o-EPA
            United States      Industrial Environmental Research  EPA-600/7-78-119
            Environmental Protection  Laboratory          June 1978
            Agency        Research Triangle Park MC 27711
Demetallization
Catalyst Tests on
Heavy Residual Oils

Interagency
Energy/Environment
R&D Program Report

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                                         EPA-600/7-78-119
                                                    June 1978
Demetallization  Catalyst Tests
                        on
         Heavy  Residual  Oils
                          by

      V.V. Manshilin, Yu K. Vail, B.A. Lipkind, and A.V. Agafonov

     All Union Scientific Research Institute of Oil Refining, VNIINP
                     Moscow 111116
                 Aviamotornaya St 6 USSR
   MMKhP Main Directorate of the USSR Hydrometeorological Service

                         and

                 P. Maruhnic and G Nongbri

                 Hydrocarbon Research, Inc.
                New York and Puritan Avenues
               Lawrenceville, New Jersey 08648
                  Contract No. 68-02-0293
               Program Element No. EHE623A
                         and

                    William J. Rhodes

          Industrial Environmental Research Laboratory
            Office of Energy, Minerals, and Industry
             U.S. Environmental Protection Agency
              Research Triangle Park, N.C. 27711
                      Prepared for

          U.S. ENVIRONMENTAL PROTECTION AGENCY
             Office of Research and Development
                  Washington, DC 20460

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ABSTRACT
A cooperative project between the USA and USSR was undertaken to
exchange technology on the demetallization step of an overall pro-
cess to produce low sulfur fuel oil from heavy petroleum residua.
This joint project was initiated so that each country could learn
the state of the art in the other country. Catalysts and petroleum
residua feedstocks were exchanged and tests carried out by each
country using its own equipment and operating procedures. The
results of the tests were exchanged and discussed at meetings held
in the USSR and the USA.
In this report, all tests using USA catalyst have been described
by the United States and all tests using USSR catalyst have been
described by the USSR, and each country describes its equipment
and operating procedures used in carrying out the tests. Included
for each aging test are graphs showing degree of demetallization
and desulfurization and the rate of catalyst deactivation. Fresh
and used catalyst analyses are presented along with detailed run
sumaries and product inspections.
Results showed that each country’s molybdenum impregnated catalyst
exhibited about equal demetallization capability while the USA
catalyst exhibited higher desulfurization capability during
demetallization.
Sections of this report collaborated on and reported jointly in-
clude the sumary, introduction and conclusions. Each country
considered the project mutually beneficial.
ii

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TABLE OF CONTENTS
Page
Section No .
Abstract ii
List of Figures iv
List of Tables viii
1.0 Introduction 1
2.0 Conclusions 2
3.0 Feedstocks 3
L 4 .O Tests Conducted
5.0 Description of Catalysts 8
5.1 USSR Catalyst 8
5.2 USA Catalysts 8
6.0 Description of Units and Test Methods l 4
6.1 USSR 1k
6.2 USA 18
7.0 Discussion of Results 21
7.1 Tests on USSR Catalyst 21
7.2 Tests on USA Catalysts 39
7.2.1 Used Catalyst Analyses 51
7.2.2 Pore Size Distribution 51
8.0 References 60
9.0 Appendices 61
9.1 Tests Reported by USSR 61
9.2 Tests Reported by USA 69
II I

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LIST OF FIGURES
Figure Page
No. No .
Fresh USSR T—3 Catalyst
2 Porogram of Fresh USA Demetallization
Catalyst (1 Mo) HRI No. 3634 12
3 Porogram of Fresh USA Demetallization
Catalyst (0 Mo) HRI No. 3309 13
4 Diagram of the USSR Pilot Equipment
5 Schematic Drawing of the USSR Reactor 16
6 USA Unit Flow Diagram 19
7 Schematic Drawing of the USA Reactor 20
8 Variation of Vanadium Removal with Mid-Hours
on Stream During the Demetallization of
Tia Juana and Rornashkin Vacuum Resids
over USSR Catalyst (T-3) - Runs made in
the USSR 24
9 Variation of Vanadium Removal with Mid-Hours
on Stream During the Demetallization of Gach
Saran Vacuum Resid over USSR catalyst(t3) —
Run made in the USSR 25
10 Variation of Vanadium Removal with Mid—Hours
on Stream During the Demetallization of Tia
Juana Vacuum Resid over USSR Catalyst (T-3) -
Run made in the USA 27
11 Variation of Vanadium Removal with Mid-Hours on
Stream During the Demetallization of Tia Juana
Vacuum Resid over USSR Catalyst (T-3) - Run
made in the USA 27
12 Desulfurization Obtained During Demetallization
of Tia Juana Vacuum Resid over USSR Catalyst
(T—3) - Run made in the USSR 28
iv

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LIST OF FIGURES (Continued )
Figure Page
No. No .
13 Desulfurization Obtained During the Demetalfl-
zation of Romashkin Vacuum Resid over USSR
Catalyst (T-3) - Run made in the USSR 29
Desulfurization Obtained During the Demetalli-
zation of Gach Saran Vacuum Resid over USSR
Catalyst (1—3) - Run made in the USSR 30
15 Desulfurization Obtained During the Demetalli-
zation of Tia Juana Vacuum Resid over USSR
Catalyst (1—3) - Run made in the USSR 31
16 Desulfurization Obtained During Demetallization
of Romashkin Vacuum Resid over USSR Catalyst
(T-3) - Run made in the USA 32
Comparison of Porograms of New and Used(T-3)
Catalyst after Operating on Tia Juana Vacuem
Resid 34
18 Comparison of Porograms of New and Used(T-3)
Catalyst after Operating on Romashkin Vacuum
Resid 35
19 Comparison of Porograms of New and Used (1-3)
Catalyst after Operating on Gach Saran
Vacuum Resid 36
20 Comparison of Porograms of Fresh USSR Catalyst
(T-3) and Used Catalyst after Operating on
ha Juana Vacuum Resid - Run made in the USA 37
21 ComparisonofPorograms of Fresh USSR Catalyst
(T—3) and Used Catalyst after Operating on
Romashkin Vacuum Resid - Run made in the USA 38
22 Variation of Vanadium Removal with Mid—Hours on
Stream During the Demetallization of Romashkin
Vacuum Resid over USA Catalyst (1 Mo) -
Run made in the USA 42
V

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LIST OF FIGURES (Continued )
Figure Page
No. No .
23 Desulfurization Obtained During the Demetal-
lization of Romashkin Vacuum Resid over
USA Catalyst (1 Mo) - Run made in the USA 43
24 Variation of Vanadium Removal with Mid-Hours
on Stream During the Demetallization of
Romashkin Vacuum Resid over USA Catalyst
(1 Mo) - Run made in the USSR 44
25 Desulfurization Obtained During the Demetal-
lization of Romashkin Vacuum Resid over USA
Catalyst (1 Mo) — Run made in the USSR 45
26 Variation of Vanadium Removal with Mid—Hours
on Stream During the Demetallization of
Romashkin Atmospheric Resid over USA
Catalyst (1 Mo) - Run made in the USA 47
27 Desulfurization Obtained During Demetallization
of Roniashkin Atmospheric Resid over USA
Catalyst (1 ? Mo) - Run made in the USA 48
28 Variaiton of Vanadium Removal with Mid—Hours
on Stream During the Demetallization of
Romashkin Atmospheric Resid over USA
Catalyst (0 Mo) - Run made in the USSR 49
29 Desulfurization Obtained During the Demetalli-
zation of Romashkin Atmospheric Resid over
USA Catalyst (0 Mo) - Run made in the USSR 50
30 Variaitor. of Vanadium Removal with Mid-Hours
on St 4 ream During the Demetallization of Tia
Juana Vacuum Resid over USA Catalyst (1 Mo)—
Run made in the USSR 52
31 Desulfurization Obtained During the Demetalli-
zation of ha Juana Vacuum Resid over USA
Catalyst (1 Mo) - Run made in the USSR 53
vi

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L)ST OF FiGURES (Continued )
Figure Page
No. No .
32 Comparison of Porograms of Fresh USA Catalyst
(1 Mo) and Used Catalyst after Operating
on Romashkin (USSR) Atmospheric Resid -
Run made in the USA 55
33 Comparison of Porograms of Fresh USA Catalyst
(I Mo) and Used Catalyst after Operating
on Rornashkin (USSR) Vacuum Resid - Run
made in the USA 56
3L Comparison of Porograms of Fresh USA Catalyst
(0 Mo) and Used Catalyst after Operating
on Rocnashkin (USSR) Atmospheric Resid -
Run made in the USSR 57
35 Comparison of Porograms of Fresh USA Catalyst
(1 Mo) and Used Catalyst after Operating
on (USSR) Vacuum Resid - Run made in the
USSR
36 Comparison of Porograms of Fresh USA Catalyst
(1 ? Mo) and Used Catalyst after Operating
on ha Juana Vacuum Resid — Run made in the
USSR 59
VI I

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LIST OF TABLES
Table Page
No. No .
Feedstock Analyses 5
2 Demetallization Tests Carried Out in USSR 6
3 Dernetallization Tests Carried Out in USA 7
4 Properties of USSR Catalyst 9
5 Properties of USA Catalyst 11
6 Results on USSR Demetallization Catalyst
Tests Made in Both Countries 22
7 Characteristics of Used USSR Demetallization
Catalyst (T—3) 33
8 Results on USA Demetallization Catalysts
Tests Made in Both Countries 1 +0
9 Analyses on USA Catalyst
From Aging Tests Made in USA and USSR 54
10 Demetallization Run Summary of Tia Juana
Vacuum Resid over USA Catalyst (1 Mo) -
Run made in USSR 62
11 Demetallization Run Summary of Romashkin
Vacuum Resid over USA Catalyst (1 Mo) -
Run made in USSR 63
12 Demetallization Run Summery of Tia Juana
Vacuum Resid over USSR Catalyst (1 Mo) -
Run made in USSR 64
13 Demetallization Run Summary of Romashkin
Atmospheric Resid over USA Catalyst (I Mo) -
Run made in USSR 65
Demetallization Run Summary of Gach Saran
Vacuum Resid over USSR Catalyst - Run made
in USSR 66
Viii

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LIST OF TABLES (Continued )
Table Page
No. No .
15 Demetallization Run Summary of Romashkin
Vacuum Resid over USSR Catalyst - Run
made in USSR 67
16 Demetallization Run Summary of Romashkin
Atmospheric Resid over USSR Catalyst -
Run made in USSR 68
Demetallization Run Summary of Roniashkin
Vacuum Resid over USSR Catalyst -
Run made in USA 70
18 Demetallization Run Summary of Tia Juana
Vacuum Resid over USSR Catalyst — Run Made
in USA 71
19 Demetallization Run Summary of Romashkin
Atmospheric Resid over USA Catalyst
(1 Mo) - Run made in USA 72
20 Demetallization Run Summary of Rornashkin
Vacuum Resid over USA Catalyst (1 ° Mo) -
Run made in USA 73
ix

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1.0 INTRODUCTION
Air pollution with oxides of sulfur from burning high sulfur fuel
oils is of universal concern. Fuel oils containing l sulfur or
less are produced commercially by catalytic hydrodesulfurization
of low metals petroleum residua. Production of low sulfur fuel
oils from heavy petroleum residua containing large concentrations
of metals, mainly vanadium and nickel, is economically unattractive
because of the rapid deactivation of the hydrodesulfurization cata-
lysts due to metals deposition. By removing the bulk of the metals
from heavy residua prior to desulfurization, the overall economics
can be improved and best use can be made of this petroleum fraction.
Industrial experience in the use of desulfurization equipment for
atmospheric residua in a fixed bed operation has shown that when
the metals content in the feed is greater than 100 ppm, demetal-
lization of the feed is first required. Therefore, careful salt
removal from the feed to a level of 3-5 mg/l is necessary.
To increase the effective life of desulfurization catalysts at the
present time, there are various methods used to pretreat the feed-
stock based on methods to remove asphaltenes and metalorganic com-
plexes related to them with hydrocarbon solvents (processes of
I%Dobenu, Domex”, the firms Shell, Finn, etc.). The disadvantages
of these processes are the reduction of the fuel oil output to
75—855 of the feed and the problem of utilizing the salt removal
res idua.
One method of reducing the metals concentration is by pretreating the
resid over a relatively cheap scavenger catalyst prior to final sulfur
reduction over the more expensive desulfurization catalyst. The
overall resid desulfurizatjon then becomes more attractive economically.
The present cooperative project between the USA and the USSR had
as its objective an exchange of technology in the field of demetal-
lization of heavy petroleum residua in a scheme to produce low
sulfur fuel oil, in order for each country to gain knowledge of
the state of the art in the other country.
At a meeting in 197L held in the USA, a program to meet this objec-
tive was agreed upon. After an exchange of materials consisting
of dernetallization catalysts (independently developed by each
country) and feedstocks of atmospheric and vacuum residua, tests

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were carried out by each country on these materials at similar
operating conditions using its own equipment and procedures. At
the conclusion of the tests, product and used catalyst samples
were exchanged to afford comparison of results.
In a preliminary report, each side sumarized the results of
tests it conducted. At meetings in June 1976 in the USSR and
January 1977 in the USA, reports were exchanged, discussed and
translations clarified. At the June meeting, agreement was reached
on the format for a final report. All tests using USA catalyst
would be described by the USA and all tests using USSR catalyst
would be described by the USSR, regardless of which country con-
ducted the tests. Each country would also describe its catalyst,
test units and operating procedures, and materials supplied.
Parts of the final report to be reported jointly would include
the suninary, introduction, feedstock analyses, and conclusions.
To further carry out the objective of the project, the USSR dele-
gation, on their visit to the USA, was afforded on—site inspections
of test units actually used iii conducting test runs on the project
as well as an inspection of laboratory facilities and the equipment
used for the tests. The USA delegation, on their visit to the USSR,
was afforded inspection of test units similar to those used for the
test runs. The delegation also inspected laboratory facilities and
equipment.
2.0 CONCLUSIONS
The objective of the cooperative project between the USA and USSR
was realized in that each country had an opportunity to evaluate
technology in the other country pertaining to the dernetailization
of heavy petroleum residua in the course of producing low sulfur
fuel oil. Each side was afforded on-site inspections of experi-
mental test units and laboratory facilities.
Generally, the results of the experimental work showed the two
molybdenum impregnated demetallization catalysts to be about equal
in their capacity to reduce vanadium content of petroleum residua
while the USA catalyst exhibited consistently higher desulfurization
capability during demetallization.
2

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The series of comparative tests conducted in both countries on
Soviet vacuum resid using the American catalyst showed that results
obtained in the USA differ slightly from those obtained in the USSR.
The data showed that in the demetallizatiort of Romashkin vacuum
resid in tests conducted in the USA, the US catalyst achieved a
higher degree of vanadium removal, greater depth of desulfurization,
and a lower rate of catalyst deactivation than in analogous tests
conducted in the USSR.
In cooperative tests with vacuum resids from the heavy crude oils of
ha Juana and Gach Saran for both US and USSR.catalysts, similar
results were obtained in both countries. These differences in the
demetallization of Romashkin vacuum resid may be attributed to
differences in test equipment and/or method of operation.
The project was carried out in a spirit of cooperation. The meet-
ings held in each country were conducted in a friendly, business-
like manner, and each host country showed every courtesy and
hospitality to the other’s delegations.
3.0 FEEDSTOCKS
Comparative tests of catalysts were carried out using atmospheric
and vacuum residua from Romashkin petroleum, ha Juana vacuum
resid from Venezuela and Gach Saran vacuum resid from Iran.
Tia Juana vacuum resid used by both countries on this project was
supplied by the USA. This feed originated in the Lake Maracaibo
area of Venezuela and was obtained from the Creole Petroleum
Corporation, a subsidiary of Exxon. The 1973 production of ha
Juana crude was 120-million barrels, equivalent to 36-million
barrels of vacuum residua, with estimated crude reserves of
l,702—million barrels.
Gach Saran vacuum resid used by the USSR was also supplied by the
USA. Gach Saran crude originates in the Persian/Arabian Gulf in
Iran. In 1973, the production of Gach Saran crude was 324-million
barrels, equivalent to 75—million barrels of vacuum resid, with an
estimated reserve of 8 ,1k0-million barrels. The vacuum resid feed
used on this project was obtained from Kashima Oil Company of Japan.
3

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ha Juana vacuum resid is heavier than the Romashkin vacuum resid
from the Soviet Union. The density is higher than 1.0 g/cm 3 . The
coking capacity is above 20.0, and it has approximately the same
sulfur content as the Romashkin vacuum resid, but contains much
larger amounts of asphaltenes (12.9 and 9.4, as compared to 6.5?
for the Romashkin vacuum resid). There is a much higher metals
content in ha Juana vacuum resid, 666 ppm (V = 588 ppm and Ni =
78 ppm) and Gach Saran vacuum resid, 469 ppm (V = 324 ppm and
Ni = 145 ppm) compared to 323 ppm (V = 242 ppm and Ni = 81 ppm) in
the omashkin vacuum resid.
Romashkin vacuum resid and Romashkin atmospheric resid used on this
project were supplied by the USSR. Table 1 lists the inspections
on these four feeds. The analyses are the average values obtained
from analyses carried out by each country.
In calculating and reporting results of tests made in the USA, values
from inspections made on the same batch of feedstock as fed to the
unit were used rather than average values.
The difference in vanadium content of USSR vacuum resid as reported
by the USA and the USSR may be due to variation in feed composition
which might explain differences in test results obtained in each
country.
4.0 TESTS CONDUCTED
In accordance with the Protocol of December 13, 1974, Appendix 3,
A-7, both countries agreed to conduct two types of demetallization
catalyst tests. The first were called screening tests, and their
purpose was to determine whether results in each country could be
accurately reproduced in the other country. Tests of the second
type were called aging tests, and their purpose was to obtain data
on demetallization using different feeds and catalysts so that
each country could study the state of the art in this field in the
other country and also determine the advantages and disadvantages
of each combination of feed and catalysts.
After an exchange of feeds and catalysts, each side carried out
the screening and aging tests in accordance with the schedule
presented in Tables 2 and 3.
4

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Table 1. FEEDSTOCK ANALYSES
Romashk in
Atm. Resid
0.9616 (15.7)
2.71
0.27
8.8
1 36
48
281
48
0.926
2.2 1+
52
1 . 000
3.35
* Analyses performed by USSR only
Analyses performed by USA only
Romashk in
Vac. Resid
1.001 ( .9)
3.08
0.49
16.0
236
81
379
6.9
0.948
2.45
93. 1
1.010
3.25
Tia Juana
Vac. Resid
1.012 (8.3)
2.95
0.48
20.7
588
78
1+27 (8oo)
3.2
0.946 (18.1)
2.31
96.8
1.014 (8.0)
3.05
*Gach Saran
Vac. Resid
1.0176 (7.6)
3.29
0.60
20.9
324
145
8.0
0.91+33 (18.5)
2.00
92.0
1.0369 (5.0)
3.40
0
Density, g/cm ( API)
Sulfur, W
Nitrogen Total, W
*Coke, W
(Conradson C)
Vanadium, ppm
Nickel, ppm
**IBP—°C (°F)
Vol. * (IBP—500°C)
Density, g/cm 3 (°API)
Sulfur, U *
Vol. ? (500°C+)
Density, g/cm 3 (°API)
Sulfur, U
Notes:
(538)
(21.3)
(10.0)
(711+)
(17.8)
(8.6)
5

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Table 2. DEMETALLIZATION TESTS CARRIED OUT IN THE USSR
I. Screening Tests Lasting 100-150 Hours
Run Number
2
Catalyst
USA l Mo
USA 1 Mo
Feed
Tia Juana Vac. Resid
Gach Saran Vac. Resid
II. Aging Tests Lasting 500 Hours
Run Number
2
3
4
5
6
7
8
Catalyst
USA l Mo
USA l  Mo
USSR (o.7 Mo)
USA (o Mo)
USSR (o.7 Mo)
USSR (0.7 Mo)
USSR (o.fl Mo)
USA (l Mo)
Feed
Tia Juana Vac. Resid
USSR Vac. Resid
Tia Juana Vac. Resid
USSR Atm. Resid
Gach Saran Vac. Resid
USSR Vac. Resid
USSR Atm. Resid
USSR Atm. Resid
6

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Table 3. DEMETALLIZATION TESTS CARRIED OUT IN THE USA
I. Screening Tests Lasting 100—150 Hours
Run Number
Catalyst
USSR (O.72 Mo)
Feed
USSR Atm. Resid.
II Aging Tests Lasting 500 Hours
Run Number
2
3
4
Catalyst
USSR (o.7 Mo)
USSR (0.7 Mo)
USA (l Mo)
USA (l Mo)
USSR Vac.
Tia Juana
USSR Atm.
USSR Vac.
Feed
Resid
Vac. Resid
Resid
Resid
7

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5.0 DESCRIPTION OF CATALYSTS
5.1 USSR Catalyst
The physical—chemical properties of the recent T-3 catalyst of the
Soviet Union and its poromeric characteristics are given in Table 4
and Figure 1.
The 1-3 catalyst has a low bulk density of 0.52 g/cm 3 , a high sur-
face area of 235 M 2 /g, and contains 0.7* Mo.
Figure 1 gives a curve showing the distribution of the pore radii
in the new T-3 catalyst. The catalyst has a polydispersed
structure, with pores having a radius from 30—50 — 51.6*, from
50-100 ° - 21.4*, from 100-500 - 7.9*, and above 500 - 19.1*,
and above 5000 A - 13.4*.
5.2 USA Catalysts
Two aging demetallization tests made in the USA and two tests made
in the USSR used the catalyst developed by KRI. This catalyst,
activated bauxite impregnated with one weight percent molybdenum
and designated as HRI 3634, was part of a comercial run made by
the Minerals and Chemical Division of Engelhard Corporation. One
other test made in the USSR used unpromoted activated bauxite
(0* Mo), designated as HRI 3309, which was also obtained from
Engeihard Corporation.
Table 5 lists the chemical and physical characteristics of the two
catalysts and Figure 2 and Figure 3 give the respective pore size
distribution curves.
In the course of earlier development work carried out on the de-
metallizaton catalyst, the one weight percent molybdenum level
impregnation was chosen after evaluations were made on 0.5, 1.0,
and 2.0 weight percent molybdenum preparations. The 0.5* Mo
catalyst was inferior with respect to the level of demetallization
and desulfurization as compared to the 2.0* Mo catalyst, while the
2.0* Mo catalyst did not exhibit significant superiority over the
1.0* Mo catalyst.
8

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Table 4. PROPERTIES OF USSR CATALYST
USSR Catalyst with
Indices O.7? Mo
Type of Catalyst Activated Bauxite
Compacted Bulk Density, g/cm 3 0.52
Surface Area, M 2 /g
(based on toluene) 235
Volume of Pores, cm 3 /g 0.51
Average Pore Radius, 44.0
Fractional Composition, MM — W
0.8 4.28
0.63 56.0
Less than 0.5 38.8
Strength Index, kg/mm 0.95
9

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0.6
0.5
0 )
E
oJ
Q)
E
r oO.3
0• >
0
0.2
0.1
100000
Pore Radius (Angstroms)
/
30000 10000 5000 1001) 500 100 50 30
Figure 1. FRESH USSR 1-3 CATALYST

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Table 5. PROPERTIES OF USA CATALYSTS
l Mo O Mo
HRI Number 3634 3309
Molybdenum, W 1.06 0
Volatile Matter, W 2.0 2.0
Compacted Bulk Density, g/cm 3 0.978 1.04
Surfac€. Area, M 2 /g (B.E.T. Nitrogen) 195.6 175
Pore Volume, cm 3 /g 0.317 0.225
Particle Size Range, W
0.84/0.59 mm (20/30 Mesh) 52.4 45.3
0.59/0.42 mr (30/40 Mesh) 30.7 31.8
0.42/0.297 mm (40/50 Mesh) 16.9 22.9
11

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I I I I I
I I I
NJ -.
0
D 0
0 0
o o
0
Pore Dameter (Angstroms)
0.1+ — I
U
E
0
—
NJ
0
0.3
0.2 —
0.1
0.0
0
0
0
0
NJ —
o o
o D
o
o 0
I
% fl
0
0
0
NJ
0
0
0
0
0
0
% fl
0
0
I I
NJ —
0 0
o 0
0 CD
Figure 2.
POROGRAM OF FRESH USA DEMETALLIZATION CATALYST Q° Mo) HRI NO. 3 j

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I I
I I
¼fl
0
0
0
Pore Diameter (Angstronis)
E
U
a)
E
0
‘JJ
a)
L
0
0
0.3
0.2
0.1
0.0
NJ -
C D 0
C D D
C D 0
0 0
0 0
CD
0
0
NJ —
0
o
0 0
o 0
NJ
CD
C D
0
C
0
0
U,
0
C D
NJ
0 0
CD 0
Lfl L.J
0 0
Figure 3.
POROGRAM OF FRESH USA DEMETALL ZATION CATALYST (o Mo) HRI NO. 3309

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6.0 DESCRIPTION OF UNITS AND TEST METHODS
6.1 USSR
All tests were carried out in fixe bed bench scale units, the reactor
having a catalyst volume of 200 cm . The direction of feed oil was
upflow. Figures 4 and 5 present schematic diagrams of the unit and
reactor.
The preheated feed was mixed with preheated hydrogen containing gas
and fed to the bottom of the reactor. After leaving the reactor the
liquid products, together with the hydrogen containing gas, were
cooled and fed to the high pressure separator. From here, hydrogen
sulfide was removed from the hydrogen containing gas and recycled.
The liquid products were fed to the low pressure separator from
which it was periodically removed and measured.
The reactor was fabricated from a tube having the following dimensions:
External diameter - 50 mm
Internal diameter - 28 mm
Length - 800 mm
A housing for three thermocouples was located in the center of the
reactor.
Two hundred milliliters of catalyst werecharged to the reactor on
a layer of ceramics of a similar particle size. A layer of ceramics
was also placed on top of the catalyst bed.
The startup procedure was as follows:
(a) Nitrogen purge under one third, one—half and one working
pressure.
(b) Purging of the system with hydrogen and preliminary drying of
the catalyst by circulating hydrogen containing gas at 500
normal liters per liter (nl/l) (2841 SCF/Bbl) with gradual
increase in temperature of 50°C (122°F) per hour. When a
temperature of 300°C (572°F) was reached, it was held for 2
hours. The feed was then introduced and the temperature
gradually increased at 50°C per hour up to a temperature of
370°C (698°F).
14

-------
Fiqure 1 • DIAGRAM OF THE USSR PILOT EQUIPMENT
- “a
Pump
Liquid Product Sample Line
4-

-------
Output of Reaction Products
I ,2,3 Thermocouples
Input of Feed + Hydrogen Containing Gas
External Diameter - 58 mm
Internal Diameter - 28 mm
External Thermocouple Rousing
Diameter - 10 mm
Internal Diameter of Feed
Input - 5 mm
Operational Conditions: P = 200 Atm.
t = L 5 j0 C
Fi gure 5. SCHEMATIC DRAWING OF THE USSR REACTOR
16

-------
(c) Presulfiding of the catalyst was carried out at a temperature of
370°C (698°F) for 18 hours using a virgin 350-500°C fraction gas
oil (containing a moderate amount of sulfur) at a liquid feed
rate of 1000 nI/i (5612 SCF/Bbl). Then the temperature was
increased up to a given level.
(d) The test was then initiated and the run data taken six hours
after startup.
According to the Protocol of December 13, 1974, conditions of the
tests were carried out at a hydrogen pressure of lL+0 atmospheres,
a temperature of 400°C (725°F), liquid space velocity of I Hrl for
atmospheric residua and a temperature of 420°C (788°F) and liquid
space velocity of 0.75 Hr1 for vacuum residua. The circulation
of the gas-containing hydrogen was maintained in all the experiments
at a level of 1000 nl/l (5612 SCF/Bbl) on feed. Each test lasted
500 hours.
The hydrogenation product which was periodically removed from the
low pressure separator was subsequently analyzed (once every 24
hours):
(a) Density determination, g/cm 3
(b) Fractionation under vacuum (according to Bogdanov)
Cc) Determination of sulfur content, W
Cd) Conradson carbon determination, W
The used catalyst, after discharge from the reactor, must be washed
for two hours in a Soxhiet device with benzene and the following are
determined:
(a) Bulk weight, g/cm 3
(b) Specific surface, M 2 /g
(c) Pore volume, crn 3 /g
Cd) Content of carbon and hydrogen
(e) Content of nickel and vanadium
(f) Sulfur content
17

-------
Results of the used catalyst are given in this report (Tables 7 and 8).
Preliminary experiments showed that in the case of demetallization
on catalysts-adsorbents, the demetallization kinetics (with respect
to removal of vanadium) may be adequately described by the following
first order equation:
Mf
ln—= K —
M mV
p
where Mf and is the content of vanadium in the feed and the hydro-
genation product in ppm;
K is the demetallization rate constant; and
m
V is the volumetric rate of feed supply, in HR1
The deactivation rate of the demetallization catalyst was determined
by the change in the demetallization constant as a function of catalyst
mid hours on stream.
To compare the desulfurization activity of the catalysts, graphs
were drawn showing degree of desulfurization versus operational
t i me.
6.2 USA
All demetallization runs were carried out in continuous, downf low
fixed bed reactor systems. A schematic diagram is shown in Figure 6.
The reactor, fabricated of 1-1/2-inch (38 mm) 0.D. by one-inch
(25.4 mm) I.D. stainless steel tubing, has a catalyst bed length of
approximately sixteen inches (406 mm). A drawing of the reactor tube
is shown in Figure 7. The volume (loose) of catalyst charged to the
reactor was 200 cm 3 . Provision was made for an internal thermocouple
which was positioned in the center of the catalyst bed approximately
midway between the top and bottom. Heat to the reactor was supplied
by a lead bath.
The melted charge stock was pumped to reactor pressure with a meter-
ing pump, mixed with hydrogen makeup gas, and fed to the top of the
reactor. The hydrogen concentration of the makeup gas was 100* and
no recycle of the exit gases was employed. 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 hgh pressure receiver
from which gas was sampled, metered, ar d vented. The net product

-------
HYDROGEN
THERMOCOUPLES
LIQUID PRODUCT
TO
FLARE
KNOCKOUT
PUMP
Figure 6. USA UNIT FLOW DIAGRAM

-------
INLET
OUTLET
—
29 1/2”
DRILL & TAP FOR
1” THREAD
DETAIL “A”
DETAIL “B”
F;gure 7. SCHEMATIC DRAWING OF THE USA REACTOR
6 /2”
/
CATALYST
BED LEVEL
TC
OF REACTOR
20

-------
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
analysis. Three essentially identical units, 115, 148, and 184 were
used for these runs.
A standard startup procedure was used to condition the catalyst at
lower temperature for a short period of time. The startup procedure
was as follows:
1B,2
Period I A Etc .
Temperature, (°F) °C (750)400 (775)415 (790)420 (790)420
Pressure, (psig) atm. (2050)140 (2050)140 (2050)140 (2050)140
Hydrogen Rate, (SCF/Bbi) ni/i (4000)712 (4000)712 (4000)712 (4000)712
Liquid Space Velocity,
Vo/Hr/Vr Constant
Time on Temperature, Hours 4 4 1 Continue
At Conditions
For operation at 400°C, the temperature for the first four hours was
held at 370°C then increased to 400°c and held for the duration of
the run.
Gas samples from the highpressure receiver were analyzed twice weekly
on a mass spectrometer, Du Pont Model 2l-103C. Daily inspections of
the liquid product included: density by hydrometer, atmospheric
distillation to 550°F (288°C), sulfur analyses on the 550°F+ fraction
by Leco induction furnace method ASTM D-1552, and metals analysis for
vanadium and nickel by atomic absorption Perkin Elmer Model 303.
Besides the daily inspections, about twice weekly sulfur analyses
were made on the initial to 550 F (288°C) fraction and appropriate
corrections made on total product sulfur.
Prior to analyzing used catalysts, the oil was first removed by
benzene extraction in a Soxhiet extractor, then analyzed for carbon,
sulfur, vanadium, and nickel. Metals and sulfur were analyzed using
the same equipment as for liquid products while carbon was analyzed
by high temperature combustion in oxygen using Perkin Elmer Model
240 elemental analyzer. Pore size distribution curves were obtained
by mercury intrusion on Aminco’s 60,000 psi (4083 atm.) Porosimeter.
7.0 DISCUSSION OF RESULTS
7.1 Tests on USSR Catalyst
Table 6 gives the results of tests on the T—3 catalyst for Romashkin
atmospheric and vacuum residua, ha Juana vacuum resid, and Gach Saran
vacuum resid carried out in the USSR and USA.
21

-------
TABLE 6. RESULTS ON USSR DEMETALLIZATION CATALYST TESTS MADE IN BOTH COUNTRIES
Catalyst USSR (o.7 Mo)
Feed
USSR
Vac. Resid
USSR
Vac. Resid
Tia Juana
Vac. Resid
ha Juana
Vac. Resid
Gach Saran
Vac. Resid
USSR
Atm. Resid
Testing Country
USA
USSR
USA
USSR
USSR
USSR
Hours On Stream
24
471
48
480
96
469
48
480
48
480
48
480
Product
F ”)
N.) Density,
Gravity,
0
g/cm 3
°AP I
.973
14.0
2.53
47
34
Sulfur, W °
Vanadium, ppm
Nickel, ppm
0.97 1
14.2
2.58
4c
414
0.982
12.6
2.45
40
25
0.979
13.0
2.59
51
32
0.984
12.8
2.32
208
57
0.98 1
12.7
2.32
234
57
0.986
12.0
2.26
190
30
0.982
12.6
2.20
228
34
0.98 1
12.7
2.57
43
46
0.991
11.3
2.51
60
49
0.946
18.1
2.04
26
17
0.949
17.6
2.15
30
22

-------
An analysis of the results obtained confirms the preliminary data in-
dicating that there was generally good reproducibility of results
(except in one case) carried out on identical catalysts and feed in
different countries.
Figures 8 and 9 give the deactivation of the T-3 catalyst versus time
on stream for different types of feedstocks. There is a difference
between the degree of vanadium removal in the T-3 catalyst when pro-
cessing Tia Juana vacuum resid and Romashkin vacuum resid.
After 500 hours, the residual content of vanadium in the product when
processing Tia Juana Vacuum resid was 223-228 ppm during tests of the
USSR catalyst. This corresponds to a demetallization degree of about
62 percent. in the demetallization of Romashkin vacuum resid, it was
about 44-51 ppm or 80 percent.
The chemical composition of the feed and the properties of the metal-
organic compounds had a great influence upon the demetallization rate
constant of the feedstock. Although the content of vanadium in ha
Juana vacuum resid was approximately 2.5 times greater than in
Romashkin vacuum resid (as may be seen from Figures 8, 9, 10 and 11)the
demetallization rate constant was approximately 1.5 times lower than
for Romashkin vacuum resid. It must be noted that for all types of
feeds studied, the degree of nickel removal was much lower than the
degree of vanadium removal (see Appendix).
On T—3 catalyst tests, the degree of desulfurization on all types of
feeds varied from 17 to 27 percent which cooresporids to a residual
sulfur content of 2.2 percent in the product at the end of the run
using Tia Juana vacuum resid and 2.6 percent sulfur for Romashkin
vacuum resid (see Figures 12, 13, 14, 15 and 16).
The deactivation of the catalyst is a result of the cracking reactions
taking place at the same time as the reactions of demetallization and
desulfurization and deposition of coke in the catalyst pores. There-
fore, to predict the stable operations of the catalyst and the poten-
tial of its adsorption metal capacity, the characteristics of the
used catalyst are of great importance in terms of their content of
coke deposits and metal deposits, as well as on the volume of the
pores (porograms) and specific surface.
Table 7 gives the characteristics of the used 1—3 catalyst after
operations using different types of feeds, and Figures 17, 18, 19, 20
and 21 give the curves for the pore radius distribution. In accordance
with the recommendations of the USA the pore volumes and the specific
surfaces for the used catalyst were corrected with respect to a new
catalyst to make a comparison of the data. The following formula was
used:
23

-------
Tia Juana V.R. Roniashkin V.R .
Run Conditions
Feed Composition
24 72 120 168 216 26 4 312 360 408 456 504
MID-HOURS ON STREAM
>
0
E
0
E
-
>
0.75
Figure 8.
VARIATION
OF VAN
ADIUM REMOVAL WITH
MiD-HOURS ON
STREAM
DURING THE
ROMASHKIN VACUUM
DEMETALLIZATIOU OF hA JUANA AND
RESIDS OVER USSR CATALYST (T-3)
MADE IN THE USSR
RUNS
140
420
Density, g/cm 3
Sulfur, W %
1.028
2.95
1.001
3.13
Hydrogen. Pressure, Atm.
Temperature, °C
Vanadium, ppm
Nickel, ppm
588
78
242
81
Liquid Space
V/Hr/V
Velocity,
I0
8
6
5
,
0
0
i
00
i
i
‘
‘
‘
‘ I
0
I
0o
I
I
I I I
1
85
80
70
60
.E
50
J
3.00
0
4.J
0
0
L
a-
E
-u
Co
to
>
0
0
2
o 0
0000000000
I I I - _A __ _ I _ I I I I I
0 00
I I I I I I I I _ 1 __ . _ .I I

-------
Feed Composition Run Conditions
Density, glcm 3 1.0176 Hydrogen Pressure, Atm. 140
Sulfur, W °‘ 5.29 Temperature,’°C 1420
Vanadium, ppm 32 4 Liquid Space Velocity, V/Hr/V 0.75
Nickel, ppm 145
10: I t I , i i 90
8 85
0 o 0 OA
0 0 o o °‘j °“e
- 6 0 0 00 70
5 0 0 co 0 0 60
L O 0 0
L i 0
50 E
Q)
F”, E— 3 40 °
‘ -I -’
-o
c-o
2 30
>C
(0 >
_L I L ( I I I i i I I i I I I I I I I I
24 72 120 168 216 264 312 360 408 4 6 o4
MID-HOURS ON STREAM
Figure 9. VARIATION OF VANADIUM REMOVAL WITH MID1IOURS ON STREAM DURIN
— THE DEMETALLIZAT ION OF GACH SARAN VACUUM RESID OVER USSR
CATALYST (1-3) RUN MADE IN THE USSR

-------
Feed Composition Operating Conditions
Density, g/cm 3 1.012 Hydrogen Pressure,Atm. l40
Sulfur, W ? 2.95 Temperature, 0 C 20
Vanadium, ppm 588 Liquid Space Velocity,
Nickel, ppm 78 V/Hr/V 0.75
(V
5 I I I I I I I I I L 80
L O 7° .
6O
I j _________________ I 1 —1 50
48 q6 144 192 240 288 336 384 432 480
MID-HOURS ON STREAM
Figure 10. VARIATION OF VANADIUM REMOVAL WITH MID-HOURS ON STREAM DURING THE
DEMETALLIZATION OF 114 JUANA VACUUM PESID OVER USSR CATALYST (T-3)
RUN MADE IN THE USA

-------
Density, glcm 3
Sulfur, W
Vanadium, ppm
Nickel, ppm
Run Conditions
Hydrogen Pressure, Atm.
Temperature, 0 C
Liquid Space Velocity,
V/Hr/V
l +0
1+20
0.75
OF VANADIUM REMOVAL WITH MID-HOURS ON STREAM DURING THE
DEMETALLIZATION OF ROMASHKIN VACUUM RESID OVER USSR CATALYST (T- T ,
RUN MADE IN THE USA
Feed Composition
0.001
3.09
236
81
F. ’,
—4
0)
0)
U-
E
C
(U
>
4-,
U
0
L
C
E
C
(0
10 —
9-.-
8—
7—
6—
5—
It—
3—
2_
‘I —
Figure 11.
I I I I I I I I I__i 88
• I84
e.G..,
J . -8o
I F I I I ii
1144 192 240 298 336 381+ 1+32 480
(0
>
0
E
0 )
a:
E
(0
C
CU
4-,
C
0)
U
L
4)
a-
1+8 96
VARIATION

-------
Feed Composition Run Conditions
Density, 9/cm 3 1.028 Hydrogen Pressure, Atm. 1 o
Sulfur, W 2.95 Temperature, °C 2O
Vanadium, ppm 588 LiquId Space Velocity, V/Hr/V 0.75
Nickel, ppm 78
>
0
E
cl) -
30 0 0
L
0000000 0000000000
20
CO U)
4 -J
c i)
0
L
c i )
a-
I I I I I —1
148 96 1144 192 2140 288 336 3814 1432 480 528
MID-HOURS ON STREAM
Figure 12. DESULFURIZATION OBTAINED DURING DEMETALLIZATION OF TIA JUANA VACUUM R ID
OVER USSR CATALYST (T-3) RUN MADE IN THE USSR

-------
Feed Composition Run Conditions
Density, 9/cm 3 1 .001 Hydrogen Pressure, Atm. l +0
Sulfur, W 3.13 Temperature, 0 C 420
Vanadium, ppm 2 +2 Liquid Space Velocity, V/Hr/V 0.75
Nickel, ppm 81
—
(U
>
0
E
a)
30
1
ooo o ° 0000
20 0o0o 000000
V)
C
10
L
a)
I I F I
1+8 96 11+1+ 192 21+0 288 332 381+ 432 480 501+
MID-HOURS ON STREAM
Figure 13. DESULFURIZATION OBTAINED DURING THE DEMETALLIZATION OFROMASHKIN VACUUM RESID
OVER USSR CATALYST (1-3) RUN MADE IN THE USSR

-------
Feed Composition Run Conditions
Density, g/cm 3 1.0176 Hydrogen Pressure, Atm. 1110
Sulfur, W 3.29 Temperature, °C 1 e2 0
Vanadium, ppm 3211 Liquid Space Velocity, V/Hr/V 0.75
Nickel, ppm l 45
hO -
(t
>
30 0
0
I T°T°T°T°T°T°T°T° 101
148 96 11+t 1 192 2140 288 332 3814 432 480 5011
MID-HOURS ON STREAM
Figure 14. DESULFURIZATION OBTAINED DURING THE DEMETALLIZATION OF GACH SARAN VACUUM RESID
RUN MADE IN THE USSR

-------
Hydrogen Pressure, Atm.
0
Temperature, C
Liquid Space Velocity,
V/Hr/V
(U
>
70
U)
60
504
14 Q
30
10
U)
0
Feed Composition
Density, 9/cm 3 1.0)2
Sulfur, W 2.95
Vanadium, ppm 588
Nickel, ppm
Operating Condi tions
1110
1 120
0.75
II: I I I I I I I
1 18 96 11411 192 240 2 8 — 3 2 3 i 4 2 48 bo
MID-HOURS ON STREAM
fI ure 15. DESULFURIZATION OBTAINED DURING THE DEMETALLIZATION OF hA JIJANA VACUUM RESID
OVER USSR CATALYST (1-3) RUN MADE IN THE USA

-------
Feed Composition Run Conditions
Density, 9/cm 3 1.00) Hydrogen Pressure, Atm. 140
Sulfur, W ° c 3.09 Temperature, °C 420
Vanadium, ppm 236 Liquid Space Velocity,
Nickel, ppm RI V/Hr/V 0.75
5 I I L —
>
0
— E
U)
L
- 0
U) 3
‘4-
—
L
CQ
(I ,
C
2 _ i0
‘4.- %_
U)
U
U)
• * I. .•O ..•.
—10
1 —
0 100 200 300 400 500
HID-HOURS ON STREAM
Fiqur 16. DESULFURIZATION OBTAINED DURING DEMETALLIZATION OF ROMASHK1N VACUUM RFSID OVER
USSR CATALYST (T-3) RUN MADE IN THE USA

-------
Table 7. CHARACTERISTICS OF USED USSR DEMETALLIZATION CATALYST (1-3 )
0.754 (2.14)
1.137
0.141
99. 5
12.91
12.04
8.0
1.8
0.0458
0.0056
0.0095
0.0047
0.0397
0.0511
0.746 (2.12)
1.17
0. 199
62.6
14.40
13.5
9.5
3.69
Pore Volume, cm 3 /g
0. 0698
0.0048
0.0161
0.02 15
0. 0654
0.0213
Vacuum Resid of
Romashkin
Petrol eum
0.869 (2.47)
0.930
0.229
49.6
12.29
9.57
6.43
2.21
0.0338
0.0212
0. 0109
0. 0040
0. 0319
0.1276
Indices
Feed
Tia Juana
Vacuum Resid
Gach-Saran
Vacuum Resid
Catalyst Age, 11 3 /kg (Bbl/Lb)
Bulk Density, g/cm 3
Volume of Pores, g/cm 3
Specific Surface, M 2 /g
Carbon Content, W *
Sulfur Content, W *
‘ Vanadium Content, W *
Nickel Content, W *
Distribution of PoreRadius, Angstroms
30-50 X
50-100
100-500
500-1000
1000-5000
5000
Characteristics of used catalyst are given after 600 hour run.

-------
I $ I
I I I
100000 30000 10000 5000 1000 500 100 50 30
Pore Radius (Angstrorns)
Figure 17 - COMPARISON OF POROGRAMS OF NEW AND USED (T-3) CATALYST AFTER OPERATING ON hA JUANA VACUUM RESID
E
U
E
0
>
L
0
0
0.6
0.5
0.3
0.2
0.1
1. New 1-3 Catalyst
2. 1-3 After Operating On
Tia Juana Vacuum Resid

-------
0.
I I I I
100000 30000 10000 5000 1000 300 100 50 30
Pore Radius (Angstroms)
0.
0.L+
E
0
a)
E
0
>
a)
L
0
C-
1.
0.3
2.
Hew T-3CatalySt
0.2
1-3 After Operating On
Romashkin Vacuum Resid
0.1
Figure 18. COMPARISON OF POROGRAMS OF NEW AND USED 1-3 CATALYST AFTER OPERATING ONROMASHKIN VACUUM RESID

-------
I I I
0.6
0.5
I. New 1-3 Catalyst
Oi 2. 1-3 After Operatinq On
Gach Sar n Vacuum Resid
E
C’ 0.2
0. 1 - - I
100000 30000 10000 5000 1000 500 100 50 30
Pore Radius (Anystroms)
Figure 19. COMPARISON OF POROGRAMS OF NEW AND USED T3 CATALYST AFTER OPERATING ON GACH SARAN VACUUM RESID

-------
I I IL
E
o 0.14
LU
z
1
0
>
LU
C
100000 30000
PORE RADIUS (ANGSTROMS)
Figure 20. COMPARISON OF POROGRAMS OF FRESH USSR CATALYST (1-3) AND USED CATALYST AFTER OPERATING
ON TIA JUANA VACUUM RESID RUN MADE IN THE USA
I I
2.
Fresh USSR Catalyst (T-3)
Used Catalyst
10000 5000 1000 500 100 50 30

-------
E
° 0.4
w
z
-J
0
> 0.2
(Li
0
0
100000
PORE RADIUS (ANGSTROMS)
Fhiure 21. COMPARISON OF POROGRAMS OF FRESH USSR CATALYST (1-3) AND USED CATALYST
AFTER OPERATING ONROMASHKINVACUIJM RESID RUN MADE IN THE USA
I I
Fresh USSR Catalyst (1-3)
Used Catalyst
2.
I I I I I I.._._.
1
30000 10000 5000 1000 500 100 50 30

-------
cm 3 /g of new catalysts = l.OO—E + 1/2 Es x crn 3 lg of used catalyst
F 1 — is the weight portion of vanadium, nickel and carbon for the
used catalyst; and
F 5 — is the weight portion of sulfur for the used catalyst.
It may be seen from Table 7 that the carbon content in the catalyst
is approximately the same for processing different types of feeds.
On the other hand, the pore volume for a used T-3 catalyst during
demetallization of ha Juana vacuum resid is approximately 1.5 less
than for Romashkin vacuum resid.
A comparison of the porograrns for a new and used 1-3 catalyst when
processing ha Juana vacuum resid and Romashkin vacuum resid shows
changes in every case. The portion of pores with a radius less than
100 decreases greatly, and to a lesser extent the pore portion
changes from 100 to 1000 A and there is a great increase in the
portion of pores above 1000 (see Figures 13, 14, and 15).
The appendix to this report gives the detailed characteristics of
the hydrogenation products obtained during the operating period for
all types of feeds.
7.2 Tests on USA Catalysts
Table 8 presents a summary of results achieved from tests made in
each country using the USA catalysts on various feedstocks. There
follows a discussion of each test conducted and a presentation of
graphs showing vanadium removal versus mid—hours on stream, and the
desulfurization achieved during demetallization. Used catalyst
analyses and evaluations are also given along with pore size
distribution curves.
Test Carried Out In USA
Catalyst: USA 1 ? Mo (HRI 3634)
Feed: USSR Vacuum Resid (Gudron)
This aging dernetallization test was carried out in Run 184-202 at a
hydrogen pressure of 140 atm., temperature of 420°C and liquid space
velocity of 0.75 V/Hr/V for a duration of 474 hours on stream until
it was voluntarily shutdown. No operating difficulties were
39

-------
Table 8. RESULTS ON USA DEMETALLIZATION CATALYST TESTS MADE IN BOTH COUNTRIES
Catalyst
USA (I? Mo)
USA (l Mo)
USA (l? Mo)
USA (O Mo)
USA (l Mo)
USA (l c Mo)
Feed
USSR
Vac. Resid
USSR
Vac. Resid
USSR
Atm. Resid
USSR
Atm. Resid
ha Juana
Vac. Resid
USSR
Atm. Resid
Testing Country
USA
USSR
USA
USSR
USSR
USSR
Hours On Stream
43
1474
138
5014
45
1477
48
5014
1i8
504
148
480
Prod u c t
Density, g/cm 3 0.9335 0.9554 0.9636 0.9760 0.9328 0.91402 0.9490 0.9433 0.9791 0.9810 0.935 0.939
Gravity, °API 20.1 16. 6 15.3 13.5 20.2 19.0 17.6 18.5 13.0 12.7 19.8 19.2
Sulfur, W 0.92 1.49 1.29 2.38 1.16 1.50 2.38 2.16 2.01 1.98 1.38 1.87
Vanadium, ppm 17 35 1t3 68 20 28 71 50 195 290 22 35
Nickel, ppm 23 31 38 64 114 23 25 19 37 58 14 14

-------
experienced during this test. The catalyst dumped freely from the
reactor. Demetallization and desulfurization data obtained from
this test are summarized in Figures 22 and 23, respectively. In
these figures the vanadium and sulfur data are expressed as the ratio
of vanadium or sulfur in the product versus mid-hours on stream. The
mid-hours on stream is used because it represents the middle age of
a 214 hour product period on which the analyses were conducted.
In this test vanadium removal started at about 9O level and dropped
to about 8o after 60 hours gradually to 82 at the end of the test.
Desulfurization obtained in this ranged from 69 at the beginning
and dropped to 56 at the end of the test.
Average demetallization achieved was 84% vanadium removal and the
average desulfurization during the demetallization test was 61.5%
sulfur removal producing a product oil containing 1.26 W % sulfur
and 31 ppm vanadium. Average values for sulfur and vanadium in the
products were calculated by an arithmetic average of values obtained
during the life of the test.
Test Carried Out in USSR
Catalyst: USA 1 % Mo (HRI 3634)
Feed: USSR Vacuum Resid (Gudron)
This test made in the USSR corresponds to the test made in the USA
as Run 1814—202. It was carried out at a total pressure of 150 atm.
(approximately 140 atm. hydrogen partial pressure), temperature of
420°C and liquid space velocity of 0.75 V/Hr/V.
Demetallization and desulfurization data obtained are summarized in
Figures 213 and 25, respectively. In these figures the vanadium and
sulfur data are plotted as ratios of vanadium or sulfur in the feed
to vanadium or sulfur in the product against mid—hours on stream.
In this run vanadium removal started at 83% and dropped to 682 at
the end of the run. Desulfurizaiton started at about 60% and dropped
to 23% at 350 hours and remained at this level until the end of the
run.
The average demetallization achieved was 72% vanadium removal and
the average desulfurization during the demetallization test was
34% sulfur removal producing a product oil containing 2.01 W %
sulfur and 63 ppm vanadium. The feed and product analyses used
in the above calculations were supplied by the USSR.
41

-------
CATALYST: USA ( I rio) FIRI NO. 36311
FEED: USSR VACUUM RESID
RUN: 1814 -202
FEED COMPOSITION OPERATING CONDITIONS
Density,g/cm 3 1.00614 Hydro jen Pressure, Atm. 11+0
Sulfur, W 3.27 Temperature, °C 1420
Vanadium, ppm 198 Liquid Space Velocity, V/Hr/V: 0.75
Nickel, ppm 80
20 I I I
1 1
U

4 )0
U.. L
9O
C JO
—C
E 8
(0
86 _
6 (0
>
(0 0 -
• • 83
oc CE
80
>
L
4)
75 -
3
I I
0 100 200 300 1+00 500
Mid-Hours On Stream
Figure 22. VARIATION OF VANADIUM REMOVAL WITH MID-HOURS 011 STREAM DURING THE DEMETALLIZATION
OF ROMASHKIN VACUUM RESID OVER USA CATALYST (1 Mo) RUN MADE IN THE USA

-------
CATALYST: USA (1 Mo) HRI MO. 3631+
FEED: USSR VACUUtI RESID
RUN: 18’+-202
FEED COMPOSITION OPERATING CONDITIONS
Density g/cm 3 1.0061+ hydrogen Pressure, Atm. 11+0
Sulfur, W ; 3.27 Temperature, °C 420
Vanadium, ppm 198 Liquid Space Velocity,
V/Hr/V: 0.75
Nickel, ppm 80
6.
I I I
5’
L
14 9-
IS .
67
>
0)
3.
75
CE
60
L 5
4)0 )
2
C a.
L
50
4)
a.
U -. L
—
D 4-
‘I )
1— I I I
0 100 200 300 1+00 500
Mid-Flours On Stream
Figure 23. OES(JLFURIZATION OBTAINED DURING THE DEMETALLIZATION OFROMASHKIN VACUUM RESID OVER
USA CATALYST (i Mo) RUN MADE IN THE USA

-------
CATALYST: USA (1 plo) HRI NO. 363 4
FEED: USSR VACUUM RESID
FEED COMPOSITIOII OPERATIH(’ 1 CONDITIONS
Density,g/Cm 3 1.0005 Hydrogen Pressure, Atm. IL 0
Sulfur, W 2 3.03 Temperature, °C
Vanadium, ppm 229 Liquid Space Velocity, V/Hr/V: 0.75
Nftkel, ppm 80
E
6- -
Ro
(0 (0
5-
0
U 75 - E
-D
67
U
L
--
U. L
3_ 3-
C
—c
2..
(0
cr0
(oc
> (0
>
• I I I I
0 100 200 300 400 500
tiid-Hours On Stream
Figure 21+. VARIATION OF VANADIUM REMOVAL WITH MID-HOURS ON STREAM DURING THE DEMETALLIZATION
OF ROMASHKIN VACUUM RESID OVER USA CATALYST (1° Mo) RUN MADE IN THE USSR

-------
CATALYST: USA (I Mo) HRI NO. 363 i
FEED: USSR VACUUM RESID
FEED COMPOSITION OPERATING CONDITIONS
Density, 9/cm 3 1.0005 Hydrogen Pressure, Atm. 140
Sulfur, 11 3.03 Temperature, °C 420
Vanadium, ppm 229 Liquid Space Velocity, V/IIrfV: 0.75
Nickel, ppm 80
6- i I I
5..
4..
-w U
3-.
(4 O
L
L
4-
2..
4 .-L >
— . .
—- c E
QJQ)
. . . • • • • • • •-20
1-
0 100 200 300 4oo 500
Mid-Hours On Stream
Figure 25. DESULFURIZATION OBTAINED DURING THE DEMETALLIZATION OF ROMASHKIN VACUUM RESID OVER USA
CATALYST (l0/ M6) RUN MADE IN THE USSR

-------
Results obtained by the USSR showed a lower level of vanadium removal
and higher deactivation slope. There is no apparent explanation for
this difference. Difference in initial startup of the unit, if any,
may have caused this difference in the results.
Test Carried Out in USA
Catalyst: USA 1 Mo (HRI 3634)
Feed: USSR Atmospheric Resid (Mazut)
This test was carried out in Run 184-203 at 140 atm hydrogen pressure,
temperature of 400°C and liquid space velocity of 1.0 V/Hr/V.
The average demetallization achieved was 78 vanadium removal and
the average desulfurization was 5l sulfur removal producing a
product oil containing 1.42 W sulfur and 29 ppm vanadium.
Figure 26 shows the catalyst deactivation slope of vanadium removal
and Figure 27 shows the sulfur removal slope during the demetallization
test.
Test Carried Out in USSR
Catalyst: USA O Mo (HRI 3309)
Feed: USSR Atmospheric Resid (Mazut)
This test was carried out at a total pressure of 150 atm, temperature
of 400°C and a liquid space velocity of 1.00 V/Hr/V.
The average demetallization achieved during this test was 64 vana-
dium remcval and the average sulfur removal was l6 producing a
product oil containing 2.27 W sulfur and 50 ppm vanadium.
Figure 28 sh is the catalyst deactivation slope for vanadium removal
and Figure 29 for sulfur removal. The catalyst deactivation slope
shows that this catalyst improves with age in its capacity to remove
vanadium from this particular feed indicating catalytic effect of
deposited metals on the catalyst. This effect was not evident on
sulfur removal.
46

-------
CATALYST: USA (1 c Mo) I IRI NO. 3631+
FEED: USSR ATtIOSPIIERIC RESID
RUN: 18 1 +_2o3
FEED COIIPOSITION OPERATING CONDITIONS
Density, g/cm 3 0.9652 Hydrogen Pressure, Atm. 1140
Sulfur, W 2.88 Temperature, °C 1+00
Vanadium, ppm 130 Liquid Space Velocity, V/Hr/V: 1.0
Nickel, ppm 145
8 i i
E
7..
0
186
Q)C
6 S • —183
> >
0
0
• •• • • • • • • • • _I80
— C
c4)
a) a
14. —175°
L
a)
0 -
(0 -
cm 3•.
mc
2 - I
0 100 200 300 1+00 500
Mid-Hours On Stream
Figure 26. VARIATION OF VANADIUM REMOVAL WITh M1D-HOITflS 09 STREAM DURING THE DEMETALLIZATI0NJ
ROMASHKIN ATMOSPHERIC RESID OVER USA CATALYST (1% Mo) RUN MADE IN THE USA

-------
CATALYST: USA (I 2 Mo) HRI tl0. 3631.
FEED: USSR ATHOSPHERIC RESID
RUN: 1814—203
FEED COIIPOSITIOIi OPERATIUG CONDITIONS
Density, g/cm 3 0.9652 Hydrogen Pressure, Atm. 140
Sulfur, W 2.83 Temperature, °C 1400
Vanadium, ppm 130 Liquid Space Velocity,
V/ I lr/V: 1.0
Nickel, ppm 45
6- i I
5-
0
3 L
0 )0 4—
L L
• —6 0:,_
2-- • •S.
L • ••••••• 50
>
I GJ0.)
4- I °
I33
a.
‘1,
I — I I I I
0 100 200 301) 4oo 500
Mid-Hours On Stream
Figure 27. DESULFURIZATION OBTAINED DURING DEMETALLIZATION OF ROMASHKIN ATMOSPHERIC RESID OVER USA
CATALYST (1 Mo) RUN MADE IN USA

-------
CATALYST: USA (0 2 Mo) HRI HO. 3309
FEED: USSR ATMOSPHERIC RESID
FEED COMPOSITION OPERATING CONDITIONS
Density, g/cm 3 0.96 16 Hydrogen Pressure, Atm. 140
Sulfur, W 2.71 Temperature, °c 400
Vanadium, ppm 136 Liquid Space Velocity, V/Hr/V: 1.0
Nickel, ppm 1 9
6 I
5.
E
‘.0
‘
U
>
)O 3. . • 7(Ufl3
U. L
0
- • • , 4o E
a)c
E 2-. vU
OL
0 .
( C
—
0 100 200 300 400 500
Mid-Hours On Stream
Figure 28. VARIATION OF VANADIUM REMOVAL WITH MID-HOURS ON STREAM DURING THE DEMETALLIZATION OF
ROMASI-IKIN ATMOSPHERIC RESID OVER USA CATALYST (o Mo) RUN MADE IN THE USSR

-------
CATALYST: USA (0 Mo) HRI NO. 3309
FEED: USSR ATMOSPHERIC RESID
FEED COtIPOSITION OPERATING CONDITIONS
Density, 9/cm 3 0.9616 Hydrogen Pressure, Atm.
Sulfur, W 2.71 Temperature, °C 1400
Vanadium, ppm 136 Liquid Space Velocity, V/Ilr/V: 1.0
Nickel, ppm 149
6 i
5.
0
J 4
U
a) -D
U L 3
L
c
33
—C 50
L 2-.
>
CE
(I )
L
••. •I•• • I I
I I
0 100 200 300 400 500
Mid-Hours On Stream
Figure 29. DESULFURIZATION OBTAINED DURING THE DEMETALLIZATION OF ROMASHKIN ATMOSPHERIC RESID OVER
USA CATALYST (0 Mo) RUN MADE IN THE USSR

-------
Test Carried Out in USSR
Catalyst: USA l Mo (HRI 3634)
Feed: Tia Juana Vacuum Resid
This test was carried out at a total pressure of 150 atmospheres,
temperature of 420°C and a liquid space velocity of 0.75 V/Hr/V.
The average demetallization achieved during this test was 6o°
vanadium removal and the average desulfurization during demetal-
lization was 35 sulfur removal producing a product oil containing
1.93 W sulfur and 239 ppm vanadium.
Figure 30 sho s the catalyst deactivation slope of vanadium removal
and Figure 31 shows the sulfur removal during demetallization.
7.2.1 Used Catalyst Analyses
The results of used catalyst analyses are sumarized in Table 9.
The fairly low carbon levels on all used catalysts indicate no coking
problems were encountered during the tests.
On the only two comparable tests made in both countries, that is USA
l Mo catalyst on USSR vacuum resid, the loss in surface area and total
pore volume was greater on the catalyst from the test made in the USSR
than in the USA. Since the demetallizatior, in the USA test was
greater (84? versus 72 vanadium removal) and the desulfurization
was also deeper (62 versus 34 ), at the same operating conditions,
the differences might be attributed to methods of operation and/or
differences in test equipment.
Figures 32, 33, 34, 35, and 36 present the pore size distribution
curves on the used catalysts which are compared to the fresh catalysts
used.
7.2.2 Pore Size Distribution Determinations and Interpretation
Pore size distributions on all catalysts were determined using Aminco’s
Model J5-7125D 60,000 psi (1+083 atm.) mercury intrusion porosimeter.
The range of pore sizes which can be measured using this instrument
is from 30 to about 180,000 in diameter. The upper range corres-
ponds to 10 psi (0.68 atm.), the pressure needed to fill with mercury
the interstitial voids between catalyst particles. A correction was
made before reporting results by subtracting the volume of mercury
intruded at 10 psi (0.68 atm.) from the total volume of mercury in-
truded into the catalyst sample.
51

-------
CATALYST: USA (1 Mo) IIRI MO. 3634
FEED: hA JUANA VACUUM RESID
FEED COMPOSITION OPERATIMG CONDITIOFIS
Density, q/cm 3 1.038 Hydrogen Pressure, Atm. 140
Sulfur, W 2.95 Temperature, °C 420
Vanadium, ppm 589 Liquid Space Velocity,
V/hrIV: 0.75
Nickel, ppm 78
6.
I I I I
5
1 75 E
0
0
• I. •-67 ‘
a)-t 3
S •. 6o
LL
S ••.
S S 550 1’ E
E 2
I ..
a)
.33
(0 -
:, (0
>1• I I I
0 tOO 200 300 400 500
Mid-Hours On Stream
Figure 30. VARIATION OF VANADIUM REMOVAL WITH MID-HOURS ON STREAM DURING THE DEMETALLIZATION OF
hA JUANA VACUUM RESID OVER USA CATALYST (1 Mo) RUN MADE IN THE USSR

-------
CATALYST: USA (1 % Mo) 1 -IRI NO. 3631k
FEED: TIA JUANA VACUUN RESID
FEED COMPOSITION
________________ OPERATING CONDITIONS
Density, g/cm 3 1.038 Hydrogen Pressure, Atm. 1140
Sulfur, W 2.95 Temperature, °C 1420
Vanadium, ppm 589 Liquid Space Velocity, V/Hr/V: 0.75
Nickel, ppm 78
6
‘.ri
5
‘4
U
-D
00 3
L L
4-
C —
C
2
(1) (0
>
4 . Q
‘4-
•
CE
—4-
U Q
ci 3
0)
a-
I — I I I I I
0 100 200 300 ‘ 4O() 500
Mid-Hours On Stream
Figure 31. DESLJLFURIZATION OBTAINED DURING THE DEMETALLIZATION OF hA JUANA VACUUM RESID OVER
USA CATALYST (1 °‘ Mo) RUN MADE IN THE USSR

-------
Table 9. ANALYSES ON USA CATALYST FROM AGING TESTS MADE IN USA AND.USSR
Country
Making Test
Catalyst
Identifi ion
Fresh (0 Mo)
URI 3309
Fresh (l Mo)
HRI 36314
USA l Mo
184-203
USA I° Mo
l81+ -202
USSR 0 l; Mo
HRI 3817
USSR I Mo
HRI 3816
USSR I Mo
HRI 3815
Carbon Sulfur
Feed W W
USSR
Atm. Resid 8.92
USSR
Vac. Resid 7.81
USSR
Atm. Resld 7.69
USSR
Vac. Resid 8.30
Tia Juana
Vac. Res d 8.28
Vanadium Nickel C.B.D.
______ W g/cm 3
-- 1.0140
Surface Total Pore
Area Volume
M 2 /g __________
1.05 1.2514 1145.7
1.52 1.306 66.2
0.67 1.140 112.3
0.83 1.256 146.3
0.59 1.390 32.1
175 0.225
0.317
Loss
In Total
Pore Volume
0.181 42.9
0.136 57.1
0.133
0.085 73.2
0.088 12.2
Temperature, °C (°F)
Pressure, Atm. ,( sig)
L,quid Space Velocity, Vo/Hr/Vr
Atm. Resids
400 (752)
1140 (2050)
1.0
Vac. Resids
20 (790)
140 (2050)
0. 75
Note: Pore volume and surface area data
were corrected to fresh catalyst
basis. Pore volumes were also
corrected for interstitial voids.
(SEE TEXT)
U,
3.31
6.43
5.30
7.93
8.89
-- - - 0.978 195.6
3.78
3.12
7.58
OPERATING CONDITIONS

-------
U
V
E
0
>
‘U
L
0
Q•!4
0.3
0.2
0.1
I I I I I I I I
o 0
o 0
o 0
Pore Diameter (Anqstroms)
Figure 32.
COMPARISON OF POROGRAMS OF FRESH USA CATALYST (1 % Mo) AND USED CATALYST AFTER OPERATING
1. Fresh Catalyst (1 plo)
2. Used Catalyst
2
0.0 r :
0
0
C)
0
0
0
C)
C)
0
0
0
0
0
0
—I
0 o
o o
0 0
o 0
0
0
0
I I I I I I
r1
0
0
C) C)
0 0
U,
0 0
ON ROMASHKIN (USSR) ATMOSPHERIC RESID RUN MADE IN THE USA

-------
I I I
I I I I
E
U
E
0
>
(1)
L
0 ’
—
0
o 0
0 0
o 0
o 0
U - I
0 0
Fiqure 33.
COMPARISON OF POROGRAMS OF FRESH USA CATALYST (1 Mo) AND USED CATALYST AFTER OPERATING
0.4 — j I
1. Fresh Catalyst (1 Mo)
2. Used Catalyst
0.3 —
0.2
0.1
2
0.0
F ’) — ‘-I,
o 0 0
c
o 0 •0 0
o 0 0 CD
o CD C)
I I I I I I
F’)
o 0
0 0
0 CD
Pore Diameter (Angstroms)
0
0
N) —
CD CD
o 0
ON ROMASHKIN (USSR) VACUUM RESID RUN MADE
IN THE USA

-------
0.
I I I I I I I I
1. Fresh Catalyst (0 Mo)
2. Used Catalyst
J,
NJ
—
f1
NJ
Q
0
0
•
.
-
‘.
..
0
0
0
0
o
0
0
0
0
0
c
0
0
0
0
Pore Diameter (Angstroms)
Figure 3Z .
COMPARISON OF POROGRAMS OF FRESH USA CATALYST (o ? Mo) AND USED CATALYST AFTER OPERATING
C. -’
E
U
‘1)
E
0
>
c i)
L
0
0
0.3
0.2
0.1
0.0
2
0
0
0
0
C :,
I I I I I
C:,
C D
0
0
0
0
0
0
I I
¼J1
0
0
NJ —
o o
0 0
‘.11 C.A)
0 0
ON ROMASHKIN (USSR) ATMOSPHERIC RESID RUN MADE IN THE USSR

-------
I I I I
Pore Diameter (Angstroms)
I I I I
Figure 35.
COMPARISON OF POROGRAMS OF FRESH USA CATALYST (I Mo) AND USED CATALYST
E
U
4,
0
4,
0
a-
I. Fresh Catalyst (I Mo)
0.
0.3
0.2
0.1 —
0.0
2. Used Catalyst
% fl
a,
2
NJ
0
0
0
0
0
0
0
0
0
0
U i
0
0
0
0
C
0
0
0
C
0
0
0
U i
0
0
0
NJ —
o
o
Ui
0
C
I I I I I I
NJ —
0 0
0 0
Ui
0 0
AFTER OPERATING ON ROMASUKIN (ussR) VACUUM RESID RUN MADE IN THE USSR

-------
cv
E
U
4)
E
0
t_D 4)
L
0
a-
0.z — I I
0.3
0.2
0.1
C)
o 0
o 0
0 0
—
o 0
C ) C)
o 0
o 0
Figure 36. COMPARISON OF POROGRAMS OF FRESH USA CATALYST (1 ? Mo) AND USED CATALYST AFTER OPERATING
I I I I
1. Fresh Cata’yst (1 Mo)
2. Used Catalyst
0.0
I I I I
\ fl
0
0
0
C)
2
U,
0
C)
0
N J
D -o
0 0
O 0
Pore Diameter (Angstroms)
I I I I
U,
0
0
NJ —
0 0
o o
U,
0 0
ON hA JUANA VACUUM RESID RUN MADE IN THE USSR

-------
Pore size and surface area data on used catalysts were corrected to
fresh catalyst basis using the following relationship:
cm 3 /g Fresh Catalyst = + x cm 3 lg Used Catalyst
where F 1 = weight fraction of V, Ni, C on used catalyst
F 5 = weight fraction sulfur on used catalyst
8.0 LIST OF REFERENCES
1. Oil & Gas Journal, 70, 31, pp. 98-100 (1972)
2. Bitumen—Tare-Asphalte—Pache, 1/2, c. 9—22, pp. 122—128 (1975)
60

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9.0 APPENDICES
9.1 TESTS REPORTED BY USSR

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Table O. DEMETALLIZATION RUN SUMMARY OF hA JUANA VACUUM RESID OVER USA CATALYST
( 1 ? Mo) RUN MADE IN THE USSR
CataIys USA Omnetalll,atlon Catalyst (I 7. MO)
URI Idt ’ntlficatlon Ho. 363 ,
Feed Source ha Juana ttacuum Re ld
0.n3Ity. 1.038 9/cm 3
Sulfur, 2.95 W 7.
VanadIum/NIckel, ppm 589/78
Hours On Stream
Operating tondit ions
temperature,
Pressure, Atm.
Space Velocity,
O/Hr/Vr
Catalyst. 141, Cans.
Catalyst, V. cm 3
Ll . jld Product
Den l ty , q/cm 3
Sulfur, V ‘7 ,
Total Product
500°C
Vanadium, ppm
NIckel, ppm
1NP-3S0°C, V P.
IBP-SO0°t, V
248 195 227 200 235 180 200 275 236 717 22 4 232 215 260 252 248 256
48 3/ 50 40 ‘.8 50 42 8 c2 35 58 42 39 58 51, 62
5 14.5 5 S 5 5 5 5 5 5 5 5 5 5 6 6 5 5.5
18 21 21 20 25 23 2 . 24 24 25 24 24 21, 23 21 22.5 22 2)
290 290 290
58 35 58
5 5 5
21 20.5 21.5
1420 420 1420 420
350 150 ISO 150
21, 148 72 96 120 144 168 192 216 2140 2614 288 312 336 360 381. 408 432
0 ’
0.75
196
200
0.75 0.15 0.75
196 196 196
200 200 200
1420 1.20 1.20 1.20 420 1.20 1.20 420 420 1.20 420 1.20 420 420
ISO ISO ISO ISO ISO 150 ISO ISO ISO 150 ISO ISO ISO ISO
0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.75 0.15 0.75 0.75 0.75 0.75 0.75
196 196 196 196 196 196 196 196 196 196 196 196 196 196
200 200 200 200 200 200 200 200 200 200 200 200 200 200
lop, “C
1456 4P’i 504
1.20 420 1420
ISO ISO ISO
0.75 0.75 0.75
196 196 196
200 200 200
2.08
34
2.21
82
0.9803 .9791 0.9819 .9780 .9182 .9/86 .9790 .9790 .9710 .9769 .9798 .9791 .9015 .9789 .9815 .9805 .9199 .9785 .9799 .9801 .9810
2.01 1.92 1.85 1.81. 1.90 1.87 1.86 1,91 1.86 1.87 194 1.83 1.93 1.95 1.93 1.99 1.97
1.37 1.29 1,37 1.30 1.39 1,40 1.35 1.50 1.38 1.40 1.41 I. 6 1.35 1.31 1.30 1,33 1.35
2.15 2.00 1.89 1.96 1,99 1.98 1.97 2.0$ 1.97 2.00 2.0’. 3.95 1.99 2.13 2.05 2.11 2.09
77 86 99 too too 87 III 95 100 79 89 8 ’. 97 78 97 90 106
1.99 1.99 1.98
3.37 I. )) 137
2.13 2.11 2,13
76 90 79

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Table 11. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN VACUUM RESID OVER USA CATALYST (1 Mo)
RUN MADE IN THE USSR
Calyst: l iSA 04’n’etaIlI7atlon Catalyst (I % Mo)
HAl hlentIfIcatI o No. 3634
Feed Sowcs. USSR Vacuum A,sld (Guironl
DensIty, 1.0005 q/cm
Sulfur, 3.03 U 3.
VanadIum/Nickel, ppm 229/80
420 420 420 420 420 420
150 150 150 150 ISO ISO
420 420 420
150 ISO ISO
Hours On Sjseam
Oper at l ondlt.lons
Temperature, “C
0’
froduct
DensIty, g ./cm 3
9fl r
lotal Product
I BP-500°C
500°C 4
lAP. °C
Vanadium. Isprn
Nickel, ppm
IBP-350°C, V %
1.23
0.76
1.42
86
1.29 1.45
.81 1.01
1.59 1.71
10 ’s 96
24
48
/2
96
120
144
168
192
216
240
26’i
288
312
6
360
384
408
1432
456
480
5014
420
420
1420
420
420
620
420
620
420
1420
1420
1420
Pressure, Atm.
ISO
ISO
ISO
150
150
50
ISO
ISO
150
ISO
150
ISO
Space Velocity Vr,/Hr/Vr
0.15
0.15
0./5
0.75
0.15
0.15
0.15
0.15
0.15
0.15
0.15
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.15
0.75
0.75
Catalyst, U, Cars.
196
196
196
196
196
196
196
I
196
196
196
196
196
196
196
196
196
196
196
196
196
Catalyst. V. cm
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
0,9761
.9636
.9638
.9682
.9658
.9658
.9698
.9696
.9616
.9708
.9754
.9/50
.9754
.9750
.9758
.9173
.9775
.9716
.97814
.9754
.9760
2.42
1.91
2.53
106
2.38
.97
2.56
108
8
43
38
7
/
7
62
149
8
14’.
35
8
66
‘.1
1
28
60
38
7
30
49
39
9
31,
73
41
8
29
65
142
8
30
66
58
8
29
72
61.
8
29
56
52
1
29
64
62
7
28
68
/2
7
27
80
/4
8
28
76
64
6
27
64
68
7
27
64
62
7
28
68
64
7
28
48
.99
I .66
96
.70
1.06
I .90
93
1.73
I .114
1.89
78
1.87
1.31
2.05
102
1.89
I .37
2.01
lot)
.96
1.50
2.18
80
2.08
1.55
2.37
102
2 .09
1.60
2.31
92
2.16
I .66
2.38
95
2.28
.71
2.50
98
2.25
1.851
2.140
97
2.32
1.814
2.55
98
2.40
1.90
2.54
1014
2.41
I .98
2.63
los
2.49
.96
2.5/
98
2 . 40
I .92
2.
89
IBP-500°C, V 9,
32.5 28 30 30 32 32

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Table 12. DEMETALLIZATION RUN SUMMARY OF hA JUANA VACUUM RESID OVER USSR CATALYST RUN MADE IN THE USSR
0 ’
Operating Cond ltioni P. 135 atm. 1.470°C V—o.85 Hr
24 48 72 96 120 i i14 168 192 216 240 264 288 312 336 360 386 608 632 656 480 504
0.9819 0.9863 0.9861 0.9196 0.9863 0.98 0.9782 0.97914 0.9183 0.9814 0.912 1 0.9806 0.9636 0.9825 0.9805 0.96 0.9624 0.9822 0.9822 0.9820 0.9818
2.36 2,26 2.23 2.18 2.19 2.28 2.25 2.25 2.13 2.15 2.11 2.11 2.26 2.21 2.16 2.26 2.20 2.21 2.20 2.21 2.16
1.12 1.90 1.76 1.75 1.82 1.85 1.73 1.82 1.77 1.76 1.69 1.71 1.88 1.77 1.91 1.91 1.80 1.78 1.79 1.85 1.83
2.56 2.62 2.141 2.33 2.37 2.35 2.37 2.35 2.30 2.29 2.25 2.23 2.35 2.60 2.30 2.31, 2.31 2.29 2.30 2.21 2,20
6.6 11.7 17.6 17.1 17.7 17.6 17.8 18.3 11.4 17.0 15.5 17.8 17.4 17.2 17.3 17.7 17.3 17.5 16.9 17.2 17.3
H4,Urs On Stre n
Density, qfcm 3
Sulfur, U
total Product
I BP -500°C
500°Cu
Conradson C, U
Nitroqen, W 1,
lap, °C
l0 . °C
Boiling Range, °C
1BP-350. V ‘I,
1DP-500. V %
180-350, V (,
Vanadiun, ppm
Nickel, ppm
Demetal II zat Ion
Rate Constant
0.39
0.33
0.38
0.35
0.37
0.38
0,314
ItO
90
97
92
98
80
83
98
96
84
94
94
86
112
92
112
100
93
88
89
tOO
423
4314
431
423
430
416
431
423
420
416
399
438
1451
442
441
445
445
1449
435
450
448
6.0
5.0
5.0
5.5
5.0
7.0
5.0
5.0
6.0
6.0
6.0
5.0
4.5
5.0
5.0
5.0
5.0
5.0
5.5
5.5
5.0
71.0
22.0
21.0
22.0
20.0
214.0
22.0
23.0
23.0
23.0
27.0
20.0
21.0
20.0
21.0
20.0
20.0
20.0
21.0
20.0
20.0
4.
3,5
3.5
4.0
3.5
5.0
6.0
4.0
5.0
14.5
14.5
14.o
3.5
4.0
4.0
4.0
4.0
14.0
4.5
4.0
14.0
188
168
180
174
170
115
114
190
215
228
223
29
30
29
29
30
29
52
34
35
0.89
0.98 0.93 0.955 0.955 0.9S5
0.89 0.80 0.75 0.77

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Table 13. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN ATMOSPHERIC RESID OVER USA CATALYST (0 Mo)
RUN MADE IN THE USSR
Catalyst: USA OemetaIIIz ,ltIOn Catalyst (0 Mn)
URI I Inot I Ilcat Inn P In. 3309
Feed Sou4ce: USSR At splu rlc R.sld (H.1?u%)
D nsUy. 0 9616 q/r.n
Sulfur. 7.7%
Vsnjjltj ,n/NIckeI . 136/1*9 ppm
Hours On SIrr.uo 21* 68 77 96 120 64 $68 197 716 240 768 788 112 336 360. 384 1408 1432 456 480 506
o n
Ten p atUre, 1 1*00 1400 400 1400 400 1400 1400 1400 1400 1400 1400 *00 400 1*00 1400 1400 1400 1400 1400 $*00 400
Pr ccure, Atm. $50 $50 $50 $50 150 ISO 150 150 $50 ISO $50 ISO $50 150 150 ISO ISO 150 ISO ISO 150
Space VelocIty.
Vo/lIr/Ar 1.0 1.0 1.0 .0 1.0 .0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 P.O 1.0 1.0 1.0 1.0
Catalyst. 14. t a*s. 208 208 208 208 208 206 208 208 208 208 208 208 208 208 208 208 208 208 208 208 208
Catalyst, V. rn 200 200 200 200 200 700 200 700 200 200 200 200 200 200 200 200 200 200 200 200 200
DenSity, q/r,n .91439 .91*90 .9 1*76 .91412 .9505 .91450 .9468 .91463 .91455 .9 14149 .9655 .9463 .9423 .9433 9669 .9475 .9669 .9469 .9439 .9633
Sulfur w V
0ot ,l Prrlt,ct 2.31 2.38 2. 1*0 2.36 2.29 2.40 2.30 2.21 2.26 2.26 2.29 2.40 7.38 2.15 2.08 2.22 2.19 2.19 2.11 2.17 2.16
lee, °C 96 II) $19 113 II? $09 115 126 98 13 14 106
V ar *ad lurn,pp*n 58 71 71 56 55 57 41 $45 41 38 31 35 86 69 52 1*6 65 66 50
Nlckel,ppm 22 25 24 23 20 23 20 70 9 19 $8 $7 26 24 21 2$ 2$ $9 $9
leP S0°t. V 8 6 8 8 7 7 8 8.5 7 6 8
IRP-500°C. V . 62 63 614 63 F .? 614 1414 6 1.5 62 61 6$

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Table 14. DEMETALLIZATION RUN SUMMARY OF GACH SARAN VACUUM RESID OVER USSR CATALYST RUN MADE IN THE USSR
Operating Conditions P .135 atm. 1 . 420 °C V—O.75 Hr
Hours On Strr ,,m 24 48 72 96 120 144 $68 192 216 240 264 288 312 336 360 384 408 432 456 480 504
Density. q/cm 0.9824 0.9808 0.9884 0.9820 0.9902 0.9856 0.9888 0.9890 0.9904 0.9902 0.9900 0.9894 0.9894 0.9894 0,9888 0.9928 0.9922 9.9916 0.9900 0.9910 0.9920
Sulfur, W
Total Product 2.79 257 2.54 2.63 2.61 2.61 2.66 2.63 2.61 2.57 2.65 2.65 2.65 2.66 2.64 2.68 2.65 2,72 2.65 2.51 2.71
18P-500,°C 1.16 2.3 2.10 2.16 2.22 2.18 2.26 2.27 2.29 2.30 2.25 2.211 2.22 2.22 2.23 2.27 2.32 2.33 2.18 2.25 1.93
500, °C 2.119 2.81 2.69 2.71 2.68 2.65 2.69 2.69 2.72 2.70 2.70 2.67 2.75 2.60 2.75 2.75 2.10 2.82 2.68 2.65 2.80
Conradson C, I ‘I 15.8 17.3 $6.6 $7.0 16.9 15.8 $7.1 17.3 $7.1 $7.0 17.1 17.6 $7.3 17.7 $7.6 17.5 17.1 $7.0 $7.1 $7.7 17.4
NItrogen, W ‘I. 0.52 0.56 0.56 0.57 0.59 0.52 0.57
IBP, °C 85 115 80 04 88 75 100 84 84 84 90 96 92 91 76 84 90 80 60 $02 92
10%. °C 391 424 414 415 411 414 416 423 1123 411 416 416 1115 1116 416 422 411 410 381 410 417
Boiling R ingc,°C
IBP-350, V 7, 8.0 6.0 7.0 7.0 7.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 8.0 6.0 6.0
lOP-SOn, V 7. 23.0 29.0 21.0 22.0 21.0 23.0 21.0 21.0 21.0 22.0 21.0 21.0 71.0 21.0 22.0 20.0 22.0 23.0 23.0 22.0 22.0
18 0-350,V ‘. 6.0 4.5 5.0 5.0 5.0 11.5 6.0 4.0 4.0 4.5 4.0 4.0 4.0 4.0 4.0 11.0 4.o 4.0 5.0 4.0 4.5
V.u’,adium. ppm 2 1 1 43 117 57 44 47 51 61 53 49 60 49 68 43 64 65 42 56 57 60 68
Nickel, ppm 314 111, 47 48 38 1,6 47 46 52 54 51 52 51 50 52 51 49 46 51 49 119

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Table 15. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN VACUUM RESID OVER USSR CATALYST RUN MADE IN USSR
Operating Conditions P— 135 ate. T—l 120°C. V—0.75 Hr 1
Hours On Stream 26 148 72 96 120 IkIi 168 192 216 2140 266 288 312 336 360 3814 408 432 1456 1180 5014
Oensity, q/cm 3 0.97117 0.9821 0.9813 0.9779 0.9775 0.9828 0.97014 0.9796
SuUur, H 2.6 4 2.45 2.110 2.31 2. 1i2 2.34 2.38 2.50 2.53 2.51 2.53 2.1.8 2.140 2.37 2.47 2.55 2.63 2.60 2.59 2.59 2.60
Conradson C, W % 12.9 13.1 1.37 12.6 12.’. 12.6 12.8 114.6 114.1 16.1 13.8 16.0 114.0 12.1 14.5 111.5 14.5 114.0 15.1 15.3 14.7
NItro er ., H 0.46 0.48 0.46 0.46 0.45 0.46
18P, °C 117 109 80 94 80 91 102 I I I
iot, °c 372 )3 36 381 375 409 606 500
0
801 1mg Range, C
18P-350, V 4 8 8 9 9 8 7.0 1.0 1.0
IBP-500, V % 26 26 29 29 27 21.0 28.0 11.0
180-350, V Y. 5 6 6 6 5 5.0 5.0 4.0
Van. .,dlon.ppn 36 60 145 62 64 35 35 59 51 ‘ .6 35 44 51 49
NlckeI.ppm 18 25 27 23 21 18 20 29 31 26 24 31 32 31

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Table 16. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN ATMOSPHERIC RESID OVER USSR CATALYST RUN MADE
IN THE USSR
Opera11nq Condltlori P.135 atm., t.1.O& (, V.1.0 Hr 1
Hours On Stream 24 48 72 96 120 11.11 168 192 216 21.0 261. 288 312 336 360 38’. 408 1.32 ‘.56 1.80 501.
nsit , gitm 3 0.9412 0.9464 0.9464 0.948! 0.9487 0.946! 0.9489 0.9481 0.9502 0.91.87 0.9491 0.9478 0.948! 0.9500 0.9494 0.9486 0.9481 O.9 ’ .79 0.9485 0.9494 0.9492
Sulfur, W ) 2.04 7,Ql 2.36 2.30 2.28 2.33 2.22 2.16 2.21 2.27 2.33 2.31. 2.31. 2.22 2.20 2.16 2.21. 2.19 2.17 2.15 2.22
Conradson C, U 7.6 7.6 7.3 7.5 7.5 1.3 7.5 7.2 7.5 7.l 7.2 7.1 7.3 7.3 7.0 7,3 1.! 7.4 7.2 7.2 7.4
NItrogen, U 0.2g. 0.21. 0.23 0.21 0.24
ISP, °C 138 325 13o ItO 146 12’. 118 116 736 118 116 114 120 126 119 120 32! 116 118 122 120
‘0%, °C 371 310 368 365 383 369 360 358 379 355 360 351 36? 369 361 364 361 360 359 366 365
SoIling Range, 0 C
ISP-350, V 7.0 6.0 6.0 7.0 5.0 6.0 8.0 8.0 5.0 7.0 6.0 6.0 6.0 1.0 7.0 7.0 6.0 8.0 7.0 8.0 8.0
ISP-500, V % 61,0 59.0 60.0 60.0 53.0 60.0 63,0 60.0 53.0 61.0 61.0 64.0 62.0 60.0 61.0 62.0 60.0 61.0 61.0 60.0 60.0
180-350, V 6.5 s.s 5.0 6.0 4.5 5.5 7.0 1.0 6.5 6.5 5. 5.5 5.0 6.0 6.5 6.S 6.5 7.5 6.5 7.5 7.0
VanadIum, ppm 16 26 26 28 3! 27 Il 16 22 Il 23 20 13 24 28 21 24 30 311 30 32
NIckel, ppm 12 Il 20 20 22 IS 35 36 20 16 16 39 iS 20 20 22 20 21 23 22 23

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9.2 TESTS REPORTED BY USA
69

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Table 17. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN VACUUM RESID OVER USSR CATALYST RUN MADE IN THE USA
Catalyst USSR T-3 (Oh Mo)
Run Nunber 115-1250
Feed Ronashkln Vacqum Pesd
Density, q/cm’ 1.006 11
Sulfur, W t 321
V snaalum/NickeI, ppm 98/80
Hours Or. Strean’ 14 38 62 86 110 13’ 158 182 206 230 2511 278 302 326 350 37 1k 398 422 1447 1471
!rating Condit ions
lemperature, “C ‘42) 421 420 420 42) 1421 1420 42) 1120 42) 1470 1420 1,21 1420 420 42) 42) 1420 42) 420
“ .1 H 2 Pressure, Atm. 136 136 13€ 136 135 136 1314 136 136 136 136 136 136 13€ 136 135 136 136 136 136
Space Velocity
V/Hr/V 0.75 0.15 0.82 0.74 0.76 0.74 0.76 0.1’I 0.75 0.80 0.75 0.77 0.74 0.70 0.82 0.83 0.80 0.15 0.711 0.75
liquid Product
Density, q/c .n 3 0.9725 09806 0.9745 0.9705 0.9752 0.9725 0.9792 0.9772 0.9718 0.9738 0.98’sO 0.9732 0.9692 0.97)2 0.9738 0.9125 0.9705 0.9799 0.96920.9112
Sulfur, Id V 2.53 2.65 2.12 2.143 2.41 2.148 2.46 2.5) 2.5) 2.4) 2.57 2.54 2.57 2.48 2.64 2.27 2.57 2.60 2.57 2.58
lOP “C 232 182 199 199 193 196 202 199 192 $91 186 196 190 192 195 20) 2)5 182 200 191
Vanadium, ppm 147 30 3) 33 34 32 140 38 35 3/ 40 40 40 32 38 39 39 36 38 40
Nickel, ppm 3 1 s 38 43 42 42 44 43 43 40 4) 45 45 45 37 iii 44 414 39 38 39
lRP-288°C,Vt 4 6 6 7 7 6 6 6 6 6 7 8 7 8 6 6 5 7 6 6

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Table 18. DEMETALLIZATION RUN SUMMARY OF hA JUANA VACUUM RESID OVER USSR CATALYST RUN MADE IN THE USA
Hours On Stream
USSR T- (0.7* Ho)
ha Juana Vacuum Resid
Dersity. 5/cmi 10122
Sal fur. U 7 3. II
Vanaror/ 4 liclrel. ppm 552//5
12 36 60 84 108 132 156 180 204 228 252 276 300 324 348 372 396 421 1445 469
! L ng Conditions
Temperature. “C 420 420 42) 421 42) 42) 42) 42) 42) 421 422 420 42) 42) 423 42) 42) 42) 1420 420
H 2 Pressure, Atm. 135 136 136 135 136 134 137 I I! 137 135 135 135 136 136 136 135 136 136 136 135
Space Velocity
V/Hr/V 0.80 0.76 0.72 0.77 0.80 0.77 0./5 0.7) 0.84 0.82 0.76 0.614 0.85 0.67 0.90 0.71 0.80 0.75 0.69
liquid .! _‘ .!
Density, u/cm 3
Sulfur. ‘1 3
I OP, °C
Vanadium, ppm
Nickel,
IRP-288°C, V 7
0.91)2 0.9786 0.9792 0.9847 0.9871 , 0.9840 0.9765 0.9779 0.986) 0.9820 0.97145 0.9632 0.9786 0.9833 0.9813 0.9786 0.9792 0.9833 0.98680.99)3
2./3 2.62 2.143 2,37 2.32 2.36 2.36 2.38 2.32 2.36 2.35 2.40 2.28 2.5) 2.12 2.27 2.36 2.34 2.38 2.32
2146 20g. 2)) 205 2014 206 209 223 2)6 238 211 23) 193 195 200 196 204 201 211 196
222 222 2)0 208 22) 2)0 204 2)2 2)) 210 209 223 20) 240 203 235 2140 2)6 2141 2311
50 54 53 57 58 56 56 52 52 54 55 57 149 52 53 55 59 56 58 si
2 4 6 6 6 5 5 5 S 5 5 5 5 i 6 7 6 8
Catalyst:
Run N,,mber 148-360
Feed:

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Table 19. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN ATMOSPHER$C RES D OVER USA CATALYST (1 Mo)
RUN MADE IN THE USA
Catalyst: USA Oemetalli atlon C.talyut (1% Mo) 178 g
URI Identification No. 36314 182 cm 3
Run Number 1814-203
Feed Source: USSR Atmospheric Re,d (Mazut)
Oensity . g/cis 09652
Sulfur. W 2.88
Vanadium/Nickel, ppm 130/1*5
Hours 0 Stream 20 145 69 93 ill 141 65 189 213 237 261 285 309 333 357 381 405 1*29 1451. 1.77
Operating Conditions
Temperature, °C 1*00 400 400 400 1100 400 403 400 400 400 1400 399 399 1*00 400 400 400 400 400 400
H 2 Pressure, Atm. 140 140 1140 140 140 1110 139 140 139 138 138 139 138 139 140 11*0 1140 11*0 139 11*0
Space Velocity
V/Hr/V 1.07 1.04 I II 1.13 1.09 1.11 1.09 1.03 1.13 1.11 1.06 1.05 1.08 1.08 1.06 1.06 1.03 1.02 1.08 1.05
roduc
Density g/cm 3 .9303 .9328 .9334 .937 1 .93311 .9365 .9346 .9358 .9371 .9358 .93446 .9371 .9340 .9358 .931.0 .9377 .9352 .9334 .9352 .9402
Sulfur, 14 t 1.36 1.16 i.32 1.31 1.25 ,l4i4 1.30 1.31 1.55 1.37 1.42 1.43 1.53 1.48 1.55 1.51 l.54 1.42 1.59 1.50
181’, °C 188 237 2314 252 22’. 271 266 249 199 288 252 282 251. 215 199 202 189 177 200 169
Vanadium, ppm 22 20 26 25 25 27 28 29 42 35 30 30 30 29 29 29 29 28 29 28
Nickel, ppm Iii 14 6 21 21 22 21 20 2S 23 20 21 21 21 25 25 2 * 23 23 23
IBP-288°C .y 3 2 I I I I I 2 2 2 2 I 2 2 2 I 2 I 2 2

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Table 20. DEMETALLIZATION RUN SUMMARY OF ROMASHKIN VACUUM RESID OVER USA CATALYST (1 % Mo) RUN MADE
IN THE USA
Catalyst: USA Demetalllcatlon Catalyst (It Mo) 378 g
HRI IdentiFication No. 363li 182 cm 3
Run Number: %8i. 2O2
Feed Source: USSR Vacuum Re id (Gudron)
Density g/ce 3 3.00611
Sulfur, V 3.27
Vanadium/Nickel, ppm 398/60
Hours On Stream 39 43 61 91 115 139 163 187 211 235 259 283 307 331 354 378 1102 i26 1,50 474
-4
Operat ngCond t ions
Temperature, °C 423 1421 418 421 12% 1121 423 1421 1121 1123 1121 1120 112% 42% 1123 42% 42% 421 42% 1121
Pressure, Atm. 331 l 4O 339 338 339 139 139 139 139 339 139 1111 1111 139 139 139 138 139 339 339
Space Velocity
V/Hr/V 0.67 0.13 0.87 0.72 0.83 0.76 0.84 0.73 0.711 0.76 0.84 0.78 0.79 0.72 0.711 0.73 0.76 0.13 0.88 0.79
J uid_Product
Density 9/cm 3 .3529 .3535 .9593 .9529 .9567 .9563 .9563 .9567 .9567 .9600 .9639 .9606 .9535 .9600 .95511 .9561 .9529 .9503 .9652 .9554
Sulfur, V 2 0.98 0.92 1.16 1.05 1.18 1.18 1.12 1.18 1.20 1.30 1.110 3.32 3.34 1.21 1.37 3.40 u.48 3.28 1.61 .49
laP, °C 390 49 1, I 377 376 Ill 369 165 I 9 204 382 3534 380 379 373 370 178 384 3734 382
Vanadium, ppm 20 37 28 25 28 21 30 30 33 30 43 38 32 32 37 39 39 33 36 35
Nickel ppm 22 23 30 29 32 34 34 30 31 30 35 33 29 29 32 33 32 28 33 33
IRP-2 8°C,V3 7 9 8 7 B 8 8 8 1 7 8 7 6 9 7 B 7 7 7

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TECHNICAL REPORT DATA
(Please read Thun cfions on the reverse before co,npletingl
iT PORT NO. 2.
EPA-600/7-78-119
3. RECIP1ENTS ACCESSIOI* NO.
4.rrrLE AND SUBTITLE
5. REPORT DATE
Demetallization Catalyst Tests on Heavy Residual OHs
June 1978
6. PERFORMING ORGANIZATION CODE
AumOR(S) y V. Manshi]in et al. (USSR), W. J. Rhodes
(EPA, IERL-RTP), and P. Maruhnic and G. Nongbri
( y drocarbon Research)
J.PERFORMING OROANIZAT!ON NAME AND ADDRESS
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
Hydrocarbon Research, Inc.
New York and Puritan Avenues
EHE623A
11. CONTRACT/GRANT NO.
Lawrenceville, New Jersey 08648 .
68-02-0293
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
13. TYPE OF 9EPORT ND PERIOD COVERED
CODE
Research Triangle Park, NC 27’lll
EPA/600/13
15.SUPPLEMENTARY NOTES IERL-RTP coauthor/project officer is W.J. Rhodes, Mail Drop
61, 919/541-2851.
The report gives results of a cooperative project between the U.S. and the
USSR to exchange technology on the demetallization step of an overall process to pro-
duce low sulfur fuel oil from heavy petroleum residua. Catalysts and petroleum
residua feedstocks were exchanged and tests were carried out by each nation using
its own equipment and operating procedures. Test results were exchanged and dis -
cussed at meetings in both the USSR and the U.S. In this report, all tests using U. S.
catalysts were described by the U.S. and all tests using USSR catalysts were des-
cribed by the USSR. Each nation described its own test equipment and operating pro-
cedures. Included for each aging test are graphs showing the degree of demetalli-
zation and desulfurization and the rate of catalyst deactivation. Fresh and used cat-
alyst analyses are presented, along with detailed run summaries and product inspec-
tions. Each nation’s molybdenum-impregnated catalyst exhibited about equal demetal-
ization capability; however, the U.S. catalyst exhibited higher desulfurization capa-
bility during demetallization. Sections of this report collaborated on and reported
jointly include the summary, introduction, and conclusions. The project was con-
sidered mutually beneficial.
7. KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
C. COSATI Field/Group
Air Pollution Molybdenum
Petroleum Products Testing
Metals Vanadlium
Desuiftirization
Fuel Oil
Residual Oils
Air Pollution Control
Stationary Sources
Demetallization
USSR
l3B
UG l4B
llF , O7B
07A , 07D
llH , 2lD

Catalysis
18. DISTRIBUTION STATEMENT
Unlimited
_______________
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
8
20. SECURITY CLASS (This page)
Unclassified
22. PRICE
EPA Form 2220.1 (9.73)
r4r4

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