EPA-650/2-73-041
December 1973
Environmental Protection Technology Series
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EPA-650/2-73-041
DEMETALIIZATION OF HEAVY
RESIDUAL OILS
by
William C. Rovesti and Ronald H. Wolk
Hydrocarbon Research, Inc.
P. 0. Box 1416
New York and Puritan Avenues
Trenton, New Jersey 08607
Contract No. 68-02-0293
Program Element No. IABOI3
ROAP No. 2IADD-50
EPA Project Officer: William J. Rhodes
Control Systems Laboratory
National Environmental Research Center
Research Triangle Park, North Carolina 27711
Prepared for
OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
Washington, D. C. 20460
December 1973
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This report has been reviewed by the Environmental Protection Agency and
approved for publication. Approval does not signify that the contents
necessarily reflect the views and policies of the Agency, nor does
mention of trade names or commercial products constitute endorsement
or recommendation for use.
11
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ABSTRACT
The current energy shortage in the United States, combined with
the present and anticipated sulfur dioxide and other pollutant
emission standards, have increased the need for and the value
of clean, low sulfur fuel oil. Many large crude oil reserves
exist in the world which have high sulfur contents and contain
nickel and vanadium contaminants in high enough concentrations
to rapidly poison hydrodesulfurization catalysts. This combina-
tion makes it economically unattractive to desulfurize the re-
sidual fraction of these crudes.
The purpose of this program, carried out at the Trenton, New Jer-
sey laboratories of Hydrocarbon Research, Inc., a subsidiary of
Dynalectron Corporation, was to develop an improved demetalliza-
tion catalyst so that desulfurization of the residuum could be
carried out economically. A total of twenty-seven catalysts
were prepared representing a number of combinations of supports
and promoters.
It was found that 20 x 50 mesh granulated activated bauxite when
impregnated with a molybdenum promoter provided the necessary
catalytic activity and resistance to poisoning.
Demetal1ization of Tia Juana, Bachaquero, and Gach Saran vacuum
residua was carried out and the products of this operation were
subsequently desulfurized to produce 0.5 weight percent sulfur
fuel oil. Economic analysis of the data indicated that the fuel
oil could be produced for $1.19, $1.^6, and $1.6^ per barrel for
the Gach Saran, Tia Juana, and Bachaquero vacuum residua, respec-
tively, in a United States Gulf Coast facility with a capacity of
20,000 barrels per day. These costs include hydrogen, catalyst,
all other operating expenses, and capital charges of 25 percent
of investment.
i i i
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IV
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CONTENTS
Page
No.
Abstract iii
List of Figures vi ?
List of Tables xi
SECTIONS
I. CONCLUSIONS 1
II. RECOMMENDATIONS 3
III. INTRODUCTION 5
IV. EXPERIMENTAL PROGRAM 9
V. PROCESS ECONOMICS 73
VI. APPENDICES 83
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V I
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LIST OF FIGURES
Figure Page
No. Title No.
1 Pore Volume Distribution of Demetal1ization
Catalyst Supports 1^
2 Fixed Bed Demetal1ization Unit 18
3 Fixed Bed Demetal1ization Reactor 19
k Alteration of the Pore Volume Distribution
of Activated Bauxite During Impregnation
with Molybdenum 32
5 Cumulative Pore Size Distribution of
Various LX-22 Preparations 33
6 Electron Probe and X-Ray Studies of LX-22-1
at 100X 3^
7 Electron Probe and X-Ray Studies of LX-22-5
at 200X 36
8 Demetallization of Tia Juana Vacuum
Residuum over 2% Molybdenum/20 x 50 Mesh
Bauxite 40
9 Demetal1ization of Tia Juana Vacuum
Residuum over 2% Molybdenum/20 x 50 Mesh
Activated Bauxite (HRI 2765) ^3
10 Change in Activated Bauxite Pore Size
Distribution When Demetallizing Tia
Juana Vacuum Residuum kk
11 Change in Pore Size Distribution of LX-22-1
When Demetal1izing Tia Juana Vacuum
Residuum 46
vH
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LIST OF FIGURES
Figure Page
No. Title No.
12 Change in Pore Size Distribution of LX-22-5
When Demetal1izing Tfa Juana Vacuum
Residuum ^7
13 Demetal1ization of Bachaquero Vacuum
Residuum over 2% Molybdenum/20 x 50 Mesh
Bauxite ^8
l^t Demetal 1 ization of Bachaquero Vacuum
Residuum over 2% Molybdenum/20 x 50 Mesh
Bauxite 50
15 Change in Pore Size Distribution of LX-22-4
When Demetal1izing Bachaquero Vacuum
Residuum 51
16 Change in Pore Size Distribution of LX-22-3
When Demetal1izing Bachaquero Vacuum
Residuum 52
17 Demetallization of Gach Saran Vacuum
Residuum over 2% Mo/20 x 50 Mesh Bauxite 53
18 Change in Pore Size Distribution of LX-22-2
When Demetal1izing Gach Saran Vacuum
Residuum 5^
19 Desulfurization of Demetallized Gach Saran
Vacuum Residuum 60
20 Desulfurlzation of Demetallized Bachaquero
Vacuum Residuum 61
21 Desulfurization of Demetallized Tia Juana
Vacuum Residuum 62
VIII
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LIST OF FIGURES
Figure Page
No. Title No.
22 Total Operating Cost: Two-Stage Demetalli-
zation-Desulfurization of Gach Saran
Vacuum Residuum 7^
23 Total Operating Cost: Two-Stage DemetalH-
zation-Desulfurization of Tia Juana
Vacuum Residuum 76
24 Total Operating Cost: Two-Stage Demetalli-
zation-Desulfurization of Bachaquero
Vacuum Residuum 77
25 Overall Costs for Producing Low Sulfur Fuel
Oil from Bachaquero Vacuum Residuum 78
IX
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LIST OF TABLES
Table Page
No. Title No.
1 Residual Fuel Oil Prices 6
2 Petroleum Demetal1ization Catalyst
Bibliography of U.S. Patents 195^-1973 10
3 Catalyst Supports 13
4 Demetal1ization Catalysts 16
5 Summary of Demetal1ization Catalyst
Screening Operations Using Tia Juana
Vacuum Residuum 22
6 Summary of DemetalIization Catalyst
Screening Data 28
7 Description and Analyses of the Activated
Bauxite Support Used in the Preparation
of LX-22 Catalysts 30
8 Molybdenum Content and Compacted Bulk
Density of Various LX-22 Preparations 31
9 1971 Vacuum Bottoms Production Rates for
Feeds Studied in Program 37
10 Vacuum Residuum Feed Inspections 39
11 Analyses of Spent Demetallization Catalyst k2
12 Composition of Demetallized Residua Fed to
the Desulfurization Reactor 56
13 Demetal Hzed Feed Inspections 57
XI
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LIST OF TABLES
Page
Title No.
l*f Summary of Inspections on American Cyanamid
0.02" High Activity Beaded Catalyst 58
15 Analyses of Spent Desulfurization Catalyst 63
16 Vanadium and Nickel Balances from Desulfuri-
zatfon Runs 64
17 Effect of Metals Removal from High Metals
Feed on Metals Laydown on Catalyst 66
18 Summary of Results on the Demetallization
and Desulfurization of Vacuum Residua 67
19 Quantitative N.A.A. Analyses of Vacuum
Residua 69
20 Trace Element Analyses 70
21 Trace Metal Analyses on Tia Juana Vacuum
Residuum Feed and Selected Demetallized
Products Using Neutron Activation and
Atomic Absorption Analyses 71
22 Estimated Overall Yields and Product Pro-
perties: Consecutive Demeta11ization
and Desulfurization of Gach Saran Vacuum
Residuum 80
23 Estimated Overall Yields and Product Pro-
perties: Consecutive Demetal1ization
and Desulfurization of Tia Juana Vacuum
Residuum 81
x i i
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LIST OF TABLES
Table Page
No. Title Nn.
24 Estimated Overall Yields and Product Proper-
ties: Consecutive Demetal1ization and
Desulfurization of Bachaquero Vacuum
Residuum 82
C-l Summary of Catalyst Screening Runs 109
D-l Summary of Demetal1ization Runs 117
E-l Summary of Desulfurization Runs 123
F-l to Operating Conditions, Yields, and Product
F-12 Inspections 129
XIII
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XIV
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SECTION I
CONCLUSIONS
In this program, a number of catalyst promoters, mainly from
Group VIM of the Periodic Table, were deposited on low cost
catalyst supports. Twenty-seven combinations in all were pre-
pared. Evaluation of these catalysts was carried out in a down-
flow, fixed bed, continuous reactor by measuring the amount of
demetallization obtained on Tia Juana vacuum residuum. This re-
siduum was selected for use in the screening procedure because
it is a material produced in large volume in Venezuela, has been
historically imported to the East Coast of the United States,
and has high metals and sulfur concentrations.
Results of the screening tests indicated that 20 x 50 mesh acti-
vated bauxite, impregnated with two weight percent molybdenum,
provided a catalyst with greatly improved demetal1ization activi-
ty, reasonable stability to poisoning, and relatively low cost.
Present day commercial hydrodesulfurization catalysts cost be-
tween $0.85 and $1.50 per pound. It appears that this new cata-
lyst can be sold for about $0.20 per pound.
In order to test the overall combination of demeta11ization fol-
lowed by desulfurization, quantities of demetallized product were
gathered by demetal1izing Tia Juana, Bachaquero, and Gach Saran
vacuum residua. The first two are major Venezuelan export crudes
and the latter is a major Iranian export crude. In 1972, the
combined production of these crudes was about 2,000,000 barrels
per day. Normally, the residua from these Venezuelan crudes are
blended with refined distillates to meet product specifications
or are used as ship bunkers. The Iranian crude, however, is ex-
ported as whole crude.
The demetallized residua were then desulfurized by a high activi-
ty desulfurization catalyst to produce about 96 volume percent
yield of 0.5 weight percent sulfur fuel oil (350°F+). Naphtha
was the other major product and amounted to about eight percent,
which gave an overall liquid yield of about 10^ volume percent.
Process economic studies were made and the overall costs for pro-
ducing 0.5 weight percent sulfur fuel oil, including capital
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charges of 25 percent, in a United States Gulf Coast unit with
a 20,000 barrel per day capacity would be:
Tia Juana $1,k6 per barrel
Bachaquero $1.64 per barrel
Gach Saran $1.19 per barrel
These costs are far less than the current differential between
0.5 percent sulfur fuel oil and high sulfur residual oil.
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SECTION II
RECOMMENDATIONS
It is recommended that this work be continued by carrying out
the work listed below.
1. Long term aging test on catalyst sample promoted with 0.5
weight percent molybdenum to obtain data to provide a com-
parison with catalyst promoted with 2.0 weight percent
molybdenum.
2. Preparation in laboratory equipment of small batches of
catalyst by catalyst manufacturers.
3. Screening tests to (a) establish initial activity of cata-
lyst samples, (b) obtain estimates of cost-activity rela-
tionships, (c) obtain some short term aging data.
4. Long term aging test on the best laboratory samples evalu-
ated in (3).
5. Production of 5,000-10,000 pounds of catalyst by catalyst
manufacturer.
6. Initial screening test on catalyst produced in (5).
7. Long term deactivation studies over commercially produced
catalyst using one feed from the original program.
8. Additional two-stage demetallization and desulfurization
studies on other feeds with optimization of level of de-
metallization to be selected from high metals Venezuelan,
Canadian, Middle East, or domestic crudes.
If the effort contemplated in the tasks above proves to be suc-
cessful, it should be followed by a large scale pilot plant de-
monstration of the demetal1ization operation. Desulfurization
studies of the demetallized product from the pilot operation
would then be in order. A detailed commercial plant design
based on these results should then be prepared.
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SECTION III
INTRODUCTION
The United States has developed a position which is unique in
its history in that, for the first time, it has become neces-
sary to look to overseas sources to provide enough petroleum
to meet projected needs. This increase in the demand for pe-
troleum products occurs at a time when domestic reserves are
capable of producing about 10,000,000 barrels of crude oil per
day. In 1972, total consumption was of the order of 15,000,000
barrels per day.
Along with the need for increased imports, the recent clean fuel
requirements have created a price differential system in the
cost of imported oil as a function of its sulfur content. Na-
tions which export oil have been quick to realize that low sul-
fur oil, which is in short supply, is much more valuable that
high sulfur residual oils. Technology has been available in
the past for producing low sulfur fuel oil from high sulfur re-
sidual oil, but this technology has heretofore been too expen-
sive to apply on a large scale since there was no economic in-
centive for refiners to desulfurize high sulfur residuum oils.
Obviously, in the recent past, the situation has changed and
the cost of desulfurization can be passed on to the consumer
because of the short supply of low sulfur oil. It can be seen
from Table 1, which was taken from the July 23, 1973 issue of
Oil and Gas Journal (published weekly), that the cost of 0.3 per-
cent sulfur fuel oil in the New York City market is about $5.50
per barrel. For fuel oil with 1.0 percent sulfur, the price is
about $4.50 per barrel. The value of bunker C oil in the Carib-
bean is $2.40 per barrel. It is most interesting to note that
the last figure of $2.40 per barrel for bunker C oil has not
changed for at least two years. Comparable data is presented
from a July 26, 1971 Oil and Gas Journal publication. The point
of greatest interest is, of course, that the value of low sulfur
oil has gone up sharply. There has been a difference of about
$3.00 per barrel between the value of low sulfur oil at the
point of consumption and high sulfur oil at the point of produc-
tion. The cost of transporting oil from the Caribbean to the
East Coast markets Is on the order of $0.30 per barrel (at world-
scale tanker rate of W100). It can therefore be seen that the
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Table 1. RESIDUAL FUEL OIL PRICES
(Source: Oil and Gas Journal)
Hid Continent (Group 3)
No. 6 (Less than 1% S)
No. 6 (1% S and Above)
Chicago
No. 6 (Max 1% S)
No. 6 (Max. 1.25% S)
No. 5 (Max. 1% S)
Gulf Coast (Cargoes)
Bunker C Fuel (0.6% S)
Bunker C Fuel
New York Harbor (Barges)
No. 6 (Max. 1% S)
No. 6 (Max. 0.3% S)
No. 5 (Max. 1% S)
California (Tank-Car-Truck)
Bunker C Los Angeles Rack
Caribbean Area (Venezuelan Ports)
Bunker C Fuel
July 26, 1971
$/Bbl
2.60
2.50
4.62
4.52
3.70-3.80
3.00-3.25
4.10
3.60-3.70
2.41
July 23, 1973
$/Bbl
2.60
2.50
5.57
5.99
4.15
5.54-5.66
4.59
3.70
2.35-2.40
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price differential that one could apply to a processing opera-
tion is on the order of $2.50-2.70 per barrel.
In the past, the major difficulty in desulfurizing high sulfur
oil has been Its tendency to poison catalysts by deposition of
heavy metals, such as nickel and vanadium. An intermediate
step to solving this problem was the construction in the late
1960's and early 1970's of very large heavy gas oil desulfuri-
zation units in the Caribbean. These units are capable of re-
moving the heavy gas oil fraction, which normally contains only
trace quantities of catalyst poisons, from the crude oil by
vacuum distillation and desulfurizing It to 0.3 weight percent
sulfur or less. This kind of operation is only a temporary solu-
tion since there is still a large amount of residual oil left
for disposal. This material can be blended off with lower sul-
fur materials, such as desulfurized heavy gas oil, and marketed
as fuel oil, which can be used as refinery fuel or for ships'
bunkers. The latter two uses concentrate the use of high sulfur
fractions in areas in which there are no sulfur emission speci-
fications at the present time. However, this material is still
quite valuable as a source of energy.
Technology had been developed earlier to remove the metals from
the residual oil fraction so that the desulfurization catalyst,
which is used in a subsequent operation, would not be rapidly
poisoned. This technology Is commercially viable, but Is still
relatively expensive because the demetal1ization removal reac-
tion proceeds quite slowly over low cost, naturally occurring
catalysts, which have been used for the demetal1ization step.
It was the purpose of this work to develop materials which would
allow much higher rates of metals removal from the petroleum re-
siduum so the overall economics of desulfurization to environ-
mentally acceptable levels would be improved.
The use of high pressure hydrogenation to desulfurize fuel oil
is a capital intensive process. A significant portion of the
capital required is devoted to the construction and installation
of high pressure, large volume, continuous reactors. At the
same time, the use of inactive demetal1ization agents to accom-
plish the demetal1izatlon requires that the residence time in
these large reactors be lengthy. This results in unwanted con-
sumption of hydrogen which is associated with the cracking of
these residual oils, which does not of itself contribute to de-
sul furizat ion. The use of a more active demetal1ization catalyst
reduces costs in that it reduces capital requirements and im-
proves hydrogen utilization, In that hydrogen is used for desul-
furization rather than cracking. These Improvements in cost
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must be weighed against the use of an improved demetal1ization
catalyst which, of necessity, must cost more than the simple
natural catalysts used previously.
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SECTION IV
EXPERIMENTAL PROGRAM
LITERATURE SURVEY
A survey of U.S. Patents and other literature from 195^ to
1973 was made as the first step in the Experimental Program.
The subject area was limited to the contacting of nickel- and
vanadium-containing petroleum oils with solid catalysts or ad-
sorbents at elevated temperatures and pressures under hydro-
genation conditions. Furthermore, only literature which speci-
fically referred to removal of these and/or other metallic con-
taminants (rather than general reference to metals laydown on
catalysts with no specifics as to the nature of the contacting
material or its demetal1ization capabilities) by contacting
with solids as opposed to acid treating, etc., was considered.
The bulk of the specific information on the subject was found
?n the patent literature. A list of the patents reviewed is
presented in Table 2. Appendix A contains a detailed analysis
of each patent.
Cited in the literature as petroleum demetal1ization catalysts
were the oxides, sulfides, and other compounds of the Group V-B,
Group VI-B, and Group VIII metals of the Periodic Table, unsup-
ported or supported on a variety of solids. Most frequently
cited as of potential interest were vanadium, chromium, molyb-
denum, tungsten, iron, cobalt, nickel, boron, manganese, and
zinc. Others used in conjunction with solid supports were phos-
phorus compounds, such as phosphoric acid and titania. The de-
metallization superiority of one or more of these catalytic
agents could not be gleaned from the literature.
Solids either employed as supports or containing no added cata-
lytic agents are the refractory oxides alumina, silica, zirconia,
magnesia, titania, and complexes of two or more of these oxides.
Also cited were naturally occurring bauxites and clays, as well
as solid carbons. Most frequently mentioned and employed in
examples in patents were alumina, silica alumina, bauxites, clays,
and solid carbons. Price considerations would also tend to sin-
gle out many of this latter group.
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Table 2. PETROLEUM DEMETALLIZATION CATALYSTS
BIBLIOGRAPHY OF U.S. PATENTS 1951*-1973
U.S. Patent
Number
3,725,251
3,716,1*79
3,712,861
3,696,027
3,691,063
3,617,1*81
3,607,725
3,576,737
3,563,887
3,553,106
3,530,066
3,383,301
3,362,901
3,297,589
3,227,61*5
3,180,820
2.987.1*70
2,970,957
2,91*5,803
2,891 ,005
2,891 ,00i*
2,769,758
2, 761*. 525
2,730,1*87
2,687,985
1 nventor(s)
S. B. Alpert et al
P. B. Weisz and A. J. Silvestri
E. J. Rosinski and F. A. Smith
A. G. Bridge
M. C. Kirk, Jr.
A. Voorhies and G. P. Hammer
R. L. Irving
D. S. Mitchel 1
M. 0. Frazier et al
H. A. Hami 1 ton et al
T. Kuwata et al
H. Beuther and B. K. Schmid
S. L. Szeke et al
W. K. T. Gleim
H. A. Frumkin et al
W. K. T. Gleim et al
M. Turken
R. P. Northcrott et al
H. Beuther et a)
R. L. Heinrich
W. J. Mattox
F. W. B. Porter et al
F. W. B. Porter et al
F. W. B. Porter et al
F. W. B. Porter et al
Year of Iss
1973
1973
1973
1972
1972
1971
1971
1971
1971
1971
1970
1968
1968
1967
1966
1965
1961
1961
I960
1959
1959
1956
1956
1956
1951*
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Most of the literature published in recent years stresses the
need for extensive macroporosity (even at the expense of high
internal surface area) to allow access of the high molecular
weight metal-containing species into the catalyst and prevent
pore plugging or deactivation of the demetal1ization catalyst.
This macroporosity is defined variously as pores of average
diameter greater than a few hundred angstroms to a plurality of
pores of diameters between 1,000 and 50,000 angstroms (i.e. 0.1
to 5.0 microns).
DEHETALLIZATION CATALYST PREPARATION
In order to meet the requirements of developing an improved,
yet low cost, demeta11ization catalyst only compounds of iron,
cobalt, vanadium, nickel, chromium, and molybdenum of the poten-
tial metals in Groups V-B, VI-B, and VIM of the Periodic Table
were employed in the preparation of the catalysts described in
the following pages,, The other metals in these Groups, such as
platinum and palladium, for example, were considered too expen-
sive to be employed in a low cost, "throw-away" type of demeta1-
1ization catalyst.
Although a number of catalyst preparation methods, such as copre-
cipitation of promoter metal and support material, impregnation
of specially prepared supports, or the incorporation of one type
of support material in a matrix of a different type of support
material, were cited in the literature, these methods would not
allow the resulting catalysts to be available at a maximum $0.25
per pound. This limiting price was based on our calculations
which indicated that the catalyst would probably have twice the
activity (and the same bulk density) of the lowest cost, unpro-
moted activated bauxite demeta11ization catalyst known to us.
For this reason, the promoter metals were incorporated into the
support materials using a simple solution impregnation followed
by drying and air calcination.
Although a wide variety of support materials were cited in the
literature, many of these were either not readily available for
use in the program, judged as not having a sufficiently open pore
structure for use with the heavy vacuum residua used in this pro-
gram, or else too costly to meet the requirements of a low cost
catalyst. Since the development of specialized support materials
is beyond the scope of this program, the supports used were chosen
on the basis of their ready commercial availability, low or
11
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moderate cost, or as "model type" porous structures that would
provide guidance for the choice of a commercially available sup-
port material.
Table 3 summarizes data on the six types of support materials
used in this study. Although these materials came in different
sizes, all, except supports 3 and k, were crushed and sieved to
either 12 x 20 mesh or 20 x 50 mesh. In the case of support 3
(the activated clay), which came in 16 x 30 mesh granules, crush-
ing to 20 x 50 mesh was required for some preparations. Support
k (the activated bauxite) came from the supplier in both 10 x 20
mesh (HRI 2J65) and 20 x 60 mesh (HRI 3309) sizes and only had
to be sieved to remove the oversize in the former and the under-
size in the latter.
Pore volume distribution curves, as obtained using a 60,000 psia
AMINCO (American Instrument Company, Silver Springs, Maryland)
mercury porosimeter, for the six supports are presented in Figure
1. This technique is based on filling the catalyst pores with
mercury by continuously increasing the applied pressure. The
pressure required to fill the pores of a specific size is mathe-
matically related to the size of the pores. The upper and lower
absissa scales provide the equivalent values of the pressure and
pore diameter.
In order to compare the pore volume distributions on a common
basis, the specific pore volumes (cc/g) in pores above a given
diameter were multiplied by the compacted bulk densities given
in Table 3 (cc/g) yielding curves of cumulative pore volume per
volume of packed catalyst (cc/cc) versus pore diameter. Since
all but one of the packed densities were determined on the same
size material (12 x 20 mesh), the assumption of uniform particle
packing is felt to be a reasonable approximation. Furthermore,
the distribution curves for both the 12 x 20 mesh and 20 x 50
mesh materials represented by support k (the activated bauxite)
could be superimposed one upon the other and therefore appear as
a single curve.
As shown in Figure 1, the pore size distributions of these sup-
ports range from very macroporous, monodisperse systems (support
5) to bidisperse systems with a broad distribution in both macro-
and micropores (support 4). Although not shown in the figure,
the high surface area activated carbon has a significant volume
in pores less than about 25 angstroms (0.025 microns) in diameter.
12
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Table 3. CATALYST SUPPORTS
Support No.a
HRI No.
1-1243
2-2496
3-3444
4-2765/3309
5-3443
6-1084
Description
Norton Intermediate Surface
Area (35 M^/g) Macroporous
Alumina
Cyanamid Unpromoted Alumina
Extrudates (Surface Area
270 M2/g)
Engelhard LVM Attasorb® Acti-
vated Attapulgus Clay (Surface
Area 125 M2/g)
Engelhard Regular Iron 2% V.M.
Porocel® Activated Bauxite
(Surface Area ^175 M2/g)
Norton Low Surface Area
(< 1 M2/g) Type LA956 Alumina
Pittsburgh Activated Carbon
Type CAL (Surface Area 1000-
1100 M2/g)
Compacted
Bulk Density,
q/cc
0.83
0.55
0.52
0.98/1.04
1.35
0.44
a. Refers to Support No. in Figure 1.
b. Although "as received" supports were of various sizes,
either 12 x 20 mesh or 20 x 50 mesh sizes were used in
the preparation of demetal1ization catalysts.
13
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Figure 1. PORE VOLUME DISTRIBUTION OF DEMETALLIZATION CATALYST SUPPORTS
Pore Diameter (Angstroms)
Support - HRI No.
- 1243
- 2^96
Macroporous
Extruded A1203
Activated Clay
Activated Bauxite - 27&5/3309
Low S.A. A1203 - 3^3
Activated Carbon - 108^
0.00
§o o oooo
o o oooo
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Generalized Demetal1ization Catalyst Preparation Procedure
A total of twenty-seven different demetal1Ization catalysts were
prepared. Table 4 lists the code number, impregnant, porous sup-
port, and the compounds used in the preparation of the catalysts.
In nearly all cases, the supports were air calcined at 950°F for
a minimum of four hours prior to impregnation from solution. The
starting compounds were dissolved in water except where indicated
in the table. Impregnation was accomplished by contacting the
support with just enough liquid to cover and evaporating slowly
to dryness. A final 950°F air calcination was made to decompose
the impregnating salts and convert the metals to their oxides.
One exception was the air calcination of LX-16 at 650°F. This
was done to prevent the gasification of the activated carbon sup-
port. Although titanium and its compounds supported on porous
solids were mentioned earlier in this report, no titanium cata-
lyst was prepared due to problems encountered in the preparation
chemistry.
Detailed preparation procedures for each catalyst are given in
Appendix B.
APPARATUS AND PROCEDURE
Using the demetal1ization catalysts that were prepared, short
term demetal1ization runs were carried out using a single pe-
troleum residuum for the purpose of determining the effective-
ness of these materials. The feed chosen for the screening runs
was Tia Juana vacuum residuum, a high vanadium and nickel con-
tent Venezuelan residuum. Nominal inspections on this feed are
2.8 weight percent sulfur, 550 ppm vanadium, Jk ppm nickel, and
7.0°API gravity. This residuum consists mainly of that fraction
of crude which boils above 975°F.
All screening runs were carried out in continuous, downflow,
fixed bed reactor systems. A schematic diagram is shown in
Figure 2. The reactor, fabricated of 1-1/2-inch O.D. by 1-inch
I.D. stainless steel tubing, has a catalyst bed length of approxi-
mately 16 inches. A drawing of the reactor tube is shown in
Figure 3. The volume (loose) of catalyst charged to the reactor
was 200 cc. Provision was made for an internal thermocouple which
is positioned in the center of the catalyst bed approximately
15
-------
Table k, DEMETALLIZATION CATALYSTS
Code
Number
Impregnant
Support Sol id
LX-1 5.0 W % as Fe
LX-2 5.0 W % as Co
LX-3a 5.0 W % as V
LX-4 5.0 W % as Mo
LX-5 5.0 W 7, as V
LX-6 5.0 U % as (HP03)
LX-7 7.6 W 7, as Ni
LX-8 5.0 W 7: as CR
LX-9 10.0 W 7 as Fe
LX-10 10.0 W 7-. as V
LX-11 5.0 W 7 as Fe
LX-12 5.0 W 7 as Fe
LX-I3 1.5 W 7, as Co
5.0 W % as Mo
LX-14 5.0 W % as Mo
12 x 20 Mesh Activated Bauxite
(HRI 2765)
12 x 20 Mesh Activated Bauxite
(HRI 2765)
12 x 20 Mesh Activated Bauxite
(HRI 2765)
12 x 20 Mesh Activated Bauxite
(HRI 2765)
12 x 20 Mesh Activated Bauxite
(HRI 2765)
12 x 20 Mesh Activated Bauxite
(HRI 2765)
12 x 20 Mesh Activated Bauxite
(HRI 2765)
12 x 20 Mesh Activated Bauxite
(HRI 2765)
12 x 20 Mesh Activated Bauxite
(HRI 2765)
12 x 20 Mesh Activated Bauxite
(HRI 2765)
12 x 20 Mesh Low Si02 Activated
Bauxite (HRI 2753)
12 x 20 Mesh Macroporous Alumina
(HRI 1243)
12 x 20 Mesh Activated Bauxite
(HRI 2765)
12 x 20 Mesh Macroporous AI203
(HRI 1243)
Starting Compounds
Fe(N03)3 9H20
6H20
, NaOH
Mo03, NH^OH
- Oxal ic Acid
Ni(N03)2 6H20
CR(N03)3 9H20
Fe(N03)3 9H20
V20i;, Oxalic Acid
Fe(N03)3 9H20
Fe(N03)3 9H20
Co(N03)2 6H20
Mo03>
Mo03, NH^OH
i. No screening runs were made using these catalysts.
16
-------
Table k (continued). DEHETALLIZATION CATALYSTS
Code
Number
Imp regnant
LX-15 9.5 W % as Mo
Support Solid
12 x 20 Mesh Attapulgus Clay
(HRI 3Wf)
Starting Compounds
, NH/jOH
LX-16 11.0 W % as Mo
LX-17 3.8 W % as Mo
LX-18 2.0 W % as Mo
12 x 20 Mesh CAL Activated Carbon
(HRI 108*0
12 x 20 Mesh Low Surface Area
(HRI
12 x 20 Mesh Activated Bauxite
(HRI 2765)
Mo03, NH^OH
Mo03, NH^OH
MoOj, NH^OH
LX-19 8.9 W % as Mo
1/16" High Porosity Extruded AI20,
(HRI 2^96)
LX-20 2.0 W % as Mo
12 x 20 Mesh Activated Attapulgus
Clay (HRI 3W»)
LX-21 1.0 W 7= as Mo
LX-22b 2.0 W % as Mo
LX-23 0.5 W % as Mo
12 x 20 Mesh Activated Bauxite
(HRI 2765)
20 x 50 Mesh Activated Bauxite
(HRI 3309)
12 x 20 Mesh Activated Bauxite
(HRI 3309)
MoOj, NHZjOH
MoOj, NHjjOH
, NH^OH
LX-24 1.0 W 7 as Zn
12 x 20 Mesh Activated Bauxite
(HRI 3309)
, NH40H
LX-25a 0.3 W 7- as Ni
1.0 W % as Mo
12 x 20 Mesh Activated Bauxite
(HRI 3309)
Ni (N03>2 6H20
LX-26 0.5 W 7 as Mo
20 x 50 Mesh Activated Bauxite
(HRI 3309)
LX-27 1.0 W % as Mn
20 x 50 Mesh Activated Bauxite
(HRI 3309)
a. No screening runs were made using these catalysts.
b. Five different preparations (LX-22-1, -2, -3, -^, and -5) of this catalyst were made
for use in various demetalIization operations.
17
-------
Figure 2. FIXED BED DEMETALLIZATI ON UNIT
oo
HYDROGEN
WATER
THERMOCOUPLES
(g>t>
-------
Figure 3. FIXED BED DEMETALLIZATION REACTOR
INLET j fl
OUTLET
DRILL ft TAP FOR
CATALYST
BED LEVEL
DETAIL "B"
19
-------
midway between the top and bottom.
plied by a lead bath.
Heat to the reactor was sup-
The melted charge stock was pumped to reactor pressure with a
metering pump, mixed with hydrogen makeup gas, and fed to the top
of the reactor. The hydrogen concentration of the makeup gas was
100 percent and no recycle of the exit gases was employed. In
the reactor, the feed was contacted with the catalyst. The mixed
vapor and liquid product from the reactor was cooled and passed
to a high pressure receiver from which gas was sampled, metered,
and vented. The net product was let down in pressure and passed
to a low pressure receiver from which gas was sampled periodically,
metered, and vented. The liquid product was collected and weighed
periodically. Upon completion of a run, the catalyst was removed
from the reactor for inspection and/or analyses. Three essentially
identical units, 184, 185, and 201, were used for these runs.
A standard procedure was devised to screen the demetal1ization
catalysts in short term operations. This consisted of an initial
startup period which conditioned the fresh catalyst at lower tem-
peratures for a short period of time. This startup schedule was
as follows:
Period
Temperature, °F
Pressure, psig
Hydrogen Rate, SCF/Bbl
Liquid Space Velocity,
Vo/hr/Vp
Time on Temp., Mrs.
750
2000
4000
0.75
4
775
2000
4000
0.75
4
790
2000
4000
0.50
1
IB, 2, etc.
790
2000
4000
0.50
Continue at
above conditions
unti1 shutdown.
After the unit was lined out at 790°F, the period was ended and
the remainder of the run continued at 790°F, 2000 psig, 4000 SCF/
Bbl, and 0.50 Vo/hr/Vr for a period of two to fifteen days, de-
pending upon the performance of the catalyst being screened.
A standard demetal1ization screening run using Tia Juana vacuum
bottoms and 12 x 20 mesh Porocel was made at the conditions cited
above to establish a reference point.
A preliminary study of the kinetics of vanadium removal over Poro-
cel indicated that simple first order kinetics are adequate to de-
scribe the rate of vanadium (the major metal contaminant) removal
over the range of variation In space velocities that occur during
the screening run. The kinetic equation used to correct for varia-
tions in space velocities and obtain rate constants for use later
20
-------
in this program Is given in Equation (1).
In Vp/Vp = ) 0)
CATALYST SCREENING TEST RESULTS
A summary of the 33 screening runs that were made with either im-
pregnated supports (29 runs) or the supports themselves is pre-
sented in Table 5. Each of the catalysts prepared is identified
by an LX number and will be referred to by that number for conven-
ience.
The demetall ization and desul funzation levels were essentially
constant for the duration of some of the screening runs and aver-
age values to the nearest five percent are cited in these cases.
However, when there was a significant decrease in either demetal-
1ization or desulfurization with age, the initial and final levels
are given along with the run duration. More complete operating
data on these screening runs are given in Appendix C.
In order to simplify discussion of the screening tests, the runs
are grouped in such a way that some common objectives and conclu-
sions can be made for each grouping.
Group A - Promoter Metals: LX-1 through -10. -13. -2*t. and -27
Before attempting to test other support materials, 12 x 20 mesh
activated bauxite was impregnated with six metals (Fe, Co, Mo,
Cr, V, and Ni) and one nonmetal (phosphoric acid) at the five
percent level, to test the effect that these promoters would have
in improving demetal1ization activity. The effect of concentra-
tion was studied by looking at 10 percent V (LX-9) and 10 percent
Fe (LX-10) levels. Later In the program, a combination of 1.5
percent Co together with five percent Mo (LX-13), one percent
Zn (LX-2*0 and one percent Mn (LX-27) were evaluated.
Conclusions drawn from these screening runs were:
1. Although impregnation of the 12 x 20 mesh activated bauxite
with these known hydrogenation catalysts resulted in as
much as a 30 percent improvement in vanadium removal and
21
-------
Table 5. SUMMARY OF DEMETALLIZATIQN CATALYST SCREENING
OPERATIONS USING TIA JUANA VACUUM RESIDUUM
Run
Catalyst3
185-192 Activated Bauxite, HRI 2765 (Stan-
dard Catalyst)
185-157 5% Fe/Activated Bauxite, LX-1
185-193 5% Co/Activated Bauxite, LX-2
185-194 5% Mo/Activated Bauxite, LX-4
184-158 5% V/Activated Bauxite, LX-5
185-195 5% (HP03)/Activated Bauxite, LX-6
184-159 7.5% Ni/Activated Bauxite, LX-7
185-196 5% CR/Activated Bauxite, LX-8
184-160 1070 Fe/Activated Bauxite, LX-9
185-197 10% V/Activated Bauxite, LX-10
184-161 57, Fe/Low Si02 Activated Bauxite,
LX-11
185-198 5% Fe/Macroporous Alumina, LX-12
% Metals
RemovaI
V Ni
Run
% Duration,
Desulfurization Days
50
20
20
(Involuntary shutdown due to
pump malfunction)
185-199 Activated Attapulgus Clay, HRI 3444 55 20
184-164 5% Fe/Macroporous A1203-I243, LX-12 50 10
20
15
184-162 1.57, Co + 5% Mo/Activated Bauxite, 70-65 45-40 60
LX-13
184-163 57 Mo/Macroporous A1203-1243, LX-14 70-60 25-10 35-30
a. All support materials are 12 x 20 mesh unless otherwise indicated.
62
55
65
60
48
60
65-50
63
70-60
58
20
15
45
25
10
20
20
35
40-30
20
20
20
60
20
10
20
15
20
25
20
8
4
3
4
3
3
3
4
3
3
22
-------
Table 5 (continued). SUMMARY OF DEMETALLIZATION CATALYST SCREENING
OPERATIONS USING TIA JUANA VACUUM RESIDUUM
'/ Metals Run
Remova 1 7 Duration,
Run _ Catalyst9 _ V Ni Desul furizat ion Days
185-200 9.57 Mo/Activated Attapulgus Clay, 70-60 45-20 35-25 4
LX-15
185-201 117 Mo/Activated Carbon 1084, LX-16 60 35 40 3
185-202 3.87 Mo/Low Surface Area, Al203-3443, 20 Nil 10 2
LX-17
184-165 27 Mo/Activated Bauxite, LX-18 65-60 35 50 11
185-203 8.97 Mo/High Porosity Extruded 60 40 50 3
, LX-19
185-204 27 Mo/Activated Attapulgus Clay, 70-55 40-25 35-25
LX-20
185-205 17 Mo/Activated Bauxite, LX-21 70-65 40-30 50
184-166 27 Mo/20 x 50 Mesh Activated 80-75 45-40 60
Bauxite, LX-22-1
185-207 LX-22-1 (At 1000 psig hydrogen 75-50 25 40
pressure)
185-21 lb 27 Mo/20 x 50 Mesh Activated 80-70 55-40 60
Bauxite, LX-22-3
185-206 0.57 Mo/Activated Bauxite, LX-23 65 35 40
184-167 20 x 50 Mesh Activated Bauxite, 55 15 10
HRI 3309
185-208 30 x 60 Mesh Activated Attapulgus 70-60 40-25 25
Clay, HRI 3310
185-168 17 Zn/Activated Bauxite, LX-24 55 5 20
184-169 0.5/ Mo/20 x 50 Mesh Activated 75 35 40
Bauxite, LX-26
184-171 17 Mn/20 x 50 Mesh Activated 65 30 25
Bauxite, LX-27
a. All support materials are 12 x 20 mesh unless otherwise indicated.
b. Run to confirm the results obtained in Run 184-166 with a different preparation of the
27 Mo/20 x 50 mesh activated bauxite catalyst.
23
-------
150 percent improvement in nickel removal (in the case of
5% molybdenum on the activated bauxite) for a short term
operation, none of the catalysts prepared offered the im-
provement in activity (approximately 75% metals removal
at the standard conditions) which was sought.
2. The lack of response to increases in the level of cataly-
tic impregnants, 10 percent Fe (LX-9) versus five percent
Fe (LX-1), and/or the rapid loss in activity when the
level of impregnant is increased, 10 percent V (LX-10)
compared to five percent V (LX-5), indicated that an im-
provement in the demetal1ization activity may be limited
by the limited macroporosity of the standard activated
bauxite support or the high Si02 content of the bauxite
promoted cracking and subsequent deactivation due to
coke laydown.
3. The impregnation of molybdenum, while offering essenti-
ally the same or slightly more improvement in demetal1i-
zation, also was much more selective for the simultaneous
removal of sulfur and nickel than any of the other pro-
moters.
Group B - Supports: LX-11, -12, -14. -15. -16. -17. -19 and Ac-
tivated Clay
Several other supports were evaluated to determine if the type of
support and/or porous structure might enable a higher demetalli-
zation activity to be obtained either through better access of the
metal-containing species to the promoter metal in the catalyst
pores or by the prevention of rapid catalyst deactivation by pore
blockage with either metals or coke. When using supports having
a different density than Porocel, the standard catalyst, the weight
percent metals were adjusted so that the amount of the catalytic
element charged to the reactor was equal to that corresponding to
an impregnated Porocel. In this way, the effect of pore structure
rather than amount of catalytic impregnant was studied.
The conclusions of this set of runs were:
1. When five percent iron was added to the low Si02 Porocel
(LX-11), vanadium removal was somewhat lower than five
percent iron on regular Porocel. Since the low SiO£
Porocel only had 1,5 percent iron as Fe203 compared to
about 12 percent iron as Fe203 on regular Porocel, it
-------
may be that the iron content of the activated bauxite
itself may be catalyzing the demetal1ization reaction.
Because of this effect, it is not possible to deter-
mine if the lower Si02 content reduced cracking and
subsequent pore blockage.
2. Although a certain amount of macroporosity is required
to enable the large metal-containing asphaltene species
to gain entry into the catalyst, a broad distribution
of both macropores (broadly defmed as pores with a
pore diameter greater than 100 A) and micropores (again,
broadly defined as pores having a diameter less than
about 100 A) are needed for both high demetal1ization
activity, both vanadium and nickel removal, and the
maintenance of this activity. The activated bauxite
appears to be the best compromise between having the
required type of overall pore size distribution and
low cost. Unimpregnated activated Attapulgus clay
was about equal to or slightly better than the unim-
pregnated bauxite. However, the molybdenum impregnated
clay (LX-15) deactivated at a significantly higher rate
than did the molybdenum impregnated bauxite. It is be-
lieved that the more "narrow" pore size distribution of
the clay (Curve 3, Figure 1) compared to the bauxite
results in a greater rate of deactivation due to pore
blockage by the deposited metals and "coke". Demetal-
1ization activity ranged from poor for the low surface
area alumina (LX-17, Curve 5) to a level approximating
that of the activated bauxite (Curve k) for the acti-
vated carbon (LX-16) and the other aluminas (Curves 1
and 3, LX-1^ and LX-19, respectively). The impregna-
tion of molybdenum onto an alumina support having the
broad size distribution characteristic of a commercial
porous type hydrodesulfurization catalyst (LX-19) did
not produce the improvement in demetal1ization expected
of this "model" support. This suggests that perhaps
there are definite limitations on the level to which
Tia Juana vacuum bottoms can be demetallized at the
standard screening conditions. Since these other sup-
ports are more costly than the $0.05 per pound acti-
vated bauxite, they offer no advantage.
3. The Tia Juana vacuum residuum is a very difficult feed
to demetallize. This is thought to be due in part to
the fact that it is a very "heavy" residuum and mass
transport of the higher molecular weight, metals-con-
taining species into the interior of the 12 x 20 mesh
("-' 1.8 mm diameter) granules may limit the effective
25
-------
demetal1ization activity of the impregnated supports
and result in a low catalyst effectiveness factor.
This suggested that a reduction in particle size might
improve the situation.
Group C - Promoter Levels and Particle Size: LX-18. -20. -21.-22,
and -23
In order to try to meet the objective of keeping the cost of the
demetal1ization catalyst to a minimum, the effect of lower levels
of molybdenum promoter were investigated. Samples containing 2.0
(LX-20), 1.0 (LX-21), and 0.5 (LX-22) percent showed that neither
the initial demetal1ization activity nor the rate of deactivation
(up to five days) were significantly different for these samples
compared to each other. When the level of molybdenum on Porocel
is reduced from five percent to two percent (LX-18), there is no
difference in the level of vanadium removal (65%), but some reduc-
tion in the levels of nickel (45% down to 35%) and sulfur (60%
down to 50%). Therefore, it appears very low levels of Mo are
capable of catalyzing demetal1ization by Porocel. This is an im-
portant cost consideration. However, some question remains about
the aging rate as a function of the promoter level.
By reducing the size of the Porocel support from 12 x 20 mesh to
20 x 50 mesh for preparation LX-22 containing two percent molyb-
denum, it was possible to attain initial vanadium removal levels
in excess of 75 percent. Operations of seven days indicated only
a slight activity decline. However, when the hydrogen pressure
was reduced from 2000 psig to 1000 psig in an attempt to determine
if satisfactory operation could be achieved at a lower pressure,
a rapid decline in vanadium removal activity occurred. This was
probably due to rapid coking occurring in the catalyst pores re-
sulting from low pressure operations, since the initial level (75%)
is just slightly under the initial level (80%) for the 2000 psig
operation. Higher Mo levels, for example five percent, might pro-
vide the hydrogenation activity to limit coking at 1000 psig, but
would add considerably to the cost (•—' $0.02/percent Mo) of a
cheap demetal1ization catalyst.
!n order to determine the effect of particle size on demetal1iza-
tion, 20 x 50 mesh activated bauxite was investigated. Reduction
of the size to 20 x 50 mesh resulted in a somewhat higher vanadium
removal activity. However, it was lower than the Mo impregnated
12 x 20 mesh Porocel and substantially lower than the Mo impreg-
nated 20 x 50 mesh Porocel.
26
-------
Although the two percent Mo/activated Attapulgus clay (LX-20) had
initial demetallization and desulfurization activities of the 9.5
percent Mo/activated clay, this catalyst suffered a rapid deacti-
vation compared to the two percent Mo/Porocel. Although the clay
support offers a definite cost advantage ($0.02/pound versus $O.OV
pound for Porocel), Porocel appears to be a better support, possi-
bly because of its more broad pore size distribution. Evaluation
of unpromoted 30 x 60 mesh Attapulgus clay indicated the same ra-
pid decline in demetal1ization activity noted with the other clay
preparations.
Results of Screening Program
As a result of the screening program, activated bauxite impreg-
nated with small amounts of molybdenum was found to be the best
overall demetal1ization catalyst system on the basis of both high
demetal1ization activity (i.e., the rates of nickel and vanadium
removal achieved) and the maintenance of this high activity when
used for the demetal1ization of heavy vacuum residua. An added
plus for this catalyst system is its moderately high desulfuriza-
tion activity considering Its low Mo loading. The effects of
molybdenum loading and particle size for the molybdenum/activated
bauxite catalyst system is shown in Table 6. The rate of metals
removal does not appear to be a strong function of the level of
molybdenum loading on a given sized support. Although a signifi-
cant increase in demetal1ization activity over the unpromoted
bauxite is found for the larger 12 x 20 mesh (0.066" to 0.033")
catalyst, only a reduction in particle size, to 20 x 50 mesh
(0.033" to 0.012"), allows the attainment of the 75-80 percent
vanadium removal rate that has been the goal of this program.
In kinetic terms'", the rate constant for vanadium removal for the
two percent Mo/20 x 50 mesh activated bauxite catalyst is approxi-
mately twice that of the unpromoted activated bauxite. The super-
ior performance of the smaller 20 x 50 mesh catalyst is thought
to be due to the greater accessibility of the molybdenum impreg-
nant to the high molecular weight metals-containing components
known to be in heavy vacuum residua such as Tia Juana. Since the
other vacuum residua chosen for demetal1ization also contain high
The rate of vanadium removal is approximately first order in
vanadium concentrations over the range of vanadium removal
studied.
27
-------
Table 6. SUMMARY OF DEMETALLIZATION CATALYST SCREENING DATA
Percent Metals Removal at Standard Conditions
Mo Loading (W %) 2.0 1.0 0.5
V Ni V Ni V Ni V Ni
Support/Mesh Size
oo
Activated Bauxite/12 x 20 65-60 35 70-65 ^0-30 65 35 50 20
Activated Bauxite/20 x 50 80-75 ^0 75 35 55 15
-------
molecular weight metal-containing species, the two percent Mo/20
x 50 mesh activated bauxite catalyst, referred to from this point
on as the LX-22 series catalyst, was chosen for the preparation of
demetallized feeds discussed in the following section. Although
the short term screening runs indicate the 0.5 percent Mo/20 x 50
mesh activated bauxite has nearly the same activity, the scope of
this program is not such that the optimization of Mo loading could
be studied in the subsequent demetal1ization runs which followed.
DETAILED ANALYSES OF LX-22: TWO PERCENT MOLYBDENUM ON 20 x 50
MESH ACTIVATED BAUXITE
The activated bauxite used for the preparation of the LX-22 cata-
lyst was obtained from Minerals and Chemicals Division of Engel-
hard, Inc., and is commercially known as Porocel. Analyses of
this material are given in Table 7. Atomic absorption spectropho-
tometry was used to measure the molybdenum concentration on the
various LX-22 preparations that were used in the screening work,
as well as in subsequent preparations made for the long term de-
metallization feed production runs. These data are summarized in
Table 8. All the other metal analyses previously given in Table
5 were calculated from the amount of impregnating solution ab-
sorbed during catalyst preparation. This approach was necessary
since lamps for many of the other elements were not on hand for
the spectrophotometer and it was not deemed necessary to purchase
them.
Pore volume distribution curves for 20 x 50 mesh Porocel support,
LX-22 blank preparation, and a typical LX-22 impregnated demetal-
lization catalyst support are presented in Figure 40 These show
that treatment of the support with NH^OH, followed by drying and
air calcination, develops additional porosity over the support.
Possible mechanisms include (a) leaching of soluble mineral or (b)
structural rearrangement upon dehydration of the minerals in the
activated bauxite. Although some differences are indicated in
the pore size distribution in Figure 5, they are not considered
s ignifleant.
Figure 6 presents pictures of the scanning electron microscope
studies done on LX-22-1, along with X-Ray mappings of the loca-
tion of Al and Mo on the finished catalyst. The catalyst samples
were prepared by embedding the particles in an epoxy resin. Af-
ter hardening, the solid mass was partially immersed in liquid
nitrogen. This resulted in the fracture of the granular particles
29
-------
Table 7. DESCRIPTION AND ANALYSES OF THE ACTIVATED BAUXITE
SUPPORT USED IN THE PREPARATION OF THE LX-22 CATALYSTS
Supplier
Engelhard Minerals &
Chemicals Corporation
Menlo Park
Edison, New Jersey 08817
Grade
Regular Porocel®
Volatile Matter, W %
(Weight Loss at 1800°F)
Size (As Received)
20 x 60 U.S. Mesh
Chemical Composition
(Volatile Free Basis)
A1203, W %
Fe20,, W %
T|02; W %
Si02, W %
Insolubles, W %
78.0
8.0
k.O
9-0
1.0
Surface Area,
175
Bulk Density, g/cc
0.90
a. Analyses furnished by supplier (nominal values) from
Technical Information Report No.
30
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Table 8. MOLYBDENUM CONTENT AND COMPACTED BULK
DENSITY OF VARIOUS LX-22 PREPARATIONS
Compacted
Bulk Density
W 7o Mo g/cc
LX-22-1 2.09 0.97
LX-22-2 2.40 1.00
LX-22-3 2.27 0.97
LX-22-4 2.17 1.02
LX-22-5 2.24 1.04
LX-22 Blank 0.0 1.07
HRI 3309 (20 x 50 Mesh Porocel) 0.0 1.04
31
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Figure 4. ALTERATION OF THE PORE VOLUME DISTRIBUTION
OF ACTIVATED BAUXITE DURING IMPREGNATION WITH MOLYBDENUM
Pore Diameter (Angstroms)
ro
LX-22 Blank Preparation,
0% Mo/20 X 50 Mesh Bauxite
2.17% Mo/20 X 50 Mesh Bauxite
(LX-22-4)
Untreated 20 X 50 Mesh Bauxite
p p p oppo
*
0.0
-------
Figure 5. CUMULATIVE PORE SIZE DISTRIBUTION OF VARIOUS LX-22 PREPARATIONS
o
o
«•
o
o
o
vn
o
o
o
o
o
o
o
Pore Diameter (Angstroms)
o
o
o
o
o
o
NJ
O
O
O
O
o
o
o
o
ro
o
o
o
o
ui
o
N>
O
^ABSOLUTE PRESSURE, PSI
I 111
o o oo-
o o ooo
o o o oo
o
8
o
o
o
.
-------
Fiqure 6. ELECTRON PROBE AND X-RAY STUDIES OF LX-22-1 AT 100X
LX-22-1 Electron Probe Scan
X-Ray Indication of
LX-22-1 Aluminum Distribution
X-Ray Indication of
LX-22-1 Molybdenum Distribution
-------
thereby exposing their interior cross-section. By use of this
technique, smearing of the molybdenum across the particle was
avoided. Smearing could result if a grinding operation was em-
ployed to expose the interior of the small particles embedded
in the epoxy matrix.
After preparation, the samples were introduced into a JEOLCO
JCM-U3 scanning electron microscope with the capability of per-
forming an X-Ray mapping of the cross-section of the pellet for
both aluminum (the matrix metal) and molybdenum. The electron
probe scan defines the shape of the particle being studied, as
well as cracks (which are indicated by long thin lines), other
surface irregularities, and inclusions of nonhomogeneous mater-
ials. These inclusions show up on the photograph as large, light-
er colored areas. Light areas on the X-Ray scans indicate the
presence of the element being scanned for while the dark areas
indicate the absence of that element.
It is obvious from these pictures that the molybdenum is uni-
formly deposited over the cross-section of the catalyst. Analo-
gous pictures are presented in Figure 7 for preparation LX-22-5.
PREPARATION OF DEMETALLIZED VACUUM RESIDUUM FEEDSTOCKS
Three vacuum residuum feeds, Tia Juana vacuum residuum, Gach
Saran vacuum residuum, and Bachaquero vacuum residuum, were used
for our demeta11ization demonstration runs. Sufficient quantities
of each feed were prepared to allow for lengthy desulfurization
tests.
Both Tia Juana and Bachaquero crudes originate in the Lake Maracai-
bo area of Venezuela, while the Gach Saran crude is obtained from
Iran. All three crudes represent major fields. In 1971, the to-
tal production of Bachaquero and Tia Juana crudes was 270,000,000
and 136,000,000 barrels, respectively. The estimated reserves of
each are approximately ten times that. In 1971, the production
rate of Gach Saran was 322,000,000 barrels with the reserves es-
timated at approximately twenty-five times that. These feeds are
representative of major high metals crudes available in the world
and are, for the most part, sold as export material. The daily
production rates for these feeds are given in Table 9.
Interestingly, and perhaps because of their high metals content,
the 1972 production of these crudes fell to 213, 111, and 316
35
-------
Figure 7. ELECTRON PROBE AND X-RAY STUDIES OF LX-22-5 AT 200X
LX-22-5 Electron Probe Scan
X-Ray Indication of
LX-22-5 Aluminum Distribution
X-Ray Indication of
LX-22-5 Molybdenum Distribution
36
-------
Table 9. 1971 VACUUM BOTTOMS PRODUCTION
RATES FOR FEEDS STUDIED IN PROGRAM
1971 Crude Volume Percent
Production Vacuum Bottoms B/D
Feed B/D on Crude Vacuum Bottoms
Gach Saran 882,000 21 185,000
Tia Juana 373,000 (30) 112,000
Bachaquero 7^0.000 32 237,000
1,995,000
37
-------
million barrels for Bachaquero, Tia Juana, and Gach Saran, re-
spectively.
The Bachaquero vacuum residuum for this purpose was obtained by
distillation at the HRI® Laboratory of atmospheric residuum,
which had been distilled from Bachaquero crude. The Tia Juana
vacuum residuum was obtained from the Creole Petroleum Corpora-
tion, a subsidiary of Exxon.
Detailed inspections of the three vacuum residua are presented
in Table 10. Summaries of operating data for these runs are
given in Appendix D.
Long Term Demetal1?zation Runs with Tia Juana Vacuum Bottoms
A total of four runs were made with Tia Juana vacuum bottoms to
investigate the aging characteristics of the LX-22 catalyst and
to produce feed for the desulfurization study. The first of these
runs, Run 184-166, was part of the screening program and was made
with preparation LX-22-1. In order to reduce the unit time re-
quired to achieve the age required, the spent catalyst from Run
184-166, which was a screening run, was recharged to a reactor
and a new run, Run 185-210, was begun.
After following the original deactivation trend established in
Run 184-166 for the eighth through eleventh days of operation,
vanadium removal suddenly dropped from 70 to 60 percent and re-
mained more or less constant at this level. A rapid drop off in
the rate of both sulfur and nickel removal also occurred at this
point.
Since this sudden drop off in catalyst activity could not be ex-
plained, another run, Run 185-211, using a new preparation, LX-
22-3, of the two percent Mo/20 x 50 mesh activated bauxite, was
used for this run. Figure 8 shows that, although the initial ac-
tivity of the new preparation was the same as the original cata-
lyst preparation (LX-22-1), the decline in vanadium removal was
more rapid during the first seven days of operation. Unlike the
first run, the demetal1ization activity decreased during the re-
mainder of the run (days eight to fifteen) in a manner predicted
by the results obtained during the first seven days of operation.
However, after a total of fifteen days, the activity of the LX-22-
3 was lower than that of LX-22-1.
38
-------
Table 10. VACUUM RESIDUUM FEED INSPECTIONS
Feed Tia Juana Bachaquero Gach Saran
Vacuum Bottoms Vacuum Bottoms Vacuum Bottoms
Volume Percent on Crude 31.8 20.8
HRI Identification No. 24l4 L-354 L-352
Gravity, °API 7.5 6.3 6.1
Sulfur, W % 2.91 3.44/3.63 3.30
Carbon, W % 85.37 83.94 82.93
Hydrogen, W % 10.68 10.29 10.40
Nitrogen, ppm 5400 5715 6037
vo RCR, W % 20.3 20.8 18.5
Vandium, ppm 550 685 324
Nickel, ppm 74 108 149
Viscosity, SFS @ 300°F 220 253 150
IBP-975°F
Volume % 11.0 15 12.0
Gravity, °API 17.5 18.3
Sulfur, W % 2.28 2.00
975°F+
Volume % 89.0 85.0 88.0
Gravity, °API 4.1 5.1
Sulfur, W % 3.51 3.40
RCR, W % 24.9 21.6
-------
-p-
o
Figure 8. DEHETALLIZATION OF TIA JUANA VACUUM RESIDUUM
OVER 2°/0 MOLYBDENUM/20 X 50 MESH BAUXITE
Feed Composition: 7.2-7.6°AP!, 2.9% Sulfur, 550 ppm Vartadium, 7k ppm Nickel
Run
184-166
185-210
185*211
1 84- 1 Ik
184-16?
A.
B.
C.
D.
E.
Catalyst
LX-22-1
LX-22-1 (Recharged)
LX-22-3
LX-22-5
20 x 50 Mesh Acti-
vated Bauxite
Temperature
°F
790
790
790
790
790
Pressure
psig
2000
2000
2000
2000
2000
Vn/hr/Vr
0.50
0.50
0.50
0.75
0.50
fa
3
0)
CL
C
73
a>
o
o>
6.2
0.4
0.6 0.8
Catalyst Age, Bbl/Lb
1.0
1.2
-------
It was thought at first that the accelerated deactivation of LX-
22-3 was due to a variation in catalyst properties or a varia-
tion in feed properties. Coincidental ly, a new drum of feed was
started approximately the same time that the sudden drop off in
activity occurred during Run 185-210. This same drum was used
throughout Run 185-211. The standard analyses indicated that
this feed was essentially equivalent to that previously used and
subsequent investigation revealed no significant difference among
any of five different LX-22 catalyst preparations. The catalyst
deactivation curves for these three runs (184-166, 185-210, and
185-211) and a fourth run (184-17*0, using yet another prepara-
tion of the two percent Mo/20 x 50 mesh bauxite catalyst, are
also given in Figure 8. The last run was made at a space velo-
city of 0.75 V0/hr/Vr instead of the 0.50 Vo/hr/Vr used in pre-
vious runs,,
Although operation at 0.75 V0/hr/Vr results in a lower initial
rate of vanadium removal, the rate of catalyst deactivation up to
an age of 0.9 barrels per pound is so much lower that the useful
life of the catalyst is double that obtained in the 0.5 Vo/hr/Vr
operations. Therefore, operation at lower severity (higher space
velocity) results in a significant improvement in catalyst perfor-
mance when considered on the basis of total vanadium removed per
pound of catalyst. It is postulated that operation at the higher
severity (lower space velocity) with this heavy vacuum residuum
results in an accelerated rate of coke laydown which rapidly poi-
sons the catalyst.
The catalyst analyses results presented in Table 11 clearly show
the low level.of carbon obtained in this last run, 8.54 percent,
compared to the earlier runs that deactivated rapidly, 13.2 and
15.1 percent. Carbon on catalyst results from cracking reactions
that are occurring simultaneously with demetal1ization and desul-
furization. At the higher throughput, 0.75 Vo/hr/Vr, instead of
0.50 V0/hr/Vr, the cracking reactions are minimized.
A run, Run 185-192, was made with unpromoted bauxite to generate
comparable deactivation and demetal1ization data. This informa-
tion is given in Figure 9. The deactivation of the activated
bauxite seems to be controlled to a large extent by pore blockage.
Figure 10 compares the difference in pore strucutre between vir-
gin activated bauxite and spent material from Run 185-192, con-
ducted with Tia Juana vacuum residuum. There is almost no change
in the pore volume in pores larger than 2000 A, while aosubstan-
tial reduction is noted in pores between 2000 A and 50 A. All
of the pore volume in pores less than 50 A appears to be gone.
-------
Table 11. ANALYSES OF J>PENT DEMETALLIZATION CATALYST
-p-
M
Weight Percent Element on Spent Catalyst
Run No.
1 84- 1 73
1 84- 1 74
185-210
185-211
185-213
185-215
185-216
Feed
Gach Saran
Tia Juana
Tia Juana
Tia Juana
Bachaquero
Bachaquero
Bachaquero
C
7.1
8.54
13.2
15.1
14.81
12.94
9.68
S
11.33
8.14
6.18
8.26
7.18
6.44
6.69
V
11.02
9.19
5.32
4.90
8.74
7.11
6.42
Ni
2.85
0.77
5.48
0.44
0.87
0.72
0.68
-------
Figure 9. DEMETALLIZATION OF TIA JUANA VACUUM RESIDUUM
OVER 12 X 20 MESH ACTIVITED BAUXITE (HRI 2765)
Feed Composition
7.2°API
2.9% Sulfur
550 ppm Vanadium
7k ppm Nickel
Operating Conditions
790° F
2000 psfg
4800 SCF H2/Bbl
0.5-0.8 V0/hr/Vr
Note; Data corrected to
0.5 V0/hr/Vr on curve
u
3
TD
8
Q-
E
to
c
(0
"8 2.0
B
-a
re
c
re
4-1
re
o 1.0
0.1 0.2 0.3
Catalyst Age, Bbl/Lb
-------
Figure 10. CHANGE IN ACTIVATED BAUXITE PORE SIZE DISTRIBUTION
WHEN DEMETALLIZING TIA JUANA VACUUM RESIDUUM
Pore Diameter (Angstroms)
o.k *
03
(D
CJ
0)
£ 0.3
en
\
O
O
E
I 0.2
o
Q.
-------
Similar patterns of pore volume reduction are noted in Figures
11 and 12. The spent catalyst from Run 185-210 is compared with
the LX-22-1 preparation that was used for that run in Figure 11.
Figure 12 compares preparation LX-22-5 with the 184-174 dump cata-
lyst. There are some differences in the pore volume of the LX-22-
2 and LX-22-5 preparations and, therefore, the pore volume of the
spent catalysts is also different. However, the difference be-
tween the fresh and spent catalyst pore volumes appears to be
about the same in both cases. In spite of the difference in car-
bon level, 8.5 weight percent versus 13.2 weight percent, the
amount of measurable pore volume seems about the same.
Long Term Demetal1ization Run with Bachaquero Vacuum Residuum
A total of four runs were made with the Bachaquero vacuum residuum
to provide feed for desulfurization runs and aging data. Unpro-
moted bauxite was used to gather comparison data in a fifth run,
Run 185-217.
The rapid deactivation of the catalyst as a result of low space
velocity operation was further substantiated during the demetal-
1ization (Run 185-213) of Bachaquero vacuum residuum as shown in
Figure 13. After operation at 0.75 Vo/hr/Vr up to an age of 0.6
barrels per pound, the feed rate was reduced to 0.5 Vo/hr/Vr and
a rapid rate of deactivation followed. The Bachaquero demetalli-
zation was repeated at 0.75 Vo/hr/Vr and demonstrated that rapid
deactivation could be avoided by operation at a sufficiently high
feed rate. It is believed that operations at the lower space
velocity resulted in the rapid deposition of coke on the catalyst
resulting in deactivation. Since a similar rapid deactivation
occurred during the demetal1ization of Tia Juana vacuum residuum
at 0.50 Vo/hr/Vr, there appears to be a limit to the severity at
which the demetal1ization of these two feeds can be carried out.
This limits the extent to which these feeds can be demetallized
prior to desulfurization. However, the metals-containing species
remaining in these demetallized feeds deposit on a desulfuriza-
tion catalyst at a substantially lower rate than those removed
from the feed by the demetal1ization catalyst. Therefore, al-
though these feeds cannot be demetallized to levels in excess of
75 percent vanadium removal, the rates of metals deposition on a
high activity desulfurization catalyst during subsequent desul-
furization operations are low enough to prevent rapid deactiva-
tion of this more expensive catalyst.
-------
Figure 11. CHANGE IN PORE SIZE DISTRIBUTION
OF LX-22-1 WHEN DEMETALLIZING TIA JUANA VACUUM RESIDUUM
Pore Diameter (Angstroms)
in
•5°.*
4->
ft!
O
^0.3
o
o
0)
E
0.2
Spent LX-22-1
(Run 185-210)
O 0000 000
~ o oooooo
8
o
o
o
o
o
o
o o o o o o o
o o oo"o"o.°
o oooooo
o oooooo
o
-------
Figure 12. CHANGE IN PORE SIZE DISTRIBUTION
OF LX-22-5 WHEN DEMETALLIZING TIA JUANA VACUUM RESIDUUM
Pore Diameter (Angstroms)
o
o
o
o
o
un
o
»•
o
o
o
O
O
O
O
O
O
o
Ul
o
o
o
o
o
o
o
o
o
un
o
o
o
o
o
o
Spent LX-22-5
(Run 184-17*0
P = ABSOLUTE PRESSURE, PSI
8OOO
000
-------
Figure 13. DEMETALLIZATION OF BACHAQUERO VACUUM RESIDUUM
OVER 2% MOLYBDENUM/20 X 50 MESH BAUXITE
Feed Composition
6.3 "API
3.4 % Sulfur
685 ppm Vanadium
108 ppm Nickel
Operating Conditions
790 °F
2000 psig
4000 SCF H2.Bbl
0.75 Vo/hr/Vr
(0.055 Bbl/D/Lb)
Note: Data at 0.5
Vo/hr/Vr corrected to
0.75 V0/hr/Vr on curve
0.4 0.6
Catalyst Age, Bbl/Lb
80
1. Run 185-213
Catalyst: LX-22-5
0.75 Vo/hr/Vr
Feed Rate
-------
These five runs have been corrected to standard operating condi-
tions and the deactivation curves are presented in Figure 14.
Figures 15 and 16 show the reduction in pore volume which occurred
in Runs 185-215 and 185-216. On a total loss of pore volume basis,
it is similar to that obtained in the Tia Juana operation. As in
the Tia Juana operation, the lower severity operation of Run 185-
216 did not result in a lesser loss of pore volume than was ex-
perienced in the higher severity operation. It may be that the
higher severity operation caused carbon deposition at the pore
mouth which resulted in added diffusional resistance within the
catalyst. This type of deposit would not materially affect total
pore volume.
Demetal1ization of Gach Saran Vacuum Residuum
Demetal1ization of Gach Saran vacuum residuum was carried out in
Run 184-173- The operating conditions and the results of that
operation are summarized in Figure 17= The most noteworthy thing
about this operation was the ease with which the demeta11ization
was accomplished. Significantly higher levels of demetal1ization
were obtained with this feed than with the Bachaquero or Tia Juana
vacuum bottoms. The activity decline was also modest when compared
with the results of the other feeds. The spent catalyst results
from these operations were presented previously in Table 11. They
show the highest level of vanadium loading, along with the lowest
carbon level, 11.0 and 7.0 percent, respectively. The ease of
vanadium removal makes it desirable to remove as much as possible
since it has been determined that the ease of removal in the de-
metallization stage correlates well with the ease of removal in
the desulfurization stage. Therefore, in order to protect the de-
sulfurization catalyst, it is necessary to go to higher levels of
demetal1ization in the demetal1ization stage, but, of course, it
is not as difficult to achieve for this feed.
The type of reduction in pore volume previously noted for Tia Juana
vacuum residuum was obtained with Gach Saran vacuum residuum. This
is shown in Figure 18.
49
-------
Figure 14. DEMETALLIZATION OF BACHAQUERO VACUUM RESIDUUM
OVER 2% MOLYBDENUM/20 X 50 MESH BAUXITE
Feed Composition: 6.1-6.3°API, 3.^-3.63% Sulfur,
685 ppm Vanadium, 108 ppm Nickel
Run
Catalyst
Temperature Pressure
°F psig
790
790
790
790
790
Note1: All Data Corrected to 0.75 Vo/hr/Vr on Curve
V^/hr/Vr
185-213
185-214
185-215
185-216
185-217
A.
B.
c.
D.
E.
LX-22-5
LX-22-4
LX-22-4
LX-22-3
Un promo ted
Bauxite
2000
2000
2000
2000
2000
0.5-1.0
0.7-1.0
0.7-1.0
0.7-1.0
0.6
Is
(0
c
-------
Figure 15. CHANGE IN PORE SIZE DISTRIBUTION
OF LX-22-4 WHEN DEMETALLIZING BACHAQUERO VACUUM RESIDUUM
0.3
U
o
0)
0.2
o
Q_
JH 0.1
E
o
Pore Diameter (Angstroms).
o
o
•j
o
o
o
o
o
o
ro —•
o o
>* -*
o o
o o
o o
o
o
o
o
o
o
o
o
o
U1
o
o
N)
O
o
o
o
\_n
o
ro
o
Spent LX-22-4
(Run 185-215)
P-ABSOLUTE PRESSURE, PSI
o o o o o
o o o o o.
o o oooo
o o ooog
-------
Figure 16. CHANGE IN PORE SIZE DISTRIBUTION
OF LX-22-3 WHEN DEHETALLIZING BACHAQUERO VACUUM RESIDUUM
Pore Diameter (Angstroms)
o
o
o
o
o
o
o
o
O
O
o
o
o
o
o
o
o
1-0
v*
o
o
o
o
o
o
un
o
o
CO —
o o
o o
V/1
o
,0.3
o
u
CD
E
0.2
NJ
O
O
Q.
0)
0.1
E
o
Spent LX-22-3
(Run 185-216)
P=ABSOLUTE PRESSURE, PSI
mi
O- VI 00
-------
Figure 17. DEMETALLIZATIQEf OF GACH SARAN VACUUM RESIDUUM
OVER 2°/0 MOLYBDENUM/20 X 50 MESH BAUXITE
Run 18U-173 - Catalyst LX-22-2
Feed Composition
6.1 °API
3.3% Sulfur
328 ppm Vanadium
ppm Nickel
Operating Conditions
790° F
2000 psig
*K>00 SCF Ha/BBl
0.75 Vo/hr/Vr (0.055 B/D/Lb)
tlnpromoted Bauxite
1.0
Catalyst Age, Bbl/Lb
-------
Figure 18. CHANGE IN PORE SIZE DISTRIBUTION
OF LX-22-2 WHEN DEMETALLIZING GACH SARAN VACUUM RESIDUUM
VJ1
-p-
Pore Diameter (Angstroms)
o
o
o
o
o
vn
o
o
o
o
o
o
o
o
o
o
o
o
o
NJ
4
o
o
o
o
o
o
Ul
o
o
o
o
o
o
Ul
o
fO
o
(0
o
cn
u
o
0)
0.3
0.2
o
Q.
JE 0.1
E
O
Spent LX-22-2
(Run 184-173)
— - O- Nf 00 -O -
p o ooppo
o "o o 000-°
o o o oooo
o o o oooo
o
-------
FEEDSTOCK PREPARATION
Demetallized residua from various test runs were collected and
blended so that a feed having constant properties could be fed
to the desulfurization step. The products that were blended to
make the feed to the desulfurization unft are listed in Table 12.
The requirement for blending was made necessary in the case of
the Bachaquero and Tia Juana vacuum bottoms residua since some
difficulties were encountered in maintaining the desired demetal-
1ization level when higher severity operations were attempted.
However, since the primary criteria for selection for the desul-
furization unit was the metals content of the feed, it was felt
that the use of material blended from various operations, as long
as the metals content was about the same for all components
blended, would result in a justifiable desulfurization operation.
The inspections on the blended feeds for each of the desulfuriza-
tion runs are listed in Table 13.
CATALYST SELECTION
The catalyst selected for the desulfurization operations was a
high activity American Cyanamid preparation. The catalyst had
shown the ability to produce low sulfur products from vacuum re-
sidua in other test work not covered by this program. Its small
particle size, ^-'O.02-inch diameter, makes it particularly re-
sistant to deactivation due to metals deposition. It was on this
basis then, that this catalyst was selected as the most likely to
be part of a large-scale demetal1ization-desulfurization combina-
tion process. The properties of the catalyst are summarized in
Table 14.
OPERATING CONDITIONS
Desulfurization operating conditions were selected so that a maxi-
mum degree of desulfurization with a minimum hydrogen utilization
would be obtained. All runs were conducted In the same fixed bed
downflow apparatus previously described. Each run was conducted
at 760°F, 2000 psig hydrogen partial pressure, ~"4500 SCF of hydro-
gen per barrel, and a space velocity of 0.106 barrels of oil per
day per pound of catalyst. The runs were generally carried out to
55
-------
Table 12. COMPOSITION OF DEMETALLIZED RESIDUA
FED TO THE DESULFURIZATION REACTOR
Feed
Demetal1ized
Tia Juana
Vacuum Residuum
Demetal1Ized
Bachaquero
Vacuum Residuum
Demetal1ized
Gach Saran
Vacuum Residuum
HRI Number
L-357
L-358
L-359
L-356
Products Blended to
make Composite Feed
185-205
185-210
185-211
184-166
184-169
184-174
185-213
185-214
185-215
(Periods 3-5)
185-216
(Periods 1-8)
18k-173
(Periods 5-22)
-------
Table 13. DEMETALLIZED FEED INSPECTIONS
Feed
Catalyst
HRI Identification No.
Gravity, °API
Sulfur, W
Carbon, W
Hydrogen ,
Ni t rogen ,
RCR, W %
Vanad i urn,
°/
10
%
W %
ppm
ppm
N ickel , ppm
IBP-975°F
Volume %
Gravity, °API
Sulfur, W %
975° F+
Volume %
Gravity,
Sulfur, W
RCR, W %
Vanadium, ppm
°API
%
Demetal1ized
Tia Juana
Vacuum Bottoms
LX-22
L-357
13.0
1.50
86.65
10.79
4984
13.7
177
47
20.0
19.8
0.92
70.7
9.6
1.75
19.6
222
Demetal1ized
Bachaquero
Vacuum Bottoms
LX-22
L-358
13.5
1.67
85.86
10.87
5686
1^.7
180
71
23.3
19.1
1.02
63.4
7.1
1.96
22.3
LX-22
L-359
12.0
1.61
182
60
Demeta11ized
Gach Saran
Vacuum Bottoms
LX-22
L-356
12.1
1.31
85.79
11.25
14.0
67
58
23.3
19.2
0.81
66.7
7.7
1.75
19.9
-------
Table 14. 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 0.6?
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 5.0
50/70 0,5
70/100 0.1
-100
Chemical Analysis, W %
(15.0)
CoO (3.0)
58
-------
a catalyst age between 2.6 and 3.1 barrels per pound. Runs of
this duration provide an accurate measure of the catalyst deac-
tivation rate and provide information about ultimate catalyst
utilization required to get a given product desulfurization level.
In addition, additional information was gathered on the amount
of metals laydown on the catalyst for a given operation. Detailed
operating conditions for each run of this series is presented in
Appendix E.
RESULTS
The demetallized Gach Saran vacuum residuum was desulfurized in
Run 201-69 until a catalyst age of 2.63 barrels per pound was
achieved. Run 201-70, with a demetallized Bachaquero vacuum re-
siduum, was run to a catalyst age of 2.72 and Run 184-175, with
a demetallized Tia Juana vacuum residuum, was run to a cata-
lyst age of 3.09 barrels per pounds. The operating conditions
were such that correlations could be used to predict the operat-
ing conditions required for 0.5 percent sulfur product in an
equilibrium catalyst situation. The experimental data is plotted
in Figures 19, 20, and 21 for each of the feedstocks. The out-
standing result noted from these operations is the very low rate
of catalyst deactivation throughout the run. Of course, in a
commercial operation, the ultimate catalyst lives would be on the
order of 10.0 barrels per pound, but little was to be gained from
further continuation of these runs in that the deactivation can
be extrapolated with confidence.
CATALYST DEACTIVATION
The analyses of the spent catalyst from the desulfurization opera-
tion is presented in Table 15. The amount of vanadium contained
on these catalysts is low, of course, in comparison to that which
would have been observed if the feeds had not been demetallized.
The data presented in Table 16 show that the absolute amount of
vanadium removal over the length of the run was highest for the
Bachaquero feed and followed by the Gach Saran and Tia Juana feeds,
respectively. The amount of vanadium removed in the desulfuriza-
tion operation for the three feeds were 35, 24, and 26 ppm, re-
spectively. Comparable data for nickel are 26, 23, and 26 ppm,
respectively.
59
-------
Figure 19. DESULFURIZATION OF DEHETALLIZED GACH SARAN VACUUM RESIDUUM
Run 201-69
Feed Composition
12.1°API
1.31% Sulfur
67 ppm Vanadium
58 ppm Nickel
Operating Conditions
760° F
2000 psig
8300 SCF H2/Bbl
1 .0 V0/nr/Vr
0.106 B/D/Lb
1.5 2.0
Catalyst Age, Bbl/Lb
2.5
3.0
3.5
75
o
ft
67
-h
c
50
33
-------
Figure 20. DESULFURIZATION OF DEMETALLIZED BACHAQ.UERO VACUUM RESIDUUM
Run 201-70
Feed Composition
12-13.5°API
1.64% Sulfur
181 ppm Vanadium
60-71 ppm Nickel
Operating Conditions
760 °F
2000 psig
4800 SCF H2/Bb1
1.0 Vo/hr/Vr
O.i06 B/D/Lb
0.5
1.0
1.5 2.0
Catalyst Age, Bbl/Lb
2.5
3.0
315
-------
Figure 21. DESULFURIZATION OF DEMETALLIZED TIA JUANA VACUUM RESIDUUM
Run t8*f-175
Feed Composition
13.0°API
1.50% Sulfur
177 ppm Vanadium
^•7 ppm Nickel
Operating Conditions
760° F
2000 psig
4500 SCF H2/Bbl
1.0 V0/hr/Vr
0.106 B/D/Lb
ON
ho
in
c
-h
N
Q>
1.5 2.0
Catalyst Age, Bbl/Lb
2.5
3.0
3.5
-------
Table 15. ANALYSES OF SPENT DESULFURIZATION CATALYST
Demetal1ized
Vacuum Residuum Weight Percent Element on Spent Catalyst
Run No. Feed CSV Ni
201-69 Gach Saran 15.67 5.11 1.55 1.01
201-70 Bachaquero 13.71 5.36 2.72 0.86
184-175 Tia Juana 14.78 4.75 0.85 0.26
-------
Table 16. VANADIUM AND NICKEL BALANCES FROM DESULFURIZATION RUNS
Run Number
Desulfurization Catalyst Age,
Bbl/Lb
Feed
v,
Ni
ppm
ppm
In
Feed
Vanadi urn
Nickel
Out
Vanadi urn
Liquid Product
On Catalyst
Total
Nickel
Liquid Product
On Catalyst
Total
201-69
2.63
Demeta11Ized
Gach Saran
Vacuum Resid
Grams
3.99
3.45
2.76
1.27
4.03
2.16
0.84
3.00
67
58
W % Feed
69.2
31 .8
101.0
62.5
24.3
86.8
201-70
2.72
Demeta11Ized
Bachaquero
Vacuum Resid
180-182
60-71
Grams
10.96
3.82
8.96
2.27
11.23
2.82
0.69
3.51
W % Feed
81.
20.
102,
73.7
18.0
91.7
18k-1 75
3.09
Demeta11Ized
Tia Juana
Vacuum Resid
177
47
Grams
12.05
3.20
10.27
0.62
10.89
2.95
0.20
3.15
W % Feed
85.
5.
90,
92.2
6.3
98.5
-------
The amount of vanadium in the original feeds that deposited on
the catalyst is presented in Table 17. For Gach Saran, Bacha-
quero, and Tia Juana, it amounts to 7.^, 5.1, and 1.6 percent,
respectively. These data show the effectiveness of utilizing a
demetal1ization step before desulfurization in order to protect
the life of the catalyst. The advantage of using a demetal1iza-
tion catalyst having some desulfurization activity is best gained
by a reduction in the severity of the desulfurization step. The
severities utilized here for obtaining these low sulfur products
are certainly within the realm of today's commercial heavy oil
treating experience. It should also be noted that metals removal
during desulfurization, such as encountered in these experiments,
is similar to current commercial operations where atmospheric re-
sidua having low levels of vanadium, such as are obtained from
Kuwait and Light Arabian crudes, are being desulfurized to low
levels.
PRODUCT INSPECTIONS
Detailed product inspections were obtained on two products from
each of the desulfurization runs, one product from near the be-
ginning of the run, and the second one from near the end of the
run. These inspections, which are In Appendix F, are provided
so that enough information is available to those who might use
this data in the future for considering the possibility of split-
ting the product into various fractions and marketing them accord-
ing to their various sulfur levels. This combination may result
in a higher total net value of the products.
An overall summary table of the demetal1ization and desulfuriza-
tion process to produce 0.5 weight percent 400°F+ fuel oil from
the three vacuum residua is presented in Table 18. In all cases,
the yield of fuel oil product exceeds 36 volume percent on re-
siduum charged. The balance of the liquid product, averaging
about eight percent is C4~350°F naphtha, which is quite valuable
in today's economy.
65
-------
Table 17. EFFECT DF METALS REMOVAL FROM HIGH METALS FEED ON METALS LAYDOWN ON CATALYST
% of Demetal1ized Feed
Metals Removed from Metals on Grams of Metals
Original Demetal1ized Virgin Feed in Desulfurlzation from Feed on Oesuifurization
Feed Feed Demetal lization Step Catalyst Catalyst Catalyst Quantity,
Vacuun Residuum Feed Run No. V Ni V Ni % V % Ni V Ni V Ni Grams
Gsch Saran 201-69 328 147 67 58 80 61 32 24 1.27 0.84 65.7
Bachaquero 201-70 685 108 181 65 74 40 21 18 2.27 0.69 64.4
Tia Juana 184-175 550 74 177 47 68 36 5 6 0.62 0.20 64.3
-------
Table 18. SUMMARY OF RESULTS ON THE DEMETALLIZATION
AND DESULFURIZATION OF VACUUM RESIDUA
(Feed and Product Analyses)
Vacuum Bottoms
Gach Saran
% Sulfur
Vanadium, ppm
Nickel, ppm
C4-400°F+, V %
400°F+. V %
Tia Juana
% Sulfur
Vanadium, ppm
Nickel, ppm
0^-400°F, V %
400°F+. V %
Raw Feed
3.4
328
147
2.9
550
74
Demetal1ized
Feed
1.3
67
(80% V Removal)
58
1.5
177
(68% V Removal)
47
Desulfurized
Product3
0.5
43
35
8.2
96.2
0.5
141
41
9.0
96.2
Bachaquero
% Sulfur
Vanadium, ppm
Nickel, ppm
C4-400°F, V 7o
400°F+, V %
3.6
685
108
1.7
180
(74% V Removal)
71
0.5
145
45
10.0
96.9
a. Sulfur and metals analyses are for 400°F+ fuel oil fractions,
Product yields are based on volume of raw feed.
67
-------
SUMMARY OF TRACE ELEMENTS
At the inception of this project, the Environmental Protection
Agency requested that measurements be made on the trace elements
that are normally present in the three vacuum residuum feeds and
the demetallized and desulfurized products that were obtained.
Neutron activation analysis was selected as the most promising
analytical technique by which this goal could be accomplished.
A summary of the quantitative neutron activation analyses (N.A.A.)
run by Gulf Radiation Technology on the raw Bachaquero, Gach Saran,
and Tia Juana vacuum residua is presented In Table 19. Only the
calculated upper limits, i.e., the maximum concentration at which
the element may be present and avoid detection, were obtained for
the remainder of the elements scanned, which are indicated in
Table 20. Besides nickel and vanadium, which were run routinely
in the Laboratory, only four elements (manganese, arsenic, copper,
and silver) that are of the most interest to the Environmental
Protection Agency, could be determined quantitatively. Without
costly sample preparation techniques, N.A.A. has very limited ca-
pabilities for determining the extent of removal of the majority
of trace elements of interest in the demetal1Tzation and desulfuri-
zation operations. For this reason, further trace elements analy-
ses using the N.A.A. technique were suspended.
Three selected products of demetallized Tia Juana vacuum residuum
were sent to Gulf Radiation Technology for N.A.A. No other pro-
duct samples were sent out since it was discovered that the levels
of most of the elements in this feed were below the detection li-
mits for N.A.A. A summary of the product analyses and feed analy-
sis for the detectable elements is presented in Table 21. Corres-
ponding atomic absorption analyses run by HRI are also presented.
The levels of five of the six elements were reduced as a result
of contact with the three different demetal1ization solids. The
level of manganese in the feed would appear to be lower than that
in the demetallized products according to the values presented.
No explanation for this apparent discrepancy can be given. The
relative ability of the catalysts to remove the other metals is
activated bauxite
-------
Table 19. QUANTITATIVE N.A.A. ANALYSES OF VACUUM RESIDUA
Concentration (ppm)
El etnent
Vanadium
Manganese
Nickel
Arsenic
Copper
Si Iver
Sodium
Cobalt
Chlorine
Bromine
lodi ne
Gal 1 i urn
Gold
Bachaquero V. B.
977 + 200
0.676 + 0.140
99 + 22
0.088 + 0.019
3.55 ± 0.71
0.97 + 0.38
11.7 ± 2.3
0.59 + 0.16
28.2 + 5.7
0.146 + 0.044
0.0044 + 0.0012
Gach Saran V. B. Tia Juana V. B.
445 + 89 662 + 130
0.307 + 0.061 0.056 + 0.01 1
111+23 55.8 + 12.0
0.261 + 0.093
1.76 + 0.35
4.36 + 0.87 18.0 + 3.6
0.565 + 0.130
17.2 + 3.5
1.63 + 0.33
0.69 + 0.14
0.275 + 0.071
-------
Table 20. TRACE ELEMENT ANALYSES
COMPUTER CALCULATED UPPER LIMITS FROM INSTRUMENTAL NEUTRON ACTIVATION ANALYSES OF VACUUM RESIDUA
(Results - Upper Limits Only)
Calculated Upper Limits (Parts Per Million)
Element
AG
AL
AS
AU
BA
BR
CD
CE
CL
CO
CR
CS
CU
DY
ER
EU
FE
GA
GO
GE
HF
HG
HO
I
IN
IR
K
LA
LU
MG
MN
MO
NA
NB
ND
Nl
OS
PD
PR
PT
RB
RE
RH
RU
SB
SC
SE
SM
SN
SR
TA
TB
TE
TH
Tl
TM
U
V
W
Y
YB
ZN
ZR
Above results for 4 data sets.
Bachaquero
34.00000
0.37000
1.60000
2.00000
3.10000
0.06600
0.00380
0.19000
0.00078
250.00000
0.07300
1 .00000
1.40000
0.16000
0.15000
0.01400
0.15000
0.00078
0.00240
5.10000
0.05900
0.01400
550.00000
0.92000
570.00000
0.71000
0.27000
0.35000
0.84000
0.87000
8.50000
0.01 100
1 .00000
1.20000
0.04300
0.02200
2.10000
0.00420
3.80000
0.80000
0. 16000
0.08200
0.95000
0.12000
670.00000
1.90000
0.01300
0.05600
29.00000
0.06800
5.30000
25.00000
Gach Saran
1.10000
10.00000
0.03800
0.00160
0.28000
1.30000
2.00000
0.55000
3.20000
0.05300
0.00300
0. 16000
0.00064
230.00000
0.95000
1.00000
0.17000
0.13000
0.01200
0.00053
0.00260
3.30000
0.04200
0.01300
1 10.00000
0.80000
520.00000
0.54000
0.26000
0.29000
0.60000
0.76000
7.80000
0.00960
0.53000
1.30000
0.03700
0.02100
2.00000
0.00360
2.50000
0.63000
o. 15000
0.08100
0.51000
0. 1 1000
390.00000
1.80000
0.00700
0.04800
23.00000
0.07100
4.80000
18.00000
Tia Juana
0.43000
1 10.00000
0.00060
0.30000
0.05700
0.76000
0.95000
4.40000
1.30000
0.03300
0.07400
0.00210
0.06800
0.00030
110.00000
0.05600
0.63000
1.20000
0.06700
0.08400
0.00870
1.20000
0.00110
0.00097
3.60000
0.03700
0.00610
2500.00000
0.48000
240.00000
0.44000
0. 13000
0.22000
0.61000
0.45000
3.60000
0.00720
1 .20000
0.53000
0.01700
0.00940
0.82000
0.00230
3.50000
0.40000
0.07600
0.03400
0.93000
0.04400
840.00000
0.90000
0.01800
0.03500
13.00000
0.02800
3.90000
17.00000
70
-------
Table 21. TRACE METAL ANALYSES ON TIA JUANA VACUl'H RESIDUUM FEED
AND SELECTED DEMETALLIZEO PRODUCTS USING NEUTRON ACTIVATION AND ATOMIC ABSORPTION ANALYSES
Product3(or Feed)
Catalyst Employed
Element
Vanadium
Manganese
Nickel
Arsenic
Sod i urn
Cobalt
HRI 2414 (Feed)
No Catalyst
N.A.A.
662 + 130
0.0559 + 0.0110
55.8 + 12.0
0.0261 + 0.0093
18.0 + 3.6
0.565 + 0.130
A.A.°
550
185-192-6
12 x 20 Mesh Act. Bauxite
N.A.A. A.A.
Concentration (ppm)
0.186 + 0.001
0.017 + 0.003
0.0665 + 0.008
0.18 0.02
286
185-199-5
12 x 20 Mesh Act. Clay
N.A.A. A.A.
0.11*9 ± 0.001
0.010 + 0.003
0.133 ± 0.005
0.1? + 0.02
266
62
184-165-7
27 Mo/Act. Bauxite, LX-18
N.A.A. A.A.
0.139 + 0.001
0.0078 + 0.0026
0. 122 +_ 0.005
0.11+ 0.02
211
50
a. Identifying product code: Unit-Run No.-Period No.
b. Analyses run by HRI using atmoic absorption. Value represents an average of several samples and analyses of the Tia Juana vacuum feed.
-------
72
-------
SECTION V
PROCESS ECONOMICS
The major costs in producing low sulfur fuel oil from high metals
residua are related to the cost of the facility necessary to car-
ry out the desulfurization, the amount of hydrogen consumed, and
the cost of the catalyst. Summaries have been prepared of the
processing costs, including investment requirements, for produc-
ing 0.3, 0.5, and 1.0 weight percent sulfur fuel oil from Tia
Juana vacuum bottoms, Bachaquero vacuum bottoms, and Gach Saran
vacuum bottoms utilizing unpromoted bauxite and the new LX-22
catalyst for the demetal1ization step.
The data computations for the 0.5 weight percent sulfur fuel oil
product case requires almost no amount of extrapolation from the
operating conditions utilized in the experimental program. For
those cases where 0.3 weight percent sulfur and 1.0 weight per-
cent sulfur fuel oil is produced, some extrapolation of the data
is necessary.
Curves have been prepared which show these operating costs, in-
cluding a 25 percent charge for investment for producing 0.5 weight
percent sulfur from the three residua studied as a function of the
level of demeta11ization achieved in the demeta11ization step and
a demetal1ization catalyst cost of $0.12, $0.16, and $0.20 per
pound,, The cost calculations are based on 1973 Gulf Coast con-
struction costs and are for a 20,000 barrels per day plant, which
is perhaps the minimum size that a refiner would build.
Figure 22 shows that, for Gach Saran vacuum bottoms, there was
an optimum demetal1ization level of 85 percent, which minimizes
the overall costs. At this optimum point, the cost is $1.19 per
barrel if the demetal1ization catalyst cost is $0.20 per pound.
With the two Venezuelan feeds, the overall costs of producing the
desulfurized fuel oil product decreased as demeta11ization in-
creased, but it was difficult to achieve more than 69 percent de-
metallization on Tia Juana vacuum residuum or 73 percent demetal-
1ization on Bachaquero vacuum residuum. The reason for this is
that the operating severities became too great to confidently pre-
dict that long term satisfactory demetal1ization catalyst life
73
-------
Figure 22. TOTAL OPERATING COST
TWO-STAGE DEMETALLIZATION-DESULFURIZATION OF GACH SARAN VACUUM RESIDUUM
Bases: (I) 20,000 B/D, (2) 1973 Gulf Coast Construction Costs, (3) SO.50/1000
SCF H2, CO Capital Charges - 25' of Investment
LEGEND
Symbo I
O
D
Catalyst
Demetal1ization/Desulfurization
Activated Bauxite/Beads
LX-22/Beads
LX-22/Beads
LX-22/Beads
DemetaI Iization Catalyst
Cost. S/Lb
0.05
0.20
0. 16
0. 12
1.6
1.5
1.3
1 .0
0.9 _
0.3 ' Fuel 011
0.5- Fuel Oil
I
I
85
70 75 80
/ Vanadium in Demetal1ization Stage
90
95
-------
could be achieved. Furthermore, the actual removal of metals from
these stocks beyond this level is believed to be unnecessary or
of limited economic value since these metal compounds are hard to
remove and, therefore, would also be difficult to remove with the
desulfurization catalyst. Overall costs for these two feeds are
$1.46 and $1.64 per barrel, respectively, and are shown in Figures
23 and 24. The sets of curves for the production of 0.3 percent
sulfur fuel oil and 1.0 percent sulfur fuel oil show an additional
cost of about $0.40 per barrel of product to produce the 0.3 per-
cent material and a cost of about $0.40 per barrel less to produce
the 1.0 percent material. These calculations were made assuming
a constant set of demeta11ization operating conditions for a given
level of demetal1ization with the only variation being the operat-
ing conditions of the desulfurization plant.
The overall processing costs are sharply dependent on plant capa-
city. With this in mind, costs have been prepared for Bachaquero
vacuum residuum using $0.20 per pound as the price of the demetal-
1ization catalyst and varied plant size between 20,000 and 100,000
barrels per day. As can be seen from Figure 25, raising plant ca-
pacity from 20,000 to 100,000 barrels per day reduces the per bar-
rel cost of 0.5 percent sulfur fuel oil from $1.64 to $1.46.
One of the original objectives of the program was to try and re-
duce the overall hydrogen consumption to produce the desulfurized
fuel oil product. Calculations have not been done on all the feeds
and product sulfur levels, but for a Bachaquero vacuum residuum
case for the production of 0.5 percent sulfur fuel oil, the demetal-
1ization step at the optimum level requires 740 SCF per barrel and
the desulfurization step requires 360 SCF per barrel for a total
of 1100 SCF. With the activated bauxite, the comparable values
are 590 SCF per barrel for demeta11ization and 760 SCF per barrel
for desulfurization, making a total of 1350 SCF per barrel. The
difference of 250 SCF per barrel is worth on the order of $0.125
per barrel in direct processing cost reductions. The higher hy-
drogen consumption utilization in the first stage demeta11ization
step with the improved catalyst is due to its having a definite
hydrogenation function. Some of the sulfur which is removed with
the demetallization step requires the addition of hydrogen. How-
ever, since less desulfurization has to be done in the desulfuri-
zation stage, the operating requirements are less severe in that
stage and the total hydrogen consumed worked out to be less with
the new improved catalyst.
The influence on the overall economics of the price of the demetal-
1ization catalyst is obviously strong as indicated by Figures 22,
23, and 24. Consultation with a leading catalyst manufacturer
75
-------
Figure 23. TOTAL OPERATING COST
TWO-STAGE DEMETALLIZATION-DESULFURIZATION OF TIA JUANA VACUUM RESIDUUM
Bases: (!) 20,000 B/D, (2) 1973 Gulf Coast Construction Costs, (3) $0.50/1000
SCF \\2, (k) Capital Charges - 25'/ of Investment
LEGEND
Symbol
O
Q
Catalyst
DemetalIizat!on/DesulfurizatIon
Activated Bauxite
LX-22/Beads
LX-22/Beads
LX-22/Beads
DemetalIization Catalyst
Cost, $/Lb
0.05
0.20
0.16
0.12
1.9 -
1.7 —
0.3C/, Fuel Of!
1.6 —
1.5 -
£ I .it
-------
Figure 24. TOTAL OPERATING COST
TWO-STAGE DEHETALLIZATIQN-DESULFURIZATION OF BACHAQUERO VACUUM RESIDUUM
Bases: (1) 20,000 B/D, (2) 1973 Gulf Coast Construction Costs, (3) SO.50/1000
SCF H2, CO Capital Charges - 257 of Investment
Symbol
O
Q
LEGEND
Catalyst
Demetal1ization/Desulfurlzation
Activated Bauxite/Beads
LX-22/Beads
LX-22/Beads
LX-22/Beads
Demetal1ization Catalyst
Cost, S/Lb
0.05
0.20
0.16
0.12
2.2 _
2.1 —
2.0 _
1.9 -
0.37 Fuel Oil
0.57 Fuel Oil
1.7 —
.^ 1.6-
"> 1 5 •
4J ' • J
o
1.O/ Fuel Oi1
•e-
1.3 —
1.2 —
-B-
60
( ! I
64 68 72
7, Vanadium Removal in Demetal I izat ion Stage
77
-------
Figure 25. OVERALL COSTS FOR PRODUCING LOW SULFUR FUEL OIL FROM BACHAQUERO VACUUM RESIDUUM
CO
2.20
i.oo
0.3% Fuel Oil
0.5% Fuel Oil
1.0% Fuel Oil
20 kO 60 80
Plant Capacity, BPSD (Thousands)
100
-------
indicated that the costs of impregnation of the cheapest support
are on the order of $0.10 per pound minimum regardless of the
material to be impregnated. The activated bauxite used in this
work sells in massive quantities for on the order of about $0.05
per pound. The value of the molybdenum and other chemicals used
in the preparation of the catalyst are on the order of $0.04 per
pound. Therefore, the cost of the finished catalyst will be of
the order of $0.20 per pound. If some economies in production
can be obtained as the result of future development work and/or
the amount of molybdenum necessary to achieve the desired result
can be lowered, it is conceivable that the cost of the finished
demetal1ization catalyst can come down. Curves have been presented
in all cases for alternate prices of $0.12 and $0.16 per pound.
Estimates of the overall yield structure and properties of the
various fractions are given in Tables 22, 23 and 2k for the pro-
duction of 400°F+ fuel oil containing 1.0, 0.5, and 0.3 weight
percent sulfur from Gach Saran, Tia Juana, and Bachaquero vacuum
res idua.
79
-------
Table 22. ESTIMATED OVERALL VIELDS AND PRODUCT PROPERTIES
CONSECUTIVE DEHETALLIZATION AND DESULFURIZATION OF GACH SARAN VACUUM RESIDUUM
400°F+ Fuel Oil Sulfur, W
YIELDS
1 .0
0.5
0.3
oo
O H2S 6 NH}
c,-c3
C{,-400°F
400-650°F
650-975°F
975°F+
400 °F+
_WX V/ API /S
2.7
0.9
3.9 5.5 63 * 0.07
7.9 9.6 35 0.10
25.8 28.4 20 0.26
59.7 61.0 9.2 1.1*3
93.4 99.0 14.3 1.0
VX API
/S
wx
3.4
1. 1
5.0 7.0 63 CO. 07
10.3 12.5 35 <.0.07
27.2 30.0 20 0.10
54.3 55.8 10 0.78
91.8 98.3 15.8 0.5
WX
VX °API XS
3.6
1.5
6.7 9.5
13.4 16.2
63 <0.07
35 <0.07
28.1 30.9 20 <0.07
48.1 49.8 11 0.50
89.6 96.9 17.3 0.3
TOTAL
100.9 104.5 16.3 0.96
101.3 105.3 18.2 0.47
101.4 106.4 20.5 0.28
-------
Table 23. ESTIMATED OVERALL YIELDS AND PRODUCT PROPERTIES
CONSECUTIVE DEHETALLIZATION AND DESULFURIZATION OF TIA JUANA VACUUM RESIDUUM
oo
400°F+ Fuel Oil Sulfur, W /
YIELDS
1.0
0.5
0.3
H2S & NH3
crc3
C^OO'F
400-650°F
650-975°F
975° F+
400 °F+
wy
"API 75
4.7 6.5 62 <0.07
9.8 11.7 34 0.10
25.2 27.5 20 0.27
57.9 58.9 10 1.46
92.9 98.1 15.3 1.0
wy vy °API 75
2.9
1.6
6.5 9.0 62 <0.07
12.7 15.1 34
26.5 29.1 21
51.1 52.4 11
90.3 96.6 17.2 0.50
wy vy "API /s
0.07
0.07
0.10
0.81
3.2
2.0
7.9 11.0
14.8 17.8
27.3 30.0
46.2 47.7
62 <0.07
35 <0.07
21 <0.07
12 0.53
3.3 95.5 18.8 0.30
TOTAL
101.0 104.6 17.** 0.95
101.3 105.6 20.1 0.46
101.4 106.5 22.4 0.28
-------
Table 2*4. ESTIMATED OVERALL YIELDS AND PRODUCT PROPERTIES
CONSECUTIVE OEHETALLIZATION AND DESULFURIZATION OF BACHAQUERO VACUUM RESIDUUM
400°F+ Fuel Oil Sulfur, W
I .0
0.5
0.3
YIELDS
00
H2S S. NH.J
c,-c3
Cit-I*00°F
400-650° F
650-975° F
975° F+
400 °F+
V/
"API /S
3.0
4.3 6.0 63 <0.07
9.7 11.7 35 0.10
28.7 31.6 20 0.28
54.5 55.6 9 1.53
92.9 98.9 '5.2 1.0
W7 V7 °API 75
3.6
1.6
6.0 8.5 63 <0.07
15.0 35 <0.07
29.9 33.1
21 0.11
48.1 Ug.U 10 0.85
90.4 97.5 17.1 0.50
wy vy "API ys
3.9
2.0
7.2 10.2 63 <0.07
14.5 17.5 35 <0.07
30.5 33.I
21 <0.07
43.7 45.3 11.4 0.55
88.7 96.6 18.6 0.3
TOTAL
101.3 104.9 17.2 0.95
101.6 106.0 20.0 0.46
101.8 106.8 21.9 0.28
-------
SECTION VI
APPENDICES
G. Conversion Table
H. Glossary
Page
No.
A. Detailed Analysis of Demetal1ization Patents 85
B. Outline of Detailed Procedures for Catalyst
Preparation 99
C. Summary of Catalyst Screening Runs 109
D. Summary of Demetal1ization Runs 117
E. Summary of Desulfurization Runs 123
F. Operating Conditions, Yields, and Product
Properties 129
83
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APPENDIX A
DETAILED ANALYSIS OF DEMETALLIZATION PATENTS
85
-------
86
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APPENDIX A
DETAILED ANALYSIS OF DEMETALLIZATI ON PATENTS
U.S. Patent 3,725.251
A multistage process for the hydrodesulfurization of high me-
tals (Ni and V) content petroleum residua wherein the first
reaction zone is an ebullated bed contacting system using a
powdered (40 x 325 mesh) demetal1ization catalyst to effect
improved demetal1ization and thereby lower catalyst deactiva-
tion in subsequent desulfurization stages. Enhanced demetal-
Hzation is shown to be effected through the reduction in the
particle size of an alumina or silica and alumina catalyst
promoted with metals and their compounds from Group VI-B (Cr,
Mo, W) and Group VIM (Fe, Co, Ni primarily) of the Periodic
Table. Furthermore, improved demetal1ization was further ef-
fected by incorporating access channels comprising from 20 to
80 percent of the total pore volume into the structure of the
demetal1ization catalyst. These access channels are intersti-
tial ly spaced throughout the microporous matrix and have dia-
meters greater than 100 angstroms. Furthermore, the size of
these access pores should have a broad distribution such that
10 to 40 percent of the total pore volume is in pores about
1,000 angstroms diameter and another 10 to 40 percent in pores
of diameter between 100 and 1,000 angstroms in diameter.
U.S. Patent 3.716.479
The patent describes a process whereby petroleum residua are
contacted with a demetal1ization catalyst prepared from na-
turally occurring underwater deposits known as manganese nodules,
In addition to manganese, these catalysts also contain vary-
ing amounts of other metals, including iron, cobalt, nickel,
and copper. The catalysts are prepared from the manganese
nodules by simply crushing to size, washing (in the case of
the ocean nodules to remove sodium chloride), and drying.
87
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These high surface area catalysts (100-250 M2/g) can be further
modified by leaching out certain of the metals or sulfiding the
metals contained in the nodules. High levels of nickel and
vanadium removal are reported at moderate hydrogenation condi-
tions considering the type of processing involved. A signifi-
cant advantage of the manganese nodule demetal1ization catalyst
is their low activity for the hydrogenation of aromatic rings,
thereby effecting low hydrogen consumption during demetalliza-
tion. No details regarding porous structure were given.
U.S. Patent 3,712,861
This patent relates to a process in which petroleum residua is
contacted with a porous alumina which contains sulfides of the
Group VI and Group VIII metals. The aluminas used are large
pore adsorbents with average pore diameters greater than 100
angstroms and preferably less than 100 M^/g. This is to per-
mit the relatively unrestricted movement of the large metal
containing molecules into the catalyst and to allow relative-
ly high metal deposition before deactivation would occur. The
demetal1ization catalyst is used to effect a substantial metals
removal in the first stage of a two-stage hydrogenation opera-
tion.
U.S. Patent 3,696,027
This patent describes a process where a metals contaminated
heavy petroleum oil is treated under hydroconverting conditions
by successive contact with fixed beds of (a) macroporous cata-
lyst particles having a high metals capacity and low desulfuri-
zation activity, (b) macroporous catalysts of moderate desul-
furization activity, and (c) catalyst with a high desulfurization
activity. In this case, the term macropore refers to pores,
channels, or openings in the catalyst particle greater than 500
angstroms in diameter. The first catalyst zone has at least 30
volume percent of the catalyst pore volume in the macropore re-
gion, the second between five and ^fO volume percent and the
third less than five volume percent. This "graded catalyst"
arrangement takes advantage of the macroporous catalysts' en-
hanced capacity for metals removal. The composition of the
-------
catalysts employed was nickel-molybdenum on alumina-silica
supports.
U.S. Patent 3,691,063
The patent describes a process in which petroleum residua to
be hydrocracked is first treated in a guard case containing
demetal1ization catalyst. The catalyst is said to be a sul-
fided form of nickel, nickel-tungsten, nickel-molybdenum, co-
balt, cobalt-tungsten, or cobalt-molybdenum supported on sili-
ca-alumina or alumina. The guard case catalyst is regenerated
using oxygen and steam which removes coke deposits.
U.S. Patent 3.617.
This patent describes a novel demetal1ization process in which
the contact solid is prepared by coking the heavy, high metals
fraction of petroleum residua. Mild deactivation of the coke
with air and steam is employed to increase the porosity and
expose nickel and vanadium which in turn act as demetal1iza-
tion catalysts. Alternately, the activated coke can also be
impregnated with compounds of cobalt, molybdenum, and addi-
tional quantities of nickel and vanadium to further enhance
demetal1ization activity. Alkali metals carbonates may be em-
ployed to promote the gasification reaction and produce a high
surface area coke which Is said to be a more active metals re-
moval catalyst.
U.S. Patent 3,607.725
This patent describes a process in which metals in crude or
residua are removed using a multibed reactor with descending
catalyst and ascending feed, i.e., a series of fluidized beds.
The demetal1ization catalyst is only described as a nickel-
molybdenum on alumina type. Use of this relatively inexpen-
sive demetal1ization catalyst in the multibed demetal1ization
reactor system ahead of a hydrocracker protects the relatively
expensive, high activity catalyst from deactivation and allows
89
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the use of lower pressure than would normally be the case with-
out prior demetal1ization.
U.S. Patent 3.576.737
This patent describes a process for the demetal1ization of at-
mospheric residua in which the demetal1ization catalyst Is 0.5
to 10 weight percent vanadium on a macroporous support. The
support should have an average pore diameter which is greater
than 300 angstroms and preferably greater than 500 angstroms.
The preferred catalyst is a macroporous 8 x 14 mesh alundum
support with a surface area of 23 M^/g and an average pore dia-
meter of 840 angstroms onto which vanadium is impregnated from
solution. Vanadium pentoxide, M2®5> dissolved in oxalic acid
was used as the impregnant. However, large pore diameter char-
coal, alumina, silica, and alumina silica particles may also
be used.
Demeta11ization activity was found to proceed in this order:
vanadium on alundum
-------
catalyst particle size enables the catalyst in the guard cham-
ber to do an effective job of metals removal while maintaining
the desulfurization activity of the bulk of the catalyst in
the main reactor. Thus, the importance of a small demetalliza-
tion catalyst particle size in obtaining both the maximum de-
metallization rate and metals deposition capacity is shown.
U.S. Patent 3.553,106
This patent discloses a process for the hydrogenative removal
of vanadium from both crudes and atmospheric residua using a
preferred vanadium oxide catalyst on activated alumina. This
catalyst is claimed to have both higher activity and higher
vanadium removal capacity than the more expensive nickel-co-
balt-molybdenum on alumina hydrogenation catalysts. Prepara-
tion of the catalyst is achieved through impregnation of the
alumina support with a non-oily solution of vanadium compounds
including vanadium oxalate, vanadyl acetyl, acetonate, and the
like. Vanadium levels of from 0.5 to 5.0 weight percent are
the preferred loadings with one to about three weight percent
being especially preferred. After drying the impregnated sup-
port, an air calcination is carried out to decompose the vana-
dium compound and form vanadium oxide in an active state. Al-
though a wide range of aluminas having surface areas between
40 and about 400 M^/g may be employed, an especially preferred
activated alumina is one comprising major amounts of gamma and
eta aluminas. Furthermore, this type of vanadium removal cata-
lyst was found to be more active than is a catalyst resulting
from the in situ deposition of vanadium from the oil onto an
initially vanadium-free alumina.
U.S. Patent 3.530.066
This patent describes an improved process to eliminate asphal-
tenes and metallic contaminants with a catalytic solid having
a plurality of pores between 1,000 and 50,000 angstroms in
diameter. Further, these pores are present in a pore volume of
0.05-0.9 cc/g of the solid. The majority of this porosity is
preferred to be in the range of 2,000 to 35,000 angstroms.
This type of porosity is obtained by mixing refractory particles
of 20-500 microns with 1-15 weight percent of alumina hydrogel,
followed by molding, drying, and calcination. The refractory
91
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particles chosen from the group consisting of bauxite, magne-
tite, laterite, diatomaceous earth, clays, ochre, and bento-
mite are to contain unspecified amounts of at least one member
selected from the group consisting of iron, cobalt, nickel,
tungsten, chromium, molybdenum, and vanadium. The purpose of
incorporating this extensive macroporosity into the catalyst
is mainly to overcome the rapid pore blockage accompanying the
laydown of both coke and asphaltene products which accompany
the treatment of heavy petroleum oils with conventional hydro-
treating catalysts.
U.S. Patent 3.383,301
This patent discloses a process for catalytically hydrodesul-
furizing a sulfur-containing petroleum oil containing residual
components and organometal1ic components normally capable of
poisoning catalysts due to the buildup of both deposited metals
and coke in or at the mouths of the pores. To overcome the
poisoning effects of both coke and metals deposition and conse-
quently maintain both high desulfurization and demetal1ization
capabilities, an alumina based catalyst containing at least one
hydrogenation component from the metals of Group VI-B and Group
VIM of the Periodic Table having a relatively uniform, wide
distribution of pores in the range of 0 to 300 angstroms in
radius is employed. More specifically, the catalyst should not
have more than 15 percent of the volume of pores having a radius
in the range of 0 to 300 angstroms in any 10 angstrom unit in-
crement, starting at 0 angstrom, while having at least 10 per-
cent in the 0 to 30 angstrom range, at least 15 percent in the
30 to 70 angstrom range, and at least 30 percent in the 70 to
120 angstrom range. This catalyst also has a minimum surface
area of 100 M2/g.
U.S. Patent 3.362.901
This patent describes a two-stage hydrogenation process in
which a catalyst is employed in the first stage which causes
the asphaltenes in a petroleum residua to agglomerate after
which the agglomerates are removed before further hydrogena-
tion of the oil is carried out in the subsequent stage. In
the process of removing the agglomerated asphaltenes, a sub-
stantial portion of the feed metals is accomplished. The first
92
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stage catalyst can either be an inert particulate, such as
tabular alumina, extruded alumina, or a low activity catalyst.
Alternatively, the first stage catalyst can be a support such
as alumina, silica, silica alumina, magnesia, titania, etc.,
promoted with about 0.5 to three percent of a metal in Group
VII of the Periodic Table in combination with two to 15 per-
cent of a Group VI-B metal. Obviously, the operating condi-
tion must be such that the metal-containing asphaltene ag-
glomerates rather than deposits to a significant degree on
the first stage catalyst itself as would normally be the case.
U.S. Patent 3.297.589
This patent is directed toward the preparation of a novel hy-
drorefining catalyst which is used in processes for the re-
moval of organometal1ic contaminants from residual petroleum
fractions. The carrier used for the preparation of the cata-
lyst is a refractory inorganic oxide, preferably a composite
of alumina and silica, with alumina being the greater propor-
tion. However, other refractory inorganic oxides, e.g., zir-
conia, magnesia, titania, boria, strontia, hafia, and mixtures
of two or more, could be employed in conjunction with alumina.
Pore size distribution and surface area are described in such
broad terms as not to yield any specific information in these
areas .
After drying and calcination to remove the physically-bound,
and a large portion of the chemically-bound, water the carri-
er is impregnated with an aqueous or nonaqueous decomposable
vanadium compound such as vanadium trichloride, but not limited
to this species, such that the final catalyst contains between
1.0 and 30.0 percent by weight of vanadium as the metal. After
drying in such a way as not to decompose the vanadium compounds,
if other than vanadium trichloride, the catalyst is treated
with sulfur monochloride, sulfur dichloride, or mixtures of
these two compounds with the results that vanadium trichlor-
ide is dispersed throughout the catalyst support in a complex
with components in the carrier material. After a further cal-
cination at 150°F to 500°F, the catalyst is used to remove a
substantial fraction of both the metal and asphaltenic con-
taminants. Regeneration is achieved by burning off deposited
coke and again treating with sulfur mono- or dichloride.
93
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U.S. Patent 3.227.645
This patent describes a catalytic hydrogenation process for the
removal of metal contaminants from hydrocarbon feeds prior to
hydrocracking or catalytic cracking. The demetal1ization cata-
lyst is composed of one or more of the oxides, sulfides, or
other compounds of metals of Group VI and/or Group VIM of the
Periodic Table alone or supported on a carrier. Typically,
the carrier is a refractory oxide, such as alumia, silica, or
silica alumina. However, charcoal and other "inert" materials
may also be used.
U.S. Patent 3.180.820
This patent discloses a catalytic hydrogenation process for re-
moving metals contaminants from a variety of hydrocarbon oil
feeds. The catalyst is described as comprising a metallic com-
ponent having hydrogenation activity which may be employed in
the unsupported state or in a supported form. The supports
are described as refractory inorganic oxide materials having
a medium to high surface area and a well developed pore struc-
ture. Suitable metal components include metals of Groups V-B,
VI-B, and VIII of the Periodic Table.
U.S. Patent 2.987.470
This patent relates to an improved hydrogenation process for
the removal of metallic impurities from hydrocarbon oils in
an ebullated bed reactor system, i.e., a fluidized bed consist-
ing of three phases; gas, liquid, and solid particulate in in-
timate contact. A particle size of about three to 20 mesh can
be fluidized in this type of system without carryover of the
catalyst. The particulate contact material onto which the me-
tal contaminants are deposited may be bauxite, alumina, sand,
coke, beryl, silicon carbide, magnesia, and iron ore. No spe-
cific requirements as to physical or chemical structure of
these contact solids are mentioned. Alumina and bauxite appear
to be the preferred solids.
94
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U.S. Patent 2.970.957
This patent describes a catalytic hydrogenation process for
the removal of vanadium and/or sodium from petroleum residua
using a regenerated cobalt molybdate hydrotreating catalyst.
Although the type of catalyst suffers a permanent loss in ac-
tivity for desulfurization due to the presence of deposited
metal contaminants, the inventors found that the activity for
vanadium and sodium removal does not decline at the same rate.
Therefore, the regenerated catalyst can be used in the process
long after the effectiveness for desulfurization has fallen be-
low an economical level. Even after prolonged use and nine re-
generations (i.e., coke burn-off), this type of catalyst is
superior to fresh activated bauxite for vanadium removal.
U.S. Patent 2,9^5.803
This patent describes a hydrogen treatment process in which de-
metallization catalysts composed of oxides or sulfides of the
Group VI metals, such as molybdenum, tungsten, vanadium, etc.,
are used alone or in combination with the oxides or sulfides
of the iron group metals such as nickel, cobalt, or iron. The
catalysts are composited with a carrier such as activated alu-
mina, alumina, silica, "Alfrax" or kieselguhr. One of the
major considerations in the distillation of the crude is that
the residue fed to the demetal1ization stage of the process
not have a sulfur-to-meta 1 s ratio less than 200 or else this
treatment will not effectively remove the metals contaminants.
This would appear to indicate some difficulty when a vacuum re-
siduum is demetallized using the general type of hydrotreating
catalysts just described.
U.S. Patent 2.891.005
This describes a process in which residual oils are hydrogenated
in the presence of a cobalt molybdenum on alumina catalyst in
such a manner that microcoke particles, containing much of the
metal contaminants presented in the feed, are formed. Thus,
the metals contaminants are reduced by subsequent removal of
these microcoke particles rather than by deposition on the cata-
lyst itself.
95
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U.S. Patent 2.891.00^
This describes a process for removing metals contaminants from
petroleum by treating the feed with boron compounds either sup-
ported or unsupported, such as boron oxide or boric acid. The
boron compounds form complexes with the feed metals which can
be separated from the oil through settling of the complex it-
self or, in the case of the supported boron compounds, through
a separation of the solid support.
U.S. Patent 2,769.758
This patent describes a process for the removal of sodium and
vanadium contaminants from petroleum hydrocarbon feeds prior
to desulfurization. The porous contacting agent employed in
the metals removal stages is bauxite. The sodium removal is
accomplished through a nonhydrogenative step prior to removal
of vanadium in a subsequent hydrogenative step. This is ac-
complished in a single bed of bauxite by admitting recycle
hydrogen at a point in the bed calculated to afford the opti-
mum space velocities for both sodium and vanadium removal.
U.S. Patent 2,76^,758
This patent disclosed still another catalytic hydrogenation
process for the removal of metallic contaminants from petrole-
um feeds. This patent is directed to the removal of both vana-
dium and/or sodium by contacting petroleum or petroleum products
with a catalyst composed of five to 15 weight percent ferric
oxide on alumina.
U.S. Patent 2,730,^87
This patent is essentially identical to U.S. 2,76^,758 except
that the demetal1ization catalyst is composed of one to ten
weight percent of Tj02 on alumina. In this case, the Tfd2
96
-------
alumina catalyst has a higher demetallization activity than
does ferric oxide/alumina catalyst cited in U.S. 2,764,758.
U.S. Patent 2.687.985
This patent complements U.S. 2,769,758 in that it effects the
removal of both sodium and vanadium from residual oils at con-
ditions which are optimum for the nonhydrogenative removal of
sodium and for the subsequent removal of vanadium prior to hy-
drodesulfurization.
97
-------
98
-------
APPENDIX B
OUTLINE OF DETAILED PROCEDURES FOR CATALYST PREPARATION
99
-------
100
-------
APPENDIX B
OUTLINE OF DETAILED PROCEDURES FOR CATALYST PREPARATION
Catalyst LX-1: Activated Bauxite Impregnated with 5% Fe
Five hundred ml of 12 x 20 mesh bauxite was heated in air at
950°F for 16 hours, then cooled and weighed. The weight was
448 grams. On a separate sample of support, it was determined
that 62 ml of water covered 100 grams of support.
The impregnating solution was prepared by adding 181 grams Fe
(1^103)3.9H20, equivalent to 26 grams Fe, to water in a gradu-
ated beaker. After dissolving, additional water was added so
that the total water was 310 ml.
The support was placed in a Pyrex tray, 8 x 12 x 2 inches,
and the solution was poured evenly over the support. The tray
was heated on a hot plate with continuous stirring. Near the
end of the heating, which took about two hours, continuous agi-
tation with a wide flat spatula was required to keep the cata-
lyst from agglomerating.
The catalyst was transferred to a 600 ml porcelain evaporat-
ing dish and placed in a muffle furnace held at 950°F 4; 25°F
having a small air bleed. After 16 hours, the catalyst was
removed from the furnace, covered with a watch glass, and
allowed to cool to approximately room temperature. It was
then transferred to a glass jar and tightly stoppered.
A total of 488 grams of catalyst was recovered.
Catalyst LX-2: Activated Bauxite Impregnated with 5% Co
The same amount of support was prepared by the method used for
LX-1. The impregnating solution was prepared by dissolving
128 grams Co(N03)2.6H20, equivalent to 26 grams of Co, in water
and diluting to a final volume of 310 ml. The impregnation,
101
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drying, and calcining were the same as used for LX-1. A total
of 488 grams of catalyst was recovered.
Catalyst LX-3: Activated Bauxite Impregnated with 5% V
A total of 500 ml (447 grams) of support was prepared by the
same method used for LX-1. The impregnating solution was pre-
pared by suspending 54 grams NH4V03, equivalent to 23.5 grams
of V, in 275 ml water. The mixture was heated to about 125°F
and a solution of 18.5 grams of NaOH in 35 ml of water was
added slowly while stirring. The impregnation, drying, and
calcining were the same as used for LX-1. A total of 496.4
grams of catalyst was recovered.
Catalyst LX-4: Activated Bauxite Impregnated with 5% Mo
A total of 500 ml (448 grams) of support was prepared by the
same method used for LX-1. The impregnating solution was pre-
pared by heating 310 ml of concentrated NH40H to about 120°F
while slowly adding 35.6 grams of Mo03, equivalent to 23.6
grams of Mo, and stirring constantly. The impregnation, dry-
ing, and calcining were the same as used for LX-1. A total
of 483.2 grams of catalyst was recovered.
Catalyst LX-5: Activated Bauxite Impregnated with 5% V
A total of 500 ml (440 grams) of support was prepared by the
same method as used for LX-1. Then 141 grams of oxalic acid
was dissolved in water and diluted to 310 ml. This solution
was heated to l40°F and 42 grams of ^^05, equivalent to 23.5
grams of V, was slowly added with stirring until dissolved.
The impregnation, drying, and calcining were the same as used
for LX-1. A total of 471.8 grams of catalyst was recovered.
102
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Catalyst LX-6: Activated Bauxite Impregnated with 5%
A total of 500 ml (450.4 grams) of support was prepared by the
same method used for LX-1. Then 34.2 grams h^PO^ (85%), equi-
valent to 23.7 grams of HP03, was dissolved in water and di-
luted to 310 ml. This solution was poured slowly over the sup-
port and dried on a hot plate with stirring. Calcination was
carried out at 650°F for 16 hours. A total of 474.6 grams of
catalyst was recovered.
Catalyst LX-7: Activated Bauxite Impregnated with 7.5% Ni
A total of 500 ml (450.8 grams) of support was prepared by the
same method used for LX-1. Then 182 grams Ni (N03)2-6H20, equi-
valent to 23.7 grams of Ni, was dissolved in water and diluted
to 310 ml. The impregnation, drying, and calcining were the
same as used for LX-1. A total of 398.4 grams of catalyst was
recovered.
Catalyst LX-8: Activated Bauxite Impregnated with 5% Cr
A total of 500 ml (4-56.3 grams) of support was prepared as in
LX-1. Then 185 grams Cr (N03)3_9H20, equivalent to 24.0 grams
of Cr, was dissolved in water and diluted to 310 ml. The im-
pregnation, drying, and calcining were the same as used for LX-
1. A total of 492.9 grams of catalyst was recovered.
Catalyst LX-9: Activated Bauxite Impregnated with 10% Fe
A total of 500 ml (450 grams) of support was prepared by the
same method used for LX-1. Then 362 grams Fe(N03)3.9H20, equi-
valent to 50 grams of Fe, was dissolved in water and diluted to
310 ml. The impregnation, drying, and calcining were the same
as used for LX-1. A total of 526.1 grams of catalyst was re-
covered.
103
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Catalyst LX-11: Activated Bauxite with Low SI0? Impregnated
with 5% Fe
A total of 500 ml (451.1 grams) of support was prepared in the
same manner as LX-1 . Then 171.4 grams Fe (^3)3 .S^O, equiva-
lent to 23.7 grams of Fe, was dissolved in water and diluted
to 310 ml. The impregnation, drying, and calcining were the
same as used for LX-1. A total of 483.7 grams of catalyst was
recovered.
Catalyst LX-12: Macroporous Alumina Impregnated with 5% Fe
The alumina was crushed in a mortar and sized to 12 x 20 mesh.
A total of 248 ml (185 grams) of the support was prepared and
it was calcined at 950°F for 16 hours. Then 70 grams F
9H20, equivalent to 9.7 grams of Fe, was dissolved in water
and diluted to 155 ml. Impregnation, drying, and calcining
were the same as used for LX-1. A total of 199 grams of cata
lyst was recovered.
Catalyst LX-13: Activated Bauxite Impregnated with 1.5% Co
and 5% Mo
A total of 500 ml (450 grams) of support was prepared by the
same procedure used for LX-1. Then 36.2 grams of Mo03, equi-
valent to 24.1 grams of Mo, were dissolved in 155 ml of hot
OH and diluted with water to 310 ml. This solution was poured
over the support which was then dried on a hot plate with stir
ring. Then 35.6 grams Co(N03)2-6H20, equivalent to 7.2 grams
of Co, were dissolved in water and diluted to 310 ml. This
solution was poured over the Mo-impregnated catalyst, which
was then dried on a hot plate with stirring, transferred to a
porcelain evaporating dish and calcined in a muffle furnace
held at 950°F for 16 hours. A total of 499 grams of catalyst
was recovered.
104
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Catalyst LX-14: Macroporous Alumina Impregnated with 5% Mo
The alumina support, totaling 250 ml (186.2 grams), was pre-
pared in the same manner as LX-1. Then 14.7 grams of MoO?,
equivalent to 9.8 grams of Mo, was dissolved in 85 ml of not
NH^OH and diluted to 175 ml with water. Impregnation, drying,
and calcining were done in the same manner as used for LX-1.
A total of 202.9 grams of catalyst was recovered.
Catalyst LX-15: Activated Attapulgus Clay Impregnated with
9.5% Mo
The clay was ground in a mortar and 500 ml (263.5 grams) of
12 x 20 mesh material was recovered. It was then calcined at
950°F for 16 hours. Then 41.6 grams of Mo03, equivalent to
27.7 grams of Mo, was dissolved in 150 ml of hot NH^OH and di-
luted to 350 ml with water. Impregnation, drying, and calcin-
ing were the same as used for LX-1. A total of 298 grams of
catalyst was recovered.
Catalyst LX-16: Activated Carbon Impregnated with 11% Mo
The support was crushed and 500 ml (207 grams) of 12 x 20 mesh
material was recovered. It was then calcined at 650°F for 16
hours. Then 38.5 grams of MoO^, equivalent to 25.6 grams of
Mo, was dissolved in 150 ml of hot Nh^OH and diluted to 350 ml
with water. The impregnation and drying were the same as used
for LX-1, but the calcining was done at 650°F for two hours.
Some carbon was burned off as evidenced by a white ash on top
of the catalyst. A total of 239.5 grams of catalyst was re-
covered.
Catalyst LX-17: Low Surface Area Alumina Impregnated with
3.8% Mo
The support, totaling 250 ml (337.1 grams), was prepared in
the same manner used for LX-1. Then 20 grams of Mo03, equi-
valent to 13.3 grams of Mo, was dissolved in 75 ml of hot NHi|OH
105
-------
diluted to 175 ml with water. The impregnation, drying, and
calcining were done in the same manner as in LX-1. A total
of 355.7 grams of catalyst was recovered.
Catalyst LX-18: Activated Bauxite Impregnated with 2% Mo
A total of 500 ml (455.5 grams) of support was prepared in the
same manner as LX-1. Then 14 grams of Mo03, equivalent to 9.3
grams of Mo, was dissolved in 75 ml of hot NHlfOH and diluted
to 310 ml with water. Impregnation, drying, and calcining
were done in the same manner as LX-1. A total of 471.8 grams
of catalyst was recovered.
Catalyst LX-19: High Porosity Alumina Impregnated with 8.9%
Mo
A total of 300 ml (165.4 grams) of support was prepared in the
same manner as LX-1. Then 24.3 grams of MoOj, equivalent to
16.2 grams of Mo, was dissolved in 75 ml of hot NH^OH and di-
luted to 210 ml with water. Impregnation, drying, and calcin-
ing were done in the same manner as LX-1. A total of 188.1
grams of catalyst was recovered.
Catalyst LX-20: Activated Attapulgus Clay Impregnated with
2% Mo
A total of 500 ml (263.2 grams) of support was prepared by
crushing in a mortar and separating out the 12 x 20 mesh frac-
tion. The remainder of the treatment was the same as used for
LX-1. The 8.1 grams of MoO^, equivalent to 5.4 grams of Mo,
was dissolved in 75 ml of hot NHZ|OH and diluted to 350 ml with
water. Impregnation, drying, and calcining were done In the
same manner as used for LX-1. A total of 268 grams of cata-
lyst was recovered.
106
-------
Catalyst LX-21: Activated Bauxite Impregnated with 1% Mo
A total of 500 ml (456.9 grams) of support was prepared in the
same manner as used for LX-1. Then 6.9 grams of Mo03, equiva-
lent to 4.6 grams of Mo, was dissolved in hot NHi,.OH and diluted
to 350 ml with water. Impregnation, drying, and calcining were
done in the same manner as for LX-1. A total of 460.5 grams of
catalyst was recovered.
Catalyst LX-22: Activated Bauxite Impregnated with 2% Mo
A total of 500 ml (478.4 grams) of 20 x 50 mesh support was
prepared in the same manner as LX-1. Then 14.7 grams of
equivalent to 9.8 grams of No, was dissolved in 50 ml of hot
NH^OH and diluted to 350 ml with water. Impregnation, drying,
and calcining were done in the same manner as used for LX-1.
A total of 488.7 grams of catalyst was recovered.
Catalyst LX-23: Activated Bauxite Impregnated with 1% Zn
A total of 500 ml (458.9 grams) of support was prepared in the
same manner used for LX-1. Then 20.9 grams of Zn ((^03)2-61^0,
equivalent to 4.6 grams of Zn, was dissolved in water and di-
luted to 350 ml. Impregnation, drying, and calcining proce-
dures were the same as used for LX-1. A total of 462.6 grams
of catalyst was recovered.
Catalyst LX-24: Activated Bauxite Impregnated with 0.5% Mo
A total of 500 ml (459.9 grams) of support was prepared in the
same manner used for LX-1. Then 3.45 grams of Mo03, equiva-
lent to 2.3 grams of Mo, was dissolved in 50 ml of hot NHifOH
and diluted to 350 ml with water. Impregnation, drying, and
calcining procedures were the same as used for LX-1. A total
of 463-5 grams of catalyst was recovered.
107
-------
Catalyst LX-25: Activated Bauxite Impregnated with 0.3% N?
1 1 O/ M _
and 1% Mo
A total of 500 ml (452 grams) of support was prepared in the
same manner as used for LX-1. Then 6.9 grams of Mo03, equiva-
lent to 4.6 grams of Mo, was dissolved in 50 ml of hot NHZ^OH
and diluted to 200 ml with water. Following this step, 6.9
grams of Ni(N03)2.6H20, equivalent to 1.4 grams of Ni, was
dissolved in water and diluted to 150 ml. The two were com-
bined and the support was impregnated, dried, and calcined in
the same manner that was used for LX-1. A total of 457.2 grams
of catalyst was recovered.
Catalyst LX-26: Activated Bauxite Impregnated with 0.5% Mo
A total of 500 ml (502.6 grams) of 20 x 50 mesh support was
prepared in the same manner as used for LX-1. Then 3.75 grams
of Mo03, equivalent to 2.5 grams of Mo, was dissolved in 50 ml
of hot NH40H and diluted to 350 ml with water. Impregnating,
drying, and calcining procedures were the same as used for LX-1
A total of 499 grams of catalyst was recovered.
Catalyst LX-27: Activated Bauxite Impregnated with 1% Mn
A total of 500 ml (498.5 grams) of 20 x 50 mesh support was
prepared in the same manner that was used for LX-1. Then 32.1
grams of a 50. 7% aqueous solution of Mn(N03)o, equivalent to
five grams of Mn, was diluted to 350 ml with water. Impreg-
nating, drying, and calcining procedures were the same as used
for LX-1. A total of 4gg grams of catalyst was recovered.
108
-------
APPENDIX C
SUMMARY OF CATALYST SCREENING RUNS
109
-------
-------
Table C-l. SUMMARY OF CATALYST SCREENING RUNS
(Feed: Tia Juana Vacuum Bottoms)
Run No.
185-192
184-157
185-193
185-194
1 8V 1 58
Catalyst
Period Catalyst Base Promoter
IB Porocel
12 x 20 Mesh
2
38
4
5
6
7
8
9
IB Porocel 57 Fe
2 12 x 20 Mesh
3
4
5
6
7
8
IB Porocel 57 Co
2 12 x 20 Mesh
3
4
IB Porocel 57, Mo
2 12 x 20 Mesh
3
IB Porocel 57, V
2 12 x 20 Mesh
3
4
Temp
°F
790
791
791
788
790
790
789
790
789
791
790
790
790
790
788
789
789
790
790
790
790
790
791
790
788
789
790
790
Hydrogen
Pressure
ps ig
2015
2025
2000
1995
1995
2000
2000
2005
2000
1980
2005
2010
2010
2000
1990
2005
2000
2015
2000
2000
1985
2025
2010
2000
2000
1980
1995
2010
Space Velocity
VQ/hr/Vc
0.83
0.83
0.47
0.44
0.58
0.51
0.51
0.54
0.55
0.65
0.55
0.4g
0.4g
0.53
0.55
0.53
0.4g
0.62
0.55
0.55
0.46
0.61
0.50
0.53
0.53
0.56
0.55
0.52
B/D/Lb
0.064
0.064
0.036
0.034
0.044
0.040
0.039
0.041
0.043
0.049
0.042
0.037
0.037
0.041
0.042
0.040
0.037
0.046
0.041
0.042
0.035
0.045
0.038
0.040
0.040
0.042
0.041
0.039
H2
Rate
SCF/Bbl
3340
3510
6630
7860
5200
4400
4250
4280
3740
2580
4130
4570
4440
4100
3350
4290
4150
3650
4100
3640
4140
4140
3870
3630
4090
3830
3770
2700
Catalyst
Age
Bbl/Lb.
0.049
0.113
0.158
0.186
0.230
0.270
0.309
0.340
0.383
0.047
0.082
0.1 19
0.156
0.197
0.239
0.279
0.311
0.051
0.087
0.129
0.160
0.037
0.075
0.110
0.045
0.087
0.128
0.167
Product Inspections
Gravity
"API
11.0
10.5
10.0
10.5
10.3
10.5
10.6
10.4
10.2
10.7
11.6
11.7
13.2
12.8
11.9
11.5
10.6
10.5
10.3
10.7
12.6
14.9
15.1
14.6
12.5
12.1
12.5
12.9
% S
2.42
2.31
2.53
2.26
2.31
2.13
2.42
2.20
2.32
2.19
2.16
2.28
2.11
2.18
2.40
2.21
2.30
2.35
1.24
1.04
1.27
2.30
2.20
2.34
2.32
V
ppm
350
370
324
285
305
284
262
261
265
225
225
210
210
215
245
226
238
276
266
252
235
235
175
203
194
240
222
210
Ni
PPm
62
68
67
62
66
64
64
61
62
52
54
56
62
58
54
51
55
61
63
63
57
40
39
43
48
53
64
55
IBP-550°F.V7
Cracked
Cracked
7.0
7.0
7.0
8.0
5.0
4.0
8.0
5.0
6.0
8.0
8.0
7.0
6.0
8.0
10.0
6.0
7.0
8.0
7.0
7.0
7.0
7.0
7.0
5.0
7.0
6.0
-------
Table C-1 (continued). SUMMARY OF CATALYST SCREENING RUNS
(Feed: Tia Juana Vacuum Bottoms)
Run No.
181*- 166
185-209
185-207
184-167
Period
IB
2
3
4
5
6
7
IB
2
3
4
5
IB
2
3
IB
2
3
Catalyst
Catalyst Base Promoter
Porocel 2/ Mo
20 x 50 Mesh
Porocel 0.57 Mo
12 x 20 Mesh
Porocel 27 Mo
20 x 50 Mesh
Porocel
20 x 50 Mesh
Temp
°F
791
790
790
790
790
790
790
790
790
790
789
790
787
791
791
790
790
790
Hyd rogen
Pressure
ps ig
2000
2000
2010
2005
2010
2040
1995
2000
2000
2030
1905
2000
1010
1000
1000
2000
2010
2000
Space Veloci ty
Vo/hr/Vc
0.58
0.56
0.53
0.55
0.52
0.50
0.49
0.54
0.4g
0.63
0.54
0.54
0.88
0.54
0.50
0.58
0.51
0.43
B/O/Lb
0.046
0.044
0.042
0.043
0.041
0.039
0.038
0.044
0.040
0.051
0.044
0.044
0.068
0.042
0.038
0.042
0.037
0.031
H2
Rate
SCF/Bbl
4060
3820
4370
3770
4030
3940
3620
4250
4570
3160
3740
3870
3460
4320
4260
4200
4350
4920
Catalyst
Age
Bbl/Lb
0.037
0.081
0.123
0.166
0.207
0.246
0.279
0.041
0.081
0.132
0.176
0.214
0.052
0.094
0.127
0.039
0.076
0.103
Product Inspections
Gravity
"API 7 S
14.7
16.1
16.1
16.4
15.2
15.3
15.4
15.5
13.8
14.4
14.0
13.5
11.7 :
14.4
.49
.02
.00
.19
.13
.08
.06
.70
.77
.84
.63
.62
-.00
.59
13.9 .67
14.1 2.32
14.2 2.56
13.1 1.86
V
ppm
142
125
128
135
137
134
133
195
196
207
192
188
260
237
236
272
228
208
Ni
ppm
44
46
43
47
46
45
45
46
48
53
52
55
64
55
56
69
63
64
IBP-550°F,V7
10.0
12.0
8.0
8.0
8.0
8.0
5.0
5.0
8.0
6.0
5.0
8.0
5.0
9.0
10.0
6.0
8.0
9.0
184-168
185-208
IB
2
3
IB
2
3
4
5
6
Porocel
Attapulgus
Activated
Clay
30 x 60 Mesh
17 Zn
791
792
791
790
789
790
789
791
789
2005
1995
1995
2010
1990
1995
1975
1995
2000
0.55
0.47
0.52
0.51
0.44
0.53
0.50
0.52
0.54
0.044
0.038
0.042
0.073
0.062
0.075
0.071
0.074
0.076
4410
3670
3850
3880
5510
4190
5770
4500
4560
0.037
0.075
0.117
0.089
0.151
0.226
0.297
0.371
0.447
12.4
12.5
13.7
13.8
14.1
13.5
14.5
12.3
11.4
2.43
2.23
2.23
2.12
2.24
2.23
2.19
2.10
2.32
252
234
261
157
170
194
208
220
297
60
63
64
47
51
57
52
57
63
6.0
12.0
10.0
9.0
11.0
10.0
8.0
9.0
7.0
-------
Table C-l (continued). SUMMARY OF CATALYST SCREENING RUNS
(Feed: Tia Juana Vacuum Bottoms)
Run No. Period
184-165 IB
2
3
4
5
6
7
SB
9
10B
1 1
185-203 IB
2
3
185-204 IB
2
3
It
5
6
185-205 IB
2
3
it
5
6
7
Catalyst Base
Porocel
12 x 20 Mesh
ACCO Porous
AI203
(1/16")
Attapulgus
Act tvated
Clay
Porocel
12 x 20 Mesh
Catalyst Temp
Promoter °F
2% Mo 790
790
790
790
790
791
790
791
789
789
790
8.90/ Mo 789
789
790
27 Mo 790
794
790
790
790
790
17 Mo 788
790
790
790
790
791
789
Hydrogen
Pressure
psig
2000
2010
1985
2000
2010
2000
2005
2020
2000
2005
2000
2000
1985
2000
1995
2000
2000
2005
1995
2005
2000
1995
1980
2000
2000
2000
2000
Space Velocity
Vo/hr/Ve
0.46
0.48
0.51
0.53
0.52
0.52
0.53
0.33
0.38
0.49
0.53
0.49
0.54
0.53
0.60
0.52
0.47
0.59
0.43
0.57
0.54
0.51
0.53
0.54
0.52
0.48
0.53
B/D/Lb
0.036
0.037
0.040
0.042
0.041
0.041
0.041
0.026
0.030
0.038
0.041
0.058
0.065
0.064
0.083
0.072
0.065
0.082
0.060
0.079
0.045
0.043
0.044
0.045
0.044
0.040
0.044
H2
Rate
SCF/Bbl
4300
4550
3900
3800
3990
4000
4130
5780
4980
4980
4230
4820
4000
4400
3980
4050
4630
3420
4880
3740
4890
4600
4230
3810
3740
4720
4440
Catalyst
Age
Bbl/Lb.
0.033
0.070
0.110
0.152
0.193
0.234
0.275
0.308
0.338
0.377
0.413
0.068
0.133
0.189
0.084
0.156
0.221
0.303
0.363
0.432
0.037
0.080
0.124
0.169
0.213
0.253
0.292
Product Inspections
Gravi ty
"API % S
14.6 1.76
15.9 ' 1.35
15. ^ l.H
15.2
15.9
14.4
15.9
15.8
15.9
15.5
14.4
16.9
15.8
14.5
.41
.23
.26
.32
.10
.10
.22
.28
.41
.43
.56
14.7 2.03
14.4 1.97
15.1 2.09
13.1 2.10
13.8 2.36
13.3 2.07
14.5 1.73
14.2 1.41
13.9 l.W
13.5 1.41
14.9
It f, 1.41
14.8 1.36
V
ppm
241
176
185
191
193
210
21 1
170
162
217
217
204
240
248
208
205
214
263
325
264
178
168
186
193
191
178
193
Ni
ppm
48
40
50
50
46
50
50
45
44
50
49
42
44
45
45
46
53
59
58
:s
45
49
50
52
51
51
53
IBP-550°F,V%
2.0
3.0
7.0
11.0
8.0
11. 0
8.0
8.0
8.0
8.0
11 .0
7.0
10.0
9.0
5.0
7.0
5.0
9.0
7.0
9.0
7.0
7.0
7.0
7.0
7.0
7.0
8.0
-------
Table C-l (continued). SUMMARY OF CATALYST SCREENING RUNS
(Feed: Tia Juana Vacuum Bottoms)
Run No.
185-195
184-159
185-196
184- ] 60
185-197
185-198
184-161
184-162
Period
IB
2
3
IB
2
3
IB
2
3
IB
2
3
4
IB
2
3
18
2
3
IB
2
3
4
5
6
Catalyst Base
Porocel
12 x 20 Mesh
Porocel
12 x 20 Mesh
Porocel
12 x 20 Mesh
Porocel
12 x 20 Mesh
Porocel
12 x 20 Mesh
Low S i 02
Porocel
(Sil ica)
Porocel
12 x 20 Mesh
Catalyst Temp
Promoter °F
H3P04 789
790
790
11 Ni 787
790
797
5/ CR 788
790
790
10/ Fe 790
791
789
790
10/ V 789
791
789
_ Run
5/ Fe 790
790
790
1.5/ Co/ 795
57 Mo 790
790
786
790
790
Hydrogen
Pressure
psig
1970
1995
2005
1990
1990
1995
1950
1995
2005
2000
1985
2005
2000
2000
2000
1990
2005
2005
2000
2000
2010
2000
2000
1990
1985
Space Velocity
V^/hr/Vc
0.56
0.53
0.57
0.49
0.50
0.56
0.59
0.57
0.49
0.56
O.S't
0.5**
0.55
0.63
0.60
0.50
0.59
0.53
0.49
0.71
0.51*
0.57
0.47
0.51*
0.53
B/D/Lb
0.044
0.041
0.044
0.037
0.038
0.043
0.044
0.042
0.036
0.043
0.042
0.042
0.042
0.046
0.041
0.036
0.046
0.041
0.039
O.OS't
0.041
0.043
0.036
0.041
0.040
H2
Rate
SCF/Bbl
2880
3990
3200
4290
4020
3950
2710
3808
3537
3480
3220
4000
3580
3260
3530
3660
3840
4190
3890
3480
4050
3970
4380
3920
3860
Catalyst
Age
Bbl/Lb.
0.049
0.090
0.134
0.033
0.065
0.103
0.031
0.071
0.102
0.042
0.084
0.126
0.163
0.035
0.076
0.107
0.043
0.084
0.118
0.050
0.091
0.134
0.170
0.211
0.246
Product Inspections
Gravi ty
"API
12.6
11.4
11.3
13.6
13.3
14.2
11.9
11.7
14.7
13.8
12.1
12.1
12.9
12.9
12.3
14.1
13.0
13.3
13.2
16.2
15.5
15.1
15.1
15. <+
14.1
% S
2.54
2.62
2.54
2.33
2.31
2.27
2.50
2.53
2.30
2.32
2.24
2.40
2.36
2.31
2.18
2.04
2.45
2.18
2.32
1.05
1.14
1.14
1.31
1.24
1.21
V
ppm
308
310
280
217
220
240
223
253
247
215
222
217
230
198
190
202
260
250
224
194
186
200
196
203
205
Ni
ppm IBP-550°F,V7.
64
68
65
57
62
62
57
58
55
^5
49
49
51
45
50
53
60
58
55
42
42
1*7
46
46
<*5
5.0
6.0
6.0
7.0
6.0
8.0
6.0
8.0
9.0
6.0
8.0
8.0
6.0
4.0
5.0
5.0
6.0
9.0
8.0
6.0
7.0
6.0
8.0
7.0
8.0
-------
Table C-l (continued). SUMMARY OF CATALYST SCREENING RUNS
(Feed: Tia Juana Vacuum Bottoms)
Run No. Period Catalyst Base
185-199
1 84-163
185-200
184-161*
185-201
185-202
IB
2
3
4
5
6
7
IB
2
3
4
5
6
IB
2
3
Act ivated
Clay
(Engelhard)
A'2°3
(35 M2?g-HRI
1243 - 12 x
20 Mesh)
Activated
Clay
IB
2
IB
2
3
IB
2
Macroporous
12 x 20 Mesh)
CAL
(Activated
Carbon)
Low Surface
Area Al20j
(HRI 3443)
Catalyst Temp
Promoter °F
792
791
791
790
790
790
789
57 Mo 792
790
790
790
787
790
9.5/ Mo 790
790
789
787
57 Fe 790
788
Hyd rogen
Pressure
ps iq
2000
2005
2000
2010
2000
1990
2000
2010
2000
2000
2010
2005
2005
1995
1990
2005
2010
2020
2020
Space Velocity
Vo/hr/Vc
0.47
0.56
0.50
0.53
0.48
0.58
0.52
0.58
0.53
0.51
0.55
0.49
0.53
0.49
0.48
0.57
0.43
0.58
0.55
B/D/Lb
0.069
0.082
0.074
0.077
0.070
0.085
0.077
0.053
0.04g
0.047
0.050
0.045
0.048
0.060
0.058
0.070
0.052
0.051
0.048
H2
Rate
SCF/Bbl
6380
3860
4200
31 10
3930
3760
3500
3980
4040
2660
5060
4140
3720
4180
4390
3420
4690
3870
3960
Catalyst
Age
Bbl/Lb
0.083
0.165
0.239
0.316
0.386
0.471
0.516
0.046
0.084
0. 130
0. 174
0.219
0.228
0.059
0.117
0.187
0.233
0.047
0.095
Product Inspections
Gravi ty
"API
13.2
12.4
13.5
12.7
12.9
12.7
1?.^
14.6
14.3
13.1
14.0
13.5
12.5
14.1
14.6
15.2
14.0
13.2
12.5
% S
2.23
2. 11
2.09
2.31
2.17
2.12
2.25
1.83
2.10
2.07
2.05
2.10
1.99
1.88
1.80
2. 1 1
1.96
2.47
2.36
ppm
234
236
255
274
266
289
243
176
176
207
215
204
232
170
197
246
207
300
274
ppm
48
54
57
59
62
59
59
52
56
58
59
61
67
42
46
53
60
69
67
IBP-550°F,V7
6.0
7.0
8.0
7.0
8.0
7.0
6.0
6.0
8.0
8.0
10.0
9.0
8.0
7.0
8.0
7.0
8.0
5.0
6.0
1 17 Mo
3.87 Mo
791
790
790
790
790
1995
2010
2005
2000
1995
0.48
0.54
0.61
0.56
0.45
0.075
0.085
0.096
0.029
0.023
4070
3670
3610
3570
4430
0.059
0.144
0.212
0.029
0.052
16.2
14.9
14.2
12.9
9.3
1.57
1.81
1.77
2.59
2.59
224
249
272
448
413
47
53
52
75
72
7.0
6.0
6.0
3-0
5.0
-------
Table C-l (continued). SUMMARY OF CATALYST SCREENING RUNS
Run No. Period Catalyst Base
4-169
181*-17!
IB
2
3
It
5
6
IB
2
3
Porocel
20 x 50 Mesh
Porocel
20 x 50 Mesh
Catalyst
Promoter
0.5% Mo
17, Mn
Temp
°F
790
790
790
790
791
789
792
789
790
Hydrogen
Pressure
psig
2000
2000
2005
2010
2010
2000
2000
2000
2000
Space
Vn/hr/V
0.1*9
0.51
0.52
0.50
0.58
0.50
0.1*9
0.50
0.53
Velocity
c B/D/Lb
0.038
0.040
0.041
0.038
0.01*5
0.038
0.038
0.038
0.041
H2
Rate
SCF/Bbl
4400
3910
39^0
3820
3720
1*020
1*020
1*210
3090
Catalyst
Age
Bbl/lb
0.039
0.079
0.120
0.158
0.203
0.236
0.032
0.070
0.106
Product Inspections
Gravity
"API
14.5
12.9
11*. 9
15.2
13.6
15.2
11*. 1*
11*. 6
13.7
% S
.71
.62
.55
.62
.51*
1.62
2.22
2.12
2.22
V
PP"i
162
11*5
153
1 1*0
155
11*9
190
199
181
Ni
PP"i
1*5
1*8
1*9
1*8
i«9
1*8
48
52
59
IBP-550°F,V70
7.0
11.0
8.0
9.0
8.0
8.0
8.0
9.0
8.0
-------
APPENDIX D
SUMMARY OF DEMETALLIZATION RUNS
117
-------
118
-------
Table D-l. SUMMARY OF DEMETALLIZATI ON RUNS
Run No.-Period Catalyst Base
I85-210-8B
9
10
11
12
13
11*
15
18^ 172-2 IB
22
23
185-211-1B
2
3
i+
5
6
7
8
9
10
11
12
13
1/4
15
185-21 2-1B
2
3
Porocel
(18U-166 Dump
20 x 50 Mesh)
Catalyst
Promoter
27 Mo
Porocel
(201-58 Dump)
Porocel 27 Mo
(20 x 50 Mesh)
HDS-|l*lt2B
(HRI 31*56)
Crushed to
20 x 50 Mesh
Product Inspections
Feed
Tia Juana
V.B.
Gach Saran
V.B.
Tia Juana
V.B.
Tia Juana
V.B.
Temp
°F
791
790
791
789
791
789
788
787
791
790
708
790
789
790
792
790
789
790
792
792
790
793
791
789
791
790
790
790
790
790
788
H2
Pres.
psig
2005
2005
2010
2010
1995
2015
1990
2010
2000
2010
1985
2015
2005
2005
2010
2015
2005
2000
2005
2000
2000
2000
2005
1995
2005
2000
1980
1995
1990
2000
2005
Space
Vn/hr/V
0.61*
0.63
0.56
0.56
0.48
0.38
0.1*7
0.1*2
0.69
0.78
0.7^
0.1*3
0.1*3
0.1*6
0.1*8
0.50
0.50
0.46
0.47
0.1*8
0.51
0.1*9
0.1*7
0.51
0.1*9
0.47
0.52
0.51
0.49
0.59
0.52
Velocity
c B/D/Lb
0.01*8
0.048
0.01*3
0.01*3
0.037
0.029
0.036
0.032
0.051*
0.060
0.057
0.032
0.032
0.035
0.036
0.038
0.038
0.035
0.035
0.036
0.038
0.037
0.035
0.039
0.037
0.035
0.071
0.068
0.066
0.080
0.071
H2
Rate
SCF/Bbl
2670
3820
1*1*80
1*1*80
1*370
5^00
1*510
7830
1*230
3990
1*060
1*690
5130
1*290
1*960
1*550
1*820
1*1*60
1*21*0
5120
1*070
1*950
1*1*00
1*1*60
5820
3910
1*000
1*270
1*310
1*330
1*060
Cat.
Age
Bbl/Lb
0.308
0.356
0.399
0.1*1*2
0.1*79
0.508
0.51*1*
0.51*9
0.055
0.115
0.165
0.031
0.063
0.098
0.131*
0.172
0.211
0.21*6
0.281
0.317
0.355
0.392
0.1*25
0.1*61*
0.501
0.532
0.061
0.129
0.195
0.275
0.361*
Gravity
°API
11*. 6
15.1*
16.2
15.7
15.0
15.9
15.9
11*. 6
13.1
13.1*
12.9
16.3
16.3
16.1*
16.1
15.5
15.8
15.5
15.9
15.1*
15.8
15.7
15.8
11*. 8
15.0
17.8
17.1*
16.6
16.5
16.8
7. S
.36
.25
.25
.35
.31
.25
.27
.36
2.21*
2.17
2.16
1.09
1 .10
1.15
1.22
1.20
0.97
.33
.21*
.51
.1*5
.32
.34
.50
.60
0.69
0.71*
0.90
0.92
0.89
V
PP"i
191
179
172
176
220
170
183
185
115
98
92
97
92
106
120
131*
11*9
11*5
155
163
212
191*
191
195
251*
212
50
105
89
123
101
Ni
ppm
51*
51
51
1*7
51*
1*1*
1*9
1*7
78
75
71*
29
32
38
1*2
1*6
1*9
1*3
1*5
1*8
51*
52
53
51
57
52
22
31*
33
36
37
IBP-
550°F
v%
6.0
8.0
6.0
7.0
7.0
9.0
7.0
6.0
6.0
7.0
7.0
8.0
8.0
10.0
9.0
10.0
10.0
9.0
10.0
8.0
9.0
8.0
8.0
13.0
8.0
i*.o
10.0
8.0
7.0
7.0
-------
Table D-l (continued). SUMMARY OF DEMETALLIZATI ON RUNS
Product Inspections
ro
o
Catalyst
Run No. -Period Catalyst Base Promoter Feed
185-213-IB Porocel 27 Mo Bachaquero
2 (20 x 50 Mesh) V.B.
3
4
5
6
7
8
9
10
11
12
13
14
I85-2I4-1B Porocel 27 Mo Sachaquero
2 (20 x 50 Mesh) V.B.
3
4
5
6
184-174-IB Porocel 27 Mo Tia' Juana
2 (20 x 50 Mesh) V.B.
3
4
5
6
7
8
9
10
11
!2
13
Temp
°F
789
790
790
790
790
790
789
790
789
791
787
791
790
789
791
790
790
791
792
790
792
790
792
792
791
791
790
79'
790
790
790
792
791
H2
Pres.
psig
2000
2010
2005
2000
2020
2000
1995
1985
2010
2000
1990
2000
2005
2000
1995
1990
2005
1990
2000
2000
2000
2005
2000
1990
1990
1995
2005
2000
2000
2000
2010
2005
2015
Space Veloci ty
Vo/hr/Vc
1.00
1.00
1.04
0.73
0.73
0.71
0.77
0.73
0.75
0.73
0.53
0.59
0.64
0.69
0.93
0.95
1.01
0.73
0.75
0.70
0.92
0.99
0.97
0.72
0.77
0.74
0.72
0.72
0.71
0.74
0.76
0.75
0.76
B/D/Lb
0.075
0.075
0.078
0.054
0.055
0.053
0.058
0.054
0.056
0.055
0.039
0.044
0.047
0.051
0.069
0.070
0.075
0.054
0.056
0.052
0.067
0.072
0.070
0.052
0.056
0.054
0.052
0.052
0.051
0.054
0.055
0.055
0.055
H2
Rate
SCF/Bbl
4110
3900
4160
3900
4250
4110
5470
4380
4400
4310
4100
3790
4750
6010
4130
2600
4220
4810
3330
4140
4090
4000
4160
4150
4010
4050
4320
3990
4130
4220
4060
3940
3940
Cat.
Age
Bbl/Lb
0.058
0.133
0.211
0.265
0.320
0.373
0.431
0.485
0.541
0.596
0.635
0.679
0.726
0.745
0.064
0.134
0.209
0.263
0.319
0.371
0.089
0.161
0.231
0.283
0.339
0.393
0.445
0.497
0.548
0.602
0.678
0.753
0.808
Gravi ty
°API
14.9
14.9
14.4
15.2
14.9
15.1
14.8
15.2
14.7
14.3
14.1
12.8
14.2
14.0
18.1
13.5
13.8
14.2
13.2
14.0
16.4
15.0
15.2
14.9
15.0
15.2
15.3
15.0
15.7
15.5
1^.3
13.7
14.8
% s
1.75
.49
.61
.52
.17
.22
.36
.50
.62
.44
2.45
1.59
1.82
1.71
1.52
1.64
1.52
1.23
1.31
1.52
1.30
1.39
1.20
1.45
1.39
1.31
1.34
1.61
1.37
1.33
V
ppm
176
193
209
168
174
171
188
183
186
189
157
330
455
167
267
342
243
312
270
151
175
179
159
169
174
174
174
168
172
192
185
183
Ni
ppm
53
59
64
61
62
61
62
60
60
67
50
74
99
54
73
83
70
77
65
47
48
60
52
54
52
44
45
42
45
53
48
56
IBP-
550°F
V 7
6.0
6.0
6.0
8.0
10.0
9.0
8.0
8.0
8.0
9.0
9.0
7.0
8.0
8.0
7.0
8.0
7.0
7.0
6.0
5.0
9.0
8.0
8.0
6.0
6.0
6.0
6.0
5.0
3.0
7.0
-------
Table D-l (continued). SUMMARY OF DErJETALUZATION RUNS
Product Inspections
Run No.-Period Catalyst Base
184-174-14
15
16
17
18
19
20
21B
22
185-215-18
2
3
4
5
6
7
Porocel
(20 x 50 Mesh)
Porocel
(20 x 50 Mesh)
185-216-1B
2
3
4
5
6
7
185-217-1B
2
Catalyst
Promoter
2% Mo
Feed
Tia Juana
V.B.
27, Mo
Bachaquero
V.B.
Porocei
(20 x 50 Mesh)
27 Mo
Bachaquero
V.B.
Regular
Porocel
Bachaquero
V.B.
Temp.
°F
791
792
791
790
790
789
788
791
792
790
789
790
791
789
790
792
790
788
791
791
790
787
789
791
789
790
792
H2
Pres.
psig
2000
1995
1995
1990
1990
1985
1980
1990
1995
2000
1995
1995
1990
2000
2010
2005
2000
2000
1990
2000
2000
2000
2030
2020
1990
2000
2010
Space
Vo/hr/V
0.71
0.75
0.72
0.73
0.72
0.76
0.78
0.36
0.51
1. 01
0.98
0.96
0.78
0.70
0.73
0.77
0.67
0.76
0.95
0.94
0.95
0.69
0.78
0.68
0.75
0.61
0.65
Velocity
f. B/D/Lb
0.052
0.05**
0.052
0.053
0.052
0.055
0.057
0.026
0.037
0.075
0.072
0.071
0.058
0.052
0.05*4
0.057
0.050
0.056
0.074
0.073
0.074
0.054
0.0060
0.053
0.059
0.04g
0.052
H2
Rate
SCF/Bbl
4400
4330
4400
4080
4220
3880
3780
5500
4270
3270
3910
3650
3820
4270
4790
3790
5120
4lgo
4650
5000
3990
5840
4910
5960
4560
4720
6590
Cat.
Age
Bbl/Lb
0.879
0.933
0.985
1.038
1.090
1.145
1.202
1.239
1.271
0.064
0.136
0.207
0.265
0.317
0.371
0.428
0.478
0.534
0.064
0.137
0.211
0.265
0.325
0.378
0.437
0.046
0.081
Gravity
°API °/
14.2
14.9
14.9
14.3
14.1
13.5
14.1
15.9
15.0
16.7
14.5
14.0
13.8
13.7
13.3
13.5
13.5
14.5
16.1
14.4
14.3
13.9
12.9
15.2
14.3
11.5
11.9
= S
.34
.33
.58
.53
.50
.56
.51
.23
.19
.53
.42
.63
.55
.59
.93
.89
.89
.80
.62
.44
.42
.49
.42
.18
1.48
2.76
2.89
V
ppm
173
193
198
217
218
226
226
149
178
174
190
208
183
225
341
282
282
283
189
183
202
172
179
158
197
311
340
Ni
ppm
58
49
55
51
51
52
54
37
44
57
63
64
60
63
80
70
70
71
61
60
71
75
56
52
56
76
84
IBP-
550°F
V %
4.0
7.0
7.0
3.0
9.0
8.0
8.0
9.0
9.0
6.0
7.0
7.0
8.0
9.0
9.0
12.0
12.0
9.0
8.0
8.0
6.0
9.0
6.0
10.0
9.0
9.0
12.0
-------
Table D-l (continued). SUMMARY OF DEMETALLIZATION RUNS
Product Inspections
10
r-o
Run No.-Period
201-68
184-173-1B
2
3
it
5
6
7
10
11
12
13
li*
15
16
17
18
19
20
21
22
23
2k
25
26
27
28
Catalyst
Catalyst Base Promoter
Attrited 185-
2 1 1 Dump , 75%
Initial Chg.
Porocel 2% Mo
20 x 50 Mesh
Temp
Feed ° F
Gach Saran 791
V.B. 790
790
790
788
790
791
790
791
790
790
790
790
790
789
790
790
790
790
791
790
790
791
791
790
792
791
790
H2
Pres.
psiq
2000
2000
2000
2020
1995
2000
2020
2005
1995
2000
2000
2005
2000
2000
2000
2000
1995
1995
1995
2000
2005
2000
2000
2000
1980
1965
2020
2010
Space
VQ/hr/V
0.71*
0.70
0.70
0.73
0.75
0.76
0.76
0.75
0.98
0.99
1.00
1.00
0.98
1.01
0.98
0.97
0.93
O.gi*
1.02
1.01
1.01
0.98
0.98
0.96
0.96
0.71
0.72
0.71
Velocity
£ B/D/Lb
pump fa i lure
0.056
0.052
0.052
0.055
0.056
0.057
0.057
0.056
0.073
0.071*
0.075
0.075
0.073
0.075
0.073
0.072
0.070
0.071
0.076
0.075
0.076
0.073
0.073
0.072
0.072
0.053
0.05**
0.053
H2
Rate
SCF/Bbl
Run
boko
^310
1*230
1*090
3810
1+030
1*090
3910
3670
3650
361*0
3820
1*100
1*070
1*190
1*230
1*160
1*260
1*000
3990
3930
1*060
1*01*0
1*210
1*220
1*200
1*030
1*21*0
Cat.
Age
Bbl/Lb
terminated
0.01*1*
0.096
0.11*9
0.201*
0.260
0.317
0.371*
0.1*30
0.503
0.577
0.652
0.727
0.797
0.872
0.91*5
.017
.087
.198
.231+
.309
.385
.1*58
.531
.603
.675
.728
.782
.828
Gravity
"API % S
during start
15.9 1.01
15.3 0.9'
15.1 0.98
16.7
]i*.9
li*. i*
15.7
11*. 7
13.9
11*. 0
11*. 3
lit.it
11*. 0
13.8
11*. 5
11*. 7
li*. 1
13.9
13.8
li*. 1
lit. 0
13.9
13.8
11*. i*
14.1*
11*. 2
11*. 6
11*. 2
.08
.39
.13
.26
.10
.1*6
.1*0
.1*3
.20
.35
.11*
.35
.58
.1*1*
.1*9
.11*
.61
.1+5
.61*
.70
.61*
.62
.1*2
.1*3
.59
V
ppm
31
33
1*1
1*1
1*7
1*9
50
1*7
61
63
62
61*
61*
70
63
60
58
65
68
71*
71*
80
87
88
100
91
88
81
Ni
ppm
19
31
37
1*2
1*5
1*5
1*5
1*8
58
57
55
57
57
59
56
59
56
51+
56
57
57
55
56
61*
63
51*
51*
51*
IBP-
550°F
VX.
6.0
7.0
7.0
8.0
10.0
8.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
7.0
6.0
6.0
7.0
7.0
7.0
8.0
7.0
11.0
10.0
8.0
-------
APPENDIX E
SUMMARY OF DESULFURIZATION RUNS
123
-------
124
-------
Table E-l. SUMMARY OF DESULFURIZATION RUNS
Product Inspections
Run No. Period
185-209
201-69
Ul
185-218
IB
2
3
it
5
6
IB
2
3
4
5
6
7
8
9
10
11
12
13
\k
15
16
17
18
19
20
2)
22
23
24
IB
2
3
4
Catalyst Base
American Cyanatnid HDS-
1442B (HRI 3456) 1/32"
American Cyanamid 0.02"
Beads (HRI 3104)
20 x 50 Mesh
American Cyanamid 0.02"
Beads (HRI 3104)
20 x 50 Mesh
Feed
Tia Juana
V.B.
Demetal 1 ized
Gach Saran
V.B.
Demetal 1 ized
Gach Saran
V.B.
Temp.
°F
790
791
791
790
790
791
760
759
760
762
760
760
760
760
761
761
760
760
761
761
760
757
760
761
759
760
760
761
759
760
762
760
758
1 761
H2
Pres.
psig
2020
2010
2000
2015
2000
2010
2000
1975
1970
1975
1985
1990
1995
1980
1955
1990
1995
1985
1990
1990
1995
1980
1975
1995
1985
1990
1990
1985
1985
1980
2000
2005
2010
2000
Space Veloci ty
Vn/hr/Vr
0.53
0.54
0.53
0.65
0.51
0.44
1.00
1.03
1.08
1.07
1.00
0.97
0.99
1.08
1.14
1.04
1.04
1 .04
1.09
0.96
1.02
1.02
0.95
1.12
1.17
1.09
1.08
1.13
1.07
1.02
1.14
1.05
1.12
1.04
B/D/Lb
0.077
0.077
0.077
0.094
0.074
0.063
0.105
0.108
0.112
0.111
0.105
0.102
0.104
0.112
0.120
0.109
0.109
0.109
0.113
0.101
0.107
0.107
0.100
0.117
0.122
0.113
0.112
0.118
0.111
0.107
0.122
0.112
0.120
0.111
H2
Rate
SCF/Bbl
3460
4210
4230
3240
3840
5030
5680
8820
9290
9690
7230
7040
7650
9080
6500
5380
7060
10030
7720
9820
5970
8680
8430
6940
8100
8650
7450
12350
9150
9720
3470
3880
3750
4140
Cat.
Age
Bbl/Lb
0.063
0.134
0.211
0.305
0.379
0.434
0.098
0.206
0.318
0.429
0.534
0.636
0.740
0.852
0.972
.081
.190
.299
.412
.513
.620
.727
.827
.944
2.066
2.179
2.291
2.409
2.520
2.627
0.098
0.210
0.333
0.441
Gravity
"API
16.5
16.2
15.4
13.5
15.2
15.1
17.1
16.8
15.8
16.1
16.1
16.6
16.1
16.4
16.0
16.2
16.4
16.6
15.8
16.1
16.4
16.0
15.6
15.9
15.3
15.7
15.8
15.7
15.8
17.9
17.7
17.1
17.7
•/<, s
1.11
0.99
1.14
1.41
1.29
1.26
0.57
0.39
0.41
0.36
0.28
0.51
0.39
0.37
0.37
0.44
0.56
0.41
0.54
0.49
0.46
0.45
0.63
0.43
0.52
0.46
V
ppm
175
186
194
222
198
175
60
63
42
41
48
40
34
36
33
46
46
60
51
43
45
53
42
42
40
Ni
ppm
41
42
48
52
44
52
25
30
33
36
40
31
40
43
43
39
36
32
37
35
36
26
27
30
29
IBP-
600°F
V7
7.0a
9.0
8.0
7.0
7.0
7.0
9.0
8.0
9.0
8.0
9.0
6.0
7.0
5.0
5.0
5.0
6.0
< 3.0
4.0
5.0
7.0
4.0
12.0
9.0
9.0
7.0
IBP-550°F for Run 185-209.
-------
Table E-l (continued). SUMMARY OF OESULFURIZATION RUNS
Product Inspections
Run No. Period
185-219
184-175
IB
2
3
4
IB
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
Catalyst Base Feed
American Cyanamid 0.02" Demetalltzed
Beads (HRI 3104) Tia Juana
20 x 50 Mesh V.B.
American Cyanamid 0.02" Demetal 1 ized
Beads (HRI 3104) Tia Juana
20 x 50 Mesh V.B.
Temp
°F
762
759
759
760
755
759
759
760
758
760
760
761
761
760
760
760
759
762
760
762
761
759
760
761
759
759
760
761
760
755
759
760
760
H2
Pres. Space Velocity
psig V0/hr/Vr
1990 0.76
2000 0.73
1990 0.72
2000 0.74
2000 1.05
2010
2050
2000
2000
1995
1995 (
2000
2030
2025
2000
2000
2005
2005
.19
.03
.07
.04
.03
)-99
.05
.03
.21
.15
.07
.04
.04
1990 0.87
2000 0.87
2000 0.87
2000 0.90
1985 0.95
1990 1.02
1995 1.01
2000 0.97
1990 i.oo
2000 0.94
2000 0.94
1995 0.93
1995 0.94
1990 0.92
1990 0.92
B/O/Lb
0.081
0.078
0.077
0.079
0.112
0.127
0.110
0.114
0.111
0.110
0.106
0.1 12
0.109
0.130
0.123
0.114
0.111
0.1 11
0.093
0.093
0.093
0.096
0.101
0.109
0.108
0.103
0.107
0.100
0.100
0.099
0.100
0.098
0.098
H2
Rate
SCF/Bbl
5920
6820
8150
5850
3910
3790
5020
4270
4330
3860
4340
3920
4040
3780
3400
4320
4570
5&90
6540
4880
4970
4910
4820
4580
4550
5000
4560
4060
4030
4380
4300
4700
4530
Cat.
Age
Bbl/Lb
0.087
0.165
0.242
0.321
0.101
0.228
0.338
0.452
0.563
0.673
0.779
0.891
.000
.130
.253
.367
.478
.589
.682
.775
.868
1.964
2.065
2.174
2.282
2.385
2.492
2.592
2.692
2.791
2.891
2.989
3.087
Gravi ty
"API
16.8
17.4
17.1
17.2
17.1
16.6
16.7
16.2
16.1
16.6
16.4
16.3
15.3
15.5
15.6
16.2
16.7
16.1
17.2
16.6
16.5
16.6
17.0
16.4
16.4
16.0
15.9
16.2
16.1
16.3
15.5
15.9
17.2
% s
0.97
0.43
0.64
0.48
0.66
0.47
0.57
0.51
0.62
0.62
0.48
0.73
0.57
0.62
0.60
0.52
0.65
0.70
0.65
0.67
0.51
V
ppm
167
161
188
179
144
137
147
141
146
147
151
149
149
140
156
159
157
160
155
154
150
Ni
ppm
41
39
37
34
36
40
43
39
41
44
54
51
50
45
39
40
44
43
42
40
39
IBP-
600 °F
V%
8.0
9.0
8.0
8.0
7.0b
5.0
3.0
3.0
2.0
3.0
< 1 .0
2.0
4.0
5.0
5.0
3.0
4.0
4.0
4.0
5.0
5.0
b. IBP-550°F for Run 184-175
-------
Table E-l (continued). SUMMARY OF DESULFURIZATION RUNS
Product Inspections
Run No.
201-70
ro
Period
IB
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
2k
25
26
Catalyst Base Feed
American Cyanamid 0.02" Demetal 1 ized
Beads (HRI 3104) Bachaquero
12 x 50 Mesh V.B.
Temp
°F
760
760
761
760
762
761
760
759
758
759
761
760
761
760
760
760
760
761
760
760
760
762
760
761
763
759
H2
Pres.
psig
2020
2040
2015
1980
2015
2025
2010
2015
2015
2000
1985
2010
1990
2015
1990
2000
2030
2010
1985
2000
1990
2050
1995
2005
2000
2000
Space
Vo/hr/V
] .Ok
0.92
.20
.23
.11
.15
.10
.10
0.80
0.88
0.99
0.95
0.99
0.98
1.04
0.99
0.93
1.05
0.94
0.88
0.86
0.96
0.94
0.85
0.87
0.91
Velocity
£ B/O/Lb
0.111
0.098
0.127
0.131
0.118
0.122
0.117
0.118
0.085
0.094
0.106
0.101
0.106
0.105
1.111
0.106
0.099
0.112
0.100
0.094
0.092
0.103
0.100
0.091
0.093
0.097
H2
Rate
Age
SCF/Bbl Bbl/Lb
5030
0.096
5740 0.188
5670 0.315
4050 0.446
3720 0.564
3250 0.686
3930 0.803
4730 0.921
5880
5960
4goo
4170
3495
4250
4590
4850
4430
3790
.006
.100
.206
.307
.413
.518
.629
.735
.834
.946
6240 2.046
5510 2.140
5620 2.232
4550 2.335
5340 2.435
5180 2.526
4810 2.619
5140 2.716
Gravi ty
°API
17.0
17.6
16.4
15.5
15.7
15.3
15.7
16.5
15.6
15.5
16.1
15.7
15.6
15.4
16.1
15.1
15.3
15.5
15.4
16.2
16.0
15.8
14.8
14.9
15.2
7 S
0.56
0.57
0.59
0.62
0.56
0.55
0.66
0.60
0.56
0.60
0.63
0.57
0.75
0.60
0.63
0.61
0.66
V
ppni
109
120
136
145
145
141
139
159
148
154
164
155
154
152
151
Ni
PP"
40
47
43
44
45
46
46
49
45
48
50
46
45
48
46
53
IBP-
600° F
V7
13.0
11.0
12.0
11.0
9.0
7.0
7.0
8.0
8.0
4.0
4.0
6.0
8.0
10.0
7.0
8.0
7.0
-------
128
-------
APPENDIX F
OPERATING CONDITIONS. YIELDS. AND PRODUCT PROPERTIES
129
-------
130
-------
Table F-l. OPERATING CONDITIONS. YIELDS. AND PRODUCT INSPECTIONS
Run No.
Catalyst Age, Bbl/Lb
Feed
HRI No. (Feed)
Catalyst
184-166-5
0.21
Tia Juana Vacuum Bottoms
2414
LX-22
V/J
OPERATING CONDITIONS
Hydrogen Pressure, nsig
Temperature, °F
Liquid Space Velocity, V/hr/V
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B
Reactor Type
Hydrogen Consumption, SCF/B
975°F+ Conversion, V 7
2010
790
0.52
0.041
1*030
Downflow
730
21.0
YIELDS
Cut Points
W 7
V 7
Gravity, "API
Sulfur, W 7
Flash Point, °F
Pour Point, °F
Carbon, W 7
Hydrogen, W 7,
Nitrogen, ppm
Bromine No.
Vis SFS ® 210°F
RCR, W 7
Vanadium, ppm
Nickel, ppm
H2S 6- NH-j
2.1
|BP-400°F
2.7
3.6
50.0
<0.02
8.2
400-650°F
6.6
7.8
31.7
0.22
10.5
650-975°
19-8
21.7
19.9
0.83
975"F+
68.8
70.3
9.6
19.6
19^. 0
64.0
400°F+
95.2
99.8
14.2
1.25
335
60.0
60.0
Collected
Liquid
103.4
15.2
1.13
85.81
11.52
4200
Calculated from correlation.
-------
Table F-2. OPERATING CONDITIONS, YIELDS. AND PRODUCT INSPECTIONS
ro
Run No.
Catalyst Age, Bbl/Lb
Feed
HRI No. (Feed)
Catalyst
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/hr/V
Catalyst Space Velocity, B/D/lb
Hydrogen Rate, SCF/B
Reactor Type
Hydrogen Consumption, SCF/B
975°F+ Conversion, V /
185-211-3
0.10
Tia Juana Vacuum Bottoms
2414
LX-22-3
2005
790
0.46
0.035
4290
Downflow
615
24
YIELDS
Cut Points
W 7
V 7
Gravity, "API
Sulfur, W /
Flash Point, °F
Pour Point, °F
Carbon, W 7
Hydrogen, W 7
Nitrogen, ppm
Bromine No.
Vis SFS ® 210°F
RCR, W 7
Vanadium, ppm
Nickel, ppm
H?S £.
2.2
0.8
0.4
0.7
IBP-400°F
2.7
3.7
54.2
<0.02
6.3
400-650"F
7.7
9.3
34.3
0.14
11.4
650-975°F
21.2
23.3
20.0
0.71
975°F
65.9
67.4
9.1
1.44
19.6
156.0
57.0
400° F+
94.8
100.0
15.1
1.17
330
60
51
Collected
Liquid
103.7
16.3
1.10
84.84
11.19
3550
a. Calculated from correlation.
-------
Table F-3. OPERATING CONDITIONS. YIELDS. AND PRODUCT INSPECTIONS
Run No.
Catalyst Age, Bbl/Lb
Feed
HRI No. (Feed)
Catalyst
185-211-12
0.43
Tia Juana Vacuum Bottoms
2414
LX-22-3
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/hr/V
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B
Reactor Type
Hydrogen Consumption, SCF/B
975°F+ Conversion, V 7
2005
791
0.1*7
0.035
Down flow
653
26
YIELDS
Cut Points
w 7
V 7
Gravity, "API
Sulfur, W 7
Flash Point, °F
Pour Point, "F
Carbon, W 7
Hydrogen, W /
Nitrogen, ppm
Bromine No.
Vis SFS a 210°F
RCR, W 7
Vanadium, ppm
Nickel, ppm
H2S & NHl
1.9
0.4
0.7
IBP-400°F
3.2
4.2
50.3
<0.02
9.4
400-650°F
8.2
9.9
33.5
0.23
650-975°F
21.6
23.8
20.0
0.75
21.9
268.0
71*.0
l400°F+
9^.7
99.5
1^.5
1.51
295
65
53
Collected
Liquid
103.7
15.7
1.32
86.83
11.54
4380
a. Calculated from correlation
-------
Table F-4. OPERATING CONDITIONS. YIELDS. AND PRODUCT INSPECTIONS
Run No.
Catalyst Age, 8bI/Lb
Feed
HRI No. (Feed)
Catalyst
184-173-**
0.2
Gach Saran Vacuum Bottoms
L-352
LX-22-2
OJ
-p-
OPERATING CONDITIONS
Hydrogen Pressure, pslg
Temperature, °F
Liquid Space Velocity, V/hr/V
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B
Reactor Type
Hydrogen Consumption, SCF/B
975° F+ Conversion, V 7,
2020
790
0.73
0.055
4090
Down f1ow
770
20
YIELDS
Cut Points
W 7
V °/
Gravity, "API
Sulfur, W 'I,
Flash Point, °F
Pour Point, °F
Carbon, U %
Hydrogen, U %
Nitrogen, ppm
Bromine No.
Vis SFS @ 210°F
RCR, W %
Vanadium, ppm
Nickef, ppm
H2S S. NHt
2.6
0.7
IBP-400°F
2.3
3.2
50.2
<0.02
7.4
400-650°F
6.0
7.3
32.9
0.10
11.0
650-975°F
21.2
23.6
19.6
0.72
19.2
56.0
63.0
400°F+
95.0
101.7
15.8
1.16
300
65
50
Collected
Liquid
104.9
16.7
1.08
86.73
10.93
5800
a. Calculated from correlation.
-------
Table F-5. OPERATING CONDITIONS. YIELDS. AND PRODUCT INSPECTIONS
Run No.
Catalyst Age, Bbl/Lb
Feed
HRI No. (Feed)
Catalyst
184-173-20
1.3!
Gach Saran Vacuum Bottoms
L-352
LX-22-2
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/hr/V
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B
Reactor Type
Hydrogen Consumption, SCF/B
975°F+ Conversion, V %
2000
791
1.01
0.075
3990
Down f1ow
600
25
YIELDS
Cut Points
W /
v %
Gravity, "API
Sulfur, W 7,
Flash Point, °F
Pour Point, °F
Carbon, W 7,
Hydrogen, W 7,
Nitrogen, ppm
Bromine No.
Vis SFS @ 2!0°F
RCR, W 7,
Vanadium, ppm
Nickel , ppn-
H2S & NH3
2.0
0.5
0.8
1BP-400°F
1.3
1.8
55.1
< 0.02
9.7
400-650°F
8.6
10.3
32.6
0.1*7
14.1
650-975°F
22.5
24.8
18.7
0.92
400°F+
96.2
101.4
13.5
1.71
310
65
75
20.4
114
Coilected
Liquid
103.2
14.1
1.61
85.16
10.72
5700
a. Calculated from correlation
-------
Table F-6. OPERATING CONDITIONS, YIELDS, AND PRODUCT INSPECTIONS
Run No.
Catalyst Age, Bbl/Lb
Feed
HRI No. (Feed)
Catalyst
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/hr/V
Catalyst Space Veloc
Hydrogen Rate, SCF/B
Reactor Type
YIELDS
Cut Points
V %
Gravity, °API
Sulfur, W %
Aniline Point, °F
Pour Point, °F
Bromine No.
Vis SFS @ 210°F
ASTM Color
RCR, W %
Vanadium, ppm
Nickel, ppm
185-216-6
0.38
Bachaquero Vacuum Bottoms
LX-22-3
1
V/hr/V
', B/D/Lb
IBP-
400° F
3.3
44.3
< 0.02
10.3
400-
650° F
11.7
31.3
0.24
148
11.8
2020
791
0.68
0.053
5956
Down flow
650-
975° F 975° F+
24.0 61.0
19.8 6.0
0.66 1.69
172
40
650° F+
85.0
9.8a
1.42
70
97
Coll.
Liquid
100.0
15.2
1.26
D8.0
22.1
262
95
a. Calculated from fractions,
-------
Table F-7. OPERATING CONDITIONS. YIELDS. AND PRODUCT INSPECTIONS
Run No.
Catalyst Age, Bbl/Lb
Feed
HRI No. (Feed)
Catalyst
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V
Catalyst Space Velocity,
Hydrogen Rate, SCF/B
Reactor Type
YIELDS
Cut Point
V %
Gravity, °API
Sulfur, W %
Aniline Point, °F
Pour Point, °F
Bromine No.
Vis SFS @ 210°F
ASTM Color
RCR, W %
Vanadium, ppm
Nickel, ppm
185-192-7
0.309
Tia Juana Vacuum Bottoms
2414
12 x 20 Mesh Porocel (HRI 27&5)
/hr/V
B/D/Lb
IBP
500° F
3.3
40.8
0.53
30.5
500-
650°F
5.0
29.6
1.65
149
28.0
650-
975° F
16.0
19.0
2.08
173
55
08. 0
2000
789
0.51
0.039
4250
Down flow
975° F+
75.7
7.2
2.72
21.9
333
80
650° F+
91.7
9.1a
2.62a
95
183
Coll.
Liquid
100.0
10.6
2.52a
261
60
a. Calculated from fractions,
-------
Table F-8. OPERATING CONDITIONS. YIELDS. AND PRODUCT INSPECTIONS
Run No.
Catalyst Age, Bbl/Lb
Feed
HRI No. (Feed)
Catalyst
201-70-25
2.619
Demetal1Ized Bachaquero Vacuum Bottoms3
L3-59
0.02" Beads (HRI 3104)
CO
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/hr/V
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B
Reactor Type
2000
763
0.87
0.093
Down flow
YIELDS
Cut Points
W 7 (0.8)
V /
Gravity, "API
Sulfur, W 7
An! 1 ine Point, °F
Pour Point, °F
Bromine No.
Vis SFS O 210°F
ASTM Color
RCR, W 7
Vanadium, ppm
Nickel, ppm
a. Demetal lized over LX-22
b. Calculated from fractions
c. Results questionable.
(0.3)
IBP-500°F
3.3
37.1
<0.02
5.7
500-650°F
7.0
29.8
<0.02
140
6.8
650-975°F
28.7
21.1
0.06
175
60
L6.5
975°F+
61.QC
8.0
0.95
20.)
251
82
89.3
11 jb
60
63
Collected
Liquid
100.0
l*f.9
0.62b
-------
Table F-9. OPERATING CONDITIONS, YIELDS. AND PRODUCT INSPECTIONS
UD
Run No.
Catalyst Age, Bbl/Lb
Feed
HRI No. (Feed)
Catalyst
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/hr/V
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B
Reactor Type
YIELDS
Cut Points
V %
Gravity, °API
Sulfur, W %
Anil ine Point,
Pour Point, °F
Bromine No.
Vis SFS @ 210°
ASTM Color
RCR, W %
Vanadium, ppm
Nickel , ppm
185-219-4
0.32
Demetallized Tia Juana Vacuum3
L-361
0.02" Beads (HRI 3104)
2000
760
0.74
0.079
5850
Downflow
IBP-
500° F
0.02
3.4
500-
650°F
8.7
30.2
0.02
148
4.2
650-
975°F
26.7
21.4
0.02
182
55
975° F+
60.6
13.2
0.69
650 °F+
87.3
15. 6b
50
68
Coll.
L iquid
100.0
17.2
0.43b
D8.0
17.6
302
64
a. Demetallized over Porocel.
b. Calculated from fractions.
-------
Table F-10. OPERATING CONDITIONS. YIELDS. AND PRODUCT INSPECTIONS
Run No.
Catalyst Age, Bbl/Lb
Feed
HRI No. (Feed)
Catalyst
184-175-29
3.087
Demetal1ized Tia Juana Vacuum Bottoms3
L-J57
0.02" Beads (HRI 3104)
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/hr/V
Catalyst Space Velocity, B/D/lb
Hydrogen Rate, SCF/B
Reactor Type
1990
760
0.92
0.098
4527
Downflow
YIELDS
Cut Points
U /
V 7
Gravity, "API
Sulfur, W 7
AniIine Point, °
Pour Point, °F
Bromine No.
Vis SFS @ 210°F
ASTM Color
RCR, W 7
Vanadium, ppm
Nickel, ppm
(0.7)
(0.4)
IBP-500°F
3.0
39.5
fO.02
500-650°F
7.0
30.1
<0.02
143
5.84
650-975°F
30.0
21.3
0.10
180
45
08.0
975"F+
60.0
10.9
0.98
19.9
226
65
90.0
14.2b
0.70b
55
70
Collected
Liquid
100.0
15.9b
0.64b
150
39
a.
b.
Demetal1ized over LX-22
Calculated from fractions.
-------
Table Ml. OPERATING CONDITIONS. YIELDS, AND PRODUCT INSPECTIONS
Run No.
Catalyst Age, Bbl/Lb
Feed
HRI No. (Feed)
Catalyst
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/hr/V
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B
Reactor Type
YIELDS
Cut Points
V %
Gravity, °API
Sulfur, W %
Aniline Point,
Pour Point, °F
Bromine No.
Vis SUS @ 210°F
ASTM Color
RCR, W 7o
Vanadium, ppm
Nickel, ppm
a. Demetal1ized over Porocel.
b. Calculated from fractions.
185-218-4
0.44
Demetal1ized Gach Saran Vacuum Bottoms9
L-360
0.02" Beads (HRI 3104)
2000
761
1.04
0.110
Down f 1 ow
IBP-
500° F
37^9
<0.02
5.3
500-
650°F
10.0
30.3
<0.02
147
5.5
650-
975°F
29.3
20.7
-CO. 02
176
60
975° F+
56.0
9.7
0.54
650°F
85.3
13. 3b
45
364
Coll.
Liquid
100.0
15. 9b
D8.0
16.4
66
57
40
29
-------
Table F-12. OPERATING CONDITIONS. YIELDS. AND PRODUCT INSPECTIONS
Run No.
Catalyst Age, Bbl/Lb
Feed
HRI No. (Feed)
Catalyst
201-69-23
2.52
Demetal1ized Gach Saran Vacuum Bottoms3
L-356
0.02" Beads (HRI 3104)
-p-
NJ
OPERATING CONDITIONS
Hydrogen Pressure, psig
Temperature, °F
Liquid Space Velocity, V/hr/V
Catalyst Space Velocity, B/D/Lb
Hydrogen Rate, SCF/B
Reactor Type
2000
759
1.07
0.111
Down flow
YIELDS
Cut Point
W %
V f,
Gravity, "API
Sulfur, W %
Aniline Point, °
Pour Point, °F
Bromine No.
Vis SFS ® I22°F
ASTM Color
RCR, W 7
Vanadium, ppm
Nickel, ppm
C4-C6
1 "
(0.3)
IBP-500°F
3.3
38.4
< 0.02
8.5
500-650° F
6.0
28.7
< 0.02
142
8.0
650-975° F
28.0
20.2
0.07
176
75
975" F+
62.7
10.7
0.80
650° F+
90.7
13. 5b
0.59b
55
935
Col lected
Liquid
100.0
15.7.
0.52b
D8.0
16.8
63
62
45
36
a. Feed demeta!Iized over LX-22
b. Calculated from fractions.
-------
APPENDIX G
CONVERSION TABLE
-------
-------
APPENDIX G
CONVERSION TABLE
Variable British Units Metric Units Conversion Factor
Temperature Degrees Fahrenheit, °F Degrees Centigrade, °C °C = 5/9(°F-32)
Pressure Pounds per Square Inch Kilograms per Square Kg/cm2 = ps'q
Gauge, psig Centimeter, Kg/cm2 l^t.22
Hydrogen Rate Standard Cubic Feet per Normal Cubic Meters per
Barrel, (60°F, 1 Atm.) Cubic Meter, NM3/M3 NM3/M3 = 0.168(SCF/Bbl)
(0°C, 760 mm Hg)
-------
146
-------
APPENDIX H
GLOSSARY
-------
-------
APPENDIX H
GLOSSARY
1 Micron
g/cc
M2/g
Mesh Sizes
psig
SCF/Bbl
V0/hr/Vr
C.S.V.
Bbl/Day/Lb
100X
200X
B/D
ppm
SFS
V.B.
10^ Angstroms
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.)
Volumes of oi1/hour/volume of reactor
Catalyst space velocity, barrels of oil/day/
pound of catalyst
Barrels of oi1/day/pound of catalyst
Magnification of 100 times
Magnification of 200 times
Barrels per day
Parts per mi 11 ion
Saybolt Furol Seconds
Vacuum Bottoms = Vacuum Residuum
-------
150
-------
BIBLIOGRAPHIC DATA
SHEET
1. Report No.
EPA-650/2-73-041
2.
4. 1 icle and Subtitle
Demetallization of Heavy Oils
7. Author(s)
William C. Roves ti and Ronald H. Wolk
9. Performing Organization Name and Address
Hydrocarbon Research, Inc.
New York and Puritan Avenues
Trenton, New Jersey 08607
12. Sponsoring Organization Name and Address
EPA, Office of Research and Development
NERC-RTP, Control Systems Laboratory
Research Triangle Park, North Carolina 27711
S.^ecipient's Accession No.
'5. Report Date
December 1973
6.
8- Performing Organization Rept.
No.
10. Project/Task/Work Unit
ROAP 21ADD-50
No.
11. Contract/Grant No.
68-02-0293
13. Type of Report & Period
Covered
Final
14.
15. Supplementary Notes
16. Abstracts
The report gives results of a program to develop an improved demetallization
catalyst so that residuum with high-sulfur and high-metals content could be
desulfurized economically. Twenty-eight catalysts were prepared, representing
a number of combinations of supports and promoters. Impregnating 20 x 50 mesh
granulated activated bauxite with promoters provided the necessary catalytic
activity and resistance to poisoning. The residua that were demetallized were
Tia Juana, Bachaquero, and Gach Saran vacuum residua. Indications are that
these residua can be economically desulfurized to 0. 5 weight percent sulfur
fuel oil.
17. Key Words and Document Analysis.
Residual Oils
Hydrogenation
Metals
Vanadium
Sulfur
Nickel
Contaminants
Catalysts
Scavengers (Materials)
17b. Identifiers/Open-Ended Terms
Air Pollution Control
Demetallization
Promoter
Pretreatment
Clean Fuels
17a. Descriptors
Air Pollution
Fossil Fuels
Desulfurization
17c. COSATI Field/Group
13B
18. Availability Statement
Unlimited
151
19.
20.
Security Class (This
Report)
UNCLASSIFIED
Security Class (This
Page
UNCLASSIFIED
21.
22.
N'o. of Pages
151
Price
FORM MTIS-35 (REV. 3-72)
THIS FORM MAY BE REPRODUCED
U5COMM-DC M952-P72
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