements were proposed: reduced HCl and co-fermentation
scenarios (see descriptions in Section 2.2.5) and their environmental benefits analysed.
A cradle-to-gate LCA of the system was performed. The sludge is
a waste resulting from the production of pulp and paper and no
impacts were associated with this waste for the production of
bioethanol (this is the procedure typically followed for the evaluation of systems that use wastes as raw materials EU directive
2009/28/CE). The analysed system represents the valorisation of
the sludge into a biofuel and all the impacts connected with the
sludge were assumed to be allocated to the pulp and paper plant.
Additionally, the amount of sludge not converted for the production of bioethanol was assumed to be recycled back to the WWT
unit and is therefore not accounted as a waste emission of the process under study (Fig. 2).
System boundaries (Fig. 2) account for all the process stages in
the ethanol plant (Fig. 2, blue boxes), production of the ancillary
chemicals (Fig. 2, white boxes) especially the enzyme and yeast
needed. The main process stages and their processes and ancillary
chemicals are: (1) neutralisation and hydrolysis (includes enzymatic hydrolysis, CaCO3 neutralisation and the production of the
enzyme and HCl needed); (2) concentration (includes the belt filter
press, further wet solid processing and the evaporation) (3) fermentation (includes yeast production and rehydration, fermentation supplements production and the hydrolysate fermentation)
and (4) DSP (includes the belt filter press and further wet solid processing, the distillation and the dehydration). The functional unit
(FU) was defined as 1 MJ of bioethanol produced. An energy based
FU allows for the unbiased comparison of fuels with different heating values (ethanol and gasoline) (Daystar and Treasure, 2015), justifying the choice for this work.
2.3.2. Life cycle inventory
Inventory data for the sludge processing to bioethanol was generated using SuperPro Designer as described in the previous section (Section 2.2). Inventory data for the ancillary chemicals and
heat and power inputs production was collected from Ecoinvent
3.1 database, except for CSL (used in the production of the enzyme
and as supplement to the fermentation) which was collected from
the Agri-footprint database (Blonk Agri-footprint, 2014). The life
cycle inventory (materials and energy balances) for the production
of the enzyme and yeast was based on the work of Dunn et al.
(2012) (see Table 1). The infrastructures production impacts were
not considered due to their large throughput and long useful life.
The electricity and heat needed were considered as coming
from a cogeneration unit, present at the pulp and paper mill, using
wood chips as fuel. The cooling water was not included in the LCA
because river water is typically used by pulp and paper mills and
later returned to the river having no impacts associated.
The carbon dioxide released during the fermentation step was
accounted as biogenic having therefore no impact associated as
described by the EU directive 2009/28/CE and other LCA guidelines,
since also no sequestration of carbon was considered during biomass production. This carbon dioxide released during fermentation
of sugars is highly pure and often sold for the beverage industry,

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D. Sebastio et al. / Bioresource Technology 208 (2016) 100109

Fig. 2. LCA system boundaries for the bioethanol production process. No impact was associated with biogenic carbon emissions.

for manufacturing dry ice among other applications (Bothas and

Schlicher, 2005). The solid waste collected in the process was considered as sent to landfill and the liquid effluents treated in a WWT
plant (Fig. 2).
Table 3 presents the life cycle inventory for the three studied
scenarios.
2.3.3. Life cycle impact assessment (LCIA)
SimaPro 8.0.4.26 was used together with the CML-IA impact
assessment method to calculate the following impacts: abiotic
depletion, global warming (GWP100a), ozone layer depletion
(ODP), human toxicity, fresh water aquatic ecotoxicity, marine

aquatic ecotoxicity, terrestrial ecotoxicity, photochemical oxidation, acidification and eutrophication.

2.3.4. Sensitivity analysis assuming variations of the feedstock
composition
The sludge composition described in Section 2.1 was chosen in
this study as model composition of a sludge sample studied for
bioethanol production. As reported before, the composition of the
sludge depends on the operation conditions of the pulp and paper
mill. The main variables that affect the sludge composition in a
pulping process are the bleaching extent (removal of lignin during
the production of the pulp) and the addition of carbonate. So if

Table 3
Life cycle inventory for the production of 1 MJ of bioethanol for the three modelled cases.
Base case
Neutralisation and hydrolysis

Concentration

Fermentation

Downstream processing

Inputs
Sludge (kg)
HCl (37% w/w) (kg)
Water (kg)
Enzyme (kg)
Belt conveyors (kW h)
Hydrolysis tanks agitation (kW h)
Hydrolysis tanks heating (MJ)
Outputs
Carbon dioxide
Inputs
Evaporator heating (MJ)
Outputs
Wastewater
COD (kg)
Volume (m3)
Inputs
CuSO4
5H2O (kg)
Urea (kg)
Magnesium sulphate (kg)
CSL (kg)
Yeast (kg)
Fermenters agitation (kW h)
Hydration tank agitation (kW h)
Outputs
Biogenic carbon dioxide* (kg)
Inputs
Distillation columns heating (MJ)
Outputs
Wastewater
COD (kg)
Volume (m3)
Solid to landfill (kg)

Biogenic carbon dioxide had no impacts associated.

Reduced HCl

4.37  10
8.31  10
4.86  10
4.46  10
4.37  10
1.26  10
8.72  10

1.31  10

6.91  10

1.09  10

4.27  10

4.43  10

3.52  10

1.37  10
1.76  10

1.38  10
2.30  10

1.14  10
1.46  10

7.49  10
5.74  10
4.63  10
1.11  10
3.60  10
3.35  10
7.99  10

2
1
3
4
2
2

4
4
2
4
3
8

4.63  10
4.40  10
3.87  10
4.71  10
4.63  10
1.33  10
9.32  10

7.48  10
5.74  10
4.63  10
1.10  10
3.60  10
3.35  10
8.07  10

Co-fermentation

2
1
3
4
2
2

6
4
4
2
4
3
8

3.63  10
6.91  10
4.06  10
3.70  10
3.63  10
1.05  10
7.25  10

7.43  10
5.70  10
4.60  10
1.10  10
5.99  10
2.80  10
1.33  10

1
2
1
3
4
2
2

6
4
4
2
4
3
7

3.74  10

3.73  10

3.71  10

6.23  10

6.36  10

5.30  10

3.40  10
7.42  10
1.02  10

3.38  10
7.38  10
1.02  10

1.49  10
6.11  10
1.01  10

4
3

4
3

4
3

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D. Sebastio et al. / Bioresource Technology 208 (2016) 100109

Table 4
Life cycle impact assessment results for the three modelled cases and all impact categories using the CML-IA method.
Impact category
Abiotic depletion
Abiotic depletion (fossil fuels)
Global warming (GWP100a)
Ozone layer depletion
Human toxicity
Fresh water aquatic ecotox.
Marine aquatic ecotoxicity
Terrestrial ecotoxicity
Photochemical oxidation
Acidification
Eutrophication

Unit
kg Sbeq
MJ
kg CO2eq
kg CFC-11eq
kg 1,4-DBeq
kg 1,4-DBeq
kg 1,4-DBeq
kg 1,4-DBeq
kg C2H4eq
kg SO2eq
kg PO34eq

during the pulping process more carbonate is added and the degree
of bleaching is low, the concentration of sugars present in the
sludge is lower when compared with the opposite operation
conditions.
In order to understand the importance of the sludge composition in the life cycle assessment results, two extreme cases of
sludge composition were considered (they correspond to actual
sludge samples analysed by the authors): in the first one, the mill
was producing bleached pulp with a lignin content close to zero
and no carbonate was added, this corresponded to a sludge composition of: 74% cellulose, 18% hemicellulose, 2% lignin, 1% other
organics and 5% sands; in the second one, the mill was producing
unbleached pulp with no removal of lignin and with carbonate
addition, this corresponded to a sludge composition of: 14% cellulose, 3% hemicellulose, 12% lignin, 70% CaCO3 and 1% sands). Both
cases were simulated in SuperPro Designer using the same parameters as the base case and all the impact categories were calculated
for the production of bioethanol using these two sludge compositions as input.
3. Results and discussion
Bioethanol production using pulp and paper sludge was modelled in SuperPro Designer. Three different scenarios were analysed
with the objective of identifying possible system improvements.
Co-fermentation and the base case scenario allowed for a sludge
conversion which represents a 71%-reduction of the initial pulp
and paper sludge (it is the percentage difference between the initial sludge and the remaining sludge in the end of the process),
whereas the reduced HCl scenario allowed for 60%-reduction. This
aspect brings an important benefit for the pulp and paper mills by
reducing the sludge landfilled every year. Additionally, the valorisation of this sludge within the pulp and paper plant not only benefits from its onsite availability, with minor impacts of
collection/transportation, but also from some of the facilities
required in a bioethanol plant, such as low-grade heat, materials
handling equipment and skilled personnel.
The environmental impacts of the system were calculated using
the inputs described in Section 2.3.2 in order to obtain a complete
picture of the environmental performance of the system, identify
its environmental hotspots and propose two optimisation scenarios able to decrease the impacts. Table 4 presents the LCIA results
for all the three modelled scenarios and all the impact categories of
the CML-IA impact assessment method. As expected, the optimised
scenarios resulted in a decrease of the environmental impacts.
These results in terms of GWP are comparable with results published in the literature for bioethanol production, as they fall
within the ranges reported in the literature for both first and second generation biofuels (see Section 1). Comparisons with other
published studies are difficult due to different assumptions when
modelling the process. Lower GWP values are usually reported

Base case

Reduced HCl
7

3.72  10
7.83  10 1
7.17  10 2
1.72  10 8
4.92  10 2
2.68  10 2
6.62  101
3.26  10 4
4.12  10 5
5.75  10 4
8.56  10 4

2.44  10
6.27  10 1
5.50  10 2
1.12  10 8
3.61  10 2
1.95  10 2
4.70  101
2.19  10 4
3.86  10 5
5.06  10 4
8.28  10 4

Co-fermentation
3.12  10 7
6.69  10 1
6.12  10 2
1.44  10 8
4.12  10 2
2.26  10 2
5.57  101
2.69  10 4
3.47  10 5
4.91  10 4
7.20  10 4

for second generation bioethanol when waste streams (generated

within the bioethanol production systems) are used for energy
recovery, which was not considered in the present study (by burning the wet fermentation wastes, 65% moisture, it could be possible
to obtain 8210.73 kW h/year of electricity).
From the results on abiotic depletion of fossil fuels, it is shown
that the production of 1 MJ of bioethanol from sludge requires less
than 1 MJ of fossil fuels (for all three scenarios). This is extremely
important since it reveals that there is a net gain in terms of energy
in this production process, in agreement with other published
studies (von Blottnitz and Curran, 2007).
There are few studies available that report other impact categories, besides GWP and abiotic depletion. Janssen et al. (2014)
reports photochemical oxidation of 4.52 8.31  10 5 kg C2H4eq/
MJ bioethanol and acidification of 6.18 9.56  10 4 kg SO2eq/MJ
bioethanol using wheat straw as raw material, both higher from
the ones obtained in the present study. Higher values are typically
found for biofuels that rely on agricultural raw materials (even lignocellulosic materials) due to the use of fertilisers and other agricultural activities with high contributions to acidification and
eutrophication impact categories.
The results obtained for the environmental impacts depend, in
part, on the bioethanol yields from of each scenario. The base case,
the reduced HCl and the co-fermentation scenarios had bioethanol
yields of 0.21, 0.19 and 0.25 kg/dry kg biomass, respectively (corresponding to 5.54, 5.23 and 6.66 MJ/dry kg biomass, respectively).
The reported yields are in the same range of the yield reported
by NREL for a co-fermentation process of bioethanol production
using corn stover with a yield of 0.23 kg/dry kg biomass (6.28 MJ/
dry kg biomass). Inbicon A/S demonstration plant reports a
bioethanol yield of 0.15 kg/dry kg biomass (4.16 MJ/dry kg biomass) only from cellulose (Larsen et al., 2012), lower than any
result here presented. Wang et al. (2012) reported higher yields,
of 0.29 kg/dry kg biomass (7.88 MJ/dry kg biomass), which are closer to the maximum theoretical yields of both the present study
and the NREL report (0.33 and 0.31 kg/dry kg biomass or 8.82
and 8.26 MJ/dry kg biomass, respectively considering C6/C5 cofermentation).
Figs. 3 and 4 show the contribution of the different bioethanol
production stages to the final results.
Fig. 3 shows the results obtained with the base case for all the
impact categories. It shows that neutralisation and enzymatic
hydrolysis (both performed in the same reactor) have the highest
impact in almost all categories. The exceptions are photochemical
oxidation and eutrophication where DSP is the most contributing
step. For the photochemical oxidation the main contributor is the
production of the heat needed for the system, because the cogeneration with wood chips emits carbon monoxide that is responsible for photochemical ozone formation and 52% of the total
impact of this category. Other contributions include sulphur dioxide emitted in the HCl production process (25% of the total

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D. Sebastio et al. / Bioresource Technology 208 (2016) 100109

Fig. 3. Base case life cycle impact assessment results for all impact categories per MJ of bioethanol using the CML-IA method.

Fig. 4. Contribution of the main sections of sludge-to-bioethanol plant towards abiotic depletion, global warming potential, acidification and eutrophication impact results
for the three modelled cases per MJ of bioethanol using the CML-IA method.

impacts). Regarding the eutrophication, the WWT of the DSP

effluents is the main contributor.
Fig. 4 shows the results for the four impact categories that were
chosen to be analysed more thoroughly. GWP and abiotic depletion
of fossil fuels were chosen because they are highly reported in the
literature. Acidification and eutrophication impact categories were
chosen because usually comparing with oil derived fuels, biofuels
production shifts environmental burdens, from GWP to acidification and eutrophication among others (Daystar and Treasure,
2015; Uihlein and Schebek, 2009). This burden shifting causes significant challenges in the interpretation of the environmental

results but will be significant as the demand for biofuels increase,

increasing also the amount of biomass, water, air and ancillary
chemicals needed. These impacts however are sometimes
neglected by other LCA studies. It can also be seen in Fig. 3 that
these two impact categories have the major variances in terms of
contribution by the different processes.
The reduced HCl scenario performs better for the majority of
the impact categories analysed except for photochemical
oxidation, acidification and eutrophication categories where the
co-fermentation scenario appears with lower impacts (Table 4
and Fig. 4).

D. Sebastio et al. / Bioresource Technology 208 (2016) 100109

Regarding the GWP impact, the reduced HCl scenario and the
co-fermentation scenario had a reduction of 23% and 15%, respectively, when compared with the base case scenario. The two scenarios, reduced HCl and co-fermentation, revealed, respectively:
20% and 15% reduction for the abiotic depletion of fossil fuels;
12% and 15% reduction for the acidification; and 3% and 16% reduction for the eutrophication. Additionally, the combination of both
optimised scenarios could lead to further decrease of the impacts,
e.g. an overall reduction in the GWP impact category close to 38%
(the combined effect will be subject to a decrease in the yield of the
co-fermentation due to the reduction of the degree of
neutralisation).
The lower impacts observed in the reduced HCl scenario are due
to the decrease of emissions associated with the neutralisation
stage (Fig. 5, representing the GWP impacts results for the three
analysed scenarios, where the neutralisation and enzymatic
hydrolysis part was separated in its components and the other process parts are grouped in the category Total Process). This figure
shows that both HCl production and neutralisation emissions are
the major contributors (more than 53% for the base case) to the
total GWP impact. Similar trends were depicted to the other
impact categories, except for photochemical oxidation, acidification and eutrophication. The HCl needed for the neutralisation of
the CaCO3 present in the sludge is the highest contributor to the
total environmental impacts. Any reduction in the HCl required
amount (without significantly affecting the ethanol output) will
increase the environmental performance of the system (as shown
by the results of the optimisation scenario). HCl is a hazardous
material and Uihlein and Schebek (2009) had already reported a
high contribution of its production to the environmental impacts
of a lignocellulosic biorefinery.
The atmospheric emissions (carbon dioxide), associated with
the neutralisation and enzymatic hydrolysis stage, are a consequence of the CaCO3 neutralisation. Therefore, the presence of this
compound in the sludge imposes a high impact on the overall environmental performance of the process, indicating that paper
sludge composition will influence the final results. The possibility
of performing a previous mechanical separation of the sludge fibre
and inorganic matter, as reported by Chen et al. (2014b), could also
decrease the higher impacts associated with the neutralisation
process, however as reported the fractionation can lead to carbohydrate losses.

107

The decrease of the impacts obtained with the co-fermentation

scenario (when compared with the base case) is a consequence of
the improved bioethanol production yield, from 0.21 kg/dry kg biomass (5.54 MJ/dry kg biomass) in the base case to 0.25 kg/dry
kg biomass (6.66 MJ/dry kg biomass). This led to a global reduction
of all the LCA impacts.
Additionally, to the neutralisation contributions to the overall
impacts, the production of enzymes appears also to have an important contribution with 21% of the total impacts in the base case,
29% in the reduced HCl scenario and 20% in the co-fermentation
scenario.
The contribution of enzymes production to the LCA of bioethanol is often disregarded in the literature. The results of the present
study show that this aspect can greatly alter the results of the environmental assessment. Few publications include enzyme production in their LCA as MacLean and Spatari (2009), Dunn et al.
(2012) and Janssen et al. (2014).
Dunn et al. (2012) also reported the importance of enzyme production to the overall environmental performance of lignocellulosic
ethanol. They also showed the dependence of the results on the
enzyme dose applied: (1) the enzyme production contributed with
5.6 g CO2eq/MJ to climate change when a dose of 10 kg enzyme/dry
ton of biomass is used in the hydrolysis, which represented the lowest dose provided by the industry (between 10 and 100 kg enzyme/
dry ton of biomass); (2) it contributed with 17 g CO2eq/MJ using
50 kg enzyme/dry ton of biomass. In the present work, the contribution of enzyme production to climate change was 15.2 g CO2eq/
MJ for the base case, and 16.0 g CO2eq/MJ and 12.5 g CO2eq/MJ for
the reduced HCl and co-fermentation scenarios, respectively, using
an enzyme dosage of 25 kg enzyme/dry ton of biomass. In the production of bioethanol from wheat straw, Janssen et al. (2014)
obtained a GWP of 0.124 kg CO2eq/MJ, which was much higher than
any of the results obtained in the present study. In their study, the
enzyme production was the life cycle stage that dominated the
environmental impacts. These results demonstrate that the enzyme
dosage optimisation is of vital importance.
Any improvement associated with the enzyme production and
hydrolysis can increase the environmental performance of any lignocellulosic bioethanol system, such as the system under study. To
achieve this, four options can be proposed: decrease enzyme
dosage, without a significant effect on hydrolysis yield and final
ethanol productivity (which could lead to higher environmental

Fig. 5. Contribution of the relative impacts from the different neutralisation and enzymatic hydrolysis components towards global warming potential impact, using the CMLIA method, for the three modelled cases per MJ of bioethanol.

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D. Sebastio et al. / Bioresource Technology 208 (2016) 100109

impacts); improving enzyme production process; apply enzyme

recycling (Weiss et al., 2013); employ recombinant yeasts harbouring hydrolytic enzymes, which may reduce ethanol yield and productivity but eliminates the enzyme production step. Enzyme
recycling after hydrolysis of lignocellulosic materials is under
development and could allow for lower enzyme dosages, reflecting
on reduced costs and environmental impacts (Qi et al., 2012; Weiss
et al., 2013). Alternatively, in a more disruptive way, a significant
improvement in the LCA impacts can be attained if enzyme utilisation can be eliminated or drastically reduced, e.g., by employing
novel integrated low-energy biomass pre-treatment and fermentation using combined bioprocessing strains that avoids the use of
enzyme production either exogenous or in situ.
Other improvements could also be achieved by: (1) producing
the required enzyme on the bioethanol plant using the same carbon source (pulp and paper sludge) and benefiting from the better
environmental performance of the heat and electricity being used
by the process (CHP of biomass); (2) the use of waste streams
(e.g. lignin, remaining fibbers, yeasts and COD in the wastewater)
for energy recovery or valorisation.
It should be also taken into account, that paper sludge composition depends on the paper manufacture and WWT process at the
pulp and paper mill, and even varies along each pulping process
(due to often chemicals adjustments). Boni et al. (2004) reported
a primary sludge from the production of virgin wood fibre with
40.5% of CaCO3 dry content (with water content off 88.3%).
Monte et al. (2009) reported sludge similar to the one under study,
a mineral content (clay and calcium carbonate) ranging from 5% to
25% dry content and 4060% of cellulose fibre. In the current study
two extreme cases of sludge composition were considered (as
explained in Section 2.3.4), one resulting from the production of
bleached pulp and the other resulting from unbleached pulp. In
the first case, the bioethanol yield obtained was 0.30 and in the
second one 0.05 kg/dry kg biomass (8.05 and 1.40 MJ/dry kg biomass, respectively). This resulted in the following LCA results (for
the first and second cases, respectively): for abiotic depletion
3.67  10 1 and 4.52 MJ/MJ bioethanol, for global warming
2.98  10 2 and 4.39  10 1 kg CO2eq/MJ bioethanol, for acidification 3.30  10 4 and 3.02  10 3 kg SO2eq/MJ bioethanol and for
eutrophication 6.06  10 4 and 3.59  10 3 kg PO34eq/MJ bioethanol. The sludge originating from the bleached pulp mill has lower
impacts in all categories even when comparing with the optimised
cases presented in this work. This mainly results from the avoidance of HCl usage and from the higher sugars composition (which
resulted in higher conversion yields). The sludge originating from
the unbleached pulp mill has higher impacts, in one order of magnitude, when comparing with the base case, as a result from higher
HCl use and from lower ethanol yields. As a conclusion, higher
environmental performances are obtained with sludge coming
from bleached pulp processes with the lowest addition of carbonate possible. This bleaching procedure allows for maximal sugar
content in the sludge, which can then be valorised with the proposed bioethanol production system.
4. Conclusions
The present study demonstrated that the use of pulp and paper
sludge for bioethanol production allows, simultaneously, for the
valorisation of this waste and to reduce its final amount. Hydrolysis and neutralisation of the CaCO3 are the environmental hotspots
of the system. Environmental benefits were demonstrated by lowering the amount of HCl used in the neutralisation step and the use
of a recombinant yeast able to co-ferment glucose and xylose. The
ideal scenario for the future sludge-to-bioethanol plant would
include a combination of both optimised scenarios studied, with
high process efficiency and high environmental performance.

Acknowledgements
This work was funded by FEDER funds through Programa
Operacional Factores de Competitividade COMPETE and national
funds by FCT Fundao para a Cincia e a Tecnologia through
the
project
FCOMP-01-0124-FEDER-029055
(PTDC/EMSENE/1839/2012) Sustainable mobility: perspectives for the future
of biofuels production.
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