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Maleic anhydride from bio-based 1-butanol and

Cite this: Green Chem., 2023, 25,
furfural: a life cycle assessment at the pilot scale†
Open Access Article. Published on 07 June 2023. Downloaded on 6/5/2024 6:49:26 PM.

5922
Raffaele Cucciniello, ‡a Daniele Cespi, *‡b,c Matteo Riccardi,d,e Elena Neri,d,f
Fabrizio Passarini b,c and Federico Maria Pulsellid,f

The necessity to feed the chemical industry with bio-based platform chemicals encourages the usage of
a life cycle perspective in order to evaluate potentialities and drawbacks, before launching them at the
industrial scale. In this study, we proposed a life cycle assessment of two bio-based routes for the pro-
duction of maleic anhydride (1000 kg as the functional unit, FU): from butanol (bio-ButOH MA) and fur-
fural (bio-Furf MA). In both cases, dedicated biomasses were used to feed the pilot plants, since it rep-
resents a more realistic scenario. The study considers two levels of analysis. The first one takes into
account the simplest situation, in which no energy recovery is considered within the system boundaries.
In the second assessment level it is assumed that 100% of the heat released by the reaction is recovered
to feed the plant and co-produce steam (available for other commodities). In both scenarios, the pro-
duction of MA from bio-Furf results in being more competitive. Models were evaluated in terms of carbon
footprint (IPCC), cumulative energy demand (CED) and following a multi-impact approach (ReCiPe
method). The life cycle impact assessment phase confirms the scores achieved from the application of
the E-factor (green metric). In fact, the higher selectivity of the catalytic system used to convert bio-Furf
Received 3rd October 2022, into MA implies a lower amount of raw materials per FU with consequent minor potential impacts on the
Accepted 31st May 2023
several impact categories considered. Results, also confirmed by Monte Carlo analysis, could be used to
DOI: 10.1039/d2gc03707f attain future improvements and support the design or the retrofit of innovative industrial plants able to
rsc.li/greenchem enhance the whole efficiency.

Introduction threats such as climate change, pollution, resource exhaustion,

ecosystem damage, as well as consequences for human health.
The proliferation of plastic material production and the conse- The economy of plastics is supported by a plentiful number of
quent release of litter and residues into the environment seem stakeholders2 who are involved in different ways, along the
unstoppable. The world production of synthetic macro- cycle of raw materials, products, and wastes. This means that
molecules reached more than 360 million metric tonnes in the dynamics of this sector (among others) and the related
2020 1 following a continuous growth pattern only slowed by concerns are not easily manageable. In fact, solutions to some
the COVID-19 pandemic. In addition, the fossil-based pro- of the abovementioned dilemmas can only emerge as a combi-
duction of this impressive flow of materials imposes several nation of contributions coming from several subjects, at
different levels and scales: legislative, economic, industrial,
and planning(macro); design, processing, technological, and
chemical (micro). Companies, factories, and enterprises are
a
Department of Chemistry and Biology “Adolfo Zambelli”, University of Salerno, Via progressively embodying this approach among their strategies
Giovanni Paolo II 132, 84084 Fisciano (SA), SA, Italy especially because paying attention to problem prevention and
b
Department of Industrial Chemistry “Toso Montanari”, University of Bologna, Viale innovation towards more sustainable production processes is
Del Risorgimento 4, 40136 Bologna, BO, Italy. E-mail: [email protected]
increasing their competitiveness. In particular, much effort is
c
Center for Chemical Catalysis – C3, Alma Mater Studiorum Università di Bologna,
Viale del Risorgimento 4, Bologna, BO, Italy currently made to detect and better understand the character-
d
Ecodynamics Group, Department of Physical, Earth and Environmental Sciences, istics of the production processes and products, even among
University of Siena, Pian dei Mantellini 44, Siena, SI, Italy actors all over the entire value chain, including industrial tech-
e
NIER INGEGNERIA S.p.A, Via C. Bonazzi 2, 40013 Castel Maggiore, BO, Italy nicians and engineers, entrepreneurs and managers. By virtue
f
INDACO2 Srl, Colle di Val d’Elsa, Siena, SI, Italy
of increasing awareness of these questions, recycling and use
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/
10.1039/d2gc03707f of plastic waste are progressively increasing, whereas landfill-
‡ These authors contributed equally to the manuscript. ing these substances without processing is decreasing.

5922 | Green Chem., 2023, 25, 5922–5935 This journal is © The Royal Society of Chemistry 2023
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Green Chemistry Paper

Many investigation tools and indicators exist that enable

studying in depth any component of an industrial synthesis
pathway, facilitating problem identification and possible
improvement. The life cycle assessment (LCA), in particular, is
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a standardized investigation tool, disciplined by the

International Standard Organization,3,4 that is able to contex-
tualize punctual chemical/technological data within the wider
view of the entire life cycle of a product, from the extraction of
raw materials to the end of life and consequent disposal of it
(and its components) as a waste. The application of this
method enables the acquisition of important information on Fig. 1 MA market volume in Mt. Dashed fill: forecast based on a CAGR
Open Access Article. Published on 07 June 2023. Downloaded on 6/5/2024 6:49:26 PM.

all the process steps related to the entire life of an object and (Compound Annual Growth Rate) of 2.5 percent from 2022–2029.
stimulates the identification and assignment of responsibility
to all the actors/stakeholders directly and indirectly involved in
these dynamics – from raw material providers to final consu- of MA is historically based on the partial oxidation of two
mers. This approach provides a link between the chemical alternative precursors: benzene and n-butane.
essence of a project/process and the system-level optimization Introduced in 1933, the benzene-based MA synthesis is the
of all the components in all the phases of the production-con- oldest industrial production method. The synthesis of MA
sumption-disposal of a product, also in order to facilitate the involves the selective oxidation of benzene in the gas phase, at
transformation from a linear to a circular configuration of its a temperature between 350–450 °C.12 The reaction is catalysed
production. by mixed oxides of vanadium and molybdenum (V2O5 and
In recent years, the adoption of a life cycle thinking MoO3) supported by inert materials. It allows obtaining a
approach to the chemical sector was used as a basic concept to selectivity of MA equal to 74% with a conversion of benzene
develop a new framework to support the release on the market estimated at around 96–98%.13 However, due to its toxicity, the
of Safe and Sustainable-by-Design (SSbD) molecules. Several usage of benzene has been gradually abandoned in Europe
efforts were made by the EU institutions on SSbD molecules. (except for some plants) and in the United States, whereas it is
Cefic (The European Chemical Industry Council) and JRC still in force in some parts of Asia.14
(Joint Research Center)5,6 have worked on the standardization Nowadays, MA is mainly synthesized through the n-butane
of an innovative assessment scheme that takes into consider- route. Since the 1970s, the butane-based route has afforded
ation safety aspects, environmental sustainability, and social 80% of the worldwide production of MA.14 It involves the selec-
and economic sustainability when designing new chemicals. It tive oxidation of the C4 alkane in the presence of vanadyl pyro-
is expected that an SSbD approach will be more followed by phosphate as the catalyst (VO2P2O7). It consists of mixed
researchers and companies, also in combination with a tra- oxides of phosphorus and vanadium(IV). Depending on the
ditional LCA. After all, it represents the starting point for the type of technology used for the synthesis, the selectivity of MA
development of a benign-by-design society.7 reaches 53–65% and the conversion of n-butane does not
exceed 90%.13 The usage of n-butane, as previously men-
tioned, can reduce the intrinsic toxicity of the process and its
Background of the maleic anhydride production
environmental impacts as already reported in the
Maleic anhydride (MA, C4H2O3) represents a polyfunctional literature.14–18
platform molecule with several uses (e.g., polymers, alkyd
resins and intermediates in the fine chemical industry).8 MA is
the anhydride of maleic acid and within the category of bulk Bio-based routes to MA: an overview
chemicals, it represents one of the most important building Recently, to overcome the fossil-based production of MA, fol-
blocks since it is used in the synthesis of several compounds, lowing the 7th principle of green chemistry,19 new synthetic
such as phthalic-type alkyd and unsaturated polyester resins routes have been investigated. In detail, great relevance in this
(used in the production of fiberglass reinforced plastics, in the scenario is attributed to the MA preparation from two bio-
construction and electrical industries, and in pipeline and based molecules: 1-butanol (bio-ButOH) and furfural (bio-
marine construction), surface coatings, lubricants, additives, Furf ). Both represent viable and alternative substrates, cur-
plasticizers, copolymers (e.g. MA – styrene and MA – acrylic rently used at the pilot scale. However, thanks to the sensible
acid), and agricultural chemicals (e.g. pesticides and growth increase in the market of bio-based building blocks,20 it is con-
inhibitors).9,10 As reported in Fig. 1, theMA market volume ceivable to expect that both may support the traditional routes
experienced an exponential increase since 1984, achieving an from petroleum.
annual world production of 2.88 Mt in 2019. After a slight As reported by Pavarelli et al.,21 bio-ButOH can play a sig-
decrease in 2020–2021 (around 2.76–2.79 Mt), probably due to nificant role in the bio-based chemical industry. It is mainly
the effects of the COVID-19 pandemic, the overall amount is obtained from biomass fermentation through the ABE
expected to reach 3.40 Mt in 2029.11 The industrial production (acetone–butanol–ethanol) process, in particular, corn and

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Paper Green Chemistry

sugarcane are the most used. Literature reports on the yield such tools, as well as their mechanism the journal published a
values of the ABE process starting from these precursors, esti- tutorial review44 that can be used by readers to follow each
mated at around 4.54 kg of corn per liter of ButOH (corn step of our manuscript.
worldwide production of 1.2 billion Mt in 2021)22 and on In the present study, the reactions were considered in the
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

25 kg of sugarcane per L ButOH (sugarcane worldwide pro- gas phase on a pilot scale. They were compared to allow the
duction of 181 Mt in 2021).23,24 Alternatively, it can be identification of the main weaknesses in terms of environ-
obtained from propylene (hydroformylation to butyraldehyde mental sustainability and support future scale-up procedures.
and hydrogenation to 1-butanol), ethanol (dehydrogenation to
acetaldehyde, aldol condensation, dehydration and hydrogen-
ation of crotonaldehyde) or the catalytic hydrogenation of Materials and methods
CO.21 Bio-ButOH world production ranges from 3.0 Mt to 3.6
Open Access Article. Published on 07 June 2023. Downloaded on 6/5/2024 6:49:26 PM.

Mt.25,26 In 2022 the US production was estimated to be around As mentioned above, the methodological approach followed in
to 1.7 Mt, with a global market volume of 17.8 billion USD.27 this research combined Ef and LCA to evaluate the potential-
The production of ButOH from biomass seems to be a consoli- ities of renewable feedstocks in the synthesis of MA. Ef is one
dated process on the pilot scale. of the most recognized green metrics, focused on a single
In this scenario, the usage of bio-Furf has also been widely problem (waste generation). On the other hand, LCA rep-
investigated by researchers, in particular on the pilot scale.18 resents one of the most widespread methodologies used to
Bio-Furf derives from the hemicellulose transformation that address potential environmental impacts arising from pro-
could be extracted from dedicated biomass (e.g. switchgrass) duction processes. Both are very well-known tools for chemists,
or in part from agricultural by-products (e.g., sawdust and who are familiar with the application at each stage (e.g., lab-
corncobs).28 This aspect makes furfural a good candidate also oratory, scaling-up and industry) and sector (e.g., oil and gas,
toward 5-hydroxymethylfurfural (HMF) which has been used bio-based, nanoparticles, etc.). The combined use was adopted
with good results for MA synthesis.29,30 However, on the global in order to cover more impact categories and achieve in-depth
scale the production of Bio-Furf is far from that of bio-ButOH. knowledge of the potential impacts at the environmental level.
In 2016, it was estimated to be around 370 kt (ref. 31) with a Despite the Ef value and the other green metrics being faster
market value of 551 million USD in 2019 and a projection to and simpler than a complete life cycle they are not able to
achieve 700 million USD by 2024.31 inform on the burdens on ecosystems and human health. For
In the last years, some researchers have investigated the instance, Ef does not discriminate against the dangerousness
environmental impacts related to fossil-based MA preparations of the waste generated.43 In addition, they take into consider-
through an LCA perspective.14,15–17 In 2022, Blanco et al.18 ation just one category at a time. On the other hand, LCA is
reported the characterization of novel technologies for MA pro- more time-consuming and expensive since an extensive knowl-
duction based on the use of furfural as a feedstock. Data for edge of the software and database is needed. However, it can
bio-Furf synthesis and its conversion to MA, both in the liquid orient better the decision-making processes thanks to its struc-
and gas phase, were modeled considering the results of pre- ture and standardization according to the ISO 14040 series3,4
vious experiments.32,33 In their work, Blanco et al. highlighted that identifies it as a key methodology to support ecolabel-
the room for the future development of an alternative synthetic ling45 and within the environmental management systems.46
route toMA, by highlighting that the fossil-based syntheses are In this study, Ef was applied to both reactions to address
still competitive from an environmental point of view. the importance of including co-products in the case of multi-
Therefore, to extend the scope of the proposed reaction output systems like biorefineries. In fact, during the first level
pathways for MA synthesis from bio-based feedstocks, we of analysis (level I Ef ) the metric was calculated considering
reported the usage of the E-factor (Ef )34–36 and the LCA MA as the only product (since the target molecule). In this
methodology3,4 to assess the potential burdens of the MA syn- case, all the other streams were labelled as wastes. During the
thesis using bio-ButOH and bio-Furf as starting materials. second level of analysis (level II Ef ) the boundaries were
Ef is well-known among chemists and easily applicable to extended to co-products ( phthalic anhydride, acetic acid,
each synthetic step.37,38 It is also a useful tool for acrylic acid and formaldehyde in the case of bio-ButOH MA;
companies,39–41 which have used it alone or together with 2-furoic acid in the case of bio-Furf MA). Calculation steps and
other metrics.42 The importance of a combined usage of Ef results are collected in the ESI (Table S1†).
and LCA, already largely discussed in the literature,43 depends In the case of LCA, a cradle-to-gate approach was applied by
on the possibility of extending the simple analysis conducted selecting 1000 kg of MA as the functional unit (FU) for the
on waste production to other aspects (such as resources) and study. Downstream stages (MA usage and its EoL – End of Life)
the possibility to translate all the inefficiencies in terms of were not included since they are equivalent for both routes
potential impacts through the life cycle. and out of the scope of the study. Fig. 2 describes the entire
The LCA methodology is currently a consolidated approach supply chain and its boundaries, including each mass and
for assessing the benefits behind the adoption of the green energy flow necessary to synthesize MA on a pilot scale (e.g.,
chemistry principles at different scales. In order to help syn- reagents, catalysts, electricity, average transportation within
thetic chemists understand the importance and limitation of the entire supply chain, waste treatment processes, etc.). Co-

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Green Chemistry Paper

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
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Fig. 2 System boundaries of the MA production from different biobased precursors, (a) Bio-ButOH and (b) Bio-Furf, without considering the energy
recovery from vessel. Flows related to by-products recovery were not included in the system boundaries due to mass allocation.

products were considered for mass allocation, as already done generation and re-circulation (since it is considered
previously for other bio-based building blocks.47 Mass bal- negligible within the system boundaries). Energy consumption
ances for MA were compiled starting from the reaction efficien- for the MA synthesis has been obtained from thermodynamic
cies (Y, C and S) reported in the literature for lab-scale routes. evaluations, according to the methodology described in the
Values from the work of Pavarelli et al.21 were used in the case literature by Andraos.51 MA syntheses are extremely
of bio-ButOH MA. On the other hand, bio-Furf MA was simu- exothermic. In the ESI†, the enthalpy values of the reaction cal-
lated using data from Li et al.48 Unfortunately, no data regard- culated by considering stoichiometry ðΔr HBio‐ButOH°
MA ¼
ing the efficiency of the catalyst during the upscaling were 2585:8 MJ kmol ; Δr HBio‐Furf MA  1362:0 MJ kmol1 Þ
1 °
has
available due to the corporate know-how. However, since lab been reported.
tests were conducted using the circulating-fluid-bed reactor In order to evaluate how results are influenced by energy
and the fixed-bed reactor, we assumed that the catalyst flows, two different levels of analysis were considered. In the
efficiency remained constant (to allow a complete evaluation first level (level IEN), non-optimization was assumed: the
of the mass balances). Catalytic systems were modelled energy released by the reaction was lost in the vessel as heat
through a peer-reviewed procedure.49,50 Since no data waste (already described by the system boundaries depicted in
were available (due to the corporate know-how), the catalyst Fig. 2). The second level (level IIEN) represents an optimised
amount was assumed to be 1% (in mass) of the inlet model since it takes into account that 100% of the ΔrH° is
organic stream. None of the energetic flow was included for re- recovered to pre-heat reagents, without further transformation.

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Updated system boundaries are reported in Fig. S1.† In both international standard.59 This method, differently from others,
cases, the net energy inputs were calculated as a difference (q is able to split the carbon footprint into the main components:
tot reaction – ΔrH°). Full energy balances are reported in the fossils, biogenic, land transformation and CO2 uptake. The
ESI (Tables S8–S11†). Since energy from the reaction is higher latter one represents the contribution of the system in terms of
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

than the input request for the heat reagent, a negative energy carbon dioxide sequestration during the life cycle. We
balance was obtained for both the optimised cases. In these included this aspect, especially relevant for bio-based pro-
cases, a further recovery is introduced to simulate the recovery ducts, in order to identify the potential uptake of the starting
of heat in the form of steam (steam, in the chemical industry biomasses.
{RER}| production | APOS, U) that can be used for other pro- CED represents “the entire demand, valued as primary
cesses on a pilot scale. energy, which arises in connection with the production, use
Upstream processes for the production of the main precur- and disposal of an economic good”,60 since it “quantifies the
Open Access Article. Published on 07 June 2023. Downloaded on 6/5/2024 6:49:26 PM.

sors, bio-ButOH and bio-Furf, were simulated using values energy content of all different energy resources when they actu-
extrapolated from TEA (Techno-Economic Analysis) ally cross the boundary between the biosphere and the techno-
studies.52–54 The main infrastructures (i.e. reactors and fer- sphere”.61 In other words, it addresses renewable and non-
menters) were neglected since not being relevant to the study. renewable resource consumption (expressed in terms of GJeq.).
All models were created using SimaPro software (v.9.2).55 In order to check a wider spectrum of the impacts, the
Ecoinvent database (v.3.8) was used for simulating all the ReCiPe 2016 methodology62 was also adopted (v.1.07). It rep-
background information,56 by selecting the market scenarios resents a method of so-called multiple issues, able to classify
(to include impacts from average transportation distances) and and characterize the full LCI into 18 midpoint impact cat-
the allocation at the point of substitution (APOS) unit models. egories ( problem-oriented) and aggregate them within 3 end-
The APOS model was selected in line with the attributional point receptors (damage-oriented). In line with the aim of the
approach adopted in the study and considered more conserva- study, all the methods selected have global relevance.
tive rather than the other common approaches available on
the ecoinvent database (cut-off and consequential). A conse- Bio-ButOH MA
quential approach could be used, for example, in case the Recently, the possibility of transforming bio-ButOH into MA
model includes bio-based sources from wastes. However, since through a gas-phase oxidation has been successfully explored
no primary data were available and the world production of using a bifunctional catalyst which can both dehydrate alco-
MA needs a constant feed (as far as possible) we did not simu- hols and oxidise the butenes (reaction intermediates) into
late this scenario. MA.21 In particular, the catalyst used for this purpose is
Pilot plants were settled in Europe, dedicated energy mix vanadyl pyrophosphate (VPP) which was used before for the
was simulated by the use of the process “Electricity, medium preparation of MA through 1-butene oxidation.
voltage {Europe without Switzerland}| market group for The reaction mechanism (Fig. 3) involves the preliminary
| APOS, U”. Where available, the same rule was applied for dehydration of ButOH to 1-butene and then through isomeri-
chemicals and auxiliaries (dedicated database processes were zation its conversion to 2-butenes. The latter is further oxi-
selected accordingly, mostly RER and European without dized to crotonaldehyde. Crotonaldehyde is as a key reaction
Switzerland). Where not available, GLO and RoW scenarios intermediate which, in turn, forms maleic acid and furan in
were used. In the case of sugarcane, it was decided to adopt two parallel reactions. Maleic acid and furan reacted to form
the most predominant market (Sugarcane {BR}| market for MA through dehydration and oxidation, respectively. The
| APOS, U). Data used, for modelling the production of bio-pre- process was optimized at feeding 1% mol ButOH in air and
cursors and MA syntheses, range from 2014–2020. These
aspects were taken into consideration during the uncertainty
analysis (see Table S20†). LCIs were modelled using the most
recent ecoinvent unit processes, by avoiding obsolete and
superseded ones.
Full LCI is described in the ESI (Tables S2–S7†). Fig. 2
reports a detailed description of each route.
Potential environmental burdens were evaluated using both
the single-issue and multi-impact approach. The method
developed by the Intergovernmental Panel of Climate Change,
GWP100 (incl. CO2 uptake), v.1.01,57 and the CED (Cumulative
Energy Demand, v.1.11)58 were used to address the single
issue.
The IPCC 2021 method is specific for estimating impacts
on the climate change by expressing results in terms of carbon
footprint (e.g., kg CO2 eq.) in a 100-year time horizon. For this
reason, it is suggested as a reference method by the related Fig. 3 MA synthesis from bio-ButOH. Adapted from Pavarelli et al.21

5926 | Green Chem., 2023, 25, 5922–5935 This journal is © The Royal Society of Chemistry 2023
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Green Chemistry Paper

340 °C with a 40% of selectivity toward MA (the conversion of ous gas phase reaction at a furfural concentration of 1.6% in
the alcohol was completed). The reaction produces butenes, the feed and 54% yield in the batch reaction in the presence
light acids (acrylic and acetic acid), carbon oxides, phthalic of H5PMo10V2O40 heteropolyacid in combination with
anhydride, and minor amounts of other oxygenated com- Cu(CF3SO3)2 as the catalytic system and acetonitrile/acetic acid
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

pounds (furan and formaldehyde). mixture as the solvent.64

In the LCI the scenario starts with the production of the Recently, Li described the MA synthesis from bio-Furf in
bio-ButOH from three main sources of dedicated biomass in the presence of Mo4VO14 mixed metal oxides (reaction con-
equal amounts, such as maize, sugarcane and switchgrass ditions: furfural 2 mmol, catalyst 30 mg, acetic acid, 10 ml, O2
(Panicum virgatum), the latter being one of the most promising 20 bar, 120 °C, 16 h) with a 62% MA isolated yield.65 In 2018,
and economically important herbaceous crops.63 The choice of Li reported improved results using a vanadium phosphorus
using three different feedstocks is in line with what has been oxide (VPO) catalyst plate synthesized by a hydrothermal
Open Access Article. Published on 07 June 2023. Downloaded on 6/5/2024 6:49:26 PM.

suggested in the literature,52 because the pilot plant was method. In this case, MA was obtained (90% yield, 90.8%
designed to operate with various kinds of lignocellulosic selectivity to MA) at 360 °C using air as the oxidant and 10
biomass materials to satisfy the biofuel requests. Full LCI for vol% of bio-Furf in the feed. Herein, the reaction involves the
the alcohol synthesis was obtained by re-scaling the values bio-Furf oxidation to furoic acid (rate determining step) and
from literature52 on the basis of the mass allocation with then the consequential oxidation to furan and then MA (see
respect to the main product (bio-ButOH 79.3%; bio-Acetone Fig. 4). The VPO catalyst was synthesized by a hydrothermal
10.3% and bio-EtOH 10.3%). The system was modelled assum- method which shows high activity also after 25 h. The reaction
ing that biomass residues (lignin and off-specific) are burned proceeds into a fixed bed micro-reactor operating in a down-
in a boiler to produce steam, then transformed into electricity flow mode with an air-flow rate of 20 mL min−1 with a contact
and used on-site to feed the fermenter. Combustion produces time of 1.5 seconds. The main by-products are CO (7%),
also ash (assumed to be disposed of ) and air emissions 2-furoic acid (1.5), non-identified products and water (<1%).48
(amount and type derived from the ecoinvent process “Heat, In order to fill the LCI for the upstream process, the pro-
district or industrial, other than natural gas {ASCC}| heat and duction of the bio-Furf was simulated using the results from
power co-generation, wood chips, 6667 kW, state-of-the-art TEA reported by Zang et al.,53,54 which used switchgrass as the
2014 | APOS, U”). main precursor. The usage of a dedicated biomass is in line
Bio-ButOH was then combined with oxygen (from air) with the work of Blanco et al.18 2,3-BDO (57.8%) was co-pro-
within the gas-phase reactor, using the (VO)2P2O7 : SiO2 duced through fermentation. Input and output flows were allo-
(90 : 10) catalyst to obtain MA assuming a quantitative conver- catedwith respect to bio-Furf (42.2%). In line with the previous
sion and selectivity affording MA in 39% yield.21 The reaction scenario, the lignin content is assumed to be burned in a
proceeds with the co-production of phthalic anhydride (PA, Y = boiler to produce steam, then transformed into electricity and
12.0%), acetic acid (AcA, Y = 8.0%), acrylic acid (AA, Y = 8.0%), used on-site to feed the fermenter. Combustion also produced
formaldehyde (FAL, Y = 1.0%) and butene (BUT, Y = 1.0%). A ash (assumed to be disposed of ) and air emissions (amount
mass allocation with respect to MA (56.7%) was considered. and type derived from the ecoinvent process: “Heat, district or
The catalyst system was modelled assuming stoichiometric industrial, other than natural gas {ASCC}| heat and power co-
elements enter the system as primary resources since they are generation, wood chips, 6667 kW, state-of-the-art 2014 | APOS,
directly extracted from mineral ores (except SiO2 which was U”). In this case, the amount of electricity auto-produced
simulated using the process: Silica sand {GLO}| market for (4.1 kW FU−U) is not enough for feeding the entire system.
| APOS, U) following a peer-reviewed procedure.49,50 Full LCI is Therefore, an electricity input from the grid is necessary
reported in Tables S2, S3 and S6 in the ESI.† (322.4kW h FU−1).
Energy input was evaluated following the procedure already Bio-Furf was then sent to a gas-phase reactor to be partially
described and discussed in detail in the ESI (Tables S8 and oxidised to MA in the presence of the (VO)2P2O7:VOPO4 – VPO
S10†). In the level IEN, which considers not to recover the heat catalyst. Almost complete conversion was obtained (99.2%)
released from the reaction, an energy input of 1.2 × 102 kW h with a selectivity of 97.9% to MA. 2-Furoic acid and PA were co-
per ton of MA was imputed using the following process: generated during the reaction. Mass balance was re-built on
Electricity, medium voltage {RER}| market group for | APOS, the basis of the data from Li et al. by considering a mass allo-
U. Full inventory of the scenario with 100% energy recovery cation with respect to MA (92.9%).48 The catalyst system was
from the reaction vessel to produce steam is reported in modelled following a peer-reviewed procedure.49,50 Full LCI is
Table S12.† Steam amount was derived from energy balance reported in Tables S4, S5 and S7 in the ESI.†
considering an LHV of 2.75 MJ kg−1, as suggested by the refer-
ence process: Steam, in the chemical industry {RER}| pro-
duction | APOS, U.

Bio-Furf MA
One of the first examples reported in the literature showed
that bio-Furf is converted into MA (70% yield) in the continu- Fig. 4 MA synthesis from bio-Furf.

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In the case in which no energetic recovery was included in

the boundaries (level IEN), an energy input of 1.3 × 102 kW h
per FU was evaluated following the procedure already
described and discussed in detail in the ESI (Tables S9 and
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

S11†). This flow was simulated using the following : process

Electricity, medium voltage {RER}| market group for | APOS,
U. Full inventory of the scenario with 100% energy recovery
from the reaction vessel to produce steam is reported in
Table S13.† The steam amount was derived from the energy
balance by considering an LHV of 2.75 MJ kg−1, as suggested
by the reference process: Steam, in chemical the industry
Open Access Article. Published on 07 June 2023. Downloaded on 6/5/2024 6:49:26 PM.

{RER}| production | APOS, U.

Results and discussion

LCIs were first investigated using the Ef values. The green
metric was used as a screening tool to support the choice to
consider MA as the sole valuable output (level I Ef ) or to
include co-products within the mass allocation (Level II Ef ). In
fact, switching from a one-product system (MA) to a multi-
Fig. 5 Carbon footprint of bio-based MA routes using. IPCC 2021
output process the decrease in the E-factor values is relevant:
GWP100 (incl. CO2 uptake), v.1.01.
−79% in the case of bio-ButOH MA (1.22 vs. 0.26) and −96%
for the bio-Furf MA pathway (0.08 vs. 0.003). This is quite
common in bio-based routes, where co-productions allow an
overall impact reduction. Results from Ef also reflect a greater
competitiveness of the bio-Furf MA than the alternative. These
scores clearly demonstrate a major reaction selectivity (97.9%)
to MA in this case, with an almost complete conversion of the
precursor (99.2%). On the other hand, the reaction selectivity
of bio-ButOH to MA is lower (39%), with a sensible co-pro-
duction of non-valuable substances (e.g., CO2 (18%), CO (12%)
and uncharacterized heavy compounds (1%)). However, the Ef
value is limited to the amount of waste generated per product,
by reflecting a common gate-to-gate boundaries approach.
Therefore, the LCA methodology was also applied to investi-
gate other environmental issues and to include the potential
burdens of upstream stages in the study. As outlined before,
the LCIA (life cycle impact assessment) phase was performed
by the application of a single-impact and a multiple-impacts
approach, in order to obtain a wider spectrum and R&D
support. The first one can be used to identify where the main Fig. 6 Resource for energy consumption of bio-based MA routes using
hotspots are located. Fig. 5 and 6 show the results expressed in CED method (v.1.11).
terms of carbon footprint and resource consumption respect-
ively (see also Tables S14 and S15†). Graphs depict the scores
achieved by the simplified scenarios, without the (w/o) the all these tree sub-indicators reflect the intensity of the
energy recovery (level IEN), and those obtained for the resources and energies requested within the supply chain of
level IIEN. the dedicated biomasses used as precursors. In the ESI a con-
In the case of level IEN the bio-ButOH MA pathway achieves tribution analysis run on both bio-based building blocks (see
a greater impact for the carbon footprint in terms of fossil Tables S16 and S17†) has been reported. It has been confirmed
(−1.2 tCO2eq. per FU) and biogenic (−0.8 tCO2eq. per FU) that the mixed usage of biomasses (bio-ButOH) leads to a
flows, and for the land transformation index (−0.01 tCO2eq. per higher CO2 subtraction during growth rather than the single
FU). On the other hand, the indicator CO2 uptake results are use of Panicum virgatum (bio-Furf ), despite greater impacts on
more competitive in the case of bio-ButOH MA. The trends fossil, biogenic and land transformation indicators related to
achieved for the biogenic, land transformation and CO2 maize and sugarcane cultivation (that require intensive
uptake are similar and all related to the same reason. In fact, resources for exploitation, such as water and fertilizers). On

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Table 1 Impact assessment of bio-based MA routes: problem oriented (midpoint) process using the ReCiPe 2016 method (v.1.07). Colour shades
represent different percentage contribution achieved by each scenario per category, in line with the following scale
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Fig. 7 Contribution analysis ofbio-ButOH MA + En.Recov. (A) and bio-Furf MA + En.Recov. (B) using the ReCiPe 2016 method (v.1.07).

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the other hand, the GWP100 – fossil represents all fossil-based (green) burden within each category. bio-Furf MA + En.Recov.
resources consumed for materials (e.g., chemicals) and energy achieved the best results for almost the totality of the cat-
vectors (e.g., fuel and electricity). egories studied (16 on 18). The bio-Furf MA process w/o the
The results obtained for the optimised cases (level IIEN), in energy recovery is still competitive for 14 categories. On the
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which a boundary extension occurred (Fig. S1†), are flagged as other hand, the bio-ButOH MA cases seem to have lower
“+ En.Recov”. In this case, the energy recovery and its usage impacts for SOD and FWEu. In addition, bio-ButOH MA + En.
within the plant increase the competitiveness of each route Recov. denotes good results also in the case of FRS, thanks to
compared to the former (the non-optimised model, level IEN). the steam recovered. Results for GW and FRS confirm the
Despite the fact that bio-ButOH MA + En.Recov. contributes to scores previously shown through IPCC and CED.
mitigating the fossil indicator with −1.5 tCO2eq. per FU (with In accordance with the scores previously discussed, a con-
respect to bio-ButOH MA w/o the energy recovery) bio-Furf MA tribution analysis was carried out only focusing the attention
Open Access Article. Published on 07 June 2023. Downloaded on 6/5/2024 6:49:26 PM.

+ En.Recov. still remains the more sustainable case in terms of on the optimised cases. This assessment allows the identifi-
fossil carbon footprint. With respect to the counterpart from cation of the main environmental hotspots, settling thus the
bio-ButOH (i.e., bio-ButOH MA + En.Recov.) a potential basis for improvement. Scores are shown in Fig. 7 and pre-
reduction of −0.9 tCO2eq./FU was detected. The same trends sented in Table S19.† The production of bio-based precursors
were achieved for the biogenic and land transformation are the most influencing stages for the majority of the impact
components.
On the other hand, bio-ButOH MA cases (with and w/o the
energy recovery) remained those with better trends for the CO2
uptake (due to the extended usage of sugarcane and corn,
Tables S16 and S17†). A network analysis carried out on the
bio-ButOH supply chain for the fossil CO2 eq. indicator, shown
in the ESI in the form of a Sankey-based diagram (Fig. S3†),
confirms that despite the high contribution of the maize to
the carbon uptake, its supply chain presents sensible impacts
due to the exploitation of the resource during drying activities.
In addition, the results from the network depict a significant
burden connected to the glucose chain, the nutrient used
within the fermentation to activate the process. Also in this
case the leading cause is the maize supply chain, the main
source used in the production of the carbohydrate.
Similar achievements were attained using CED (Fig. 6),
which reflects the consumption and exploitation of resources
(renewable and non-renewable) expressed as the energy equi-
valent (GJeq.). Among those studied, bio-Furf MA + En.Recov.
achieves the best results in terms of the total amount of
resources (see pairwise comparison in Table S18†). Negative
results for the non-renewable, fossil are due to the avoided pro-
duction of the steam generated from the energy recovery. Even
though bio-ButOH MA + En.Recov. can recover a higher
amount of heat per FU respect to bio-Furf MA + En.Recov. (9.4
tsteam vs. 4.9 tsteam), the lower selectivity (also detected by the
usage of the Ef ) affects negatively the overall results, by invol-
ving the necessity of using a greater quantity of the precursor
(bio-ButOH) in the synthesis. As expected, the contribution of
the bio-based starting chemicals on the consumption of whole
resources is significant, and also has been depicted by the
renewables share as shown in Fig. S2.†
Cases were then assessed using the ReCiPe 2016 method, in
order to evaluate the better solution from an environmental
point of view through the use of a wider spectrum of potential
impacts and confirm scores previously achieved. In Table 1 the
results at the midpoint level have been collected. It consists of
18 categories that reflect problem-oriented impacts (e.g., terres-
trial acidification potential, freshwater ecotoxicity, etc.). Colour Fig. 8 Contribution analysis forbio-ButOH (A) and bio-Furf (B) pro-
shades highlight the cases with the higher (red) and lower duction chains, using the ReCiPe 2016 method (v.1.07).

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categories in both cases. This trend confirms the results dis- {GLO}| market for | APOS, U), switchgrass (Grass, Swiss inte-
cussed previously for CED and IPCC. As expected, in both cases grated production {GLO}| market for | APOS, U) and sugarcane
the resource consumption for the catalyst production only pre- (Sugarcane {BR}| market for | APOS, U) lead to the main
sents a notable impact in the MRS category, with 86% contri- impacts on different categories in both precursors. Those
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

bution in A and 97% in B. In case A, the bio-ButOH chain notice- reflect the potential effects related to the cultivation of a dedi-
ably affects some categories with a greater contribution for SOD, cated biomass. For example, corn requires an adequate
MEu, FWEc, MEc, HNCT, LU and WC. Differently, the prepa- amount of water (0.169 m3 per kg of maize, considering direct
ration of bio-Furf shows a greater effect on SOD, FWEu, MEu, LU and embodied consumption) and fertilizers. Also, the pro-
and WC. According to the network analysis (Fig. S4–S8†), higher cesses that simulate the other dedicated feedstocks achieved
scores on SOD, MEu and, LU are mostly related to the chain of high burdens in the majority of the 18 categories. In particular
switchgrass (Grass, Swiss integrated production {GLO}| market the switchgrass contribution was not negligible as depicted in
Open Access Article. Published on 07 June 2023. Downloaded on 6/5/2024 6:49:26 PM.

for | APOS, U). On the other hand, results obtained for FWEu and the ESI (see the Sankey-based diagram, Fig. S3†). The results
WC are due to the consumption of auxiliaries, in particular here depicted are in line with those already reported in recent
4 methyl-2-pentanone (MIBK) and acetone. works concerning the sector of bio-based chemicals,18,38,47,66,67
In order to verify where the impacts are concentrated within which confirm that the competitiveness of a biorefinery
the precursors, a list of procedures was then set to guide process is in its possibility of using a combination of dedicated
future improvements, and a further contribution analysis was and marginal crops (or waste), and in the co-production of
run. Results, collected in Tables S20–S21,† are shown in Fig. 8 mass and energy flows. Otherwise, the overall efficiency
using a colour shade matrix. decreases drastically (as seen for Ef ).
Moving from yellow to purpura squares the contribution of In conclusion we can affirm that LCA has shown some pre-
the LCI flows (mass or energy) per category increase drastically. liminary results using three analysis methods that confirm the
Dashed green cells represent avoided impacts. In the case of synthesis from bio-Furf to be more competitive. Despite the
the bio- Furf MA + En.Recov. the energy recovery column has fact that the production of bio-ButOH is largely diffused ( pro-
not been reported since the model just considers the net con- duction of fuel), the efficiency of the catalyst used to convert
sumption (equal to energy input minus that recovered from the alcohol into MA should to be increased. The lower selecti-
lignin combustion). It has also been depicted that, the cultiva- vity to MA, despite the co-production of some valuable chemi-
tion and the market distribution of the maize (Maize grain cals, lead to a lower Ef value that reflects a higher quantity of

Fig. 9 Uncertainty analysis of bio-based MA routes: the single score impact of each impact category using the ReCiPe 2016 method (v.1.1). Monte
Carlo simulation (1000 runs).

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Fig. 10 Uncertainty analysis of bio-based MA routes: cumulative single score impact using the ReCiPe 2016 method (v.1.1). Monte Carlo simulation
(1000 runs). Light blue bars: 99.8% of the runs with Bio-ButOH MA ≥ Bio-Furf MA. Green bars: 0.2% of the runs with Bio-ButOH MA < Bio-Furf MA.

reactants used per FU. This is converted into potential higher both cases, dedicated biomasses were used, in order to simu-
impacts on the selected categories. As expected, the results are late the more conservative scenarios from an environmental
affected by the catalyst efficiencies assumed constant to those and technological point of view. In fact, the usage of crops rep-
conducted at the laboratory scale due to the absence of further resents a more consolidated alternative to petroleum-based
details. This assumption, despite being considered a valuable precursors (e.g., butane, benzene) on a pilot scale. The bio-
approximation of pilot scale reactors, could represent a limit- based routes studied here are not intended to replace large-
ation of the study. scale plants, but to support them and lead to the start-up of
Finally, in order to verify the robustness of the LCA models the bio-MA market, as already proposed to promote the devel-
a Monte Carlo analysis was performed. A data pedigree opment of a sustainable bioeconomy.45
matrix68 was used to calculate uncertainty ranges for the LCI The scores presented above have classified bio-Furf MA as more
data concerning reagents, catalyst, energy input, emissions and suitable for upscaling, compared to the counterpart from bio-
waste streams. The lognormal statistical distribution, with a 95% ButOH. However, the results of the study should be intended as
confidence interval and an iterative calculation number of 1000 a screening benchmark to set future scale-up strategies and not
simulations, was applied. This approach is consolidated within the to give MA from bio-ButOH a bad name. As largely discussed,
LCA practitioners. Early works were related to building and con- both bio-based pathways are far from being considered net zero
struction materials.69–71 Now it is also used to support the (in particular regarding the climate change impacts). First of all,
assessment of some fundamental environmental issues, as done the results discussed are valid within the boundaries considered.
by Poncelet et al.72 in the case of minerals criticality. The results A different geographic scope (e.g., lower carbon energy, more
are collected in Fig. 9, by considering problem oriented ReCiPe local sources, etc.) may affect drastically the final results. In
2016 (endpoint – characterization). The impact categories are addition, as said, further mitigation can be achieved by focusing
shown on the y-axis, while the x-axis shows the percentage the efforts on reducing the energy input for the syntheses by
values achieved by the scenarios at the end of the simulations recovery enthalpy of the reaction and used the surplus to gene-
(after 1000 runs). Light blue bars depict the number of times rate steam. This assessment could be also useful to support new
the bio-ButOH MA process achieved a greater impact than the plant design and set better synergies to recover and valorise
bio-Furf MA process. Conversely, the light green bars represent such energy stream (e.g., in combination with energy intensive
the opposite situation. The sensitivity analysis has confirmed processes).
that the bio-Furf MA process reaches lower impacts for the Then, as outlined for both, one of the main criticalities is
majority of the categories assessed (except for FWEu). In order the catalysts activity (that reflects the inefficiencies detected by
to assess the overall robustness, the trend was also verified at the LCA models). R&D efforts on developing new catalytic
the single score level (Fig. 10). Light blue bars represent the fre- systems will have a prominent effect on mass balances, by also
quency of the runs (99.8%) for which bio-ButOH MA achieved a affecting LCI and LCIA. Further improvements within the cata-
higher cumulative impact than bio-Furf MA. Green bars confirm lytic systems yield are those set of data that are expected to
that only in 0.2% of the runs the bio-Furf MA is more impacting promote better environmental results.
from an environmental point of view. Additional studies may be also addressed to the exploita-
tion of marginal or waste vegetable biomasses in combination
with the dedicated ones. Balat and Ayar73 estimated an annual
Conclusions world biomass production of around 146 billion metric tons.
Concentrating the efforts on the residual part only, it is poss-
We presented a LCA of two alternative MA production pro- ible to co-feed bio-based chemical reactors. However, given its
cesses, by selecting bio-ButOH and bio-Furf as precursors. In high volumes worldwide the possibility of producing 100%

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waste-based MA (like the other main building blocks) seems to Acknowledgements

remain limited to the pilot scale only.
R. C. is grateful to Italian Ministero dell’Istruzione
dell’Università e della Ricerca for the financial support pro-
This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.

vided through the LEVANTE project PRIN-Bando 2020, Prot.

Abbreviations 2020CZCJN7. D. C. and F. P. are grateful for the support
AA Acrylic acid received from “Ecosystem for Sustainable Transition in Emilia-
ABE Acetone–butanol–ethanol Romagna, project funded by European Union under the
AcA Acetic acid National Recovery and Resilience Plan (NRRP), Mission 04
APOS Allocation at the point of substitution Component 2 Investment 1.5—NextGenerationEU, Call for
bio-ButOH Bio-based 1-butanol tender n. 3277 dated 30/12/2021, Award Number: 0001052
Open Access Article. Published on 07 June 2023. Downloaded on 6/5/2024 6:49:26 PM.

bio-Furf Bio-based furfural dated 23/06/2022” and from “Agritech National Research
BUT Butene Center and received funding from the European Union Next-
Ef E-Factor Generation EU (PIANO NAZIONALE DI RIPRESA E
EoL End of life RESILIENZA (PNRR) – MISSIONE 4 COMPONENTE 2,
FAL Formaldehyde INVESTIMENTO 1.4 – D.D. 1032 17/06/2022, CN00000022)”.
FPMF Fine particulate matter formation
FRS Fossil resource scarcity
FWEc Freshwater ecotoxicity References
FWEu Freshwater eutrophication
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