The catalytic desulfurization of Wyoming fuel oil
by Franklin C Silvey
A THESIS Submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree
of Master of Science in Chemical Engineering
Montana State University
© Copyright by Franklin C Silvey (1953)
Abstract:
This investigation was conducted to determine the applicability of molybdenum oxide and cobalt
molybdate as desulfurization agents in the catalytic desulfurization of a number three fuel oil produced
from a high-sulfur-containing Oregon Basin, Wyoming crude oil. The desulfurization studies were
carried out in a pilot plant unit capable of holding 100 grams of catalyst, operated at a pressure of 500
psig and a temperature of 415°C. A space velocity of approximately 1.0 grams of oil per gram catalyst
per hour and recycled "catforming" gas as a desulfurization atmosphere were employed in all the
desulfurization studies. To meet specifications, the effluent oil was to contain less than 0.5 percent
sulfur.
When a number three fuel oil was desulfurized using a molybdenum oxide catalyst and a recycle gas
hydrogen content above the critical value, successful desulfurization was accomplished for 495 hours
without air regeneration. Air regeneration had ho noticeable effect on the original activity of the
molybdenum oxide.
The critical hydrogen content of the recycle gas was found to be a function of and increased with
catalyst on-stream time.
Cobalt molybdate was used successfully as a desulfurization agent for 864 hours of continuous
operation with no air regeneration. This catalyst showed a considerably higher activity and a longer
catalyst life than the molybdenum oxide. THE CATALYTIC DESULFURIZATION OF
WYOMING FUEL OIL
by
FRANKLIN C. SlLVEY
A THESIS
Submitted to the Graduate Faculty
in
partial fulfillment of the requirements
for the degree of
Master of Science in Chemical Engineering
at
Montana State College
Approved;
Head, Major Departpiefft
'''''/.IfXzj
'''V'/1/7
-2-
SiMe,
TABLE OF CONTENTS
Page
Abstract. . . ..........
3
Introduction. ..........
4
Thermodynamic Calculations
6
Equipment ..............
7
Materials . ............
10
Methods . . .
10
..........
Sample Calculations . . .
13
Discussion of Results . .
15
S u m m a r y ............ .. .
19
Literature Cited. . . . .
20
Acknowledgment
21
Appendix. . .
22
/•i
-3ABSTRACT
This investigation was conducted to determine the applicability of
molybdenum oxide and cobalt,.,molybdate as desulfurization agents in the
catalytic desulfurization of a number three fuel oil produced from a highsulfur-containing Oregon Basin5 Wyoming crude oil* The desulfurization
studies were carried out in a pilot plant unit capable-o f holding lOO grams
of catalyst5 operated at a pressure of $00 psig and a temperature of 41$0C<,
A- space velocity o f .approximately 1,0 grams of oil per gram catalyst per
hour and recycled "catforming" gas as a desulfurization atmosphere were
employed in all the desulfurization studies. To meet specifications, the
effluent oil was to contain less than 0,5 percent sulfur,
When a number three fuel oil was desulfurized using a molybdenum
oxide catalyst and a recycle gas hydrogen content above the critical value,
successful desulfurization was accomplished for 495 hours without air re­
generation, Air regeneration had ho noticeable effect on the original
activity of the molybdenum oxide®
The critical hydrogen content of the recycle gas was found to be a
function of and increased with catalyst on-stream time.
Cobalt molybdate was used successfully as a desulfurization agent for
This catalyst
showed a considerably higher activity and a longer catalyst life than the
molybdenum oxide.
864 hours of continuous operation with no- air regeneration.
[
108575
BrrRODUGTIbW ■
With the increased demand for heavier distillates for-use in. Diesel
engines, gas turbines and jet aircraft motors, and the depletion of high
quality low sulfur crudes, petroleum refiners have been forced to turn to
crude stocks with high sulfur contents.
Such crudes can be utilized only
if an economical method for reducing the sulfur content can- be devised.
Sulfur has been found to occur in crudes -and refined fractions as
elemental sulfur, mereaptans, hydrogen sulfide, thiophenes, thiophahes,
thioalcohols, organic sulfides, disulfides, and polysulfides (9 ),
The
objection to sulfur compounds in refined products are their actual or
potential corrosive action on metal surfaces, reduction of the-effective­
ness of tetra-ethyl lead addition, detrimental effect on color stability,
disagreeable odor and undesirable oxidation characteristics-.
The literature contains numerous processes for treating light dis­
tillates,
These generally remove the simple sulfur compounds by absorption
or extraction or convert the sulfur to a less objectionable form without
reducing the total sulfur content.
The methods used for light distillates
are not applicable to heavier fractions since they do not affect the more
complex sulfur compounds found in heavy distillates, do not reduce the
potential corrosiveness due to sulfur or cause excessive charge losses if
extraction methods are used..
The most successful means of reducing the sulfur content of heavy
fractions to meet required specifications with minimum losses is catalytic
decomposition,
Koski (5) studied the effect of bauxite and alumina
catalysts under mild conditions and found that a maximum of 50 percent
sulfur removal could be achieved.
Using destructive dehydrogenation cata­
lysts, such as molybdenum sulfide, as desulfurization agents in the
presence of.a hydrogen atmosphere. Green (3 ) and Muhro (7 ) reported success­
ful desulfurization, long catalyst life and easy catalyst regeneration.
The mechanism of desulfurization in the presence of hydrogen is destructive
dehydrogenation which converts the sulfur compound to a hydrocarbon and
Hartwig (4 ) studied the effect of using a hydrogep
hydrogen sulfide.
.
A
rich gas, such as the off-gas from a "catforming" up-grading process, as a
desulfurization atmosphere with a molybdenum sulfide catalyst.
are comparable to those of Green (3 ) and Munro (?)*
His results
Using the off-gas
from a "catforming" unit eliminates the necessity of constructing a hydro­
gen plant in conjunction with the desulfurization process.
The purpose of this research was to study the effect of recycling
"catforming" gas, using molybdenum oxide and cobalt molybdate catalysts on
the desulfurization of number three fuel oil.
Hie maximum allowable sulfur
content for number three fuel oil was to be 0.5 percent.
-6THERMODYNAMIC CALCULATIONS
Tabulated thermodynamic data and calculations are presented in Tables
I - III of the appendix.
Two reaction mechanisms were postulated for the conversion of molybden­
um oxide to molybdenum sulfide during the desulfurization of a number three
fuel oil.
Either or both of these reactions may take place.
(1)
M 0 O3 + 3H2S -- >
(2)
MoO3 + 3C4 H4S + 12H2 — >
MoS3 + 3H20
MoS3 + 3C4H10 + 3H20
These reactions were considered since the conversion of the oxide to
the sulfide may be due to the hydrogen sulfide present in the recycle gas
or the sulfur in the fuel oil.
Although thiophene is not present in number
three fuel oils, it was considered in the absence of thermodynamic data on
higher alkyl thiophenes and should approximate the results that would be
obtained with higher alkyl thiophenes.
The following free energies show that reaction (l) is feasible at
400°C while reaction (2) is not.
Reaction
I
2
F at 25°C
Cal/mol
F at 400°C
Cal/mol
-32,930
-27,350
-12,660
+ 61,040
The thermodynamic calculations of four mechanisms postulated for
desulfurization of fuel oil by molybdenum sulfide catalyst are given by
Green (3).
The results of these calculations help to confirm the postulated
mechanism for desulfurization but are not of much value when used to fix
the proper conditions under which the overall reaction should be.run since
the equilibrium constants are all very high in the paraetical operating
rangee
EQUIPMENT
A diagram of the reactor is shown in Figure I*
The reactor consisted
of a 16 inch length of I^ inch extra-strong black iron pipe fitted with a
Ig to 3/4 inch reducer at the top and a Ig to g inch reducer at the bottom^
The top of the reactor was fitted with a union, two crosses, and an assembly
of valves for feed gas inlet, oil inlet, oil feed-line bleed, an inlet for
regeneration, blowout-disk exhaust system, and thermowell tube.
The thermo­
well tube was a ^ inch black iron pipe which extended from the cross at the.
top of the reactor along the vertical axis of the reactor to within one inch
of the bottom.
The thermowell tube wqs capped at the bottom, and three
thermocouples were inserted from the top.
The hot junctions of the .thermo­
couples could be adjusted to any desired position in the thermowell.
At the bottom of the reactor a condenser was connected with a g inch
pipe union.
The condenser consisted of a 21 inch length of g inch pipe
with a 3 inch pipe as a water jacket.
Below the condenser were fitted a
cross, two tees, a pressure gage, a Jerguson receiver, a Mason-Neilan
small volume air-to-close regulator valve and a 23 inch length of g inch
pipe which served as an overflow standpipe.
A Fisher-Wizard proportional
controller was used in connection with the Mason-Neilan valve to maintain
the correct pressure in the system.
The condensed vapors were removed from the Jerguson receiver and
collected in a one liter ErlennQrer flask„
The non-condensable exhaust
gases entrained in the effluent oil were passed through two scrubbing
flasks in series containing a concentrated sodium hydroxide solution to
remove the hydrogen sulfide.
The sweetened gas was metered in a wet test
meter manufactured by the Precision Scientific Company,
The recycle system consisted of a surge tank, a compression tank, and
a feed tank,
A number two gas cylinder served as the surge tank and was
fitted at the top with a 3 inch length, of 3 /4 inch pipe, a cross, a
pressure gage and two valves.
The compression tank was a number two gas
cylinder. .At the top of the compression tank were a small sight glass, a
cross, pressure gage and two valves used to isolate the tank from the re­
cycle system.
A ^ inch standard black iron pipe was welded to the bottom
of the compression tank.
Fitted to the i inch pipe through a ^ to % inch
reducing elbow was a length of ^ inch pipe which connected the compression
tank to the compression pump.
On the ^ inch pipe was a tee one side of
which was connected to a two cylinder adjustable stroke high pressure
HillS'^S'dCahna piston pump, the other side was fitted with a valve for
l^dturhing the compression oil to the oil storage reservoir.
reservoir was a five gallon oil barrell.
The oil storage
The feed tank was a number two
gad cylinder fitted at the top with a cross and a pressure gage and with a
valve at the bottom.
All connections between tanks in the recycle system
were made with high pressure steel tubing.
Tie heating elements for the reactor consisted of three 33 foot
-9-
iehgths of beaded Nichrome wire supplied with current from three 110-volt
■Powerstat variacs„
The coils were wound around the reactor over a layer of
asbestos tape and insulated with an additional covering of asbestos tape
and a one inch layer of magnesia mud,
/
One-eighth inch aluhdum balls were used as the preheat medium.
The
catalyst bed was located below the preheat section and. below the catalyst
bed was another layer of alundum balls supported by a wire screen.
The oil feed system consisted of a two cylinder adjustable stroke
piston pump and an oil reservoirT
Auxilliary equipment included a Fisher Flowrator3 a Brooks Eotameter3
and gas cylinders with pressure regulators.
Iron-constantan thermocouples
were used in conjunction with a Leeds and Northrup indicating potentiometer for temperature measurement.
Analysis of recycle gas samples was made in a low temperature
fractionation column.
-I Q -
MATERIALS
The materials used for the desulfurization studies were a number three
fuel oil, compressed hydrogen, methane, "catforming" gas, and various
catalysts.
The number three fuel oils, produced by the Husky Oil Company from
Oregon Basin, Wyoming crudes, contained from 2.09 to 2.176 percent sulfur.
Additional inspection data of the oil are listed in Table I?.
The catalysts investigated were'10% molybdenum oxide, 16% molybdenum
oxide and cobalt molybdate; all on alumina.
The code letters and compo­
sitions of these catalysts may be found in Table V.
The hydrogen gas used in this research was obtained from the Whitmore
Oxygen Company of Salt Lake City, Utah.
The methane gas and "catforming"
gas used in the studies were obtained from the Matheson Company of East
Rutherford, Mew Jersey.
The composition of the "catforming" gas was 89
percent hydrogen, 3 ,5 percent methane, 1 .5 percent ethane, 2 .5 percent .
propane and 3 .5 percent propylene.
METHODS
The desulfurization unit was put into operation by applying current
to the heating coils.
When the temperature in the catalyst bed reached
3OO0 G, "catforming” gas flow was started and the reactor was pressurized by
adjusting the back, pressure valve.
When the catalyst temperature reached
38©°G, the oil to be desulfurized was charged to the reactor by the oil
pump and the heating coil current was adjusted to maintain the proper
-11-
reactor temperatureo
Recorded readings were not made until the reactor
conditions became constant.
Recycling the "catforming" gas was accomplished by compressing the gas
flowing from the reactor through the back pressure valve and. returning it
to the feed tank.
When the pressure in the surge and compression tanks
reached 3 PO psig, the compression tank was isolated from the system and
the compression pump was started.
Oil was pumped into the bottom of the
compression tank until the pressure was equal to the pressure in the feed
tank.
Having reached equal pressures, the valve between the compression
tank and the feed tank was opened and the compression continued.
When
the pressure in the feed and compression tanks had reached 600 psig, the
compression pump was turned off and the valve between the feed and compres­
sion tanks was closed.
The oil in the compression tank was forced out by
opening the valve between the compression tank and the oil storage tank.
After the oil had been removed from the compression tank, the pressures in
the surge and compression tanks were equalized and the compression cycle
was completed.
The "catforming" gas flow rate was measured by means of a Fisher
Flowrator and was controlled by a high pressure needle valve.
Gas flow
through the reactor was maintained by supplying the "catforming" gas at
a pressure higher than the reactor pressure setting of the back pressure
valve.
The reactor pressure was .controlled by supplying the proper amount
of air pressure to the diaphragm of the back pressure valve.
The temperatures at the top and bottom of the catalyst bed and in the
“12-
preheat section were controlled by varying the current in the beaded
Niehrome heating coils„
The temperature in the preheat section was main­
tained at approximately 95°C below the catalyst bed temperature,
The
temperatures at the top and bottom of the catalyst bed were recorded at
30 minute intervals and these readings were averaged over a period of eight
hours'.
The effluent oil was removed.continuously from the Jerguson receiver
at a rate which maintained a continuous liquid seal in the receiver.
Samples of the effluent oil were taken at eight hour intervals.
The space
velocity was controlled by adjusting the pumping rate of the oil charge
pump.
Space velocity calculations for the sample intervals were based on
the weight of charge oil and the weight of catalyst in the reactor.
The samples of the effluent oil were weighed and a portion of the oil
removed from each sample for sulfur content determination.
The dissolved
hydrogen sulfide gas was removed from the portion by washing with a 10
percent solution of sodium hydroxide followed by two distilled water
washes.
The sulfur content was determined by a modified lamp sulfur method
(l) in which a sodium carbonate solution was used to absorb the sulfur
dioxide from the lamp combustion gases.
The excess sodium carbonate was
titrated with dilute hydrochloric acid with brom-phenol blue indicator.
-1 3 -
SAMPLE CALCULATIONS
A TYPICAL SHORT DURATION RUN
MoS-III
V-3 JHFS
Oil - Husky #3 Fuel Oil ( 2.0# S)
Catalyst - 100 Grams Harshaw Mo-0203 T 1/8-160A-2-1
Reactor Pressure - 500 Psig
Sample
Number
Total
Hours
2
8
16
3
4
5
24
32
40
I
Sample
Weight
Grams
Percent
Sulfur
Per Samp.
755
741
755
761
Average
Temp. 0C
.561
.584
Liters STP
Makeup Gas
Liters STP
Bleed-off
Gas
0
0
7.6
7.6
7.2
6.9
415
414
.666
416
.691
.725
415
413
74.9
25.1
41.7
6 .8
37^
Oil Charged = 3893 grams
Calculation of Average Space Velocity
(3893 grams oil charged)
(lOO grams catalyst)(40 hours)
= 0.973 grams oil/gram cat./hour
Calculation of Average Gas Consumption
Total Liters (STP) Make-up Gas = 141.7
Total Liters (STP) Bleed-off Gas = 36.1
Total Liters (STP) Consumed = 105.6
105.6 Liters Consumed
3893 Grams Oil
1000 grams
Kilogram
27.1 Liters , I f t 3 _______
Kgm
28.316 liters
_
p? I
°
Liters Consumed
Kilogram Oil
3.78 Kgm „
„ 42.0 gal _
1 2 9 .8 ft^bl
I gal
X 0 a
bbl
-14-
Calculation of Weight Percent Loss
Charge Oil Weight = 3893 grams
Effluent Oil Wt. = 3768 grams
125 grams loss
x 100
3.21*
Calculation of Grams Sulfur Removed From Oil Per Gram of Catalyst Per
Eight Hour Sample
For Sample One
Charge Oil = 7 8 1 Grams at 2.09* Sulfur
Effluent Oil ■ 755 Grams at O.56I* Sulfur
Grams Sulfur in Charge Oil
= 781 x 2.090 =
Grams Sulfur in Effluent Oil = 755 x 0.561 *
Grams Sulfur Removed
=
12.08 Grams Sulfur Removed
100 Grams Catalyst
16.31
4.23
12.08
0.1208 Grams Sulfur Removed/Gm. Cat.
Calculation of Composite Sulfur Percent
Sample Weight
Percent Sulfur
0.561
755
741
755
761
756
3768
x 100 =
0.584
0.666
0.691
0.725
0.645* Sulfur
Grams Sulfur
4.23
4.32
5.02
5.26
5.48
24.31
-1 5 -
DISCUSSION OF RESULTS
The catalysts employed, in the investigations were 10 percent molyb­
denum oxide, 16 percent molybdenum oxide and cobalt molybdate.
The operat­
ing conditions of the various runs were a reactor pressure of 500 psig, an
average temperature of 4150 C* space velocities of approximately 1 .0 grams
of oil per gram of catalyst per hour, and "catforming" gas recycle rates of
approximately 147 standard liters per hour.
Several molybdenum oxide studies were made to determine the applica­
bility of this catalyst as a desulfurization catalyst.
The results of these
runs are shown in Figures 2 and 3 on which calculated composite- sulfur con­
tents are plotted versus catalyst on stream time.
The data for the first molybdenum oxide study, MOS-l, are shown in
Table VI.
Using a 16 percent molybdenum oxide catalyst, the results ;of
the MOS-I run were in no way comparable to the molybdenum sulfide studies
made by Hartwig (4), or to similar runs performed by the Husky Oil Company.
The sulfur content of the effluent oil Exceeded 0.5 percent after only 40
hours of on-stream operation, so the run was discontinued. .
.
" W 'f,:.
Considering the possibility of incorrect designation of the composi­
tion of the catalyst used in the MQS-I run, a second molybdenuin oxide study
using a 10 percent molybdenum oxide catalyst was made.
run are shown in Table VII.
The data for this
In the MOS-II run Ijie sulfur content of the
effluent oil exceeded 0«i5 percent after only 32 hours of operation.
run indicated that the compositions of the catalysts were properly
designated.
This
=16—
A third molybdenum oxide study, using a 16 percent molybdenum oxide
catalyst obtained from the Husky Oil Company, did not produce specification
. oil during any part of the run and was discontinued after 40 hours of
operation.
The data fbr this run, MOS=III are shown in Table VIIi0
A molybdenum sulfide catalyst was prepared.by sulfiding a 16 percent
molybdenum oxide catalyst with hydrogen sulfide at 300oC-o
catalyst, the sulfided catalyst study run,.SCS=I, was made.
Using this
The sulfur
content of the effluent oil exceeded 0 .5 percent after 8 hours of the run,
and the catalyst was regenerated with an air burn-off after 40 -hours. „of
operation.
When the run was continued after the catalyst regeneration, a
space velocity of 0 .5 was used for the first 16 hours of operation and
then increased to approximately 1.0 for the remainder of the run*
The
sulfur content of the effluent oil was correspondingly low at the low
space velocity but exceeded 0*5 percent soon after the space velocity
reached 1.0.
The gas rate was increased from 147 to 157 standard liters
per hour at sample number 13.
This increased rate.did not have any notice­
able effect oh the sulfur content of the effluent oil*
discontinued•108 hours' after the catalyst regeneration.
The SCS-I run was
Tabulated data for
this run are shown in Table IX*
The MOS-IV run, using a 16 percent molybdenum oxide catalyst, was
started with pure hydrogen as" feed gas on a one pass basis and changed to
"oatforming" gas on recycle when the hydrogen supply became exhausted after
8.5 hours of Operation.
In this run the charge oil was started through the
reactor at IOO0 C .and the reactor temperature was allowed to increase slowly
-17-
over a period of 11 hours to 4150 Co
During this same period the space
velocity was increased from 0*57 to 0,87,
After the first U
hours, the
space velocity was slowly increased to approximately 1*0 and held at this
rate for the remainder of the run*
For" the first seven samples, excluding
sample number one, specification oil was produced*
However, as soon as the
unit was switched to "catforming" gas on recycle and the space velocity
increased, the sulfur content in the effluent oil began to rise*
At the
end of 335 hours of operation,.the MOS-IV run was discontinued.
The tabu­
lated data for this run are shown in Table X 0
Gas analyses of samples of the Recycle gas used in the molybdenum
oxide studies are shown in Table XIII*
Analysis of the recycle gas at the
end of the MOS-IV run showed a hydrogen content* of 76 percent*
Hartwig (4)
found that specification oil was produced using a recycle gas containing
81*1% hydrogen*
This indicated that if the molybdenum sulfide and oxide
catalysts, have similar properties, the preceding molybdenum oxide studies
were made with a deficiency of hydrogen in the recycle gas*
For the MOS-V run, the recycle gas was enriched to 87*5 percent hydro­
gen and the unregenerated catalyst from the preceding run, MOS-IV, was used*
Data for the MOS-V run are shown in Table XI*
Since the sulfur content of
the effluent oil regained over 0*5 percent for the first 92*5 hours of the
run, the catalyst was air regenerated*
an initial
Using the regenerated catalyst and
space velocity of 0*346, the MOS-V run was continued*
The
space velocity was increased slowly to approximately 1*0 and continued at
this rate for the remainder of the run*
During the remainder of the run.
specification oil, which yielded a calculated composite sulfur content of
0 .418 , was produced for 495 hpurs of continuous operation,.
Satisfied- that molybdenum oxide was comparable to molybdenum sulfide
as a desulfurization catalyst, the catalyst was regenerated with a,n air
burn-off and the MQS-V run was continued to determine the critical hydrogen
content In the recycle gas.
For the first 72 hours of the continued run,
"catforming" gas-was used as ipake-up gas .until it was evident that the
catalyst was responding normally.
When normal catalyst response was
established, methane gas was substituted as make-up gas for 120 hours
'
until the sulfur content of' the effluent oil exceeded 0.5 percent.
When
specification oil was no longer produced, the methane was replaced, and
pure hydrogen gas was used as make-up gas for the remainder of the run.
Samples of the recycle gas were taken at fbequent intervals during the run
and their analyses are shown, in Table XIII. The results of this study are
shown on Figure 4, where percent sulfur for each sample gnd the hydrogen
content of the recycle gas are plotted versus hours on-stream time.
Using
Figure 4, the critical hydrogen content of the recycle gas can be evaluated
at several different periods during the run.
These values are shown oh
Figure 5» where percent hydrogen is plotted versus catalyst on-stream time
for an operating space velocity of l.Q.
The critipal hydrogen content was
found to increase with catalyst on-stream time.
The data for the cobalt-molybdate comparison run, CMR-I, are- shown in
Table XII.
This run was operated for 864 hours under the same conditions
used for the preceding molybdenum oxide, studies.
Specification oil was
■=19™
produced for the entire run and.the calculated composite sulfur content
was found to be.,1082.
only O0206 percent.
The highest sulfur content for a single sample was
The gas consumption averaged 201 ft3 per barrell which
is somewhat lower than values determined in previous studies.
The results
of the OMR-I run, as shown in Figure 6, in which percent sulfur for each
sample and composite sulfur percent are plotted versus catalyst on-stream
time, clearly shows that cobalt molybdate catalyst exhibited considerably
higher activity than the molybdenum oxide catalysts studied previously,
SUMMARY
A catalyst containing 16 percent molybdenum oxide can be successfully
employed as a desulfurization agent using "catforming" gas on recycle,' - The
results indicate that this catalyst will produce a calculated composite
sulfur content of less than 0 ,5 percent for a period of 495 hours without
an air regeneration from a number three fuel oil originally containing
2 .176 percent sulfur.
Air regeneration does not produce a noticeable effect on the original
activity of molybdenum oxide.
The critical hydrogen content of the recycle gas, utilized with a 16
percent molybdenum oxide catalyst operated at a space velocity of approxi­
mately 1,0., was found to increase with catalyst on-stream time.
As shown
in Figure 5, the critical hydrogen content increased from 66% at 160 hours
on-stream to 88 % at 536 hours on-stream.
The presence of a small amount of cobalt oxide with the molybdenum
oxide greatly increased the activity and extended the catalyst life.
-20-
LITERATURE CITED
(1)
A eS0T 9M. STANDARDS ON PETROLEUM AND LUBRICANTS, American Society for
Testive Materials, Philadelphia, Pa., p 2?2 (1941).
(2)
Glasstone, Samiiel, THERMODYNAMICS FOR CHEMISTS, D. Van'Nostrand
Company, Inc., New York, N. Y., Fourth Printing (1949).
(3)
preen, K 0 J., M 0 S 0 Thesis, Montana State College (1952).
(4)
Hartwig, J 0 R., M. S. Thesis, Montana State College (1953)»
(5)
Koski, 0. H., M. S. Thesis, Montana State College (1952).
(6)
Lange, N. A., HANDBOOK OF CHEMISTRY, Sixth Edition, Handbook
Publishers, Inc., Sandusky, Ohio, (I946 ).
(7)
Muhro, B. L., M, 8 . Thesis, Montana State College (1952).
(8 )
Perry, J 0 H., CHEMICAL ENGINEERS HANDBOOK, McGraw-Hill Publishing
Company, New York,- N. Y., Third Edition (1950).
(9)
Sachanen, A., CONVERSION OF PETROLEUM, Reinhold Publishing Company,
New York, N. Y., Second Edition, (1948).
(I©) United States Bureau of Mines Bulletin No. 406.
(Il) United States Bureau of Mines Bulletin No. 477«
-21-
• ACKIiOliLEDGMENT
The author wishes to thank the Husky Oil Company of Cody5 looming for
sponsoring this research work and for supplying the fuel oil used through­
out the project.
22-
«=
APPENDIX
Page
Table I
Thermodynamic Calculations for the reaction:
M 0 O3 +
MoS^ + SHgOe e 0
0
Table II
0
0
0
0
0
0
0
0
0
• 23
4
Thermodynamic Calculations for the reactions
M 063 '+ 3 O4 H4 S + 12Hg —
MoS^ + SC4H 10 + 3 H2 O
Table III
General Thermodynamic Data. .
o
e
Table IV
Number 3 Fuel Oil Inspection Data
Table V
Catalysts
o
o
e
o
o
o
o
o
o
o
o
o
o
0
o
o
o
0
o
o
o
^
o
o
o
o
i
» 24
0
0
0
0
0
0
0
0
4
- 24
e
e
o
o
o
t
. 25
0
o
o
- 23
o
o
o
Table VI
Tabulated Data for Molybdenum Oxide Sulfiding
Eun Ope .
. 26
Table VII
Tabulated Data for Molybdenum Oxide Sulfiding
Run Two .
» 2?
Table VIII
Tabulated Data for Molybdenum ChdLde Sulfiding
Run Three
e 28
Table it
Tabulated Data for Stilfided Catalyst Study Run One,
. 29
Table X
Tabulated Data for Molybdenum Oxide Sulfiding
Run Four.
. 30
Table Xl
Tabulated Data for Molybdenum Oxide Sulfiding
Run Five.
. 32
Table XII
Tabulated Data for Cobalt Molybdajie Rup One
Table XlII Recycle Gas Analyses,
>0
0- 0
0
0
0
e : o
0
0
0
0 0 0 6 0 0 « .38
0
0
0
0
0
Figure I
Diagram of Reactor 0
Figure 2
Effect of On-Stream Time on Desulfurization for
Molybdenum Oxide Catalysts,
0
0
0
0
0
>
Figure 3
Figure 5
0
6
•
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
«
. 42
. 43
. 44
0
. 45
•
Desulfurization and Percent Hydrogen in Recycle Gas vs
On-Stream TiMe ftir 16$ Molybdenum Oxide Catalyst,
9O
O
O
O
O
0 46
Critical Hydrogen Content of Recycle Gas for 16$
Molybdenum Oxide Catalyst
0
0
0
0
. 47
Effect of On-Stream Time on Desulfurization for
Cobalt Molybdate Catalyst .
0
0
0
0
a\ 48
0
Figure 6
'
0
Effect of On-Stream Time on Desulfurization for
. Molybdenum Oxide Catalysts. . . . . . . . . . . . . . .
it
Figure 4
0
0
0
0
6
0
6
0
0
0
0
0
0
0
0
0
0
0
0
0
6
0
0
0
-23'
TABLE I
THERMODYNAMIC CALCULATIONS FOR THE REACTION
MoO^ + 3H2S-- ^
A
ft
Temperature
6K
OC
25
298
100
200
300
373
473
573
350
623
400
673
MoS^ + 3 HgO
H2^g - T A s 2^g
A
f
-32 ,9 3 0
-31 ,8 2 0
-30,320
-28,830
-28,080
-27,350
eq
1024.1
IOltie/
IO1^
IO11
IOtie9
TABLE II
THERMODYNAMIC CALCULATIONS FOR THE REACTION
M 0 O3 + 3C^H^S + 12H2 — ^ MoS^ + 3C^H10 + 3H 2 O
A
Temperature
OC
°K
25
298
100
200
300
373
473
573
623
673
350
400
ft
“ ^ h298 - t ^ s298
AF
cal/mol
Ke
—
-12,660
4,340
27,040
38,540
IO 9 «3
10-2.5
10-12.5
10-14.7
10-21.4
10-23.5
61,040
72,540
-24-
TABLE III
GENERAL THERMODYNAMIC DATA*
Compound
K IllJmol
E.U%
MoOg(S)
MoS3 (S)
iWg)
H2 °(g) x
-180.39
—6 l *48
-4.77
-57.80
SSi
-29.81
18.7
15.9
49.15
45.11
69.3
74.21
0
31.21
27.82
%(&)
*Data obtained from the following sources: U.S. Bureau of
Mines Bulletin No. 406 (10), U.S. Bureau of Mines Bulletin
No. 477 (11), Glasstone (2), Lange (6 ), Perry (8 ).
TABLE IV
NUMBER 3 FUEL OIL INSPECTION DATA
A.P.I. at 60°F
Sp. Gr.
d. 6 O0F (calc)
Ave. Mol. W t .
U.O.P. K factor
3 0 .6
Bromine No.
0.8729
0.8709
% Olefin
Wgt. % Sulfur
Wgt. % H2 in Oil
222
11.5
A. S. T. M. Distillation
I.B.P.
5%
10%
20%
3#
bO%
50%
60%
70%
80%
9#
95%
E.P.
Recovered
Residue
Loss
425 °F
504
520
536
548
558
567
575
584
594
611
625
652
99.0*
0 .8%
0 .2*
7.57
10.5
2.223
10.9
-25-
TABLE V
CATALYSTS
Producer: Harshaw Chemical Co.
Catalyst and Composition
Identification Code
Molybdenum Oxide
16 % MoOo
AlgO^ Balance
M0 -X-L73 9-21-3 T-3 /8 "
Molybdenum Oxide
10% M 0 O3
AI2O3 Balance
Mo-X-L739-21-lT-3/8"
Molybdenum Oxide
16% MoOo
AlgO^ Balance
Mo-0203 T l/8"-l60-A-2-l
Cobalt Molybdate
M 0 O3 - 9.5^
CoO — 3,0%
SiO2 - 5.0%
Graphite - 2.0%
AlgO^ - balance
Co-Mo-0201-T-3/l6"
TABLE TI
TABULATED DATA FOR MOLYBDENUM OXIDE SULFIDING RUN (MOS-I)
Harshaw Mo-X-L 739-21-3-T 3/8" was used at $00 Psig
Husky #3 Fuel Oil + catforming gas on recycle
Composite sulfur percent = .483
Percent loss (weight basis) = 3.16
I
8
2
16
3
4
5
24
32
40
48
56
64
72
6
7
8
9
Sample
Space vel. Liters
* S
wt. gms. per
gms oil/
Recycle
Samp. gm cat/hr Gas/gm oil
715
723
788
786
786
785
782
78$
779
.337
.439
.438
.479
.511
.518
.523
.514
.564
.924
.935
1.015
1.014
1.014
1.013
1 .010
1.013
1.003
1 .4 2 0
1.401
1.285
1 .3 0 0
1 .3 0 0
Gms. S
removed/gm
cat/hr
.1249
.1188
.1295
.1262
.1237
.1229
1.295
1.297
1.295
.1220
.1232
1.306
.1183
Ave.
consumed/ Temp
bbl oil
0C
cumulative
Average
—
415
141
414
78
415
416
185
138
415
107
414
416
143
150
415
CU. ft.
130
410
Compos:
S %
.337
.389
.407
.426
.443
.456
•466
.472
.483
“92“
lamp. Total
No. Hours
TABLE VII
TABULATED DATA FOR MOLYBDENUM OXIDE SULFIDING RUN TWO (MOS-Il)
Harshaw Mo-X-L 739-21-1-T 3/8" was used at $00 Psig.
Husky #3 Fuel Oil and catforming gas on recycle
Composite Percent Sulfur = .523
Percent loss (weight basis) = 1.28
Samp, Total
No. Hours
I
2
3
4
5
6
7
8
9
10
11
8
16
24
32
40
48
56
64
72
80
88
Sample
Wt.Gms.
737
729
793
779
810
800
831
879
% S
Ave. Space Vel.
per
Temp. Gms oil/
Samp. 0C
Gm Cat./Hr
.336
.427
.478
.516
.526
.552
.536
852
.568
.608
786
780
.581
.597
415
415
416
415
414
415
417
415
414
416
415
.932
.923
1.003
.987
1.025
Liters
Recycle
Gas/Gm Oil
1.408
1 .4 2 0
1 .381
1.079
.996
1.329
1.279
1.295
1.249
1.209
1.215
1.316
.988
1.328
1.012
1.052
1.112
Gms. S
Removed/Gm
Cat/Hr.
.1310
.1230
.1298
.1248
.1289
.1252
.1314
.1363
.1285
.1208
.1184
Cu. Ft.
Consumed/
Bbl Oil
Cumulative
Average
•
—
—
11.5
32.5
94.5
75.3
105.7
136
129
160
Composite
Sulfur %
.336
.382
.416
.442
.459
.476
.484
.496
.509
.517
.523
T3
TABLE Till
TABULATED DATA FOR MOLYBDENUM OXIDE SULFIDING RUN THREE (MOS-III)
Harshaw Mo-0203 T 1/8" 160 A-2-1 was used at $00 Psig.
Husky #3 Fuel Oil and catforming gas on recycle.
Composite Percent Sulfur = .645
Percent loss (weight basis) = 3»21
Total
Hours
I
2
8
16
3
4
5
24
32
40
Sample
Wt.Gms.
Ave.
* S
Per
Temp.
Samp. °C
755
741
755
.561
.584
761
.691
.72$
756
.666
415
414
416
415
413
Space Vel. Liters
Recycle
Gms oil/
Gm Cat./Hr Gas/Gm Oil
.977
.958
.977
.983
.978
1.352
1.392
1.345
1.325
1.342
Gms. S
Removed/Gm
Cat/Hr.
.1208
.1147
.1124
Cu. Ft.
Consumed/
Bbl Oil
Cumulative
Average
—
.1116
105.7
107.5
.1084
129.8
Composite
Sulfur %
.561
.573
.603
.626
.645
-9Z
Samp.
No.
TABLE IX
TABULATED DATA FOR SULFIDED CATALYST STUDY RUN (SCS-I)
Harshaw Mo-0203 T 1/8» 160 A-2-1 Sulfided with HgS
Husky #3 Fuel Oil, catforming gas on recycle, 500 Psig reactor pressure
Composite Percent Sulfur = .580
Percent loss (weight basis) = 2.72
Samp.
No.
Total
Hours
I
8
16
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
24
32
40
48
56
64
72
80
Sample
Ave o Space Vel.
* S
Wt.Gms. Per
Temp. Gms Oil/
Samp. °C
Gm Cat/Hr
740
749
750
747
735
380
.457
.527
.546
.557
.585
.342
.345
.443
.557
96
104
461
761
787
799
784
783
822
112
120
852
842
128
136
144
148
822
.708
826
.604
855
356
.605
88
.608
.631
.634
.598
.621
.715
-
415
415
416
416
415
415
414
416
416
415
416
414
414
415
415
415
415
415
413
.957
.971
.972
.968
.952
.493
.597
.985
1.018
1.033
1.016
1.012
1.063
1 .1 0 2
1.091
1.065
1.069
1.108
.923
Liters
Recycle
Gas/Cm Oil
Gms. S
Removed/Gm
Cat/Hr.
1.391
1.352
1.351
1.358
.1262
.1226
1.380
2.680
2.205
1.332
1.289
1.275
1.292
1.295
1.511
1.478
1.492
.1213
.1201
.1161
.0693
.0816
.1309
.1262
.1243
.1204
.1196
.1380
.1410
.1316
.1291
1.528
1.520
1.468
.1382
1.761
.0589
Catalyst regenerated with air after sample five
-
Cu. Ft.
Consumed/
Bbl Oil
Cumulative
Average
—
212
124.2
78.3
54.9
157
126.5
104.1
137.2
118.6
1 2 5 .8
111.6
122.1
Composite
Sulfur %
.457
.493
.512
.521
.534
.342
.344
.391
.445
.486
.508
.534
.546
.554
.572
131.0
135.5
139.4
141.8
149.8
.577
.579
168.0
.580
.586
TABLE X
TABULATED DATA FOR MOLYBDENUM OXIDE SULFIDING RUN FOUR (MOS-IV)
Harshaw Mo-0203-T-l/8 11 160A-2-1 was used at 500 Psig.
Husky #3 Fuel Oil and Catforming gas on recycle or hydrogen with no recycle.
Composite Percent Sulfur = 0.609.
Percent loss (weight basis) = 2.66
Samp.
No.
I
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
Total
Hours
Sample
Wt.Gms.
Percent
Sulfur
Per
Samp.
Ave.
Temp.
0 C.
6
11
333
427
1.732
19
27
35
43
51
59
67
75
83
91
99
107
115
123
131
139
147
155
163
171
179
187
195
628
638
.174
.356
716
732
734
744
763
.422
769
742
740
.690
.712
762
.523
761
762
.716
.686
221.5
415.5
415
414.5
415
414.7
414.2
415.5
415
415
415
414.5
414.7
414.5
415
415
415.5
414
415
415.5
414
416.5
780
.684
416
762
.686
753
.571
413.5
414
766
779
775
735
737
763
762
.248
.477
.462
.541
.589
.554
.552
.630
.637
.647
.658
.706
.638
Space Vel.
Gms Oil/
Gm Cat/Hr.
.570
.869
.808
.820
.919
.940
.942
.954
.979
.984
Liters
Recycle
Gas/Gm Oil
*790
*391/1.500
1.631
1.569
1.429
1.393
1.431
1.373
1.338
1.370
1 .0 0 0
1.302
.996
.944
.948
1.317
1.396
1.390
.980
1 .3 6 0
.978
1.348
1.341
.988
.952
.951
.978
.976
.978
1 .4 1 0
.978
1.387
1.371
1.335
1.353
1.340
1.348
.966
1.380
1.001
Cu. Ft.
Consumed/
Bbl Oil
Cumulative
Average
1741
1760/1140
835
710
588
493
472
415
436
394
358
354
356
347
337
331
310
291
286
293
308
Composite
Sulfur %
—
.248
.204
.250
.308
.348
.372
.399
.426
.441
.455
.471
.486
.500
.512
.516
.536
.538
.544
.542
.559
293
.568
278
.574
294
.580
308
.579
TABLE X (cont'd)
TABULATED DATA FOR MOLYBDENUM OXIDE SULFIDING RUN FOUR (MOS-IV)
Samp.
No.
Total
Hours
26
203
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
211
219
227
235
243
251
259
26 ?
275
283
291
299
307
315
323
331
335
Sample
Wt .Gms.
Percent
Sulfur
Per Samp.
761
761
762
767
763
747
771
763
755
751
792
746
775
737
811
740
.636
726
.630
357
.590
-
.740
.672
.783
.726
.631
.604
.595
.616
.582
.627
.616
.685
.604
.552
Ave „
Temp.
°c.
416
414.5
413
415
415
415
414.5
417
416
414.5
416
416
418.5
416.5
415
416
414.5
416.5
Space Vel.
(has Oil/
(ha Cat/Hr.
.976
.976
.978
.986
.980
.961
.989
.979
.971
.964
1.018
.958
.996
.948
1.041
.951
.932
.917
Liters
Recycle
Gas/Gm Oil
1.356
1.343
1 .3 1 0
1.330
1.336
1.403
1.323
1.338
1.365
1.365
Cu. Ft.
Consumed/
Bbl Oil
Cumulative
Average
295
289
295
297
304
317
319
317
307
Compos
Sulfur
.581
.587
.594
.598
.600
.604
.605
298
.606
.606
.606
.606
.606
.606
.608
.608
.608
299
294
.609
.609
318
1.296
309
1.391
1.349
1.395
1.280
1.387
1.405
1.463
296
28?
294
286
*For sample #L and 2 .5 hours of sample #2 these numbers are liters feed gas
r
TABLE XI
TABULATED DATA FOR MOLYBDENUM OXIDE SULFIDING RUN FIVE (MOS V)
Harshaw Mo-0203-T-l/8 160-A-2-1 (Previously on MOS IV 355 Hrs)
Reactor Pressure-500 Psig Husky #3 Fuel Oil Cat forming & Hydrogen Mixture on Recycle
Composite Percent Sulfur
Percent Loss (weight basis) = 3.52
Sample 14 thru 75 = .418
Sample 75 thru 143 = .506
Catalyst regenerated with air after samples 13» 75» and 144
Samp.
No.
Total
Hours
I
5
2
10
3
4
5
18
26
Sample
Wt.Gms.
334
524
756
789
810
811
81?
Percent
Sulfur
Per Samp.
1.880
1 .0 0 2
.690
.636
.660
.728
8
34
42
50
58
9
66
758
.713
.397
.625
74
82
90
92.5
99.5
107.5
115.5
123.5
131.5
139.5
147.5
155.5
700
.670
701
.637
692
221
.663
6
7
10
11
12
13
14
15
16
17
18
19
20
21
366
419
453
629
644
649
.649
.336
.169
.129
.156
.213
.224
.273
648
.263
234
406
Ave.
Temp.
°c .
227
410.5
414
416.5
416
416
414
415.5
415
415
414
414
413
415
415
414
417
414.2
416
416.5
414
Space Vel.
Gms Oil/
Gm Cat/Hr.
Liters
Recycle
Gas/Gm Oil
Cu. Ft.
Consumed/
Bbl Oil
Cumulative
Average
.682
2.100
580
1 .0 7 0
1.361
1.477
429
1 .460
1 .4 0 0
418
383
369
356
431
455
404
423
411
430
394
364
337
314
294
308
303
286
.965
1.007
1.003
1.040
1.438
1.429
3.240
1.043
.467
.970
• .892
.894
.882
1.619
1.642
1.663
.902
1.588
.346
4.830
.526
2.780
2.710
.543
.588
.815
.835
.843
.840
1 .500
2.490
1.800
1.770
1.749
1.760
406
Composite
Sulfur #
•
*
ee
■
—
■
*
_
.336
.231
.191
.180
.190
.191
.212
.221
TABLE XI (continued)
TABULATED DATA FOR MOLYBDENUM OXIDE SULFIDING RUN FIVE (MOS-V)
Samp.
No.
Total
Hours
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
163.5
171.5
179.5
187.5
195.5
203.5
211.5
219.5
227.5
235.5
243.5
251.5
259.5
267.5
275.5
283.5
291.5
299.5
307.5
315.5
323.5
331.5
339.5
347.5
355.5
363.5
371.5
379.5
387.5
Sample
Wt.Gms.
651
795
865
746
741
733
734
743
735
716
720
746
734
723
728
759
772
768
771
761
717
740
749
727
786
734
806
755
792
Percent
Sulfur
Per Samp.
.249
.379
.456
.308
.354
.361
.354
.363
.366
.357
.394
.422
.348
.360
.418
.389
.393
.477
.445
.418
.399
.443
.436
.436
.457
.453
.491
.475
.464
Ave.
Temp.
°C.
414.5
416.5
415
415
415
414
415.5
416.5
414
414.5
415
413.5
413.5
415
414.5
417
416.5
415
414
417.5
414.5
415
416
414.5
415.5
416
414
415
416
Space Vel.
Gms Oil/
Gm Cat/Hr.
.845
1 .0 3 0
1.121
.965
.960
.950
.951
.964
.951
.926
.931
.966
.952
.937
.945
.982
1.000
.994
.997
.986
.931
.958
.971
.944
1.018
.952
1.042
.979
1.026
Liters
Recycle
Gas/Gm Oil
1.755
1.439
1 .320
1.519
1.530
1.550
1.540
1.490
1.540
1.580
1.575
1 .5 2 0
1.550
1 .5 6 8
1.559
1.510
1.468
1.495
1.468
1.496
1.580
1.518
1.505
1.551
1.438
1.538
1.382
1.495
1.430
Cu. Ft.
Consumed/
Bbl Oil
Cumulative
Average
281
303
295
304
295
286
285
294
312
314
328
334
332
340
334
326
333
329
326
323
330
325
316
315
327
325
317
329
321
Composite
Sulfur %
.225
.246
.275
.278
.285
.292
.297
.301
.306
.309
.314
.320
.322
.323
.328
.331
.334
.340
.345
.347
.349
.353
.355
.358
.362
.365
.369
.373
.376
TABLE XI (continued)
TABULATED DATA FOR MOLYBDENUM OXIDE SULFIDING RUN FIVE (MOS-V)
Samp.
No.
Total
Hours
51
52
53
54
55
56
57
58
59
395.5
403.5
411.5
419.5
427.5
435.5
443.5
451.5
459.5
467.5
475.5
483.5
491.5
499.5
507.5
515.5
523.5
531.5
539.5
547.5
555.5
563.5
571.5
579.5
587.5
595.5
603.5
611.5
619.5
60
61
62
63
64
65
66
67
68
69
70
Tl
72
73
74
75
76
77
78
79
Sample
Wt .Gms.
758
780
784
834
815
753
745
750
757
764
752
698
735
750
739
774
764
752
753
729
762
734
795
727
759
668
713
785
722
Percent
Sulfur
Per Samp.
.475
.467
.520
.561
.505
.453
.470
.442
.484
•484
.452
.638
.458
.514
.447
.516
.456
.486
.496
.480
.488
.527
.459
.475
.485
.199
.255
.298
.297
Ave.
Temp.
°C.
415
416
416
415.5
413.5
415.5
415
414.5
416
413
414.5
390
414.5
415
416
416.5
416
416
416
416
416
415
415
415.5
415
416
416
414
418
Space Vel.
Gms Oil/
Gm Cat/Hr.
.983
1.010
1.016
1.072
1.042
.976
.966
.972
.981
.991
.974
.905
.953
.972
.958
1.003
.991
.975
.976
.945
.988
.952
1.030
.942
.984
.868
.926
1.020
.951
Liters
Recycle
Gas/Gm Oil
1.490
1.438
1.438
1.350
1.415
1.512
1.518
1.538
1.491
1.490
1.521
1.561
1.578
1.525
1.528
1.458
1.481
1 .5 2 0
1.480
1.555
1.452
1.538
1.402
1.559
1.492
1.692
1.560
1.429
1.553
Cu. Ft.
Composite
Consumed/ Sulfur $
Bbl Oil
Cumulative
Average
319
.379
.382
324
344
.385
.390
337
330
.393
334
.395
327
.397
.398
323
.400
324
322
.402
.402
333
—
332
327
.404
342
.406
336
.404
337
.407
.408
337
335
.409
334
.411
.412
334
330
.413
.416
334
329
.417
326
.417
.418
333
190
.199
238
.228
213
.253
241
.264
TABLE XI (continued)
TABULATED DATA FOR MOLYBDENUM OXIDE SULFIDING RUN FIVE (MOS-V)
Sampe
No,
Total
Hours
Sample
Wt.Gms.
80
81
82
$3
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
627.5
635.5
643.5
651.5
659.5
667.5
675.5
683.5
691.5
699.5
707.5
715.5
723.5
731.5
739.5
747.5
755.5
763.5
771.5
779.5
787.5
795.5
803.5
811.5
819.5
827.5
835.5
843.5
773
759
752
751
756
763
738
735
780
743
757
749
752
762
758
739
753
712
717
709
• 722
716
725
751
743
748
742
726
Percent
Sulfur
Per Samp,
,312
.317
.326
.337
.346
.341
.343
.347
.380
.371
.391
.374
.431
.465
.524
.493
.521
.528
.575
.551
.602
.573
.582
.591
.659
.633
.622
.704
Ave.
Temp.
°C.
Space Vel.
Gms Oil/
Gm Cat/Hr.
Liters
Recycle
Gas/Gm Oil
Cu. Ft.
Consumed/
Bbl Oil
Cumulative
Average
Composite
Sulfur %
416
415
415
414
415
415
416
416
417
417
415
415
413
416.5
415
416
415
416
416
415
416
416
415
417
415
416
415.5
415
1.005
.988
.979
.978
.983
.993
.960
.957
1.014
.966
.984
.975
.979
.990
.986
.961
.979
.926
.932
.923
.939
.931
.942
.976
.966
.972
.965
.944
1.461
1.472
231
299
319
275
320
319
285
348
331
344
332
385
397
469
471
486
493
499
476
472
477
476
467
472
461
470
462
445
.276
.284
.289
.295
.302
.305
.308
.311
.317
.320
.325
.328
.335
.342
.351
.358
.367
.373
.381
.389
.397
.403
.409
.416
.424
.431
.437
.445
1 .5 0 0
1.516
1 .502
1.480
1.529
1.538
1.449
1.521
1.492
1.508
1.501
1.544
1.495
1.529
1.508
1.600
1.596
1.591
1.555
1.576
1.558
1.511
1.535
1.525
1.538
1.490
TABLE XI (continued)
TABULATED DATA FOR MOLYBDENUM OXIDE SULFIDING RUN FIVE (MOS-V)
Sampe
No.
851.5
859.5
867.5
875.5
883.5
891.5
899.5
907.5
915.5
923.5
931.5
939.5
947.5
955.5
963.5
971.5
979.5
987.5
995.5
1003.5
1011.5
1019.5
1027.5
1035.5
1043.5
1051.5
1059.5
1067.5
1075.5
Sample
Wt.Gms,
Percent
Sulfur
Per Samp,
742
724
729
737
513
683
713
734
708
731
735
732
738
719
732
757
742
734
780
776
793
769
779
771
794
769
790
781
779
.652
.604
.611
.638
.585
.568
.612
.553
.605
.575
.568
.585
.567
.564
.545
.548
.542
.568
.483
.545
.542
.504
.485
.566
.570
.566
.572
.558
.526
Ave .
Temp.
°C.
415.5
417
415
415
415
415
414.5
417.5
415
415
415.5
415
415
416
415
415.5
415.5
415
415.5
415.5
415
416
417.5
415
415
415
415
415
415.5
Space Vel0
Gms Oil/
Gm Cat/Hr.
.965
.943
.949
.957
.669
.889
.928
.955
.922
.950
.957
.951
.961
.935
.951
.984
.965
.955
1.014
1.009
1.030
1.000
1.012
1.002
1.031
1.000
1.029
1.015
1.012
Liters
Recycle
Gas/Gm Oil
1.521
1.559
1.549
1.535
2.200
1.652
1.540
1.495
1.592
1.561
1.537
1.542
1.529
1.570
1.542
1.498
1.521
1.552
1.462
1.455
1.425
1.468
1.450
1.470
1.425
1.475
1.429
1.445
1.450
Cu. Ft.
Consumed/
Bbl Oil
Cumulative
Average
443
433
419
412
424
412
425
414
402
394
398
388
389
388
379
385
385
377
387
381
379
375
367
369
370
371
369
359
353
Composite
Sulfur %
.452
.457
.462
.466
.468
.470
.474
.476
.478
.481
.483
•486
.488
.488
.490
.491
.492
.493
.493
.494
.496
.496
.496
.497
.498
.499
.501
.502
.503
—36—
108
109
HO
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
Total
Hours
TABLE XI (continued)
TABULATED DATA FOR MOLYBDENUM OXIDE SULFIDING RUN FIVE (MOS-V)
Samp.
No.
137
138
139
UO
Ul
U2
U3
144
Total
Hours
1083.5
1091.5
1099.5
1107.5
1115.5
1123.5
1131.5
1133.0
Sample
WtoGms.
772
781
792
744
795
791
767
155
Percent
Sulfur
Per Samp.
.530
.542
.544
.531
.537
.481
.584
-
Ave. Space Vel.
Temp. Gms Oil/
0C
Gm Cat/Hr.
415
4U.5
416
415
417
419
415.5
412.5
1.002
1.015
1.030
.968
1.032
1.029
.997
1.072
Liters
Recycle
Gas/Gm Oil
1.470
1.445
1.425
1.525
1.422
1.429
1.472
1.369
Cu. Ft.
Consumed/
Bbl Oil
Cumulative
Average
359
353
364
359
369
367
364
358
Composite
Sulfur %
.504
.503
.503
.504
.504
.504
.506
vi.
TABLE XII
TABULATED DATA FOR COBALT MOLYBDATE RUN (CMR-I)
Harshaw Co-Mo-0201-T-3/16 was used at 500 Psig
Husky #3 Fuel Oil and catforming gas on recycle.
Composite Percent Sulfur = .1082 Percent loss (weight basis) = 2.8?
Samp.
No.
Total
Hours
8
16
I
2
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
*
24
32
40
48
56
64
72
80
535
535
717
767
773
778
793
TOO
Percent
Sulfur
Per Samp.
.156
.0986
.0637
.0536
.0354
.0725
.0830
686
.0758
.0756
747
.0981
88
760
96
104
759
773
754
770
765
778
783
.0874
.0794
.0926
.101
836
.117
793
753
728
754
740
.0942
.119
.113
.0886
112
120
128
136
144
152
160
168
176
184
192
.0700
.0617
.0873
.0942
.102
Ave.
Temp.
°c .
418.5
414.5
414.5
420
414
415.5
416
415
416.5
415
415
415
415
416
415
415
414.5
415.5
416
415
415
415
413
417
Space Vel.
Gms Oil/
Gm Cat/Hr.
.694
.694
.930
.995
1.000
1.008
1.028
.906
.889
.970
.986
.981
1.000
.976
.996
.990
Liters
Recycle
Gas/Gm Oil
2.118
2.110
1.589
1.470
1.470
1.450
1.430
1.629
1.625
1.522
1 .4 8 0
1.459
1.476
1.496
1 .4 8 0
1.485
1 .0 1 0
1 .4 6 0
1.015
1.083
1.027
.976
.945
.977
.958
1.440
1.350
1.219
1.344
1.548
1 .5 0 2
1.531
Cu. Ft.
Consumed/
Bbl Oil
Cumulative
Average
Composi
Sulfur ]
.156
330
165
143
98
255
231
259
.0874
.0753
.0747
.0761
222
.0761
190
218
198
242
.0761
.0783
.0792
.0792
.0784
240
.0772
241
257
239
.0779
.0789
.0802
216
232
222
208
196
213
208
197
.127
.102
.0816
.0832
.0847
.O852
.0866
.0877
.0877
—38—
3
4
5
Sample
Wt .Gms.
TABLE XII (continued)
TABULATED DATA FOR COBALT MOLYBDATE RUN (CMR-I)
Samp.
No.
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
Total
Hours
200
208
216
224
232
240
248
256
264
272
280
288
296
304
312
320
328
336
344
352
360
368
376
384
392
400
408
416
424
Sample
Wt .Gms.
731
747
796
767
809
786
779
790
788
789
794
797
797
793
805
822
795
835
789
811
799
776
821
78?
791
802
81?
877
836
Percent
Sulfur
Per Samp.
.0785
.0754
.0835
.115
.0501
.0286
.0864
.0805
.0795
.0754
.0623
.0834
.0702
.0945
.1047
.0922
.1225
.142
.139
.148
.135
.154
.144
.164
.159
.139
.145
.124
.145
Ave.
Temp.
°c .
414.5
415
415.5
416
415
415
415.5
415
416.5
417.5
416.5
416.5
416.5
417
415
416.5
415.5
417
415.5
415
414.5
416
416
415
416.5
415
414
415
415.5
Space Vel.
Gtos Oil/
Gm Cat/Hr.
.949
.969
1.031
.994
1.049
1.020
1.010
1.025
1.021
1.022
1.029
1.031
1.031
1.026
1.044
1.064
1.030
1.083
1.022
1.051
1.037
1.008
1.065
1.020
1.025
1.039
1.061
1.071
1.082
Liters
Recycle
Gas/Gm Oil
1.549
1.515
1.430
1.484
1.371
1.455
1.450
1.440
1.442
1.436
1.436
1.420
1.410
1.433
1.404
1.381
1.425
1.369
1.462
1.389
1.445
1.456
1.376
1.452
1.436
1.420
1.391
1.375
1.362
Cu. Ft.
Consumed/
Bbl Oil
Cumulative
Average
210
201
197
206
206
206
212
215
207
210
211
213
214
218
217
219
221
215
220
214
212
220
220
219
218
221
224
228
230
Composite
Sulfur %
.0872
.0869
.0869
.0882
.0869
.0848
.0850
.0848
.0846
.0843
.0838
.0836
.0833
.0835
.0830
.0843
.0853
.0869
.0882
.0895
.0906
.0918
.0925
.0942
.0954
.0965
.0976
.0982
.0992
TABLE XII (continued)
TABULATED DATA FOR COBALT MOLYBDATE RUN (CMR-I)
Samp.
No.
Total
Hours
Sample
Wt .Gms.
54
55
56
57
58
59
60
432
440
448
456
464
472
480
488
496
504
512
854
789
809
728
769
78?
790
786
830
741
753
777
773
759
774
740
727
724
762
743
754
785
801
802
793
790
813
800
791
61
62
63
64
65
66
67
68
69
70
Tl
72
73
74
75
76
77
78
79
80
81
82
520
528
536
544
552
560
568
576
584
592
600
608
616
624
632
640
648
656
Percent
Sulfur
Per Samp.
.133
.151
.128
.138
.148
.116
.103
.157
.137
.0683
.1252
.1038
.1057
.1467
.1429
.109
.115
.1105
.1496
.1195
.1176
.128
.122
.115
.127
.111
.130
.117
.120
Ave.
Temp.
°C.
417
415
414.5
415.5
415
415
415.5
415.5
414.5
415.5
416
414.5
415.5
414.5
419.5
416
417
414
416.5
417
416
415.5
415.5
416
415.5
414.5
415
414
416.5
Space VeI.
Gms Oil/
Gm Cat/Hr.
1.108
1.022
1.049
.943
.996
1.016
1.024
1.020
1.075
.961
.975
1.005
1.001
.983
1.001
.960
.943
.938
.988
.963
.976
1.018
1.038
1.040
1.025
1.024
1.055
1 .030
1.020
Liters
Recycle
Gas/Gm Oil
1.333
1.450
1.400
1.556
1.475
1.430
1.440
1.450
1.416
1.530
1.505
1.460
1.465
1 .500
1.470
1.540
1.561
1.571
1.380
1.531
1.505
1.455
1.410
1.375
1.432
1.425
1.400
1.428
1.442
Cu. Ft.
Consumed
BBl Oil
Cumulative
Average
228
227
224
222
222
220
215
220
215
211
211
206
209
207
205
204
204
203
203
203
202
204
201
199
197
198
197
195
196
Composite
Sulfur %
.0999
.1008
.1015
.1021
.1026
.1028
.1030
.1038
.1043
.1042
.1042
.1042
.1042
.1048
.1055
.1055
.1057
.1057
.1062
.1065
.1065
.1069
.1071
.1072
.1074
.1074
.1078
.1080
.1075
TABLE XII (continued)
TABULATED DATA FOR COBALT MOLYBDATE RUN (CIffi-I)
Samp.
No.
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
Total
Hours
Sample
Wt.Gms.
664
672
680
688
696
704
712
720
728
736
744
752
760
768
776
784
792
800
808
816
824
832
840
848
856
864
811
769
754
784
782
843
764
760
755
773
760
786
775
765
755
774
764
755
773
770
757
769
771
767
804
749
Percent
Sulfur
Per Samp.
.119
.085
.080
.120
.206
.099
.087
.062
.066
.063
.077
.135
.089
.1312
.1312
.1042
.1213
.141
.1325
.1108
.1158
.1202
.1222
.1183
.1174
.1125
Ave.
Temp.
0C.
415
416
415
416
415
415.5
415
415
416
415
415.5
415
415
416.5
415
415.5
414.5
416
414
416
416
414
415.5
415
415
416
Space Vel.
Gms Oil/
Gm Cat/Hr.
1.042
.990
.969
1.009
1.006
1.084
.984
.978
.972
.995
.979
1.012
.997
.985
.972
.995
.984
.972
.995
.990
.975
.990
.992
.988
1.035
.965
Liters
Recycle
Gas/Gm Oil
1.408
1.490
1.530
1.450
1.467
1.360
1.485
1.509
1.526
1.476
1.509
1.450
1.472
1.500
1.511
1.492
1.494
1.525
1.476
1.483
1.515
1.487
1.480
1.510
1.408
1.530
Cu. Ft.
Consumed
Bbl Oil
Cumulative
Average
196
195
193
194
193
196
195
193
198
195
195
196
196
197
197
196
196
197
197
197
197
201
201
201
201
201
Composite
Sulfur %
.1078
.1078
.1072
.1072
.1082
.1082
.1080
.1072
.1070
.1065
.1062
.1065
.1068
.1068
.1070
.1070
.1069
.1072
.1077
.1078
.1078
.1079
.1079
.1081
.1082
.1082
-42“
TABLE XIII
RECYCLE GAS ANALYSES
Run
Designation
MOS-III
SCS-I
MOS-IV
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
MOS-V
Hours
on Run
40
148
335
0
92.5
184
256
373
475
588
680
750
822
922
970
997
1062
1095
1114
1133
% H2
* CH^
80.8
79.2
76.0
87.5
87.0
85.6
87.0
86.0
82.9
82.2
81.6
65.5
58.6
15.7
16.8
17.3
6.0
7.8
8.3
9.8
11.1
11.2
13.5
14.1
7 2 .2
75.4
77.6
82.1
84.0
86.4
88.1
3 0 .0
27 .6
23.3
21.2
18.1
13.8
12.4
10.7
8.2
$ C,
3.5
4.0
6.7
6.5
5.2
6.1
3.2
2.9
5.9
4.3
4.3
4.5
13.8
4.5
3.4
4.3
4.1
3.6
2.9
3.8
THERMOWELL
BLOW OUT
LINE
REGENERATION
AIR LINE
ROTAMETER
OIL RESERVOIR
HEATING COILS
PRESSURE G A G E --
FLO WRA T OR
/
MAKE UP GAS TANK
Figure I. Reactor Diagram
FEED GAS TANK
A L U N DU M
BALLS
FEED
PUMP
PRESSURE
GAGE
CATALYST
CONDENSER
RESSURE GAGE
BACK PRESSURE
VALVE
SIGHT
GLASS
COMPRESS­
I O N TANK
SURGE TANK
/
STANDPIPE— H
P RE SSURE GAGE
C ON TR OL LE R
JERGUSON
"RECEIVER
EXHAUST
LINE
RECEIVING
FLASK
COMPRESSION
PUMP
COMPRESSION OIL
RESERVOIR
W E T TEST M E T E R
CAUSTIC W A S H
COMPOSITE PERCENT SULFUR IN EFFLUENT OIL
o M O S - I RUN
• M O S - n RUN
D
M O S - HI RUN
■ SCS-I R U N
a
SCS-I A F T E R REGENERATION
HOURS ON S TREAM
Figure 2.
E f f e c t of O n - S t r e a m Time on D e s u l f urization
for M o l y b d e n u m Oxide Catalysts
COMPOSITE PERCENT SULFUR IN EFFLUENT OIL
O MOS- U
RUN
• M O S - Y RUN
n M O S - Y RUN, GAS STUDY
240
320
400
HOURS ON S T R E A M
Figure 3.
E f f e c t o f O n - S t r e a m Time o n D e sulfurization
for M o l y b d e n u m Oxide Catalysts
480
70
60
50
160
240
—
PERCENT SULFUR PER SAMPLE
—
PERCENT HYDROGEN
320
HOURS ON S T R E A M
Figure 4
Deaxilfurizatlon and Paroent Hydrogen in Recycle Gas vs
On-Stream Time for 16# Molybdenum Oxide Catalyst
PERCENT HYDROGEN IN REC YLE GAS
80
PERCENT H Y D R O G E N IN RECYLE GAS
240
320
H O U R S ON S T R E A M
Figure 5.
C r itical H y d r o g e n Content of R e c y c l e Oas
for 1 6$ M o l y b d e n u m Oxide Catalyst
PERCENT SULFUR PER SAMPLE
PERCENT SULFUR IN EFFLUENT OIL
OF EFFLUENT OIL
0.20
COMPOSITE
PERCENT SULFUR
0.15
0.10
0.05
80
160
240
320
400
480
HOURS ON STR EAM
Figure 6.
Effect of On-Stream Time on Desulfurization
for Cobalt Molybdate Catalyst
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