FUEL

PROCESSING
TECHNOLOGY
EISEVIER Fuel Processing Technology 46 (1996) 195-215

Thermal and catalytic

coprocessing of waste tires with coal
Ying Tang, Christine W. Curtis*
Chemical Engineering Department, Auburn University, 230 Ross Hall, Auburn, AL 36849-5127, USA

Received 28 June 1995; accepted 6 October 1995

Abstract

Thermal and catalytic coprocessing of waste tires and coal was performed using waste tires
from two sources and coals of three different ranks. Bituminous coals yielded higher conver-
sions than either subbituminous coal or lignite when coprocessed with waste tire. In this study
waste tires from tire buffing processes were used. One of these materials provided by Rouse
Rubber represented the typical composition of most automotive tires while the other
material supplied by Uniroyal contained a substantial amount of mineral fillers because the
material obtained from buffing the white lettering on the sidewall of the tire. Each of these
waste tires when used as a solvent in coprocessing had different solvent qualities; the Rouse
waste tire was typically a much better solvent for coal than Uniroyal waste tire. Catalytic
coprocessing of waste tires with coal using slurry phase hydrogenation catalysts increased
total and coal conversions compared to thermal reactions. Addition of carbon black to the
coprocessing system had minimal effect on the conversion or product distributions, while the
addition of the heat-treated residue from the liquefied waste tires resulted in enhanced con-
version and hexane solubles production from coprocessing systems. The mineral-rich Uniroyal
residue was more active than the carbon black-rich Rouse residue. Combining the residues
with slurry phase hydrogenation catalysts enhanced their activity even further.

Keywords: Waste tire; Coal; Coprocessing

1. Introduction

The coprocessing of waste tires with coal offers an alternative technology to the
disposal of waste tires. Currently, waste tires are disposed of primarily through land-
filling [l] but are also used in the generation of electricity [2], as filler in asphalt road
pavements [3], and as raw material for the production of secondary products [4].
Pyrolysis, thermal gasification, and liquefaction have been examined as technologies
that can be used to process waste tires and other solid wastes [5,6]. Since waste

* Corresponding author. Tel.: + l-334-844-4827; Fax: + l-334-844-2063.

037%3820/96/$15.00 0 1996 Elsevier Science B.V. All rights reserved

SSDI 0378-3820(95)00064-X
196 Y. Tang, C. K Curtis/Fuel Processing Technology 46 (1996) 195-215

rubber tires are composed of materials like aromatic oils and synthetic rubber pro-
duced from petroleum processing, a feasible use of the waste tires is to reprocess
them to produce transportation fuels. Recent work in Germany has successfully
applied coal upgrading technology to the conversion of organic wastes and biomass
[7]. Waste tires, however, contain a variety of materials such as carbon black, ZnO,
sulfur and other fillers, which are required to attain the desired tires properties but
must be removed during the processing of these materials.
Coprocessing of waste tires with coal involves the simultaneous liquefaction of the
two materials at coal liquefaction temperatures of 380-440°C and hydrogen pres-
sures of 17-18 MPa at reaction temperature. This combined processing has been
shown to benefit both materials since the waste tire has a relatively high hydrogen
content and good solvent properties for liquefying coal [S, 93.A number of researchers
have investigated the coprocessing of coal with waste tires and/or waste plastics and
have investigated the effect of reaction variables of temperature, time, catalyst type
and waste polymer to coal ratio on the conversion of coprocessing system [8-131.
Sharma et al. [lo] investigated the conversion and product distribution of coal and
waste tire coprocessing systems, including the effects of coal to tire ratio, hydrogen
pressure, catalyst loading and introduction method. In their study, coal conversion
increased from 35% without tire to more than 65% with tire at a tire to coal ratio
of 4. Increased HZ pressure affected both materials positively. Impregnation of the
Fez& catalyst onto the coal was the most effective method of catalyst introduction
for the combined system. Liu et al. [9] investigated the liquefaction of coal and waste
tire, individually and combinatorially. The conversion of the mixture was greater
than the combination of the individual conversions. The effect of waste tire as a sol-
vent was similar to that of tetralin. Coliquefaction of coal with polymers and waste
tires was beneficial for both materials. Orr et al. reported that synergism was observed
for lo-30% loading of waste tires at 350°C and for almost all loadings of waste tires
at 430°C [13]. The coliquefaction of coal and waste tires and coal and waste
polymers was demonstrated in a proof of concept process of 3 tons/day [14]. The
processing involved 12 tons of plastics and coal and 5 tons of waste tire. Coal
conversion was maintained at 92%, nearly complete conversion of the organic
material occurred, and light oils were produced which contained 40 ppm of
nitrogen and 20 ppm of sulfur. Hydrogen consumption for the process was reduced
when either waste tire or waste plastic was processed compared to traditional coal
liquefaction materials.
Carbon black is a substantial constituent in waste tires, typically composing
20-30% of the tire material. Carbon black has been shown to be an effective
hydrocracking catalyst when Tang and Curtis [15] evaluated the hydrocracking
of 4-(1-naphthylmethyl)bibenzyl in conjunction with different components in
waste tire. Carbon black showed strong hydrocracking activity in comparison
with other waste tire components or slurry phase hydrotreating catalysts under
typical coal liquefaction conditions. Farcasiu and Smith [16] have found similar
hydrocracking activities for the model 4-(1naphthylmethyl)bibenzyl reacted in
the presence of 9, lo-dihydrophenanthrene, an air atmosphere, and temperature
ranging from 320 to 429°C. The carbon black released from the waste tire during
 Y. Tang, C. W. Curtis/Fuel Processing Technology 46 (1996) 195-215 191

liquefaction could act either as a catalyst itself or as a catalyst support for metals
released from waste tire during coprocessing. The literature describes a number of
applications where carbon has been used as a catalyst support for MO, Ni-Mo, Ni
MO-F, and CO-MO, in testing the hydrodenitrogenation and hydrodesulfurization
activity of these catalysts [17-201. When these catalysts were used in gas oil hydropro-
cessing, carbon covered alumina supports seemed to have less propensity for
coke deposition than alumina supports. Carbon-supported bimetallic catalysts
containing iron as a common metal showed a substantial decrease in hydrogenation
activity when iron was present compared to a single noble metal and nonnoble metal
catalysts [17].
Since waste tires contain ZnO as well as smaller amounts of Co and other trace
metals [21] and coal contains a wide variety of trace metals such as Fe, Si and Al,
the carbon black released from waste tire during coprocessing may serve as an avail-
able support for these trace metals. Mastral and Palacios [22] used a Zn and MO
catalyst which was deposited on coal in coprocessing reactions of coal and coal-
derived asphaltenes. A synergy was observed with the Zn-Mo combination which
resulted in increased oil formation. Farcasiu and Smith [l] have shown that copro-
cessing reactions of coal with waste tire containing carbon black produced higher
conversions than reactions without carbon black. Evidence presented in this study
indicates that the addition of carbon black to coal and waste tire systems had little
effect on the total conversion of the coal and waste tires to THF soluble material.
Dadyburjor et al. [23] also showed that carbon black did not catalyze conversion in
coal and waste tire coliquefaction reactions.
The objective of the current study was to evaluate the coprocessing of coal with
waste tires under thermal and catalytic conditions. Coals of different rank were
reacted with two different waste tires. The amount of coal conversion as well as total
conversion for both solid materials was determined. The efficacy of the waste tires
as coal liquefaction solvents was evaluated in both thermal and catalytic reactions.
In addition, the activity of two slurry phase hydrotreating catalysts, iron naphthenate
and molybdenum naphthenate, for converting and upgrading the waste tire and coal
system was evaluated.
Two different waste tire materials were used for this study. One sample originated
from a tire buffing process and was supplied from Rouse Rubber Industries.
The second material, which was supplied by Uniroyal-Michelin, was also produced
from a tire buffing operation in which the white letters on the tire were buffed.
The liquefaction residues of each of these materials represented a potential catalytic
material since the residues were composed of carbon black and the metals or
fillers present in the waste tire material. The catalytic activity of these residue
materials for enhancing the conversion and product quality from the coprocessing
of coal and waste tires was tested. The liquefaction residues were obtained by
removing the solids from the liquefied waste tire, heat treating the solid residue,
and then using the residue in coprocessing reactions. The amount of conversion
and product distribution obtained with the treated residues was compared to
that obtained with slurry phase catalysts and by combining residue with slurry phase
catalysts.
198 Y. Tang, C. W. Curtis/Fuel Processing Technology 46 (1996) 195-215

2. Experimental

2.1. Materials

Coprocessing reactions were performed with two different waste tire materials,
which were supplied by Rouse Rubber Industries, Vicksburg, MS and by Uniroyal-
Michelin, Opelika, AL, in conjunction with four coals supplied by the Argonne
Premium Coal Sample Bank. The four coals used were Beulah Zap lignite, Wyodak
Anderson subbituminous coal, and Pittsburgh No 8. and Illinois No. 6 bituminous
coals. Base line reactions were performed with the four coals and hexadecane which
was obtained from Aldrich Chemical Co. Analyses of the waste tires and coals used
in this study are given in Table 1. Analyses of the residues generated from the waste
tire are presented in Table 2. The carbon, hydrogen, and metal analyses were per-
formed by Galbraith Laboratory, Knoxville, TN. The ash, sulfur, and surface area
analyses were performed in our laboratory.
Catalytic reactions were performed using slurry phase hydrotreating catalysts,
molybdenum naphthenate (MoNaph) (6% MO), obtained from Shepherd Chemical,
and iron naphthenate (FeNaph) (6% Fe), obtained from Strem. Elemental sulfur
obtained from Aldrich was added to the catalytic reactions. The carbon black addi-
tives consisted of Black Pearls 2000, a high surface area material, and Mongal L, a
low surface area material, both supplied by Cabot Industries. The carbon blacks
were heated at 560 + 30°C in a flowing NZ stream of 3 I/min for 1 h prior to intro-
duction into the reactor. Other additives used in these experiments were residues
from liquefied Rouse and Uniroyal waste tires. These residues were prepared by
liquefying the waste tires at 400°C for 30 min in a H:! atmosphere of 6.9 MPa intro-
duced at ambient temperature and then extracting the reaction product with hexane
and THF, thereby removing the soluble material and retaining the solid product.
The extracted residue was then heated at 560 k 30°C in flowing NZ for 1 h.

2.2. Reaction procedures

The coprocessing reactions were performed in - 20 cm3 stainless steel tubular

microreactors at 400°C for 30 min. Hydrogen was introduced at 6.9 MPa at ambi-
ent temperature. The total charge to the reactor was 4g with the solvent to mois-
ture and ash-free (maf) coal ratio being 1 : 1. In the catalytic reactions, the catalyst
was charged at 900-l 100 ppm of active metal per total reactor charge. Elemental
sulfur was added to the catalytic reactions in a 3 : 1 stoichiometric ratio of sulfur to
metal using the assumption that either MO& or Fe7Sg was formed depending upon
the metal added. For the reactions with either the carbon blacks or residues as
additives, 0.4 g of additive was added to the reactor giving a solvent to maf coal to
additive ratio of 1: 1: 0.2.

2.3. Analysis

The liquefied products from the coprocessing and liquefied tire reactions were
obtained by extracting the products with 200ml of hexane to obtain the hexane
 Y. Tang, C. W Curtis/Fuel Processing Technology 46 (1996) 195-215 199

Table 1
Analysis of waste tires and coal?

Waste tires CoalsC

Uniroyalb Rouseb Beulah Wyodak Pittsburgh Illinois

Zap Anderson No. 8 No. 6

Ultimate analysis (%)

C 56 85 13 75 83 78
H 8.0 1.4 4.8 5.4 5.3 5.0
N NMd NM 1.1 1.1 1.6 1.4
s 1.0 1.6 0.8 0.6 2.2 4.8
0 NM NM 20 18 9 14

Proximate analysis (%)

Moisture 0.15 0.83 32.24 28.09 1.65 1.91
Ash 31.04 3.60 6.59 6.31 9.10 14.25
Volatile matter 63.29 65.81 30.45 32.11 37.20 36.86
Fixed carbon 5.52 29.76 30.72 33.43 52.05 40.92

Product distribution of liquejed waste tire (%). maf basise

Uniroyal waste tire Rouse waste tire
Hexane solubles 78.0 + 1.0 63.4 f 1.5
THF solublesf 3.6 f 1.2 4.8 f 1.1
IOMs 18.4 f 1.0 31.8 k 1.5
Conversion 81.6 * 1.0 68.2 f 1.5

Product distribution of liquefied waste tire (%), macf basise

Uniroyal waste tire Rouse waste tire
Gas + hexane solubles 85.7 + 1.1 90.8 + 2.2
THF solubles 4.0 * 1.3 6.9 f 1.6
IOM 10.3 + 1.1 2.3 k 2.2
Conversion 89.7 f 1.1 91.7 * 2.2

Distribution of untreated waste tire (%), maf basis

Uniroyal waste tire Rouse waste tire
Hexane solubles 10.3 k 1.6 10.1 + 1.7
THF solubles 2.3 f 0.7 2.7 k 0.5
IOM 87.4 k 1.6 87.2 + 1.7

“Reaction conditions: 400°C 30 min, 6.9 MPa Hz introduced at ambient temperature.

bUniroyal = waste tire from Uniroyal-Michelin Tire Company, Opelika, AL, Rouse = waste tire from
Rouse Rubber, Vicksburg, MS.
‘Coal data were quoted from Argonne Premium Coal Sample Program Users Handbook. Ultimate
and proximate analysis of waste tires were performed by Galbraith Laboratories, Inc. Other waste tire
analysis were performed by the authors.
dNM = not measured.
emaf basis = moisture and ash-free basis, macf basis = moisture, ash, and carbon black free basis.
fTHF solubles = THF soluble and hexane insoluble matter.
sIOM = insoluble organic matter.
200 I’. Tang, C. W. Curtis/Fuel Processing Technology 46 (1996) 195-215

Table 2
Analysis of carbon black and waste tire residuea

Analysis Samples

Carbon blackb Carbon black Rouse residue Uniroyal residue

(high) (low)

cc (%) NMd NM 85.0 + 0.2 14.5 * 0.1

H (%) NM NM < 0.5 co.5
se (%) 0.6 k 0.03 0.7 f 0.07 3.0 + 0.02 1.9 + 0.08
Sic (%) NM NM 1.2 * 0.1 19.1 f 0.1
Al (%) NM NM 0.3 f 0.1 16.5 f 0.1
Ti (%) NM NM co.1 17.3 + 0.1
Zn (%) NM NM 4.6 f 0.02 6.0 k 0.03
Ashf (%) 0.5 f 0.1 NM 10.9 + 0.2 84.2 f 0.3
Surface areag (m2/g) 1432 + 26 138 + 3 98 *1 27 kl

a The residues were obtained by liquefying waste tire, extracting the solid product of the reaction with
THF, and then heating the solid in flowing Nz at 560°C.
bCarbon black (high) has a high surface area of 1432 m2/g; carbon black (low) has a low surface area
of 138 m’/g; both provided by Cabot Industries.
‘C, H, Si, Al, Ti, and Zn, contents were determined by Galbraith Laboratories, Inc.
d NM = not measured.
e Sulfur contents were determined by sulfur analyzer using a Leco Sulfur Analyzer Model SC32.
fAsh amounts were determined by ASTM D3 174-82.
sSurface areas were determined by BET surface analyzer using a Quantasorb BET Analyzer.

soluble material and then with 200 ml of THF to obtain the THF soluble but hexane
insoluble material. The organic material that was not soluble in THF was defined
as insoluble organic matter or IOM which was ash-free.
The carbon blacks and waste tire residues were analyzed for their ash and sulfur
content as well as surface area (Table 2). The ash analysis was performed using
ASTM D 3174-8 in which 0.5 g of sample was placed in a crucible and heated to
450-500°C for the first hour. Heating continued until the temperature of the sam-
ple reached 700-750°C in the second hour and then continued heating at 700-750°C
for two additional hours. The ash content was determined by weighing the ash residue
remaining after the heating process was completed. The sulfur content was deter-
mined by using a Leco Model SC32. A sulfur calibration curve was prepared by
using NBS sulfur standards and was used to determine the amount of sulfur in each
additive. BET surface areas were determined using a Quantachrome Model
Quantasorb with NZ as the adsorbent gas. The residues were analyzed for their Si,
Al, Ti and Zn content by Galbraith Laboratories, Inc., Knoxville, TN.

3. Results and discussion

3.1. Composition and reactivity of waste tires

The composition of the two waste tires samples was quite different although both
materials were generated during tire buffing processes. Rouse waste tire contained
 Y. Tang, C. W. Curtis/Fuel Processing Technology 46 (1996) 195-215 201

85% C and 7.4% H while Uniroyal waste tire contained only 56% C and 8.0% H.
The Rouse waste tire was a fine black powder while the Uniroyal waste tire was a
whitish gray granular mixture. The amount of volatile matter was similar in the two
materials ranging between - 63 and - 66%; however, the ash and fixed carbon con-
tents were substantially different. The Rouse waste tire contained 29.8% fixed car-
bon and 3.6% ash; the fixed carbon was composed of carbon black while the ash
included ZnO and other inorganic constituents. The formulation for the Rouse waste
tire was typical of that which would be obtained from automobile tires and, there-
fore, was representative of waste tire material produced from the collection and
shredding of waste tires. By contrast, the Uniroyal waste tire material contained
31% ash and only 5.5% fixed carbon. The Uniroyal waste tire was generated from
the white lettering on the sidewalls of the tires and contained ZnO and fillers like
alumina, silica, and titania as shown in Table 2. The Uniroyal waste tire was more
typical of the type of waste streams generated from processing where the waste
stream is particular to a process. The solubility of the waste tires prior to liquefac-
tion was tested using hexane and THF and using the same solvent fractionation
procedure as was used after liquefaction. Approximately, 13% of both Rouse and
Uniroyal waste tires was soluble in THF and hexane as shown in Table 1.

3.2. Thermal and catalytic reactions of waste tires

The two waste tire materials were reacted at 400°C for 30 min under thermal and
catalytic conditions as presented in Table 3. The catalysts and additives used were
slurry phase hydrotreating catalysts, MoNaph + S and FeNaph + S, commercial
grade carbon black, and residues obtained from the liquefaction of Uniroyal and
Rouse waste tires that had been extracted with hexane and THF and heat-treated
at 560°C for 1 hr. The recovery from the Rouse waste tire liquefaction reactions
ranged from 90 to 95% while the recovery from Uniroyal waste tire was less,
ranging from 75 to 90%.
The conversion of waste tire after liquefaction is presented on two bases: mois-
ture- and ash-free (maf) basis and moisture-, ash- and carbon-black-free (mace) basis.
Using the macf basis removes all nonconvertible material including carbon black
from the conversion calculation so that only the convertible fraction is considered
in the calculation. Rouse waste tire, which contains 29.8% carbon black, yielded
under thermal conditions 68.2% conversion on a maf basis and 97.7% conversion
on a macf basis. When Rouse waste tire was liquefied using slurry phase MoNaph + S
and FeNaph + S catalysts, the waste tires totally converted on a macf basis yielding
98.3 and 99.8% conversion, respectively. By contrast, the addition of carbon black
or heat-treated residue from the waste tires inhibited conversion of the convertible
waste tire, lowering the macf conversion to 86.9% for the carbon black additive and
to 91-94% for the residue additives.
Uniroyal waste tires contain much less carbon black, only 5.5%, than typical waste
tire materials. Thermal conversion resulted in 81.6% conversion on a maf basis and
89.7% conversion on a macf basis, leaving - 10% of the convertible waste tire uncon-
verted under these reaction conditions. Addition of both slurry phase catalysts and
202 Y. Tang, C. W. Curtis/Fuel Processing Technology 46 (1996) 19S-215

Table 3
Reaction of waste tire with catalysts or additivesa

Waste tire Catalysts Product distribution (wt%) Waste tire Waste tire
and additives conversion conversion
Gas + hexane THF solublesb (%) (%)
solubles (ma0 (ma@

Rousee None 63.4 + 1.5 4.8 f 1.1 68.2 f 1.5 97.7 f 2.2
waste tire FeNaph + Sd 65.3 f 1.9 3.3 f 0.9 68.6 * 1.9 98.3 + 2.7
MoNaph + S 66.9 k 2.0 2.7 k 0.8 69.6 + 2.0 99.8 + 2.9
Carbon black’s (high) 56.1 ) 1.5 4.5 rt 0.8 60.6 f 1.5 86.9 f 2.2
Uniroyal residues 62.5 k2.1 3.1 f 0.7 65.6 + 2.1 94.0 f 3.0
Rouse residues 59.2 f 2.0 4.3 f 0.9 63.5 k 2.0 91.0 + 2.9

Uniroyalh None 78.0 f 1.0 3.6 It 1.2 81.6 + 1.0 89.7 f 1.1
waste tire FeNaph + S 85.1 k 1.5 2.5 k 0.5 87.6 f 1.5 96.6 &-1.7
MoNaph + S 86.1 + 1.8 2.9 f 0.7 89.0 & 1.8 98.1 k 2.0
Carbon Black ‘(high) 74.6 k 1.9 2.9 f 0.7 77.5 f 1.9 85.4 f 2.1
Uniroyal residues 80.2 ) 2.0 5.2 + 1.6 85.4 f 2.0 94.2 f 2.2
Rouse residues 76.5 f 2.3 8.0 f 1.9 84.5 f 2.3 93.2 + 2.5

a Reaction conditions: 4OO”C,30 min, 6.9 MPa HZ introduced at ambient temperature.

bTHF solubles = THF soluble and hexane insoluble matter.
‘maf = moisture and ash free basis; macf = moisture, ash, and carbon black free basis.
d 1000 ppm Fe or MO. S: Fe or S: MO = 3 : 1 in the catalytic reaction systems.
e waste tire from Rouse Company.
‘Carbon black has a high surface area of 1432 m2/g.
sWeight ratio of waste tire to additives was 10: 1.
h waste tire from Uniroyal Company.

both heat-treated residues increased conversion of Uniroyal waste tire as shown in

Table 3; the highest amount obtained on a macf basis was 98.1% using MoNaph + S.
Addition of commercial carbon black inhibited conversion of the waste tire, con-
verting only 85.4% on a macf basis which was less than that obtained without any
additive.

3.3. Thermal coprocessing reactions with coals of d@erent rank

Thermal liquefaction reactions were performed with coals of different rank using
hexadecane as a baseline solvent and waste tires from Rouse and Uniroyal as copro-
cessing solvents. The coals showed different thermal reactivity in hexadecane as given
in Table 4. The product distribution is given on two bases: the total distribution
which includes the solvent, either hexadecane or the waste tire, in the calculations
and the solvent-free distribution which removes the solvent including the waste tires
from the calculation. The total distribution describes the product that emerges from
the reactor and includes the distribution of liquefied waste tire and coal while the
solvent-free calculation describes the products from coal alone. In the solvent-free
distribution, the effect of the waste tires is only observed in terms of their effect on
coal conversion.
 Y. Tang, C. W. Curtis/Fuel Processing Technology 46 (1996) 195-215 203

Table 4
Thermal reactions of coals of different rank with waste tire?

Coal and Product distribution (wt%) Conversion (%)

solvent
Total Solvent free Total Coal

Gas + hexane THF Gas + hexane THF

solubles solublesb solubles solubles

Hexadecane
Beulah Zap 51.0 f 1.2 2.4 + 0.2 14.0 f 2.3 4.8 kO.4 18.8 k2.3 18.8 k2.3
Wyodak 56.4 k 1.0 4.6 f 0.4 12.8 + 1.9 9.2 kO.9 22.0 f 1.9 22.0 * 1.9
Pittsburgh No. 8 55.3 + 1.1 14.8 + 0.5 10.6 f 2.2 29.6 + 1.0 40.2 + 2.2 40.2 f 2.2
Illinois No. 6 56.8 + 1.0 17.9 5 0.9 13.6 + 2.1 35.8 f 1.9 49.4 f 2.1 49.4 * 2.1

Rouse waste tire

Beulah Zap 44.3 * 1.5 13.1 + 1.2 12.1 f. 2.4 17.4 f 2.0 57.4 + 1.5 29.5 f 2.4
Wyodak 41.8 + 0.7 17.1 * 1.0 8.1 k 2.1 24.1 k 1.8 58.9 k 1.2 32.2 + 2.1
Pittsburgh No. 8 39.1 k 1.1 28.6 k 0.8 3.6 + 1.9 43.0 f 1.4 67.7 &-1.1 46.6 + 1.9
Illinois No. 6 40.5 + 1.3 35.8 k 1.2 5.8 k 2.2 55.0 & 2.1 76.3 + 1.3 60.8 * 2.2

Uniroyal waste tire

Beulah Zap 46.3 f 0.9 3.5 kO.3 18.1 + 1.4 3.6 k 0.5 49.8 + 0.9 21.7 f 1.4
Wyodak 46.0 f 1.0 5.1 kO.2 17.7 + 1.6 6.0 k 0.3 51.1 + 1.0 23.7 k 1.6
Pittsburgh No. 8 42.8 f 1.6 16.1 kO.4 12.8 f 2.5 23.2 k 0.9 55.7 f 1.6 36.0 + 2.5
Illinois No. 6 41.6 k 1.7 27.4 f 0.5 11.0 f. 2.7 40.8 f 0.8 69.0 + 1.7 51.8 f 2.7

aReaction conditions: 400°C, 30 min, 6.9 MPa HZ introduced at ambient temperature, maf coal:
solvent = 1: 1~
bTHF solubles = THF soluble and hexane insoluble matter.

Conversion is also given on a total basis which describes the amount of total solids
that are converted to THF solubles and on a coal conversion basis which describes
the amount of coal conversion achieved. Total conversion for the waste tire systems
is defined as
total conversion = [l-g IOM/(g maf coal + g CM,ire)] x lOO%,
where IOM is defined as the insoluble organic matter which is free of ash from coal
and waste tire and free of carbon black from waste tire and CM,i, is defined as the
convertible matter in waste tire. Coal conversion for waste tires and hexadecane sys-
tems is defined as
coal conversion = (1 - g IOM/g maf coal) x loo%,
where IOM is defined as ash-free insoluble organic matter from coal. This latter
definition also applies to total conversion in the hexadecane system since hexade-
cane does not contain any solid material. If a solvent is totally soluble in THF prior
to liquefaction and if no coking occurs, the amount of total conversion and coal
conversion is the same. However, when a solid material such as waste tire is used
204 Y. Tang, C. H! Curtis/Fuel Processing Technology 46 (1996) 195-215

as solvent, the total conversion describes the amount of THF soluble material
generated from both solids, while coal conversion describes only the conversion from
coal. The recoveries obtained with these thermal reactions ranged from 85 to 95%.
Thermal coprocessing reactions of low and high rank coals in waste tires showed
that the conversion was rank dependent. Both Beulah Zap lignite and Wyodak sub-
bituminous coal gave much less conversion than the bituminous coals as shown in
Table 4. The same effect of rank was observed in hexadecane, which is a relatively
inert solvent. Coal conversions for Beulah Zap and Wyodak were 18.8 and 22.0%,
respectively, in hexadecane while the bituminous coals were higher at 40.2 and 49.4%.
Higher thermal coal conversions were obtained in Rouse waste tire yielding 29.5 and
32.2% for Beulah Zap and Wyodak, respectively, while the bituminous coals yielded
coal conversions of 46.6 and 60.8% for Pittsburgh No. 8 and Illinois No. 6, respec-
tively. The Uniroyal waste tire was not as effective a solvent for coal as Rouse waste
tire. Illinois No. 6 coal in Uniroyal waste tire and hexadecane had similar conver-
sion while Pittsburgh No. 8 converted less in Uniroyal waste tire than hexadecane.
These results indicated that the solvent quality of Uniroyal waste tire was as poor
or poorer than that of hexadecane. The lower rank coals also had similar conver-
sions in Uniroyal waste tire and in hexadecane, which also indicated that Uniroyal
waste tire had poor solvent quality.
Comparison of the total conversion obtained from the two waste tire and
coal coprocessing systems showed that total conversion was dependent on the
composition of waste tire used as solvent. Rouse waste tire solvent yielded the
highest total conversion for the three different ranks of coal. The contribution of
waste tire to the total conversion of the low rank coals was between 25 and 30%
for both waste tires. Waste tires contributed less to the total conversion for the
bituminous coals which showed a higher inherent reactivity at these coprocessing
conditions than did the low rank coals. The Uniroyal waste tire, a poorer solvent
for coal than Rouse waste tire, contributed more to the total conversion for the
bituminous coals than did Rouse waste tires. The product distributions showed
that Uniroyal waste tire promoted gas plus hexane soluble production slightly more
than did Rouse waste tire. The gas portion of the value given for gas plus a
hexane solubles for the Uniroyal waste tire systems ranged from 5.8 to 6.2% for the
low rank coals and from 4.2 and 4.7% for the higher rank coals. The gas portion
of the value given for gas plus hexane solubles for Rouse waste tires ranged from
4.1 to 4.6% for the low rank coals and from 2.4 to 2.9% for the high rank coals.
These results indicated that a higher gas make was produced from the low rank coals
than from the high rank coals and that Uniroyal waste tire produced more gas than
Rouse waste tire.

3.4. Catalytic reactions of waste tires and coal

Two coals, Illinois No. 6 and Wyodak, were selected for reactions evaluating
slurry phase catalysts because of their different ranks and levels of thermal reactiv-
ity. The slurry phase hydrotreating catalysts, MoNaph +S and FeNaph+ S,
were both introduced at 1OOOppm of active metal. As in the thermal reactions,
 Y. Tang, C. W. Curtis/Fuel Processing Technology 46 (1996) 195-215 205

three solvents were used: hexadecane as a baseline solvent and waste tires
from Rouse and Uniroyal. Typical recoveries obtained for Illinois No. 6 coal
systems were 93-95% for hexadecane as solvent, 90-92% for Rouse waste tire
as solvent and 84-86% for Uniroyal waste tire as solvent. Wyodak coal systems
gave similar recoveries except that each system’s range was one percentage
point less.
Illinois No. 6 bituminous coal showed substantially more reactivity in the cata-
lytic coprocessing reactions than Wyodak subbituminous coal. This reactivity level
was similar in the thermal reactions. As presented in Table 5, both catalysts increased
coal conversion and total conversion in the coprocessing reactions compared to the
thermal reaction. The two waste tires affected the coal reactivity and conversions in
the catalytic reactions in a similar manner as they did in the thermal reactions.
Higher total and coal conversions were attained in the catalytic reactions with Rouse
waste tire than with Uniroyal waste tire using both Illinois No. 6 and Wyodak coals.
MoNaph + S was more active for converting coal and waste tire than FeNaph + S.
When Illinois No. 6 coal was used, the differences in the conversions obtained with
the two catalysts were between 1.6 and 2.3% conversion which was less than those
with Wyodak coal. Wyodak coal with its lower reactivity responded more favorably
to MoNaph + S than FeNaph+ S, particularly when Rouse waste tire was
used, giving differences of 14.6% conversion for Rouse and 5.4% conversion for
Uniroyal.
The effect of catalyst on Illinois No. 6 coprocessing reactions with all three
solvents was greatest on the reactions with hexadecane. Illinois No. 6 coal in hexa-
decane showed high N 89-91% and nearly equivalent coal conversion for FeNaph + S
and MoNaph+S. The solvent-free product distribution indicated that these cata-
lysts were primarily active for converting coal to THF soluble material. When Rouse
waste tire was used as the solvent, coal conversion was slightly higher using
MoNaph + S at 78.7% compared to 75.0% for FeNaph + S. Both THF solubles and
gas and hexane solubles increased with catalyst addition. The reaction of Uniroyal
waste tire with Illinois No. 6 coal showed an effect of both catalysts compared to
the thermal case, although the difference between the two catalytic systems was small.
The catalysts contributed more to the total conversion of Illinois No. 6 and waste
tire with Uniroyal waste tire than with Rouse; for each reaction the difference between
the coal conversion and the total conversion was greater with Uniroyal waste tire
as coprocessing solvent.
Catalytic coprocessing of Wyodak increased coal conversion compared to the ther-
mal reactions with all three solvents. MoNaph + S was the more active of the cata-
lysts. The activity of the catalysts affected the product distributions differently in the
two waste tire solvents. In Rouse waste tire systems, both catalysts promoted the
production of THF soluble material rather than the production of gas and hexane
solubles. By contrast, in the Uniroyal waste tire systems, the catalysts promoted
production of gas and hexane soluble material in preference to THF soluble
material. The contribution of the catalysts to the total conversion in the Wyodak/
Uniroyal coprocessing system was greater than in the Wyodak/Rouse coprocessing
system.
Table 5
Catalytic coprocessing reactions of waste tires with Illinois No. 6 and Wyodak coal?

Coal and solvent Catalyst Product distribution (wt%) Conversion (%)

Total Solvent free Total Coal !Y

Y
Gas + hexane THF Gas + hexane THF 3
9
solubles solublesb solubles solubles

Illinois No. 6
Hexadecane None 56.8 f 1.0 17.9 f0.9 13.6 + 2.1 35.8 f 1.9 49.4 *2.1c 49.4 *2.1c
Hexadecane FeNaph + S 58.0 f 2.0 36.7 +0.8 16.0 f 2.0 73.4 f 1.6 89.4 f 2.0 89.4 f2.0
Hexadecane MoNaph + S 56.3 k2.4 39.3 f 1.0 12.6 k 2.4 78.7 & 2.0 91.3 *2.4 91.3 k2.4
Rouse waste tire None 40.5 * 1.3 35.8 f 1.2 5.8 f 2.2 55.0 k2.1 76.3 f 1.3d 60.8 *2.2d
Rouse waste tire FeNaph + S 45.1 +1.2 39.8 kO.6 12.0 f 2.0 62.9 + 1.2 84.9 + 1.2 75.0 +2.0
Rouse waste tire MoNaph + S 46.0 f 1.4 41.2 f 1.0 12.9 f 2.3 65.8 f 1.7 87.2 f 1.4 78.7 k2.3
Uniroyal waste tire None 41.6 k1.7 27.4 kO.5 11.0 + 2.7 40.8 +0.8 69.0 f 1.7 51.8 k2.7
Uniroyal waste tire FeNaph + S 45.7 f 1.1 27.1 kO.8 15.8 f 1.9 41.4 * 1.4 72.8 f 1.1 57.2 f 1.9
Uniroyal waste tire MO Naph + S 46.2 f 1.5 28.2 + 1.1 17.2 + 2.5 42.8 f 1.7 74.4 f 1.5 60.0 +2.5
Wyodak
Hexadecane None 56.4 f 1.O 4.6 f 0.4 12.8 k 1.9 9.2 f 0.9 22.0 * 1.9 22.0 & 1.9
Hexadecane FeNaph + S 56.9 f 1.3 7.4 f 0.7 13.9 f 2.6 14.8 k 2.6 28.7 + 2.6 28.7 k2.6
Hexadecane MoNaph + S 55.4 f 1.4 12.3 + 1.0 10.8 f 2.8 24.6 + 2.1 35.4 f 2.8 35.4 f 2.8
Rouse waste tire None 41.8 f 1.2 17.1 f 1.0 8.1 + 2.1 24.1 If: 1.8 58.9 f 1.2 32.2 f 2.1
Rouse waste tire FeNaph + S 46.6 + 1.4 19.2 k 0.8 14.5 + 2.3 29.0 f 1.3 65.8 f 1.4 43.5 f 2.3
Rouse waste tire MoNaph + S 50.4 + 1.3 30.0 f 1.1 20.2 f 2.2 47.3 f 1.9 80.4 + 1.3 67.5 k 2.2
Uniroyal waste tire None 46.0 + 1.0 5.1 f 0.3 17.7 f 1.6 6.0 + 0.5 51.1 f 1.0 23.7 f 1.6
Uniroyal waste tire FeNaph + S 49.5 f 1.3 6.4 f 0.5 22.2 * 2.1 8.8 + 0.7 55.9 f 1.3 31.0 f 2.1
Uniroyal waste tire MoNaph + S 52.3 f 1.4 9.0 k 0.8 26.9 + 2.3 12.6 k 1.2 61.3 f 1.4 39.5 f 2.3

aReactionconditions: 4OO”C,30 min, 6.9 MPa Hz introduced at ambient temperature, 1000 ppm Fe or MO for catalytic reactions, S: Fe or S: MO = 3: 1.
bTHF solubles = THF soluble and hexane insoluble matter.
Table 6
Coprocessing reactions of Illinois No. 6 coal and hexadecane with additives and catalystsa

Coal and Additive and/or Product distribution (wt%) Conversion (%)

solvent catalystb
Total Solvent free Total Coal

Gas + hexane THF Gas + hexane THF

solubles solublesC solubles solubles

Illinois No. 6 No additive 56.8 f 1.0 11.9 + 0.9 13.6 k2.1 35.8 + 1.9 49.4 + 2.1 49.4 k2.1
and FeNaph + S 58.0 + 2.0 36.1 + 0.8 16.0 + 2.0 73.4 f 1.6 89.4 f 2.0 89.4 + 2.0
hexadecane MoNaph + S 56.3 f 2.4 39.3 * 1.0 12.6 f 2.4 78.7 + 2.0 91.3 ) 2.4 91.3 +2.4
Carbon black (high)d 51.7 f 1.2 19.3 + 1.1 15.4 f 2.4 38.5 f 2.2 53.9 + 2.4 53.9 f 2.4
Carbon black (10~)~ 57.9 * 1.0 19.3 f 1.1 15.8 f 2.0 46.3 f 1.8 62.1 k2.0 62.1 k2.0
Uniroyal residue 57.8 f 1.6 30.3 f 1.2 15.6 f 3.2 60.6 f 2.4 16.2 + 3.2 76.2 + 3.2
Rouse residue 57.4 + 1.4 28.1 f 1.0 14.7 f 2.8 56.2 + 2.0 10.9 rf: 2.8 70.9 f 2.8

aReaction conditions: 4OO”C,30min, 6.9 MPa Ha introduced at ambient temperature, 1OOOppmFe or MO, S:Fe or S:Mo = 3: 1.
bmaf coal: hexadecane: additive = 1: 1:0.2.
‘THF solubles = THF soluble and hexane insoluble matter.
dCarbon black (high) = high surface area of - 1432 m2/g.
“Carbon black (low) = low surface area of - 138 m2/g.
Table I
Reactions of Illinois No. 6 coal and waste tires with additives and catalysta

Coal and Additive and/or Product distribution (wt%) Conversion (%)

waste tire catalystb
Total Solvent free Total Coal

Gas + hexane THF Gas + hexane THF

solubles solubles’ solubles solubles

Illinois No. 6 coal No additive 41.6 f 1.7 27.4 k 0.5 11.0 + 2.7 40.8 & 0.8 69.0 f 1.7 51.8 f 2.7
and Uniroyal Carbon black (high)d 42.9 f 1.8 21.2 f 1.1 12.6 f 2.8 40.6 f 1.7 70.1 f 1.7 53.2 f 2.8
waste tire Carbon black (low)e 44.1 f 1.2 26.8 f 0.9 14.6 f 1.9 40.0 f 1.4 70.9 f 1.2 54.6 f 1.9
FeNaph + Sa 45.7 f 1.1 27.1 + 0.8 15.8 f 1.9 41.4 f 1.4 72.8 + 1.1 57.2 f 1.9
MoNaph + S 46.2 + 1.5 28.2 + 1.1 17.2 f 2.5 42.8 f 1.7 14.4 * 1.5 60.0 k 2.5
Uniroyal residueb 46.4 f 1.4 35.5 f 1.2 18.1 f 2.2 53.6 f 2.0 81.9 + 1.4 71.6 f 2.2
Uniroyal residue + FeNaph + S 46.0 f 1.6 39.5 * 1.1 16.5 + 2.6 60.8 f 1.8 85.5 + 1.6 77.3 f 2.6
Uniroyal residue + MoNaph + S 46.1 f 2.2 41.1 f 1.3 17.9 f 3.1 63.0 f 2.2 81.8 f 1.9 80.9 f 3.1
Rouse residue 45.8 f 1.8 32.8 f 1.2 17.2 f 2.9 49.4 f 1.9 78.6 f 1.8 66.6 f 2.9
Rouse residue + FeNaph + S 48.0 f 1.9 34.3 * 1.3 19.7 + 3.0 52.6 + 2.1 82.3 + 1.9 72.3 + 3.0
Rouse residue + MoNaph + S 47.6 + 2.1 38.4 + 1.4 19.5 f 3.3 58.6 f 2.3 86.0 + 2.1 78.1 f 3.3

Illinois No. 6 coal No additive 40.5 f 1.3 35.8 f 1.2 5.8 f 2.2 55.0 + 2.1 76.3 f 1.3 60.8 * 2.2
and Rouse Carbon black (high) 42.7 + 1.4 34.0 + 0.8 9.1 f. 2.8 52.2 + 1.4 76.7 + 1.6 61.3 + 2.8
waste tire Carbon black (low) 42.8 + 1.0 36.1 & 0.8 9.6 + 1.7 55.5 * 1.3 78.9 f 1.0 65.1 f 1.7
FeNaph + S 45.1 f 1.2 39.8 f 0.6 12.0 + 2.0 62.9 f 1.0 84.9 f 1.2 75.0 f 2.0
MoNaph + S 46.0 f 1.4 41.2 + 1.0 12.9 + 2.3 65.8 + 1.7 87.2 + 1.4 78.1 + 2.2
Uniroyal residue 45.5 + 1.5 38.0 k 1.2 13.8 + 2.4 58.8 f 2.0 83.5 f 2.0 72.6 f 2.4
Uniroyal residue + FeNaph + S 46.8 f 1.3 41.0 f 1.1 14.8 f 2.3 64.9 f 1.8 87.8 f 1.3 19.7 f 2.3
Uniroyal residue + MoNaph + S 48.7 f 1.5 42.8 + 0.9 17.2 + 2.5 68.7 k 1.5 91.5 + 1.5 85.9 f 2.5
Rouse residue 44.6 + 1.1 37.1 f 0.9 12.4 f 1.8 57.2 f 1.6 81.7 f 1.1 69.6 f 1.8
Rouse residue + FeNaph + S 46.6 + 1.2 39.5 f 1.1 14.5 f 2.1 62.5 f 1.9 86.1 f 1.2 77.0 f 2.1
Rouse residue + MoNaph + S 47.2 f 1.5 41.1 f 1.3 15.6 k 2.6 65.2 f 2.2 88.3 + 1.5 80.3 + 2.6

aReaction conditions: 400 “C, 30min, 6.9 MPa H2 introduced at ambient temperature, 1000 ppm Fe or MO, S:Fe or S:Mo = 3: 1.
bmaf coal: waste tire: additive = 1: 1:0.2.
‘THF solubles = THF soluble and hexane insoluble matter.
d Carbon black (high) = high surface area of - 1432 m2/g.
eCarbon black (low) = low surface area of - 138 m2/g.
 Y. Tang, C. W Curtis/Fuel Processing Technology 46 (1996) 195-215 209

3.5. Reactions of Illinois No. 6 coal and waste tires with additives and catalysts

Coprocessing reactions of Illinois No. 6 with Uniroyal and Rouse waste tires were
performed with a variety of additives and catalysts as given Table 7. The same set
of additives was used for both waste tire solvents and hexadecane. Reactions of
Illinois No. 6 and additives in hexadecane are given in Table 6 to present a base-
line level of additive activity in a relatively inert solvent. The carbon black additive,
that had been heat-treated prior to addition, had a small positive effect on coal con-
version in hexadecane. The addition of FeNaph + S or MoNaph + S increased coal
conversion more than the heat-treated residues from either waste tire. Waste tire
residue was obtained from the liquefaction of both waste tires and subsequent
removal of the liquefied material. The THF-washed residue was heat-treated at 560°C
in a flowing NZ stream for 1 h. The heat-treated residues increased coal conversion
in hexadecane compared to no catalyst and the two carbon blacks but not com-
pared to either slurry phase catalyst. Addition of Uniroyal residue to the Illinois
No. 6/Uniroyal waste tire system increased both coal and total conversions com-
pared to the catalytic reaction with MoNaph + S without residue.
Coprocessing reactions of coal with waste tires performed in the presence of addi-
tives such as carbon black, waste tire residues, or waste tire residues plus slurry
phase catalysts showed increased conversions compared to those from the no addi-
tive reaction. Total and coal conversions for these reactions as well as their prod-
uct distribution are given in Table 7. Two sets of reactions were performed: Illinois
No. 6 reacted with Uniroyal waste tire and Illinois No. 6 reacted with Rouse waste
tire. The response of the two coprocessing systems to the different additives was
dependent upon the composition of the waste tire used as solvent. Both the total
and coal conversions for the reactions with Uniroyal waste tire were always less than
those for corresponding reactions with Rouse waste tire.
The most active additives for promoting coal and total conversion were the com-
binations of waste tire residues with slurry phase MoNaph+ S catalyst, while the
next most active additives were the combinations of waste tire residue with
FeNaph + S. Both residues also promoted conversion of Illinois No. 6 coal, although
to a lesser extent than did the residues combined with a slurry phase catalyst. In
each reaction set, Uniroyal waste tire residue had a higher catalytic activity than did
Rouse waste tire residue. This increased activity may be attributed to the high
mineral content of the Uniroyal residue compared to the carbon black-rich com-
position of Rouse.

3.6. Coprocessing efect

The effect of coprocessing coal with waste tire on total conversion and product
distribution was evaluated in comparison to reactions that were performed individ-
ually. These comparisons are given in Tables 8 and 9. The coprocessing effect is
defined as the difference between values obtained from reactions of coal and waste
tires and values obtained from reactions with the individual reactants. In Table 8,
the coprocessing effect of Illinois No. 6. and Wyodak coals with waste tires was
Table 8
Coprocessing effect on reactions of coal and waste tire with slurry phase catalysts

Coprocessing reaction system? Gas + hexane Coprocessing THF solublese Coprocessing Total conversion Coprocessing
solubles (%) effect* (%) effect effect

EXPb HYPC EXP-HYP EXP HYP EXP-HYP EXP HYP EXP-HYP

Illinois No. 6

Rouse WTr 40.5 38.0 +2.5 35.8 20.6 + 15.2 76.3 58.6 + 11.1
Rouse WT + FeNaph + S 45.1 40.2 +4.9 39.8 39.1 +0.7 84.9 19.3 +5.6
Rouse WT + MoNaph + S 46.0 39.2 +6.8 41.2 41.4 -0.2 87.2 80.6 +6.6
Uniroyal WT 41.6 39.1 +1.9 21.4 22.7 +4.1 69.0 62.4 +6.6
Uniroyal WT + FeNaph + S 45.1 44.5 +1.2 27.1 44.2 -17.1 12.8 88.7 - 15.9
Uniroyal WT + MoNaph + S 46.2 42.9 +3.3 28.2 47.5 - 19.3 14.4 90.4 - 16.0

Wyodak

Rouse WT 41.8 37.5 +4.3 17.1 1.0 + 10.1 58.9 44.5 + 14.4
Rouse WT + FeNaph + S 46.6 39.1 +7.5 19.2 9.2 + 10.0 65.8 48.3 + 17.5
Rouse WT + MoNaph + S 50.4 38.3 + 12.1 30.0 13.9 +16.1 80.4 52.2 + 28.2
Uniroyal WT 46.0 39.4 +6.6 5.1 6.9 -1.8 51.1 46.3 +4.8
Uniroyal WT + FeNaph + S 49.5 43.0 +6.5 6.4 9.8 -3.4 55.9 52.8 +3.1
Uniroyal WT + MoNaph+S 52.3 41.5 + 10.8 9.0 15.7 -6.7 61.3 51.3 +4.1

aReaction conditions: 4OO”C,30 min, 6.9 MPa Hz introduced at ambient temperature, 1000 ppm Fe or MO for catalytic reaction systems with FeNaph
or MoNaph, S:Fe or S:Mo = 3: 1.
bEXP = experimental data obtained from coprocessing reactions.
‘HYP = hypothetical values calculated by the data obtained from the reactions with individual reactants under the same reaction conditions as copro-
cessing reactions.
*Coprocessing effects are expressed by difference between the experimental data and the hypothetical values.
eTHF solubles = THF soluble and hexane insoluble matter.
‘WT = waste tire.
 Y. Tang, C. W. Curtis/Fuel Processing Technology 46 (1996) 195-215 211

evaluated thermally and catalytically with MoNaph and FeNaph, both of which
were reacted with sulfur. The hypothetical values used for the coal plus waste tire
reactions were obtained for the coal by measuring the conversion of coal in
a reaction with hexadecane as the solvent while the waste tire values were taken
directly from the reactions of the individual waste tires. For the catalytic reactions,
the hypothetical values were obtained from individual reactions of coal with
catalyst in hexadecane and individual reactions of the waste tires with catalyst. In
Table 8 the coprocessing effect for each portion of the product distribution and
total conversion is presented as well as the experimental and hypothetical values for
each product.
The coprocessing effect was dependent upon the type of coal and waste tire used.
Coprocessing Illinois No. 6 coal and Rouse waste tire increased the total conver-
sion of the system in both catalytic and thermal reactions compared to the hypo-
thetical values from individual reactions. Thermal coprocessing reactions using both
Rouse and Uniroyal waste tires showed more benefit of coprocessing compared to
the catalytic reactions. In fact, catalytic coprocessing with Uniroyal waste tire gave
less conversion than did the catalytic individual reactions, indicating that the min-
eral composition of the Uniroyal material was detrimental to the catalyst’s activity
for converting coal. The coprocessing effect gave a positive value for the hexane sol-
uble and gas fraction of all the Illinois No. 6 and waste tire systems while the THF
soluble fraction gave positive values for half of the reactions.
The presence of catalysts in the coprocessing of waste tires with Wyodak sub-
bituminous coal was more beneficial than with Illinois No. 6 bituminous coal. In
both thermal and catalytic coprocessing reactions with both Rouse and Uniroyal
waste tires, the coprocessing effect was positive, indicating that combining waste tire
with coal was beneficial to the total conversion. The benefit was larger for the Wyodak
and Rouse system than for the Wyodak and Uniroyal system. The greatest increase
in total conversion was Wyodak and Rouse waste tire with MoNaph + S, where the
overall conversion was 28% greater than the conversion in the individual reactions.
Both the FeNaph + S and thermal reactions with Wyodak and Rouse showed sub-
stantial increases in conversion compared to the individual reactions. The Wyodak
and Uniroyal coprocessing systems yielded slightly more conversion than the indi-
vidual reactions and gave similar values regardless of the additive. The coprocessed
Wyodak and waste tire systems all showed a positive effect of coprocessing on the
hexane soluble and gas fractions. The values obtained were higher than those
observed with Illinois No. 6 coal. The coprocessing effect for the THF soluble frac-
tion was positive for Wyodak with Rouse waste tire but was negative for the Wyodak
and Uniroyal systems.
The coprocessing effect observed with Illinois No. 6 coal and Rouse and Uniroyal
waste tires with additives in the system is presented in Table 9. The experimental
values that are given were obtained directly from the conversion and product dis-
tribution values obtained in the coprocessing reactions with the different additives
and catalysts. The hypothetical values for the coal were obtained from the indivi-
dual reactions of Illinois No. 6 coal and additives in hexadecane or additives plus
catalysts in hexadecane. The hypothetical values for the waste tires were obtained
Table 9
Coprocessing effect on coal and waste tire reactions with additives and catalyst?

Coprocessing reaction Gas + hexane Coprocessing THF soluble@ Coprocessing Total conversion Coprocessing
systems= soluble (%) effect* (W effect (W effect

EXPb HYPC EXP-HYP EXP HYP EXP-HYP EXP HYP EXP-HYP

Uniroyal waste tire

Carbon black (high)f 42.9 39.6 +3.3 27.2 23.9 +3.3 70.1 63.5 +6.6
Carbon black (1ow)s 44.1 39.6 +4.5 26.8 23.9 +2.9 70.9 63.5 +7.4
Uniroyal residue 46.4 42.0 +4.4 35.5 37.9 -2.4 81.9 19.9 + 2.0
Rouse residue 45.8 40:o +5.8 32.8 36.5 -3.7 78.9 76.5 +2.1
Uniroyal residue + FeNaph + S 46.0 44.4 +1.6 39.5 44.2 -4.1 85.5 88.6 -3.1
Uniroyal residue + MoNaph + S 46.7 42.7 +4.0 41.1 47.7 -6.6 87.8 90.4 -2.6
Rouse residue + FeNaph + S 48.0 44.3 i-3.7 34.3 44.3 - 10.0 82.3 88.6 -6.3
Rouse residue + MoNaph + S 47.6 42.6 +4.0 38.4 47.7 -9.3 86.0 90.3 -5.3

Rouse wasfe tire

Carbon black (high) 42.7 35.4 +7.3 34.0 21.8 +21.8 76.1 57.2 + 19.5
Carbon black (low) 42.8 35.4 +7.4 36.1 21.8 + 14.3 78.9 57.2 +21.7
Uniroyal residue 45.5 38.6 +6.9 38.0 32.4 +5.6 83.5 71.0 + 12.5
Rouse residue 44.6 36.5 +8.1 37.1 30.7 +6.4 81.7 61.2 + 14.5
Uniroyal residue + FeNaph + S 46.8 40.1 +6.7 41.0 39.1 +1.9 87.8 79.2 +8.6
Uniroyal residue + MoNaph + S 48.7 39.3 +9.4 42.8 41.3 +1.5 91.5 80.6 + 10.9
Rouse residue + FeNaph + S 46.6 40.1 +6.5 39.5 39.1 +0.4 86.1 19.2 +6.9
Rouse residue + MoNaph + S 47.2 39.2 +8.0 41.1 41.5 -0.4 88.3 80.7 +7.6

aRaction conditions: 4OO”C,30min, 6.9 MPa HZ introduced at ambient temperature, 1000 ppm Fe or MO for catalytic reaction systems with FeNaph or
MoNaph, S:Fe or S: Mo=3:1, maf coal: waste tire: additive=1:1:0.2.
bEXP = experimental data obtained from coprocessing reactions.
‘HYP = hypothetical values calculated by the data obtained from the reactions with the individual reactants under the same reaction conditions as copro-
cessing reactions.
*Coprocessing effects are expressed by difference between the experimental data and the hypothetical values.
eTHF solubles = THF soluble and hexane insoluble matter.
‘Carbon black (high) has a high surface area of N 1432 m’/g.
gCarbon black (low) has a low surface area of _ 138 m2/g.
 Y. Tang, C. W. Curtis/Fuel Processing Technology 46 (1996) 195-215 213

from individual reactions of either Rouse or Uniroyal waste tire with the additive
or the catalyst.
The coprocessing effect observed with the additives clearly showed the difference
between the two waste tire solvent systems. Coprocessing of Illinois No. 6 coal with
Uniroyal waste tire resulted in a positive coprocessing effect for the carbon black
additives and the two residues. The positive coprocessing effect indicated that
the addition of Uniroyal waste tire solvent with its associated mineral matter
promoted coal conversion compared to the carbon black or residue additives alone.
However, the addition of the slurry phase catalysts to the residues resulted in a
negative coprocessing effect. A similar result was observed with coprocessing Illinois
No. 6 with Uniroyal waste tire and slurry phase catalysts (Table 8), although the
catalytic effect of the residue in the residue plus catalyst reactions seemed to over-
come some of the poisoning caused by the minerals in Uniroyal waste tire. Since a
negative coprocessing effect means that more coal was converted with residue and
slurry phase catalyst using hexadecane as a solvent than with Uniroyal waste tire,
a negative coprocessing effect means that the waste tire solvent inhibited conversion.
All of the additives gave positive coprocessing effects for the gas and hexane
soluble fractions while mostly negative values were obtained for the THF soluble
fraction.
Rouse waste tire enhanced the total conversion for the Illinois coprocessing sys-
tem, resulting in positive coprocessing effect values for conversion for all of the addi-
tives. The largest improvements for coprocessing were in the systems containing
carbon black and residue alone. These positive values ranged from 12.5 to 21.7%.
The residue plus catalyst additive also resulted in increased conversion during co-
processing giving positive values that ranged from 6.9 to 10.9. All gas and hexane
soluble values were positive as were the THF soluble values except for the values
for Rouse residue plus slurry phase catalysts that were near zero.

4. Summary and conclusions

Coprocessing of waste tires with coal is a feasible technology for converting the
waste tires and coal to liquid products. The efficacy of the conversion process was
dependent on the rank of coal and on the composition of the waste tire. Higher rank
bituminous coals yielded higher conversions than did the lower rank lignite and sub-
bituminous coals. Waste tires that contained the typical percentages of rubber, car-
bon black, aromatic oil, and ZnO and other fillers provided good solvents for
coprocessing. Waste tire material from processing plants that contained substantial
amounts of filler like alumina, silica, and titania did not solvate the coal as well.
These high mineral materials, depending upon their composition, have the poten-
tial to poison catalysts that are introduced into the catalyst system.
Addition of slurry phase hydrogenation catalysts to the coprocessing systems
improved the amount of total and coal conversion obtained compared to no cata-
lyst addition. Activity of molybdenum naphthenate plus sulfur was greater than that
of iron naphthenate plus sulfur although the difference in activity was dependent on
214 I’? Tang, C. W. Curtis/Fuel Processing Technology 46 (1996) N-215

coal rank and waste tire composition. Addition of other additives such as carbon
black and the residue from waste tire also resulted in increased conversions
compared to the no additive case. Carbon black was the least effective additive. The
mineral-rich residue from Uniroyal waste tire was more effective than the carbon
black-rich residue from Rouse waste tire, regardless of the waste tire used as
solvent in coprocessing. The combination of slurry phase catalysts, particularly moly-
bdenum naphthenate, with the waste tire residue was the most effective additive for
increasing conversion in the coprocessing systems.
The high mineral content of the Uniroyal waste tire system was detrimental to
catalyst activity. Lower conversions were observed when Uniroyal waste tire was
coprocessed with slurry phase catalyst compared to individual reactions with hexa-
decane, the baseline solvent. However, when the Uniroyal waste tire residue was
obtained from liquefaction and subsequent removal of liquefied material and heat
treatment, the residue became effective as a catalytic agent for the coprocessing sys-
tem. The Rouse waste tire residue, which was more representative of residues that
would be obtained from most waste tires, was also effective in promoting conver-
sion and upgrading of coal coprocessed with waste tire, although not as effective as
Uniroyal. Use of waste tire residue as an effective additive in waste tire and coal
coprocessing offers an opportunity for utilization of all components of the waste tire
and effective recycling of an ubiquitous waste.

Acknowledgements

The authors gratefully acknowledge the support of the U.S. Department of Energy
through the Consortium for Fossil Fuel Liquefaction Science Contract No. UKRF-
4-26973-93-201. The supply of waste tires from Rouse Rubber and from Uniroyal
Michelin and molybdenum naphthenate from Shepherd Chemical are gratefully
acknowledged.

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