An improved ebullated bed hydroconversion process is disclosed that utilizes a bimodal heterogeneous catalyst and a metal containing oil-miscible-catalysts compound to achieve a reduction in sediment, an increase in conversion, a reduction in the energy utilized to maintain reaction conditions and increases the stability of the ebullated catalyst bed. The oil-miscible compound may be provided in a concentration so as to provide about 1 to about 60 wppm metal based on the charge hydrocarbon oil.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to the hydroconversion of heavy hydrocarbon oils. 
More particularly it relates to a hydroconversion catalyst system which 
permits operation to be carried out with decreased power consumption and 
better ebullation in the reactor bed. 
2. Background 
Often a petroleum refiner wishes to convert high boiling fractions such as 
vacuum resid to lower boiling fractions which are of higher value and more 
readily handled and/or marketable. Illustrative of the large body of 
patents directed to this problem are the following: 
U.S. Pat. No. 4,579,646 discloses a bottoms visbreaking hydroconversion 
process wherein hydrocarbon charge is partially coked, and the coke is 
contacted within the charge stock with an oil-miscible metal catalyst 
compound of a metal of Group IV-B, V-B, VII-B, or VIII to yield a 
hydroconversion catalyst. 
U.S. Pat. No. 4,724,069 discloses hydrofining in the presence of a 
supported catalyst bearing a VI-B, VII-B, or VIII metal on alumina, 
silica, or silica-alumina. There is introduced with the charge oil, as 
additive, a naphthenate of Co or Fe. 
U.S. Pat. No. 4,567,156 discloses hydroconversion in the presence of a 
chromium catalyst prepared by adding a water-soluble aliphatic polyhydroxy 
compound (such as glycerol) to an aqueous solution of chromic acid, adding 
a hydrocarbon thereto, and heating the mixture in the presence of hydrogen 
sulfide to yield a slurry. 
U.S. Pat. No. 4,564,441 discloses hydrofining in the presence of a 
decomposable compound of a metal (Cu, Zn, III-B, IV-B, VII-B, or VIII) 
mixed with a hydrocarbon-containing feed stream; and the mixture is then 
contacted with a "suitable refractory inorganic material" such as alumina. 
U.S. Pat. No. 4,557,823 discloses hydrofining in the presence of a 
decomposable compound of a IV-B metal and a supported catalyst containing 
a metal of VI-B, VII-B, or VIII. 
U.S. Pat. No. 4,557,824 discloses demetallization in the presence of a 
decomposable compound of VI-B, VII-B, or VIII metal admitted with the 
charge and a heterogeneous catalyst containing a phosphate of Zr, Co, or 
Fe. 
U.S. Pat. No. 4,551,230 discloses demetallization in the presence of a 
decomposable compound of a IV-B, V-B, VI-B, VII-B, or VIII metal admitted 
with the charge and a heterogeneous catalyst containing NiAs.sub.x on 
alumina. 
U.S. Pat. No. 4,430,207 discloses demetallization in the presence of a 
decomposable compound of V-B, VI-B, VII-B, or VIII metal admitted with the 
charge and a heterogeneous catalyst containing a phosphate of Zr or Cr. 
U.S. Pat. No. 4,389,301 discloses hydroprocessing in the presence of added 
dispersed hydrogenation catalyst (typically ammonium molybdate) and added 
porous contact particles (typically FCC catalyst fines, alumina, or 
naturally occurring clay). 
U.S. Pat. No. 4,352,729 discloses hydrotreating in the presence of a 
molybdenum blue solution in polar organic solvent introduced with the 
hydrocarbon charge. 
U.S. Pat. No. 4,338,183 discloses liquefaction of coal in the presence of 
unsupported finely divided metal catalyst. 
U.S. Pat. No. 4,298,454 discloses hydroconversion of a coal-oil mixture in 
the presence of a thermally decomposable compound of a IV-B, V-B, VI-B, 
VII-B, or VIII metal, preferably Mo. 
U.S. Pat. No. 4,134,825 discloses hydroconversion of heavy hydrocarbons in 
the presence of an oil-miscible compound of IV-B, V-B, VI-B, VII-B, or 
VIII metal added to charge, the compound being converted to solid, 
non-colloidal form by heating in the presence of hydrogen. 
U.S. Pat. No. 4,125,455 discloses hydrotreating in the presence of a fatty 
acid salt of a VI-B metal, typically molybdenum octoate. 
U.S. Pat. No. 4,077,867 discloses hydroconversion of coal in the presence 
of oil-miscible compound of V-B, VI-B, VII-B, or VIII metal plus hydrogen 
donor solvent. 
U.S. Pat. No. 4,067,799 discloses hydroconversion in the presence of a 
metal phthalocyanine plus dispersed iron particles. 
U.S. Pat. No. 4,066,530 discloses hydroconversion in the presence of (i) an 
iron component and (ii) a catalytically active other metal component 
prepared by dissolving an oil-miscible metal compound in the oil and 
converting the metal compound in the oil to the corresponding 
catalytically active metal component. 
U.S. Pat. No. 5,108,581 principally discloses hydroconversion in a stirred 
batch reactor using homogeneous catalytic systems using various metal 
compounds. 
SUMMARY OF THE INVENTION 
One aspect of the present invention is generally directed to an ebullated 
bed hydroconversion process for converting a charge hydrocarbon oil 
containing a substantial quantity of components boiling above about 
1000.degree. F. to a product containing an increased quantity of 
components boiling below 1000.degree. F. The process includes contacting 
the charge hydrocarbon oil, with a solid heterogeneous catalyst, the 
heterogeneous catalyst including elements selected from Groups IV-B, V-B, 
VI-B, VII-B or VIII of the Periodic Table on a catalyst support, and an 
oil-miscible catalyst compound in a reaction zone. Hydroconversion 
conditions in the reaction zone are utilized in the presence of hydrogen 
and mercaptan, thus the components of the charge hydrocarbon oil boiling 
above about 1000.degree. F. are converted to components boiling below 
1000.degree. F. after which the product is recovered. The improvement of 
this process by the present invention includes utilizing a heterogeneous 
catalyst characterized as having a density between about 32 and about 75 
lb/ft.sup.3, a particle diameter of about 1/64 to about 1/16 inches, a 
surface area from about 50 to about 500 m.sup.2 /g, a total pore volume of 
about 0.2 to about 1.2 cc/g and a pore volume distribution of: 35 to 55% 
for pore diameters of 0 to 50 .ANG.; 5 to 25% for pore diameters of 50 to 
100 .ANG.; 3 to 10% for pore diameters of 100 to 150 .ANG.; and, 25 to 45% 
for pore diameters greater than 150 .ANG.. 
The oil-miscible catalyst compound may be introduced in an amount 
sufficient to provide metal in an amount from about 1 to about 60 wppm 
based on the charge hydrocarbon oil. Such an oil-miscible catalyst 
compound may be selected from the group including: metal salts of 
aliphatic carboxylic acids, metal salts of naphthenic carboxylic acids, 
metal salts of alicyclic carboxylic acids, metal salts of aromatic 
carboxylic acids, metal salts of sulfonic acids, metal salts of sulfinic 
acids, metal salts of phosphoric acids, metal salts of mercaptans, metal 
salts of phenols, metal salts of polyhydroxy aromatic compounds, 
organometallic compounds, metal chelates and metal salts of organic 
amines, wherein the metal is a element of Groups IV-B, V-B, VI-B, VII-B, 
or VII of the Periodic Table. Preferably the oil miscible catalyst 
compound is chosen from the group including cobalt naphthenate, molybdenum 
hexacarbonyl, molybdenum naphthenate, molybdenum octoate, molybdenum 
hexanoate and combinations thereof. 
Another aspect of the present invention is generally directed to a method 
of reducing the energy consumed in operating an ebullated bed 
hydroconversion reaction. This method includes contacting the charge 
hydrocarbon oil, with a solid heterogeneous catalyst and an oil-miscible 
catalyst compound in the presence of hydrogen and mercaptan under 
hydroconversion conditions, so as to convert the components of the charge 
hydrocarbon oil boiling above about 1000.degree. F. to components boiling 
below 1000.degree. F.; and, recovering the product. The heterogeneous 
catalyst may include elements selected from Groups IV-B, V-B, VI-B, VII-B 
or VIII of the Periodic Table on a catalyst support, and which is 
characterized as having a density between about 32 and about 75 
lb/ft.sup.3, a particle diameter of about 1/64 to about 1/16 inches, a 
surface area from about 50 to about 500 m.sup.2 /g, a total pore volume of 
about 0.2 to about 1.2 cc/g and a pore volume distribution of: 35 to 55% 
for pore diameters of 0 to 50 .ANG.; 5 to 25% for pore diameters of 50 to 
100 .ANG.; 3 to 10% for pore diameters of 100 to 150 .ANG.; and, 25 to 45% 
for pore diameters greater than 150 .ANG.. The oil-miscible catalyst 
compound is present in an amount sufficient so as to reduce the energy 
consumed in operating the ebullated bed hydroconversion reaction to a 
level less than that of the energy utilized in the absence of the 
oil-miscible catalyst compound. In one embodiment, the oil-miscible 
catalyst compound is present in an amount sufficient so as to reduce the 
energy consumed in operating the ebullated bed hydroconversion reaction to 
a level between about 99% and about 80% that of the energy consumed in the 
absence of the oil-miscible catalyst compound. 
Yet another aspect of the present invention is a method of increasing the 
operational stability of an ebullated bed hydroconversion process which 
converts a charge hydrocarbon oil containing a substantial quantity of 
components boiling above about 1000.degree. F. to a product containing an 
increased quantity of components boiling below 1000.degree. F. In this 
aspect, the charge hydrocarbon oil is contacted with a solid heterogeneous 
catalyst and an oil-miscible catalyst compound in the presence of hydrogen 
and mercaptan under hydroconversion conditions, so as to convert the 
components of the charge hydrocarbon oil boiling above about 1000.degree. 
F. to components boiling below 1000.degree. F. and the product is 
recovered. The heterogeneous catalyst includes elements selected from 
Groups IV-B, V-B, VI-B, VII-B or VIII of the Periodic Table on a catalyst 
support, and is characterized as having a density between about 32 and 
about 75 lb/ft.sup.3, a particle diameter of about 1/64 to about 1/16 
inches, a surface area from about 50 to about 500 m.sup.2 /g, a total pore 
volume of about 0.2 to about 1.2 cc/g and a pore volume distribution of: 
35 to 55% for pore diameters of 0 to 50 .ANG.; 5 to 25% for pore diameters 
of 50 to 100 .ANG.; 3 to 10% for pore diameters of 100 to 150 .ANG.; and, 
25 to 45% for pore diameters greater than 150 .ANG.. The oil-miscible 
catalyst compound is present in an amount sufficient so as to increase the 
operational stability of the ebullated bed when compared to the 
operational stability of the ebullated bed in the absence of the 
oil-miscible catalyst compound. In one embodiment, the oil-miscible 
catalyst compound is present in an amount of about 1 to about 60 wppm 
based on the charge hydrocarbon oil. In another embodiment, the 
oil-miscible catalyst is present in an amount sufficient to decrease the 
sediment in the product.

DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS 
The charge hydrocarbon oil which may be treated by the process of this 
invention may include high boiling hydrocarbons typically those having an 
initial boiling point (ibp) above about 650.degree. F. This process is 
particularly useful to treat charge hydrocarbons containing a substantial 
quantity of components boiling above about 1000.degree. F. to convert a 
substantial portion thereof to components boiling below 1000.degree. F. 
Typical of these streams are heavy crude oil, topped crude, atmospheric 
resid, vacuum resid, asphaltenes, tars, coal liquids, visbreaker bottoms, 
etc. Illustrative of such charge streams may be a vacuum resid obtained by 
blending vacuum resid fractions from Alaska North Slope Crude (59v %), 
Arabian Medium Crude (5v %), Arabian Heavy Crude (27%), and Bonny Light 
Crude (9v %) having the characteristics listed in Table I: 
TABLE I 
______________________________________ 
PROPERTY Charge 
______________________________________ 
API Gravity 5.8 
1000.degree. F. + (W %) 
93.1 
Composition (W %) 
C 84.8 
H 10.09 
N 0.52 
s 3.64 
Alcor Microcarbon Residue (McR) (%) 
19.86 
n-C.sub.7 insolubles (%) 
11.97 
Metals content (wppm) 
Ni 52 
V 131 
Fe 9 
Cr 0.7 
Na 5. 
______________________________________ 
The hydrocarbon oil generally contains undesirable components typified by 
nitrogen (in amount up to about 1 w %, typically about 0.2 to about 0.8 w 
%, say about 0.52 w %), sulfur (in amount up to about 10 w %, typically 2 
to about 6 w %, say about 3.64 w %), and metals including Ni, V, Fe, Cr, 
Na, etc. in amounts up to about 900 wppm, typically about 40 to about 400 
wppm, say 198 wppm). The undesirable asphaltene content of the charge 
hydrocarbon may be as high as about 22 w %, typically about 8 to about 16 
w %, say 11.97 w % (analyzed as components insoluble in normal heptane). 
The API gravity of the charge may be as low as about minus 5, typically 
about minus 5 to about plus 35, say about 5.8. The content of components 
boiling above about 1000.degree. F. may be as high as about 100 w %, 
typically about 50 to about 98+w %, say 93.1 w %. The Alcor MCR Carbon 
content may be as high as about 30 w %, typically about 15 to about 25 w 
%, say 19.86 w %. 
The charge hydrocarbon oil may be passed to a hydroconversion operation 
wherein conversion occurs in liquid phase at conversion conditions 
including about 700.degree. F. to about 850.degree. F., preferably about 
750.degree. F. to about 810.degree. F., say 800.degree. F. at hydrogen 
partial pressure of about 500 to about 5000 psig, preferably about 1500 to 
about 2500 psig, say 2000 psig. 
A catalytically effective amount of oil-miscible, preferably an 
oil-soluble, catalyst compound of a metal of Group IV-B, V-B, VI-B, VII-B 
or VIII of the Periodic Table is introduced in the hydroconversion 
operation. As the term is used herein, the oil-miscible catalyst compounds 
to be employed may be either oil-miscible or oil soluble, but preferably 
oil-soluble i.e. they are soluble in the charge hydrocarbon oil in amount 
of at least about 0.01 g/100 g typically about 0.025 to about 0.25 g/100 
g, say about 0.1 g/100 g or alternatively they are readily dispersible in 
the charge hydrocarbon oil in amount of at least those amounts. The 
oil-miscible catalyst compounds may, when activated as hereinafter set 
forth, become oil-miscible or oil soluble in the hydrocarbon oils under 
the conditions of the hydroconversion process. When the metal is a Group 
IV-B metal, it may be titanium (Ti), zirconium (Zr), or hafnium (Hf). When 
the metal is a Group V-B metal, it may be vanadium (V), niobium (Nb), or 
tantalum (Ta). When the metal is a Group VI-B metal, it may be chromium 
(Cr), molybdenum (Mo), or tungsten (W). When the metal is a Group VII-B 
metal, it may be manganese (Mn) or rhenium (Re). When the metal is a Group 
VIII metal, it may be a non-noble metal such as iron (Fe), cobalt (Co), or 
nickel (Ni) or a noble metal such as ruthenium (Ru) , rhodium (Rh), 
palladium (Pd), osmium (Os), iridium (Ir), or platinum (Pt). Preferably 
the metal is a Group VI-B metal--most preferably molybdenum (Mo). 
Typical oil-miscible or oil-soluble catalyst compounds include, among 
others, one or mixtures of the following: metal salts of aliphatic 
carboxylic acids, for example molybdenum stearate, molybdenum palmitate, 
molybdenum myristate, molybdenum octoate; metal salts of naphthenic 
carboxylic acids, for example cobalt naphthenate, iron naphthenate, 
molybdenum naphthenate; metal salts of alicyclic carboxylic acids, for 
example molybdenum cyclohexane carboxylate; metal salts of aromatic 
carboxylic acids, for example cobalt benzoate, cobalt o-methyl benzoate, 
cobalt m-methyl benzoate, cobalt phthallate, molybdenum p-methyl benzoate; 
metal salts of sulfonic acids, for example molybdenum benzene sulfonate, 
cobalt p-toluene sulfonate iron xylene sulfonate; metal salts of sulfinic 
acids, molybdenum benzene sulfinate iron benzene sulfinate; metal salts of 
phosphoric acids, for example molybdenum phenyl phosphate; metal salts of 
mercaptans, for example iron octyl mercaptide, cobalt hexyl mercaptide; 
metal salts of phenols, for example cobalt phenolate, iron phenolate; 
metal salts of polyhydroxy aromatic compounds, for example iron 
catecholate, molybdenum resorcinate; organometallic compounds, for example 
molybdenum hexacarbonyl, iron hexacarbonyl, cyclopentadienyl molybdenum 
tricarbonyl; metal chelates, for example ethylene diamine tetra carboxylic 
acid-di-ferous salt; and metal salts of organic amines, for example cobalt 
salt of pyrrole. Preferred examples of the above compounds include: cobalt 
naphthenate, molybdenum hexacarbonyl, molybdenum naphthenate, molybdenum 
octoate, and molybdenum hexanoate. 
It is found that the impact of the oil-miscible catalyst compound may be 
augmented by use of oil-miscible catalyst compounds of more than one 
metal. For example if molybdenum (e.g. as the naphthenate) is employed, it 
is found desirable to add an additional quantity of cobalt (e.g. as the 
naphthenate). This yields a positive synergistic promotional effect on 
catalytic desulfurization and demetallization. Typically cobalt may be 
added in amount of about 0.2 to about 2 moles, say 0.4 moles per mole of 
molybdenum. 
The oil-miscible catalyst compound should be present in amount less than 
about 60 wppm (i.e. of metal) say about 1 to about 60 wppm based on 
hydrocarbon oil to be hydroconverted. In one embodiment the amount of 
oil-miscible catalyst compound should be present in an amount of about 15 
to about 45 wppm based on the charge hydrocarbon oil. 
It has been unexpectedly found, that the energy consumption utilized in the 
operation of the ebullated bed process is decreases as the amount of 
oil-miscible catalyst compound increases. Specifically the total energy 
(i.e. thermal energy) required to maintain the reaction temperature at set 
point in the ebullated bed, may be decreased from about 1200 KBTU/BBL 
(which is the energy consumption at 0 ppm metal) down to a minimum of 
about 1000 KBTU/BBL. This is an improvement of about 24% in energy saving. 
This is attained at a conversion of about 61.2v % which is about 11% 
greater than the base line conversion of about 54.6v %; and it is also 
noted that the sediment remains about the same. 
One of skill in the art should know that hydrodynamic environment of an 
ebullated bed reactor is very complex and is very different from a batch 
or flow through fixed or stirred bed reactor. In particular variations in 
the reactor parameters such as the size and shape of the reaction vessel, 
the catalyst size and density, the flow rates of reactants into the 
ebullated bed, the rate of product recovery, are just a few among the many 
parameters that need to be considered if the bed is to be stable and safe 
to operate. It has also been unexpectedly found that upon addition of the 
oil-miscible catalyst compound the stability of the ebullated bed 
hydroconversion reaction is increased. As is shown in FIG. 1a, in the 
absence of oil-miscible catalyst compound, the ebullated bed utilized in 
carrying out the hydroconversion process has areas of instability as shown 
by the peaks and the low reactor bed height. Upon addition of oil-miscible 
catalyst compounds under generally the same conditions, the ebullated bed 
becomes more stable as evidenced by the lack of peaks in FIG. 1b and a 
suitable catalyst bed height of about 13 to about 15 feet. However, it has 
also been found that an excess of oil-miscible catalyst compound can have 
a destabilizing effect on the ebullated bed. Upon addition of 60 wppm of 
oil-miscible catalyst compound, an accumulation of metal on the surface of 
the heterogeneous catalyst particles is observed. This increase in the 
molybdenum concentration on the surface of the heterogeneous catalyst 
particles destabilizes the ebullated bed under approximately the same 
conditions of those used to generate FIGS. 1a and 1b and cause the 
catalyst bed height to decrease as shown in FIG. 2a. Rather than operate 
an unstable reactor, an increase in the ebullation rate from about 25.9 
gph to about 33.6 gph was required to expand the catalyst bed to the 
desired height. (FIG. 2b) Further addition of oil-miscible catalyst 
compound was not attempted due to the danger of creating an unstable 
ebullated bed in the hydroconversion reactor. Thus it has been 
unexpectedly discovered that there exists a previously unknown 
relationship between the amount of oil-miscible catalyst compound that can 
be added to the hydrocarbon charge and the stability of an ebullated bed 
hydroconversion reaction. 
In addition to these unexpected results which may be attained in energy 
consumption and ebullated bed stability, it is particularly significant 
that an improvement in the level of sediment in the product oils is 
attained. It has been unexpectedly found that sediment formation in the 
effluent from the ebullated bed may be minimized by use of oil-miscible 
metal catalyst compound in amount sufficient to provide a metal content of 
about 15 to about 45 wppm, preferably about 30 wppm. It is found for 
example that the sediment in the product oil when about 15 wppm of metal 
is present is only about (0.037/0.092 or) about 40% of that observed for 
the base case. Sediment in the effluent from the ebullated bed is measured 
by IP Test 375/86 entitled Total Sediment Residual Fuel Oils the contents 
of which are hereby incorporated herein by reference. 
It should be apparent to those skilled in the art that the specific amount 
of soluble metal, present, which may be in an amount of about 1 to about 
60 wppm, will depend upon the particular charge hydrocarbon to the 
ebullated bed, the selection of the catalyst, the reactor design, the 
level of conversion desired, the level of sediment desired amongst several 
factors. In any instance, an economic study will permit a ready 
determination of the desired level of soluble metal to be employed. It is 
to be noted however that in most instances, while the conversion and the 
power consumption are significant, it is usually found that the stability 
of the ebullated bed and the sediment levels in the product will be 
determinative. The former factor should be apparent to one of skill in the 
art since reactor stability and safety are very important. The impact of 
the latter factor should likewise be apparent to one of skill in the art 
because an undesirable high level of sediment will result in plugging of 
various pieces of equipment with resulting short run times. This latter 
factor may be found to be economically controlling-especially when the 
feed is characterized by a high propensity to generate sediment which can 
rapidly clog and force the shut down and clean out of the refinery unit. 
The oil-miscible catalyst compound may be added by many different 
reasonable means that should be apparent to one of skill in the art. For 
example, it is possible to introduce the oil-miscible metal catalyst 
compound as a solution of or mixture with a highly aromatic heavy oil. The 
highly aromatic heavy oil which may be employed, typically those oils 
which contain sulfur such as a heavy cycle gas oil (HCGO), may be 
characterized as follows: 
TABLE II 
______________________________________ 
Value 
Property Broad Narrow Typical 
______________________________________ 
API Gravity -5 to 20 0-10 2 
Temperature .degree.F. 
ibp 500-1000 650-850 650 
50% 800-900 825-875 850 
ep 1000-1200 1000-1100 1050 
Aromatics Content w % 
25-90 30-85 85 
Sulfur Content w % 
0.5-5 2-4 3.5 
______________________________________ 
Illustrative highly aromatic heavy oils which may be employed may include: 
TABLE III 
______________________________________ 
Value 
______________________________________ 
A - Heavy Cycle Gas Oil 
API Gravity 
Temp .degree.F. -3.0 
ibp 435 
10% 632 
50% 762 
90% 902 
ep 1056 
Aromatics Content w % 85 
Sulfur Content w % 2.5-3.5 
B - MP Extract 
API Gravity 
Temp .degree.F. 8 
ibp 600 
ep 1000 
Aromatics Content w % 50-90 
Sulfur Content w % 3 
C - Decant Oil 
API Gravity -2.7 
Temp .degree.F. 
ibp 525 
10% 708 
50% 935 
90% 975 
ep 1100 
Aromatic Content w % 80 
Sulfur Content w % 1.75 
______________________________________ 
The oil-miscible catalyst compound may be added in amount to form a 
solution/mixture with the heavy oil typically about 0.01 w % to about 0.04 
w %, preferably about 0.01 w % to about 0.03 w %, say about 0.02 w %. The 
oil-miscible catalyst compound may be added to the heavy oil and stored 
and used in the form of the solution or mixture formed. When this is added 
to the charge hydrocarbon oil, the amount added may be about 5 w % to 
about 20 w %, preferably about 15 w %, say about 13 w % of 
solution/mixture which will provide the about 10 to about 60 wppm of metal 
desired to effect the results noted previously. Typically, the 
oil-miscible catalyst compound is added continuously, for example as part 
of the charge hydrocarbon. However this does not exclude the addition of 
the oil-miscible catalyst compound as a separate feed stream or in a batch 
wise manner so as to maintain a fixed level of catalyst compound in the 
hydroconversion reaction. The oil-miscible catalyst compound may be added 
at any stage of the hydroconversion reaction, preferably during the first 
stage of a multi stage reaction. 
Activation of the oil-miscible catalyst compound may be effected either by 
pre-treatment (prior to hydroconversion) or in situ (during 
hydroconversion). It is preferred to effect activation in situ in the 
presence of the hydrogenation catalyst to achieve a highly dispersed 
catalytic species. 
Activation may be carried out by adding metal catalyst compound (in amount 
to provide desired metal content) to charge hydrocarbon at about 
60.degree. F. to about 300.degree. F., say about 200.degree. F. The 
mixture is activated by heating to about 400.degree. F. to about 
835.degree. F., typically about 500.degree. F. to about 700.degree. F., 
say about 600.degree. F. at partial pressure of hydrogen of about 500 to 
about 5000 psig, typically about 1000 to about 3000 psig, say about 2000 
psig and at partial pressure of a gaseous mercaptan of about 5 to about 
500 psig, typically about 10 to about 300 psig, say about 50 psig. Total 
pressure may be about 500 to about 5500 psig, typically about 1000 to 
about 3300 psig, say about 2650 psig. Commonly the gas-may contain about 
40 to about 99v %, typically about 90 to about 99v %, say about 98v % 
hydrogen and about 1 to about 10v %, say about 2v % mercaptan such as 
hydrogen sulfide. Time of activation may be about 1 to about 12, typically 
about 2 to about 6, say about 3 hours. In some cases, activation may occur 
at temperature which is lower than the temperature of conversion. 
The mercaptans which may be employed may include one or more of the 
following including hydrogen sulfide, aliphatic mercaptans, typified by 
methyl mercaptan, lauryl mercaptan, etc. aromatic mercaptans; dimethyl 
disulfide, carbon disulfide, etc. It is believed that the mercaptans at 
least partially decompose during the activation process. It is not clear 
why this treatment activates the metal catalyst compound. It may be 
possible that the activity is generated as a result of metal sulfides 
formed during the treatment. When the sulfur content of the charge 
hydrocarbon is above about 2 w %, it may not be necessary to add a 
mercaptan during activation i.e. hydrodesulfurization of the charge may 
provide enough mercaptan to properly activate (i.e. sulfide) the 
oil-miscible decomposable catalyst. 
It is possible to activate the oil-miscible metal catalyst compound in the 
solution/mixture with the heavy aromatic oil. Activation may be effected 
under the same conditions as are used when activation is carried out in 
the charge stream. The compatible oil containing the now activated metal 
may be admitted to the charge stream in amount sufficient to provide 
therein activated oil-miscible metal catalyst compound in desired amount. 
In still another embodiment, activation may be carried out by subjecting 
the charge hydrocarbon oil containing the oil-miscible metal catalyst 
compound to hydroconversion conditions including temperature of about 
700.degree. F. to about 850.degree. F., preferably about 750.degree. F. to 
about 810.degree. F., say about 800.degree. F. at hydrogen partial 
pressure of about 500 to about 5000 psig, preferably about 1500 to about 
2000 psig, say 2000 psig, in the presence of a mercaptan but in the 
absence of heterogeneous hydroconversion catalyst. 
In yet a third embodiment activation may be carried out by subjecting the 
charge hydrocarbon oil containing the oil-miscible catalyst compound to 
hydroconversion conditions including temperature of about 700.degree. F. 
to about 850.degree. F., preferably about 750.degree. F. to about 
810.degree. F. say 800.degree. F. at hydrogen partial pressure of about 
500 to 5,000 psig, preferably about 1,500 to about 2,000 psig, say 2,000 
psig, in the presence of mercaptan but in the absence of heterogeneous 
hydroconversion catalyst. 
In yet another embodiment, activation may be carried out during 
hydroconversion in the presence of the heterogeneous, hydroconversion 
catalyst, hydrogen and mercaptan. 
Hydroconversion is carried out in the presence of solid heterogeneous 
catalyst containing, as a hydrogenating component, a metal of Group IV-B, 
V-B, VI-B, VII-B, or VIII on a support which may typically contain carbon 
or an oxide of aluminum, silicon, titanium, magnesium, or zirconium. 
Preferably the catalyst may contain a metal of Group VI-B and 
VIII--typically nickel and molybdenum. When the metal is a Group IV-B 
metal, it may be titanium (Ti) or zirconium (Zr). When the metal is a 
Group V-B metal, it may be vanadium (V), niobium (Nb), or tantalum (Ta). 
When the metal is a Group VI-B metal, it may be chromium (Cr), molybdenum 
(Mo), or tungsten (W). When the metal is a Group VII-B metal, it may be 
manganese (Mn) or rhenium (Re). When the metal is a Group VIII metal, it 
may be a non-noble metal such as iron (Fe), cobalt (Co), or nickel (Ni) or 
a noble metal such as ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium 
(Os), iridium. (Ir), or platinum (Pt). 
The solid heterogeneous catalyst may also contain, as a promoter, a metal 
of Groups I-A, I-B, II-A, II-B, or V-A. When the promoter is a metal of 
Group I-A, it may preferably be sodium (Na) or potassium (K). When the 
promoter is a metal of Group IB, it may preferably be copper (Cu). When 
the promoter is a metal of Group II-A, it may be beryllium (Be), magnesium 
(Mg), calcium (Ca), strontium (Sr), barium (Ba), or radium (Ra). When the 
promoter is a metal of Group II-B, it may be zinc (Zn), cadmium (Cd), or 
mercury (Hg). When the promoter is a metal of Group IV-B, it may be 
titanium (Ti), zirconium (Zr), or hafnium, (Hf). When the promoter is a 
metal of Group V-A, it may preferably be arsenic (As), antimony (Sb), or 
bismuth (Bi). 
The hydrogenating metal may be loaded onto the solid heterogeneous catalyst 
by immersing the catalyst support in solution (e.g. ammonium 
heptamolybdate) for about 2 to about 24 hours, say about 24 hours, 
followed by drying at about 60.degree. F. to about 300.degree. F., say 
about 200.degree. F. for about 1 to about 24 hours, say about 8 hours and 
calcining for about 1 to about 24 hours, say about 3 hours at about 
750.degree. F. to about 1100.degree. F., say about 930.degree. F. 
The promoter metal may preferably be loaded onto the solid heterogeneous 
catalyst by immersing the catalyst support (preferably bearing the 
calcined hydrogenating metal--although they may be added simultaneously or 
in any order) in solution (e.g. bismuth nitrate) for about 2 to about 24 
hours, say about 24 hours, followed by drying at about 60.degree. F. to 
about 300.degree. F., say about 200.degree. F. for about 1 to about 24 
hours, say about 3 hours, and calcining at about 570.degree. F. to about 
1100.degree. F., say about 750.degree. F. for about 1 to about 12 hours, 
say about 3 hours. 
The solid heterogeneous catalyst employed in the method of this invention 
may be characterized by a Total Pore Volume of about 0.2 to about 1.2 
cc/g, say about 0.77 cc/g; a surface area of about 50 to about 500 m.sup.2 
/g, say about 280 m.sup.2 /g. It is preferred that the pore structure of 
the solid heterogeneous catalyst be bi-modal. In one embodiment of the 
present invention, the solid heterogeneous catalyst has an approximate 
pore size distribution as follows: 
______________________________________ 
Pore Diameter (.ANG.) 
Pore Volume (cc/q) 
Typically 
______________________________________ 
30-100 0.15-0.8 0.42, 
100-1000 0.10-0.50 0.19 
1000-10,000 0.01-0.40 0.16 
______________________________________ 
In another embodiment, it may have an approximate pore size distribution as 
follows: 
______________________________________ 
Pore Diameter (.ANG.) 
Pore Volume (cc/q) 
Typically 
______________________________________ 
&gt;250 0.12-0.35 0.28 
&gt;500 0.11-0.29 0.21 
&gt;1500 0.08-0.26 0.19 
&gt;4000 0.04-0.18 0.11 
______________________________________ 
In yet a third embodiment the pore distribution may be approximately as 
follows: 
______________________________________ 
Pore Diameter (.ANG.) 
Pore Volume (%) 
Typically (%) 
______________________________________ 
0 to 50 35-55 43-47 
50 to 100 5-25 14"18 
100 to 150 3-10 6-8 
greater than 150 
25-45 30-34 
______________________________________ 
And in still another embodiment the pore distribution may be approximately 
as follows: 
______________________________________ 
Pore Diameter (.ANG.) 
Pore Volume (%) 
Typically (%) 
______________________________________ 
0 to 50 42-46 45.0 
50 to 100 11-17 16.0 
100 to 150 6-7 6.7 
greater than 150 
31-40 32.0 
______________________________________ 
The pore volume distribution of the solid heterogeneous catalyst utilized 
in the present invention is very different than that utilized in previous 
hydroconversion systems in which a oil-miscible catalyst compound is used. 
An exemplary sample of values are compared with the heterogeneous catalyst 
of the present invention in Table VI below. 
TABLE IV 
______________________________________ 
Pore Diameter (.ANG.) 
U.S. Pat. No. 
0-50 50-100 100-150 
150+ 
______________________________________ 
4,306,965 1.5 65.3 32.2 1.0 % 
1.3 53.8 43.6 1.3 PORE 
43.9 53.3 1.1 1.1 VOL- 
4,181,602 0-10 30-80 0-10 UME 
4,224,144 43.9 53.3 1.1 1.7 
1.5 65.3 32.2 1.0 
1.3 53.8 43.6 1.3 
20-30 30-70 0-20 0-10 
4,297,242 4.9 75 19.6 0.5 
7.5 64.4 16.2 11.9 
12.1 84.4 0.8 2.1 
4.9 58.0 33.8 2.1 
38 59.5 1.2 1.3 
5.4 69.5 24.0 1.1 
4.0 61.8 33.0 1.2 
7.2 59.7 28.4 4.7 
Embodiments of the 
Present Invention 
35-55 5-25 3-10 25-45 
43-47 14-18 6-8 30-34 
42-46 11-17 6-7 31-40 
45.0 16.0 6.7 32.0 
______________________________________ 
Upon review of the above, one of ordinary skill in the art should readily 
recognize that the catalyst of the present invention has a very different 
pore volume distribution than those previously found to be suitable. In 
particular, there is a considerable difference in the percentage of pore 
volume that is attributable to pores greater than 150 angstroms. It has 
been unexpectedly found that the combination of the heterogeneous 
catalysts and the oil-miscible catalyst compounds disclosed herein give 
many unexpected advantages over previously disclosed catalyst systems. 
These advantages include a reduction of the formation of sediment in the 
product, increased conversion of 1000.degree. F.+material in the charge 
hydrocarbon, reduction in the amount of energy required to operate the 
ebullated bed hydroconvertion reaction, and increased stability in the 
ebullated bed, amongst many others that should be apparent to one of 
ordinary skill in the art. 
The solid heterogeneous catalyst typically may contain about 4 to about 30 
w %, say 9.5 w % Mo, about 0 to about 6 w %, say 3.1 w % Ni and about 0 to 
about 6 w %, say 3.1 w % of promoter metal e.g. bismuth. Liquid hourly 
space velocity (LHSV) in the hydroconversion reactors may be about 0.1 to 
about 2, say 0.7. Preferably the heterogeneous catalyst may be employed in 
the form of extrudates of diameter of about 0.7 to about 6.5 mm, say 1 mm 
and of length of about 0.2 to about 25 mm, say 5 mm. 
On a commercial scale, hydroconversion may be carried out in one or more 
ebullated bed reactors. One of skill in the art should appreciate that 
such ebullated bed reactors may be 5 to 20 feet in diameter and greater 
than 50 feet in height, and utilize hundreds, if not thousands of pounds 
of catalyst. Further, one of skill in the art should recognize that such 
reactors are very different from small laboratory scale stirred bed batch 
reactors and that the effect of scaling-up from the laboratory scale to 
the ebullated bed reactors described herein is inherently unpredictable. 
Effluent from hydroconversion is typically characterized by an increase in 
the content of liquids boiling below 1000.degree. F. Commonly the w % 
conversion of the 1000.degree. F.+boiling material is about 30% to about 
90%, say 67% which is typically about 5% to about 25%, say 12% better than 
is attained by the prior art techniques. As the term is used herein, 
conversion is calculated as the percentage of 1000.degree. F.+material in 
the feed minus the percentage of 1000.degree. F.+material in the Product 
divided by the percentage of 1000.degree. F.+material in the feed. 
One aspect of this invention is that it permits attainment of improved 
removal of sulfur (HDS Conversion), of nitrogen (HDN Conversion), and of 
metals (HDNi and HDV Conversion). Typically HDS Conversion may be about 30 
to about 90%, say 65% which is about 1% to about 10%, say 4% higher than 
the control runs. Typically HDN Conversion may be about 20% to about 60%, 
say 45% which is about 1% to about 10%, say 4% higher than control runs. 
Typically HDNi plus HDV Conversion may be about 70% to about 99%, say 90% 
which is about 5% to about 20%, say 13% higher than control runs. 
The following examples are included to demonstrate preferred embodiments of 
the invention. It should be appreciated by those of skill in the art that 
the techniques disclosed in the examples which follow represent techniques 
discovered by the inventors to function well in the practice of the 
invention, and thus can be considered to constitute preferred modes for 
its practice. However, those of skill in the art should, in light of the 
present disclosure, appreciate that many changes can be made in the 
specific embodiments which are disclosed and still obtain a like or 
similar result without departing from the spirit and scope of the 
invention. 
EXAMPLES 1-13 
In these Examples oil-miscible catalyst was molybdenum naphthenate in 
amount to provide about 30 wppm, molybdenum in the feed to the unit in 
Example 1-9: and as noted in the Table below for Examples 10-13. 
The feedstock was a blend of (i) vacuum resid, (ii) visbreaker bottoms, 
(iii) vacuum bottoms recycle (iv) and heavy cycle gas oil having the 
following properties: 
TABLE V 
______________________________________ 
Property Value 
______________________________________ 
API Gravity 4.8 
&gt;1000.degree. F. w % 88 
Composition w % Leco 
C 75 
H 10.5 
N 0.54 
S 5.0 
Alcor Microcarbon Residue (MCR) % 
22.3 
n-C.sub.7 insolubles w % 
13.5 
Metals Content wppm 
Ni 41 
V 17 
Fe 15.0 
Cr 0.2 
Na 5.5 
Kinematic Visc. Cst (ASTM D-445) 
@ 212.degree. F. 2368 
@ 250.degree. F. 665 
@ 300.degree. F. 117 
______________________________________ 
The feedstock was injected into the reaction zone through a feed heater and 
injection port. The heavy cycle gas oil containing the oil-miscible 
molybdenum naphthenate was charged from a separate charge vessel into the 
reactor. Both the feedstock and the heavy cycle gas oil containing the 
oil-miscible catalyst compound contacted the ebullated heterogeneous 
catalyst at about 780.degree. F. and about 2500 psig and about 0.39 LHSV. 
Hydrogen feed was about 4300 SCFB of about 92% hydrogen. 
Supported catalyst in the ebullated bed was cylinders (about 0.8 mm 
diameter and about 5 mm length) of commercially available catalyst 
containing about 2.83 w % nickel and about 8.75 w % molybdenum on alumina. 
Surface area was about 285.2 m.sup.2 /g and Total Pore Volume was about 
0.78 cc/g. Pore Size Distribution was 0.28 cc/g&gt;250 A; 0.21 cc/g&gt;500 A; 
0.19 cc/g&gt;1550 A; 0.11 cc/g&gt;4000 A. 
The catalyst was activated in situ during hydroconversion. 
During hydroconversion, the oil-miscible catalyst (in the heavy cycle gas 
oil) was pulsed in so that the effect of addition may be observed. The 
duration of each pulse (i.e. the time during which the oil-miscible 
catalyst was added) was about 24 hours during which molybdenum (as 
molybdenum naphthenate) was added to yield a concentration of about 30 ppm 
of molybdenum based on fresh feed. At the beginning of each pulsed 
addition, the sediment content (w %) of the product decreased; and over 
about 1 to about 6 days, it rose again during a decay period. A further 
pulse over about 24 hours was admitted and then a similar decay period 
ensued. 
A base line (prior to catalyst addition) analysis of conversion (vol %) and 
sediment (w %) was taken (Example I*); and similar determinations were 
made at the end of each pulsed addition and at the end of each decay 
period of about 1 to about 6 days. 
In Example 10, the molybdenum (as molybdenum naphthenate) was admitted at a 
constant rate over about 9 days to yield a molybdenum concentration of 
about 15 wppm. Then the concentration of molybdenum was increased to about 
30 wppm. (for Example 11) and maintained at the new increased level for 
nine additional days. Similar increases are made after subsequent nine day 
periods (for Examples 12 and 13) to attain the desired level of 
molybdenum. During each nine day run, conversion, sediment, and power 
consumption are measured. 
TABLE VI 
______________________________________ 
Example 
Pulsed Conversion 
Additions Avg Max Max Delta 
Sediment 
______________________________________ 
1 54.6 0.0923 
2 56.5 59.9 5.3 
3 57.8 
4 59.2 60.1 5.5 0.0326 
5 54.3 
6 58.1 58.8 4.2 0.0342 
7 54.4 
8 56.9 59.7 5.1 0.0430 
9 55.2 
______________________________________ 
TABLE VII 
______________________________________ 
Energy Con 
Conversion % 
Wppm Max KBTU/ Baseline 
Exampl 
additive 
Avg Max Delta 
Sediment 
BBL Powercon 
______________________________________ 
1 0 54.6 0.0923 1200 100 
10 15 54.9 56.5 1.9 0.0356 1079 90 
11 30 57.1 60.1 5.5 0.0481 1047 88 
12 45 60.8 61.2 6.2 0.0944 1006 84 
13 60 61.5 61.9 6.9 0.0800 1025 80 
______________________________________ 
From Table VII above, it should be apparent to one of ordinary skill in the 
art that a minimum amount of sediment in the product was unexpectedly 
attained at about 15 wppm of added oil-miscible catalyst. This low level 
of sediment was attained at a Conversion (54.9v % in Example 10) which was 
better than the baseline conversion (54.6v %) attained with no addition of 
oil-miscible catalyst in Example I. In addition the total energy utilized 
to maintain the hydroconvertion reaction conditions was reduced by about 
90% that in the absence of oil-miscible catalyst. It should also be noted 
that the stability of the ebullated bed has increase upon the addition of 
the oil-miscible catalyst compound. This was shown in FIG. 1b which shows 
that the ebullated bed was much more stable than in the absence of 
oil-miscible catalyst compound (FIG. 1a). 
In further view of the above, one of ordinary skill in the art should 
notice that conversion reached a maximum (61.9v % in Example 13) at about 
60 wppm of added oil-miscible catalyst. This high level of conversion was 
attained at a sediment level (0.0800 w %) which represents an improvement 
over the baseline of Example 1 (of 0.0923). In addition the energy 
required to maintain hydroconversion reaction conditions was reduced to an 
amount 80% that required to maintain the conditions in the absence of the 
oil-miscible catalyst compound. However, it should be noted that the 
ebullation rate was increased from about 25.9 gph to about 33.6 gph to 
maintain a stable catalyst bed when the amount of oil-miscible catalyst 
was increased so as to achieve an about 60 wppm metal constant. It is 
believed that the increased deposition of molybdenum on the surface of the 
heterogeneous catalyst resulted in the need to increase ebulation rate. 
Levels greater than about 60 wppm were not tested because of the extreme 
danger of creating an unstable ebullated bed. 
EXAMPLES 14-17 
In these Examples oil-miscible catalyst compound was molybdenum naphthenate 
in amount to provide about 30 wppm, molybdenum in the feed to the unit in 
Example 15 and 17: and was absent in Examples 14 and 16. The solid 
heterogeneous catalyst utilized in Examples 14 and 15 was the same as that 
noted above in Examples 1-13. The solid heterogeneous catalyst utilized in 
examples 16 and 17 had a pore volume distribution as follows: 12.5% for 
pores less than 100 .ANG.; 73% for pores between 100 and 160 .ANG.; and, 
14.5% for pores greater than 250 .ANG.. The results are presented below in 
Table VIII. 
TABLE VIII 
______________________________________ 
Example No. 14 15 16 17 
______________________________________ 
Oil-miscible Catalyst Injection 
No Yes No Yes 
#1 Reactor Temp. (.degree.F.) 
780 780 775 775 
#2 Reactor Temp. (.degree.F.) 
790 790 785 785 
Charge Hydrocarbon Space 
0.41 0.41 0.41 0.41 
Velocity (V/Hr/V) 
H.sub.2 Partial Pressure (psia) 
2060 2060 1940 1940 
Catalyst Age (bbl/lb) 
2.05 2.05 2.05 2.05 
IP Sediment in Product (wt %) 
0.12 0.048 0.28 0.13 
Conversion (vol %) 
54.8 59.8 57.7 55.3 
HDS (wt %) 69.2 68.5 75.7 74.4 
______________________________________ 
Given the above, one of ordinary skill in the art should notice that the 
presence of oil-miscible catalyst compound reduces the amount of sediment 
in the product to a lesser extent when the heterogeneous catalyst does not 
have the pore distributions disclosed herein. It also should be noticed 
that the level of conversion in Example 16 (57.7) actually decreased in 
the presence of oil-miscible catalyst Example 17 (55.3). This is in direct 
contrast with that shown by the heterogeneous catalyst utilized in the 
present invention which shows an increase in conversion. Lastly in both 
cases the level of hydrodesulfurization (HDS) decreased in the presence of 
oil-miscible catalyst. However, the decrease is smaller, when measured as 
a percentage of value obtained in the absence of oil-miscible catalyst 
compound, for the heterogeneous catalyst of the present invention (about 
1.4%) as opposed to the other catalyst (about 1.7%). 
In summary, it is possible to obtain an unexpected improvement in operation 
(to improve those factors of interest in a particular case) by use of 
specific quantities of additive oil-miscible catalyst in combination with 
a solid heterogeneous catalyst as described herein. 
While the compositions and methods of this invention have been described in 
terms of preferred embodiments, it will be apparent to those of skill in 
the art that variations may be applied to the process described herein 
without departing from the concept, spirit and scope of the invention. All 
such similar substitutes and modifications apparent to those skilled in 
the art are deemed to be within the spirit, scope and concept of the 
invention as it is set out in the following claims.