The catalytic hydrodesulfurization of Wyoming fuel oil
by John R Hartwig
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 John R Hartwig (1952)
Abstract:
This investigation was primarily concerned with the effect of gas recycle on the catalytic
hydrodesulfurization of a number-three-fuel oil from a sulfur content of 2.2 percent to 0.5 percent or
below. Initial gas compositions were either pure hydrogen or a gas mixture that was approximately 84
percent hydrogen. In the runs with an initial gas composition of pure hydrogen the make-up gas added
was also pure hydrogen. Make-up gas for runs where gas mixtures were used was the same
composition as the initial gas composition (i. e. approximately 84 percent hydrogen).
Nickel oxide and nickel hydroxide catalysts were studied briefly, but the major emphasis was on
molybdenum sulfide catalysts.
Optimum desulfurization conditions were not evaluated. The emphasis was on the determination of gas
consumption during continuous gas recycle operation.
Conditions for the nickel study runs were: space velocity 0.1 to 3.0 gm. oil/gm. cat-hr., temperature
385 to 390°C, pressure 60 to 100 psig, and gas recycle rate from 0.4 to 2.0 liters gas/gm oil. Process
variables for the molybdenum runs were: space velocity 0.7 to 1.3 gm oil/gm cat-hr, temperature 410 to
415°C pressure 500 psig, and gas recycle rate 0.9 to 1.8 liters gas/gm oil.
The gas. consumption when pure hydrogen was used as the recycle gas was approximately 140
SCF/bbl and the gas consumption with a gas mixture on recycle was between 250 to 300 SCF/bbl.
These consumption figures were obtained with molybdenum catalysts.
The effectiveness of the desulfurization process when a gas recycle system was used was hot
noticeably different than that when the process ; was carried out with the gas oh a one pass system.
Specification oil was produced with molybdenum catalysts and a recycle gas with a hydrogen con-tent
as low as 80 percent by volume.
The molybdenum catalysts were far superior to the nickel catalysts as far as catalyst life and the degree
of desulfurization were concerned. THE CATALYTIC HYDRODESULFURIZATION
OF WYOMING FUEL O H
• by
■ JOHN R«: HARTWIG
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:
Chairman ^/Examining (ksfnmlttee
Bozeman, Montana
August, 1952
' 'y-i'j/j
—2—
TABLE OF CONTENTS
page
Abstract.....................................................
Introduction. . . . . . . . . . . . . .
3
..........................
• 4
Equipment, Materials, and M e t h o d s .................
7
Equipment ..................................
7
Materials. .....................................................
9
Methods.......................................................... 10
Calculations.....................................
Results and Discussion..................
14
Conclusions..................................
Acknowledgement . . . . . . .
................................
...
25
Literature Cited.....................................
Appendix..........................................
108556
ABSTRACT"..
This investigation was primarily concerned with the -effect’-of-gas •
recycle on the catalytic hydrodesulfurization- of a number three-fuel oil
from a sulfur content of 2»2 percent to 0»5 percent or below; Initial-gascompositions were either pure hydrogen or a gas mixture that was -approx­
imately 84 percent hydrogen. In the runs with an initial gas-compositionof pure hydrogen the make-up gas added was also pure hydrogen. Make-up
gas for runs where gas mixtures were used was the same composition as the
initial gas composition (i. e. approximately 84 percent hydrogen)*
Nickel oxide and nickel hydroxide catalysts were studied briefly, but
the major emphasis was on molybdenum sulfide catalysts.
Optimum desulfurization conditions were not evaluated. The emphasis
was on the determination of gas consumption during continuous gas recycle
operation.
Conditions for the nickel study runs were; space velocity 0.1 to 3.0
gm. oil/gm. cat-hr., temperature 385 to 390°C, pressure 60 to 100 psig,
and gas recycle rate from 0.4 to 2.0 liters gas/gm oil. Process variables
for the molybdenum runs were: space velocity 0.7 to 1.3 gm. oil/gm cat-hr,
temperature 410 to 415^0* pressure 500 psig, and gas recycle rate 0.9 to |r;
1 .8 liters gas/gm oil.
The gas. consumption when pure hydrogen was used as the recycle gas •
was approximately 140 SCF/bbl and the gas'consumption with a gas mixture '
on recycle was between 250 to 300 SCF/bbl. These consumption figures we^e
obtained with molybdenum catalysts.
The effectiveness of the desulfurization process when a gas recycle
system was used was hot noticeably different than that when the process
;
was carried out with the gas oh a one pass system. Specification oil was
produced with molybdenum catalysts and a recycle gas with a hydrogen con- -i
tent as low as 80 percent by volume.
The molybdenum catalysts were far superior to the nickel catalysts as
far as catalyst life and the degree of desulfurization were concerned.
I M E Q D i r C T im
The depletion of low sulfur content crudes in the United States is
forcing refiners to employ increasing amounts of high sulfur crudes.
Utilization of these crudes has forced refiners to develop economical pro­
cesses for removal dr conversion of sulfur compounds in the various products
refined from them.
Methods commonly used for desulfurization of gasoline
are not satisfactory for the treatment of higher boiling petroleum fractions
such as diesel and fuel oils.
Such commercial processes as the Unisol
process, the Solutizer.and Tannin Solutizer processes, hypochlorite treat­
ment j Gray desulfurization, treatment with bauxite catalysts, as well as
caustic and acid washes, either do not reduce the sulfur content in the
heavier distillates to the desired percentages or hydrocarbon losses are
excessive.
Although the identification of specific sulfur compounds in
any particular petroleum fraction is a difficult task, and research in
this direction has not been extensive until fairly recently (8 ) (9),
it has been fairly well established (9 ) that the sulfur compounds in
kerosine and fuel oil distillates are predominantly 'thlophenic in nature.
These compounds are not receptive to any of the desulfurization treatments
mentioned above.
Successful desulfurization of fuel oil distillates to very low limits,
has been accomplished by catalytic hydrodesulfurization.
Work by Green (6 )
and Munro (3) with a molybdenum sulfide catalyst in a hydrogen atmosphere
reduced the sulfur content -in a number^three fuel oil from approximately
2.2 percent to less than 0*5 percent.
Several commercially adaptable
-5catalytic desulfurization processes haVe been patented by the AngloIranian and Union Oil Companies (10) (Il) 6
These processes utilize cobalt
and molybdena catalysts and hydrogen gas atmospheres at various pressures
(200-700 psig) 6The inherent economic disadvantage of these catalytic hydrodesulfurizatioh processes is the need for a relatively rich (greater than 90%)
hydrogen gas supply.
This difficulty can be overcome^ however, by using
the desulfurization process in conjunction with a '!catforming" unit for
upgrading low octane gasolind,
In a typical catalytic, reforming process
(12 ) there is a net make of a gas mixture -which is: predominantly hydrogen'
(approximately 90%)} with small quantities of methane, ethane, and propane
present.
The capacity of such a desulfurization unit would naturally be
regulated by the quantity of make gas from the catformer and the amount of
gas consumed in the desulfurization process.
The primary objective of this
research was the determination of gas consumption (as SGF/bbl,) for the
catalytic hydrodesulfurization process developed here in the past few
years by Koski (2), Munro (3), and Green (6 ),
This process was developed
for the desulfurization of Husky Oil Company’s number three fuel oil.
The
sulfur content in this fuel oil was to be reduced from 2 ,2 percent to 0 ,5
percent or below,
As mentioned previously, the catalyst used was molyb­
denum sulfide (approximately 15$ Mo) impregnated oh an alumina carrier.
The process variables for this catalyst were fairly well established in
the preceding work.
The optimum conditions found were:
pressure,'500
psigj temperature 400-41O0C (752-770°F)$ gas to oil ratio, I «3 to 1„5
liters gas/gm oil; and a variable space.velocity, (this varied between
approximately 0,4 and I eO gm oil/gm cate-hr„, depending upon the activity
of the catalyst)o
Aside.from the stated objective of the determination of gas con­
sumption data, three runs were made using nickel catalysts e
The purpose
of these runs was a final attempt (see work by Goykendall (?) and Haas ($))
to determine if there was any true catalytic effect with nickel catalysts,
and to prove whether the process with nickel catalysts would work in the
recycle apparatus used for the molybdenum catalyst studies.
The gas recycle study (GRS) and the molybdenum comparison run (MCR)
were made using pure hydrogen gas.
The cat forming gas study run (GGR)
used a gas mixture typical of the make gas from a "catforming" unit,
In all the runs with molybdenum catalysts (i»e,, GRS, MCR & CGR),
the effect of gas recycle on catalyst activity was also observed.
The
molybdenum comparison run (MGR), as the name indicates, was primarily a
■comparison test on a different batch of molybdenum catalyst delivered
from the Harshaw Chemical Company,
=7“
E QPIFMEMr, MATERIALS, AND'METHODS''
EQUIPMENT
A schematic diagram of the recycle unit is shown in Figure I e
The
reactor itself is the same as that used by both Munro (3) and Green (6 ).
Essentially it consists of a 16 inch length of Ig inch extra strong black
iron pipe fitted with a Ig to 3 /4 inch reducer at the top and a Ig to |
inch reducer at the bottom.
Both the top and bottom of the reactor were
fitted with unions to allow for easy takedown of the reactbr for loading
I
and unloading.
Fitted on the top of the reactor were two crosses and an
assembly of valves for gas, oil, and regeneration air inlet.
line and thermowell tube were also fitted to this assembly.
A -blow-out
The thermowell
tube was a zp inch black iron pipe which extended from the cross at the top
of the reactor down through the vertical" axis of the reactor to within one
inch of the bottom.
It was possible to position three thermocouples at
any point within the reactor with this system.
The thermocouple^ were
iron-constahtan and were used in conjunction with a Leeds and Northrup
indicating potentiometer for temperature measurement.
Fitted at the bottom of the reactor was a water cooled condenser.
At7
the bottom of the condenser, connected from a cross, was the reactor .
pressure gage, high pressure product receiver (a 12 inch Jerguson sight
gage), a standpipe, and the reactor back pressure valve.
At the bottom of the Jerguson product receiver was the receiving
flask, caustic scrubbing train, and a wet test meter manufactured by the
Precision Scientific Company.
A constant oil level was maintained in the
Jerguson receive** by hand adjustment of a needle valve at the bottom of the
receiver»
The reactor pressure was maintained by a Hason-Neilan small-volume
air-to-close regulator valve»
This pressure regulator was controlled by
a Fisher Wizard proportional controllero
A two cylinder, adjustable stroke, high pressure piston pump and an
oil reservoir comprised the oil feed system.
Three 33-foot lengths of beaded Nichrome wire, supplied with current
from three 110-volt Powerstat autotransformers, provided variable heat
input for the reactor.
Two of these heating coils were located near the
bottom of the reactor to heat the catalyst section and one was located
higher up on the reactor to heat the preheat section.
Alundum balls were
used as preheat media.
Gas flow to the reactor was metered by a Fisher fldwrater and regulat­
ed by a needle valve manufactured by the American Instrument Company.
This
needle valve was located ahead of the flowrater.
The remaining equipment of the unit made up the gas recycle system*
The compression pump was a two cylinder Hills-McCanna high pressure
proportioning pump.
The feed tank was made from a number one gas cylinder
and the surge and compression tanks were made from number two gas cylinders,
A- Brook's Rotameter metered the flow from the make-up tank.
Extra strong black iron pipe and high pressure fittings were used
throughout the unit where piping is indicated by double lines on Figure I.
Single lines on the drawing indicate I / 8 inch stainless steel high pressure
tubing
Before the recycle unit as shown in Figure I was constructed, a
different unit was used.
This unit was essentially the same as the later
unit with the exception of the gas recycle system.
Instead of using an
oil displacement method for gas compression, a small refrigerator compres­
sor was used to move the gas from the surge tank to the feed tank.
This
system worked quite well uqtil the middle of the "catforming" gas study
run.
At that time repeated compressor breakdowns caused so much trouble
and unit shutdown time that the recycle unit as shown on Figure I was
constructed.
This unit did not cause any operational troubles and proved
to be a great improvement over the old system.
MATERIALS
The oil used throughout this work was Husky Oil Company's number three
fuel oil.
percent.
The sulfur content of this oil varied between 2.09 and 2.19
Additional data for this oil can be found on Table I in the
appendix.
Table II presents data for all the catalysts used in this research.
Recycle gas used was either pure hydrogen or a gas mixture.
The
„
hydrogen was obtained from the Whitmore Oxygen Company of Salt Lake City,
Utah.
The gas mixture was obtained from the Matheson Chemical Company in
East Rutherford, New Jersey.
ordered) was:
The composition of this gas mixture (as
hydrogen, 89 percent$ methane, 3.5 percentj ethane, 1.5
percent5 propane, 2.5 percent; and propylene, 3»5 percent.
To obtain this
gas composition a Husky gasoline stock was sent to the Atlantic Refining
ewIOw
Company and run through their catalytic reforming unit®
Analysis of the
make gas from the run with the Husky stock gave the above composition®
METHODS
/rhe unit was started by applying heat to the heating coils with the
gas flowing through the reactor®
The" reactor wa‘s set at the desired
pressure during this period or when the catalyst temperature reached 3OO0 C 0
/
Oil flow was started and the space velocity adjusted whten this catalyst
temperature reached 3SO0 C 0
Readings were recorded after the desired cata­
lyst temperature was reached, with the gas flcjw, reactor pressure, and
space velocity properly adjusted and maintained®
•
I
1
As the product oil collected in the"Jerguson pressure receiver it was
allowed to drip slowly to the receiving flask® The receiving flask was '
.
i
N
removed and replaced at"the desired sampling periods® Dissolved gases
(predominately H 2S ), which flashed from the Qil when the oil left the
pressure receiver, went to the caustic scrubbing train and then to the wet
test meter where the gases were metered and passed to the exhaust line®
In the operation of the unit, the recycle gas flowed from the feed
tank through the flowrator and to the reactor®
After the gas passed
Y
through the reactor and. the reactor back-pressure regulator, it flowed to
the surge and compression tanks®
I
Mhen the pressure in these two tanks
-
reached 300 psig the surge tank was isolated from the compression tank and
the compression pump was started®
Compression oil (Husky’s number three
fuel oil) was pumped from the compression- oil reservoir to the compression
tank, compressing the gas in the compression tank®
Mhen the pressure in
■=»11=*
the compression tank became equal to 1that in'the feed tank (usually between
550 and 56G) psig) the valve between these two tanks was opened and the gas
in the compression tank was pushed over to the feed tank.
When all the gas
in the compression tank had been pushed to the feed tank (as indicated by
the appearance of oil in the sight glass on the compression tank) or when
the pressure in the feed tank reached 600 psig, the compression pump was
stopped and the valve between the feed and compression tank was closed.
The valve between the surge and compression tank was then opened.
The oil
in the compression tank was forced back to the compression oil reservoir
by the pressure from the surge- tank when the valve between the oil reser­
voir and the compression tank was opened.
The compression cycle was
'f
started again when the pressures in the compression and surge tanks again
reached 300 psig.
The compression cycle usually took about 1.5 hours for
completion with 45 minutes to an hour between cycles.^)
Arbitrary, standard pressures were set for the feed tank and the
compression and surge tanks5 that for the feed tank was 600 psig, and for
the compression and surge tanks it was 250 psig.
When the pressure in the
surge and compression tanks fell below 250 psig (with the pressure in the
feed tank up to 600 psig) at the end of a compression cycle, make-up gas
was added to bring the pressure in these two tanks back to 250 psig.
fldw from the make-up tank was metered through the Brooks
Gas
rotameter and
this flow was timed with a stopwatch.
When desired, recycle gas samples Were taken from a bleed-off valve
located on the downstream side of the reactdr back pressure regulator.
=IS"
The gas sample was passed through the caustic scrubbing train and the wet
test meter before it was collected over water in eight liter glass sample
bottles „
Analysis of the gas samples was made in a low -temperature^
fractionation column*
Sulfur analysis of each oil sample was made by the lamp method (l)„
- SALGULATIONS ■
Tables IV, V, VI, VII, and VIII contain the tabulated data for all
the runs made in this investigation*
Th'e space velocity recorded was based on input oil*
Each individual
sample weight was corrected by the percent loss over a longtime period of
the run as calculated from oil weight balances*
For example;
Percent loss, wt. basis = 2$.
Then, for an individual sample" weigh-
' ing 800 gms*, input weight =
= 8l 6 gms.
Then, for an 8 hr. sample
period with a l00 gm. catalyst charge, space velocity =
816 gms* oil
- 1 .020 *
(100 gms* c a t * K 8 hrs*)
The gas flow (as recycle gas, SGF/bbl*) was calculated by dividing
the gas flow per sample period by the oil weight per sample period*
For example;
_
With ah 80© gm. oil sample (816 corrected wt.) and a gas recycle rate
(as indicated by the Fisher fIowrater) of 1070 liters (STP) per 8
hours;
2521 = 1.3 liters gas/gm oil.
Then 1*31 liters gas/gm. oil
28*32
x .87$ gm. oil/cc* oil x lGOO ce/liters x
liters/gal x
816
42 gal/bbl x
Ft3/ liters = 6430 Ft3 A b l . (STP)*
-13Hydrogen consumption was calculated from the make-up and bleed-off
gas figures recorded for each sample period.
Bleed-off figures were the
wet test meter readings„ Make-up figures were from the Brook’s rotameter
readings„
For example;
For an 800 gm-oil sample (8l6 corrected) and gas make-up equal to
40 liters (STP) and bleed-off equal to 8 liters (STP)9 the gas
consumed would be 32 liters (STP)o
Then
x 5 ^ 2 = 39,2 liters consumed/kilogram oil*
39*2 x 4=91 (conversion factor) = 193 Ft^ consumed/bbl oil*
Gas. consumption, for any individual sample period varied widely so the
figures presented in the data were cumulative averages *
Por example;
After ten samples, total gas eonsumtion equalled 3100 Ft^0 -Then
for the tenth sample, 2^22
10
- 310 Ft^/bbl*
-The catalyst temperatures presented in the data are averaged temper­
atures for each sample period indicated*
The thermocouples for the cata­
lyst bed were located at the top and bottom of the catalyst bed*
The top
and bottom catalyst temperatures were averaged and these average tempera­
tures were averaged over the sample period*
A thermodynamic study of probable reaction mechanisms for the cata­
lysts used and reported in this paper was not made since this was done
previously by Munro (3 ) and Green (6 ) for the molybdenum sulfide catalysts,
and by Haas (5 ) for the nickel catalysts*
EESULTS M D DISCUSSION
•
With the exception of three relatively short runs using nickel
catalysts a only one type of catalyst (MoS2 ) was used 0
The primary concern
of this research was the study of the effect of gas recycle on the de­
sulfurization process, with determination of gas consumption especially
emphasizede
Tabulated data for all runs made in this study are presented
in the appendix*
■All of the studies made on nickel catalysts were made primarily to
observe the effectiveness of these nickel catalysts in the recycle unit
and to determine whether the nickel catalysts1 desulfurization action was
a chemical or catalytic reaction.
In respect to the type of reaction of ■
the nickel catalysts, Haas (5) has already stated that the desulfurization
by nickel catalysts was strictly a chemical reaction.
,If desulfurization was accomplished through a catalytic mechanism
when nickel catalysts were used, a certain amount of hydrogen would neces­
sarily have to be consumed.
The hydrogen is consumed by the combination
with the sulfur in the oil (to form H 2S) and the combination with the
hydrocarbon from which the sulfur was removed.
However, for NSR-I and
MSBkII (Tables III and B r) gas was produced and it was not necessary to
add any make-up gas.
For the third nickel study run (NSR-III, Table V)
a total of 21.8 SCF/bbl was consumed.
When compared to gas consumption
with molybdenum catalysts (140 to 300 SCF/bbl) the consumption of 21.8
SCF/bbl is not large.
A possible conclusion to be drawn from the above discussion would be
=■15"
t h a t the s ulfur w a s r e m o v e d b y some o t h e r m e a n s
(e»g« b y c h e m i c a l com­
b i n a t i o n w i t h t h e nickel.) a n d not b y c a r b o n to sulfur b o n d fissure w i t h
subsequent f o r m a t i o n o f H 3S s a n d r e s u l t a n t h y d r o g e n consumption*
For all the nickel study runs, gas analysis of the recycle gas re­
vealed a high hydrocarbon gas buildup (predominately methane).
The hydro­
carbon buildup in the recycle gas that occurred when nickel catalysts were
used indicates to'some extent the non-selectivity of these catalysts when
they are used as desulfurization agents,
Instead of breaking the carbon
to sulfur bonds the nickel catalysts evidently induced a predominate carbon
to carbon cracking with the production of large amounts of methane,
Haas (5) also states that the desulfurization depends in a large part
on space velocity.
HSR-Il with HSR-III,
This is amply demonstrated by comparison of HSR-I and
The average space velocity for the first two runs
was approximately 3 ,0 gm oil/gm cat,-hr, whereas that for the last run
(HSR-III) was 0,1 gm oil/gm cat,-hr,
In the first two*runs no specification
oil was produced at all, whereas approximately 12 throughputs (i,e.
2400 gms oil ,) were achieved by blending samples I through 27 in the third
200 gms, cat,
nickel study run.
The different pressures used (i,e, 60 psig for HSR-I and- NSR-H, and
100 psig for HSR-III) in the nickel runs did not have any apparent affect
on the degree of desulfurization.
Results from the three nickel runs show that the nickel catalysts do
not have a long catalyst life and that their desulfurization action is
quickly lost after only a few oil throughputs»
*=»3.6="
•Operating conditions for the HSR runs were established by the research
laboratory of Husky Oil Company in Cody, Wyoming.
The Gas Recycle Study (GRS, Table VI) was the first run made with gas
recycle operation with an MoS 2 catalyst.
The molybdenum catalyst used for
this run had been used previously by Green (6 ) in his mixture .study run
for a total of 60? hours.
Successful desulfurization was accomplished for
an additional 526 hours with this catalyst.
During the GRS run the space
velocity varied between 0.5 and O.S gm oil/gm cat.“hr.
Gas recycle varied
between 6000 and 11,000 SCP/bbl. -Pure hydrogen was used as make-up during
this run.
At the start of the run the recycle gas was approximately 100 percent
hydrogen.
At the end of the run the hydrocarbon buildup in the recycle
gas did not exceed five percent.
Gas consumption calculations were not made during the first 26
samples of ihis run.
During this period, considerable difficulty was en­
countered in establishing operating procedures with the gas recycle
system, and in establishing standard tank pressures to assure continuous
gas flow and an accurate gas balance.
Calculation of gas consumption was^started after sample 26.
Frdm
sample 26 through 36 there was a gas leak in one of the valve stems on the
unit.
Rather than shut down the unit and repair this leak, the gas escap­
ing from the ,valve stem was metered and the run was continued.
The amount
of gas leaking from the valve stem was approximately one-tenth of the gas
recycle rate.
Gas consumption during this period of gas bleed-off and
including the gas bleed-off was between 220 to 275 SCF/bbl oil*
-From sample 37 to the end of the run the gab leak was repaired and
with no gas bleed-off the gas consumption leveled off at about 140 SCF/bbl,
Gas samples were taken from the recycle unit at various times during
the GRS run.
Analysis of these gas samples revealed a buildup of hydro­
carbon gases.
In order to ascertain the trend of this hydrocarbon gas
buildup a method had to be developed to correlate the hydrocarbon buildup
with some factor which would be independent of the size of the recycle
unit and the total amount of gas being recycled.
-1Mhen the space velocity and gas flow are kept constant, the rate of
hydrocarbon gas buildup should also remain constant.
However, the time
it would take to obtain a specified hydrocarbon buildup would vary with
the size of the reactor system and the total amount of gas in the system.
-Correlation between hydrocarbon gas buildup and hours on stream would be
meaningless if applied to other reactors.
To overcome this, the number of
gas recycles was calculated at each gas sample period and in this way it
was possible to compare the hydrocarbon content of the recycle gas with
the number of times the total volume of gas in. the reactor system had been
passed through the reactor proper.
■The following calculation was applied to the GRS run to determine
the number of recycles at each gas sample period.
The calculation cited
is for a ten day period of the run.
109 = average cubic feet recycled per day.
IG = number1of days for which the calculation was made.
70 = cubic feet of gas in the reactor system at the arbitrary
standard pressures,
12 = average cubic feet of make-up gas added per day during the
period of calculation,
= 13 recycles,
Dttien the above method of calculation was applied to the G-RS run the
hydrocarbon buildup after 8 recycles was 4 ,4 percent (volume percent)s
after 9 recycles it was 5 ,0 percent, after 11 recycles it was 6 ,0 percent,
and after 13 recycles the hydrocarbon content in the recycle gas was 4«6
percent.
These calculations indicate that the amount of hydrocarbon gas
buildup in the recycle gas was not excessive and that the percentage in­
crease in hydrocarbon content per recycle was relatively small (i,e, after
8 recycles it was .55 percent per recycle and after 13 recycles it was „35
percent per recycle).
Oil losses for the gas recycle study on a weight basis were 3*1 per­
cent,
In the work by Munro (3) and Green (6 ), oil losses averaged around
6,0 percent.
In their studies the oil samples were collected at atmospher­
ic pressure and some oil was carried off as a mist.
With the recycle unit-
the oil samples were collected under pressure and no oil loss as a mist
occurred.
The M 0 S2 catalyst used in the GRS (Table Vi) run was used previously
by Green (6 ) in his mixture study run.
The same operating conditions were
used for the first 34 samples of Green’s mixture e&idy run as were used in
the gas recycle study.
The only difference in that part of the mixture
“19-
study run being cited and the GRS run was the recycle of gas during the
GRS run.
With this in mind a comparison of the relative catalyst activity
during the GRS run can be made with the activity of the same catalyst when
no gas recycle was being used.
Green’s mixture study run had an average
space velocity (samples I through 34) of approximately 0,7 gm oil/gm
cat.“hr.
With this space velocity the average sulfur content of the
effluent oil was approximately 0 .3 percent.
In the gas recycle study the
average space velocity was also •approximately 0.7«
content in the product oil was about 0.4 percent.
The average sulfur
From these figures it
would seem that the catalyst was not as active under gas recycle conditions.
However, when the deactivation of catalyst with use is considered (the
mixture study run by Green added 333 hours on stream time to the catalyst
before it was used in the gas recycle study)
the activity of the catalyst
with gas recycle would seem to be the same as. that without gas recycle.
The molybdenum comparison run (MGR, Table VII) was started with
approximately the same operating conditions as were used for the gas
recycle study.
This run was made to compare the activity of MoS2 catalysts
used in the past with a MoS2 catalyst prepared on a larger scale by the
Harshaw Chemidal Company.
With an initial space velocity of 0.7 gm oil/
»m cat.“hr the sulfur content of the effluent oil was only
0« .1
percent,
, ►
*...
- .
»■*
W
•
When the space velocity was nearly doubled, the percent sulfur in the
product oil also increased, but it did not exceed 0.5 percent until the
space velocity was raised above 1,35 gm oil/gm cat,“hr*
The percent sulfur
dropped from .519 to .304 when the space velocity was lowered from 1.331 to
-20-
.869 gm oil/gm cat.-hr.
-Although this run (MOE) was comparatively short (l6 © hours), the
above results demonstrate readily the higher activity of the MoS 2 catalyst
used as compared to any of the molybdenum sulfide catalyst used previously,
either in this research or in the work by Munro (3) and Green (6 ).
In
these studies specification oil was rarely produced if the space velocity
exceeded 1.0.
The average gas consumption was 140 SCF/bbl which was the
same as the gas consumption for the gas recycle study.
The buildup of
hydrocarbons in the recycle gas was 4.2 percent after 10 recycles.
This
is also comparable to the gas recycle study.
There is no apparent reason for the greater activity shown by the
catalyst used in the MGR run (Table VII).
The composition of this catalyst
was nearly the same as the composition of MoS2 catalysts used previously
(see Table II).
The catalyst used for this run was a part of a somewhat
larger batch than was usually ordered from the Harshaw Chemical Company for
desulfurization studies.
Usually, small (5 to 10 pounds) samples of
catalyst were ordered, but in this ease about 40 pounds of the catalyst
was made.
A possible reason then, for the higher catalyst activity could
be the method of manufacture of the catalyst.
The same catalyst that was used for the MCE run was used for the
"catforming" gas study run (CGR), Table VIII. The catalyst had been used
for 160 hours during the MGR run.
It was not regenerated or treated in
any other way prior to its use in the GGR run*
This catalyst exhibited a
somewhat higher activity than those used in the past, but as the CGR run
-21-
progress ed the activity of the catalyst did declinee
During the CGR run two air regenerations of the catalyst were made.
The regenerations were made with, the catalyst in the reactor.
air regeneration was made after sample 6l.
The first
In a total time of 2^ hours
938 liters (STP) of air was passed over the catalyst.
Theaverage temp­
erature during this time was 450 dC and the maximum temperature attained
in the catalyst bed was 600°Ge
In the second catalyst regeneration (after
sample 168) a total of 700 liters (STP) of air was passed over the catalyst
for a period of 2 hours.
The maximum temperature of the catalyst'during
this regeneration was 620°G.
The level of the catalyst activity was in­
creased after each air regeneration.
Sample 61 had a sulfur content of
„533 percent. Sample 62 (the first sample after the first catalyst re­
generation) had a sulfur content of .279 percent.
The sulfur content of
the product oil before the second regeneration was „569 percent.
After
this regeneration the sulfur content dropped to .264 percent.
The gas used for the CGR run was a gas mixture considered typical of
the make gas from a "catforming" unit.
The analysis of this gas (as
volume percent) was presented in the materials section.
gas delivered was made as a check on its composition*
An analysis of the
Presented below is
this analysis along with the composition specified when the gas mixtures
were ordered.
Specified composition
(percent by volume)
Delivered composition
CH4
0^6
G3H 6
°3h8
89
3.5
1.5
3.5
2.5
84
6 .0
3.7
3.9
2.4
H2
=22=
This check analysis indicated a somewhat leaner hydrogen composition than
was anticipatedo
The initial hydrogen content of the recycle gas was 84 percent.
The
hydrogen content of the recycle gas after 1341 hours of operation had
dropped to 81,1 percent.
This small decrease in hydrogen content did not
noticeably affect the effective desulfurization during the run.
Green (6)
investigated the effect of gas composition on effective desulfurization
and Silvey (4) has made a more thorough search in this direction.
The average gas consumption for the CGE run was approximately twice
that found for previous runs (GRS and MGR) where pure hydrogen was used
for recycle and make=up, .Average consumption data for the CGR run varied
between 280 to 290 SGF/bbl.
The temperature readings shown on the data for samples 30, 35» and
36 (Table VIII) are not the actual temperatures for these samples.
The
dry cell in the temperature indicating potentiometer was nearly dead for
the period between samples 30 to 3 6 ,
For the three samples cited, a close .
cheek on the standardization of the potentiometer was not made and the
temperatures for samples 30, 35» and 36 were lower than the actual readings
taken.
The fact that temperature is a critical factor in effective de­
sulfurization is readily shown by these three sample periods.
They show
that when the temperature is below a certain critical level (Munro (3 )
thought this was below 4d0°C) the sulfur content is correspondingly higher.
For samples 30, 35, and 36 respectively the sulfur content of the effluent
oil was ,646, ,552, and ,568 percent.
The other samples taken during this
*»23period were all below 0 o5 percent sulfur.
From sample 99 to sample 106 gas consumption calculations were not
made,
At this time the'-method of gas compression was changed (see
Equipment section)9 and establishment of new operating procedure, precluded
any gas balance or gas consumption calculations.
The period of the run from sample 130 to sample 145 also did not have
any gas consumption data,
At this time the pressure in the gas make-up
cylinder fell below the pressure for which the Brooks rotameter .was
calibrated and it was not possible to measure the quantity of make-up gas
added to the reactor system.
When, new cylinders of the make-up gas were
delivered the gas consumption calculations.were resumed with sample 146 ,
The primary purpose of the CGR run (Table VIII) up to sample 6l was
the determination of gas consumption and catalyst life using the "catforming" gas on recycle.
After sample 6l it was decided to run at- a space
velicity of 1 .0 until the sulfur content in the product oil exceeded 0.5
percent,
When this occurred the catalyst was to be regenerated and the
process repeated until the time between regeneration periods became
excessively short,
As the run progressed from sample 61«, the decision was
then made to run until the composite blend of the product oil samples
reached 0.5 percent sulfur.
The catalyst would then be regenerated, and
a composite blend equal to 6 ,5 percent sulfur would again be the point at
which catalyst regeneration would take place.
The run was ended, however, when it became obvious that the time in­
terval between catalyst regeneration was prohibitively long if the
ultimate deterioration of the catalyst was to be determined«
CONCLUSIONS
The brief studies made with nickel catalysts indicate that these
catalysts are inferior to molybdenum catalysts as far as catalyst life
and the degree of desulfurization are concerned.
Data from these studies
also substantiate in some measure the contention that the nickel catalysts
desulfurize for the most part through a chemical reaction mechanism and
that they do not act as true catalytic desulfurization agents.
Gas consumption data found with HoS 2 catalysts indicate a higher
consumption figure with a Mcatformingtt gas mixture than with pure hydrogen
when these gases are.recycled.
When either hydrogen or a gas mixture was. used as the recycle gas,
the hydrocarbon gas buildup per recycle was not excessive and the buildup
of hydrocarbon gases that did occur did not noticeably affect the de­
sulfurization process.
Use of a gas mixture in the desulfurization process, as well as the
continuous recycle of the effluent gases, did not noticeably affect the
degree of desulfurization obtained with HoSg catalysts.
Deactivation of the molybdenum catalysts with prolonged use was in­
dicated by the studies made, but air regeneration restored the activity
of these catalysts to a higher level than that of the fresh catalyst,.
Although the molybdenum catalysts did exhibit some deterioration
with use, specification oil was produced for 526 hours without catalyst
regeneration when pure hydrogen was used as make-up and for 493 hours
before regeneration was necessary when "cat'forming".gas was used as make*=
up. .
At^IJOWIEmEMENT
The author wishes to thank the Husky Oil Company who sponsored the
fellowship under which this work was carried out.
-
26-
LITERATURE CITED
(I)
A 0 S 0 T. M 5 STANDARDS■GN PETROLEUM AND LUBRICANTS, American Society
for Testing Materials, Philadelphia9 (1941),«
(.2)
Koski5 O 0 H 05 M 0S 0 Thesis5 Montana State College (1951)*
(.3 ) Mnnro 5 B> L 05 M 0S 0 Thesis5 Montana State College (1952)*
(4)
Silvey5 F 0 C 05 M 0S 0 Thesis5 Montana State College (1953)«
(.5 )
Haas 5 P 0 A 05 M 0S 0 Thesis5 Montana State College (1951)*
(6 )
Green 5 K 0 J 05 M 0S 0 Thesis5 Montana State College (1952)*
(7 )
Cdykendall5 J.0 W 05 M 0S 0.Thesis5 Montana State College (1952).*
(5) Brovm 5 H 0 R 05 and Meyersori5 S 05 Ind0 Epg 0 Chem05 44, Hp 0 Il 5
2620-2631, (1 9 5 2 ).
(.9 )
Hatch 5 L 0 F -05 Petroleum Refiner5 32 5 No. 6 5 105-107 (1953)*
(IO) Anon5 Petroleum Refiner5 3l, Np. 6 5 108 (1952)*
(II) Anon5 Petroleum Refiner5 31, No. 9, 226 (1952)*
(12) Anon 5 Petroleum Refiner, 31, No*.9, 114 (1952)*
”27"
APPEIfflIX
page
28
Table I
Fuel Oil Inspection Data,
Table II
Catalysts
Table III
Tabulated Data for Nickel Study Run One
0
0
0
0
0
*
0
0
Table IV
Tabulated Data for Nickel Study Run Two
o
o
o
o
o
o
o
o
Table V
Tabulated Data for Nickel- Study Run Three
o
o
o
o
o
o
o
o
32
Table VI
Tabulated Data for Gas Recycle Study
0
0
0
0
0
*
0
0
34
Table VII
Tabulated Data for Molybdenum Comparison Run, »
Table VIII
Tabulated Data for Catforming Gas Study Run
Figure I
Reactor Diagram
o
o
o
o
o
,
o
b
o
o
o
o
0
*
o
0
o
o
O
o
O
o
.
31
37
O
o
30
0
O
e
O
o
O
O
o
o
’ TABLE I
FUEL OIL INSPECTION DATA
Sample
Designation
Charge Stock
No. 3 Oil
CGR
Comp. 103-10?
CGR
Comp. 60-168
A e-P6I
Ao-5,-ToM„ Distillation
I6BoPo
5%
1#
2#
3#
4#
50#
60#
70#
80#
90#
95#
E. -P.
3P.6
op
425
504
520
536
548 ■
558
567
575
584
594
6ii
625
652
3 4 .6
PF
160
3 4 .2
418
411
461
572
6Q3
630
649
599
627
645
Recovery
9 9.9#
9 7 .0 #
97.5#
462
497
513
526
538
550
562
op
145
• 494
512
524
536
548
560
575
Residue
0.8#
I .2 5 #
1 .5 #
Loss
0 .2#
1 .7 5 #
1.0#
Wt 6 # Sulfur
• 2.19#
■ «460 #
.539#
-29-
TABLE II
CATALYSTS
Run
Number
Catalyst and Composition
N S M
and
NSR=III
Nickel Oxide
NiO
10,
AlgO^ Balance
NSR=II
Nickel-Hydroxide
Ni(OH)2
GRS
Molybdenum Sulfide
MpS2
1556
Ai2O3
Balance
MCR
and
CGR
Molybdenum Sulfide
. Mo
9.66$
S
7.97$
Al2 O3
Balance
Identification Code
Harshaw Number 3
Calcined
. Ni-0301 T 1/8"
Harshaw Number 3
Harshaw Mo-X-L32l
-42 T 1/8"
Harshaw Mo-0801=T 1/8"
RI 34-1 Lot. 191- A-l-1
TABLE T H
T A B U L A T E D D A T A F O R N I C K E L S T U D Y R U N O N E (NSR-I)
Rtin N u m b e r s ’ '
NSR-I
G r a m s “Catalyst s
100
Catalyst.,Reference: N i O H a r s h a w #3 Calcined, N i » 0 3 0 1
O i l Charge 0 API;
-^*30
Percent Sulfur:
2,19
Samp 6 Total Avg, Cat. Reactor Space Vel, Recycle
Ft3/bbl
Nb, Hours Temp, °F
psig ,-Gms/gm/hr
I
2 I
3
4
5
I
3
5
7
.9
6
11
7
13
15
17
8
9
Yields
Wt4
734
673
711
732
714
723
730
729
729
97.7
59
63
1.94
3.12
3.07
3.24
60
2 ,6 6
64
64
6l
2.67
3.21
3.03
• 3.41
60
6l
62
T 1/8"
Hp Consumpe
Ft3Zbbl
3530
.
2100
2070
2010
2260
2260
1920
2040
2010
-7.13
!field Product
gms oil
# S
190
612
.68
1 .2 2
600
634
1.24
1.43
520
522
629
1.71
1.69
Recycle Gas
He
H2
96.9
3 .1
1 .6 8
594
1 .6 1
658
1.76
83.4. 1 6 .6
T A B L E 'TV
T A B U L A T E D D A T A F O R N I C K E L S T U D Y R U N T W O (NSR-II)
R u n Number:""
Grams C a t a l y s t :
Catalyst-Referenced
Oil" Charge 0 API;
—
Percent Sulfur;
Samp6 Total
No6 Hours
I
2
3
4
5
6
7
B
9
10
il
12
I
2
4
6
8'
10
12
14
16
18
20
21
Yield;
NSR-II
IOO
N i ( O H ) ^ s H a r s h a w #3
30
2=19
Avg^6Cat6 Reactor
Temp60F
psig
.
59
757
729
725
721
725
725
725
725
725
725
725
725
Wte %
61
58
60
57
58
61
61
61
62
60
61
98.6
Space Vel6 ,Recycle
Ft^/bbl
gms/gm/hr
2.09
3.07
2.99
3.37
-3.12
3.05
3.22
2.89
3.12
3.08
3.14
3.47
Ho Consump6
Ft3/Tbbl
3120
1970
2130
1890
2040
206
304
590
665
615
. 601
635
572
616
608
2030
187©
22l0
1980
2060
2030
1880
Yield Product
gms oil % 8
620
-9.65
342
.83
1.18
1.44
1.58
1.70
1.70
1.71
1.76
1.82
1.82
1.87
1.89
Recycle Gas
H2
He
~ 10 Q
—
’
V-
86.7
13.3
TABLE V
TABUL A T E D D A T A F OR N I C K E L S T U D Y R U N T HREE (NSR-IIl)
R u n Numbers
NSR-III
G r a m s Catalysts
200
Catalyst R e f e r e n c e s . N i O H a r s h a w #3 C alcined
O i l Charge 0 APls
»,30
P e rcent Sulfur:
2,19
Samp,
No,
I
2
3
4
5
6
7
8
9
10
Il
.12
13
14
15
16
17
18
19
20
21
22
23
24
25
Total
Hours
3
11
15
19
23
27
31
35
39
43
47
51
55
59
63
67
71
75
79
83
87
91
95
99
103
AvgeCat, Reactor
Tempe0F
psig
579
741
102
,0588
18,400
loo
.0264
40,300
,0869
,1081
.1243
,1238
.1211
,1205
,1175
,1191
,1300
,1175
,1125
.1250
.1053
.1204
.1225
.1125
.1175
.1132
,1090
.1211
.1225
.1131
.1190
11*300
9,080
720
98
723
723
725
99
99
97
725
lol
723
725
725
97
723
IOO
loo
. 725
723
725
725
725
723
725
725
725
725
725
725
725
725
Space Vel, Recycle
Ft3/bbl
gms/gm/hr
96
98
102
103
105.
102
i03
105
104
101
102
99
99
IQl
101
8,500
9 ,230
' 9,430
8,800
9i710
8;250
8,150
9,720*
9,420
8,500
10,100
8,800
8,660
9i440
9,7©0
8,660
9 ,oio
8,750
8,660
8,690
8,910
H 2 Consump.
Ft^/bbl
Yield
gms oil
Product
# S
1.18
31
37 , .27
6-1
.09
76
.17
88 ■
.14
.87
.13
85
.19
.22
84
82
,25
.24
84
92
.26
82
.31
80
.38
88
.36
74
.41
84
.43
86
.4 7
.56
79
82
.65
81
.68
76
.77
.84
85
86
.9 0
80
.92
84
.9 7
Recycle Gas
H2
-He
~100
.
■ ••
34.4
•
.
65.6
T A B E E V (continued) •
T A B U L A T E D DA T A F O R N I C K E L S T U D Y R U N T H R E E (-NSR-Hl)
Samp0
No o
26
27
28
29
30
Yield;
Total
Hours
107
Hl
115
H9'
123
Avg, Cat,
Temp00F
97
99
90
98
96
725
725
725
723
725
Wt0 £
Vol. %
Reactor
psig
Space Vel0
gms/gm/hr
.1190
»1131
»1219
.1225
.1769
Recycle
Ft3/bbl
8,910
9s370
8,710
8,660
6,040
87.8
90.4
Composite Samples #1=27:
«514^ S e
Composite Samples #1=27 consumed 21e8'Ft3 H^/bbl oil*
H2 Consump.
Ft3/bbl
Yield Broduct Recycle
gms oil
~% S
-Oas
%
He
84
80
86
86
124
1.04
1.08
1.10
1.10
1.20 37.7
62.3
TABlA V T
TABULATED DATA FGE GAS RECYCLE STUDY
Run WiamberT
GRS
Grams Catalysts
100
Catalyst"Reference: Harshaw MoX=L321-42
OiT''Charge-0API: " ~ 3 0 '
Percent Sulfur:
2,19
Slamp,
No.
Total
Hours
6
I
2
14
22
3
30
4
■ 5 . 38
6
46
54
7
62
8
70
9
10
78
ii
86
12
94
102
13
HO
14
118
15
16
126
17
134
18
142
150
19
20
158
166
21
22
174
182
23
ISLQ24-
Avg. Cat.
Temp °F
Space Velo Recycle
gms/gm/hr .Ft3/bbl
H2 Consump.
Ft3/bbl
770
770
770
772
770
770
770
770
770
770
770
774 '
772
774
770
770
768
770
770
.900
.664
.637
.670
.540
.575
.572
.550
.535
.554
.565
.561
11,2 5 0
—~
11,200
11,100
11,100
11,600
***”
——
.566
10,900
.527
.530
11 ,3 0 0
.604
10,200
.655
9 ,6 2 0
.636
0626
768
.631
770
770
770
768
.632
9,660
10,000
9,430
9,720
9,230
9,360
9,610
.655
=655
.619.
5,350
8,740
10,000
9 ,3 4 0
12,020
11,100
11,150
11,450
— —
— ™
=■”
Yield
gms oil
Product
^ 8
500
.681
493
474
497
401
426
425
408
397
410
418
416
418
391
394
.566
464
504
488
481
484
=■—
™—
=«=”
476
502
502
474
.511
.471
.453
-415
.400
.396
.397
»375
.403
.403
.375
.388
. .356
.397
.452
.437
.402
.397
.423
.458
.417
.403
Recycle Gas
He
H2
—100
&
f
;
96:5
3.5
95.7
4.3
- TABLET 371 (continued)
TA B U L A T E D D A T A F O R G A S R E C Y C L E S T U D Y
Samp.
No.
25
26
27
28
29
30
31
32
33
34
35
36
37
33
39
40
41
42
. 43
44
45
46
47
48
49
50
51
52
5354
55
Total
Hours
198 '
206
214
222
230
238
246
254
262
270
278
286
294
302
310
318
326
334
342
350
358
366
374
382
. 390
398
406
"414
422
430
438
Space Vel.
gms/gm/hr
Recycle
Ft3/bbl
768
.648
770
770
770
772
768
768
770
772
770
770
770 ’
774
772
772
770
770
772
772
770
772
770
768
770
770
770
772
770
770
770
772
.681
9,520
9,230
9,660
9,030
9,520
9,030
9,370
9,660
9,910
9,180
8,840
Avg. Cat.
Temp. °F
.650
.664
.641
.652
.633
.622
.633
.672
.718
.682
.96?
*854
.606
.567
.531
.672
.688
.678
„688
.685
*713
.690
.690
.697
*705
.715
.707
.722 .
.712
9 ,0 8 0
6,480
7,410
10,450
11,100
1 1 ,4 4 0
9,420
. 9,130
8,980
9,270
9,130
8,740
8,940
9,040
9,220
8,880
8,740
8,740
8,780
8,840
Ho Consump.
Ft3/bbl
Yield
gms oil
Product
^ S
.. .
498
174
217
277
286
275
242
269
521
.438
.408
.413
.431
.393
.417
.428
.395
.382
.397
.412
.414
.528
.504
*425
.358
.381
246
258
257
249
55
68
89
94
96
82
82
82
73
69
89
103
123
131
133
134
141
134
132
499
504
490
499
484
476
485
514
552
523
750
660
464
434
425
518
532
523
532
530
552
532
532
535
550
558
551
560
553
Recycle Gas H2
He
95*2
4.8
96.3
3.7
95.6
4.4
.422
.456
.454
»455
.447
.467
.447
*452
.454
.460
.467
.481
.474
.464
T A B L E .T I (continued)
T A B U LATED D A T A F O R GA S RECYCLE' S T U D Y
Samp *
No.
Total
Hours
56
57
446
454
462
470
478
486
494
58
59
60
61
62
63
64
65
66
Yields
Avg. Cat a
Temp. 0F
502
510
518
526
Wti %
768
770
770
770
770
772
770
770
772
768
770
96.9
Space Tel.
gms/gtn/hr
Recycle
Ft3/bbl
i7l3
»699
.718
' »725
.720
.675
.703
.691
»692
. .680
.769
8,780
9,080
8,740
8,740
8,840
9,340
9,080
9,230
9,520
9,230
. 8,590
Ho Consump.
Ft3/bbl
142
137
135
134
132
131
130
134
137
141
140
■ Yield
gms oil
.
560 .
543
558
564
560
525
546
536
537
528
596
Rpoduct
Recycle Gas
H2
He
.464
«472:
.471
«481
.476
.443
*480
.471
.478
.455
.478
95.0
5.0
94.0
6.0
95.4
4.6
.
TABLE VII
TABULATED DATA FOR. MOLYBDENUM COMPARISON RUN
Run Number?
MCR
Grams Catalyst;
• 100
Catalyst Reference; HarshawMo-0801 T l/8" RI 34=1 Lot 191A-1-1
Oil Charge 0APi;
^30
Percent Sulfur;
2.19
Reactor Pressure;
500 psig
2
3
4
5 '
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Space Vel 0
gms/gm/hr
Recycle
Ft3/bbl
I
16
24
32
40
48
56
64
72
80
761
.743
8,550
128
574
768
.6??
9,000
126
770
0694
8,820
74
538
536
.109
770
.961.
6,260
100
743
.211
770
770
1 .0 1 2 ■
1=021
6,180
Ho
6 ,0 6 0
107
768
1.289
i255
.224 ■
.421
770
772
1.301
4*800
4,540
783
790
997
138
88
779
772
770
768
770
772
768
770
772
770
96
104
Il2
120
128
136
144
152
160
1.298
1.296
1.300
768 .
Composite Yield;
•1 .3 0 0
• 1.310
1.300
1.365
1.350
1.369
1.331
.869
.868
Wt0 %
97=5
Ho Consump;,
I
I
Total Avg. Cat0
Hours Temp-. 0F
£
Samp=
No.
127
Yield;
gms oil
Product
% 8
=Ioi
.086
4.4
- .491
95.5
.496
.515 '
.532
4.5
4,780
4,650
. Iooi
.420
?423
4,750
123
ioii
4,860
4,710
4,600
4,600
140
141
132
138
141
134
139
.143
1015
1011
4,550
4,810
5,140
. 5,150
1016
1065
1052
1067
1039
'-«100
95.6
1017
1002
.413
123
130
133
4,920
,Recycle Gas
He
%
=419
=442
=457
678
.519
.304
677
.317
95.8 .
4.2
TABLE' V I H
TABULATED DATA FOR CATFORMING GAS STUDY RUN
Run Number;
Grains Catalyst
Catalyst References
Oil Charge 0APIs
Percent Sulfurs
Reactor Pressures
Samp.
No.
Total
Hours
I
3
2
11
19
3
4 . 27
35
5
6
43
5l
7
8
59
67
9
10
75
Il .
83
12
91
99
13
107
14
115
15
16
123
131
17
18
139
19
147
20
155
21
163
22
171
179
23
CGR
IOO
Harshaw Mo-0801 T 1/8" RI 34=1? Let 191A-1-1s
Previously on MCR 160 Hrs»
— 30
2,19
500 psig
Avg. Cat.
Temp. °F
. 766
770
768
768
770
772
768
766
766
765
768
768
772
770
770
768
768
770
770
765
772
770
775
H2 Consump.
Ft3/bbl
Space Vel0
gms/gm/hr
Recycle
Ft3/bbl
1.140
.936
.662
. 1.031
.849
1.000
.901
.740
1.005
1.008
1.045
1.0l2
1.004
.990
1.078
1.012
.895
.874
.917
.944
.946
.926
.940
5,610
—83
5,600
9,550
—82
6 ,0 4 0
234
279
245
247
296
284
288
7,280
6 ,250
'
7,120
8,640
6 ,4 0 0
6,350
.6 ,1 3 0 ■
6,230
6,0706,380
5,940
6,190
7,240
7,500
7,350
7,050
6,730
7,000
6,866
216
Yield
gms oil
333
730
515
825
660
779
70l
576
783
785
288
814
286
284
293
786
• 781
779
838
787
301
298
306
311
318
314
308
306
292
696
670
716
734
736
720
732
Product
$ S
.515
O441
.304
.427
.377
.457
.421
.379
.459
.498
.491
.481
.450
.495
.518
.474
.472
.473
.478
.496 .479
«448
,453
Recycle Gas
H2
He
84.0
16.0
TABLE'VIII (continued)
TABULATED DATA FQB C A T FO R M IN G GAS STUDY RUN.
Samp. Total
No. ■Hours
24
25
•26
27
28
29
3031
32
33
34
35
36
37
3#
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
. 187
195
203
211
219
227
235
243
251
259
267
275
283
291
299
307
315
323
341
349
357
365
373
381
389
397
405
413 '
42l
429
Avg, Cat.
Temp. 0F
768
772
759
770
770
770
763*
772'
770
774
770
770*
770%
772
. 772
770
768
772
768
770
768
770
770
774
770
770
772
770
772
772
Space Vel.
gms/gm/hr
Recycle
Ft^/bbl
.906
.964
.860
.934
.943
.934
.918
7,250
6,760
7,460
6,840
6,960
■
.869
• .765
.732
.784
. .793
.789
.773.
.808
.782
.797
.865
.842
.921
1.048
.888
.864
.957
.854
.743
.692
.695
.698
.706
6 ,9 0 0
7,000
7,400
8,410
8,910
8,260
8,060
8,220
%
Consump.
Ft3/bbl
291
275
261
276
263
255
264
268
264
262
8,020
7,660
7,770
6,980
6 >070
7,150
7,550
6,810
7,610
264
265
267
258
265
266
■ 263
262
261
260
258
258
258
257
254
8 ,650
256
9,210
9,300
9,260
9,110
257
259
260
261
8,320
8,290
8,320
Yield
gms oil
705
751
669
727
734
726
714 .
675
594
569
610
624
613
600
628
608
628
673
655
718
816
692
673
747
666
578
541
542
543
55©
Product
# 8
.483
.483
.494
.438
.481
.576
Recycle Gas
Hg
He
82.6
17.4
82.3
17.7
.646
.482
.439
.448
.467
.552
.568
.456
.425
.468
.450
.436
»46$
.447
.496
.514
.483
.482
.496
,455
.393
»417
.368
.415
T A B E E V H I (continued)
TA B U LATED D A T A F O R CATFO R M I N G G A S S T U D Y R U N
54
55
56
57
$8
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
Total
Hours
437
445
453
461
469
477
485
493
501
509
517
525
533
541
549
557
565
573
581
5d9
597
605
613
621
629
637 .
645
653
661
669
677
Avgc Cat.
Temp. °F
770
768
770
768
770
781
777
779
775
768
775
775
775
779
774
770
775
781
779
777
775
775
779
781
781
775
779
779
779
772
775
Space Vel.
gms/gm/hr
.686
0737
.709
' .694
.804
1*139
1.148
.926
*915
.932
1.075
1.103
1.095
1.059.
1.080
1.080
.990
.976
.998
1.006
1.032
.979
1.006
.989
.940
.968
*975
,961
.963
1.081
1.062
Recycle
Ft3/bbl
9,450
8,820
9,460
9,310
, 7,760
5,800
5,640
6*910
7,150
7,190
5,980
5,590
5,540
5,910 ^
5,940
5,860
6,580
6,600
6,450
6*380
6^370
6,380
6,550
6,530
6,830
6 ,6 4 0
6 ,650
6*750
6,320
' 5,930
6 ,1 4 0
Ho Conpumpe
Ft3/bbl
262
263
264
265
265
264
261
263
256
255
253
255
254
251
251
252
254
253
254
252
252
252
248
249
247
246
246
245
243
245
241
Yield
gms oil
535
574
552
542
627
88?
895
743
TH
725
835
893
875
846
863
863
759
758
776
783
803
761
783
768
730
746
752
741
743
835
822
Product
# S
R e c y c l e Gas
H2
He
.424
.477
.466
.482
.472
.579
.592
.533
.279
.353
.359
.387
.384
»399
*455
.450
«416
.400
.393
.413
.458
.419
.423
*436
.414
.441
.438
.437
.443.460
.491
81.0
19.0
"Otr
Samp.
No.
■TABLE! V I I I (Goptinued)
T A B ULATED D A T A •F O R 'C A T F O R M I N G G AS S T U D Y R U N
Samp.
No.
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
iob"
ioi
102
103
104 .
105
106
107
108
109
110
111
112
113
114
115
Total .Avg. Cat.
Hours Temp. °F
685
693
701
709
717
725
733
741
749
757
765
773
781
789
797
805
813
821
829
837
845
853
861
869
877
885
893
901
909
917
925
77,7
777
. 779
775
779
781
775
777
779
779
779
779
779
779
781
779
779
779
777
779
779
779
779
779
779
779
777
777
.781
779
777
.
Space Velo
gms/gm/hr
1.068
1.091
1.098
1.098
1.062
1.058
. .981
.981
.972
1.175
1.114
1.061
1.031
.956
.947
.974
.968
,990
.976
6973
.923
.943
.963
1.021
1.036
1.041
1.034
. 1.048
1.062
1.043 ‘
1.034
Recycle.
Ft3/bbl
6,140
6,170
5,960
5,800
6,000
6,010
6,600
6,830
6,730
5^540
5,670
5,950
6.240
6,220
6,700
H2 Consump.
FtVbbl
239
239
237
235
233
231
230
231
23l
234
233
237
232
232
e-™=a
6,780
6,810
6,520
6 ,460
6,710
6,980
6,650
6,780
6,340
6,250
6,230
6 ,2 5 0
6,070
6,080
6,190
6,100
—
=
560
364
299
309
308
269
290
357
310
Yield.
gms oil
•824
842
847
842
821
81?
757
757
749
923
892
850
809
750
736
758
753
771
759
757
718
749
749
795
807
810
806
814
829
813
' 806
Product
# S
R e c y c l e Gas
H2
He
.503
.514
.516
i545
.500
.506
.468
•
.470
.468
.557
.558
.507
.487
.536
.425
.448
.461
.475
.477
.453
.i424
.436
«460
.431
.473
.489
.510
.543
.514
*534
.517
81.5
18.5
$
TABEET-'VIII (continued)
T A B U L A T E D D A T A F OR C A T F O M B T G G A S S T U D Y RUIf
Samp,
No,
Total
Hours
ii6
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
933
941
949
957
965
973
981
989
997
1005
1013
1021
1029
1037
1045
1053
1061
1069
1077
1085
1093
iioi
1109
1117
1125
1133
1141
1149
1157
1165
1173
Space Vel»
Avg, Gat,
Temp, 0F • gms/gm/hr
781
779
770
781
777
775
779
784
772
777
777
775
779
781
779
781
779
777
779
781
775
782
782
777
779
779
777
782
779
777
781
1.019
.991
.991
.969
.945
.980
»968
.972
»940
.930
.956
1,028
1.039
1.025
1.025
1.039
1.011
1.034
1.008
.986
1.005
1.025
.975
1.022
1 .0 0 6
1.006
1.000'
.995
1.006
1.013
1.03l
Recycle
Ft3/bbl
Ho Consump0
Ft3/bbl
Yield
gms oil
Product
jg g
6,420
6,540
315
282
270
298
293
304
336
363
361
340
354
364
794
772
773
754
744
763
753
756
731
723
744
800
808
799
798
808
787
806
785
769
782
798
759
796
783
783
778
774
783
789
804
.491
»502
.531
.500
.430
.535
.503
.517
.513
.465
.469
.527
.535
.531
.538
6,500
6^680
6,810
6 ,4 0 0
5,980
6,670
6,920
6,930
6,750
6,260
6,200
6,280
6,280
6,600
5,950
3,830
5,450
6,530
6,420.
6,280
6,610
6,310
6,840
6,410
6*450
6,370
6,410
6,360
6,660
364
346
cooes*
= = * =
O = O
O = O
=
O = O
=
=
= O O
C=^=O
S3 = O
=
O
.
=
0 = 0
356
.526
.514
.570
.546
.514
.534
.520
.500.
.571
.558
.547
.548
.548
.529
.571
.548
Recy c l e Gas
H2
He
TABIE V H I Cc o n t i n u e d )
T A B U L A T E D D A T A F O R .CATFO R M I N G G AS S T U D Y R U N
Samp6
No6
Total
Hours
Avg., Cat,
Temp6 °F
147
148
149
159
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
16 ?
168
169
170
171
172
173
174
175
176
177
1181
1189
1197
1205
1213
1221
1229
1237
1245
1253
1261
1269
1277
1285
1293
1301
1309
1317
1325
1333
1341
1349
1357
1365
1373
1381
1389
1397
1405
1413
1421
779
781
. 779
777
779
779
777
779
781
777
779
781
779
777
78l
777
779
781
777
779
781
779
779
777
781
779
775
779
777
775
781
Space Vel6
gms/gm/hr
6,486
6,310
6,300
6,380
6,390
6^330
6,830
5,850
5,960
6,160
6,310
.992
1,021
1,022
1,010
1,007
1,019
1 ,006
1,100
1,079
1.047
1,021
1,020
i995
1,000
.995
.997
1.031
1,019
.989
.994
1,045
1,028
1,031
.989
.945
1 ,015
1,009
1,027
1,002
1,024
1.034
Recycle
Ft3/bbl
346
344
348
341
338
337
326
6 ,2 7 0
315
316
307
310
313
6,510
322
6 ,3 0 0
313
319
322
320
326
317 ’
309
321
314
313
305
6,530
6,480
6,250
6,330
6,510
-
■
Hg Consump,
Ft3Zbbl
6,520.
6,230
6,560
6,280
6,520
6,850
6 ,36 ©
6,370
6,270
6,440
6 ,3 2 0
6 ,2 5 0
310
303
300
299
293
292
297
-
Yield
gms oil
772
796
797
786
784
7.93
783
856
840
815
798
795
774
778
775
777
803
794
791
795
836
823
803
768
. 734
790
786
798
780
797
806
Product
% S
Recycle Gas
H2
He
.562
.574
.565
.599
»567
.578
.645
.581
.582
,605
.517
.575
<*465
,581
,548
.548
,618
¥
.665
.617
.588
.578
.589
.264
.331
.345
.352
.359
.370
.382
.393
.423
81,1
18,9
TABLET VIII (continued)
■ TABULATED DATA FOR GATFORMIEG GAS STUDY RUE
Samp,
Eoe
Total
Hours
178
1429
1437
179
180
1445
181
1453
182
1461
183
1469
184
1477
1485
185
186
1493
1501
18?
188 . 1509
189
1517
190
1525
191
•1533
1541
192
1549
193
Space Vel,
gms/gm/hr
Avg, Cat
Teppe °F
781
779
781
779
779
. 779
779
779
78l
779
779
783
779
775
781
777
Composite Yields
•
Wte
Wte
Wte
Wte
'^
.994
.949
.994
.977
.964
.982
.960
,968
.972
.940
.981
.934
1.909
.937
.952
.945
% 97.3
97.2
96.8
97.3
101
99.1
%
%
%
1q\ $
Wte %
Recycle
Ft-Vbbl
Ho Consump,
Ft-5Zbbl
6,500
6,790
6,510
6,600
6,700
6 ,5 6 0
6,TlG
6,660
294 ■
294
296
297
292
293
298
295
6 ,7 0 0
296
7,180
7,140
291
292 .
28?
291
6 ,9 0 0
290
6,780
6,810
285
287
6 ,6 2 0
6 ,9 0 0
(Samples I through 8)
(Samples 9 through 61)
(Samples 99 through 123.)
(Samples 99 through 123 ) .
(Samples 169 through 193)
Yield
gms oil
Product
$ S
772
i414
738
.429
772
»405
.448
753.
748 . .475
.425
763
746
.451
.445
753
.448
755
743
.425
776
.483
.458
739
720
.478
.467
741
.468
752
.447
747
Recycle Gas
.
Composite %'S:
.464 (Samples 62 through 123 )
,502 (Sampled 62 through 168)
»414 (Samples 169 through 193)
Total Oil throughputs 145,232 Gme
First catalyst regeneration at Sample .61,
Second catalyst regeneration at Sample 168,
^Temperatures for these samples are incorrect due to non-standardization of potentiometer.
r
THERMOWELL
ROTAMETER
BLOW OUT
LINE
REGENERATION
AIR LINE
OIL RESERVOIR
HEATING COILS
PRESSURE GAGE-----
FLOWRATOR
/
- M A K E UP GAS TANK
Figure I. Reactor Diagram
r-FEED GAS TANK
ALUNDUM
BALLS
FEED.
PUMP
PRESSURE
GAGE 7
CATALYST
CONDENSER
RESSURE GAGE
BACK PRESSURE
VALVE
SIGHT
"GLASS l— [ X
COMPRESS/ ~ l ON TANK
SURGE TANK
CONTROLLER
STANDPIPE-^
PRESSURE GAGE
EXHAUST
RECEIVING
FLASK
COMPRESSION
PUMP
'I
CO
rn
rn
ro
COMPRESSION OIL
RESERVOIR
WET T EST METER
CAUSTIC WASH
MONTANA STATE UNIVERSITY LIBRARIES
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