Journal of Industrial and Engineering Chemistry 16 (2010) 79

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Journal of Industrial and Engineering Chemistry

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Short communication

CO2 reforming of waste plastics

Hiroshi Yamada *, Hiromasa Mori, Tomohiko Tagawa
Department of Chemical Engineering, Nagoya University, Chikusa, Nagoya, 464-8603, Japan

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 20 April 2009
Accepted 6 August 2009

Carbon dioxide reforming of polyethylene was carried out. Pyrolysis and catalytic carbon dioxide
reforming were combined. Polyethylene was packed at the bottom of the reactor and the catalyst, Pd/
Al2O3, was packed at the top of the reactor. The pyrolysis of the polyethylene occurred at the bottom of
the reactor, and the pyrolysis products reacted with carbon dioxide on the catalyst bed. Carbon dioxide
reforming occurred on the catalyst bed zone. Hydrogen, carbon monoxide, methane, ethane, ethene were
produced at 910 and 720 K which were the catalyst and polyethylene temperature, respectively.
Polyethylene was completely reformed to carbon monoxide and hydrogen when catalyst temperature
was increased or polyethylene temperature was decreased.
2010 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Keywords:
Waste plastic
Carbon dioxide reforming
Pyrolysis
Plastic reuse
Catalytic bed reactor

1. Introduction
The amount of plastics discarded as waste each year is
constantly increasing and is causing serious problem. If this
material can be chemically recycled, it will become a cheap and
abundant source for useful chemicals and energy reuse.
An alternative to plastic waste is incineration, pyrolysis and
gasication. Pyrolysis has been extensively studied [1], but the
production of large amounts of char and tar, which are difcult to
handle, limits its application. Gasication, on the contrary, can be
considered as an extension of the well-known technology of coal
gasication [2,3].
Carbon dioxide reforming of polyethylene was carried in this
study. Objective products were CO and H2.

the bottom of the reactor and the catalyst was placed at the top of
the reactor. Catalyst was pretreated with H2 for 3 h, at 50 K higher
than reaction temperature when Type 2 reactor was used. CO2 and
N2 were own into the reactors continuously. Reaction conditions
will be shown in the bottom of the each gure. Experiment was
started when heater for the polyethylene was turned on.
Polyethylene temperature increased from the room temperature
to the reaction temperature. The catalyst was heated before the
heater for polyethylene was turned on when Type 2 reactor was
used.
Products were analyzed by TCD gas chromatograph with a WG100 column (GL Science inc.).
3. Results and discussion

2. Experimental

3.1. Effect of catalyst (Type 1 reactor)

Two kinds of reactors were used as shown in Fig. 1. Fig. 1a

indicates the reactor used for preliminary experiment. The reactor
consisted from quartz glass tube with an inner diameter of 25 and
380 mm in height. Polyethylene was packed at the bottom of the
reactor. 0.5 wt% Pd/Al2O3 pellets (Aldrich Chemical Company Inc.),
3.2 mm in length, was packed at the top of the reactor as catalyst.
One heater heated both polyethylene and catalyst. Fig. 1b shows
the reactor that could control the temperature separately for
catalyst and polyethylene. Two quartz glass tubes, 20 and 8 mm in
inner diameter, were connected each other. Polyethylene placed at

Pyrolysis of polyethylene was examined. Type 1 reactor was

used without catalyst and CO2. Fig. 2 shows the experimental
results. Small amount of H2, C2H4 and C2H6 were produced at
900 K, while no CO was produced. The main products were yellow
solid. GCMS analysis suggested the formation of high molecular
weight hydrocarbons and they were deposited on the outlet of the
reactor at room temperature. Reaction stopped after 30 min,
because polyethylene was completely consumed.
Then the catalyst was packed at the top of the reactor. Fig. 3
shows the experimental results. Yellow solid was deposited again.
Also, it was noticed that H2 was produced at a temperature above
690 K of the polyethylene temperature. Moreover, the production
of H2 was increased when catalyst was used and the H2 yield was
15%. The catalyst was able to reform high molecular weight

* Corresponding author. Tel.: +81 52 789 4529; fax: +81 52 789 3261.
E-mail address: yamada@nuce.nagoya-u.ac.jp (H. Yamada).

1226-086X/$ see front matter 2010 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jiec.2010.01.029

H. Yamada et al. / Journal of Industrial and Engineering Chemistry 16 (2010) 79

Fig. 1. Reactors.

Fig. 4. Pyrolysis in Type 2 reactor. Polyethylene: 3.00 g; N2: 4.70  10

4.13  10 5 mol/s.

mol/s; CO2:

happened because, temperatures of pyrolysis section and catalyst

bed were almost the same in Type 1 reactor. The temperature of
catalyst bed is not enough to complete CO2 reforming.
3.2. Effect of catalyst (Type 2 reactor)

Fig. 2. Pyrolysis in Type 1 reactor. Polyethylene: 3.00 g; N2: 7.82  10

mol/s.

Type 2 reactor could control the catalyst and polyethylene

temperatures independently. After this experiment, Type 2 reactor
was used. At rst, reactor was operated without catalyst. Fig. 4
shows the experimental results. The difference in these experiments from Fig. 2 was observed at that high temperature area,
860 K, which existed at the top of the reactor, and CO2 was used.
This is pyrolysispyrolysis process because CO was not observed.
CO2 reforming was not occurred though CO2 was used. Hydrogen
was produced at the polyethylene temperature of 680 K. It was
very low temperature in comparison with that in Fig. 2. The
secondly pyrolysis of hydrocarbon was occurred at higher

Fig. 3. CO2 reforming in Type 1 reactor. Polyethylene: 1.00 g; Pd/Al2O3: 18.5 g; N2:
4.70  10 5 mol/s; CO2: 4.13  10 5 mol/s.

hydrocarbon but its activity was not enough. Thus higher catalyst
temperature was required to reform hydrocarbons to H2 and CO
completely. Fig. 3 suggests that polyethylene pyrolysis could be
completed at low temperature and polyethylene was distinguished before catalyst reached reaction temperature. This

Fig. 5. CO2 Reforming in Type 2 reactor. Polyethylene: 3.00 g. Pd/Al2O3: 33.5 g; N2:
2.35  10 5 mol/s; CO2: 3.75  10 5 mol/s.

H. Yamada et al. / Journal of Industrial and Engineering Chemistry 16 (2010) 79

Fig. 6. Effect of catalyst temperature on Type 2 reactor. Polyethylene: 3.00 g; Pd/

Al2O3: 33.5 g; N2: 2.35  10 5 mol/s; CO2: 3.75  10 5 mol/s.

temperature zone. And H2 production was 8.5 times as much as

that shown in Fig. 2.
Fig. 5 shows the experimental results when the catalyst packed
at the top of the reactor. Polyethylene temperature was increased
from room temperature up to 720 K and kept constant at that
temperature. Gas production was noticed when polyethylene
temperature reached 680 K. CO was produced, and the formation
of H2 was increased compared to the results given in Fig. 3.
Comparing Figs. 4 and 5, combined pyrolysis-reforming process
produced hydrogen 20 times as much as pyrolysispyrolysis
system. Combined system was required for CO production. In
Fig. 5, CO production indicated that not only pyrolysis but also CO2
reforming was occurred in the reactor. Increase of the catalyst
temperature increased the catalyst activity.
3.3. Effect of catalyst temperature (Type 2 reactor)
Fig. 6 shows the effect of catalyst temperature on the yields of
CO and H2. The yields increased with the increase of the catalyst
temperature. Solid and gaseous hydrocarbon that were produced
by pyrolysis, reformed to CO and H2 with the increase of catalyst
temperature. Polyethylene was completely reformed to CO and H2
when the catalyst temperature was 1120 K.

Fig. 7. Effect of polyethylene temperature using Type 2 reactor. Polyethylene:

3.00 g; Pd/Al2O3: 33.5 g; N2: 2.35  10 5 mol/s; CO2 1.76  10 5 mol/s.

into the catalyst bed. Because time factor at catalyst bed was
increased, pyrolysis products completely reformed to CO and H2 in
the catalyst bed. Few hydrocarbons were detected.
4. Conclusion
CO2 reforming of polyethylene was carried out. Pyrolysis and
catalytic reforming were combined as gasication process from
polyethylene to CO and H2. When catalyst was used, gasication
was occurred at lower polyethylene temperature. Polyethylene
was completely reformed to CO and H2 at the catalyst temperature
1120 K. Polyethylene temperature affected the yield of CO and H2.
If polyethylene temperature was high, thermal decomposition rate
was high so catalyst could not reform all reactants to CO and H2. If
polyethylene temperature was low, thermal decomposition was
slowly occurred and completely reformed to CO and H2. But, long
time was required for consumption of all polyethylene.
References

3.4. Effect of polyethylene temperature (Type 2 reactor)

The product distributions of pyrolysis were depended on the
reactant temperature [4]. When polyethylene reaction temperature was decreased from 720 to 680 K, the pyrolysis occurred at
slower rate, therefore CO and H2 produced longer time as shown in
Fig. 7. Low pyrolysis rate indicated the low reactants supplying rate

[1] R. Aguado, M. Olazar, B. Gaisan, R. Prieto, J. Bilbao, Chem. Eng. J. 92 (2003) 91;
J. Chattopadhyay, C.H. Kim, R.H. Kim, D.W. Pak, J. Ind. Eng. Chem. 15 (2009) 72.
[2] T. Ido, S. Mizuno, T. Yoshimori, M. Mori, S. Goto, Kagaku Kogaku Ronbunshuu 25
(1999) 303.
[3] F. Pinto, C. Franco, R.N. Andre, C. Tavares, M. Dias, I. Gulyurtlu, I. Cabrita, Fuel 82
(2003) 1967.
[4] T. Yamagishi, H. Kani, M. Yoshida, K. Yamaguchi, S. Ookubo, I. Kunita, Hokkaido
Kougyoushikenjo Houkoku 301 (2002) 89.