DL

= liquid phase diffusivity, cm2 sec-'

(De) = Deborah number = XN, dimensionless
d = impeller diameter, cm
g = gravitational constant, cm sec-*
K = fluid consistency index, g cm-' secn-2
KGU = volumetric coefficient of overall mass transfer, mol
sec-1 cm-3 atm-'
kL = liquid phase mass transfer coefficient, cm sec-l
kLu = volumetric liquid phase mass transfer coefficient,
sec-l
N = rotational speed of impeller, sec-l
n = flow behavior index, dimensionless
r = radius, cm
t = time, sec
u = linear velocity, cm sec-l
V , = superficial gas velocity, cm sec-'

Greek Letters
X = characteristic material time, sec
p = liquid viscosity, g cm-' sec-l
pa = apparent viscosity, g cm-' sec-l
p~ = gas viscosity, g cm-l sec-l
p = liquid density, g ~ m - ~

a = surface tension, g sec-2

7 = shear stress, g cm-' sec-2

Literature Cited
Aiba, S., Someya, J., J. Ferment. Techno/. (in Japanese), 45, 706 (1967).
Akita, K., personal communication, 1974.
Calderbank, P. H., Trans. Inst. Chem. Eng., 36, 443 (1958).
Calderbank. P. H., Trans. Inst. Chem. Eng., 37, 173 (1959).
Calderbank, P. H.. Moo-Young, M. B., Trans. inst. Chem. Eng., 37, 26 (1959).
Calderbank, P. H., Moo-Young, M. B.. Chem. Eng. Sci., 16, 39 (1961).
Cooper, C. E., Fernstrom, G. A.. Miller, S. A., Ind. Eng. Chem., 38, 504
(1944).
Johnson, D. L., Saito, H., Polejes, J. D., Hougen. 0. A,, AIChE J.. 3, 411
(1957).
Metzner, A. B., Otto,R. E., AIChEJ., 3, 3 (1957).
Ohyama, Y., Endoh, K., Kagaku Kogaku, 19, 2 (1955).
Perez, J. F.. Sandall. 0. C., AIChEJ., 20, 770 (1974).
Prest, W. M., Porter, R. S., O'Reilly, J. M., J. Appl. Polym. Sci,, 14, 2697
(1970).
Sideman, S.. Hortacsu. H.. Fuiton, J. W., hd. Eng. Chem., 58, 32 (1966).
Yagi, H., Yoshida, F., J. Ferment. Techno/., 52, 905 (1974).
Yoshida, F., Ikeda. A., Imakawa, S., Miura, Y.. Ind. Eng. Chem., 52, 435
(1 960).

Received for review February 4, 1975

Accepted June 4,1975

The Heat of HydrodesulfurizationReaction of Heavy Oil

Shigeru Ueda' and Shinichi Yokoyama
The Government Industrial Development Laboratory, Hokkaido, 4 1-2 Higashi-Tsukisamu, Sapporo, Japan

Tadao Ishii, Kazuo Maklno, and Gen Takeya

Department of Applied Chemistry, Hokkaido University, Sapporo, Japan

Using an apparatus for differential thermal analysis (DTA) under high pressure, the heat of hydrodesulfurization
reaction of heavy oil was measured between 425 and 44OOC under 200 kg/cm2. Hitherto measurement of the
heat of the reaction by conventional DTA method was difficult because the heat was relatively low. Hence, a
new method for the solution of this problem was developed, involving rapid starting of the reaction by charging
with hydrogen and simultaneous stirring of the sample when the sample reached the desired temperature.
Applying this method, the heats of reaction obtained for five samples were 5-54 cal/g and the test runs on hydrodesulfurization reaction of tetrahydrothiophene indicated that the results should not have a deviation greater
than 10%.

Introduction
The present investigation was conducted to determine
the heat of hydrodesulfurization reaction, necessary for efficient designing of a heavy oil hydrodesulfurization plant.
A few papers related to the study of heat of hydrogenation
reaction under high pressure for coal, its hydrogenation
products, and coal tar are available. These studies are similar to the hydrodesulfurization of heavy oil in reaction and
its conditions. Regarding this, Mitsui and Yamaguchi
(1939) and Takagi et al. (1942) reported on thermochemical
calculations by simplifying numerous complicated reactions, and Shibata (1952) dealt with the heat balance using
a pilot plant reactor. Gunther (1970) measured the heat of
coal tar hydrogenation by the temperature difference of
twin-type flow reactors. However, the above investigations
seem to lack in accuracy and are not applicable for common
laboratory work. In line with the above, Lee et al. (1968)
measured the heat of reaction of hydrogen against coal and
chars using two specially designed calorimeters. However,

this method cannot be applied to gas, liquid, and solid

reactions such as hydrodesulfurization of heavy oil which
proceeds with the stirring of the samples.
A high-pressure DTA apparatus was developed and applied to reactions of gas, liquid, and solid in our previous
reports (Takeya et al., 1965, 1966; Ishii et al., 1967, 1968,
1969; Ueda et al., 1971) and the reaction heat of coal hydrogenation was also measured (Itoh, et al., 1971). In this
paper, the heat of hydrodesulfurization reaction of heavy
oil was measured by a new method proposed here since the
measurement was difficult by the above conventional DTA
method where the heat is relatively low.

Experimental Section
Apparatus. The high-pressure DTA apparatus reported
here is shown in Figure 1. The apparatus can be operated
a t temperatures up to 500C and pressures up to 300 kgl
cm2. The main body consists of identical autoclave chambers for reaction and reference with a capacity of 60 ml, reInd. Eng. Chem., Process Des. Dev., Vol. 14, No. 4, 1975

493

PRESSURE
TRANSDUCER

PRESSURE
TRANSDUCER
LL

$1 I

GAS

lL

01

E 200

IL

300

400

TEMPERATURE

510

Figure 2. DTA and DPA curves in hydrodesulfurization reaction

of heavy oil.

Figure 1. High-pressure DTA apparatus: (1) reaction chamber, (2)

reference chamber, (3) differential thermocouple, (4) insulation,
( 5 ) heater embedded cast aluminum, (6) small electric heater, ( 7 )
magnet piece, (8) auto stirrer.
spectively. Chromel-alumel thermocouples are placed in
each chamber to enable measurements of differential temperature and temperature of the sample. While the measurement of DTA is made, simultaneous measurement of
the pressure difference between the reaction chamber and
the reference chamber (DPA) can be measured using pressure transducers. The reaction chamber is equipped with
an agitator. Hence the apparatus can be applied to catalytic reactions between gas and liquid under high pressure.
The reaction chamber is also equipped with a small electric
heater by which the reaction heat can be calibrated.
Materials. The heavy oils used in this work were three
kinds of atmospheric distillation residues (3OOOC +) of
Khafji, Kuwait and Gach Saran and two kinds of Khafji
residues pretreated with a slight hydrodesulfurization.
Properties of heavy oils were as shown in Table IV. These
were measured using the methods of JIS K 2249,2283,2270
and JPI-5T-1-59T. Tetrahydrothiophene used for determination of accuracy of this method was a special grade reagent available on the market which was used without further purification. Catalysts used were two kinds of industrial CoO-Mo03-Al203 catalysts which were crushed to a
size of -100 mesh. The hydrogen and helium were used as
obtained from commercial cylinders.
Experimental Procedure. Since the sensitivity of the
high-pressure DTA apparatus used hitherto was about 5
cal/min for heat evolution, in cases of reactions of the low
heat and slow reaction rate, it was difficult to obtain sharp
exothermic peaks because of the heat evolution in the vicinity of the sensitivity. As a first step, preliminary experiments for the hydrodesulfurization of heavy oil were conducted to obtain exothermic peaks with the conventional
DTA method used hitherto. The following were used in the
operation; 9 g of heavy oil and 0.9 g of catalyst were placed
in the reaction chamber, while 5 g of a-A1203was placed in
the reference chamber. The heating rate was 3.3OC/min
with a stirring of 560 rpm (externally attached magnetic
stirrer) and an initial hydrogen pressure of 100 kg/cm2 in
both chambers. Typical DTA and DPA curves in the hydrodesulfurization reaction of heavy oil with a COO-Moos494

Ind. Eng. Chem., Process Des. Dev., Vol. 14, No. 4, 1975

A1203 catalyst are shown in Figure 2. From the DPA curve,

it was shown that the pressure decrease is induced at 300C
and the rate of pressure decrease increases with the temperature rise. From the DTA curves, the evolution of heat
is detected at temperatures above approximately 350C
taking the deviation of base line into consideration. However, the DTA curve deviates only in the direction of exotherm and the exothermic peak is not formed in the presence of a temperature rise. It is difficult to detect the termination temperature of the hydrodesulfurization reaction
of heavy oil by the DTA curve, since the reaction proceeds
continuously to hydrocracking, dehydrogenation, and carbonization with the temperature rise.
Thus, a new method to cope with this problem was developed, in which the exothermic peak with a high detection sensitivity was measured. The experimental operations were done as follows. The sample and catalyst were
the same as described above. An initial hydrogen pressure
of 10 kg/cm2 was charged in both chambers which suppressed evaporation and thermal decomposition of the
sample. Both chambers were raised to the desired temperature at a heating rate of 3.3OC/min. After the temperature
was maintained at the desired reaction temperature for
about 10 min, the DTA curve on the recorder returned to
the base line. Then, the reaction was violently induced by
charging with the desired hydrogen pressure into both
chambers with simultaneous stirring of the sample and satisfactory DTA, DPA curves were measured under constant
temperature. In this new DTA technique, it is desirable
that the reaction rate is high and therefore the heat generation per unit time is high and since the desired main reaction is hydrodesulfurization, hyper hydrocracking, dehydrogenation, and carbonization do not occur. Therefore
after considering the results of Figure 2 together with the
commonly known reaction conditions related to this reaction, the following reaction conditions were selected, namely with the reaction temperature from 425 to 440C under a
reaction pressure of 200 kg/cm2 and stirring of 560 rpm.
Subsequently, the new method was applied to the hydrodesulfurization reaction of tetrahydrothiophene where the
heat of reaction was obtainable by thermochemical calculations and further the measurement accuracy of this method
was discussed. The conventional DTA and DPA shown in
Figure 3 and the reaction conditions of heavy oil were considered which resulted in the selection of the reaction conditions of tetrahydrothiophene as follows; reaction temperatures from 400 to 41OoC, reaction pressure 160 kg/cm2,
stirring of 560 rpm, with a sample of 3.0 ml (2.88 g) and
catalyst of 0.3 g.
In the case of calibration experiments by electric energy
with a small electric heater installed in the reaction chamber, the reaction conditions for heavy oil and tetrahydrothiophene were the same as that mentioned above, respec-

460 0

450 w

LL

440
4
LL
W

?
c

-LL
O

LL

,Lo

200

300
TEMPERATURE

400

,bo

Figure 3. DTA and DPA curves in hydrodesulfurization reaction

of tetrahydrothiophene (no. 470).
tively, with the exception that helium was used instead of
hydrogen, since helium is an inert gas and has a thermal
conductivity close to hydrogen. Peak area integration was
done using tracing paper from which the peak was cut out
and weighed. This was used as an arbitrary scale. Analysis
of the sulfur contained in the heavy oil was performed by
using a commercial apparatus "Coulomatic S" manufactured by Kokusai Denki Co., Ltd.

TIME

min

Figure 4. Disorder of base line at charging and purging with hydrogen in both chambers and temperature of reaction chamber.

Nc 477

Results and Discussion

Disorder of Base Line at Gas Charging. Prior to the
reaction runs, the following experiments with respect to the
disorder of the base line on the DTA curve were done to examine the stability and reproducibility of this new method.
The reference chamber was left uncharged and the reaction
chamber was equipped with only the magnet piece. Then,
both chambers were charged with the initial hydrogen
pressure of 10 kg/cm2 and raised to the desired temperature of 45OoC with a subsequent pressure increase of 20
kg/cm2. When the stability of the base line on DTA curve
was attained after approximately 10 min, both chambers
were charged with the desired hydrogen pressure of 200
kg/cm2 within 40 sec with simultaneous stirring which generated a disorder such as an endothermic peak as shown in
Figure 4. In contrast, when both chambers were purged of
hydrogen pressure from 200 kg/cm2 to 20 kg/cm2 within 40
sec, the disorder such as an exothermic peak was measured
on the opposing side. In the former, both temperatures of
the reaction and reference chambers showed an increase
amounting to 10C over 45OoC when the hydrogen was
charged, in the latter, in contrast a decrease in temperature
amounting to 10C when the hydrogen was purged. I t
seems plausible to consider that these phenomena may be
considered as endotherm and exotherm arising from the
apparent adiabatic compression and expansion. However,
since these heat generations were compensated by differential thermocouples in the reaction and reference chambers,
theoretically the disorder should not arise and in fact endothermic and exothermic peaks made their appearance.
In order to discuss the reason, the following experiments
were conducted. First, experiments were carried out placing the differential thermocouples into 100C water. It was
confirmed that the response sensitivity of the thermocouples was uniform. Next, experiments were conducted to determine whether the phenomena were independent of and
were not influenced by the stirring magnet piece in the reaction chamber at the time of charging with hydrogen.
Also, when inert helium gas was used instead of hydrogen,
similar phenomena were observed as shown in Figure 5 . In
addition, experiments similar to the above were carried out
using other reaction chambers of the same scale. As a result, it was shown that the direction and magnitude of the
disorder of base line differed distinctly. From the experi-

I
PRESSURE CHAQGING

I
I
I

~1

DRESSLIRE CHARGING
S TI Q R I NG

S'IRRING

I
I
8

8
TIME

0s 2

IO

min

Figure 5. DTA curves of blank heat evolution test with helium at

390, 420C for tetrahydrothiophene and heavy oil, respectively.

mental results described above, it was concluded that the

disorder of the base line was due to the difference of the response sensitivity induced by the delicate inequality of
thickness a t the pointed end of the pressure proof tube of
the differential thermocouples.
However, since such disorders of the base line showed
good reproducibility under fixed experimental conditions
as shown in Figure 5 , it may be considered that no large effect on the measurement accuracy of the reaction heat was
present.
Calibration Using an Electric Heater. In the case of
heat evolution tests using a small electric heater in the
reaction chamber, the experimental conditions were the
same as those in the case of measurement of true reaction
heat with the exception that inert helium gas was used instead of hydrogen and therefore electric energy was used
instead of reaction heat. Tables I and I1 present the results
of heat evolution tests in tetrahydrothiophene and heavy
oil, respectively, namely the relationship between the exothermic peak area and electric energy generating within the
sample in the reaction chamber. Figure 5 presents DTA
curves of blank heat evolution tests for tetrahydrothiophene and heavy oil without heat evolution by the small
electric heater. When, at the point indicated by an arrow,
helium was charged with simultaneous stirring of the sample, the disorder of the base line returned rapidly to the
base line within 4 min and its reproducibility was also good.
Figures 6 and 7 present typical exothermic peaks of heat
evolution tests for tetrahydrothiophene and heavy oil, reInd. Eng. Chem., Process Des. Dev., Vol. 14, No. 4, 1975

495

Table I. Heat Evolution Tests Using a Small Electric Heater with Tetrahydrothiophene and Helium
Expt no.

Temp, "C

463
355
474
370
475
390
476
390
47ya
390
471b
150-2 10
471b
2 6 0-3 0 0
a Blank test. Conventional heating method.

Pressure,
kg/cm2

Helium charge
time, sec

Electric
heat, cal

Peak area

160
160
160
160
160
110-1 1 5
140-1 4 5

34
30
35
35
30

296
719
634
409
0
872
328

20
46
42
26
0
43
17

Table 11. Heat Evolution Tests Using a Small Electric Heater with Heavy Oil and Helium
Expt no.

Temp, "C

446
405
447
400
448
400
449
3 80
450
375
451
380
452
380
453
3 80
454"
420
455a
425
456*
400
457
400
445"
420
465'
420
a Irregular mixing. No stirring. C Blank test.

Pressure,
kg/cm2

Helium charge
time, sec

Electric
heat, cal

190
200
200
200
200
180
200
200
200
200
200
200
200
200

40
30
35
64
45
45
40
40
45
40
40
45
42
45

3 63
903
595
676
66 1
664
623
3 67
83 8
864
669
801

Peak area
31
72
45
48
55
50
49
27
75
73
309
61
0
0

0
0

- 4
l
Y
3

c
4

N o 453

HEAVY OIL

4w

-I

+ -2

PRESSURE CHARGING

1 ELECTRIC

CURRENT

iL - 4

0
TIME

Figure 6. Typical exothermic peak of heat evolution test for tetrahydrothiophene at 390OC.

IO

5
TIME

min

min

Figure 7. Typical exothermic peak of heat evolution test for heavy

oil at 38OOC.
, I

lOOOr

spectively. From the results of Table I and 11, although the

effects of measurement temperature and pressure on peak
area could not be recognized, in the case where the time for
gas chargine ruas longer than for others, namely 64 sec as
shown in no. 4-19 of Table 11; the peak area was somewhat
smaller. In cases of no. 454 and 455 in which mixing was irregular on stirring, the peak area was somewhat larger. In
addition, when this was considered together with the results which were very large in the case of no. 456 with no
stirring, it was found that stirring of the sample under the
experimental conditions showed the greatest influence on
the peak area. Figure 8 presents the relationship between
electric energy and peak area obtained under fixed measurement conditions presented in Tables I and 11. This relationship of the so-called calibration lines was used for the
measurement of reaction heat of tetrahydrothiophene and
heavy oil. From these calibration lines, it was also found
that the measurement sensitivity of the peak area by the
496

Ind. Eng. Chem., Process Des. Dev., Vol. 14, No. 4, 1975

-t
800

400
0 HEAVY OIL
A TETRAHYDROTHIOPHENE

200

0 CONVENTIONAL HEATING METHOD

FOR TETRAHYDROTHIOPHENE

20

30

40

P E A K AREA

io

$0

o;

80

Figure 8. Calibration lines for measurement of reaction heat.

new constant temperature method was higher than that by
the conventional heating method. In addition, this new
method can be measured at a higher sensitivity in which
the reaction was violently induced and which proceeded to
generate a large reaction heat per unit time.

Table 111. Heat of Hydrodesulfurization Reaction of Tetrahydrothiophene

Reaction
temp, "C

Expt no.

Reaction
pressure kg/cm2 Peak area

479
400
480
410
481
405
555a
410
470b
340400
a Blank test. * Conventional heating method.

160
160
160
30
1 80 -1 7 0

Exptl,
cal/g

Theoret,
cal/g

Exptl/
theoret, %

46
50
46

308
333
303

327
327
327

94.2
101.8
92.7

...

...

,..

45

310

327

94.8

...

Heat of Hydrodesulfurization Reaction of Tetrahydrothiophene. Prior to the experimental runs in which the
heat of hydrodesulfurization reaction of heavy oil was measured, the new method was applied to the hydrodesulfurization reaction of tetrahydrothiophene where the reaction
heat could be obtained by calculation and the measurement accuracy was discussed based on a comparison of the
experimental results with the calculated values.
Under elevated temperature and pressure with cobaltmolybdenum catalyst, tetrahydrothiophene undergoes the
reaction as shown in eq 1 (Emmett, 1957).
C H&H,

\I/

C H CH,

2H,

CH,CH,CH,CH,

IO

TIME
f

H,S

15
1

25
..

20

min)

Figure 9. Typical DTA and DPA curves of hydrodesulfurization

reaction of tetrahydrothiophene at 405'C and 160 kg/cm2.

(AH7000K= -28.73 kcal/mol) (1)

After the reaction was completed, from the analysis by gas
chromatography for gases produced, traces of methane,
ethane, propane, and isobutane were detected within n butane which was the main gas produced. However, when
the calculation of the heat of reaction was carried out, these
side reactions were neglected. Therefore, in the autoclave
of the reaction chamber, the heat of reaction under conditions of 700K and 160 kg/cm2 was obtained by which the
heat of reaction a t constant pressure shown in eq 1 was
converted a t a constant volume. In addition, the effect of
the pressure on the heat of reaction was calculated. The re160 kg/cm2 = -28.87 kcal/mol.
sult was as follows: AH,o~K,
Next, until the time when the reaction is violently induced by charging with hydrogen and stirring the sample,
it can be considered that the reaction proceeds slowly even
under the experimental conditions as mentioned above.
Thus it became necessary to discount the value of the reaction prior to the target reaction. This, a so-called blank test
shown in no. 555 of Table 111, was done by cooling the autoclave a t a rate of 20C/min a t the point where the reaction
was assumed to be initiated. From the n-butane produced,
it was shown that 0.45 g of the tetrahydrothiophene had
completed its reaction. Hence, deducting 0.45 g from 2.88 g
we have 2.34 g which indicates that 2.34 g of tetrahydrothiophene was involved in the exothermic peak.
Figure 9 presents typical DTA and DPA curves (no. 481)
of the hydrodesulfurization reaction of tetrahydrothiophene. The exothermic peak was obtained by the heat of
reaction which was violently induced by charging with hydrogen and by stirring the sample a t the point indicated by
an arrow. Although the time required for the DTA curve to
revert to the base line was about 25 min, from the DPA
curve it was found that the reaction was completed within
about 5 min. Table I11 presents the results of the heat of
reactions measured three times under similar experimental
conditions. With regard to the new method, from the above
results, it was found that the reproducibility was good and
the deviation from theoretical value did not exceed 10%.
Finally, results measured by the conventional heating
method were added as reference in Table 111.

w -1

PRESSURE CHARGING
STIRRING

10
TIME

-18 !&
0

15

20

25

30

mid

Figure 10. Typical DTA and DPA curves of hydrodesulfurization

reaction of heavy oil at 435'C and 200 kg/cm2.

Heat of Hydrodesulfurization Reaction of Heavy Oil.

Table IV presents the heat of the hydrodesulfurization
reaction and analyses of products using five kinds of heavy
oil and two kinds of catalyst. Figure 10 presents typical
DTA and DPA curves (no. 462) of hydrodesulfurization reaction of heavy oil. Although the time required for the exothermic peak to revert to the base line was about 30 min, it
was shown that the reaction was not completely terminated
a t the time; this may be said because limited hydrogen absorption was noted on the DPA curve. In other words, since
the reaction was still slightly in progress a t the termination
point of the exothermic peak, it was considered that this
may exert a slight effect on the measurement accuracy of
this method. The results when the autoclave was rapidly
cooled down at the point where the reaction was assumed
to be initiated are shown in no. 466 of Table IV. This was a
blank test. Therefore, a t the time when the heat of reaction
per gram of sulfur hydrodesulfurized was obtained, the
value of sulfur removal (11.0%) of no. 466 was considered.
In line with the above, it may be surmised that the heat of
reaction per gram of heavy oil reacted showed values somewhat lower than the true value. Next, it was found that the
sulfur removal increased with a rise in reaction temperature. Similarly, it can be seen from the results of the yield
of gases produced and hydrogen consumption that the hyInd. Eng. Chem., Process Des. Dev.. Vol. 14, No. 4, 1975

497

0
0

frl

0
0
fd

0
0

td
-

0
0

rl

0
0

0
.d

bD

b
cd
0

498

Ind. Eng. Chem., Process Des. Dev.. Vol. 14, No. 4, 1975

Table V. Heat of Hydrogenation Reaction and Hydrogen Consumption

Heat of
reaction, kcal/kg

Reaction

Hydrogen
consumption,
mol/kg

Literature

30
43
27
25

Mitsui and Yamaguchi (1939)

Mitsui and Yamaguchi (1939)
Shibata (1952)
Takagi et al. (1942)

20

G k t h e r (1970)
Lee et al. (1968)
Lee et al. (1968)
This work

~~

Coal hydrogenation
Coal hydrogenation
Coal hydrogenation
Hydrogenation of coal hydro genation products
Hydrogenation of coal tar
Hydrogasification of coal
Hydrogasification of coal char
Hydrodesulfurization of heavy
oil

571, 642
723, 942
440
210
24 0-3 3 0
300-570
150-540
5-67

HEAT O F REACTION

-.
M

HYDROGEN CONSUMPTION

0
o a

LL

301

-3

201

-2 0

ul
3

z
w

-I 0

g
LL

SULFUR CONTENT

Figure 11. Effects of sulfur content of heavy oil on heat of reaction and hydrogen consumption under conditions of 425OC and
200 kg/cm2.

it//
=

1 0

00

20

3 0

4 0

HYDROGEN CONSUMPTION mal kg

Figure 12. Relationship between heat of reaction and hydrogen

consumption for hydrodesulfurization reaction of heavy oil.

l"""

0 COAL

COAL

800-

PRODUCT

0 600 -

...
0.6-2.9

drocracking of heavy oil also proceeded gradually with the

temperature rise. Consequently, the heat of reaction per
gram of heavy oil reacted increased with the temperature
rise. Figure 11 presents the effects of the sulfur content of
heavy oil on the heat of the reaction and hydrogen consumption under conditions of 425'C and 200 kg/cm2 shown
in Table IV. From these results, in the case of hydrodesulfurization reaction of heavy oil under a fixed reaction condition, it was shown that both the heat of reaction and the
hydrogen consumption increased with the amount of sulfur
content. In addition, it seems probable that the heat of the
reaction has an approximately linear relationship with the
hydrogen consumption as shown in Figure 12.
Table V presents the heat of reaction and the hydrogen
consumption for hydrogenation of coal, coal tar, and so on,
obtained from the literature. Figure 13 indicates that an
approximately linear relationship exists between the heat
of reaction and the hydrogen consumption. The three
points which showed a relative deviation from the linear
line were not experimental results, but that which was calculated thermochemically by simplifying numerous complicated reaction. Moreover, the values obtained by the authors shown in Figure 12 and this line almost agreed as
shown in Figure 13. Therefore, it was ascertained that the
heat of reaction of hydrogen with heavy oil, coal, coal tar,
etc, could be roughly estimated from the amount of hydrogen consumption.

Literature Cited
Emmett, P.H., "Catalysis". Vol. V, p 426,Reinhold. New York, N.Y., 1957.
anther, G., Chem. Techno/., 22, 552 (1970).
Ishii, T., Yahata, T., Takeya. G., Kagaku Kogaku, 31, 896 (1967).
Ishii, T.. Sanada. U., Takeya, G., J. Chem. SOC. Jon.. lnd. Chem. Sect.. 71.

1783 (1968).
Ishii, T., Sanada. U., Takeya, G.. J. Chem. SOC. Jpn., lnd. Chem. Sect., 72,

CALCULATED

1269 I1 9691.
---,

A COAL HYDROGENATION

...

~~~

>

Itho. H., Makino, K., Umeda, N.. Takeya, G.. Ueda, S.. J. FuelSoc. Jpn., 50,

CALCULATED

919 (1971).

COAL TAR

0 HEAVY OIL

Lee, A. L., Feldkirchner, H. L., Schora, F. C.. Henry, J. J.. lnd. Eng. Chem.,
Process Des. Dev., 7, 244 (1968).
Mitsui. K., Yamaguchi, S., "Catalysis-Coal Hydrogenation", p 72,Shukyosha,
Tokyo, 1942.
Shibata, K., J. FuelSoc. Jpn., 31, 267 (1952).
Takagi, T., Higashi, M.. Morikawa, K., J. FuelSoc. Jpn., 21, 476 (1942).
Takeya, G..Ishii, T., Makino, K., Ueda, S., J. Chem. SOC. Jpn., lnd. Chem.
Sect., 69, 1654 (1966).
Ueda, S., Yokoyama, S., Ishii. T., Takeya, G., J. Chem. SOC.Jpn., lnd. Chem.
Sect, 74, 1377 (1971).

zooL
00

IO

20

30

HYDROGEN CONSUMPTION

40

50

mal kg

Figure 13. Relationship between heat of reaction and hydrogen

consumption for hydrogenation reaction.

Received f o r review March 4, 1975

Accepted May 28, 1975

Ind. Eng. Chem., Process Des. Dev., Vol. 14, No. 4, 1975

499