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Research Article

Cite This: ACS Sustainable Chem. Eng. 2018, 6, 9725−9733

Exploring Comparative Energy and Environmental Benefits of

Virgin, Recycled, and Bio-Derived PET Bottles
Pahola Thathiana Benavides,*,† Jennifer B. Dunn,† Jeongwoo Han,† Mary Biddy,‡
and Jennifer Markham‡
†
Systems Assessment Group, Energy Systems Division, Argonne National Laboratory (ANL), 9700 S. Cass Avenue, Argonne, Illinois
60439, United States
‡
National Bioenergy Center, National Renewable Energy Laboratory (NREL), 15013 Denver West Parkway, Golden, Colorado
80401, United States
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*
S Supporting Information

ABSTRACT: Polyethylene terephthalate (PET) is a common

Downloaded via 194.224.31.235 on November 2, 2021 at 09:36:27 (UTC).

plastic resin used to produce packaging, notably plastic bottles.

Most PET bottles are produced from fossil fuel-derived
feedstocks. Bio-derived and recycling-based pathways to PET
bottles, however, could offer lower greenhouse gas (GHG)
emissions than the conventional route. In this paper, we use life-
cycle analysis to evaluate the GHG emissions, fossil fuel
consumption, and water consumption of producing one PET
bottle from virgin fossil resources, recycled plastic, and biomass,
considering each supply chain stage. We considered two routes
to produce bottles from biomass: one in which all PET
precursors (ethylene glycol and teraphthalic acid) are bio-
derived and one in which only ethylene glycol is bio-derived. Bio-derived and recycled PET bottles offer both GHG emissions
and fossil fuel consumption reductions ranging from 12% to 82% and 13% to 56%, respectively, on a cradle-to-grave basis
compared to fossil fuel-derived PET bottles assuming PET bottles are landfilled. However, water consumption is lower in the
conventional pathway to PET bottles. Water demand is high during feedstock production and conversion in the case of
biomass-derived PET and during recycling in the case of bottles made from recycled PET.
KEYWORDS: Bio-derived PET bottle, Recycled-based PET bottle, Life-cycle analysis, Water consumption

■ INTRODUCTION
Polyethylene terephthalate (PET) is increasingly used in
packaging and electrical insulation, textiles, and carpets. A
barrier to oxygen, water, and carbon dioxide,1 PET is
commonly used to produce beverage bottles. PET product
consumption grew in the European Union from 1.9 to 2.9
million tonnes between 2001 and 2008.2 Furthermore, PET
global production is expected to increase from 42 million
tonnes (2014) to 73 million tonnes by 2020.3 On the other
hand, plastic beverage bottle consumption has increased
worldwide from 300 billion plastic drinking bottles in the
2000s to 480 billion in 2016. By 2021, this consumption will
increase to 583 billion plastic drinking bottles.4 As PET
undergoes such notable expansion, it is important to consider
what role bio-derived and recycled PET could play in the
sustainability of PET in terms of fossil fuel consumption,
greenhouse gas (GHG) emissions, and water consumption
associated. Recycled PET provides opportunities to reduce
virgin crude oil and natural gas consumption and carbon
dioxide emissions associated with plastic bottles. Moreover,
plastic waste accumulating in landfills and natural habitats as
plastic consumption increases is a well-known concern.5−7 In
2012, the amount of waste PET in municipal solid waste
(MSW) in the United States was 4.1 million tonnes, out of
which 1.3 million tonnes of PET, or 31% of waste PET, was
recycled.8 Using recycled PET to produce bottle-grade PET is
a viable option to ameliorate PET waste. PET can be recycled
multiple times into many products.9,10 Although there are
many advantages to using recycled PET to displace virgin PET,
not all demand for PET can be met through recycling.11 It is
therefore important to explore other options to reduce energy
and environmental impacts of PET products, including
producing them from biomass.
Production of bio-derived chemicals provides an oppor-
tunity to reduce United States dependence on imported oil,
encourage the creation of new domestic bioproducts industry,
and improve the overall economic and sustainability of
integrated biorefineries.12 Moving in this direction, companies
including Coca-Cola, Ford Motor Company, H.J. Heinz, Nike,
and Procter & Gamble have partnered with biobased product
Received: February 13, 2018
Revised: May 17, 2018
Published: June 28, 2018

© 2018 American Chemical Society 9725 DOI: 10.1021/acssuschemeng.8b00750

ACS Sustainable Chem. Eng. 2018, 6, 9725−9733
ACS Sustainable Chemistry & Engineering Research Article

Figure 1. Fossil fuel- and bio-derived pathways for production of PET resin and PET bottles.

Table 1. Material and Energy Used To Produce vPET Pellets from Fossil Fuels25,26 and 100% and Partially Bio-Derived vPET
Pellets24,25,29−33,a
Bio- Bio-ethylene Bio-ethylene 100% Bio-derived Partially bio-
Fossil vPET23,24,c ethylene24,30 oxide31 glycol29,32 vPET33 Xylene25 Paraxylene25 derived PET
Ethanol24,b 1.70
Oxygen24 0.9
Bio-ethylene 0.8
Bio-ethylene oxide 0.9
Bio-ethylene 0.3 0.3
glycold
Bio-TPA 0.9
Naphtha24 1.0
Xylene 1.0
Acetic acid24 0.04
Methanol24 0.04
Paraxylene 0.5
Water (l kg) 8.2 0.001 0.5
Natural gas 0.21 (10 MJ/kg)
Crude oil 0.59 (25 MJ/kg)
Natural gas 13.4 2.6 4.2 4.9 1.7 6.4 4.1
Electricity 3.1 1.3 2.4 1.4 0.02 0.4 1.4 6.6
Coal 0.8 0.2 0.7 0.5
Liquefied 0.1 0.06 0.2
petroleum gas
Residual oil 3.1 1.9
Diesel 0.5
Gasoline 0.02
Total 21.1 3.9 6.6 1.4 4.9 2.4 8.7 13
a
Material and energy input listed in this table is related to processing for each material presented in each column; for example, to produce 1 kg of
ethanol requires 3.6 kg of corn stover and so on.24 bCorn stover is the process feedstock used to produce ethanol. Details regarding corn stover
collection, fertilizer use, handling, storage, and processing and transportation as well as ethanol production pathways are presented in GREET
2017.24 cEnergy to make pellets in fossil-derived vPET is already included in the values presented in this table according to process descriptions
elsewhere.25,26 dThe reaction to produce bioethylene glycol is exothermic.29 Therefore, we assume that no energy is consumed to carry out the
reaction. Some electricity, however, is used in glycol distillation.32

manufacturers like GEVO, Virent, and Avatium to accelerate
the development and deployment of biomass-derived
plastics.13,14
In this paper, we study the environmental impact of PET
bottle production from different sources: virgin fossil fuel
feedstocks, recycled PET, and cellulosic biomass (Figure 1).
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Although polylactic acid (PLA)15,16 and other biomaterials can
be used as plastic bottle feedstocks, our analysis adopts PET,
the most common biomass-derived feedstock for plastic
bottles17 We use life-cycle analysis (LCA) to characterize the
life-cycle energy and environmental impacts of PET bottles
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produced from these three sources including GHG emissions,
fossil fuel consumption (FFC), and water consumption.
Compared to previous studies,16,18−22 our analysis presents a
comprehensive study of several PET production pathways
including fossil-, bio-, and recycling-derived feedstocks,
including two routes to biomass-derived terephthalic acid
(TPA) through building blocks ethylene glycol (EG) and
terephthalic acid (TPA), which are both conventionally
derived from fossil fuels. For example, only one previous
study provided results that included the different life-cycle
stages.19 Our analysis includes feedstock production, bottle
fabrication, and end-of-life. Typically, analyses of biomass-
derived PET adopt ethanol made from food crops such as
sugar cane and maize as the PET feedstock with the exception
of Chen et al.20 In contrast, we use corn stover, a second
generation, cellulosic feedstock. Previous studies highlighted
TPA as a driver of GHG emissions in PET or PET bottle
production.19,20 Consequently, we explore different TPA
production pathways. Additionally, we include water intensity,
a generally overlooked metric,23 considered in only two
previous studies.19,21 Significant water consumers in the PET
bottle supply chain are bottle production and recycling. In the
latter case, recycled materials must meet mandatory hygienic
and safety standards that apply to virgin PET (vPET). In our
analysis, we use the 2017 release of the Greenhouse gases,
Regulated Emissions and Energy use in Transportation
(GREET) model.24 The GREET model, publicly available
and developed with the support of the U.S. Department of
Energy, is an LCA tool and permits users to investigate energy
and environmental impacts such us fossil energy, petroleum,
and total energy use (including renewable energy in biomass),
GHG emissions, and water consumption of conventional and
emerging fuels, vehicle technologies, and bioproducts.
■ METHODOLOGY
We analyzed several different pathways to PET. In this section,
we present key methodological details and assumptions
concerning our analysis. Figure 1 illustrates the steps involved
in fossil fuel- and bio-derived vPET bottle production.
Fossil Fuel-Derived vPET. Section S1 of the Supporting
Information describes the different routes to produce PET
resin from fossil fuels through either reaction of ethylene glycol
(EG) and TPA or reaction of dimethyl phthalate (DMT) and
EG. Frankiln Associates, a division of the Eastern Research
Group, reported the material and energy flows of PET
production through a combination of these two routes (85%
by mass EG and TPA, 15% by mass DMT and EG).25 The
mass shares they used are based on the North American PET
market. These data (Table 1) have been adopted in GREET
and are used in this analysis.26 Most of the energy input is
natural gas (64%), while the balance is distributed between
residual oil, diesel, coal-liquefied petroleum gas, gasoline, and
electricity. Table S1 of the Supporting Information presents
noncombustion emissions from fossil fuel-derived PET
production.
100% and Partially Bio-Derived vPET. The first case we
considered for the production of PET bottles from biomass is a
fully biomass-derived case with both EG and TPA produced
from biomass. Uniquely, we investigated two biochemical
routes to TPA: direct fermentation of sugars (TPA1) and via
an isobutanol intermediate (TPA2).27,28 Route TPA1 uses
aerobic fermentation to directly convert oxygenated biomass
into TPA. Route TPA2 goes through isobutanol to paraxylene
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which then undergoes partial oxidation to TPA. This later
process is an established, high-volume commercial process.
Companies are working to demonstrate production of para-
xylene from isobutanol at a demonstration scale (e.g., Gevo).
Although TPA via direct fermentation is less mature than the
isobutanol route, the motivation for studying this pathway is to
understand the benefits of directly converting biomass to TPA
rather than going through multiple conversion steps, losing
carbon and increasing capital/operating costs throughout the
process. Furthermore, conducting environmental analysis of
bioproducts at the research and development stage will allow
designers and engineers to improve product sustainability.23
Details of both of these pathways can be found in the
Supporting Information. The second case considered for
producing PET bottles from biomass involves production of
EG from biomass and TPA from fossil fuel feedstocks. Table 1
summarizes the material and energy input for bio-derived
vPET production. The energy input of PET production
includes consumption of 1031 kg of PET and 252 MJ of
natural gas energy to transform the PET into pellets.22
PET from Recycling (rPET). PET recycling involves
transportation and separation activities which incur energy
and environmental impacts. The recycling process starts with
collection of postconsumer waste material, which is trans-
ported to a recycling, or material recovery facility (MRF),
where waste material is separated and reprocessed into pellets.
Then, the recycled PET (rPET) pellets are transported to a
bottle manufacturing facility where injection and blow molding
are performed.
We incorporated material and energy flow data to represent
the PET recycling process in GREET using efficiency, material,
and energy inputs from previous studies to sort and reprocess
waste plastic in order to recycle PET.21,22 Table 2 summarizes
Table 2. Material and Energy Used for Sorting and
Processing rPET Pellets21,22
Material (kg/kg rPET)
Mixed plastic waste 2.4
NaOH 0.01
Sulfuric acid 0.02
Water (l kg) 3.1
Energy input (MJ/kg rPET)
Electricity 1.3
Diesel 0.15
Natural gas 2.6
Total 4.1
the material and energy input needed to produce 1 kg of rPET
pellets from PET that was recovered from waste plastic. Details
about the transportation of recycled PET resin are presented in
the Supporting Information.
Manufacturing PET Bottles. Stages involved in producing
a bottle from PET resin include injection molding, stretch
blow molding, and cooling (see more details in the Supporting
Information). The material and energy inputs for each
transformation is summarized in Table 3. These inputs are
identical for all the pathways studied in this paper.
System Boundary. Figure 2 summarizes the seven
analyzed pathways. Note that to limit discoloration the
maximum amount of waste PET in a recycled bottle is 35%.
In the case of bottles with recycled content, 35 wt % is recycled
fossil fuel-derived PET; the balance is either fossil fuel- or
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Table 3. Mass of PET Input and Energy Input Used To
Transform 1 kg of PET by Injection and Blow Molding25,26
Injection Molding Blow Molding
Material input (kg PET/kg of transformed product-PET)
(kg of PET/kg of transformed PET) 1.14 1 consumes a significant amount of natural gas and crude oil see
Energy input (MJ/kg)
Diesel 0 0.01
Liquefied petroleum gas 0 0.02
Electricity 2.9 6.2
Total 2.9 6.2
biomass-derived.22 Figure S3 in the Supporting Information
conveys the composition of a PET bottle in each scenario. The
system boundary in each case includes raw material production
and acquisition, conversion to PET pellets, and bottle
manufacture. It is assumed that PET bottles are used once
then landfilled, which is the dominant United States domestic
treatment of plastic waste. PET bottles are very stable in
landfills and may take over a century to degrade. As we have
done previously,34 we adopt a time horizon equal to 100 years
and assume no degradation of landfilled PET bottles occurs.
Therefore, the carbon within the PET bottle is effectively
captured, and no CO2 will be released to the atmosphere.
Because we consider the impact of plastic bottle production
from different PET sources, we adopt one 26 g, 500 mL PET
bottle as the functional unit for each PET pathway.35
The GREET model was used to calculate the GHG
emissions (gCO2e/bottle PET), FFC (MJ/bottle PET), and
water consumption (L/bottle PET) of the several PET
production pathways studied in this paper. The GHG
emissions include CO2, CH4, and N2O emissions calculated
on the basis of the 100-year global warming potentials for CO2,
CH4, and N2O emissions, which are 1, 25, and 265,
respectively. For the analysis, we use the United States
electricity mix as the electricity source and natural gas
produced in the United States.24
Figure 2. Summary of PET bottle production pathways.
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■ RESULTS AND DISCUSSION
Life-cycle FFC and GHG emissions for all pathways are
presented in Figure 3. Life-cycle FFC (left side, Figure 3) is
lower in all cases compared to fossil fuel-derived vPET, which
(Table 1). FFC reductions range from 13% for 100% bio-
derived vPET via TPA1 to 56% for bio-derived rPET via
TPA2. On the other hand, producing bottles with recycled
content results in notably low FFC because there is no energy-
consuming chemical transformation in PET recycling. The
right side of Figure 3 illustrates the life-cycle GHG emissions
of the seven pathways. As with the FFC results, all cases exhibit
lower life-cycle GHG emissions (12%−82%) compared to
fossil fuel-derived vPET bottles. The greatest reduction (36
gCO2e per bottle of vPET compared to 119 gCO2e per bottle
of fossil fuel-derived vPET on a cradle-to-grave basis)
corresponds to the case when bio-EG and TPA2 are used to
produce 100% bio-derived vPET. Pathways to PET bottles that
incorporate recycled PET are also less GHG intensive than
fossil fuel- or partially bio-derived vPET. PET bottles produced
with fossil fuel-derived virgin PET and 35 wt % recycled PET
are less GHG intensive than two of the bio-derived routes to
PET bottles. When recycled content is added to bio-derived
new PET, GHG emissions are lower than in case 7.
Figure 4 illustrates drivers of life-cycle GHG emissions based
on the different stages involved in the production of PET
bottles. The figure also compares the results between all the
pathways studied in this paper. The major GHG driver in the
supply chain of a fossil fuel-derived vPET bottle is the
conversion process, which contributes 52% of the total life-
cycle GHG emissions. In contrast, the conversion stage of both
100% bio-derived vPET-TPA1 and vPET-TPA2 only contrib-
utes 6% and 11% of the total GHG emissions, respectively.
The total GHG emissions to produce one vPET bottle using
TPA1 is 91 gCO2e, which is significantly higher compared to
22 gCO2e, which is emitted if PET is made using TPA2. In
these bio-derived cases, feedstock production plays an
important role. For instance, in the case of 100% bio-derived
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Figure 3. Life-cycle GHG emissions and FFC for different PET bottle production pathways.
Figure 4. Breakdown of the life-cycle GHG emission for each pathway of virgin and recycled PET production.
vPET-TPA1, life-cycle GHG emissions of feedstock produc-
tion are 99 gCO2e per bottle, while for the second case (100%
bio-derived vPET-TPA2) life-cycle GHG emissions of the
feedstock production are 61% less or 38 gCO2e per bottle.
This difference stems from the technology used to produce
TPA. TPA is the biggest contributor to the total GHG
emissions of vPET as 72 wt % of vPET is made with biobased
TPA and only 28 wt % is bio-EG. Therefore, biobased TPA
production via direct fermentation (TPA1) is more GHG-
intensive compared to TPA production via isobutanol (TPA2).
Sodium hydroxide (NaOH) contributes 59% to TPA1
production GHG emissions (Table S5, Supporting Informa-
tion). NaOH is predominantly used to recover TPA from the
fermentation broth. It is also used to control the pH during
TPA production and during biomass deconstruction (up-front
deacetylation) to remove inert materials and to make the
biomass more amenable to further deconstruction pretreat-
ment. Reducing NaOH consumption in TPA1 production
would greatly lower GHG emissions associated with this
conversion route. Regardless of the biomass-based TPA
production pathway, bio-TPA can potentially offer lower
GHG emissions compared to conventional fossil fuel-derived
TPA. For example, we found that the cradle-to-gate GHG
emissions of TPA1 and TPA2 were 50% less and 138% less
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GHG intensive, respectively, than cradle-to-gate GHG
emission of fossil fuel-derived TPA produced via the
conventional mid-century process based on an estimated of
3.1 kg CO2e per kg of TPA.36
In general, biogenic carbon credits afforded to biomass-
derived PET bottles are a significant reason why these bottles
have lower life-cycle GHG emissions than PET bottles
produced from fossil fuels. The biogenic carbon credit is also
included in the partially bio-derived vPET and bio-derived
rPET. The biogenic carbon in corn stover is either emitted
during the PET production or stored in the final PET product.
The biogenic carbon emissions during PET production are
canceled by the biogenic carbon absorbed during the biomass
growth. This analysis does not present these emissions and
credits as they dwarf the other GHG emissions and credits.
The biogenic carbon stored in the final PET product is
calculated based on the carbon content of the final PET
product and its biogenic portion. For example, the biogenic
portion of 100% bio-derived vPET is 100%. The biogenic
portion of partially bio-derived vPET is estimated based on the
bio-derived portion of PET (bioethylene) which is approx-
imately 35%. As shown in Figure 4, these credits varied from
60 gCO2e per bottle of PET for both 100% bio-derived cases
(TPA1 and TPA2) to 39 and 21 gCO2e per bottle of PET for
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Figure 5. Life-cycle water consumption for different PET bottle production pathways.

Table 4. Comparison of Results with Other Papersa14−19

Pathways Additional information
Fossil- 100% bio- Bio-derived Fossil-
derived derived vPET- Partially bio- rPET − derived End-of-life
Literature review vPET TPA2 derived vPET TPA2 rPET Feedstock System boundary assumption
This study 4.6 1.4 (70%) 4.1 (10%) 1.6 (65%) 3.7 (19%) Corn stover Cradle-to-grave Landfill
Shen et al.16 4.7 n/a 3.8/4.0b (19/ 3.3/3.7b,c 4.3 (8.5%) Maize (60%) and sugar Cradle-to-grave Incineration
15%) (30/21%) cane (40%) with energy
recovery
Chen and Patel18 4.4 3.4 (23%) 3.7 (16%) n/a n/a Maize Cradle-to-grave Incineration
Shen et al.22 3.4 n/a 2.5 (26%) 2.1 (38%) n/a Maize (50%) and sugar Cradle-to-grave Incineration
cane (50%) with energy
recovery
Tsiropoulos et al.19 2.2 n/a (2/2.3)d n/a n/a Sugar cane Cradle-to-gate Excluded from
(±10%) the analysis
Chen et al.20 4.7 ∼4.1−6.5e ∼4.2−6.3 n/a n/a wood, corn, corn Cradle-to-gate Excluded from
(13%/+38%) (11%/+34%) stover, switchgrass, the analysis
wheat straw
a
Values presented in parentheses correspond to the percentage of reduction compared to fossil fuel-derived vPET. bLower values refer to sugar
cane-based PET, while higher values refer to maize-based PET. cThis case refers to recycled PET produced with 35% recycled PET and 65%
partially bio-derived vPET. dAverage values are based on difference allocation scenarios and the source of ethanol. Lower values refer to sugar cane-
based ethanol produced in India while higher values refer to sugar cane-based ethanol produced in Brazil. eMinimum and maximum values of 12
scenario studies that depended on feedstock type, coproduct allocation methods, and carbon credits implemented for the analyses.

both bio-derived rPET (TPA1 and TPA2) and partially bio-
derived vPET, respectively. The latter cases have a biogenic
carbon credit less than that of the 100% bio-derived vPET
bottles because these bottles are not entirely produced from
biomass. The GHG emissions associated with corn stover
ethanol in this analysis include the land use change (LUC)
related GHG emissions, which take into account the impact of
soil organic carbon (SOC) change. However, as corn stover is
a byproduct of corn, the impact of LUC (as well as the SOC
change) is minimal.37
The feedstock and conversion stages for partially bio-derived
vPET bottles have similar contributions (33% and 32%,
respectively) to life-cycle GHG emissions. The bio-derived
portion (which comes from bio-EG) is less GHG intensive that
bio-TPA; however, the fossil fuel-derived portion (which
comes from fossil-TPA) requires more energy and material
input compared to 100% bio-derived vPET. The bio-derived
rPET is also affected by the high GHG contribution of
feedstock production (especially due to bio-TPA production),
while the fossil fuel-derived rPET is affected by the high
emissions in the conversion stage of fossil fuel-derived vPET.
Emissions from transportation of PET pellets to bottle
manufacturing have a low impact in the life-cycle GHG
emissions. These emissions were the same in all pathways (0.4
gCO2e/PET bottle) because we used uniform assumptions for
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travel distance, fuel economy, and payload (Supporting
Information, Section 4).
Finally, the GHG emissions of injection and blow molding
are comparable in all cases with ranges from 34 to 46 gCO2e.
The lower value represents 100% bio-derived PET via TPA2,
while the higher range represents the 100% fossil fuel-derived
PET. Although the same energy inputs and loss factors (kg of
PET/kg PET transformed from Table 3) are used in the
injection and blow molding processes for all the pathways, the
difference in these ranges are due to the upstream GHG
emissions of the PET resin production.
Figure 5 presents life-cycle water consumption results. In
contrast to the previous impacts analyzed, water consumption
is significantly higher in all the alternative cases compared to
the fossil fuel-derived vPET and rPET. The major driver of this
result is the water consumed in both biomass-based routes to
TPA. It is important to note that the process designs for TPA
production have not yet been optimized, and opportunities
exist to cut water consumption that remain to be explored.
TPA1 production consumes 62% (around 1 L per bottle) of
water in the production of 100% bio-derived vPET-TPA1
bottles. Similarly, 54% of the total water used in the production
of 100% bio-derived vPET-TPA2 bottle corresponds to the
water consumed in the TPA2 production. Table S6 of the
Supporting Information presents the breakdown of water
consumed for both TPA production pathways and the
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contribution according to the material input. For TPA1, corn
steep liquor is the greatest contributor to the water
consumption. This material contributes 37% of the total
water used to produce 1 kg of TPA. Corn steep liquor is used
in enzyme production and in the fermentation step to produce
TPA. This material is derived from corn, which consumes
irrigation water.24,38 For TPA2, corn steep liquor continues to
play an important role, contributing 34% of total water
consumption. However, process water (needed for cooling and
steam) is the greatest contributor to water consumed in TPA2
production, contributing 36% of the total water consumed to
produce 1 kg of TPA. Compared to pathways using virgin fossil
materials (0.001 L/kg vPET), recycling biobased pathways to
PET bottles require higher amounts of water to clean waste
PET because the water needed for feedstock, such as TPA,
production is significantly higher than the input water required
in the process.
■
COMPARISON WITH OTHER LCA RESULTS FOR
BOTTLE GRADE PET
Previous LCAs have studied the environmental impact of
different bottle-grade PET pathways.16,18−22 They found that
alternative pathways to PET resin or bottles provide
approximately 10%−30% reduction in the GHG emission in
comparison to fossil fuel-derived PET resin or bottles. Table 4
compares these results with those presented in this paper. The
values presented in this table are per kg of PET basis because
most of the studies chose this as the functional unit to compare
to their analyses. Previous studies that considered supply
chains involving bio-derived TPA only examined the TPA2
route to this compound. Earlier studies reported higher life-
cycle GHG emissions than we report. Some aspects that could
contribute to this difference are assuming incineration at end-
of-life, which emits GHGs, the use of first generation biomass
(sugar cane and corn) and the bio-derived portion of rPET.
For this latter aspect, the literature presents a bio-derived rPET
that uses partially bio-derived vPET (i.e., biobased EG and
petrochemical TPA),16,19 instead of 100% bio-derived vPET
which we assume. Shen et al. assumed MSW incineration with
energy recovery as the end-of-life of their product which is a
common waste management practice in Europe where the
authors are based.16 Similarly, in Chen and Patel, the end-of-
life treatment is incineration and the raw material used in the
biobased pathways was corn-derived ethanol.20 Shen et al.
compared fossil fuel-derived and different options of recycled
bottle-grade PET on a cradle-to-grave basis.22 The last two
analyses presented in Table 4 cannot be directely compared to
our results because they ended the system boundary at the gate
rather than grave.
■
CONCLUSIONS
In this paper, we explored the environmental impact of
producing one plastic bottle from bio-derived and recycled
PET and compared those results for a fossil fuel-derived PET
bottle. The results showed that bio-derived vPET−TPA2
offered the largest life-cycle GHG reduction (82%) compared
to fossil fuel-derived PET. One of the major drivers of GHG
emission reductions was the biogenic carbon credit assigned to
the biomass-derived portion of the PET bottles. In the fossil
fuel-derived vPET pathway, the primary life-cycle GHG
emission contributor was the conversion stage because
transforming EG and TPA into PET is energy intensive. In
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the case of bio-derived vPET, feedstock production was the
largest contributor to the life-cycle GHG emission, whereas
TPA production played an important role in determining these
emissions. Production of TPA via direct fermentation of sugars
is more GHG intensive than producing this chemical from an
isobutanol intermediate. The former route uses significant
amounts of sodium hydroxide, a very GHG-intensive chemical.
Reducing NaOH consumption or finding a less GHG-intensive
base will reduce GHG emissions associated with producing
TPA in this manner. It is possible to add separations systems
that can recover the bulk of the caustic chemical utilized in the
fermentation and recycle NaOH to the fermentation which will
minimize the makeup requirement of this chemical and would
lower the burden on the recovery process. Partially bio-derived
vPET and rPET also offered life-cycle GHG emission
reductions compared to conventional PET production. The
overall impact of the rPET bottle GHG emissions was
determined by the origin of the virgin PET (fossil fuel or
biomass). While life-cycle GHG emissions are generally lower
when PET production includes bio-derived inputs, water
consumption of bio-derived PET production pathways was
significantly higher than the fossil fuel-derived pathway,
especially when water-intensive chemicals (NaOH, corn
steep liquor) were used in the direct fermentation route to
TPA (TPA1). Given that bio-derived pathways are at an early
stage of development, there is ample opportunity for process
optimization to limit water and GHG-intensive inputs and
energy consumption to advance the sustainability of bio-
derived PET and associated products.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acssusche-
meng.8b00750.
Information as mentioned in the text. (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*Phone: 01-630-252-2361. E-mail: pbenavides@anl.gov.
ORCID
Pahola Thathiana Benavides: 0000-0002-8253-7877
Jennifer B. Dunn: 0000-0002-2065-5106
Mary Biddy: 0000-0002-6228-2790
Notes
The views and opinions of the authors expressed herein do not
necessarily state or reflect those of the United States
Government or any agency thereof. Neither the United States
Government nor any agency thereof, nor any of their
employees, 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. The United States.
Government retains and the publisher, by accepting the article
for publication, acknowledges that the United States. Govern-
ment retains a nonexclusive, paid-up, irrevocable, worldwide
license to publish or reproduce the published form of this
work, or allow others to do so, for United States. Government
purposes.
The authors declare no competing financial interest.
DOI: 10.1021/acssuschemeng.8b00750
ACS Sustainable Chem. Eng. 2018, 6, 9725−9733
ACS Sustainable Chemistry & Engineering
■ ACKNOWLEDGMENTS
This work was supported by the Bioenergy Technologies
Office of the Office of Energy Efficiency and Renewable
Energy of the United States. Department of Energy (Contract
DE-AC02-06CH11357). In addition, this work was authored
in part by Alliance for Sustainable Energy, LLC, the manager
and operator of the National Renewable Energy Laboratory for
the United States. Department of Energy (Contract DE-AC36-
08GO28308). We thank Maggie Mann, Gregg Beckham, and
Chris Johnson at National Renewable Energy Laboratory
(NREL) for helpful discussions and Brandon Knott at NREL
for initially developing the process model. Part of this work was
developed under the Clean Energy Manufacturing Analysis
Center (http://www.manufacturingcleanenergy.org/).
■
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9733 DOI: 10.1021/acssuschemeng.8b00750

ACS Sustainable Chem. Eng. 2018, 6, 9725−9733