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Journal of Analpical and Applied Fyrolysis

40-41 (1997) 347-363

ELSEWER

Analysis of products derived from the fast pyrolysis of


plastic waste
Elizabeth A. Williams *, Paul T. Williams

Plastic Waste has become an increased problem in many industrialiscd countries. Concern
over the vol~~mes king created has lead to a numlzcr of govermnen ts introducing new
legislation for its recovery as a rcsoutrr. Traditional recovq
methods have gem
concentrated on recyclingof materialsor Mncration for energy.Tk majority of poIynws
in waste are mainly hydrocarbon in nature and so can bc used as a feedstock for the
chemical industries or as a fuel. Pyrolysis is a tertiary rccycIi.ng process and has an ability to
provide three end products: a gas, an oil and a char which all havt the potential to lx further
utilised. It is anticipated that if waste recovery targets currently being set are to h met then
methods. such as pyrolysis, will have to be cioseIy examined. The py~111ysisof a plastic
mixture in a fluid&d bed reactor was studied. The mixture was a simulated fraction of that
found in municipal solid waste in Europe. The reactor was constructed of stainkss steel and
was 70 cm high x 10 cm diameter, with a 17 cm high x 20 cm diameter expander s&on. The
sample was introduced batchwist into the bed. The iniluence of temperature on product yield
and composition was studied. Pyrolysis was carried out at temperatures bctwat 500 and
7OO*C. This gave widely diRering product yields of bctwcen 9.79 and 88.76% gas and
between 18.44 and 57.1 f % oil. The oils were analysed for their functional groups using
Fourier transform infrared spcctrosuopy. The molccuIar weight distribution was also dctcrmined using size exclusion chromatography. It was found that as temperature was &reascd
the amount of aromatic compounds in the oil increased. The molecular weight range was
also affected. Potential applicatioas for the oils was also investigated. Q 1997 EIscvier
Science B.V.
Keywords: Pyrolysis: Plastic waste; Analysis

Compnding

??

author. Tel: + 44 I13 2332504, fax: + 44 I13 2440572.

Oh%-2370/97/$17.00 0 1997 Ekvier

PII SOl65-2370(97)00048-X

Sckna

B.V. All

rights rmrvcd.

348

E. A. Williun~s. P. T. Wiiliunu

1J. Anal.

Appl.

Pp!rsix

40-41

(I 997) 347. 363

1. Introduction
Polymers are becoming a necessity in modern life in many Western countries.
Their discovery and subsequent utilisation meant that by the mid 1960s total world
consumption of thermoplastics alone was I3 million tonnes [I]. With an increasing
number of applications being found for these materials, today the demand for the
main commodity thermoplastics is more than 70 million tonnes [I]. Although a
significant amount of the thermoplastics are utilised in products with a long life
span, the majority are used in short term applications such as packaging. Thus, the
quantity of thermoplastics found in waste is increasing correspondingly.
Plastic waste can originate from a multitude of sources. The major areas of waste
creation are from the distribution industries representing 21.7% of all plastic waste
121and municipal solid waste (MSW) which accounts for 60.4O/o[2]. Municipal solid
waste is being targeted as an issue for improvement. However, the nature of MSW
is very complex, making its treatment difficult. Other forms of waste are easier to
handle, because of their uniformity and can be treated as they are created by, for
example. feeding back into the production process.
Currently 80% of MSW goes to landfifl, 10% is recycled and 1050is incinerated
in the USA [3]. However, landfill is becoming an iucreasingly expensive option. Not
only are suitable sites less available close to the point of waste generation. leading
to a rise in transportation costs, but costs of disposal are set to become even more
inflated. A landfill tax of E7 per tonne has been introduced by the UK Government
which becomes effective this year [4]. It is hoped that this will reduce the amount
of waste going to landfill and in conjunction with this aim, the Government in the
UK has set targets for waste recovery. The aim is to recycle 25% of all household
waste by the year 2ooO [5] and to reclaim for energy recovery 40% of waste by 2005
[41.
Treatment of homogeneous materials available in large quantities such as paper,
glass and metal has been shown to be viable via materials recycling. These can also
be separated from MSW for material recycling. The plastic fraction of MSW found
in Europe represents approximately 7% by weight. In Germany 80% of all packaging waste, including plastics, must be separated from other waste [I ] and a% is to
be recycled as material. However, viable markets for certain recycled plastics are
only available at rates of IO-15% plastic recycling [6] due to its inferior quality
when compared to virgin polymers.
So, if enough industrial and domestic waste is to be utilised so as to meet new
recycling targets then not only will contaminated and mixed plastics have to be
dealt with but also alternatives to landfill and materials recycling will have to be
found.
Incineration currently handles approximately 10% of waste produced in Europe
[3] to give energy via electricity generation. district heating or combined heat and
power schemes. However, incineration units emit dioxins, furans, acids gases and
heavy metals which can cause damage to the environment and to health. Limits of
emissions have been set so as to reduce any hazardous compounds. However this
means new clean-up systems will have to be incorporated into many existing plants.
dramatically increasing their operating costs,

&.A. lVit/ianu. P.T.

Williums jJ. And. Appl. Fydyk

40-41 (1997) 347-363

w9

Pyrolysis is an alternative process to incineration and materials recycling. This


approach of hydrocarbon processing has been investigated previously [7j but only
recently has this interest increased [S]. If applications for the products formed are
found, then perhaps it coutd IX a potential route for chemical or fuel production.
To study this potential a mixture of plastics was pyrolysed using a sand Auidising
bed to produce gases, oils and chars which were collected and subsequently
analysed.

2. ExperimeIltal

The plastic mixture used in this study was a simulated fraction of that found in
MSW throughout Europe. The actual composition of the polymers used can be
seen in Table 1. The polymers were virgin pellets of 2-5 mm in diameter, which
were obtained from BP Chemicals in Grangemouth, UK. A small particle size was
chosen to reduce the effect of heat transfer.

The pyrolysis was carried out using a Buidised bed reactor. A schematic diagram
of the reactor can be seen in Fig. I. The sample was fed in batches via a gate valve.
In total three batches each of 3 g in weight were dropped in at each temperature.
The reactor was stainless steel with a 10 cm diameter and approximately 70 cm
total height. An expander section at the top of the reactor enabled the velocity of
the carrier gas and pyrolysis vapours to be reduced before they entered into the
cyclone. Silica sand was used as the bed material and this was 10 cm high at rest.
Nitrogen was used as the fluidising gas which was set at 12 l min- from the
cylinder at room temperature. This provided enough fluidising gas to em ble the bed
to be operated at 3 tunes the minimum fluidising velocity (Umf), which had an
average value of 2.4 cm s--I at the temperatures studied. This gave good mixing of
Table 1
Camposition of polymer

sampleused in the study

Polymw

Pcrccntage (Yu)

LDPE
HDPE
PP
Ps
PVC
PET

31.25
31.25
7.29
13.50
Il.44
5.21

I: __

:f

Fig. I. khcmalic
diagram of !luidised bed rcxtor. (I ) Control Pund. (2) Rotmeicr, (3) Fccdcr. (4)
Main Rci~cior, (5) Ring Furnace. (6) Sund Bed, (7) Cyclone,
(8)Cutchyol,(9) Knirtmesh,
(10)Mclut
Curchpol. 11 I) GlassCondcnxrs.
(12) ColdTrups. (13) Gas Sampling Bny, (141 Ciluss Wool

the sand. The residence time of gases in the reactor was 53 s at room temperature
and approximately I5 s at the range of operating temperatures of the reactor.
Heat was supplied to the unit via nitrogen preheated to a temperature of 450C.
The reactor was also externally heated using an electric ring furnace. The temperature in the reactor was varied between 500 and 700C, Five thermocouples were
used to give a temperature profile of the entire height of the reactor. These were
positioned evenly along the reactor section with the tip being exposed to the sand
or gas stream. After the pyrolysis vapours and fluidising gas had passed through the
cyclone to remove any particulate matter, all vapours were passed through a heated
metal line filled with an icdustrial de-mister. This had the effect of knocking heavy
particles out of the gas stream where they were then collected in a metal catchpot.
The remaining lighter components were condensed using four glass condensers in
dry ice and acetone traps. A vessel containing glass wool was put in-line after the
condensers to catch any oil particles which had failed to be retrieved. In addition
a dreschel bottle of de-iocised water was placed in-line, so all the gas could be
bubbled through with &heaim of dissolving any HCI produced by PVC degradation. The HCI in water samples were analysed using a Coming pH/ion meter !35
with a chloride electrode calibrated between 100 and 1000 ppm.
The fluid&d bed used m this study, and described above. was similar in design
and operation to reactors used by other researchers. Kaminsky [9] used a quartz
sand bed heated !o between 600 and 9tWC to pyrolyse samples of plastic waste and
tyres. Conesa et al. [IO] used a similar reactor, this being 6.9 cm in diameter and
43.2 cm in height. Scott et al. [7j also had a comparable fluid&d bed to the one
used here, though the residence time was only 0.5 s.

The entire product gas was collected in a 100 I Teflon bag. The samphng
therefore continued for approximately g min to ensure all gases had been collected.
This was then analysed off-line using three packed column gas chromatographs.
Hydrocarbons were analysed using a GCD chromatograph with a 2.2 m x 6 mm
glass column packed with 80-100 mesh n-octane Porasil C. Permanent gases wcrc
identified on a Pye 204 chromatograph with a 1.8 m x 6 mm stainless steel cohunn
packed with molecular sieve 5 A. Carbon dioxide analysis was carried out on a
Gow Mac chromatagraph with a 1.8 m x 6 mm stainless steel column packed with
100-120 mesh silica gel. A flame ionisaiion detector identified the hydrocarbons
and thermal conductivity detectors were uscd to determine the other gases. Data
manipulation was carried out using a Harley Peakmaster data analysis system.
Three samples were injected into each gas chromatograph, The gases identified were
permanent gases, CO and CO,, and hydrocarbons up to C,. The total weight of gas
produced was calculated by comkariwn to the known nitrogen flow rate and a
mass balance was obtained.
2.4. Elemental

umlpis

During pyrolysis a char was formed which remained in tht and btd. It was
thepefore only retrieved after the reactor had cooled to room temperature and could
be dismantled. Chars were analysed on a Perkin-Elmer model 240C elemental
analyzer. The chars tended to form a fused mass with a portion of the sand bed.
These were then ground and sieved so that a uniform sample was achieved. Each
sample was analysed twice.
2.5. Fourier trunsform ittfrtweti specrroscopy (FTIR)
Functional group analysis of each pyrolytic oil and wax was carried out using
Fourier Transform infra-red spectroscopy. A Perkin-Elmer 1750 spectrometer was
used which had data processing and spectral library search facilities. A small
amount of the liquid fraction derived from the polymer pyrolysis was mountecon
a potassium bromide (KBr) disc which had been previously scanned as a background, The infra-red spectra of the sample was then taken. The multing spectra
were normalised to the C-H peak around 3000 cm - I_Direct comparisons of peak
intensity were then taken,
2.6. Size exclusion

chronaatogruphy

{SEC]

Size exclusion chromatography, which is aIso known as gel-permeation chromatography, is a non-destructive method which gives information on the molecular
weight distribution of the sample. The equipment used was similar t? that of
KPLC. The cohunas used were two 4.6 K 150 mm 5 pm RPSEC IO0 A type in
series. This method differs from HPLC in that here the elution order is in reverse

352

E.A.

Willims,

P, T. Wihms

/J,

Arral,

Appl. qvmlysis

4U-4J

(1997)

347-363

molecular size. That is, the targest molecule is eluted firs:. Two detectors were used,
these being a refractive index (RI) detector and an ultra-violet (UV) detector. The
RI detector gave information on the molecular mass of the whole oil and the UV
detector gave an indication of the samples aromaticity. The analytical set-up was
linked to a chart recorder in addition to a computer with data processing facilities.
A small amount of the oils and waxes were dissolved in 10 ml of tetrahydrofuran
(THF). This solvent was also the eluent through the system.

3. Results and discussion


3. I. Praducr

yield

Table 2 shows the product yield from the pyrolysis of the plastic mixture. It is
evident i.rat as the temperature is increased the percentage of gas increases. Burton
et al, [I 1) stated that high temperature-high heating rate environments favour
increased gas formation as the molecules breakdown and form a wide range of
smaller organic molecules. In addition, with the higher amount of energy available
at the higher temperature there is a tendency for an increased number of secondary
reactions. The amount of oil and wax decreases with an increase in temperature,
Thus, it is reasonable to suggest that the cracking down of the liquid products
formed initially is the cause of increased gas evolution at high temperatures. Scott
et al. [7] also showed in their work that at temperatures lower than 700C the major
part of thh product was solid. Whereas at higher temperatures the main product
was a gas [7]. Research by Conesa [IO] again noted this observation.
Two liquid fractions were collected. The first was trapped by the industrial
de-mister in the metal condensers (No. 10. Fig. I) and the second in the glass
condensers (No. 12, Fig. I). At pyrolysis temperatures of between SO0and 600C a
wax was found in both traps. !-Iowever, above 600C an oil was found only in the
glass condensers. The fact that no heavy wax was produced at the higher tcmperatures would also suggest that the increase in energy was resulting in these waxes
being broken up to form either lighter waxes or gaseous products.

Product yields from the pyrolysis of plastic mixtures


Product

Tempcmture

with change in temperature

of finidised bed reactor IT)

500

550

600

650

700

Gas
Wax
Oil
Char

9.79
17 28
37.79
2.82

24 52
18.5>
38.55
5.87

43.33
8.72
34 44
7.59

88.76
000
20.49
-a

68.81
o.lH
18.44
-4

HCI

1.76

I.42

I .43

0.80

0.51

Unavailable.

E.A.

Wiliiams. P.T.

Wilhhs/J.

Anal. Appl. P_wdys~

IO--U

IlW7)

37-363

353

Fig. 2. Cwmpuriron of gaseous mixrum produced from rhe pyrolysis of a pl;lsric mixlurc in a Ruidixd
bed reactor with change in !cmperarurr.

3.2. Gas analysis

As has been mentioned the affect of temperature on the quantity of gases evolvPed
was quite significant. At the lowest temperature 4.79% of gas was produced with
this figure more than quadrupling to 88.76% at 65OT and then decreasing
marginally to 68.81% at 700C. Coma et al. [lo] produced similar results during
their pyrolysis of polyethylene in a fluid&d bed. They found that the gas yield
represented only 5.7% of the total products collected at XMC whereas at 800C the
gases represented 96.5% [IO]. The majority of the gases collected here were
hydrocarbon in nature with a smaller amount oi carbon dioxide. No carl~n
monoxide was detected during pyrolysis. The gas chromatograph was accurate
down to approximately 0.1% of the total gas analyzed. It can therefore be assumed
that if carbon monoxide was present the quantity was less than 0.1%.
Examination of the actual change in composition with temperature found that a
significant proportion of the gaseous mixture remained remarkably similar. Fig. 2
shows the contribution, by weight percentage, of each gas in the gas stream. The
gases hydrogen and butane are those with the lowest conc~~~trationand are hardly
detectabk on the chart. Methane and ethane fluctuated between 0 and 1% of the
original weight of polymer, remaining essentially constant regardless of temperature. Therefore, the pyrolysis temperature has little effect on the concentration of
these gases.
The rest of the gases were, however, influenced by temperarun?. At the lower
pyrolysis temperature of 5OOC the major gaseous species was propenc, with
smaller, though significant quantities of ethene. As the temperature was increased

354

E.A.

Wil1imz.c. P. T. Wihrnr

,J. Ad.

Appi. Pyrolpiris JO -41 (1997) 347-363

the amount of propene decreased with a corresponding increase in ethene formation. The reduction in the amount of propene has also been highlighted by
Kaminsky [I 21and Conesa et al [I OJ.The overall order, in increasing concentration,
was butane, propane, ethane, methane, bu!ene, propene and ethene.
Thus, the trend of gases produced shows that there is a tendency for the smaller
gases in any series to be formed in the majority. That is, there is more ethene than
propene and in turn more of this than butenc. The same is true of the alkant gas
distribution. The reason for this is that smaller gaseous molecules could be more
stable than larger ones. Also the probability of a smaller molecule forming during
random s&ion is greater than the probability of large gaseous species forming. In
addition to this, as the temperature is increased and the energy in the system is
greater then this series of formation is emphasised with the smaller hydrocarbons
increasing their contribution.
Looking at the hydrogen chloride (HCI) gas evolved it is evident that the volume
decreases with increased temperature. This may be because at the elevated temperatures there are an increased number of radicals available to react with the free
HCI from the first step of PVC degradation. At the lower temperatures fewer
reactive species are awilable to combine with the HCI and so it is able to escape
from the system as HCi gas. The amount of HCI actually determined was smaller
than that anticipated. The monomer unit of PVC, which can be seen in Fig. 3.
shows that the chlorine molecule contributes more than 56% by weight of the whole
polymer, and 6.4% of the samnle pyrolysed. Here, only between 1.76 and 0.51%
was trapped using the de-ioni%; v.ater, which represents less than one third of that
potentially available. Thus, either the high flow rate of gas was such that insufficient time was given for complete dissolution IO occur and part of the HCI formed
was atrowed to escape. Alternatively, chloro-organic compounds could be present in
the derived pyrolysis oil.

The char produced during pyrolysis was found in the sand bed amalgamated with
sand. This mixture was heated to &KKKin a furnace to quantify the weight of char.
At 500C 2.82% of the original sample produced char, whereas at the higher
temperature of 600C the amount collected was 7.59?/billustrating an increase in the
char yield. This trend was also obsetvecl by Williams et al. [13].
The results of the elemental analysis are shown in Table 3. The ash values were
extremely high. However, a large proportion of this was thought to be sand which
remained unseparated from the char during analysis. To be suitable as a fuel then
chars should be low in ash. The values of ash seemed to decrease with an increase
in temperature. However. due to the presence of sand this effect cannot be
confirmed. An efficient method for separating the sand from ;he char should be
dtveloped enabling any trend to be established.

E.A.

Wilhms,

P.T.

WilCwns /J.

Anal. Appl. P~rol+s

M-41

(JS7)

347-363

355

3.4. Oil analysis


3.4.I. I;TIR
The FTIR spectra taken of all the pyrolytic oils produced between 500 and 700C
are shown in Fig. 4. It is evident that temperature increase has a significant effect
on the resuttant oil. The spectra of the !XWC pyrolytic oil is far less complex than
that obtained at 7OOC,indicating a greater variety of compound types present at
higher temperatures.
The initial sample pyrolysed was mainly hydrocarbon in nature, with the
exception of PET. Thcrrfore, the compounds expected are also hydrocarbons. The
peaks bctwccn 3000 and 2800 cm- and again bctwccn 1350 and 1450 cm-
represent C-H deformations and show the presence of -CH,, CH, and C-H
groups which highlight the aliphatic nature of the oils. HDPE, LDPE and PP
represent more than 60% of the initial sample. This dtrmir?stion in each of the
spectra by these absorbar&s is therefore expected because oi the random depoly-

i
+c+;

Pd~~lCaTarpblhrlrrO

c-o-c-H*-m-0

3
a

Fig. 3. Structures of rcpcatiag units of the thermoplastics used.

Table 3
Elemental analysis of chars obtained [torn the pyrolysis of a plastic mixture in a fluidised bed reactor
with change in temperurure
Temperature of Ouidised bed reactor (C)

Nitro,gen
Carbon
Hydrogen
Ash

500

550

0.05
1.73
KU7
96.92

_. -L
_- *L

(1

600

650

700

0 02
2.35
0.08
77.86

0.32
13.49
Q.fO
81.20

0.77
34.53
O.SI
53.81

U Unavailuble.

merisation process which takes place during HDPE, LDPE and PP pyrolysis
resulting in an array of smaller oligomer compounds. Alkenes are also shown to be
in the oil. Peaks between 1575 and 1675 cm- as wet1 as those between 875 and 950
cm - indicate C-C stretches. At the higher pyrolysis temperatures the stretches
around I650 c,m.- appear at a lower wavenumber than those present in the low
temperature pyrolysis oils. This suggests a move from monosubstituted groups to
dienes [14].
The peaks at 2850 (CH,) and 2950 cm- (CH,) change with increasing temperature. At SOO*Cthey are quite sharp and defined whereas at 650 and 7OOC they

Fig. 4. FUR

speara of plustic mixlure pyrolysis oils from the Auidised bed with change in remperature.

E.A. WiJJJums,P.T. Williams /.I. Awl.

Appl. PyroJpir

Fig. 5. Changes in intec;ity of absorbuncy pnks fra*? the FTIR


pyrolysis of a plarric mixture in a fluidiscd bed rcaclor.

40-41 (1997) 347-363

spectra of oils prdud

357

kom Iht:

become less separated. This could be due to the increase in unsaturated compounds
in the system which will tcad to broadening of CHJ and CH, absorption bands.
This broadening is therefore indicative of au increase in mndary
reactions
resulting in an increased amount of compounds with alkenc end groups,
Polystyrene (PS) represents 13.5%and polyethykne terephlhalatc (PET) 5.21% of
the original sample. Both their structures contain a benzene ring and so the
decomposition products are likely to be aromatic in nature. Looking at the XKPC
spectra there is some evidence of aromatic functional groups. Two peaks in the
region 7F?D-750cm - could mean the presence of mono, di and tri substituted
benzeao rings. The absorbance values of these groups at 780-750 cm - are
apprximately 10% at !iWC, whereas at XWC the absorb-attcyincream dramatito the 2850 cm - peak then
cally to more than 1W/o. As eack spectra is ~ormlkd
this increase represents it higher concentration of these aromatic groups at higher
temperatures.
The peak at 910 cm -I represents C-H ouMf-plane deformations which are
characteristic of monosubstitutcd alkcncs. As the substitution imxeaxs, so the
wxenumber can shift higher or lower, Fig. 5 shows that the baud at 910 cm-
does not follow a constant rise with tcmperatuhe increase. The intensity of the
absorbance peaks at 550C and then falls above this temperature. The reason for
this is the change in compound types at these hi&r temperatures. An increase in
substitution and the formation of dienes would result in these spectral change
Gent formation was noted earlier due to changes in the C=C stretches and so
would seem to support this theory.

358

E.A.

Wihmr,

P. T. Williumr /J.

Anal. Appt. P,wuljxir

40 -41 (1997) 347-363

This reduction in the 910 cm- band is coupled with an increase in the CH
out-of-plane bending between 690 and 840 cm -. which is representative of uromatic rings. Thus the FTIK spectra illustrates the move from mainly alkanes to
alkenes, dienes and ultimately aromatic compounds with an increase in pyrolysis
temperature.
Peaks which are between 3500 and 3CHMcm - also show the presence of =C- H
stretches and consequently alkene groups in addition to aromatic groups if attached
to a ring. possibly mono or poly substituted benzene compounds. The intensity of
these is hardly deteclable in the spectra of the 500C wax. However, al 700C their
contribution to the sample matrix is quite significant. Fig. 5 illustrates this increase.
Polyethylene terephthalate (PET) contains an oxygen in its structure, The
monomer unit (Fig. 3) shows that 33% of the molecular weight represents oxygen.
This translates to 1.74% of the initial sample being representative of oxygen. The
gas analysis showed that at 500C 1.65% and at 7WC 1.93% was evolved as CO,
which leaves a minute amount in the oil fraction. In general, stretches around 1695
cm - show the presence of oxygenated compounds. Absorbances of around O,I
were found in atl spectra. though there was no distinct trend with change in
temperature.
The chlorine content of PVC is almost 57% (Fig. 3). It has been documented [ 151
that up to 90% of this is evolved as HCI during pyrolysis. Therefore negligible
amounts of orgdno-chloride compounds were expected. These generally occur
within the absorbance bands 625-675 cm - I. No absorbance bunds associated with
these groups were identified.

Both the light and heavy liquid fractions were analysed using size exclusion
chromatography to determine the molecular weight of the oils and waxes. All
samples were made up to a 1% solution in tetrahydrofuran (THF). Of this, 5 ~1 was
injected onto the column.
The molecular weight distribution of the samples collected using the incldstrial
demister are shown in Fig. 6(z) and (b), whereas Fig. 7(a) and (b) show the lighter
fractions. The range shown by the refractive index detector is indicative of the
whole oil, since RI is capable of detectin, n 11:
,. hydrocarbons. Aliphatic compounds
are not detectable in the UV raugc and so only aromatic compounds were able to
be detected using the ultra-violet detector.
It is clear that in Fig. 6(a) the heavy fractions do indeed reveal a high molecular
weight distribution. No sample is present with a molecular weight in the region
between log I.5 and 2, that is, with a weight less than 100 Do. This confirms that
the &mister used in the pyrolysis system is capable of collecting high molecular
weight compounds which may normally pass through the system. The maximum
weight in lhis range had a log vaIue of more than 3.5 at all temperatures. It is also
evident that two molecular weight ranges are present in the sample matrix. That is,
more than and less than log 2.6 (400 Da), with the peaks at a molecular weight of
2.3 and 2.7. SEC data can also yield information concerning the boiling point of
these waxes. Here, the two peaks in the distribution gave boiling points of 300 and

E.A. Wllium.

P.T. Willimm/J.

359

And. Appt. Pyrolysis 40-41 (1#7) 347-M

7WC The atmospheric residue cut of crude oil has a boiling range greater than
350C and the wax produced here appears comparable in this characteristic.
The effect which temprature
had on this distribution of products is quite
distinct. At pyrolysis temperatures of 500 and SWC the largest percentage of the
wax had a molecular weight higher than 400 Da. Whereas at 600C the opposite is

IS
---.....

_
-

..-

2s

5.5

~_L%+!F!E~_...
._.

--___-._--__-.

+mFc
_ .._

-=-rwc

+5oaT
_.....
--._.-_..

___-_-_L

111

I?

2.5

3.5

-._-..--

------

Lq-Wig
--

;b)

tswc

+5m

---__

+6lax

Fig. 6. (a) Comparison of molecular wei@ distribution of heavy waxes pro&toed from Ux pyrol@s of
a plastic mixture in II fluidiscd LUGreactor with cbatqc in tcmpra~urc-Rl
d~cctor. (b) Ccmparkm of
mol-xular weight distribution of heavy waxes produced fmm the pyrolysis of a plastic rli..ture in a
fluid&d bed nactor with change in temperature-LJV dctcctor.

360

E.A.

Williar,ts, P.T,

Wifliun~s /J.

.. . . _ - ., - -

Anal. Appl. Pwo~vsis 40-41

(1997)

347-363

I5

4-55GT
_

+-5cwC

,, .

-4-6aPC

+mT

*650oc
__ _ _

.._.

14
r-r

I5

,,. ._.. +5cwc


__~~~~_.
.__

25

2
.._.. __
~

_--

-s-P.oT

_....

35

Log Vddsulu Wci$r


&6woc

-)-

65WC

-.--

-=-?wc
._... .---.--

(b)

FIN. 7. (a) Comparison ur molecular weight distribution of oils producd from ihe pyrolysis of a plastic
mixtur.7 in a fluid&d bed reactor with change in temperature-LV
detector. (b] Comparison of
moleculcr weight distribution of oils produced from the pyrolysis of a plastic mixture in a fluid&d bed
reactor with change in temperature-RI
detector.

true. Here 55% of the sample has a moiecular weight less than 400 Da. Thus, at
higher temperatures, the peak boiling point was shifted to a value around 3WC.
The explanation for this may be that due to an increase in temperature some of the
heavy molecules break up to Form much lighter compounds. It is thought that the
major component of these heavy waxes is long chained aliphatic compounds.

E.A.

Williams,

P.T.

Willian~/J. Ad.

Appt. Pyrolysis 40-41 (1997) 347-363

351

During their time in the hot zone of the reactor random s&ion [I61 is occurring.
At higher temperatures, breaking of long chains may halve the chain length and
thus the mokcular weight leading to a shift in peak values from 1000 to apprctximalely 500 Da.
Sample detection with the W detector illustrates the presence of aromatic
compounds within the waxes. Fig. 6(b), again illustrates a shift to lower molecular
weight compounds with an increase in temperature.
The molecular weight range of the oils from the condensers is simiIar to the
heavier fractions. Though, as expected there is a much greater proportion of the
sample with a low molecular weight. Again the peakmolecular weight vaIue of the
sample changes with temperature. Fig. 7(a) highlights this eBct. It rev& three
major regions of molecular weight. These are around log v&es 2,2.3 and 2.7 that
is, actual molecular weights of 100, 200 and 500 Da. At pyrolysis temperatures of
between 500 and 6CWCtwo of these peaks are or=!, that is at 2.3 and 2.7. This
illustrates that a large proportion of the sample has a heavy molecular weight. The
distribution between these two peaks is approximately 5050.
At the higher temperatures the distribution changes. The oils produced at 6M
and 700C have a mokcuitrr weight peak of approximately bg 2.2, &at is ahnost
I60 Da. This is very similar to the boiling range of naptha [17]_The region around
log 3 contributes much less to the composition of the oil, with this being around
25% of the sample, much less than with the other lower temperature oils. Again, it
seems that at higher temperatures much smaller molecules are formed than at the
lower temperatures. This is probably due to the heavier mohxuks breaking up to
form the smaller ones. Fig. 7(b), that of the W detector, shows that aromatic
compounds are displayed in the sample. However, no clear trends in molecular
weight with change in pyrolysis temperature are observed.
3.5 Product

applications

The commercial application of the gases could be as a fwl. The calor& value
of all hydrocarbon gases 1181produced is more than or qd to 40 MJ kg-.
Their accumulative CV is therefore sufficient to fuel the pyrolysis process itself. if
high temperatuB were conmntrated on then more than 80% of the original
feedstr;ck can be converted into gaseous products, Ethcne and propene are valuabk
gases within the chemical industry. Ethene is a key intermediate in the macufiacture
of polyethylene, vinyl chloride, styrene, ethanol, and other important products [19].
Propene is used to make polypropylene and aetone, and is an intermediate in the
production of polyurethane foam [17].
In addition to the direct use of gaseous ole6ns in the production of chemicals,
heavier fractions of crude oil are cracked down to form these gaseous intermediates
before reprocessing. For example, napthas, a complex mixture of allanes, cycloalkanes and aromatics [t7], are cracked to produce ethene as the main product
and propene as a by-product. Gasoline, a widely demanded fuel, GUIbe produced
from the heaviest fraction of crude oil, atmospheric residue, by catalytic cracking
1171.
(CV)

362

EA.

William,

P. TV Williumr / 1. Anal. Appl. Pyrolysis 40-41 Cl9971 347-363

These and other products are of great importance in the chemical industries. So,
if the products of plastic pyrolysis can be utilised in these processes then economic
benefit will he forthcoming.

4. conclusions
Two valuable products are formed from the pyrolysis of mixed plastic waste.
These are a gas and oil. Depending on the reaction conditions used the products
have varying compositions and properties.
At lower pyrolysis temperatures a heavy wax is formed. This is comparable in its
molecular weight range, boiling point and functional group composition to an
atmospheric residue cut from crude oil, Thus, catalytic cracking could be carried
out on the wax forming a gasoline type mixture of hydrocarbons. A lighter, mainly
aliphatic wax is also a product of pyrolysis at temperatures below 550C which
again could be commerciaIly cracked to form gasoline.
At higher temperatures, the oil formed is much more aromatic and has a lower
modal boiling point of between 120 and 220C. It is similar to naptha and could be
cracked to form ethene. A hydrocarbon gas is produced at all temperatures with its
concentration increasing at higher temperatures.
The results therefore indicate that depending on the product type required the
operating conditions can be changed accordingly. It can also be inferred that if the
temperature was increased to higher than 700C then due to increased secondary
reactions, it is possible that the resultant oil would directly resemble gasoline
without any further processing.
It is therefore evident, that pyrolysis of mixed plastic waste shows a huge
potential not only in dealing with waste reduction but also in producing products
which show a real ability to be adapted for chemical feedstock production.

Acknowledgements
The authors would like to thank the Department of Trade and Industry via the
Energy Technology Support Unit, Harwelf, Oxfordshire for support for this work
(Grant number B/TI/O0397/00/00)+Also, David Wilson of BP Chemicals for the
supply of polymer samples.
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