EPA-600/2-76-165
June 1976
Environmental Protection Technology Series
DEMETALLIZATION OF HEAVY RESIDUAL OILS
Phase Iff
Industrial Environmental Research Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Research Triangle Park, North Carolina 27711
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into five series. These five broad
categories were Established to facilitate further development and application of
environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interlace in related fields.
The five series are:
1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
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.
EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental
Protection Agency, and approved for publication. Approval
does not signify that the contents necessarily reflect the
views and policy of the Agency, nor does mention of trade
names or commercial products constitute endorsement or
recommendation for use.
This document is available to the public through the National Technical Informa-
tion Service. Springfield, Virginia 22161.
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EPA-600/2-76-165
June 1976
DE METALLIZATION
OF HEAVY RESIDUAL OILS
PHASE III
by
M. C. Chervenak, P. Maruhnic, and G. Nongbri
Hydrocarbon Research, Inc.
New York and Puritan Avenues
Trenton, New Jersey 08607
Contract No. 68-02-0293
ROAPNo. 21ADD-050
Program Element No. 1AB013
EPA Project Officer: William J. Rhodes
Industrial Environmental Research Laboratory
Office of Energy, Minerals, and Industry
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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ABSTRACT
Under Phase I work of Contract No. 68-02-0293 funded by the
Environmental Protection Agency, a new low cost demetalHzation
catalyst for heavy petroleum residual oils was developed at the
Trenton laboratory of Hydrocarbon Research, Inc., a subsidiary
of Dynalectron Corp. Work under Phase I I optimized promoter
metal on the support,-commercial production capabilities were
demonstrated by the production of a 10,000 pound batch by Minerals
and Chemicals Division of Engelhard Corporation, and activity and
aging characteristics were tested on two vacuum residua. The
dernetallized products from these two residua were desulfurized
over commercial HDS beads and costs were calculated to produce
low sulfur fuel oil and compared against costs using unpromoted
activated bauxite.
The present Phase III work optimized operating conditions in
the demetal1ization step for overall desulfurization. Bachaquero
Export and Lloydminster vacuum residua were demetallized to
different levels of vanadium .removal, the products desulfurized
over commercial HDS catalyst at various operating conditions and
minimum operating costs were calculated to produce low sulfur
fuel oil.
Descriptions of test units, operating conditions and procedures
are given, including run summaries, and tables of feedstock,
product and catalyst inspections. Graphs and tables depicting
operating costs for producing 0.3, 0.5 and 1.0 weight percent
(W %) sulfur fuel oil are given, along with various correlations
among demeta11ization levels, catalyst deactivation, demetal1-
ization rate constant and contaminant metals deposited on
catalyst.
Conclusions based on experimental results are given.
m
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iv
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CONTENTS
Page
No.
Abstract Mi
List of Figures vil
List of Tables xi
Glossary xv
1. CONCLUSIONS 1
2. INTRODUCTION 3
3. EXPERIMENTAL; DEMETALLIZATION 5
3.1 Apparatus and Procedures 5
3.2 Catalyst Description and Inspections 8
3.3 Bachaquero Export Vacuum Residuum;
Preparation and Inspections 8
3.3.1 Low Level Demetal1ization ]]
3.3.2 Medium Level Demetal1ization 15
3.3.3 High Level Demeta11ization 17
3.** Lloydminster Vacuum Residuum;
Preparation and Inspections 21
3.4.1 Demeta11ization to 45-60%
Vanadium Removal 21
3.^.2 Demetal1Ization to 80-85%
Vanadium Removal 25
3.5 Kinetics of Demetal1ization 25
3.6 Spent Demeta11ization Catalyst Inspections 28
3.7 Catalyst Deactivation Correlations 31
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CONTENTS
Page
No.
4. EXPERIMENTAL; DESULFURIZATION 35
4.1 Apparatus and Procedures 35
4.2 Catalyst Description and Inspections 35
4.3 Demetallized Bachaquero Export
Vacuum Residuum 36
4.3.1 Products from Low Level
Demetalltzation 36
4.3.2 Products from Medium Level
Demetallization 36
4.3.3 Products from High Level
Demetallizat7on 40
4.4 Demetallized Lloydminster Vacuum Residuum 45
4.4.1 Products .from Medium Level
Demetallizat?on 45
4.4.2 Products from High Level
Demetallization 45
4.5 Spent Desulfurization Catalyst Inspections 49
4.6 Desulfurization Correlations 52
4.7 Correlated Fuel Oil Properties 56
5. PROCESS ECONOMICS 61
6. APPENDICES: 71
A Summary of Demetallization Runs 73
A-l Demetallization Operating Conditions,
Yields and Product Properties 79
B Summary of Desulfurization Runs 89
B-l Desulfurization Operating Conditions,
Yields and Product Properties 97
vi
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LIST OF FIGURES
Figure Page
No. Title No.
1 Fixed Bed Demetallization Unit 6
2 Fixed Bed Demetallization Reactor 7
3 Demetallization Catalyst HRI 363^ 10
k Demetallization of Bachaquero Export
Vacuum Residuum Over 1.0 W % Molybdenum/
20x50 Mesh Bauxite 13
5 Desulfurization Obtained During Demetal-
lization of Bachaquero Export Vacuum
Residuum Over 1.0 W % Molybdenum/20x50
Mesh Bauxite ]k
6 Demetallization and Desulfurization j
Obtained During Demetallization of
Bachaquero Export Vacuum Residuum Over
1.0 W % Molybdenum/20x5Q Mesh Bauxite '6
7 • Demetallization of Bachaquero Export
Vacuum Residuum Over 1.0 W % Molybdenum/
20x50 Mesh Bauxite 19
8 Sulfur and Nickel Removals as Function of
Vanadium Removal During Demetallization of
Bachaquero Export Vacuum Residuum on 1 %
Molybdenum/20x50 Mesh Bauxite 20
9 Demetallization of Lloydminster Vacuum
Residuum Over 1 W % Molybdenum/20x50
Mesh Bauxite 23
10 Desulfurization Obtained During Demetal-
lization of Lloydminster Vacuum Residuum
Over 1 W % Molybdenum/20x50 Mesh Bauxite 2k
11 Sulfur and Nickel Removal as Function of
Vanadium Removal During Demetallization of
Lloydminster Vacuum Residuum on 1 % Molyb-
denum/20x50 Mesh Bauxite 26
vii
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LIST OF FIGURES
Figure Page
No. Title No.
12 Kinetics of Demetal1ization 27
13 Effect of Level of Vanadium Removal on the
Rate of Catalyst Deactivation 32
14 Variation of Demetal1ization Rate Constant
with Vanadium Loading on the Catalyst 33
15 Desulfurization of Low Level (40-45% Vana-
dium Removal) Demetallized Bachaquero
Export Vacuum Residuum Over 0.02" HDS Beads 39
16 Desulfurization of Medium Level (65-70%
Vanadium Removal) Demetallized Bachaquero
Export Vacuum Residuum Over 0.02" Beads 41
17 Desulfurization of Medium Level (65-70%
Vanadium Removal) Demetallized Bachaquero
Export Vacuum Residuum Over 0.02" Beads 42
18 Desulfurization of High Level (80-85%
Vanadium Removal) Demetallized Bachaquero
Export Vacuum Residuum Over 0.02" Beads A3
19 Desulfurization of Demetallized Bachaquero
Export Vacuum Residuum.Liquid Product Sulfur 44
20 Desulfurization of Demetallized Lloydminster
Vacuum Residuum Over 0.02" Beads 47
21 Desulfurization of Demetallized Lloydminster
Vacuum Residuum Over 0.02" Beads- Liquid
Product Sulfur 48
~f
22 Effect of Metals Content of Demetallized
Feeds on Deactivation Slope of "the Desulfur-
ization Catalyst 53
vii?
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LIST OF FIGURES
Figure Page
No. Title No.
23 Metals Level in Demeta11!zed Feed Versus
Metals Loading of Desulfurization Catalysts 54
2k Effect of Level of Desulfurization On De-
activation Slope of Desulfurization
Catalysts 55
25 Fuel Oil Viscosity Vs. °API 57
26 400°F+ Fuel Oil Viscosity Vs. Pour Point 58
27 650°F+ Fuel Oil Viscosity Vs. Pour Point 59
28 Total Operating Cost for a Two Stage
Demeta11ization-Desulfurization of
Bachaquero Export Vacuum Residuum 64
29 Total Operating Cost for a Two Stage
Demetallization-Desulfurization of
Lloydminster Vacuum Residuum 66
30 Total Operating Cost for a Two Stage
Demetallization-Desulfurization Versus
Direct Desulfurization 67
ix
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LIST OF TABLES
Table
No.
1
2
3
*
5
6
7
8
9
10
Title
Deme tall ization Catalyst inspections
Feedstock Inspect ions-Bachaquero Export V. R.
Feedstock Inspections-Lloydminster V. R.
Analyses of Spent Demetal 1 ization Catalysts
Pore Size Distribution of Spent Demetal-
1 ization Catalysts
Summary of Inspections on American Cyanamid
0.02" High Activity Beaded Catalyst
Feedstock Inspect ions-Demetal 1 ized Bachaquero
Export V. R.
Feedstock Inspect ions-Demetal 1 ized Lloydminster
V. R.
Analyses of Spent Desulfurization Catalysts
Pore Size Distribution of Spent Desul fur-
Page
No.
9
12
22
29
30
37
38
k6
50
ization Catalysts 51
11 Investment and Operating Cost for a Two-Stage
Demetallization-Desulfurization Operation of
Bachaquero Export Vacuum Residuum 62
12 Investment and Operating Cost for a Two-Stage
Demetalization-Desulfurization Operation of
Lloydminster Vacuum Residuum 63
13 Estimated Overall Yields and Product Properties
from Consecutive Demetal1ization and Desulfur-
ization of Bachaquero Export Vacuum Residuum 69
]k Estimated Overall Yields and Product Properties
from Consecutive Demetal1ization and Desulfur-
ization of Lloydminster Vacuum Residuum 70
xf
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LIST OF TABLES
Table
No.
A •
A-l
A-2
A-3
A-4
A-5
A-6
A- 7
B
B-l
B-2
B-3
B-4
B-5
B-6
Title
Summary of Demetal 1 izatlon Runs
Operating Conditions, Yields, and Product
Properties-Run 115-1233-5B
Operating Conditions, Yields, and Product
Properties-Run 115-1238-4
Operating Conditions, Yields, and Product
Properties-Run 115-1238-14
Operating Conditions, Yields, and Product
Properties-Run 115-1240-3
Operating Conditions, Yields, and Product
Properties-Run 115-1240-8
Operating Conditions, Yields, and Product
Properties-Run 115-1248-9B
Operating Conditions, Yields, and Product
Properties-Run 115-1249-9
Summary of Desulfurization Runs
Operating Conditions, Yields, and Product
Properties-Run 184-194-17
Operating Conditions, Yields, and Product
Properties-Run 184-195-4
Operating Conditions, Yields, and Product
Properties-Run 184-195-19
Operating Conditions, Yields, and Product
Properties-Run 184-196-4
Operating Conditions, Yields, and Product
Properties-Run 184-196-20
Operating Conditions, Yields, and Product
Properties-Run 185-248-3
Page
No.
73
79
82
83
84
85
86
87
89
99
100
101
102
103
104
xii
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LIST OF TABLES
Table Page
No. Title No.
B-7 Operating Conditions, Yields, and Product
Properties-Run 185-248-11 105
B-8 Operating Conditions, Yields, and Product
Properties-Run 185-249-4 ?o6
B-9 Operating Conditions, Yields, and Product
Properties-Run 185-249-15 107
B-10 Operating Conditions, Yields, and Product
Properties-Run 185-250-14 108
B-ll Operating Conditions, Yields, and Product
Properties-Run 185-250-25 109
B-12 Operating Conditions, Yields, and Product
Properties-Run 185-251-4 n-°
B-13 Operating Conditions, Yields, and Product
Properties-Run 185-251-20 n?
xIH
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XIV
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GLOSSARY
MM
1 Angstrom (A)
g/cc
M2/g
Mesh Sizes
psig
SCF/Bbl
L.S.V.
Vo/Hr/Vr
MMB
Bbl/D/Lb
BPSD
ppm
SFS
SUS
VB
Millions
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 Oi1/Hour/Volume of Reactor
Mi 1-1 ion Barrels
Barrels of Oil/Day/Pound of Catalyst
Barrels per Stream Day
Parts per mill ion
Saybolt Furol Seconds
Saybolt Universal Seconds
Vacuum Bottoms - Vacuum Residuum
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I. CONCLUSIONS
The newly developed demetal1ization catalyst, granular 20 x 50
mesh activated bauxite impregnated with 1.0 weight percent
molybdenum, when used in the first stage of a two-stage demetal-
1ization desulfurization process, offers a substantial operating
cost advantage over a direct desulfurization process in the pro-
duction of low sulfur fuel oil from high metals petroleum vacuum
residua.
For a typical case on Bachaquero Export vacuum residuum, a high
metals stock from Venezuela, the saving in operating cost to
produce 0.3 weight percent fuel oil was $1.15/Bbl, to produce
0.5 weight percent sulfur fuel oil the saving was $0.78/Bbl, and
a saving of $0.44/Bbl was realized to produce 1.0 weight percent
sulfur fuel oil. Similar cost advantages were realized in the
production of low sulfur fuel oils from Lloydminster vacuum
residuum, a high sulfur Canadian stock.
These cost calculations were based on a 20,000 barrels per day
plant, which is perhaps the minimum size plant a refiner would
build. Operating costs would be lowered as the size of the plant
is increased resulting in increased savings.
The optimum demetal1ization level to achieve minimum overall
operating costs from Bachaquero Export to produce 1.0 weight
percent sulfur fuel oil was about k$ .percent vanadium removal. To
produce 0.5 weight percent sulfur fuel oil to optimum demetal-
1 ization level was about 55 percent vanadium removal.' For the pro-
duction of 0.3 weight percent sulfur fuel oil the operating costs
decreased with increasing levels of vanadium removal. However,
levels above 80 percent vanadium removal were difficult to achieve
because of the rapid rate of catalyst deactivation, but removal of
metals above this level are believed to be of dubious economic
value, since these metal compounds are difficult to remove by the
demetalHzation catalyst, they would also be difficult to remove
by the commercial desulfurization catalyst.
For Lloydminster vacuum residuum, the optimum demetallization
level to produce 1.0 weight percent sulfur fuel oil was about 65
percent vanadium removal. To produce 0.5 weight percent sulfur
fuel oil the level was 75 percent and for 0.3 weight percent sul-
fur fuel oil the optimum level was about 85 percent vanadium
remova1.
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2. INTRODUCTION
Because of more stringent federal environmental pollution standards
along wfth the increased demands for energy in the 1970's, the
need for and value of clean low sulfur fuel oil has been well
established and documented. Given the finite nature of fossil
fuels, full and best use of all petroleum fractions is not only
desirable but imperative if we are to meet the energy demand
before alternative sources are developed.
There are substantial reserves of high sulfur petroleum resids,
foreign and domestic, containing contaminant metals vanadium
and nickel, which rapidly poison HDS catalysts and render the
overall processing of these resids economically unattractive.
In order to improve removal of contaminants from these fuels
while economically producing low sulfur fuel oil from petro-
leum resids, HRI undertook a project funded by the Environmental
Protection Agency, under Contract No. 68-02-0293, to develop a
low cost scavenger catalyst to remove contaminant metals from
petroleum resids prior to desulfurization over commercial HDS
catalysts.
In Phase I work of the present contract, a literature review
was made for guidance in choosing catalyst supports and promoter
metals for possible development. After evaluating catalyst
supports, alumina, silica-alumina, bauxites, clays and solid
carbons, activated bauxite was found to be the best support of
those tested in terms of availability, low cost and relatively
high demetal1ization activity. To further improve activity,
activated bauxite was impregnated with promoter metals, V, Cr,
Mo, W, Fe, Co, Ni, B, Mn, and Zn. It was found that low levels
of molybdenum on activated bauxite was most effective in
terms of demeta11ization activity, aging characteristics and
surprisingly high desulfurization activity considering the low
molybdenum loading.
Under Phase II work, optimization of molybdenum loading on
activated bauxite was found to be 1.0 weight percent-and particle
size for fixedjbed operations to_be 20 x 50 mesh. To demonstrate
commercial production capability, Minerals and Chemicals Division
of Engelhard Corporation produced a 10,000 pound batch on com-
mercial production equipment. The newly developed commercially
produced catalyst was tested for activity and aging character-
istics followed by desulfurization of the demetallized products
over a commercial HDS catalyst. Preliminary costs to produce
low sulfur fuel oil from Tia Juana and Gach Saran vacuum residua
were calculated and found to offer substantial cost advantages
-------
over unpromoted bauxite in the demetal1ization step of a two
stage system.
The objectives under the present Phase III work were to optimize
operating conditions in the demetallization and desulfurization
steps in order to obtain more accurate cost figures to produce
low sulfur fuel oil. The oils used for this phase were Bachaquero
Export and Lloydminster vacuum residua. Bachaquero Export vacuum
residuum, a high metals Venezuelan stock, was demetallized to
three levels of vanadium removal (45, 65 and 83%), the blended
products desulfurized over commercial HDS beads, and operating
costs were calculated to produce 1.0, 0.5, and 0.3 weight percent
sulfur fuel oils. Lloydminster vacuum residuum, a high sulfur
medium metals stock from Canada, was demetallized to two levels
of vanadium removal (63 and 85%), desulfurized over commercial
HDS beads and costs calculated to produce low sulfur fuel oil.
The operating costs and plant investment for producing low sulfur
fuel oil from Bachaquero Export and Lloydminster vacuum residua
were compared to costs using a direct desulfurization process.
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3. EXPERIMENTAL; DEMETALLIZflTION
3.1 Apparatus and Procedures
All demetal1ization operations were carried out in a continuous
downflow, fixed bed reactor system. Figure 1 shows a schematic
diagram of Unit 115 having two reactors connected in series con-
tained in a single lead bath. Each reactor shown in Figure 2
was fabricated from l^" O.D. by 1" I.D. stainless steel tubing,
and has a catalyst bed length of approximately 16". The volume
of catalyst charged to each reactor was approximately 200 cc
(loose). Temperatures were continuously recorded by means of a
thermocouple situated at the center of each catalyst bed. Heat
was supplied to the reactor by means of an electrically heated
lead bath.
The reason two reactors were connected in series, was to increase
production of demetallized product for subsequent desulfurization
runs, while maintaining normal liquid space velocities for cata-
lyst deactivation studies. A standard startup procedure was
used to condition the catalyst at lower temperatures for a short
period of time. The startup schedule was as follows:
Period 1A IB, 2, Etc.
Temperature 750 775 790 790
Pressure, psig 2000 2000 2000 2000
Hydrogen Rate, SCF/Bbl 4000 4000 4000 4000
Liquid Space Velocity,
Vo/Hr/Vr ————— Constant
Time on Temp., Hrs. 4 4 1 Continue at
above conditions
All demeta11ization runs in this series were carried out at
790°F except one which was at 770°F. In that one case the
final temperature was not exceeded in the startup procedure.
Liquid space velocities varied from 0.25 to 2.0 Vo/Hr/Vr.
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% and no recycle of the exit gases was employed.
The mixed vapor and liquid product from the reactors was cooled
and passed to a high pressure receiver from which gas was
-------
FIGURE 1
HYDROGEN
::
-CXJ-
~-^»
THERMOCOUPLES WATER
AUX.CHARGE CHARGE1
POT POT
s
f
\
•>.
L
»
n^»^
f
\
«•
^
t
i
HUH*
••••
LEAD
BATH
PUMP REACTOR
-tx»-
H/P PRODUCT
RECEIVER
HYDROCARBON RESEARCH. INC.
DYNAUC11ION COKPOBATION
4
I C*d—»-
TO
FLARE
T
L/P PRODUCT
RECEIVER
FIXED BED
DEMETALLIZATIOK UNIT
P.
CN6B:
DATCt
DW6
NO.
AF-2681
-------
Figure 2. FIXED BED DEMETALLIZATION REACTOR
Figure 2
INLET
OUTLET
DRILL a TAP FOR
DETAIL "A"
I DIA7
DETAIL "B"
-------
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 gases
were analyzed twice weekly on a mass spectrometer, Du Pont
Model 21-103C. The liquid product was collected and weighed
periodically. Daily inspections of the liquid product in-
cluded; gravity by hydrometer, atmospheric distillation to
550°F, sulfur analysis on the 550°F+ fraction by Leco induc-
tion furnace method ASTM-D-1552, and metals analysis for
vanadium and nickel by atomic absorption Perkin Elmer Model
303. Besides the daily inspections, about twice weekly and
after a change in operating condition, sulfurs were analyzed
on the initial to 550°F fraction, and appropriate corrections
made on total product sulfurs.
Detailed operating conditions and liquid product inspections
for each run in this series is given in Appendix A.
Upon completion of a run, the catalyst was removed from each
reactor and analyzed. First the oil was removed from the
catalyst by means of a Soxhlet extractor using benzene, then
analyzed for carbon, sulfur, vanadium and nickel.
Metals and sulfurs were analyzed using the same equipment as
for liquid products while carbon was analyzed by high temper-
ature combustion in oxygen using Perkin Elmer Model 2^0 C H N
analyzer. Pore size distribution curves were obtained by
mercury intrusion on Aminco's 60,000 PSI Porosimeter.
3.2 Catalyst Description and Inspections
The catalyst used in all demetal1ization runs was a represent-
ative portion from the 10,000 pound commercial production run
made by Minerals and Chemical Division of Engelhard Corporation,
and designated HRI 363^. This catalyst, activated bauxite
Impregnated with one weight per cent molybdenum, was developed
by HRI under Phase 1 of the current contract and produced and
evaluated under Phase II. Table 1 lists the physical and
chemical characteristics and Figure 3 the pore size distribution
of the catalyst.
3.3 Bachaquero Export Vacuum Residuum; Preparation and
Inspections
The feed selected for this study was Bachaquero Export Vacuum
Residuum. This feed originated in the Lake Maracaibo area of
Venezuela. In 197**, the total production of this crude was about
8
-------
Table], DEMETALLIZATION CATALYST INSPECTIONS
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
Surface Area, M2/g 195.6
Pore Volume, cc/g 0.3^7
Sieve Analysis. W %
20/30 Mesh 52.k
30/40 Mesh 30.7
40/50 Mesh 16-9
-------
AM1NCO FORM
Cat.No. 5-713SA
Figure 3. DEMETAYllZATION CATALYST HRI 363**
PORE SIZE DISTRIBUTION
EQUIVALENT PORE DIAMETER (MICRONS) = 175/PSI
ICONTACT ANGLE = 130°)
— K) C» ^ Ul O- MOB -O ^
Oi o O _0 O 00000
-------
20k million barrels equivalent to about 98 million barrels of
vacuum residuum (based on a typical 48 percent by volume of
950°F+ resid on crude), with an estimated crude reserve of about
1837 million barrels. The vacuum residuum used for the three
levels of demetallization runs was prepared by vacuum distilling
Bachaquero Export atmospheric residuum obtained from the Amuay
Refinery of Creole Petroleum Corporation, a subsidiary of Exxon
Corporation. Three drums of approximately 400 pounds each of
vacuum residuum were recovered from 6.5 drums of atmospheric
residuum. Inspections on this material designated as HRI L-397
are given in Table 2.
These inspections are somewhat different from published values
for pure Bachaquero vacuum residua. Residua designated as
"Export" in general contain small quantities of residua from
different-crudes from a refinery run. The refinery at Amuay
obtains its crude from the Lake Maracaibo field in Venezuela
through a pipeline. This field is a continuous field compri-
sing Bachaquero, Lagunillas, and Tia Juana crudes, among others.
The Bachaquero Export atmospheric residuum shipped and used for
this study contains unknown quantities of residua from these
other crudes but is representative of residual oils from this
major field available for world markets
3.3.1 Low Level Demetallization
The objective of this operation was to demetallize Bachaquero
Export vacuum residuum to 45-50 percent vanadium removal level,
produce sufficient feed for a subsequent 20 day desulfurization
run, and obtain catalyst deactivation data.
The operation was carried out in Run 115-1233 at 790°F, hydrogen
pressure of 2000 psig, liquid space velocity of 1,5 Vo/Hr/Vr and
catalyst space velocity of 0.114 Bbl/D/Lb. The actual demetal-
lization achieved was 44 percent vanadium removal and 35 percent
desulfurization. Six days of operation produced sufficient feed
for a 20 day desulfurization run.
Figure 4 shows the rate of vanadium removal, Vp/Vp, (vanadium
in the feed/vanadium in the product) against catalyst age in
Bbl/Lb. These results show that, at this level of vanadium re-
moval, the catalyst deactivation is quite low. Desulfurization
data obtained from this operation are summarized in Figure 5.
11
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Table 2« FEEDSTOCK INSPECTIONS
Feedstock Bachaquero Export Vacuum Residuum
HRI Identification No. L-397
Gravity, °API 7.6
Sulfur, W % 3.08
RCR, W % 17,9
Carbon, W % 86.28
Hydrogen, W % 10.67
Nitrogen, ppm 5313
Vanadium, ppm 577
Nickel, ppm 81
Viscosity, SFS & 210°F 19^5
SUS & 210°F 118
IBP-975°F, V % 10.0
Gravity, "API 20.3
Sulfur, W % 2.62
975°F+, V % 90.0
Gravity, °API 6.6
Sulfur, W % 3.10
RCR, W % 22.0
12
-------
o
g
(£.
<
<
<
z
OVER 1.0
W % MOLYBDENUM/20x50 MESH BAUXITE
Demetallization
Feed Composition
Legend
Low Level Medium Level
A
B
Gravity. °API 7.5 to 7.6
Sulfur,
W % 2.95 - 3.08
Run No.
Vanadium, ppm 547
Nickel,
ppm 74
115-1233 115-1238
Operating Conditions
Hydrogen Pressure,
Temperature,
Catalyst HRI No. 3634
5.0
4.0
3.0
2.0
.
1
-
;
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CATALYST AGE, BBL/LB
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fr
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U.
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to
OVER 1
Feed Composition
Gravity, °API 7.5 to 7.6
Sulfur, W % 2.95 - 3.08
Vanadium, ppm 5^7
Nickel, ppm 7^
Run
.0 W % MOLYBDENUM/20x50 MESH BAUXITE
Legend
No.
Operating Conditions
Hydrogen Pressure, psig
Temperature, °F
Catalyst HRI No. 363k
3.0
2.0
1.5
... j .
i
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Demetall ization
Low Level Medium Level
A B
115-1233 115-1238
2000 2000
790 790
Liquid Space Velocity, V/HR/V 1.5 »•:>
Catalyst, Space Velocity, B/D/LB 0.114 0.037
t
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3.3.2 Medium Level Demetal1ization
The objective of this operation was to demetallize Bachaquero
Export vacuum residuum to 65-70 percent vanadium removal level,
produce sufficient feed for three desulfurization runs of 20 days
each, and obtain catalyst deactivation data.
This operation was carried out in Run 115-1238 at 790QF, hydrogen
pressure of 2000 psig, liquid space velocity of 0.5 Vo/Hr/Vr and
catalyst space velocity of 0.037 Bbl/D/Lb. The initial vanadium
removal rate was 70 percent which fell to 67 percent after 10
days, corresponding to a catalyst age of 0.36 Bbl/Lb. When the
vanadium removal rate reached 60 percent after 20 days, corres-
ponding to a catalyst age of 0.76 Bbl/Lb, the run was terminated.
The average demeta11ization achieved during this run was 67 per-
cent vanadium removal and 53 percent desulfurization.
The catalyst deactivation rate is shown in Figure 4 along with
results from the low level demeta11ization operation. Desulfur-
ization data obtained during this operation are given in Figure 5.
Indications are that catalyst deactivation rates are strongly
dependent on the level of vanadium removal. The catalyst deacti-
vation slope from the low level demeta11ization operation (47
percent initial vanadium removal) was 0.11, but when the demetal-
liaation level was increased to 70 percent initial vanadium re-
moval, the catalyst deactivation slope increased four-fold to
0.44. This rapid deactivation of the catalyst may limit the
severity at which Bachaquero Export vacuum residuum can be de-
metallized over this catalyst.
This one medium level demetallization run produced insufficient
feed to sustain three 20 day desulfurization runs. Consequently,
a second run was started as Run 115-1239 under identical condi-
tions. Demeta11ization and desulfurization from this operation
are summarized in Figure 6. Initial dernetal 1 ization and up to
catalyst age of O.I Bbl/Lb was 74 percent vanadium removal.
There was a sudden drop to 54 percent vanadium removal which
gradually increased to 62 percent at catalyst age 0.5 Bbl/Lb.
At this time, the feed rate was reduced from 0.5 to 0.35 Vo/Hr/Vr.
This change resulted in improved demeta11ization to about 70 per-
cent vanadium removal level. However, after catalyst age of
0.65 Bbl/Lb, the vanadium level again dropped unexpectedly to
50 percent. For this reason the run was terminated, the cat-
alyst removed and analyzed. Visual inspection revealed no
abnormalities in the reactors, catalyst, or product lines. Anal-
ysis of the used catalysts, (tabulated in Table 4 at the end of
the demeta11ization section) showed the carbon level to be higher
in the second reactor from this run than the corresponding reactor
from the first run. This indicated that some coking may have
-------
Figure 6 DEMETALLIZATION AND DESULFURIZATION OBTAINED DURING DEMETALLIZATION OF
BACHAQUERO EXPORT VACUUM RESIDUUM.OVER 1.0 W % MOLYBDENUM/20x50 MESH BAU3ITE
Symbol
Feed Composition: 7-3 °API, 3.0 % S, 577 ppm V, 81 ppm Ni
Run No.
115-1239
115-1239
Hydrogen
Pressure
psig
2000
2000
Temp
790
790
A Vp/Vp, Vanadium In Feed/Vanadium in Product
B Sp/Sp, Sulfur in Feed/Sulfur in Product
Liquid
Space Velocity
V/Hr/V
0.5
0.35
Catalyst
Space Velocity
B/D/LB
(
0.038
0.027
a.
to
u.
CO
cc
o
0.1
0.2
0.3 0.¥ 0.5
CATALYST AGE, BBL/LB
0.
0.7
•ya
n>
o
<
o>
ua
c
A
-------
occurred during the course of the second run. Since no diffi-
culty was encountered in the first run under identical conditions,
it was inferred that either the liquid feed and/or the hydrogen
flow was interrupted during the course of the run. This con-
dition may have existed for too short a period of time to be
noted and logged on the daily log sheet.
3.3.3 High Level Demetallization
The objective of the high level demetallization operation was to
demetallize Bachaquero Export vacuum residuum to 80-85 percent
vanadium removal level, produce sufficient feed for a 20 day de-
sulfurization run, and obtain catalyst deactivation data.
In all, five runs were required to produce sufficient feed for
a 20 day desulfurization run. The first four runs were made at
790°F, hydrogen pressure of 2000 psig, liquid space velocity of
0.3 Vo/Hr/Vr and catalyst space velocity 0.023 Bbl/D/Lb.
The first run (115-1240) operated for nine days, at which time
pressure buildup in the unit forced a premature shutdown.
Average demetal1ization achieved was 84 percent vanadium removal
and 69 percent desulfurization. Although catalyst dumped from
the reactor was free-flowing, carbon level on catalyst from the
second reactor was unusually high (17.62 W %), indicating coking
had occurred during the course of the run.
The second run (115-1241) operated for five days before pressure
buildup forced termination of the run. Average demetal1ization
was 85 percent vanadium removal and 67 percent desulfurization.
Carbon level on catalyst from second reactor was 15.62 weight
percent.
The third run (115-1242) operated for five days before pressure
buildup was encountered. An attempt was made to save the run
by flushing the reactors with light oil, which restored normal
pressure drop. However, on restarting the unit, vanadium removal
was sharply reduced and the run had to be terminated. The average
demetallization achieved during the first five days of operation
was 85 percent vanadium removal and 69 percent desulfurization.
Carbon levels on the catalyst were again unusually high indi-
cating coking. It was believed at this time that coking was due
to interruption of either feed or hydrogen flow at some time
during the run because of difficulty in controlling the very low
flow rates used, rather than the severity of the operating con-
ditions.
After again changing the hydrogen metering orifice and clearing
17
-------
product line and check valve, a fourth run (115-1243) was started.
Pressure buildup was encountered after four days, forcing a shut-
down. Demetallization was 84 percent vanadium removal and 67 per-
cent desulfurization. Carbon levels were very high on catalysts
from both reactors; 21.43 weight percent on catalyst from bottom
of first reactor and 19.69 weight percent from the second reactor.
The fifth run (115-1244) was carried out at a lower temperature
(770°F) and lower liquid space velocity (0.25 Vo/Hr/Vr). The
initial vanadium removal was 79 percent dropping to 75 percent
after six days on stream. At this time, the temperature was ;•
raised to 780°F which restored the vanadium removal level to 79
percent. After eight days on stream, this run was voluntarily
terminated because sufficient demetallized product had been accu-
mulated to make a 20 day desulfurization run. Since no evidence
of coking was experienced during the course of the fifth run, the
conclusion was that in this equipment and at the very low liquid
space velocities used, 790°F reactor temperature is above the
threshold of coking on this feedstock.
Figure 7 shows the catalyst deactivation plots of the five high
level demetallization runs. The first four runs (115-1240, 1241,
1242, and 1243) are reproducible and show a rapid rate of deacti-
vation. The fifth run (115-1244) operated at a lower temperature
(770 and 780°F) and slightly lower liquid space velocity, showed
a lower rate of deactivation.
Sulfur removal and nickel removal as function of vanadium
removal are summarized in Figure 8.
It can be concluded from the results of the high level demetal-
1ization operation that:
1. High levels of demetallization, up to about 80
percent vanadium removal, can be achieved on
Bachaquero Export vacuum residuum over the newly
developed catalyst. However, deactivation slope
of the catalyst was high.
2i» . In this equipment temperatures above about 780°F
combined with very low liquid space velocities,
below about 0.25 Vo/Hr/Vr may pose operability
problems because of coking. At high reaction
rates, hot spots in the reactor which were not
recorded, may have been the cause of the coking
in our test unit. However, run away temperatures
in commercial equipment can be prevented where
18
-------
Figure?,. DEMETALLIZATION OF BACHAQUERO EXPORT VACUUM R1SIDUUM
4-1
U
D
•D
O
0.
T3
(D
C
-D
0)
115-1242 2000 790
B 115-1243 2000 790
A 115-1244 2000 780
A 115-1244 2000 770
10
8
1 I
! i ;
i
'•• \ i' > i
[ • i
i i i \ . \ ; J 1
. n. I J I ! ' i •: 1 :
-.-.. H-- .-—.^-j— rr r -.r
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A. :j'~ -^ ".L A t:~7T "ir
1 .i - J_. .I... 1 : :776°F i ;
'!'!'.; l i • |
i i i. : ." iTf
I
ppm V, 81 ppm Ni
V/HR/V B/D/LB
0.30 0.023
0.30 0.023
0.30 0.023
0.30 0.023
0.25 0.019
0.25 0.019
i . ' • !
: i , ; ! : Li
: J ; : ' ; :
' • 1 1
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. ...|.. . 7800F;. . . ; . ; ......;....
i ... . ;
1 1 • ;
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9°
80
75
0.05
0.10
CATALYST AGE BBL/LB
0.15
0.20
o>
3
Q>
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85
ua
c
(D
-------
Figure 8
Figure 8. SULFUR AND NICKEL REMOVALS AS FUNCTION OF VANADIUM REMOVAL
DURING DEMETALLIZATION OF BACHAQUERO EXPORT VACUUM RESIDUUM
ON 1 % MOLYBDENUM/20x50 MESH BAUXITE
:
u
D
-a
2
a.
c
0)
0)
U.
1.
3
3
in
a.
c
U
u
T3
(U
0)
2
0)
u
z
:.. |. ....!...; .1. !
_% (Vanadium1 Removal ! : i
™-, ........ . . ...
1 23^6
Vanadium in feed/Vanadium in Product
c
-t
n
7T
(D
o
0)
20
-------
quenching is normally practiced.
3. Catalyst deactivation rates increase sharply
with demetallization operations above 70 percent
vanadium removal.
3.4 Lloydminster Vacuum Residuum; Preparation and Inspections
Lloydminster crude originates in Western Canada in the provinces
of Alberta and Saskatchewan. In 1975, the daily production rate
of this crude was 33,000 barrels per day which corresponds to
a yearly production of about 12 million barrels. The equivalent
production of the vacuum residuum was about 6.6 million barrels.
The Lloydminster vacuum residuum used in this program was obtained
from Husky Oil Ltd., Lloydminster, Alberta. This feed is high in
sulfur content (5.4 % S) and contains moderate amounts of vanadium
and nickel. Detailed inspections on this feed are give in Table 3.
3.4.1 Demeta11?zation to 45-60 Percent Vanadium Removal
The objective of this operation was to demetallize Lloydminster
vacuum residuum to 45-60 percent vanadium removal, produce suffi-
cient demetallized feed for a subsequent desulfurization run to
last about 30 days and obtain catalyst deactivation data.
This operation was carried out in Run 115-1248 at 790°F, hydrogen
pressure of 2000 psig, liquid space velocity of 2.0 Vo/Hr/Vr and
catalyst space velocity of 0.15 Bbl/D/Lb. The run was started at
a liquid space velocity of 1.5 Vo/Hr/Vr which resulted In 73 per-
cent vanadium removal, higher than the intended demetallization
level. The liquid space velocity was increased to 2.0 Vo/Hr/Vr
after two days, lowering the demetal1ization level to 64 percent
vanadium removal. The run was continued for nine days at the
higher feed rate, at which time the run was voluntarily terminated
because sufficient feed had been accumulated for the desulfur-
ization run.
Figure 9 shows the catalyst deactivation with age and Figure 10
shows the desulfurization achieved during this operation. The
average demetalIization was 61 percent vanadium removal and
average desulfurlzation was 50 percent.
21
-------
Table 3. FEEDSTOCK INSPECTION
Feedstock Lloydminster Vacuum Residuum
HRI Identification No. 3744
Gravity, °API 6.4
Sulfur, W % 5.40
RCR, W % 15.8
Nitrogen, ppm 5900
Carbon, W % 83.18
Hydrogen, W % 10.37
Vanadium, ppm - 164
Nickel, ppm 95
Viscosity, SFS & 210°F 1489
IBP-975°F, V % 20.9
Gravity, °API 17.0
Sulfur, W % 3.1*9
975°F+, V % 79.1
Gravity, °API 3.1
Sulfur, W % 5.88
RCR, W % 20.8
22
-------
M»
Symbol'
A
B
/* ••
Product
o u
Vanadium In Feed/Vanadium in
** w *- c* oo
': ' ',
— — J
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MMIMM
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Run No.
115-1248
115-1249
>•»
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m*f>'fim
••
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OVER 1 W % MOLYBDENUM/20x50 MESH BAUXITE
HRI No. 3634
Feed Composftlon: 6.4 °API, 5
HRI 3744
Hydrogen
Pressure Temperature
, pslg °F
". ':
"•*"*
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v •
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2000
2000
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.4 % Sulfur, 169 ppm V, 95 ppm Nl
V/Hr/V B/D/Lb.
1.5-2.0 0.112-0.15
0.62-0.77 0,048-0.059
:...
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Data Corrected To
V/Hr/V B/D/Lb
2.0 0.15
0.65 0.05
•
' .
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1
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i
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CATALYST AGE, BBL/LB
-------
Symbol
A
B
Figure 10 DESULFURIZAT10N OBTAINED DURING DEHETALLIZATION OF LLOYDMINSTER VACUUM RESIDUUM
OVER 1 W % HOLYBDENUM/20x50 MESH BAUXITE
HRI 3634
Feed Composition: 6.4 °API, 5.4 % S, 169 ppm V, 95 ppm Ml
HRI 3744
Run No.
115-1248
115-1249
Hydrogen
Pressure
psiq
2000
2000
Temperature
790
790
V/Hr/V B/D/Lb
1.5-2.0 0.15-0.112
0.62-0.77 0.048-0.059
Data Corrected to
V/Hr/V B/D/Lb
0.15
0.05
£
U
•O
O
-------
3.^.2 Demetallization to 80-85 Percent Vanadium Removal
Lloydminster vacuum residuum was demetallfzed to 80-85 percent
vanadium removal, sufficient demetallized feed was produced for
a 25 day desulfurization run and catalyst deactivation data was
obtained.
This operation was carried out in Run 115-1249 at 790°F, hydrogen
pressure of 2000 psig, liquid space velocity ranged between 0.62
and 0.80 Vo/Hr/Vr and catalyst space velocity ranged between
0.048 and 0.059 Bbl/D/Lb.
Figure 9 shows the rate of catalyst deactivation with age and
Figure 10 shows the desulfurization achieved during this demetal-
lization run.
Initial demetal1ization was 87 percent vanadium removal which
gradually fell to 79 percent after seven days on stream. At this
time feed rate was lowered to 0.62 Vo/Hr/Vr restoring the demetal-
1ization level to 88 percent. After 13 days on stream the demetal-
lization rate was still at about 82 percent but sufficient feed
had been collected for a desulfurization run, so the unit was
shut down.
Sulfur removal and nickel removal as function of vanadium removal
are summarized in Figure 11.
3.5 Kinetics of Demetallization
Demetallization data obtained on Bachaquero Export vacuum residuum
in the liquid space velocity range of 0.3 to 1.5 Vo/Hr/Vr corres-
ponding to catalyst space velocities of 0.023 to 0.114 Bbl/D/Lb
were used to develop a kinetic model for vanadium removal over a
commercial demetalUzation catalyst containing 1 percent Molybdenum
on 20 x 50 mesh activated bauxite. These data are summarized
graphically in Figure 12, showing that the rates of vanadium re-
moval over the given catalyst space velocities follow a pseudo
first order kinetics. The kinetic model developed above also fits
the data obtained on Lloydminster vacuum residuum over the same
demetal1ization catalyst. These data are included in Figure 12
over the liquid space velocity range 0.65 to 2.0 Vo/Hr/Vr, corres-
ponding to catalyst space velocity range 0.05 to 0.15 Bbl/D/Lb.
The kinetic equation used to correct for variations in space
velocities to obtain rate constants for use later in this program
25
-------
Figure 11
Figure 11. SUfFUR AND NICKEL REMOVALS AS FUNCTION OF VANADIUM REMOVAL
DURING DEMETALLIZATION.OF LLOYDMINSTER VACUUM RESIDUUM
ON 1 % XOLYBDENUM/20x50 MESH BAUXITE
% Vanadium Removal
75 80,
33 5Q.--6-Q—47 2
i ; i
•M
U
1-
•a
V
a
5
k
V)
*5 •,-,--.- -11--. *-- -.
c
-h
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•a
2
OL
0)
«
j*
U
z
2 34 6 8 10
Vanadium In Feed/Vanadium In Product
n
jr
26
-------
K-.
"
SEMI-LOGARITHMIC Z CYCI-fcS A 2UU
KEUFFEL a, ESSER CO. MADE IN U s »
46 5250
1O—
9—
-------
is given in equation (1):
Km = (C.S.V.) nin — (1)
P
where Km = Pseudo First order rate constant
C.S.V. = Catalyst space velocity, Bbl Oil/Day/Lb Catalyst
V
F = Vanadium in feed, in ppm
y
P = Vandal urn in product, in ppm
n = 0.8
As seen from the slopes of initial rate constants for the two
residua in Figure 12, the rate of vanadium removal for Lloydminster
vacuum residuum is about twice that for Bach.aquero Export. Actual
slope for Lloydminster was 0.22, and for Bachaquero Export it was
0.10.
3.6 Spent Demetal1Ization Catalyst Inspections
The results of analyses on spent demetal1ization catalysts are
summarized in Table 4. Carbon levels ranged from about eight weight
-percent to over 20 weight percent. In all runs where operability
problems were encountered with pressure buildup, the carbon level
on catalyst was over 15 weight percent while ho other operable runs
exhibited this high level'carbon content. No correlation could be
found between carbon level and catalyst age. It appears carbon is
deposited rapidly on the catalyst at the beginning of a run, the
level being dependent on temperature and liquid space velocity, then
remaining fairly constant for the duration of the run. The pore size
distribution of the spent demeta11ization catalyst are summarized
in Table 5. The pore volumes of the spent catalysts were corrected
to fresh basis using the following relationship:
1
cc/g Fresh Catalyst = ——————— x cc/g Spent Catalyst
1.000 - J"F? + i Fs
where Fi = weight fraction Impurities on spent catalyst
Fs = weight fraction sulfur on spent catalyst
The loss in total pore volume of all demetal1ization catalysts fell
28
-------
Table 4. ANALYSES OF SPENT DEMETALLIZATION CATALYSTS
VO
RUN
NUMBER
115-1233
115-1233
115-1238
115-1238
115-1239
115-1239
115-1240
115-1240
115-1241
115-1241
115-1242
115-1242
115-1242
15-1243
15-1243
15-1243
15-1244
15-1244
115-1248
115-1248
115-1249
115-1249
FEED
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Bachaquero
Lloydminster
Lloydminster
Lloydminster
Lloydminster
REACTOR
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
No.
1
2
1
2
1
2
1
2
1
2
1 Top
1 Bottom
2
1 Top
I Bottom
2
1
2
1
2
1
2
LHSV
Vo/Hr/Vr
1.
1.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
1.
0.
0.
50
50
50
50
35-0.50
35-0.50
30
30
30
30
30
30
30
30
30
30
25
25
50-2.00
50-2.00
62-0.80
62-0.80
CATALYST AGE
BBL/LB
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
1.
1.
0.
0.
64
64
76
76
73 :
73
20
20
10
10
22
22
22
08
08
08
15
15
21
21
69
69
CARBON
W %
8.92
10.46
9.32
12.83
9.88
15-22
14.06
17.62
13.30
15.62
8.45
17.84
15-37
14.87
21.43
19.69
10.49
13.77
8.03
8.01
9.50
11.40
SULFUR
W %
2.56
2.16
5-36
3.51
5-58
2.86
2.63
2.37
2.38
2.24
2.21
2.20
2.04
3.09
3.18
2.56
2.91
2.53
5-50
3.78
4.87
2.78
VANAD 1 UM
W %
7.08
3.44
12.96
3.90
12.97
2.81
3.43
1.05
2.48
0.69
8.27
1.20
1.01
3.56
0.91
0.47
3.60
0.95
5.09
2.51
4.58
1.18
NICKEL
W %
0.44
0.30
0.81
0.39
0.85
0.36
0.35
0.16
0.22
0. 14
0.41
0.18
0.17
0.25
0.12
0.09
0.30
0. 15
1.72
1.10
1.92
0.64
-------
TABLES PORE SIZE DISTRIBUTION OF SPENT DEMETALLIZATION CATALYSTS
SPENT
CATALYST
From Run No.
CATALYST
AGE
Bbl/Lb
Fresh 3634
115-1233
115-1233
115-1238
115-1238
115-1239
115-1239
115-1241
115-1241
115-1242
115-1242
115-1242
115-1244
115-1244
115-1248
115-1248
115-1249
115-1249
R-l
R-2
R-l
R-2
R-l
R-2
R-1
R-2
R-l Top
R-1 Btm
R-2
R-1
R-2
R-l
R-2
R-l
R-2
0.64
0.64
0^76
0.76
0.73
0.73
0.10
0.10
0.22
0.22
0.22
0.15
0.15
1.21
1.21
0.69
0.69
PORE DIAMETER RANGE ANGSTROMS
WT %
C
r
8.92
10.46
9.32
12.83
9.88
15.22
13.30
15.62
8.45
17.84
15.37
10.49
13.77
8.03
8.01
9.50
11.40
V+Ni
7-52
3.74
13.77
4.29
13-82
3.17
2.70
0.83
8.68
1.38
1.18
3.90
1.10
6.81
3.61
6.50
1.82
30-100
0.142
0.039
0.034
0.021
0.027
0.031
0.021
0.030
0.021
0.029
0.033
0.032
0.025
0.017
0.026
0.016
0.026
0.013
100-500 500-1000
PORE VOLUME cc/gm
0.078
0.047
0.048
0.046
0.038
0.039
0.044
0.033
0.038
0.041
0.054
0.050
0.042
0.036
0.058
0.054
0.046
0.045
0.034
0.017
0.021
0.014
0.016
0.012
0.024
0.019
0.022
0.032
0.014
0.019
0.021
0.020
0.024
0.026
0.015
0.024
1000+
0.057
0.034
0.044
0.035
0.043
0.042
0.041
0.042
0.043
0.037
0.043
0.038
0.046
0.038
0.039
0.045
0.054
0.048
TOTAL
PORE
VOLUME
cc/gm
LOSS IN
.TOTAL
PORE VOLUME
0.311
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
0.
137
147
116
124
124
130
124
124
139
144
139
134
111
147
141
141
130
55-9
52.7
62.7
60.1
60. 1
58.2
60.1
60.1
55-3
53-7
55.3
56.9
64.3
52.7
54.7
54.7
58.2
Note: Pore size distribution and total pore volumes on spent catalysts were corrected to fresh catalyst basis.
-------
into a rather narrow range (53 to 63% loss) considering the
large variation in catalyst age (0.1 to 1.21 Bbl/Lb), carbon
level (8.0 to 17.8 W %) and metals deposited (0.83 to 13.8 %
V S- Ni). The greatest loss in pore volume occurred in micro-
pores 30-100 Angstroms in diameter, however no significant
correlation could be found between the loss in micropores and
the variables catalyst age, carbon or metals level on catalysts.
3.7 Catalyst Deactivation Correlations
The correlation between demetal1ization level (vanadium removal
level) and catalyst deactivation is shown in Figure 13. The
data for curve A was obtained from runs made on Bachaquero
Export vacuum residuum to produce demetallized feeds containing
three levels of vanadium. Data from runs made on Tia Juana
(point B) and Gach Saran (point D) vacuum residua, from Phase
II work, as well as data from the operation on Lloydminster
vacuum residuum (curve C) are included in this Figure.
Curve A indicated that for Bachaquero Export and Tia Juana
vacuum residua, vanadium removal above 70 percent will result in
rapid catalyst deactivation. The same phenomenon is observed in
the case of the Lloydminster feed, but the level of vanadium re-
moval where a sharp increase in deactivation started was about
80 percent. From a single data point on Gach Saran, the corres-
ponding vanadium removal where a sharp increase in deactivation
slope occurred is around 88 percent.
The above results also show that the deactivation slope of the
catalyst does not depend on the amount of metals in the feed.
Demeta11ization of the lower metals Lloydminster feed resulted
in higher deactivation slope than from the corresponding oper-
ation on the higher metals Gach Saran feed.
Figure 1*4- shows the effect of catalyst vanadium loading on the
rate constant for Bachaquero and Lloydminster vacuum residua.
These results show that the demeta 11 ization rate constant de-
pends on the vanadium loading on the catalyst as well as on the
level of vanadium removal. For the same level of metals loading
on the catalyst, the rate constant for the same feed is higher
for the lower level-vanadium removal operation. This obser-
vation is true for both Lloydminster (lines A and B) and
Bachaquero (lines C and D) vacuum residua. However, the effect
is lower with Bachaquero feed. For the Bachaquero feed, the
variation of the rate constant at medium level (72% initial
vanadium removal) and at high level (88% initial vanadium re-
moval) versus vanadium loading on the catalyst (line 0) was about
the same.
31
-------
32
-------
M-..
<0 X 10 TO THE CENTIMETER IB X 25 CM
KEUFFEL ft ESSER CO. MADE IN u s.«.
461510
-------
A drop fn the value of the demetallizatJon rate constant with
Increasing metals loading on the catalyst Is expected. As the
amount of metals deposition on the catalyst is increased the
number of active sites is reduced with resulting drop in value
of the rate constant.
The change in the value of the demetallizatIon rate constant
with level of vanadium removal Is believed to be diffusion con-
trolled. At low level vanadium removal operations, metals are
removed from smaller molecules which readily diffuse through
the pores of the catalyst to the active sites resulting in a
high rate constant. At high level vanadium removal operations,
metals from larger molecules must be removed which diffuse
more slowly to the active sites resulting in lower rate con-
stants.
Based on the above postu-lation, it appears that the metals
containing molecules in Gach Saran feed are smaller than those
In Lloydminster feed. Consequently the catalyst deactivatlon
rate is lower for Gach Saran than for Lloydminster feeds at a
given vanadium removal level even though Gach Saran has more
metals.
The above results indicate that we cannot generalize the effect
of metals content of the feed on the deactivation slope of the
catalyst, and extrapolation to other feeds should be carried
out with caution.
-------
4. EXPERIMENTAL; DESULFURIZATION
The objectives of the desulfurization operations were as follows:
1. Study the effect of metals level in the demetallized
feed on the rate of deactivation of the desulfurization
catalyst.
2. Study the effect of level of desulfurization on the
deactivation rate of the desulfurization catalyst.
3. To determine operating conditions required to produce
0.3 weight percBnt fuel oil.
4.J Apparatus and Procedures
All desulfurization operations were carried out in continuous,
downflow, fixed bed units 184 and 185. These units are identical
to unit 115 shown in Figure 1 except for having a single reactor
contained in the lead bath. The reactor shown in Figure 2 was
used in all desulfurization runs. In all but three runs full
reactor catalyst charge was used (approximately 200 cc loose).
In runs 184-196, 197 and 185-248 the volume of catalyst charged
to the reactor was approximately 100 cc (loose).
The reduced volume of catalyst charge enabled us to obtain
longer catalyst ages, at normal liquid space velocities, using
the limited quantities of feedstock available.
The startup and operating procedures used were similar to ones
used with the demetallization runs described previously under
the demetal1ization section.
Most of the aging runs were carried out to a catalyst age of
2 to 3. Bbl/Lb. Runs of this duration, together with results
from aging desulfurization runs made during Phases I and II of
this contract, provide an accurate measure of catalyst deacti-
vation rates which can be translated to the catalyst utilization
required to obtain a given product desulfurization level.
Detailed operating conditions and liquid product inspections
for each run in this series are given in Appendix B.
4.2 Catalyst Description and Inspections
The catalyst used in all desulfurization runs was high activity
35
-------
HDS beads obtained from American Cyanamid, designated as HRI
3104. The small size, about 0.02 inch diameter spheres, makes
this catalyst particularly resistant to deactivation due to
metals deposition, thus making it a likely candidate for use
in a commercial process. The properties of the catalyst are
summarized in Table 6.
4.3 Demetallized Bachaquero Export Vacuum Residuum
4.3.1 Products from Low Level Demetallization
The demetallized products from Run 115-1233 were blended and
designated as HRI L-400. Table 7 summarizes inspections on
this blended feed. This operation was carried out in Run 184-
194 at 760°F, hydrogen pressure of 2000 psig, liquid space
velocity of 1.00 Vo/Hr/Vr corresponding to a catalyst space
velocity of 0.107 Bbl/D/Lb. This run lasted 20 days to catalyst
age of 2.2 Bbl/Lb at which time it was voluntarily shut down.
Figure 15 shows the desulfuriza.tion rate and catalyst deacti-
vation. The initial suTfur removal rate was 65 percent pro-
ducing 0.68 weight percent sulfur product oil and the final
desulfurization rate was 55 percent producing 0.91 weight per-
cent sulfur product. The- vanadium removal rate at the beginning
of this run was 21 percent and at the end it was 14 percent pro-
ducing a product with 240 parts per million vanadium (ppm V) and
49 parts per million nickel (ppm Ni).
4.3.2 Products from Medium Level Demetal1ization
at Conditions A, B, and C
The demetallized products from the medium level, 65-75 percent
vanadium removal operations, were blended and designated HRI
L-401, 405, 406. Table 7 shows the inspections of these feeds.
Three conditions (A, B, and C) were run.
Condition A desulfurization was conducted in Run 184-195 at 760°F,
hydrogen pressure of 2000 psig, liquid space velocity of 1.00
Vo/Hr/Vr corresponding to a catalyst space velocity of 0.107
Bbl/D/Lb. Feed designated L-401 was used in this -run which lasted
20 days to a catalyst age of 2.3 Bbl/Lb.
Condition B was run using feed L-405 in unit 184-196 at 760°F,
hydrogen pressure 2000 psig, liquid space velocity of 0.53
Vo/Hr/Vr corresponding to a catalyst space velocity of 0.056
Bbl/D/Lb. The run lasted 20 days to a catalyst age of 1.1 Bbl/Lb.
36
-------
TABLE 6 SUMMARY OF INSPECTIONS ON AMERICAN
CYANAMID 0.02" HIGH ACTIVITY BEADED CATALYST
HRI Identification Number 3104
Physical Properties
Surface Area, M2/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
30/40 76'2
40/50 5'°
50/70 °'5
70/100 0<1
-100
Chemical Analysis. W 7.
Mo03
(3'0)
A1203
( ) Manufacturers Specifications
37 '
-------
TABLE 7 FEED STOCK INSPECTIONS
Feedstock: Demetallfzed Bachaquero Export Vacuum Residuum
Vanadium Removal, % 45 65 65 65 83
HRI Identification No. L-400 L-401 L-405 L-406 L-408
Gravity, 8API 11.3 13.1 14.4 15.0 17.5
Sulfur, W % 1.98 1.39 1.40 1.25 1.00
RCR, W % 13.3 13.9 13.5 10.7
Nitrogen, ppm 4061 4637 4508 4501 3935
Carbon, W %
Hydrogen, W %
Vanadium, ppm 305 191 192 190 100
Nickel, ppm 65 48 50 50 34
Viscosity, SFS & 210°F 216 58 50 32
SUS & 210°F 420 348 199
IBP-650°F
Volume, %
Gravity, °API
Sulfur, W %
650-975°F
Volume, %
Gravity, "API
Sulfur, W %
975°F+
Volume, %
Gravity, °API
Sulfur, W %
RCR, W %
(1) Compared to feed into demetallization
4.0
33.0
0.43
7.0
33.8
0.23
9.0
35.2
0.14
11.0
35.9
0.11
13.0
36.1
0.13
18.7
18.9
1.07
20.0
20.3
0.68
23.3
20.7
0.75
24.7
21.3
0.67
23.3
21.8
0.29
77.3
8.2
2.19
20.4
73.0
10.1
1.71
18.4
67.7
8.9
1.68
19.9
64.3
8.7
1.75
21,5
63.7
10.8
1.29
16.6
38
-------
FIGURE
DESULFURIZATION OF LOW LEVEL (40-45% VANADIUM REMOVAL) DEMETALLIZED BACHAQUERO EXPORT VACUUM RESIDUUM
OVER 0.02" HDS BEADS
RUN NO. 184-194
FEED COMPOSITION
HRJ - L-400
Gravity, °API 11.3
Sulfur, W % 1.98
Vanadium, ppm 305
Nickel, ppm 65
OPERATING CONDITIONS
H2 Pressure, psig 2000
Temperature, °F 760
Liquid Sp. Vel., V/Hr/V l-.OO
Cat. Sp. Vel. B/D/Lb 0.107
VO
u
-a
o
M
fk
.3
CO
•a
01
-------
Condition C desulfurization was carried out in Run 184-197
using L-405 and 406 feed. The conditions of this operation
were 780°F, 2000 psig hydrogen pressure, liquid space velocity
of 0.5 Vo/Hr/Vr and catalyst space velocity of 0.052 Bbl/D/Lb.
After six days of operation, hydrogen flow could not be main-
tained and the run had to be terminated. The hydrogen metering
orifice was found to be partially restricted.
A new run was started in unit 185-248 under identical conditions.
This run lasted 12 days to catalyst age 0.68 Bbl/Lb before the
demetal1ized feed was exhausted.
The desulfurization results achieved using conditions A, B, and
C are plotted in Figure 16. Under condition A, desulfurization
achieved was 54 weight percent sulfur removal producing 0.64
weight percent sulfur product containing 159 ppm V and 41 ppm
Ni. Under Condition B desulfurization was 72 percent producing
0.4 weight percent sulfur product containing 137 ppm V and
35 ppm Ni, and under condition C 78 percent desulfurization
producing 0.3 weight percent1sulfur product containing 88 ppm V
and 26 ppm Ni.
The rate of catalyst deactivation increases with increasing level
of desulfurization. At condition C, the highest level of desul-
furization, the catalyst deactivation slope was 0.34 while con-
dition B had a slope of 0.22 and condition A was 0.097.
Figure 17 shows the sulfur level in the products versus catalyst
age for conditions A, B,-and C.
4.3.3 Products from High Level Demetal1ization
The demetal1ized products from the high level demetal1ization
operations, 80-85 percent vanadium removal, were blended and
designated as HRI L-408, inspections given in Table 7.
This blend was used as feed to Run 185-249 carried out at 760°F,
hydrogen pressure of 2000 psig, liquid space velocity of 1.0 Vo/Hr/Vr
corresponding to a catalyst space velocity of 0.107 Bbl/D/Lb.
This run lasted 17 days to catalyst age of 1.9 Bbl/Lb using up
all the available feedstock. Figure 18 shows the catalyst deacti-
vation with age.
Average desulfurization level achieved during this run was 55 per-
cent sulfur removal producing oil containing 0.45 weight percent
sulfur and 66 ppm V and 24 ppm Ni. Figure 19 shows a plot of weight
40
-------
FIGURE 16
nESIIT.FTTRTZATTnN OP IliniTIIM T.EVKT. <6S-7O7_ VANADIUM REMOVAL) DEMETALLIZED BACHAQUERO EXPORT VACUUM RESIDUUM
OVER 0.02 INCH BEADS
(VANADIUM REMOVED IN DEMETALLIZED
DESULFURIZATIOM FEED CHARACTERISTICS
Symbol
A
B
C
Sulfur in Feed/ Sulfur in Product
ts> W ** ; -. . Ul O*
i
f
**• -.
.. .j
J :1
"— •
—
— -
mwM
|
Run No.
184-195
184-196
185-248
• ;
•9*.
ji— —
mm^m
T*
TTT1
—
1
1
: :
•MM
MMMB
TT!*
—
i
•*»:».
:;::
:
M^^H
•
- - ',
•HMV
°API
13.1
14.4
15.0
•
:.::
^•MM
"I- ; •! i
1 •
% S ppm V
T39 191
1.40 192
1.25 190
•::.:
*•. •.
•(•M
i^HM
:.::
•mm
~— «
— .
,
i
;••
c
:.:::
....
•— .
—
1 .
.1 •
-,.:),..
• .j
• •
••
: :: :
••
::•:
•••Hi
;
•^MM^HIM
.
: ..
TT
B
••^•w
ppm Ni
STAGE *-- 657.)
OPERATING CONDITIONS
Condition Temp °F PSIG
48 A 760 200U
50 B 760 2000
' 47 C 780 2000
i i
: ;.
t : :
t • •
~^"
. ! i
•
__
1
•
....
•^•M
....
':':'.•
':":
MNHH
i
• • 1 •
•::•
....
• • i •
r~~
* " "
:;:
::r
— —
•:
: .
•MM
1
'.
MHMM
• .: : :
.'.'.'.
•MMOT
1
'
:'.'.
•
^MiHM
:
1 '. '. '.
MMi^^
•:: :
— -
' . .'.
....
V/HR/V
1.00
0.5?
0.50
'
:•.
::;•'
'. ; : '.
•
• : . :
':'.•:
'.'.'.
: :
'.:'•-
:
B/D/Lb
0.107
0.056
0.052
i
-i— :
.„...
• : : • 1
'.':':•
••'•:
. . . ,
83
an
75
(.->
o /
60
50
0
0.5
1.0
CATALYST AGE, BBL/LB
1.5
2.0
to
(Q
-I
(D
ON
-------
K
«,
-------
FIGURE 18
DESULFURIZATION OF HIGH LEVEL (80-85% VANADIUM REMOVAL) DEMETALLIZED BACHAQUERO EXPORT VACUUM RESIDUUM
OVER 0.02" BEADS
Run 185-249
FEED COMPOSITION
OPERATING CONDITIONS
17.5 °API
1.0 % Sulfur
100 ppm V
34 ppm Ni
2000 Psig H2 Pressure
760°F, Reactor Temperature
1.0 V/HR/V Liq. Sp. Vel.
0.107 B/D/LB Cat. Sp. Vel.
CATALYST AGE, BBL/LB
to
-------
K0
10 X 10 TO THE CENTIMETER 18 X 25 CM.
KEUFFEL & ESSER CO. MADE IK us*
461510
FIGURE 19
-------
percent sulfur in the product versus catalyst age and is compared
with sulfur levels in the products from low level and medium level
demetal1ization"operatfohs'conducted"at srmilar desulfurization
conditions.
4.4 Perietal lized Llovdminster Vacuum Residuum
4.4.1 Products from Medium Level Demetal1ization
Products from demeta11Ization Run 115-1248 were blended and
designated HRI L-422. The inspections on this blended feed
are presented in Table 8.
This operation using L-422 as feed was carried out In Run 185-
250 at 760°F, hydrogen pressure of 2000 psig, liquid space
velocity of 1.0 Vo/Hr/Vr and catalyst space velocity of 0.107
Bbl/D/Lb. This run lasted for 26 days to a catalyst age of
3.0 Bbl/Ub. Aging results from this run are summarized in
Figure 20.
*
4.4.2 Products from High Level Demeta11ization
Products from demetal1ization Run 115-1249 were blended and
designated HRI L-424, with inspections presented in Table 8.
This operation was carried out in Run 185-251 using L-424 as
feed at 760°F, hydrogen pressure of 2000 psig, liquid space
velocity of 1.0 Vo/Hr/Vr and catalyst space velocity of 0.107
Bbl/Hr/Lb. This run lasted for 2k days to a catalyst age of
2.9 Bbl/Lb.
Catalyst deactivation with age is plotted in Figure 20, along
with results obtained on the lower demetallized feed (45-60%
vanadium removal) carried out in Run 185-250. The catalyst
slopes of these two runs are about the same, and correlate
well with previously determined data on Tia Juana, Bachaquero
and Gach Saran which showed that highly demeta Hi zed feeds
generally give lower deactivation slopes.
Figure 21 shows the sulfur levels versus catalyst age which
were achieved during desulfurization of the two levels of de-
metallized Lloydminster feeds. Sulfur levels ranged from
0.62 to 0.80 weight percent on the lower demetal lized feed and
from 0.46 to 0.65 weight percent sulfur on the higher demetal-
lized feed . The overall desulfurization was lower on the
higher demetallized feed because the last trace of sulfur is
more difficult to remove.
45
-------
TABLE 8 FEED STOCK INSPECTIONS
Feedstock: Demetallized Lloydmfnster Vacuum Residuum
(0
Vanadium Removed, % 63 85
HRI Identification No. L-422 L-424
Gravity, "API 13.2 16.4
Sulfur, W % 2.83 1.88
RCR, W % 13.5 • 9.5
Nitrogen, ppm 4375 3785
Carbon, W % 85.84 85.72
Hydrogen, W % 11.03 11.02
Vanadium, ppm 63 31
Nickel, ppm 59 31
Viscosity, SFS @ 210°F 111 24
SUS (5) 210°F 1075 286
IBP-650°F
Volume, % 12 0
Gravity, °API 34.5
Sulfur, W % 0.41
650-975°F
Volume, % 27.7
Gravity, °API 20*2
Sulfur, W % 0.89
975°F+
Volume, % (65) 60.3
Gravity, °API g 1
Sulfur, W % 2 21
RCR, W % ,6
(1) Compared to feed into demetal1ization
46
-------
FIGURE 20
DESULFURIZATION OF DEMETALLIZED LLOYDMINSTER VACUUM RESIDUUM
OVER 0.
02" BEADS
FEED CHARACTERISTICS
Symbol
A
B
Run No.
185-250
185-251
°API
13.2
16.4
% S
2.83
1.88
ppm V
63
31
ppm Ni
59
31
FEED
HRI NO.
L-422
L-424
% VANADIUM REMOVED
In Demet. Stage
63
82
OPERATING CONDITIONS
psig Temp. F V/Hr/V B/D/Lb.
2000 760 1.0 0.107
2000 760 1.0 0.107
0 -
CATALYST AGE, BBL/LB
-------
M.C 10 X 10 TO THE CENTIMETER la X 25 CM.
£• KEUFFEL a ESSER CO. MADE IN us*.
461510
FIGURE 21
to
c
(D
10
CATALYST AGE, BBL/LB
-------
The amount of vanadium to be removed in the demetall Tzation
stage depends on the final sulfur level of the fuel oil. For
a given sulfur level fuel oil the optimum combination of vanadium
removal in the demetallization stage with optimum sulfur removal
in the desulfurization stage is presented below.
% Vanadium % Sulfur
Fuel Oil Sulfur Removal in the Removal in the
Level Demetallization Stage Desulfurization Stage
1 W % 65 60
0.5 W % 75 76.5
0.3 W % 82.5 83.2
4.5 Spent Desulfurization Catalyst Inspections
Analyses on the spent desulfurization catalysts are tabulated
in Table 9. The carbon content ranged from about 12 to 20 weight
percent but did not correlate with catalyst age, temperature or
liquid space velocity.
However, the metals laydown (vanadium S- nickel) was strongly
influenced by the demetal1ization level achieved in the demetal-
lization step. For example, feeding Bachaquero Export vacuum
residuum which was demetallized to 44 percent metals removal
level, deposited 3.65 weight percent metals on the commercial
HDS catalyst while the same feed demetal lized to 64 percent level
deposited only 1.93 weight percent metals on the HDS catalyst at
a comparable catalyst age and identical operating conditions.
Similar results were obtained on Lloydminster vacuum residuum.
Feed which was demetallized to a 53 percent level, deposited 3.82
weight percent metals on the HDS catalyst while the feed demetal-
lized to a 76 percent level deposited only 1.49 weight percent
metals at a comparable catalyst age and operating conditions.
The results on Bachaquero and Lloydminster residua further prove
the ability of the newly developed scavenger catalyst to sub-
stantially prolong the life of a commercial HDS catalyst as was
the case previously demonstrated on Tia Juana and Gach Saran
residua.
The pore size distribution of the spent desulfurization catalysts
are shown in Table 10. The loss in total pore volumes was not
as extensive as was the case with the demetal1ization catalysts.
-------
RUN NO.
184-194 Bachaquero
40-45% V-Removal
184-195 Bachaquero
65-70% V-Removal
184-196 Bachaquero
65-70% V-Removal
184-197 Bachaquero
65-70% V-Removal
vn 184-248 Bachaquero
° 65-70% V-Removal
185-249 Bachaquero
80-85% V-Removal
185-250 Lloydminster
45-60% V-Removal
185-251 Lloydminster
80-85% V-Removal
TABLE 9 ANALYSES OF SPENT DESULFURIZATiON CATALYSTS
LHSV CATALYST AGE WT %
TEMP. °F
760
760
760
780
780
760
760
760
Vo/Hr/Vr
1.00
1.00
0.53
0.50
0.50
1.00
- 1.00
1.00
Bbl/Lb
2.20
2.30
1.10
0.45
0.68
1.90
3.00
2.90
C
15.63
18.44
14.74
15-80
20.51
20.28
12.13
17-73
S
6.48
4.58
4.90
2.52
4.13
3.68
6.53
4.80
V
3.07
1.47
1.00
0.52
0.80
0.80
2.22
0.69
Ni
0.58
0.46
0.35
0.21
0.28
0.30
1.60
0.80
-------
TABLE 10 PORE SIZE DISTRIBUTION OF SPENT DESULFURIZATION CATALYSTS
SPENT
CATALYST
From Run No.
Fresh 3401
184-194
184-195
184-196
184-197
185-248
185-249
185-250
185-251
CATALYST
AGE
Bbl/Lb
2.20
2.30
1.10
0.45
0.68
1.90
3.00
2.90
WT %
C
...
15-63
18.44
14.74
15.80
20.51
20.28
12.13
17.73
V + Ni
---
3.65
1.93
1.35
0.73
1.08
1.10
3.82
1.49
PORE DIAMETER RANGE ANGSTROMS . ->
30-50
0.
0.
0.
0.
0.
0.
0.
0.
0.
114
128
124
100
105
114
148
084
112
50-70 70-100
PORE VOLUME cc/g
0.207
0.129
0.085
0.170
0.150
0.095
0.051
0.151
0.109
0.161
0.047
0.043
0.072
0.070
0.043
0.021
0.104
0.055
100+'
0.087
0.049
0.045
0.070
0.067
0.055
0.030
0.049
0.057
TOTAL
PORE
VOLUME
cc/g,
LOSS IN
TOTAL
PORE VOLUME
%
0.569
0.
0.
0.
0.
0.
0.
0.
0.
353
297
412
392
307
250
388
333
38.0
47.8
27.6
31.1
46.0
56.1
31.8
41.5
Note: Pore size distribution and total pore volumes on spent catalysts were corrected to fresh
catalyst basis. (See section 4.6 for method used.)
-------
k.6 Desulfurizatlon Correlations
The effect of residual metals (vanadium & nickel) in the demetal-
lized feed on the deactivation slope of the commercial HDS cat-
alyst is shown in Figure 22. Depicted are results obtained on
Bachaquero Export and Lloydminster vacuum residua from the present
Phase III work and data obtained on Tia Juana and Gach Saran
vacuum residua under Phase II work.
Results from data accumulated on Bachaquero Export vacuum residuum
indicated that the higher the level of metals removal in the de-
metallization stage, the lower would be the deactivation slope of
the commercial HDS catalyst. However, above 65 percent vanadium
removal, corresponding to about 2kO ppm metals, the increase in
the deactivation slope is only about one half of that between k$
and 65 percent vanadium removal.
For Lloydminster vacuum residuum the difference in the deacti-
vation slopes between 63 and 82 percent vanadium removal was quite
small, less than 0.1. Figure 23 summarizes the contaminant metals
deposited on the desulfurfzation catalyst versus metals in the
demetallized feed with each feed at approximately the same catalyst
age. As expected, less metals are deposited on the catalyst
feeding lower metals containing feed, with a corresponding in-
creased life expectancy of the desulfurization catalyst.
The most important factor to influence deactivation of the de-
sulfurization catalyst appears to be the level of the desulfur-
ization operation being carried out. Figure 2k shows the vari-
ation in the deactivation slope versus desulfurization level on
Bachaquero Export demetallized to 65 percent vanadium removal
level. Variation in the desulfurization level was achieved by
varying the liquid space velocity between 0.5 and 1.0 Vo/Hr/Vr
and varying the temperature between 760 and 780°F. The catalyst
deactivation slope increases by a factor of three for an increase
in the desulfurization level from 60 percent to 80 percent. This
sharp increase In the rate of catalyst deactivation as indicated
in Figure 2k seems to suggest that the rate of sulfur removal
for Bachaquero Export feed Is strongly diffusion controlled as
was the case with vanadium removal in the demetal1ization step
(See section 3.7 for explanation). A demetal1ization catalyst
with the added ability to remove sulfur during demetallization
would be an ideal catalyst to produce low sulfur fuel oil in a
two stage demetalllzation process. This Is so because the level
of sulfur removal that is necessary in the second step to achieve
a low sulfur fuel oil would be greatly decreased thus allowing
HDS in the regime of slow catalyst deactivation. The newly de-
veloped demetal1ization catalyst appears to fit the above
requirements.
52
-------
Ka
"
LOGARITHMIC 48 72SO
a x 2.7 CVCLCS ..». .. u ....
ESSER co.
ed Identiflcatforf
-------
LOGARITHMIC 46 728O
2 X 2.7 CYCLES ««oi IN u. ».«.
KEUFFEL ft ESSER CO.
£ • i um
ETALS LOADING OF 0
jiged Identtfjcattk
-------
-------
4.7 Correlated Fuel Oil Properties
Detailed inspections were obtained on products from each de-
sulfurization run. Two twenty-four hour periods were analyzed,
one near the beginning of the run and the other near the end of
the run. Summaries of product yields and inspections are given
in Tables B-l to B-13 of the Appendix B.
Viscosity variation as a function of API gravity for fuel oils
obtained from Bachaquero Export and Lloydminster vacuum residua
are presented in Figure 25. Variation of pour point with vis-
cosity on the 400°F+ fuel oils is given in Figure 26, and for
the 650°F+ fuel oils in Figure 27.
Viscosity determinations were performed using ASTM D-88 "Standard
Method of Test for Saybolt Viscosity" at standard temperatures
of 122 and 210°F.
The pour point determinations were performed using ASTM D-97
"Standard Method of Test for Pour Point of Petroleum Oils."
56
-------
Figure 25
4000
10
FUEL OIL VISCOSITY VS. aAPI GRAVITY
A Bachaquero Export Vacuum Residuum
B Lloydmlnster Vacuum Residuum
FUEL OIL GRAVITY, °AP!
57.
-------
Figue 26
10,000
en
LU
en
UJ
o
en
o
o
en
1000
100
10
400°F+ FUEL OIL VISCOSITY VS. POUR POINT
A Bachaquero Export Vacuum Residuum
B Lloydminster Vacuum Residuum
POUR POINT, °F
58
-------
Figure 27
10,000
1,000
100
650°F+ FUEL OIL VISCOSITY VS. POUR POINT
A Bachaquero Export Vacuum Residuum
B Lloydminster Vacuum Residuum
POUR POINT °F
59
-------
60
-------
5. PROCESS ECONOMICS
The major costs In producing low sulfur fuel oil from vacuum
residua depend on the cost of the facility necessary to carry
out the demetallizatlon and desulfurization operations, the
amount of hydrogen consumed during the process, and the cost
of the demetallization and desulfurization catalysts. Summaries
have been prepared of the processing costs, including investment
requirements for producing 1.0, 0.5 and 0.3 weight percent sul-
fur fuel oil from Bachaquero Export and Lloydminster vacuum
residua utilizing the commercially prepared 1.0 weight percent
molybdenum on 20 x 50 mesh activated bauxite in the demeta1-
lization step and commercial HDS beads in the desulfurization
step. These results are gfven in Tables 11 and 12.
Data used in cost computations for the Bachaquero Export vacuum
residuum cases and the 0.5 and 1.0 weight percent sulfur fuel
oil cases for the Lloydminster residuum required only a small
amount of extrapolation from the operating conditions used in
the experimental program. For the 0.3 weight percent sulfur
fuel oil case from the Lloydminster feed, a greater extrapolation
of the data was necessary.
Curves showing the variation of the overall operating cost for
producing 1.0, 0.5, and 0.3 weight .percent sulfur fuel oil as a
function of vanadium removal in the demetal1ization stage for
the Bachaquero and Lloydminster feeds are given in the Exhibit A
portion of Figures 28 and 29. These operating costs include
capital charges of 25 percent on investment. The cost calcula-
tions are based on 1976 Gulf Coast construction costs and are
for a 20,000 barrels per day plant, which is perhaps the minimum
size plant that a refiner would build. These operating costs
would be lowered as the plant capacity is Increased.
Figure 28, Exhibit A shows that for Bachaquero Export vacuum
resfduum, there were optimum demeta11Ization levels which mini-
mize overall operating costs for the production of 1.0 and 0.5
percent sulfur fuel oil. The 0.5 weight percent sulfur fuel
oil curve shows the optimum demeta11ization to be about 55 per-
cent vanadium removal, corresponding to a total operating cost
of $2.72 per barrel. The optimum demetallizatron for producing
1.0 weight percent sulfur fuel oil appears to be about k<=> per-
cent vanadium removal, the condition utilized in the experi-
mental program. At this optimum level, the total operating cost
is $2.01 per barrel. Costs for producing 0.3 weight percent
sulfur fuel oil decreased with increasing levels of demetalli*-
zation, but it was difficult to achieve sustained vanadium
61
-------
TABLE 11
INVESTMENT AND OPERATING COST FOR A TWO STAGE
DEMETALLIZATION - DESULFURIZATION
OPERATION OF BACHAQUERO EXPORT
VACUUM RESIDUUM
BASES
1.
3.
5.
7-
9.
II.
Plant Capacity - 20,000 BPSD
Hydrogen Cost - $1.0/MSCF
Fuel - $2.0/MMBTU
Process Water - $0.25/1000 Gal.
Demetallization Catalyst - $0.35/Lb.
2. 1976 Gulf Coast Construction
*f. Power - $0.025/KWH
6. Steam - $2.5/1000 Lb.
8. Cooling Water - $O.OV1000 Gal.
10. Desulfurization Catalyst - $2.0/Lb.
•^ ^nvil*^* ^ ^BV • t • A* *p« ^ • ^r m • ^^«4 w *»• v ¥ *f ** V ^ v ^ ^ f j^mr • • ^f 9 ^ ^f +f «•• t • VH • • ^B ^^ v» • ^f • • ^f ••* ^* ^
Capital Charges - 25% of investment included in the operating cost.
% Vanadium removed
in Demetal1ization Stage
1 W % Sulfur Fuel Oil
Investment, MM$
Operating Cost,$/BBL
15-93
2.017
65
18.89
2.155
80
25.51
2.575
0.5 W % Sulfur Fuel Oil
Investment, MM$
Operating Cost, $/BBL
20.58
2.763
23.80
2.7^0
30.98
3.029
0.3 W % Sulfur Fuel Oil
Investment, MM$
Operating Cost, $/BBL
4.323
28.13
3.737
35.22
3.528
-------
TABLE 12
INVESTMENT AND OPERATING COST FOR A TWO STAGE
DEMETALLIZATION - DESULFURIZATION
OEERAT1PN OF LLOYDMINStER .
VACUUM RESIDUUM
BASES
I.
3.
5,
7.
9-
11.
Plant Capacity - 20,000 BPSD
Hydrogen cost - $l.O/MSCF
Fuel T.$2.0/MMBTU
Process Water - $0.25/1000 Gal.
Demetallization Catalyst - $0.35/Lb
2. 1976 Gulf Coast Construction
k. Power - $0.025/KWH
6. Steam - $2.5/1000 Lb.
8. Cooling Water - $O.OVlOOO Gal.
10. Desulfurization Catalyst - $2.0/Lb
Capital Charges - 25% of investment included in the operating cost.
% Vanadium removed
in Deinstall ization Stage
1 W % Sulfur Fuel Oil
Investment, MM$
Operating Cost, $/BBL
65
16.24
2.122
80
18.50
2.199
85
19-90
2.257
0.5 W
% Sulfur
Fuel Oil
Investment, MM$
Operating Cost, $/BBL
19.73
2.678
22.37
2.650
23.80
2.672
0.3 W % Sulfur Fuel Oil
Investment, MM$
Operating Cost, $/BBL
23.98
3.196
27-32
3.082
29-78
3.082
-------
M«,
-------
removal above 80 percent, due to the rapid rate of catalyst
deactlvation. However, the actual removal of metals beyond
this level is believed to be of limited economic value since
these metal compounds are hard to remove in the demetallization
step and, therefore, are also not easily deposited on the de-
sulfurizatlon catalyst.
The variation in total operating cost as a function.of fuel oil
sulfur level for the Bachaquero feed is summarized in the form
of a plot in Figure 28, Exhibit B. These results show that an
additional cost of 71 cents per barrel was required to go from
1 to 0.5 weight percent sulfur and an additional 82<;/Bbl was
required to go from 0.5 to 0.3 weight percent sulfur.
The saving in overall operating cost by the inclusion of the
demetallization step in the process for the Bachaquero feed is
summarized in Figure 30. The savings ranged from 44^/Bbl for
the one weight percent sulfur fuel oil to $l.I5/Bbl for the
0.3 weight percent sulfur fuel .oil.
Figure 29, Exhibit A shows that for Lloyminster vacuum residuum
feed (lower metals, high sulfur feed), there were also optimum
demetallization levels which minimize overall costs for the pro-
duction of fuel oils. The one weight percent fuel oil curve
shows the optimum demetallization to be about 65 percent vanadium
removal which corresponds to a total operating cost of $2.12 per
barrel. The optimum demetallization for producing 0.5 weight
percent sulfur fuel oil is about 75 percent vanadium removal and
corresponds to a total operating cost of $2.64 per barrel. The
optimum demetallization for producting 0.3 weight percent sulfur
fuel oil is about 83 percent vanadium removal. The overall
operating cost for this operation is $3.08 per barrel.
Figure 29, Exhibit B summarized the variation in overall oper-
ating cost as a function of fuel oil sulfur levels for the
Lloydminster feed. These results indicate that the incremental
cost to produce 0.5 weight percent sulfur fuel oil is 52^/Bbl
over the cost to produce one weight percent sulfur fuel oil.
Another incremental cost of 44
-------
10 X 10 TO THE CENTIMETER 18 X 25 CM
KEUFFEL & ESSER CO. MADE IN us*
461510
Figure 29
TOTAL OPERATING COST FOR A
UM REMOVAL IN DE
-------
Figure 30
TOTAL OPERATING COST FOR A
TWO STAGE DEMETALLIZATION-DESULFUR!ZAT!ON
VERSUS
B
0-3 0.4 0.5
FUEL OIL SULFUR, W %
.9 1.0
67
-------
production of 400°F+ fuel oil containing 1.0, 0.5 and 0.3 weight
percent sulfur from Bachaquero Export and Lloydminster vacuum
residua are given in Table 13 and 14 respectively.
68
-------
Table 13 ESTIMATED OVERALL YIELDS AND PRODUCT PROPERTIES FROM
CONSECUTIVE DEMETALLIZATION AND DESULFURIZATION OF BACHAQUERO EXPORT VACUUM RESIDUUM
400°F+ Fuel Ofl Sulfur, W% 1.0 -------- - ----------- 0.5 .................... 0.3
Yields
W% n "API %S W% V% "API %S W% V% "API %S
H2S £- NH3 2.4 3.0 3.3
r3
ON
CrC3 0.8 1.5 1.7
C^OO°F 1.5 2.0 60 <0.03 3.6 5.0 60 <0.03 5.1 7.0 60 *0.03
400-650°F 6.8 8.0 33 0.07 10.6 12.6 33 <0.05 12.4 14.7 33 <0.03
650-975°F 23.9 26.4 22 0.29 30.0 33.4 23 0.12 32.0 35.5 23 0.07
975°F+ 65.6 67.4 11.5 1.35 52.8 54.5 12 0.81 47.1 48.8 12.5 0.53
400°F+ 96.3 101.8 15.6 1.0 93.4 100.5 18.3 0.5 91.5 99 19 0.30
TOTAL 101. 0 103.8 16.2 0.97 101.5 105.5 19.7 0.47 101.6 106.0 21.2 0.28
-------
Table 14 ESTIMATED OVERALL YIELDS AND PRODUCT PROPERTIES FROM
CONSECUTIVE DEMETALLIZATiON AND DESULFURIZATION OF LLOYDMINSTER VACUUM RESIDUUM
400°F+ Fuel Oil Sulfur, W% 1.0 0.5 - 0.3
Yields
W% V°/0 "API %S W% V°/0 "API S% _W%_ V% "API %S
H2S & NH3 5.1 5.7 5.9
C,-C3 I.I 1.6 2.0
^j
° C^-400 1.7 2.2 55 ^0.03 2.2 3.0 55 <0.03 2.7 3-6 55 <0.03
400-650°P 8.0 9.^ 30 40.03 11.3 13.3 30 <0.03 13.2 15.6 31 <0.03
650-975°F 3^.^ 38.0 21 0.28 39.3 ^3.5 21 0.19 M.O tf7.9 22 O.]k
975°F+ 51.0 52.7 11 1.64 41.5 43.2 12 0.92 34.9 36.6 13 0.59
400°^. 93.4 100.1 16.3 1.0 92.1 100.0 18.2 0.5 91.1 100.1 20 0.3
TOTAL 101.3 102.3 16.9 0.98 101.6 103.0 19.2 0.49 101.7 103.7 21.0 0,29
-------
APPENDICES
-------
72
-------
APPENDIX A
SUMMARY OF DEMETALLIZATION RUNS
73
-------
-------
Table A SUMMARY OF DEHETALLIZATION RUNS
Product Inspections
Run No.-Period
115-1233-IC
2A
2B
3A
3B
4A
48
5A
SB
6A
H5-I237-1B
2
3
4
1I5-I238-IB
2
3
4
5
6
7
8
9
10
II
12
13
14
15
16
17
18
19
20
Catalyst
HRI No.
3634
3634
3634
Catalyst Catalyst
Base Promoter Preparation Feed
Porocel 1% Mo Engelhard Bachaquero
20 x 50 Mesh Commercial Export
Vacuum
Residuum
L-397
"
Porocel |% Ho Engelhard Bachaquero
20 x 50 Mesh Commercial Export
Vacuum
Res 1 duum
Porocel 1% Mo Engelhard Bachaquero
20 x 50 Mesh Commercial Export
Vacuum
Residuum
Temp.
°F
789
791
791
789
789
790
790
790
790
792
775
774
778
778
792
790
791
790
789
789
792
790
790
790
791
790
790
790
788
790
790
790
790
791
H
Pres.
psig
2030
2020
2020
1990
1990
2000
2000
2000
2000
1950
1990
2000
2015
2000
2010
2005
2000
2000
2000
1990
2005
2015
2000
2000
2000
2000
2010
2000
2010
2000
2015
2020
2000
2010
Space
V/Hr/V
.47
.44
.52
.54
.51
.50
.48
.49
.46
- .32
.52
.48
.51
.49
.50
.51
.51
.51
.53
.53
.52
.51
.52
.51
.53
.51
.51
.50
.51
.51
.49
.48
.51
.51
Velocity
r B/D/Lfa
.111
.109
.115
.117
.114
.114
.112
.113
.110
.100
.040
.036
.039
.037
.037
.038
.038
.038
.040
.040
.039
.038
.039
.038
.040
.038
.038
.037
.039
.038
.037
.036
.038
.038
Hi
'*2
Rate
SCF/Bbl
4300
4580
4580
3920
3920
4370
4370
3950
3950
3650
6280
6440
5100
5570
4320
4240
4780
4500
3750
4250
4)50
4190
4430
4240
4220
4390
4090
3600
4290
3960
3920
4580
4190
4200
Cat.
Age.
Bbl/Lb
•^mMMMMkMMMV
.136
.190
.248
.307
.364
.421
.477
.534
.589
.639
.024
.072
.III
.148
.031
.069
.107
.145
.185
.225
.264
.302
.341
..379
.4)9
.457
.495
.532
.571
.609
.646
.682
.720
.758
Gravity
"API
12.8 !
12.7 2
12.5 2
12.1 2
11.6 3
12.0 1
12.7
15.5
16.1
16.4
16.0
16.1
15.5
14.9
15.6
15.0
12.5
13.6
15.1
15.0
15.1
15.0
14.0
15.9
15.7
13.7
15.4
16.0
15.8
15.6
% S
!.09
i.Ol
i.OI
£.00
1.02
.97
.87
.50
.52
.41
.50
.38
.35
.41
.40
.37
.37
.39
.37
.43
.46
.36
.44
.33
.38
.34
.35
.38
.33
.52
V
ppm
310
311
315
310
308
307
216
206
199
172
149
161
175
186
180
189
188
177
175
183
181
187
186
184
199
203
209
207
214
219
Nl
ppm
65
67
65
63
63
67
49
48
49
46
40
45
49
55
50
52
52
51
51
51
51
50
55
55
49
49
50
49
51
52
IBP-
550" F
V %
3
1
1
6
7
6
6
6
4
7
3
7
8
2
5
6
6
4
4
5
5
6
6
10
9
o
J
8
10
8
7
-------
Table A SUMMARY OF DEMETALIIZATION RUNS
Product Inspections
Run No.-Period
115-1239-1B
2
3
5
6
7
8
9
-J 10
* 11
12
13
14
15
16
17
18
19
20
21
22
115-1240-18
2
3
4
5
6
7
8
9
Catalyst Catalyst Catalyst
HRI No. Base Promoter Preparation Feed
3634 Porocel |% Mo Engelhard Bachaquero
20 x 50 Mesh Conmerclal Export
Vacuum
Res I duurn
L-397
3634 Porocel ,% Mo Engelhard Bachaquero
20 x 50 Mesh Conmerclal Export
Vacuum
Res 1 duum
Temp.
°F
790
790
793
790
790
790
790
789
789
790
790
790
790
790
792
790
790
790
790
791
790
792
789
790
790
790
790
790
790
791
790
H2
Pres.
pslg
2010
2000
2005
2030
2000
2010
2015
1995
1985
2000
2000
2000
1990
1990
1990
1990
1990
1990
2000
2000
2010
2000
1990
1975
2000
1995
1990
2000
2000
2005
2010
Space
V/Hr/Vr
.52
.51
.50
.48
.50
.50
.50
.51
.52
.49
.50
.49
.43
.35
.36
.&
.3<»
.35
.33
.35
.3*
.36
.30
.29
.30
.29 .
.30
.29
.30
.30
.29
Velocity^
B/D/Lb
.039
.039
.038
.037
.038
.038
.038
.039
.039
.038
.038
.038
.033
.026
.028
.026
.026
.027
.026
.027
.026
.027
.023
.022
.022
.022
.023
.022
.023
.023
.022
H2
Rate
SCF/Bbl
4450
4620
<<560
4680
1(190
3970
3880
3500
4050
3920
4590
4130
1*050
1*720
1*300
1*1*50
5030
1*130
5660
l*7i»0
1*61*0
5340
6170
1*81*0
5220
501*0
1*310
5070
5670
1*570
5080
Cat.
Age.
Bbl/Lb
.030
.069
.107
.144
.182
.220
.258
.297
.336
.374
.1*21*
.1*62
.495
.521
.549
.575
.601
.628
.654
.681
.707
.734
.016
.039
.061
.083
.106
.128
.151
.174
.196
Gravity
°API
16.0
16.5
17.2
16.4
16.8
17.5
16.8
16.5
16.0
16.7
16.2
16.8
17.1
17.6
18.1
17.5
16.5
17. *»
17.2
17. *»
16.6
17.5
18.6
17.9
18.4
18.1
18.4
18.3
16.8
16.9
% S
.40
.51
.24
.51
.24
.29
.39
.33
.53
.21
.23
.32
.28
.18
.19
.14
.13
.13
.21
.52
.51
.99
.87
.89
.90
.00
.93
.9*
.98
.98
V
ppm
137
158
136
250
2)4
203
202
205
201
209
218
213
206
163
157
157
161
162
173
283
284
84
62
81
99
98
96
109
102
95
Nl
EEE
37
44
41
46
45
44
46
46
49
49
51
49
52
46
44
45
45
45
45
53
52
27
25
31
35
3«*
3<*
36
38
38
IBP-
550° F
V %
8
8
10
12
11
9
9
9
8
9
6
7
9
9
8
12
13
13
18
12
16
II
12
12
II
11
12
12
14
13
-------
Table A
SUMMARY OF OEHETALLIZATION RUNS
Product Inspections
Run No.-Period
M5-I241-IB
2
3
4
5
115-1242-18
2
3
4
5*
-^ 6A
^ 6B
8
1I5-I243-IB
2
3
4
II5-1244-IB
2
3
4
5
6
7
8
Catalyst Catalyst Catalyst
HRI No, Base Promoter
3634 Porocel |% MO
20 x 50 Mesh
3634 Porocel |% Mo
20 x 50 Mesh
3634 Porocel 1% Mo
20 x 50 Mesh
3634 Porocel 1% Mo
20 x 50 Mesh
-
Preparation
Engelhard
Commercial
Engelhard
Commercial
Engelhard
Commercial
Engelhard
Commercial
Feed
Bachaquero
Export
Vacuum
Residuum
Bachaquero
Export
Vacuum
Residuum.
Bachaquero
Export
Vacuum
Residuum
Bachaquero
Export
Vacuum
Res I duum
Temp.
°F
789
790
789
790
789
791
79*
788
790
789
790
790
790
791
791
790
790
769
770
770
770
770
770
780
780
H2
Pre's.
pslg
2000
2015
2015
1995
2000
2000
1980
2000
2005
2010
2010
2005
2000
2005
2005
2010
2000
1990
2000
1995
2000
1985
1975
1990
2000
Space Velocity
V/Hr/Ur
.35
.31
.32
.32
.33
.53
.30
.30
.28
.29
.34
.29
.31
.31
.31
.31
.31
.30
.25
.25
.25
.25
.25
.25
.25
.25
B/P/Lb
.026
.024
.024
.024
.025
.040
.023
.022
.021
.022
.026
.022
.023
.023
.023
.023
.024
.023
.019
.019
.019
.019
.019
.019
.019
.019
"2
Rate
SCF/Bbl
5590
4580
4310
4090
3260
3730
5880
5310
4470
5300
5040
4690
5590
4270
5240
5060
6210
6890
6150
5450
5260
7500
6450
5910
5570
Cat .
Age
Bbl/Lb
.018
.042
.066
,090
,103
.021
.044
.066
.08?
.109
.207
.271
.294
.317
.018
.041
.065
.077
.024
.043
.062
.081
.100
.119
.138
.157
Gravity
•API
17.9
19.0
17.9
18.5
17.6
18.0
19.8
17.5
18.2
17.0
17.6
17.7
18.4
18.7
18.2
16.9
17.6
16.8
17.2
16.7
16.5
17.2
17.1
17.1
%s
1.12
.89
.94
.97
1.04
1.11
.83
.87
.78
1.02
1.52
1.13
1.07
.88
.97
1.00
1.09
.99
.09
.07
.15
.11
.00
.88
V
ppm
76
75
87
91
99
84
64
89
92
100
103
79
88
104
120
118
124
152
143
131
118
Nl
fipm
26
26
30
30
35
28
27
31
32
32
28
29
30
32
33
35
35
43
42
41
44
IBP-
550° F
V %
8
15
10
II
12
8
12
13
12
13
10
15
11
12
13
11
9
9
II
9
10
8
10
10
After Period 5, the Unit was on Wash for 8 hours.
-------
Table A SUMMARY OF DEHETALLIZATION RUNS
Product Inspections
Run No.-Period
115-12*8-18
2A
2B
3A
3B
*A
*B
5A
SB
00 6B
7A
7B
8A
88
9A
9B
115-12*9-18
2
3
*
5
6
7
8
9
10
II
12
13
Catalyst Catalyst Catalyst Temp.
HRI No. Base Promoter Preparation Feed °F
3634 porocel 1 % Engelhard Lloydmlnster 792
20 x 50 Mesh Commercial Vacuum 791
Residuum 791
HRI 37** 788
788
791
791
790
790
792
792
790
790
791
791
789
789
363<» Porocel ( % Engelhard Lloydmlnster 790
20 x 50 Mesh Commercial Vacuum 789
Residuum 791
77*
792
786
786
788
791
791
790
791
792
H2
Pres.
pslg
Jin-i-S
2020
2020
2020
2010
2010
2000
2000
2000
2000
1950
1950
2010
2010
2000
2000
2000
2000
2015
2000
2010
2010
2000
2000
1995
1990
1985
1980
2000
2000
2025
Space
V/Hr/Vr
.54
.50
.*9
.65
.87
.93
.86
.93
.98
2.09
2.06
2.06
2.03
2.02
2.00
1.97
2.00
.80
.77
.77
.77
.77
.78
.76
.63
.62
.62
.63
.67
.67
Velocltv
B/D/Lb
.115
.112
.III
.123
.1*0
.1**
.139
.1**
.1*8
.156
.154
.15*
.152
.151
.150
.1*7
.1*9
.061
.059
.059
.059
.059
.060
.058
.0*8
.0*8
.0*8
.0*8
.051
.051
"2
Rate
SCF/Bbl
3970
3770
*300
3870
*6*0
*200
*320
*2*0
*2*0
3700
*UO
1*660
*IIO
*170
*550
*150
3650
*260
*190
5160
*320
5630
Cat.
Age
Bbl/Lb
.069
.125
.181
.2*3
.313
.385
.*55
.527
.601
.679
.756
.833
.909
.985
1.060
1.13*
1.209
.0*3
.102
.161
.220
.279
.339
.397
,**5
.*93
.5*1
.589
.6*0
.691
Gravity
"API
13.3 3
13.6 'A
15.2 J
15.5 3
16.5 3
13.8 i
12.* !
12.7 :
12.8 :
16.7
17.5
16.8
16.1
15.9
17.*
16.5
17.6
17.7
17.0
15.7
16.1
15.8
% S
M2
MS
!.6l
!.*2
!.63
S.7I
2.75
2.76
f.92
.50
.*5
.*0
.73
.68
.27
.73
.6*
.59
.82
.79
.88
V
ppm
*6
*2
57
58
62
61
68
67
67
22
2*
20
36
35
3*
31
27
21
20
30
27
39
Nl
ppm
51
*7
*8
*9
*8
61
*8
*7
55
25
30
29
33
33
33
32
31
31
29
37
39
*3
IBP-
550° F
v %
*
8
*
8
*
8
10
8
6
6
6
9
6
8
6
5
7
7
7
5
7
8
-------
APPENDIX A-1
DEMETALLIZATION OPERATING CONDITIONS. YIELDS AND PRODUCT PROPERTIES
79
-------
80
-------
DEMETALLIZATION
Table A-l. 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, VF/Hr/Vp
Catalyst Space Velocity, B/D/LE
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
115-1233-5B
0.59
Bachaquero Export Vacuum Residuum
L-397
(7.6 °API, 3.08 W% S)
Engelhard Commercial
(20 x 50 Mesh Porocel - 1% Mo)
2000
790
1.46
0.11
Two-Stage Downflow
3950
320
YIELDS
H2S 6- NH3
CI-CB
Cif-650°F
650-975°F
975°F+
Total
CM-
Gravity,
sj t u v i w ^ 9 IK
Sulfur, W %
API
FRACTION. *F
V % on Collected Liquid
Gravity, °API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SFS <5>2lO°F
SFS (3)250° F
Asphaltenes, W %
Sulfur, W %
Vanadium, ppm
Nickel, ppm
Asphaltene - free oil
Vanadium, ppm
Nickel, ppm
Coll.
1 •
100
11.6
2.02
86.23
11.05
1.53
5394
16.8
292
46
3.93
269
70
30
12
W % V %
1.0? '
0.23
4.35 5.24
18.17 19.67
76.66 77.17
100.48
99-17 102.08
11.7
2.07
IBP- 650- 975-
650° F 650° F+ 975° F 975° F+ 1050°F
5.0 95 19.3 75.7 9.52
34.5 10.4 19.2 8.0 18.8
0.37 2.13 1.18 2.37 1.30
179
550
65
20.2
438
103
1050°F+
66V18
'•7.3
2.37
22.1
453
90
81
-------
DEHETALLIZATION -
Table A-2. 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
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975^+Conversion, V %
115-1238-4
0.14
Bachaquero Export Vacuum Residuum
1-397
(7.6 °API, 3.07 W % S).
Engelhard Commercial
(20 x 50 Mesh Porocel - 1% Mo)
3634
2000
790
0.51
0.04
Two-s tage-Oownf1ow
4500
400
18.7
YIELDS
H2S & NH3
Cl-C3
fy-6500F
650-975°F
975°F+
Total
Gravity, °API
Sulfur, W %
1.30
15.3
V %
8.88
20.33
73.17
102.38
Coll.
FRACTION. °F
V % on Collected Liquid
Gravity, °API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
RCR, W %
Vanadium, ppm
Nickel, ppm
Bromine No., cgs/gm
Viscosity, SFS @210°F
SFS @250°F
100
14.9
1.41
87.75
IT. 21
1.52
4878
186
55
140
10.5
650e F+
92.0
11.6
1.81
650-
975° F
20.0
20.2
0.67
535
70
130
49
172
975°F+
72.0
10.2
1.57
18.6
82
-------
- DEMETALL+ZATION
Table A-3. 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, VF/Hr/VR
Catalyst Space Velocity, B/D/LB
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
115-1238-14
D u °-53
Bachaquero Export Vacuum Residuum
L-397
(7.6 °API, 3.08 W % S)
Engelhard Commercial
(20 x 50 Mesh Porocel - 1% Mo)
3634
2000
790
0.50
0.04
Two-Stage Downflow
3600
620
16.6
YIELDS
H2S & NH,
C1-C3
Cj.-650°F
650-975°F
975°F+
Total
Gravity, °API
Sulfur, W %
FRACTION. °F
V % on Collected Liquid
Gravity, °API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No., cgs/gm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
RCR, W %
Vanadium, ppm
Nickel,' ppm
Viscosity, SFS (2)250°F
1.32
184
55
8.5
140
16.3
9.97
18.51
75.07
103.55
IBP-
650° F
9.0
36
0.16
650° F+
91.0
14.2
1.45
650-
975° F
18.0
23.4
0.64
975* F+
73.0
10.2
1.61
515
60
44
173
18.4
83
-------
DEMETALLIZATION
Table A-4. 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, VF/Hr/VR
Catalyst Space Velocity, B/D/LB
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BB1
975°F+ Conversion V %
115-1240-3
0.06
Bachaquero Export Vacuum Residuum
L-397
(7.6 °API, 3.08 W %)
Engelhard Commercial
(20 x 50 Mesh Porocel - 1% Mo)
3634
2000
790
0.3
0.02
Two-Stage Downflow
5220
720
29.3
YIELDS
H£S &
C,-C3
W %
650-975° F
975° F+
Total
Gravity, API
Sulfur, W %
FRACTION. °F
V % on Collected Liquid
Gravity, "API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No., cgs/gm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
RCR, W % •
Vanadium, ppm
Nickel,^ppm
Viscosity, SFS ®. 122°F
.. . ~SFS(2>2100F
0.97
81
31
140
18.3
15.54
25.47
63.61
105.62
IBP-
650° F
15.0
35.5
0.07
650° F+
85.0
15.2
1.12
650-
975° F
24.3
21.5
0.59
975° F+
60.7
11.2
1.30
485
40
1420
57
170
17.8
122
46
230
84
-------
- DEMETALLIZATIOH
Table A-5- 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, Vjr/Hr/VR
Catalyst Space Velocity, B/O/LB
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
115-1240-8
0.17
Bachaquero Export Vacuum Residuum
L-397
(7.6 "API, 3.08 W % S)
Enge 1 ha rd Commere i a 1
(20 x 50 Mesh Porocel - 1% Mo)
3634
2000
791
0.30
0.02
Two-Stage Downflow
4570
63k
32.11
YIELDS
H2S & NH3
Cl-Cj
CU-650°F
650-975°F
975°F+
Total
Gravity, "API
Sulfur, W %
FRACTION. "F
V % on Collected Liquid
Gravity, °API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No., cgs/gm
Aniline Point, °F
Flash Point, °F .
Pour Point. 8F
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SFS @122°F
SFS @210°F
0.98
102
38
14.66
29. rs
61.10
104.91
17.2
Coll.
100
16.8
0.98
86.24
11.41
1.58
4585
IBP-
650° F
13.3
35.5
0.13
650° Ft
TT7
13.7
1.25
650-
975°!
28.0
21.6
0.57
975° F+
58.7
9.0
1.36
13.2
510
55
1587
60
168
19.1
425
85
-------
DEMETALLIZATION
Table A-6. 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, Vp/Hr/VR
Catalyst Space Velocity, B/D/LB
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+. Conversion, V %
115-1248-9B
1.21
Lloydminster Vacuum Residuum
3744
(6.4 "API, 5.4 W % S)
Engelhard Commercial
(20 x 50 Mesh Porocel - 1% Mo)
3634
2000
789
2.00
0.15
Two-stage Downflow
4240
420
16.6
YIELDS
& NH3
C]-C3
650-975° F
975° F+
Total
Gravity, °API
Sulfur, W %
2.92
12.9
V %
6.95
28.74
66.01
101.70
FRACTION. °F
V % on Collected Liquid
Gravity, "API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SFS 210°F
67
55
131
650°F+
93.3
10.2
3.05
510
65
144
650-
975° F
28.3
18.0
1.45
163
6.7
3.67
16.9
86
-------
DEMETALLIZATION
Table A-7. 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, Vp/Hr/Vr
Catalyst Space Velocity, B/D/LE
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
115-1249-9
0^9
Lloydminster Vacuum Residuum
3744
(6.4 "API, 5.4 W % S)
Engelhard Commercial
20 x 50 Mesh Porocel - 1% Mo)
3634
1980
791 •
0.62
0.05
Downflow
3960
640
30.9
YIELDS
W %
V %
CA-650°F
650-975°F
975°F+
Total
Gravity, °API
Sulfur, W %
FRACTION. °F
V % on Collected Liquid
Gravity, °API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SFS @210°F
0.54
10.97
33.17
51.80
100.94
95.94
1.59
Coll. IBP-
Liq. 650°F
100 13
17.7 32.9
1.59 0.14
86.13
11.35
1.57
3360
137
21
31
13.63
35.57
34.65
103.86
17.8
650-
650° F+ 975° F
87 34.3
10.8 19.7
1.63 0.74
"
167
475
60
1.0
975° F+
52.7
8.5
2.27
17.2
87
-------
-------
APPENDIX B
SUMMARY OF DESULFURIZAT10N RUNS
89
-------
90
-------
Table B SUMMARY OF DESULFURIZATION RUMS
Hun No.-Period
184-194-IB
2
4
5
6
7
8
9
10
11
12
13
14
15
« 5
18
19
20
184-I95-1B
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Catalyst Catalyst Demetalllzed Demetalllzed Temp.
HRI No. Base Feed Over °F
3104 Amer. Cy. Bachaquero Conn. Decnet. 756
0.02" Beads Export Catalyst - 760
Vacuum HRI 363** 761
Residuum 761
L-400 762
760
761
762
760
759
760
760
763
762
762
751
760
759
757
756
3104 Amer. Cy. Bachaquero Comra. Demet. 76!
0.02" Beads Export Catalyst 759
Vacuum HRI 3634 761
Residuum 761
L-401 760
761
759
762
761
761
760
762
762
760
758
760
761
759
762
760
Hydrogen
Pressure Space Velocity
pslg tf/Hr/Vr
I960 .13
2025
2005
2000
2010
2000
2000
1990
1975
1990
1950
1985
2000
2000
2000
2000
2000
1995
2010
2025
2020
2010
2000
2005
2000
1990
2010
2020
2025
2015
2005
2010
2000
2005
2010
2025
2000
2005
.06
.03
.00
.95
.99
.02
.05
.94
.04
.05
.03
.15
.11
.05
.02
.05
.10
.04
.07
.19
.22
.11
.07
.01
.11
3.99
.12
.05
.03
.06
.03
.09
.05
.06
.97
.05
.12
2010 .93
1985 1.16
B/O/Lb
.121
.113
.110
.107
.101
.105
.109
.112
.100
.III
.112
.110
.123
.119
.112
.109
.112
.118
.111
.114
.127
.131
.119
.114
.108
.119
.106
.120
.112
.110
.113
.110
.117
.112
.113
.103
.112
.120
.099
.124
Hydrogen
Rate
SCF/Bbl
4500
4460
4040
4210
4400
4820
4690
4150
4260
4270
4770
5080
4190
4270
4780
4820
3950
3900
3900
4270
3860
3660
4340
4310
3710
4050
4430
3580
4980
4910
4050
4660
3980
4030
4280
4360
4300
3880
5110
Catalyst
Age
Bbl/Lb
.083
.196
.306
.413
.514
.619
.728
.840
.940
.051
.163
.273
.396
.515
.627
.736
.848
.966
2.077
2.191
.110
.241
.360
.474
.582
.701
.807
.927
.039
.149
.262
.372
.489
.601
.714
.817
.929
2.049
2.148
2.272
Product Inspections
Gravity
°API
14.2
15.5
15.5
15.3
15.1
14.9
14.7
15.7
15.5
16.4
16.4
15.9
16.2
16.2
16.6
16.5
16.3
16.0
15.5
14.0
16.9
17.5
17.0
16.7
16.3
15.8
15.9
16.8
16.6
16.7
17.2
16.7
15.8
17.6
17.4
17.8
17.2
17.4
17.1
16.4
JLS.
1.31
.69
.68
.80
.69
.75
.75
.82
.82
.82
.83
.84
.83
.91
.93
.97
.90
.86
.91
.91
.59
.64
.63
.69
.67
.59
.57
.64
.66
.65
.65
.68
.59
.69
.68
.71
.60
.63
.64
.68
V
ppm
230
240
236
231
229
248
248
245
215
216
217
220
221
260
253
254
254
254
260
263
148
155
154
153
153
158
152
169
168
168
161
159
164
Nl IBP-550°F
ppm
43
44
42
42
47
48
49
49
47
47
47
47
46
50
54
54
54
59
59
54
39
40
41
45
45
40
41
40
41
4)
38
37
39
V %
1
6
4
4
6
2
•
2
5
4
6
6
8
7
5
9
6
5
5
4
6
6
5
^
6
5
5
^
5
ff
5
J
4
-------
Table
SUMMARY OF DESULFURIZATION RUNS
Run No.-Period
I84-I96-IB
2
3
1*
5
6
7
8
9
10
II
» "
14
15
16
17
18
19
20
184-I97-IB
2
3
4
5
6
7
8
9
I84-I98-1B
2
3
4
Catalyst Catalyst
HRI No. Base
3104 Amer> Cy.
0.02" Beads
3104 Amer. Cy.
0.02" Beads
3104 Amer. Cy.
0.02" Beads
Detneta 1 1 1 zed
Feed
Bachaquero
Export
Vacuum
Residuum
L-405
Bachaquero
Export
Vacuum
Residuum
L-405
Bachaquero
Export
Vacuum
Residuum
L-406
Oemetalllzed
Over
Comm. Demet.
Catalyst
HRI 3634
Comm. Demet.
Catalyst
HRI 3634
Comm. Demet.
Catalyst
HRI 3634
Temp.
•f
760
760
760
762
760
759
760
760
759
760
762
760
760
761
76(1
761
760
760
759
760
780
779
782
781
779
781
749
782
770
772
771
767
Hydrogen
Pressure
pslq
1950
2010
2000
2000
2010
2000
1995
2000
2000
1990
2010
2000
2010
2000
1995
2020
1995
2000
2000
1995
2000
2000
2010
2010
2010
2010
2000
1990
1990
2000
2000
2000
Space Velocity
V/Hr/Vr
.32
.57
.54
.53
.53
.52
.55
.53
.54
.54
.52
.53
.52
.49
.54
.50
.55
.57
.56
.57
.58
.56
.57
.54
.55
.52
.58
.62
.57
.46
.46
.49
.47
B/D/Lb
.034
.061
.057
.057
.056
.055
.058
.056
.055
.055
.054
.055
.055
.052
.057
.053
.058
.060
.059
.061
.061
.059
.060
.057
.058
.055
.062
.065
.061
.048
.048
.051
.049
Hydrogen
Rate
SCF/Bbl
4970
3980
4390
3860
3810
4150
3730
4220
4200
4400
3780
4560
4050
4710
4620
4440
4280
4220
4310
4530
3650
4140
3530
4280
4310
4140
4080
3310
5400
4050
3590
1850
Catalyst
Age
Bbl/tb
.029
.089
.146
.203
.258
.313
.371
.424
.478
.532
.584
.637
.692
.744
.801
.854
.909
.969
1.028
1.088
.041
.100
.160
.217
.275
.330
.384
.449
.454
.038
.086
.137
.172
Product Inspections
Gravity
'API
20.6
19.2
18.5
19.4
20.2
19.6
23.7
19.2
19.8
19.8
21.1
19.4
19.3
19.9
20.0
19.7
18.6
19.0
18.0
19.3
20.9
21.0
19-7
19.6
20.5
20.7
20.0
20.9
21.7
21.7
21.5
20.4
% S
.45
.38
.37
.45
.43
.51
.44
.39
.37
.39
.38
.37
.35
.41
.36
.40
.45
.44
.48
.27
.29
.33
.31
.33
.34
.51
.427.46
.40
.31
.33
.65
V
ppm
95
118
118
124
129
133
130
131
142
144
135
143
146
142
145
145
148
150
158
160
96
111
118
120
126
148
137
99
106
106
Nl
ppm
25
27
30
29
35
35
39
39
40
39
37
35
34
36
35
37
37
38
37
38
26
30
30
32
32
36
32
29
29
30
IBP-550°F
V %
9
8
12
9
9
7
to
12
11
9
10
13
10
9
9
10
12
9
9
11
12
11
10
13
13
14
14
13
12
13
15
13
-------
Table B SUMMARY OF DESULFURIZATION RUMS
Run No.-Period
I85-248-IB
2
3
4
5
6
7
8
9
10
11
12
VQ! 85-249-IB
\ft 2
3
l»
5
6
7
8
9
10
II
12
13
lit
15
16
17
185-250-18
2
3
4
S
6
Catalyst Catalyst Demetalllzed Demetalllzed
HRI No. Base Feed Over
3104 Amer. Cy. Bachaquero Cairo. Demet.
0.02" Beads Export Catalyst
Vacuum HRI 3634
Residuum
L-406
3104 Amer. Cy. Bachaquero Comm. Demet.
0.02" Beads Export Catalyst
Vacuum HRI 3634
Res 1 duum
L-408
.
3104 Amer. Cy. Lloydmlnster Comm. Demet.
0.02" Beads Vacuum Catalyst
Residuum HRI 3634
L-422
Temp.
°F
780
782
780
778
779
781
783
781
785
781
780
781
763
762
762
760
761
760
759
760
761
759
760
760
759
759
761
761
761
760
763
759
761
758
758
Hydrogen
Pressure Space Velocity
pslq V/Hr/Vr
1970 .56
2010 .55
2000 .56
2000 .57
2000 .60
2000 .56
2010 .56
2000 .56
2000 .50
1990 .53
2015 .55
2000 .53
2020
2005
1990
2000
2010
2015
2010
2010
2010
2010
2015
2005
2000
2000
2000
2005
2010
2015
2015
1985
1980
1995
2005
.21
.11
.15
.11
.08
.06
.11
.13
.11
.11
.10
.18
.18
.19
.07
.84
.03
.00
•07
.08
.11
.09
.11
B/D/tb
.059
.059
.059
.061
.063
.060
.060
.059
.052
.056
.058
.056
.129
.119
.123
.119
.115
.113
.119
.121
.119
.119
.118
.125
.125
.127
.114
.090
.110
.107
.114
.115
.119
.117
.119
Hydrogen
Rate
SCF/Bbl
4710
3540
4060
3870
4540
3090
3770
4340
4530
4440
4310
3970
3690
4290
4430
4360
4250
4350
3950
3840
3960
3950
4770
3580
3690
3750
4160
5430
4510
9510
8680
8890
8280
8450
7960
Catalyst
Age
Bbl/Lb
.039
.098
.157
.218
.281
.341
.401
.460
.512
.568
.626
.682
.084
.203
.326
.445
.560
.673
.792
.913
.032
.151
.269
.394
.519
.640
.760
.850
.905
.100
.214
.329
.448
.565
.684
Product Inspections
Gravity
"API
22.0
22.1
22.5
20.3
20.4
21.3
21.4
21.6
21.5
21.6
21.2
21.2
19.7
19.6
19.0
17.9
17.7
17.5
17-4
18.4
18.5
19.1
18.7
18.2
18.0
18.0
18.6
18.8
18.2
15.0
18.6
18.3
18.5
17.8
18.3
% S
.24
.28
.31
.33
.26
.31
.32
.27
.26
.30
.31
.56
.43
.47
.51
.41
.52
.50
.45
.45
.56
.48
,45
.50
.41
.47
.49
.60
.79
.66
.66
.65
.72
.72
V
£PJS
63
77
90
90
87
92
99
95
98
63
62
63
66
67
66
70
70
68
63
40
40
38
38
39
40
Nl
ppm
19
23
27
28
27
27
28
27
25
29
30
20
20
20
22
24
24
26
26
27
27
28
28
28
29
IBP-550'F
V %
13
15
14
15
14
16
17
16
17
16
16
16
IBP-600°F
12
14
17
10
10
10
12
II
13
10
13
13
11
13
II
12
13
IBP-550eF
6
5
f
5
5
5
f
4
-------
Table B
SUMMARY OF DESULFURIZATION RUMS
Run No.-Period
185-250-7
8
9
10
II
12
13
14
15
16
17
U> '8
-f 19
20
21
22
23
24
25
26
185-25I-1B
2
3
4
5
6
7
8
9
10
II
12
13
14
15
Catalyst Catalyst Demetal II zed Demetalllzed Temp.
HRI No. Base Feed Over °F
3104 Amer. Cy. Lloydmlnster Comm. Deroet. 759
0.02" Beads Vacuum Catalyst 760
Residuum HRI 3634 755
L-422 755
760
752
760
764
759
760
759
761
760
766
766
770
760
758
758
759
3104 Amer. Cy. Lloydmlnster Comm. Demet. 758
0.02" Beads Vacuum Catalyst 757
Residuum HRI 3634 76 1
L.424 760
761
761'
759
761
760
761
760
761
759
760
760
Hydrogen
Pressure Space Velocity
pslg V/Hr/Vr
I960 .25
1985
2010
2020
2015
2000
1995
2005
2005
1995
2000
2010
1995
2010
2015
2010
2000
1985
1980
1995
2000
2000
2015
2005
2000
2010
1995
1995
2000
2000
2005
1990
2000
1990
1980
.08
.94
.87
.16
.27
.88
.21
.10
.15
.00
.99
.00
.23
.23
.19
.01
.06
.Ok
.93
.18
.15
.It*
.11
.18
.06
.11
.24
.20
.21
.12
.01
.05
.15
.30
B/D/lb
.134
.115
.100
.093
.124
.136
.094
.130
.118
.123
.107
.106
.107
.132
.132
.127
.108
.113
.III
.100
.124
.122
.121
.118
.124
.112
.118
.131
.127
.128
.119
.107
.III
.122
.138
Hydrogen
Rate
SCF/Bbl
7040
5650
4350
5410
4460
3220
5000
3610
3930
3770
4340
4420
4500
3830
3720
3920
4270
4560
5150
5110
4230
4150
4450
4730
5290
4300
4110
3900
3710
3660
3990
5090
3760
3980
3620
Catalyst
Age
Bbl/Lb
.818
• 933
.033
.126
.250
.386
.480
.610
.728
.851
.958
2.064
2.171
2.303
2.435
2.562
2.670
2.783
2.894
2.994
.130
.252
• 373
.491
.620
.732
.850
.981
. .108
.236
.355
.462
.573
.695
.833
Product Inspections
Gravity
"API
18.4
18.2
19.0
17-1
17-1
16.8
17-9
17.6
18.2
17-6
16.7
17-6
17-9
15-9
17.6
I7-I
18.4
17-9
17.2
17.9
18.3
19.4
19.3
18.9
19.2
19.4
18.9
18.4
18.7
18.0
18.6
18.9
18.5
19.1
18.2
% S
.73
.68
.68
.73
• 79
.92
.70
.69
.75
-78
.72
.65
-71
.80
.81
.82
.72
.79
.85
• 79
.58
-59
.40
.49
.55
-47
-50
.53
.65
.61
.66
.45
.57
.54
.61
V
ppm
i*ta^—
40
39
38
49
43
40
50
49
50
46
38
44
45
45
12
12
18
18
17
16
16
18
20
20
20
21
18
Nl IBP-550°F
ppm
31
30
30
33
34
34
31
30
30
33
29
32
33
32
21
22
16
16
19
20
20
20
20
22
20
21
21
V %
4
4
4
3
5
4
4
4
4
3
4
4
2
3
4
1
4
4
4
4
4
3
4
4
4
5
5
6
S
5
5
3
6
4
5
-------
Table B SUMMARY OF DESULFURIZATION RUNS
Run No.-Period
185-251-16
17
18
19
20
21
22
23
24
Catalyst
HRI No.
3104
Catalyst
Base
Amer. Cy.
0.02" Beads
Demetalllzed
feed
Uoydminster
Vacuum
Residuum
L-424
Demetalllzed
Over
Conrn. Oemet.
Catalyst
HRI 3634
Temp.
*F
760
761
761
758
761
760
759
760
760
Hydrogen
Pressure
pslg
1980
1990
2000
1990
1990
1995
1980
1995
2000
Space Velocity
V/Hr/Vr
.21
.16
.09
.15
.13
.20
.08
.08
.13
B/D/Lb
.128
.122
.115
.122
.120
.127
.114
. 114
.120
Hydrogen
Rate
SCF/Bbl
3340
3780
4540
5100
3670
3550
3740
4150
3250
Catalyst
Age
Bbl/Lb
1.961
2.083
2.198
2.320
2.440
2.567
2.681
2.795
2.915
Product Inspections
Gravity
"API
18.3
18.7
18.7
18.6
18.5
18.5
18.0
19.6
18.8
% S
.69
.58
.64
.64
.59
.64
.73
.70
.65
V
ppm
18
20
20
20
Ni IBP-550°F
ppm
23
24
24
25
V %
4
4
6
6
5
6
5
6
5
-------
96
-------
APPENDIX B-l
DESULFURIZATION OPERATING CONDITIONS. YIELDS AND PRODUCT PROPERTIES
97
-------
98
-------
DESULFURIZATION
Table B-l. 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, VF/Hr/VR
Catalyst Space Velocity, B/D/LB
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
184-194-17
1.85
Demetallized Bachaquero Export
Vacuum Residuum
L-400
(11.3 °API, 1.98W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3104
2000
760
1.05
0.112
Downflow
3950
365
9.2
YIELDS
H2S Sr NH,
C]-C3
C£.-650°F
6?0°F-975°F
975° F
Total
Gravity, °API
Sulfur, W %
FRACTION. °F
V % on Collected Liquid
Gravity, °API
Sulfur, W %
Carbon, W %
Hydrogen, W %
Nitrogen, ppm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
RCR, W %
Viscosity, SFS (5>210°.F
0.89
16.9
8.38
23.55
70.15
102.08
Coll.
100
16.3
0.90
86.92
11. 5**
3735
IBP-
650° F
7.3
32.1
650° F+
92.7
14.4
1.03
650-
975° F
23.3
22.9
0.13
975° F+
69.4
11.1
1.22
137
535
50
124
155
16.7
99
-------
DESULFURIZATION
Table B-2. 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
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
184-195-4
0.47
Demetal 1 ized Bachaquero Export
Vacuum Residuum
L-401
(13.1 °APt, 1.39 W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3104
2000
761
1.07
0.11
Downflow
4300
310
5.6
YIELDS
H2S & NH3
C--C3
CU-400°F
450-650° F
650-975° F
975° F+
Total
C4+
Gravity, °API
Sulfur, W %
FRACTION, °F
V % on Collected Liquid
Gravity, ° API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No. cgs/gm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
Smoke Point, °F
ASTM Color
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS @210°F
SFS @122°F
SFS (SfclO'F
SFS @250° F
W %
0.92
0.40
1.24
7.57
22.29
68.06
100.48
99.16
0.67
Coll. IBP-
Liq. 400° F
100 1.25
16.7 47.2
0.69 ^0.03
86.34
11.59
1.60
3527
4.4
153
45
V %
1.65
8.78
24.26
68.92
103.61
19.6
400° F+
98.75
15.7
0.68
360
25
364
521
400-
650° F
8.50
32.5
<0.03
6.1
141
L-4.5
650-
650° F+ 975° F
90.25 23.5
14.2 22.4
0.72/0.69 0.15
177
510
60
693
960
975° F+
66.75
11.7
0.92
16.8
330
114
100
-------
DESULFURIZATION
Table B-3- 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
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
184-195-19
2.15
65-79% Demetallized Bachaquero Export
Vacuum Residuum
L-401
(13.1 °APt, 1.39 W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3104
2010
762
0.93
0.10
Downflow
5110
275
9.7
YIELDS
H2$ & NH,
c,-c3
Ci.-4008F
400-650° F
650-975° F
975° F+
Total
C4+
Gravity, "API
Sulfur, W %
FRACTION. °F
V % on Collected Liquid
Gravity, ° API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No. cgs/gm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
Smoke Point, °F
ASTM Color
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS <3>2100F
SFS @122°F
SFS @210°F
SFS. 0250° F
Coll.
Uq,
100
17.1
0.64
86.50
11.59
35^0
164
39
W %
1.12
0.40
1.03
7.5^
24.24
66.09
100.42
98.90
0.48
IBP-
400° F 400° F+
1.0 99.0
49.4 15.6
^0.03 0.49
3.7
430
35
335
644
17.3
400-
650° F
8.5
32.9
^0.03
5.9
139
6.0
650° F+
90.5
14.2
0.63
500
55
& A 4*
630
956
V %
1.37
8.62
25.87
65.91
101.77
650-
975° F 975° F+
25.5 65.0
22.0 12.0
0.13 0.76
1_x
76
15.9
"3 jO
1 ft 1™
105
101
-------
DESULFURIZATION
Table B-4. 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,
Catalyst Space Velocity, B/D/LB
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
184-196-4
0.20
65-70% Demetallized Bachaquero Export
Vacuum Residuum
L-405
(14.4 "API, 1.40 W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3104
2000
762
0.53
0.06
Downflow
3860
410
8.0
YIELDS
H2S & NH,
crc3
C,-400°F
400-650° F
650-975° F
975° F+
Total
C4+
Gravity, "API
Sulfur, W %
FRACTION, °F
V % on Collected Liquid
Gravity, ° API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No. cgs/gm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
Smoke Point, °F
ASTM Color
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS <5>210°F
SFS @1220F
SFS @210°F
SFS <2>210°F
W %
Coll.
LIq.
100
19>
0.37
86.68
11.77
1.62
3316
124
29
1.35
0.40
2.6
9.^3
24.48
62.32
100.64
98.89
0.3^
IBP-
400 QF
3.0
50.4
<0.03
4.1
129
L-2.5
V °/o
3.^2
10.72
26.02
62.25
102.41
19.6
400° F+
97.0
18.5
0.33
390
30
202
180
400-
650° F
10.5
33.2
^0.03
6.7
141
11
5.0
650-
650° F+ 975° F
86.5 25.5
15.7 22.5
0.50 0.05
176
500
60
526
582
37
975° F+
61.0
13.2
0.52
l^.S
22i
9C
102
-------
DESULFURIZATION
Table B-5. OPERATING CONDITIONS. YIELDS. AND PRODUCT PROPFRTI
Run Number
Catalyst Age, BBL/LB
Feed .
HRI Identification No.
Catalyst
HRI No.
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, Vp/Hr/VR
Catalyst Space Velocity, B/D/LB
Reactor Type
Hydrogen Rate, SCF/B8L
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
184-196-20
65-701 Demeta11ized Bachaquero Export
Vacuum Residuum
L-405
(14.4 °API, 1.40 W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3104
1990
760
0.57
0.06
Downflow
4530
345
16.6
YIELDS
H2S & NH,
Ci-C,
C4-400°F
400-650°F
650-975°F
975°F+
Total
St .
Gravity,
W %
'API
Sulfur, W %
FRACTION. °F
V % on Collected Liquid
Gravity, ° API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No. cgs/gm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
Smoke Point, °F
ASTM Color
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS @210°F
SFS @122°F
SFS @210°F
SFS (3250°F
160
38
V %
0.40
3.54
9.44
28.35
57.60
100.53
98.93
0.48
IBP-
400° F 400° F+
4.0 96.0
47.3 17.2
0.45
4.38
10.59
29.76
56.49
101.22
17.8
400- 650-
650° F 650° F+ 975° F 975°
10.5 85.5 29.5 5§
33.2 15.3 22.5 12
0.56 <0.03 0.
F+
.0
.4
80
2.6
131
410
20
5.8
137
12.0
L-5.0
181
500
45
236
195
540
650
16.5
393
120
103
-------
DESULFURIZATION
Table B-6. 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
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
185-248-3
0.15
65-70% Demetallized Bachaquero Export
Vacuum Residuum
L-406
(15.0 °API, 1.25 W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3104
2000
780
0.56
0.06
Downflow
4060
480
16.0
YIELDS
& NH3
H2S
C,-C3
400-650°F
650-975°F
975°F+
Total
Gravity, °API
Sulfur, W %
22.8
6.82
13.84
29.24
54.03
103.93
0.37
FRACTION. °F
V % on Collected Liquid
Gravity, "API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No., cgs/gm
Aniline Point, °F
Flash Point, °F
Pour Point,
Smoke Point,
ASTM Color
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS 210°F
SFS 210°F
°F
°F
Coll. IBP-
Liq. 400 400° F+
100 6.:o •
22.5 50.6
0.28
86.41
IK93
1.64
2635
94.0
19.9
0.31
400-
650° F
13.4
32.4
0.04
650° F+
80.6
17.8
0.40
650-
975° F
28.3
22.8
0.12
975° F+
52.3
13.9
0.61
3.7
128
L-2.0
77
23
365
35
117
4.8
141
12.5
4.5
480
45
272
180
14.6
155
104:
-------
DESULFURIZATION
Table B-7- 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
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
185-248-11
0.63
65-70% Demetallized Bachaquerp Export
Vacuum Residuum
L-406
(15 "API, 1.25 W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3104
2010
780
0.55
0.06
Downflow
4300
480
26.7
YIELDS
H2S & NH,
Cj-C
400-650°F
650-975°F
975°F+
Total
Gravity, °API
Sulfur, W %
FRACTION. °F
V % on Collected Liquid
Gravity, ° API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No.,cgs/gm
Aniline Point, °F
Flash Point, °F
Pour Point,
Smoke Point,
ASTM Color
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS <2>210°F
SFS 210°F
°F
. °F
W %
1 .33
0.71
6.60
12.72
32.06
47.27
100.75
98.71
Coll.
Liq.
100
21.2
0.31
86.66
11.98
1.64
2487
0.30
IBP-
400° F
7.7
49.9
3.1
•V • •
130
• ^ •»
0.5
400° F+
92.3
20.1
0.36
335
35
21.5
400-
650° F
13.0
32.4
0.04
4.6
140
13.0
L-3.5
V %
8.44
13.33
34.14
47.16
103.06
650° F+
79.3
17.6
0.37
475
50
650-
975° F
33.3
22.6
184
76
28
123
302
5°F*
12.9
0.67
15.49
308
105
-------
DESULFURIZATION
Table B-8. 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
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
185-249-4
0.44
80-85% Demetallized Bachaquero Export
Vacuum Residuum
L-408
(17.5 °API, 1.00 W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3104
2000
760
1.11
0.12
Downflow
4360
10.4
YIELDS
H2S & NH,
crc3
C,-400°F
400-650°F
650-975°F
975°F+
Total
Gravity, °API
Sulfur, W %
FRACTION. °F
V % on Collected Liquid
Gravity, ° API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No. cgs/gm
Aniline Point, QF
Flash Point, °F
Pour Point,
Smoke Point,
ASTM Color
RCR, W %
Vanadium, ppm °3
Nickel, ppm 20
Viscosity, SUS @210°F
SFS @ 122°F
SFS @ 210°F
°F
°F
Col 1 .
Lfq.
100
17.9
0.51
86.30
11.71
1.62
3201
W %
"6758
0.48
1.56
10.42
28.10
59.23
100.37
99.31
0.55
IBP-
400° F
1.7
49.4
400 °F+
98.3
18.7
0.45
18.
400-
650° F
its
32.6
<0.02
0
650° F+
86.7
14.9
0.59
V %
1.94
11.53
29.13
57.06
99.66
650-
975° F
29.3
22.2
0.19
975° F+
57.4
11.4
0.82
2.67
410
20
5.19
12.0
490
35
165
175
745
34
15.9
184
106
-------
DESULFURIZATION
Table B-q. 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
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
185-249-15
1.76
80-85% Demeta11ized Bachaquero Export
Vacuum Residuum
L-408
(17.5 °API, 1.00 W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3104
2000
761
1.07
0.11
Downflow
4160
10.7
YIELDS
H2S & NH,
C]-C?
Cj.-400'F
400-650°F
650-975°F
975°F+
Total
C4+
Gravity,
w %
'API
Sulfur, W %
FRACTION. °F
V % on Collected Liquid
Gravity, ° API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Bromine No. cgs/gm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
Smoke Point, °F
ASTM Color
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS <3>210°F
SFS (S>122°F
SFS 2100F
63
26
Coll.
Liq.
100
18.6
0.47
86.84
11.67
1.60
3377
0.52
1.64
10.78
28.25
58.60
100.25
99.27
18.7
0.64
IBP- 400-
400° F 400° F+ 650° F
1.7 98.3 12.0
39.2 17.9 32.8
0.66 ^.0.02
- - C Q
2.1
140
320
25
12.5
177
270
0°F+
.3
16.9
0.55
v %
1.90
11.98
29.25
56.90
100.08
650-
975°F 975°F+
165
480
40
606
29.3
21.5
0.21
57.0
12.0
0.97
15.0
166
107
-------
DESULFURIZATION
Table B-10. 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, Vp/Hr/VR
Catalyst Space Velocity, B/D/LB
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
185-250-14
1.61
60-65% Demetallized Lloydminster
Vacuum Residuum
L-422
(13.2 "API, 2.83 W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3104
2000
764
1.21
0.13
Downflow
3950
420
6.1
YIELDS
H2S & NH3
C,-C-3
C^-400
400-650°F
650-975°F
975°F+
Total
Gravity, "API
Sulfur, W %
FRACTION. °F
V % on Collected Liquid
Gravity, °API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS <5>210°F
SFS @210°F
W %
2.22
0.66
1.81
6.51
28.39
61.06
100.65
97.77
17.
8
V %
2.32
7.34
30.16
61.02
100.84
0.94
Coll.
Liq.
100
17.6
86.95
11.61
1.60
5347
IBP-
400° F
2.0
50.2
121
400 °F+
98.0
16.9
0.90
430
35
400-
650° F
7.3
31.0
<0.03
127
•
650° F+
90.7
14.5
0.96
485
55
650-
975° F
30.0
21.7
0.19
167
975° F+
60.7
12.6
1.41
34
1.3.9
215
39
108
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DESULFURIZATION
Tab 1eB-11. 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, VF/Hr/VR
Catalyst Space Velocity, B/D/LB
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
185-250-25
2.89
60-65% Demetallized Lloydminster
Vacuum Residuum
L-422
(13.2 °API, 2.83 W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3101*
1980
760
1.04
0.11
Downflow
5150
520
11.9
YIELDS
V %
cc
400-650°F
650-975°F
975°F+
Total
C4+
Gravity, "API
Sulfur, W %
FRACTION. °F
V % on Collected Liquid
Gravity, "API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS (S>210°F
SFS @210°F
Coll.
Lig.
"
100
17.2
86.56
11.70
1.61
2665
2.28
0.66
1.93
7.18
31.04
57.71
100.80
97.86
0.9^
IBP-
400° F
2.3
50.7
0.12
400° F+
97.7
16.1
1.0
17.
400-
650° F
~To
29-7
/-0.03
3
650° F+
89.7
14.6
1.21
2.47
8.04
32.85
57.26
100.62
650-
975° F
32.7
20.8
0.23
* ^f\
975° F+
57.0
11.3
1.46
33
117
425
25
223
128
495
55
14.7
39
109
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DESULFURIZATION
Table B-12. 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, VF/Hr/VR
Catalyst Space Velocity, B/D/LB
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
185-251-4
0.49
85% Demetallized Lloydminster
Vacuum Residuum
L-424
(16.4 "API, 1.88 W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3104
2000
761
1.11
0.12
Downflow
4720
460
14.6
YIELDS
H2S &
C1
C.
40
, o
C.-400°F
0-650° F
650-975° F
975° F+
Total
C4+
Gravity,
'API
Sulfur, W %
FRACTION. °F
V % Collected Liquid
Gravity, °API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS <5>210°F
98.28
0.49
Coll.
100
18.9
0.49
86.92
11.96
1.64
2495
18
16
129
19.0
1.50
11.38
35.63
51.50
100.00
IBP-
650° F
12.7
31.7
0.03
650 °F+
87.3
16.1
0.55
650-
975° F
35.7
21.4
0.15
975° F+
51.6
12.8
0.85
485
45
259
167
12.8
110
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DESULFURIZATION
Table B-13. 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, VF/Hr/VR
Catalyst Space Velocity, B/D/LB
Reactor Type
Hydrogen Rate, SCF/BBL
Hydrogen Consumption, SCF/BBL
975°F+ Conversion, V %
185-251-20
2.44
85% Demetallized Lloydminster
Vacuum Residuum
L-424
(16.4 °API, 1.88 W % S)
American Cyanamid Co-Mo
0.02" diameter beads
3104
^ 1990
760
1.13
0.12
Downflow
3670
310
8.0
YIELDS
H2S & NH3
C,-C3
Clf-400°F
400-650° F
650-975° F
975° F+
Total
C^+
Gravity, °API
Sulfur, W %
FRACTION. °F
V % on Collected Liquid
Gravity, °API
Sulfur, W %
Carbon, W %
Hydrogen, W %
H/C Atomic Ratio
Nitrogen, ppm
Aniline Point, °F
Flash Point, °F
Pour Point, °F
RCR, W %
Vanadium, ppm
Nickel, ppm
Viscosity, SUS @122°F
SUS
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO.
EPA-600/2-76-165
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Demetallization of Heavy Residual Oils—Phase in
S. REPORT DATE
June 1976
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(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, New Jersey 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
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
Phase m Final: 1/75-3/76
14. SPONSORING AGENCY CODE
EPA-ORD
is.SUPPLEMENTARY NOTES EPA.650/2-73-041 and -041a are earlier reports in this series.
IERL-RTP project officer for this report is W.J.Rhodes, Mail Drop 61, 919/549-8411,
Ext 2851.
16. ABSTRACT
The report gives results of Phase HI work to optimize operating conditions in the
demetallization step for overall desulfurization of heavy petroleum residual oils.
Bachaquero and Lloydrainster vacuum residua were demetallized to different levels
of vanadium removal, the products desulfurized over commercial hydrodesulfurization
catalyst at various operating conditions, and minimum operating costs were calcu-
lated to produce low sulfur fuel oil. The report describes test units, operating condi-
tions, and procedures, and includes run summaries and tables of feedstock, product,
and catalyst inspections. Graphs and tables depicting operating costs for producing
0.3, 0.5, and 1.0 wt % sulfur fuel oil are given, along with various correlations
between demetallization levels, catalyst deactivation, demetallization rate constant,
and contaminant metals deposited on catalyst.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Air Pollution Catalysis
Petroleum Industry Operating Costs
Residual Oils
Fuel Oil
Desulfurization
Vanadium
Air Pollution Control
Stationary Sources
Demetallization
Hydrodesulfurization
13B
05C
21D
14A,05A
07A,07D
07B
3. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
112
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-731
112
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