Materials Today Communications 33 (2022) 104588

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Materials Today Communications

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Simplified, fast, and efficient microwave assisted chemical recycling of poly

(ethylene terephthalate) waste
Karzan H. Zangana a, b, *, Antonio Fernandez c, **, Justin D. Holmes a, b
a
School of Chemistry, University College Cork, Cork T12 YN60, Ireland
b
AMBER Centre, Environmental Research Institute (ERI), University College Cork, Lee Road, Cork T23 XE10, Ireland
c
School of Science, Loughborough University, Loughborough LE11 3TU, United Kingdom

A R T I C L E I N F O A B S T R A C T

Keywords: The widespread adoption of chemical recycling of poly (ethylene terephthalate) (PET) is hampered by long
PET waste reaction times, high energy consumption and the use of metal catalysts that are either toxic or cost prohibitive for
Microwave-assisted depolymerisation industrial use. Herein, we report a simple PET glycolytic process that combines an environmentally friendly and
Glycolysis
cheap heterogenous catalyst, calcium oxide (CaO) with microwave irradiation to obtain the monomer bis(2-
Transesterification
Heterogeneous catalysis
hydroxyethyl) terephthalate (BHET), which can be easily separated by crystallisation. After the process opti­
Calcium oxide misation, depolymerisation of PET waste was achieved in 3.5 min under atmospheric pressure, to obtain highly
crystalline BHET with a yield of 75%. To our knowledge, this is the fastest heterogeneous glycolytic process
reported in the literature to-date, using a cheap and eco- friendly catalyst. Moreover, by using a heterogenous
catalyst and avoiding the need for product precipitation by water addition, CaO and ethylene glycol materials
were separated and reused, thus validating this protocol as a potential green and scalable route for PET recycling.

1. Introduction depolymerisation, including glycolysis, hydrolysis and methanolysis. In

glycolysis, the main product formed is bis(2-hydroxyethyl tere­
Plastics play a significant role in almost every aspect of our daily phthalate) (BHET), [5] that can be easily repolymerised to virgin PET, or
lives. They are used in food and drink containers, clothing and furniture converted to other products like softeners for the textile industry and
[1]. Among all plastics, poly (ethylene terephthalate) (PET) is the most unsaturated polyester resins. Glycolysis is also the most common recy­
popular polyester, with an estimated consumption of ~100 million tons cling route used at pilot and industrial scale due to the use of
per year [2]. Due to its mechanical and chemical properties, PET has non-volatile solvents and ease of scale-up. However, despite recent
very high resistance to degradative assimilation into the environment progress, glycolysis continues to be an energy demanding route that
[3], and consequently, generates leakage to the environment in the form requires high temperatures, prolonged reaction times and sometimes the
of fibres and macro and microplastics. Among the current recycling use of toxic catalysts. Herein, we report a simple, fast, and efficient PET
options for PET, mechanical recycling is the most commonly employed glycolytic process combining CaO and microwave irradiation. We used
option, albeit only being a temporary solution, as for each cycle the microwave heating for glycolysis due to its numerous advantages over
economic value of PET is reduced (downcycling) due to the loss of conventional thermal heating, such as the combination of lower acti­
mechanical properties. Other options include enzymatic recycling for vation energy for transesterification reactions [6] and the high energy
PET-to-PET conversion, while maintaining the original properties of the absorption of ethylene glycol, thus increasing energy efficiency [7,8]. In
polymer. However, enzymatic recycling is far from being optimised and order to avoid commonly used catalysts in PET glycolysis that rely on
still presents several challenges i.e., long reaction times, expensive en­ heavy metal cations and are expensive or toxic [9–17], we chose CaO
zymes, energy intensive separation and purification steps. Chemical and CaO/Activated Carbon due to its low toxicity, low cost, thermal
depolymerisation of PET is currently considered a very promising route stability and high transesterification activity [18–28]. The product
and could, in principle, solve the problem of downcycling [4]. There are monomer, BHET, was also separated directly by crystallisation. Both, the
several chemical recycling methods developed for PET catalyst and ethylene glycol, were reused after product crystallisation

* Corresponding author at: AMBER Centre, Environmental Research Institute (ERI), University College Cork, Lee Road, Cork T23 XE10, Ireland.
** Corresponding author.

https://doi.org/10.1016/j.mtcomm.2022.104588
Received 28 August 2022; Received in revised form 28 September 2022; Accepted 30 September 2022
Available online 25 October 2022
2352-4928/Crown Copyright © 2022 Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
K.H. Zangana et al. Materials Today Communications 33 (2022) 104588

Fig. 1. PET glycolysis using microwave irradiation and CaO as catalyst and 2 different PET sources. A: post-industrial textiles and B: post-consumer water bottles.
The BHET product is separated by crystallisation and, CaO and Ethylene glycol, recovered by filtration and reused.

and filtration. To our knowledge, this is the fastest heterogeneous

glycolytic process reported to-date, that uses a cheap and eco-friendly
catalyst and simplifies the product separation.

2. Experimental section

2.1. Materials and methods

2.1.1. Materials
Post-industrial textile was kindly supplied by O′ Neills Ltd (Northern
Ireland). Bottles of waste plastic drinking water were collected from
post- consumer PET, used after removal of the polyethylene caps and the
polypropylene label. The plastic samples were washed with distilled
water, dried and then shredded into small pieces (5 ×5 mm2).

2.1.2. Chemicals
Ethylene glycol, calcium oxide (CaO, 99%), Ca(NO3)20.4 H2O, acti­
vated carbon support (100 mesh particle size), standard BHET and
dimethylsulfoxide (DMSO-d6) were purchased from Aldrich (Steinheim,
Germany) and used without further purification.
Fig. 2. FTIR spectra of (a) PET and (b) recrystallised BHET generated after
2.1.3. Characterisation techniques glycolysis from post-industrial PET fibres.
The FT-IR spectra were recorded with a Nicolet 6700 FT-IR spec­
trometer (Thermo Scientific, the USA) equipped with a diamond ATR maximum 5 min. The catalyst used was calcium oxide (CaO) with
attachment, the FT-IR spectra were recorded between 4000 and 400 different concentrations of 3%, 5% and 10% (w/w) in the reaction
cm− 1. Analysis of thermal stability of BHET was obtained by TGA 4000 mixture, and we further optimised the reaction conditions using sup­
(Perkin Elmer, Waltham, MA, United States) under a nitrogen atmo­ ported calcium oxide on activated carbon catalysts CaO/AC. All the
sphere. Sample of 10 mg were heated from 30 to 995 ⁰C at a heating rate reactions were performed at EG boiling temperature of 197 ◦ C. PET (1 g)
of 10.00 ⁰C/min. Differential scanning calorimetry (DSC) were carried and a certain amount of EG and catalyst were added in a 250 mL
out from 20 to 150 ⁰ C at a rate of 10 ⁰ C min− 1 under a nitrogen at­ round-bottom flask with a magnetic stirring bar and reflux condenser
mosphere. High-Performance Liquid Chromatography (HPLC) analysis and subject to microwave radiation (800 W). The reaction was consid­
was performed on an Agilent 1200 HPLC System, 4.6 × 250 mm2 ered completed when no visual decrease in the mass of The PET could be
analytical column and UV detector measuring at 254 nm. A mixture of detected, which matched with complete dissolution and/or glycolysis of
methanol/water at a volume fraction of 70/30 was used as the mobile more than 95% of the initial PET (Fig. S11). At the end of the reaction
phase at a flow rate of 1 mL/min. 1H NMR and 13C NMR spectra were the catalyst was separated by filtration. The solution was cooled down
recorded on 400 MHz on a Bruker Avance III spectrometer in deuterated and the crystals obtained were filtered to separate BHET from EG. The
dimethyl sulfoxide (DMSO-d6). Gas chromatography (GC-MS) was car­ BHET product was further purified by recrystallisation in water, dried in
ried out in a GC Agilent 6890 N, in a HP5-MS column, scan mode, with a an oven at 85 ⁰ C for 12 h, and then weighed for calculating the yield.
MS Agilent 5793 N. The ORIGIN (v.9.0 PRO, OriginLab Corporation, Fig. 1.
USA) was used to process the recorded spectra. For the catalyst recycling studies, in each step, the catalyst was
filtered, washed with methanol and then dried in an oven at 85 ⁰ C for
2.1.4. PET depolymerisation 6 h. The calculation of the BHET yield was determined using the
Supported CaO catalysts were prepared by impregnation of aqueous following equation:
solutions of the Ca(NO3)20.4 H2O on an activated carbon support (100 MBHET MPET
mesh particle size, Darco). Calcium nitrate was fully dissolved in BHET yield(%) = ÷ × 100 (1)
MWBHET MWPET
deionised H2O at room temperature with a metal loading of 20 mmol
metal/g of support. The support was then added into the solution fol­ where, MBHET and MPET refer to the mass of BHET and PET; MWBHET,
lowed by mixing for 4 h, the paste was dried overnight in an oven at 120 MWPET refer to the molecular mass of BHET (254 g mol− 1) and the PET
⁰ C. Finally, the solid was calcined for 4 h at 450 ⁰ C [29]. PET waste was repeating unit (192 g mol− 1) respectively.
treated with ethylene glycol using different PET:EG molar ratios (1:4,
1:6, 1:10 and 1:20) using the microwave oven for time periods up to

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K.H. Zangana et al. Materials Today Communications 33 (2022) 104588

Fig. 3. 1H NMR spectrum of recrystallised BHET generated from post- industrial PET fibres.

Fig. 4. GC-MS spectrum of recrystallised BHET generated from post- industrial off-cut fibres: (a) GC spectrum; (b) MS spectrum.

3. Results and discussion 3450 cm− 1 is characteristic of BHET (–OH stretching vibration), which
is absent in PET. There are common bands for PET and the crystallised
The initial PET source was post-industrial PET fibres and post- con­ monomer such as the vibration of alkyl C-H groups at 2950 cm− 1 and
sumers PET bottles, the product obtained after the glycolysis, BHET, was 2879 cm− 1, a C– – O stretching vibration at around 1712 cm− 1, and a
separated by recrystallisation and characterised by FTIR NMR, GCMS, para-substitute group on a benzene ring at about 1400 cm− 1 [30,31].
1
TGA-DSC and HPLC. FT-IR spectra of the original PET and the BHET H- and 13C NMR spectra also confirmed BHET as the main product after
obtained are compared in Fig. 2 and Fig. S1. The strong IR band at crystallisation, as shown in Fig. 3, S2, S3 and S4. The structure of BHET

Fig. 5. (a) DSC and (b) TGA curves of recrystallised BHET generated from post-industrial off-cut fibres.

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K.H. Zangana et al. Materials Today Communications 33 (2022) 104588

indicates the presence of the four aromatic protons on the aromatic

benzene ring. The 1H- and 13C NMR spectra of the BHET match with the
reported literature values for pure BHET [32,33].
The GC-MS spectra of the main product from the glycolysis of PET
also confirms the presence of only a single compound, which gives a
peak at 21.85 min Fig. 4a, attributable to the main product BHET. The
peak at 4.47 min corresponds to the solvent (methanol). The intense
peaks at m/z 211, 193, 149, 121, 104, 85, 44 and 31 relate to fragments
of BHET (MW = 254 g mol− 1) Fig. 4b. These data demonstrate the high
purity of BHET obtained during the crystallisation process. The recrys­
tallised BHET products from all samples were analysed by DSC and TGA.
The DSC curve in Fig. 5a shows a sharp endothermic peak at 110 ◦ C,
which is consistent with the reported melting point of BHET. [34,35].
The melting onset temperature and peak temperature of BHET are
110.9 ◦ C and 110 ◦ C, respectively.
The TGA curve Fig. 5b shows the first onset of weight loss for the
glycolysis sample between 250 ◦ C and 318 ◦ C in which 39% of the
material was lost and can be attributed to the thermal decomposition of
the monomer. The 56% loss in weight between 375 and 488 ◦ C, can be
attributed to thermal polymerisation of BHET during the TGA in
accordance with previous reports for commercial BHET [36,37].
Analysis of the crude product obtained from direct crystallization
from the reaction by HPLC (Fig. S5) shows a BHET as main product
accounting for 82.6%, with dimers and oligomers accounting for 7.7%
and 9.7%, respectively. Analysis of the recrystallized BHET product by
HPLC, using a reversed-phase column, revealed the presence of a single
peak, at a retention times of 3.1 min, assigned to the BHET monomer,
similar to the BHET purchased commercially as reference, and consis­
tent with previous reports [38]. This highlights that the monomer
fraction consists of pure BHET Fig. 6, S5–S8.

4. Optimal parameters on PET glycolysis

Fig. 6. HPLC data of (a) commercially available BHET, (b) recrystallised BHET The effect of reaction parameters on the depolymerisation of PET and
generated from post-industrial PET fibers. the yield of crystallised BHET were investigated and optimised Fig. 7.
The yield of BHET was significantly increased when the ratio of EG:
monomer has symmetry around the aromatic benzene ring, therefore the PET (w/w) was increased from 4:1–10:1. According to previous studies,
protons of a certain group present on either side of the benzene ring an equilibrium between BHET monomer, dimer and other oligomers
resonate at the same frequency. The signal at δ 3.7 ppm (peak 3) rep­ exists in glycolysis, therefore, an excess amount of solvent is required to
resents the protons of the methylene group (–CH2–) adjacent to the decrease the formation of products other than BHET monomers [39,40].
hydroxyl group (–OH). Signals at δ 4.3 (Peak 2) and 4.9 ppm (peak 4) Although the reaction progressed efficiently at lower ratios, the final
indicates that the protons of the methylene group near COO group and yield of BHET was lower (65%) when compared with the use of higher
the hydroxyl group, respectively. The signal at δ 8.13 ppm (Peak 1) EG to PET ratios i.e. 10:1 (75%). Larger EG to PET (w/w) ratios, i.e. 20:1,

Fig. 7. Results obtained during the optimisation conditions for solvent use (EG: PET ratio (w/w)) and catalyst loading (catalyst: PET ratio (w/w)) and its comparison
with the introduction of activated carbon as microwave absorbing material. Conditions: (a) 10 wt% catalyst CaO, 4 min microwave reaction; (b) 10 wt% catalyst
CaO, 10 mL of ethylene glycol, 4 min microwave reaction and (c) 15 wt% catalyst, 10 mL of ethylene glycol, 3.5 min microwave reaction.

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K.H. Zangana et al. Materials Today Communications 33 (2022) 104588

Fig. 8. Reusability of CaO and CaO on AC catalyst represented in terms of yield. (a) 4 min, 10% CaO, (b) 7 min, 10% CaO, (c) 16 min, 10% CaO, (d) 3.5 min, 15%
CaO on AC, (e) 6 min, 15% CaO on AC and (f) 16 min, 15% CaO on AC, (g) CaO+ EG reused, 11 min.

did not deliver any significant improvement in yield terms, relative to

Table 1
10:1. The effect of the % catalyst used on the depolymerisation of PET
Optimisation parameters for 2 different PET waste sources: a) EG:PET ratio; b)
and the yield of BHET is also shown in Fig. 7. When the mass ratio of the
CaO:PET ratio; c) CaO on AC:PET ratio and d) CaO +added AC:PET. i) post-
catalyst to PET was increased from 5 to 10 wt%, the total BHET yield
industrial textiles: ii) post-consumer bottles.
increased by approximately 15%, reaching its highest level of 75%. i ii
a) EG:PET (w/w) BHET Yield (%) BHET Yield (%)
Increasing the catalyst loading above 10 wt% did not result in any
substantial improvement in the yield of BHET. The use of activated 20: 1 75 71
carbon as a support for the CaO catalyst was also investigated. Activated 10: 1 75 73
6: 1 72 68
carbon has previously been shown to be an effective catalyst support in 4: 1 67 63
liquid and vapour phase reactions such as heterogeneous trans­ b) CaO:PET (w/w) i
BHET Yield (%) ii
BHET Yield (%)
esterification reactions, due to its inert nature and its ability to absorb 0.5: 10 63 59
microwave irradiation [41]. Adding 50 mg (5 wt%) of activated carbon 1: 10 75 73
2: 10 74 70
reduced the glycolysis reaction time by 16%, from 4 to 3.5 min, while i ii
c) CaO on AC:PET (w/w) BHET Yield (%) BHET Yield (%)
having a minimal effect on the BHET yield (75% for 4 min vs 72% for 15 75 72
3.5 min).
The optimised parameters were used to evaluate the ‘green chemistry
metrics’ for the microwave glycolysis process. These parameters have production decreased slightly after three cycles, by approximately 16%,
recently been proposed to evaluate the efficiency and environmental and an increase in the reaction time (6 min vs 16 min). This increase in
performance of a chemical process [42], while allowing comparison reaction time and decrease in the yield within each repeated cycle might
between chemical processes in terms of fundamental parameters such as be attributed to the leaching of the catalyst’s active sites in the reaction,
temperature, reaction time and the amount of catalyst used. Three main the filtration procedure and the initial presence of residual water in the
metrics were calculated, (i) the energy efficiency coefficient ε, (ii) the ethylene glycol [46].
environmental factor or E factor, and (iii) the environmental energy Moreover, the recyclability of the CaO/Activated Carbon support
impact ξ (Fig. S12). An efficient process is represented by high values of was also investigated (Fig. 7d-f). The support was found to improve the
ε, and low values of E and ξ. The values obtained for the microwave catalytic stability of the CaO and decreased leaching [47]. However, the
glycolysis reaction were ε = 0.00084, E = 1.44 and ξ = 1740 for the catalyst activity to BHET production was reduced after the third cycle by
optimised parameters using CaO as catalyst and ε = 0.00101, E = 1.48 about 10%. This decay in catalytic activity could be due to the leaching
and ξ = 1480 for CaO on activated carbon Fig. S9, where both represent of active sites to the reaction media and the presence of water in the
the highest ε values reported for any glycolytic process of PET [43]. Both solvent. Overall, the use of CaO/Activated Carbon has a positive effect
the low E and ξ values obtained for the unsupported and supported on the reusability of the catalyst, which is consistent with previous
catalysts reaction indicates the great potential of our process in terms of studies [48]. The reuse of both, CaO and EG was also tested in a 2nd
energy efficiency and environmental impact compared to the values cycle Fig. 7g, showing a 65% yield, similar to the yield obtained for 2nd
found in the literature [41]. Another important factor to consider when cycle recycling CaO only. This result is promising and shows the great
evaluating the potential of the chemical process is the cost of catalyst potential of this process for scale-up.
used, which is cheap for CaO [44].

4.2. PET feedstock

4.1. Reusability of the catalyst
To evaluate the versatility of the process, post-consumable PET
Although CaO is considered a low-cost catalyst that can be obtained bottles were also recycled and compared with the polyester fabrics. As
from waste sources [43–45], the ability to recycle the catalyst is shown in Table 1, the microwave process was able generate crystalline
important from a commercial perspective. The reusability of the CaO BHET, with a 73% yield, from the PET bottles after 6 min in the mi­
catalyst in the microwave glycolysis of PET was studied for three cycles crowave reactor. These data indicate that our glycolysis process is a
Fig. 8, Table S1-S2, Fig. S10. The total catalyst selectivity towards BHET versatile route for recycling different PET sources/types, with only small

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K.H. Zangana et al. Materials Today Communications 33 (2022) 104588

Scheme 1. Depolymerization of PET into bis (2-hydroxyehtyl)terephthalate (BHET) through glycolytic cleavage by CaO catalyst.

variability in BHET yield, suggesting promising possibilities in further Data Availability

practical applications.
Data will be made available on request.
5. Glycolysis mechanism
Acknowledgements
The proposed mechanism for the glycolysis of PET catalysed by CaO
is displayed in Scheme 1. To enhance the electrophilicity of the carbon Justin D. Holmes reports financial support was provided by Science
from the C– – O group, the coordination between PET and Ca2+ cation Foundation Ireland (Grant No 12/RC/2278_P2).
occurs as the first step, which favours the subsequent nucleophilic attack
of ethylene glycol to produce a hydroxyethyl terminal. Apart from the Appendix A. Supporting information
BHET monomer, the repeating cycle could produce oligomers and di­
mers as by-products. By increasing the catalyst loading, the basicity of Supplementary data associated with this article can be found in the
the reaction is increased, which leads to a higher concentration of hy­ online version at doi:10.1016/j.mtcomm.2022.104588.
droxide ions and promoting the hydrolysis of PET for conversion ter­
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