pubs.acs.

org/journal/ascecg Research Article

Life-Cycle Assessment of Biochemicals with Clear Near-Term Market

Potential
Chao Liang, Ulises R. Gracida-Alvarez, Troy R. Hawkins,* and Jennifer B. Dunn*
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ABSTRACT: The urgent need for greenhouse gas (GHG) emission reductions
to mitigate climate change calls for accelerated biorefinery development and
biochemical deployment to the market as structural or functional replacements
for chemicals produced from fossil-derived feedstocks. This study evaluated the
energy and environmental impacts of 15 biochemicals with clear near-term
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market potential and their fossil-based counterparts, when applicable, on a

cradle-to-gate basis. Three of these chemicals are produced exclusively from
biomass; eight are predominantly produced from fossil-derived feedstocks; and
four are predominantly produced from biomass. For the 12 cases that can be
produced from either feedstock, eight exhibited fossil energy consumption and
GHG emission reductions when produced from biomass instead of fossil-derived
feedstocks between 41%−85% and 35%−350%, respectively. Water consumption
results were mixed because several of the biobased pathways consumed more
water. Annually, replacing the predominantly fossil-fuel-based chemicals with biobased alternatives could avoid 120 MMT CO2e
emissions and save 1,500 PJ of fossil energy. The potential of these chemicals as coproducts in integrated biorefineries was analyzed
in terms of market, economics, and environmental effects with an emphasis on GHG emissions. Adipic acid, succinic acid, acrylic
acid, propylene glycol, 1,4-butanediol, 1,3-butadiene, furfural, and fatty alcohol are promising coproduct candidates based on their
low life-cycle GHG emissions.
KEYWORDS: Life-cycle assessment, Biochemicals, Fossil-based chemicals, Market analysis, GHG mitigation, Carbon credit, Supply chain,
Integrated biorefinery

■ INTRODUCTION
The development of biomass-derived products offers a
promising opportunity to improve the overall sustainability
of the United States (U.S.) industry and mitigate climate
change.1,2 According to the U.S. Department of Agriculture
(USDA), in 2016, U.S. biobased products were estimated to
displace approximately 9.4 million barrels of oil and reduce as
much as 12.7 million tonnes of greenhouse gas (GHG)
emissions (CO2 equivalents).3 Biobased products include
bioplastics and biochemicals. Biochemicals are estimated to
account for only 4 wt % of the chemicals manufactured in the
U.S.3 Therefore, tremendous growth in market share for
biochemicals is possible. The replacement of conventional
chemicals with biochemicals has the potential to reduce GHG
emissions and to promote a domestic biomass industry while
reducing dependence on fossil resources. There are, however,
an extensive number of bioderived chemicals that could be
manufactured. Understanding which bioderived chemicals
should be prioritized because they may be able to grow in
market share in the near term given the consumer demand for
environmentally responsible materials or other market drivers
could help guide bioprocessing research and development
along with commercialization strategies. Moreover, there may
© 2023 The Authors. Published by
American Chemical Society
2773
be advantages to manufacturing chemicals with readily
available, domestically produced biomass. Gaining this insight,
however, relies on consistent and transparent analyses.
Life-cycle assessment (LCA) is widely used in the evaluation
of the environmental benefits of biochemicals and bioproducts.
LCA is a technique for assessing the environmental impacts of
a product over its life cycle. Most biochemical LCAs focus on a
single product. For example, Benavides et al.4 concentrated on
polyethylene terephthalate (PET), a notable plastic resin with
rapid market expansion, using LCA to evaluate fossil fuel
consumption, GHG emissions, and water consumption of
producing biobased PET. These effects were compared with
virgin fossil-fuel-based PET and recycled PET. Several
researchers performed LCAs of multiple biochemicals with
existing or future commercial potential. For example,
Moutousidi and Kookos5 undertook LCA to examine the
Received: September 26, 2022
Revised: January 2, 2023
Published: February 6, 2023
https://doi.org/10.1021/acssuschemeng.2c05764
ACS Sustainable Chem. Eng. 2023, 11, 2773−2783
 Table 1. Fossil- and Biobased Production Pathways, LCI Data Sources, and Feedstocks of the 15 Chemicals with Clear Near-Term Market Potentiala
Fossil-based pathway Biobased pathway
Market pro-
duction
Chemicals Brief pathway description and data source Feedstock Brief pathway description and data source Feedstock pathways
14
Adipic acid Cyclohexane is oxidized to intermediates, followed by nitric acid oxidation to obtain adipic acid. NG, O Sugar is first produced from corn stover and then converted to glucaric Corn Mostly Fossil
acid through aerobic oxidation, followed by catalytic hydrogenation stover
to obtain adipic acid.14
Succinic acid N-Butane is converted to maleic anhydride via oxidation, followed by hydrogenation to produce NG, O Corn stover is hydrolyzed to sugar and then fermented to succinic Corn Mainly Fossil
succinic acid.16 acid.14 stover
Acrylic acid Propylene is catalytically oxidized to acrolein, which is then converted to acrylic acid.14 NG, O Glycerol is first produced from algae via lipid extraction and Algae Mostly Fossil
hydrogenation, which is then fermented to 3-hydroxypropionic acid,
followed by catalytic dehydration to obtain acrylic acid.14
Propylene glycol Propylene is converted to propylene chlorohydrin with hypochlorous acid and then reacted with NG, O Glycerol is first produced from algae via lipid extraction and Algae Mainly Fossil
calcium hydroxide to obtain propylene oxide; propylene oxide is converted to propylene glycol via hydrogenation, which is then converted to propylene glycol through
hydration.14 catalytic hydrogenolysis.14
1,4-Butanediol Formaldehyde and acetylene are first reacted to form 1,4-butynediol, followed by hydrogenation to NG, O Corn stover is hydrolyzed to sugar and then fermented to succinic Corn Mainly Fossil
produce 1,4-butanediol.14 acid; succinic acid is then reacted with corn-stover-derived ethanol stover
ACS Sustainable Chemistry & Engineering

to obtain 1,4-butanediol.14
1,3-Butadiene 1,3-Butadiene is produced during the production of ethylene via naphtha cracking, which is a NG, O Corn stover is hydrolyzed to sugar and then fermented to ethanol; Corn Mostly Fossil
byproduct.17 ethanol is catalytically converted to 1,3-butadiene via the Lebedev stover
pathway.17
Isoprene Isobutylene is reacted with methanol and oxygen to obtain isoprene.18 NG, O Corn stover is hydrolyzed to sugar and then fermented to itaconic Corn Mostly Fossil
acid; itaconic acid is converted to isoprene through hydrogenation stover
and dehydration.19,20
p-Xylene p-Xylene is produced via the isomerization and catalytic reforming of mixed xylenes from refinery NG, O Corn stover is hydrolyzed to sugar and then fermented to isobutanol; Corn Mainly Fossil

2774
reformate streams.14 isobutanol is converted to p-xylene through the GEVO process.21 stover
Fatty alcohol Fatty alcohol is produced via the mixture of two pathways: (1) Ziegler process: using hydrogenated NG, O Fatty alcohol is produced through the transesterification of algae oil Algae Mainly bio-
catalyst for alkylation of ethylene. (2) Oxo process: using syngas for the hydroformylation of long- followed by hydrogenation.22 based
chain olefins.22
1,3-Propanediol Ethylene oxide is converted to 1,3-hydroxypropanol through hydroformylation; then the 1,3- NG, O Glycerol is first produced from algae via lipid extraction and Algae Mainly bio-
hydroxypropanol is hydrogenated to obtain 1,3-propanediol.14 hydrogenation, which is then fermented to 1,3-propanediol.14 based
Lactic acid Natural gas is fermented to lactic acid.23 NG Corn stover is hydrolyzed to sugar and then fermented to lactic acid.14 Corn Mostly bio-
stover based
Glycerol Propene is chlorinated to allyl chloride and then oxidized with hypochlorite to obtain dichlorohydrin; NG, O Glycerol is produced from algae via lipid extraction and hydro- Algae Mainly bio-
dichlorohydrin is converted to epichlorohydrin and then hydrolyzed to glycerol with sodium genation.14 based
hydroxide.14
pubs.acs.org/journal/ascecg

Furfural N/A N/A Corn stover (corncob) is hydrolyzed to xylose and then dehydrated to Corn Mostly bio-
obtain furfural.24 stover based
Ethyl lactate N/A N/A Corn stover is hydrolyzed to sugar and then fermented to lactic acid; Corn Mostly bio-
lactic acid is reacted with corn-stover-derived ethanol to obtain ethyl stover based
lactate.14
2,5-Furandicarbox- N/A N/A Corn stover is hydrolyzed to sugar and then catalytically converted to Corn Mostly bio-
ylic acid (FDCA) 5-hydroxymethyl furfural; 5-hydroxymethyl furfural is converted to stover based
FDCA through catalytic oxidation.25,26
a
NG: natural gas. O: crude oil. N/A: not available. “Mostly Fossil” indicates that a given chemical is produced nearly exclusively via the fossil pathway. It is rare in the market for these chemicals to be
made via the biobased pathway. “Mainly Fossil” indicates that the chemicals are made in practice from both fossil and bio feedstocks, but the fossil pathway is more prevalent in the marketplace.
Similarly, “Mostly Biobased” and “Mainly Biobased” indicate the chemical is produced nearly exclusively or mixed but more prevalently via the biobased pathway.
Research Article

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https://doi.org/10.1021/acssuschemeng.2c05764
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Table 2. Supply Chain and Market Analysis of the 15 Chemicalsa

Annual global production Global market value, Compound annual growth Market value, $/kg Gross biomass needed
Chemical volume, kilo tonne/year million $/year rate (market value), % (2021 U.S. dollar) (million tonne/year)
p-Xylene 48,00028 48,00029 6.529,30 1.14b 1,100
1,3-Butadiene 14,00031 32,00032 5.532 1.77c 50
Acrylic acid 6,30033 16,00034 5.033,34 1.73d 87
Glycerol 4,70035 2,40036 6.436 1.10b 25
Adipic acid 4,20037 5,20038 4.438 1.71c 14
Fatty alcohol 3,00039 6,40040 5.140 1.51d 15
Propylene glycol 2,70041 4,00042 4.442 1.97d 20
1,4-Butanediol 2,20043 9,70044 8.344 2.89c 9.3
Lactic acid 1,30045 2,70046 8.046 1.50b 2.3
Isoprene 80047 2,90048 6.048 2.2149 5.8
FDCA 50050 44051 8.951 1.32b 1.5
Furfural 36052 58052 4.952 1.2753 3.6
1,3-Propanediol 20054 70054 5.854 1.65b 2.2
Succinic acid 7755 15056 8.256 2.10b 0.2
Ethyl lactate 3857 8458 3.246 2.90b 0.1
a
The chemicals are ranked in descending order of annual global production volume. The chemicals in bold font are currently dominantly produced
through fossil-based pathways. bData are estimated based on alibaba.com. cData are estimated based on echemi.com. dData are estimated based on
chemanalyst.com. FDCA: 2,5-furandicarboxylic acid.

global warming potential, acidification potential, and eutro-
phication potential of producing nine biobased platform
chemicals and biopolymers that are produced at a full-
commercial scale. Huang et al.2 selected the top 17 commodity
chemicals in the U.S. market and eight potential biorefinery
platform chemicals and assessed their GHG mitigation
potential with LCA. Due to the urgent need for GHG
emission reduction and climate change mitigation, identifying
biochemicals that have near-term market and GHG reduction
potential is critical.
While several of these previous studies addressed more than
one biochemical, none consistently evaluated market potential
along with the environmental impacts of key emerging
biochemicals in the U.S. Furthermore, they did not evaluate
how these biochemicals might be strategic coproducts for
integrated biorefineries that also produce fuels. Notably, Biddy
et al.6 provided a basis for accomplishing this objective,
reviewing the technology readiness and market potential of
numerous biomass-derived chemicals. These authors identified
12 biochemicals with clear near-term market potential. These
biochemicals were 1,4-butanediol, ethyl lactate, glycerol, lactic
acid, 1,3-propanediol, propylene glycol, succinic acid, 1,3-
butadiene, fatty alcohol, furfural, isoprene, and p-xylene. These
12 biochemicals were evaluated based on seven metrics: (1)
sufficiently high market volume and high value; (2) the
existence of a well-established and mature market for the
chemical; (3) the potential to be integrated with representative
hydrocarbon conversion pathways; (4) feedstock flexibility;
(5) the option to be produced from lignocellulosic feedstocks;
(6) limited direct competition with inexpensive natural-gas-
derived petrochemicals; and (7) potential to be made at a
lower cost from biomass compared to petroleum.6 In addition
to these 12 biochemicals, the report identified three additional
emerging biochemicals that held promise. These three
biochemicals, acrylic acid, 2,5-furandicarboxylic acid
(FDCA), and adipic acid, which are undergoing pilot-scale
demonstration and show potential for further development and
scale-up, were also included.6 In total, Biddy et al.6 evaluated
15 biochemicals.
In this study, we add to the previous study by Biddy et al.6
and develop LCAs of the 15 promising chemicals identified in
the previous study. This work builds on previous studies by
Adom et al.7 and Dunn et al.8 who evaluated the energy and
environmental performance of seven nonfood biomass-derived
chemicals (propylene glycol, 1,3-propanediol, acrylic acid,
succinic acid, 1,4-butanediol, lactic acid, and ethyl lactate) and
compared those with their conventional counterparts. Each
biochemical offered life-cycle GHG emission reductions. In
this study, we include the production pathways of these seven
chemicals and expand them to include the pathways of the
remaining eight, completing a holistic evaluation of all 15
chemicals identified by Biddy et al.6 We report life-cycle GHG
emissions, fossil energy consumption, and water consumption
of these biochemicals compared to contemporary baseline
compounds. As biochemicals are often viewed as coproducts of
biofuels or coproduced bioproducts, we developed profiles of
these 15 biochemicals as potential coproducts that could
improve the economics, market prospects, or environmental
effects of the main products of bioprocessing.6,9−13 Further-
more, we consider how these 15 compounds in total might
reduce the environmental effects of conventional chemical
production in aggregate.
■ METHODS
Life-Cycle Assessment. The goal of this study is to evaluate the
cradle-to-gate environmental impacts of 15 biochemicals with clear
near-term market potential6 and, when there is a fossil-based
counterpart, to assess and compare the biobased chemicals with
these fossil-based pathways.
Table 1 summarizes the selected fossil- and biobased production
pathways for each chemical. Note that while 12 of these chemicals can
be produced from fossil-derived feedstocks or biomass three of them
are not made from fossil-derived feedstocks at all. When multiple
fossil- or biobased production pathways for a specific chemical are
available, this study prioritizes commercialized pathways or those that
show high potential for scale-up. For the biobased pathways, although
food biomass (e.g., corn) is currently the main feedstock for the
production of most biochemicals in industry, the pathways using
nonfood biomass (e.g., corn stover, algae) are selected in this study
since they avoid competition with food resources and usually have
minimal land-use impacts.7 The waste vegetable oil from the biodiesel

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Figure 1. (a) Fossil energy consumption, (b) GHG emissions, and (c) water consumption of the 15 chemicals produced through fossil- and
biobased pathways. FDCA: 2,5-furandicarboxylic acid. The label “mostly” indicates that a given chemical is produced nearly exclusively from either
bio or fossil feedstocks. It is rare for these chemicals to be made from the other (fossil or bio) feedstock. The label “mainly” indicates that the
chemicals are made in practice from both fossil and bio feedstocks, but one of these two routes tends to be more prevalent in the marketplace.

industry also has great potential as a feedstock for glycerol and
glycerol-derived chemicals (acrylic acid, propylene glycol, and 1,3-
propanediol) on a commercial scale. The environmental impacts of
these pathways are discussed in the Supporting Information.
In this study, the life-cycle inventory (LCI) data were all collected
from public databases and peer-reviewed literature to enable others to
locate, check, and use the data in this analysis easily. Table 1 lists the
LCI data sources that we used. We integrated LCI data for each
pathway into the Greenhouse Gases Regulated Emissions and Energy
Technologies (GREET) model, developed by Argonne National
Laboratory. It is a U.S.-based publicly available LCA tool, which
includes the evaluations of energy and environmental impacts of a
wide range of fossil- and biobased products.14 The LCA results of
these pathways have all been added to GREET and will be released
with the GREET 2022 release.
The functional unit used for this study is 1 kg of each biochemical.
The LCA system boundary includes the full supply chain of all inputs
to the production of each chemical pathway. Where not otherwise
described, the supply chains for material and energy inputs involved in
this study were estimated using the default U.S. average values from
GREET. We used mass allocation to handle biochemical coproducts.
We chose this method over energy allocation because these
biochemicals are not energy products like fuels or electricity. Given
market value fluctuations, we opted not to use market value allocation.
Finally, applying system expansion for coproduct handling requires
knowledge of alternative production routes for coproducts which at
times did not exist or were hard to characterize.
In this study, we evaluated fossil energy consumption, life-cycle
GHG emissions, and water consumption. These metrics were assessed
using the GREET model. Generally, the feedstock inventories were

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ACS Sustainable Chemistry & Engineering
already available from GREET. The data sources used for new
conversion processes are summarized in Table 1. The GHG
assessment used the 100-year global warming potential (GWP100)
from the fifth assessment of the Intergovernmental Panel on Climate
Change.15
Supply Chain and Market Analysis. To provide a thorough
understanding of the global environmental impacts of producing these
chemicals, we analyzed each chemical’s supply chain and market
globally (Table 2). For several of the chemicals we evaluated, the U.S.
produces a relatively small share (e.g., furfural, of which China
produces more than 80% of global production27). The chemicals’
global market values, annual production volumes, and compound
annual growth rates were mainly extracted from market reports and
the literature, which reflect conditions in 2020 or 2021. The dominant
production pathways and feedstocks used for the 15 chemicals were
determined by analyzing market reports, peer-reviewed literature, and
companies’ Web sites. The unit market value (bulk price, $/kg) of the
15 chemicals varies worldwide. We estimated the 2021 U.S. bulk
prices based on data from the following sources: (1) business analysis
Web sites (echemi.com); (2) the peer-reviewed literature; (3)
historical price data (chemanalyst.com) corrected to 2021 prices
with the Producer Price Index by Commodity; and (4) trade Web
sites and quotes from the seller (alibaba.com). We assumed the
market value of a chemical would be the same whether it is made from
fossil-derived feedstocks or biomass. Notably, the estimates and
analyses in these sources might have been performed before 2020,
when the influence of the pandemic on the market was not
considered. In addition, because of the rapid inflation in the U.S.
and the surging fossil fuel price across the world, the market value of
these chemicals could vary dramatically within days. The estimates
might significantly differ from the scenarios today. The amount of
biomass feedstock required to scale up to the full production volume
of each chemical was calculated by the conversion of the biobased
pathways and the global production volume. The demand summation
of each type of biomass (corn stover and algae) was compared with its
annual global availability, which was obtained from the literature.
Effect of Carbon Credit. The reduced carbon emissions that
result from supply chain shifts to biobased chemicals could be
incentivized to offset production costs. We evaluated the effect of
carbon credits on the biochemicals’ market value, focusing on the
chemicals that are dominantly produced from fossil-derived feed-
stocks and could have lower GHG emissions when shifting the supply
chain to biomass. Three carbon credit values, $50, 150, and 200/
tCO2e, are used. The value range is set by considering (1) the Paris
agreement’s estimation that the value of carbon credit should reach
$40−80/tCO2e to limit global warming to within 2 °C59 and (2) the
value peak of the California Low Carbon Fuel Standard Credit which
has exceeded $200/tCO2e in the last three years.60
■ RESULTS AND DISCUSSION
Fossil Energy Consumption of Fossil-Fuel- and
Biobased Pathways. Table 1 defines fossil-fuel- and
biobased pathways for each chemical. For most of the 12
chemicals that can be made from both fossil fuel and biomass,
the biobased pathways consume much less fossil energy than
the comparative fossil-based pathways. As shown in Figure 1a,
biobased pathways have between 41% (acrylic acid) and 85%
(1,3-butadiene) lower fossil fuel consumption. Of the
chemicals we considered, the only two compounds that were
more fossil-fuel intensive when produced from biomass are p-
xylene and isoprene. Producing the bioisobutanol intermediate
for biobased p-xylene contributes to 78% of biobased p-
xylene’s life-cycle fossil energy consumption. The production
of itaconic acid, the intermediate for biobased isoprene, and
the refrigerant (NH3) used in the isoprene production process
account for 79% of isoprene’s life-cycle fossil energy
consumption. Another biochemical that has relatively high
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fossil energy consumption is FDCA (171 MJ/kg). For this
compound, 85% of fossil energy consumption stems from
using natural gas to heat and cool unit operations. The detailed
breakdown of the energy consumption for the production of
biobased p-xylene, isoprene, and FDCA is shown in Figure S1.
For all the other bioderived chemicals we considered, the life-
cycle fossil energy consumption is below 80 MJ/kg.
Greenhouse Gas Emissions of Fossil- and Biobased
Pathways. For the 12 chemicals with both routes available,
the GHG intensity of the biobased chemicals is generally lower
than those made from fossil feedstocks. We calculated that
GHG emission reductions achieved from producing chemicals
from biomass instead of fossil-derived feedstocks ranged from
1.9 (fatty alcohol) to 8.9 (adipic acid) kg CO2e/kg chemical.
Percentage reductions in GHG emissions ranged from 35
(acrylic acid) to 350% (1,3-butadiene) (Figure 1b). Adipic
acid, succinic acid, and lactic acid exhibit the largest reduction
in GHG intensity when shifting from the fossil- to biobased
route (8.9, 8.1, and 7.2 kg CO2e/kg chemical, respectively).
The GWP totals range between −2.7 and 6.0 kg CO2e/kg for
the biobased chemicals. Production of bioderived 1,3-
butadiene, furfural, and fatty alcohol has GHG intensities of
−2.7, −1.9, and −0.2 kg CO2e/kg chemical, respectively.
These results indicate that these biomass-to-chemical pathways
sequester more carbon dioxide than the greenhouse gases they
release. Production of biobased adipic acid, succinic acid, 1,4-
butanediol, lactic acid, and ethyl lactate also has low GHG
emissions (0−1 kg CO2e/kg chemical). The underlying factors
behind these results include carbon in the feedstocks for these
biochemicals, relatively energy-efficient processes, and high
yields. The detailed breakdown of GHG emissions for the
production of biobased chemicals that are not from GREET is
shown in Figure S2.
Water Consumption of Fossil- and Biobased Path-
ways. For the chemicals with both pathways available, the
results are mixed, and generally, the biobased pathways do not
exhibit lower water consumption (Figure 1c). This finding is
consistent with past work.4 The water consumption of the 12
chemicals produced from fossil-derived feedstocks ranges
between 2.1 and 31.1 kg water/kg chemical, while biobased
production routes have water consumption of 4.7−69.6 kg
water/kg chemical. The production of biobased p-xylene and
isoprene has the highest water demand with 69.6 and 68.4 kg
water/kg chemical, respectively. Fermentation and crystalliza-
tion steps are large water consumers. These two processes in
the production of bioitaconic acid (isoprene intermediate)
contribute more than 60% of isoprene’s water consumption.
For the biobased p-xylene, the productions of corn-stover-
derived sugar (48%) and corn steep liquor (47%) are the main
water consumers.
The evaluation and comparison of the energy and
environmental impacts of the 15 chemicals produced from
fossil- and biobased pathways provides guidance for future
development of these chemicals from nonfood biomass. Efforts
to improve energy, process, and water efficiency can be
diverted to biochemicals with high fossil energy consumption,
GHG emissions, and water consumption, such as biobased p-
xylene, isoprene, and FDCA.
Gross Environmental Impacts. Pairing the global
production volumes for the 12 chemicals that are made from
either biomass or fossil-derived feedstocks (Table 2) along
with the LCA results (Figure 1), we calculated that replacing
the predominantly fossil-fuel-derived chemicals with their
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biobased alternatives would save 120 million tonnes (MMT)

of CO2e and 1500 PJ fossil energy consumption annually.
Reducing this amount of GHG emissions is roughly equivalent
to taking 26 million vehicles off the road in the U.S.61
The global production volume and market value of the
investigated chemicals are notably different, ranging between
38 thousand tonnes per year (kt/yr) with a market value of 84
million dollars per year (MM$/yr) (ethyl lactate) and 48
MMT/yr with a market value of 48 billion $/yr (p-xylene)
(Table 2). Currently, eight of the investigated chemicals
(adipic acid, succinic acid, acrylic acid, propylene glycol, 1,4-
butanediol, 1,3-butadiene, isoprene, and p-xylene) are mainly
produced from fossil-derived feedstocks. Of these, adipic acid,
acrylic acid, isoprene, and 1,3-butadiene are not produced from
biomass commercially at a large capacity.6 For the chemicals
that are mostly produced from biomass, the scale of producing
these same chemicals from fossil-derived feedstocks varies. For
example, fossil-based fatty alcohols are produced commercially
at volumes that are comparable with biobased production of
these alcohols in some countries.62 For example, in 2015 Asian
countries produced 1.57 million tons of biobased fatty
alcohols, led by Malaysia, which produced 29% of these
alcohols. On the other hand, the fossil-based production
pathway of lactic acid is reported in the literature as merely a
process concept without supporting laboratory data.63 To the
best of our knowledge, furfural, ethyl lactate, and FDCA are
not produced from fossil-derived feedstocks.
If the supply chains of the chemicals produced largely from
fossil-derived feedstocks shifted to biomass feedstocks, large
gross GHG emission reduction and fossil energy savings could
be achieved. As shown in Figure 2a, gross GHG emission
reductions are greatest when the feedstock for the production
of 1,3-butadiene, adipic acid, and acrylic acid shifts from fossil-
derived feedstocks to biomass, reducing 53, 37, and 13 MMT
of CO2e emissions per year, respectively. These estimates are
calculated based on the relative GHG intensity of producing
these chemicals from biomass rather than fossil-derived
feedstocks. Moving to biobased production of these three
chemicals also achieves the greatest gross reduction in fossil
energy consumption, saving 720, 310, and 300 PJ of fossil
energy per year, respectively (Figure 2b). More efforts can be Figure 2. (a) GHG emissions of fossil- and biobased pathways. (b)
diverted to accelerate the supply chain shift of the three Fossil energy consumption between fossil- and biobased pathways.
chemicals and expedite the market deployment of their The green area of the blocks represents the gross environmental
biobased alternatives to obtain considerable environmental impacts of the biobased pathways. The gray + green area of the blocks
benefits in the short term. represents the gross environmental impacts of the fossil-based
If the biobased pathways of the investigated chemicals are pathways (gray only for the GHG of 1,3-butadiene). The gray area
scaled up to a full global production volume, the annual of the blocks represents the gross environmental benefits when
availability of corn stover and algae biomass could not satisfy shifting fossil- to biobased pathways (gray + green for GHG of 1,3-
the feedstock demand. In particular, p-xylene is a core chemical butadiene). To create this figure, we assumed all the fossil-fuel-
dominant chemicals are made 100% from fossil-derived feedstocks
building block and is produced at very large volumes annually and assessed the gross benefits of exclusively producing these
that would place a great demand on biobased resources. As chemicals from biomass. The area of the blocks is reported in
shown in Table 2, scaling up the biobased p-xylene production Supporting Information, Table S14.
to full volume requires 1100 MMT of corn stover per year.
This biomass resource, however, cannot meet this demand
because its supply is limited to approximately one billion tons in this study requires 150 MMT/yr of feedstock. This amount
per year.64 The total biomass demand of all other corn-stover- vastly exceeds algae biomass’ annual global production volume
derived chemicals is 83 MMT/year. The current corn stover (6 MMT/yr).14,66 The global algae market is expected to grow
supply could meet this demand. Other lignocellulosic biomass, at a compound annual growth rate of 10.9% in the next ten
such as forest residue, can also be considered as a potential years,67 which could facilitate the fast development of algae
feedstock for sugar-derived chemicals, which in total have an cultivation and increase algae biomass availability.
annual production of 180 billion tonnes,65 exceeding the mass Effect of Carbon Credit. The conventional market value
feedstock required to produce the chemicals included in this of chemicals could be largely or even fully offset by carbon
study. Producing the full volume of the algae-derived chemicals credits. As shown in Figure 3, for the evaluated chemicals in
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ACS Sustainable Chemistry & Engineering
Figure 3. Effect of carbon credit on the chemical market value. The
full bar length represents the conventional market value. “50”, “150”,
and “200” in the figure represent the carbon credits $50, 150, and
200/tCO2e. The values after applying $50, 150, and 200/tCO2e
carbon credits are presented.
this section, when applying 50, 150, and 200 USD/tCO2e
carbon credits, the conventional value of the chemicals could
be offset by 5−26%, 16−78%, and 21−104%, respectively.
Adipic acid is most impacted by the carbon credit. Using a
high-end 200 USD/tCO2e value, the credit is even slightly
higher than its conventional value. 1,4-Butanediol was least
influenced as it has a high cost, and producing it from biomass
offers a relatively small GHG emissions benefit.
Potential of Biochemicals as Coproducts in an
Integrated Biorefinery. Recently, the integrated biorefinery
concept has been actively investigated. In it, unused feedstock
components (e.g., cellulose, lignin) in the production of
hydrocarbon fuels from biomass are used to produce biobased
chemicals as coproducts. Coproducts can enhance the
feedstock utilization efficiency, improve the economic viability
of the biorefinery, and increase GHG emission reductions for
the biorefinery products.68−70 Generally, there are several
options for conversion of these unused feedstock components
to any number of intermediates or final products. Under such a
variety of options, potential biochemical coproduct candidates
need to be thoroughly evaluated. This section discusses the
potential of the 15 chemicals as coproducts considering the
chemicals market, economics, and environments.
A strong coproduct candidate should ideally have at least
either a high market volume (true of the 15 chemicals we
considered) or a high selling price. Taken together, these two
factors would yield a very attractive coproduct that would have
a strong, beneficial impact on the market. There are several
other critical factors to consider. First, a coproduct candidate’s
production capacity should not exceed its demand in the
market. This is especially true for the chemicals with smaller
markets, such as ethyl lactate and succinic acid (Table 2).
High-volume production of these compounds as biorefinery
coproducts could saturate the market. Second, the compound
annual growth rate is an important indicator. High rates point
to the market’s increasing capacity to accommodate increasing
production volumes of a chemical. From this standpoint,
chemicals with a compound annual growth rate that is among
the highest in Table 2 (perhaps above 8.0%), such as FDCA
and 1,4-butanediol, may be preferred. A third consideration is
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the potential of a biobased chemical to be cost competitive.
Chemicals with production costs that are insensitive to
feedstock cost or that are currently predominantly produced
from biomass are likely to be competitive. Biobased equivalents
of chemicals produced predominantly from fossil-derived
feedstocks usually face stiff competition on a cost basis. This
barrier to cost competitiveness is often driven by feedstock
costs. In an integrated biorefinery, however, this cost is largely
shared with other products. When infrastructure and operation
costs are spread among multiple products, this can effectively
reduce the cost of an individual biochemical compared to if it
were produced in a stand-alone facility.10−13 Finally, the role of
carbon credits in biobased chemicals’ costs is important,
particularly when a biobased alternative exhibits substantially
lower GHG emissions, as is the case for adipic acid.
To maximize the environmental benefits of a biorefinery, the
selection of the coproducts might be best based on two main
factors. First, ideally, coproduced biochemicals would have the
potential to achieve negative life-cycle GHG emissions. Of the
chemicals we considered, biobased 1,3-butadiene, furfural, and
fatty alcohol have this potential. Choosing them as coproducts
could offer large system-level benefits and lower biorefinery
life-cycle GHG emissions because of the remarkable GHG
advantage that arises from producing them from biomass
instead of fossil-derived feedstocks, although it should be noted
that coproduct handling methods in biorefinery LCA,
especially displacement, require special consideration.68
Second, it would be advantageous to choose biochemicals
that could replace predominantly fossil-fuel-derived chemicals
with comparatively greater environmental impacts. Multiple
factors affect the relative environmental effects of fossil-fuel-
and biomass-derived chemicals. These include fossil energy
consumption, GHG emissions, and water consumption.
Considering that climate change mitigation is an immediate,
urgent need, this section focuses on the potential GHG
emission benefits of biobased chemicals. Biobased production
of adipic acid, succinic acid, acrylic acid, propylene glycol, and
1,4-butanediol could offer large system-level GHG emission
reductions because these pathways emit notably lower levels of
GHGs than incumbent methods of producing these chemicals
from fossil-derived feedstocks.
On the other hand, some chemicals may offer limited
environmental benefit from a displacement perspective and
have a minimal influence on biorefinery LCA results because
the process they would displace would have near-identical
GHG emissions. Of the chemicals we considered, 1,3-
propanediol, glycerol, lactic acid, ethyl lactate, and FDCA are
generally biomass-derived and fall into this category.
Finally, some biochemicals exhibit higher life-cycle GHG
emissions than comparable chemicals made from fossil-derived
feedstocks. For example, biobased p-xylene is more GHG
intensive based on our analysis. Importantly, technology for
producing biobased chemicals is advancing, and pathways with
near-term commercial potential should be monitored for such
advances that could decrease their life-cycle GHG emissions.
Of the chemicals in this study, adipic acid, succinic acid, acrylic
acid, propylene glycol, 1,4-butanediol, 1,3-butadiene, furfural,
and fatty alcohol are promising coproduct candidates based on
their cradle-to-gate GHG emissions.
Our discussion has emphasized biochemicals as a drop-in
replacement. Functional replacement could also be considered
based on the main target markets of the coproducts. For
example, poly(lactic acid) and poly(ethylene furanoate),
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ACS Sustainable Chem. Eng. 2023, 11, 2773−2783
ACS Sustainable Chemistry & Engineering
derived from lactic acid and FDCA, respectively, can both
replace conventional PET in certain applications. Thus, this
analysis could be extended to encompass functional replace-
ments for polymers or other more complex products produced
from these biochemical intermediates. In the instance a
biochemical fulfills an entirely new market, the influence of
the new product in its application should be considered. For
example, an LCA of new thermal insulation material for
buildings should consider the extra energy savings that the
material brings during use.71−73
A biorefinery’s coproduct should be chosen based on the
existing or expected characteristics of the biorefinery.
Important factors to address include: (1) the feedstock(s)
that will be used to produce the coproducts, (2) potential
candidate coproduct biochemicals based on feedstocks and
technology, (3) the maximum production capacity of the
candidate coproducts and existing and projected market size,
and (4) the relative importance of economic and environ-
mental benefits from the coproduct(s).
Addressing these points may uncover several possible
options for coproducts to pursue at the biorefinery. For
example, succinic acid may be a better coproduct candidate
than 1,4-butanediol because the acid has lower life-cycle GHG
emissions. The global market size of succinic acid (77 kt/yr) is
much smaller than that of 1,4-butanediol (14,000 kt/yr). For a
biorefinery system with a large production capacity, selecting
biobased 1,4-butanediol as the coproduct may result in a
higher gross environmental benefit. Biorefinery decision
makers may turn to multicriteria decision analysis to help
them choose among different coproduct options.74 This study
provides a basis for using such a method because it identifies
and explicitly evaluates various alternatives of the coproducts,
providing significant inputs that this method would need.
■ CONCLUSION
In this study, we assessed the energy and environmental
impacts of 15 biochemicals that have clear near-term market
potential and their fossil-based counterparts on a cradle-to-gate
basis. The potential of these chemicals as candidates for
coproducts in the integrated biorefinery was analyzed
considering market, cost, and environmental factors. Bio-
chemicals, especially those with lower life-cycle GHG
emissions than incumbent chemicals produced from fossil-
derived feedstocks and potentially high market volumes, can
offer important avenues to GHG reduction from the chemical
sector and for integrated biorefineries.
There are several potential extensions of this work. One is
considering functional biochemicals as functional rather than
drop-in replacements, as previously mentioned. A second is to
extend the system boundary to end-use and end-of-life. In
particular, different market applications (e.g., long-lived
polymers versus applications that may entail rapid degrada-
tion) and waste management methods affect biogenic carbon
cycling. Biochemicals that do not degrade and are landfilled
sequester biogenic carbon permanently. Incinerated biochem-
icals release biogenic carbon to the atmosphere. The uptake of
biogenic carbon into the biochemical feedstocks offsets these
combustion emissions, which are then often considered carbon
neutral, especially if the feedstock has a brief planting-to-
harvest time window (e.g., agricultural residues like corn
stover). Biochemicals that enter supply chains with high
recycling rates (e.g., tires) contribute to a circular economy
because their biogenic carbon is circulated in the production−
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use−recycling loop. Evaluating these benefits should consider
the environmental impact of recycling and the total circulation
time of the carbon based on the recycling method.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.2c05764.
Life cycle inventory data of the chemicals (Tables S1−
S13); Fossil energy consumption and GHG emissions of
the biobased chemicals (Figures S1 and S2); LCA of
soybean-based and algae-based glycerol (Figure S3);
Details of market data (Table S14) (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Jennifer B. Dunn − Department of Chemical and Biological
Engineering, Northwestern University, Evanston, Illinois
60208, United States; Northwestern-Argonne Institute of
Science and Engineering, Evanston, Illinois 60208, United
States; orcid.org/0000-0002-2065-5106; Phone: +1-
847-467-6285; Email: jennifer.dunn1@northwestern.edu
Troy R. Hawkins − Systems Assessment Center, Energy
Systems and Infrastructure Analysis Division, Argonne
National Laboratory, Lemont, Illinois 60439, United States;
orcid.org/0000-0001-6897-175X; Phone: +1-630-252-
6428; Email: thawkins@anl.gov
Authors
Chao Liang − Institute for Sustainability and Energy at
Northwestern, Northwestern University, Evanston, Illinois
60208, United States; orcid.org/0000-0002-3307-7712
Ulises R. Gracida-Alvarez − Systems Assessment Center,
Energy Systems and Infrastructure Analysis Division, Argonne
National Laboratory, Lemont, Illinois 60439, United States;
orcid.org/0000-0002-5061-169X
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.2c05764
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
Northwestern University and Argonne National Laboratory
were supported by the Office of Energy Efficiency and
Renewable Energy of the U.S. Department of Energy (DOE)
under contracts DE-EE0008928 and DE-AC02-06CH11357,
respectively. We are grateful to Nichole Fitzgerald and Andrea
Bailey of the Bioenergy Technologies Office for their support
and guidance. The views and opinions of the authors expressed
herein do not necessarily state or reflect those of the U.S.
Government or any agency thereof or of any commercial
entity. Neither the U.S. Government nor any agency thereof,
nor any of their employees or employees of contributing
companies, makes any warranty, expressed or implied, or
assumes any legal liability or responsibility for the accuracy,
completeness, or usefulness of any information, apparatus,
product, or process disclosed or represents that its use would
not infringe privately owned rights.
https://doi.org/10.1021/acssuschemeng.2c05764
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ACS Sustainable Chemistry & Engineering
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