Applied Catalysis A: General 242 (2003) 51–62

Catalytic and thermal degradation of high-density polyethylene in

vacuum gas oil over non-acidic and acidic catalysts
Selhan Karagöz a , Jale Yanik b,∗ , Suat Uçar a , Mehmet Saglam c , Chunshan Song d
a Refinery and Petrochemical Program, Dokuz Eylul University, IMYO, 35160 Buca-Izmir, Turkey
b Department of Chemistry, Faculty of Science, Ege University, 35100 Bornova-Izmir, Turkey
c Department of Chemical Engineering, Faculty of Engineering, Ege University, 35100 Bornova-Izmir, Turkey
d Fuel Science Program, The Pennsylvania State University, 209 Academic Project Building, University Park, PA, 16802, USA
Received 30 May 2002; received in revised form 4 September 2002; accepted 5 September 2002

Abstract
In this study, the conversion of HDPE in VGO to fuels was carried out in absence and presence of catalyst. The blend
containing 20% HDPE was co-processed in presence of hydrogen at the temperatures of 435 and 450 ◦ C. Five kinds of metal
supported on active carbon catalysts (M-Ac) and acidic catalysts (HZSM-5 and DHC-8) were tested. The product distribution
and the quality of liquid product changed depending upon the temperature and the type of catalyst. Among the metal supported
active carbon catalyst, Co-Ac showed the highest cracking activity where as Mo-Ac showed the highest hydrodesulfurization
activity. Co-Ac had better cracking activity than commercial hydrocracking catalyst (DHC-8). Although HZSM-5 had the best
cracking effect in the hydrocracking of HDPE/VGO blend, the liquid product from HZSM-5 contained the highest sulphur.
The use of carbon-supported metal catalysts in the co-processing of HDPE with VGO looks promising solution from an
environmental viewpoint.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Active carbon; High density polyethylene; Co-processing; Hydrocracking; HDS

1. Introduction polyethylene (HDPE) as it is one of the main polymers

Nowadays, governments and environmental foun-
dations have to take into consideration, more and
more, the generation of large amount of waste plastics
as they cause serious pollution. Most waste plastics are
disposed of by landfill or incineration resulting in the
loss of their energy content. Therefore, the conversion
of waste plastics to valuable chemicals or fuels is a
promising solution. There have been many reports on
the thermal and catalytic degradation of High-density
∗ Corresponding author. Fax: +90-232-3888264.
E-mail addresses: jyanik@sci.ege.edu.tr, jryanik@yahoo.com
(J. Yanik).
in municipal solid wastes. Ding et al. studied [1] the
hydrocracking and hydroisomerization of HDPE and
waste plastic over zeolite and silica-alumina-supported
Ni and Ni-Mo sulphides. They investigated the effect
of Ni and Ni-Mo sulphides loaded on a hybrid support
(HSiAl), a mixture of HZSM-5 and silica-alumina on
the conversion of HDPE and plastic waste at 375 ◦ C,
1000 psig H2 (initial). They reported that Ni/HSiAl
had higher hydrocracking and hydroisomerization
ability than Ni-Mo/HSiAl. Ding et al. [2] also investi-
gated thermal and catalytic degradation of HDPE and
post-consumer plastic waste (CP#2) at 400 ◦ C-435 ◦ C,
for 60 min. under H2 or N2 with or without TiCl3
or HZSM-5. They concluded that HZSM-5 catalyzed

0926-860X/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 5 0 5 - 7
52 S. Karagöz et al. / Applied Catalysis A: General 242 (2003) 51–62
cyclization and amortization reactions while TiCl3
catalyzed recombination and disproportionation re-
actions. They also found that TiCl3 and HZSM-5
always have better catalytic effects on the degrada-
tion of HDPE than on the decomposition of CP#2. In
another study Luo et al. [3] studied catalytic degra-
dation of HDPE and polypropylene (PP) into liquid
fuel with two kinds of catalyst (F9:Silica/Alumina,
SA) at 400–550 ◦ C under nitrogen atmosphere. They
found that between two kinds of catalyst, SA pro-
duced higher yield of liquid fuel and more valuable
gas product under temperature range from 400 to
550 ◦ C. In another study, Garforth et al. [4] studied
the catalytic degradation of HDPE over different cat-
alysts in a fluidized-bed reactor. The acidic catalysts
(HZSM-5, HMOR and HUSY) are more effective
in converting the polymer to volatile hydrocarbons
than the less acidic amorphous SAHA. HZSM-5 and
alumina-silica produced more olefin products whereas
both HMOR and HUSY produced more paraffin
products. They concluded that differences in product
yields and product distributions could be attributed to
the microstructure of the catalysts used. Park et al. [5]
studied the catalytic degradation of HDPE over solid
acid catalysts in the range of 450–500 ◦ C. They ob-
tained the liquid fraction contained large amounts of
iso-paraffins and aromatics, as are present in the gaso-
line fraction of petroleum. They also concluded that
compared to other tested catalysts (solid acid cata-
lysts; silica-alumina and natural zeolite), liquids from
the HZSM-5 catalyst contained much larger amounts
of aromatics. Another approach in degradation of
HDPE is co-processing which has a special impor-
tance from the viewpoint of chemical process. Feng
et al. [6] studied the direct liquefaction of HDPE, PP
and coal-plastic mixtures over different types of cat-
alysts, which are HZSM-5, ferrihydrite treated with
citric acid, coprecipitated Al2 O3 -SiO2 , and a ternary
ferrihydrite-Al2 O3 -SiO2 . They found that for HDPE,
temperatures of 430 ◦ C or higher are required for good
yields while PP gives excellent yields at 420 ◦ C. Luo
and Curtis [7] investigated the thermal and catalytic
co-processing of coal with model (HDPE, LDPE,
polyisoprene and polystyrene) and commingled waste
plastics in the presence and absence hydrogen donor
solvent and catalysts at 400–440 ◦ C. They found the
co-processing reactions with commingled plastics pri-
marily of HDPE with some PP, and coal yielded less
conversion and less hexane-soluble materials than the
LDPE co-processing system. Besides co-processing
of coal with model and waste plastic, co-processing
of vacuum gas oil (VGO) with model and waste plas-
tic has been studied. Ng [8] studied the co-processing
of HDPE with VGO in the absence and presence of
catalyst in a fixed-bed reactor. In this study, it was re-
ported that higher gasoline yield was obtained in cat-
alytic process and also synergic effect was observed.
The effect of red mud (RM) on the liquefaction of
waste plastics in heavy vacuum gas oil (HVGO) was
investigated by Yanik et al. [9]. Experiments were car-
ried out by two ways, one- and two-step process. In
this study, RM was used as a dechlorination catalyst.
What is interesting in this study is that the chlorine
content of the liquid product was 1127 ppm in the
absence of RM, whereas it decreased to the very low
level of 90 ppm in the presence of RM. Yanik et al.
[10] also studied the catalytic and thermal degradation
of polyvinyl chloride containing polymer mixtures,
PVC/PE, PVC/PP and PVC/PS over RM. They found
that RM and iron oxides sorbents showed good effect
on the fixation of evolved HCl. Uçar et al. [11] also
investigated the catalytic degradation of LDPE/VGO
and PP/VGO blends in the presence of different type
of catalysts (neutral and acidic) under H2 atmosphere.
The product distribution varied with the kind of poly-
mer in the blend and the type of catalysts. To date, the
most commonly used catalysts in the catalytic degra-
dation of polymers are solid acid catalysts (zeolite and
silica-alumina) because of their high cracking abili-
ties. However, especially co-processing waste plastics
with VGO, catalysts must be neutral. Since the basic
nitrogen which is existed in waste plastics poisons
the active site of acidic catalysts. For this purpose, we
choose metal-supported on active carbon catalysts in
the degradation of HDPE in VGO. Metal supported on
activated carbon catalysts were used by Uemichi et al.
to obtain aromatic hydrocarbons from LDPE and PP
[12,13]. They reported that Pt, Fe and Mo supported
activated carbon catalysts were found to be effective
catalysts for the pyrolysis of LDPE and PP. These two
studies have shown that activated carbon catalysts are
active for cleavage of C–C bonds. In this study, we
aimed to investigate the processing of HDPE in the
presence of non-conventional catalysts in a refinery
stream. For this purpose, the hydrocracking of HDPE
in VGO over active carbon-supported metal catalysts
 S. Karagöz et al. / Applied Catalysis A: General 242 (2003) 51–62
was carried out to obtain liquid fuel. The effects of
the temperature and the metal type on active carbon
on the product distribution were discussed.
2. Experimental
2.1. Materials
Active carbon was purchased from Carla Erba
Reagent (code number: 332658). The active carbon
was manufactured from biomass powder. The vacuum
gas oil (VGO) used in this work was a broad vacuum
distillate with a boiling range 242–578 ◦ C, and which
is a base feed for hydrocracking unit in a refinery
in Izmir, Turkey. The vacuum gas oil sample con-
tains of 2.55% total sulphur and 766 ppm nitrogen.
High-density polyethylene, as 3.2 mm extruded pel-
lets, was supplied by ALPET-Izmir, Turkey. It did not
contain filling, stabilizers, etc. The DHC-8 catalyst
used is a commercial catalyst, which is being used
in hydrocracking unit in the refinery. DHC-8 (BET
surface area: 102 m2 /g) powder in sulfided form is
an amorphous hydrocracking catalyst consisting of
non-precious metals on a silica-alumina support. It
is a bifunctional catalyst incorporating both hydro-
genating and hydrocracking functions. HZSM-5 [BET
surface area: 300 m2 /g, (SiO2 /Al2 O3 = 216 (molar
ratio)] was supplied by Toso Chem. Ind., Japan. Metal
salts including Co (NO3 )2 ·6H2 O, Ni(NO3 )2 ·6H2 O,
(NH4 )6 Mo7 O24 ·4H2 O were purchased from Aldrich
and used as received. The solvent including tetrahy-
drofuran, hexane, xylenes (mixed) were purchased
from Aldrich.
2.2. Catalyst preparation
The commercial active carbon was purified (for
elimination of inorganic impurities) by treating with
solution of HCl (10 wt.%) at room temperature for
24 h. After HCl treatments, the carbon was repeatedly
washed with deionized water up to pH = 7, and then
it was dried at 105 ◦ C for 24 h. All catalysts were
prepared by wet impregnation method using excess
water. Metal salts were dissolved in deionized water
to a nominal metal concentration of 5 wt.%, and then
loaded onto activate carbon by wet impregnated under
continuous agitation. This slurry was dried at 105 ◦ C
53
for 24 h and then thermally treated at 300 ◦ C under
a nitrogen atmosphere to remove the nitrate or am-
monium groups. For bimetallic catalysts, metal salts
were impregnated from their solutions at nominal a
metal concentration of 5 wt.% for each metal. Acti-
vate carbon-supported Co, Ni, Mo, Co-Ni and Co-Mo
are denoted as Co-Ac, Ni-Ac, Mo-Ac, Co-Ni/Ac and
Co-Mo/Ac, respectively.
2.3. Hydrocracking reactions
Reactions were conducted in 100 ml 316 stainless
steel shaking type batch autoclave at, respectively, 425,
435 and 450 ◦ C for 2 h. The reaction time is 2 h. In a
typical catalytic hydrocracking experiment, the reac-
tor was loaded with 20 g vacuum gas oil (VGO), 5 g
polymer and 2.5 g catalyst. The reactor was purged
three times with hydrogen and then pressurized with
hydrogen to 6.5 MPa. The reactor was agitated hori-
zontally at ∼
=200 cycles/min. After the reaction, the re-
actor was quenched to room temperature by fan. The
gases were released. Reactor content was centrifuged
to separate the liquid products. The remained prod-
uct in form slurry was extracted with THF to remove
waxy compounds. The THF insoluble materials con-
sisted of coke, catalyst, and undegraded HDPE. The
THF insoluble was extracted with xylene at 130 ◦ C to
separate the undegraded HDPE. The xylene-insoluble
consisted of coke formed during the reaction. Details
of the product analysis procedure are available in the
literature [11].
2.4. Analyses of liquid products
The liquid products were analyzed by gas chro-
matography with a flame ionization detector us-
ing a Hewlett-Packard Model 6890GC. The col-
umn was HP z-530300 column (30 m long ×
0.32 mm diameter) coated with phenylmethylsilox-
ane crosslinked at a thickness of 0.50 ␮m. GC-FID
was temperature-programmed from 40 to 280 ◦ C at
5 ◦ C/min with a final holding time of 30 min. The
data obtained from GC-FID was used to evaluate
the simulated distillation curves [14]. The amounts
of sulphur in liquid products were determined using
Sulphur Determinator SC-132 instrument, which was
calibrated by using standard containing 3% sulphur.
Analyses were repeated two times for each sample.
54 S. Karagöz et al. / Applied Catalysis A: General 242 (2003) 51–62

Table 1 Research Institute (MRI), The Pennsylvania State

Concentration of elements on/near surface of metal loaded active University, USA. Some properties of metal loaded
carbon (at.%)
active carbon catalysts are given in Tables 1 and 2.
Catalyst Sample

C O N Co Mo Ni
3. Results and discussion
Co-Ac 85.10 10.70 1.40 2.70 0.00 0.00
Mo-Ac 84.80 11.30 3.10 0.00 0.80 0.00
Ni-Ac 79.30 15.10 0.00 0.00 0.00 5.70 3.1. Degradation of HDPE over M-Ac catalysts
Co-Mo/Ac 83.20 12.00 2.90 1.20 0.70 0.00
Co-Ni/Ac 67.70 20.70 0.00 5.20 0.00 6.50 In this study, to investigate the cracking ability of
active carbon catalyst, HDPE was chosen as one of
the model polymers because HDPE is predominant
2.5. Catalyst characterization polymer in waste plastics and its degradation is more
difficult than other polyolefinic polymers. The effect
The BET surface area of the metal supported on of temperature on the yields of hydrocracking prod-
active carbon catalysts were measured using a mi- ucts is shown in Table 3. For five kinds of M-Ac cat-
cromeritics ASAP 2000 instrument. The metal con- alysts, both the temperature and the type of catalysts
tents of the metal supported on active carbon catalysts effected the degradation of HDPE. We obtained the
were determined by chemical analysis using an induc- waxy products instead of liquids in the hydrocracking
tively coupled plasma emission spectrometer. Metal at 425 ◦ C so we gave the product distribution only for
supported on active carbon catalysts were acid-washed the temperature of 435 and 450 ◦ C. It seems that ther-
and metal concentration in active carbon determined mal run produced higher liquid product than that of
in the wash using a Leeman labs PS-3000UV. To de- hydrocracking over M-Ac catalysts. In order to under-
termine the concentration of elements on/near surface stand the differences between thermal and catalytic
of active carbon, X-ray photoelectron spectrometry run we should consider the degradation mechanisms.
(XPS) were recorded with Kratos Analytical XSAM Although both of them are radicallic, the formation
800 pci. XPS quantification was performed by apply- of radical is different each other. In the absence of
ing the appropriate relative sensitivity factors (RSFS) M-Ac catalyst, hydrocarbon radicals formed by ther-
for the Kratos instrument to the integrated peak ar- mal cracking and the recombination of these radicals
eas. These RSFS take into consideration the X-ray is hindered due to the presence of H2 S. In our reaction
cross-section and the transmission function of the conditions besides H2 gas, H2 S was also exist because
spectrometer. of sulphur compounds in VGO. The hydrogen of
Scanning electron microscope (SEM-EDX) spectra H2 S is abstracted by the hydrocarbon radical to form
were recorded with Jeol JSM-6300FV. X-ray diffrac- a stable hydrocarbon and HS• . The HS• abstracted
tion (XRD) analyze were carried out at Materials hydrogen from the hydrocarbon. Thus, the lifetime

Table 2
Metal contents and physical properties of metal loaded active carbon catalyst
Catalyst

Co-Ac Mo-Ac Ni-Ac Co-Mo/Ac Co-Ni/Ac

Metal content (wt.%)

Co 4.13 – – 4.31 4.32
Mo – 3.55 – 3.76 –
Ni – – 5.00 – 5.00
Surface area (m2 /g) 200.33 152.03 233.13 204.26 223.65
Pore volume (cm3 /g) 0.042 0.019 0.045 0.035 0.050
Pore size (Å) 50.98 54.35 51.01 45.13 57.50
 S. Karagöz et al. / Applied Catalysis A: General 242 (2003) 51–62 55

Table 3
Product distribution from hydrocracking of HDPE/VGO blend over M-Ac catalyst
Reaction products (wt.%) Catalyst (M-Ac)

– Co Mo Ni Co-Ni Co-Mo

Reaction temperature: 435 ◦ C

Gasa 22.16 26.00 22.96 33.60 45.48 34.28
Liquid 60.52 44.60 48.24 31.60 11.52 –
Wax 16.96 24.88 23.44 29.48 40.64 62.84
Asphaltene 0.68 0.76 0.84 0.88 0.80 0.80
Coke – 3.32 – – – –
Undegraded polymerb 2.20 6.00 26.80 24.50 11.80 14.40
Reaction temperature: 450 ◦ C
Gasa 42.50 47.80 38.92 45.28 42.36 45.04
Liquid 49.88 37.28 41.96 41.48 44.00 42.84
Wax 7.50 12.92 18.16 13.04 13.64 12.12
Asphaltene 0.40 1.40 1.24 0.92 1.00 0.84
Coke – 2.00 – – 0.6 –
Undegraded polymerb – – 4.80 1.00 – –
a Calculated from mass balance.
b Based on HDPE charge.

of hydrocarbon radicals cannot be reduced. However, In the presence of M-Ac;

in the presence of M-Ac catalyst, H• and HS• are
metal
formed. HS• is stabilized on the supported metal cata- H2 S → H• + HS•
lyst by hydrogenation as well as it abstracts hydrogen metal
from the hydrocarbon. The H• caused the termination HS• + H2 → H2 S + H•
of radicallic products from both HDPE and VGO. The
amount of H• radicals may depend on the metal type
or/and metal concentration on Ac. These explanations
are also supported by Nakamura’s result [15,16] and
can be shown schematically as follows:
In the absence of M-Ac;
56 S. Karagöz et al. / Applied Catalysis A: General 242 (2003) 51–62
The reason of less amount of liquid product over
M-Ac catalyst may be the fact that the active carbon
leads to form more H• or HS• which terminates the
radicallic degradation products from both HDPE and
vacuum gas oil. Co-Ac and Mo-Ac gave the simi-
lar product distribution, but Ni-Ac produced higher
amount of gas and lower amount of liquids than
that of Co-Ac and Mo-Ac. This may be due to the
higher concentration of metal on the surface of Ni-Ac
catalyst compared to those of Co-Ac and Mo-Ac
(Table 1). Although Ni-Ac was more effective on the
degradation of HDPE/VGO blend, Co-Ac had more
cracking ability from the point of undegraded polymer
even though metal concentration of on active carbon
surface is lower than Ni-Ac. It can be concluded that
the type of metal was more pronounced instead of the
concentration of metal in degradation of HDPE. In the
case of bimetallic catalysts, we observed anti-synergic
effect. This may stem from two possible reasons. One
is that the formation of alloys at 435 ◦ C. The other
is that in the case of bimetallic catalysts, Co is pre-
dominant metal, which had effect on the degradation
of HDPE/VGO blend. The concentration of cobalt on
the surface of Co-Ni/Ac catalyst was more than that
Fig. 1. Fractions in the liquid from hydrocracking of HDPE/VGO blend at 435 ◦ C over M-Ac catalysts. (䊐) Naphtha fraction, (
distillate, ( ) heavy distillate.
of Co-Ac catalysts, whereas the Ni concentrations
were almost the same both in Ni-Ac and Co-Ni/Ac.
The high concentration of the cobalt led to over
cracking (more gas and waxy compounds). In terms
of Co-Mo/Ac the concentration of cobalt on the cata-
lyst surface was lower than that of Co/Ac. Therefore,
hydrocracking of HDPE/VGO blend over Co-Mo/Ac
produced waxy compounds instead of liquids at
435 ◦ C. From the point of degradation of HDPE,
cobalt had an important affect as in monometallic cat-
alysts. It is noted that physical properties of catalysts
such as surface area, pore volume and pore size were
similar for all kinds of metal loaded active carbon
catalysts. So, we cannot discuss the effect of these
properties on degradation of HDPE or HDPE/VGO
blend. With the increasing temperature from 435 to
450 ◦ C, correspondingly the yield of gas product in-
creased except Co-Ni/Ac. At 450 ◦ C, the liquid yield
decreased in Co-Ac, Mo-Ac and thermal run whereas
the liquid yield increased over Ni-Ac. In bimetallic
case, the liquid yields increased drastically. At this
temperature product distribution were independent on
the metal type on active carbon. There were no im-
portant differences among M-Ac catalysts in product
) middle
 S. Karagöz et al. / Applied Catalysis A: General 242 (2003) 51–62 57

Fig. 2. Fractions in the liquid from hydrocracking of HDPE/VGO blend at 450 ◦ C over M-Ac catalysts. (䊐) Naphtha fraction, ( ) middle
distillate, ( ) heavy distillate.

distribution. The fractions in liquids obtained from it was necessary to investigate sulphur amount of liq-
M-Ac catalysts are given in Figs. 1 and 2. Thermal run uid products. The sulphur amounts in liquid products
gave the liquid product having more naphtha fraction obtained from hydrocracking of HDPE/VGO blend at
than that of catalytic runs, especially at 435 ◦ C. The 435 ◦ C are given in Table 4. The results showed that
compositions of the liquid obtained over Co-Ac and metal loaded on active carbon catalysts had also a hy-
Mo-Ac were the same. They contained 45% naphtha drodesulphurization (HDS) effect. The effect of metal
(b.p. < 172 ◦ C) and 18% middle distillate (172 ◦ C < type (except Mo) can be explained depending upon
b.p. < 2 32 ◦ C). The liquid from Co-Ni/Ac had heav- the metal concentration and the oxygen on/or near the
ier compounds due to over cracking effect of excess surface of active carbon. By considering the sulphur
amount of cobalt on active carbon surface as explained
above. The increase in the hydrocracking temperature
led to obtain lighter compounds. At 450 ◦ C, in the Table 4
The concentration of sulfur in liquids from hydrocracking of
case of bimetallic catalysts, the composition of the VGO/HDPE blend over different catalysts at 435 ◦ C
liquids was almost the same (50% naphtha, 20–25%
Catalyst Sulphur amount, wt.% (±0.01)
middle distillate). Co-Mo/Ac gave the liquid a little
bit lighter compounds than the others (55% naphtha, None 1.4117
27% middle distillate). From all above results, ther- Active carbon 1.2405
Co-Ac 1.1013
mal hydrocracking of HDPE/VGO blend looks better Ni-Ac 0.9755
than catalytic hydrocracking. However, our aim was Mo-Ac 0.9211
not only to convert the polymer to fuels and also to Co-Ni/Ac 0.9325
obtain high quality liquid fuels. Sulphur concentration Co-Mo/Ac 0.8875
in liquid fuels is an important criteria for fuel quality. HZSM-5 2.2504
DHC-8 0.6705
In our case, base stock VGO had 2.55% sulphur, so
58 S. Karagöz et al. / Applied Catalysis A: General 242 (2003) 51–62

amounts in liquids, the order of HDS activity of M-Ac
as follows, Co-Ni/Ac > Ni-Ac > Co-Ac. It may be
suggested that HDS activity depend on the concen-
tration of metal and/or oxygen groups on the surface
of active carbon. However, in the case of Mo-Ac, the
HDS activity was independent on the concentration
of metal and oxygen groups. Although the amounts
of both oxygen groups and Mo was lower than that of
over other M-Ac catalysts, the liquids obtained over
Mo-Ac and Co-Mo/Ac had lower sulphur amounts.
Calafat et al. also observed the same effect of Mo in
the thiophene hydrodesulfurization [17]. We obtained
also similar results in our previous study [18] related
to hydrocracking of LDPE/VGO blend. From our two
studies, we concluded that the type of polymer was
not responsible for HDS during the hydrocracking
of polymer containing VGO. In order to investigate
the formation of metal sulphur during the hydroc-
racking, one of the M-Ac catalysts was tested before
and after reaction by using XRD. Fig. 3 shows that

Fig. 3. XRD patterns of Co-Ni/Ac.

 S. Karagöz et al. / Applied Catalysis A: General 242 (2003) 51–62
Fig. 4. SEM photographs of Co-Ni/Ac.
XRD pattern of Co-Ni/Ac catalyst before and after
use in hydrocracking process. Before the hydrocrack-
ing reactions, Co-Ni/Ac catalyst was oxide form and
fits 3CoO·5NiO (all metal loaded on active carbon
catalysts were oxide form before the hydrocracking
reaction which was determined by XRD) and after
the hydrocracking reactions, the crystalline portion of
Co-Ni/Ac is solid solution sulfide (the peaks in 4.8 and
5.2). Fig. 4 shows that scanning electron microscopy
(SEM) of Co-Ni/Ac before and after use in the hy-
drocracking of HDPE. We observed no any big dif-
ference between before and after use of SEM photo-
graph of Co-Ni/Ac. However, from the EDX spectra’s
(Fig. 5) of Co-Ni/Ac catalyst before and after use
in the hydrocracking experiments, it can be clearly
seen that before the reaction there was no any sul-
phur peak in the EDX spectra whereas after the re-
action high sulphur peak was observed in the EDX
spectra.
59
3.2. Comparison of Co-Ac and acidic catalysts
in the degradation of HDPE
In order to compare the cracking ability of M-Ac
catalysts with acidic catalysts, the hydrocracking of
HDPE/VGO blend was also carried out with two
acidic catalysts (DHC-8, HZSM-5) As Co-Ac gave
better results than the others Co-Ac catalyst was
chosen for comparison. Table 5 shows the product
distribution from the hydrocracking in presence of
acidic catalysts at the temperature of 435 and 450 ◦ C.
Not too surprisingly, HZSM-5 showed more catalytic
activity than both DHC-8 and Co-Ac. It gave more
gas and less waxy compounds at 435 ◦ C. However,
less amount of liquid was obtained at 450 ◦ C over
HZSM-5. DHC-8 showed sufficient cracking activity
only at 450 ◦ C. Co-Ac had a good cracking effect
at both 435 and 450 ◦ C. By increasing the tempera-
ture from 435 to 450 ◦ C led to conversion of liquid
60 S. Karagöz et al. / Applied Catalysis A: General 242 (2003) 51–62

Fig. 5. EDX spectra’s of Co-Ni/Ac before and after use in HDPE degradation.

compounds to gases over HZSM-5 whereas over
DHC-8, waxy compounds were degraded to liquids
with increasing the temperature. Degradation route is
as follows:
wax → liquid → gas
By comparing the above results with the results
from our previous study related to hydrocracking of
PP and LDPE in VGO over the same catalysts [11],
we mentioned the conclusions as below. The degrada-
tion route of blend depending on increasing the tem-
perature was changed by polymer type in the case
of DHC-8, However, it was not up to the polymer
type in the cases of Co-Ac and HZSM-5. Thus, for
all three blends (LDPE/VGO, PP/VGO, HDPE/VGO),
gas yield increased, liquid yield decreased over both
HZSM-5 and Co-Ac. The increase in temperature led
to the formation of waxy compounds and the decrease
in gas yield for PP/VGO blend while it led to degra-
dation of waxy compounds to liquid for HDPE/VGO.
 S. Karagöz et al. / Applied Catalysis A: General 242 (2003) 51–62 61

Table 5 the cracking properties of VGO. For this VGO alone

Product distribution from hydrocracking of HDPE/VGO blend over hydrocracked at 435 ◦ C with and without catalysts.
acidic catalysts
The results are given in Table 6. By comparing the
Reaction Catalyst (2.5 g) Tables 3, 5 and 6, it seems that the effect of polymer
products on the cracking of VGO was changed depending on
(wt.%) DHC-8 HZSM-5 DHC-8 HZSM-5
(435 ◦ C) (435 ◦ C) (450 ◦ C) (450 ◦ C) the type of catalysts. Over Co-Ac and DHC-8, the liq-
Gasa 46.40 44.76 43.48 55.04 uid yields from HDPE/VGO blend were less and waxy
Liquid 8.00 42.96 41.52 26.52 compounds were more than from VGO alone. How-
Wax 41.24 12.24 11.04 15.40 ever, the yields are similar for both HDPE/VGO blend
Asphaltene 0.80 0.92 1.00 0.84 and VGO alone over HZSM-5, the quality of liquids
Coke 1.88 Trace 1.96 3.04
were different from each other for two kind of acidic
Undegraded 12.40 0.20 – – catalysts at 435 ◦ C. (Fig. 6). As expected, the liquids
Polymerb
obtained from HZSM-5 contained lighter compounds
than that of DHC-8. However, at 450 ◦ C, DHC-8 pro-
a Calculated from mass balance.
b Based on HDPE charge.
duced the liquid containing 60% naphtha, 12% mid-
dle distillate whereas from HZSM-5 the naphtha and
Since the polymer effected the degradation of VGO, middle distillate were 55 and 21%, respectively. At
the percentages of products from hydrocracking of low temperature, Co-Ac gave the liquid containing
polymer containing VGO were different for all three lighter compounds than DHC-8. Although, the liquid
kinds of blend. A series of experiments were carried from HZSM-5 at low temperature contained lighter
out in order to investigate the effect of polymer on compounds than that from Co-Ac and DHC-8, the

Fig. 6. Fractions in the liquid from hydrocracking of HDPE/VGO blend over acidic catalysts. (䊐) Naphtha fraction, ( ) middle distillate,
( ) heavy distillate.
62 S. Karagöz et al. / Applied Catalysis A: General 242 (2003) 51–62

Table 6 in co-processing of polymers with heavy petroleum

Product distribution from hydrocracking of VGO at 435 ◦ C over fractions.
different catalysts
Reaction Catalyst (2.5 g)
products (wt.%) Acknowledgements
– DHC-8 HZSM-5 Co-Ac

Gas 33.72 27.08 44.92 22.64 Ege University, Faculty of Science under the con-
Liquid 60.88 60.08 40.42 60.84 tract 2000-Fen-022 and The Energy Institute of The
Wax 5.40 12.52 14.24 14.28
Asphaltene 0.20 0.32 0.72 0.56
Pennsylvania State University supported this work. We
Coke – 0.32 0.36 2.24 thank the NATO-A2 Science Doctoral Fellowship Pro-
gramme by TUBITAK to Selhan Karagöz to visit the
USA and perform a part of this work at The Penn-
concentration of sulphur in liquid was the highest. sylvania State University. It is pleasure to thank Mr.
Not too surprisingly, the liquid from DHC-8 contained Ronald Vasco, Mr. Michael J. Sprague for many helps
the lowest sulphur amount, since it has been using in in the laboratory.
refinery for hydrocracking of VGO.
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