1148 Energy & Fuels 1998, 12, 1148-1152

Catalytic Conversion of Used Oil to Hydrocarbon Fuels

in a Fractionating Pyrolysis Reactor
Levent Dandik, H. Ayse Aksoy,* and Ayse Erdem-Senatalar
Istanbul Technical University, Chemical Engineering Department,
80626 Maslak, Istanbul, Turkey

Received January 21, 1998

Pyrolysis of used sunflower oil was carried out in the presence of different amounts of HZSM-5
at 400 and 420 °C in a reactor equipped with a fractionating packed column, the length of which
was varied. The products consisted of gaseous and liquid hydrocarbons, acids, CO, CO2, water,
and coke. The compositions of the gaseous and liquid products were studied by gas chromatog-
raphy. The product yields and compositions were affected by catalyst content, temperature, and
column length. Nearly complete conversion (96.6%) of the used oil and the maximum liquid
hydrocarbon yield (33%) were obtained at the highest temperature (420 °C), highest catalyst
content (20%), and the lowest column length (180 mm) employed. The aromatic hydrocarbon
contents of the liquid hydrocarbon products, which consisted of hydrocarbons of gasoline range,
were in general lower than those obtained using fixed bed reactors but increased parallel to the
increase in catalyst content. Additional thermal reactions taking place in this type of reactor
increased with the increase in column length. Although the total conversion and total liquid
hydrocarbon yields were influenced adversely by these reactions, liquid products with higher
isomeric hydrocarbon contents were obtained with longer columns.

Introduction fuels have been studied under different reaction condi-

Recently, increasing attention has been focused on
biomass as a renewable source of fuels and chemicals
due to environmental reasons and the problem of energy
assurance.1 Because of their suitable properties (neg-
ligible sulfur, nitrogen, and metal content), plant oils
have been suggested as important biomass sources for
the production of synthetic fuels and useful chemicals.2,3
However, the plant oils have alternative uses and their
initial costs are generally high. On the other hand, in
several branches of industry, especially in the food
industry and rendering plants, large quantities of oils
are produced as waste. Also, the disposal of these waste
oils is of environmental concern.4 Therefore, using the
waste oils as feed materials to produce synthetic fuels
and valuable chemicals would be advantageous.
Various attempts have been made to use plant oils
directly, but their use in the direct injection-type diesel
engine has caused serious problems such as the forma-
tion of carbon deposits in the combustion chamber,
crankcase oil dilution, and oxidation.5 One of the most
promising ways for the production of liquid fuels and
chemicals from plant oils is pyrolysis. The pyrolysis of
plant oils to obtain products suitable for being used as
* Author to whom all correspondence should be addressed.
(1) Schwab, A. W.; Dykstra, G. J.; Selke, E.; Sorenson, S. C.; Pryde,
E. H. J. Am. Oil Chem. Soc. 1988, 65, 1781-1786.
(2) Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed.;
Interscience Publishers: New York, 1980; Vol. 11, pp 344-345.
(3) Sharma, R. K.; Bakhshi, N. N. Can. J. Chem. Eng. 1991, 69,
1071-1081.
(4) Katikaneni, S. P. R.; Adjaye, J. D.; Bakhshi, N. N. Energy Fuels
1995, 9, 599-609.
(5) Schwab, A. W.; Bagby, M. O.; Freedman, B. Fuel 1987, 66, 1372-
1378.
tions with and without addition of catalysts.1-14 Espe-
cially since the discovery of the high-silica zeolite
catalyst HZSM-5 by Mobil workers, a number of inves-
tigations employing this catalyst have been report-
ed.3,15-16 The shape-selective pentasil HZSM-5 catalyst
was first used by Weisz et al.17 to convert plant oils to
hydrocarbons. They achieved a complete conversion of
jojoba oil at 400 °C over HZSM-5, whereas both castor
and corn oils required a temperature of 500 °C for
complete conversion. In all the cases, 42-78 wt % of
the oil was converted to aromatic hydrocarbons. Weisz
et al. proposed that the triglyceride molecule could
penetrate into the zeolite pores at elevated temperatures
(6) Chang, C. C.; Wan, S. W. Ind. Eng. Chem. 1947, 39, 1543-1548.
(7) Crosley, A.; Heyes, T. D.; Hudson, B. J. F. J. Am. Oil Chem. Soc.
1962, 39, 9-14.
(8) Nawar,W. W. J. Agric. Food Chem. 1969, 17, 18-21.
(9) Alencar, W.; Alves, P. B.; Craveiro, A. A. J. Agric. Food Chem.
1983, 31, 1268-1270.
(10) Konwer, D.; Taylor, S. E.; Gordon, B. E.; Otuos, J. W.; Calvin,
M. J. Am. Oil Chem. Soc. 1989, 66, 223-226.
(11) Filho, G. N. R.; Bentes, M. H. S.; Brodzki, D.; Mariadassou, G.
D. J. Am. Oil Chem. Soc. 1992, 69, 266-271.
(12) Agra, I. B.; Warnijati, S.; Pratama, M. S. Catalytic Pyrolysis of
Nyamplung Seeds Oil to Mineral Oil-Like Fuel; Proceedings of 2nd
World Renewable Energy Congress; Sayigh, A. A. M., Ed.; Pergamon
Press: New York, 1992; pp 1346-1351.
(13) Filho, G. N. R.; Brodzki, D.; Mariadassou, G. D. Fuel 1993, 72,
543-549.
(14) Dandik, L.; Aksoy, H. A. Converting Used Oil to Fuel and
Chemical Feedstock through the Use of a Fractionating Pyrolysis
Reactor; Proceedings of the World Conference on Oilseed and Edible
Oils Processing; Koseoglu, S. S., Rhee, K. C., Wilson, R. F., Eds.; AOCS
Press: Champaign, 1998; Vol. 1, pp 126-129.
(15) Prasad, Y. S.; Bakhshi, N. N. Appl. Catal. 1985, 18, 71-85.
(16) Yarlagadda, P. S.; Yaollang, H.; Bakhshi, N. N. Ind. Eng. Chem.
Prod. Res. Dev. 1986, 25, 251-257.
(17) Weisz, P. B.; Haag, W. O.; Rodewald, P. G. Science 1979, 206,
57-58.

10.1021/ef980012u CCC: $15.00 © 1998 American Chemical Society

Published on Web 09/19/1998
Catalytic Conversion of Used Oil Energy & Fuels, Vol. 12, No. 6, 1998 1149

Table 1. Fatty Acid Composition and Main

Characteristics of Used Oil
acid value (mg of KOH/g) 2.32
saponification value (mg of KOH/g) 194
iodine value (g of I/100 g) 117.82
density, 21 °C (g/mL) 0.9383
viscosity, 37.8 °C (mm2/s) 89.39
refractive index (nD20) 1.4785
fatty acid composition (wt %)
palmitic 9.49
stearic 5.62
oleic 31.14
linoleic 53.75

Table 2. Conditions of Gas Chromatographic Analyses

conditions hydrocarbons acids gas
detector FID FID TCD Figure 1. Sample chromatogram for gaseous products.
detector temp, °C 280 280 300
injector temp, °C 250 250 250
gas flow, mL/min
a
carrier gas, N2 1.11 1.72 10.17
hydrogen 30 30
air 400 400
split ratio 370/1 175/1
column Ultra 1a Ultra 2b Chromosorb 102c
oven temp, °C temp prog.d temp proge temp progf
a 25 m, 0.32 mm, 0.52 µm film thickness, 100% dimethyl

polysiloxane. b 25 m, 0.32 mm, 0.52 µm film thickness, 5% diphenyl

and 95% dimethyl polysiloxane. c 80/100 mesh, 2 m, 1/8 in., 2.2 mm.
d 24 °C (5 min), 24-30 °C (1 °C/min, 5 min), 30-70 °C (1.5 °C/
b
min, 20 min), 70-200 °C (3 °C/min, 30 min). e 30 °C (5 min), 30-
170 °C (5 °C/min, 10 min), 170-200 °C (3 °C/min, 30 min). f 30 °C
(2 min), 30-200 °C (10 °C/min, 10 min).

by assuming a slender configurational alignment. An-

other possibility was thought to be that the initial c
fragmentation occurs on the external surface of the
catalyst followed by the diffusion of the intermediate
products into the pores.18 The subsequent reactions,
namely, cyclization, isomerization, and hydrogen trans-
fer, leading to the formation of mainly aromatic hydro-
carbons from the carbonium ions produced in the pores
of the HZSM-5 catalyst are well-understood. Kati-
kaneni et al.19 investigated the catalytic conversion of Figure 2. Sample chromatogram for liquid products: (a)
canola oil over various cracking catalysts. They ob- retention time 0-40 min, (b) retention time 40-80 min, and
served that at 400 °C, among the six catalysts, HZSM-5 (c) retention time 80-120 min.
gave the highest amount of organic liquid product (63 Table 3. Overall Product Distribution at 400 °C (wt %)
wt %) and it was more selective for aromatic hydrocar-
1% HZSM-5 5% HZSM-5 10% HZSM-5
bons compared with the other zeolitic and nonzeolitic column (mm) column (mm) column (mm)
catalysts. In another study, canola oil and steam were
products 180 360 540 540 180 540
co-fed continuously to a fixed-bed reactor loaded with
liquid hydrocarbon 23.18 19.66 16.20 18.10 28.92 20.75
HZSM-5 catalyst at varying process conditions. The phase
liquid hydrocarbon product contained 60-70 wt % n-alkenes 7.22 6.66 5.65 3.93 4.33 3.06
aromatics. The gaseous product was reported to be n-alkanes 10.09 8.13 6.50 7.35 12.30 5.70
highly olefinic.20 aromatics 0.54 0.53 0.48 1.04 1.81 1.73
others 5.34 4.34 3.57 5.78 10.48 10.26
The compositions of the pyrolysis products with or C5-C11 hyrocarbons 16.77 17.96 15.93 17.64 24.90 20.15
without catalyst are known to depend on the charac- aqueous phase 3.88 4.48 9.28 5.63 6.12 5.49
teristics of oils and catalysts.9,10 Catalytic conversion acid phase 16.50 7.25 1.21 2.53 12.50 1.58
gas 16.30 16.14 9.66 13.52 19.10 18.29
of saturated and unsaturated fatty acids and a plant coke-residual oil 40.14 52.47 63.65 60.22 33.36 53.89
oil using 1-20% Na2CO3 at the same conditions resulted conversion 59.86 47.53 36.35 39.78 66.64 46.11
in pyrolysis products consisting of hydrocarbons in and C18:2) contained more aromatic hydrocarbons than
different quantities.10 The liquid pyrolysis products of those of the saturated fatty acids (C16:0 and C18:0). On
boiling range 60-320 °C of unsaturated fatty acids (C18:1 the contrary, the pyrolytic oils of saturated fatty acids
(18) Prasad, Y. S.; Bakhshi, N. N.; Mathews, J. F.; Eager, R. L. Can.
contained more olefinic hydrocarbons than aromatics.
J. Chem. Eng. 1986, 64, 278. Information on the pyrolysis products of sunflower oil
(19) Katikaneni, S. P. R.; Adjaye, J. D.; Bakhshi, N. N. Can. J. Chem. is not available in the literature. Expecting the char-
Eng. 1995, 73, 484-497.
(20) Prasad, Y. S.; Bakhshi, N. N.; Mathews, J. F.; Eager, R. L. Can. acteristics of the oil to affect the composition of pyrolysis
J. Chem. Eng. 1986, 64, 285-292. products, we have investigated the pyrolysis of this
1150 Energy & Fuels, Vol. 12, No. 6, 1998 Dandik et al.

Table 4. Overall Product Distribution at 420 °C (wt %)

1% HZSM-5 5% HZSM-5 10% HZSM-5 20% HZSM-5
column (mm) column (mm) column (mm) column (mm)
products 180 360 540 540 180 540 180
liquid hydrocarbon phase 26.40 25.42 21.32 22.12 38.05 25.57 32.88
n-alkenes 8.52 8.95 7.94 8.05 6.59 6.42 0.34
n-alkanes 11.06 10.03 8.23 7.08 14.23 6.41 1.38
aromatics 0.56 0.79 0.68 1.00 3.64 2.22 16.05
others 6.25 5.66 4.48 5.99 13.59 10.52 15.11
C5-C11 hyrocarbons 16.59 17.93 19.45 21.62 31.19 24.43 32.59
aqueous phase 2.47 3.35 3.74 5.46 4.58 5.88 5.01
acid phase 24.03 12.78 7.08 3.12 19.41 4.07 8.36
gas 26.21 25.50 24.20 26.90 24.44 26.22 50.32
coke-residual oil 20.89 32.95 43.66 42.40 13.51 38.26 3.44
conversion 79.11 67.05 56.34 57.60 86.49 61.74 96.56

Table 5. Compositions of the Liquid Hydrocarbon

waste oil, which has a fatty acid composition similar to Products at 400 °C (wt %)
that of sunflower oil.
1% HZSM-5 5% HZSM-5 10% HZSM-5
The present study was, therefore, undertaken in order column (mm) column (mm) column (mm)
to investigate the conversion of used sunflower oil with carbon no. 180 360 540 540 180 540
HZSM-5 catalyst by using a special fractionating py-
C5 11.73 9.57 9.36 1.94 19.48 14.90
rolysis reactor and the effects of process parameters, i.e., C6 14.39 16.58 20.55 16.78 21.28 25.86
temperature, catalyst content, and fractionating column C7 16.09 21.26 24.30 29.17 20.79 28.26
length, on the nature and yield of the products obtained. C8 13.36 19.09 20.67 24.41 12.69 17.79
C9 7.08 12.09 14.05 14.93 4.54 6.67
C10 4.58 7.25 6.55 7.93 4.63 3.65
Experimental Section C11 5.01 5.52 2.86 2.30 2.70 1.42
C12 2.57 2.37 0.86 1.22 3.04 0.36
Materials. The oil which was used twice for frying of C13 3.59 2.01 0.42 0.45 1.65 0.17
C14 3.05 1.09 0.19 0.31 1.45 0.18
vegetables, obtained from the campus cafeteria, was filtered C15-C17 18.55 3.17 0.19 0.56 7.74 0.74
to remove pieces of food and used directly without any special ∑n-alkenes 31.13 33.90 34.85 21.69 14.97 14.76
purification. The fatty acid composition and the main char- ∑n-alkanes 43.21 41.33 40.14 40.62 42.52 27.49
acteristics of used oil are shown in Table 1. HZSM-5 catalyst ∑aromatics 2.33 2.70 2.99 5.73 6.25 8.32
∑isomers 23.03 22.07 22.02 31.96 36.25 49.43
was synthesized following the procedure described elsewhere.21
The X-ray powder diffraction pattern confirmed that the zeolite
synthesized was highly crystalline HZSM-5. The surface area Liquid product was separated in a separatory funnel into
of the catalyst was determined to be 338 m2 g-1 using BET aqueous and organic phases. The organic phase consisted of
analysis. HZSM-5 catalyst was found to consist of 1.32% Al, hydrocarbons and carboxylic acids. Using the acid value of
0.79% Na, and 40.90% Si by inductively coupled plasma (ICP) the organic phase, as determined by base titration, a corre-
analysis. The catalyst powder was dried overnight at 110 °C sponding amount of base was added to the organic phase to
and under atmospheric pressure in air before being used in separate it into a liquid hydrocarbon and an acid phase, the
the experiments. Other reagents were of analytical grade latter being converted to methyl esters by using the BF3-
(Merck, Darmstadt, Germany). methanol esterification procedure.22 The aqueous phase was
Experimental Setup and Procedure. The pyrolysis discarded.
reactor (#316 SS tubing, 210 mm long, 75 mm i.d.) was Analysis. The analyses of the liquid hydrocarbon and acid
equipped with thermocouples, an inert gas connection, and a phases were carried out quantitatively by using Ultra 1 (25
fractionating packed column (#316 SS tubing, 45 mm i.d., m, 0.32 mm, 0.52 µm film thickness of 100% dimethyl poly-
packed with ceramic rings having 7 mm i.d., length of 180, siloxane) and Ultra 2 (25 m, 0.32 mm, 0.52 µm film thickness
360, or 540 mm). The reactor was heated using a tubular of 5% diphenyl and 95% dimethyl polysiloxane) capillary
furnace (220 mm long, 78 mm i.d.). columns with a Hewlett-Packard gas chromatograph (5890
For the batch cracking experiments, the reactor was loaded Series II) fitted with a flame ionization detector (Waldron,
with 100 g of oil. Then HZSM-5 catalyst (1%, 5%, 10%, or 20% Germany). The average molecular weight of component fatty
based on the weight of oil) was added to the oil, and the acids was calculated, and the weight of the acid phase was
mixture was stirred to disperse the catalyst in oil. After the determined.
air was purged with N2, the mixture was heated to the reaction Standard mixtures of n- and i-alkanes (C5-C8) and aromatic
temperature with a heating rate of 40 °C/min. Temperature hydrocarbons (benzene, toluene, and xylene) were used to
was kept constant until the end of the experiments. calculate the response factors. The response factors of the
The gaseous and liquid reaction products leaving the alkanes changed between 0.98 and 1.22 and were slightly
fractionating column were collected separately. The liquid higher than those of the aromatic hydrocarbons (0.90-0.93).
product was collected in two glass traps cooled with an ice- Since the response factors varied in a rather narrow range
salt mixture and ice, respectively. The gaseous products were and since there were several unidentified peaks in the chro-
trapped over a saturated solution of NaCl in a gas holder. The matograms, the area percents were considered as weight
reaction time was kept at 3 h. At the end of the experiments, percents (wt %) for the components of the liquid products.
the reactor was left to cool at ambient temperature. The The gas product was further analyzed by using a packed
amounts of the collected liquid, gas, and residual oil-coke were column (Chromosorb-102, 2 m, 1/8 in., 2.2 mm, 80/100 mesh)
measured. The conversion was calculated from the difference with a gas chromatograph equipped with a thermal conductiv-
between the weights of the feed and that of coke and residual ity detector.
oil. The conditions of the gas chromatographic analyses and
sample choromatograms for gaseous and liquid products are
(21) Altun, M. Control of Si/Al Ratio, Crystal Size and Morphology presented in Table 2 and Figures 1 and 2, respectively.
in ZSM-5 Synthesis, M.S. Thesis, Istanbul Tecnical University, Istan-
bul, 1993. (22) AOCS Official Method Ce 2-66, Rev. 1969, reappeared 1973.
Catalytic Conversion of Used Oil Energy & Fuels, Vol. 12, No. 6, 1998 1151

Table 6. Compositions of the Liquid Hydrocarbon Products at 420 °C (wt %)

1% HZSM-5 5% HZSM-5 10% HZSM-5 20% HZSM-5
column (mm) column (mm) column (mm) column (mm)
carbon no. 180 360 540 540 180 540 180
C5 10.63 6.77 10.35 9.05 18.69 20.71 42.57
C6 13.76 15.64 17.36 20.81 22.99 27.16 13.23
C7 14.98 18.37 20.91 26.28 21.43 28.28 17.88
C8 11.77 13.58 17.14 21.67 6.80 12.49 16.92a
C9 4.82 6.11 12.60 12.56 4.19 4.02 7.18
C10 3.35 5.16 7.54 5.03 4.54 3.30 1.33
C11 3.52 4.90 5.33 2.36 3.30 1.65 0.44
C12 2.45 2.81 2.83 1.14 3.40 1.15 0.44
C13 2.95 4.89 2.11 0.51 1.99 0.45
C14 5.50 2.69 1.40 0.30 1.77 0.34
C15-C17 25.59 18.06 2.43 0.29 9.90 0.48
∑n-alkenes 32.29 35.19 37.23 36.40 17.33 25.11 1.02
∑n-alkanes 41.90 39.46 38.60 32.00 37.39 25.07 4.20
∑aromatics 2.13 3.10 3.17 4.54 9.57 8.67 45.97
∑isomers 23.68 22.25 21.00 27.06 35.72 41.15 48.81
a 4.47% Ethyl benzene and 12.45% o,m,p-xylenes.

Results and Discussion The distributions of the hydrocarbons in the liquid

As expected, the pyrolysis products of used oil con-
sisted of gaseous and liquid hydrocarbons, carboxylic
acids, CO, CO2, H2, water, and coke. Although no
information has been published on the mechanism of
the conversion of the used vegetable oils to hydrocar-
bons, the reaction pathways previously suggested17-19
for the conversion of triacylglycerol molecules on zeolite
catalysts are expected to be valid in this case too.
Initially, cracking and deoxygenation may take place
at the external surface of HZSM-5; then the heavy liquid
hydrocarbons produced and the remaining oxygenates
may undergo secondary cracking and deoxygenation
reactions to produce light alkenes, alkanes, water, CO,
and CO2 in the pores of HZSM-5 catalyst. Oligomer-
ization of the alkenes may produce a mixture of C2-
C10 alkanes and alkenes, some of which may be con-
verted to hydrocarbon gases and the remaining to
aromatic hydrocarbons by cyclization, H-transfer, and
isomerization reactions that occur via carbonium ion
mechanisms. Additionally, coke is formed from the
polymerization of some aromatic hydrocarbons.
The conversions of used oil and the overall product
distributions obtained from the reactions conducted with
different amounts of HZSM-5 (1%, 5%, 10%, and 20%
based on oil weight) at 400 and 420 °C by using a
fractionating pyrolysis reactor equipped with a packed
column of three different lengths (180, 360, and 540
mm) are shown in Tables 3 and 4, respectively. Reac-
tion temperature, packed column length, and catalyst
content were all found to have significant effects on the
conversion and product distribution obtained from the
oil. As seen from the tables, conversion was observed
to increase significanly with the increase in the reaction
temperature and catalyst content whereas it decreased
with an increase in the column length. At 420 °C, with
20% HZSM-5 addition and a 180 mm column length,
nearly complete conversion (96 wt %) was observed. An
increase in reaction temperature increased the amount
of liquid hydrocarbon and gaseous products and de-
creased the coke-residual oil yield. On the other hand,
the major effects of increasing the column length were
to increase the coke-residual oil yield and decrease the
yields of acid and liquid hydrocarbon phases.
products are presented in Tables 5 and 6. As can be
seen from the tables, the liquid product consisted mainly
of alkanes, alkenes, and their isomers. It was very poor
in aromatics (about 2-10 wt %) when 1%, 5%, and 10%
of the catalyst was used in the reactions. This is
contrary to the other results in the literature but can
be explained by the fractionating batch reactor config-
uration used in our study. Prasad and co-workers 18
observed that the pyrolysis oil produced by the catalytic
conversion of canola oil on HZSM-5 in a continuous
fixed-bed reactor contained 60-70 wt % of aromatic
hydrocarbons. A significant aromatic hydrocarbon con-
tent of the liquid product (46 wt %) was obtained only
with the addition of 20% HZSM-5 at 420 °C in our
fractionating pyrolysis reactor.
The content of the hydrocarbons that have 5-11
carbon atoms, which are in the gasoline boiling range,
also increased parallel to the increase in the catalyst
content and reaction temperature. The liquid products
mainly consisted of C5-C9 hydrocarbons in all cases.
The effect of the column length on the composition of
the liquid hydrocarbon phase was less pronounced at
lower catalyst contents. At a relatively high catalyst
content of 10%, the increase in the content of isomers
in addition to the decrease in the content of n-alkanes
became significant, parallel to the increase in column
length. At 420 °C, the total content of n-alkenes was
also seen to increase significantly with increasing
column length.
The gaseous product consisted of H2, CO, and CO2 in
addition to saturated and unsaturated hydrocarbons
consisting mostly of those in the C1-C3 range (Tables
7 and 8). Changes in the reaction conditions are also
seen to affect the composition of the gaseous product to
some extent. The most striking change was the increase
in the alkenes/alkanes ratio of the gases with 20%
catalyst addition at 420 °C.
From the product distribution, it can be concluded
that the relative importance of the thermal reactions
with respect to the catalytic reactions is higher in the
fractionating reactor used in this study than in the
fixed-bed reactors used previously.18-20 This is espe-
cially true when longer column lengths are employed.
In other words, secondary thermal reactions take place
1152 Energy & Fuels, Vol. 12, No. 6, 1998 Dandik et al.

Table 7. Compositions of Gaseous Products at 400 °C recent requirements imposed on fuels are considered.23
(Area %) It seems possible to choose appropriate values for
1% HZSM-5 5% HZSM-5 10% HZSM-5 column length, temperature, and catalyst content to
carbon column (mm) column (mm) column (mm) optimize the yield and composition of the products by
no. 180 360 540 540 180 540 monitoring the relative importance of the catalytic and
H2 18.10 23.27 32.11 20.18 18.33 16.82 thermal reactions taking place in the system. Further
CO 8.05 6.26 6.93 6.90 6.41 7.12 processing requirements for these liquid products to be
CO2 9.22 8.00 7.15 5.85 8.99 5.65 used as high-octane fuels may be decreased in this
C1 10.85 10.07 7.30 8.21 13.80 9.09
C2d 10.11 7.56 3.44 5.19 6.96 6.58
manner.
C2 9.74 10.50 7.46 8.76 9.84 10.50
C3d 6.65 8.58 9.45 12.08 8.70 9.43 Conclusions
C3 9.88 5.24 5.43 12.59 12.82 11.88
C4d 3.96 3.99 3.51 3.25 2.95 4.92 Used oil could be converted to liquid products con-
C4 6.44 7.30 7.11 8.54 6.05 9.65 taining gasoline-range hydrocarbons. The highest con-
C5d 2.42 2.60 1.73 1.24 1.43 1.29
version (96.6%) of used oil and the maximum liquid
C5 3.21 4.61 6.29 5.84 2.85 6.04
C6+d 1.27 2.01 2.09 1.37 0.87 1.03 hydrocarbon yield (33%) were obtained at the highest
∑alkenes 23.14 22.73 18.13 21.76 20.04 22.22 temperature (420 °C), highest catalyst content (20%),
∑alkanes 41.49 39.74 35.68 45.31 46.23 48.19 and the lowest column length (180 mm) employed. The
aromatic contents of the liquid hydrocarbon product
Table 8. Compositions of Gaseous Products at 420 °C
(Area %) was, in general, lower than those obtained using fixed-
bed reactors. Using the fractionating column causes,
1% HZSM-5 5% HZSM-5 10% HZSM-5 20% HZSM-5
column (mm) column (mm) column (mm) column (mm) in addition to the catalytic reactions on HZSM-5,
carbon
no. 180 360 540 540 180 540 180 additional thermal reactions to occur in the liquid and
H2 19.52 20.18 22.44 19.96 13.88 16.70 8.42
vapor phases. Thermal effects became more pronounced
CO 5.82 6.61 5.97 6.79 11.68 7.28 11.68 with increasing column length. Isomeric hydrocarbon
CO2 6.67 5.59 4.97 4.77 4.32 4.11 1.51 content of the liquid hydrocarbon product increased with
C1 12.34 12.76 14.47 14.80 14.15 17.12 4.48 the increase in column length while the n-alkane
C2d 8.97 8.53 8.72 9.70 6.96 10.57 12.95
C2 12.87 12.83 11.74 11.07 11.64 16.11 3.71 content decreased. At 420 °C, n-alkene content in-
C3d 8.39 9.77 9.93 5.12 9.98 5.86 23.36 creased significantly with increasing column length.
C3 6.43 4.27 3.19 11.59 11.54 4.89 9.37 It seems possible to employ the length of the frac-
C4d 3.94 3.87 4.32 3.48 4.16 3.79 10.51
C4 6.85 6.77 5.93 5.53 6.31 6.17 6.95
tionating column as an additional variable, in addition
C5d 2.05 2.86 3.11 1.86 1.49 1.57 3.49 to the temperature and catalyst amount, to optimize the
C5 4.17 4.04 3.79 3.60 2.98 3.94 2.55 aromatic, paraffinic, and olefinic hydrocarbon contents
C6+d 1.98 1.92 1.74 1.73 0.92 1.89 1.02 of the liquid product in order to be used as high-octane
∑alkenes 23.35 25.03 26.08 20.16 22.58 21.79 50.30
∑alkanes 44.64 42.59 40.54 48.32 47.53 50.12 28.08 fuels of acceptable composition.

in the fractionator in this type of reactor, one obvious Acknowledgment. The authors are grateful to the
consequence of which is the increased coke yields. Istanbul Technical University Research Fund for finan-
Although the total conversion and total liquid hydro- cial support.
carbon yields are influenced adversely by these reac- EF980012U
tions, the lower aromatic and higher isomeric hydro-
carbon contents of the liquid are advantages when the (23) EFOA Newsletter, 1995, 13, 3.