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Article history: Aligned with Singapore's commitment to sustainable development and investment in renewable re-
Received 30 October 2017 sources, cleaner energy and technology (Sustainable Singapore Blueprint), we report a techno-economic
Received in revised form analysis of the biorefinery process in Southeast Asia. The considerations in this study provide an over-
2 February 2018
view of the current and future challenges in the biomass-to-chemical processes with life-cycle thinking,
Accepted 3 March 2018
Available online 10 March 2018
linking the land used for agriculture and biomass to the levulinic acid production. 7e8 kg of lignocel-
lulosic feedstock (glucan content 30e35 wt%) from agriculture residues empty fruit bunches (EFB) or rice
straw (RS) can be processed to yield 1 kg of levulinic acid. Comparisons of both traditional and “green”
Keywords:
Biomass
alternative solvents and separation techniques for the chemical process were modelled and their relative
Levulinic acid energy profiles evaluated. Using 2-methyltetrahydrofuran (2-MeTHF) as the process solvent showed to
Biorefinery model approx. 20 fold less energy demand compared to methyl isobutyl ketone (MIBK) or approx. 180 fold less
Sustainability energy demand compared to direct distillation from aqueous stream. Greenhouse gases emissions of the
major operations throughout the supply chain (energy and solvent use, transport, field emissions) were
estimated and compared against the impact of deforestation to make space for agriculture purposes. A
biorefinery process for the production of 20 ktonne/year of levulinic acid from two different types of
lignocellulosic feedstock was hypothesized for different scenarios. In one scenario the chemical plant
producing levulinic acid was located in Singapore whereas in other scenarios, its location was placed in a
neighboring country, closer to the biomass source. Results from this study show the importance of
feedstock choices, as well as the associated plant locations, in the quest for sustainability objectives.
© 2018 Elsevier Ltd. All rights reserved.
1. Introduction glucose, EFB, and kenaf to levulinic acid over a new hybrid catalyst.
They reported 55.2% yield of LA at the experimental conditions of
There is a growing demand for “greener” products, notably 145.2 C reaction temperature, 146.7 min reaction time and 12.0% of
those that are derived from renewable resources (Pawelzik et al., catalyst loading. Upare et al. (2013) achieved a yield of 75% LA via
2013). An increasing number of chemical companies are attempt- the selective decomposition of hexose sugars, glucose and fructose
ing to produce solvents and fine chemicals from biomass for sus- by making use of a heterogeneous graphene oxide (GO)-based
tainable reasons, and at the same time stop relying on fossil-based catalysts with sulfonic acid (SO3H) functional groups (GOeSO3H).
products due to the concern over the depletion of non-renewable LA produced from bagasse and RS mixed with different concen-
feedstock (Biotech Industry Organization, ). trations of hydrochloride acid (HCl) in a pressurized reactor was
Levulinic acid is a platform chemical, important intermediate for done by Yan et al. (2008) They found that maximum yields of LA
both fine chemicals and solvent production (Bozell et al., 2000; (22.8 and 23.7% for bagasse and paddy straw, respectively) was
Rackemann and Doherty, 2011; Luterbacher et al., 2014). Various achieved with a reaction temperature of 220 C, reaction time of
research and experimental studies concerning the production of 45 min and 4.45% concentration of HCl.
Levulinic Acid (LA) from biomass have been carried out; Ya'aini Lately, ionic liquids have being applied in the area of lignocel-
et al. (Yaaini et al., 2012) for example, investigated the conversion of lulose to LA conversion. Fu et al. (2016) produced LA via the hy-
drothermal decomposition reactions of cellulose, glucose, and
fructose. The substrates were catalyzed by 18 types of ionic liquids
* Corresponding author. with different anions. Reusability tests for [PrSO3HMIm]Cl and
E-mail address: isoniva@ices.a-star.edu.sg (V. Isoni).
https://doi.org/10.1016/j.jenvman.2018.03.012
0301-4797/© 2018 Elsevier Ltd. All rights reserved.
268 V. Isoni et al. / Journal of Environmental Management 214 (2018) 267e275
[BSO3HMIm]HSO4 were carried out and revealed that [BSO3HMIm] quantified service value (known as functional unit) of the product
HSO4 can be used over four cycles without a loss of activity. In (Khoo et al., 2016). Owing to the variety of biomass feedstock for
another more recent investigation, Liu at al (Liu et al., 2018). applied biorefinery processes, along with the debates on the final envi-
acidic ionic liquid [C3SO3Hmim]HSO4 to catalyze lignocellulose ronmental benefits or drawbacks of such systems, LCA has been
conversion to LA. By optimizing reaction conditions, the highest increasingly used to compare various bio-based material produc-
yield of LA was reported as 96.6 mol% (21.6 wt%) based on the tion chains. In many cases, the focus of investigation is on the en-
amount of C6-sugars in the biomass raw material. Various other ergy demands and CO2 emissions of the life cycle stages, starting
discussions and works have been published on the production of LA from agriculture land to the final conversion of biomass to chem-
from a variety of biomass resources; among them are the icals (refer to Fig. 1).
comprehensive reviews provided by Pileidis and Titirici (2016) and For the techno-economic investigation, the following are
Antonetti et al. (2016) The challenges and possible mechanisms for considered in the LCA system:
the transformation of carbohydrates and raw biomass into levulinic
acid were highlighted by Pileidis and Titirici (2016) Antonetti at al ▪ Different feedstock choices including cultivation and land use
(Antonetti et al., 2016). discussed in their study several catalytic ▪ Logistics and storage
systems that have been developed to produce LA from waste and ▪ Energy demands
raw biomass. ▪ CO2-eq emissions
▪ Plant capacity (20 ktonne/year)
1.1. Industrial production ▪ Costs
Fig. 1. Dashed line box defines the boundaries of the life cycle approach adopted in this work.
Fig. 2. Major chemical transformations occurring in a biomass-to-levulinic acid process. 1) The biomass is treated to remove lignin (delignification) leaving cellulose and hemi-
cellulose 2) Under acidic conditions, depolymerization occurs 3) The monomeric C6 and C5 sugars are rapidly converted into HMF and furfural, respectively 4) Under pressure and
high temperature HMF is converted into levulinic acid, formic acid and acetic acid whereas furfural yields formic acid and decomposition products. Subsequent separation and
purification steps are needed in order to yield pure levulinic acid.
270 V. Isoni et al. / Journal of Environmental Management 214 (2018) 267e275
pillars of a sustainable development: environment (emissions, the mills). The cost of feedstock is currently volatile and is observed
energy), economy (profit, logistics) and social (impact to local to fluctuate according to collection/transportation practices and
community). small market uncertainties. High costs of biomass, including pre-
The growing demand for bio-based materials and chemicals also treatment and on-site delivery, would affect the overall profit
led to the increased pressure for available land to grow crops used margins, discouraging those companies initially motivated to invest
for food (Pawelzik et al., 2013; Bringezu et al., 2012). Residual or into biomass-to-chemicals technology. Conversely, if the proposed
waste biomass is considered in this article as a potential sustainable price for the biomass is too low, it is foreseeable that the farmers
resource for the production of bio-products, with the consideration would rather use the biomass for other applications such as
that food supply will not become a threat to society. The environ- mulching, energy generation or organic fertilization instead of
mental impacts of crop cultivation involving palm trees grown in selling it (Gadde et al., 2009a, 2009b). Energy costs associated to
Malaysia and Indonesia have already been reported in the literature run the plant varied with the composition of the distillation
(Harsono et al., 2013; Kamahara et al., 2010). Field emissions from streams; in the best case scenario (2-MeTHF) the energy cost was
rice cultivation in Thailand were extracted from Silalertruksa et al. estimated to be around 66000 USD/year, resulting in little or no
(Silalertruksa and Gheewala, 2013) Depending on the feedstock impact in the economics of the plant (for an estimated minimum
choices, yields of crops and amount of feedstock demanded by the selling price of levulinic acid at 774 USD/tonne). However, when a
biorefinery, the area of agricultural land necessary to produce more conventional organic solvent (MIBK) or direct distillation of
enough biomass supply to feed the process will be analyzed. the aqueous stream were analyzed as alternatives, a much higher
energy cost was observed, estimated in 1.80M USD/year and 14.2M
USD/year respectively.
2.3. Logistics and cost
Table 1
Energy comparison for the isolation of levulinic acid via distillation from different streams.
Fig. 4. Simplified schematic representation of the biorefinery process under the three scenarios illustrated in Table 1. The biomass is fed to the mill and subsequently mixed in a
tank with sulfuric acid. The resulting heterogeneous mixture is fed into the reactor (cyan); the stream from the reactor undergoes a filtration step, followed by liquid-liquid
extraction (green) with an organic solvent (2-MeTHF or MIBK), neutralization and distillation (purple). In the scenario where direct distillation of the aqueous stream is per-
formed, the only difference resides in the missing liquid-liquid extraction step (green). (For interpretation of the references to colour in this figure legend, the reader is referred to
the Web version of this article.)
energy cost and indirect greenhouse gases emissions; for these The corresponding GHG emissions are:
reasons, liquid-liquid extraction with 2-MeTHF followed by distil- h i
lation was considered in our analysis as the best available tech- Eqnð1Þ Ef þ ½GHGT þ Field emissions Feed (2)
nology for the process.
Since the majority of the energy going into the process was
attributed to heating of the materials stream for distillation pur-
poses, a simplified equation can was used to calculate the total Ef GHG Emission factor for natural gas in Malaysia, Indonesia,
energy required: Thailand and Singapore (in tonne/GJ)
Total energy: GHGT Emissions from transportation (ships or trucks) in tonne/
tonne feed
Field emissions Emissions related to agricultural activities
DHi;j;k ¼ mi;j;k $ Cpi;j;k $DT þ mi;j;k $ Hvi;j;k $Cap=year (1) (tonne/tonne feed)
Feed Biomass (tonne) required to feed Cap/year
biomass source in which the lignocellulosic material is converted 3.3. Comparison between the two scenarios
into levulinic acid and shipped to Singapore, ready for use. In the
second scenario we assumed that the biorefinery plant is located in As expected the emissions for transport of levulinic acid resulted
Jurong Island (Singapore) where the biomass is received from lower in the first scenario due to the higher density of levulinic acid
overseas (Thailand, Malaysia or Indonesia) and converted into compared to the biomass, requiring a minor number of trips. The
levulinic acid, ready for use. In both cases the emissions were traced energy used to run the process (based on liquid-liquid extraction
back to land use for agriculture and mass-allocated to the biomass. using 2-MeTHF followed by distillation) was assumed to be the
The lignocellulosic biomass was assumed to have similar chemical same in every country, but the different mode of producing elec-
and physical properties which do not require any changes in the tricity provided a different GHG emission profile, with Singapore
process plant. The yield of levulinic acid was based on claims by having the lowest CO2-eq emissions. The emissions for the solvent
Biofine, related to the glucan content per kg of dry feedstock production were calculated as emission from the field to produce
(Appendix 1). the amount of biomass required to yield the desired quantity of 2-
MeTHF. The GHG emissions arising from energy use, solvent pro-
3.1. Scenario 1: biorefinery near biomass source duction, transportation and field emissions for each country were
summed up and compared against each other and the two possible
The agricultural residue was assumed to be transported to the scenarios (Fig. 6).
nearby biorefinery from the biomass growing area (rice straw) or
from the mill (EFB). The emissions related to the transport from the
mill to the plant were neglected due to the postulated proximity
(<35 km). The levulinic acid obtained from the biorefinery was
assumed to be stored in barrel/drums, packed in intermodal con-
tainers and shipped to Singapore ready for use (transport
emissions).
Rice straw from Thailand generated the highest CO2-eq results, 100% deforestation) than the same process using biomass deriving
due to emissions of CH4 and N2O from the rice fields during the from land not related to deforestation (Fig. 7).
cultivation of rice crop (Li et al., 2011). It was observed that for EFB,
the slight difference between Malaysia and Indonesia was mostly 3.5. EFB or rice straw?
due to the different way of transportation. An interesting result was
to observe that the overall emissions in both scenarios were similar, Both EFB and rice straw were chosen in this study because of
indicating that the choice of the location for the biorefinery would their abundant availability in the region and no land-food compe-
be driven more by business motivations rather than for ecological tition. Paddy fields contribute to CO2 emissions due to high
purposes. It is important to note that most of the biorefineries methane production, however palm trees cultivation is more often
prefer to generate energy to fuel their process by burning lignin- associated with deforestation issues (Gilbert, 2012). Both crops
containing material because of its average energy content of constitute source of food and wealth both locally and globally, and
6.81 MJ/kg (Hayes et al., 2006). However, in our study we consid- due to forecasted increase of world population, a bigger demand of
ered lignin as important raw material for production of higher both products and related lignocellulosic biomass is expected. In
value products, therefore we assumed that lignin was separated recent years, companies in the food and cosmetics industry started
from cellulose and hemicellulose, but not burned. Also, this to shift to traceable sustainable supply chains for palm oil and
approach allowed a better assessment of the indirect GHGs emis- derivatives because of both environmental and socio-economic
sions (energy use) instead of relying on estimations. aspects, selecting farmers who are members of the roundtable for
sustainable palm oil (RSPO) (Roundtable, ; P and G, 2017; Unilever,
2014). This led to an increased volume in the last few years of the so
3.4. Deforestation: impact on emissions
called certified sustainable palm oil (CSPO) and related “certified
EFB”. In January 2018 it was reported that 11.9 Mtonne/year of CSPO
Sustainable, long-term resources and food security concerns
were produced globally. (Roundtable on Sustainable Palm Oil, )
have motivated research efforts into developing efficient methods
However, only a fraction of this CSPO was certified as 100% sus-
to convert biomass to materials (Pawelzik et al., 2013; Bringezu
tainable throughout the supply chain (19%), showing the niche
et al., 2012). However, higher levels of biomass utilization will
market for such a commodity. In economic terms, this poses an
require the demand for more land. In the previous sections,
issue on the long term, since more companies would be interested
deforestation was not considered in the emissions profile (Fig. 6).
into a traceable sustainable feedstock for their purposes and due to
However, this aspect can profoundly change all the considerations
the limited amount of certified biomass, this would lead to a situ-
presented in this article. Endangered animal species are threatened
ation in which there will not be enough certified EFB for the market,
of extinction with irreversible adverse effect of biodiversity
resulting in an increased cost of what was originally considered
(Fitzherbert et al., 2008; Koh and Wilcove, 2008). Fires on peatland
agriculture waste. Moreover, criticism on the RSPO for having “a
and clearing of forest contribute to other social issues such as haze,
pro-industry bias that appears to be compromising its broader
which result in negative impacts on the local community and
mission to promote environmental sustainability” have been re-
neighboring countries. According to Baccini et al. (2012) and Harris
ported, complicating the assessment of sustainable palm oil
et al. (2012a) impacts of deforestation are estimated to be around
(Laurance et al., 2010).
0.33 ktonne CO2 per ha/year of land cleared from virgin rainforest
Arguably rice straw, the side product of rice cultivation, could be
(Harris et al., 2012b). On a similar note, another study showed the
seen as an alternative lignocellulosic feedstock for the biorefinery
“carbon debt” expressed as years required by the new cultivation to
process, because of the perceived minor impact on deforestation.
recapture CO2 emitted from converting native habitats (e.g. rain-
Moreover, as the largest staple food in the world, rice crops
forest) into croplands (Fargione et al., 2008). For our case study, we
generate an abundant amount of straw which can be utilized as a
analyzed the influence of deforestation on different percentages of
cheap biomass resource. With an increasing global human popu-
the land dedicated to the main crop (rice or palm trees) was ob-
lation requiring more food (rice), it is foreseeable that more land
tained from previously existent virgin rainforest, then we
dedicated to agriculture would be made available. We caution that
compared resulting the emissions (CO2-eq) from such practice with
this should not occur at the expense of destroying forest lands as it
the overall supply chain. The results suggested that deforestation
happened for example in Thailand between 1976 and 1989
would contribute with additional CO2 emissions ranging from 3 to
(Cropper et al., 1999). Our conclusion was that in order to be in line
16 times (for 1% deforestation) up to 294e1600 times higher (for
with sustainability objectives, the land yielding biomass should not
be related to deforestation, irrespectively of the primary use of that
land (agriculture for food or energy crops) or when the deforesta-
tion happened.
important factor for the food security (Dobermann and Fairhurst, nutrients is in play. The results of this study suggest that designing
2002). A possible solution could be in the biorefinery process, an efficient and “green” biomass-to-chemicals process based on a
considering the aqueous streams from acid hydrolysis of the renewable feedstock is certainly a step forward towards a sus-
biomass. We can imagine that the aqueous streams from the lignin tainable development, but in the quest for sustainability it is
separation step could be adjusted to a suitable pH with potassium important to stretch the life-cycle boundaries enough to uncover
bases (e.g. hydroxide, carbonate, oxide), providing a mixture of potential trade-off.
both organic (deriving from lignin) and inorganic nutrients to serve
as potential fertilizers for the original crop cultivation. A concep- Appendix A. Supplementary data
tually similar approach was described by Cuzens et al. (Cuzens and
Farone, 1998) for the production of gypsum and silica gel as valu- Supplementary data related to this article can be found at
able side products while converting rice straw into fermentable https://doi.org/10.1016/j.jenvman.2018.03.012.
sugars.
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