Catalysis Communications 150 (2021) 106274

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Catalysis Communications
journal homepage: www.elsevier.com/locate/catcom

Short communication

Non-thermal plasma-assisted hydrogenolysis of polyethylene to

light hydrocarbons
Libo Yao a, Jaelynne King b, Dezhen Wu a, Steven S.C. Chuang b, *, Zhenmeng Peng a, *
a
Department of Chemical, Biomolecular, and Corrosion Engineering, The University of Akron, Akron, OH 44325, United States
b
School of Polymer Science and Polymer Engineering, The University of Akron, Akron, OH 44325, United States

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

Keywords: Upcycling is an attractive approach for valorization of waste plastics to valuable chemicals. Here we report the
Plastic upcycling first case study of non-thermal plasma-assisted hydrogenolysis of high-density polyethylene (HDPE) to C1-C3
Non-thermal plasma hydrocarbons. Light alkanes, predominately CH4, C2H6 and C3H8 with >95% selectivity, were obtained under
Hydrogenolysis
ambient condition as result of favorable thermodynamics and fast reaction kinetics. The findings demonstrated
Light hydrocarbon
that hydrogenolysis that typically demands above 300 ◦ C with thermal catalysis can occur at room temperature
in assistance of non-thermal plasma. This proof-of-concept study showcases a novel strategy for upcycling of
plastics to valuable hydrocarbons under ambient condition.

1. Introduction depolymerization can be effectively reversed by adding H2 to the reac­

tion [19]. Via hydrogenolysis/hydrocracking, the upcycling of plastics
While the wide application of plastic materials has significantly turns into exothermic and significantly reduces the reaction temperature
improved the convenience and quality of human life, the processing and to about 300 ◦ C and a narrower product distribution (light alkanes,
recycling of waste plastics (WP) have become an ever-growing challenge diesel fuel and wax) compared with typical pyrolysis process was also
[1–3]. In US only, over 35 million tons WP are generated annually and witnessed [20,21]. But the temperature was still not low enough to
most of them are processed by landfill or incineration, with less than claim a good energy advantage. Hereby, we report the use of non-
10% being recycled [4]. The inability to recycle WP has not only caused thermal H2 plasma for initiating ambient-condition hydrogenolysis of
huge pressure to the environment, but also wasted tremendous amount high-density polyethylene (HDPE) to produce light hydrocarbons
of carbon resource. (C1–C3). By means of plasma-activated H2, the hydrogenolysis of poly­
“Upcycling” involves conversion of waste materials to more valuable ethylene can effectively take place at room temperature, resulting in
chemicals and fuels, which is an attractive approach to recover hydro­ highly selective production of light alkanes (C1–C3, >95% selectivity).
carbon resource from its polymeric structure [5–7]. Currently, pyrolysis The employment of Pt/C and SAPO-34 zeolites, two routinely used
and gasification are the most intensively investigated methods for catalysts in hydrogenation and pyrolysis of plastics [9,20,21], shows
plastic upcycling [8–12]. Aiming at producing liquid fuels and limited improvement in gas production but pronounced enhancement in
hydrogen-rich gases that have relatively high commercial values, the energy efficiency. The proof-of-concept study provides a novel approach
research in terms of reaction parameters, catalyst and process design of for energy efficient upcycling of plastics.
pyrolysis and gasification has been well developed in the past few de­
cades [9,13–16]. However, the inevitable high energy input (400–1000 2. Experiments
◦
C reaction temperature), with or without catalysts, demanded by highly
endothermic feature of depolymerization process makes it less preferred 2.1. Materials
from energy cost-effectiveness point of view [17,18]. In addition, the
complex product distribution (syngas, gasoline and diesel fuels, pyrol­ High density polyethylene (HDPE, Sigma Aldrich, Merck KGaA,
ysis oil and char, etc.) is another factor that limits application of this Darmstaht. Stock No. 427985), 20% platinum on Vulcan XC-72R carbon
approach. Thermodynamically, the endothermic deficiency of plastic (20 wt% Pt/C, Fuel Cell Store, College Station, TX, USA. Product Code

* Corresponding author.
E-mail addresses: [email protected] (S.S.C. Chuang), [email protected] (Z. Peng).

https://doi.org/10.1016/j.catcom.2020.106274
Received 18 November 2020; Received in revised form 11 December 2020; Accepted 19 December 2020
Available online 23 December 2020
1566-7367/© 2020 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
L. Yao et al. Catalysis Communications 150 (2021) 106274

Fig. 1. Effects of (a–b) H2 flow rate, (c–d) H2 partial pressure (balanced by Ar with 100 ml/min total flow rate) and (e–f) plasma power on the HDPE hydrogenolysis
rate and product selectivity.

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L. Yao et al. Catalysis Communications 150 (2021) 106274

3151721), SAPO-34 zeolite (ACS material, Pasadena, CA, USA) were

used. H2 (99.999%) and Ar (99.999%) gases were purchased from
Praxair, Linde.

2.2. Plasma hydrogenolysis of HDPE

Non-thermal plasma-assisted HDPE hydrogenolysis experiments

were conducted in a quartz tube reactor equipped with a dielectric
barrier discharge (DBD) plasma generator, where cold hydrogen plasma
was generated (Fig. S1). In a typical experiment, 200 mg HDPE pellets
sieved to 125–250 μm was mixed in the center of plasma generation
zone (5 wt% catalyst when introduced), with standard reaction condi­
tion of 100 ml/min H2 flow rate, 101 kPa H2 partial pressure and 90 W
plasma power unless being stated otherwise. The HDPE pellets take up
0.47 ml of the reactor, which equals to 12,900 h− 1 gas hourly space
velocity (GHSV, Eq. (1)) at 100 ml/min H2 flow rate. The gas effluent
products were analyzed with an online Agilent 6890 GC–MS equipped
with automatic gas injector. The gas chromatography is equipped with a
0.33 mm (internal diameter) silica column. Influences of various reac­
tion parameters, including H2 flow rate (20–100 ml/min), H2 partial
pressure (0–101 kPa), plasma power (60–90 W), as well as catalyst (Pt/C
and SAPO-34) were examined. Gas products, including CH4, C2H2, C2H4,
C3H6 and C3H8, were quantified separately by externally feeding stan­
dard calibration gas. Calibration curves at 0–5% v/v% were obtained for
each gas. Selectivity was calculated by respective gas production rate
divided by the overall production rate (g/min).
νH2 100 ml/min
GHSV = = = 12900 h− 1
(1)
VHDPE 0.47 ml
The energy efficiency (η) is represented by total formation rate (mg/
min) over input power (W):
mg
( g ) total product min *60 totoal product (mg)
1000
Energy efficiency = P(W)
= 60
kWh 1000
P (W)
(2)

2.3. FT-IR characterization

The HDPE, Pt/C + HPDE and SAPO + HPDE samples before and after
reaction were characterized by an FTIR spectrometer (Nicolet 6700,
Thermo Scientific) in the diffuse reflectance infrared Fourier transform
spectroscopy (DRIFTS) mode at 25 ◦ C. The SAPO-34 and Pt/C catalysts
were heated in situ from 25 ◦ C to 150 ◦ C under an argon flow rate of 40
ml/min for analysis of surface hydroxyl in an effort to determine
possible active sites for the reaction.

3. Results and discussions

3.1. Evaluation of HDPE hydrogenolysis

Non-thermal plasma-assisted hydrogenolysis of HDPE leads to a total

of six gas products, including methane (CH4), acetylene (C2H2), ethylene
(C2H4), ethane (C2H6), propene (C3H6) and propane (C3H8), were
detected (Fig. S2), suggesting successful demonstration of the plasma-
assisted plastic hydrogenolysis concept (Fig. S3a). No liquid product
was observed in the retrieved samples from the flow reactor (Fig. S4). An Fig. 2. Influence of catalysts on plasma-assisted HDPE hydrogenolysis: (a, b)
increase of νH2 leads to an enhanced generation rate of all gas products formation rate and selectivity of individual products and total gas products.
(Fig. 1a), indicating an improved hydrogenolysis efficiency that could be Reaction condition: 100 ml/min H2, 101 kPa, 90 W. (c) energy efficiency as a
function of plasma power input. Reaction condition: 100 ml/min H2, 101 kPa.
attributed to more available H2 plasma for reaction. CH4 accounts for a
majority of the gas products (>70% in selectivity), with a higher νH2
resulting in a decrease in SCH4 that produces more fractions of C2H6 and atmosphere (Fig. 1c) although intense Ar plasma was generated in the
C3H8 (Fig. 1b). Despite of the intriguing phenomenon of unsaturated reactor (Fig. S3b). The little reaction can be attributed to endothermic
hydrocarbons formation, their overall selectivity is smaller than 5%, characteristic of HDPE decomposition in Ar plasma atmosphere. The
likely due to unfavorable thermodynamics. The study on effect of H2 addition of H2 is evidently critical to drive exothermic HDPE hydro­
partial pressure found negligible gas product formation in pure Ar genolysis, with plasma H2 to overcome the activation barrier for

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L. Yao et al. Catalysis Communications 150 (2021) 106274

Fig. 3. Normalized absorbance spectra of the SAPO + HDPE reactant before and after plasma hydrogenolysis. (a) IR and near IR spectra, (b) absorbance spectra of
the surface hydroxyls, and (c)-(d) absorbance spectra of the samples after reaction indicate the formation of vinyl groups and enolic β-diketone.

reaction under ambient condition. Less methane but more other gas catalyst under this specific testing condition (Fig. 2a), suggesting
products were produced with an increase of PH2, resulting in a lower hydrogen plasma still plays a dominant role in controlling the overall
SCH4 and a higher SC2H6 (Fig. 1d). With stepwise increase of the plasma hydrogenolysis kinetics. One major difference caused by the catalyst is
power from 60 W to 90 W, all products exhibited a monotonous increase the products selectivity. The production of alkanes (CH4 and C2H6) was
in the formation rate that could be associated with more intense H2 moderately enhanced and meanwhile the formation of unsaturated
generation and thus faster reaction kinetics (Fig. 1e–f). products (C2H2, C2H4 and C3H6) was significantly suppressed when the
The catalyst effect on plasma hydrogenolysis of HDPE was investi­ Pt catalyst was used. In contrast, significantly improvement of unsatu­
gated by mixing HDPE with Pt/C and SAPO-34 zeolite (denoted as PtC + rated products generation was observed when the SAPO-34 catalyst was
HDPE and SAPO + HDPE, 5 wt% catalyst loading) respectively and in use, with 1.3 and 4.9 times higher SC2H4, and 1.8 and 4.5 times higher
examining the influences on the reaction properties. Overall, the PtC + SC3H6 compared with the HDPE and PtC + HDPE experiments, respec­
HDPE and SAPO + HDPE experiments exhibit a similar trend of tively. The results suggest the Pt/C and SAPO-34 play a role in affecting
hydrogenolysis rate dependency on the examined reaction parameters the distribution of different product formation reactions. Likely, the
as those without catalyst employment (Figs. S5 and S6). Fig. 2a–b presence of Pt is beneficial for generating adsorbed hydrogen due to
compares the reaction properties achieved with and without catalyst efficient H2 dissociative adsorption, which consequently boosts hydro­
under 100 ml/min H2, 101 kPa, 90 W condition. The total gas produc­ genation of produced unsaturated hydrocarbons to alkanes. As a com­
tion rate was improved to only a limited extent (<10%) in presence of mon methanol-to-olefin (MTO) catalyst, the acid sites on SAPO-34 are

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L. Yao et al. Catalysis Communications 150 (2021) 106274

Fig. 4. (a) Proposed reaction pathway. (b) Reaction formula and Gibbs free energies (ΔG0) under standard condition. Product selectivity value obtained from HDPE
hydrogenolysis reaction. Reaction condition: 100 ml/min H2, 101 kPa, 90 W.

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capable of catalyzing low carbon number olefin formation via coupling into account, the ΔG0 for the overall reaction is − 166.2 kJ/mol as
of C–C bond, which could explain a higher olefin selectivity in this calculated by summation of selectivity-weighted free energy. This
study. It needs noted, despite the improvement, the production of olefin confirmed the plasma-assisted HDPE hydrogenolysis is favorable in
still accounts for a low fraction of all products, as restricted by reaction terms of reaction thermodynamics.
thermodynamics (Fig. 2a, Figs. S7 and S8). Energy efficiency (η) was
calculated for evaluating the utilization of plasma in assisting HDPE 4. Conclusions
hydrogenolysis (Fig. 2c). A generic trend of higher η with an increase in
the plasma power was observed, regardless of catalyst in use or not. In this study, we successfully demonstrated a proof-of-concept
Interestingly, the influence of catalyst on η was found to be plasma method for polyethylene upcycling by means of non-thermal plasma-
power dependent. At a high power of 90 W, the efficiency improvement assisted hydrogenolysis which produces over 95% selectivity of light
was very limited. However, in a lower power range the catalyst can alkanes (C1-C3) and low fractions of unsaturated hydrocarbons (<5%)
dramatically improve the η value to be as high as nine times. This in­ with promising reaction rate under ambient condition. The fast reaction
dicates the catalyst plays a more dominant role in improving the HDPE kinetics was attributed to the cold H2 plasma that can effectively break
hydrogenolysis kinetics under a lower plasma intensity condition. polymeric structure to generate fragment intermediates for further hy­
drogenation and recombination into the final products. The shrinkage of
3.2. Solid product analysis by FTIR hydrocarbon chains as well as detection of unsaturated bonds observed
by FTIR spectra of solid residue of reacted samples indicate effectiveness
The solid mixture of SAPO + HDPE after 4.5 min plasma reaction was of bond cleavage by plasma hydrogenolysis. Introduction of Pt/C and
analyzed by FTIR. Fig. S9 revealed infrared spectra of hydroxyls at 3600, SAPO-34 shows limited influence on production formation rate (<10%),
3625 and 3680 cm− 1 by in situ heating SAPO-34 from 25 ◦ C to 150 ◦ C. but its effect on energy efficiency is significant, exhibiting as high as nine
Hydroxyls at 3600 and 3625 cm− 1 are assigned to Si-OH-Al bonding times improvement at lower plasma power. The highly spontaneous
while the hydroxyl at 3680 cm− 1 is indicative of P-OH bonding [22]. The thermodynamic feature (ΔG ~ -166 kJ/mol) and fast kinetics induced
hydroxyls at 3600 and 3625 cm− 1 in SAPO-34 have been shown to be by energy-intensive H2 plasma collectively drive the efficient hydro­
acidic active sites for solid acid catalysis [22]. The absorbance spectra of genolysis reaction. This novel strategy provides a simple approach in
the SAPO + HDPE and PtC + HDPE were taken before and after plasma upcycling of not only polyethylene but also many other polymeric ma­
hydrogenolysis. Fig. 3 shows the absorbance spectra of HDPE, SAPO + terials, which we will conduct more careful investigations in our future
HDPE before and after reaction. All the IR features of HDPE stay intact study.
after mixing with SAPO. Plasma hydrogenolysis decreases the IR in­
tensity of C–H stretching bands in 2700–3100 cm− 1 and C–H bending
Declaration of Competing Interest
bands in the finger print region as well as C–C bonds in 1065–1080
cm− 1 region [23], suggesting that solid products produced from plasma
The authors declare that they have no known competing financial
hydrogenolysis was resulted from C–H and C–C bond breaking of
interests or personal relationships that could have appeared to influence
HDPE. Fig. 3a also shows the reaction decreased the intensity of CH2 at
the work reported in this paper.
5661 and 5775 cm− 1 in the near IR, further indicating the long chain
HDPE had been fragmented and shortened since the intensity of these
near IR bands is proportional to the chain length of polyethylene [24]. Acknowledgement
These fragmented species may reside on the acidic site of SAPO,
decreasing the intensity of surface hydroxyl in Fig. 3b. Fig. 3c and We acknowledge the financial support of this work by National
d show peaks at 910 cm− 1 and 1641 cm− 1 indicating the formation of a Science Foundation (1955452).
vinyl (-CH=CH2-) and the possible formation of enolic β-diketones,
respectively [25]. Similar features can be observed on HDPE (Fig. S14), Appendix A. Supplementary data
but not on Pt + HDPE (Fig. S10–13). Although IR was not able to
determine the structure of HDPE, the results of IR do provide an indirect Supplementary data to this article can be found online at https://doi.
evidence to show plasma hydrogenolysis is effective in breaking C–H org/10.1016/j.catcom.2020.106274.
and C–C bonds in HDPE.
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