3112 Ind. Eng. Chem. Res.

1993,32, 3112-3116

Acid Properties of Silica-Alumina Catalysts and Catalytic Degradation

of Polyethylene
Hironobu Ohkita, Ryuji Nishiyama, Yoshihisa Tochihara, Takanori Mizushima,
Noriyoshi Kakuta, Yoshio Morioka? Akifumi Ueno,’J Yukihiko Namiki,t
Susumu Tanifujif Hiroshi Katohf Hideo Sunazuka,t Reikichi Nakayama) and
Takashi Kuroyanagit
Toyohashi University of Technology, Tempaku, Toyohashi, Aichi 441, Japan, Shizuoka University,
Johoku, Hamamatsu, Shizuoka 432, Japan, and Japan Electric Cable Technology Centre,
Hamamatsu, Shizuoka 431 -21, Japan

A relationship between the acid strengths and amounts of silica-alumina catalysts and the
compositions of products formed by the catalytic degradation of polyethylene a t 673 K was studied.
The acid strengths and amounts were varied with SiOdA1203weight ratio in the catalysts. Although
the resulting products consisted of gases, oils, and wax, the fraction of gases increased, and, inversely,
the fraction of oils decreased, as the acid amounts over the catalysts increased The fraction of
aromatics in the oils was enhanced, however, as the acid amounts over the catalysis increased, which
was discussed in terms of the acid types: Bronsted and Lewis acids generated on silica-aluminas.
Since some inorganic compounds such as MgO, ZnO, TiO2, and carbon are incorporated into plastics,
the catalytic activities and selectivities of these additives for polyethylene degradation were also
discussed.

Introduction Since in an electric cable, generally consisting of poly-

Though several methods have been proposed for recy-
cling waste plastics, Williams (1993) is of a opinion that
material recovery will not be a long-term solution to the
present problem and that energy or chemical recovery is
more attractive. In this method, the waste plastics are
thermally or catalytically degraded into gases and oils,
which can be utilized as resources of either fuels or
chemicals. A wide range distribution of carbon atom
numbers has been reported by Murata and Makino (1973,
1975) and Nishizaki et al. (1977) in the gases and oils
obtained by thermal degradation of polyethylene and
polypropylene. For the gases and oils produced by
degradations over solid acid catalysts, relatively sharp
distribution curves with peak tops at the lighter hydro-
carbons have been reported by Uemichi et al. (1983) and
Audisio et al. (1984). It is well-known that the oils
produced by catalytic degradation over solid acids contain
less olefinic compounds and are rich in the aromatics
compared to the oils obtained by thermal degradation.
Although the catalysts used in these works were solid acids
such as silica-alumina and zeolite,the relationship between
the acid amounts and strength of the catalysts and the
compositions of the resulting oils is not yet well defined.
Consequently, the purpose of this work is to investigate
this relationship using silica-alumina catalysts, varying
the Si02/A1203 weight ratio and hence the acid amounts
and strengths. The results obtained were discussed in
terms of the types of the acid sites; Lewis and Bronsted
sites, and were compared with those obtained by degra-
dation over HZSM-5 zeolite, since this zeolite is considered
to possess large amounts of Bronsted acid sites. Note
that the catalytic degradation considered in this work is
just the cracking of volatile products of the thermal
degradation of polyethylene, as will be seen in the
apparatus used in this work.
I t is also well-known that several kinds of inorganic
additives are incorporated into plastics in order to improve
the mechanical strength and/or the thermal resistance.
+ Shizmoka University.
f Japan Electric Cable Technology Centre.
0888-5885/93/2632-3112$04.00/0
ethylene, inorganic compounds such as Si02, MgO,
TiO2, and ZnO are dispersed as flame retardants, we are
pleased’thatthese inorganic additives will play important
roles for the degradation of polyethylene so as not torequire
additions of other Catalysts. Accordingly, the studies on
the roles of Si02, A1203, MgO, TiO2, and ZnO for the
polyethylene degradation are another purpose of the
present work. Since in some cases carbon powders were
also incorporated into the plastics, the roles of carbon
powders for polyethylene degradation were also investi-
gated.
Experimental Section
1. Catalyst Preparation. The catalysts employed in
this work are given in Table I with their catalytic
performances for polyethylene degradation at 673 K. ,5302,
A1203, and Ti02 were prepared from gels, obtained by
hydrolysis of the corresponding metal alkoxides such as
tetraethoxysilane, aluminum triisopropoxide, and titanium
tetraisopropoxide, according to papers by Ueno et al.
(19831, Ishikawa et al. (1992), and Nishiwaki et al. (1989),
respectively. MgO and ZnO were formed from the aqueous
solution of the corresponding metal nitrates using aqueous
ammonia as a precipitant. The precipitates obtained were
dried in an oven at 383 K for 12 h, followed by calcination
at 773 K for 4 h. ZSM-5 zeolite, with a Si/Al ratio of 14,
was prepared from aerosil silica, sodium aluminate, and
tetra-n-propylammonium hydroxide according to a US.
patent (1972) and was cation-exchanged to HZSM-5 by
using ammonium hydroxide. Active carbon was obtained
from Sumitomo Kagaku Co. and was used as a catalyst
without further purification.
Silica-aluminas were prepared from gels obtained by
hydrolysis of a mixed alkoxide solutions of tetraethox-
ysilane and aluminium triisopropoxide, varying the SiOd
A1203weight ratio from 0.25 to 4.0. The gels were dried
and then calcined in the same manner as mentioned above.
Unless otherwise specified, silica-alumina with a weight
ratio of 4.0 was used in the present work.
2. Catalytic Degradation of Polyethylene. The
catalytic degradation was carried out using 15 g of low-
@ 1993 American Chemical Society
 Ind. Eng. Chem. Res., Vol. 32, No. 12, 1993 3113
Table I. Catalysts Employed and Their Catalytic Performances for the Degradation of Polyethylene at 673 K Fractions of
Gases, Oils, and Wax and Expressed in Terms of wt 7’ 0 (1.5 g of the Catalyst Was Used for 15 g of Polyethylene)
HZSM-5 si02(4)/&03(1) Si02 A1203 ZnO MgO Ti02 carbon thermal
oils (wt 5%) 45 52 69 67 70 61 68 60 44
straight (wt %) 19 34 54 75 85 68 70 78 68
gases (wt %) 50 37 16 13 12 14 14 12 20
waxes (wt 5%) 1 4 6 10 5 9 7 7 13
residues (wt % ) trace trace trace trace 3 trace 3 5 17
reaction time (h) c3 4 5 5 7 7 7 7 >7
material balance ( % ) 96 93 91 90 90 84 92 84 94
I4
peaks observed at 1625,1490,and 1455cm-l were assigned
to pyridine on the Lewis sites, and the peaks at 1545 and
1490 cm-l were ascribed to pyridine adsorbed on the
Bronsted sites, reported by Hughes and White (1967) and
by Gates et al. (1979). Change in the fraction of Bronsted
sites with the change in SiOz/A1203 weight ratio of silica-
aluminas was tentatively determined by measuring the
W
10
absorption peak intensities at 1625 and 1545 cm-l. The
amounts of Bronsted and Lewis acids per gram of the
1 R e g d l a r a r 2 F l o w meter 3 G a l meter 4 Thermocouple
catalysts were estimated from the peak intensity ratios
5 F l e x i b l e h e a t e r 6 E l e c r r ~ c‘urnace I Reactor 1iu5/(11545 + 1iszs) and IlSZS/(11545 + 11625) multiplied by
8 C a t a l y s t 9 C o n d e i i c r 10 T r a ~
the total acid amounts measured by the titration, respec-
Figure 1. Schematic drawing of the apparatus for catalytic tively.
degradation of polyethylene.

density polyethylene powder (NUC-9025 from Nippon Results

Unicar Co. Ltd., 10 pm in size, &fn= 16.2 X 103,&fw= 63.5
X lo3) packed at the bottom of a stainless steel reactor (45 1. Catalytic Performances of Inorganic Additives.
mm in diameter) heated at 673 K. In the middle part of The catalytic performances of inorganic additives em-
the reactor 1.5 g of the catalyst powder was held in a ployed are given in Table I, expressed in terms of the
stainless steel gauze, which separates the catalyst from weight percent fractions of the gases, oils, and wax
polymer powders so that the vapor of thermally degraded produced at 673 K. In Table I, “straight” means the weight
products may pass through the catalyst bed. Nitrogen percent fraction of n-alkanes and 1-alkenes in the resulting
gas was supplied at the bottom of the reactor with a flow oils and “residue” means the carbonaceous compounds
rate of 50 mL/min in order to purge oxygen from the reactor remaining in the reactor after degradation for 7 h. The
and assist the vapor to be carried into the catalyst bed. time required to complete the degradation of 15 g of
Exactly speaking,the catalytic degradation of polyethylene polyethylene powder at 673 K is given in Table I. It was
in this work means “the catalytic cracking of the volatile assumed in this work that the degradation was completed
compounds in the thermally degraded polyethylene vapor”, in the reactor when no more formation of oils was detected
but in the present paper the term “catalytic degradation in the coolingtube. The materials balance of around 90 % ,
of polyethylene” was used as the abbreviated form. Note given at the bottom of the table, was obtained for all the
that the reaction temperature was controlled at the bottom experimental runs. The lack of 10% will be mainly
of the reactor. The degraded products were introduced attributed to the experimental errors for a measure of the
into a cooling glass tube, where gases (C1 to C4) were residue remained in the reactor, since it adhered too tightly
separated from oils (C5 to CZO)to be measured by a gas on the reactor wall to be thoroughly released.
meter. Low-volatilitycompounds such as waxes deposited The product distribution curves for the thermal deg-
on the cooling tube were eliminated by n-hexane. A radation and the catalytic degradations over HZSM-5 and
schematic drawing of the apparatus used is shown in Figure ZnO, as the representatives of solid acid and base catalysts,
1.
respectively, are given in Figure 2. In Table I1 are
The gases were analyzed by GC (Shimadzu GC-8A)using summarized the fractions of 1-olefins, n-paraffins, and
a column packed with VZ-10. The oils were analyzed by aromatics in the oils produced by thermal degradation
GC (HP-5890) using a 10-m DB-2887 capillary column and by catalytic degradations over ZnO, silica-alumina,
and were identified by comparison of the retention indices
with those of authentic compounds (n-alkanes and n-al- and HZSM-5 at 673 K. The compositions of oils produced
kenes) in a calibration mixture of a known composition. by the degradation on MgO, TiOz, and A1203 were almost
More precise assignments of aromatics in the oils were the same as those on ZnO. Others in Table I1 mainly
carried out, if necessary, by GC-MS (HP-5890) using a consisted of branched isomers of n-paraffins and 1-olefins.
30-m DB-1 capillary column. The oils produced on HZSM-5 consisted of significant
3. Measurements of Acid Amounts and Strengths. amounts of aromatics including naphthalene compounds,
The acid amounts and strengths of silica-alumina cata- identified by GC-MS. In Figure 3 are shown the assign-
lysts, heated again at 623 K for 1h in air followed by an ments of some of the naphthalene compounds on a GC
evacuation at the same temperature for 30 min, were strip chart.
measured by titration using n-butylamine and various color 2. Acid Properties of Catalysts and Product Com-
indicators according to a paper by Hirashima et al. (1988). positions. Changes in the acid amounts and strengths of
In order to distinguish Bronsted acid sites from Lewis silica-aluminas with varied SiOz/A1203ratios are given in
acid sites generated on the silica-alumina catalysts, Figure 4, where the highest acid strength was HO= -3.0 for
infrared spectra of pyridine adsorbed on the catalysts at all the silica-aluminas employed. The largest acid amount
473 K were recorded in order to avoid problems caused by was observed for the silica-alumina possessing the ratio
the physical adsorption of pyridine. The IR absorption ranging from 4.0 to 1.5. The relationship between the
3114 Ind. Eng. Chem. Res., Vol. 32, No. 12, 1993
1 2 3 4 5 6 7 8 9 10111213141516+
Carbon n u m b e r
Figure 2. Product distributions against carbon atom numbers in
the PE degradation catalyzed by HZSM-5and ZnO and in the thermal
degradation.
Table 11. Fractions of 1-Olefins,a-Paraffins, Aromatics,
and Others (Mainly Branched Isomers) in the Oils
Produced on HZSM-6, Silica-Alumina, and ZnO and by
Thermal Degradation at 673 K
catalytic degradation (wt % )
SiOA4)I thermal
components HZSM-5 AlzOa(1) ZnO degradation (wt %)
l-olefins 7 4 34 24
n-paraffins 12 30 51 44
aromatics 35 13 0 3
others 46 53 15 30
fraction of gases, oils, and wax formed and the SiOdA1203
weight ratio in the catalysts employed is depicted in Figure
5.
The changes in the amounts of Brdnsted and Lewis acid
sites per gram of the silica-alumina catalysts with the
change in the SiO~/A1203weight ratio are shown in Figure
6, together with the change in the amounts of aromatics
in the resulting oils.
Discussion
1. Roles of Inorganic Additives for Polyethylene
Degradation. As is mentioned in the Introduction of
this paper, several kinds of inorganic compounds, such as
Si02, Al203, ZnO, MgO, TiO2, and carbon, are incorporated
in the polymer layer of electric cables as flame retardants
in order to improve the thermal properties of the polymer.
Although these additives would have been expected to be
good catalysts for the polyethylene degradation, no
significant differences from the single thermal degradation
were observed in the results, shown in Table I, except that
the fractions of residue remained in the reactor were much
reduced by using these inorganic compounds as catalysts.
Since thermal degradation has been considered to pass
through hydrocarbon radicals, the residue remaining on
the reactor wall might be attributed to the low-volatility
compounds, probably formed by recombination of these
radicals. One of the roles of inorganic additives is to
scavengethese radical species on the surfaces and to crack
them into light hydrocarbons depending on the catalytic
performances of the additives. The weak acidic and/or
basic additives such as SiOz, A1203, ZnO, MgO, and Ti02
seem to scavenge these radicals but do no convert them
significantly into the light hydrocarbons. The scavenged
radicals were released from these solid surfaces as the
corresponding l-olefins, leaving hydrogen atoms on the
surfaces. In turn, the hydrogen atoms left on the solid
surfaces reacted with other radicals scavenged on the
surfaces to produce n-paraffins. Thus, the oils produced
on these solids were rich in l-olefins and n-parafhs, as
shown in Table 11,and less residue remained in the reactor
compared with the thermal degradation (see Table I).
Things were the same when carbon was used as a catalyst.
Consequently, similar product distribution curves were
obtained for both thermal and catalytic degradations over
these inorganic additives, although only the distribution
curve obtained for the degradation over ZnO is exhibited.
It was concluded that the inorganic additives incorporated
into the polyethylene layer of electric cables could not be
expected to work as good catalysts for the catalytic
degradation of waste polyethylene.
2. Relationship between Acid Properties and
Product Compositions. The enhanced production of
gases, shown in Table I, is one of the features of the
degradation products of plastics over solid acids such as
silica-alumina and HZSM-5 zeolite. This is more pro-
nounced in Figure 2, where the gases consisting of C3 and
Cq compounds are predominant in the products for the
polyethylene degradation over HZSM-5 zealite. In ad-
dition, the time required to complete the degradation of
15 g of polyethylene on HZSM-5 was shorter than 3 h, less
than one-half of the time required for the single thermal
degradation (see Table I).
It might be better, however, to use silica-alumina
catalysts to study the relationship between acid properties
of the catalysts and the composition of the degradation
products of polyethylene, since the acid amounts and
strengths can be easily controlled by the SiOdA1203ratio
in the catalysts. The highest acid strength was HO= -3.0,
observed for all the silica-alumina catalysts used, and the
largest acid amount was observed for the catalyst pos-
sessing the sioz/&o3 ratio ranging from 4.0 to 1.5, as
shown in Figure 4. Considering these results together with
the results shown in Figure 5, the fraction of oils produced
by the degradation on silica-alumina catalysts decreased
and, inversely, the fraction of gases increased as the acid
amounts on the Catalysts increased. This means that
cracking of the higher hydrocarbons takes place on the
acid sites of the catalyst surfaces, as has already been
accepted. The relationship between the fraction of gases
produced and the SiOz/Al203ratio in the catalysts, shown
in Figure 5, is similar to the relationship between the
amount of Brdnsted acids, but not of Lewis acids, and the
SiOdA120 ratio, shown in Figure 6. This suggests that the
cracking of olefinic compounds in the thermally degraded
polyethylene occurred predominantly on the silica-alu-
minas, since olefinic compounds have been considered to
be more selectively converted into light hydrocarbons on
the Bronsted acids, reported by Turkevich and Ono (1969).
Consequently, the fraction of olefins in the oils produced
over silica-alumina and HZSM-5, possessing a lot of
Brdnsted acid sites, are significantly small,as given in
Table 11. The amounts of wax and residue in the reactor
were negligibly small on the catalyst having a considerable
amount of acid.
Another feature of the product compositions over solid
acids is the formation of aromatics in the oils, which was
never observed in the oils produced over solid bases. The
change in the fraction of aromatics in the oils with the
change in the SiOz/A1203 weight ratio in the catalysts,
shown in Figure 6, seems to follow the change in the total
acid amounts given in Figure 4. Thus, the aromatizations
likely occurred on the acid sites of the catalysts. Two
types of acid sites, Lewis and Brdnsted acids, are generated
on the silica-alumina catalysts, and they can be distin-
 Ind. Eng. Chem. Res., Vol. 32,No. 12, 1993 3115
HaZSM-5

Figure 3. Assignments of aromatic compounds in the oils produced on HZSM-5.

1.o
0 Ho 1-3.0 1.o 1.6
0 Brtlnatsd ac#

0.8 I ,A------&-..
A Lewk acM
0 Aromatlca I 1.2

o-2f122.si
00
0
20
20
40
40
60
60
80
80
Alumina content I wt#
100
100

Figure4. Changesin the acid amount and strength of silica-aluminas

with the SiOZ/Al208weight ratio.
0 20 40 60
Ahmine content
80 100

Figure 6. Relationship between the amount of aromatics in the oile

produced on silica-aluminas and the amounts of BrBnsted and Lewis
acid sites detected on the catalysts.

of hydrogen atoms on the surface of solid acids, and these

hydrogen atoms were consumed for the hydrogenation of
0 gases olefins, as reported by Ayame et al. (1979). Thus, the
fraction of 1-olefinsin the oils produced on the solid acids
was significantly small (see Table 11).
Since plenty of C3 and C4 compounds were produced
over solid acids, the precursors of CSand C4 species on the
catalyst surfacesmight be released from the surfaceseither
as CBand C4 gases or as aromatic compounds depending
on the interactions between the precursors and the catalyst
surfaces, modified by the acid properies of the catalysts
employed.

" Literature Cited

0 20 40 60 80 100
Alumha content I wt%
Figure 5. Changes in the fractions of gases, oils,and wax produced
on silica-aluminas with the SiOZ/Al203weight ratio.
guished by measuring infrared spectra of pyridine ad-
sorbed. The changes in the amounts of Briinsted and Lewis
acid sites with the change in the Si02/A1203weight ratio
are also given in Figure 6, suggesting that the formation
of aromatics could not be specified to occur selectively
either on the Brdnsted acids or on the Lewis acids.
However, considering that significant amounts of aro-
matics were produced over HZSM-5 possessing a lot of
Brdnsted acids (see Table 111, aromatization seems to be
favorable on the Briinsted acids. Aromatization left a lot
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Received for review April 29, 1993
Revised manuscript received August 25, 1993
Accepted August 30, 19930
* Abstract published in Advance ACS Abstracts, October 15,
1993.