Journal of Analytical and Applied Pyrolysis

51 (1999) 157 – 166

Recycling of waste plastics by ultrapyrolysis

using an internally circulating fluidized bed
reactor
Bruce J. Milne a, Leo A. Behie a,*, Franco Berruti b
a
Department of Chemical and Petroleum Engineering, Uni6ersity of Calgary, Calgary, AB,
T2N 1N4, Canada
b
Department of Chemical Engineering, Uni6ersity of Saskatchewan, Saskatoon S7N 5C9, Canada

Received 16 June 1998; accepted 29 September 1998

Abstract

The recycling of plastic waste through pyrolysis offers great potential for dealing with this
problematic waste stream. Previous work on the ultra-rapid pyrolysis of polyethylene in a
micro-scale reactor indicated that reactor residence time is an important consideration in
optimizing product yield. A pilot-plant scale internally circulating fluidized bed (ICFB)
reactor, capable of achieving the residence time required for the high yield conversion of
waste plastics to olefins, has been investigated. The pyrolysis of low density polyethylene
(LDPE) was studied at temperatures ranging from 780 to 860°C and residence times of
400–600 ms. Total gas yields in excess of 90 wt.% were achieved with total olefin yields as
high as 75 wt.%, demonstrating the effectiveness of the ICFB reactor as a means of waste
plastics recycling. © 1999 Elsevier Science B.V. All rights reserved.

Keywords: Plastics recycling; Polyethylene pyrolysis; Olefins; Fluidized bed reactor

1. Introduction

Waste plastics account for 7% by weight of municipal waste streams in North

America [1] and global production of plastics resins is increasing at 4% annually [2].
Plastic waste is expected to reach 18 million tonnes per year in the United States by

* Corresponding author. Tel.: +1-403-2206692; fax: + 1-403-2844852.

E-mail address: behie@ucalgary.ca (L.A. Behie)

0165-2370/99/$ - see front matter © 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 5 - 2 3 7 0 ( 9 9 ) 0 0 0 1 0 - 8
158 B.J. Milne et al. / J. Anal. Appl. Pyrolysis 51 (1999) 157–166

the year 2000 [3]. The current rate of recycling plastics currently in the United
States is 3% [4]. Although recycling rates have steadily increased in North America,
technological advancements are required to reduce the plastics waste problem.
Tertiary recycling through pyrolysis offers great potential for the reduction of
plastics waste. Tertiary recycling is the degradation of a polymer to its component
monomers by chemical or thermal means. The primary goal of tertiary recycling is
the recovery of the source monomer, however, the conversion of waste polymers to
liquid fuel or other valuable products is also possible. Pyrolysis has been shown to
be an effective means of tertiary recycling for acrylics and polystyrene. For
example, Lovett [5] studied the pyrolysis of polystyrene in a Curie point microreac-
tor and obtained greater than 90% recovery of the styrene monomer. The recovery
of the olefin monomers from polyethylene and polypropylene is problematic
however, as the pyrolysis of these polymers under conventional conditions is highly
non-specific resulting in a wide product component distribution and low monomer
yield. The development of a tertiary recycling process for polyethylene is of
particular importance as this material comprises the single largest component of the
plastics waste stream.
The pyrolysis of plastics waste has been the subject the numerous studies. These
studies may be categorized into two groups depending on reactor residence time.
The long residence time processes typically operate at temperatures in the range
450–750°C and residence times ranging from several tens of seconds to several
minutes. The short residence time processes typically operate at temperatures
ranging from 600 to 1000°C and residence times ranging from a few hundred
milliseconds to several seconds. The long residence time studies have utilized
conventional pyrolysis reactor technology including rotating kilns, fluidized beds
and screw-fed tubular reactors. Several of these processes have achieved commercial
scale operation. At low temperatures and long residence times, the primary product
is a liquid fuel, and the conversion to base monomer is very low. The product yield
and composition is highly temperature dependent, while the effect of residence time
is less significant.
The short residence time plastics pyrolysis studies have utilized next-generation
pyrolysis reactor technology including fast fluidized beds and other rapid fluid-par-
ticle contacting equipment. At high temperatures and short residence times the
primary product is a high olefin content gas. Studies in our laboratory have
established the importance of both temperature and residence time in rapid
contacting, high temperature pyrolysis processes. Sodero et al. [6] utilized a Curie
point microreactor to investigate the pyrolysis of low density polyethylene (LDPE).
Fig. 1 shows the effect of residence time on product gas yield at 900°C. The yields
of ethylene, propylene and butadiene exhibit a maximum at 750 ms residence time
and the total olefin yield approaches 50 wt.% of the feed. This indicates that high
temperature, rapid contacting time pyrolysis processes have the potential of achiev-
ing high olefin yield, provided that adequate control of the residence time can be
maintained. This strict residence time requirement presents a significant challenge to
the reactor designer.
 B.J. Milne et al. / J. Anal. Appl. Pyrolysis 51 (1999) 157–166 159

The bubbling fluidized bed reactor has been widely applied to pyrolysis process-
ing. The bed is comprised of an inert particulate material such as sand, which is
used to convey the required heat for the highly endothermic pyrolysis reactions. A
stream of the bed material may be removed from the reactor, heated in an external
vessel and then returned to the reactor as occurs in the well known fluid coking
process for upgrading heavy crude oil. Alternatively the entire reactor may be
externally heated. The bed material is aerated by a stream of gas entering the base
of the reactor. A substantial portion of the inlet gas passes through the bed as
bubbles which provide vigorous backmixing of the bed material resulting in
temperature uniformity within the reactor. In the case of waste plastics pyrolysis,
the plastic feed material may be introduced into the reactor as solid particles or
injected into the bed as a melt. The pyrolysis gases produced are rapidly stripped
off by the inlet fluidizing gas and removed from the reactor.
The flow of gas within the bubbling fluidized bed may be considered to exist as
two distinct streams having different residence times; the bubble stream, and a
stream that percolates through the interstitial spaces between the particles. The gas
bubbles rise through the bed very rapidly while the remaining interstitial gas
percolates through the bed rather slowly. This disparity in gas velocity has a minor
effect on product yield and composition provided that the overall gas residence time
is relatively long. Bubbling fluidized beds are therefore suitable for processes where
polymer conversion to liquid hydrocarbons is desired. To achieve the high ethylene
yields reported by Sodero et al. [6] would require residence times much shorter than
that normally attainable in a bubbling bed.

Fig. 1. Ethylene yield for pyrolysis of LDPE at 900°C in a Curie point microreactor.
160 B.J. Milne et al. / J. Anal. Appl. Pyrolysis 51 (1999) 157–166

Fig. 2. Schematic diagram of the circulating fluidized bed (CFB).

A recent development in fluidized reactor technology is the circulating fluidized

bed (CFB). Fig. 2 depicts the essential features of the CFB. Solid particles enter the
base of a vertical riser and are entrained in an upward moving, high velocity gas
stream. The particles are conveyed up the riser in the fast fluidization regime into
a cyclone where they are separated and returned to the base of the riser through a
downward moving packed bed standpipe. The circulation rate of the particles is
controlled by adjusting the flow rate of an auxiliary gas stream to a non-mechanical
solids flow valve. The riser gas travels rapidly through the unit in essentially plug
flow with a well defined gas residence time. The riser of the CFB is therefore
suitable for application as a short contact time pyrolysis reactor where waste
polymer conversion to base olefins is desired.
An ongoing research program in our laboratory has been directed at the
pyrolytic upgrading of heavy crude oil and bitumen to higher value products. A
 B.J. Milne et al. / J. Anal. Appl. Pyrolysis 51 (1999) 157–166 161

product of this research has been the development of a new type of fluidized bed
reactor called the internally circulating fluidized bed (ICFB). The ICFB is an
adaptation of the CFB in which the riser is centrally located within an annular
moving packed bed standpipe. Solid particles enter the base of the riser through an
annular ring of orifices and are entrained by the inlet riser gas. A centrifugal
gas/solids separator at the top of the riser separates the riser gas from the particles
which return to the annular bed. The annular bed is equipped with an auxiliary gas
distributor. The auxiliary gas enhances the flow of particles into the riser and
prevents the escape of riser gas through the orifices into the annular bed. As in the
CFB, the riser gas stream in the ICFB has a short, well defined residence time
making the ICFB an appropriate design for rapid pyrolysis. In an ICFB pyrolysis
reactor, the feed material is injected into the base of the riser where it is
immediately contacted by hot inflowing solid particles. As in a bubbling fluidized
bed reactor, the ICFB reactor may be externally heated, or a stream of the bed
material may be removed for heating in an external vessel.
The ICFB is suitable for processes requiring short residence times, however, this
capability is not achieved without cost. Circulating beds are more susceptible to
process upset than bubbling beds due to the delicate pressure balance required to
maintain solids circulation. The flowrate of inert riser gas required to lift the solids
in a circulating bed unit is larger than that required to maintain adequate solids
mixing in a bubbling bed unit. An ICFB polymer recycling unit would therefore be
expected to have higher operating costs than a bubbling bed unit of similar size.
The ICFB has been successfully demonstrated for the rapid pyrolysis of heavy
crude oil in a pilot-plant scale unit [7]. Riser gas residence times as short as 300 ms
are routinely achieved in the unit. In this paper we examine the application of the
ICFB unit to the tertiary recycling of waste polyethylene to olefins.

2. Experimental

A pilot scale ICFB reactor was initially constructed to pyrolyze up to 100 g

min − 1 of 10° API heavy crude oil at temperatures up to 950°C and pressures less
than 200 kPa [7]. The reactor was later modified to accept up to 50 g min − 1 of
powdered LDPE feed. A detailed description of the apparatus, as configured for
plastics pyrolysis is given by Lovett et al. [5]. A simplified diagram of the reactor is
shown in Fig. 3.
The reactor was constructed of 18 gauge Inconel alloy 601 with a diameter of
15.2 cm and a length of 123 cm. The riser was made from Inconel alloy 600 tubing
having an inside diameter of 3.49 cm and a length of 107 cm. The riser was fitted
with two thermowells to accept 1.6 mm type K thermocouples. The reactor was
externally heated by a cylindrical electric 15.5 kW furnace. Steam was used as the
riser gas and the auxiliary gas. The reactor was filled with 40 kg of 20/40 mesh
Ottawa sand having a mean diameter of 0.63 mm. Virgin LDPE resin was obtained
from Novacor Chemical Co. and ground to a mean particle size of 0.63 mm. The
LDPE particles were injected into the base of the riser using a nitrogen fluidized
162 B.J. Milne et al. / J. Anal. Appl. Pyrolysis 51 (1999) 157–166

pneumatic conveying system and feeder nozzle described by Sodero [8]. Under
typical operating conditions, the superficial mass flow rate of sand in the riser was
in the range 350 – 380 kg m − 2 s − 1, three orders of magnitude greater than that of
the plastic feed. The plastic particles were therefore rapidly heated to the reactor
temperature. The gas superficial velocity in the riser was determined to be in the
range 7.4 – 8.4 m s − 1, corresponding to the fast fluidization regime. At the top of
the riser the steam and pyrolysis gases were rapidly separated from the sand in a
patented centrifugal solids separation device [9], and exited the reactor via a
transfer line. The product gas was then direct quenched with atomized water to
130°C in a vertical quench column. Liquid products were collected in a separation
vessel and the remaining gaseous product was further quenched with atomized
water to 85°C in a second quench column. The product steam was then cooled to
20°C in a shell and tube heat exchanger prior to entering a second liquid separation

Fig. 3. Schematic diagram of the ICFB.

 B.J. Milne et al. / J. Anal. Appl. Pyrolysis 51 (1999) 157–166 163

Fig. 4. Product gas yields for pyrolysis of LPDE in the ICFB reactor, residence time = 600 ms.

vessel. Trace quantities of malodorous compounds were then removed from the gas
stream in bed of activated carbon, prior to flow metering and final venting.
Product gas samples were collected just upstream of the activated carbon column.
For all experimental conditions either two or three samples of product gas were
taken and analyzed in triplicate. The gas samples were analyzed using a Hewlett
Packard 5890 Gas Chromatograph and a Hewlett Packard 5790 Mass Spectrome-
ter. A 50 m long, 0.2 mm I.D., 0.5 mm film thickness PONA (paraffins, olefins,
napthas and aromatics) capillary column was utilized. The products of interest were
the light components which consisted primarily of methane, ethane, ethylene,
propylene, butene and butadiene.

3. Results and discussion

Figs. 4 and 5 give the yields of the major products of the LDPE pyrolysis
experiments at 600 ms reactor residence time. The flow rate of LDPE particles was
a constant 21 g min − 1 throughout these experiments. Each experiment lasted  10
min. Ethylene exhibits its highest yield of  37 wt.% at a temperature of 865°C.
The yields of ethane and propylene were approximately constant over the tempera-
ture range studied. Both methane and ethylene yields increased with increasing
temperature. The yields of butene and butadiene decreased from  8–11 wt.% at
780°C to 7 wt.% at 860°C.
Figs. 6 and 7 give the major product yields at 400 ms reactor residence time. The
LDPE feed rate during these experiments was constant at 27 g min − 1 and each
164 B.J. Milne et al. / J. Anal. Appl. Pyrolysis 51 (1999) 157–166

Fig. 5. Product gas yields for pyrolysis of LPDE in the ICFB reactor, residence time = 600 ms.

experiment lasted 10 min. The yields of methane, ethylene and propylene were
substantially lower at 400 ms residence time, while the yields of butene and ethane
were not effected significantly. The most significant effect of the reduction in

Fig. 6. Product gas yields for pyrolysis of LPDE in the ICFB reactor, residence time = 400 ms.
 B.J. Milne et al. / J. Anal. Appl. Pyrolysis 51 (1999) 157–166 165

Fig. 7. Product gas yields for pyrolysis of LPDE in the ICFB reactor, residence time = 400 ms.

residence time was on the yields of butadiene which were, on average, 20 wt.%
higher for the same temperature range.
A comparison of the results of this work with the results of other studies in the
literature is made in Table 1. Scott et al. [10] conducted experiments on LDPE

Table 1
Product yields (wt.% of feed) for pyrolysis of LDPE in the ICFB compared to literature data

ICFB reactor Scott et al. [10] Westerhout [11]

Temperature (°C) 797 825 780 805 730 790 725 750

Residence time 400 400 600 600 500 500 5000 5000
(ms)

Methane 10.9 10.7 22.3 23.3 4.6 6.4 38.9 13.1

Ethylene 18.7 22.9 28.2 32.3 19.4 31.1 31.6 33.6
Propylene 13.4 13.4 17.8 17 12 12.8 10 23.4
other alkanes 1.8 1.8 1.3 1.8 3 3.5 11.5 8.8
C4 42.6 39 18.4 15.6 13.1 7.7 6.3 13.5
C5+ 5.4 5 0 0 6.3 0.7 1.7 6.9
Total olefins 74.7 75.3 64.4 64.9 44.5 51.6 48 70.5
Total gas yield 92.9 92.9 88 90 58.4 62.2 87.8 93
Condensate 5 5 8 8 31.2 32.1 — —
Char 2 2 4 2 2.1 0.2 — —
Total 99.9 99.9 99.9 90 91.7 94.5 — —
166 B.J. Milne et al. / J. Anal. Appl. Pyrolysis 51 (1999) 157–166

pyrolysis in a conventional fluidized bed at temperatures and residence times in the

same range as those of the ICFB reactor. The results of Westerhout [11] were
generated in a rotating cone reactor at similar temperatures but much longer
residence times than the present study. Kaminsky et al. [12] and Conesa et al. [13]
have both reported data for the high temperature pyrolysis of polyethylene,
however neither paper reported the reactor residence time, so these results are not
considered in Table 1.
The results of the present study are consistent with those of Scott et al. [10] with
the notable exceptions of the methane and C4 yields which were significantly higher
in the ICFB. The total yield of olefins was also higher in the ICFB. Comparing the
results of the ICFB study to the data of Westerhout [11] at 750°C, it can be seen
that the total olefin yield is similar but there are large differences in the yields of
individual components. A possible explanation for the different product yields may
be the considerably longer residence time of the reactor used by Westerhout [11].

4. Conclusions

An ICFB reactor, originally constructed for the thermal upgrading of heavy

crude oils, has been successfully modified for the pyrolysis of polyethylene. The
design allows for high temperature operation at short residence times, conditions
favorable for the conversion of waste plastic to olefins. Total gas yields in excess of
90 wt.% were achieved with total olefin yields as high as 75 wt.%.

Acknowledgements

Support for this project was provided by the Environmental Science and Tech-
nology Alliance Canada (ESTAC), the Natural Sciences and Engineering Research
Council of Canada (NSERC) and the National Center for Upgrading Technology
(NCUT).

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