Fuel 81 (2002) 473481

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Engine fuel derived from waste plastics by thermal treatment q

Jerzy Walendziewski*
Institute of Chemistry and Technology of Petroleum and Coal, Technical University of Wrocaw, ul. Gdnska 7/9, 50-310 Wrocaw, Poland
Received 15 February 2001; revised 11 June 2001; accepted 20 June 2001; available online 25 July

Abstract
Two series of experiments of waste polymers cracking were carried out. The rst series of polymer cracking experiments was carried out in
a glass reactor of 0.5 dm 3 volume at atmospheric pressure and in a temperature range 3504208C, the second one in autoclaves under
hydrogen pressure (,35 MPa) in the temperature range 3804408C. The inuence of cracking parameters, i.e. reaction temperature,
presence and amount of cracking catalysts and composition of the polymer feed on product yields and composition of gas and liquid
fractions are discussed. It was stated that the proper selection of the process parameters makes it possible to control, in the limited range, the
product composition distribution as well as yields and composition of gas, gasoline and diesel oil fractions. Basic physicochemical properties
of gasoline and diesel fuels obtained in both type of processes were characterised and discussed. q 2001 Elsevier Science Ltd. All rights
reserved.
Keywords: Plastics; Polyolenes cracking; Engine fuels; Diesel fuels; Gasolines

1. Introduction compound was also found [9]. The extent of conversion of

Thermal and rst of all catalytic cracking processes of
waste polymers are economically and environmentally
accepted methods of their utilisation. The products of such
processes are liquid mixtures of hydrocarbons boiling in the
temperature range ,353608C, gaseous hydrocarbons as
well as solid residues, similar to wax or coke. Different
type of catalysts, acid silicaalumina or zeolite (HY,
HZSM-5, mordenite) containing ones as well as alkaline
compounds such as ZnO, CaO and K2O can be applied
[13], but in the course of the process all these materials
deactivate very quickly [1]. An interesting method of poly-
mer utilization is catalytic cracking, similar to cracking of
VGO in the presence of cracking catalysts exchanged Y and
other zeolites containing catalysts [4,5]. There are also
proposals to convert melted polymers together with petro-
leum or carbon derived fractions in the presence of cracking
or hydrocracking catalysts [68]. In this type of process
application of catalyst of higher acidity (HY, ZSM-5,
silicaalumina) results mainly in C5 C12 liquid hydrocar-
bons while in the case of thermal or process with the use of
nonacid catalysts somewhat higher content of C12 C22z
* Tel.: 148-71-3203551; fax: 148-71-3203551.
E-mail address: walendziewski@nafta1.nw.pwr.wroc.pl
(J. Walendziewski).
q
Published rst on the web via Fuelrst.comhttp://www.fuelrst.com
0016-2361/02/$ - see front matter q 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0016-236 1(01)00118-1
plastics or plastic derived waxes into light engine fuels can
be enlarged by the application of stable hydrocracking cata-
lysts [10]. In the case of hydrocracking the task of catalyst
and the presence of hydrogen is not only hydrocracking of
long parafn or polymer chains but also hydrogenation of
olens.
Similarly to petroleum derived cracking products the
fractions from plastic processing contain appreciable
quantities of aromatic and unsaturated hydrocarbons
[4,11]. Because of olens content it would be reasonable
to submit the derived fractions to the hydrogenation step,
typical of pyrolysis or cracking gasoline hydrorening
process [10]. Similarly, because of large quantity of linear
n-parafnic hydrocarbons it would be protable to isomerise
them in order to lower cloud and freezing points. It is also
possible to admix small quantities of plastics cracking
products to low sulphur fuel oils without any treatment.
In this paper results of thermal and catalytic cracking of
the most popular polyolenes using autoclave and pressure-
less reactor are presented. It was shown that all these
materials can be thermally cracked giving liquid and gas
fuels with over 95% efciency. Application of cracking
catalyst enables lowering of process temperature and at
the same time lower the boiling temperature range and
density of the obtained liquid products. Highly unsaturated
liquid products of polymer cracking can be hydrogenated
over Pd/Al2O3 catalyst and bromine number lowered to less
474 J. Walendziewski / Fuel 81 (2002) 473481
than 0.5 g Br2/100 g. In comparison with the atmospheric
cracking the pressure cracking of waste plastics in auto-
claves resulted in higher conversion level, larger gas and
gasoline yield and quality but at the same time relatively
lower boiling and freezing points as well as lower cetane
numbers of the obtained diesel fuel fractions.
2. Experiment
2.1. Raw materials
Waste polyethylene (PE), polystyrene (PS) and polypro-
pylene (PP) and their mixtures were used as raw materials in
the cracking process experiments.
2.2. Cracking of waste plastics
The rst series of the polymer cracking experiments was
carried out under atmospheric pressure, (batch reactor,
100 g feed) in the presence of 010% of cracking catalyst
in a glass reactor equipped with a heating device and a
distillation cooler. The plastics were cracked at a change-
able temperature during the test, increased from 350 to
4408C, measured directly in the cracked feed, and products
after condensing were collected in liquid and gas product
receivers.
The second series of cracking experiments of polymers
was carried out in autoclaves (volume 1 dm 3) placed in a
rotary kiln (10 min 21) equipped with the necessary
measurement devices, inlet and outlet valves, and tempera-
ture and pressure gaugers. The experiments were carried out
at the reaction temperature range, 3804408C, most of them
in the presence of cracking catalyst. In this case, the crack-
ing temperature was xed during the test and was measured
using thermocouple placed at the centre of the autoclave (in
thermowell). Gas products were submitted for determina-
tion of volume, density and chemical composition using gas
chromatography. Autoclave liquid products were weighed
and submitted for normal distillation, gas chromatography
as well as IR, UV spectroscopy and bromine number
analysis. Molecular mass of solid and liquid cracking
residue was also determined. Liquid products of poly-
olenes cracking, gasoline fractions with boiling point
,2208C, were submitted to the hydrogenation step using
noble metal catalysts in ow continuous micro-reactor
(3 cm 3 of catalyst, 3 MPa, 2803208C).
2.3. Determination of physicochemical properties of the
obtained products
Chemical composition of gas and fraction composition of
liquid products were determined by gas chromatography
methods, using FID and MS detectors and standard
columns.
Bromine number according to ASTM-D 1491-60 (1971),
normal distillation according to the Polish Standard
PN-67/C-04010, ignition point, cloud point, freezing
point, cetane number according to the Polish Standards:
PN-67/C-04009, PN-/C-04018, PN-57/C-04031 were
determined.
Aromatics' content in liquid products was determined
by measuring absorption band at 16001610 cm 21.
The semi-quantitative determination of aromatic and
unsaturated hydrocarbons in gasoline and diesel oil
samples was done by the analysis of IR spectra in the
range 15252025 cm 21 wavelengths.
Octane numbers and benzene contents in gasoline
fractions were determined by chromatographic methods.
3. Results and discussion
3.1. Cracking of polymers in batch, atmospheric pressure
process
The results of our studies on cracking of individual
polymers, i.e. polyethylene (PE), polystyrene (PS) and poly-
propylene (PP) as well as their mixtures under atmospheric
pressure showed that thermal and catalytic cracking can be
carried out with 7098 wt% efciency (up to 23 wt% of
coke residue) in the temperature range 3504408C. An
application of cracking catalysts lowers the process
temperature by about 10308C in comparison with the
thermal process.
Some literature data suggests that the alkaline and base
metal oxides such as MgO, CaO or ZnO and CdO can also
be applied as good catalysts for polymer cracking [13].
However, according to the results of our experiments the
alkaline catalysts to a very small extent catalyse cracking
reaction. Process in the batch cycle in the presence of
alkaline catalyst proceeds with similar temperature and
rate as in the case of thermal cracking, temperature range
3904108C, higher by 10308C in relation to the process
catalysed by the acid catalysts (Fig. 1).
Differences in cracking catalyst efciency also resulted in
distillation temperature range of the cracking products. For
instance, initial boiling point of the cracking products in the
case of catalysed process was ca. 258C and end boiling point
ca. 658C lower in comparison with the suitable boiling
points of the liquid fractions obtained from both the thermal
as well as alkaline material catalysed processes (Fig. 1). The
inuence of the amount of catalyst on process efciency to
some extent was found. An increase in the amount of the
applied cracking catalyst (from 0 to 10 wt%) in the cracking
of mixture of PS and PE resulted in lowering of the average
cracking temperature and mainly boiling temperatures of
the obtained products. The average difference in cracking
temperature is ca. 208C while the difference in product
boiling temperature is from 5 to 508C. Similar inuence
of the quantity of catalyst on cracking and distillation
temperature of products was found in the cracking process
of individual PE and PS feeds. The inuence of the content
 J. Walendziewski / Fuel 81 (2002) 473481
Fig. 1. Temperature of cracking and distillation temperature of cracked products versus volume of distilled liquid products from cracking of PE 1 PP mixture
in atmospheric batch reactor as well as type of the used catalyst (cracking and ZnO catalyst) and thermal process (Tcr1, Tcr2, Tcr3 cracking temperatures,
Td1, Td2, Td3 distillation temperature of liquid product).
of the cracking catalyst on cracking process efciency is
distinctly visible in liquid product density. The increase in
the amount of used catalyst in cracking of plastics mixture
from 0 to 10 wt% resulted in lowering of density of liquid
product from 0.837 to 0.81 kg/dm 3, as follows:
Catalyst d (kg/dm 3) Catalyst d (kg/dm 3)
content (wt%) content (wt%)
0 0.838 7.5 0.812
2.5 0.829 10.0 0.810
5.0 0.827
An appreciable inuence of plastics (PP, PE, PS) compo-
sition used as the cracking feed on the product properties
and composition was found. In the case of cracking of
mixtures containing PP or PE relatively large amounts of
light hydrocarbons, boiling below C7 are formed which
resulted in lowering of boiling temperature of cracking
products, while in the case PS or PS containing feeds the
main cracking products are styrene and its derivatives with
boiling temperature in the range 1301808C. In the case of
batch process, cracking of polymers at the initial stage is
relatively easier and can be carried out at lower temperature
(3503808C) than at the later and nish stage of the batch
process, higher than 4008C. That is why it is necessary to
increase steadily the temperature of the process and as a
475
result, higher boiling products are obtained when the
batch cracking process tends to the end. This phenomenon
can be observed in Fig. 1 where higher tabled curve groups
present the changes in the cracking temperature and lower
tabled curve groups present temperature of the received
cracking products in distillation cooler during the course
of batch cracking experiment. This type of batch cracking
process is quite similar to the distillation operation of heavy
oil fractions.
In the case of atmospheric, batch or continuous process of
cracking of polymers two different modes of the process can
be considered. In the rst mode the total cracking can be
executed up to obtaining of the coke residue (9598%
process efciency), the whole feed is converted to gas and
liquid products as well as coke. This process is quite similar
to petroleum residue cooking. In the second mode of the
process, partial cracking of plastics can be realised, up to
7090 wt% efciency of gas and liquid products, while the
rest of the feed builds wax like products, with melting
temperature higher than ca. 308C, which can be used as
component of heavy fuel oil. The author has found that
molecular weight of the wax residue is between 350 and
500. It is necessary to notice that in the case of partial
cracking of higher amounts of polystyrene containing
feeds the main component of residue is similar to coke.
Selected results of batch, atmospheric cracking of two
polymer mixtures (PE 1 PP and PE 1 PS) are presented
in Table 1.
476 J. Walendziewski / Fuel 81 (2002) 473481

Table 1
The selected results of atmospheric cracking of mixtures of PS 1 PE and PE 1 PP mixtures (1:1 weight ratio)

Nr Feed composition Yield of liquid Bromine number Liquid product Gas yield Gas density Residue yield
(ratio) 1 cat. wt% product (wt%) (gBr2/100 g) density (g/cm 3) (wt %) (g/dm 3) (wt%)

1 1PE/1PS 1 10 wt% 86.5 28.3 0.82 3.7 0.98 6.4

2 1PE/1PS 1 5 wt% 86.8 29.3 0.84 2.9 1.00 7.2
3 1PE/1PS 1 2.5 wt% 89.8 24.3 0.83 3.1 1.02 5.6
4 1PE/1PS 87.8 28.3 0.84 3.3 1.00 6.3
5 1PE/1PP 1 10 wt% 88.7 17.2 0.72 3.4 1.09 4.8
6 1PE/1PP 88.3 22.4 0.73 2.7 1.07 5.1

As a rule, the obtained yields of liquid products attained
more than 85 wt% while yields of gas products ca. 3 wt%.
Yields of residue, without weight of catalyst attained 57%
but it was possible to obtain higher conversion level
and, respectively, lower solid residue weight by further
continuing the cracking process. There was no found
distinct inuence of catalyst amount on gas or liquid
product yield as well as on gas density. Similarly, one
can say that there was no visible inuence of catalyst
amount on bromine number but as it was stated earlier
that the liquid product density was almost a linear
function of the amount of the applied cracking catalyst.
As a rule, cracking of PP and PE mixture resulted in
lower density liquid product and higher density gas product
in comparison with the densities of PS 1 PE cracking
product. Determination of gas density and GC results
showed that in the case of PE 1 PP feed cracking the
highest content of C3 C4 hydrocarbons was produced
while in the case of cracking of polystyrene or polystyrene
containing feeds (PS 1 PE) the highest contents of ethane
and methane were determined.
This information and results of gas chromatographic
analysis of gases from polymers cracking leads to the
conclusion that in the case of polystyrene, cracking of
benzene ring is difcult while one of the possible reaction
is dealkylation of ethane from styrene. In the case of
polyethylene and propylene both thermal and catalytic
cracking give relatively large quantities of propane and
butanes. Therefore gases from cracking of polystyrene
containing feeds were characterised by lower density
(larger C1 1 C2 content) than from PP and PE containing
feeds (larger C3 1 C4 content).
3.2. Cracking of polymers in autoclaves under heightened
pressure
The selected results of cracking of polymers in autoclaves
are presented in Table 2. The total conversion was calcu-
lated as the difference between the weight of the feed and
the weight of the residue in autoclave. Because of the leaks
and evaporation of light products during evacuation of the
autoclaves noticeable light product losses were stated and
the mass balance could not be closed.
The noticeable inuence of catalyst present on polymer
cracking, especially at lower temperatures, 380 and 4108C
was stated. At the highest temperature, 4408C, besides
cracking of PS the differences in process efciency between
the thermal and catalytic processes were relatively small. In
comparison to the catalytic process, appreciably lower
total conversions, 1225 wt%, and lower gas yields, from
3 to 5 wt%, were stated in thermal cracking at 3808C. The
highest gas yield for PE cracking process was found. On
the other hand, in the catalytic process the conversion of
polystyrene was the lowest one while the highest conver-
sions were obtained for mixed (PE 1 PS) feed, although
the differences in plastics conversion were not large. In
the whole studied temperature range the cracking process
of PE gave an intermediate total yield of products while

Table 2
The inuence of polymer type, process temperature and catalyst on total conversion and gas yield in pressure cracking of polymers (reaction time 2 h)

Nr Temperature (8C) Feed Catalytic process (wt%) Thermal process (wt%)

Total conversion Yield of gas Total conversion Yield of gas

1 380 PS 84.6 12.6 72.0 8.1

2 PE 92.4 17.2 67.6 12.0
3 PS 1 PE 96.6 12.4 70.4 9.2
1 410 PS 91.2 15.0 80.2 8.4
2 PE 96.2 23.6 89.7 15.6
3 PS 1 PE 98.5 21.0 91.6 11.2
1 440 PS 94.0 18.0 86.0 12.0
2 PE 98.6 44.1 97.2 34.2
3 PS 1 PE 98.5 28.0 97.4 20.6
 J. Walendziewski / Fuel 81 (2002) 473481
Fig. 2. Inuence of cracking temperature on bromine number of liquid products from closed, pressure reactor system, for three type of reactor feeds.
the weight of the produced gases was the highest one.
Similar gas yields in relation to the total polymer
conversion were stated in thermal cracking although, as
it was discussed earlier, generally total gas yields were
visibly lower in thermal cracking in comparison to the
catalytic one.
Taking into account the efciency of the process, the
results of catalytic cracking (time reaction 2 h) at the lowest
temperature are satised because relatively small yields of
residue, especially in the case of cracking of PE containing
feeds and no large volume of gaseous products were
obtained. The increase in process temperature up to 410
and 4408C resulted in lowering of solid reaction residue
for all types of the feed but it is necessary to notice that
the weight of gas produced in the process considerably
increased. In the highest process temperature (4408C)
almost 50% of the product of PE catalytic cracking was
undesirable gas, lower gas yields were found for other
feeds. Similar dependencies were also stated in the case of
thermal cracking although the total product and gas yields
were visibly lower. Although it is difcult to nd compar-
able results in both the type of processes (thermal and
catalytic) on the basis of liquid products and gas yields
the preferred polymer cracking temperature ought to be
ca. 4108C. It is also necessary to add that the pressure cracking
of waste plastics, in closed autoclaves, gave much higher
gas volumes and therefore is less benecial from liquid
product yield point of view than atmospheric cracking.
477
As a rule, end boiling temperatures of liquid products
obtained in autoclaves attained values 2603108C. It
means that under applied process parameters in pressure
cracking, the products consisted mainly of gasoline and
light diesel oil. In the case of cracking experiments carried
out in open, atmospheric reactor typical diesel fuels with
end boiling point 3503608C were obtained.
Independently on process temperature and application of
catalyst bromine number of liquid products did not change
very much and attained values 57 and 1519 g Br2/100 g
for PS and PS 1 PE feed, respectively (Fig. 2). Only in the
case of PE cracking bromine number was considerably
higher, from 22 to 47 g Br2/100 g, the highest value as
well as the highest olen content was stated for the process
temperature 4108C.
As it was stated earlier aromatic contents in liquid
product were determined semi-quantitatively by IR spectro-
scopy method. It is evident that in the case of cracking of PS
and PS containing feeds large contents of aromatics have to
be present. Results of IR analysis, conrmed by GC MS
analysis, indicates that even in the case PE or PP cracking
some quantities of aromatic hydrocarbons are present. Data
presented in Fig. 3 indicate that the application of the high-
est cracking temperature gave appreciable increase in
aromatics content. It means that cyclisation and aromatisa-
tion of parafnic hydrocarbons can occur in the high
temperature cracking of waste plastics, similarly as in the
typical, renery cracking process.
478 J. Walendziewski / Fuel 81 (2002) 473481

Fig. 3. Inuence of cracking temperature on content of carbon atoms in aromatic structures for liquid products from closed, pressure autoclave system, for
three type of feeds.

3.3. Physicochemical properties of gasoline and diesel fuel
fractions from cracking of polymers
Typical yields of cracking products (gas, gasoline and
diesel fractions, residue) depending on feed composition
and process type are shown in Fig. 4. Gasoline and diesel
fuel fraction yields in the liquid products were determined
by normal distillation, boiling temperature 2208C was
accepted as the boundary point. As the rule, the closed
reactor, pressure cracking in comparison to the atmospheric

Fig. 4. Distribution of cracking products, gases, gasoline, diesel fuels and residues for both applied reactor systems.
 J. Walendziewski / Fuel 81 (2002) 473481 479

Fig. 5. Distillation curves for gasolines obtained in both systems of polymer cracking.

open reactor cracking of PS containing feeds gave higher
yields of gas and gasoline and lower diesel oil and residue
weight. It can be explained partially by longer reaction time
in the case of pressure cracking although the catalyst to feed
ratio was larger in atmospheric cracking. On the other hand
in both the type of processes of PE and PP cracking similar
volumes of gasoline and diesel fuel can be produced,
although total volume of liquid products was lower by
about 10% in the case of the pressure, autoclave cracking.
The relation between volumes of two liquid fractions
depends also on the end boiling point of gasoline and initial
boiling point of diesel fuel (data in Fig. 4 were determined
for boundary temperature 2208C).
Characteristics of boiling range of the gasoline fractions
obtained in applied processes and feeds are presented in
Fig. 5. For gasoline fractions PE and PP cracking depend-
encies of distilled volume of gasoline on temperature are
almost linear while in the case of PS cracking the majority
of gasoline fraction distillates at a very narrow temperature
range, i.e. 1201408C. It means that the main components
of PS cracking products are styrene derivatives, C6 C9
hydrocarbons with boiling temperature in this range while
distribution of hydrocarbons concentration in gasoline from
PE (and PP) cracking are much more uniform.
The base physicochemical properties of the fractions of
gasoline and diesel fuel boiling range are presented in
Tables 3 and 4. One can see that there are distinct differ-
ences between physicochemical properties of gasolines
obtained in the atmospheric reactor and the pressurised
autoclave.
The rst essential difference in properties of gasoline
fractions obtained in two types of processes is the con-
tent of aromatic hydrocarbons, appreciably lower in the
atmospheric cracking products. Taking into account

Table 3
Composition and physicochemical properties of gasolines fraction produced in polymers cracking in pressure autoclave (PA) and pressure-less, atmospheric
reactor (AR)

Parameter PE(PA) PE 1 PS(PA) PS(PA) PE 1 PS(AR) PE 1 PP(AR)

Benzene content (wt%) 1.2 0.9 0.9 0.2 1.1

Aromatics content (wt%) 16.7 63.7 83.4 56.7 6.5
Bromine number (gBr2/100 g) 35.4 14.4 6 20.1 21.9
Parafnes content (wt%) 63.3 26.9 12.5 25,5 61.3
Range of boiling temp (8C) 61209 56204 81178 56208 44220
Density (kg/m 3) 0.762 0.826 0.857 0.846 0.723
RON 80.9 90.5 106.8 95.8 88.6
MON 75.0 83.1 98.4 84.0 78.6
RON 1 MON/2 78.0 86.8 102.6 89.9 83.6
480 J. Walendziewski / Fuel 81 (2002) 473481
Table 4
Physicochemical properties of diesel oil fractions produced in polymers cracking in pressure autoclave (PA) and pressureless, atmospheric reactor (AR)
Parameter PE(PA)
Bromine number (g Br2/100 g) 20.5
Aromatics content (wt%) 28.7
Boiling point range (8C) 186261
Density (kg/m 3) 0.835
Ignition temperature (8C) 41
Cloud point (8C) 211
Cetane index 32
bromine number more or less comparable level of olens
content in the case of pressureless cracking was stated.
Products of pressure PS cracking contained appreciable
lower olene quantity. Content of PE or PP and PS in crack-
ing feed determines process product composition, e.g.
appreciably high content of parafns in PP and PE cracking
products and adequately high aromatics content in PS crack-
ing products (even more than 95 wt%). GC MS analysis
showed that the main products of PS cracking was styrene,
ethylbenzene, toluene, and trimethylbenzene while
benzene, propylbenzene and parafnic hydrocarbons were
found in 13 wt% content. In the case of mixed feed,
PS 1 PE cracked in closed and open systems similar
aromatic hydrocarbons were found but also typical paraf-
nic hydrocarbons such as heptane, octane and decane hydro-
carbon derivatives were determined.
Liquid products from PE and PP cracking, contained
mainly parafnic hydrocarbons and smaller quantity, ca.
1% benzene and other, higher molecular aromatics. It is
necessary to add that as far as identication of PS cracking
product is quite simple and reliable insomuch identication
of PE cracking product is difcult and uncertain, mainly
because of large quantity of chemical components. Content
of aromatic and unsaturated hydrocarbons in gasoline
fraction causes comparatively high octane number, both
research and motor method characterises it. On the other
hand, similarly as in the case of other cracked products
the gasoline from cracking of plastics is very unstable and
prone to polymerisation. Hydrogenation of olenes in
hydrorening process over Pd catalyst, 3003208C, 3 MPa
hydrogen pressure, enabled to decrease bromine number
to less than 0.5 g Br2/100 g, to improve gasoline colour
and stability but as a result octane number decreased by
23 units.
Relatively low styrene content and high content of ethyl-
benzene in liquid product of PS containing feeds cracking
seems to be a very interesting statement. As it was earlier
stated the pressure cracking experiments were carried out
under initial 1.5 MPa hydrogen pressure (45 MPa at
process temperature). The obtained results of GC MS
analysis indicates that partial hydrogenation of olens in
this process despite of absence of hydrogenation catalyst
or counteraction olen yielding in the presence of hydrogen
partial pressure took place.
PE 1 PS(PA) PS(PA) PS 1 PE(AR) PE 1 PP(AR)
10.5 5.6 9.9 14.0
56.7 .90 48.9 3.6
143273 152290 170360 151347
0.863 0.921 0.845 0.799
57 63 58 56
216 224 28 24
26 15 50 59.5
The inuence of the feed composition and process type
on product IR spectra is presented in Fig. 6. Very strong
absorption band at 1610 cm 21 (aromatics content) is visible
for all PS containing feed samples as well as for PE and PP
feeds, although distinctly weaker. It is surprising that much
smaller was the same absorption band in gasoline spectra
obtained for product from PE 1 PP cracking. It is also
necessary to notice that in the case of gasoline from PS
containing feed there are visible absorption bands charac-
teristic for dienes and monolenes (19501750 cm 21)
which were weakly visible in IR spectra for PE 1 PP and
PE cracking products despite of high bromine number.
The diesel oil fractions in comparison to the gasoline
fractions were characterised generally by lower olens
and aromatic hydrocarbons content (Table 4). Because of
lower conversion level in the atmospheric reactor in relation
to the pressure diesel oil fractions had higher end boiling
temperature than fractions from the pressure autoclave. This
property in connection with higher content of parafnic
hydrocarbons and relatively lower aromatics content
resulted in quite high cetane number, even more than 50.
The other physicochemical properties of this fraction,
ignition temperature as well as cloud and freezing points
were a little too higher in relation to the petroleum standard
for commercial diesel oil. It is necessary to notice that
diesel fuels obtained from autoclaves presented much
worse properties, especially in the case of cetane number
of fuel obtained from PS containing feeds. Even in the case
of diesel fuels from PE cracking in pressure reactor cetane
number was very low mainly because of aromatisation and
isomerisation of cracking product as well as low average
boiling temperature. It is mainly a result of relatively
high process temperature, up to 4408C and long reaction
time (2 h).
As it was earlier stated the essential drawback of fuels
from cracking processes, not only from polymers cracking,
is mono- and diolen content prone to polymerisation and
formation of deposits. It is possible to hydrogenate unstable
olens and improve fuel properties however, hydrogenation
is a pressure process and engaging it to the technological
scheme considerably boost investment costs. Therefore it
seems that it would be economically reasonable to construct
large plants for processing of waste polymers into engine
fuels or fuel oils, output ca 50,000 tons per year or larger,
 J. Walendziewski / Fuel 81 (2002) 473481
Fig. 6. IR spectra for gasolines obtained in both systems of polymer cracking, marked the most important absorption bands.
equipped with hydrorening plant or, what is more
feasible, is to construct small local polymer cracking
plants and deliver the obtained hydrocarbon fractions to
the hydrorening plant in the nearest renery.
4. Conclusions
1. Thermal and catalytic cracking of the most popular
polymers, PE, PS, PP and their mixtures enable to
convert them to liquid and gas fuels with over 95%
efciency,
2. Application of cracking catalyst results in lowering of
polymers cracking process temperature as well as boiling
temperature range and density of the obtained liquid
products.
3. Application of catalyst increases gas product yields but
no visible inuence of catalyst on gas composition was
found. Gas composition depends on feed composition
and process conditions.
4. In comparison to the atmospheric process, the pressure
cracking of waste plastics in autoclaves at long
contact time and high temperature resulted in larger
conversion level, larger gas and gasoline fraction
yields and relatively lower boiling and lower freezing
points however lower cetane number of diesel fuel
fractions.
5. Products of polymers cracking, are highly unsaturated,
481
contain olens and diolens which can be hydrogenated
over Pd/Al2O3 catalyst, bromine number lowers to lower
than 0.5 g Br2/100 g.
6. Gasoline fractions are characterised by high octane
number especially in the case when PS is the component
of the reaction feed. For the same reasons, somewhat
higher aromatic contents and low boiling temperature,
diesel fuels from pressure system presents low cetane
number while cloud point and ignition points respond
to the suitable petroleum standards.
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