76 Energy & Fuels 1997, 11, 76-87

Depolymerization-Liquefaction of Plastics and Rubbers.

1. Polyethylene, Polypropylene, and Polybutadiene
Joseph Shabtai,* Xin Xiao, and W. Zmierczak
Department of Chemical and Fuels Engineering, University of Utah,
Salt Lake City, Utah 84112

Received May 20, 1996X

The solid superacid-catalyzed depolymerization-liquefaction (DL) reactions of high-density

polyethylene (HDPE), isotactic polypropylene (PPR), and cis-polybutadiene (PB) samples were
systematically investigated as a function of processing conditions, i.e., temperature (350-450
C), time (0.5-3.0 h), H2 pressure (500-2000 psig), catalyst type and concentration, and the
presence of solvents. Catalysts used included SO42-/Fe2O3, SO42-/ZrO2, and a Pt-modified SO42-/
ZrO2. At temperatures >400 C, with 1-2 wt % of SO42-/Fe2O3 or SO42-/ZrO2 as catalyst, there
is an overlap of catalytic and noncatalytic, viz. thermal DL, reactions. Under such conditions
HDPE yields a liquid product consisting of C5-C30 (mostly C5-C12) normal and branched paraffins,
accompanied by small amounts of cycloparaffins and olefins. Selective catalytic DL of HDPE
was achieved at lower temperature (350 C) in the presence of 17-33 wt % of SO42-/ZrO2 or the
more active Pt/SO42-/ZrO2 catalyst, preferably in the presence of a chemically compatible solvent,
i.e., n-octadecane. Under such conditions the high-yield (>90 wt %) product predominantly
consists of branched paraffins in the gasoline boiling range. PPR, which shows high DL reactivity
due to its multiply branched polymeric chain structure, yields a similar gasoline-like mixture of
C5-C12 branched paraffins as main product. The change in product composition from HDPE
and PPR as a function of temperature and reaction time allows for elucidation of mechanistic
aspects of the stepwise DL reactions of these polymers. For HDPE results are rationalized in
terms of a carbonium ion mechanism involving extensive skeletal isomerization and attendant
-cleavage reactions leading to low branched paraffins as final products. Results obtained
demonstrate that at mild temperatures, under properly designed catalytic conditions, waste HDPE
and PRR feeds could be effectively converted into desirable multibranched paraffins which
represent potential blending components for reformulated, nonaromatic gasolines.

Introduction as a potentially cheap and abundant source for trans-

In 1993, the total production of plastics in the United
States was 19.3 million tons.1 A predominant part of
such materials is ultimately disposed as waste. Fur-
ther, about 280 million automotive tires were discarded
in the United States in 1990.2 As a result, the effective
disposal of waste polymers is now recognized as a major
environmental problem. Plastics and rubbers are un-
desirable components for landfilling, since they are not
presently biodegradable. Their destruction by incinera-
tion poses air pollution problems due to the release of
airborne particles and carbon dioxide into the atmo-
sphere. An alternative would be true recycling, i.e.,
conversion into monomers that can be reused. For
example, DuPont has commercialized a depolymeriza-
tion process for polyethylene terephthalate (PET) to
reclaim ethylene glycol and terephthalic acid for reuse
in the production of new PET. However, waste streams
usually consist of polymer mixtures; furthermore, even
pure polymers do not depolymerize thermally to corre-
sponding monomers with sufficient selectivity. On the
other hand, waste plastics and rubbers can be regarded
X Abstract published in Advance ACS Abstracts, November 15, 1996.
(1) U.S. EPA. Characterization of Municipal Solid Waste, 1994
Update; U.S. GPO: Washington, DC, 1994.
(2) Hearing before the Subcommittee on Environment and Labor
and the Subcommittee on Regulation, Business Opportunities, and
Energy of the Committee on Small Business, House of Representatives,
April 18, 1990: Scrap Tire Management and Recycling Opportunities,
Serial No. 101-52; U.S. GPO: Washington, DC, 1990.
portation fuels and useful chemicals. Thermodegrada-
tion of polymers has been investigated extensively since
World War II,3-7 but relatively few studies on the
catalytic conversion of polymers have been carried out,
especially for production of liquid fuels.
Considerable research has been carried out aimed at
production of olefins and aromatics through polymer
pyrolysis at temperatures above 700 C. However,
relatively limited systematic studies have been reported
on the reactivity of individual polymers and product
distributions obtained. Recently, there have been some
reports on the thermal cracking of plastics to hydrocar-
bon feedstocks. Kastner and Kaminsky8 investigated
the thermolysis of polyolefins in N2 using a fluidized
bed reactor. At temperatures below 550 C, good yields
of high-boiling waxes and other useful products were
found with low yields of gas and aromatics. Kaminsky
and Rossler9 indicated that, in the temperature range
of 650-820 C, pyrolysis of plastic wastes, used tires,
and waste oil residues produces olefins and other
(3) Jellinek, H. H. G. J. Polym. Sci. 1949, 4, 13.
(4) Madorsky, L. J. Polym. Sci. 1952, 9, 133.
(5) Kuroki, T.; Honda, T.; Sekiguchi, Y.; Ogawa, T.; Sawaguchi, T.;
Ikemura, T. Nippon Kagaku Kaishi 1977, 894.
(6) Murata, K.; Sato, K. Kagaku Kogaku Ronbunshu 1981, 7, 64.
(7) Lechert, H.; Woebes, V.; Sung, Q.; Kaminsky, W.; Sinn, H. Eur.
Pat. Appl. EP 321807, 1989; Appl. DE 3743752, 1987.
(8) Kastner, H.; Kaminsky, W. Hydrocarbon Process. 1995, 109-
112.
(9) Kaminsky, W.; Rossler, H. CHEMTECH 1992, 108-113.

S0887-0624(96)00076-X CCC: $14.00 1997 American Chemical Society

DL of Plastics and Rubbers
hydrocarbons that can be used as petrochemicals. Son-
gip et al.10 have indicated that a two-stage process for
pyrolysis of waste polymers followed by reforming of
the heavy oil pyrolysate is more economical. Solid
polyethylene was pyrolyzed at 450 C, yielding an oil
with a gasoline fraction of 34 wt %, having a research
octane number (RON) value practically equal to zero.
After reforming at 400 C with a REY zeolite catalyst,
the gasoline yield increased to 48 wt % and the RON
value of this fraction was 67. Catalysts activities and
properties were also compared. It was concluded that
large pore size and strong acidity are necessary for
effective cracking of polymeric molecules. Scott et al.11
investigated the fast pyrolysis of low-density polyeth-
ylene at 600 C using an activated carbon fluidized bed
reactor. They observed feed conversions of 80% into
gaseous and liquid products, the latter having a high
aromatic content. Over 60% of the pyrolysis product
was a liquid hydrocarbon fraction of relatively low-
boiling range. Yamamoto and Takamiya12 studied the
cracking of polyethylene on SiO2-Al2O3 under N2. In
the absence of a catalyst, the pyrolysis yielded 77.1% of
gas at 600 C. The products were mainly ethylene,
propylene, and 1-butene. With SiO2-Al2O3 as catalyst,
a higher gas yield (87.8%) was obtained even at 450 C.
The gas consisted mainly of isobutylene (45.6%).
Uemichi and co-workers13 studied the pyrolysis of
polyolefins to aromatic hydrocarbons under N2 using
activated carbon-supported metal (Pt, Fe, or Mo) cata-
lysts. Polyethylene was converted to C6-C14 aromatics
at 526 C with a selectivity of 60%. Benzene was
produced as the main aromatic component over the Pt-
containing catalyst, while catalysts containing Fe or Mo
yielded preferentially toluene. The presence of methyl
branching in polypropylene was found to be unfavorable
for the formation of aromatics.14
Audisio and Silvani15 studied the catalytic degrada-
tion of polypropylene under vacuum (10-1 Torr). Cata-
lysts, e.g., Al2O3, SiO2, SiO2-Al2O3, and Y-type zeolites,
were screened at 200, 400, and 600 C. The authors
concluded that SiO2-Al2O3, HY, and REY were the most
efficient catalysts for this reaction. Smith16 studied the
catalytic cracking of byproduct (amorphous) polyprop-
ylene into fuel oil with a SiO2-Al2O3 catalyst. In
another study, Carle and Hann17 mixed up to 2.5% of
amorphous polypropylene into the feed of a fluid cata-
lytic cracker.
Wagener and Puts18 studied the depolymerization of
polybutadiene and polyisoprene using THF or toluene
as solvent and bubbling ethylene gas as an additive.
Significant amounts of oligomers were formed via an
acyclic diene metathesis mechanism. Nanbu et al.19
(10) Songip, A. R.; Masuda, T.; Kuwahara, H.; Hashimoto, K. Appl.
Catal. B: Environ. 1993, 2, 153-164.
(11) Scott, D. S.; Czernik, S. R.; Piskorz, J.; Radlein, D. St. A. G.
Energy Fuels 1990, 4, 407-411.
(12) Yamamoto, M.; Takamiya, N. Bull. Sci. Eng. Res. Lab. Waseda
Univ. 1985, 111, 8-14.
(13) Uemichi, Y.; Makino, Y.; Kanazuka, T. J. Anal. Appl. Pyrol.
1989, 14, 331-344.
(14) Uemichi, Y.; Makino, Y.; Kanazuka, T. J. Anal. Appl. Pyrol.
1989, 16, 229-238.
(15) Audisio, G.; Silvani, A. J. Anal. Appl. Pyrol. 1984, 7, 83-90.
(16) Smith, V. C. U.S. Pat. 4,151,216, 1979.
(17) Carle, R. A.; Hann, P. D. U.S. Pat. 4,143,086, 1979.
(18) Wagener, K. B.; Puts, R. D. Polym. Prepr. (Am. Chem. Soc.,
Div. Polym. Chem.) 1991, 32 (1), 379-380.
(19) Nanbu, H.; Ishihara, Y.; Takesue, T.; Ikemura, T. Polym. J.
1986, 18 (11), 871-875.
Energy & Fuels, Vol. 11, No. 1, 1997 77
studied the monomer formation from polyisobutylene in
the presence of a SiO2-Al2O3 catalyst. Isobutylene
started forming even at 160 C and reached a yield of
22% at 240 C. The authors found that the polymer can
be converted to the corresponding monomer and oligo-
mers having 2-10 monomeric units, but the latter
cannot be converted to the monomer under the mild
reaction conditions used. Williams et al.20 studied the
influence of temperature and heating rate on product
composition in pyrolysis of scrap automotive tires.
Pyrolysis between 420 and 720 C resulted in significant
yields of hydrocarbon liquids, solid char, and gases.
There was, gradually, an increase in aromaticity and
decrease in aliphatic compounds as the temperature was
increased.
It should be pointed out that conventional pyrolysis
of polymers usually results in unsaturated and unstable
oils in low yields and of low value that can be used
mainly for direct combustion. Further, most of the
catalytic studies so far have been conducted under
nitrogen at ambient or low pressure. It is also apparent
that development of efficient coprocessing of coal and
waste polymers is being hindered by the lack of detailed
fundamental data on the catalytic breakdown reactions
of a variety of plastics and rubbers.
The present research was concerned with a systematic
investigation of the catalytic depolymerization-lique-
faction (DL) reactions of three representative com-
mercial polymers, i.e., polyethylene, polypropylene, and
polybutadiene under H2 pressure, using finely dispersed
superacid catalysts, i.e., SO42-/Fe2O3, SO42-/ZrO2, and
SO42-/Al2O3.21-28 Products were identified by a combi-
nation of GC/MS and FTIR and, in some cases, by
comparison with authentic reference samples. Quan-
titative analysis was performed by gas chromatography.
The change in product composition as a function of
processing variables, i.e., temperature, reaction time,
hydrogen pressure, and catalyst type and concentration,
was studied. The objective was to determine suitable
conditions for conversion of the above polymers into
high-quality liquid fuels, as well as to obtain data
needed for predictive modeling of waste polymer copro-
cessing with coal.
Experimental Section
Materials. Samples of high-density polyethylene (HDPE)
(d, 0.959 g/cm3; average MW, 125 000; Tm, 130 C) and isotactic
polypropylene (PPR) (d, 0.900 g/cm3; average MW, 250 000;
Tm, 189 C) were obtained from Aldrich Chemical Co. A
polybutadiene sample (98% cis; d, 0.910 g/cm3; average MW,
197 000; softening point, 140-170 C) was provided by Scien-
tific Polymer Products, Inc.
Catalysts. Four types of solid superacid catalysts were
employed in the DL studies, i.e., SO42-/Fe2O3, SO42-/ZrO2,
(20) Williams, P. T.; Besler, S.; Taylor, D. T. Fuel 1990, 69, 1474-
1482.
(21) Yamaguchi, T.; Jin, T.; Tanabe, K. J. Phys. Chem. 1986, 90,
3148.
(22) Hino, M.; Arata, K. Chem. Lett. 1979, 477.
(23) Hino, M.; Arata, K. Chem. Lett. 1979, 1259.
(24) Wen, M. Y.; Wender, I.; Tierney, J. W. Energy Fuels 1990, 4,
372-379.
(25) Arata, K.; Hino, M. Appl. Catal. 1990, 59, 197-204.
(26) Garin, F.; Andriamasinoro, D.; Abdulsamad, A.; Sommer, J. J.
Catal. 1991, 131, 199-203.
(27) Zmierczak, W.; Xiao, X.; Shabtai, J. Energy Fuels 1994, 8, 113-
116.
(28) Xiao, X.; Zmierczak, W.; Shabtai, J. Prepr. Pap.sAm. Chem.
Soc., Div. Fuel Chem. 1995, 40 (1), 4-8.
78 Energy & Fuels, Vol. 11, No. 1, 1997
SO42-/Al2O3, and a Pt-modified SO42-/ZrO2. The method of
preparation and properties of the first two were described in
detail elsewhere.27,28 SO42-/Al2O3 was prepared according to
the following procedure: 12.4 g of Al2(SO4)3(14-18)H2O was
dissolved in 44 mL of distilled water, and a 30% aqueous
ammonia solution was slowly added with vigorous mixing,
until a pH 8.5 was reached. The precipitate formed was
filtered, washed with distilled water, and then dried at 110
C for 2 h. The dry solid was pulverized and calcined at 550
C for 2 h. A portion of the resulting Al2O3, 2.0 g, was treated
with 50 mL of a 1.5 M (NH4)2SO4 plus 1.0 M H2SO4 aqueous
solution for 1 h with constant stirring. The resulting solid,
i.e., SO42-/Al2O3, was then filtered, washed with 100 mL of
water, dried at 110 C for 2 h, calcined at 600 C for 3 h, and
stored in a desiccator. The Pt/SO42-/ZrO2 catalyst was pre-
pared by impregnating 20.0 g of SO42-/ZrO2 with 11.0 mL of
an aqueous H2PtCl6 solution, followed by drying at 110 C for
24 h and subsequent calcination at 550 C for 3 h. The final
catalyst contained 0.5 wt % of Pt.
Reactors. The catalytic DL studies were performed mostly
in a 50 mL Microclave reactor (Autoclave Engineers) equipped
with a MagneDrive stirrer, pressure gauge, tachometer, gas
sampling device, vent valves, external electric heating furnace,
and temperature controller. A 300 mL EZE-seal Autoclave
reactor (Autoclave Engineers) was also employed in some of
the runs.
Experimental Procedure. In most of the runs a mixture
of the polymer, 5.0-20.0 g, and catalyst, 1-2 wt % (without
any solvent), was introduced in the autoclave reactor. The
latter was closed, purged sequentially with nitrogen and
hydrogen, and then pressurized with hydrogen to a selected
initial pressure. The reactor was heated to the desired
temperature in 12-15 min (50 mL Microclave reactor) or 40
min (300 mL autoclave reactor), and stirring (500 rpm) was
started after the melting or softening point of the polymer was
reached. At the end of each experiment, the reactor was
quickly cooled to room temperature with a fan (about 20 min),
and the liquid product (plus any unconverted solid feed) was
removed from the reactor and weighed. The liquid was
separated by decantation and filtration. The solid residue was
rinsed with n-hexane to remove any liquid product, dried, and
weighed. Then the catalyst was separated from the uncon-
verted polymer feed by washing sequentially with n-hexade-
cane (80 C) and n-hexane (room temperature). The solid
residue was dried and weighed to determine the weight of
recovered catalyst (including coke). Gaseous and some volatile
liquid products were collected in a stainless steel trap kept at
liquid nitrogen temperature and weighed. This way, the
product was separated and the weights of gas, liquid, solid,
and recovered catalyst were determined.
In the presence of a solvent and larger amounts of catalyst,
the following modified procedure was applied: 5.0 g of polymer,
e.g., HDPE, 5.0 g of n-octadecane (mp 30 C), and the desired
amount of catalyst (2.0-5.0 g) were charged into the Micro-
clave reactor. The reactor was sealed, purged sequentially
with N2 and H2, charged with H2 to an initial pressure of 500
psig, and heated to 350 C. After reaction (60 min), the reactor
was cooled and about 1 mL of the liquid product was sampled
by a pipet for GC/MS and quantitative GC analysis. To
determine total conversion, the main product in the reactor
was removed and subjected to Soxhlet extraction with n-
pentane. Conversion was determined on the basis of the
insoluble solid residue. After removal of the n-pentane solvent,
the main part of the liquid product was collected and analyzed.
Products from polybutadiene required special treatment
because of their high viscosity at partial conversions. After
the removal of gas products, 20 mL of methanol was added
to the product. The reactor was then sealed, purged with
nitrogen, heated to 200 C with continuous stirring, and then
cooled. The methanolic solution was subjected to GC analysis,
whereas the solid residue was used to determine the total
conversion. To avoid the loss of volatile product components,
Shabtai et al.
GC/MS examination and quantitative GC analyses were
performed directly with samples of the original product, viz.,
before the treatment with methanol.
Product Analysis. Gas and liquid products were identified
by a combination of GC/MS and FTIR and, in some cases, by
comparison with authentic reference samples. A HP 5890
Series II gas chromatograph/HP 5971 mass selective detector
(GC/MS) system and a Perkin-Elmer 1600 series FTIR were
used in the analyses. GC/MS analysis of liquid products was
performed using a 30 m 0.25 mm i.d. DB-5 capillary column
provided by J&W Scientific.
Quantitative analysis was performed by gas chromatogra-
phy and simulated distillation (SIMD). HP 5880A and Varian
3700 gas chromatographs equipped with FID detectors were
used in the analysis. Columns used for quantitative analysis
of gas products were 4 m 0.3 cm o.d. stainless steel packed
with Chromosorb 102. Columns used for quantitative analysis
of liquid products were 4 m 0.3 cm o.d. stainless steel packed
with 10% OV-17 on Chromosorb W-HP and 30 m 0.25 mm
i.d. DB-225 or DB-5 capillary columns provided by J&W
Scientific. SIMD was performed according to ASTM Methods
D5307 and D2887 except for the following modifications: the
temperature correlation curve was made using C6-C18 normal
paraffins, and the internal standard was a mixture of about
equal amounts of C7, C8, and C9 normal paraffins. SIMD was
performed with a 0.5 m 0.3 cm o.d. stainless steel Supelco
PETROCOL B column.
Mass Balance. The mass balance of the runs was in the
range of 90-95% (relative to the feed weight) for polyethylene
and polypropylene and 80-90% for polybutadiene. Conver-
sions were determined on the basis of the difference between
the weight of the feed used and the solid polymer residue after
reaction. The gas samples consisted mostly of C1-C4 hydro-
carbons, accompanied by some C5, C6, and traces of C7, C8
compounds. The liquid samples contained mostly C5-C12
components, accompanied by some C13-C30, and traces of C2-
C4 compounds. The product composition was calculated from
GC data (FID detector). The C2-C4 gas components found in
the liquid product were added to the gas composition, and the
C5-C8 components found in the gaseous product were added
to the liquid composition, correspondingly.
Results and Discussion
A. DL Reactions of Polyethylene. Results of the
GC/MS analysis of a typical polyethylene DL product,
obtained at 450 C with 0.5 wt % of SO42-/Fe2O3 as
catalyst, are given in Figure 1. As seen, the liquid
product obtained consists of a mixture of C5-C32 (mostly
C5-C12) normal and branched paraffins, accompanied
by some amounts of 5- and 6-ring nonsubstituted and
mono-, di-, and trialkylsubstituted cycloparaffins. The
proportion of cycloparaffins decreases to some extent
with increase in the C number of the product compo-
nent. In addition to n-paraffins, branched paraffins,
and cycloparaffins, the product contains small amounts
of olefins and cycloolefins. An example of the boiling
point distribution of the total liquid product is given in
Figure 2.
The composition of the DL product from HDPE
changes markedly with changes in processing variables,
e.g., temperature and reaction time, as described below.
Table 1 summarizes data on the change in product
composition as a function of increase in reaction tem-
perature, between 420 and 465 C, keeping other
processing conditions constant, i.e., catalyst, SO42-/ZrO2,
2.0 wt %; H2 pressure, 1500 psig; reaction time, 2.0 h.
As seen, under such conditions the feed conversion is
very high and increases from 82.5 wt % at 420 C to
DL of Plastics and Rubbers Energy & Fuels, Vol. 11, No. 1, 1997 79

Figure 1. GC/MS analysis of the liquid product from DL of HDPE (450 C, 2.0 h, 1200 psig of H2, SO42-/Fe2O3).

Figure 2. Boiling point distribution of the liquid product from DL of HDPE by simulated distillation (450 C, 2.0 h, 1200 psig
of H2, SO42-/Fe2O3).

100 wt % at 450-465 C. At 420 C the product is
predominantly liquid. With increase in temperature,
however, the yield of liquid products gradually decreases
(from 92.8 wt % at 420 C to 60.2 wt % at 465 C), while
that of C1-C4 gaseous products correspondingly in-
creases (from 7.2 wt % at 420 C to 39.8 wt % at 465
C). The changes in the composition of gaseous (C1-
C4) and liquid (C5-C12 and C13+) product fractions as a
function of temperature are plotted in Figures 3 and 4,
respectively. As seen from Figure 3, C3 and C4 hydro-
carbons predominate in the gaseous product in the
entire temperature range studied. Further, Figure 4
shows that higher molecular weight liquids (C13+)
steeply decrease (from 54.0 wt % at 420 C to 11.7 wt %
at 465 C), as expected for these intermediate depolym-
erization products, while the C5-C12 fraction passes
through a maximum and then declines. The compo-
nents of the predominant gasoline-range (C5-C12) frac-
tion (Table 1) either increase (C5 and C6 hydrocarbons)
or pass through a maximum and then slightly decrease
(C7-C12 hydrocarbons) with increase in temperature.
The above trends clearly demonstrate the gradual
breakdown of the polyethylene polymeric chains. Table
2 and Figure 5 show that the same trends, although in
80 Energy & Fuels, Vol. 11, No. 1, 1997 Shabtai et al.

Table 1. Composition of Products from DL of HDPE as a

Function of Reaction Temperaturea
temp
420 C 435 C 450 C 465 C
convrn,b wt % 82.5 98.9 100 100
product distrbn,c wt %
gas (C1-C4) 7.2 11.9 21.6 39.8
liquid 92.8 88.1 78.4 60.2
gasoline boiling range,c wt %
C5-C12 42.7 58.0 63.0 53.2
liquid product distrbn,d wt %
C5H12e (+C5H10)e 4.6 7.5 10.6 19.1
C6H14 (+C6H12) 5.5 8.7 11.8 17.4
C7H16 (+C7H14) 6.8 10.2 13.0 14.3
C8H18 (+C8H16) 7.3 10.8 13.5 12.2
C9H20 (+C9H18) 6.3 9.0 11.1 9.3
C10H22 (+C10H20) 5.9 7.9 8.7 7.5
C11H24 (+C11H22) 5.0 6.3 6.6 5.0
C12H26 (+C12H24) 4.6 5.4 5.0 3.5
C13+ 54.0 34.2 19.7 11.7
a In each run were used 10.0 g of polyethylene feed and 0.20 g

of SO42-/ZrO2 catalyst; initial H2 pressure was 1500 psig, and

reaction time was 2.0 h. b Weight percent of feed converted into
products. c Calculated in weight percent of total product. d Weight
percent of liquid product. e All fractions of a given C number
consist of mixtures of normal and branched paraffins, accompanied
by some cycloparaffins and trace amounts of olefins.

Figure 4. Change in product composition from DL of HDPE

as a function of reaction temperature (1500 psig of H2, 2 h,
SO42-/ZrO2).

Table 2. Composition of Products from DL of HDPE as a

Function of Reaction Timea
reaction time
0.5 h 1.0 h 2.0 h 3.0 h
convrn,b wt % 99.4 99.9 100 100
product distrbn,c wt %
gas (C1-C4) 12.5 17.9 22.9 29.3
liquid 87.5 82.1 77.1 70.7
gasoline boiling range,c wt %
C5-C12 52.2 57.9 58.7 55.4
liquid product distrbn,d wt %
C5H12e (+C5H10)e 6.5 8.9 10.1 11.7
C6H14 (+C6H12) 7.2 9.3 10.9 12.5
C7H16 (+C7H14) 7.7 10.5 12.5 13.6
C8H18 (+C8H16) 8.1 11.1 13.1 12.0
C9H20 (+C9H18) 8.7 10.3 10.1 9.7
C10H22 (+C10H20) 7.9 8.1 8.4 8.2
C11H24 (+C11H22) 7.1 6.7 6.3 6.1
C12H26 (+C12H24) 6.4 5.6 4.7 4.5
C13+ 40.4 29.5 23.9 21.7
a In each run were used 10.0 g of polyethylene feed and 0.10 g

of SO42-/ZrO2 catalyst; reaction temperature was 450 C and initial

H2 pressure was 1500 psig. b Weight percent of feed converted into
products. c Calculated in weight percnet of total product. d Weight
percent of liquid product. e All fractions of a given C number
Figure 3. Change in gas product composition from DL of
consist of mixtures of normal and branched paraffins, accompanied
HDPE as a function of reaction temperature (1500 psig of H2,
by some cycloparaffins and trace amounts of olefins.
2 h, SO42-/ZrO2).

a less pronounced manner, are observed for a series of
runs on the change of product composition as a function
of reaction time between 0.5 and 3.0 h. It should be
noted that in this series of runs the catalyst concentra-
tion was reduced from 2.0 wt % (Table 1, footnote a) to
1.0 wt % (Table 2, footnote a).
The effect of H2 pressure, in the range of 500-2000
psig, upon the product composition was relatively
weaker in comparison with the temperature and time
effects. Increase in H2 pressure from 500 to 1500 psig
resulted in some increase in the yield of the gasoline
(C5-C12) fraction and a corresponding decrease in the
yield of the C13+ fraction. However, at H2 pressures
above 1500 psig, the concentrations of the gasoline and
C13+ fractions remained essentially unchanged.
A comparison of HDPE conversions in the presence
of different superacid catalysts indicated that the DL
activities of the latter were in the order SO42-/ZrO2 >
SO42-/Al2O3 > SO42-/Fe2O3. This was in agreement
with a previous study on the relative acidities and
dealkylation activities of these superacid catalysts.27,28
B. DL Reactions of Polypropylene. Table 3
summarizes results obtained on the change in product
composition from SO42-/ZrO2-catalyzed DL of PPR as a
function of reaction temperature between 380 and 450
C, with other processing conditions kept constant
DL of Plastics and Rubbers Energy & Fuels, Vol. 11, No. 1, 1997 81

Figure 5. Change in product composition from DL of HDPE Figure 6. Change in product composition from DL of PPR as
as a function of reaction time (1500 psig of H2, 450 C, SO42-/ a function of reaction temperature (1500 psig of H2, 2 h, SO42-/
ZrO2). ZrO2).
(footnote a). It is found that at 380-400 C the total Figure 8 summarize the change in DL product composi-
conversion of the PPR feed is markedly higher than that tion as a function of reaction time between 0.5 and 3.0
of HDPE (<20 wt %), and it increases with increase in h (410 C). The general trends, although less pro-
temperature (from 79.8 wt % at 380 C to 100 wt % at nounced, are similar with those found for the above-
400 C). The yield of the predominantly liquid product described temperature effect.
decreases gradually with increase in temperature (from Compositional changes within the gasoline-range
95.1 wt % at 380 C to 56.8 wt % at 450 C), whereas fraction from PPR as a function of temperature are
that of C1-C4 gaseous products correspondingly in- plotted in Figure 9. It is found that the lower boiling
creases. The predominant gasoline-range (C5-C12) frac- C5-C9 hydrocarbon components increase with increase
tion increases with temperature up to a maximum of in temperature from 380 to 450 C, whereas C10-C12
67 wt % at 410 C and then slightly decreases. These components pass through a maximum and then decline.
trends are plotted in Figure 6. The GC/MS profile of These trends, together with the observed parallel de-
the predominant C5-C12 fraction is given in Figure 7. cline of C13+ components, are consistent with the
As seen, the fraction consists mainly of C5-C12 branched anticipated gradual depolymerization of oligomeric hy-
paraffins accompanied by minor amounts of correspond- drocarbon intermediates.
ing branched olefins and polymethyl-substituted naph- Compositional changes in the C1-C4 gas product from
thenes, e.g., 1,3,5-trimethylcyclohexane. Table 4 and PPR as a function of temperature are given in Figure
Table 3. Composition of Products from DL of PPR as a Function of Reaction Temperaturea
temp
380 C 390 C 400 C 410 C 420 C 450 C
convrn,b wt % 79.8 97.0 99.8 100 100 100
product distrbn,c wt %
gas (C1-C4) 4.9 6.5 10.7 14.9 21.7 43.3
liquid 95.1 93.5 89.3 85.2 78.3 56.8
gasoline boiling range,c wt %
C5-C12 55.3 64.0 66.3 66.6 64.1 52.3
liquid product distrbn,d wt %
C5H12e (+C5H10)e 5.0 6.7 8.2 9.8 11.4 17.5
C6H14 (+C6H12) 6.3 7.9 9.4 10.7 12.2 18.0
C7H16 (+C7H14) 5.8 7.3 7.9 8.4 9.1 12.4
C8H18 (+C8H16) 6.9 8.4 9.3 9.8 10.7 12.3
C9H20 (+C9H18) 12.1 14.1 14.9 15.4 15.6 15.5
C10H22 (+C10H20) 6.7 7.6 8.3 8.4 8.2 7.0
C11H24 (+C11H22) 6.8 7.1 6.9 6.7 6.5 4.2
C12H26 (+C12H24) 8.6 9.5 9.3 9.0 8.2 5.3
C13+ 41.9 31.5 25.7 21.8 18.1 7.9
a In each run were used 10.0 g of polypropylene feed and 0.10 g of SO 2-/ZrO catalyst; initial H pressure was 1500 psig and reaction
4 2 2
time was 2.0 h. b Weight percent of feed converted into products. c Calculated in weight percent of total product. d Weight percent of
liquid product. e All fractions of a given C number consist of mixtures of branched paraffins, accompanied by small amount of cycloparaffins
and trace amounts of olefins.
82 Energy & Fuels, Vol. 11, No. 1, 1997 Shabtai et al.

Figure 7. GC/MS analysis of liquid product (gasoline-range fraction) from DL of PPR (410 C, 2.0 h, 1500 psig of H2, SO42-/
Fe2O3).

Table 4. Composition of Products from DL of PPR as a

Function of Reaction Timea
reaction time
0.5 h 1.0 h 2.0 h 3.0 h
convrn,b wt % 87.1 97.8 99.9 100
product distrbn,c wt %
gas (C1-C4) 6.7 7.8 11.1 14.1
liquid 93.3 92.2 88.9 85.9
gasoline boiling range,c wt %
C5-C12 59.8 66.2 68.0 66.2
liquid product distrbn,d wt %
C5H12e (+C5H10)e 5.8 6.1 6.6 6.9
C6H14 (+C6H12) 10.3 12.7 13.5 13.7
C7H16 (+C7H14) 8.4 9.5 9.8 9.8
C8H18 (+C8H16) 7.4 8.5 9.9 10.1
C9H20 (+C9H18) 13.0 14.6 14.9 14.7
C10H22 (+C10H20) 6.8 7.6 8.1 8.6
C11H24 (+C11H22) 5.3 5.3 6.1 5.8
C12H26 (+C12H24) 7.1 7.5 7.6 7.6
C13+ 35.9 28.2 23.5 22.9
a In each run were used 10.0 g of polypropylene feed and 0.10

g of SO42-/ZrO2 catalyst; reaction temperature was 410 C and

initial H2 pressure was 1500 psig. b Weight percent of feed
converted into products. c Calculated in weight percent of total
product. d Weight percent of liquid product. e All fractions of a
given C number consist of mixtures of branched paraffins, ac-
companied by small amount of cycloparaffins and trace amounts
of olefins.
10. As in the case of HDPE (Figure 3) C3-C4 hydro-
carbons are formed in markedly higher yields than C1-
C2 products. However, whereas C4 products are more
abundant than C3 hydrocarbons from polyethylene, a
higher yield of C3 hydrocarbons, corresponding to the
propylene monomer, is found from polypropylene de-
composition, especially at 450 C (Figure 10).
C. Catalytic and Solvent Effects. The above
results were obtained with very small amounts (0.5-
2.0 wt %) of finely dispersed superacid catalysts. The
purpose was to identify an inexpensive superacid as a
disposable catalyst in coprocessing of waste polymers
with coal. Further, it was indicated that polyethylene
Figure 8. Change in product composition from DL of PPR as
a function of reaction time (1500 psig of H2, 410 C, SO42-/
ZrO2).
exhibits low DL reactivity at temperatures <400 C. At
temperatures <130 C, i.e., in the solid state, this is
probably due to the presence of nonreactive crystallites29
in this polymer, while in the molten state (Tm 130
C), at temperatures <400 C, the polymeric chains
apparently remain associated to a significant extent by
nonbonding interactions, thereby inhibiting free access
(29) Schmidt-Rohr, K.; Spiess, H. W. Multidimensional Solid-State
NMR and Polymers; Academic Press: San Diego, CA, 1994; pp 171-
174 and references cited therein.
DL of Plastics and Rubbers
Figure 9. Change in composition of the gasoline (C5-C12)
fraction from DL of PPR as a function of reaction temperature
(1500 psig of H2, 2 h, SO42-/ZrO2).
Figure 10. Change in gas product composition from DL of
polypropylene as a function of reaction temperature (1500 psig
of H2, 2 h, SO42-/ZrO2).
of the catalyst to potentially reactive sites in the chains.
On the basis of the composition of products (Table 1 and
Figure 1), it is indicated that at higher temperatures,
i.e. >400 C, DL of polyethylene in the presence of small
amounts (1-2 wt %) of superacid catalysts involves an
Energy & Fuels, Vol. 11, No. 1, 1997 83
overlap of catalytic and thermal reactions. The catalytic
effects under such conditions were relatively weak and
were reflected in somewhat better yields and product
distribution (higher concentration of lower boiling com-
ponents) in the presence as compared with in the
absence of the small amounts of superacid catalysts
used. To determine in a more precise manner these and
other effects, a series of specifically designed experi-
ments were performed in which (1) the catalyst/
polyethylene feed ratios were markedly increased (1:5
or 1:2 by weight), thereby simulating or approaching
typical ratios used in FCC flow reactors;30 (2) the
conventional superacid catalysts were replaced with a
Pt-modified catalyst, i.e., Pt/SO42-/ZrO2, which is mark-
edly more resistant to deactivation; (3) a chemically
compatible solvent, i.e., n-octadecane, was added to the
polyethylene feed to untangle the polymeric chains
during reaction and make them accessible to the dis-
persed catalyst; and (4) the reaction temperature was
reduced to 350 C, at which thermal, noncatalytic
decomposition of polyethylene is essentially excluded.
It should be noted that nonmodified SO42-/ZrO2 catalyst
is resistant to deactivation at high hydrogen pressures
(g500 psig)26 and that this resistance as well as the
isomerization activity of the catalyst is markedly in-
creased by modification with Pt.31 Results obtained
from comparative DL runs with and without catalysts,
as well as with and without n-octadecane as solvent,
are summarized in Table 5.
As seen, with about 17-33 wt % of Pt/SO42-/ZrO2 as
catalyst and in the presence of n-C18H38 as solvent,
polyethylene (PE) undergoes almost complete DL at 350
C (runs DL-1 and DL-2). In contrast, there is es-
sentially no reaction of this polymer in the absence of
the catalyst under otherwise identical processing condi-
tions (run DL-5). With the nonmodified SO42-/ZrO2 as
catalyst (runs DL-3 and DL-4) there is considerable
reaction, but the total conversion is markedly lower. A
high activity of Pt/SO42-/ZrO2, in concentrations of 17-
33 wt % (relative to the feed), is exhibited even in the
absence of the solvent (runs DL-6 and DL-7). However,
the nonmodified SO42-/ZrO2 catalyst shows sharply
lower activity under such conditions (run DL-8). As
expected, in the absence of both a catalyst and the
solvent, PE undergoes no reaction whatsoever at 350
C (run DL-9).
The GC/MS profile of the liquid product from run
DL-2 (350 C; 17 wt % of Pt/SO42-/ZrO2, n-C18H38
solvent) is given in Figure 11. As seen, the product
consists predominantly of C5-C12 branched paraffins
accompanied by very small amounts of n-paraffins.
Although partial catalytic hydrocracking of the n-C18H38
solvent contributes to the liquid product, it is found, as
shown in Figure 12, that the GC/MS profile of the liquid
product from PE only, viz. in the absence of this solvent
(run DL-7), is essentially identical. The predominance
of isoparaffins in the DL product (Figures 11 and 12)
indicates that in the presence of sufficient catalyst
concentrations, preferably in the presence of an n-
paraffinic solvent, PE undergoes in-depth depolymeri-
zation, accompanied by extensive hydroisomerization,
(30) Gary, J. H. Petroleum Refining: Technology and Economics,
2nd ed.; Dekker: New York, 1984; p 101.
(31) Tanabe, K.; Yamaguchi, T. In Successful Design of Catalysts;
Inui, T., Ed.; Elsevier Science Publishers: Amsterdam, 1988; pp 99-
110.
84 Energy & Fuels, Vol. 11, No. 1, 1997 Shabtai et al.

Table 5. Catalyst and Solvent Effects in DL of HDPEa

run no.
DL-1 DL-2 DL-3 DL-4 DL-5 DL-6 DL-7 DL-8 DL-9
catalyst Pt/SO42-/ZrO2 Pt/SO42-/ZrO2 SO42-/ZrO2 SO42-/ZrO2 no Pt/SO42-/ZrO2 Pt/SO42-/ZrO2 SO42-/ZrO2 no
catalyst catalyst
solventb n-C18H38 n-C18H38 n-C18H38 n-C18H38 n-C18H38 none none none none
catalyst/feed 1:2 1:5 1:2 1:5 1:2 1:5 1:5
wt ratioa
H2 pressure, 750 750 820 820 900 700 700 780 820
psigc
total convrn,d,e 92.5 88.9 77.5 45.0 <2.0 64.7 55.1 30.0 <0.5
wt %
a In each run were used 10.0 g of HDPE feed and a calculated amount (2.0 or 5.0 g) of catalyst; reaction temperature was 350 C and

reaction time was 1.0 h. b In runs with n-C18H38, 5.0 g of this solvent and 5.0 g of HDPE feed were used for reaction. c Reaction pressure;
initial H2 pressure in all runs was 500 psig. d Total HDPE conversion into liquid and gaseous products, as determined by the weight of
unreacted HDPE residue (see Experimental Section). e Based on runs without solvent (DL-6 to DL-8), C1-C4 gases formed from HDPE
represent only 4-7 wt % of the total products.

Figure 11. GC/MS analysis of the liquid product from DL of HDPE (350 C, 1.0 h, 20% Pt/SO42-/ZrO2, 500 psig of H2, n-octadecane
as solvent).

even at 350 C. This is quite different from the
composition of products from PE at elevated tempera-
ture (450 C) in the presence of small amounts (1-2 wt
%) of nonmodified SO42-/ZrO2, which is characterized
by significant concentration of n-paraffinic components
(Figure 1). The results obtained provide the basis for
bona fide catalytic conversion of waste PE into gasoline-
range isoparaffins, as potential high-grade fuel compo-
nents.
It should be noted that, compared to HDPE, PPR
shows markedly higher depolymerization reactivity even
in the presence of small amounts, e.g., 1 wt %, of
superacid catalysts (Table 3). This higher reactivity can
be ascribed to the presence of multiple tertiary carbons
in the branched polypropylene chains, with consequent
fast formation of tertiary carbonium ions and attendant
cleavage reactions leading to isoparaffinic products (vide
infra).
D. DL Reactions of Polybutadiene. Figure 13
provides the GC/MS analysis of the liquid product
obtained by DL of a polybutadiene sample (average MW
197 000) at 415 C with 1.0 wt % of SO42-/ZrO2 as
catalyst. As seen, the product consists of a mixture of
the following main types of compounds: (1) C5-C12
paraffins and alkyl-substituted naphthenes; (2) benzene
and (C1-C6) alkylbenzenes; (3) tetralins and indanes;
and (4) bicyclic arenes. Results on the change in product
composition from DL of this polymer as a function of
reaction temperature (350-430 C), using SO42-/ZrO2
as catalyst, are summarized in Table 6. As seen, C5-
C10 paraffins and naphthenes are major components
(45 wt %) at 350 C but decrease moderately with
increase in temperature. Alkylbenzenes are also im-
portant components (21.7 wt % at 350 C) but gradually
decrease with increase in temperature up to 415 C,
probably as a result of acid-catalyzed intramolecular
cyclization reactions of (C3-C6) alkylbenzenes to yield
indanes and tetralins. Consistent with that is the
observed gradual increase in the concentration of the
latter types of compounds in the same temperature
range, i.e., from 350 to 415 C. Bicyclic arenes, in
particular alkylnaphthalenes, increase slightly with
temperature, probably as a result of dehydrogenation
reactions of tetralins and alkylindanes above 400 C.
E. Mechanistic Aspects of DL Reactions. The
change in product composition from DL of polyethylene
and polypropylene as a function of temperature and
reaction time (sections A and B above), coupled with the
DL of Plastics and Rubbers Energy & Fuels, Vol. 11, No. 1, 1997 85

Figure 12. GC/MS analysis of the liquid product from DL of HDPE (350 C, 1.0 h, 20% Pt/SO42-/ZrO2, 500 psig of H2, no solvent).

Figure 13. GC/MS analysis of the liquid product from DL of cis-polybutadiene, MW 197 000 (415 C, 2.0 h, 1500 psig of H2,
SO42-/ZrO2).

data on the observed catalytic effects (Table 5), can be
rationalized in terms of stepwise cleavage reactions of
these polymers by a carbonium ion mechanism.
The high reactivity of polypropylene can be ascribed
to the presence of multiple tertiary carbons in the
polymeric chains and the consequent fast formation of
tertiary carbonium ions in the presence of strongly
acidic catalysts. Such carbonium ions undergo -cleav-
age reactions to yield lower branched paraffins and
olefins by a sequence proposed in Figure 14. Lower
molecular weight carbonium ions yield corresponding
branched paraffins by metathesis with molecular hy-
drogen, a reaction that involves a low activation energy
and results in regeneration of the acidic catalyst.32
Branched olefins produced by -cleavage reactions
undergo to a major extent hydrogenation to the corre-
sponding paraffins. Such reactions involve fast proto-
nation of the olefinic intermediate to yield a carbonium
ion which in turn, by metathesis with hydrogen, yields
the skeletally analogous paraffin. Limited hydrogena-
tion of olefins has been previously found even in
noncatalytic hydropyrolysis proceeding by a free radical
(32) Shabtai, J.; Ramakrishnan, R.; Oblad, A. G. Thermal Hydro-
carbon Chemistry; Advances in Chemistry Series 183; Oblad, A. G.,
Davis, H. G., Eddouger, R. T., Eds.; American Chemical Society:
Washington, DC, 1979; pp 297-328.
86 Energy & Fuels, Vol. 11, No. 1, 1997 Shabtai et al.

Table 6. Composition of Products from DL of cis-Polybutadiene as a Function of Reaction Temperaturea

temp
350 C 375 C 400 C 415 C 430 C
convrn,b wt % 12.6 24.6 72.9 98.5 100
product distrbn,c wt %
C1-C4 gases 2.5 2.8 2.9 4.4 5.9
liquid products 95.9 93.5 91.3 87.7 84.0
coke plus losses 1.6 3.7 5.8 7.9 10.1
liquid product distrbn, wt %
C5-C10 paraffinsd and 45.0 32.8 29.9 26.9 25.8
cycloparaffinse
benzene and 21.7 20.5 20.4 17.9 17.5
alkylbenzenesf
tetralins and indansg 14.9 19.1 21.6 22.5 21.0
bicyclic arenesh 18.5 27.6 28.1 32.7 35.7
aIn each run were used 5.0 g of polybutadiene feed and 0.05 g of SO 2-/ZrO catalyst; initial H pressure was 1500 psig and reaction
4 2 2
time was 1.0 h. b Weight percent of feed converted into products. c Calculated in weight percent of total product. d C5-C10 paraffins and
small amount of olefins. Cyclopentane, cyclohexane, and (C1-C4) alkyl-substituted derivatives. f (C1-C6) alkyl-substituted benzenes.
e
g Tetralin, indan, and (C -C ) alkyl-substituted derivatives. h (C -C ) alkyl-substituted naphthalenes and (C -C ) alkyl-substituted
1 2 1 3 1 2
biphenyls.

Figure 14. Proposed mechanistic scheme for acid-catalyzed

polypropylene DL.

mechanism.32 The latter involves addition of a hydro-

gen atom to the olefin to form a radical which by
metathesis with molecular hydrogen yields the paraf-
finic product. It should be noted that at temperatures
>400 C and in the absence of sufficient amounts of
catalyst there is probably an overlap of catalytic and
purely thermal PE depolymerization. The latter could
proceed by a radical mechanism resulting in markedly
lower formation of isoparaffinic products.
The formation of branched paraffins as main products
from PE indicates that the DL reactions of this straight-
chain polymer in the presence of superacid catalysts
(Table 5) involve extensive skeletal rearrangement of
intermediate cleavage products. Highly selective hy-
droisomerization of n-paraffins to branched paraffins,
in the presence of strongly acidic Y-type zeolites, was
previously observed.33-35 For example, in the presence
of a PtCaY zeolite catalyst at 210 C and 1000 psig of
H2 pressure, n-hexadecane was converted into a mixture
(33) Coppola, E. N. M.S. Thesis, University of Utah, 1987.
(34) Coppola, E. N.; Oblad, A. G.; Shabtai, J. Prepr.sAm. Chem.
Soc., Div. Pet. Chem. 1987, 32 (2), 559.
(35) Schultz, H. F.; Weitkamp, J. H. Ind. Eng. Chem. Prod. Res. Dev.
1972, 11, 46.
Figure 15. Example of proposed mechanistic sequences for
conversion of PE into branched paraffins.
of isomeric methylpentadecanes, dimethyltetradecanes,
and multiply branched hexadecanes with a selectivity
of >95 wt %.33,34 Further, skeletal isomerization was
found to represent a necessary step preceding the
catalytic cracking of n-paraffinic feeds.35 By analogy,
as indicated in Figure 15, straight-chain fragments from
PE can undergo extensive branching by multiple hy-
dride and methide (or higher alkide) 1,2-shifts, prior to
subsequent cleavage and associated reactions leading
to lower branched paraffins. Initiation of the reaction
involves formation of a secondary carbonium ion, which
is somewhat slower compared to the initial formation
of tertiary carbonium ions from polypropylene (Figure
14). -Cleavage yields an olefin and a lower carbonium
DL of Plastics and Rubbers
ion in which the charge is delocalized along the chain
by fast hydride shifts. Multiple methide (or higher
alkide) shifts result in extensive branching of the chain
prior to -cleavage reactions, leading to lower branched
paraffins. Olefins produced by -cleavage undergo
protonation to yield carbonium ions which undergo the
same types of skeletal rearrangement and attendant
cleavage reactions.
DL reactions of polybutadiene, unlike those of poly-
ethylene and polypropylene, yield cyclic compounds as
predominant products (Figure 13 and Table 6). Forma-
tion of the latter can be tentatively explained on the
basis of previous studies of the thermal reactions of
butadiene.36,37 Monomeric butadiene, and possibly also
some higher dienes, derived by initial depolymerization,
can undergo fast Diels-Alder cyclodimerization to form
4-vinylcyclohexene (and alkyl-substituted derivatives),
which by a sequence of rearrangement and hydrogen
transfer reactions yield a full range of alkylbenzenes and
alkyl-substituted naphthenes.36,37 Some bicyclic arenes
can be produced by secondary Diels-Alder additions of
butadiene to unsaturated monocyclic intermediates and/
or intramolecular cyclizations of alkyl- or alkenylben-
zenes.36,37
(36) Gil-Av, E.; Shabtai, J.; Steckel, F. Ind. Eng. Chem. 1960, 52,
31.
(37) Shabtai, J.; Gil-Av, E. Tetrahedron 1962, 18, 87-94.
Energy & Fuels, Vol. 11, No. 1, 1997 87
Conclusions
It was demonstrated that the DL of HDPE and PPR
is a gradual breakdown process, which can be conve-
niently controlled to produce C5-C12 hydrocarbons as
predominant products. For HDPE, a highly selective
catalytic DL procedure for production of C5-C12 branched
paraffins was achieved by using a relatively low tem-
perature and applying a high Pt/SO42-/ZrO2 catalyst/
feed ratio, preferably in the presence of a chemically
compatible n-paraffinic solvent. For PPR, processing
conditions for selective conversion of the polymer into
a gasoline-like product, consisting of C5-C12 branched
paraffins, were likewise identified.
The results obtained provide fundamental data and
possible processing concepts for conversion of HDPE,
PPR, and other polyolefins into desirable isoparaffinic
products representing potential blending components for
reformulated, nonaromatic gasolines.
Acknowledgment. We thank the U.S. Department
of Energy for financial support through the Consortium
for Fossil Fuel Liquefaction Science (DE-FC22-
93PC93053).
EF960076+