pubs.acs.

org/journal/ascecg Research Article

Development of Eco-Friendly and Sustainable PET Glycolysis Using

Sodium Alkoxides as Catalysts
Saqib Javed and Dieter Vogt*
Cite This: ACS Sustainable Chem. Eng. 2023, 11, 11541−11547 Read Online

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ABSTRACT: The massive accumulation of postconsumer polyethylene

Downloaded via INDIAN INST OF TECH KHARAGPUR on January 25, 2025 at 19:55:06 (UTC).

terephthalate (PET) waste in the environment demands enhancement in the

recycling rate to tackle global pollution. At the same time, efficient recycling
will contribute to a future circular economy. PET glycolysis has emerged as a
promising chemical recycling method that turns PET into a widely used
monomer, bis(2-hydroxyethyl)terephthalate (BHET), and adds value to
waste. For reasons of comparability, all reported studies on PET glycolysis so
far used the same work-up procedure to separate residual PET from the
BHET product: Addition of hot water to the reaction mixture, filtration to
remove residual PET, and crystallization of BHET from the filtrate by
cooling. Water not only destroys the catalyst but also has to be removed to
reuse ethylene glycol. We herein report a new “green” glycolysis approach
without the need for an anti-solvent using simple sodium alkoxides (MeONa
and EtONa) as catalysts. A response surface methodology (RSM) based on
the Box−Behnken design was applied to optimize the reaction parameters. Under optimum conditions, the results demonstrated the
validity of the optimization. EG was successfully recycled and PET conversion was found close to the initial recycling run. The
optimum recipe was applied to analyze the tolerance of the catalysts, MeONa and EtONa, in depolymerizing colored PET waste and
mixed PET waste. The findings indicate that both catalysts can effectively break down both types of waste under eco-friendly
glycolysis conditions, with MeONa resulting in higher PET conversion. This demonstrates that BHET precipitation is achievable
without the use of water, reusing the EG and maintaining catalyst activity for mixed PET waste. These outcomes offer a promising
basis for further developing a new and more efficient PET recycling technology.
KEYWORDS: chemical recycling, PET depolymerization, green glycolysis, response surface methodology, alkoxide catalysts

■ INTRODUCTION
Single-use plastics, which are essential components of modern
transparent, and durable nature has led to the production of a
staggering 583.3 billion PET bottles in 2021 alone, primarily
daily life, generate an alarming 400 million tonnes of waste for use in the beverage industry.5 While PET is not inherently
annually and are known for their remarkable persistence in the toxic, single-use PET bottles do not decompose readily and
ecosystem due to poor biodegradability.1 Between 1950 and instead undergo degradation into microplastics when exposed
2015, the world generated an estimated 6300 million tonnes of to UV/heat in marine environments.6 PET is also derived from
primary and secondary plastic waste, with projections petroleum, making it important to recycle to achieve a circular
indicating that accumulated plastic waste generation may economy.
exceed 12,000 Mt by 2050. Despite this, less than 9% of plastic Chemical recycling is a potential approach to managing PET
waste is recycled, with over 80% ending up in landfills or the waste, wherein post-consumer polymers are broken down into
natural environment, and 12% is incinerated.2 The accumu- monomers or other useful products. Reported methods of the
lation of post-consumer plastic waste poses a significant threat chemical recycling of PET waste usually involve aminolysis,7
to the environment and society as a whole.3 ammonolysis,8 hydrolysis,9,10 glycolysis,11 and methanoly-
Polyethylene terephthalate (PET) is a semi-crystalline sis.12,13 The glycolysis method has attracted significant
thermoplastic polymer formed by the condensation reaction
of terephthalic acid (TPA) and ethylene glycol (EG) or by the Received: March 29, 2023
polycondensation of bis(2-hydroxyethyl) terephthalate Revised: July 11, 2023
(BHET). Due to its unique physiochemical properties, PET Published: July 25, 2023
is widely used in fibers, packaging, and bottle production,
making it the fourth most produced polymer and accounting
for 12% of the world’s solid waste volume.4 Its lightweight,

© 2023 American Chemical Society https://doi.org/10.1021/acssuschemeng.3c01872

11541 ACS Sustainable Chem. Eng. 2023, 11, 11541−11547
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Figure 1. Experimental setup for green glycolysis.

attention for PET waste management due to mild reaction

conditions, the use of low-volatility solvents, and the possibility
■ EXPERIMENTAL SECTION
Materials. Ethylene glycol with a purity greater than 99.5% was
of continuous operation.14 Many companies have commercial- procured from Carl Roth, Germany, while sodium methoxide and
ized this process.15 However, efficient depolymerization in sodium ethoxide, with a purity of 95%, were acquired from Sigma
PET glycolysis requires the addition of a transesterification Aldrich. Methanol of both HPLC and technical grade was purchased
from VWR Germany. VWR Germany also supplied isopropanol,
catalyst since it is a slow reaction. Various catalysts have been which was utilized as a rinsing solvent. Deutero, Germany, provided
reported in the literature, including acetates of metals like deuterated chloroform, used for NMR analysis. VWR, Germany,
cobalt, lead, zinc, and manganese,16,17 as well as mild catalyst supplied glass microfiber filters of type GF/C and grade MN GF-1,
options like sodium carbonate and sodium bicarbonate.18 which were utilized to filter PET residue and glycolysis products,
Other catalysts include titanium phosphate,19 deep eutectic respectively. Postconsumer soft drink soda bottles were used as
POSTC-PET waste sources, and the bottles were cleaned, washed,
solvents,20 organo-catalysts,21 heterogeneous catalysts,22−25 and crushed to be used as a substrate, as shown in Figure 1S (SI).
and ionic liquids of zinc and copper acetate.26 Depolymerization of POSTC-PET Waste. The postconsumer
The use of heavy metal-based catalysts in PET depolyme- PET bottles were utilized as a substrate by removing their labels and
rization has some drawbacks, such as extra environmental caps, manually cutting them into smaller pieces, and washing them.
issues and being expensive for large-scale applications.27 To The PET was then shredded into small particles using a kitchen
grinder and sorted into a range of various particle size fractions
address these challenges, López-Fonseca et al. investigated the
(0.25−1 mm) using a sieving tower. The particles were rinsed with
glycolysis of PET bottles using excess EG and sodium isopropanol and dried (60 °C overnight). The glycolysis experiments
carbonate as a depolymerization catalyst.28 The emergence of were conducted in a round-bottom flask, with a predetermined
green and cost-effective catalysts that can efficiently depoly- amount of PET of the desired particle size, along with EG and the
merize and upcycle PET is under development.29,30 catalyst. The flask was placed onto a reflux condenser system with a
In the conventional procedure of PET glycolysis, the temperature controller and magnetically stirred at 500 rpm for the
desired time. At the end of the reaction, the heating was stopped, and
removal of residual, unconverted PET typically involves the the glycolysis mixture was filtered using microfiber filter-type GF/C
addition of hot water as PET is insoluble in water but BHET is under vacuum, separating the mixture into two fractions. The solid
soluble. However, this destroys the catalyst and makes it residual fraction, mainly composed of unconverted PET (if any), was
impossible to reuse the EG. Recently, Veregue et al.31 named (A), and the liquid filtrate fraction, mainly consisting of BHET
discovered a waterless method for precipitating BHET using and EG, was named (B). The residue fraction (A) was dried overnight
in an oven at a temperature of 60 °C to determine the conversion
ultrasmall cobalt nanoparticles as a heterogeneous catalyst. using the following formula:
However, this method required the use of a large excess of EG
mPET,0 mPET, t
with respect to PET, necessitating further optimization. In this PET Conversion, X (%) = × 100
study, we present an environmentally friendly and cost- mPET,0 (1)
effective method, precipitating BHET directly from the EG
The initial mass of PET in gram is indicated by mPET,0, while the
solution and using homogeneous sodium alkoxides as the mass of incompletely depolymerized PET in gram after a certain
glycolysis catalysts. Using a design of experiment approach, we reaction time t is represented as mPET, t. To crystallize the product, the
optimized various parameters of the glycolysis procedure, filtrate fraction (B) was refrigerated at 4 °C overnight, and white
including the amount of EG, reaction time, and temperature. crystalline BHET was filtered using glass microfiber filter grade MN
The resulting model can predict conversion and identify the GF-1 under vacuum. The resulting solid crystals, designated as a
fraction (C), were then dried overnight in an oven at 60 °C. To assess
optimal conditions for PET glycolysis. We have effectively the possibility of BHET crystal growth, the remaining filtrate was
utilized the modified method to treat both “colored” PET stored in the refrigerator and identified as a fraction (D). The isolated
waste and mixed PET waste. Furthermore, we have successfully BHET yield was calculated using the following formula:
demonstrated the viability of recycling EG, which contributes
mBHET /MBHET
to a more sustainable and efficient glycolysis process for BHET yield, Y (%) = × 100
recycling PET waste. mPET,0 /MPRU (2)

11542 https://doi.org/10.1021/acssuschemeng.3c01872
ACS Sustainable Chem. Eng. 2023, 11, 11541−11547
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Figure 2. Influence of operating parameters, conditions: PET/Cat = 25 (mol/mol), rpm = 500, T = 190 °C, PET = 1 g (a) EG = 20 mL, t = 1−3 h,
PS = 1 mm (b) EG = 10−30 mL, t = 2 h, PS = 1 mm (c) EG = 20 mL, t = 2 h, PS = 0.25−2 mm, (d) EG = 10 mL, t = 2 h, PS = 1 mm, T = 160−
196 °C. EG (10 mL) is equivalent to 34 mol of EG used for 1 g PET.

The mass of collected BHET crystals in gram is represented by glycolysis product without using water as an antisolvent during
mBHET while MBHET denotes the molecular weight of BHET (254 g/ filtration. Investigation of the influence of the particle size and
mol), and MPRU is the molecular weight of the PET-repeating-unit temperature showed that conversion is higher for smaller PET
(PRU) (192 g/mol). The stored BHET was subjected to further
analysis to verify the product. The experimental configuration for the particles (Figure 2c) and that the reaction proceeds faster at a
green glycolysis method is depicted in Figure 1. higher temperature, as expected (Figure 2d). XRD (Figure 3S)
Product Characterization. The BHET product was analyzed and DSC (Figure 4S) measurements confirmed that the
using various techniques such as nuclear magnetic resonance (NMR) obtained product under various operating conditions is BHET.
spectroscopy, differential scanning calorimetry (DSC), high-perform- The XRD spectrum of PET in Figure 3S shows the typical
ance liquid chromatography (HPLC), and powder X-ray diffraction broad diffraction peak of a polyester structure. These peaks
(PXRD). In addition, inductively coupled plasma atomic emission
appear at 2θ = 16°, 17.4°, 22.4°, and 26°. The XRD spectra of
spectroscopy (ICP-OES) was utilized to detect the presence of
sodium metal in the filtered residue. Further information and methods the BHET product (also in Figure 3S) show the narrower and
are provided in the Supporting Information. more intense diffraction peaks of BHET, which appear at 2θ =
6.6°, 13.5°, 16.3°, 21.1, 23.1°, 26.3°, and 27.18°. The XRD
■ RESULTS AND DISCUSSION
The impact of different operating conditions on the EtONa-
spectra illustrate that the BHET obtained by this method has
high crystallinity and a different crystalline structure than PET.
catalyzed PET glycolysis was examined, and outcomes are Furthermore, the obtained product under different operating
given in Figure 2. As expected, a prolonged reaction time conditions is still the BHET. DSC curves in Figure 4S showed
increases PET conversion (Figure 2a). After 2 h of reaction, a that BHET from all the samples starts melting at around 110
conversion of 92% was achieved, increasing to 97% after 3 h. °C. The endothermic peak (∼170 °C)32 for the dimer was not
Figure 2b shows the influence of EG on conversion. It can be observed for these samples, showing that the major product of
seen that an excess EG of up to 20 mL (EG/PET = 68 mol/ glycolysis is the BHET monomer.
mol)) is required for good conversion that significantly drops In pursuit of an optimum recipe for the modified glycolysis
upon using 30 mL of EG. The decrease in the conversion method, a full study on the combined effects of all the
beyond 20 mL of EG is considered to be due to the diminished operating parameters is desirable as the single-factor
ratio of the catalyst to EG (dilution of catalyst). This indicates investigation is insufficient to seek optimal conditions. Based
the minimum amount of EG to be used to sufficiently on the conclusions drawn from Figure 2c, the particle size was
depolymerize PET (1 g substrate) and efficiently extract the fixed at 1 mm due to the ease and availability of grinding with a
11543 https://doi.org/10.1021/acssuschemeng.3c01872
ACS Sustainable Chem. Eng. 2023, 11, 11541−11547
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

kitchen grinder. An experimental layout was made using the Table 2. Statistics Parameters for the Quadratic Model
design of the experiment’s methodology. With this approach,
response PET conversion (X)
not only the parameters can be studied together but also a
predictive mathematical model for the glycolysis performance R2 0.9124
will be developed that can be used to forecast the conversion adjusted R2 0.7546
and select the optimal conditions in PET glycolysis. adequate precision (>4) 5.6
Design of Experiments (DoE). To determine the optimal lack of fit 1.07
conditions, an experimental plan was conducted using the significant terms B, A2, C2
response surface methodology (RSM) with a Box−Behnken
design (BBD) approach. The Box−Behnken design can The ANOVA results for the quadratic model of PET
significantly decrease the number of experimental sets required conversion are presented in Table 5S (SI). If the p-value is less
in comparison to conventional factorial design techniques, than 0.05, it indicates that both the model and its terms are
without compromising the accuracy of the optimization.33,34 significant. Conversely, if the p-value exceeds 0.10, the terms
Three independent variables EG (mL), reaction time (h), and are considered insignificant, as shown in Table 5S. Table 2
temperature (°C) were investigated through 15 experiments. highlights the significant terms, while eq 3 provides the
The observed response was the PET conversion X (%). The mathematical quadratic model in terms of significant terms for
BBD approach determines the required number of experiments PET conversion. However, SEq 2 (SI) presents the complete
according to the expression N = k2 + k + Cp, where k is the quadratic model, including insignificant terms.
factor number and Cp is the replicate number of the central PET Conversion (X )
point.35 Table 1 provides the coded and uncoded values of the
independent factors, along with their respective ranges. = 52.76 + 10.36 × B + 18.33 × A2 + 24.21 × C 2
(3)
Table 1. Coded and Uncoded Values of Independent Figure 9S presents a comparison between the predicted and
Variables actual values of the measured response (PET conversion). The
results demonstrate that in most experimental runs, the values
symbol coded levels
predicted by the model were very close to the actual
independent variable actual (Vi) coded (Ci) −1 (L) 0 (M) +1 (H) experimental values. Therefore, the model can be utilized to
EG (mL) A C1 10 15 20 navigate the design space as it explains the relationship
reaction time (h) B C2 1 2 3 between independent variables and observed responses. The
temperature (°C) C C3 190 193 196 maximum PET conversion achieved within the design space
for depolymerizing POSTC-PET waste was 96%.
After analyzing the experimental results in Table 3S, the next
Table 3S (SI) displays the BBD matrix obtained from 15 step is to optimize all independent parameters to achieve the
experimental runs along with the corresponding observed maximum PET conversion. The input variables were
responses. Subsequently, the observed responses were considered within the designated range. Table 6S presents a
incorporated using analysis of variance (ANOVA) to derive list of tentative optimal solutions resulting from the
the regression model. optimization process. Since the desirability function of entries
Development and Optimization of the Regression 1 and 2 are similar (Figures 10S and 11S) and entry 2 is
Model. Experimental data for PET conversion as given in offering less amount of EG; therefore, it was selected as the
Table 3S were fitted to three different models: two-factor optimum. The trade-off between EG and temperature is
interaction (2FI), quadratic, and cubic models. To assess the evident from the contour plot for optimum conversion for the
suitability of these models, three tests were performed. These desirability function of entries 1 and 2, which are given in
tests included the sequential model sum of squares, lack of fit, Figures 12S and 13S, respectively. To depolymerize 1 g of PET
and model summary statistics, with the outcomes presented in waste, the regression model predicted 97% PET conversion at
Table 4S. The sequential model sum of squares determined the 196 °C, a reaction time of 2.97 h, and 10 mL of EG. The
highest-order polynomial by identifying the additional optimization experiment was performed 3 times and the
significant terms. It was important to avoid using an aliased experimental average PET conversion (92%) was found to be
model, which results in unstable and inaccurate coefficients with a slight deviation of approximately 5% from the predicted
and graphs. The lack of fit tests evaluated the selected model, response. The isolated BHET yield at the optimum conditions
to have an insignificant lack-of-fit (p-value greater than 0.05). was found to be 75%. Hence, the regression model is adequate
The model summary statistics focused on maximizing the in predicting the response in the investigated design space.
adjusted R2 and predicted R2, and minimizing the prediction EG Recycling. To further validate the process, we utilized
error sum of squares (PRESS). Based on the criteria and data the optimum recipe for recycling the EG, and the results are
presented in Table 4S, a quadratic model was selected for the presented in Figure 3. It can be seen that at given reaction
response surface methodology. The essential fit statistics for conditions, MeONa has better conversion (92%) as compared
the quadratic model are presented in Table 2. The model has a to EtONa (90%) due to its better catalytic activity. ICP
good fit for PET conversion, with an R2 value exceeding 0.91. measurements indicated the presence of Na+ in the filtrate of
The high values of both R2 and adjusted R2 suggest that the various samples (Table 1S). To confirm the catalytic activity,
regression model is reliable. The “Adequate Precision” EG was recycled two times (R1 and R2) and the results are
evaluates the signal-to-noise ratio, with a value above 4 being comparable to the initial run for both catalysts. The optimum
preferable.36 In this particular instance, the ratio is greater than conditions were also implemented on colored PET waste and
19, indicating a satisfactory signal. The “Lack of Fit F-value” of results show that both catalysts can also depolymerize colored
1.07 implies that the Lack of Fit is not significant. PET waste. Furthermore, GR1 results show that both filtrates
11544 https://doi.org/10.1021/acssuschemeng.3c01872
ACS Sustainable Chem. Eng. 2023, 11, 11541−11547
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Figure 3. Upscaling and recycling of EG, conditions: cat = EtONa Figure 4. Catalyst tolerance with mixed PET waste conditions: cat =
and MeONa, T = 196 °C, PET/Cat = 25 (mol/mol), EG = 30 mL, EtONa and MeONa, T = 196 °C, PET:Cat = 25 (mol/mol), EG = 10
reaction time = 3 h, rpm = 500, PS = 1 mm, PET = 3 g. mL, reaction time = 3 h, rpm = 500, PS = 1 mm, PET = 1 g.

BHET monomer, indicating that the main glycolysis product

from colored PET waste were successfully recycled to get PET with the colored PET substrate is the monomer BHET.
conversion up to 95%. The BHET crystals obtained under The glycolysis procedure discussed in this paper study
various conditions were subjected to 13C NMR and signals at δ BHET precipitation without using water and is comparable in
= 61, 67, 130, 134, and 166 ppm can be seen in Figure 5S. terms of glycolysis time and PET conversion.31,37−39 The
These signals are attributed to the BHET monomer, optimized glycolysis procedure was also implemented to
confirming that the main product of PET glycolysis with colored PET waste and mixed PET waste, resulting in
both catalysts (EtONa and MeONa), with both substrates substantial PET conversion signifying the potential of both
(white and colored PET), and after multiple recycling runs is catalysts. The possibility of reusing the filtrate containing EG
the monomer BHET. Furthermore, 13C NMR of EG after and catalyst is another attractive aspect. From an industrial
recycling run R2 was also performed and is given in Figure 6S standpoint, EG can be recycled without further processing if
showing that NMR spectra after initial and recycling run R2 no water is added. Additionally, it will reduce the requirement
are similar, thereby conforming the filtrate after multiple for unit operations that involve heating water first, followed by
glycolysis runs still constitute EG. The 13C NMR results are filtration and evaporation. As a result, these characteristics
also validated by HPLC and the chromatogram shown in make the PET depolymerization procedure more efficient and
Figure 7S indicates that the BHET monomer is the main affordable.
product of PET glycolysis. These results demonstrate the
reusability of the EG solution containing the catalyst; however,
the results in Figure 3 show that the PET conversion of
■ CONCLUSIONS
In response to the growing need for eco-friendly and
multiple glycolysis runs is slightly lower than that of the initial sustainable processes in PET recycling, this study focused on
run. This might be due to the loss of EG (having dissolved the development and optimization of a modified glycolysis
catalyst) inherited from the adopted filtration process in each procedure utilizing sodium alkoxides as catalysts. To address
cycle. the limitations of the conventional method, a response surface
The depolymerization performance of both catalysts was methodology based on the Box−Behnken model was
also studied for mixed PET waste (colored + white) and the implemented to optimize the amount of EG, reaction
results of catalyst tolerance are presented in Figure 4. GR100 temperature, and time. The analysis of variance was carried
means the substrate sample consists of 100% colored PET out, and a regression model was found to be adequate in
waste and GR0 means the substrate consists of only white PET predicting PET conversion. The optimization process showed
waste. It is recognizable from Figure 4 that MeONa and that there is a tradeoff between the amount of EG and the
EtONa have better depolymerization performance when the operating temperature. Using the desirability function, an
substrate mainly consists of colored PET waste as compared to optimum conversion of 97% was obtained at a temperature of
white PET waste. However, a 50−50% composition of mixed 196 °C, 10 mL of EG, and 2.97 h. EG was successfully
PET waste provides almost similar PET conversion as of recycled, producing PET conversion similar to the initial run
GR100 (only colored PET) for both the studied catalyst, for both catalysts. DSC, XRD, HPLC, and NMR analyses
indicating an appropriate catalyst tolerance while processing confirmed that the main product of this modified method, as
large volumes of mixed PET waste with both catalysts. Hence, well as the recycling runs, was BHET. The use of a high
both catalysts have outstanding depolymerization performance amount of EG was justified by the effective recycling of EG to
with mixed PET waste; however, MeONa performs com- depolymerize more PET. MeONa and EtONa were also used
paratively better than EtONa, indicating its better catalytic to depolymerize colored and mixed PET waste under optimum
activity. HPLC analysis obtained with colored PET waste is glycolysis conditions. With MeONa, a PET conversion of 98%
given in Figure 8S and a sharp absorption peak at a retention was achieved with colored PET waste, and a 93% conversion
time of 8.54 min is attributed to the characteristic peak of the was achieved with white PET waste. MeONa demonstrated a
11545 https://doi.org/10.1021/acssuschemeng.3c01872
ACS Sustainable Chem. Eng. 2023, 11, 11541−11547
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

better performance in depolymerizing mixed PET waste. Thus,

the potential of BHET precipitation without the need for
■ ACKNOWLEDGMENTS
S.J. would like to acknowledge the financial assistance from the
water, subsequent reuse of EG, and catalyst tolerance in mixed Higher Education Commission, Pakistan, and Deutscher
PET waste provide valuable insights in developing more Akademischer Austauschdienst (DAAD), Germany.
sustainable approaches for PET glycolysis to meet the future
demands of waste recycling.
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■
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