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food and bioproducts processing 9 9 ( 2 0 1 6 ) 58–70

Contents lists available at ScienceDirect

Food and Bioproducts Processing

journal homepage: www.elsevier.com/locate/fbp

Environmental impact assessment of


lignocellulosic lactic acid production: Integrated
with existing sugar mills

Asfaw Gezae Daful a,∗ , Kathleen Haigh a , Pavel Vaskan b ,


Johann F. Görgens a
aDepartment of Process Engineering, Stellenbosch University, Private Bag X1, Stellenbosch 7602, South Africa
bBioenergy and Energy Planning Research Group, GR-GN, INTER, ENAC, Station 18, EPFL, 1015 Lausanne,
Switzerland

a r t i c l e i n f o a b s t r a c t

Article history: Lactic acid (LA) is considered for the diversification and value addition to sugar industry in
Received 10 December 2015 South Africa, through a bioconversion of sugarcane bagasse and leaves. A bioconversion pro-
Received in revised form 4 April cess was modeled in Aspen Plus® V8.6 and its environmental impacts were evaluated using
2016 the Life Cycle Assessment method using SimaPro® considering its integration into exist-
Accepted 10 April 2016 ing South African Sugar mills. The life cycle approach took into account the whole sugar
Available online 16 April 2016 production chain, including sugarcane cultivation stage, harvesting and transportation of
sugarcane, sugar mill, and LA production. The life cycle inventories of the sugarcane culti-
Keywords: vation and sugar mill were obtained from literature while Aspen Plus® simulation data were
Lactic acid used for the LA production. The ecoinvent database of SimaPro® was used for all external
Environmental impacts inputs and fossil-based LA production. Environmental impacts of the biobased and fossil
Lignocellulose based LA productions were assessed and compared. The total environmental savings of the
Sugarcane bagasse major impact categories obtained upon replacing a tonne of fossil-based LA with biobased
Gypsum free LA are: 3925.65 kg CO2 eq. of global warming potential; 1742.05 kg fossil fuel eq. of abiotic
depletion potential; 1296.16 kg 1,4-DB eq. of human toxicity potential; 397.79 kBq U235 eq.
of ionizing radiation potential; 253.97 kg Fe eq. of metal depletion potential; 43.48 kg 1,4-DB
eq. of marine aquatic ecotoxicity potential; 42.97 kg 1,4-DB eq. of fresh water aquatic eco-
toxicity potential and 18.23 kg SO2 eq. of acidification potential. Auxiliary chemicals used
in the biobased LA production are most relevant to the total environmental impacts. Thus,
biobased LA production has significantly reduced the impact on the environment, giving
80–99% environmental savings compared to fossil-derived LA.
© 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction of the existing fossil based economy with a green economy


within the framework of sustainable development is one of
The ongoing depletion of petroleum reserves and the the challenges of our time. The environmental impacts of
associated environmental impacts are driving research to the growing demand for petroleum-derived chemicals and
investigate the potential substitution of the current petro- fuels can be mitigated by the use of lignocellulosic bio-
chemically derived building blocks with equivalent molecules chemicals and biofuels. Significant research efforts have been
from renewable resources (Avelino et al., 2007). Substitution directed to the conversion of such bio-derived feedstocks into


Corresponding author. Tel.: +27 617018907.
E-mail address: agezae@gmail.com (A.G. Daful).
http://dx.doi.org/10.1016/j.fbp.2016.04.005
0960-3085/© 2016 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
food and bioproducts processing 9 9 ( 2 0 1 6 ) 58–70 59

chemicals as a means to replace fossil-derived products, mit- bagasse by improving the energy efficiency of the existing
igate global warming and meet the societal needs for greener sugar mills (Rocha et al., 2011, 2012). In this way there is
products (Avelino et al., 2007). In this context, lactic acid the potential for the South African sugar industry to provide
(LA) has gained significant interest (Päivi et al., 2014). LA, about 10.6 million tonne of combined sugarcane bagasse
the simplest hydroxy carboxylic acid is a bulk chemical with and leaves (SCBL) as a lignocellulosic feedstock for biobased
two optically active enantiomers (d(−) and l(+)). LA is a plat- energy, chemical and material production, leaving the tops in
form chemical with wide industrial applications, in the food, the field for enriching the agricultural land. This development
chemical, pharmaceutical and health care industries (Abdel- is fueled by the potential they hold to reduce greenhouse gas
Rahman et al., 2013; Chao et al., 2011). It is primarily used emissions and to increase the security of raw material sup-
for food and pharmaceutical applications, preferentially the ply through the transition from fossil feedstocks to renewable
l(+) isomer since it is the only LA isomer produced in the and sustainably exploited biobased feedstocks. Moreover, this
human body (Martinez et al., 2013). LA can be used as feedstock leads to diversification of the sugar industry by integration of
to generate multiple commodity and intermediate chemi- LA production facility to better mitigate greenhouse gas (GHG)
cals (Päivi et al., 2014; Dusselier et al., 2013; Abdel-Rahman emissions and increase the environmental sustainability of
et al., 2013), such as acrylic acid, 1,2-propanediol, pyruvic the sector.
acid, acetaldehyde, and 2,3-pentanedione. These LA-based An Aspen plus® simulation has been developed to investi-
products and others may increase the world market share sig- gate LA production from lignocellulosic biomass SCBL, to be
nificantly, which includes the use of derivatives such as ethyl integrated with a typical South African sugar mill and a life
esters to replace hazardous solvents like chlorinated hydro- cycle Assessment (LCA) of the process has been conducted
carbon solvents in certain industrial applications. It can also based on the developed model. LCA studies of bioproducts
be polymerized into a novel biodegradable plastic suitable in the public literature are sparse and for biobased LA are
for packagings, i.e. polylactic acid (PLA). This polymer has a scarce. Hermann et al. (2007) developed LCAs of a number of
current global market demand of approximately 105 metric bioproducts produced from sugars sourced from corn, sugar
tonnes per annum and is anticipated to grow by at least 28% cane, or corn stover and concluded that, when corn stover is
per annum until 2025 (Cellulac) particularly given that PLA the feedstock, bioproducts can result in a 25% to nearly 100%
could replace polyethylene terephthalate (PET) in 20% of the reduction in GHG emissions when compared to their petro-
current applications (Päivi et al., 2014; Dusselier et al., 2013; chemical counterparts. Adom et al. (2014) conducted LCAs for
Abdel-Rahman et al., 2013). eight bioproducts produced from algal glycerol and from corn
LA can be produced either by anaerobic fermentation stover-derived sugars and determined GHG emission reduc-
(Wang et al., 2015; Abdel-Rahman et al., 2011, 2013; Rathin tions ranging from 39% for 1,3-propanediol to 86% for succinic
and Michael, 2006) or by chemical synthesis (Pal et al., 2009; acid compared with their fossil based equivalents. Similarly
Narayanan et al., 2004; John et al., 2007). The chemical syn- Lammens et al. (2011) showed 50% and 35% potential reduc-
thesis pathway (Martinez et al., 2013) produces an optically tions in GHG emissions for biobased N-methylpyrrolidone and
inactive racemic mixture (equal quantities of the l and d N-vinylpyrrolidone respectively compared with their petro-
isomers), while the anaerobic fermentation pathway gener- chemical counterparts. Cok et al. (2014) examined succinic
ally yields one of the two stereoisomers, depending on the acid production from corn-derived dextrose via cradle-to-gate
microorganism used. LA can be produced via fermentation of LCA and show a 90% reduction in GHG emissions compared
sugars from various types of biomass, including starch crops, with production from petrochemical feedstocks. Other LCA
sugar crops, and lignocellulosic materials and whey. Technolo- studies of biobased products focus on bioethanol (Borrion
gies to produce LA from lignocellulosic derived sugars are the et al., 2012; Raman and Gnansounou, 2015; Morales et al., 2015)
least advanced while the use of sugars from starch, sugar crops and bipolymers (Tsiropoulos et al., 2015; Hottle et al., 2013;
and whey are commercially available (Abdel-Rahman et al., Avolio et al., 2015; Pietrini et al., 2007). To the best knowledge
2011). of the authors, no LCA study has been carried out to assess the
Within South Africa, there is the potential to liberate lig- environmental impacts of LA production from lignocellulosic
nocellulosic feedstock from the sugar industry which could biomass. This paper focuses on lignocellulosic LA from SCBL
be converted to LA. Sugarcane bagasse is the solid residue and its environmental performances.
remaining after crushing the sugarcane to obtain the juice The aim of this paper is to present a quantitative evaluation
used for sugar production. In addition, current sugarcane har- of the environmental loads associated with the produc-
vesting practices involve burning the majority of the leaves tion of LA from lignocellulose biomass, SCBL, and compare
and tops, although in future these could be harvested sepa- this to the petrochemical equivalent via a cradle-to-gate
rately as a feedstock for production of value added products. LCA. In combination with the techno-economic assess-
An average of 20 million tonnes per year (SASA; Meyer and ment, this environmental impact assessment will help the
Fenwick, 2003) of sugarcane is crushed in the South African industry to consider replacing petrochemical products with
sugar industry which generates about 5.6 million tonnes of biobased ones and annexing such a facility to the exist-
bagasse. About 5 million tonnes of tops and leaves is burnt ing sugar mill in South Africa. Furthermore, it will indicate
in the sugarcane field during harvesting, emitting high levels weak points (hot spots) of the production process that need
of particulate matter, CO, NOx , SOx and CH4 (Leal et al., 2013), further investigation to reduce the overall environmental
that causes serious health problems for workers, who breathe impact.
in the soot while working, as well as those who live in nearby The paper is organized as follows. In Section 2, the produc-
areas. tion of LA from lignocellulosic residues (sugarcane bagasse
Sugarcane bagasse is currently used as a source of energy and leaves) and fossil feedstocks is described. The details of
for the sugar mills. It may be possible to satisfy the energy the LCA methodology and inventory used in this work are
requirements of the sugar mills with half of the produced given in Section 3, followed by Section 4 which provides an
60 food and bioproducts processing 9 9 ( 2 0 1 6 ) 58–70

Fig. 1 – An overview of LA production processes: (a) microbial fermentation from renewable recourses and (b) chemical
synthesis from non-renewable recourses.

analysis of the results. Finally, the paper finishes with Sec- and xylose, by means of hydrolytic enzymes, (c) fermentation-
tion 5, where the main conclusions are reviewed. metabolizing the sugars to LA using homolactic acid strains
(Tamakawa et al., 2012; Ying et al., 2014; Zhao et al., 2013) (d)
2. Lactic acid production separation and purification of LA – purification of LA to meet
the standards of commercial applications.
The two methods with industrial importance for the produc- A rigorous process model was developed for the produc-
tion of LA are microbial fermentation, and chemical synthesis tion of LA from sugarcane lignocelluloses in Aspen Plus® V8.6
as depicted in Fig. 1. Chemical synthesis from petrochemi- process simulation software. The Aspen Plus® model is based
cal resources always result in a racemic mixture of dl-lactic on literature data and includes the pretreatment, hydrolysis,
acid, while an optically pure d(−) or l(+) LA can be pro- fermentation and LA separation and purification as outlined
duced via microbial fermentation. Moreover, microbial LA in Fig. 2.
fermentation offers an advantage in terms of the utilization In this study, steam explosion pretreatment (Rocha et al.,
of renewable carbohydrate biomass, low production tem- 2012; Oliveira et al., 2013; Agbor et al., 2011) is used to fraction-
peratures, low energy consumption, and the production of ate the lignocellulosic matrix and break down the inter- and
optically high purity LA by selecting an appropriate strain. intra-molecular linkages so as to separate the hemicellulose
While homopolymer polylactic acid, PLA, forms regular struc- and improve the accessibility of the cellulose for enzymatic
tures and develops a crystalline phase, copolymerization with hydrolysis and fermentation. Fermentation of the dissolved
d(−) and l(+) LA leads to the interruption of the regular struc- liquid hemicellulose fraction and simultaneous saccharifi-
tures and the formation of amorphous materials. In order to cation and fermentation (SSF) of the cellu-lignin solid fraction
achieve the desired polymer properties, high purity d(−) or l(+) are modeled.
LA monomers are necessary (Yebo and Fengjie, 2010). Biobased During a typical LA fermentation, the low pH (due to LA
and fossil based LA production process are presented in Sec- production) has an inhibitory effect on the metabolic activities
tions 2.1 and 2.2 respectively. of the producing microbial cells (Hongo et al., 1986). The addi-
tion of Ca(OH)2 or CaCO3 to neutralize the LA is a conventional
2.1. Lactic acid from renewable resources operation to minimize the negative effects of undissociated
LA accumulation in industrial processes (Hongo et al., 1986;
The demand for LA has increased due to an increase in the Abdel-Rahman et al., 2013). However, additional operations
range of applications, with an increased focus on the use of are required to regenerate undissociated LA from its salt, Ca-
low-cost non-food materials for LA production. In this regard, Lactate, and to dispose of or recycle the neutralizing cation,
lignocellulosic biomass, SCBL, is a promising feedstock for LA by an acidification reaction with H2 SO4 . One prominent envi-
production considering its availability, sustainability, and low ronmental issue related to this manufacturing method is the
cost compared to refined sugars. However, the commercial use coproduction of large amounts of gypsum (∼1 tonne CaSO4
of lignocellulose for LA production is still challenging due to per 1 tonne of LA), which has to be discarded (Abdel-Rahman
its complexity. The major constituents of lignocellulose are et al., 2013) as waste resulting in high chemical cost and waste
cellulose, hemicellulose, and lignin polymers that are inter- generation. To overcome this environmental burden, in this
connected, hence the recalcitrance of this type of biomass work Mg(OH)2 is used as neutralizer which forms Mg-lactate
to biological conversions (Abdel-Rahman et al., 2011; Mazzoli (Krieken, 2012). The latter will react with triethylamine(R3 N),
et al., 2014; Benjamin et al., 2014). Eq. (1), forming Mg(OH)2 crystal and a triethylamine-LA com-
The conventional processes for producing LA from lig- plex, (R3 N-LA) in an exchange reactor referred as a SWAP
nocellulosic biomass, depicted in Fig. 1a, includes four reactor. The Mg(OH)2 crystal will be filtered and recycled
main steps (Taherzadeh and Karimi, 2008): (a) pretreatment back to fermentation (SSF in case of LA from cellu-lignin)
(Sreenath et al., 2001) – breaking down the structure of the and the triethylamine-LA complex will be thermally decom-
lignocellulosic matrix, (b) enzymatic hydrolysis – depolymer- posed to release LA where triethylamine will be recycled back
izing lignocellulose to fermentable sugars, such as glucose to the SWAP reactor, Eq. (2). The lignin residues and cell
food and bioproducts processing 9 9 ( 2 0 1 6 ) 58–70 61

Lignocellulose, SCBL

Steam
Explosion

Hemicellulose Cellu-lignin
liquid fraction Filtration
solid fraction

Mg(OH)2 Fermentation Mg(OH)2 SSF

Cell Lignin &


Filtration Filtration
removal Cell removal

Evaporation Evaporation
CHP
SWAP R3 N
SWAP R3 N
Filtration
Filtration
Decomposition
Decomposition

Separation &
Purification

Lactic
Acid

Fig. 2 – A process flow chart for LA production from lignocellulosic biomass materials, sugarcane bagasse, leaves and tops
(SCBL).

pellets are used as energy in the combined heat and power distillation and recycled back (ETOH-REC) to the esterification
plant(CHP). section.

Mg-Lactate + R3 N → Mg(OH)2 ↓ +R3 N-LA-Complex (1) [Esterification]


C3 H6 O3 + C2 H5 OH  C3 H5 O3 C2 H5 + H2 O (3)
Lactic acid Ethanol [Hydrolysis] Ethyl lactate Water

R3 N-LA-Complex → R3 N + Lactic acid (2)

2.2. Lactic acid from non-renewable resources


The recovery of LA from the fermentation broth is difficult
because of its low volatility and the presence of nonvolatile
The commercial process for chemical synthesis from fossil
impurities and other organic acids. Several processes for the
fuels is based on lactonitrile (Wee et al., 2006), CH3 CH(OH)CN
recovery of LA from the fermentation broth have been stud-
as shown in Fig. 1b. Feedstock preparation involves extraction
ied and reported such as electrodialysis (Hábová et al., 2004;
of crude oil and refining to produce ethane. Ethane is then used
Wee et al., 2005), nanofiltration (González et al., 2008; Pal
to make ethylene and which is then converted to acetalde-
et al., 2009), adsorption (Sena et al., 2011), solvent extraction
hyde, CH3 CHO, as depicted in Eq. (4). Acetaldehyde is used as
(Udachan and Sahoo, 2014), membrane separation (Gudena
a raw material to produce lactonitrile (acetaldehyde cyanohy-
et al., 2013), ion-exchange resins (González et al., 2006), and
drin) by a catalytic reaction of acetaldehyde with hydrogen
reactive distillation (Chien-Yuan et al., 2013; Mo et al., 2011).
cyanide (HCN) in the presence of a base catalyst under high
Reactive distillation (Taylor and Krishna, 2000; Gezae Daful,
pressure, Eq. (5). Crude lactonitrile is then purified by distil-
2012) was found to be promising at the industrial scale, with
lation and subsequently hydrolyzed to LA, Eq. (6), by H2 SO4
some cost advantages (Chien-Yuan et al., 2013) and thus two-
(Pal et al., 2009; Narayanan et al., 2004). LA is then esterified
step reactive distillation processes are modeled in the present
using methanol to produce methyl lactate, Eq. (7), which is
work. LA recovery involves two catalyzed reversible reactions,
removed and purified by distillation and hydrolyzed by water
esterification and hydrolysis, as shown in Eq. (3). As depicted
under acid catalyst to produce LA and the methanol, Eq. (8),
in Fig. 3, in the esterification column LA from the fermentation
which is recycled. The chemical synthesis route produces a
broth is converted to the more volatile ethyl ester (ETLA) using
racemic mixture of dl-lactic acid whereas in most of the cases,
ethanol and this ethyl ester is then removed from the col-
l-lactic acid is the preferred product.
umn by distillation. Pure LA, (99 wt.% l(+) LA) is subsequently
recovered by hydrolysis of the ester with water, in a hydrol-
ysis reactive distillation column. The ethanol from the top
of hydrolysis reactive distillation will be purified by normal Crude oil → Ethane → Ethylene → acetaldehyde (4)
62 food and bioproducts processing 9 9 ( 2 0 1 6 ) 58–70

Fig. 3 – Process flow sheet for the purification of crude LA from the fermentation broth via reactive distillation columns.

1. Addition of hydrogen cyanide and catalyst comparison purposes. The LCA for biobased LA production
covers the environmental impacts for all processes up to the
[catalyst] point where LA leaves the factory gate and includes all raw
CH3 CHO + HCN → CH3 CH(OH)CN (5)
Acetaldehyde Hydrogen cyanide Lactonitrile materials and emissions of sugarcane cultivations, sugar mill,
industrial activities related to auxiliary chemicals, distribu-
2. Hydrolysis by H2 SO4 tion of raw materials, processing of sugarcane bagasse and
harvest residues (brown leaves) into LA. The system bound-
1
CH3 CH(OH)CN + 2H2 O + H2 SO4 → CH3 CHOHCOOH ary is thus described as a “cradle-to-gate” analysis including
Lactonitrile 2 Lactic acid
sugarcane cultivation, harvesting and transport, sugarcane
1 milling, auxiliary chemicals production, harvesting, trans-
+ (NH4 )2 SO4 (6)
2 Ammonium salt port, and production of LA as depicted in Fig. 4. All external
inputs are also included in the background processes for the
production and delivery of fertilizers, pesticides, electricity,
3. Esterification
harvesting and transport. Farm machinery and infrastructure
as well as the sugar mill infrastructure have not been included
CH3 CHOHCOOH + CH3 OH → CH3 CHOHCOOCH3 + H2 O
Lactic acid Methanol Methyl lactate as the large throughput and long lifetimes of farm and sugar
(7) mills make the impacts of their establishment and decom-
missioning per unit of product output insignificant (Renouf,
2006). To perform the LCA the intermediate products at each
4. Hydrolysis by H 2O stage require an allocation. For this study, allocation and sys-
tem expansion were relevant for all production units within
CH3 CHOHCOOCH3 → CH3 CHOHCOOH + CH3 OH (8) the system boundary considered. An economic allocation is
Methyl lactate Lactic acid Methanol
applied for the sugar mill among the products sugar, molasses
and bagasse. System expansion is used for accounting the
3. Methodology of Life Cycle Assessment avoided environmental impacts of fossil based LA production
upon replacing it with biobased LA.
The potential environmental impacts of a lignocellulosic The biobased and fossil based LAs are assumed to be func-
biomass based LA process have been investigated by means tionally equivalent because they can be used in the same
of a Life Cycle Assessment (LCA) (Guinée et al., 2004). An LCA way. All resources, refers to the consumption and depletion of
was carried out for L(+) lactic acid (LA) from lignocellulosic
SCBL and compared with fossil-based LA, as described in Sec-
tions 2.1 and 2.2 respectively. The LCA complies with ISO (ISO,
2006a,b) standards, consisting of four stages: goal and scope
definition, inventory analysis, impact assessment and inter-
pretation.

3.1. Goal and scope definition

In this section, the system boundaries, reference system, func-


tional unit, level of detail, the impact categories and the
allocation method are identified. The goal is to assess the
potential environmental impacts of an LA production process
unit annexed to an existing South African sugar mill which
is represented using a generic sugar mill and consider how
this compares to fossil based LA production. Thus the func-
tional unit is 1 tonne of LA at the factory gate, in South Africa.
Though a racemic mixture of dl-lactic acid is obtained from
the fossil resources while the biobased LA produced in this Fig. 4 – System boundary for a biobased LA production,
work is an optically pure l(+)-lactic acid (as discussed in Sec- that comprises sugarcane cultivation including collection
tion 2), it is assumed that both have similar functionality for and transportation, sugar mill and LA production.
food and bioproducts processing 9 9 ( 2 0 1 6 ) 58–70 63

approximately 400,000 ha and delivered to 15 factories vary-


Table 1 – Environmental impact categories considered
for comparison of biobased LA and fossil based LA ing in size between 90 and 550 tonnes per hour, with an
production for the LCA study. average of 300 tonnes per hour or 1.5 million tonnes of sugar-
cane per annum (Mashoko et al., 2010, 2013; Smithers, 2014).
Symbol Description
The South African sugar industry is diverse in location, typ-
ADP Abiotic depletion potential measured in kg of ical sugarcane cultivation, that can be representative of the
Substance eq. diverse cultivation practices that differs from place to place is
AP Acidification potential measured in kg SO2 eq.
considered. Data covering the inventory analysis of such typi-
FWEP Freshwater eutrophication potential measured in kg
PO3−
cal sugarcane cultivation is derived from literature (Smithers,
4 eq.
MEP Marine eutrophication potential measured in kg NO− 2014; SASA; Mashoko et al., 2010, 2013; Groot and Borén, 2010;
3
eq. Ramjeawon, 2004) and the South African Sugarcane Research
GWP Global warming potential measured in kg CO2 eq. Institute (SASRI), as depicted in Table 2. Only 20% of the sug-
ODP Ozone layer depletion potential measured in kg arcane cultivation area and 35% of the sugarcane produced
CFC-11 eq. (chlorofluorocarbon)
are under irrigation as most of the cane areas rely on rain-
HTP Human toxicity potential measured in kg 1,4-DB eq.
fall (Mashoko et al., 2010). The total fossil energy required for
(DB:dichlorobenzene)
FWAETP Fresh water aquatic ecotoxicity potential measured in farming purposes is 38.65 (Mashoko et al., 2010) MJ/tonne of
kg of 1,4-DB eq. sugarcane produced.
MAETP Marine aquatic ecotoxicity potential measured in kg
1,4-DB eq. 3.2.2. Sugarcane milling
TETP Terrestrial ecotoxicity potential measured in kg 1,4-DB The assessment has been carried out based on a typical South
eq.
African sugar mill with an intake of sugarcane to produce raw
POCP Photochemical oxidation potential measured in kg
sugar, molasses, and electricity. An average sugar mill with an
C2 H4 eq.
MDP Metal depletion potential measured in kg Fe eq. average sugarcane throughput of 300 tonnes/h over an eight
IRP Ionizing radiation potential measured in kBq U235 eq. to nine month crushing season during which time the mills
PM Particulate matter formation potential measured in kg operate continuously has been considered (Mashoko et al.,
PM10 eq. 2010). Relevant literature data (Mashoko et al., 2010, 2013) are
WDP Water depletion potential measured in m3 water used summarized in Table 3.
ALO Agricultural land occupation measured in m2 a
The resource inputs for production (Mashoko et al., 2010,
ULO Urban land occupation measured in m2 a
NLT Natural land transformation measured in m2
2013) of 1 tonne of raw sugar are 846 tonnes of sugar cane,
17,000 m3 raw water, 0.15 ha of land. Emissions to soil from
production of 1 tonne of raw sugar include 368 kg of ashes and
abiotic and biotic resources, used by all process units depicted
silage and 0.03 kg of hazardous waste. The emissions to air and
in Fig. 4 and their respective emissions to air, water and solid
water per tonne of raw sugar produced is depicted in Table 3.
wastes are considered.
Two byproducts with annual mean (Mashoko et al., 2013) of
As can be observed from Fig. 4 there are different blocks in
0.38 tonne of molasses and 0.56 tonne of filter cake per tonne
the system boundaries: Sugarcane cultivation and harvesting
of raw sugar produced are considered. An economic allocation
phases including sugarcane transportation block, sugar mill
was applied to emissions and their associated environmen-
block and the LA production block, and all associated inputs
tal impacts from the sugar mill among the different products,
and emissions.
raw sugars, molasses and bagasse based on their respective
The software package SimaPro® v8.0 and ReCiPe Mid-
market prices (760, 250, 7$/tonne, for raw sugars, molasses
point(H) methodology were used as tools for the envi-
and bagasse respectively) (Dias, 2011). The integrated system
ronmental impact assessment. The environmental impacts
of sugar mill and LA production is energy self-sufficient and
the biobased LA production are evaluated through several
emissions associated with the CHP unit are added up to cal-
environmental impact categories, depicted in Table 1. The
culate the emissions per kg of raw sugar produced as shown
functional unit is 1 tonne of LA produced. The fossil based LA
in Table 3.
production is used as a reference system for the evaluations
of these environmental impacts. The results were interpreted,
3.2.3. Biobased LA production
analyzed and sets of conclusions are formulated in the follow-
In the inventory analysis for biobased LA production, the mass
ing section.
and energy balance from an Aspen Plus® simulation, devel-
3.2. Data inventory oped as described in Section 2.1, was used. The resources and
utilities used and generated waste are given in Table 4. The
The inventories of the biobased LA production were based on plant capacity is considered to produce 3624.10 kg/h from a
the computer simulations of the process developed in Aspen feedstock of 200 tonne/day (8333.33 kg/h) bagasse and brown
Plus® v8.6 and described in Section 2.1. For sugarcane cul- leaves. Auxiliary chemicals used in the production, magne-
tivation stages average data were taken from literature and sium hydroxide (Mg(OH)2 ), triethylamine (TEA), and ethanol
from the South African Sugarcane Research Institute (SASRI). are recycled, with the make-up streams shown in Table 4. The
Data for the sugar mill were taken from literature. Eco-invent eco-invent database of SimaPro® was used for the environ-
database was employed for all external input chemicals and mental profile of the auxiliary chemicals and for the substrate
for the fossil based LA production. and nutrients used in fermentation.

3.2.1. Sugarcane cultivation 3.2.4. Fossil based LA production


Most of the sugarcane cultivation in South Africa occurs in the Data for the most important processes of the chemical syn-
province of KwaZulu Natal, on the east coast. Approximately thesis of LA described in Section 2.2, were taken from the
20 million tonnes of sugarcane are produced per year, from Eco-invent database of SimaPro® .
64 food and bioproducts processing 9 9 ( 2 0 1 6 ) 58–70

Table 2 – Data used for a typical sugarcane cultivation (Mashoko et al., 2010; Groot and Borén, 2010; Ramjeawon, 2004) in
South Africa.
Value Unit

Sugar cane agriculture


Cultivation area 400,000 ha
Average cane harvest 60 t/ha
Irrigation water requirements 8000 m3 /ha
Electricity consumption for irrigation 108 kWh/ha
N2 O emissions from soil 1.5 (1.25% of N input) kg
NOx emissions from soil 0.6 (0.5% of N input) kg

Fertilizer application rate/ha


Urea N 120 kg
DAP P2 O5 30 kg
Potassium oxide KCl 125 kg
Herbicides use 1614 (26.9 g/tonne sugar cane) g
Herbicides loss in water bodies 3.228 (0.2%) g
Nitrogen loss in water bodies 161.4 (10%) g
Phosphorus loss in surface runoff/ha 1 kg
Pesticide use 132.6 g

Cane transportation
Transportation, average distance, by
Toad (94% of cane) 25 km
Rail (6% of cane) 50 km
Diesel consumption
Truck 1.08 MJ/tkm
Rail 0.68 MJ/tkm
Fertilizers and herbicides transport distance 60 km

4. Results and discussion depicted in Table 1. These environmental impact indicators


are analyzed using ReCiPe Midpoint(H) to better understand
The environmental loads associated with the production of LA the environmental significance of the inventory results and
from a lignocellulosic sugarcane bagasse and leaves have been identify areas with a substantial environmental impact within
evaluated and compared to the petrochemical equivalent. The the process. The environmental impact categories have been
environmental impacts are categorized into eighteen environ- assessed and compared for both biobased and fossil based
mental categories obtained from the SimaPro LCA analysis LA as shown in Fig. 6 and discussed in Sections 4.1–4.13.
As depicted in Fig. 6, 16 of the 18 impact categories had a
much lower environmental impact for biobased LA than fossil
Table 3 – Sugar processing and emissions to air and based LA. Exceptions were agricultural land occupation and
water, kg per tonne of raw sugar produced (Mashoko water depletion potential. The higher contribution from the
et al., 2010, 2013). biobased LA to agricultural land occupation was mainly due
Sugar processing to agricultural land use for sugarcane cultivation and thus
Sugar produced/ha 6.0 tonne expected to be higher (Lammens et al., 2011). Similarly the
Bagasse produced 27.8% of cane water depletion potential was slightly higher for biobased LA
Molasses produced 4.1% of cane due to the process water used in the LA production and the
Filter cake produced 6.8% of cane
sugar mill as well as water used in sugarcane cultivation.
Steam consumed/tonne of cane 520 kg
Electricity consumption/tonne of cane 35 kWh
Electricity generation/tonne of cane 150 kWh
Coal consumption/tonne of cane 8.4 kg Table 4 – Input and output flow rates of LA production
water used for cane processing/tonne cane 0.6 m3 from Lignocellulosic biomass, SCBL, from Aspen Plus®
Pollutant loadings of COD/tonne of cane 3320 simulation, based on 200 tonne of SCBL per day
Pollutant loadings of BOD5/tonne of cane 1590
Lactic acid (LA), kg/h 3624.10
Air emissions
Resources, kg/h
CH4 7.5
Feed (SCBL) 8333.33
CO2 196
Process water 14,833.97
N2 O 0.5
TEA 87.80
SO2 2.18
Mg(OH)2 194.65
NO2 7.5
Ethanol 49.46
NMVOC2 0.07
Strains &nutrients 549.12
Suspended particulate matter 0.85
Utilities
Water emissions
Steam LPS, kg/h 1545.31
BOD7 6.6
Steam HPS, kg/h 11,445.90
COD 19
Electricity, kWh 123.84
NO− 3
12
PO3−
4 0.15 Waste
Suspended solids 0.05 Solid waste 4477.93
Fe 0.00126 Waste water 13,339.69
food and bioproducts processing 9 9 ( 2 0 1 6 ) 58–70 65

99
97 98
100
96 97
94 95 95 96
90 91
Environmental Savings (%)
90
86
84
82 81
80

70

61
60
P

EP

CP

TP

T
AP

PM

TP

IRP

P
NL
GW

OD

ME

HT

ET

AD

MD
UL
FW

AE
TE
PO

MA
FW
Fig. 5 – Environmental savings in different impact categories upon replacing a tonne of fossil based LA produced with its
equivalent biobased LA.

The environmental savings of the rest of the impact cate- et al., 2014; Borrion et al., 2012; Raman and Gnansounou, 2015;
gories upon replacing the fossil based LA with lignocellulosic Tsiropoulos et al., 2015; Hottle et al., 2013; Avolio et al., 2015;
biomass based LA ranges from 81% for particulate forma- Pietrini et al., 2007) discussed in Section 2. The main environ-
tion potential to 99% for ozone layer depletion potential, as mental impact contributions for the total impacts of biobased
shown in Fig. 5, with a 61% saving for terrestrial ecotoxic- LA production are depicted in Fig. 7. The main contributions
ity potential. These range of saving potentials (61–99%) of the for most of the environmental impact categories considered
environmental impact categories are in agreement with other are found to be associated with the lignocellulosic biomass
LCA studies of other bioproducts in the literature (Hermann (which includes all environmental impacts associated with
et al., 2007; Adom et al., 2014; Lammens et al., 2011; Cok the sugarcane cultivation, sugar mill per unit mass of

Fig. 6 – Comparison of environmental impacts for the production of 1 tonne of biobased LA production and the equivalent
fossil-based LA (using ReCiPe Midpoint(H)). Total environmental savings are shown as the difference between the
environmental impacts of the biobased and fossil based LA productions. Some impacts have been scaled to fit. To obtain the
original values of the impacts, multiply the values shown on the graph by the factor shown on the x-axis for relevant
impacts. For the symbols of the impact categories and their descriptions refer to Table 1.
66
food and bioproducts processing 9 9 ( 2 0 1 6 ) 58–70
Fig. 7 – Environmental impact contributions of the main contributors for the total impacts for biobased LA production. SCBL: sugarcane bagasse and leaves, TEA: triethylamine, EtOH:
ethanol, MgOH2 : magnesium hydroxide.
food and bioproducts processing 9 9 ( 2 0 1 6 ) 58–70 67

sugarcane bagasse and leaves), and auxiliary chemicals used NO− 3 eq./tonne of LA. Thus the net environmental savings of
in the LA production particularly triethylamine, magnesium replacing fossil based LA with biobased LA are 0.966 kg PO3−
4
hydroxide and ethanol as depicted in Fig. 7a–r. eq. per tonne of LA and 5.89 kg NO− 3 eq. per tonne of LA for
Considering that this work is based on several assumptions FWEP and MEP respectively. Thus reducing the environmental
and data collected from literature sources (as discussed in burden by 95.4% and 95.8% for FWEP and MEP, compared to
Section 3) uncertainty analysis by Monte Carlo method within fossil-derived LA. The eutrophication potential contribution
SimaPro® v8.0 was carried out to check robustness. Accord- of biobased LA is attributed to the impacts associated with
ing to the recommendation from SimaPro® tutorial (Goedkoop Mg(OH)2 , triethylamine and ethanol production, depicted in
et al., 2013) lognormal distribution was assumed. The results Fig. 7o and p.
show that for all scenarios Climate change impact obtained
from biobased LA production is lower than impacts from asso- 4.4. Abiotic depletion potential (ADP)
ciated fossil based LA, i.e. the reference system. The results
shown that for almost all environmental impacts obtained This category covers a variety of sub-impacts with the main
from biobased LA production is lower than impacts associated concept, the consumption of non-biological resources such as
with fossil based LA in 100% cases, except for terrestrial tox- fossil fuels, minerals, metals, water, etc. In this work the value
icity, water depletion, agricultural land occupation. Analysis of the abiotic resource consumption of crude oil is considered.
for water depletion potential and agricultural land occupa- A negative impact indicants a saving in the abiotic resources.
tion show the reference system is environmentally friendlier The biobased LA is the best option with ADP of 60.97 kg fos-
in 75% and 100% of cases respectively. However, for terres- sil fuel eq. per tonne of LA, while the fossil based LA needs
trial toxicity potential the biobased LA is environmentally about 1803.02 kg fossil fuel eq. per tonne of LA, giving a sav-
friendlier than the fossil based LA in 80% of the Monte Carlo ing of 1742.05 kg fossil fuel eq. per tonne of LA, i.e. reducing
runs. Comparison results of uncertainty analysis and relative the environmental burden by 96.6%. The ADP of biobased LA
results of LCA, showing the LCA results are consistent and production is primarily associated with the triethylamine and
robust. Mg(OH)2 as depicted in Fig. 7b.

4.1. Global warming potential (GWP)


4.5. Ecotoxicity potentials (ETP)
Global warming potential (Valdivia et al., 2013; Perimenis et al.,
Environmental toxicity is measured as three separate impact
2011) is the ability of greenhouse gases to trap heat in the
categories which examine the effects on freshwater, marine
atmosphere relative to carbon dioxide, which serves as the
and land. The total terrestrial ecotoxicity potential (TETP),
reference gas. The global warming potential of biobased and
freshwater Aquatic ecotoxicity potential (FWAETP), and
fossil based LA are 412.50 and 4338.14 kg CO2 eq./tonne of LA
marine aquatic ecotoxicity (MAETP) from biobased LA are
respectively, giving total environmental saving of 3925.65 kg
approximately 0.57, 8.45 and 7.29 kg 1,4-DB eq. per tonne of
CO2 eq./tonne of LA upon replacing the fossil based LA
LA, respectively. While these impact categories from fossil
with biobased LA, i.e. reducing the environmental burden by
based LA production are 0.71, 51.42 and 50.76 kg 1,4-DB eq.
90.5%. The main GWP contribution for the biobased LA comes
per tonne of LA, respectively, giving a net environmental sav-
from the Mg(OH)2 and triethylamine (TEA) productions with
ings of 0.14, 42.97 and 43.48 kg 1,4-DB eq. per tonne of LA
324.0 kg CO2 eq. and 73.55 kg CO2 eq. respectively, as depicted
for TETP, FWAETP and MAETP respectively, i.e. reducing their
in Fig. 7a.
respective environmental burdens by 19.1%, 83.6% and 85.6%.
The total environmental impact regarding TETP, FWAETP and
4.2. Acidification potential (AP)
MAETP is negative, showing an order of magnitude saving in
freshwater and marine ecotoxicity potential. Considering the
Acidic gases such as sulfur dioxide (SO2 ) react with water in
total eco-toxicity potentials, ETP, 16.30 and 102.89 kg 1,4-DB
the atmosphere to form ‘acid rain’, where it causes ecosystem
eq. per tonne of LA for biobased and fossil based LA produc-
damage of varying degree, depending upon the nature of the
tions respectively, resulting a net environmental benefit of
landscape ecosystems. Biobased LA contributes an acidifica-
86.59 kg 1,4-DB eq. per tonne of LA upon replacing the fossil
tion potential of 1.09 kg SO2 eq./tonne of LA, while the fossil
based LA with biobased LA. Mg(OH)2 is the major contributor
based LA contributes an acidification potential of 19.32 kg SO2
for the MAETP and FWAETP (see Fig. 7i and j) while ethanol
eq./tonne of LA, resulting in a net environmental saving of
contributes to TETP, as shown in Fig. 7k.
18.23 kg SO2 eq./tonne of LA produced upon replacing the
fossil based LA with biobased LA, i.e. reducing the environ-
mental burden by 94.3%. The terrestrial acidification potential 4.6. Human toxicity potential (HTP)
of biobased LA is largely due to Mg(OH)2 and triethylamine, as
shown in Fig. 7q. The human toxicity potential is a calculated index that reflects
the potential harm of a unit of chemical released into the
4.3. Eutrophication potential (EP) environment, and is based on both the inherent toxicity of a
compound and its potential dose. The human toxicity poten-
Eutrophication is the accumulation of chemical nutrients in an tial of producing LA from lignocellulosic biomass and that of
ecosystem which leads to abnormal productivity. Freshwater fossil resources results in 137.05 and 1433.22 kg 1,4-DB eq. per
eutrophication potential (FWEP) and marine eutrophication tonne of LA respectively. Thus the total environmental sav-
potential (MEP) are considered in this study. The FWEP con- ing in terms of HTP upon replacing the fossil based LA with
tributions of biobased and fossil based LA are 0.046 and 1.01 kg biobased LA is 1296.16 kg 1,4-DB eq. per tonne of LA produced,
PO3− i.e. reducing the environmental burden by 90.4%. As shown in
4 eq./tonne of LA, respectively. Similarly the MEP contrib-
utions of biobased and fossil based LA are 0.256 and 6.15 kg Fig. 7n Mg(OH)2 is the major contributor for HTP.
68 food and bioproducts processing 9 9 ( 2 0 1 6 ) 58–70

4.7. Ozone layer depletion potential (ODP) respectively, giving a net environmental saving of 397.79 kBq
U235 eq. upon replacing the fossil based LA with biobased LA,
Ozone-depleting gases cause damage to stratospheric ozone i.e. reducing the environmental burden by 96.8%. About 72%
or the ‘ozone layer’. There is great uncertainty about the of the ionizing radiations of biobased LA is associated with
combined effects of different gases in the stratosphere, and Mg(OH)2 production while 24.2% of the IRP is associated with
all chlorinated and brominated compounds that are stable triethylamine as depicted in Fig. 7h.
enough to reach the stratosphere can have an effect. Chlo-
rofluorocarbons (CFCs), halons and hydrochlorofluorocarbons 4.12. Particulate matter formation (PM)
(HCFCs) are the major causes of ozone depletion. The ozone
layer depletion potential for biobased and fossil based LA pro- Particulate matter (PM) is a complex mixture of extremely
duction are 7.69 × 10−6 and 5.73 × 10−4 kg CFC-11 eq. per tonne small particles. Particle pollution can be made up of a number
of LA produced respectively, giving a net environmental saving of components, including acids (such as nitrates and sulfates),
potential of 5.65 × 10−4 kg CFC-11 eq. per tonne of LA pro- organic chemicals, metals, and soil or dust particles. A mul-
duced up on replacing the fossil based LA with biobased LA, titude of health problems, especially of the respiratory tract,
i.e. reducing the environmental burden by 98.7%. As shown in are linked to particulate pollution. PM is measured in PM10
Fig. 7r Mg(OH)2 and triethylamine are the major contributors equivalents, i.e. particles with a size of 10 ␮m. The potential
for ODP. particulate matter formation for the biobased LA production
is 1.24 and that of fossil based LA 6.55 kg PM10 eq. per tonne of
4.8. Photochemical oxidant creation potential (POCP) LA produced. The total environmental saving is thus, 5.31 kg
PM10 eq. per tonne of LA produced up on replacing the fossil
Ozone is protective in the stratosphere, but on the ground- based LA with biobased LA, i.e. reducing the environmental
level it is toxic to humans in high concentrations. Also known burden by 81.1%. Mg(OH)2 is the major contributor for the PM
as, photochemical ozone, it is formed by the reaction of of the biobased LA production as depicted in Fig. 7l.
volatile organic compounds and nitrogen oxides in the pres-
ence of heat and sunlight. The photochemical oxidant creation 4.13. Land use (LU)
potential measures the potential for the creation of photo-
chemical (summer) smog due to the reaction of relevant The total land use potential for agricultural land occupation
chemical compounds when exposed to sunlight. The POCP (ALO) and urban land occupation (ULO) is 6.62 × 106 m2 a and
for biobased and fossil based LA productions are 2.44 and 157.31 m2 a per tonne of LA produced for biobased and fos-
13.08 kg C2 H4 eq. per tonne of LA produced respectively, giving sil based LA respectively, which is mainly contributed from
a net environmental saving potential of 10.64 kg C2 H4 eq. per the agricultural land use for sugarcane cultivation. Of the
tonne of LA produced upon replacing the fossil based LA with total land use potential 99.9% is associated with the agri-
biobased LA, i.e. reducing the environmental burden by 81.3%. cultural land occupation for the biobased while 75.9% of
Electricity is the main contributor for POCP (not shown) along the land use potential for fossil based LA is associated with
with triethylamine and Mg(OH)2 are the major contributor for the urban land occupation. Land use for the production of
POCP as shown in Fig. 7m. biobased LA was mainly due to sugarcane cultivation to
provide the lignocellulosic biomass SCBL as feedstock. Land
4.9. Water depletion potential (WDP) use for biobased chemicals is generally expected to be higher
than that for equivalent fossil based products (Lammens et al.,
The water depletion potential is higher for the biobased LA 2011; Hermann et al., 2007).
production, 15.48 m3 , than its equivalent from fossil based LA Similarly, it can be seen that the natural land transfor-
12.09 m3 . This is due to the impact associated with sugarcane mation (NLT) per tonne of LA produced from lignocellulosic
cultivation for biobased LA production amounts as shown in biomass and fossil sources are 0.016 and 0.394 m2 respectively,
Fig. 7d. giving a net saving of 0.378 m2 per tonne of LA up on replacing
the fossil based LA with biobased LA, i.e. reducing the envi-
4.10. Metal depletion potential (MDP) ronmental burden by 95.9%. The major contributor for NLT
and ULO are Mg(OH)2 and triethylamine as depicted in Fig. 7e
The potential for metal depletion of biobased and fossil based and f, while the feedstock (sugarcane bagasse, leaves and tops)
LA are 5.48 and 259.46 kg Fe eq. per tonne of LA respectively, contributes to ALO as depicted in Fig. 7g.
resulting in a net environmental saving of 253.97 kg Fe eq. per
tonne of LA upon replacing the fossil based LA with biobased 5. Conclusion
LA, i.e. reducing the environmental burden by 97.9%. The
contributions for this impact category for the biobased LA This study evaluated the environmental performance of LA
production are 63.47% associated with triethylamine, 23.06% produced from lignocellulosic biomass SCBL and petrochem-
associated with Mg(OH)2 and 10% associated with ethanol, as ical sources using a life cycle approach. Functional similarity
shown in Fig. 7c. is assumed for both biobased and fossil based LA, and eco-
nomic allocation and system expansion are applied for the
4.11. Ionizing radiation potential (IRP) sugar mill and the biobased LA production units respectively.
From this analysis it has been found that biobased LA has
Ionizing radiation is an impact category in LCA relating to lower values in almost all environmental impact categories
the damage to human health and ecosystems that is linked considered, except for water depletion potential and agricul-
to the emissions of radionuclides throughout a process. The tural land occupation with uncertainties of 75% and 100% of
ionizing radiation potentials of biobased and fossil based LA the cases respectively. The dominant environmental impacts
productions are 13.16 and 410.95 kBq U235 eq. per tonne of LA of the analyzed categories from which large environmental
food and bioproducts processing 9 9 ( 2 0 1 6 ) 58–70 69

savings obtained per tonne of LA produced are global warm- Dias, M.O., Pereira, D.M., Filho, R.M., Bonomi, A., Jesus, C.D.,
ing potential (3925.65 kg CO2 eq.), abiotic depletion potential Rossell, C.E., 2011. Simulation of integrated first and second
(1742.05 kg fossil fuel eq.), human toxicity potential (1296.16 kg generation bioethanol production from sugarcane:
comparison between different biomass pretreatment
1,4-DB eq.), ionizing radiation potential (397.79 kBq U235 eq.)
methods. J. Ind. Microbiol. Biotechnol. 38 (8), 955–966,
and metal depletion potential (253.97 kg Fe eq.). About 80–99% http://dx.doi.org/10.1007/s10295-010-0867-6.
of the environmental burdens of most of the environmental Dusselier, M., Van Wouwe, P., De Smet, S., De Clercq, R., Verbelen,
impact categories of the fossil based LA can be reduced upon L., Van Puyvelde, P., Du Prez, F.E., Sels, B.F., 2013. Toward
replacing with its biobased equivalent. The Monte Carlo uncer- functional polyester building blocks from renewable
tainty analysis shows almost 100% of the cases in most of the glycolaldehyde with Sn cascade catalysis. ACS Catal. 3 (8),
impact categories biobased LA is environmentally friendlier 1786–1800.
Gezae Daful, A., 2012. Simulation of reactive distillation:
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quantitatively shows that the biobased LA is environmentally Int. J. Chem. Eng. 6 (10), 1231–1239.
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South Africa’, funded by the Green Fund, an environmental recovery from whey ultrafiltrate fermentation broths and
finance mechanism implemented by the Development Bank artificial solutions by nanofiltration. Desalination 228, 84–96.
Groot, W.J., Borén, T., 2010. Life cycle assessment of the
of Southern Africa (DBSA) on behalf of the Department of
manufacture of lactide and PLA biopolymers from sugarcane
Environmental Affairs (DEA). The authors would like to thank
in Thailand. Int. J. Life Cycle Assess. 15 (9), 970–984.
South African Sugarcane Research Institute (SASRI), for pro- Gudena, K., Rangaiah, G.P., Lakshminarayanan, S., 2013. Modeling
viding data for the sugarcane cultivation stages. Aspen Plus® and analysis of hybrid reactive stripper-membrane process for
is a registered trademark of Aspen Technology Inc. lactic acid recovery. Ind. Eng. Chem. Res. 52 (8), 2907–2916.
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