Catalytic hydrodesulfurization of fuel oil
by Kenneth J Green
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
Montana State University
© Copyright by Kenneth J Green (1952)
Abstract:
This investigation was conducted to determine operating variables in the catalytic hydrodesulfurization
of number one and number three fuel oils obtained from a high-sulfur-containing Oregon Basin,
Wyoming crude. Desulfurization was carried out in pilot plant equipment capable of holding 100 ml of
catalyst and operable at pressures up to 500 psig, The catalysts investigated were eyclocel (activated
bauxite) and molybdenum oxide and sulfide. The variables temperature, pressure, and space velocity
were studied using hydrogen or hydrogen-methane gas mixtures, Desulfurization was considered
satisfactory when the sulfur content of number three oil was reduced from 2,2 percent to below 0,5
percent and of the number one oil from 1,1 percent to below 0,5 percent.
When number three fuel oil was desulfurized over cydocel the percent sulfur of the product oil
increased from an initial 1.1 to 1.9 after 100 hours. Cydocel was air regenerated after desulfurization of
number three fuel oil and the catalyst regained its original activity, Number one fuel oil was
desulfurized to below 0,5 percent sulfur content for a total time of 178 hours and there was no
noticeable deactivation of the catalyst.
The effect of pressure during desulfurization of number three fuel oil using molybdenum sulfide
catalyst indicated that increased pressure affected increased sulfur removal from the oil. Number three
fuel oil with less than 0,5 percent sulfur content was produced at 500 psig and 300 psig, but could not
be produced at 200 psig or below.
Hydrogen-methane gas mixtures were used during desulfurization of number three fuel oil over
molybdenum sulfide, When the percent methane in the mixture was increased the sulfur removal from
the oil decreased. Oil with less than 0,5 percent sulfur content was produced using hydrogen-methane
mixtures which contained five percent, 15 percent, and 25 percent methane respectively, but could not
be produced at space velocities above 0.45 using a mixture containing 40 percent methane, No
appreciable carbon deposition on the catalyst was found during this study.
The effect of carbon burn-off from molybdenum sulfide was studied after desulfurization with a heavy
gas oil. The gas oil was used in a deliberate attempt to make carbon lay-down on the catalyst. After
burning the carbon off with air the activity of the catalyst doubled (as measured by grams of sulfur
removed per gram of catalyst). CATALYTIC HIDRODESULFURIZATION OF FUEL OIL
ty
KENNETH J. GREEN
\X
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 9 Major Department//
Ghairman9- Examining Gomm/tee
iean9 G^duatelDivision
Bozeman 9 Montana
August 9 1952
FV//.'’(j/r
'I
/\f3 7 f
-2TABLE OF CONTENTS
page
ABSTRACT...................................... ........................... 3
I
Introduction. . . . . . . . . .
................ . . . . . . . . .
II
Thermodynamic Calculations............
6
III
Equipment, Methods, and M a t e r i a l s ..........
8
A.
Equipment . . . . . . . . . . . . . . . . . . . . . . . . . .
S
B,
Methods .....................
Ce
Materials . . . . . . . . . . . . . . . . . . . . . . . . . . 1 2
. . . .
IV
Sample Calculations . .............
V
Discussion of Results . . . . . . .
. . . .
4
10
13
........... . . . . . . . . . 1 5
A.
Desulfurization of Fuel Oils Using Cyclocel Catalyst. . . . .
B,
Effect of Pressure on the Desulfurization of Fuel Oil
15
Using Molybdenum Sulfide Catalyst . . . . . . . . . . . . . . 1 6
C.
Effect of Methane-Hydrogen Mixtures on Fuel Oil
Desulfurization Using Molybdenum Sulfide Catalyst . . . . . .
D,
I?
Effects of Gas Oil Desulfurization and Air Regeneration
on Molybdenum Sulfide Catalyst..............
19
VI
Summary ..................................
VII
Acknowledgement . . . . .
VIII
Literature Cited. . . . . . . . . . . . . . . . . . . . . . . . . 2 4
IX
A
p
p
. . . . . . . . . . . . 2 2
......... . . . . . . . . . . . . . . . 2 3
e
n
d
i
103331
x
25
ABSTRACT
This investigation was conducted to determine operating variables in
the catalytic hydrodesulfurization of number one and number three fuel oils
obtained from a high-sulfur-containing Oregon Basin 3 Wyoming crudee De­
sulfurization was carried out in pilot plant equipment capable of holding
100 ml of catalyst and operable at pressures up to $00 psig, The catalysts
investigated were eyclqeel (activated bauxite) and molybdenum oxide and
sulfide. The variables temperature 3 pressure 3 and space velocity were
studied using hydrogen or hydrogen-methane gas mixtures„ Desulfurization
was considered, satisfactory when the sulfur content of number three oil
was reduced from 2 ,2 percent to below' 0 ,5 percent and of the number one oil
from 1 .1 percent to below 0 ,5 percent.
When number three fuel oil was desulfurized over c y d o c e l the percent
sulfur of the product oil increased from an initial 1,1 to 1,9 after 100
hours, C y d o c e l was air regenerated after desulfurization of number three
fuel oil and the catalyst regained its original activity. Number one fuel
oil was desulfurized to below 0 ,5 percent sulfur,content for a total time
of 178 hours and there was no noticeable deactivation of the catalyst.
The effect of pressure during desulfurization of number three fuel oil
using molybdenum sulfide catalyst indicated that increased pressure affected
increased sulfur removal from the oil. Number three fuel oil with less than
0 .5 percent sulfur content was produced at 560 psig and 300 psig 3 but could
not be produced at 200 psig or below.
.
'.
Hydrogen-methane gas mixtures were used during desulfurization of
number three fuel oil over■molybdenum sulfide, When the percent methane in
the mixture was increased the sulfur removal from the oil decreased. Oil
with less than 0 .5 percent sulfur content was produced using hydrogen- "
methane mixtures which contained five percent 3 15 percent 3 and 25 percent
methane respectively, but could not be produced at space velocities above
0.45 using a mixture containing 40 percent methane. No appreciable carbon
deposition on the catalyst was found during this study.
The effect of carbon burn-off from molybdenum sulfide w a s .studied
after desulfurization with a heavy gas oil. The gas oil was used in a
deliberate attempt to make carbon lay-down on the catalyst. After burn­
ing the carbon off with air the activity of the catalyst doubled (as
measured by grams of sulfur removed per gram of catalyst).
I
INTRODUCTION
With the depletion of high-quality low sulfur Crudes5 petroleum refin­
ers have been forced to turn to crudes with higher sulfur content.
variety of sulfur compounds-have been found in petroleum.
A large
Elemental sulfur5
hydrogen sulfide, mercaptans5 thioethers5 disulfides2 and thiopheness have
been found in the various fractions.
It was the purpose of this-research to determine the conditions for
the catalytic desulfurization of number one andrnumber' three fuel oils.
.'3
.-■-
•
-
The maximum allowable sulfur specification for fuel oil was to be 0.5 pAr
cent.
Sulfur compounds in kerosene and fuel oil may give rise to objection­
able odor5 corrosive action on metals5 poor Stability5 and are responsible
for acrid fumes on burning (3).
A considerable number of methods are in
existence for the-removal of sulfur from light distillates.
.A few of these
methods which are.in commercial use are the Unisol process 5 the Solutizer
■
and Tannin Solutizer processes 5 hypochlorite treatment 5 Gray desulfuriza: ' -y
. .
tion 5 and- treatment with- bauxite catalysts.- In addition to these proces­
ses 5 hydrogen sulfide can be removed by caustic scrubbing,, and certain
other sulfur compounds are removed during sulfuric acid treatment.
Gener­
ally Speaking 5 sulfur compounds are distributed.'"in-lar-ger percentages in .
the higher boiling
petroleum
fractions. -When
the above-methods are
used
to desulfurize high boiling petroleum fractions-the sulfur compounds are
either not removed to the desired percentage or the losses- are excessive.
One method used to remove a large portion of the sulfur--compounds in higher
boiling fractions,, without excessive, charge Iosses 5 is catalytic decomposi­
tion in the presence of hydrogen®
The mechanism of desulfurization in the
presence of hydrogen is one of destructive dehydrogenations whereby the
sulfur compound is converted to a hydrocarbon and hydrogen sulfide„
Three
catalysts which have been used for hydrodesulfurization of petroleum are
cobalt molybdate (2 )«, molybdenum oxide (6 )3 and-molybdenum sulfide (6 )e
Any desulfurization process used commercially must be economical®
In an attempt to find an economical process 9 Koski (4), and Munro (6 )s
O
'■
•
made an initial study on the following catalysts; • Bauxite 9 molybdenum sul=
fide9 molybdenum oxide9 tungstic Oxide9 nickel oxide9 cobalt molybdate9 and
chromic oxide®
In addition an extensive study on the life of molybdenum'
sulfide catalyst was- made (6 )®
This life study was- discontinued•after 2010
hours--of-successful desulfurization of number three fuel oil*
.
.
Because of its
.
long life the following conditions using molybdenum sulfide were studied and
the results are reported in this thesis;
■
(l)-Effect of pressure; (2) effect
of using mixtures of hydrogen and methane; (3 ) effect of t h e •desulfurization
.
of a heavy gas oil; (4) effect of air regeneration®.
f
sulfurisation using cyelocel catalyst was studied*
■
In addition hydrode-
II
THERMODYNAMIC CALCULATIONS-
Tabulated thermodynamic data and calculations are presented in Tables
I-V of the appendix.
Four reaction mechanisms were postulated for desulfurization of fuel
oil by molybdenum sulfide catalyst.
All or some of these reactions may
occur in the overall-desulfurization,
...
(1)
MoS^ -^5»
(2)
c Z1h^13 (g)
(3)
M6S2 + Q4H4Stg) + 3H2(g) ->- MoS3 + ,C4Hiotg)
U)
MoS 3 + H2tg) - S - MoS 2 + H2S tg)
2MoSp + Sp^.g)
(Thiophene)
+ ^ 2(g)
^
H2S (g)
^10(g)
(n-butane)
The first reaction was considered because sulfur was produced when the
catalyst was heated.
The calculations from reaction number -two provide in­
formation about the-ease o f .destructive hydrogenation of sulfur compounds,
■Thiophene boils at 84°C and is not present in- number-three fuel oil, but
higher alkyl thiophenes-with higher boiling points are- present.
was considered in the -absence of--thermodynamic•dat§ on higher
Thiophene-
alkyl
thio­
phenes , Results calculated- from thiophene-should, in most cases, approximate
'Ti
,
■
''
the results that -would be obtained from-higher-alkyl thiophenes„
In the third reaction the sulfur compounds i n .the oil convert MoS^ to .
MoS^o
In the fourth reaction -MoS^ is reacted -with-'hydrogen and reduced to
MoS 2 and H2S (g)0-
catalyst, according ■torthe-mechanism, acts as a
carrier
of sulfur from the oil to the- H-5S that- is expelled.
All of these-reactions are thermodynamlcallypossible at the operating
i-i.y
conditions of 410°G and 34 atmospheres.
The following free energies will,
to some degree, show the feasibility of thesq reactions.
;=
: ■-
s,
Reaction•
F at 25q C
Gal/mol_____________ ______
F at 375°C
Gal/mol
I
+25,700
+9,575
2
-41,300
-14,560
3
—365640
4
—4,660
1
- 21,330
”9,341
The results-of the calculations are tabulated in Tables■I-V»
The
calculations help to confirm the postulated mechanism for desulfurization*
The calculations are not, however? of much value when used to fix the proper
conditions under which.the overall reaction should be run*
This is because
the equilibrium constants are all very high-.in- the practical operating range 0
'
'
Practical desulfurization of fuel oil must be carried out at tempera.■
tures below incipient carbon to carbon cracking if the product oil is to
i\
■- '.I
have the same- boiling point range as the charge oil*
The energy between a
carbon to carbon bond (58*6 KCal/mol)" is -only "slightly higher than that for
a carbon to sulfur bond (54*5 KCal/mol)®
Fronrthis analysis it is evident
that any thermal cracking of the carbon to' -sulfur *-bond- would" be accompanied
- .
>■". •
by considerable- carbon to carbon- cracking*":" This'-'l's- substantiated by data (8 )
on the thermal cracking of sulfur stocks which showed that 75 per cent of the
sulfur remained in the residue*
The temperature -for-catalytic- desulfurization
of fuel oil must therefore be-below thermal cracking temperatures and the
catalyst must be selective in its action*
=“8=
III-' E Q U i m E N V METHODS, AND
A»
MATERIALS
'
EQUIPMENT .
A schematic diagram of the-reactor is shown in Figure I 0
The reactor
consisted of a 16 inch length of one-and-one-half inch O e D 0 extra strong
black pipe reduced with reducing couplings to three-fourth inch at the top
and one-half inch at -the-bottom.
The top ofT.the reactor was fitted with a
union, two crosses, and an assembly of valves for hydrogen inlet, oil in­
let, oil feed bleed line, and air for regeneration*
A thermowell tube ex­
tended from the cross- at the top down the vertical axis of the reactor to
i
within one inch of the bottom. The thermowell- tube- was -made from $ inch
black pipe.
The tube-was.capped-at the bottom, and three thermocouples
were inserted from the top.
The hot -•junctions ,of the thermocouples were
adjustable to any--desired- position in the reactor.
The botom of the -reactor
.-
tee*
was
fitted with-a-one-half inch union and a
'
There was a pressure gage and a valve fitted from the tee.
During
part of the investigation- -a -Grove spring loaded -back pressure valve was
.. .
. . .
'I .. .
used,
A Mason-Neilan air-to-close valve,controlled by a Fisher Wizard
' -- •
Controller, was used during the- remainder- of -the investigation.
The heating elements consisted of three 33 foot lengths of beaded
Nichrome- wire- which- were supplied with current from H O volt auto transformers.
’•-I"
tape,
The-coils-were-wound-on■the-reactor pver.'a layer ef asbestos
'
r'-'l
■"
Another--Iayer of -asbestos-tape was wound-over'the wire and an inch
layer of magnesia mud was placed over the final layer of asbestos tape.
One-eighth inch alundum-balls were used as the pre-heat medium.
The
pre-heat section extended for 10 inches from the top of the reactor,
-The
catalyst bed was located below -the pre-heat section-and-below the catalyst
bed a layer of alundum balls extended to the bottom of the reactor»
Auxiliary equipment consisted of a high pressure piston type pump,
■Precision -Scientific wet -test-meters, water cooled- copper-tube condensers,
-hydrogen cylinders-with pressure regulators,- receiver-flasks-,- and alkali
scrubberso
Iron-eonstantan thermocouples were, used-in conjunction with a
Leeds and Northrup indicating potentiometer-for temperature' measurement«
Analysis of the exit gas was made in a low temperature fractionation
column
...10Bo M E T H O D S ........
.■Control and measurement of process variables were conducted as summar­
ized in the following paragraphs„
I0
Sampling and Space Velocity;
intervals o
Samples were taken at eight-hour
Space velocity calculations.were made over the eight hour
sampling periods and were based on the weight of charge oil and the weight
of catalysto
2,
Space velocity was controlled by pump-adjustments„
Temperature;
Temperatures were measured-with iron cqnstantan
thermocouples in conjunction with a Leeds and -Northrup indicating potentio­
meter,
Thermdcoupies were placed near both ends of the catalyst section,
and one was placed mid-way in the pre-heat section.
The temperature in the
pro-heat section was maintained at approximately -90°C below the temperature
in the catalyst section.
Temperatures were controlled by adjustment of the
power input to the heating elements with auto-transformers,
An average of
the two temperatures in the catalyst section was recorded at l$-minute
intervals and these readings were averaged over a-period of eight hours,
3 , ■Hydrogen Rate;
Hydrogen rate was maintained by control of the
!
pressure differential across the reactor.
The actual hydrogen input was
not measured'but'a relative hydrogen rate was measured by metering the vol­
ume of exit gases,
.As seen
by gas
analysts"data-the build u p of non-conden-
sable hydrocarbons in the exit gas was- not--more-than" 3 per- -cent--per cycle.
Before the exit gases were measured, hydrogen sulfide was removed by a caustic
wash.
Exit gas meter readings were recorded every 15 minutes, and the total
exit gas over an eight-hour period was used to calculate the hydrogen-to-oil
ratio.
I
=aXlea=
4«
Pressures
The pressure was controlled by proper -adjustment of
the back pressure valve on the reactor*
5»
Air Regenerations
passed over it*
The catalyst w a s ■heated to 450°C and air was
Once the regeneration had begun the temperature was main­
tained below 550°C by proper adjustment of the air rate*
6 „ Sulfur Analysis;
lamp method (X ) 0
Sulfur content of the oil was determined by the
This method involves the combustion of a weighed sample
of oil and the absorption of the sulfur dioxide produced in- a known amount
.of alkalio
The excess alkali is determined by titration with a suitable
acid and indicator.
The gas oil used in the regeneration study run was too
viscous to be analyzed directly by the lamp method so a modification of
this method was used.
The gas oil was diluted with an approximately equal
weight of number one fuel oil which had a known sulfur content.
The diluted
gas oil was then analyzed by the conventional methoql. The per cent sulfur
I
in the gas oil was calculated from the analysis of the mixture.
*■>12“
C.
MATERIALS
'
The following catalysts ‘were used in this study:
1»
Bauxite (Cyclocel)e
10/30 mesh*
Code number SB-2446-51*
Produced by the Porocel
Corporation,
2*
Molybdenum Sulfide*
This catalyst consists of 15 per cent MoS^ impregnated on alumina
and pelleted into one-eighth inch-pellets»
L321-42*
Produced by t h e 'Harshaw- Chemical Company*
Three commercial grades of oil were uses»
A eS eT eM e distillation data
for these oils are presented in Table V I e
I0
2„
3»
Number three fuel oil,
a*
Boiling point range# 460-660°F„
b»
Specific gravity, ©»875»
cc
Sulfur content, 2„19 per cent,
Number one fuel oil*
a»
Boiling-point range, 204-495°F»
b*
Specific gravity, 0,832,
c,
Sulfur content, 1,09 per cent®
Gas oil*
a,
_
Boiling point ■range, 580=750°?»
b, - • Specific gravity^,-0^,925*
c,
Code number Mo-x-
Sulfur content, 2,85 per cent*
1•
IV
SAMPLE ■CALCULATIONS -
Data for the following calculations were taken from the mixture study
run Table XIII*
Number three fuel oil which contained 2»19 per cent sulfur
and one-hundred grams of catalyst were- used*
Sample
No6
Total
Sample
%
Liters
' Sample
Weight
Sulfur
Exit
Time
Grams
Gas
______________ Kr*___________:..-______________________ __________ ________
22
8
A6
533
0*340
1022
Ave 6
Temp 6
0C
______
410
Calculation of Space Velocity:
Assume weight loss of charge oil is seven per cento
Per cent
loss was calculated from data obtained over periods of two to
four days®
Calculation is based on weight of charge oil.
_________533
(lo0 -®© 7 ) x 8 x 100
= 0.716
- grams oil (per gram of catalyst) per hour.
B6
Calculation of Exit Gas to Gil Ratios
It was assumed that all exit gases metered were saturated with
water vapor.
Data:
Room temperature
= 24°G
Barometric pressure
= 641 ram Hg
Vapor pressure of water at 24°G
= 22»4 mm Hg
Partial pressure of exit gas
= 641.4 " 22.4
= 619 mm Hg
619 x
273
760
273 + 24
x 1022 x (l60, - .07) '= 1.34
533
I „34 = Liters exit gas
at S e T 0 -P0 per
gram charge oil
C 0 ■ Calculation of Grams of Sulfur Removed Per Gram of Catalyst Per
Eight Hours:
533 x O 00219 - 533 x .0634
(1,0 - 0.07)
_______
100
= »1074
This value was calculated on the assumption that all of the
oil reported as per cent loss was free from sulfur.
The per cent
error in this figure has a maximum value of 4.13.
D0
-Calculation of Per Cent Losses;
Data:
Kgm influent oil
Kgm
effluent
oil
= 20.916
= 19.3635
Specific gravity of number three oil
at 70°F
= 0.875
Specific gravity of product oil at 70°F
= 0.850
20.916 - 19.3631 x 100
20.915
- 7 .4 3 per cent
- loss on weight
basis
20.916
0.875
- 19.3635
0.850 x 100
20.916
=. 4 .6 per cent
0*875
= loss on volume
basis
“3.5”1
■V.
A»
DISCUSSION OF RESULTS
DESULFURIZATION OF FUEL OILS
USING
CYCLOCEL AS A CATALYST
This study was made to obtain information on catalyst Iife 5 and the
effect of hydrogen rate oh desulfurization with cyclocel catalyst«
Both
number one and number three fuel oils were used®
Tabulated data for this run are presented.in Table Vll®
The effect of desulfurization on catalyst life is shown in Figure 2®
•Number three fuel oil was first .passed over the catalyst for 160 hours»
During this time the reaction conditions were kept constant 5 and the sulfur
content of the effluent oil increased from 1*22 per cent at eight hours to
I e945 per cent at 160 hours*
The catalyst was then regenerated with air 9
and number three fuel oil was again passed over the catalyst*
After air
regeneration the sulfur content of the effluent oil increased, from 1*29
per cent at eight hours to 1*80 per cent at 120 hours*
As seen in Figure 2 the rate of decrease in activity was about the
same before and after the first air regeneration*
The near coincidence
of
the two curves (Figure 2) which show catalyst activity as a function of
time 9 indicates that the first air regeneration did not alter the level of
Z
sulfur removal*
After desulfurization of number three fuel oil the catalyst w a s ,re­
generated with air a second time*
ized over the catalyst*
.Number one fuel oil was then desulfur­
As seen in Figure 2 number one fuel oil was de­
sulfurized for 168 hours with no noticeable deactivation of the catalyst*
Charge losses were 2*38 weight per cent for number three fuel oil,and 1*23
weight per cent for number one fuel oil.
The charge losses indicate that
m o r e .cracking occurred during number three fuel oil desulfurization which
undoubtedly caused more carbon deposition on the catalyst.
For this reason
number three fuel oil propably caused deactivation of the Catalyst5.while
number one fuel oil did not.
Number three fuel oil is more susceptible to
cracking since it is heavier than number one fuel oil*
Temperature 5 space
velocity, and pressure were kept constant for desulfurization of both
number one and .number three fuel oils,
.
. . . . .
Figure 3 shows the effect of hydrogen rate on desulfurization of..num.=
T'-v':;
ber one fuel oil. The hydrogen rate, down to a certain critical point 5 has
very little effect on sulfur removal.
The point, where hydrogen rate begins
to effect sulfur removal was not determined experimentally 5 but was found
by .extrapolation of the curve in Figure 3«
The level of sulfur' removal
■ v.-:
dropped abruptly when the use of hydrogen was discontinued* - The catalyst
however, did effect some sulfur removal when hydrogen was not.used.
Temper­
ature and space velocity were hot studied as process variables*.
' B,
THE EFFECT OF PRESSURE ON "THE DESULFURIZATION OF FUEl OIL
USING MOLYBDENUM SULFIDE CATALYST
■ V"'' "
I1V-. ■
:
The effect of pressure on the. desulfurization of number three fuel.,
oil was studied at $00, 30 0 , 200 , 100 , and zero psig using a M o S ^ .catalyst*
Tables VIII and IX and Figure 4 shew the. effect of pressure on sulfur re­
moval*
Each pressure was investigated for an on-stream-time of 64 to 96
hours*
The investigation at each, pressure was discontinued when the per
cent sulfur in the effluent oil remined constant for 20 to 50 hours *
■ ■■
. "■ ;V'
■ ■" ■
The decrease in the activity of the catalyst as a function of time
was neglected during this study
“17Figure 4 and Table IX show the decrease in sulfur removal when pres=sure was decreased*
Oil with less than G„5 per cent sulfur content was
produced at 500 psig with a space velocity of Q 035 and at 300 psig with a
space velocity of 0,70«
At 200 psig, and below, oil with less than 0.5 per
cent sulfur content could not be produced at space velocities above 0 *5 »
This study clearly shows that increased reaction pressures, at the
temperatures used, give greater sulfur removals
C0
THE EFFECT OF METHME=HIDROGEKf MIXTURES ON FUEL OIL 'DESULFURIZATION
USING MOLYBDENUM SULFIDE CATALYST
■
_
.
f
When fuel oil is desulfurized, using molybdenum sulfide catalyst,
I :
methane and ethane are formed*
Data have shown that the
build-up
of meth­
ane and ethane in the exit gases is less than three per cent per pass*
Because hydrogen is relatively expensive and the separation of light-hydro­
carbons from hydrogen is difficult, it is desirable that t h e fexit gases be
recycled*
The purpose of this study was to determine the build-up of
hydrocarbons per cycle and how much methane can be tolerated in the recycle
§cLS o
The following ga.s mixtures were obtained from the Mathespn Chemical
Company*
Approximate Analysis:
a. 5# GH^, 95# Hg
b. 15# CH^, 85# Hg
e. 25 # GH^, 85# Hg
d. 40# GH^, 60# Hg
A test was made on each of the mixtures at $00 psig,
made on the five per cent and 1 $ per cent mixtures at 300
2$ per cent, and 40 per cent mixtures at 200 psig.
A run was then
psig,
and on the
The tests under $00
psig were run 16 to 24 hours and are inconclusive because it sometimes takes
30 to $0 hours for the catalyst to come to conditions of constant sulfur
removal.
Number three fuel oil was used exclusively in this study.
A plot of sulfur removal versus per cent methane in the mixtures is
shown in Figure $.
Complete tabulated data, analysis of exit gas and a
summary of the effect of gas mixtures on desulfurization are presented in
Tables X-XII.
,.
Figure $ shows a decrease in sulfur removal as the percent methane in
the gas mixtures was increased.
The decrease of sulfur removal was small
when five per cent and 1 $ per cent methane mixtures were used, but the
crease
de­
became proportionally larger when mixtures containing 2 $ per cent
and 40 per cent methane were used.
An increase in the percentage of methane in the mixture 'effectively
lowers the partial pressure of hydrogen in the reaction.. As seen"'previous­
ly in the pressure study run, a decrease of pressure gave a decrease'in
sulfur
removal.
Both the pressure study run and the mixture study run
■substantiated the importance of the partial pressure of hydrogen in the
desulfurization reaction.
By adjustment of the space velocity, oil with less than 0,5
per
cent
sulfur content was produced at $00 psig using gas mixtures which'contained
five per cent, 1$ per cent, and 2$ per cent methane,
TOien a mixture con­
taining 40 per cent methane was used, oil with less than 0 .5 per cent
I, . **.''•
™19,a
•
,
sulfur content could not be produced at space velocities above 0*5*
Space
velocities below 0*5 were not investigated*
The analysis of the exit gas is tabulated in Table X I *
TAIhen 100 per
cent hydrogen was charged the build up of methane and ethane was generally ■
over three per cent per pass*
When gas mixtures containing methane were
used the build up of methane and ethane ranged from 0*1 per cent to 2*5
per cent; with an average of about one per cent*
AU
exit gas samples were collected over a period of approximately one
hour and were taken when the gas .flow was constant*
D.
THE EFFECTS OF GAS OIL DESULFURIZATION AND A B REGENERATION'ON MOLYBDENUM SULFIDE CATALYST
'
In the work done on molybdenum sulfide catalyst; regeneration of the
catalyst was never needed*
Since there is always a possibility of deacti­
vation of the catalyst <, information concerning air regeneration was de­
sired*
A heavy gas oil with a specific gravity of 0*925 and a sulfur con­
tent of 2*£5 per cent was passed over the catalyst to see if -some deacti­
vation due to carbon lay-down might occur*
After treatment with gas oil;
number three fuel oil was passed over the catalyst to evaluate activity on
the basis of previous data obtained with number three fuel oil*
The con­
ditions used for gas oil and number three fuel oil desulfurization.were the
same*
Data from this study are tabulated in Table XlII*
I
The sequence of operations followed during this study is as followss
I*
Gas oil was charged for 160 hours*
2 , Number three fuel oil was charged for 71 hours*
3*
Gas oil was charged for 96 hours*
eaSOics
4.
Number three fuel oil was charged for 64 hours e
5o
Catalyst was air-regenerated*
6 » Number three fuel oil was charged for 88 hours*
Gas oil was first passed over the catalyst for 160 hours and no de­
activation occurred as evidenced by the sulfur content of the effluent gas
oil*
Number three fuel oil was then passed over the catalyst and the per
cent sulfur in the effluent oil gave proof that the catalyst had not been
deactivated*
Gas oil was again passed over the catalyst and after a period
of 96 hours there was no change in the sulfur content of the effluent gas
oil,
,
.
After the second treatment with gas oil, number three fuel oil was
again passed over the catalyst.
This time the desulfurization with number
three fuel oil indicated that the catalyst had the lowest level of sulfur
removal (as measured by grams sulfur removed per gram of catalyst) of any
molybdenum sulfide catalyst tested.
The catalyst was then air-regenerated at temperatures varying between
440 and 550oC,
During the regeneration the odor of sulfur dioxide was
noted in the exit gases,
.
After air regeneration number three fuel oil with a sulfur content of
0 ,0 2 per cent was produced when a space velocity of about 0*4 was used*
•The space velocity was gradually increased to about one and ,the per,,cent
sulfur in the oil increased to about 0,15, ' This increase in-.activity is
shown graphically in Figure 6 ,
The activity of the Catalybt 5 as measured
by grams of sulfur removed per gram of Catalyst 5 doubled after air regener­
ation
“
Previous to
air-regeneration
21
~
the best results had been obtained at a
space velocity of 0 .9 which resulted in.an effluent oil with a sulfur content
of 0.45 per cent.
After air regeneration number three fuel oil was desulfur­
ized for an on-stream time of 88 hours with no apparent deactivation of the
catalyst.
As seen in Figure 6 the rate of increased sulfur removal had
just begun'to level off when the run was ended.
The charge Iosses 5 on a weight basis 5 were 6.23 per cent for the gas
oil and 5.68 per cent for number three fuel oil.
This:indicates that
more cracking occurred during gas oil desulfurization.
VI
SUMMARY
The results indicate that cyclocel catalyst can be air-regenerated
without apparent effect on catalyst activity*
Number one fuel oil was de­
sulfurized using cyclocel for an on stream time of 175 hours 5 and during
this time the catalyst did not decrease in activity®
Sulfur removal with molybdenum sulfide catalyst decreased with de­
creased reactor pressure*
Number three fuel oil with a sulfur content of
less than 0*5 per cent was produced at 500 psig, and 300 psig, but could
not be produced at 200 psig or below, with liquid hourly space velocities
above 0 *5 *
VJhen gas mixtures were used which contain'ed hydrogen and methane the
%'
■
;
sulfur removal, using molybdenum sulfide catalyst, decreased with increases
in the concentration of methane®
Number three fuel oil with a sulfur con­
tent of less than 0*5 per cent was produced with hydrogen-methane mixtures
which contained five per cent, 15 per cent, and 25 per cent methane*
With
a mixture containing 40 per cent methane, oil with less than.0*5 per cent
sulfur content could not be produced*
Using molybdenum sulfide.the maxi­
mum build-up of methane and ethane in the exit gas was 3*5 per cent per
pass*
Air regeneration of molybdenum sulfide was very successful*
The cata­
lyst activity, as measured by grams of sulfur removed per gram of catalyst,
doubled after air regeneration*
-23VII ACKNOlfJLEDGEMENT
The author acknowledges with thanks the courtesy of the Husky Oil
'Company=, who sponsored the fellowship under which this work was carried
out „
■=24“
VIII
LITERATURE CITED
(1)
A 0 S a T 0 M c STANDARDS ON PETROLEUM AND LUBRICANTS, American Society
for Testive Materials, Philadelphia, P a 0, p e 272 (1941)«
(2)
Berg, Clyde, Trans 0 .Am, Inst 0 of Chem 0 Engr,, 42, No, 4 9 665=680
(1946).
(3)
Byrns, A, C 0, Bradley, W, E 0, and Lee, M 0 W,, Ind 0 Eng 0 Chem0, 35»
1160(1943).
(4)
Koski, O 0 H 0, M 0 S 0 Thesis, Montana State College (1952 ) 0
(5)
Lange, N 0 A 0, HANDBOOK OF CHEMISTRY, Sixth Edition, Handbook Publish­
ers,. Ihc0, Sandusky, Ohio, (1946) <.
(6 )
Munro, B e L 0, M e S 0 Thesis, Montana State College (1952)®
(7)
Perry, J0 H 0, CHEMICAL ENGINEERS HANDBOOK, McGraw-Hill Publishing
Company, New York, N 0 Y„, Third Edition (1950).
(8 )
Sachanen, A., CONVERSION OF PETROLEUM, Reinhold"Publishing Company,*
New York, N 0 Y., p. 216, Second Edition, (1948)«
(9)
United States Bureau of Mines Bulletin N o 0 406.
n
APPENDIX
page
Table I
Thermodynamic Calculations for the Reactions
2MoS^ —
2M 0S 2 "t" Sg^g^ o * e e » e o a e o e e o
Table II
Thermodynamic Calculations for the Reaction;
C^H^S(g) + 4H2(g) —
Table III
+
®» » «
Thermodynamic Calculations for the Reaction;
MoS2 + C^H^S(g) + 3 % ”-5s»- MoS^ + ^4%o(s) ««*<>
Table H
Thermodynamic Calculations for the Reaction;
MoS^ +'
g) ' r^Sf" M 0 S 2
H 2® (S ) ” e a o e e e o * ®
Table V
General Thermodynamic Data . . . . . . . . . . . .
Table VI
A, S, Te M 0 Distillation Data. . . . . . . , . e .
Table VII
Tabulated Data for Cyclocel Study Run. ...........
Table VIII
Tabulated Data for Pressure Study Run. . . . . .
Table IX
Effect of Pressure on Desulfurization 0 . . . . . .
Table X
Tabulated Data for Mixture Study Run . . . . . . .
Table XI
Analysis of 'Exit Gas From Mixture Study Run, * . .
Table XII
Effect of Gas Mixtures on Desulfurization.
. . , .
Table XIII
Tabulated Data for Regeneration Study Run
. . . .
Figure I
Diagram of Reactor
Figure 2
Activity vs On Stream Tine for Cyclocel Catalyst .
Figure 3
Activity vs Gas Rate for Cycloeel Catalyst . . . .
Figure 4
Sulfur Removal vs Pressure for Molybdenum. SulfideCatalyst e o o
0
0
» e e o
e
e
o
e
o
c
d
o
e
o
o
o
Figure 5
Sulfur Removal vs % Methane in Methane=-Hydrogen
Mixtures for Molybdenum Sulfide Catalyst
Figure 6
Effect of Gas Oil Treatment and A i r .Regeneration
on Molybdenum Sulfide Catalyst . . . . . . . . . . . . .
o
o
o
o
o
e
e
e
o
o
e
e
e
o
o
.
49
e”26 es»
TABLE I
THERMODYNAMIC CALCULATIONS FOR THE REACTION;
2M 0 S3 —
ZMbSg + 3 ^ \
^ 6H29s = 41.44 KOal/Mol; A S39g = 52.81 CalAvIol
=
A
= 45,580 + 13.24TlnT + 2.13 x IQ-3 T 2 - 143.OT = C a l M l
ft
Pressure
Atm.
Temp.
oc
'■
25
- 13.24T - 2 .1 3 X IO-3T2 = C a l M l
Free
Energy
■F
Equilibrium
Constant
Keq
Percent
Conversion
CalMl
•I
100
250
375
500..
1000
25
100
45»580
AHt
50
25,700
22,075
1.3 x 10-19
1.25 x. 10-13
14,962
5,6l x 107
9,575
4,352
-12,970
5 .8 8 x IO" 4
.0592
165
O
O
0.95
1 2 .0
35.
9.5.5
O
O
0.7
5.0
250
375
500
3 0 .0
1000
75.0
«=27‘
•TABLE II
THERMODYNAMIC CALCULATIONS FOR THE REACTION:
G4 H4 S(g) + 4H 2 (g)
C4 H4 Cg) + H2S(g)
A H2^g = - 6 2 .40 K G a i ykol^S2Og = -70.78 Caiykol
A H ij 55 -58,914 - 9.21T - 1 2 .2 4 x 10 " 3 t 2 = 13.07 X 10" 6 t 3 = Calykol
A Frj - -58,914 + 3.5T + 1 2 .2 5 X 10 “3 t 2 -- 6 .5 3 X 10"6t 3 + 9.21TlnT = Calykol
Temp0
OC
25
Pressure
Atm
I
-24500
-14560
-.4 5 9 0
+37600
375
500
1000
25
100
250
-41300
• -35900
100
250
Percent
Conversion
Equilibrium
Constant
Free
Energy
F
Caiykoi
V.
... .1 0 0
2.59 x ig3°
100
1 .0 x 10 Z}
1.78 x IO1^
8.035 % IO 4
...
7 0 .0
0 .5
20
4.13 x 10 “ '
100 '
ipo'
99e9
IO
375
98 .5
'
500
,
.
1000
25
50
'
100
500
1000
100
100 .
'
99.5
97.2
19.0
.
1000
375
92.7
2.0
• 100
250
375
500
25
100
250
99.6
94.75
'
100
. '
,
,
100
100
100
99*6
97.5
27.0
.
28
>
=
TABLE III
THERMODYNAMIC CALCULATIONS FOR THE REACTION:
MoSg + C^H^S(g) (Thiophene) + 3Hg —
MoS^ + C^H-^q (g ) (n-Butane)
A H 298 = - 62,840 Cal/kol; A S 398 = - 8 ?»92
A H m = - 61,730 - I 0O 57T - „0125T2 + 1.322 x 10 " 5 t 3
■A
Temp,
oc
25
ft
= - 61,730 + i„057TlnT + 0OI 25 T 2 - .661 x 10 " 5t 3 + 75 T
Pressure
Atm.
I
Free
Energy
F
Cal/Mol
=36,6 4 0
•100
-33,140
250
375
500
1000
= 25,000
- 21,330
25
100
10
50
250
375
500
1000
.317 x IO" 8
97.2
0.7
0
10#
100
99.9
72.Q
2.6
looo.
250
375
500
49,970
99.6
100
.!PO.
100
25
12,240
2.5 x IOl^
1.35 x IO 7
.323 x 10-3
100
100
99.9
99.3
■ 18.0
. .09
500
1000
, 100
5 .0 2 x I O ^
2 .1 0 x IO-Jf
Percent
Conversion
100
250
375
25
Equilibrium
Constant
100
100
100 .
100
99.7
71.0
2.55
aaQjyas*
TABLE 17
TI-IERMODYNAMIC CALCULATIONS FOR THE REACTION:
MoS^
) -aa^t** MoS^ "f* HgSCg)
A H298 = bhO Cal/Molj
A
ht
AFm
Temp,
OC
AS298 = 17-14 Cal/Mol
= 2 5800 - 8.147T + ,00076 T2 - „01602 X 10~5 t 2
=
2,800 - 8,147TlnT
Pressure
Atm.
-
-00076T2
Free
Energy
F
Cal/Mol
25
100
2$0
375
$00
1000
I
2$
100
2$0
375
$00
1000
10
2$
50
1000
250
375
$00
1000
Equilibrium
Constant
K eq
2$80
2450
2200
'1400
1080
290
- 71T
Percent
Conversion
98:i
98;o
. 97.8
.96*9
96.7
94.4
98,2
98.1
97.9
96.7
94<4
2$0
375
$00
25
„801 x 10"7 t 3
97.G
100
100
=4660
-$800
-8,019
-9,341
-10,816
—14,448
-
100
'
98.3
98.2
98.0
97.2
96.7
94.5
98.5
98.3
98.1
97.5
96i7
94.6
TABLE V
GENERAL THERMODYNAMIC
Compound
Critical
Pressure
Atm
Critical
Temp
OK
DATA***
Entropy
Heat of
Formation' Gal/Mol
298°K
Hf
KCalAlol
-Heat Capacity
Cp ,
CalAlolZ0K
298°E
HgCg)
MoS2
M 0 S3
.
88.9
33.2
690
373.4
(n-=Butane) 36
234**
426*1
1313
.12*8
(Thiophene)48
B0sila
■=.=
O
27.82
-4.77
-29.81
11.48
-$6.27
'-29.81
31.21
69.3
49.15
74.21
54.41
15.1
15.9
- 6.947 - .200x L0"3T + *04808x10'
-7.017 + 100x L0“3 t - 63.25x10-'
7.20 + 3,6x10-31
-7.017 +'100x10-31 - 63.25x103:58 x 0,3 x 10^31
19.7 + 3.15 x 10-3T
*28.1 + 5.43 x 10-3r
^Calculated by analogy with available heat capacities of SnS and SnS 50 An
assumption'was made that""the'difference in"heat"capacities between SnS
and SnSg would be the same as the difference between MoSg and MoS^e
^ Calculated by Meissner and ReddingiS method of parachors*,
- -x-SHt-Data obtained from following sources;
Perry (7)».Lange ($), Hodgman (3 )
U 0S 0 Bureau of Mines Bulletin N o 0 406 (9 ),
. TABLE VI
.
A. So To Mo' DISTILLATION DATA
Husky
Gas
Oil
Percent
Over
Husky
#3 Fuel
Oil
Husky
#1 Fuel
Oil
First Drop
#
10
20
30
40
50
460°F
204°F
580°F
500
518
264
294
534
315
546
629
637
66?
680
692
702
709
60
576
70
80
90
Final Temp6
% Recovery
% Sulfur
586
332
347
362
377
396
600
420
621
452
495'
98.7
, 556
566
660
98
2,19
1.09
y
718
727
7a
'
750'
92;o
2.85
«*32“'
TABLE VII
TABULATED DATA FOR OYCLOCEL STUDY RUN (CSR)
Cyclocel catalyst used at atmospheric pressure*
Husky #3 oil used from samples #l-#35«
Husky #1 oil used from samples #3^“#62
Air regenerations after samples #20 and #35
Maximum charge losses were 2*38% on weight basis*
Samplei Total
Hours
No*
I
2
3.
4
5
6
7
S
9
10
11
12
8
16
.
Sample ' Percent
Weight Sulfur
Grams
997.0
1.39
834.5 1.555
817.0 1.54
765.0 , 1.62
743.5 1*646
24
32
40
48
56
64
72
811*0
71-2*0
770*0
80
88
748.0
754.5
96
104
748*0
13
14
15
112
120
16
128
.
756.0
.779.0
788.5
796.5
17
136 ■
801*5
18
144
19
152
160
822.0
820.5
825.0
743.0
803.5
790.5
767.0
20
21
22
23
24
25
168
176
184
192
200
811*0
26
206
585.5
27
214
784.5
28
222
29
30
31
32
33
230
238
6.246
800.0
787.5
748.0
804.0
801.0
805.0
254
262
1*22
9 11.0
1*66
1.65 1
1.705
1.735
1.76
1.80
1.832
1.8?
1*878
1.897
1.955
1.724
1*905
1.945
1.19
1.286
1.374
1*408
1.421
1.394
1.580
1.600
1.628
1.643
1.680
1.712
1.73
Average
Temp.
0C
Space
Velocity
Grams Oil
Per Gram
Catalyst
Per Hour
Liters.
Exit Gas
Per Gram
Oil
Grams Sulfur
Removed
Per Gram
Of Catalyst
Per Eight
Hours
0.108
0.083
0.0635
0.0628
0.525
0.0492
0.0523
396
1*31
0.797
400
1.20
0.813
398
1*10
403
1.075
400 400
402
1*005
0.947
0.895
0.947
400
401
400
400
400
•401
400
400
400
400
400
400 "
400
.
■
0.997
1 .0 4 0
1*07
1.00
0.937
1.010
0.985
0.992
0.984
0.994
1.115
0.980 .
1.150
1.007
1.035
0.994
1*017
401
400
1 .0 1 0
400
400
0.980
1.937
0.975
1.002
400
400
400
400 .
400
400 ■
400
400
0.970
0.978
0.925
1*023
1.024
1.05
1.049
1.051
0.951
1.025
403
-1 ,2 6
1*020
1.007
0.955
1.028
1*028
1 .0 3 0
1 .0 1 0
1.052
0.990
0.0467
0.0461
0.0429
0,0412
0.Q380
0.0358
0.0342
0*0282
0.0270
0.023
0*0420
0.0275
0.0237
■ 0.078 '
0.0766
0.967
0.0681
0.972
1.040
0.0635
0,0668
0.945 ■
1.065
0.0665
0.0518
1,090.0510
1.06
0.0478
0.99
1.095
1*08
1.115
0*0445
0.975
0.0450
1.075
0.0426
0.974
0.0409
•
”
33“
-
■TABLE VII (continued)
TABULATED DATA FOR CYCLOCEL STUDY RUN (CSR)
Sample
No»
Liters
Grams Sulfur
Total Sample Percent Average Space
Velocity Exit Gas Removed
Hours Weight Sulfur Temp
Grams Oil Per Gram Per Gram
Grams
°C
Per Gram
Catalyst
Per Hour
34
35
36
37
38
39
40
41
42
43
44
45
46 .
47
48
49
50
51
52 ■
53
54.
55
56
57
58
59
60
61
62
270
278
286
294
302
310
318
326
334
342
350
358
366
374
382
390
398
406
414
422
430
438
446
454
462
470
478
486
494
815.0
822.0
749.5
759.0
776.5
773.0
of Catalyst
Per Eight
Hours
1.772
1.80
0.348
0.327
0.346
400
401
40l
401
1 .0 4 2
0.975
1.053
.954
•1.141
1.07
400
0.415
402
401
•400
.988
.985
.964
.995
.955
1.01.
399
1.015
0.375
779.5 0.357
748.0 0.350
790.5 0.367
797.0 0.350
787.5 0.381
767.0 0.377
798.0 0.374
783.5 0.363
780.5■ 0.379
764.5 0.387
830.5
821.0
.403
850.5
.410
811.5
837.0
833.0
.409
.405
950.5
.582
810.5
.550
769.5
.558
581.5
.510
652.5
.532 .
754.5
756.0
Oil
399
400
400
400
400
406
400
401
400
400
400
399
400
401
396
385
400
400
401
401
1 .0 6
.965
.990
.963
1 ,0 1
.88
.995
.651
.611
.672
.665
1.005
0.990
1,017
*564
1 ,0 0 0
.662
0.995
0.975
1.06
1.046
1.083
1.035
1.065
'1.060
1.210
1.030
0.980
0.742
0.831
0.963
.690
.620
.317
.279
.276
.393
.355
.363
t
j
No
■
H 2Used .
I
0.0380
0.0360
0.0551
0.0574
.0.0573
0.0517
0.0537
0.0567
0.0548
O .0566
0.0585
0.0554
0.0553
0.0567
0.0566
0.0551
0.0533
earn
0.0560
0.0549
*”c=
0.0562
0.645
0.0406
• 0.0411
0,0305'
0.0374
0.0418
=3 A”
TABLE VIII
TABULATED DATA ,FOR PRESSURE STUDY RUKf (PSR)
Molybdenum sulfide catalyst and Husky #3 fuel oil used*
Maximum charge losses were 5«48^ on weight basis
Sample Total Sample Percent Average Space
Noe
Hours Weight Sulfur Tempe
Velocity
Grams
0G
Grams Oil
Per Gram
Catalyst
Per Hour
I
2
3
4
5
6
I
S
9
10
11
12 •
13
14
15 '
16
17
IS
19
20 '
21
22
23
24
25
26
2?
2S
29
30
31
32
33
4
12
20
2S
'
.457
410
271.5
460.0
*366
410
459 „0
»401
410
410
411
410
• 410
.443.5 .405
' 36
. 528.5 .460
502.5 .420
44
546.0 .489
52
60
552.0 .465
68
549.5 .458
76
560.0 .479
84
549.5 .622
459.0 .588
92
100
389.5 .579
108
358.0 .541
116
359.0 .554
364.0 .562
124
132
361.0 .571
140
373.5 .597
148
373.5 .624
156
376.5 .621
381.0 »626
164
361.0 .589
172
ISO
. 434.5 .865
188
425.5 .872
403.0 .867
196
350.0 .850
204
344.0 .850
212
220 , 355.5 .871
228
398.0 .874
236.
.393.0 ,909
367.0 .918
244
252
376.0 .912
260
371.0 .940
410
411
410
412
411
410
411
411
410
410
410
410
410
410
410
411
410
410
412
411
411
412
410
410
410
410
.641
.611
.610
.590
.703
.670
.726
.733
.730
.746
.732
Liters
Exit Gas
Per Gram
Oil
1.295 ■
1.74
2.01
1.60
1.44
1.64
1.305
1.254
1.36
1.285
1.32 .
.611
1.51
.518
.476
.477
.485
.480
.496
1.92
2.085
2.05
1.82
1.97
2.06
2.16
1.98
1.90
.496 -
.500
.506
.480
.577
.565
.536
.465
.457
.473
.528
,524
.488
.500
.494
2.10
1.78
1.74
1.88
2.11
2.08
2.10
1.70
1.83
1.96
1.99
2.16
Grams
Reactor
Sulfur
Pressure
Removed P .S.I.G.
Per Gram
Catalyst
Per Eight
Hours
.0880
.0879
.0861
.0830
.0962
.0934
.0975
.0999
»0998
.1007
.0909
.0775
»0660
.
.0621
.0619
.0626
.0616
' .0627
.0617
.0622
.0629
«:0608
.0610
.0599
.0568
.0499
.0489
.0499
.0457
.0540
.0498
.0513
.0496
300
300
300
300
300
300
300
300
300
300
200
200
200
200
200
200
200
200
200
200
.200
200
100
100
100
100
100
100
100
100
100
100
100
"
35
"
TABLE VIII (continued)
TABULATED DATA FOE PRESSURE STUDY RUN (PSR)
.
.
Sample Total Sample Percent Average Space
No*
Hours Weight Sulfur Temp* Velocity
Grams Oil
Grams
0G
Per Gram
Catalyst
Per Hour
3&
268
2?6
284
292
300
39
40
41
308
316
324
34
35
36.
37
42.
332
43
44
45
46
47
48
49
340
348
356
364
372
380
388
352.0
401.5
0.890
1 .525
'409.5 1.390
303.0 1.60
340.0 1.663
342.0
355.0
345.5
347.5
358.5
474.0
379.0
489.0
435.5
1 .7 2 7
1.743
1.741
1.745
1.797
0.855
0.634'
0.615
0.592
414.0 0.491
453.0 0.475
410
411
411
410
410
410
410
410
410
410
411
410
0.462
2 .1 1
0.473
2.12
1.64
2.02
1.60
1.59
0 .6 2 4
0.500
0 .6 4 4
410
0.574
. 0.545
0.578
409
Liters
Exit Gas
Per Gram
Oil
2.07
0.469
0.534
1.93
0.544 . 1,96
0.405
2.53
2.29
0.453
0.455
2.37
2.19
0.473
2.38
0.460
410
410
I
1.76
1.61
Grams ■Reactor
Sulfur Pressure
Removed PoS.I.G.
Per Gram
Catalyst
Per Eight
Hours
0.0489
0.0302
0.0363
0.0203
0.0208
0.0187
0.0189
0.0185
0.0186
0.0166
0.0663
0.0632
0.0821
.0.0742
0.0746
0.0803
100
0
0
0
0
0
0
0
0
0
500
500
500
500
500.
500
TABLE K
EFFECT OF PRESSURE OH DESULFURIZATION
Data obtained from pressure study run*
Total
Hours
Percent
Sulfur
Space Velocity
Grams Oil
Per Gram
Catalyst
Per Hour
Liters
Exit Gas
Per Eight
Hour
Period'
Liters
Exit Gas
Per Gram
of Oil
Grams
Reactor
Sulfur
Pressure
Removed .
PcS 0I 0G 0
'
Per Gram
Catalyst
Per Eight ■
Hour Period
100
.450
0 *8 $
1000
1*2
*110
76
96
.460
.590
. 0.70
0.50
I *4
1*9
64
72
„880
1*70
1050
1050
1050
.1050
2.0
.096
.062
.050
2*2
*018
. 0*50
'
0.47
*-Data at $00 psig was obtained from M u nro5s (6) life study run*
$00*
300
200
100
0
“
37
“
-TABLE X
TABULATED DATA FOR MIXTURE STUDY RUN (MSR)
. Molybdenum sulfide catalyst UsecjL
Reactor pressured used,
500 psig used from samples #l-#34<>
300 psig used from samples #35“$3&,
500 psig used from samples #39”#7i»'
200 psig used from samples #72“#76,
Maximum losses were 7«43% on- weight basis.
Sample Total Sample Percent Average Space
Velocity
Hours Weight Sulfur Temp,
No,
°C.
Grams Oil'
Grams
Per Gram
Catalyst
Per Hour
I
2
3
4
5
6
7
8 '
9
10
11
12
8
16
24
32
40
48
56
64
72
14
15
80
88 '
96
104
112
120
16
128
17
18
19
137
144
152
160
13
20
21
22
23
24
25
26
168
176
184
192
200
208
397.5
423.5
461.5
536.0
558.5
0.221
540.0
0.340
0.312 .
0.260
0.269
0.2&8
0.236
0.308
536.0
532.0
531.0
482.0
495.5
522.0.
502.0
516.0
0.259
0.283
0.424
0.561
411
411
411
410
411
407
410
410
411
410
410
410
0,338
408
0.322
410
0 ,290
410
411
410
410
411
410
410
410
410
531.5
523.0 0.233
517.5 0.259
531.0 0.291
471.5 0.290
491.5 0.372
536.5. 0.330
533.0 0.340
519.5 0.325
516.5 0.348
500.0 0.341
511.5 0.360
27
216
519^0
28
29
224
232
516.0 0.314
503.5 0.389
0.333
409
411
410 .
410
410
410
'
Liters'
Exit Gas
Per Gram
of Oil
0.524 ■
0.558
0.606
0.705
0,735
1.96
1.70
1.60
0.711
1.34
I.23
1.49
0.707
0 .7 0 0
■
0.682
0.652
0.653
.0.680
0.660
0.678
0.700
0.68?
0.681
0,713
0,634
0.661■
6.722
. 0.716
0,698
0.694 .
0.672
0.688
0.697
0.693
0,676
1 ,4 6
1.31
1.33
1.61
1.54
1.13
1.32
1.44
I .2 4
1.47
1.40
1.30
1.53
1.39
1.21
1.34
1.33
1.26
Grams
■Gas
Used
Sulfur .
Removed
i CH4
Per Gram
of Catalyst
per eight
Hours
.0829
iQ866
.0931
.1008
.0975
.1059
ao?!
.1088
.1082
.0984
.1026
.1041
.0986
,1024
.1073
.1082
.1059
. ,.1095
*0973
.0975
.1086
.1074
.1053
.1035
1.43
,1004
1.53
1.371.43
I.278
.1021
.1050
.1055
»099
0
0
0 •
0
'0
0
0
0
G
0
0
0
5
5
5
5
5
5
5
5
5
.5
5
15
15
15
15
15
15
TABLE X (continued)
TABULATED DATA FOR MIXTURE STUDY RUM (MSR)
Sample Total Sample Percent Average Space
Velocity
Hours Weight Sulfur Temp.
Mo.
0G
Grams Oil
Grams
Per Gram
Catalyst
Per Hour
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
240
248
2$6
264
272
280
288
296
304
312
320
328
336
344
351
359
367
375
383
391
399
51
52
53
54
55
407
415
56
447
57
455
58
59
60
61
62
423
431
439
463
471
■ 479
487
495
63
.64
$93
.65
.66
.'519
511
4 93.5
0.385
0.282
0.406
0.379
0.403
0.434
Liters
Exit Gas
Per Gram
of Oil
Grams
Gas
Used
Sulfur
Removed
*
Per Gram
of Catalyst
Per Eight
Hours
410
0,663
1.295
»097
410
0.650
0.673
1.47
.1004
483.5
409
500.5
410
529.0
410
483.5
568.0
411
556.0 0.540 409
485.5 0.643 412
509.0 0.615 410
479.0 0.388 410
410
491.0 0.392
0.342
411
453.0
452.0 0.321 411
497.5 0.344 4 H
387.0 0.302 411
504.0 0.379 410
499.0 0.341 43-1
475.5 0.411 410
474.0 0.432 410
492.5 0.440 410
474.5 0.413 410
508.5 0.488 410'
'494.5 0.491 409
486.5 0.441' 412
483.0 0.438 410
498.0 0.405 411
476.0 0.436 410
512.0 0.494 411
507.0 0.504 411
507.5 0.697 412
486.5 0.593 410
506.0 0.603 410
457.0 0.606
411
457.5 0.588 410
; '460.0 0.577 Z1IO
/-438.5 0.585 411
410
4 4 0 4 .5 0.488
0 .7 1 0
>
0,650
0.770
0.740
0.647 .
0.676
0.638
0.653
0.590
0.589
0.647
0.588
O.672
O .664
0.632
0.631
0.655
0.632
0.675
0.657
0*646
•
0.643
O.663
0.632
0.681
0.673
0.674
0.647
O.672
0.606
0.608
. 0.611
0.582
0.537
.0976
.1048
.0945
1 .21 '
1.335
1.56
1.04 .
.1104
1.15
1.48
1.13
1.58
1.75
• 1 .6 4
1.91
1.93
1.75
1.39
1.36
1,42
1.75
1.44
1.60
1.26 '
1.32
1.52
1.46 ■
1.50
1.58
1.35
1.53
1.53
1.60
1.26
1.65
. 1.84 •
1 .4 6
1.73
1.78
'
.0995
.0819
*0870
.0931
.0950
.0879
.0887
^0963
.0895
.0983
.0992
.0910
.0900
.0932
.0909
.0937
.0907
.0917
.0912
.0958
.0901
.0939
.0924
.0827
.0844
.0873
.0783
.0796.
.0805
.0762
.0744
■
15
15
15
15
15
5
5
15
15
0
0
0
0
0
0
0
0.
25
25
25
25
25
25
25'
25
25
25
25
40
40
40
40
40
40
40
40
40
'
TABLE X (continued)
TABULATED DATA FOR MIXTURE STUDY RUN '(MSR)
Sample Total Sample Percent Average Space
Velocity
-Hours Weight Sulfur Temp,
No.
Grams Oil
0C.
Grams
Per Gram
Catalyst
. Per Hour
67
68
69
70
71
72
73
74
75
76
535
543
551
559
56?
575
583
591
599
607
401.5
*483
377.0 .520
377.5 *545
378.5 ,779
387.0 .841
354.0 .813
341.0 .780
302.5 .866
281.5 .877
294.0 .874
410
410
410
410
410
410
409
411
410
■410
.533
.500
.502
.503
.515
• .471
•
•
.453
.403
.375
.392
Liters
Exit Gas
Per Gram
of Oil
Grams
Sulfur.
Removed
P e r ■Gram
of Oil
1.82
1.94
1.88
1.87
1.88
1.99
2.08
.0741
.0684
.0676
.0588
*0578
2.40
2.44
2.15 ■
.0443
.0411
.0544
.0527
.0428
Gas
Used
J6 OH,
40
40
40
.40
25
25
25
40
40
40
=Zj,Qm
TABLE XI
ANALYSIS OF EXIT GAS FROM MIXTURE STUDY RUN
Analysis of Exit Gases
% Build-up
%Hydroz&Hydroof
HydroCarbons
carbons
carbons
in
Other
Than
Total
CK4
Exit Gas
Sample Pressure In Put Gas
No.
P.S.I.G. %■ Hydro- '
carbons
5%
15#
25%
40^
Stock
Stock
Stock
Stock
500
500
500
500
300
I
2
3
4
5
(Approx.)
(Approx)
(Approx)
(Approx)
6.5
6.5
1 6 .2
1 6 .2
. 6,5
6
3PP
1 6 ,2
7
$00
500
500
500
200
2$.6
2$.6
8
9
10
11
12
'
200
13
14
15
500
500
500
16'
$00
43 »4
43.4
25.6.
43.4 0
0
0
0
6.5
1 6 .2
93+5
83.8
2$.6
74,4
4 2 .2
56 .6
93.9
5.75 93.4
16.3 83.0
1 7 ,0 82.2
6.9 93.1
1 6 ,2 .83.8
2$.I 74.2
27,5 71.9
44.0 55.2
43 ®4 55.3
28.3 71.2
43.8 55.4
2.$? 96.89
2.2 9 6 ,6
2.48 97.0
3.1 96.5
5,45
43.4
6.1
6,6
17.0
17.8 .
6.9
16.2
25i8
28,1
44.8
44.7
28.8
44,6
3,11
3.4
1.2
0.6$
0.8$
0.70
0.80 •
-
0.7
=O0A-A0.1
0.8
1.6
0.4
0
0.2
0.6
2.$
■0.8
. 1.3
0.5
1.4
1.3
3.2
0 ,8
1.4
0.54
3.11**
3.4 **
3.0 **
3.5 **
1 .2 0
3.0
0.52
3.5
0,4
# There is an obvious error in this analysis.
-“-a- This data was obtained from MunrotS (6) life study run.
“
41
”
TABLE XII
EFFECT. OF GAS MIXTURES ON DESULFURIZATION
Data obtained from mixture study run*
Total
Gas
Mixture Hours
^CH4
0
5
15
5
15
25
40
25
40
96
88
88
16
16
88
104
24
24
Percent
Sulfur
=31
.32
.36
«48
,63
.45
■ ' .53
«82
.875
Space
Velocity
• Gm Oil Per
Gm Catalyst
Per Hour
.601
*686
.678
.760
.650
.650
.53
.47
.39
Liters
Exit
Gas
Per 8 Hr.
1050
1050
1050
1050
1050
1050
1050
1050
1050
Liters G m Sulfur Reactor
Pressure
Gas Per Removed
Per
Gm
Cat
Gm Oil
Per 8 Hr.
1.47
' 1.36
1.38
1.10
1.30
1.40
- 1.85 '
.
2.0
2.35.
.099
.104
.101
*100
.084
.0 9 2
.070
.0 5 0
.043
500
500
500
300
300
500
500
200
200
“42TABLE XIII
TABULATED.DATA FOR REGENERATION STUDY RUN (RSR)
.Molybdenum sulfide catalyst used.
Reactor was at $00 pslg.
Air regeneration after sample 0$O«
Maximum charge losses for gas oil. were 6.23% on weight
basis.
Maximum charge losses for $3 fuel oil were 5®68%
on weight basis.
Sample Total Sample Percent
No.
Hours Weight Sulfur
Grams
I
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
8
16
24
' 32
40
48
56
64
72
80
88
96
104
112
120
128
136
144
152
160
•
168
176
178
183
191
199
207
215
223
385.5 1.32
508.5 1.70
521.5 1.75
525^5 1.825
525,0 1.865
559.0 1,805
604.5 1.78$
618.5 1.921
593.0 1.90
565,0 1.89
.. 561.0 1.878
553,0 -1*840
557.5 1.810.
553,0 1.850
542.5 1.855
549.5 1.638
552.0 1.758
548.0 1.888
572.5 1.910
535.0 1.799
458.0 0.831
372.0 0.547
CU
136.5
0
.4
10
213.5
486.5 0,545
522.5 G. 56O
485.5 0.522
414.0 0.454
424.5 0.395.
Average Space
' Liters
Temp.
Velocity Exit Gas
0G.
Grams Oil Per Gram
Per Gram of Oil
Catalyst
Per Hour
410
410
410
410
410
410
410
409
410
409
411
410
412
410
410
411
410
410
410
410
410
409
™
410
411
410
410
408
410
.
0.524
0.692
0.709
0.714
0.713
0.759
.0.819 ■
0.839
0.803
0.769
0.765
0.735
0*741
0.735
0.721
0.730
0.733
0.728
0.760
0.712
0*605
0.494
0.725
0.454
0,647
0.695
0.646
0.550
0.564
Grams
Sulfur
Removed
Per Gram
Catalyst
Per 8 Hr.
.0687
1.89
.0713
1.43
.0703
1,39
1.40
.0671
.0648
1.45
.0719
1.29
.0790
1,25
1.18
.0723
.0714
1,91
,0686
1.39
.0691
1.19
.0692
1.59
1.56
.0643
.0652
1.40
.0 6 0 1
1.36
1.38
.0764
.0700
1.42
.0623
1.32
1.28
.0639
lk32
.0657
1.41
. .0685
.066$
1.91
0.903
»0656
1.90
1 .5 0
.0871
.0928
1 .4 1
.0878
1,38
1.87
.0775
.0819
1.79 '
Oil
Charged
■Gas. Oil
M
Ii
tl
H
ii
H
H
I!
U
Il
it
it
n
ft
n
'
n
n
n
ti
#3 Fuel
Oil
IJ
ti
Ii
t!
U
Il
M
"43”
.TABLE XIIX (continued)
TABULATED DATA FOR REGENERATION STUDY RUN (RSR)
Sample Total Sample Percent Average Space
Velocity
Temp,
Hours Weight Sulfur
No.
OQ
Grams Oil
Grams in
Per Gram
Effluent
Catalyst
Oil
Per Hour
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
■ 57
58
59
239
420.0 0.380
*■
496.5
247
566.0
255'
335
343
539.0
533.5 1.730
*=*
553.5
c=r‘
469.5
mat
559.0
517.0 1.90 •
«513.0
«a>
510.0
508,5 1.740
507.5 1*251
472.0 0*872
379.5 0.749
351
342,5
231
263
271
279
287
295
303
311
319
327
359
367
375
383
391
399
407
415
423
431
439
447
455
463
60
471
61
479
I,,665
0*6l6
0*616
306,5
0,618
■ 313.5
0.618
306.0
301.5 0.650
307.0 0.556
271,0 0,0356.
293.0 0,0209
411,5 0*0343
523.0 0.0513
537.0 0*050•
624.5 0,130
771,5 0.158
794.5 0,133
784.5 0,
763.5 0.192
821.5 0.145
410
410
410
409
411
410
411
411
410
410
413
411
-X-
411
412
410
411
410
411
410
410
411
410
409
411
410
411
410
410
410
410
410
1.67
1.55
1.30
0,595
0.660
0.755
0.717
0.709'
0*736
0,625
0*743
0.68?
0,682
0,678
0.676
0.675
0.628
0 .506
0.456
0,408
0.418
0.406
0,400
0.408
0,360
0*386
0.546
0.696
0.715
0.832
I.O25
1.056
1*040
1.015
. 1.09
Liters
Exit Gas
Per Gram
of Oil
Oil
Charged
Grams
Sulfur
Removed
Per Gram
Catalyst
Per 8 Hr*
,0884
#3 Fuel Oil
Gas Oil
•”
it
H
u.
1*41
1,44
■
1.33
1.36
1,35
1.42
1.37.
1.25
1.62
1.09
1.54
1.95
1.99
2.45
2.13
2.48
2.53
2.32
2*69
2.52
1.76
1.35
1*31
1*21
it
it
»
11
.
n
1*
?!
, f|
Mt
It
B
**
.0556
Fuel Oil
11
*0544
n
.0525
.0538
,0524
.0505
.0544
n
11
11
ii
it
*0621
M
.0676
.0943
IJ
.1193
II
.1224
H
. «1374
Il
1.03 - .1678
.885
*1744
.982
**
,1634
.915
1.000
.1791
Il
■
11
Il
Ii
•
U
‘
HYDtiOGEN
thermow ell
A BLOW-OUT
LINE
3 THERMOCOUPLES
OIL
RESERVOIR
AIR FOR
REGENERATION
HIGH PRESSURE
PUMP
PRESSURE
^GAUGE
CONDENSER
EXHAUST-*
RECEIVING
FLASK
WET TEST
METER
HIGH PRESSURE CONTINUOUS REACTOR
Figure I Diagram of Reactor
X 10*2
GM SULFUR REMOVED PER GM CATALYST
GM SULFUR REMOVED PER GM
CATALYST PER 8 HR VS ON
STREAM TIME IN HR
CYGLOCEL CATALYST USED
BEFORE REGENERATION (NO. 3 OIL USED)
AFTER FIRST REGENERATION (NO. 3 OIL USED)
AFTER SECOND REGENERATION (NO. I OIL USED)
ON STREAM TIME IN HOURS
Figure 2
Activity vs On Stream Time for Cyclocel Catalyst
GM SULFUR REMOVED PER GM CATALYST X 10“
65 -
o
-
5.5 -
o
o
— -- O
9—
GRAMS SULFUR REMOVED PER
GRAM OF CATALYST PER 8 HR
X I 0 " 2 VS LITERS EXIT
GAS PER GRAM OF NO. I FUEL
OIL. CYCLOCEL CATALYST USED.
4 .5 §
3.5 -
I
2.5 —
O
0.25
0.5
0.75
1.0
LITERS EXIT GAS PER GRAM OF OIL
Figure 3
Activity vs Gas Rate for Cyclocel Catalyst
1.25
f
GM SULFUR REMOVED PER GM CATALYST X IO '
CU
IO -
8
-
l-
PRESSURE VS GM SULFUR
REMOVED PER GM OF CATALYST
PER 8 HOURS X IO'2 . LINES
INDICATE RANGE OF VALUES
FOR SPECIFIED PRESSURE
4 -
2
-
I
O
I
IOO
I
200
I
300
I
400
500
PRESSURE IN POUNDS PER SQUARE INCH GAGE
Figure 4
Sulfur Removal vs Pressure for Molybdenum Sulfide Catalyst
12 CU
i
O
GM SULFUR REMOVED PER GM CATALYST
X
IO -
0%
5%
15%
25%
8
—
6 -
GM SULFUR REMOVED PER
GM CATALYST PER 8 HOUR
VS PER CENT METHANE IN
MIXTURE. REACTOR PRESSURE
WAS 5 0 0 PSIG. LINES INDICATE
RANGE OF VALUES FOR
SPECIFIED MIXTURE.
40%
4 -
2
I
-
O
IO
20
30
40
50
60
PER CENT METHANE IN MIXTURE
Figure 5
Sulfur Removal vs % Methane in Methane-Hydrogen Mixtures for Molybdenum Sulfide Catalyst
16 -
GM SULFUR REMOVED PER GM
CATALYST PER 8 HR PERIOD
VS HOURS ON STREAM TIME.
NO. 3 OIL ON STREAM TIME
PLOTTED. GAS OIL ON STREAM
TIME NOT PLOTTED.
14 -
12
-
(A)
BEFORE THIS POINT CATALYST
WAS GIVEN GAS OIL
TREATMENT.
(A-B)NO. 3 OIL TREATMENT.
(B )
GAS OIL TREATMENT.
(B-C) NO. 3 OIL TREATMENT.
(C)
AIR REGENERATION.
(C-D)NO. 3 OIL TREATMENT.
IO -
(A) Q—
O
O
O
8 —
6
O
\
\
-
5
120
160
200
240
HOURS ON STREAM TIME
Figure 6
Effect of Gas Oil Treatment and Air Regeneration on Molybdenum Sulfide Catalyst
-6T-
GM SULFUR REMOVED PER GM CATALYST
X 10"
18 -
MONTANA STATE UNIVERSITY LIBRARIES
762 1001 3909 4
S578
(1824c
105551
I
AUTHOR
Greenf Kexmeth_J---- ------— — —
TiTLECatalytic hydrodesulfurization
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