Method of preparing a catalyst for the hydroconversion of asphaltene-containing hydrocarbonaceous charge stocks

A catalyst prepared by the steps which comprise: (a) adding to an asphaltene-containing hydrocarbonaceous oil charge stock a metal compound, a heteropoly acid and water; (b) converting the metal compound and heteropoly acid within the charge stock by heating the oil to a temperature from about 120.degree. F. (43.degree. C.) to about 500.degree. F. (260.degree. C.) to produce at least one organometallic compound within the charge stock; and (c) converting the organometallic compound within the charge stock under hydroconversion conditions to produce the catalyst.

BACKGROUND OF THE INVENTION 
The field of art to which this invention pertains is the preparation of a 
catalyst for the hydroconversion of asphaltene-containing 
hydrocarbonaceous charge stocks. More specifically, the invention relates 
to a catalyst prepared by the steps which comprise: (a) adding to an 
asphaltene-containing hydrocarbonaceous oil charge stock a metal compound, 
a heteropoly acid and water; (b) converting the metal compound and 
heteropoly acid within the charge stock by heating the oil to a 
temperature from about 120.degree. F. (43.degree. C.) to about 500.degree. 
F. (260.degree. C.) to produce at least one organometallic compound within 
the charge stock; and (c) converting the organometallic compound within 
the charge stock under hydroconversion conditions to produce the catalyst. 
INFORMATION DISCLOSURE 
Hydrorefining processes utilizing dispersed catalysts in admixture with a 
hydrocarbonaceous oil are well known. The term "hydrorefining" is intended 
herein to designate a catalytic treatment, in the presence of hydrogen, of 
a hydrocarbonaceous oil to upgrade the oil by eliminating or reducing the 
concentration of contaminants in the oil such as sulfur compounds, 
nitrogenous compounds, metal contaminants and/or to convert at least a 
portion of the heavy constituents of the oil such as pentane-insoluble 
asphaltenes or coke precursors to lower boiling hydrocarbon products, and 
to reduce the Conradson carbon residue of the oil. 
U.S. Pat. No. 3,161,585 (Gleim et al) discloses a hydrorefining process in 
which a petroleum oil charge stock containing a colloidally dispersed 
catalyst selected from the group consisting of a metal of Groups VB and 
VIB, an oxide of said metal and a sulfide of said metal is reacted with 
hydrogen at hydrorefining conditions. This patent teaches that the 
concentration of the dispersed catalyst calculated as the elemental metal, 
in the oil charge stock is from about 0.1 weight percent to about 10 
weight percent of the initial charge stock. 
U.S. Pat. No. 3,331,769 (Gatsis) discloses a hydrorefining process in which 
a metal component (Group VB, Group VIB and iron group metals) colloidally 
dispersed in a hydrocarbonaceous oil is reacted in contact with a fixed 
bed of a conventional supported hydrodesulfurization catalyst in the 
hydrorefining zone. The concentration of the dispersed metal component 
which is used in the hydrorefining stage in combination with the supported 
catalyst ranges from 250 to 2500 weight parts per million (wppm). 
U.S. Pat. No. 3,657,111 (Gleim) discloses a process for hydrorefining an 
asphaltene-containing hydrocarbon charge stock which comprises dissolving 
in the charge stock a hydrocarbon-soluble oxovanadate salt and forming a 
colloidally dispersed vanadium sulfide in situ within the charge stock by 
reacting the resulting solution, at hydrorefining conditions, with 
hydrogen and hydrogen sulfide. 
U.S. Pat. No. 3,131,142 (Mills) discloses a slurry hydrocracking process in 
which an oil soluble dispersible compound of Groups IV-VIII is added to a 
heavy oil feed. The catalyst is used in amounts ranging from about 0.1 to 
1 weight percent, calculated as the metal, based on the oil feed. 
U.S. Pat. No. 1,876,270 (Zorn) discloses the use of oil soluble 
organometallic compounds in thermal cracking or in destructive 
hydrogenation (hydrocracking) of hydrocarbons to lower boiling products. 
U.S. Pat. No. 2,091,831 (Pongratz et al) discloses cracking or destructive 
hydrogenation carried out in the presence of oil soluble salts of acid 
organic compounds selected from the group consisting of carboxylic acids 
and phenols with a metal of Group VI and Group VIII of the Periodic Table. 
The oil soluble salt is used in amounts between 4 and 20 weight percent 
based on the feed. 
U.S. Pat. No. 4,226,742 (Bearden et al) discloses the addition of a minor 
amount (i.e., less than 1,000 wppm) of an oil-soluble compound of metals 
of Group IVB, VB, VIB, VIIB and VIII of the Periodic Table of Elements and 
their conversion products in the oil yield catalysts which are effective 
in a minor amount for the hydroconversion of hydrocarbonaceous oils. 
The term "hydroconversion" is used herein to designate a catalytic process 
conducted in the presence of hydrogen in which at least a portion of the 
heavy constituents and coke precursors (as measured by Conradson carbon 
residue) of the hydrocarbonaceous oil is converted to lower boiling 
hydrocarbon products while simultaneously reducing the concentration of 
nitrogenous compounds, sulfur compounds and metallic contaminants. 
U.S. Pat. No. 4,954,473 (Gatsis) discloses a process to prepare a catalyst 
prepared by the steps which comprise: (a) adding to an 
asphaltene-containing hydrocarbonaceous oil charge stock an oil-insoluble 
metal compound and water; (b) converting the oil-insoluble metal compound 
within the charge stock by heating the oil to a temperature from about 
120.degree. F. (43.degree. C.) to about 500.degree. F. (260.degree. C.) to 
produce an organometallic compound within the charge stock; and (c) 
converting the organometallic compound within the charge stock under 
hydroconversion conditions to produce the catalyst. 
U.S. Pat. No. 4,637,870 (Bearden, Jr., et al) discloses a hydroconversion 
process for converting oil, coal or mixtures thereof utilizing a catalyst 
prepared by first forming an aqueous solution of phosphomolybdic acid and 
phosphoric acid and subsequently adding this solution to a hydrocarbon 
material, followed by heating in the presence of hydrogen and/or hydrogen 
sulfide to form a solid molybdenum and phosphorus-containing catalyst. 
BRIEF SUMMARY OF THE INVENTION 
The invention provides a method for preparing a catalyst from 
organometallic compounds. A preferred use of the organometallic compounds 
is to produce high activity catalysts for utilization in slurry catalyst 
processes for hydrorefining heavy, asphaltene-containing hydrocarbonaceous 
liquids including petroleum crude oil and fractions therefrom, syncrudes, 
tar sand oils, shale oils, coal oils and for converting solid carbonaceous 
materials such as coal and oil shale into liquid products. An important 
element of the method of the present invention is the discovery that the 
preparation of a catalyst produced by the combination of an oxide, a 
sulfide or a salt of a metal selected from Group IV through Group VIII, 
and a heteropoly acid has a synergistic effect on the catalytic properties 
of the slurry catalyst produced. 
One embodiment of the present invention may be characterized as a method 
for the preparation of a catalyst which method comprises the following 
steps: (a) adding to an asphaltene-containing hydrocarbonaceous oil charge 
stock a heteropoly acid and an oxide, a sulfide or a salt of a metal 
selected from Group IV through Group VIII and mixtures thereof and water; 
(b) converting the heteropoly acid and metal within the charge stock by 
heating the oil to a temperature from about 120.degree. F. (43.degree. C.) 
to about 500.degree. F. (260.degree. C.) to produce at least one 
organometallic compound within the charge stock; and (c) converting the 
organometallic compound within the charge stock under hydroconversion 
conditions including a temperature from about 650.degree. F. (343.degree. 
C.) to about 1000.degree. F. (538.degree. C.), a hydrogen partial pressure 
from about 500 psig (3448 kPa gauge) to about 5000 psig (36480 kPa gauge) 
and a space velocity from about 0.1 to about 10 volumes of oil feed per 
hour per volume of reactor to produce the catalyst. 
Another embodiment of the invention may be characterized as a method for 
the preparation of a catalyst which method comprises the following steps: 
(a) adding to an asphaltene-containing hydrocarbonaceous oil charge stock 
a heteropoly acid and an oxide, a sulfide or a salt of a metal selected 
from Group IV through Group VIII and mixtures thereof and water; (b) 
converting the heteropoly acid and metal within the charge stock by 
heating the oil to a temperature from about 120.degree. F. (43.degree. C.) 
to about 500.degree. F. (260.degree. C.) to produce at least one 
organometallic compound within the charge stock; (c) converting the 
organometallic compound within the charge stock under hydroconversion 
conditions including a temperature from about 650.degree. F. (343.degree. 
C.) to about 1000.degree. F. (538.degree. C.), a hydrogen partial pressure 
from about 500 psig (3448 kPa gauge) to about 5000 psig (36480 kPa gauge) 
and a space velocity from about 0.1 to about 10 volumes of oil feed per 
hour per volume of reactor to produce the catalyst; and (d) separating the 
catalyst from the hydroconversion zone effluent. 
Yet another embodiment of the present invention may be characterized as a 
method for the preparation of a catalyst which method comprises the 
following steps: (a) adding to an asphaltene-containing hydrocarbonaceous 
oil charge stock a heteropoly acid and an oxide, a sulfide or a salt of a 
metal selected from Group IV through Group VIII and mixtures thereof and 
water; (b) converting the heteropoly acid and metal within the charge 
stock by heating the oil to a temperature from about 120.degree. F. 
(43.degree. C.) to about 500.degree. F. (260.degree. C.) to produce at 
least one organometallic compound within the charge stock; (c) converting 
the organometallic compound within the charge stock under hydroconversion 
conditions including a temperature from about 650.degree. F. (343.degree. 
C.) to about 1000.degree. F. (538.degree. C.), a hydrogen partial pressure 
from about 500 psig (3448 kPa gauge) to about 5000 psig (36480 kPa gauge) 
and a space velocity from about 0.1 to about 10 volumes of oil feed per 
hour per volume of reactor to produce the catalyst; (d) separating the 
catalyst from the hydroconversion zone effluent; and (e) recycling at 
least a portion of the catalyst from step (d) to the hydroconversion zone. 
Other embodiments of the present invention encompass further details such 
as exemplification of metal compounds, heteropoly acids, types of 
asphaltene-containing hydrocarbonaceous oil charge stocks, organometallic 
compound preparation conditions, and hydroconversion conditions, all of 
which are hereinafter disclosed in the following discussion of each of 
these facets of the invention. 
DETAILED DESCRIPTION OF THE INVENTION 
The method of preparation of the present invention is primarily used to 
produce high activity catalysts for utilization in slurry processes for 
hydrorefining heavy asphaltene-containing hydrocarbonaceous liquids. 
Suitable heavy asphaltene-containing hydrocarbonaceous oil charge stocks 
include whole or topped petroleum crude oils, including heavy crude oils, 
residual oils such as petroleum atmospheric distillation tower resid 
(boiling above about 650.degree. F./343.degree. C.) and a petroleum vacuum 
distillation tower resid (boiling above about 1050.degree. F./565.degree. 
C.); tars; bitumen; tar sand oils, coal oils and shale oils. Particularly 
well suited asphaltene-containing hydrocarbonaceous oils generally contain 
metallic contaminants (such as nickel, iron and vanadium, for example, a 
high content of sulfur compounds, nitrogen compounds and a high Conradson 
carbon residue. The metal content of such oils may range up to 1,000 wppm 
or more and the sulfur content may range up to 5 weight percent or more. 
The gravity of such feeds may range from about -5.degree. API to about 
+35.degree. API and the Conradson carbon residue of the heavy feeds will 
generally be at least about 5 weight percent, more preferably from about 
10 to about 50 weight percent. Preferably, the heavy hydrocarbonaceous oil 
possesses at least 10 weight percent boiling above about 1050.degree. F. 
(565.degree. C.) at atmospheric pressure, more preferably having at least 
about 25 weight percent boiling above 1050.degree. F. at atmospheric 
pressure. 
In accordance with the present invention, an oxide, a sulfide or a salt of 
a metal selected from Group IV through Group VIII of the Periodic Table of 
Elements is added to heavy asphaltene-containing hydrocarbonaceous oil. In 
addition, a heteropoly acid and water is also added to the heavy 
asphaltene-containing hydrocarbonaceous oil. I have unexpectedly 
discovered that a high activity catalyst can be prepared in accordance 
with the present invention. 
The metal constituent of the oxide, sulfide or salt that is convertible to 
a solid, non-colloidal catalyst is selected from the group consisting of 
Groups IVB, VB, VIB, VIIB and VIII and mixtures thereof of the Periodic 
Table of Elements, in accordance with the Table published by E. H. Sargent 
and Company, Copyright 1962, Dyna Slide Company, that is, titanium, 
zirconium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, 
manganese, rhenium, iron, cobalt, nickel and the noble metals including 
platinum, iridium, palladium, osmium, ruthenium and rhodium. The preferred 
metal constituent of the oxide, sulfide or salt is selected from the group 
consisting of molybdenum, vanadium, chromium and iron. Suitable metal 
compounds which may be utilized in the present invention include 
molybdenum trioxide and vanadium pentoxide, for example. 
When the metal compound is added to the heavy, asphaltene-containing 
hydrocarbonaceous oil in the presence of water, under pretreatment 
conditions hereindescribed, the metal compound is converted to an 
organometallic compound and under hydroconversion conditions herein 
described is converted to an active catalyst comprising from about 0.01 to 
about 2 weight percent, preferably from about 0.05 to about 0.5 weight 
percent of the same metal or metals or the metal or metals added, 
calculated as the elemental metal, based on the heavy, 
asphaltene-containing hydrocarbonaceous oil. 
The water present during pretreatment is preferably available in an amount 
from about 0.5 to about 100 weight percent based on the 
asphaltene-containing hydrocarbonaceous oil charge stock. 
In accordance with the present invention, a heteropoly acid is also admixed 
with the asphaltene-containing hydrocarbonaceous oil charge stock. Any 
suitable heteropoly acid may be utilized and a preferred heteropoly acid 
is phosphomolybdic acid. Phosphomolybdic acid is understood to mean any of 
the known phosphomolybdic acids including phospho-12-molybdic acid, 
phospho-10-molybdic acid and phospho-6-molybdic acid. A most preferred 
heteropoly acid is phospho-12-molybdic acid. The heterpoly acid is 
preferably present in an amount from about 0.025 to about 2 weight percent 
calculated as the elemental metal based on said charge stock.

The following examples are presented for the purpose of further 
illustrating the present invention and to indicate the benefits afforded 
by the utilization thereof. 
EXAMPLE 1 
A phospho-12-molybdic acid solution containing 54.3 weight percent 
molybdenum was prepared by placing 576 g of MoO.sub.3, 38.4 g. of H.sub.3 
PO.sub.4 (85% reagent grade) and 2800 cc of water in a 4 liter flask. The 
flask was then heated overnight on a stirred hot plate. The contents of 
the flask were then filtered with suction through a 5 micron fritted disc 
filter. The insolubles were washed with 300 cc of water. The filtrate was 
evaporated on a steam bath and yielded 500 g of phospho-12-molybdic acid. 
The insolubles were dried in an oven at 125.degree. C. to yield 177 g. 
A 1.1 g sample of the previously prepared phospho-12-molybdic acid, 0.38 g 
of MoO.sub.3 and 79 g of water were added to a flask. The flask was heated 
and stirred to solubilize the contents and then sonified by ultrasonic for 
30 minutes. The resulting contents of the flask were transferred to an 
autoclave using 25 g of water for a rinse. 
A Lloydminster vacuum resid in an amount of 439 g and having the 
characteristics presented in Table 1 was also added to the autoclave. In 
addition, 38 g of toluene was also added to the autoclave. The autoclave 
was sealed, flushed with nitrogen to remove oxygen and heated to 
150.degree. C. to remove the water and toluene. The autoclave was then 
cooled and pressured with a gas blend containing 10% hydrogen sulfide and 
90% hydrogen to a pressure of 100 atmospheres. The autoclave was then 
heated to a temperature of 420.degree. C. for two hours while maintaining 
a total pressure of 200 atmospheres by the addition of hydrogen. After 
cooling, the autoclave contents were collected, and the liquid contents 
were centrifuged to remove solid particulate matter. The reaction products 
were sampled, analyzed and the results are presented in Table 2. 
TABLE 1 
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ANALYSIS OF LLOYDMINSTER VACUUM RESID 
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API Gravity @ 15.6.degree. C. 
6.6 
Specific Gravity @ 15.6.degree. C. 
1.0246 
D-1160 Distillation, .degree.C. 
IBP, Vol. % 379 
5 455 
10 473 
20 509 
EP 512 
Vol. % Over @ EP 22.0 
371.degree. C. + Wt. % 98.9 
510.degree. C. + Wt. % 82.4 
Analysis, Wt. % 
Carbon 83.6 
Hydrogen 11.5 
Sulfur 4.77 
Nitrogen 0.51 
Carbon Residue 17.39 
Petroleum Ash 0.041 
C.sub.7 Insolubles 13.56 
Toluene Insolubles 0.012 
Nickel, PPM 82 
Vanadium, PPM 163 
Iron, PPM 34 
Molecular Weight 912 
Furol Visc., Sec (121.degree. C.) 
306 
Pour Point, .degree.C. 54 
Softening Point, .degree.C. 
37.5 
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EXAMPLE 2 
Another experiment was performed utilizing essentially the same procedure 
as described in Example 1 with the exception that in this experiment 1.25 
g of MoO.sub.3 was the sole metal catalyst precursor, the total amount of 
water used was 95 g, including 29 g of rinse water, the amount of 
Lloydminster vacuum resid was 431.7 g and the amount of toluene was 29 g. 
The resulting reaction products were sampled, analyzed and the results are 
also presented in Table 2. 
EXAMPLE 3 
Another comparative experiment was performed also utilizing essentially the 
same procedure described in Example 1 with the exception that in this 
experiment 1.55 g of the previously prepared phospho-12-molybdic acid was 
the sole metal catalyst precursor, the total amount of water used was 85.6 
g including 25.6 g of rinse water, the amount of Lloydminster vacuum resid 
was 428.5 g and the amount of toluene was 30 g. The resulting reaction 
products were then sampled, analyzed and the results are also presented in 
Table 2. Although there are very slight variations in the amounts of 
material used for the three experiments, it is believed that they 
represent a valid comparison of the various catalyst systems which have 
been tested. 
TABLE 2 
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SUMMARY OF RESULTS 
Example 1 2 3 
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Catalyst PMA--MoO.sub.3 
MoO.sub.3 
PMA 
510.degree. C..sup.+ Non-Distillable 
63.90 61.27 67.69 
Conversion, Wt. % 
Heptane Insoluble Conversion, 
80.93 68.12 74.27 
Wt. % 
Coke Yield, Weight Percent 
0.6 0.5 1.1 
Carbon Yield, Weight Percent 
0.5 0.5 0.75 
Total Liquid Product Properties 
API 21.9 19.2 22.5 
Sulfur, Weight Percent 
1.28 2.12 1.38 
Heptane Insolubles, Weight 
2.28 4.48 2.70 
Percent 
Carbon Residue, Weight Percent 
6.63 9.08 7.10 
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From Table 2, it is readily apparent that when a catalyst is produced by 
the combination of an oxide, a sulfide or a salt of a metal selected from 
Group IV through Group VIII, and a heteropoly acid there is a synergistic 
effect on the catalytic properties of the slurry catalyst produced. The 
enhanced catalytic properties include a heptane insoluble conversion of 
80.93 weight percent, sulfur reduction to 1.28 weight percent, a heptane 
insolubles reduction to 2.28 weight percent and a carbon residue reduction 
to 6.63. 
The foregoing description and examples clearly illustrate the advantages 
encompassed by the present invention and the benefits to be afforded with 
the use thereof.