Fuel Processing Technology 86 (2005) 1265 – 1278

www.elsevier.com/locate/fuproc

Continuous flow cracking of waste plastics

Jerzy Walendziewski
Institute of Chemistry and Technology of Petroleum and Coal, Wrocyaw University of Technology,
ul. Gdańska 7/9, 50-310 Wrocyaw, Poland
Received 4 October 2004; received in revised form 26 October 2004; accepted 21 December 2004

Abstract

Experiments of waste polymers cracking in a continuous flow tube reactor were carried out. The
main components of the reactor unit were a screw extruder as a waste plastics feeder and a tube
cracking reactor equipped with an internal screw mixer. Cracking process was realized at the
temperature range 420–480 8C and raw material feeding rate from 0.3 up to 2.4 kg/h.
The principal process products, gaseous and liquid hydrocarbon fractions, are similar to the
refinery cracking products. They are unstable due to the high olefins content (especially from
polystyrene cracking) and their chemical composition and properties strongly depend on the applied
feed composition, i.e. shares of polyethylene, polypropylene and polystyrene. The material balance
experiments showed that the main products, liquid or solid materials in ambient temperature, contain
typically 20–40% of gasoline fractions (range of boiling point 35–180 8C) and 60–80% of light gas
oil fractions (initial boiling pointN180 8C). The solid carbon residues are similar to coal cokes and
contain even of 50% mineral components. Their calorific values attain 20 MJ/kg and they are solid
fuels of quality similar to brown coals.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Plastics; Polyolefines; Cracking; Engine fuel; Diesel fuel; Gasoline

1. Introduction

High temperature pyrolysis and cracking of waste thermoplastic polymers, such as

polyolefines, polyethylene (PE), polypropylene (PP) and polystyrene (PS), are well-

E-mail address: jerzy.walendziewski@pwr.wroc.pl.

0378-3820/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2004.12.004
1266 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278

known and environmentally accepted methods of their utilisation. This group of

processes embraces both thermal pyrolysis and cracking, catalytic cracking and
hydrocracking in the presence of hydrogen. Pyrolysis is the typical chemical recycling
process, enabling production of monomers, mainly ethylene, propene and butene from
waste plastics. In case of cracking processes, their main products are fuels fractions,
gaseous hydrocarbons and liquid mixtures of hydrocarbons boiling in the range of
temperatures ~35–360 8C (gasoline and light gas oils) as well as the solid carbon
residues, similar to coke. Numerous papers present the results of application of various
acidic catalysts, such as silica–alumina, zeolites (HY, HZSM-5, mordenite) or alkaline
compounds such as ZnO, CaO and K2O [1–4]. An interesting method of polymers
utilization is cracking, similar to the visbreaking of vacuum residue [5] or catalytic
cracking of vacuum gas oil (VGO) in the presence of various zeolites containing
cracking catalysts [6]. Some inventors propose cracking of melted polymers together
with petroleum and carbon derived fractions or biomass with using of typical
commercial and laboratory prepared catalysts [4,7–12]. In this type of the processes,
application of catalyst of higher acidity (HY, ZSM-5, silica–alumina based catalysts)
results mainly in C5–C12 liquid hydrocarbons, while in case of thermal or process with
the use of non-acid catalysts somewhat higher content of C12–C22 compound was also
found [13].
Increase in process temperature up to 685–715 8C and application of non-catalytic
fluidized bed system for pyrolysis of mixture of municipal plastic wastes resulted in
gaseous products, e.g. over 41 wt.% in that olefins 15% and aromatic (BTX) containing
liquid products [14]. The application of water steam as fluidization agent gas enabled
higher C2–C3 olefins yield, from 48% to 60% accompanied by decrease in BTX yield from
24 to 11 wt.% [15].
Extent of conversion of plastics or plastic derived waxes into light engine fuels can
be enlarged by the application of stable hydrocracking catalysts [16]. In such a case, the
task of catalyst and hydrogen presence is not only hydrocracking of long paraffin or
polymer chains but also hydrogenation of olefins. The obtained products are of
particularly good quality. The main drawback of these proposals, though, is the high
investment costs. All the plants, fluid catalytic cracking and hydrocracking, can be
economically feasible in refinery scale and their efficiency would be low in case of
waste plastics processing.
On the one hand, the principal problem is that in the course of the cracking process
all catalysts deactivate very quickly [1]. If we consider very expensive catalysts, e.g.
with zeolites as the acidic components, the cost of waste plastics cracking process will
be so relatively high that even economically unacceptable due to the fact that the whole
catalyst is contained in coke and therefore cannot be recovered and regenerated. On the
other hand, though, quick deactivation of the catalysts by coke deposition is
characteristic of the cracking processes. Therefore, the best solution would be fluidized
bed catalytic cracking similar to the fluid catalytic cracking (FCC) process in refinery
industry with continuous regeneration of the catalyst. It enables continuous exchanging,
regeneration and recirculation of the applied catalysts. However, this solution cannot be
satisfactory for small cracking plants of waste plastics. British Petroleum proposed [7]
fluid cracking of waste plastics in the cracking plant of 100,000 tons output per year,
 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278 1267

but it seems to be the amount to small in order to consider the plant operation
profitable.
Therefore, the selection of the effective cracking reactor for waste plastic processing is
the problem of the utmost importance. Carbonaceous solid residue is one of the cracking
products (10% or more in waste plastics cracking) and its continuous removal from the
reactor is necessary. It was earlier stated that fluidized bed reactor is the best solution for
large scale refinery cracking since it ensures coke removing. There were proposed
different cracking reactors for processing of plastics or their mixture with other materials
in small scale, e.g. [9,17,18], but they did not enable the interrupted run and continuous
coke removal. The potentially effective solution is application of a tube reactor with an
internal multifunction screw mixer that removes coke from cracking reactor walls and then
from the reactor. In this paper, I present results of thermal cracking of mixtures of the
selected polyolefines in a continuous flow, laboratory cracking tube reactor with a screw
internal mixer as well as other unit elements such as a screw extruder as feeding system, a
gas–liquid separator and gas and liquid products receivers. It is shown that the application
of this reactor type allows for thermal cracking of the mixtures of various polyolefines in
continuous mode giving liquid and gas hydrocarbon products with 80–95% efficiency in
relation to the feed. Solid product of the process is continuously being removed from the
reaction zone. It is thermal, non-catalytic process. The positive factor of the application of
cracking catalyst is lowering of the process temperature. What is questionable, though, and
it should be taken into account, it is cost of the catalyst and the problems connected with
dosing of catalyst and increased attrition in dosing extruder.

2. Experimental

2.1. Raw materials

Commercial polyolefines/polyethylene (PE), polypropylene (PP) and polystyrene (PS)

and the same type of waste polyolefines from municipal waste dump.

2.2. Scheme of cracking reactor unit

Schemes of waste plastics processing and the laboratory scale cracking reactor
apparatus are presented in Fig. 1 The main part of the reactor unit are: the feed reservoir
(1), the plastics extruder (2), applied as the raw material feeder, the tube cracking reactor
equipped with the driven, internal screw mixer (3), the vapour–solid separation column
(4), a water cooler (5), the gas–liquid separator (6), the liquid product receiver (7) as well
as liquid and gas tanks (8 and 9).

2.3. Cracking test runs description

2.3.1. Supplying of waste plastics to the cracking reactor, screw extruder

In the first step of the laboratory scale studies, there was applied the extruder of low
yield, 0.5–2.5 kg/h (16 mm diameter of extruder). Mixtures of the processed waste
1268 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278

Feed reservoir (1)

Water cooler (5)

Separation column (4)

Gas holder (9)
Separator (6)

Tube reactor (3)

PLASTICS
Liquid product
receiver (7) GAS

Screw extruder (2)

COKE
LIQUID
PRODUCT
Liquid product tank (8)

Fig. 1. Scheme of continuous flow plant for waste plastics cracking.

granular polyolefines were periodically supplied to a feeding basket of the screw

extruder, which pressed the melted plastics to the cracking reactor. Increase in a rotary
speed enabled control of the feeding velocity and control of a machine yield in the
range 0.3–2.5 kg /h. Three heating spheres of the extruder screw gave the possibility to
control temperature of the supplied feed in the temperature range from 25 up to 250 8C
in the outlet of extruder and the inlet to the cracking reactor.

2.4. Cracking and cracking reactor

It was the tube reactor equipped with the screw mixer inside the tube. The role of
the screw mixer was (i) to mix and distribute the fluid, cracked plastics over internal
surface reactor walls, (ii) to remove the solid carbon residue from the internal surface
of the reactor and (iii) to transport the stripped solid carbon residue and post cracked
residue from the reactor to the vertical separation tower which is the integral part of
the cracking reactor. The upper part of separation tower is used for transport of
vapour of the light cracking product to the water cooler, while the lower part for
receiving of the solid carbon residue. In laboratory scale studies, it was a tubular,
heated compartment enabling periodic/cyclic opening and disposal of residue. All
reactor parts were furnished with electrical heaters, temperature measurements and
control systems.
The melted plastics of temperature ca. 250 8C from the screw extruder were
pressed to the tube-cracking reactor. Cracking process occurred in this apparatus in the
temperature range 420–500 8C (at the external surface of the cracking reactor tube).
The solid carbon residue was dropping to the coke receiver (lower part of the
separation column, 4), while hydrocarbon vapour mixture was flowing to the water
 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278 1269

cooler and next to the gas–liquid separator. Hydrocarbon gas, i.e. uncondensed part of
cracking product, was collected in the gas holder and its volume was measured by a
gas flow meter, while the liquid product was flowing down to the liquid product
tank-receiver.
The first series of the polymers cracking experiments was carried out under
atmospheric pressure using the stable feeding of the cracking reactor, 0.3–0.5 kg/h,
mixture of polypropylene (70 wt.%) and polystyrene (30 wt.%). In the second series of
experiments, feeding of the cracking reactor with plastics was increased up to 2.40 kg/h.
The polyolefines feed was composed of polyethylene (90 wt.%) and polystyrene (10
wt.%). Inorganic material content in the feed (mainly plastics additives, stabilizing,
lubrication agents and impurities) attained level of 0.68 wt.%.

2.5. Hydrogenation of liquid products from cracking

In the last stage of the studies, the liquid products of the cracking experiments
were submitted to hydrorefining operation in order to hydrogenate olefin hydro-
carbons. The hydrorefining studies were carried out over 0.5 wt.% Pt/Al2O3 and 0.5
wt.% Pd/Al2O3 catalysts in the continuous flow apparatus in the temperature range
240–340 8C. The selected results of the hydrorefining tests of light gas oil fraction
(bpN180 8C) from the second experiment series (90 wt.% of PP and 10 wt.% PS) are
presented in Table 9.

2.6. Determination of physicochemical properties of the obtained products

Gas product was submitted to determination of volume, density (UOP114-86 Relative

Density of Gas by Schilling Effusion Method) and chemical composition by using gas
chromatography. The liquid products were weighed and submitted to the normal
distillation, gas chromatography and other analysis.

! Chemical composition of gas product was determined by gas chromatography method,

using FID detector and standard columns,
! Bromine number according to ASTM-D 1491-60 (1971),
! Other determinations were made according to the Polish Standard Methods (or other
relevant methods):
! Density (g/cm3) according to PN-90/C-04004 (ISO 3675)
! Normal distillation according to PN-81/C-04012 (ISO 3405)
! Cetane index according to PN-91/C-04031 (ISO 4265)
! Freezing point according to PN-55/C-04016 (D2386-03)
! Cloud point, 8C, according to PN-84/C-04017 (ISO 3015)
! Viscosity, g 40 (cSt), according to PN-81/C-04011 (ISO 3104)
! Ignition temperature, 8C, according to PN-EN22719 (ISO 2719)
! Vapour pressure (Reid method) (kPa), according to PN-84/C-04036 (PN-EN 12)
! Conradson Carbon Residue, wt.%, according to PN-85/C-04075 (ISO 10370)
! Mineral components content, wt.%, according to PN-82/C-04077 (EN 26245)
! Calorific value, MJ/kg, according to D5865-04 (adiabatic bomb calorimeter)
1270 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278

3. Results and discussion

3.1. Cracking of commercial grade polyolefines

In the beginning of these cracking studies in the continuous flow reactor, I have used
commercial plastics as a feed. The same process parameters were applied in all the
experiments, i.e. plastic feeding 0.3–0.5 kg/h and cracking temperature 420–440 8C. The
selected balance results of the experiments are to be seen in Table 1.
On the one hand, from liquid hydrocarbon fraction yield point of view, polypropylene
is the most efficient plastic feed. Cracking process of this polyolefine gave the lowest
yields of coke and gaseous hydrocarbons, while liquid products presented the lowest value
of bromine number and product unsaturation level (olefine hydrocarbons content). On the
other hand, very small quantity of gaseous hydrocarbons was obtained in polystyrene
cracking process. At the same time, the yield of the solid carbon residue coke was
relatively high. Furthermore, the solid carbon residue obtained in polystyrene cracking
process was very hard, similar to hard coal. This is the result of highly aromatic structure
of polystyrene and high-level condensation of aromatic rings. As it was stated in my earlier
papers [19,20], the core part of liquid fraction from PS cracking were aromatic
hydrocarbons, styrene, ethyl benzene and their olefin, unsaturated derivatives giving very
high value of bromine number. The highest gas yield and therefore the highest yield of the
solid carbon residue and the lowest yield of the liquid product were determined in
polyethylene cracking process.

3.2. Cracking of waste polyolefines

3.2.1. Material balance

There were carried out 14 series of experiments of cracking of various waste plastics
mixtures. The cracking experiments lasted about 100 h (the whole week). Results of the
selected two series, in the form of material balance, are presented in Table 2. They were
realized by using various process parameters, which, beside the feed type, are strongly
influencing outcomes of cracking tests.
In case of series 1, the lowest reactor feeding by waste plastic (0.3–0.5 kg/h) was
applied, while in case of series 2 the reactor feeding was changed from 0.4 up to 2.4
kg/h. As a consequence at low feed supplying in the series 1 constant (420–440 8C)

Table 1
Material balance of cracking tests of commercial polyolefines+bromine number of the obtained liquid products
Raw material Product yields, % Bromine number,
Liquid hydrocarbon Gas fraction Solid carbon g Br2/100 g
products residue
Polypropylene 96.7 2.2 1.1 52.7
Polyethylene 84.5 10.2 5.1 74.5
Polyethylene+polypropylene (1:1) 90.5 5.6 3.9 60.52
Polystyrene 95.7 0.6 3.7 116.25
 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278 1271

Table 2
Material balance (total balance for 100 h tests, various process parameters in the course of each test)
Parameter Series 1 Series 2
Feed composition PP (70%)+PS (30%) PE (90%)+PS (10%)
Liquid product (hydrocarbon fraction), wt.% 82.1 85.3
Gaseous product, wt.% 7.16 9.93
Solid carbon residue, wt.% 9.17 4.17
Losses, wt.% 1.57 0.6
Share of gasoline fraction (bp.b180 8C) in liquid 51.6 30–37a
product, vol.%
Share of light gas oil fraction (180bbpb360 8C) 46.9 62–69a
in liquid product, vol.%
Distillation residue, vol.% 1.5 1
a
Range of gasoline and gas oil yield changes in the result of the increase of the reactor feeding from 0.4 up to
2.4 kg/h.

reactor temperatures were maintained (at the external reactor wall). The increased reactor
feeding in series 2 was accompanied by the increased reactor temperature, from 420 up
to 480–500 8C at the highest reactor feeding (2.4 kg/h).
The increase in feed delivery to the reactor and shortening of the reaction time resulted
in the series 2 in the decrease in hydrocarbon chain conversion and production of relatively
higher quantity of light gas oil fraction. It was accompanied by the lowering yield of
gasoline fraction (bpb180 8C) from 37 vol.% at the lowest feeding (0.4 kg/h) down to 30
vol.% at the highest reactor feeding, i.e. 2.4 kg/h (Table 2).
Extremely high yield of gasoline fraction in series 1 was a result of high content of
polystyrene in the feed. In our earlier studies, we have discovered that cracking of
polystyrene gives over 80 vol.% of gasoline fraction (bpb180 8C) [20].
The feed (waste plastics) composition influenced not only the process material balance
but also the properties of the obtained products. The heightened content of inorganic
material in the feed for series 1 gave higher yield of the solid carbon residue or/and higher
content of inorganic material. Taking into account the fact that although waste plastics
submitted to cracking process should contain mainly polyolefines (PE and PP and some
quantity of PS) in reality the cracking feed contains admixtures of other plastics (thermoset
and chemoset polymers) and inorganic additives such as stabilizers, lubricants and fillers
as well as various mineral impurities. It is the reason the distinctly higher yields of solid
residues in cracking of plastic wastes than in cracking of individual commercial pure
polyolefines and polystyrene. The results of the realized cracking experiments (series 1
and 2) confirmed this thesis and indicated that in reality the yield of solid residue can attain
even value of 10 wt.%. Ramdoss and Tarrer stated similar values of solid cracking residues
in batch thermal racking process of commingled post-consumer plastics [21]. They found
out that, in the range of cracking temperature, solid residue content attained value from ca.
4 at 475 8C up to 8 wt.% at 525 8C, while at higher cracking gas yields from 32 to 66 wt.%
at 525 8C.
It is visible that yield of the solid carbon residue (and the whole material balance)
depends also on the extent of the feed conversion, i.e. the efficiency of destroying of large
hydrocarbon molecules from partially cracked plastics and production of volatile
1272 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278

hydrocarbons (gas or liquid fraction) from solid cracking product. In case of the relatively
mild process parameters (low process temperature or high reactor loading) the solid carbon
residue yields are by far higher and accompanied by lower gas and liquid product yields in
comparison with the process of high conversion level. Therefore, the following average
indicators, calculated on the basis of the realized experiments, can be accepted for the
purpose of the material balance:

! liquid product—85 wt.%,

! gaseous product—7 wt.%,
! solid carbon residue (coke)—8 wt.%.

3.3. Liquid hydrocarbon fractions

Liquid hydrocarbon fractions are mainly mixtures of paraffinic and olefinic C5–C25
hydrocarbons, range of boiling temperatures 30–370 (400) 8C. Their initial boiling point is
a function of cooling water temperature, while the end boiling point is the result of
temperature distribution in the reactor system. In the situation of polystyrene containing
feeds, there can be found some quantity of aromatic compounds, benzene and styrene
derivatives. In the subsequent Table 3, a fractional composition of the liquid product
obtained in experimental series 1 and 2 is shown.
The main difference in properties of the presented fractions is the higher density and
bromine number found in series 1 products as a result of higher polystyrene content in the
feed. It is also visible that the content of the gasoline fraction increases as a result of
styrene cracking derivatives content in the product (ca. 40 vol.% of the liquid fraction is
obtained in the range of temperature 123–188 8C).
One of the well-known problems in rafineries is instability of liquid cracking products,
gasoline and gas oil fractions. It is a consequence of high olefin content, especially while

Table 3
Fractional composition of liquid products obtained in the selected experimental series
% of distillate volume Distillation temperature, 8C
Series 1 Series 2
Initial boiling point 24 48
10 79 97
20 123 138
30 140 175
40 150 208
50 162 262
60 188 305
70 235 330
80 270 346
90 308 cracking
End boiling point, 8C 336
Density, kg/dm3 0.791 0.775
Bromine number, g Br2/100 g 73.10 57.26
Freezing point, 8C 24 +8
 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278 1273

dealing with products of polystyrene and polyethylene cracking (Table 1). Both thermal
and catalytic cracking processes are producing olefins according to its mechanisms.
Susceptibility of olefins for polymerization and oxidation is the reason for cracking
products instability resulting in production of gums and deposits.
Composition of the applied waste plastics as the feed determines also freezing point of
the obtained liquid product. In case of larger quantities of polystyrene and polypropylene
in the feed, the main cracking products in room temperature are liquid hydrocarbons
(series 1) but solid or semi-solid ones if polyethylene is the predominant component of the
raw material (series 2). In the situation of high content of polystyrene in the feed according
to its quantity, the product of degradation of polymers contains the variable quantity of
aromatic hydrocarbons. As a rule in the temperature above 40 8C, the received products
are the liquids of yellow tinge or yellowish brown colour and characteristic scent of
paraffin and unsaturated hydrocarbons. In ambient temperature, it is the solid phase, result
of content of higher boiling paraffin hydrocarbons.
The yield of liquid or semi-liquid product attained value 80–90 wt.% of the raw
material. The received fraction should be the sulphur free product and can be sold to
refinery and after possible refining (hydrogenation of olefins) and fractionation used as a
component of fuel (diesel) oils and engine gasoline fuels. The fractional composition of
the liquid products of cracking as well as the gasoline fractions and the fraction of the
boiling range of the diesel fuels and/or fuel oils are represented in Tables 3–5. Those two
gasoline fractions (Table 4) demonstrate certain similarity to the refinery products both
from the point of view of the boiling temperature range and also the other properties.
Likewise, high cetane indexes indicate that, at higher boiling, gas oil fractions are good
raw materials for production of diesel fuels (Table 5). However, unsaturated compounds
content and high pour temperature of fractions from PE cracking makes impossible to use
them directly as fuel or diesel oil components. The content of unsaturated compounds in
gas oil fractions is the reason of their secondary, partial cracking in the course of
distillation at the temperature ca. 400 8C in the distillation flask. This behaviour of
cracking products resulted in noticeable difference in ignition temperature, freezing and
melting points determined before (35 8C) and after distillation (22 8C, Table 5). Therefore,
the best method of liquid products utilization is their delivery to the nearest refinery and

Table 4
The selected properties of gasoline fractions
Parameters Series 1 Series 2
Density, d 20, g/dm3 0.773 0.738
Distillation
Initial boiling point, 8C 41 35
Volume distilled to 70 8C 10 14
Volume distilled to 100 8C 25 28
Volume distilled to 125 8C 43 41
Volume distilled to 150 8C 85 82
Volume distilled to 180 8C 94 91
End boiling point, 8C 220 213
Vapour pressure (Reid method), kPa 28 28
1274 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278

Table 5
Selected properties of light gas oil fractions
Parameter Series 1 Series 2
Density, d 20, g/dm3 0.825 0.821
Distillation
Initial boiling point, 8C 108 145
Volume distilled to 250 8C, % 44 38
Volume distilled to 350 8C, % 95 85
End boiling point, 8C 365 cracking
Cloud point, 8C 18 26a
Freezing point, 8C 22 22a
35b
Viscosity, g 40, cSt 2.52 nd
Ignition temperature, 8C 27 24a
Cetane index 52 56
nd—not determined, too high freezing point of product from series 2.
a
Distilled fraction.
b
Residue after distillation of gasoline fraction.

processing with similar petroleum derived streams. It is necessary to admit that purity of
cracking products is the function of quality of waste plastics selection. In some liquid
products obtained in waste plastics cracking studies, both in gasoline and gas oil fractions,
I have determined some quantity of sulphur and chlorine content (100–300 ppm). It means
that some quantity of chlorine containing plastics (e.g. polyvinyl chloride, PVC) and
sulphur containing rubbers were included in the waste plastics feeds used in cracking
processes.

3.4. Gaseous products

It is mainly a mixture of light C1–C5 hydrocarbons (with some quantities of C6–C8

hydrocarbons), which cannot be condensed in water cooler in the cracking plant. The yield
of the gaseous cracking product depends on the composition of the feed (PE/PP/PS ratio),
efficiency of the applied water cooler system and temperature of cooling water. According
to the feed composition and process parameters, the yield of gaseous products attained
values from 3 to 10 wt.%. The examples of yields and densities of cracking gases obtained
in the cracking process of commercial polymers are presented in Table 6.
The highest gas yields were obtained in the polyethylene cracking process, while the
polystyrene cracking gave the lowest gas yield. In case of high polyethylene feeding and
necessity of application of high cracking reactor temperature (up to 500 8C), the yield of

Table 6
Yields and density of gases from cracking of pure commercial plastics
Type of plastics Gas yield in cracking process, wt.% Gas density, kg/m3
Polypropylene 2.2 1.60
Polyethylene 9.5 1.59
Polypropylene+polyethylene (1:1) 5.6 1.58
Polystyrene 0.6 1.19
 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278 1275

Table 7
Density and composition of hydrocarbon gas products
Component Series 1 Series 2
Density, kg/m3 2.52 2.59
Theoretical density, kg/m3 2.43 2.48
Methane, % 6.91 3.09
Ethane, % 10.8 10.76
Propane, % 31.07 36.89
Butanes, % 16.93 17.39
Pentanes, % 18.05 18.00
Hexanes+benzene, % 11.01 9.41
Heptanes+toluene+styrene, % 5.23 4.46

gaseous product attained value almost of 10 wt.%. The increased shares of polystyrene or
polypropylene in the feed resulted in decreasing in gas yields. It is necessary to add that
application of polystyrene or high share polystyrene containing feeds gave not only low
gas yields but also caused that the obtained gaseous product contains mainly the lightest
hydrocarbons, i.e. methane and ethane. Taking into account a high share of polyethylene in
plastics wastes, one can foresee rather large gas yields in the cracking process according to
the described method. Two gas compositions obtained in the presented continuous
cracking process are shown in Table 7. The main components of the obtained gases are
C2–C5 hydrocarbons. High content of C6–C8 hydrocarbons is a result of the unsatisfied
efficiency of water cooling. The determined gas density (Schilling method) is a little
higher than the calculated one.

3.5. Solid carbon residue (coke)

Solid carbon residue is black coloured, coke- or brown coal-like material produced as a
result of cracking of polyolefin and other, high boiling, organic and inorganic compounds
in the feed, e.g. additives to plastics in a forming process. The solid carbon residues can
contain also various mechanical impurities and spent catalyst (if used). According to the
obtained results, typical cracking process of 1000 kg of waste plastics should give 50–70
kg, sometimes up to 100 kg of the solid carbon residue (5–10 wt.%). There is a distinct
difference in the yield of the residue obtained in the processes of cracking commercial,
individual polyolefines (1–3 wt.%) and waste plastics collected in town refuse dump (5–
10%). Properties of the solid carbon residue obtained in these studies are shown in Table 8.
It was proved that solid carbon residue is rather good solid fuel, with calorific values 20
MJ/kg. Its properties obtained in the course of our studies are shown in Table 8.

Table 8
Composition of cracking solid residues
Parameter Series 1 Series 2
Coke content, wt.% 47.98 34.13
Mineral components content, wt.% 49.94 42.28
CCR (Carbon Conradson Residue), wt.% 95.84 71.53
Calorific value, MJ/kg 19.5 20.9
1276 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278

Table 9
1
Properties of the fuel oil fractions before and after hydrorefining process at 280 8C, 2 MPa, LHSV=3 h
Properties Feed, light gas oil Product obtained over catalyst
0.5 wt.% Pt/Al2O3 0.5 wt.% Pd/Al2O3
Distillation, initial bp 150 150 150
! 10 vol.% 181 189 182
! 90 vol.% 346 350 349
! end bp 348 365.5 364
Bromine number, g Br2/100 g 88,48 0.54 0.86
Cloud point, 8C 37 29 32
Ignition point, 8C 41 47 47
Viscosity, mm2/s 2.46 2.65 2.60

3.6. Hydrogenation of liquid products from cracking

Due to small volume of the applied reactor in hydrogenation tests (3 cm3), the low
freezing product from test 1 was applied as a feed. The results visible in Table 9 clearly
indicate that it is possible to hydrogenate olefins in cracking products even in low
temperature (240 8C) and relatively low hydrogen pressure (2 MPa). In the lower
temperature range (ca. 240 8C), application of palladium based catalyst gave better results
(lower bromine number). Hydrogenation process did not influence other physiochemical
properties of fuel oil fraction. Some increase in cloud point could be observed as a result of
hydrogenation of olefins.

3.7. The foreseen application of cracking products

1. The liquid or semi-solid products, in ambient temperature, can be sold to refineries as

hydrocarbon fractions for the further processing, distillation and hydrorefining.
2. Cracking gas can be used as fuel gas for heating of the cracking reactor or for electric
power generation in power generators.
3. Solid carbon residue can be used as low energetic value fuel (up to 50 wt.% ash
content) in grate ovens instead of hard or brown coal.

4. Conclusions

1. Continuous flow tube cracking reactor equipped with the internal screw mixer can be
satisfactorily applied to thermal cracking of waste polyolefines.
2. Large reactor loading, i.e. the short reaction time, favours larger yields of higher boiling
liquid or semi-solid products, especially higher boiling light gas oil fraction.
3. From the point of view of the cracking plant operation efficiency polypropylene wastes
are viewed as the best feed due to the factors like the highest yield of liquid, low
temperature freezing products as well as small solid carbon residue and gas yields
4. In comparison with commercial bfreshQ plastics the cracking process of the mixture of
waste plastics gives considerably lower yield of the most valuable liquid products,
 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278 1277

80–85, instead of ca. 92–93 wt.% and respectively higher gas and solid carbon
residue yields.
5. Liquid products of waste plastics cracking are similar to the refinery cracking products.
They are also unstable because of high olefins content (especially from polystyrene
cracking), with low freezing temperature (b 20 8C) in case of cracking of larger shares
of PP and PS containing wastes and high freezing temperature (N30 8C) in the presence
of cracking polyethylene wastes.
6. In the well selected process parameters, the solid carbon residues can contain up to 50%
mineral components.
7. Catalytic hydrorefining of liquid hydrocarbon fractions enables obtaining of good
quality liquid fuel components.

References

[1] Y. Uemichi, M. Hattori, T. Itoh, J. Nakamura, M. Sugioka, Deactivation behaviors of zeolite and silica–
alumina catalysts in the degradation of polyethylene, Ind. Eng. Chem. Res. 37 (1998) 867 – 872.
[2] W. Ding, L. Liang, L.L. Anderson, Thermal and catalytic degradation of high density polyethylene and
commingled post-consumer plastic waste, Fuel Process. Technol. 51 (1997) 47 – 62.
[3] Z. Zhibo, S. Nishio, Y. Morioka, A. Ueno, H. Ohkita, Y. Tochihara, Thermal and chemical recycle of waste
polymers, Catal. Today 29 (1996) 303 – 308.
[4] S. Kargfz, T. Karayildirim, S. Ucar, M. Yuksel, J. Yanik, Liquefaction of municipal waste plastics in
VGO over acidic and non-acidic catalysts, Fuel 82 (4) (2003) 415 – 423.
[5] M. Gebauer, H. Spindler, D. Schermaul, Altkunstoffe als Einsatzprodukte der Raffinerie, Erdol Kohle
Erdgas Petrochem. 47 (5) (1994) 194 – 198.
[6] A.R. Songip, T. Masuda, H. Kuwahara, K. Hashimoto, Production of high quality gasoline by catalytic
cracking over rare-earth metal exchanged Y-type zeolites of heavy oil from waste plastics, Energy Fuels 8
(1994) 136 – 140.
[7] H. Kastner, W. Kaminsky, Recycle plastics into feedstocks, Hydrocarb. Process. 5 (1995) 109 – 113.
[8] G. de la Puente, J.M. Arandes, U.A. Sedran, Recycled plastics in FCC feedstocks: specific contributions,
Ind. Eng. Chem. Res. 36 (1997) 4530 – 4534.
[9] D.P. Serrano, J. Aguado, J.M. Escola, E. Garagorri, Performance of a continuous screw kiln reactor for
the thermal and catalytic conversion of polyethylene-lubricating oil base mixtures, Appl. Catal., B
Environ. 44 (2003) 95 – 105.
[10] S. Lovett, F. Berruti, L.A. Behie, Upgrading of plastic wastes and plastic/heavy oil mixtures to valuable light
gas products, Ind. Eng. Chem. Res. 36 (11) (1997) 4436 – 4444.
[11] J.M. Arandes, J. Ereňa, M.J. Azkoiti, M. Olazar, J. Bilbao, Thermal recycling of polystyrene and
polystyrene-butadiene dissolved in a light cycle oil, J. Anal. Appl. Pyrolysis 70 (2003) 747 – 760.
[12] F. Pinto, C. Franco, R.N. Andrè, M. Miranda, I. Gulyurtlu, I. Cabrita, Co-gasification study of biomass
mixed with plastic wastes, Fuel 81 (2002) 291 – 297.
[13] Y. Sakata, M. Azhar Uddin, A. Muto, Y. Kanada, K. Koizumi, K. Murata, Catalytic degradation of
polyethylene into fuel oil over mesoporous silica (KFS-16) catalyst, J. Anal. Appl. Pyrolysis 43 (1997)
15 – 25.
[14] W. Kaminsky, J.-S. Kim, Pyrolysis of waste plastics into aromatics, J. Anal. Appl. Pyrolysis 51 (1999)
127 – 134.
[15] W. Kaminsky, B. Schlesselmann, C. Simon, Olefins from polyolefins and mixed plastics by pyrolysis,
J. Anal. Appl. Pyrolysis 32 (1995) 19 – 27.
[16] H.S. Joo, J.A. Guinn, Continuous upgrading of a plastics pyrolysis liquid to an environmentally favorable
gasoline range product, Fuel Process. Technol. 57 (1998) 25 – 40.
[17] S.C. Cardana, A. Corma, Kinetic study of the catalytic cracking of polypropylene in a semibatch stirred
reactor, Catal. Today 75 (2002) 239 – 246.
1278 J. Walendziewski / Fuel Processing Technology 86 (2005) 1265–1278

[18] S.C. Cardana, A. Corma, Tertiary recycling of polypropylene by catalytic cracking in a semibatch
stirred reactor: use of spent equilibrium FCC commercial catalyst, Appl. Catal., B Environ. 25 (2000)
151 – 162.
[19] J. Walendziewski, M. Steininger, Thermal and catalytic conversion of waste polyolefines, Catal. Today 65
(2001) 323 – 330.
[20] J. Walendziewski, Engine fuel derived from waste plastics by thermal treatment, Fuel 81 (2002)
473 – 481.
[21] P.K. Ramdoss, A.R. Tarrer, High-temperature liquefaction of waste plastics, Fuel 77 (4) (1998) 293 – 299.