Energy & Fuels 1999, 13, 907-913 907

Co-Pyrolysis of Coals and Lube Oil Wastes in a

Bench-Scale Unit
M. J. Lázaro, R. Moliner,* and I. Suelves
Departamento de Energı́a y Medio Ambiente, Instituto de Carboquı́mica, (Consejo Superior de
Investigaciones Cientı́ficas), Maria de Luna, 12. 50015 Zaragoza, Spain

Received December 21, 1998

The co-pyrolysis of a lube oil waste (LOW) and two coals has been carried out. The main objective
of this study is mainly to compare product yields from co-pyrolysis with those obtained in the
pyrolysis of coal and LOW alone. The influence of temperature, pressure, and coal nature on the
yields obtained has been studied. The work has been carried out at bench scale using mixtures
of coal and LOW in a mass ratio of 50/50. Three temperatures, 600, 650, and 700 °C and three
pressures 0.1, 0.5, and 1 MPa have been studied. Two coals largely differing in rank have been
used in order to state the influence of coal nature. Occurrence of synergetic effects on some
products has been observed which confirms that co-pyrolysis of LOW and coal as a mixture
enhances the transfer of coal hydrogen to valuable petrochemical products that otherwise would
be transferred to molecular hydrogen if coal was pyrolyzed alone. Comparing the theoretical values
with the experimental ones, there is a synergy in the hydrogen transferred to CH4 and light
alkanes, ethylene, and propylene that increases as temperature increases and the H2 transferred
to >C4 compounds does not reveal synergy. However, for the hydrogen transferred to BTX, the
theoretical values remain similar to the experimental ones. The synergy in the hydrogen
transferred to CH4 and light alkanes increases, with pressure, and also the H2 transferred to
BTX. However, pressure does favor the synergy in the hydrogen transferred to BTX. The same
considerations apply to both coal/oil mixtures, but the effect observed for the Figaredo coal (the
highest rank one)/LOW are lower than for the Samca coal/LOW.

Introduction of these products are limited because of the low hydrogen-

The co-utilization of coal and waste materials is
nowadays a very powerful technology employed as a way
of eliminating waste materials and producing at the
same time valuable products for industry. There are
many works in the literature1-8 related to the co-
pyrolysis (inert atmosphere and no catalyst) of coal and
materials of a hydrocarbon nature such as tires, plastic,
and other wastes, whose aim is to enrich two materials
of low value.
Pyrolysis of coal is a good method for producing
chemicals such as BTX and light olefins, but the yields
* Author to whom correspondence should be addressed. E-mail:
rmoliner@carbon.icb.csic.es.
(1) Williams, P. T.; Taylor, D. T. Fuel 1993, 75 (11), 1469-1474.
(2) Fontana, A.; Braekman-Danheux, C.; Laurent, P. Coal Science
and Technology 24; Pajares, J. A., Tascón, J. M. D., Eds.; Elsevier:
New York 1995; pp 1089-1092.
(3) Laurent, P.; Braekman-Danheux, C.; Fontana, A.; Lecharlier,
M. ICCS 97, Vol. II. Ziegler, A., van Heek, K. H., Klein, J., Wanzl, W.,
Eds.; Essen: Germany, 1997; pp 837-840.
(4) Hayashi, J.; Mizuta, H.; Kusakabe, K.; Morooka, S. Energy Fuels
1994, 8, 1353-1359.
(5) Blankenship, M.; Hippo, E. J.; Palmer, S. R.; Tandon, D.;
Payyavula, S.; Cloyd, S. XI International Coal Conference, Pittsburgh,
PA; Chiang, S.-H., Ed.; University of Pittsburgh: Pittsburgh, PA, 1994;
pp 717-721.
(6) Palmer, S. R.; Hippo, E. J.; Tandon, D.; Blankenship, M. Coal
Science and Technology 24; Pajares, J. A., Tascón, J. M. D., Eds.;
Elsevier: New York, 1995; pp 29-33.
(7) Moliner, R.; Suelves, I.; Lázaro, M. J. Energy Fuels 1998, 12,
963-968.
(8) Suelves, I.; Moliner, R.; Lázaro, M. J. 217th ACS Symp. Fuel Div.,
Anaheim, CA, March 21-25, 1999.
to-carbon ratio in coal.9,10 For this reason, it is necessary
to supply H2 from other sources in order to improve the
coal behavior.
In previous works 11,12 we have shown that lube oil
wastes (LOW) can be valorized by pyrolysis: By pyro-
lyzing LOW, many interesting compounds, especially
light olefins and BTX, are obtained. However, the
correct functioning of a LOW pyrolysis installation could
be limited in most cases by supply problems. This fact
would result in a small size plant below the critical size
needed for an economical explotation. By co-pyrolysis
of coal and LOW the problems related to supply would
be avoided and at the same time a benefit from the use
of coal would be achieved. Besides this, the use of LOW
presents an advantage versus solid hydrocarbonaceous
materials because the mixture can be fed to the reactor
as a fluid. A more detailed study of this ability will be
shown in a forthcoming paper.
For that reason, in the present paper, the co-pyrolysis
of two coals, differing in rank, and LOW under different
temperatures and pressures has been studied. The main
(9) Miura, K.; Mae, K.; Asaoka, S.; Hashimoto, K. Energy Fuels 1991,
5, 340-346.
(10) Miura, K.; Mae, K.; Yoshimura, T.; Masuda, K.; Hashimoto, K.
Energy Fuels 1991, 5, 803-808.
(11) Moliner, R.; Lázaro, M.; Suelves, I. Energy Fuels 1997, 11,
1165-1170.
(12) Moliner, R.; Suelves, I.; Valderrama, J. V Congreso Interna-
cional de Quı́mica de la ANQUE, Tenerife, Islas Canarias, Spain,
December 9-11, 1998.

10.1021/ef980271j CCC: $18.00 © 1999 American Chemical Society

Published on Web 06/04/1999
908 Energy & Fuels, Vol. 13, No. 4, 1999
objectives of these studies are to compare the product
yields obtained from co-pyrolysis in order to state the
occurrence of interactions between coal and LOW lead-
ing to a synergetic effect for the production of light
olefins C1-C4 and BTX and to study the influence of
variables such as temperature, pressure, and coal
nature on the intensity of these effects. To allow working
with slurries that can be easily fed into the reactor
ensuring that a benefit is obtained from the use of both
coal and LOW, 50/50 mixtures of both materials have
been used.
Experimental Section
Coal/Lube Oil Waste Samples. Two coals, Samca and
Figaredo, and a LOW have been used in this work. Samca is
a sub-bituminous coal, with a high volatile content, and
Figaredo is a low-volatile bituminous coal. The LOW sample
was taken from the homogenization tank of a waste managing
company (Melquiza Ltd.) containing the waste oils recovered
in the metropolitan area of Zaragoza (a medium size city of
Spain) for one month. The main characteristics of these
materials have been described in previous works.7,11 The coals
and the LOW were pyrolyzed separately and then as a mixture
with a mass ratio (coal/LOW) of 50/50. The mixtures were fed
as a slurry to the pyrolysis reactor.
Bench-Scale Pyrolysis Unit (BPU). The bench-scale
pyrolysis unit has been shown in a previous paper.11 Briefly,
the pyrolysis reactor is heated by an electrical oven split into
two steps. The lower one is set at the pyrolysis temperature
and is filled with ceramic rings. The sample is fed from the
upper part and it falls by gravity. In this way, the coal and
LOW particles find a mass that is at the reaction temperature,
simulating the impact produced between the feeding and the
bed particles in a fluidized bed.
A detailed study of the available commercial devices to feed
a slurry was carried out. The following specifications had to
be matched: (a) low and constant flow of feeding <0.5 g min-1,
(b) pressure up to 1 MPa, (c) no presence of valves because it
favors releasing of coal from the slurry, and (d) slurry heating
at a temperature higher than 40 °C. None of the commercial
devices tried showed a good performance with these mixtures,
so a homemade device was built. It consists of a heated (55
°C) and stirred vessel that is overpressurized in relation to
the reactor. The feed is forced to flow through the feeding pipe
toward the top of the reactor. This device also allows regulation
of the feeding flow by controlling the overpressure in the
vessel. This feeding system has proved to be very efficient for
pumping LOW/coal mixtures and it presents some advantages
versus the conventional pumping systems. First, troubleshoot-
ing derived from the blocking of moving parts, especially
valves, is avoided; second, a large rank of flows and pressures
can be regulated with the differential pressure controller as
the unique control element.
Two sets of runs have been carried out. In the first run,
temperature was varied keeping pressure at 0.1 MPa. In the
second run, pressure was varied keeping the temperature at
650 °C. Three temperatures (600, 650, and 700 °C) and three
pressures (0.1, 0.5, and 1 MPa) were tried.
Coal and LOW were mixed up in a ratio of 1 to 1. The slurry
was fed at a rate of approximately 30 g h-1 during 20 min.
The actual mass of coal/oil mixture fed into the reactor was
evaluated by ascertaining the weight loss of the feeding vessel
after the run.
Reaction products leave the reactor through the bottom. The
reactor is continuously swept by a nitrogen flow in order to
accelerate the release of the pyrolysis products from the
reactor. These are cooled in a heat exchanger cooled by Peltier
effect. Liquids are subsequently collected in a cyclone and
Lázaro et al.
gases are collected in a gas bag whose volume is measured
after each run.
Analytical Methods. The ponderal yields of char and
liquids were determined by direct weight whereas gas global-
yields were calculated from the sum of the individual yields
of each of the components obtained by gas/chromatography.
A run was considered as a valid run if the ponderal yield sum
of all recovered products was higher than 95%. Each figure
shown in the tables is the average of the results obtained from
two valid runs. Global results in tables were normalized to
100% in order to facilitate comparison between runs.
Gases were analyzed by gas chromatography using three
separate analytical methods: a packed column of Molecu-
larsieve 13X with nitrogen as carrier gas and TCD detection
for hydrogen; two packed columns: Molecularsieve 13X and
Porapak with helium as carrier and TCD detection for
permanent gases; an alumina capillar column with helium as
a carrier and FID detection for C1-C6 hydrocarbons. Hydro-
carbons chromatographed between n-pentane and n-hexane
were accounted for together as C5. In the same way, com-
pounds chromatographed between n-hexane and benzene were
accounted for as C6. Quantification of gas components was
carried out by means of standard gas mixtures.
Liquids were formed by the organic phase (tar) and water.
The separation of tar and water was very difficult, therefore
they were weighed all together. Liquids were analyzed by GC/
MS. All compounds present in the liquids were identified by
using a computerized library of mass spectra. Tri- and tetra-
methylbenzenes were accounted for as “alkyl-benzene”. All of
the compounds chromatographed between naphthalene and
phenanthrene were accounted for as “2-3 rings” and those
chromatographied after phenanthrene as “>3 rings”. Quanti-
tative composition of the liquids was determined by the
internal standard method using octane as the internal stand-
ard. Standard solutions of the compounds to be analyzed were
used for calibration.
Quantitative analyses with an internal standard show that
an important part of the collected tar is composed of com-
pounds that are not eluted in the chromatography conditions
used. The heavy fraction, not eluted by chromatography, varies
from a 30% in the oil tars to a 50% in the coal/LOW mixtures.
Results and Discussion
Evolution of the Pyrolysis Yields with the Tem-
perature (P ) 0,1 MPa). The runs at different tem-
peratures were carried out only at one pressure in order
to decrease the number of runs.
Pyrolysis of Figaredo and Samca coal. Table 1 shows
the yields obtained in the pyrolysis of both coals at the
three temperatures. The liquid yields correspond to tar
and pyrolysis water.
For the Samca coal, char yield does not significantly
vary with temperature whereas liquid yield decreases
and gas yield increases by increasing the temperature.
The pyrolysis gases are mainly formed by CO, CO2, CH4,
C2H6, and H2S with a few parts of olefinic compounds.
The char yield obtained in the pyrolysis of the Figaredo
coal is very high, even at high temperatures. This leads
to very small liquid and gas yields. Methane is the main
element of the fraction C1-C6 gases. The effect of
increasing temperature is also important for Figaredo
coal, due to its enhancing the formation of H2, CO, CO2,
methane, and ethane.
Table 2 shows the liquids obtained at different tem-
peratures. For the Samca coal, benzene yield signifi-
cantly increases as temperature increases up to 700 °C,
whereas the increase of the toluene yield is less impor-
Co-Pyrolysis of Coals and Lube Oil Wastes in a Bench-Scale Unit Energy & Fuels, Vol. 13, No. 4, 1999 909

Table 1. Yields (wt %) Obtained in the Pyrolysis of Table 3. Comparison of Experimental and Theoretical
Samca and Figaredo Coalsa Yields Obtained in the Pyrolysis of Samca Coal/LOW
Mixturea
Samca Figaredo
600 650 700
T (°C) 600 650 700 600 650 700
T (°C) theor expt theor expt theor expt
char 70.0 70.0 69.8 90.6 87.3 84.5
liquidsb 17.0 15.6 14.4 4.4 5.8 7.2 char 37.5 48.2 37.2 43.6 37.9 35.4
gases 13.0 14.4 15.8 5.0 6.9 8.3 liquidsb 38.7 28.9 25.6 24.3 25.2 24.9
H2 0.1 0.2 0.9 0.3 0.4 0.7 gases 23.8 22.5 37.0 32.1 37.7 39.7
CO 1.4 1.8 2.9 0.3 0.5 0.9 H2 0.1 0.2 0.2 0.3 0.5 0.4
CO2 5.9 5.5 7.8 1.0 1.2 1.4 CO 0.8 0.5 1.3 1.3 1.6 1.4
H2S 1.6 1.8 0.4 CO2 3.1 1.7 3.3 3.9 4.3 3.7
CH4 1.1 1.2 1.1 2.8 3.6 4.0 H2S 0.9 0.6 1.1 0.4 0.4 1.1
C2H6 0.6 0.7 0.4 0.4 0.5 0.6 CH4 2.3 2.7 5.0 6.1 5.2 6.9
C2H4 1.1 0.1 0.2 0.1 0.1 0.1 C2H6 1.6 2.7 2.9 3.8 2.6 4.4
C3H8 0.3 0.3 0.1 0.1 0.1 0.1 C2H4 3.0 3.2 4.8 4.8 5.0 7.1
C3H6 0.3 0.5 0.7 0.1 C3H8 0.7 0.7 0.9 0.8 0.6 0.8
I-butane C3H6 2.8 3.0 5.4 4.8 5.6 5.6
N-butane 0.1 0.1 I-butane 0.1 0.1 0.1 0.1 0.1
1-butene 0.1 0.1 N-butane 0.1 0.1 0.1
I-butene 0.2 0.3 0.3 0.1 1-butene 0.3 0.1 0.5 0.2 0.4 0.2
C-butene 0.1 0.1 0.1 0.1 I-butene 2.0 0.6 2.1 0.6 2.3 0.6
T-butene 0.1 C-butene 1.1 0.7 1.7 1.2 1.7 1.2
I-pentane T-butene 0.2 0.5 0.4 0.8 0.3 0.8
1,3-butadiene 0.1 0.2 I-pentane
C5 0.4 0.1 0.1 1,3-butadiene 0.6 0.5 1.3 0.7 1.8 1.2
C6 0.4 1.5 0.4 0.1 0.1 0.1 C5 0.2 0.2 0.2 1.2 0.3 0.1
C6 3.6 2.9 5.3 2.1 5.2 2.4
aBasis: 100 g of Feeding. b Water yield included (10%).
a Basis: 100 g of feeding. b Water yield included (5%).
Table 2. Yields (wt %) Obtained in the Pyrolysis of
Samca and Figaredo Coalsa
pyrolysis of the coal alone. The increase of the gas yield
Samca Figaredo as temperature increases is due mainly to methane,
T (°C) 600 650 700 600 650 700 ethylene, and propylene. The increase observed for
benzene 0.2 0.5 1.6 0.1 0.1 0.2 ethylene and propylene as the temperature increases
toluene 0.4 0.5 0.5 0.2 0.3 0.3 is of special interest, considering the high petrochemical
xylene value of these compounds. On a molar basis, the
alk-benzene increase of temperature leads to a higher production of
naphthalene 0.2 0.1 0.1
phenols 2.0 1.2 1.3 the smallest molecules to the detriment of the biggest
2-3 rings 0.5 0.4 0.4 ones.
a Basis: 100 g of feeding.
Higher temperatures enhance retrogressive reactions,
probably by cleavage of larger saturated chains that
tant. Phenols yields decrease as temperature increases increases the yields of small gas compounds such as
from 600 to 650 °C. However, it remain constant from light olefins. This trend was also observed 7,8 when
650 to 700 °C. The rest of the products does not vary petroleum residues/coal mixtures were pyrolyzed at
with temperature, thus the ratio of the rest of the analytical and bench scale.
products to BTX decreases as temperature increases. From this table it can also be observed that the
Liquids obtained from pyrolysis of the Figaredo coal experimental char yields are higher than the theoretical
were of poor quality, and chromatographic analysis one at 600 and 650 °C and lower at 700 °C. Gas and
could not be carried out. The reported yields for benzene liquid yields are similar to the theoretical yield at 700
and toluene are recovered in the gas phase, and no °C. However, at 600 °C there is a counter-synergetic
important differences are observed with the different effect in liquid yield and at 650 °C in gas yields. The
temperatures. higher synergetic effects are produced with methane,
Co-Pyrolysis of the Samca/LOW mixture. Table 3 ethane, and ethylene, while there are some counter-
shows the comparison between the yields obtained in synergetic effects in C4 and C6. The synergy observed
the co-pyrolysis of coal and oil mixtures (experimental for the ethylene at 600 and 700 °C and propylene at
yields) and the theoretical yields obtained by the addi- 600 °C is interesting, considering the high petrochemical
tion of yields of both products when they were pyrolyzed value of these compounds.
separately. Table 4 shows the comparison of the experimental and
Concerning the variation of experimental yields with theoretical yields for the liquid compounds obtained
temperature it can be shown that as the temperature from the pyrolysis of Samca coal/oil mixtures. In gen-
increases, char and liquid experimental yields decrease eral, the experimental BTX yields are slightly lower
and simultaneously, the experimental gases yield in- than the theoretical values. Only for heavy (>3 rings)
creases. This trend was observed in the pyrolysis of the aromatic compounds the experimental yields are higher
oil alone11 as well. However, in this case the variation than the theoretical ones. This trend is observed for the
is smaller and even the liquids yield almost remains three temperatures tested.
constant from 650 to 700 °C. Co-Pyrolysis of the Figaredo/LOW mixtures. Table 5
Experimental yields of some interesting gas com- shows the experimental yields obtained in the co-
pounds, such as ethylene and propylene are very high pyrolysis of the sample Figaredo/LOW at different
even at the lowest temperatures tested compared to the temperatures and the comparison with the theoretical
910 Energy & Fuels, Vol. 13, No. 4, 1999 Lázaro et al.

Table 4. Comparison of Experimental and Theoretical Table 6. Comparison of Experimental and Theoretical
Yields Obtained in the Pyrolysis of the Samca Coal/LOW Yields Obtained in the Pyrolysis of the Coal Figaredo/
Mixturea LOW Mixturea
600 650 700 600 650 700
T (°C) theor expt theor expt theor expt T (°C) theor expt theor expt theor expt
benzene 2.1 2.7 3.0 2.8 5.5 4.8 benzene 2.0 1.8 2.8 2.4 2.5 1.9
toluene 3.3 3.1 3.4 3.7 3.9 3.0 toluene 3.2 2.6 3.1 3.9 3.5 2.4
xylene 2.6 1.9 1.4 1.5 1.3 1.3 xylene 2.3 1.3 1.4 2.0 1.3 1.1
alk-benzene 4.0 3.9 3.3 3.1 3.6 3.8 alk-benzene 4.0 6.9 3.3 3.9 3.5 3.0
naphthalene 0.4 1.0 1.8 0.1 naphthalene 0.3 0.5 0.9 0.9 1.7 1.3
phenols 1.0 0.6 0.6 0.2 phenols
2-3 rings 1.6 0.4 2.8 1.3 1.0 1.4 2-3 rings 1.4 1.1 2.6 1.2 0.8 1.3
>3 rings 1.1 0.1 1.9 0.1 1.0 >3 rings 0.1 0.1 0.1 0.1 0.1
a Basis: 100 g of feeding. a Basis: 100 g of feeding.

Table 5. Comparison of Experimental and Theoretical Table 7. Yields (wt %) Obtained in the Pyrolysis of
Yields Obtained in the Pyrolysis of Figaredo Coal/LOW Samca and Figaredo Coal (T ) 650 °C)a
Mixturea
Samca Figaredo
600 650 700
P (MPa) 0.1 0.5 1 0.1 0.5 1
T (°C) theor expt theor expt theor expt
char 70.0 68.7 67.0 87.3 84.0 87.2
char 47.8 48.7 45.9 43.7 45.2 49.9 liquids 15.6 15.5 14.1 5.8 5.9 4.6
liquids 32.4 32.7 20.7 21.6 21.6 21.7 gases 14.4 15.8 18.9 6.9 10.1 8.1
gases 19.8 18.6 33.3 34.5 34.0 28.3 H2 0.2 0.5 0.4 0.4 0.6 0.5
H2 0.2 0.1 0.4 0.3 0.5 0.3 CO 1.8 1.4 2.4 0.5 0.7 0.6
CO 0.3 0.2 0.5 0.4 0.6 0.2 CO2 5.5 4.3 10.7 1.2 1.8 1.4
CO2 0.7 0.5 1.0 0.8 0.7 0.4 H2S 1.8 1.1 1.4
H2S 0.1 0.1 0.1 0.1 0.2 CH4 1.2 3.7 2.8 3.6 5.8 4.8
CH4 3.1 2.4 6.6 5.7 6.9 7.1 C2H6 0.7 1.6 0.4 0.5 0.9 0.6
C2H6 1.5 1.8 2.9 3.4 2.7 4.0 C2H4 0.1 1.0 0.3 0.1 0.2 0.1
C2H4 2.5 2.4 4.9 5.5 5.2 7.2 C3H8 0.3 0.4 0.1 0.1 0.1 0.1
C3H8 0.6 0.8 0.8 0.8 0.6 0.6 C3H6 0.5 1.0 0.1 0.1 0.1
C3H6 2.7 3.5 5.4 6.8 5.5 4.6 I-butane 0.1
I-butane 0.1 0.1 0.1 0.1 0.1 N-butane 0.1
N-butane 0.1 0.1 0.1 1-butene 0.1
1-Butene 0.3 0.2 0.4 0.4 0.4 0.1 I-butene 0.3 0.1 0.1
I-butene 1.9 2.2 2.1 2.3 2.2 0.4 C-butene 0.1 0.1 0.1
C-butene 1.6 1.3 1.8 1.8 1.7 0.9 T-butene 0.3
T-butene 0.2 0.1 0.3 0.4 0.3 0.3 I-pentane
I-pentane 1,3-butadiene 0.1
1,3-butadiene 0.6 0.7 1.2 1.2 1.8 0.7 C5 0.1
C5 0.2 0.2 0.1 0.2 0.1 C6 1.5 0.3 0.3 0.1
C6 3.3 3.4 4.6 4.0 4.7 1.3 a Basis: 100 g of feeding.
a Basis 100 g of feeding.
values. The char yield shows a minimum at 650 °C. Pyrolysis of Samca and Figaredo Coal. Table 7 shows
Liquid yield decreases as temperature increases from the variation of the yields from the pyrolysis of Samca
600 to 650 °C and does not vary from 650 to 700 °C. and Figaredo coals with pressure (0.1-1 MPa) at a
However, gas yield shows a maximum at 650 °C with a temperature of 650 °C.
slight decreasing at 700 °C. Methane, ethane and For the Samca coal, char yield slightly increases,
ethylene, yields increase until 700 °C, mainly from 600 liquid yield slightly decreases, and gas yield slightly
°C to 650 °C, but the rest of the gas compounds show a increases with pressure. This behavior, invariable al-
maximum at 650 °C. most with pressure, is typical of this kind of coal, which
A counter-synergetic effect can also be observed in gas tends toward cross-linking.13 The creation of cross-
yield at 700 °C that corresponds to the synergism in linking bridges at low temperatures during pyrolysis
char yield. The different gaseous compounds do not obstructs the existence of a plastic phase in which
evolve in the same way. A synergism in ethane and pressure can have an effect in the product yields.14
ethylene and an asynergism in C4-C6 yields is observed There is a maximum for the most part of C1-C4
and especially at 700 °C. compounds at 0.5 MPa, except for CO that shows a
Table 6 shows the yields of some interesting com- minimum at 0.5 MPa. On the other hand C4-C6 com-
pounds in the pyrolysis liquids as a function of temper- pound production is disfavored by increasing pressure.
ature. Benzene, toluene, and xylene experimental yields The pyrolysis of Figaredo coal gives very low yields
show a maximum at 650 °C. Ethylbenzene and alkyl- at the three pressures due to its high rank. There is a
benzene yields decrease and naphthalene yield increases maximum in the gas yield at 0.5 MPa. Gases are formed
as temperature increases. by carbon oxide and hydrocarbons C1-C3 since com-
Results show that there is an asynergetic effect in pounds with molecular weight higher than C3 are not
BTX production at 600 and 700 °C, and a synergism at formed.
650 °C.
Variation of Co-Pyrolysis Yields with Pressure. (13) Ibarra, J. V.; Cervero, Y.; Garcı́a, M.; Moliner, R. Fuel Process.
Technol. 1990, 24, 19-25.
Runs at different pressures were carried out at the same (14) Suuberg, E. M.; Lee, D.; Larsen, J. W. Fuel 1985, 64, 1668-
temperature (650 °C). 1671.
Co-Pyrolysis of Coals and Lube Oil Wastes in a Bench-Scale Unit Energy & Fuels, Vol. 13, No. 4, 1999 911

Table 8. Comparison of Experimental and Theoretical Table 10. Comparison of Experimental and Theoretical
Yields Obtained in the Pyrolysis of Samca/LOW Mixturea Yields in the Pyrolysis of Figaredo Coal/LOW Mixtures
0.1 0.5 1 0.1 0.5 1
P (MPa) theor expt theor expt theor expt P (MPa) theor expt theor expt theor expt
char 37.2 43.6 38.4 42.4 39.8 43.1 char 45.9 43.7 45.7 52.7 49.9 52.2
liquids 25.6 24.3 24.7 26.6 25.7 26.3 liquids 20.7 21.6 20.0 18.8 20.9 18.3
gases 37.0 32.1 36.9 31.0 34.5 30.6 gases 33.3 34.5 34.2 28.5 29.2 29.4
H2 0.3 0.7 0.6 0.6 0.3 0.4 H2 0.3 0.3 0.7 0.5 0.5 0.4
CO 1.2 1.3 1.0 1.2 1.2 0.7 CO 0.5 0.4 0.7 0.7 0.7 0.5
CO2 3.3 3.9 2.6 4.0 4.6 3.5 CO2 1.0 0.8 1.3 1.3 1.2 1.0
H2S 1.1 0.4 0.7 0.5 0.7 0.8 H2S 0.1 0.1 0.2 0.1 0.1
CH4 5.0 6.1 8.9 10.5 9.1 11.0 CH4 6.5 5.7 10.1 11.5 10.1 9.4
C2H6 2.9 3.8 6.2 6.1 6.0 7.0 C2H6 2.9 3.4 6.0 6.4 5.7 5.8
C2H4 4.8 4.4 5.2 2.9 3.3 2.7 C2H4 4.9 5.5 4.7 2.7 2.8 2.5
C3H8 0.9 0.8 1.7 0.7 1.8 1.0 C3H8 0.7 0.8 1.5 0.9 1.6 1.8
C3H6 5.4 4.8 4.9 2.3 3.7 2.2 C3H6 5.4 6.8 4.4 2.1 3.3 3.6
I-butane 0.1 0.1 0.2 0.1 0.2 0.1 I-butane 0.1 0.1 0.2 0.1 0.2 0.3
N-butane 0.1 0.1 0.1 N-butane 0.1 0.1 0.1 0.1 0.2
1-butene 0.4 0.2 0.2 0.1 0.2 0.1 1-butene 0.4 0.4 0.2 0.1 0.2 0.2
I-butene 2.2 0.6 0.6 0.1 0.4 0.1 I-butene 2.0 2.3 0.6 0.2 0.4 0.4
C-butene 1.7 1.2 1.0 0.8 0.5 C-butene 1.8 1.8 1.0 0.5 0.7 0.9
T-butene 0.3 0.8 0.7 1.4 0.6 0.2 T-butene 0.3 0.4 0.7 0.3 0.5 0.6
I-pentane 0.1 I-pentane 0.1
1,3-butadiene 1.2 0.7 0.3 0.2 0.1 1,3-butadiene 1.2 1.2 0.3 0.1 0.2 0.2
C5 0.2 0.1 0.1 0.1 0.1 C5 0.2 0.1 0.1 0.1 0.1 0.3
C6 5.3 2.1 1.5 0.2 1.0 0.2 C6 4.7 4.0 1.4 0.7 0.8 1.0
a Basis: 100 g of feeding. Table 11. Comparison of Experimental and Theoretical
Yields Obtained in the Pyrolysis of the Figaredo Coal/
Table 9. Comparison of Experimental and Theoretical LOW Mixture (T ) 650 °C)
Yields Obtained in the Pyrolysis of Samca Coal/LOW
Mixture (T ) 650 °C) 0.1 0.5 1
0.1 0.5 1 P (MPa) theor expt theor expt theor expt
P (MPa) theor expt theor expt theor expt benzene 1.3 1.7 5.1 3.6 5.8 2.7
toluene 2.5 3.2 5.6 4.5 6.1 2.9
benzene 3.5 2.8 4.1 4.5 7.1 8.2 xylene 1.4 2.0 1.0 1.6 1.0 2.1
toluene 3.3 3.7 3.2 3.2 6.5 5.9 alk-benzene 3.3 3.9 1.6 1.6 1.5 3.5
xylene 1.4 1.5 1.7 2.0 1.0 0.5 naphthalene 0.9 0.9 0.7 1.1 0.3 1.0
alk-benzene 3.3 3.1 1.8 2.6 1.5 0.3 2-3 rings 2.7 1.2 1.6 1.0 1.7 1.8
naphthalene 0.9 1.1 1.0 1.0 0.3 0.3 >3 rings 0.1 0.1 1.8 0.1 1.2 0.2
2-3 rings 2.7 2.1 1.6 2.5 1.7 1.1
>3 rings 0.1 0.2 0.2 0.4 0.3 0.2
could absorb the methyl radicals formed in the pyrolysis.
For both coals, the main part of the liquids produced There is no synergetic effect in the total BTX production.
was water, so that liquids were difficult to collect and Pyrolysis of Figaredo/LOW mixture. Table 10 shows
to analyze. The composition of the liquids obtained in a the variation of pyrolysis yields of the Figaredo coal/
pilot plant in the same conditions will be used to LOW (1:1) slurries with pressure (0.1-1 MPa). It can
estimate the synergetic effect. be observed that char yield increases and liquid and gas
Pyrolysis of Samca/LOW Mixture. Table 8 shows the yield decreases as pressure does (0.1-0.5 MPa) and
variation of pyrolysis yields of the Samca coal/LOW (1: remains constant at 1 MPa. In the same way, of
1) slurries with pressure (0.1-1 MPa). The total experi- production light olefins such as ethylene and propylene
mental yields of the three products hardly varies. decreases as pressure increases. The effect is more
However, the individual gaseous compounds show the important for hexenes. However, the yield of light
same trend as the pyrolysis of the coal. Alkanes C1-C3 alkanes, such as methane, ethane, and propane, in-
increase and olefins decrease with pressure. Comparing creases as pressure increases from 0.1 to 0.5 MPa. This
the theoretical and experimental values, there is a table also shows that there is hardly any synergetic
synergetic effect in char yield and a counter-synergetic effect in the Figaredo/oil mixture in gaseous compounds.
effect in total gas yield. However, methane and ethane Table 11 shows the yields of the individual tar
yield show a synergetic effect, which increases as compounds. The total liquid yield decreases as pressure
pressure does. This confirms that pressure favors the increases. However, benzene and toluene yields remain
production of light alkanes by promoting secondary constant or even increase and more heavy compounds
reactions. do not suffer important variations. There is a counter-
Table 9 shows the analysis of the individual tar synergetic effect for benzene and toluene.
compounds. It can be shown that benzene yield is high
at higher pressure and a synergetic effect is observed Discussion
at 1 MPa. Benzene yield increases and alkylbenzene
yield decreases as pressure does. However, toluene Interest in the co-pyrolysis of coal and LOW is based
shows a minimum at 0.5 MPa. The trend that leads to on the technological value of the products obtained.
the formation of alkylaromatic compounds observed at Results presented in tables show that experimental
0.1 MPa disappears as pressure increases, except for conditions have some influence on pyrolysis yields. In
toluene. This fact could be due to the high CH4 that particular, it is of interest to investigate into how
912 Energy & Fuels, Vol. 13, No. 4, 1999
Figure 1. Variation with temperature of the fraction of LOW
hydrogen transferred to the pyrolysis products.
temperature and pressure exert an influence on the
distribution of hydrogen among the pyrolysis products.
Figure 1 shows the variation with temperature of the
fraction of LOW/Samca coal hydrogen contained in each
of the pyrolysis products. Most of the figures obtained
at temperatures of 650 °C are similar to those obtained
at 700 °C. This confirms that conversion of LOW/coal
is nearly completed at 650 °C (96, 93%). In contrast,
the results obtained at 600 °C (69%) are significantly
lower.
The most important differences are observed for H2
and C1-C3 compounds (considering the experimental
values), since the fraction of LOW/coal hydrogen con-
tained in C4-C6 olefins and BTX varies slightly with
temperature. This behavior of hydrogen distribution
shows that increases in temperature mainly affect the
formation of the lightest compounds, in particular the
formation of methane, while the fraction of LOW/coal
hydrogen converted into BTX and C4-C6 olefins is only
slightly affected, at least in the case of the experimental
values.
Pressure also has an important influence on LOW/
coal hydrogen distribution. Figure 2 shows the variation
with pressure of the fraction of LOW/coal hydrogen to
pyrolysis products. One-third of the hydrogen in the
LOW/coal mixture is converted to methane, The fraction
of hydrogen converted into BTX only slightly increases
by increasing pressure, and the hydrogen converted into
Lázaro et al.
Figure 2. Variation with pressure of the fraction of LOW
hydrogen transferred to the pyrolysis products.
light olefins decreases. The balance of H2 is close to
100% considering all the sources of H2. These trends
are the same as those obtained in our previous paper
for the pyrolysis of the oil alone.11
Comparing the theoretical values with the experi-
mental ones, there is a synergy in the hydrogen trans-
ferred to CH4 and light alkanes, ethylene, and propylene
that increases as temperature increases and the H2
transferred to >C4 compounds does not reveal synergy.
However, for the hydrogen transferred to BTX, the
nonsynergy values remain similar to the experimental
ones. The synergy in the hydrogen transferred to CH4
and light alkanes increases, with pressure, and also the
H2 transferred to BTX. However, pressure does favor
the synergy in the hydrogen transferred to BTX.
The same considerations apply to both coal/oil mix-
tures, but the effect observed for the Figaredo coal (the
highest rank one, figures not shown)/LOW are lower
than for the Samca coal/LOW. This situation could also
be observed in the co-pyrolysis of both coals with a
petroleum residue.7,8 For those reasons, it can be
concluded that the lowest rank coal, Samca coal, is more
adequate to co-pyrolyze with LOW because valuable
effects are obtained. This way, in a future paper the co-
pyrolysis of Samca coal/LOW in a semipilot plant able
to work in continuous mode will be discussed. This plant
is able to feed 1 Kg h-1 of Samca coal/LOW mixture to
a continuous fluidized bed.
Co-Pyrolysis of Coals and Lube Oil Wastes in a Bench-Scale Unit
The operating conditions to be applied depend on the
final use of the products obtained. If the aim is to
produce light olefins and BTX, as in the refineries,
operation at atmospheric pressure and at a temperature
of 650 to 700 °C is to be preferred.
However, when the petrochemical approach is not
feasible, a “hybrid approach” consisting of obtaining a
high calorific value gas fuel and petrochemical-feedstock
grade liquids is an alternative. In this case, the fuel gas
can be used “in situ” in domestic and industrial instal-
lations, and liquids obtained can be transferred to a
separate plant for upgrading and commercialization. In
this case, the goal would be to transfer most of the
calorific value of the LOW/coal mixture to the pyrolysis
gas and to produce high yields of valuable products such
as BTX and some selected aromatic products such as
naphthalene and phenanthrene. Operating at higher
pressures, which leads to an increase of the hydrogen
fraction transferred to CH4 and light alkanes, increases
the quality of the pyrolysis-gas as a fuel. It is necessary
also to work at temperatures higher than 650 °C,
because at 600 °C there is a part of the oil is not
converted.
Occurrence of some synergetic effect confirms that co-
pyrolysis of LOW and coal as a mixture enhances
transfer of coal hydrogen to valuable petrochemical
products. This hydrogen would be transferred to mo-
lecular hydrogen if coal alone was pyrolyzed.
The co-pyrolysis of the LOW/coal mixtures results
sometimes in the slight increase of char yield. The char
yield is high at all experimental conditions as well than
in the coal pyrolysis, so its final use should be considered
in every utilization, such its gasification. In fact, Heidecke
et al.15 reported that one of the advantages of co-
pyrolysis versus coprocessing (under hydrogen and with
a catalyst) is that the chars obtained in co-pyrolysis are
enough reactive to be gasified. Moreover, in a forthcom-
ing paper, in which the co-pyrolysis of the coal/LOW
mixtures in a continuous semipilot plant will be pre-
sented, the discussion of the final use of the char
obtained will be included in more detail.
Even if the increase in the yields of some compounds
is not very high, the co-pyrolysis presents advantages
versus the pyrolysis of coal alone because the yields of
some interesting compounds are higher. The co-pyroly-
sis of coal/LOW shows a little synergy in some com-
pounds, but the coal is the major reserve of fossil fuel
and nowadays the collection of waste oils to feed a power
plant is not well enough developed. So, the co-pyrolysis
is claimed as an alternative to the pyrolysis of both coal
and oil separately by combining different percentage of
coal and LOW as a function of the availability of the
(15) Heidecke, H.; Oelert, H. H.; Xiong, L. H. Erdol, Erdgas, Kohle
1990, 456-460.
Energy & Fuels, Vol. 13, No. 4, 1999 913
LOW. In summary, in the co-pyrolysis of the coal/LOW
mixtures, the presence of coal facilitates the feed avail-
ability by using more coal in the mixture if there are
supply problems while the presence of waste improves
the conversion and yields of several interesting products
versus the coal pyrolysis.
Conclusions
The co-pyrolysis of coal and LOW increases the
quantity and quality (a higher proportion of light olefins
and BTX) of the products obtained as compared to the
products obtained in coal pyrolysis without the LOW
addition.
For both of the coals studied, increasing temperature
enhances retrogressive reactions that favor the produc-
tion of light compounds such as methane, ethylene, and
propylene. However the recombinative processes that
lead to the production of BTX do not seem to be
improved.
The effect of pressure on the yields and synergetic
effects on the co-pyrolysis are the same in the two coal/
mixtures but the effects are lower in the case of the
Figaredo coal. Those effects can be resumed as follows:
there is a synergism in char yield and a counter-
synergetic effect in gases yield as pressure increases.
However, methane and ethane show a synergetic effect,
which increases as pressure does, a fact which confirms
that pressure favors the formation of the light alkanes.
No synergetic effect is observed in BTX yields as
pressure increases.
Synergy has also been observed in the production of
valuable products, with a high amount of the hydrogen
contained in the oil/coal mixtures converted to these
products compared to the case of both oil and coal when
pyrolyzed separately. The relative distribution of prod-
uct yields can be changed in function of the pyrolysis
conditions. The selection of pyrolysis conditions depends
on the final use of the pyrolysis products. In the
“petrochemical” approach, which considers the products
as petrochemical feedstocks, a temperature window of
650-700 °C and a pressure of 0.1 MPa should be used.
At these conditions most of the hydrogen contained in
the LOW/coal mixture is transferred to ethylene and
propylene and BTX. However, in the “hybrid approach”
which produces gas fuel and liquid feedstocks, a tem-
perature of between 650 and 700 °C and a pressure of
0.5-1 MPa should be used. In this case, a higher
fraction of LOW/coal hydrogen is transferred to C1-C3
alkanes and BTX.
Acknowledgment. The financial support for this
work was obtained from the European Commission,
Agreement No. 7220/EC-763, and the Diputación Gen-
eral de Aragón.
EF980271J