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Journal of Environmental Management 214 (2018) 267e275

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Journal of Environmental Management


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

Research article

Biomass to levulinic acid: A techno-economic analysis and


sustainability of biorefinery processes in Southeast Asia
V. Isoni*, D. Kumbang, P.N. Sharratt, H.H. Khoo
Process Science and Modelling, Institute of Chemical and Engineering Sciences, 1 Pesek Road, Jurong Island, 627833, Singapore

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

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

Current industrial production includes synthesis from furfuryl


alcohol which is subsequently converted into levulinic acid by 2.1. Case study: biorefinery model
treatment with hydrogen chloride (Hart and Kenneth, 1956; Hsu
and Chasar, 1980; Klingler and Ebertz, 2000). Alternative routes In the past decade we observed large experimental efforts being
include Arkenol (Cuzens and Farone, 1998), Segetis (Mullen et al., made to test the production of lignocellulose derived bio-products,
2013), Biofine (Fitzpatrick, 1997) and other biorefinery processes with bio-ethanol being a major object of desire of agro-industrial
in which C6 and/or C5 sugars from cellulosic feedstock are con- biomass processes (Adsul et al., 2006; Girisuta et al., 2013; Saha
verted to levulinic acid and/or furfural, requiring overall less en- et al., 2013; Anwar et al., 2014). Alongside ethanol, more chemi-
ergy, solvent and chemical steps. The advantage of the biorefinery cally intriguing compounds have been accessed in recent years
technology relies on the possibility to convert lignocellulosic ma- thanks to advances in both biochemical transformations of ligno-
terial into valuable chemicals (Kamm and Kamm, 2004). This cellulosic material and catalysis to upgrade and further valorize
concept, which explores the potential of production high added- bio-products, leading to new product lines such as specialty lignins
value bio-derived chemical products, have been explored exten- or sugar-based chemicals (Brethauer and Studer, 2015; Wu et al.,
sively by Kruse and Dahmen (2017) Large-scale manufacturers of 2016; Rødsrud et al., 2012). Depending on different treatment
LA exist in China and India, but there are lack of biorefineries methods of lignocellulosic biomass, more than 200 valuable com-
producing LA within the geographical boundary of Southeast Asia. pounds can be obtained, but important factors needs to be
This forms the basis of our research. considered in production scale scenarios such as collection and
Although levulinic acid may be more easily purified by conver- storage logistics as well as biomass availability (Isikgor and Becer,
sion into derivatives (i.e. esters) (Murat Sen et al., 2012), in our LCA- 2015; Dusselier et al., 2014). Progresses towards optimization of
type approach we focused on the acid itself because of its central biomass to chemicals process have been reported in the literature
role in many downstream process (i.e. angelica lactone, gamma- (Amore et al., 2016). Such research efforts attempt to generate bio-
valerolactone, 2-MeTHF, adipic acid), in order to provide the base based chemicals that are of good economic value, are sustainable
for future studies on specific biomass-to-chemicals processes. and have the potential to reduce the chemical industry's reliance on
petroleum (Dodds and Gross, 2007). Lignocellulosic biomass is
1.2. Objectives primarily made of the three most abundant polymers in nature:
cellulose, hemicelluloses and lignin. In the first chemical step,
The objective of this case study is two-fold. One is to investigate lignin is separated from cellulose and hemicellulose and either
the environmental impacts, including energy consumption, of a burned (to furnish energy) or used for other applications (Na €gele
biomass-to-chemical biorefinery value chain; and the other is to et al., 2002). Acid hydrolysis of hemicellulose and cellulose pro-
test the economic feasibility of the plant. In both analyses, the se- duces C5 and C6 sugars which are subsequently converted into
lection of biomass feedstock, modes of transport and plant loca- furfural and/or levulinic acid, depending on the specific operating
tions will be compared. conditions of the process (Sabesan and Spado, 2013). In accordance
In the techno-economic investigation we attempt to answer the with existing data (Khoo et al., 2015), we estimated that 6.6e7.6 kg
questions of: of biomass (glucan content 30e34 wt%) are required for the pro-
duction of one kg of levulinic acid (Fig. 2).
▪ the feasibility of setting up a biorefinery plant located in
Singapore 2.2. Feedstock choices
▪ cost estimation involved in logistics, storage, and operating
capacity Indonesia and Malaysia are the two biggest producers of crude
palm oil and kernel palm oil in the world. After the milling process,
2. Materials and methods: LCA approach abundant quantity of empty fruit bunches are produced as waste. In
the context of Southeast Asia another type of lignocellulosic
Life cycle assessment (LCA) is a systematic environmental biomass available in large quantity is rice straw. Thailand is a big
management tool applied in industry for quantifying the input- producer of rice and similar considerations for the rice straw can be
output inventory of a product system throughout its life cycle done. In our study we analyzed the biorefinery process with sus-
stages, and projecting the environmental performance based on a tainability objectives in mind, taking into consideration the three
V. Isoni et al. / Journal of Environmental Management 214 (2018) 267e275 269

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

2.4. Process energy and modelling


Singapore is strategically located between the two largest
sources of empty fruit bunches (EFBs) and it houses one of the
In our analysis we considered the energy involved in the process
largest oil refining hub in the world. The infrastructure system is
to convert the lignocellulosic feedstock into levulinic acid for an
well developed and from the business point of view it represents a
annual production of 20 ktonne. The process was modelled in
low risk factor. However, land is scarce in Singapore and lease of the
HYSYS using the UNIQUAC fluids package (Fredenslund et al., 1975;
required land for the hypothesized biorefinery plant incises on the
Santiago et al., 2009), selected for its capability to model non-ideal
capital cost. In order to reduce complexity of the scenarios, we
mixes of fluids, which is the case in this system e a mix of water,
assumed that the labor involved, distance from field/mill to tran-
organic acids, mineral acids and predominantly organic solvent
sition hub, vehicles/machineries engaged, and relevant price in-
mixture. The process starts with the biomass (either EFB or rice
dexes for Indonesia, Malaysia and Thailand were all comparable.
straw) being fed into the mill; the obtained solids are mixed with
Therefore, the costs for transportation and loading/unloading
sulfuric acid in a separate tank. The obtained mixture is transferred
would not affect the relevance of the choices made. Dumai in
into a reactor where under the right reaction conditions (175  C,
Sumatra, Pontian in Johor and Laem Chabang in Thailand were
9 bar) C5 and C6 sugars are converted into LA, formic acid and
selected as the transition hub/port due to their close proximity to
acetic acid. The complex mixture is then filtered to remove any
the plantation areas.
humins followed by an alkaline wash to neutralize the excess sul-
Preliminary calculations demonstrated that the storage costs in
furic acid. At this stage the reactor output stream was modelled to
Malaysia, Indonesia and Thailand turned out to be minimal
have a composition of LA (2 wt%), water (90 wt%) and the
compared to the total cost of operation. The storage cost in
remainder as a mixture of acetic acid, formic acid and sulfuric acid,
Singapore was relatively higher ranging 160,000e600,000 USD per
similarly to what reported in literature (Fitzpatrick, 1997). In the
year at present value (Fig. 3).
next step LA is separated from the aqueous stream and three
However, considering that the capital cost amounts to at least
different isolation methods were investigated. Due to the high
hundreds of millions we concluded that from a business perspec-
water content and its associated specific heat capacity, direct
tive, the logistic arrangement for all scenarios should be subject to
distillation of the stream required a large amount of energy.
the priority of uninterrupted operation and therefore should not
Alternatively, liquid-liquid extraction of LA with two different sol-
represent itself as an economically important factor in plant site
vents (2-MeTHF or MIBK) followed by distillation to recover the
selection. The EFB feedstock can be collected directly from the mill
solvent and isolate the product, was considered. The resulting en-
after the processing of fresh fruit bunches, and subsequently
ergy consumption is summarized in Table 1.
brought to the levulinic acid (LA) plant/biorefinery. The rice straw
A schematic diagram of the biorefinery model is illustrated in
on the other hand can be collected directly from the rice plantations
Fig. 4. The model was based on quantitative extraction of LA into
after the harvesting process (only the rice grains are transported to
the organic solvent. In both cases (2-MeTHF, MIBK) the extracting
organic solvent was assumed to be recovered via distillation to a
purity of 99 wt%, a technical requirement in order to recycle the
solvent back into the system while reducing the environmental
impact.
The specific heat capacities of MIBK and 2-MeTHF were similar
at 2.14 kJ/kg/K and 1.96 kJ/kg/K respectively. However, the boiling
points for these materials were 118  C and 80.3  C respectively. This
meant that DT of MIBK was twice that of 2-MeTHF for the same
amount of material, leading to twice the amount of energy required
for heating to boiling point. The energy required for distillation is
also affected by the reflux ratio required for the separation of the
components in the stream. MIBK again requires more energy due to
Fig. 3. Major costs estimation for setting up a biomass-to-chemicals plant in Southeast its similar boiling point with acetic acid, which is also present in the
Asia. stream. A lower energy demand results in both a lower annual
V. Isoni et al. / Journal of Environmental Management 214 (2018) 267e275 271

Table 1
Energy comparison for the isolation of levulinic acid via distillation from different streams.

Separation method Distillation (aqueous) Distillation (MIBK) Distillation (2-MeTHF)

Energy use per year 214 GWh 27 GWh 1 GWh


GHG (ktonne CO2/yr) 98e161 12e20 0.6e0.9
Relative ratio 177 22 1

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

Truck emissions are based on Euro IV engines, and a 13300-


DHi,j,k Energy required for distillation of levulinic acid from tonne cargo ship is assumed for sea transportation. Data for emis-
streams i, j, k (GJ) sion factors (Ef) as well as each modes of transport (GHGT) can be
Cpi,j,k Heating capacities of i, j, k (GJ/tonne) found in Appendix 1.
DT Change in temperature ( C)
mi Mass of aqueous stream (i) in tonne
mj Mass of MIBK stream (j) in tonne 3. Results and discussions: two scenarios
mk Mass of 2-MeTHF stream (k) in tonne
Hvi,j,k Latent heat of vaporization of i, j, k (GJ) Two different scenarios were considered for the case study. In
Cap/year Plant size or annual production capacity (tonne/year) the first case we hypothesized a biorefinery plant placed near the
272 V. Isoni et al. / Journal of Environmental Management 214 (2018) 267e275

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).

3.2. Scenario 2: biomass shipped to the biorefinery located in


Singapore

The biomass was assumed to be transported to the nearby port


(Laem Chabang or Dumai) or via truck (from Pontian) to port of
Jurong Island, Singapore. Only the main transport emissions from
collection hub/port (Thailand or Indonesia) or from collection hub
(Malaysia) to Singapore were considered (Fig. 5). Fig. 6. Comparison of the GHG emissions based on both location and scenario.

Fig. 5. Visual representation of the two possible scenarios.


V. Isoni et al. / Journal of Environmental Management 214 (2018) 267e275 273

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.

3.6. Nutrients depletion from soil: silicon and potassium

Currently biomass, is left on the field and/or burned to generate


energy, kill plant disease and return part of the minerals to the soil.
Burning rice straw poses serious health issues due to the high
content of silica. Some farmers use portions of the biomass residues
for the compost, but a huge amount is unused as reported by Gadde
et al., 2009a, 2009b Previous studies reported that the high content
of potassium and silica in rice straw similarly to EFB poses a
question for the land fertility when the biomass is removed from it.
Silicon is a crucial element for high and sustainable production of
rice (Ma et al., 2006); in order not to render the land sterile after
Fig. 7. Impact of deforestation on CO2-eq emissions of the biomass-to-levulinic acid years of biomass removal, the need of fertilizers to replenish po-
process. tassium (and silicon in the case of rice straw) in the soil could be an
274 V. Isoni et al. / Journal of Environmental Management 214 (2018) 267e275

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.

3.7. Factors to green up the process/chain References

Adsul, M.G., Varma, A.J., Gokhale, D., 2006. Lactic acid production from waste
It became apparent that the choice of the lignocellulosic feed- sugarcane bagasse derived cellulose. Green Chem. 9, 58e62.
stock should be based not only on its inherent content of sugars, but Amore, A., Ciesielski, P.N., Lin, C.-Y., Salvachúa, D., i Nogue , V.S., 2016. Development
also the location of growing areas. The adopted agriculture tech- of lignocellulosic. Biorefinery technologies: recent advances and current chal-
lenges. Aus. J. Chem. 69, 1201e1218.
niques and whether or not the land used for cultivation was ob- Antonetti, C., Licursi, D., Fulignati, S., Valentini, G., Galletti, A.M.R., 2016. New
tained from clearing of rainforest impact profoundly on the frontiers in the catalytic synthesis of levulinic acid: from sugars to raw and
emissions profile of the all biorefinery supply chain. In our work, waste biomass as starting feedstock. Catalysts 6, 196e224.
Anwar, Z., Gulfraz, M., Irshad, M., 2014. Agro-industrial lignocellulosic biomass a key
two different scenarios were considered in which the biorefinery to unlock the future bio-energy: a brief review. J. Radiat. Res. App. Sci. 7,
plant was either located next to the biomass source or near the end 163e173.
user of the produced levulinic acid. The results showed limited Baccini, A., Goetz, S.J., Walker, W.S., Laporte, N.T., Sun, M., Sulla-Menashe, D.,
Hackler, J., Beck, P.S.A., Dubayah, R., Friedl, M.A., Samanta, S., Houghton, R.A.,
difference in terms of overall emissions between the two scenarios, 2012. Estimated carbon dioxide emissions from tropical deforestation improved
suggesting that the decision for the location would be driven more by carbon-density maps. Nat. Clim. Change 2, 182e185.
by business choice rather than environmental benefits. The choice Biotech Industry Organization, Biotechnology solutions for renewable specialty
chemicals & food ingredients, http://www.bio.org/sites/default/files/Biotech%
of the right solvent seemed to be critical in order to maximize the
20Derived%20Chemicals%20Updated%20May%202014%20Final.pdf (Accessed
energy efficiency of the distillation process and the related emis- Oct 2017).
sions associated with the recovery of it. Also, it emerged from our Bozell, J.J., Moens, L., Elliott, D.C., Wang, Y., Neuenscwander, G.G., Fitzpatrick, S.W.,
analysis that both deforestation and responsible use of nitrogenous Bilski, R.J., Jarnefeld, J.L., 2000. Production of levulinic acid and use as a platform
chemical for derived products. Resour. Conserv. Recy. 28, 227e239.
fertilizers are important for the carbon footprint of the process, Brethauer, S., Studer, M.H., 2015. Biochemical conversion processes of lignocellu-
hence virtuous farmers should be involved in the supply chain in losic biomass to fuels and chemicals e a review. Chim. Intl. J. Chem. 69,
order to be in line with sustainability objectives. 572e581.
Bringezu, S., O'Brien, M., Schütz, H., 2012. Beyond biofuels: assessing global land use
In order to maximize sustainability in the supply chain, priority for domestic consumption of biomass: a conceptual and empirical contribution
should be given to agriculture residues from crop-for-food culti- to sustainable management of global resources. Land Use Pol. 29, 224e232.
vation on marginal lands and/or not linked to deforestation. The Cropper, M., Griffiths, C., Mani, M., 1999. Roads, population pressures, and defor-
estation in Thailand, 1976-1989. Land Econ. 58e73.
cellulosic biomass to feed the biorefinery process showed to Cuzens, J.E., Farone, W.A., 1998. A Method for the Production of Levulinic Acid and
possess a variable content of minerals which would lead to its Derivatives. WO1998019986.
depletion from the soil on the long term, affecting adversely the Dobermann, A., Fairhurst, T., 2002. Rice straw management. Better Crops Int. 16,
7e11.
production of the primary agriculture product. A possibility to
Dodds, D.R., Gross, R.A., 2007. Chemicals from biomass. Science 318, 1250e1251.
overcome such an issue could reside in the treatment of the Dusselier, M., Mascal, M., Sels, B.F., 2014. “Top chemical opportunities from carbo-
minerals-rich aqueous streams from the biorefinery process with hydrate biomass: a Chemist's view of the biorefinery,”. In: Nicholas, K.M. (Ed.),
Selective Catalysis for Renewable Feedstocks and Chemicals. Springer Interna-
suitable base in order to yield a source of nutrients, both organic
tional Publishing, Cham, pp. 1e40.
and inorganic, to return to the soil. In this way we envisioned a Fargione, J., Hill, J., Tilman, D., Polasky, S., Hawthorne, P., 2008. Land clearing and the
feasible sustainable process able to convert agricultural waste into biofuel carbon debt. Science 319, 1235e1238.
valuable chemicals returning minerals to the land in the form of Fitzherbert, E.B., Struebig, M.J., Morel, A., Danielsen, F., Brühl, C.A., Donald, P.F.,
Phalan, B., 2008. How will oil palm expansion affect biodiversity? Trends Ecol.
nutrients/fertilizers. Evol. 23, 538e545.
Fitzpatrick, S.W., 1997. Production of Levulinic Acid from Carbohydrate-containing
4. Conclusion Materials. US5608105.
Fredenslund, A., Jones, R.L., Prausnitz, J.M., 1975. Group contribution estimation of
activity coefficients in nonideal liquid mixtures. AIChE J. 21, 1086e1099.
Sustainability has gained more attention in the past decade and Fu, J., Xu, X.X., Lu, X., Lu, X.Y., 2016. Hydrothermal decomposition of carbohydrates
it has already started to impact chemical industries' design and to levulinic acid with catalysis by ionic liquids. Ind. Eng. Chem. Res. 55,
11044e11051.
feasibility studies. However, due to its complex interdisciplinary Gadde, B., Bonnet, S., Menke, C., Garivait, S., 2009. Air pollutant emissions from rice
nature, life cycle thinking and/or assessment publications straw open field burning in India, Thailand and the Philippines. Environ. Pollut.
(excluding bio-ethanol) are still limited in the biomass-to- 157, 1554e1558.
Gadde, B., Menke, C., Wassmann, R., 2009. Rice straw as a renewable energy source
chemicals area. In the specific case of levulinic acid, we showed in India, Thailand, and the Philippines: overall potential and limitations for
that two of the most abundant types of biomass in Southeast Asia, energy contribution and greenhouse gas mitigation. Biomass Bioenergy 33,
namely empty fruit bunches and rice straw, are the main contrib- 1532e1546.
Gilbert, N., 2012. Palm-oil boom raises conservation concerns. Nature 487, 14e15.
utors to both operational cost and field emissions. In reality the
Girisuta, B., Dussan, K., Haverty, J.J., Leahy, M.H.B., Hayes, M.H.B., 2013. A kinetic
impact in terms of GHGs of the whole process can be up to 1600 study of acid catalysed hydrolysis of sugar cane bagasse to levulinic acid. Chem.
times higher than calculated if the land yielding the required Eng. J. 217, 61e70.
biomass was acquired through deforestation practices. Also, Harris, N., Brown, S., Hagen, S., Baccini, A., Houghton, R., 2012. Progress toward a
Consensus on Carbon Emissions from Tropical Deforestation. Policy Brief.
continual removal of agriculture residue would cause the land to be Winrock International. WHOI & Meridian Institute.
impoverished of minerals on the long run, unless a way to return Harris, N.L., Brown, S., Hagen, S.C., Saatchi, S.S., Petrova, S., Salas, W., Hansen, M.C.,
V. Isoni et al. / Journal of Environmental Management 214 (2018) 267e275 275

Potapov, P.V., Lotsch, A., 2012. Baseline map of carbon emissions from defor- Murat Sen, S., Gürbüz, E.I., Wettstein, S.G., Martin Alonso, D., Dumesic, J.A.,
estation in tropical regions. Science 336, 1573e1576. Maravelias, C.T., 2012. Production of butene oligomers as transportation fuels
Harsono, S.S., Grundman, P., Lau, L.H., Hansen, A., Salleh, M.A.M., Meyer-Aurich, A., using butene for esterification of levulinic acid from lignocellulosic biomass:
Idris, A., Ghazi, T.I.M., 2013. Energy balances, greenhouse gas emissions and process synthesis and technoeconomic evaluation. Green Chem. 14,
economics of biochar production from palm oil empty fruit bunches. Resour. 3289e3294.
Conserv. Recy. 77, 108e115. Na€gele, H., Pfitzer, J., Na€gele, E., Inone, E.R., Eisenreich, N., Eckl, W., Eyerer, P., 2002.
Hart, L.R., Kenneth, R., 1956. Process for the Manufacture of Levulinic acid Esters. ARBOFORM®-A Thermoplastic, Processable Material from Lignin and Natural
US2763665. Fibers. Chemical Modification, Properties, and Usage of Lignin, Springer,
Hayes, D.J., Fitzpatrick, S., Hayes, M.H., Ross, J.R., 2006. The Biofine Process: pro- pp. 101e119.
duction of levulinic acid, furfural and formic acid from lignocellulosic feed- P and G http://www.pg.com/en_US/sustainability/policies_practices/palmoil.shtml
stocks. Biorefineries 1, 139e164. (accessed Oct 2017).
Hsu, C.C., Chasar, D.W., 1980. Process for the manufacture of levulinic acid and Pawelzik, P., Carus, M., Hotchkiss, J., Narayan, R., Selke, S., Wellisch, M., Weiss, M.,
esters. US4236021. Wicke, B., Patel, M.K., 2013. Critical aspects in the life cycle assessment (LCA) of
Isikgor, F.H., Becer, C.R., 2015. Lignocellulosic biomass: a sustainable platform for bio-based materials e reviewing methodologies and deriving recommenda-
the production of bio-based chemicals and polymers. Polym. Chem. 6, tions. Resour. Conserv. Recy. 73, 211e228.
4497e4559. Pileidis, F.D., Titirici, M.M., 2016. Levulinic acid biorefineries: new challenges for
Kamahara, H., Hasanudin, U., Widiyanto, A., Tachibana, R., Atsuta, Y., Goto, N., efficient utilization of biomass. Chem. Sus. Chem. 9, 1e22.
Daimon, H., Fujie, K., 2010. Improvement potential for net energy balance of Rackemann, D.W., Doherty, W.O., 2011. The conversion of lignocellulosics to levu-
biodiesel derived from palm oil: a case study from Indonesian practice. Biomass linic acid. Biofuel. Bioprod. Bior. 5, 198e214.
Bioenergy 34, 1818e1824. Rødsrud, G., Lersch, M., Sjo €de, A., 2012. History and future of world's most advanced
Kamm, B., Kamm, M., 2004. Principles of biorefineries. Appl. Microbiol. Biotechnol. biorefinery in operation. Biomass Bioenergy 46, 46e59.
64, 137e145. Roundtable on sustainable palm oil, http://www.rspo.org/about (accessed Oct
Khoo, H.H., Wong, L.L., Tan, J., Isoni, V., Sharratt, P., 2015. Synthesis of 2-methyl 2017).
tetrahydrofuran from various lignocellulosic feedstocks: sustainability assess- Roundtable on Sustainable Palm Oil, https://rspo.org/about/impacts (Accessed Feb
ment via LCA. Resour. Conserv. Recy. 95, 174e182. 2018).
Khoo, H.H., Ee, W.L., Isoni, V., 2016. Bio-chemicals from lignocellulose feedstock: Sabesan, S., Spado, C.J., 2013. Production of Furfural from Biomass. WO2013066541.
sustainability, LCA and the green conundrum. Green Chem. 18, 1912e1922. Saha, B.C., Yoshida, T., Cotta, M.A., Sonomoto, K., 2013. Hydrothermal pretreatment
Klingler, F.D., Ebertz, W., 2000. Oxocarboxylic Acids. Ullmann's Encyclopedia of and enzymatic saccharification of corn stover for efficient ethanol production.
Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA. Ind. Crop. Prod. 44, 367e372.
Koh, L.P., Wilcove, D.S., 2008. Is oil palm agriculture really destroying tropical Santiago, R.S., Santos, G.R., Aznar, M., 2009. UNIQUAC correlation of liquideliquid
biodiversity? Conserv. Lett. 1, 60e64. equilibrium in systems involving ionic liquids: the DFTePCM approach. Fluid
Kruse, A., Dahmen, N., 2017. Hydrothermal biomass conversion: quo vadis? Phase equilibr. 278, 54e61.
J. Supercrit. Fluids. https://doi.org/10.1016/j.supflu.2017.12.035 (in press). Silalertruksa, T., Gheewala, S.H., 2013. A comparative LCA of rice straw utilization for
Laurance, W.F., Koh, L.P., Butler, R., Sodhi, N.S., Bradshaw, C.J.A., Neidel, J.D., fuels and fertilizer in Thailand. Bioresour. Technol. 150, 412e419.
Consunji, H., Mateo Vega, J., 2010. Improving the performance of the roundtable Unilever, Sustainable living, http://www.unilever.com/sustainable-living-2014/
on sustainable palm oil for nature conservation. Conserv. Biol. 24, 377e381. reducing-environmental-impact/sustainable-sourcing/sustainable-palm-oil/
Li, D., Liu, M., Cheng, Y., Wang, D., Qin, J., Jiao, J., et al., 2011. Methane emissions from our-targets/(Accessed Oct 2017).
double-rice cropping system under conventional and no tillage in southeast Upare, P.P., Yoon, J.W., Kim, M.Y., Kang, H.Y., Hwang, D.W., Hwang, Y.K., Kung, H.H.,
China. Soil Tillage Res. 113, 77e81. Chang, J.S., 2013. Chemical conversion of biomass-derived hexosesugars to
Liu, L., Li, Z., Hou, W., Shen, H., 2018. Direct conversion of lignocellulose to levulinic levulinic acid over sulfonic acid-functionalized graphene oxide catalysts. Green
acid catalyzed by ionic liquid. Carbohydr. Polym. 181, 778e784. Chem. 15, 2935e2943.
Luterbacher, J.S., Martin Alonso, D., Dumesic, J.A., 2014. Targeted chemical Wu, L., Moteki, T., Gokhale, A.A., Flaherty, D.W., Toste, F.D., 2016. Production of fuels
upgrading of lignocellulosic biomass to platform molecules. Green Chem. 16, and chemicals from biomass: condensation reactions and beyond. Chem. Bio-
4816e4838. mol. Engr. 1, 32e58.
Ma, J.F., Tamai, K., Yamaji, N., Mitani, N., Konishi, S., Katsuhara, M., Ishiguro, M., Yan, L., Yang, N., Pang, H., Liao, B., 2008. Production of levulinic acid from bagasse
Murata, Y., Yano, M., 2006. A silicon transporter in rice. Nature 440, 688e691. and paddy straw by liquefaction in the presence of hydrochloride acid. Clean.
Mullen, B.D., Leibig, C.M., Kapicak, L.A., Bunning, D.L., Strand, S.M., Brunelle, D.J., Soil Air Water 36, 158e163.
Rodwogin, D.M., Shirtum, R.P., Louwagie, A.J., Yontz, D.J., 2013. Process to Pre- Yaaini, N., Amin, N.A.S., Asmadi, M., 2012. Optimization of levulinic acid from
pare Levulinic Acid. WO2013078391. lignocellulosic biomass using a new hybrid catalyst. Biores. Technol. 116, 58e65.

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