Applied Catalysis A: General 341 (2008) 181–191

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Degradation of LDPE/VGO mixtures to fuels using a FCC equilibrium

catalyst in a sand fluidized bed reactor
Antonio Marcilla *, Ma del Remedio Hernández, Ángela N. Garcı́a
Department of Chemical Engineering, University of Alicante, P.O. Box 99, Alicante, Spain

A R T I C L E I N F O A B S T R A C T

Article history: Plastic degradation for recovery of useful products or raw materials is a very interesting alternative for
Received 28 June 2007 reducing the plastic accumulation. This paper explores the possibility of using refinery facilities to carry
Received in revised form 12 February 2008 out the plastic cracking as well as to take the most of the products obtained. In the present work, LDPE/
Accepted 27 February 2008
VGO blends with different percentages of polymer are degraded in presence of a FCC equilibrium catalyst.
Available online 4 March 2008
The reactor used in this study is a laboratory scale sand fluidized bed reactor at 500 8C, and a 7:1
catalyst:LDPE/VGO blend ratio in order to simulate the operating conditions in a large scale industrial
Keywords: reactor. Polyethylene blends evaluated show relative proportions of LDPE of 0, 6, 25, 75 and 100% (w/w).
Low-density polyethylene
Gas and liquid compounds were collected and quantified. The results obtained are compared with those
Vacuum gas oil
generated in a thermal cracking.
Low-density polyethylene–vacuum gas oil
blend In all cases, the FCC equilibrium catalyst showed a high selectivity to the production of isobutane and
Fluid catalytic cracking catalyst (FCC) isopentane in the volatile compounds as well as to aromatics in the liquid products.
Equilibrium catalyst Results shown in this paper evidences the viability of introducing plastics into FCC unit, producing
Flash pyrolysis potential valuable products from low value materials.
Fluidized bed reactor ß 2008 Elsevier B.V. All rights reserved.

1. Introduction FCC catalysts are made using zeolite particles dispersed on an

amorphous silica–alumina matrix. Since 1960, the most used
In the present society, the increase of the use of plastics is a fact zeolite in this kind of catalysts is the Y zeolite [15–17]. FCC
that acquires higher importance every day. Worrying amounts, as catalysts are used in the fluid catalytic cracking units, employed for
large as 98.1 kg per capita consumption of virgin plastics in Europe the degradation of heavy gas oils and residual fuels into different
[1] were reached in 2003. type of valuable products [17–20]. Commercial FCC catalysts can
Recycling processes have been widely developed in the last present different composition, being able to influence on the
years in order to reduce the presence of these materials in the catalytic process in different ways [21,22].
municipal solid waste. Pyrolysis of plastics has been one of the Typical products generated in a fluid catalytic cracking process
recycling processes with a large development [2–6], since this are gases such as LPG naphta and heavy residue. By catalytic
method produces raw materials with high industrial value. Among pyrolysis, polymers are converted into basic petrochemicals such
the disadvantages of the thermal degradation of plastics, it can be as C3–C5 olefins and paraffins [23] that can be used as chemical
pointed out the high amount of energy involved in the process and feedstock or fuels for a variety of processes. An interesting
the low selectivity observed in the products obtained. One possible recycling alternative may be adding polymer into the FCC process
alternative in order to improve the cracking of plastics consists in and in this way, plastics can be economically converted into
the use of a catalyst. Acid catalyst such as zeolites have been the valuable hydrocarbons. Obviously, the type of fuel and polymer
most used materials with this purpose [7–10], leading to the degraded affects the results obtained.
generation of valuable products such as ethene or propylene and From this point of view, the introduction of plastics in the FCC
compounds that can be used as fuels [11–14] as a result of the units would present different advantages: on the other hand, it
process. would allow to degrade and remove the waste plastic generated.
On the other hand, this process would convert residues by turning
them into fuels and valuable products. Furthermore, this process
could be performed in conventional installations of the petro-
* Corresponding author. chemical industry without important modifications. A wide review
E-mail address: Antonio.Marcilla@ua.es (A. Marcilla). of different petrochemical plants that have performed trials

0926-860X/$ – see front matter ß 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2008.02.041
182 A. Marcilla et al. / Applied Catalysis A: General 341 (2008) 181–191

introducing polymers in a specific unit of their process is shown by The vacuum gas oil (VGO) used is supplied by Repsol YPF and
Shelley et al. [24]. corresponds to the residue stream obtained in the vacuum
A limitation of this plastic recycling technique could be the destilation of the residue generated in the atmospheric distillation
presence of chlorine or other heteroatoms in the polymers. of the crude petroleum. Composition of this VGO is shown in
Different possibilities could be found to solve this disadvantage, Table 2 and its n-paraffins carbon number distribution is shown in
although in all of them the heteroatom removal and capture must Fig. 1.
be present. Thus, the PVC heating at low temperatures before its The inert fluidized bed is sand supplied by Resacril s.l., 70–
blend with the fuel would release the chlorine as HCl, which would 210 mm particle size, with the following composition: SiO2 98–99%,
be removed with Fe or Ca compounds [25]. On the other hand, CaO 0.19%, MgO 0.016%, Na2O 0.008%, Al2O3 0.25%, Fe2O3 0.05%, K2O
instead of pre-heating the plastic, a dry alkali could be injected to 0.30%, TiO2 0.05%. In all experiments the static bed depth is
remove acid gases formed in the cracking process [24]. Another maintained around 14.8 cm (approximately 460 g of sand).
possibility [26] would consist in a previous thermal cracking of The catalyst employed corresponds to a FCC equilibrium
plastic wastes and dechloration of gas and liquid streams formed; catalyst supplied by Repsol YPF. Characteristics of this catalyst
the co-feed with the conventional feed in the FCC unit being the are shown in Table 3. The catalyst was heated at 110 8C during 5 h
treated liquid stream instead of the original solid waste. in order to eliminate the humidity and kept it in a desiccator until
The possibility of using FCC units for recovery of valuable being used.
products from plastic waste implies the necessity of blending
polymer and fuel previously. Different researchers have worked on 2.2. Methods
the catalytic degradation of polymer–fuel blends as well as on the
raw independent materials, studying the influence of different 2.2.1. Preparation of blends
conditions on the results obtained. A significant variety of reactors, PE–VGO mixtures used in this work show relative proportions
feedstocks and catalysts have been employed to develop the of LDPE of 0, 6.4, 25.7, 75.1 and 100% (w/w). For their preparation,
process. Table 1 shows a review of the papers found on this matter. LDPE and VGO are weighted and heated at a controlled
This table is a summary of articles about thermal and catalytic temperature (90–100 8C) in separated containers. When the LDPE
cracking related with the use of FCC catalysts and/or the use of is melted, both components are mixed and the blend is stirred. The
refinery stream, polymers or their blends as raw materials. This blend is heated at 80–85 8C during three hours approximately in
table can contribute to show the context where the research order to obtain an intimate mixture between polymer and VGO.
developed in the present paper can be located. After that, the blend is withdrawn from the heating and FCC
The major of the yields found in literature are grouped by catalyst is added to the LDPE/VGO blend. The amount of catalyst
fractions, such as C1–C4 gas, gasoline, coke, etc. A detailed analysis added corresponds to a catalyst:blend ratio of 7:1, a typical
of the composition of these fractions is not usually shown. proportion in fluid catalytic cracking industrial applications. A
The percentage of polymer in the degraded blend has not been uniform distribution of the catalyst in the sample is obtained by
extensively studied and generally, blends used in these works are stirring the blend.
composed by an amount of plastic lower than 20 wt.%. Probably, In the case of thermal pyrolysis, samples were mixed with sand,
this is a high percentage of polymer in the oil to be used in a the same inert material of the bed, trying to reproduce the
refinery FCC unit. However, there are different possibilities of methodology of the catalytic process (but without catalyst). The
developing recycling processes taking the most of the refinery sand allowed the samples to be dropped inside the reactor from the
facilities. One possibility is, obviously, to include the polymer in feed hopper, even those of high viscosity.
the crude stream into the standard FCC unit. Another possibility is
to develop a similar independent process, where the polymer–oil 2.2.2. Equipment and experimental procedure
blend contents as much polymer as is technically possible. The The equipment used for the flash pyrolysis of LDPE/VGO blends
products of the separated unit could then be treated if necessary is a fluidized bed reactor. A diagram of the reactor employed is
and mixed with those from standard FCC unit, following the shown in Fig. 2. As can be seen, the reactor (C), glass traps (I),
conventional path in the refinery. gasometer (G) and sampling bag (J) are connected on line.
In the present work, LDPE/VGO blends comprising in a wide The body of the reactor is a 71 cm high cylinder with 5.8 cm of
range of polymer percentage have been pyrolyzed in the presence internal diameter. At 46 cm from the bottom of the reactor a lateral
of a commercial FCC equilibrium catalyst. The evolution of exit for the volatile compounds is located. A porous plate at the
different compounds generated in the process as a function of bottom of the reactor supports the bed and uniforms the fluidizing
the amount of plastic introduced in the VGO is shown at a gas at the entrance. The reactor is heated by a cylindrical refractory
degradation nominal temperature of 500 8C. A comparison oven (B). The process temperature selected (T1) is 500 8C. The exit
between results obtained in catalytic degradations and those of the reactor is heated at 400 8C (T2).
reached in the thermal decompositions is carried out in this work, The fluidization agent is nitrogen. The flow inside the reactor is
in order to evaluate the selectivity and activity of the catalyst 3700 ml/min measured at the process temperature, which is
employed. The reactor used is a fluidized bed reactor that assumed to be 2.9 times the minimum fluidization velocity of the
constitutes an equipment with adequate characteristics for this sand at 500 8C.
type of degradations. The conditions selected try to be close to The reactor is programmed to the set temperature (T1) and the
those in a FCC unit. exit reactor heating system (E) is switched on at the selected
temperature (T2). A valve allows the flow direction to change (to
2. Materials and methods the gas sampling bag or to the exit). During the heating time, a
nitrogen flow circulates through the system to the exit, in order to
2.1. Materials purge it.
Prior to the experiment, the sample (2 g LDPE/VGO blend + 14 g
Polyethylene employed in this work is a low-density poly- FCC equilibrium catalyst or 10 g sand) is placed into the feed
ethylene (LDPE) as a powder, supplied by Dow. Density of this hopper (D) which is purged with nitrogen to guarantee inert
polymer is 918 kg/m3. atmosphere inside the reactor during the pyrolysis.
Table 1
Pyrolysis of fuel and polymer–fuel blends (review)

Reference Material Blends Reactor T (8C) Catalyst Yields (%)

Aitani et al. [27] VGO Microactivity 500–650 USY FCC catalyst Catalyst 500 8C 600 8C 650 8C
test (MAT) with ZSM-5 as additive Cat/oil: 4.5 2.7 2.0
Dry gas: 1.1 5.3 9.1
Total C3: 5.1 8.5 9.7
Total C4: 11.6 12.2 11.0
Gasoline: 51.5 43.4 40.0
LCO: 17.8 15.0 14.4
HCO: 11.0 14.3 14.5
Coke: 1.9 1.3 1.3

Arandes et al. [28] LDPE, PP, LCO 10 wt.% Riser simulator 450–550 Catalyst prepared Catalyst (500 8C, LDPE):
LDPE, 5 wt.% PP reactor based on HY zeolites C1–C2 gas: 0.66
C3–C4 gas: 4.41
C5–C12 gasoline: 45.41
Coke: 10.09

A. Marcilla et al. / Applied Catalysis A: General 341 (2008) 181–191

Arandes et al. [4] PP, PS, 5 wt.% PP, 25 wt.% Riser simulator 450–550 Commercial Thermal (500 8C, PP): Catalyst
PS-BD, LCO PS, 25 wt.% PS-BD reactor cracking catalyst C1-C4: 1.31 equilibrated
based on REY zeolite C5+ gasoline: 1.39 (500 8C, PP):
(fresh and equilibrated) Coke: 1.71 Gas: 6
C5+ gasoline: 6
Coke: 6

Cardona et al. [26] PP – Semibath stirred 380 Resog-g spend Catalyst (reaction
reactor equilibrium time 12 min)
catalyst Gas: 10.5
Gasoline: 77.5

Corma et al. [18] Hydrotreated – MAT unit, DCR 510 Commercial Catalyst MAT: Catalyst DCR:
vacuum gas oil (riser steady state) equilibrium FCC Dry gas: 3.18 Dry gas: 4.5
catalyst LPG: 20.70 LPG: 19.87
Gasoline: 43.30 Gasoline: 46.5
LCO: 15.37 LCO: 14.31
HCO: 9.09 HCO: 10.16
Coke: 7.99 Coke: 4.55
Coke in catalyst: 1.23 Coke in catalyst: 0.59

Corma et al. [19] VGO – MAT unit 510 Fresh commercial Catalyst reaction: Catalyst capillary:
(reaction USY FCC catalyst Dry gas: 1.6 Dry gas: 1.8
tube, capillary tube) LPG: 12.1 LPG: 12.76
Gasoline: 38.7
LCO: 21.9 Gasoline: 40
Coke: 5.7 LCO: 21
Coke: 4.7

Hagelberg et al. [20] Hydrotreated – Fixed bed reactor 400–650 Commercial Catalyst (500 8C)
gas oil equilibrium FCC Gas oil: 30
Gasoline: 50
LPG: 17
Dry gas: 0.5
Coke: 1

Hollander et al. [29] Straight-run – Microriser 525 FCC equilibrium Thermal: Catalyst:
FCC gasoline catalyst Fuel gas: 0.18 Fuel gas: 0.51
LPG: 1.1 LPG: 4.8
C3: 0.1 C3: 1.6
C4: 1.0 C4: 3.1
Gasoline: 94.7 Gasoline: 89.0

183
LCO: 4.1 LCO: 4.8
 184
Table 1 (Continued )
Reference Material Blends Reactor T (8C) Catalyst Yields (%)

Coke: no present Coke: 1.0

Karagöz et al. [22] VGO, HDPE 20 wt.% HDPE Autoclave 435–450 DHC-8 commercial Thermal (450 8C): Catalyst (450 8C):
and 2.5 g catalyst (hydrocracking) hydrocracking catalyst Gas: 42.50 Gas: 43.48
Liquid: 49.88 Liquid: 41.52
Wax: 7.50 Wax: 11.04
Coke: – Coke: 1.96

Karagöz et al. [30] VGO, LDPE 20 g VGO, 5 g LDPE Autoclave 425–450 DHC-8 Thermal (435 8C): Catalyst (435 8C):
and 2.5 g catalyst (hydrocracking) commercial Gas: 21.6 Gas: 31.3
Liquid: 68.5 Liquid: 41.3
Wax: 9.2 Wax: 26.6
Coke: 0.1 Coke: –

Karagöz et al. [31] VGO, MWP 20 wt.% MWP Autoclave 425–450 DHC-8 Thermal (450 8C): Catalyst (450 8C):
(hydrocracking) commercial Gas: 48.7 Gas: 35.9
Liquid: 44.2 Liquid: 47.3

A. Marcilla et al. / Applied Catalysis A: General 341 (2008) 181–191

Wax: 6.6 Wax: 15.9
Coke: 0.5 Coke: 0.9

Karayildirim et al. [32] HVGO, LDPE, PVC 20 wt.% LDPE, Autoclave 400–450 DHC-8 catalyst Thermal (450 8C, LDPE): Catalyst (450 8C, LDPE):
5 wt.% PVC (hydrocracking) Gas: 29.26 Gas: 50
Liquid: 62.8 Liquid: 40.5
Coke: trace Coke: 3.1

Lee et al. [33] HDPE, LDPE, PP, PS – Stirred semi-batch 400 Spend fluid catalytic Catalyst (400 8C, HDPE):
reactor cracking catalyst (FCC) Gas: 18
Liquid: 80
Solid: <2
Catalyst (400 8C, LDPE):
Gas: 20
Liquid: 80
Solid: <1

Lin et al. [34] HDPE, LDPE, PP 40 wt.% HDPE, Fluidized bed 330–450 FCC commercial Catalyst (450 8C, polym: Catalyst (450 8C,
27 wt.% LDPE, reactor equilibrium catalyst cat 30 wt.%, timecollection: polym:cat 20 wt.%,
33 wt.% PP (Rcat–C1) 60 min) timecollection: 30 min)
Gas: 38.6 Gas: 83.2
Liquid: 2.8 Liquid: 4.8
Coke + involatile: 58.2 Coke + involatile: 11.2
Gasoline: 15.4 Gasoline: 55.6

Meng et al. [35] VGO, vacuum residue, – Confined 600–716 CEP-1, LCM-5, AKZO Catalyst (VGO, 600 8C):
atmospheric residue fluidized bed used in FCC technology Dry gas: 12.77
reactor LPG: 45.69
Gasoline: 24.24
Coke: 9.02

Abul-Hamayel et al. [36] Hydrotreated vacuum – MAT unit 600 USY-type base catalyst Catalyst VGO AR
gas oil (VGO), with ZSM-5 as additive Dry gas: 6.5 6.2
atmospheric residue (AR) LPG: 42.4 39.7
Gasoline: 33.6 35.1
LCO + HCO: 14.5 14.6
Coke: 2.9 4.5

Ng. [37] HDPE, VGO 5 and 10 wt.% HDPE Microactivity 510 KOB-627 Thermal (10 wt.%): Catalyst (10 wt.%):
test (MAT) Dry gas: 1.15 Dry gas: 2.16
LPG: 1.35 LPG: 14.9
Gasoline: 3.95 Gasoline: 52.6
LCO: 15.6 LCO: 16.5
HCO: 76.1 HCO: 10.8
Table 1 (Continued )
Reference Material Blends Reactor T (8C) Catalyst Yields (%)

Coke: 1.74 Coke: 3.63

Ng et al. [38] VGO MAT unit 510–520 Engelhard’s equilibrium Catalyst

catalyst Dry gas: 0.7
LPG: 15.7
Gasoline: 63.0
LCO: 13.0
HCO: 6.0
Coke: 1.3

Puente et al. [39] PS in benzene 6.5 wt.% Riser simulator 550 ZSM-5, MOR, equilibrium Catalyst (FCC)
conventional FCC Benzene: 5
Toluene: 10
Coke: 15–45

Puente et al. [40] LDPE in toluene 2.0 wt.% Riser simulator 500 Equilibrium Catalyst
commercial Dry gas: 0.3

A. Marcilla et al. / Applied Catalysis A: General 341 (2008) 181–191

FCC catalysts Isobutane: 15
Coke: >10

Puente et al. [41] PS in benzene 6.5 wt.% Stirred tank with 550 Commercial FCC catalyst Catalyst Fresh:
a fluidized (fresh and equilibrium) Benzene: 34.09
bed regimen Coke: 33.49
(3% catalyst), 58.85
(9% catalyst)
Equilibrium:
Benzene: 9.85
Coke: 18.13
(3% catalyst), 33.80
(9% catalyst)

Uçar et al. [42] HVGO, LDPE, 20 wt.% LDPE, 20 wt.% Autoclave 425–450 DHC-8 catalyst Thermal (450 8C, LDPE): Catalyst (450 8C, LDPE):
PP, PVC PP, 5 wt.% PVC (hydrocracking) Gas: 40.5 Gas: 32.0
Liquid: 56.0 Liquid: 45.2
Wax: 3.3 Wax: 21.4
Coke: trace Coke: 1.5

Wallenstein et al. [43] Heavy vacuum – Microactivity 560 REUSY FCC catalyst with Catalyst Maximum
gas oils different test unit (MAT) HZSM-5 as additive values:
C1 + C2: 1.76
LPG: 23.8
Gasoline: 49.6
LCO: 18.2
HCO: 18.0

Yanik et al. [44] MWP, HVGO 8 g MWP and Glass reactor 430 (3 8C/min) Red mud, Thermal: Red mud:
14 g HVGO silica–alumina SA-1, Gas: 7.8 Gas: 12.0
TR99300 Liquid: 77.9 Liquid: 70.2
Residue: 14.7 Residue: 17.8
TR99300:
Gas: 12.6
Liquid: 68.3
Residue: 19.2

185
186 A. Marcilla et al. / Applied Catalysis A: General 341 (2008) 181–191

Table 2 When the reactor reaches the selected temperature, the nitrogen
Composition of vacuum gas oil
flow is adjusted to the adequate value. The experiment begins by
Elemental analysis opening the valve, to allow the nitrogen flow to enter into the
Nitrogen (%) 0.05
sampling bag and connecting the cronometer. The sample (LDPE/
Carbon (%) 85.35
Hydrogen (%) 12.11 VGO + FCC catalyst or sand) is dropped onto the hot sand fluidized
Sulphur (%) 2.08 bed. The feed hopper is weighted before and after dropping the
Oxygen (%) 0.41 sample into the reactor in order to measure the exact amount
Components (mass fraction) pyrolyzed. Condensed products are trapped in the glass traps while
Lineal paraffins 0.66 gases are collected in a sampling bag. Two sampling bags are
Branched paraffins 0.10 collected in order to assure that all volatile compounds generated
Olefins 0.004
are analyzed. In Ref. [45], it is presented a kinetic and heat transfer
Naphthenes 0.14
Aromatics 0.08
model which allows us to simulate the cracking process of two
Sulphured compounds 0.03 different types of polyethylene in a fluidized bed reactor similar to
that used in this paper. According to that model, the conversion
reaches a value of 90% in 5.8 min at 500 8C. This time will be reduced
with the presence of the catalyst. In the experiments carried out in
Table 3 the present work, the collection time is 40 min approximately
Characteristics of the FCC equilibrium catalyst
(about 20 min per sampling bag), time more than enough to assure
Characteristics FCC equilibrium catalyst that most of the gases generated, even eventual dead volumes of the
2 reactor, have been collected, as well as to obtain an adequate sample
BET surface area (m /g) 268.19
Micropore volume (cm3/g)a 0.0928 dilution to analyze the gas composition by gas chromatography.
Micropore area (m2/g)a 191.6 Under the experimental conditions, C6–C8 aromatics are collected as
External surface area (m2/g)a 76.56 gas. Due to their high volatility and the long collection time, these
Total volume by pore lower than 423.9 A (m2/g) 0.2605
compounds (although liquids at room temperature) are not
Total volume by pore lower than 355 A (m2/g) 0.1783
Particle size (mm) 105–210
expected in the liquid condensed, since the amount required to
saturate the gas collected is more than the amount generated (even if
a
Obtained by application of the t-plot method. all the sample would completely convert into any of them) and if
condensed at any stage of the process they would be dragged by the
carried gas. The percentage of compounds analyzed in the second

Fig. 1. Distribution of n-paraffins by carbon number in the VGO.

Fig. 2. Experimental system: (A) manometers; (B) oven; (C) reactor; (D) feed hopper; (E) top reactor heating system; (F) ice-salt bath; (G) gasometer; (H) stainless steel Dixon
rings; (I) glass traps; (J) gas sampling bag of 25 l.
 A. Marcilla et al. / Applied Catalysis A: General 341 (2008) 181–191 187

sampling test is negligible, thus this sampling gas assures us of the

run has finished, the exit gas can be sent to the atmosphere and the
reactor can be switched off.

2.2.3. Analysis of products

Gas fractions are collected in Tedlar bags. The volatile
compounds are identified and quantified using standard gases
by an Agilent 6890N gas chromatograph with FID detector and a
GS-Alumina column (30 m  0.53 mm I.D.).
The column program includes four heating steps:

 Tinitial: 35 8C; Timeinitial: 2.5 min.

 1st heating step: 12 8C/min; Tfinal: 75 8C.
 2nd heating step: 5 8C/min; Tfinal: 80 8C.
 3rd heating step: 12 8C/min; Tfinal: 92 8C.
 4th heating step: 5 8C/min; Tfinal: 170 8C; Timefinal: 15 min.
 Timetotal: 38.43 min.
 Injector temperature: 150 8C; detector temperature: 210 8C;
carrier gas: helium; split ratio: 5:1; total flow column: 6.8 ml/min.

Condensed volatiles in the traps are formed by liquids and waxy

material. This fraction is extracted using two different solvents:
hexane and acetone. Fraction extracted with acetone presents a
more polar behaviour. In any case heavy hydrocarbons (>C30)
presents a waxy aspect and are not dissolved. Liquid fraction
(approximately C9–C30) and waxy material (approximately >C30)
are separated by filtering. Compounds dissolved in hexane or
acetone are identified and quantified similarly by GC–MS.
An Agilent GC–MS (GC 6890N-MD 5973N) with two different
columns allowed us to quantify this fraction: DB-624 is used for
the analysis of C7–C9 compounds and a HP-5MS column
(30 m  0.25 mm I.D.) is used for the analysis of C10–C30
hydrocarbons.
The column program is the following:

 Tinitial: 40 8C; Timeinitial: 5 min.

 Heating rate: 12 8C/min; Tfinal: 320 8C; Timefinal: 25 min.
 Timetotal: 53.33 min.
 Injector temperature: 250 8C; carrier gas: He 1 ml/min; average Fig. 3. Yield of the fractions obtained in the thermal and catalytic degradation of
velocity: 38 cm/s; solvent delay: 6 min. LDPE/VGO blends: (a) gaseous compounds (C1–C8); (b) solid residue; (c) condensed
fraction (calculated by difference).
Library Wiley 275 is used for the identification of the saturation
degree of the liquid compounds (paraffins, olefins or aromatics). leaves the reactor and is completely collected in the sampling bag
Previous experiments of thermal LDPE degradation show the and the solid residue remains in the reactor and it is recovered and
presence of typical triplets (n-paraffins, 1-alkenes and diolefins) quantified at the end of the run.
with the same carbon number. These triplets are easily identified, However, the quantification of the condensed volatiles is much
and this chromatogram, in addition to the standards injected are more imprecise. Part of the heavy hydrocarbons remained adhered
used for the identification of the carbon number of the hydro- to the walls of the reactor, without being possible its total
carbons detected. Paraffins and olefins different from those present collection.
in thermal pyrolysis (branched paraffins, non-terminal olefins) are In the case of thermal cracking, the mass balance reached is
quantified by groups. Thus, paraffins or olefins located between a around 80–104%. In the case of catalytic degradation, the mass
retention time at which Cn and Cn+1 paraffins are obtained in the balance of the measured fraction is around 90–106%.
thermal pyrolysis, are quantified together and assigned to Cn On the basis of this reasoning, and according to previous papers
carbon number. on this matter published by different researchers [22,31,32,42] one
The solid residue is calculated by difference of weight by of the fractions – that one more inaccurately measured – has been
burning out the reactor bed at 800 8C for 2 h. estimated by difference. In this case, condensed fraction has been
re-calculated.
3. Results and discussion Fig. 3a–c shows the measured yield of gas and solid fractions
under thermal and catalytic conditions as well as the yield of
3.1. Yield of different fractions obtained in the pyrolytic processes condensed fraction calculates as (100-gas yield–solid yield).
The results obtained suggest an approximate linear behaviour
Three different fractions can be distinguished in each run: gas with the amount of polyethylene (or VGO) in the mixture.
compounds, condensed fraction and solid residue. According to the figures shown, the presence of the catalyst
Due to the characteristics of the collection system, gas and solid favoured gas and solid fractions while condensed products are
fractions can be quantified more accurately, since gas fraction reduced.
188 A. Marcilla et al. / Applied Catalysis A: General 341 (2008) 181–191

Fig. 4. Yields of volatile compounds with the percentage of LDPE: (a) catalytic degradation and (b) thermal degradation.

These results can be related with the structure of the catalyst. This fact would suppose an easier eventual reactivation of the
The typical zeolite present in a FCC equilibrium catalyst is HUSY catalyst.
zeolite. This zeolite permits the generation of aromatic compounds
which favours the generation of coke and the yield of solid residue 3.2. Gas fraction
quantified in the present work includes the coke generated. In
thermal process the yield of solid fraction decreases from 13 to 3% Fig. 4a shows the gas compounds distribution obtained as a
with the percentage of polymer; however, experimental results function of the LDPE percentage. As can be seen, there is a gradual
obtained under catalytic conditions, show much higher values for increase of the yields with the proportion of LDPE in the blend.
this fraction (27–12.5%). These high yields indicate that FCC Fig. 4b represents the same values for the cases of thermal
equilibrium catalyst tends to generate coke from the aromatics pyrolysis of pure VGO and LDPE. The same scale has been used for
obtained in the process. This tendency of HUSY and FCC catalysts to an easy comparison and significant aspects can be remarked by
produce high yield of coke has been shown elsewhere [39–41,46]. observing both figures. As was expected, the most significant
However, this fact does not pose any limitation to the process, differences between them are the yields of isobutane and
since the catalyst used is a not fresh catalyst but a FCC equilibrium isopentane + cis-2-butene. While these compounds present very
catalyst, considered partly as a waste. Therefore, deactivation of low yields in the thermal pyrolysis, they are the major products in
the catalyst due to the coke degradation would not affect its cost the catalytic degradation, representing a third part (wt.%) of the
efficiency, specially considering it may be its last use. In any case, total gas compounds generated in the pyrolysis of pure LDPE with
the presence of polyethylene in the feedstock decreases the FCC catalyst. This fact can be related to a degradation mechanism
amount of coke generated, comparing with the cracking of VGO. that involves carbocations in presence of an acid catalyst favouring
 A. Marcilla et al. / Applied Catalysis A: General 341 (2008) 181–191 189

Table 4 be seen, the presence of FCC catalyst reduces significantly the dry gas
Yields of LPG and dry gas fractions (yield = g/100 g of blend)
fraction (C1–C2 hydrocarbons) and doubles the yield of the LPG.
LDPE (%) Some of the results shown in the papers found in literature
indicate similar tendencies for the dry gas and LPG fractions than
0 6 25 75 100
those presented in this work: significant increase of LPG fraction
Dry gas 5.5 6.4 7.2 7.7 6.6 by increasing the percentage of polyethylene in the blend and
Methane 2.4 2.8 3.0 3.1 2.6
low influence of this variable on the yield of dry gas [28,37].
Ethane 0.9 0.9 0.9 1.0 0.9
Ethene 2.2 2.8 3.3 3.7 3.1 Although tendencies are similar, in general, the yields of both
fractions obtained in this work are higher than those reached in
LPG 16.3 18.2 27.7 42.4 44.6
Propane 2.6 2.8 4.4 7.2 6.9
the other papers (Table 1). By comparing results from pure
Propene 3.8 4.4 6.3 8.9 8.2 vacuum gas oil cracking, the only cases that report LPG yields
i-Butane 5.7 6.4 10.6 17.6 20.6 higher than that shown in the present work are those where the
n-Butane 1.6 1.6 2.5 3.8 4.2 vacuum gas oil is a heavy or hydrogenated VGO, showing the
Trans-butene 0.5 0.6 0.8 1.1 1.1
important influence of the nature of refinery stream used to
1-Butene 0.5 0.6 0.8 1.0 1.0
Isobutene 1.6 1.9 2.3 2.8 2.7 blend with the plastic on the results obtained. As was
commented on previously, the different type of reactors used,
the different activity of the catalyst employed as well as the
different nature of the polymers and crude fractions (LCO, VGO,
the generation of iso-structures such as isobutane or isopentane. In etc.) affect the results obtained yielding a wide range of results.
addition to this, isomerization reactions, a typical process that take In this way, significant differences in the product distribution are
place during a catalytic degradation, leads to generation of more detected by comparing the yields and components of dry gas and
branched carbocations that increase the yield of this type of LPG fraction obtained in the FCC catalytic pyrolysis of LCO or
compounds [16]. On the other hand, while ethene and propene are VGO and gasoline, for example. Although LPG fraction reaches
clearly the major compounds in the thermal pyrolysis due to a higher yields than dry gas in the cracking of LCO, VGO and
mechanism based on free radicals [16], these products reduce their gasoline, the highest difference between both fractions is
yields significantly in the presence of FCC catalyst. Similarly, yields observed for the case of VGO. In addition to this, while methane
of 1,3-butadiene and 1-butene are reduced drastically in the and ethene reach similar yields constituting the main products in
catalytic pyrolysis. the dry gas when LCO/VGO is pyrolyzed, methane is clearly the
The gas analysis indicates that the range C6–C8, aromatic main component of dry gas in the catalytic pyrolysis of gasoline.
compounds (benzene and toluene and their derivates), and Similarly, while isobutane is the main product in the LPG fraction
compounds with a triple bond (1- and 2-butyne and propyne) obtained from LCO/VGO pyrolysis, C3 olefin reaches the max-
reach very low yields in the presence of FCC catalyst in all blends imum yields in the LPG obtained from gasoline catalytic
evaluated. degradation [28,29,38].
In general, the presence of FCC catalyst inverts the results
obtained in the thermal degradation, increasing those compounds 3.3. Condensed products
which present low yields in thermal pyrolysis (propane, n-butane,
isobutane, and isopentane + cis-2-butene C3–C5 paraffins , As was commented on previously, condensed products are
mainly) and reducing those that present significant yields in formed by liquids and waxy material that are separated by
thermal decomposition (ethene, propene, 1-butene and 1,3- filtering.
butadiene C2–C4 olefins , mainly). The spectrum of volatiles Liquids compounds collected have been analyzed in all the runs
presented in Fig. 4a shows the high selectivity of the FCC carried out. Lineal and branched paraffins, terminal and non-
equilibrium catalyst used. terminal olefins, aromatic compounds, benzothiophenes and
In Table 4 yields of dry gas and LPG (liquefied petroleum gas), naphthenes are found in this fraction.
two fractions with a high industrial interest, are shown. Dry gas The yields reached by each group as a function of the relative
fraction includes the yield of light hydrocarbons such as methane, proportion of LDPE are shown in Table 5. In the case of C7–C9
ethane, ethene and, habitually, hydrogen. In the present work, the compounds only toluene was detected in this fraction although its
yield of hydrogen is not included in the quantification of the dry proportion is almost negligible versus heavier aromatics. No other
gas fraction. On the other hand, LPG fraction is composed by hydrocarbons lighter than C7 were detected in the liquid fraction.
paraffins and olefins with three and four carbon atoms As can be seen, aromatic compounds are those that reach the
[29,37,47,48]. As can be seen, the yield reached by LPG fraction highest yield in all cases evaluated, the difference with the other
increases significantly with the percentage of LDPE in the blend, groups being specially significant. The highest yield of aromatics is
reaching nearly 45% in the case of pure LDPE. Dry gas shows a much reached by the pure VGO, around 20%, reducing its value by adding
lower variation than LPG fraction and its value is almost polyethylene to the blend down to 10% for pure LDPE. The highest
independent of the polymer proportion (around 6.4–7.7%) being yield of benzothiophenes is also reached in the pyrolysis of pure
a little lower for the case of the VGO degradation. As was
commented on previously, the FCC equilibrium catalyst shows a Table 5
high selectivity to the compounds of the LPG fraction (and Yield of liquids compounds obtained (yield = g/100 g of blend)

isopentane). Compounds 0% 6% 25% 75% 100%

By comparing these values with those obtained in the thermal
n-Paraffins 0.06 0.12 0.20 0 0
experiments, the differences detected between thermal and 1-Olefins 0 0 0.02 0 0
catalytic pyrolysis are shown again. In the case of the thermal Branched paraffins 0.15 0.09 0.02 0 0
pyrolysis, the value of the dry gas obtained from the degradation of Non-terminal olefins 0.42 0.45 0.56 0.46 0.24
pure VGO was 11 and 21.4% from the pure LDPE thermal Aromatics 20.5 13.9 15.2 15.9 13.6
Aromatics with heteroatoms 2.36 1.38 1.33 0.45 0
decomposition [49]. The yields obtained for the LPG fraction were
Naphtenes 0 0.11 0 0 0.01
8.7 and 19.5% for the pyrolysis of VGO and LDPE, respectively. As can
190 A. Marcilla et al. / Applied Catalysis A: General 341 (2008) 181–191

Table 6 Non-aromatic liquid (1-olefins, non-terminal olefins, n-paraf-

Comparison of different fractions obtained (yield = g/100 g of blend)
fins, branched paraffins and naphthenes) show very low yields,
LDPE (%) Gas Gasoline LCO HCO with values below 0.5 wt.%.
(C1–C4) (C5–C12) a (bp 216–343 8C) (bp >343 8C) By comparing with thermal results, it can be concluded that the
0 22.1 8.28 19.7 3.54 presence of FCC equilibrium catalyst decreases the yield of
5 25.1 8.64 13.2 2.72 condensed products by increasing gas and solid fractions. From
25 35.3 10.9 14.4 2.92 a composition point of view, the catalyst reduces the dry gas
75 50.6 13.3 12.6 4.06
fraction and increases significantly the LPG fraction as well as
100 51.6 14.7 12.0 1.81
aromatic liquid product yields.
a
This value includes a mixture of cis-2-butene + isopentane (C4 + C5).

Acknowledgements
VGO, decreasing significantly with the percentage of polyethylene
in the blend down to 0% for pure LDPE, since the polymer does not The authors wish to thank CICYT CTQ2004-02187, FEDER, GV
contain sulphur in its composition. (ACOMP06/162), GV (ACOMP/2007/094) and the Ministry of
The yield of non-terminal olefins is almost independent of the Education, Culture and Sport for financial support.
percentage of LDPE, around 0.5%.
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