EPA-650/2-73-041-Q
FEBRUARY 1975
Environmental Protection Technology Series
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EPA-650/2-73-041-a
DEMETALLIZATION
OF HEAVY RESIDUAL OILS
PHASE II
by
M. C. Chervenak, P. Maruhnic, andG. Nongbri
Hydrocarbon Research, Inc.
New York and Puritan Avenues
Trenton, New Jersey 08607
Contract No. 68-02-0293
ROAP No. 21ADD-050
Program Element No. 1AB013
EPA Project Officer: William J. Rhodes
Control Systems Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
February 1975
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EPA REVIEW NOTICE
This report has been reviewed by the National Environmental Research
Center - Research Triangle Park, Office of Research and Development,
EPA, and approved for publication. Approval does not signify that the
contents necessarily reflect the views and policies of the Environmental
Protection Agency, nor does mention of trade names or commercial
products constitute endorsement or recommendation for use.
RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environ-
mental Protection Agency, have been grouped into series. These broad
categories were established to facilitate further development and applica-
tion of environmental technology. Elimination of traditional grouping was
consciously planned to foster technology transfer and maximum interface
in related fields. These series are:
1. ENVIRONMENTAL HEALTH EFFECTS RESEARCH
2. ENVIRONMENTAL PROTECTION TECHNOLOGY
3. ECOLOGICAL RESEARCH
4. ENVIRONMENTAL MONITORING
5. SOC10ECONOMIC ENVIRONMENTAL STUDIES
6. SCIENTIFIC AND TECHNICAL ASSESSMENT REPORTS
9. MISCELLANEOUS
This report has been assigned to the ENVIRONMENTAL PROTECTION
TECHNOLOGY series. This series describes research performed to
develop and demonstrate instrumentation, equipment and methodology
to repair or prevent environmental degradation from point and non-
point sources of pollution. This work provides the new or improved
technology required for the control and treatment of pollution sources
to meet environmental quality standards.
This document is available to the public for sale through the National
Technical Information Service, Springfield, Virginia 22161.
11
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ABSTRACT
A new low cost demetal1ization catalyst for heavy residual oils
was developed at the Trenton Laboratory of Hydrocarbon Research,
Inc., a subsidiary of Dynalectron Corporation, during Phase I
of Contract No. 68-02-0293, funded by the Environmental Protec-
tion Agency. The purpose of Phase II was to optimize the level
of promoter metal on the support, produce a batch on commercial
scale, and evaluate the commercially produced catalyst by de-
metallizing vacuum residua containing different levels of con-
taminant metals. Screening runs were conducted on laboratory
samples of activated bauxite impregnated with low levels of
molybdenum which were prepared by Minerals and Chemicals Divi-
sion of Engelhard Corporation. To check out commercial produc-
tion capabilities, a commercial production run was made on the
best support-promoter combination as determined from the screen-
ing runs. The commercial production catalyst was tested for
activity and aging characteristics and results were compared to
the best laboratory prepared catalyst.
Two vacuum residuum feedstocks were demetal1ized, the products
desulfurized over high activity commercial HDS catalyst beads,
and costs to produce low sulfur fuel oil were calculated and
compared against costs using unpromoted activated bauxite.
Descriptions of test units, operating conditions, and procedures
are given, including detailed run summaries, as well as tables
presenting feedstock, product, and catalyst inspections.
Graphs and tables depicting operating costs for producing 0.5
weight percent sulfur fuel oil are given, along with projected
costs for producing 0.3 and 1.0 weight percent sulfur fuel oil,
Conclusions based on experimental results are also discussed.
ii
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iv
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CONTENTS
Page
No.
Abstract iii
List of Figures vii
List of Tables ix
Glossary xi
SECTIONS
I. CONCLUSIONS 1
II. RECOMMENDATIONS 3
III. INTRODUCTION 5
IV. EXPERIMENTAL PROGRAM 7
V. DEMETALLIZATION RUNS 25
VI. DESULFURIZATION RUNS 39
VI I. PROCESS ECONOMICS 51
VIII. APPENDICES 59
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vi
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LIST OF FIGURES
Page
Title No.
1 Fixed Bed Demetallization Unit 8
2 Fixed Bed Demetal1ization Reactor 9
3 Demeta11ization Aging Runs Over 20 X 50
Mesh Bauxite Impregnated with 0.5 and
2.0 W % Molybdenum 15
4 Desulfurization Obtained During Demetal-
1ization Aging Runs Over 20 X 50 Mesh
Bauxite Impregnated with 0.5 and 2.0 W %
Molybdenum 16
5 Demetal1ization Aging Runs Over 20 X 50
Mesh Bauxite Impregnated with 1.0 and
2.0 W % Molybdenum 20
6 Demetal1ization Screening Runs Over 20
X 50 Mesh Bauxite Impregnated with 1.0
W % Molybdenum 22
7 Desulfurization Obtained During Demetal-
1ization Screening Runs Over 20 X 50
Mesh Bauxite Impregnated with 1.0 W %
Molybdenum 23
8 Demetal1ization of Tia Juana Vacuum
Residuum Over 1.0 W % Molybdenum/20 X
50 Mesh Bauxite: Run 184-190 26
9 Desulfurization Obtained During Demetal-
lization of Tta Juana Vacuum Residuum
Over 1.0 W % Molybdenum/20 X 50 Mesh
Bauxite: Run 184-190 27
vii
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LIST OF FIGURES
Figure
No. Title
10 Change in Pore Size Distribution of the
Demetal1ization Catalyst When Demetalliz-
ing Tia Juana Vacuum Residuum 29
11 Demetal1ization of Gach Saran Vacuum
Residuum Over 1.0 W % Molybdenum/20 X 50
Mesh Bauxite: Run 185-235 31
12 Desulfurization Obtained During Demetal-
1ization of Gach Saran Vacuum Residuum
Over 1.0 W % Molybdenum/20 X 50 Mesh
Bauxite: Run 185-235 32
13 Variation of Demetal1ization Rate Constant
with Vanadium Loading on the Catalyst 34
1** Change in Pore Size Distribution of the
Demetal1ization Catalyst When Demetalliz-
ing Gach Saran Vacuum Residuum 35
15 Demetal1ization and Desulfurization of
Bachaquero Vacuum Residuum Over 1.0 W %
Molybdenum/20 X 50 Mesh Bauxite: Run
185-236 37
16 Desulfurization of Demetallized Tia Juana
Vacuum Residuum: Run 184-192 44
17 Desulfurization of Demetallized Gach Saran
Vacuum Residuum: Run 184-193 45
18 Total Operating Cost: Two-Stage Demetal-
1ization-Desulfurization of Gach Saran
and Tia Juana Vacuum Residua 54
vltl
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LIST OF TABLES
Table Page
No. Title No.
1 Inspections on Vacuum Residuum Feedstocks 11
2 Description and Analyses of the 1.0 W %
Molybdenum Impregnated Bauxite 13
3 Evaluation of Minerals and Chemicals
Samples: Demetal1ization of Tia Juana
Vacuum Residuum 19
k Analyses of Spent Demetal1ization Catalyst 30
5 Composition of Demetallized Residua Fed to
the Desulfurization Reactor kO
6 Inspections on Demetallized Vacuum Residuum
Feedstocks k]
7 Summary of Inspections on American Cyanamid
0.02" High Activity Beaded Catalyst k2
8 Analyses of Spent Desulfurization Catalyst kl
9 Vanadium and Nickel Balances from Desul-
furization Runs ^8
10 Summary of Results on the Demetal1ization
and Desulfurization of Vacuum Residua
(Feed and Product Analyses) ^9
11 Investment and Operating Costs for a Two-
Stage Demetal1ization-Desulfurization
Operation on Tia Juana Vacuum Residuum 52
12 Investment and Operating Costs for a Two-
Stage Demetal1ization-Desulfurization
Operation on Gach Saran Vacuum Residuum 53
IX
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LIST OF TABLES
Table Page
No. Title No.
13 Estimated Overall Yields and Product Pro-
perties - Consecutive Demetal1ization and
Desulfurization of Gach Saran Vacuum
Residuum 56
14 Estimated Overall Yields and Product Pro-
perties - Consecutive Demetal1ization and
Desulfurization of Tia Juana Vacuum
Residuum 57
A-l Summary of Catalyst Screening Runs 63
B-l Summary of Demetal1ization Runs 69
C-l Summary of Desulfurization Runs 73
D-l Operating Conditions, Yields, and Product
Properties: Run 184-190 77
D-2 Operating Conditions, Yields, and Product
Properties: Run 185-235-14 78
D-3 Operating Conditions, Yields, and Product
Properties: Run 184-192-8 79
D-4 Operating Conditions, Yields, and Product
Properties: Run 184-193-15 80
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GLOSSARY
MM
o
1 Angstrom (A)
g/cc
M2/g
Mesh Sizes
psig
SCF/Bbl
L.S.V.
V0/Hr/Vr
C.S.V.
Bbl/D/Lb
BPSD
ppm
SFS
SUS
V.B.
Mill ions
10~8 Centimeters
Grams/cubic centimeter
Square meters/gram
Mesh sizes are all United States Standard
Sieve Series
Pounds per square inch, gauge
Standard cubic feet of gas per barrel of
oil (60°F, 1 Atm.)
Liquid Space Velocity, Volume of Oil/Hour/
Volume of Reactor
Volumes of 0?1/Hour/Volume of Reactor
Catalyst Space Velocity, Barrels of Oil/Day/
Pound of Catalyst
Barrels of Oil/Day/Pound of Catalyst
Barrels per Stream Day
Parts per mi 11 ion
Saybolt Furol Seconds
Saybolt Universal Seconds
Vacuum Bottoms = Vacuum Residuum
XI
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xfi
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SECTION I
CONCLUSIONS
Granular 20 x 50 mesh activated bauxite impregnated with 1.0
weight percent molybdenum proved to be better than a 0.5 weight
percent molybdenum and equal to a 2.0 weight percent molybdenum
preparation in terms of demetal1ization and long life when used
to demetallize Tia Juana vacuum residuum under the standard
testing conditions.
Commercial technology and facilities are presently available to
at least one major catalyst manufacturer to produce this cata-
lyst on a commercial scale; the catalyst being equivalent in all
respects to the best laboratory prepared plant simulation sample.
Process economics for production of low sulfur fuel oil were ob-
tained by utilizing the commercial production catalyst in a de-
metallization stage followed by a desulfurizatfon stage over com-
mercial high activity HDS catalyst beads. High metals Tia Juana
vacuum residuum and low metals Gach Saran vacuum residuum were
processed and costs calculated. To produce 0.5 weight percent
sulfur fuel oil in a United States Gulf Coast plant of 20,000
barrels per stream day capacity, including capital charges of
25 percent of investment, from Tia Juana vacuum residuum, the
operating cost per barrel was $1.63 versus $1.69 for unpromoted
activated bauxite and investment cost of $17.07 MM for promoted
commercial catalyst versus $19.44 MM for unpromoted activated
bauxite. From Gach Saran vacuum residuum, the comparable costs
were $1.41 per barrel versus $1.47 and $16.06 MM versus $17.22 MM.
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SECTION II
RECOMMENDATIONS
In order to more accurately define technical operating para-
meters, further demonstrate flexibility of the process, and
obtain more accurate operating cost figures, the following
program is recommended:
1. On a third feedstock, other than Tia Juana or Gach Saran,
demetallize over commercial production demetal1ization
catalyst to three different levels of metals removal.
For example, k$ to 50 percent vanadium removal, 65 to 70
percent vanadium removal, and 80 to 85 percent vanadium
remova1.
2. Desulfurize low level metals removal product from item
(1) above over high activity HDS catalyst beads to pro-
duce low sulfur fuel oil product.
3. Using medium level metals removal product from item (1)
above, desulfurize at three different conditions over
HDS beads.
4. Desulfurize high level metals removal product from item
(1) above over HDS beads.
5. Using a fourth different feedstock, demetallize the vacuum
residuum over commercial production demetal1ization cata-
lyst to two different levels of vanadium removal. For
example, ^5 to 50 percent vanadium removal, and 80 to 85
percent vanadium removal.
6. Desulfurize lower level metals removal product from item
(5) above over HDS beads.
7. Desulfurize higher level metals removal product from item
(5) above over HDS beads at different operating conditions,
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Incorporating data from the above work with data obtained from
previous work on this project, technical and economic evalua-
tions would be made to more closely define operating conditions
and costs for a process to produce low sulfur (0.3 to 1.0 W %)
fuel oil. Upon the successful completion of the above tasks, a
detailed commercial plant design based on these results should
be made.
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SECTION III
INTRODUCTION
In Phase I work of the Environmental Protection Agency Contract
No. 68-02-0293 on demetal1ization of heavy residual oils, the
goals were to develop a low cost demetal1ization catalyst at
laboratory scale level, to test the catalyst in pilot plant
operations, and to make a preliminary economic evaluation for
producing low sulfur fuel oil from heavy residual oils using
the newly developed catalyst system in a demetal1ization stage,
followed by a desulfurization stage using commercial HDS beads.
These goals were achieved by the development of a 20 x 50 mesh
activated bauxite impregnated with small (0.5 to 2.0 W %) amounts
of molybdenum and the successful testing of this catalyst in a
demetal1ization stage of a two-stage demetal1ization-desulfuri-
zation operation to produce low sulfur fuel oil from Tia Juana,
Bachaquero, and Gach Saran vacuum residua.
Economic evaluations showed this catalyst to offer substantial
cost advantages over unpromoted bauxite when used in a demetal-
1 ization stage of a two-stage system. The scope of the work
under Phase II was to optimize promoter level on the 20 x 50
mesh activated bauxite support, to explore commercial techno-
logy for producing the catalyst, and to evaluate commercially
produced catalyst in order to further define costs of producing
low sulfur fuel oil in a two-stage demetal1ization-desulfuriza-
tion process.
Long term aging tests on laboratory prepared catalysts contain-
ing 0.5, 1.0, and 2.0 weight percent molybdenum promoter showed
the 1.0 weight percent molybdenum catalyst to be superior to
the 0.5 weight percent molybdenum catalyst with respect to de-
metallization activity and aging and about equal to the 2.0
weight percent molybdenum catalyst with respect to demetal1iza-
tion activity while showing slightly better aging characteris-
tics. On this basis, Minerals and Chemicals Division of Engel-
hard Corporation was contracted to produce a 10,000 pound batch
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of 20 x 50 mesh activated bauxite impregnated with 1.0 weight
percent molybdenum using commercial production equipment. This
commercially prepared catalyst proved to be equal in all re-
spects to the best laboratory prepared plant simulation catalyst
sample.
Three vacuum residua were demetallized over the commercially
produced catalyst and the demetallized products from two feeds
were desulfurized over commercial HDS beads. From these data,
costs for producing low sulfur fuel oil were calculated and com-
pared against costs when using unpromoted activated bauxite in
a demetal1ization stage.
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SECTION IV
EXPERIMENTAL PROGRAM
UNIT DESCRIPTION
All runs were carried out In continuous, downfiow, fixed bed re-
actor systems. A schematic diagram is shown in Figure 1. The
reactor, fabricated of one-and-a-half inch O.D. by one-inch I.D.
stainless steel tubing, has a catalyst bed length of approxi-
mately 16 inches. A drawing of the reactor tube is shown in
Figure 2. The volume (loose) of catalyst charged to the reac-
tor was 200 cc. Provision was made for an internal thermocouple
which is positioned in the center of the catalyst bed approxi-
mately midway between the top and bottom. Heat to the reactor
was supplied by a lead bath.
The melted charge stock was pumped to reactor pressure with a
metering pump, mixed with hydrogen makeup gas, and fed to the
top of the reactor. The hydrogen concentration of the makeup
gas was 100 percent and no recycle of the exit gases was em-
ployed. In the reactor, the feed was contacted with the cata-
lyst. The mixed vapor and liquid product from the reactor was
cooled and passed to a high pressure receiver from which gas
was sampled, metered, and vented. The net product was let down
in pressure and passed to a low pressure receiver from which
gas was sampled periodically, metered, and vented. The liquid
product was collected and weighed periodically. Upon comple-
tion of a run, the catalyst was removed from the reactor for
inspection and/or analyses. Three essentially identical units,
18**, 185, and 201, were used for these runs.
A standard procedure was devised to screen the demetal1ization
catalysts in short term operations. This consisted of an ini-
tial startup period which conditioned the fresh catalyst at
lower temperatures for a short period of time. This startup
schedule was as follows:
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Figure 1. FIXED BED DEHETALLIZATION UNIT
HYDROGEN
00
f
n
WATER
THERMOCOUPLES
T
AUX. CHARGE CHARGE'
POT POT
s^\
r_
LEAD
BATH
PUMP REACTOR
X
H/P PRODUCT
RECEIVER'
^ txi—S—^
TO
FLARE
L/P PRODUCT
RECEIVER
HYDROCARBON RESEARCH INC.
TRENTON, N. J.
FIXED BED
DEMETALIZATION UNIT
SCALE
-DATE-
CKD.-
2552
O • W fLUIPHIHT CO. 'OHM HO. tltt-l
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Figure 2. FIXED BED DEMETALLIZATION REACTOR
INLET
OUTLET
DRILL a TAP FOR
•"THREAD
V
DE
Csl
V. ^
~2"-~
:TAIL
1
24"
i
"A"
I" THD.
t"
DIA:
DETAIL "B
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Period 1A IB, 2, Etc.
Temperature, °F 750 775 790 790
Pressure, psig 2000 2000 2000 2000
Hydrogen Rate, SCF/Bbl 4000 4000 4000 4000
Liquid Space Velocity,
Vo/Hr/Vr 0.75 0.75 0.75 0.50
Time on Temp., Mrs. 4 4 ] Continue at
above conditions
unti1 shutdown.
After the unit was lined out at 790°F, the period was ended and
the remainder of the run continued at 790°F, 2000 psig, 4000
SCF/Bbl, and 0.50 Vo/Hr/Vr for a period of two to fifteen days,
depending upon the performance of the catalyst being screened.
In Phase I work, simple first order- kinetics was used to de-
scribe the rate of vanadium removal using unpromoted as well as
promoted activated bauxite. However, preliminary studies, over
the range of space velocities used in the screening runs, indi-
cated that pseudo first order kinetics more closely describe the
rate of vanadium removal over activated bauxite promoted with
2.0 weight percent molybdenum. The kinetic equation used to
correct for variations in space velocities and obtain rate con-
stants for use later in this program is given in equation (1):
KM = (C.S.V.)0'5 x In (1)
where C.S.V. = Catalyst Space Velocity, Bbl Oil/Day/Lb Cat.
Vp = Vanadium in Feed, in ppm
Vp = Vanadium in Product, in ppm
FEED SELECTION AND PREPARATION
Three vacuum residuum feeds, Tia Juana, Bachaquero, and Gach
Saran, were used for all demetal1ization runs.
Tia Juana and Bachaquero crudes originate in the Lake Maracaibo
area of Venezuela. In 1973, the total production of Tia Juana
10
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and Bachaquero crudes was 120 and 216 million barrels, equiva-
lent to 36 and ]Qk million barrels of vacuum residual oils,
with estimated crude reserves of about 1,702 and 2,0^+1 million
barrels, respectively. Tia Juana vacuum residuum and Bacha-
quero crude were obtained from the Creole Petroleum Corporation,
a subsidiary of Exxon. The Bachaquero vacuum residuum used in
this work was prepared at the HRI® Laboratory by distillation
of the atmospheric residuum obtained from Bachaquero crude. Gach
Saran crude originates in the Persian/Arabian Gulf in Iran. In
1973, the production rate of Gach Saran crude was 32*f million
barrels, equivalent to 75 million barrels of vacuum residual oil,
with an estimated crude reserve of about 8,1^0 million barrels.
The vacuum residuum feed was obtained from Kashima Oil Company
of Japan. The three feeds are representative of major high me-
tals crudes available in the world and are, for the most part,
sold as export material. Detailed inspections of the three
vacuum residua are presented in Table 1.
The Gach Saran vacuum residuum obtained from Kashima Oil Company
has a slightly higher sulfur than those given in the literature.
This is due to the presence of a small percentage of Kuwait Vacuum
Bottoms in the feed obtained from Kashima.
DEMETALLIZATION CATALYST
Table 2 summarizes inspections on the 20 x 50 mesh demetalliza-
tion catalyst obtained from Minerals and Chemicals Division of
Engelhard Corporation as part of the 10,000 pound production
using commercial manufacturing facilities. For the runs carried
out, about 184 grams of this catalyst with a static volume of 200
cc was charged to the reactor. Pore size distribution on this
catalyst is given later in Figure 10.
CHOOSING A CATALYST FOR COMMERCIAL PRODUCTION
In our previous work under Phase I of the present project, 20 x
50 mesh activated bauxite, promoted with low levels of molybdenum
(0.5 to 2.0 W % Mo), proved to be the most effective catalyst of
those tested for removing contaminant metals (vanadium and nickel)
from heavy residua.
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Table 1 . INSPECTIONS ON VACUUM RESIDUUM FEEDSTOCKS
Feedstock
HRI Identification No.
Gravity, °API
Sulfur, W %
Ramsbottom Carbon, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Vanadium, ppm
Nickel, ppm
Viscosity, SFS & 210°F
IBP-975°F, V %
Gravity, °API
Sulfur, W %
975°F+, V %
Gravity, °API
Sulfur, W %
Ramsbottom Carbon, W %
Tia Juana
Vacuum Residuum
3615
7.8
2.9
17.8
84.98
10.59
1.48
5800
570
75
1126
12.0
17.3
2.11
88.0
6.5
3.18
21.2
Gach Saran
Vacuum Residuum
3574
6.9
3.72
18.0
86.30
10.48
1.45
6850
291
110
1310
6.0
17.7
2.54
84.0
6.1
3.81
19.2
Bachaquero
Vacuum Residuum
L-388
5.3
3.49
20.4
85.16
10.24
1.43
7400
754
96
8.0
16.3
2.85
92.0
4.7
3.66
22.7
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Table 2. DESCRIPTION AND ANALYSES OF THE
]% MOLYBDENUM IMPREGNATED BAUXITE
HRI Identification Number
Size 20 x 50 U.S. Mesh
Molybdenum, W % 1.06
Volatile Matter, W % 2.0
Bulk Density, g/cc 1.01
Pore Volume, cc/gm 0.282
Screen Analyses. W %
20/30 Mesh 52.k
30AO Mesh 30.7
^0/50 Mesh 16.9
13
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Initial activity of the 0.5 weight percent molybdenum was only
slightly lower than the 2.0 weight percent molybdenum. However,
there was some doubt as to whether the 0.5 weight percent molyb-
denum catalyst would sustain its activity as well as the 2.0
weight percent molybdenum. Since the difference in molybdenum
content between 0.5 weight percent and 2.0 weight percent cata-
lyst represents about $0.03 or more per pound of molybdenum, it
was evident that a more extensive evaluation of lower promoter
level catalyst was necessary.
LONG TERM DEACTIVATION STUDY ON 0.5 WEIGHT PERCENT MOLYBDENUM
CATALYST
A laboratory prepared sample of 20 x 50 mesh activated bauxite
impregnated with 0.5 weight percent molybdenum was made and de-
signated as HRI LX-28. Demetal1ization of Tia Juana vacuum bot-
toms under standard operating conditions was carried out in Run
184-182 over LX-28. Unfortunately, it was found that it was
necessary to run at 0.5 volume of oil per hour per volume of re-
actor (Vo/Hr/Vr) to achieve the same level of demetal1Jzation
as was obtained at 0.75 Vo/Hr/Vr using the 2.0 weight percent
molybdenum catalyst. In addition, the desulfurization level
achieved was lower using the lower promoted catalyst.
Figure 3 and Figure k compare the demetal1ization and desulfuri-
zation results of this run with earlier experimental work (Run
184-17*0 on the 2.0 weight percent molybdenum laboratory pre-
pared catalyst, LX-22.
ECONOMIC COMPARISON OF 0.5 WEIGHT PERCENT MOLYBDENUM CATALYST
VERSUS 2.0 WEIGHT PERCENT MOLYBDENUM CATALYST
To compare the economics of the two catalysts, it was necessary
to determine the overall cost of the demetal1ization and desul-
furlzation steps. Demetal1ization catalyst LX-28 (0.5 W % Mo)
is less active than LX-22 (2.0 W % Mo), both in demetal1Ization
and desulfurization. Results obtained in Phase I of this con-
tract Indicated that the second order rate constant
K = (B/D/Lb) x (Sp/Sp-1)
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Figure 3. PEMETALL1ZATION AGING RUNS OVER 20 X 50 MESH BAUXITE
IMPREGNATED WITH 0.5 AND 2.0 W % MOLYBDENUM
feed:
Feed Composition:
Tla Jliana Vacuum Residuum
7.5-7.7°API, 2.85-2.91 W % S, 5^1-586 ppm V, 71-7^ ppm Ni
Legend
O
A
Run No.
184-182
Catalyst
HRI No.
LX-28
LX-22
% Mo
0.5
2.0
Hydrogen
Pressure
psfg
2000
2000
Temp.
790
790
Vo/Hr/Vr
0.5
0.75
0)
0)
CD
C
to
-------
a\
Figure 4. DESULFURIZATION OBTAINED DURING DEMETALLIZATION AGING RUNS
OVER 20 X 50 MESH BAUXITE IMPREGNATED WITH 0.5 AND Z.O W % MOLYBDENUM
Feed:
Feed Composition:
Tia Juana Vacuum Residuum
7.5-7.7°API, 2.85-2.91 W % S, 541-586 ppm V, 71-74 ppm Ni
Legend
O
A
Run No.
184-182
Catalyst
HRI No.
LX-28
LX-22
% Mo
0.5
2.0
Hydrogen
Pressure
pslq
2000
2000
Temp.
°F
790
790
Vo/Hr/Vr
0.5
0.75
T3
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In the desulfurlzation stage decreases with increase in sulfur
removal in the demetal1ization stage. In order to obtain the
initial rate constant for estimating the desulfurization operat-
ing conditions for producing the required final product, an
eight-day desulfurization run (201-83) was conducted over the
HDS beads using the feed demetallized over LX-28. As expected,
the desulfurization rate constant was slightly higher for the
higher sulfur feed prepared with LX-28. To produce fuel oil
containing the same level of sulfur, it was necessary, in spite
of the higher rate constant, to operate the desulfurization
stage for this feed at more severe conditions than those used
for the feed prepared with LX-22 because of the higher level of
sulfur in the demetallized feed from the LX-28 operation. This
resulted in higher overall operating costs when compared with
the case using LX-22. The cost difference between the LX-28
and LX-22 catalysts should be about $0.13 per pound for the two
catalysts to be equivalent. This amount of difference is un-
likely since the difference in raw chemical costs between the
two promoter levels is only about $0.03 per pound.
The results from the evaluation of the 0.5 weight percent molyb-
denum catalyst indicated the optimum level of promoter metal
must be somewhat higher than 0.5 weight percent.
EVALUATION OF CATALYST SAMPLES PREPARED BY MINERALS AND CHEMICALS
DIVISION OF ENGELHARD CORPORATION
In order to minimize the cost of this catalyst, it is necessary
to keep the manufacturing process as simple as possible. Arrange-
ments were mada with Minerals and Chemicals Division of Engelhard
Corporation to prepare samples in their laboratory which they
felt could be produced by them at minimum cost. Minerals and
Chemicals is the producer of Porocel, the activated bauxite chosen
as the support for this catalyst.
Initially, they prepared a sample by impregnating 20 x 50 mesh
activated bauxite with 1.0 weight percent molybdenum using HRI's
technique to assure that comparable results could be achieved by
both laboratories. The next seven samples, all containing 2.0
weight percent molybdenum, represented successively easier methods
of preparation. The final three samples, all representing the
easiest plant simulation preparation technique, contained 2.0,
1.0, and 0.5 weight percent molybdenum.
17
-------
All catalyst samples prepared by Minerals and Chemicals were
subjected to our standard short term screening test using stan-
dard operating conditions on Tia Juana vacuum residuum. Table
3 summarizes the results of these screening tests. Catalyst
LX-22, prepared by HRI, is included as the reference catalyst.
Minerals and Chemicals sample No. 1 (HRI 3581), laboratory
method, not a plant production simulation method, was superior
with respect to metals removal and equal in desulfurization to
LX-22. The next seven samples, Minerals and Chemicals No. 3,
6, 7, 8, 9, 10, and 11, were all about equal to each other and
to LX-22. The 0.5 weight percent molybdenum preparation, Min-
erals and Chemicals sample No. 13 (HRI 3609), was definitely
inferior to all other samples including LX-22.
Sample No. 14 (HRI 3610), representing the easiest plant simu-
lation preparation method, and Sample No. 12 (HRI 3608), using
the same easiest preparation method, but containing 1.0 weight
percent molybdenum, showed 79 percent vanadium removal compared
to 77 percent for LX-22. Both samples had higher nickel removal
rates than LX-22 and only in desulfurization did the 1.0 weight
percent molybdenum catalyst fall below LX-22.
On the basis of results from all screening runs, the last 2.0
weight percent molybdenum sample, Minerals and Chemicals No. 14
(HRI 3610) and the 1.0 weight percent molybdenum sample, Minerals
and Chemicals sample No. 12 (HRI 3608) were chosen for further
aging tests.
AGING TEST ON THE TWO BEST MINERALS AND CHEMICALS LABORATORY-
PREPARED PLANT SIMULATION CATALYSTS
Aging tests were performed in our standard test units using Tia
Juana vacuum residuum and standard testing conditions. The 2.0
weight percent molybdenum catalyst (HRI 3610) was tested in Run
184-186 lasting 22 days and the 1.0 weight percent molybdenum
catalyst (HRI 3608) was tested in Run 185-231 lasting 26 days.
Figure 5 shows the plots of demetallization activity (vanadium
removal) versus catalyst age in barrels of oil per pound of cata-
lyst (Bbl/Lb) for the two catalysts being tested, as well as a
plot of an HRI laboratory-prepared 2.0 weight percent molybdenum
catalyst (LX-22-5) previously run in 184-174 to serve as a base
for comparison.
18
-------
Table 3. EVALUATION OF MINERALS £• CHEMICALS SAMPLES
DEMETALLIZATION OF TIA JUANA VACUUM RESIDUUM
Catalyst, Bbl/Lb
0.10
790
Hydrogen Pressure, psig 2000
Liquid Space Velocity, Vo/Hr/Vr 0.5
Temperature, F
Catalyst
LX-22
M & C 3231-7, Sample #1
M & C 3231-4, Sample #6
M & C 3231-11, Sample #7
M & C Sample #10
M & C Sample #11
M & C Sample #3
M & C Sample #8
M & C Sample #9
M & C Sample #12
M & C Sample #13
M & C Sample #14
HRI
Number
3581
3582
3583
3598
3599
3594
3596
3597
3608
3609
3610
Mo
2.0
2.0
2.0
0
0
2.0
2.0
2.0
2.0
1.0
0.5
2.0
2,
2.
Evaluation
Run
184-166
185-224
185-225
185-226
185-227
184-183
185-228
184-184
185-229
184-185
185-230
201-84
Product Concentrations
%S
1.00
1.00
.58
.04
.05
.12
.00
.00
.04
.20
.49
.02
ppm V
127
85
134
133
125
127
118
128
122
109
154
106
ppm Ni
45
35
39
49
38
39
39
42
41
39
44
34
% Removal
S
65
65
45
64
63
61
65
65
64
60
50
66
V
77
84
75
75
78
77
79
77
78
79
70
79
Ni
39
52
47
34
49
47
47
43
45
44
37
51
-------
Figure 5. DEMETALLIZATION AGING RUNS OVER 20 X 50 MESH BAUXITE
ISJ
o
IMPREGNATED WITH 1.0 AND 2.
0 W % MOLYBDENUM
Feed: Tia Juana Vacuum Residuum
Feed Composition: 7.7-8.0°API, 2.85-2.98 W % S, 520-585 ppm V, 70-74 ppm Ni
Hydrogen
Catalyst Pressure Temp. Actual Data Corrected
Legend Run No. HRI No. % Mo psig °F V0/Hr/Vr to Vo/Hr/Vr
•o
A_
'•<
J
U
:
1
O G
t
-
L- -ic 5-s
• 75
3
£ -7 0
67 2;
c
1 50 o
CD
0.5
1.0
1.5
Catalyst Age, Bbl/Lb
-------
Up to a catalyst age of 0.5 Bbl/Lb, the activity of the two cata-
lysts is about equal, but below the LX-22-5 catalyst. There is
no apparent explanation for the unusually high initial demetal-
lization activity exhibited by LX-22-5. From age 0.5 Bbl/Lb to
the end of the run, the 1.0 weight percent molybdenum catalyst
exhibited slightly higher demetal1ization rates over the 2.0
weight percent molybdenum catalyst and had about the same rate
as the LX-22-5 catalyst at the end of the run.
From this technical evaluation, neither catalyst exhibited clear
cut superior qualities over the other. However, the 1.0 weight
percent molybdenum catalyst, having about $0.02 per pound cost
advantage because of the lower molybdenum loading, was chosen
for the commercial production run.
SHORT TERM TESTING OF COMMERCIALLY PREPARED 1.0 WEIGHT PERCENT
MOLYBDENUM CATALYST
Minerals and Chemicals Division of Engelhard Corporation was
contracted to produce 10,000 pounds of 1.0 weight percent molyb-
denum on 20 x 50 mesh activated bauxite using their commercial
manufacturing facilities. In their opinion, this amount of cata-
lyst would provide enough on stream time to provide a represen-
tative sample of catalyst.
The production catalyst (HRI 363*0 was subjected to our standard
five-day screening test in Run 18U-189, along with a sample re-
presenting a variation in the commercial production (HRI 3635)
in Run 185-233. The demetal1ization results of these two cata-
lyst samples are plotted in Figure 6, along with a plot of pre-
viously run Minerals and Chemicals sample containing 1.0 weight
percent molybdenum (HRI 3608) in Run 18^-185 for comparison.
Figure 7 represents the desulfurization results on these cata-
lysts from the same runs.
The variation in production catalyst (HRI 3635) showed no signi-
ficant difference with respect to demetal1ization and desulfuri-
zation when compared to the regular production catalyst (HRI
363*0.
21
-------
Figure 6. DEMETALLIZATION SCREENING RUNS
Legend
O
9
OVER 20 X_50 MESH BAUXITE IMPREGNATED WITH 1.0 W % MOLYBDENUM
Feed: Tia Juana Vacuum Residuum
Feed Composition: 7.7-8.0°API, 2.85-2.98 W % S, 520-585 ppm V,
Hydrogen
Catalyst Pressure Temperature
Run No. HRI No. % Molybdenum psiq °F
184-185 3608
185-233 3635
184-189 3634
•M -
O t
3 f:
TJ !-
i- 5 *•
O. •:
t-
c I
£ i
ro 3 -
<0
0)
-------
Figure 7. DESULFURIZATION OBTAINED DURING DEMETALLIZATION SCREENING RUNS
Legend
O
3
Feed
Feed
Run
184-
185-
184-
•o
0)
0)
U.
C
l_
•3
M-
3
10
OVER 20 X 50 MESH BAUXITE
IMPREGNATED
WITH 1.0 W % MOLYBDENUM
: Tia Juana Vacuum Residuum
Composition: 7.7-8.0°AP , 2.85-2.98 W % S, 520-585 ppm V,
Hydrogen
Catalyst Pressure, Temperature
No. HRI No. % Molybdenum psig °F
185
233
189
4-
4-1
o :
3 <•> r - -
-5 2.5
O
a.
c.
1_
3 1 C -.
^ t.t>
3
IO
C
3608
3635
3634
~-.::.
-. -r.
Z
—
._.
--
:-::
—
: .:_
—
1
1
1
• J
N
n
.._ . —
: :
•'•"-•
-: -
2000
2000
2000
r-M
:::,•.-„-
A
§
?
-r":v
::::!::::
: : ;thr:
*|n
0.10
:.-.
•
790
790
790
—
'(
(1
-•
\. :.-.
•- • ~
5
70-74 ppm Ni
LSV CSV
Vo/Hr/Vr B/D/Lb
0.5 0.039
0.5 0.034
0.5 0.038
(
>
•
0.20
Catalyst Age, Bbl/Lb
-------
On the basis of the five-day screening test, the commercial pro-
duction catalyst was accepted to be equal to the laboratory-pre-
pared plant simulation 1.0 weight percent molybdenum catalyst
with respect to demetal1ization and desulfurization. To test de-
activation rates, aging tests were scheduled using Tia Juana
vacuum residuum as well as other feedstocks.
Detailed operating conditions and liquid product inspections for
each screening run of this series are given in Appendix A.
-------
SECTION V
DEMETALLIZATION RUNS
DEMETALLIZATION OPERATING CONDITIONS
Demetal1ization operating conditions were selected so that a
modest catalyst deactivatlon was maintained during the run.
These conditions were chosen based on the results obtained in
the Phase I work of this contract. All demetal1ization runs
were carried out at a hydrogen pressure of 2000 psig, a reac-
tor temperature of 790°F, a liquid space velocity of 0.75 Vo/
Hr/Vr> and a hydrogen rate of about 4000 to 4500 SCF/B of feed.
The runs were generally carried out to a catalyst age of about
1.3 to 1.6 Bbl/Lb. Runs of this duration provide a good mea-
sure of the catalyst deactivatlon rate which can be translated
to the catalyst utilization rate for a given level of vanadium
removal. Detailed operating conditions and liquid product in-
spections for each run of this series are given in Appendix B.
LONG TERM DEMETALLIZATION OF TIA JUANA VACUUM RESIDUUM
A long term run (184-190) of 24 days duration was conducted on
Tia Juana vacuum residuum over commercially prepared demetal1i-
zation catalyst (1.0 W % molybdenum on 20 x 50 mesh bauxite).
The purpose of this run was to study the aging rate of this
catalyst and also to produce feed for a desulfurization study.
The operating conditions and the demetal1ization and desulfuri-
zation results are given in Figures 8 and 9.
Initial vanadium removal was about 69 percent. This value
dropped to about 52 percent at a catalyst age of 1.35 Bbl/Lb.
Nickel removal ranged from about 40 percent to about 24 per-
cent, and sulfur removal was between 35 and 50 percent.
In the screening run (184-185) using HRI 3608, the vanadium
removal was reported as 79 percent, which is higher than the
25
-------
Figure 8 . DEMETALLIZATION OF TIA JUANA VACUUM RESIDUUM
OVER 1.0 W % MOLYBDENUM/20 X 50 MESH BAUXITE
Run 184-190. Catalyst HRI No. 3634
Feed Composition
Gravity, °API
Sulfur, W %
Vanadium, ppm
Nickel , ppm
7.8
2.9
575
75
Operating Conditions
Hydrogen Pressure, psig 2000
Temperature, °F 790
Liquid Space Velocity, VF/Hr/VR 0.75
Catalyst Space Velocity, B/D/Lb 0.056
Hydrogen Rate, SCF/B (Vent) 4150
ON
3
01
c
0
0)
1.0
1.5
Catalyst Age, BbJ/Lb
-------
Figure 9. DESULFURIZATION OBTAINED DURING DEMETALLIZATION
OF TIA .IIIAMA VAf.niiM RFSimniM n\/FR l.o w % MOLYBDENUM/20 X 50 MESH BAUXITE
ro
Run 184-190, Catalyst HRI No. 3634
Feed Composition
8*
TJ
O
1-
O.
C
3
"5 2
to
0)
0)
LL.
C
1.
£ 1
Operating Conditions
Gravity, °API 7.8
Sulfur, W % 2.9
Vanadium, ppm 575
Nickel, ppm 75
^rfr
F
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^-M-
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T
4-
r i j j
Hydrogen Pressure, psig 2000
Temperature, °F 790
Liquid Space Velocity, VF/Hr/VR 0.75
Catalyst Space Velocity, B/D/Lb 0.056
Hydrogen Rate, SCF/B (Vent) 4150
frU
5r
S[-
"^p
I'
;!i
*t
!ij
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'•• !••• :
u
J ' '
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t
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•-•::
-
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B:
T\
JV
•>•>
H
0.5 1.0
Catalyst Age, Bbl/Lb
o
(D
1:5
-------
level obtained in this run. This is so because the screening
run was conducted at a liquid space velocity of 0.5 V0/Hr/Vr
whereas a space velocity of 0.75 V0/Hr/Vr was used in this run.
Figure 10 compares the difference in pore structure between the
fresh and spent catalyst from Run 18^-190, conducted with Tia
Juana vacuum residuum. The pore volume of the spent catalyst
was corrected to fresh basis using the following relationship:
cc/gm Fresh Catalyst = —=?-. TF~ x cc/gm Spent Catalyst
I .UUU ••Ar I + 2' S
where Fi = weight fraction impurities on spent catalyst and
Fs = weight fraction sulfur on spent catalyst.
There is a small change in the pore volume in pores larger than
1000 angstroms (A),owhi1e a substantial reduction is noted in
pores between 1000 A and 50 A. All of the pore volume in pores
less than 50 A appears to be gone.
The results of the analysis of the spent catalyst from this opera-
tion, as well as from other demetal1ization operations, are pre-
sented in Table 4. They show a vanadium loading of about 12 per-
cent and a carbon loading of about nine percent.
The variation of the demetal1ization rate constant with vanadium
loading on the catalyst is given later in Figure 13.
LONG TERM DEMETALLIZATION OF GACH SARAN VACUUM RESIDUUM
Long term demetal1ization of Gach Saran vacuum residuum over com-
mercially prepared demetal1ization catalyst (1.0 W % molybdenum
on 20 x 50 mesh bauxite) was carried out in Run 185-235. The
operating conditions and desulfurization and demetal1ization re-
sults of that operation are summarized in Figures 11 and 12. The
purpose of this run was to investigate the aging characteristics
of the catalyst and to produce feed for a desulfurization study.
A high level of vanadium removal was accomplished with this feed.
The level of vanadium removal and the rate of deactivation obtained
with this catalyst were about the same as those obtained with the
28
-------
Figure 10. CHANGE IN PORE SIZE DISTRIBUTION OF THE DEMETALLIZATION CATALYST
WHEN DEMETALUZING TIA JUANA VACUUM RESIDUUM
Pore Diameter (Angstroms)
o
o
o
V/l
o
o
ro
o
o
O
o
ro
o
VJl
0.300
NJ —
HRI 3634, Commercial Production
Porocel + 1% Molybdenum
Spent Catalyst from Run 184-190
Demetallized Tia Juana Vacuum
Residuum (Corrected to Fresh
Catalyst Basis)
P—ABSOLUTE PRESSURE, PSInji
Mi'! !|!!;!N;'|:M!II!!M|jij!ti!i.|jiN|T
O O 1
o o <
O O c
-------
Table 4 . ANALYSES OF SPENT DEMETALLIZATION CATALYST
Weight Percent Element
Run No.
1 84- 1 82
184-186
184-190
185-231
185-235
185-236
Feed
TIa Juana
Tia Juana
Tia Juana
Tia Juana
Gach Saran
Bachaquero
Catalyst
HRI No.
LX-28
3610
3634
3608
3634
3634
% Molybdenum
0.5
2.0
1.0
1.0
1.0
1.0
C
10.63
9.39
9.04
8.85
6.93
9.79
O" Spent
S
6.16
6.88
5.73
8.26
8.19
3.66
Catalyst
V
11.84
9.47
11.79
13.48
11.20
4.84
Ni
0.85
0.74
0.88
0.98
2.66
0.53
-------
Figure 11. DEMETALLIZATION OF GACH SARAN VACUUM RESIDUUM
OVER 1.0 W % MOLYBDENtH/20 X 50 MESH BAUXITE
Run 185-235. Catalyst HRI No. 3634
Feed Composition
Gravity, "API 6.9
Sulfur, W % 3.72
Vanadium, ppm 291
Nickel, ppm 110
Operating Conditions
Hydrogen Pressure, psig 2000
Temperature, °F 790
Liquid Space Velocity, VF/Hr/VR 0.75
Catalyst Space Velocity, B/D/Lb 0.057
Hydrogen Rate, SCF/B (Vent) 4700
Q)
Q_
i
0.5
1.0
Catalyst Age, Bbl/Lb
-------
Figure 12. DESULFURIZATION OBTAINED DURING DEMETALLIZATION
OF GACH SARAN VACUUM RESIDUUM OVER 1.0 W % MOLYBDENUM/20 X 50 MESH BAUXITE
Run 185-235. Catalyst HRI No. 363**
Feed Composition
Gravity, °API 6.9
Sulfur, W % 3.72
Vanadium, ppm 291
Nickel, ppm 110
Operating Conditions
Hydrogen Pressure, psig 2000
Temperature, °F 790
Liquid Space Velocity, VF/Hr/VR 0.75
Catalyst Space Velocity, B/D/Lb 0.057
Hydrogen Rate, SCF/B (Vent) ^700
u
3
T>
1*
3
CO
-o
O
o
n
o
IT
O
0
0.5
00
1.0
Catalyst Age, Bbl/Lb
1.5
,
60^
N
03
-------
LX-22 catalyst (2.0 W % molybdenum on 20 x 50 mesh bauxite, pre-
pared by HRI). Initial vanadium removal was about 89 percent
and this value dropped to about 77 percent at a catalyst age of
1.6 Bbl/Lb. Nickel removal ranged from 63 to 75 percent and sul-
fur removal was about 55 percent. While the level of vanadium
removal obtained with this feed was high, the rate of activity
decline was modest when compared with the results of other feeds,
Figure 13 shows the variation of the demetallization rate con-
stant as a function of vanadium loading on the catalyst for Gach
Saran, Tia Juana, and Bachaquero feeds. For the same vanadium
loading on the catalyst, the demetal1ization rate constant ob-
tained with Gach Saran is about twice that obtained with Tia
Juana.
In order to explain the large difference in demetallization rate
constants between Tia Juana and Gach Saran residua, further work
in characterizing these two residua may be of value. Perhaps the
distribution of metals associated with the asphaltene and oil
fractions is different for the two residua. Characterizing mole-
cular size and species may also be helpful to explain the differ-
ence.
The reduction in pore volume of the catalyst that occurred during
the process is shown in Figure ]k. As is the case with the Tia
Juana feed, a substantial reduction in pore volume in pores be-
tween 1000 A and 50 A is noted.
The results of the analysis of the spent catalys.t from this run
were presented previously in Table *t. They show a vanadium load-
ing of 11.2 percent and a carbon loading of about 6.9 percent.
This was the lowest value obtained when compared to the carbon
loading from other runs.
DEMETALLIZATION OF BACHAQUERO VACUUM RESIDUUM
A short term run (185-236) of about five days was conducted on
Bachaquero vacuum residuum over commercially prepared demetal-
lization catalyst. The original objective of this run was to
33
-------
Figure 13. VARIATION OF DEMETALLIZATION RATE CONSTANT
WITH VANADIUM LOADING ON THE CATALYST
Feed
1. Gach Saran Vacuum Residuum
2. Bachaquero Vacuum Residuum
3. Tia Juana Vacuum Residuum
Operating Conditions
Hydrogen Pressure, psig 2000
Temperature, °F 790
[KM = (B/D/Lb)'5
-------
Figure \k. CHANGE IN PORE SIZE DISTRIBUTION OF THE DEMETALLIZATION CATALYST
WHEN DEMETALLIZING GACH SARAN VACUUM RESIDUUM
Pore Diameter (Angstroms)
o
o
o
vn
o
o
ro
o
o
o
o
ro
o
HRI 363^, Commercial Production
Porocel + 1% Molybdenum
Spent Catalyst from Run 185-235
Demetallized Gach Saran Vacuum
Residuum (Corrected to Fresh
Catalyst Basis)
8 8 §
-------
study the aging characteristics of this catalyst when used with
this feed and also to produce feed for a desulfurization study;
however, due to lack of funds, the run had to be terminated.
Operating conditions, demetal1ization and desulfurization re-
sults from this work are summarized in Figure 15.
The variation of the demetal1ization rate constant with vanadium
loading on the catalyst was given previously in Figure 13. The
rate constant obtained with this feed is slightly higher than
that obtained with Tia Juana feed.
INSPECTIONS OF PRODUCTS FROM THE DEMETALLIZATION OPERATION
Detailed product inspections were obtained on one product from
each of the demetal1ization operations on Tia Juana and Gach
Saran vacuum residua over the commercially prepared 1.0 weight
percent molybdenum catalyst. These inspections are given in
Tables D-l and D-2 in Appendix D. Chemical hydrogen consump-
tion ranged from 350 SCF/B for Tia Juana vacuum residuum to 515
SCF/B for Gach Saran vacuum residuum.
36
-------
Figure 15. DEMETALLIZATION AND DESULFURIZATION OF BACHAQUERO VACUUM RESIDUUM
OVER 1.0 W % MOLYBDENUM/20 X 50 MESH BAUXITE
'Run 185-236, Catalyst HRI 363^
Feed Composition
Gravity, °API
Sulfur, W °/0
Vanadium, ppm
Nickel, ppm
5.3
3.^9
75k
96
Legend
O
Operating Conditions
Hydrogen Pressure, psig 2000
Temperature, °F 790
Liquid Space Velocity, Vo/Hr/Vr 0.75
Catalyst Space Velocity, B/D/Lb 0.057
Hydrogen Rate, SCF/B (Vent) kkOO
Vanadium in Feed/Vanadium in Product
Sulfur in Feed/Sulfur in Product
•o
e
O_
(D
C
<0
-o
V
Q.
3
"D
-I
O
Q.
C
O
0.10
0.20
0.30
Catalyst Age, Bbl/Lb
-------
38
-------
SECTION VI
DESULFURIZATION RUNS
DEMETALLIZATION FEEDSTOCK PREPARATION
DemetalHzed residua from each long term run on Tia Juana and
Gach Saran were collected and blended so that a feed having
constant properties could be fed to the desulfurization unit.
The products that were blended to make the demetal1ized feed
are listed in Table 5. Detailed inspections on the blended
feeds for each of the desulfurization runs are given in Table
6.
CATALYST
The catalyst used for the desulfurization of the demetal1ized
feeds was high activity American Cyanamid 0.02-inch beads.
This same catalyst was used in the desulfurization step in
Phase I of this contract. The properties of this catalyst are
summarized In Table 7.
DESULFURIZATION OPERATING CONDITIONS
Desulfurization operating conditions were selected so that a
maximum desulfurization with a minimum hydrogen consumption
would be obtained. All runs were carried out in the fixed
bed downflow reactor as previously described, except that the
effective volume was reduced to half that used in the demetal-
lization step. Because of the limited quantity of the demetal-
lized feed available, the reduced volume would allow a better
determination of catalyst aging characteristics. Each run was
conducted at a hydrogen pressure of 2000 psig, a reactor tem-
perature of 760°F, and a liquid space velocity of 1.0 Vo/Hr/Vr.
Hydrogen rate was maintained at about 4500 SCF/B of feed. The
39
-------
Table 5. COMPOSITION OF DEMETALLIZED RESIDUA
FED TO THE DESULFURIZATION REACTOR
Feed
Demetallized
Tfa Juana
Vacuum Residuum
Demetal1Ized
Gach Saran
Vacuum Residuum
HRI Identification
Number
L-385
L-390
Products Blended to
Make Composite Feed
Run 184-190
Period 2 to 2k
Run 185-235
Period 2 to 28
-------
Table 6. INSPECTIONS ON DEMETALLIZED VACUUM RESIDUUM FEEDSTOCKS
Demetal1ized
Feedstock Source
HRI Identification No.
Demetal1ized Over
Gravity, °API
Sulfur, W %
Ramsbottom Carbon, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Vanadium, ppm
Nickel, ppm
Viscosity, SFS <5> 210°F
IBP-650°F, V %
Gravity, "API
Sulfur, W %
650-975°F, V %
Gravity, °API
Sulfur, W %
975°F+, V %
Gravity, °API
Sulfur, W 7o
Ramsbottom Carbon, W %
Vanadium, ppm
Nickel, ppm
Tia Juana
Vacuum Residuum
L-385
Gach Saran
Vacuum Residuum
L-390
Commercial Demetal1ization Catalyst,
12.8
1.81
13.6
87.07
10.92
1 .^9
i*900
219
53
72
6.7
3^.3
0.35
22.0
19.7
!.!*»
71.3
8.6
2.12
19.0
295
67
30.5H
13.1
1.63
12.1
87.16
11.00
1.50
5700
^9
38
57
9.0
35.7
0.35
20.0
18.7
0.79
71.0
8.6
1.93
16.6
59
51
-------
Table 7. SUMMARY OF INSPECTIONS ON AMERICAN
CYANAMID 0.02" HIGH ACTIVITY BEADED CATALYST
HRI Identification Number 3104
Physical Properties
Surface Area, M^/g 250
H20 Pore Volume, cc/g 0.67
Hg Pore Volume, cc/g 0.62
Screen Analysis. U.S. Sieve No.
+20 1.3
20/30 16.9
30 AO 76.2
^0/50 5.0
50/70 0.5
70/100 0.1
-100
Chemical Analysis. W %
(15.0)
CoO (3.0)
-------
runs were generally carried out to a catalyst age of 2.0 to
2.5 Bbl/Lb. Runs of this duration, together with results ob-
tained during Phase I of this contract, provide an accurate
measure of the catalyst deactivation rate which can be trans-
lated to the catalyst utilization required to obtain a given
product desulfurization level. Detailed operating conditions
and liquid product inspections for each run of this series are
given in Appendix C.
DESULFURIZATION OF DEMETALLIZED FEEDS
The demetallized Tia Juana vacuum residuum was desulfurized in
Runs 184-191 and 184-192. Run 184-191 was carried out to a
catalyst age of 0.71 Bbl/Lb and was terminated because of an
unusually high deactivation slope. Analyses of the spent cata-
lyst after shutdown indicated no unusual loading of carbon,
vanadium, or nickel. It was concluded that this abnormal be-
havior was due to an abnormal scatter in the analytical data.
Run 184-192 was a repeat of Run 184-191 and was carried out to
a catalyst age of 1.9 Bbl/Lb. Desulfurization results for this
run are summarized in Figure 16. Demetallized Gach Saran vacuum
residuum was desulfurized In Run 184-193 to a catalyst age of
2.3 Bbl/Lb and the desulfurlzation results from this run are
given in Figure 17.
Liquid product sulfurs obtained In this series of runs ranged
from 0.49 to 0.65 weight percent for the Gach Saran feed and
0.6 to 0.85 weight percent for the Tia Juana feed. The operat-
ing conditions for these runs were such that correlations could
be used to predict the operating conditions required for 0.5
weight percent fuel oil In an equilibrium catalyst situation.
The results from these operations confirmed the low catalyst
deactivation rates obtained in previous runs made under Phase
I of the present project.
43
-------
Figure 16. DESULFURIZATION OF DEMETALLIZED TIA JUANA VACUUM RESIDUUM
Run 184-192
Feed Compos i t i on
Gravity, °API 12.8
Sulfur, W % 1.91
Vanadium, ppm 219
Nickel, ppm 53
Operating Conditions
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, VF/Hr/VR
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B (Vent)
2000
760
1.0
0.104
4400
1.0 2.0
Catalyst Age, Bbl/Lb
3.0
-------
Figure 17. DESULFURIZATION OF DEMETALLIZED GACH SARAN VACUUM RES I
DUUM
Run 18*1-193
Feed Composition
Gravity, °API 13.1
Sulfur, W % 1.63
Vanadium, ppm 49
Nickel, ppm 38
Operating Conditions
Hydrogen Pressure, psig 2000
Temperature, °F 760
Liquid Space Velocity, Vp/Hr/VR 1.0
Catalyst Space Velocity, B/D/Lb 0.105
Hydrogen Rate, SCF/B (Vent) 4250
Catalyst Age, Bbl/Lb
-------
SPENT DESULFURIZATION CATALYST
A summary of analyses on samples of spent desulfurization cata-
lysts is given in Table 8. The amounts of vanadium and nickel
on the catalyst are much lower in comparison to those which
would have been observed if the feeds had not been demetallized,
It should also be noted that, at about the same catalyst age,
the vanadium loading on the catalyst in the case of the Tia
Juana feed is only about double that of the Gach Saran feed
even though the vanadium content of the demetal1ized Tia Juana
is about four times that of the Gach Saran feed.
The total level of metals in the demetallized feed gives no in-
dication of the rate of deactivating the desulfurization cata-
lyst. The determining factor is the ease with which the re-
maining metals can be removed from the demetallized products.
Metal balances for the two desulfurization runs are summarized
in Table 9.
PRODUCT YIELDS AND INSPECTIONS
Detailed product inspections were obtained on one product from
each of the desulfurization runs. The product taken for each
run was about the middle of the run. Summaries of yields and
product inspections are given in Tables D-3 and D-k of Appen-
dix D. An overall summary of the demetal1ization and desul-
furization process to produce 0.5 weight percent ^00°F+ fuel
oil from Tia Juana and Gach Saran vacuum residua is given in
Table 10. The 400°F+ fuel oil yield was about 97.6 volume per-
cent for Tia Juana and 98.1 volume percent for Gach Saran.
Naphtha yield was 7.5 volume percent for Tia Juana and 6.9
volume percent for Gach Saran.
Chemical hydrogen consumption in the desulfurization step ranged
from about 310 SCF/B for demetallized Tia Juana to about 415
SCF/B for demetallized Gach Saran.
-------
Table 8. ANALYSES OF SPENT DESULFURIZATION CATALYST
Demetallized Vacuum Catalyst Weight Percent Element on Spent Catalyst
Run No. Residuum Feed Age, Bbl/Lb C S V NI
184-191 Tia Juana 0.7 14.25 4.38 0.99 0.28
184-192 Tla Juana 1.9 17.62 5.16 1.90 0.51
184-193 Gach Saran 2.3 17.52 5.20 1.05 0.76
-------
Table 9. VANADIUM AND NICKEL BALANCES FROM DESULFURIZATION RUNS
-P-
co
Run Number
Desulfurization Catalyst Age, Bbl/Lb
Feed
Feed Vanadium, ppm
Feed Nickel, ppm
IN WITH THE FEED
Vanadium
Nickel
VANADIUM OUT
With Liquid Product
On Catalyst
Total
NICKEL OUT
With Liquid Product
On Catalyst
Total
184-192
1.9
Demetallized Tia Juana
Vacuum Residuum
219
53
Grams W % on Feed
9.39
2.27
8.18 87.1
1.84 19.5
10.02 106.6
1.69 74.4
0.49 21.6
2.18 96.0
1 8k- 1 93
2.3
Demetallized Gach Saran
Vacuum Residuum
49
38
Grams W % on Feed
2.56
1.98
1.37 53.5
0.98 38.3
2.35 91.8
1.17 59.1
0.71 35.8
1.88 9^.9
-------
Table 10. SUMMARY OF RESULTS ON THE DEMETALLIZATION
AND DESULFURIZATION OF VACUUM RESIDUA
(Feed and Product Analyses)
Vacuum Bottoms
Raw Feed
Demetal1ized Feed
Desulfurized Product
•P-
vo
Tia Juana
% Vanadium Removal
Sulfur, W %
Vanadium, ppm
Nickel, ppm
fy-ltOO'F, V %
400°F+, V 7o
2.9
570
75
62
1.81
219
53
18
0.51
1971
391
7.52
97.62
Gach Saran
% Vanadium Removal
Sulfur, W %
Vanadium, ppm
Nickel, ppm
(V400°F, V 70
400°F+, V %
3.72
291
110
83
1.63
^9
38
0.51
271
211
6-9?
98.12
1. On 400°F+ Fraction
2. Volume % of Raw Feed
-------
50
-------
SECTION VI I
PROCESS ECONOMICS
The major cost of producing low sulfur fuel oil from high metals
residuum feeds depends on the cost of the facility necessary to
carry out the demetal1ization and desulfurization operations,
the amount of hydrogen consumed during the process, and the cost
of the demetal1ization and desulfurization catalysts. Summaries
of investment requirements and operating costs for producing 1.0,
0.5, and 0.3 weight percent sulfur fuel oil from Gach Saran and
Tia Juana vacuum residua utilizing unpromoted bauxite and the
commercially prepared 1.0 weight percent molybdenum on 20 x 50
mesh activated bauxite in the demetal1ization step and the com-
mercial HDS beads in the desulfurization step are given in Tables
11 and 12, respectively.
The data computation for the 0.5 weight percent sulfur fuel oil
product case requires very little extrapolation from the operat-
ing conditions utilized in the experimental program. For the
1.0 weight percent and 0.3 weight percent sulfur fuel oil cases,
extrapolation of the data is necessary.
Results in Tables 11 and 12 indicated that the use of commercial
1.0 weight percent molybdenum catalyst in the demetal1ization
step in place of activated bauxite contributed to a saving in
investment costs of between $1.37 MM to $2.59 MM for the Tia
Juana vacuum residuum feed and between $1.20 MM to $2.30 MM for
the Gach Saran vacuum residuum feed (20,000 BPSD plant capacity)
The saving in operating costs ranged from $0.05 per barrel to
$0.07 per barrel for the Tia Juana feed and $0.04 per barrel to
$0.07 per barrel for the Gach Saran feed.
For both feeds, the operating cost, as well as the investment
costs, increased sharply as the level of sulfur in the fuel oil
was reduced from 0.5 to 0.3 weight percent. The curves showing
the variation of the operating cost for the Gach Saran and Tia
Juana vacuum residua with the fuel oil sulfur level are given
in Figure 18. The operating cost given in Tables 11 and 12 and
-------
Table 11. INVESTMENT AND OPERATING COST FOR A TWO STAGE
DEMETALLIZATION-DESULFURIZATION OPERATI ON
OF TIA JUANA VACUUM RESIDUUM
BASES: 1. Plant Capacity - 20,000 BPSD
2. 197*t Gulf Coast Construction
3. Hydrogen Cost - $0.50/1000 SCF
^f. Capital Charges - 25% of Investment Included in
the Operating Cost
5. Activated Bauxite Cost - $0.10/Lb
6. Commercial 1% Mo Catalyst Cost - $0.23/Lb
Catalyst
1 W % Sulfur Fuel Oil
Investment, MM$
Operating Cost, $/B
Unpromoted Bauxite
15.92
1.29
Commercial 1% Mo
Catalyst
13.33
1.22
0.5 W % Sulfur Fuel Oil
Investment, MM$
Operating Cost, $/B
1.69
17.07
1.63
0.3 W % Sulfur Fuel Oil
Investment, MM$
Operating Cost, $/B
20.15
2.08
18.78
2.03
52
-------
Table 12. INVESTMENT AND OPERATING COST FOR A TV>0 STAGE
DEMETALLIZATION-DESULFURIZATI ON OPERATI ON
OF GACH SARAN VACUUM RESIDUUM
BASES: 1. Plant Capacity - 20,000 BPSD
2. 197^ Gulf Coast Construction
3. Hydrogen Cost - $0.50/1000 SCF
k. Capital Charges - 25% of Investment Included in The
Operating Cost
5. Activated Bauxite Cost - $0.10/Lb
6. Commercial 1% Mo Catalyst Cost - $0.23/Lb
Commercial 1% Mo
Catalyst Unpromoted Bauxite Catalyst
1 W % Sulfur Fuel Oil
Investment, MM$ 1U.57 12.27
Operatinb Cost, $/B 1.23 1.16
0.5 W % Sulfur Fuel Oil
Investment, MM$ 17.72 16.06
Operating Cost, $/B 1.^7 1 >1
0.3 W % Sulfur Fuel Oil
Investment, MM$ 19.21 17.92
Operating Cost, $/B 1.66 1.62
53
-------
Figure 18. TOTAL OPERATING COST
TWO STAGE DEMETALLIZATION-DESULFURIZATION
OF GACH SARAN AND TIA JUANA VACUUM RESIDUA
Demetal1ization/Desulfurization
Symbol
O
•
D
•
Feed
Gach Saran
Gach Saran
Tia Juana
Tia Juana
Catalyst
Commercial 1% Mo/Beads
Unpromoted Bauxite/Beads
Commercial 1% Mo/Beads
Unpromoted Bauxite/Beads
Demetal1ization/Desulfurizatlon
Catalyst Cost. $/Lb
0.23/1.50
0.10/1.50
0.23/1.50
0.10/1.50
2.20
2.00
CO
U1
o
1.80
g1 1.60
to
9)
Q.
O
(0
•M
O
1.20
1.00
Fuel Oil Sulfur, W %
-------
in Figure 18 include capital charges which are 25 percent of
investment.
Estimated overall yield structure and product properties for
the production of 4oO°F+ fuel oil containing 1.0, 0.5, and 0.3
weight percent sulfur from Gach Saran and TIa Juana vacuum re-
siduum feeds are given in Tables 13 and 14, respectively.
55
-------
vn
ON
Table 13. ESTIMATED OVERALL YIELDS AND PRODUCT PROPERTIES
CONSECUTIVE DEMETALLIZATION AND DESULFURIZATION OF GACH SARAN VACUUM RESIDUUM
400°F+ Fuel Oil Sulfur, W % 1.0 0.5 0.3 —
Yields
W7o V°/o °API °/0S W°/0 V% °API °/0S W°/0 V% "API °/0S
H2S & NH3 3.2 3.9 4.1
C1-C3 0.8 1.1 1.3
C/f-^oo°F 3.6 5.0 63 <0.07 4.9 6.9 63 <0.07 6.1 8.5 63 <0.07
400-650°F 7.3 8.8 35 0.10 9.7 11.7 35 <0.07 11.8 14.2 35 <0.07
650-975°F 21.0 23.2 21 0.26 22.9 25.3 21.5 0.09 2k.3 26.9 21.5 <0.07
975°F+ 65.2 67.2 11.2 1.33 58.8 61.1 12.3 0.73 53.9 56.3 13 0.^7
F+ 93.5 99.2 15.3 1.0 91.4 98.1 17 0.5 90.0 97.4 18.2 0.3
TOTAL 101.1 104.2 17 0.96 101.3 105.0 19.4 0.47 101.5 105.9 21 0.28
-------
Table 14. ESTIMATED OVERALL YIELDS AND PRODUCT PROPERTIES
CONSECUTIVE DEMETALLIZATION AND DESULFURIZATION OF TIA JUANA VACUUM RESIDUUM
vn
400°F+ Fuel Oil Sulfur, W% 1.0 0.5 0.3
Yields
W% V°/0 "API %S W% V°/0 °API %S W°/0 V% "API %S
H2S & NH3 2.3 2.9 3.2
Ci-C3 1.0 1.3 1.6
C4-400°F 4.2 5.8 62 <0.07 5.4 7.5 62 <0.07 6.5 9.0 62 (0.07
400-650°F 9.1 10.8 3^ 0.1 10.7 12.7 3^ <0.07 12.7 15.1 3^ <0.07
650-975°F 2k.S 27.1 20 0.30 26.1 28.6 21.3 0.1 27.3 29.9 21.3 (0.07
975°F+ 59.5 60.4 10 1.43 54.8 56.3 11.5 0.78 50.1 51.8 12.5 0.50
400°F+ 93.5 98.3 15 1.0 91.6 97.6 16.9 0.5 90.1 96.8 18.2 0.3
TOTAL 101.0 104.1 17 0.96 101.2 105.1 19.4 0.47 101.4 105.8 21.1 0.28
-------
58
-------
SECTION VIU
APPENDICES
59
-------
60
-------
APPENDIX A
SUMMARY OF CATALYST SCREENING RUNS
61
-------
62
-------
Table A-1. SUMMARY OF CATALYST SCREENING RUNS
(Feed: Tia Juana Vacuum Bottoms)
Run No.
184-182
184-183
Period
No.
IB
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
IB
2
3
4
5
Catalyst Catalyst Temp.
HRI No. Catalyst Base Promoter Preparation °F
LX-28 Porocel 0.57 Mo HRI Lab 789
20 x 50 Mesh 7
-------
Table A-l. SUMMARY OF CATALYST SCREENING RUNS
(Feed: Tia Juana Vacuum Bottoms)
Run No.
184-184
184-185
184-186
184-187
Period
No.
IB
2
3
4
IB
2
3
4
IS
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
IB
2
3
4
Catalyst Catalyst
HRI No. Catalyst Base Promoter Preparation
3596 Porocel 2/ Mo
20 x 50 Mesh
3608
3610
Porocel
20 x 50 Mesh
Porocel
20 x 50 Mesh
I/ Mo
27 Mo
LX-22-6 Porocel 2/ Mo
20 x 50 Mesh
Preparat ion
Eng. Lab.
Eng. Lab.
Eng. Lab.
HRI Lab.
Temp.
°F
792
790
789
790
790
790
790
789
790
790
789
790
789
791
787
786
789
789
790
790
790
790
790
790
791
791
790
790
789
792
789
792
793
789
Hydrogen
Pressure
psiq
2000
2005
2000
2000
2010
2000
2000
2010
2000
2000
2010
2000
2000
2000
1985
1975
1995
1985
2020
1995
2000
1995
2000
2005
2000
2015
2015
1985
1975
2000
1985
1980
2000
2000
Space Velocity
Vo/Hr/Vr
0.60
0.51
0.52
0.52
0.4g
0.51
0.47
0.47
0.76
0.75
0.74
0.75
0.74
0.75
0.76
0.55
0.51
0.50
0.4g
0.52
0.51
0.51
0.50
0.4g
0.51
0.51
0.74
0.75
0.69
0.75
0.79
0.76
0.60
0.75
B/D/Lb
0.045
0.039
0.040
0.040
0.038
0.040
0.037
0.037
0.058
0.057
0.056
0.057
0.056
0.057
0.058
0.042
0.039
0.038
0.037
0.039
0.039
0.039
0.038
0.037
0.039
0.039
0.056
0.057
0.052
0.057
0.060
0.058
0.046
0.057
Hydrogen
Rate
SCF/Bbl
3741
4354
4118
3868
5050
4122
4369
4227
4822
4261
4012
3864
3834
4304
3640
3656
4107
4124
3935
3761
3906
3820
4061
4079
3851
4350
3877
3911
4355
3964
3680
4301
5303
4431
Catalyst
Age,
Bbl/Lb
0.038
0.074
0.1 14
0.154
0.037
0.077
0.1 14
0.151
0.047
0.104
0.160
0.217
0.273
0.330
0.388
0.430
0.469
0.507
0.544
0.583
0.622
0.661
0.699
0.736
0.775
0.814
0.870
0.927
0.979
1 .036
0.043
0.096
0.142
0.199
Product Inspections
Gravi ty
°API 7 S
15.8 1.28
16.0 0.84
15.9 1.14
16.3 1.03
14.0
16.8
15.5
16.2
14.9
14.6
14.4
14.9
14.8
15.0
15.5
13.7
15.2
16.6
15.3
14.8
15.4
16.4
15.3
15.1
14.8
17.2
14.0
13.8
14.8
14.4
12.7
14.7
13.8
14.3
.45
.31
.14
.05
.59
.34
.17
.32
.21
.16
.21
.25
.06
.23
.27
.29
.28
.33
.30
.25
.23
.27
.54
.49
.40
.46
.42
.39
.30
.34
PPm,
V
127
120
133
130
129
123
100
99
191
177
178
182
184
182
221
193
151
165
179
182
176
203
198
168
191
180
238
230
227
234
163
164
168
177
PPm.
Ni
39
39
44
44
3P
39
39
44
49
50
50
50
50
50
53
52
47
47
48
47
49
55
49
46
49
48
51
55
55
54
46
50
50
53
IBP-550°F
V '/
9
8
8
9
8
9
10
9
10
8
7
6
8
7
7
10
12
7
8
7
7
8
8
9
9
5
7
9
9
9
6
7
7
6
NOTE: Eng. Lab. - Prepared by Engelhard in laboratory equipment.
Eng. Comm. - Prepared by Engelhard in commercial equipment.
HRI Lab. - Prepared by Hyorocarbon Research in laboratory equipment.
-------
Table A-l. SUMMARY OF CATALYST SCREENING RUNS
(Feed: Tia Juana Vacuum Bottoms)
Run No.
184-188
184-189
185-224
vn
185-225
185-226
185-227
185-228
185-229
NOTE:
Period
). No.
18
19
4
5
6
7
8
)
Eng
Eng
HRI
IB
2
3
4
5
IB
2
3
4
5
IB
2
3
4
IB
2
3
IB
2
3
4
IB
2
3
4
IB
2
3
4
IB
2
3
4
. Lab.
. Comm.
Lab.
Catalyst
Promoter Preparation
17 Mo Eng. Lab.
17 Mo Eng. Comm.
27 Mo Eng. Lab.
5:7 Mo Eng. Lab.
27 Mo Eng. Lab.
27 Mo Eng. Lab.
2/ Mo Eng. Lab.
2/ Mo Eng. Lab.
Temp.
°F
790
789
789
791
788
789
789
790
790
790
791
790
790
792
787
789
792
788
789
789
790
789
785
788
790
789
789
790
789
788
790
790
790
Hydrogen
Pressure
psig
2005
2000
2010
2005
2000
1995
2000
2000
2000
2000
1985
2005
2000
2010
1910
2010
2030
2005
2010
1995
1970
1995
2020
2010
2010
2000
2000
2005
2000
2010
2000
2005
1990
Space
Vp/Hr/V
0.62
0.38
0.46
0.47
0.51
0.47
0.54
0.48
0.52
0.64
0.55
0.49
0.48
0.50
0.51*
0.53
0.47
0.50
0.51
0.51
0.45
0.51
0.54
0.53
0.53
0.60
0.53
0.51
0.53
0.55
0.52
0.51
0.50
Velocity
£ B/D/Lb
0.047
0.029
0.036
0.036
0.039
0.036
0.041
0.036
0.039
0.049
0.042
0.037
0.037
0.038
0.043
0.043
0.038
0.037
0.038
0.038
0.034
0.039
0.042
0.041
0.041
0.045
0.041
0.039
0.041
0.043
0.040
0.040
0.039
Hydrogen
Rate,
SCF/Bbl
3750
5307
4446
4413
4256
4202
3890
4537
4308
3266
4898
4769
5481
4gi4
2473
2541
5156
4134
6236
4989
4188
6941
4go4
5085
4530
3432
4125
4443
4305
3925
5111
5784
3730
Catalyst
Age
Bbl/Lb
0.038 .
0.063
0.099
0.135
0.174
0.032
0.071
0.107
0.146
0.195
0.034
0.068
0.105
0.140
0.036
0.081
0.117
0.033
0.069
0.107
0.141
0.043
0.085
0.126
0.164
0.035
0.076
0. 103
0.141
0.039
0.079
0.119
0.155
Product Inspections
Gravity
"API
14.4
17.2
16.0
16.8
16.1
16.6
16.8
16.2
16.3
16.3
17.1
16.7
16.9
16.5
13.2
15.2
13.7
15.0
15.4
15.1
15.9
15.7
15.9
16.1
16.6
15.0
16.0
16.4
15.3
15.3
16.0
15.9
15.8
7, S
1.21
0.91
0.93
0.88
1.19
1.10
1 .08
1.07
1.00
1.12
1.18
0.87
1.13
1.00
1.41
1.58
1.69
1.25
1.02
1.06
1.06
1.17
1.01
1.03
1.10
1.30
0.99
0.90
1.11
1.27
1.12
1.01
1.00
ppm
V
155
122
149
129
162
126
138
136
165
187
101
79
91
99
141
13^
289
147
127
138
122
116
119
123
133
156
109
117
128
128
115
116
134
ppm
Ni
39
36
39
40
43
33
39
39
42
<*5
30
33
37
39
41
39
52
40
48
49
38
32
35
38
39
37
33
37
44
40
42
39
43
IBP-550°F
V /
5
10
10
9
8
7
9
9
8
8
9
9
10
11
7
11
1 1
7
11
10
12
8
10
9
11
11
9
9
10
6
8
8
12
Catalyst
HRI No. Catalyst Base
3630 Porocel
20 x 50 Mesh
3634 Porocel
20 x 50 Mesh
3581 Porocel
20 x 50 Mesh
3582 Porocel
20 x 50 Mesh
3583 Porocel
20 x 50 Mesh
3598 Porocel
20 x 50 Mesh
3594 Porocel
20 x 50 Mesh
3597 Porocel
20 x 50 Mesh
Prepared by EngeHiard in laboratory equipment.
Prepared by Engelhard in commercial equipment.
Prepared by Hydrocarbon Research in laboratory equipment.
-------
Table A-I. SUMMARY OF CATALYST SCREENING RUNS
(Feed: Tia Juana Vacuum Bottoms)
Run No.
185-230
185-231
ON
185-233
Period
No.
IB
2
3
4
IB
2
3
4
S
6
7
8
9
10
11
12
13
1A
15
16
17
18
19
20
21
22
23
2k
25
26
27
IB
2
3
4
5
Catalyst Catalyst
HRI No. Catalyst Base Promoter PreparatIon
3609 Porocel
20 x 50 Mesh
3608 Porocel
20 x 50 Mesh
0.5/ Mo
I/ Mo
3635
Porocel
20 x 50 Mesh
I/ Mo
Preparat ion
Eng. Lab.
Eng. Lab.
Eng. Comm.
Variation
Temp.
°F
791
792
790
790
786
790
788
789
792
791
790
790
790
790
790
789
788
791
791
789
790
790
789
788
791
790
791
790
790
790
790
788
791
791
791
791
Hydrogen
Pressure
psig
2015
2010
2000
2025
1970
1990
2010
2000
1990
2000
2000
2000
2000
2005
2000
1990
1975
1995
2000
1995
1990
1995
2005
1990
2005
2000
1995
2000
2000
2000
1995
2000
2000
2010
2010
2000
Space Velocity
Vp/Hr/Vr
0.52
0.52
0.5**
0.46
0.83
0.75
0.70
0.79
0.78
0.78
0.5**
0.4g
0.53
0.53
0.78
0.74
0.72
0.84
0.77
0.76
0.77
0.75
0.78
0.77
0.76
0.79
0.77
0.78
0.77
0.78
0.77
0.46
0.56
0.50
0.51
0.52
B/D/Lb
0.042
0.042
0.043
0.037
0.063
0.057
0.053
0.060
0.060
0.059
0.041
0.038
0.040
0.040
0.059
0.056
0.055
0.064
0.059
0.058
0.059
0.057
0.060
0.059
0.058
0.060
0.059
0.059
0.059
0.059
0.059
0.031
0.038
0.034
0.034
0.035
Hyd rogen
Rate,
SCF/Bbl
4259
4148
4048
4717
3644
39^8
5475
484g
^873
3801
4800
4331
3906
5572
4687
4146
5342
3699
4473
4437
4231
4431
4336
3787
4383
4436
4107
4066
3899
4259
4076
5626
3823
6569
5478
599**
Catal yst
Age,
Bbl/Lb
0.042
0.084
0. 127
0.164
0.049
0.09**
0.147
0.207
0.267
0.326
0.367
0.405
0.445
0.485
0.544
0.600
0.655
0.719
0.778
0.836
0.895
0.952
.012
.071
.129
.189
.248
.307
.366
.425
-**79
0.039
0.077
0.111
0. 145
0. 180
Product Inspections
Gravi ty
°API / S
14.7
15.5
13. <*
14.6
15.4
15.2
14.6
14.0
14 3
14!8
14.9
14.4
15.4
16.8
13.7
14.6
14.7
14.5
14.2
13.7
14.1
14.2
14.2
13.8
13.5
13.7
12.9
13.8
14.0
14.1
I1*. 5
17.6
'16.5
16.0
16.8
15.9
.59
.62
.28
.35
.68
.55
.51
.63
.49
.57
.40
.16
.23
.22
.43
.66
.48
.55
.59
.49
.58
.34
.53
.70
.75
.68
.73
.78
.85
.72
.17
.25
.10
.09
.22
.20
ppm,
V
159
161
141
138
189
185
194
199
198
209
163
199
156
151
203
203
202
218
201
212
222
223
225
246
232
233
228
231
231
228
230
97
130
131
132
ppm,
Ni
41
43
45
44
48
1*7
49
51
50
57
44
48
46
44
49
49
51
55
52
49
52
50
52
51
60
60
56
53
53
52
29
39
39
40
39
IBP-550°F
V /
8
7
9
10
5
4
4
5
5
8
6
10
8
16
7
5
6
7
6
9
6
9
6
9
9
8
9
7
7
6
8
6
9
8
9
7
NOTE: Eng. Lab. - Prepared by Engelhard in laboratory eguipment.
Eng. Cotnm. - "repared by Engelhard in commercial equipment.
HRI Lab. - Prepared by Hydrocarbon Research in laboratory equipment.
-------
APPENDIX B
SUMMARY OF DEMETALLIZATION RUNS
67
-------
68
-------
Table B-l. SUMMARY OF DEMETALLIZATION RUNS
Product Inspections
Catalyst Catalyst
Run No. -Period HRI No. Base
184- 1 90- IB 3634 Porocel
2 20 x 50 Mesh
3
it
5
6
7
8
9
10
11
12
CT> 1-3
VO 3
14
15
16
17
18
19
20
21
22
23
2l«
185-235-1B 3634 Porocel
2 20 x 50 Mesh
3
4
5
6
7
8
9
10
Catalyst Temp.
Promoter Preparation Feed °F
I0/ Mo Engelhard Tia Juana 793
Commercial Vac. Btms. 788
790
790
790
792
792
790
79^
791
792
791
790
792
791
790
791
792
792
790
790
789
790
789
17 Mo Engelhard Gach Saran 788
Commercial 790
786
787
789
788
790
787
786
790
H2
Pres.
psiq
2010
2025
2010
1S90
1995
2000
2005
2025
2000
2015
2015
2015
2030
2030
2010
2015
2035
2025
2005
2005
2010
2005
2000
2005
1980
2023
2008
2010
1995
1985
1995
1988
1970
1977
Space
Velocity
Vn/Hr/Vr B/D/Lb
0.90
0.79
0.75
0.63
0.71
0.79
0.81
0.82
0.71
0.77
0.72
0.72
0.73
0.75
0.74
0.74
0.78
0.74
0.80
0.79
0.74
0.77
0.77
0.76
0.75
0.84
0.83
0.79
0.77
0.72
0.75
0.76
0.74
0.80
0.067
0.059
0.056
0.047
0.053
0.059
0.060
0.061
0.053
0.057
0.054
0.053
0.054
0.056
0.055
0.055
0.058
0.055
0.059
0.059
0.055
0.057
0.057
0.057
0.057
0.064
0.063
0.060
0.058
0.055
0.057
0.058
0.056
0.060
H2
Rate
SCF/Bbl
3232
3833
4155
4670
4737
4306
4031
3949
4626
3932
4081
4438
4530
4328
4204
4252
4076
4253
3830
3853
4055
3888
3922
4104
3551
4399
6099
4726
4504
4816
6125
5099
3894
5683
Cat.
Age,
Bbl/Lb
0.050
0.109
0.165
0.212
0.265
0.324
0.384
0.445
0.498
0.555
0.609
0.662
0.716
0.772
0.827
0.882
0.940
0.995
.054
.113
.168
.225
.282
.339
0.050
0.114
0.177
0.237
0.295
0.350
0.407
0.465
0.521
0.581
Gravity
°API y_ s
15.5
13.8
14.6
14.9
14.9
14.9
14.2
13.6
14.3
14.1
14.9
15.8
15.1
14.2
14.4
14.1
14.1
13.0
13-4
13.2
14.0
13-8
13.8
13.4
15.7
15.3
15.1
14.9
14.6
15.3
15.0
14.6
.69
.49
.48
.43
.42
.53
.58
.67
.63
.53
.58
.45
.60
.57
.57
.68
.69
.58
.44
.64
.56
.80
.79
.99
.56
.53
.58
.54
.45
.57
.50
.53
14.5 1.79
13.7 1 . 76
V
ppm
194
198
191
185
195
201
226
226
224
219
210
210
222
235
221
252
248
242
262
259
268
278
265
272
32
35
37
36
36
37
33
39
36
40
Ni
ppm
45
46
45
47
50
50
56
56
50
48
49
49
49
50
49
49
51
50
52
50
52
57
54
54
27
29
33
39
36
38
37
40
38
41
IBP-
550°F
V 7
5
6
5
7
7
7
6
7
6
6
7
7
7
5
7
4
5
7
7
6
5
5
4
6
5
7
8
6
6
6
6
6
6
5
-------
Table B-1. SUMMARY OF DEMETALLIZATION RUNS
Product Inspections
Run No. -Period
185-235-11
12
13
I1*
15
16
17
18
19
20
21
22
23
2*4
25
26
27
28
185-236- IB
2
3
*4
5
Catalyst Catalyst Catalyst Temp.
HRI No. Base Promoter Preparation Feed °F
363*4 Porocel I/ Mo Engelhard Gach Saran 789
20 x 50 Mesh Commercial 792
790
790
790
790
789
789
790
789
789
791
790
790
789
790
791
787
363*4 Porocel 1 / Mo Engelhard Bachaquero 788
20 x 50 Mesh Commercial 792
789
790
789
H2
Pres.
psig
1985
2010
2000
1975
198*4
1998
1989
2007
2003
2000
1993
2000
1983
1990
1988
1993
2018
2008
1983
1986
1983
1981
1998
Space
Vo/Hr/V
0.72
0.76
0.81
0.75
0.79
0.75
0.71
0.7**
0.77
0.72
0.73
0.76
0.60
1.00
0.71
0.76
0.86
0.76
0.68
0.72
0.7**
0.75
0.72
Velocity
r B/D/Lb
0.05*4
0.058
0.061
0.057
0.059
0.057
0.05**
0.056
0.058
0.05'+
0.055
0.058
0.0*45
0.076
0.05*4
0.058
0.065
0.058
0.051
0.053
0.055
0.056
0.053
H2 Cat.
Rate Age,
SCF/Bbl Bbl/Lb
*4515 0.635
1436*4 0.693
5623 0.75*4
3720 0.811
39'3 0.870
*4*478 0.927
632*4 0.981
39*43
*4922
5510
*4l53
*4*405
3718
2935
6055
<4573
39*41
5833
.037
.095
. 1*49
.20*4
.262
.281
.357
.*4ll
.469
.53*4
.590
*4l9! 0.0*45
U*400 0.100
*4l78 0.153
*»0*40 0.209
51*45 0.262
Gravi ty
"API 7 S
!*».3 .65
1*4. *4
1*4.6
1*«.7
1*4.8
1*4.6
15.3
1*4.8
1*4. *4
1*4.0
l*t.9
1*4.6
15.7
1*4. *4
1*4.9
13.5
13.9
1*4.2
15.2
1*4.8
15. *4
.66
.66
.56
.61
.72
.66
.60
.71
.6*4
.68
.60
.61
.55
.5*«
.70
.65
.78
.52
.58
.*48
1*4.6 1.61
1*4.8 1.63
V
PPm
SLC. —
39
*»*4
*4*4
*4*4
*48
51
*49
*4*4
51
52
52
52
5*4
52
61
63
63
6*4
167
18*4
199
202
20*4
Ni
Ppm
^^
35
35
38
37
37
37
38
38
*4l
*4l
*40
*4l
38
39
*40
*4l
*4l
*43
*46
51
52
60
59
IBP-
550°F
V 7
8
7
8
6
5
6
9
8
13
12
9
6
6
9
9
7
7
7
6
8
8
7
8
-------
APPENDIX C
SUMMARY OF DESULFURIZATION RUNS
71
-------
72
-------
Table C-1. SUMMARY OF DESULFURIZATION RUNS
Run No.-Period
184-191-16
2
3
4
5
6
7
184-192-1B
2
3
4
5
6
7
8
I 9
» 10
II
12
13
14
15
16
17
18
184-193-1B
2
3
5
6
7
8
9
10
II
12
13
14
15
16
17
Catalyst Catalyst Demetallized Oemetallized
HRI No. Base Feed Over
3104 Amer. Cy. TIa Juana Comm. Demet.
0.02" Beads Vac. Btms. Catalyst
HRI 363^
3104 Amer. Cy. Tia Juana Comm. Demet.
0.02" Beads Vac. Btms. Catalyst
KRI 3634
3104 Amer. Cy. Gach Saran Comm. Demet.
0.02" Beads Vac. Btms. Catalyst
HRI 3634
Temp.
°F
757
761
758
759
761
763
761
757
758
762
759
762
760
760
760
760
761
758
759
760
759
761
763
760
761
758
761
761
759
759
759
761
760
758
758
763
762
762
760
760
760
760
Hydrogen
Pressure Space Velocity
psiq Vp/Hr/Vr
2000 1.00
2018
2020
2008
1992
1983
1984
1998
1980
2007
1988
2005
1997
1968
1993
2012
2007
2002
1989
1987
2002
2015
2010
2029
2032
1980
1977
2002
1992
2000
2018
2000
2020
21 18
2018
2002
2004
1993
2015
2020
2000
2035
.11
.00
.03
.08
.01
.68
.01
.96
.99
.08
.12
.08
.00
.17
.02
.04
.22
.95
.91
.17
.11
.14
.13
.08
.08
.06
.01
.04
.02
.04
.06
.04
.05
.07
.07
.04
.07
.05
.06
.1 1
.03
B/D/Lb
0.109
0.119
0.107
0.109
0.115
0.108
0.073
0.105
0.100
0.103
0.112
0.116
0.112
0.104
0. 122
0.106
0.108
0. 127
0.098
0.094
0. 122
0.116
0. 119
0.117
0.112
0.113
0.111
0.106
0. 109
0.107
0. 109
0.111
0. 109
0.111
0. 112
0. 112
0.109
0. 112
0. 1 10
0.111
0. 117
0. 108
Hydrogen
Rate
SCF/Bbl
3339
3208
3901
3929
3958
4026
5620
4753
4983
4964
4319
4619
4546
4736
3969
44ig
4386
3563
4820
5225
3834
3895
3758
4012
4290
5339
4928
4010
4253
4220
4061
4628
4652
4422
4142
409?
4287
4067
4027
4095
451 1
4663
Catalyst
Age
Bbl/Lb
0.083
0.202
0.309
0.418
0.533
0.641
0.714
0.099
0. 174
0.277
0.389
0.505
0.617
0.721
0.843
0.949
1.057
1.184
.282
.376
.498
.614
.664
.781
.893
0.117
0.233
0.335
0.444
0.551
0.660
0.771
0.880
0.991
.103
.215
.324
.436
.546
.657
.774
.882
Product Inspections
Gravi ty
"API
16.7
17.4
16.4
17.0
17.2
16.8
16.7
15.9
16.9
17.0
16.1
16.1
15.6
16.1
16.4
16.6
16.3
16.0
16.3
16.4
16.7
16.8
17.4
16.3
16.2
17.2
16.8
16.6
16.8
17.2
17.5
18.2
16.4
16.8
16.4
17.7
17.9
17.4
7- S
0.67
0.76
O.Q7
0.83
0.91
0.90
0.82
0.96
0.86
0.85
0.83
0.74
0.61
0.64
0.69
0.77
0.80
0.85
0.81
0.79
0.86
0.81
0.72
0.73
0.73
0.50
0.4g
0.59
0.55
0.58
0.60
0.52
0.50
0.56
0.52
0.56
0.65
0.66
V
ppm
176
166
169
193
191
189
191
195
193
193
197
198
194
194
189
190
194
196
192
190
207
206
199
206
207
30
29
30
29
29
30
28
28
28
29
24
25
26
Ni
ppm
39
40
41
40
39
39
40
36
36
38
41
40
41
39
43
42
42
41
43
43
43
42
39
37
41
20
19
19
22
23
24
23
23
23
22
24
25
25
IBP-550°F
V J
1
5
4
6
6
6
5
4
5
5
5
9
6
7
6
5
8
5
6
7
6
5
6
6
6
4
6
5
5
5
5
5
5
5
5
7
5
6
Amer. Cy. = American Cyanamid
No analyses were conducted on the products.
-------
Table C-l. SUMMARY OF DESULFURIZATION RUNS
Run No.-Period
184-193-18
19
20
21
201-83- IB
2
3
4
5
6
7
8
Catalyst Catalyst Demetallized Demetallized Temp.
HRI No. Base Feed Over °F
3104 Amer. Cy. Gach Saran Ccxnm. Demet . 760
0.02" Beads Vac. Btms. Catalyst 762
HRI 3634 759
760
3104 Amer. Cy. Tia Juana LX-28 763
0.02" Beads Vac. Btms. (0.5c/= Mo) 760
760
760
760
761
757
760
Hydrogen
Pressure
psiq
2000
2010
2010
2010
2000
2010
2000
2005
1990
1990
1990
2000
Space Velocity
Vo/Hr/Vr
1.08
1.07
1 .00
1.08
1.18
1.00
1.08
1.22
1.06
0.97
0.95
1.03
B/D/Lb
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
113
112
105
113
124
105
113
128
111
102
101
108
Hydrogen
Rate
SCF/Bbl
4066
4134
39^5
4661
4g6l
4269
3792
4425
4687
4888
4122
Catalyst
Age
Bbl/Lb
1.995
2.107
2.212
2.325
0.097
0.174
0.287
0.415
0.526
0.628
0.729
0.829
Product Inspections
Gravity
"API
16.6
16.0
16.7
17.0
16.6
16.0
16.0
15.8
16.1
16.0
"/ S
0.53
0.57
0.59
0.52
0.45
0.53
0.59
0.60
0.57
0.57
V
ppm
115
116
121
118
112
Ni
ppm
40
38
38
38
37
IBP-550°F
V 7
4
3
f
1
6
6
7
7
6
7
Amer. Cy. = American Cyanamid
••'•• No analyses were conducted on the products.
a. IBP-600°F for Run 201-83.
-------
APPENDIX D
OPERATING CONDITIONS. YIELDS. AND PRODUCT PROPERTIES
75
-------
-------
Table D-1. OPERATING CONDITIONS. YIELDS. AND PRODUCT PROPERTIES
Run Number
Catalyst Age, Bbl/Lb
Feed
HRI Identification No.
Catalyst
HRI No.
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/Hr/V
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B (Vent)
Reactor Type
Hydrogen Consumption, SCF/B
975°F+ Conversion, V %
YIELDS
H2S &
C,-C3
NH3
|BP-500°F
500-650°F
650°F+
650-975°F
975° F+
Total
C4+
Gravity,
API
Sulfur, W 7o
Vanadium/Nickel
£RACTION. °F
\l % on Feed
Gravity, "API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No., cgs/gm
/\nil ine Point, °F
Pour Point, °F
Flash Point, °F
ASTM Color
RCR, W %
Vanadium ppm
Nickel, ppm
Viscosity, SUS (?> 210°F
, SFS (S> 210°F
Calculated from correlations
219
53
77
184-190 Composite
0.05-1.34
Tia Juana Vacuum Residuum
3615
Comm. Demet. Catalyst
(20 x 50 Mesh Porocel - 1% Mo)
3634
2010
791
0.76
0.057
4100
Downflow
(350)
17.6
0.7*
2.5
4.5
94.7
22.2
72.5
102.4
13.2
1.80
218/53
Coll.
12J8
1.81
10^96
1.50
4900
IBP-
500-
2.5
30.3
0.11
500-
650
29 '.9
0.51
650+
llil
(1.87)
650-
2272
19.8
1.00
975+
72.5
8.6
2.12
10.6
13.5
143
110
585
174
75
185
286
19.0
295
67
-------
Table D-2. OPERATING CONDITIONS. YIELDS. AND PRODUCT PROPERTIES
Run Number
Catalyst Age, Bbl/Lb
Feed
HRI Identification No.
Catalyst
HRI No.
185-235-1*+
0.81
Gach Saran Vacuum Residuum
3574
Comm. Demet. Catalyst
(20 x 50 Mesh Porocel - 1% Mo)
3634
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/Hr/V
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B (Vent)
Reactor Type
Hydrogen Consumption, SCF/B
975° F+ Conversion, V %
YIELDS
H2S & NH3
Ci-C3
C4-C6
IBP-500°F
500-650° F
650° F+
650-975° F
975° F+
Total
Gravity, °API
Sulfur, W %
Vanadium/Nickel
FRACTION. °F
V % on Feed
Gravity, °API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No., cgs/gm
Aniline Point, °F
Pour Point, °F
Flash Point, °F
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS
, SFS
44
37
1975
790
0.75
0.057
3700
Downflow
515
20.9
W°/Q
2.5
0. 8**
0.4**
3.4
3.7
90.0
17.2
72.8
100.8
V%
IBP-
500
"473
41.2
0.02
12.5
14.1
1.49
44/37
500-
650 650+
"475 93.0
38.5 10.7
0.37 1.61
14.4
136
105
0.7**
4.3
4.6
93.0
18.6
74.4
102.6
650-
975
TO
17.6
0.84
163
90
ffi
8.9
1.78
550
122°F
210°F
17.3
59
51
132
Insufficient sample
Calculated from correlations
78
-------
Table D-3. OPERATING CONDITIONS. YIELDS. AND PRODUCT PROPERTIES
Run Number
Catalyst Age, Bbl/Lb
Feed
HRI Identification No.
Demetal 1 ized Over
Catalyst
HRI No.
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/Hr/V
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B (Vent)
Reactor Type
Hydrogen Consumption, SCF/B
975°F+ Conversion, V %
YIELDS
H2S & NH3
C,-C3
C4-C6 o
|BP-500°F
500-650° F
650°F+
650-975°F
975°F+
Total
API
184-192-8
0.84
Demetal1ized Tia Juana
Vacuum Residuum
L-385
Comm. Demet. Catalyst
(1% Moly, HRI 363*0
American Cyanamld
0.02" Beads
3104
1990
760
1.17
0.122
4000
Downflow
310
10.0
W%
%
Gravity,
Sulfur, W
Vanadium/Nickel
£RACTION . °F
V % on Feed
Gravity, °API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No. , cgs/gm
Aniline Point, °F
Pour Point, °F
Flash Point, °F
ASTM Color
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS <® 210°F
, SFS & 210°F
Coll.
Llq.
99.8
15.5
0.69
87.^7
11.28
3720
189
75
500
V°/o
0.7
0.5*
2.5
5.9
89.5
24.5
65.0
100.5
IBP-
500
3.0
39.8
<0.02
2.1
16.0
0.69
188/43
500-
650 650+
"577 90.1
31.1 13.5
<0.02 0.86
5.9
141
0.8*
3.0
6.7
90.1
25.9
64.2
100.6
650-
1Z5_
25.9
21.1
0.22
171
70
D8.0
226
11.1
0.97
16.7
315
58
* Calculated from correlations
79
-------
Table D-4. OPERATING CONDITIONS. YIELDS. AND PRODUCT PROPERTIES
Run Number
Catalyst Age, Bbl/Lb
Feed
HRI Identification No.
Demetal1ized Over
Catalyst
HRI No.
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/Hr/V
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B (Vent)
Reactor Type
Hydrogen Consumption, SCF/B
975°F+ Conversion, V %
YIELDS
H2S & NH3
Cl-C3
Ck-C6
IBP-500°F
500-650°F
650°F+
650-975°F
975°F+
Total
C4+
Gravity, °API
Sulfur, W %
184-193-15
1.66
Demetal1ized Gach Saran
Vacuum Residuum
L-390
Comm. Demet. Catalyst
(1% Holy, HRI 363^)
American Cyanamid
0.02" Beads
3104
2020
760
1.06
0.111
4100
Downflow
415
7.6
W°/0
0.8
0.5
2.8
5.6
89.5
23.7
65.8
100.6
V70
0.9
3.3
6.3
90.7
25.1
65.6
101.2
17.2
0.51
FRACTION. °F
V 7o on Feed
Gravity, °API
Sulfur, W %
Carbon, W 7o
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No., cgs/gm
Pour Point, °F
RCR, W %
Viscosity, SUS & 122°F
, SFS (3) 210°F
Coll.
• •
100.3
16.7
0.51
88.09
11.54
1.56
3900
IBP-
500
3.3
38.6
<0.02
500-
650
6.3
29.9
0.07
650+
90.7
13.8
0.57
650-
2ZL_
25.1
19.7
0.16
975+
65.6
11.0
0.66
3.5
5.5
80
54
90
204
13.5
80
-------
APPENDIX E
CONVERSION TABLE
81
-------
82
-------
APPENDIX G
CONVERSION TABLE
Variable British Units Metric Units Conversion Factor
Temperature Degrees Fahrenheit, °F Degrees Centigrade, CC °C = 5/9(°F-32)
Pressure Pounds per Square Inch Kilograms per Square Kq/cm^ = Pp'g
Gauge, psig Centimeter, Kg/cm^ 1^.22
Hydrogen Rate Standard Cubic Feet per Normal Cubic Meters per
Barrel, (60°F, 1 Atm.) Cubic Meter, NM3/M3 NM3/M3 = 0.l68(SCF/Bbl)
(08C, 760 mm Hg)
-------
-------
TECHNICAL REPORT DATA
(f lease read Instructions on the reverse before completing)
1. REPORT NO.
EPA-650/2-73-041-a
3. RECIPIENT'S ACCESSION>NO.
4. TITLE AND SUBTITLE
De metallization of Heavy Residual Oils--Phase E
5. REPORT DATE
February 1975
6. PERFORMING ORGANIZATION CODE
7. AUTHOH(S)
M. C. Chervenak, P. Maruhnic, and G. Nongbri
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Hydrocarbon Research, Inc.
New York and Puritan Avenues
Trenton, NJ 08607
10. PROGRAM ELEMENT NO.
1AB013; ROAP 21ADD-050
11. CONTRACT/GRANT NO.
68-02-0293
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
NERC-RTP, Control Systems Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPOHT AND P£RJ
Phase E; 1/74-12/74
ODCOVERED
14. SPONSORING AGENCY CODE
jg. SUPPLEMENTARY NOTES
RACT
The report gives Phase n results of a study of demetallization of heavy residual
oils. Phase I was an experimental laboratory investigation to find a new low- cost
demetallization catalyst for high metals, high sulfur residual oils. Phase n
utilized the Phase I results to test the effectiveness of a demetallization catalyst
•when prepared on a commercial scale. The commercial production catalyst was
tested for activity and aging characteristics and compared to laboratory prepared
catalysts. The report includes descriptions of the catalyst, test units, and operating
conditions and procedures.
17-
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS C. COS AT I Field/Group
Pollution
Residual Oils
jjydrogenation
Vanadium
gulfur
Nickel
Contaminants
Catalysts
Scavengers (Materials)
Fossil Fuels
Desulfurization
Air Pollution Control
Stationary Sources
Demetallization
Promoter
Pre treatment
Clean Fuels
13B
11H, 21D
07C 07D
11F, 07 B 11G
07A
DISTRIBUTION STATEMENT
tJnlimited
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
85
20. SECURITY CLASS (This page J
Unclassified
22. PRICE
If*
form 2220-1 (9-73)
85
------- |