Hydroconversion process employing a phosphorus loaded NiMo catalyst with specified pore size distribution

A process for converting a charge of heavy hydrocarbons containing components boiling above 1000.degree. F. to a product containing a decreased content of components boiling above 1000.degree. F. and decreased sediment content employing a NiMo catalyst having a specified pore distribution under hydroconversion conditions is disclosed. The process includes contacting the charge of heavy hydrocarbon with hydrogen in the presence of a heterogeneous catalyst supported on alumina and containing .ltoreq.2.5 wt % of silica and bearing 2.2 to 6 wt % of a Group VIII metal oxide, 7 to 24 wt % of a Group VIB metal oxide and 0.3 to 2 wt % of a loaded phosphorus oxide, the phosphorous being loaded onto the catalyst as aqueous phosphoric acid. The catalyst also may be characterized by having a Total Surface Area of 175 to 205 m.sup.2 /g, a Total Pore Volume of 0.82 to 0.98 cc/g, and a Pore Diameter Distribution wherein 29.6 to 33.0% of the Total Pore Volume is present as macropores of diameter greater than 250 .ANG., 67.0 to 70.4% of the Total Pore Volume is present as micropores of diameter less than 250 .ANG., .gtoreq.65% of the micropore volume is present as micropores of diameter .+-.25 .ANG. about a pore mode by volume of 110 to 130 .ANG., less than 0.05 cc/g of micropore volume is present in micropores with diameters less than 80 .ANG..

FIELD OF THE INVENTION 
This invention relates to a process for hydrotreating a hydrocarbon feed. 
More particularly it relates to a hydroconversion process employing a 
catalyst with a specified pore size distribution which achieves improved 
levels of hydroconversion of feedstock components having a boiling point 
greater than 1000.degree. F. to products having a boiling point less than 
1000.degree. F., improved hydrodesulfurization, particularly improved 
sulfur removal from the unconverted 1000.degree. F. products, and reduced 
sediment make and which allows operations at higher temperatures. 
BACKGROUND OF THE INVENTION 
As is well known to those skilled in the art, it is desirable to convert 
heavy hydrocarbons, such as those having a boiling point above about 
1000.degree. F., into lighter hydrocarbons which are characterized by 
higher economic value. It is desirable to treat hydrocarbon feedstocks, 
particularly petroleum residue, to achieve other goals including 
hydrodesulfurization (HDS), carbon residue reduction (CRR), and 
hydrodemetallation (HDM)--the latter particularly including removal of 
nickel compounds (HDNi) and vanadium compounds (HDV). 
These processes typically employ hydrotreating catalysts with specified 
ranges of pores having relatively small diameters (i.e. micropores, herein 
defined as pores having diameters less than 250 .ANG.) and pores having 
relatively large diameters (i.e. macropores, herein defined as pores 
having diameters greater than 250 .ANG.). 
One approach to developing improved catalysts for petroleum resid 
processing has involved enlarging the micropore diameters of essentially 
monomodal catalysts (having no significant macroporosities) to overcome 
diffusion limitations. Catalysts which are essentially monomodal with 
small micropore diameters and low macroporosities designed for improved 
petroleum resid HDS include for example, those disclosed in U.S. Pat. Nos. 
4,738,944; 4,652,545; 4,341,625; 4,309,278; 4,306,965; 4,297,242; 
4,066,574; 4,051,021; 4,048,060 (first-stage catalyst); U.S. Pat. Nos. 
3,770,617; and 3,692,698, discussed herein. Essentially monomodal 
catalysts with larger micropore diameters and low macroporosities designed 
for improved petroleum resid HDM are typified by those disclosed in U.S. 
Pat. Nos. 4,328,127; 4,082,695; 4,048,060 (second-stage catalyst); and 
U.S. Pat. No. 3,876,523, discussed herein. 
U.S. Pat. No. 4,738,944 (Robinson et al.) discloses a catalyst composition 
useful in the hydrotreatment of hydrocarbon oils, the catalyst containing 
nickel and phosphorus and about 19-21.5% Mo (calculated as the oxide) on a 
porous refractory oxide, having a narrow pore size distribution wherein at 
least 10% of the Total Pore Volume is in pores having diameters less than 
70 .ANG., at least 75% of the Total Pore Volume is in pores having 
diameters between 50-110 .ANG., at least 60% of the Total Pore Volume is 
in pores having diameters within about 20 .ANG. above and below the 
average pore diameter, and at most 25% of the Total Pore Volume, most 
preferably less than 10% of the Total Pore Volume is in pores having 
diameters greater than 110 .ANG.. 
U.S. Pat. No. 4,652,545 (Lindsley et al.) discloses a catalyst composition 
useful in the hydroconversion of heavy oils, the catalyst containing 
0.5-5% Ni or Co and 1.8-18% Mo (calculated as the oxides) on a porous 
alumina support, having 15-30% of the Ni or Co in an acid extractable 
form, and further characterized by having a Total Pore Volume (TPV) of 
0.5-1.5 cc/g with a pore diameter distribution such that (i) at least 70% 
TPV is in pores having 80-120 .ANG. diameters, (ii) less than 0.03 cc/g of 
TPV is in pores having diameters of less than 80 .ANG., and (iii) 0.05-0.1 
cc/g of TPV is in pores having diameters of greater than 120 .ANG.. 
U.S. Pat. No. 4,341,625 (Tamm) discloses a process for hydrodesulfurizing a 
metal-containing hydrocarbon feedstock which comprises contacting the 
feedstock with a catalyst comprising at least one hydrogenation agent 
(i.e. Group VIB or Group VIII metal, or combinations thereof) on a porous 
support, the catalyst being further characterized by having a TPV of 
0.5-1.1 cc/g with at least 70% TPV in pores having diameters of 80-150 
.ANG. and less than 3% TPV in pores having diameters greater than 1000 
.ANG.. 
U.S. Pat. No. 4,309,278 (Sawyer) discloses a process for the 
hydroconversion of a hydrocarbon feedstock comprising contacting the 
feedstock with hydrogen and a catalyst in a fixed bed, moving bed, 
ebullated bed, slurry, disperse phase, or fluidized bed reactor, where the 
catalyst comprises a hydrogenation component (i.e. Group VIB or Group VIII 
metal) on a porous support, and is further characterized by having a BET 
Surface Area of 250-450 m.sup.2 /g, a BET Pore Volume of 0.9-2.0 cc/g with 
no more than 0.05-0.20 cc/g of TPV in pores having diameters of greater 
than 400 .ANG.. 
U.S. Pat. No. 4,306,965 (Hensley, Jr. et al.) discloses a process for the 
hydrotreatment of a hydrocarbon stream comprising contacting the stream 
with hydrogen and a catalyst, the catalyst comprising chromium, 
molybdenum, and at least one Group VIII metal on a porous support, further 
characterized by having a TPV of 0.4-0.8 cc/g with 0-50% TPV in pores 
having diameters smaller than 50 .ANG., 30-80% TPV in pores having 
diameters of 50-100 .ANG., 0-50% TPV in pores having diameters of 100-150 
.ANG., and 0-20% TPV in pores having diameters greater than 150 .ANG.. 
U.S. Pat. No. 4,297,242 (Hensley, Jr. et al.) discloses a two-stage process 
for the catalytic hydrotreatment of hydrocarbon streams containing metal 
and sulfur compounds, the process comprises: (i) first contacting the 
feedstock with hydrogen and a demetallation catalyst comprising a Group 
VIB and/or Group VIII metal; and (ii) thereafter reacting the effluent 
with a catalyst consisting essentially of at least one Group VIB metal on 
a porous support, and having a TPV of 0.4-0.9 cc/g and a pore size 
distribution such that pores having diameters of 50-80 .ANG. constitute 
less than 40% TPV, pores having diameters of 80-100 .ANG. constitute 
15-65% TPV, pores having diameters of 100-130 .ANG.constitute 10-50% TPV, 
and pores having diameters of greater than 130 .ANG. less than 15% TPV. 
U.S. Pat. No. 4,066,574 (Tamm) discloses a catalyst composition useful in 
the hydrodesulfurization of a hydrocarbon feedstock containing 
organometallic compounds, the catalyst comprising Group VIB and Group VIII 
metal components on a porous support, and having a TPV of 0.5-1.1 cc/g 
with a pore diameter distribution such that at least 70% TPV is in pores 
of diameters of 80-150 .ANG. and less than 3% TPV is in pores having 
diameters greater than 1000 .ANG.. 
U.S. Pat. No. 4,051,021 (Hamner) discloses a catalytic process for the 
hydrodesulfurization of a hydrocarbon feed which comprises contacting the 
feed with hydrogen and a catalyst, the catalyst comprising a Group VIB and 
Group VIII metal on a porous support, having a TPV of 0.3-1.0 cc/g with a 
pore diameter distribution such that greater than 50% TPV is in pores of 
diameters of 70-160 .ANG., and pores having diameters below 70 .ANG. and 
above 160 .ANG. are minimized. 
U.S. Pat. No. 4,048,060 (Riley) discloses a two-stage process for 
hydrodesulfurizing a heavy hydrocarbon feed which comprises: (i) 
contacting the feed with hydrogen and a first catalyst to produce a first 
hydrodesulfurized hydrocarbon product, the first catalyst comprising a 
Group VIB and Group VIII metal on a porous support and having a mean pore 
diameter of 30-60 .ANG.; and (ii) contacting the first hydrodesulfurized 
hydrocarbon product with hydrogen and a second catalyst under 
hydrodesulfurization conditions, the second catalyst comprising a Group 
VIB and Group VIII metal on a porous support, further characterized by 
having a TPV of 0.45-1.50 cc/g with 0-0.5 cc/g of TPV in pores having 
diameters greater than 200 .ANG., 0-0.05 cc/g of TPV in pores having 
diameters below 120 .ANG., and at least 75% TPV in pores having diameters 
.+-.10 .ANG. of a mean pore diameter of 140-190 .ANG.. 
U.S. Pat. No. 3,770,617 (Riley et al.) discloses a process for the 
desulfurization of a petroleum hydrocarbon feed comprising contacting the 
feed with hydrogen and a catalyst, the catalyst comprising a Group VIB or 
Group VIII metal on a porous support having greater than 50% TPV in pores 
of 30-80 .ANG., less than 4% TPV in pores having diameters 200-2000 .ANG., 
and at least 3% TPV in pores having diameters greater than 2000 .ANG.. 
U.S. Pat. No. 3,692,698 (Riley et al.) discloses a catalyst useful in 
hydroprocessing of heavy feed stocks, the catalyst comprising a mixture of 
Group VIB and Group VIII metals on a porous support having a pore size 
distribution such that a major portion of its TPV is in pores of diameters 
ranging from 30-80 .ANG., less than 4% TPV is in pores of diameters of 
200-2000 .ANG., and at least 3% TPV is in pores of diameters greater than 
2000 .ANG.. 
U.S. Pat. No. 4,328,127 (Angevine et al.) discloses a catalyst composition 
for use in the hydrodemetallation-desulfurization of residual petroleum 
oils, the catalyst comprising a hydrogenating component (i.e. Group VIB or 
Group VIII metal, or combinations thereof) on a porous support, further 
characterized by having a is TPV of 0.45-1.5 cc/g with 40-75% TPV in pores 
having diameters of 150-200 .ANG., and up to 5% TPV in pores having 
diameters of greater than 500 .ANG.. 
U.S. Pat. No. 4,082,695 (Rosinski et al.) discloses a catalyst for use in 
the demetallation and desulfurization of petroleum oils, the catalyst 
comprising a hydrogenating component (i.e. cobalt and molybdenum) on a 
porous support, and having a surface area of 110-150 m.sup.2 /g and a pore 
size distribution such that at least 60% of TPV is in pores having 
diameters of 100-200 .ANG. and not less than 5% TPV is in pores having 
diameters greater than 500 .ANG.. 
U.S. Pat. No. 3,876,523 (Rosinski et al.) discloses a process for the 
demetallizing and desulfurizing of residual petroleum oil comprising 
contacting the oil with hydrogen and a catalyst, the catalyst comprising a 
Group VIB and Group VIII metal on a porous support having a pore size 
distribution such that greater than 60% TPV is in pores having diameters 
of 100-200 .ANG., at least 5% TPV is in pores having diameters greater 
than 500 .ANG., 10% TPV or less is in pores having diameters less than 40 
.ANG., and the surface area of the catalyst is 40-150 m.sup.2 /g. 
Early petroleum distillate hydrotreating catalysts generally were monomodal 
catalysts with very small micropore diameters (less than say 100 .ANG.) 
and rather broad pore size distributions. First generation petroleum resid 
hydrotreating catalysts were developed by introducing a large amount of 
macroporosity into a distillate hydrotreating catalyst pore structure to 
overcome the diffusion resistance of large molecules. Such catalysts, 
which are considered fully bimodal HDS/HDM catalysts, are typified by U.S. 
Pat. Nos. 4,746,419, 4,395,328, 4,395,329, and 4,089,774, discussed 
herein. 
U.S. Pat. No. 4,746,419 (Peck et al.) discloses an improved hydroconversion 
process for the hydroconversion of heavy hydrocarbon feedstocks containing 
asphaltenes, metals, and sulfur compounds, which process minimizes the 
production of carbonaceous insoluble solids and catalyst attrition rates. 
Peck et al. employs a catalyst which has 0.1 to 0.3 cc/g of its pore 
volume in pores with diameters greater than 1,200 .ANG. and no more than 
0.1 cc/g of its pore volume in pores having diameters greater than 4,000 
.ANG.. The instant invention will be distinguished from Peck, et al. (U.S. 
Pat. No. 4,746,419) in that Peck discloses only features of macropore size 
distribution useful for minimizing the production of carbonaceous 
insoluble solids and does not disclose a pore size distribution which 
would provide additional hydroconversion and hydrodesulfurization 
activities, whereas, the catalysts of the instant invention require a 
unique pore size distribution in order to provide additional 
hydroconversion of feedstock components having a boiling point greater 
than 1000.degree. F. to products having a boiling point less than 
1000.degree. F. and additional hydrodesulfurization. The instant invention 
gives improved levels of hydroconversion of feedstock components having a 
boiling point greater than 1000.degree. F. to products having a boiling 
point less than 1000.degree. F., improved hydrodesulfurization, 
particularly improved sulfur removal from the unconverted 1000.degree. F.+ 
boiling point products, and reduced sediment make at the same operating 
conditions and allows operations at higher temperatures compared to 
operations with a commercial vacuum resid hydroconversion catalyst having 
a macropore size distribution which satisfies the requirements of Peck, et 
al. (U.S. Pat. No. 4,746,419). 
U.S. Pat. No. 4,395,328 (Hensley, Jr. et al.) discloses process for the 
hydroconversion of a hydrocarbon stream containing asphaltenes and a 
substantial amount of metals, comprising contacting the stream (in the 
presence of hydrogen) with a catalyst present in one or more fixed or 
ebullating beds, the catalyst comprising at least one metal which may be a 
Group VIB or Group VIII metal, an oxide of phosphorus, and an alumina 
support, where the alumina support material initially had at least 0.8 
cc/g of TPV in pores having diameters of 0-1200 .ANG., at least 0.1 cc/g 
of TPV is in pores having diameters of 1200-50,000 .ANG., a surface area 
in the range of 140-190 m.sup.2 /g, and the support material was formed as 
a composite comprising alumina and one or more oxides of phosphorus into a 
shaped material and was thence heated with steam to increase the average 
pore diameter of the catalyst support material prior to impregnation with 
active metals. The instant invention is distinguished from Hensley, Jr., 
et al. in that the support of the instant invention does not contain one 
or more oxides of phosphorus, is not heated with steam to increase the 
average pore diameter, and requires a higher surface area of about 205-275 
m.sup.2 /g and there is a much more precise definition of pore volume 
distribution. 
U.S. Pat. No. 4,395,329 (Le Page et al.) discloses a hydrorefining process 
of a high metal-containing feedstock employing a catalyst containing 
alumina, a metal from group VI and a metal from the iron group, the 
catalyst having a Total Surface Area of 120-200 m.sup.2 /g, a Total Pore 
Volume of 0.8-1.2 cc/g, and a Pore Diameter Distribution whereby 0-10% of 
the Total Pore Volume is present as micropores with diameters less than 
100 .ANG., 35-60% of the Total Pore Volume is in pores with diameters of 
100-600 .ANG., and 35-55% of the Total Pore Volume is present as 
macropores of diameter greater than 600 .ANG.. The instant invention is 
distinguished from Le Page et al. (U.S. Pat. No. 4,395,329) in that Le 
Page et al. requires 35-55% of the TPV in pores with a diameter &gt;600 .ANG. 
and the catalysts of the instant invention have only about 21-27% of the 
PV in pores greater than 600 .ANG.. 
U.S. Pat. No. 4,089,774 (Oleck et al.) discloses a process for the 
demetallation and desulfurization of a hydrocarbon oil comprising 
contacting the oil with hydrogen and a catalyst, the catalyst comprising a 
Group VIB metal and an iron group metal (i.e. iron, cobalt, or nickel) on 
a porous support, and having a surface area of 125-210 m.sup.2 /g and TPV 
of 0.4-0.65 cc/g with at least 10% TPV in pores having diameters less than 
30 .ANG., at least 50% of pore volume accessible to mercury being in pores 
having diameters of 30-150 .ANG., and at least 16.6% of pores accessible 
to mercury being in pores having diameters greater than 300 .ANG.. The 
instant invention is distinguished from Oleck et al. (U.S. Pat. No. 
4,089,774) in that Oleck et al. requires a relatively low Total Pore 
Volume of only 0.4-0.65 cc/g, whereas, the catalysts of the instant 
invention require much higher Total Pore Volumes of 0.82-0.98 cc/g. 
U.S. Pat. No. 5,221,656, to Clark et al. discloses a hydroprocessing 
catalyst comprising at least one hydrogenation metal selected from the 
group consisting of the Group VIB metals and Group VIII metals deposited 
on an inorganic oxide support, said catalyst characterized by a surface 
area of greater than about 220 m.sup.2 /g, a pore volume of 0.23-0.31 cc/g 
in pores with radii greater than about 600 .ANG. (i.e., in pores with 
diameters greater than 1200 .ANG.), an average pore radius of about 30-70 
.ANG. in pores with radii less than about 600 .ANG. (i.e., an average pore 
diameter of about 60-140 .ANG. in pores with diameters less than about 
1200 .ANG.), and an incremental pore volume curve with a maximum at about 
20-50 .ANG. radius (i.e., at about 40-100 .ANG. diameter). In the instant 
invention, pores having a diameter greater than 1200 .ANG. are only about 
0.15-0.20 cc/g and the incremental pore volume curve has a maximum (i.e., 
Pore Mode) at 110-130 .ANG.. Also, reflective of the larger range of sizes 
of Pore Modes, the instant catalysts have much lower surface areas of 
175-205 m.sup.2 /g. 
A recent approach to developing improved catalysts for petroleum resid 
processing has involved the use of catalysts having micropore diameters 
intermediate between the above described monomodal HDS and HDM catalysts, 
as well as sufficient macroporosities so as to overcome the diffusion 
limitations for petroleum bottoms HDS (i. e., sulfur removal from 
hydrocarbon product of a hydrotreated petroleum resid having a boiling 
point greater than 1000.degree. F.) but limited macroporosities to limit 
poisoning of the interiors of the catalyst particles. Catalysts with 
micropore diameters intermediate between the above described monomodal HDS 
and HDM catalysts with limited macroporosities include those of U.S. Pat. 
Nos. 4,941,964, 5,047,142 and 5,399,259 and copending U.S. application 
Ser. No. 08/425,971 (D# 92,030-C1-D1), now U.S. Pat. No 5,545,602, which 
is a divisional of U.S. Pat. No. 5,435,908, discussed herein. 
U.S. Pat. No. 4,941,964 (to Texaco as assignee of Dai, et al.) discloses a 
process for the hydrotreatment of a sulfur- and metal-containing feed 
which comprises contacting said feed with hydrogen and a catalyst in a 
manner such that the catalyst is maintained at isothermal conditions and 
is exposed to a uniform quality of feed, the catalyst comprising an oxide 
of a Group VIII metal, an oxide of a Group VIB metal and 0-2.0 weight % of 
an oxide of phosphorus on a porous alumina support, having a surface area 
of 150-210 m.sup.2 /g and a Total Pore Volume (TPV) of 0.50-0.75 cc/g such 
that 70-85% TPV is in pores having diameters of 100-160 .ANG. and 
5.5-22.0% TPV is in pores having diameters of greater than 250 .ANG.. 
U.S. Pat. No. 5,047,142 (to Texaco as assignee of Sherwood, Jr., et al.), 
discloses a catalyst composition useful in the hydroprocessing of a sulfur 
and metal-containing feedstock comprising an oxide of nickel or cobalt and 
an oxide of molybdenum on a porous alumina support in such a manner that 
the molybdenum gradient of the catalyst has a value of less than 6.0 and 
15-30% of the nickel or cobalt is in an acid extractable form, having a 
surface area of 150-210 m.sup.2 /g, a Total Pore Volume (TPV) of 0.50-0.75 
cc/g, and a pore size distribution such that less than 25% TPV is in pores 
having diameters less than 100 .ANG., 70.0-85.0% TPV is in pores having 
diameters of 100-160 .ANG. and 1.0-15.0% TPV is in pores having diameters 
greater than 250 .ANG.. 
U.S. Pat. No. 5,399,259 (to Texaco as assignee of Dai, et al.) discloses a 
process for the hydrotreatment of a sulfur-, metals- and 
asphaltenes-containing feed which comprises contacting said feed with 
hydrogen and a catalyst in a manner such that the catalyst is maintained 
at isothermal conditions and is exposed to a uniform quality of feed, the 
catalyst comprising 3-6 wt % of an oxide of a Group VIII metal, 14.5-24 wt 
% of an oxide of a Group VIB metal and 0-6 wt % of an oxide of phosphorus 
on a porous alumina support, having a surface area of 165-230 m.sup.2 /g 
and a Total Pore Volume (TPV) of 0.5-0.8 cc/g such that less than 5% of 
TPV is in pores with diameters less than about 80 .ANG., at least 65% of 
the pore volume in pores with diameters less than 250 .ANG. is in pores 
with diameters .+-.20 .ANG. of a Pore Mode of about 100-135 .ANG. and 
22-29% TPV is in pores having diameters of greater than 250 .ANG.. The 
instant invention is distinguished from Dai et al. (U.S. Pat. No. 
5,399,259) in that Dai et al. requires a relatively low Total Pore Volume 
of only 0.5-0.8 cc/g and a relatively low macroporosity of 22-29% TPV in 
pores having diameters of greater than 250 .ANG., whereas, the catalysts 
of the instant invention require much higher Total Pore Volumes of 
0.82-0.98 cc/g and a much higher level of macroporosity of 29.6-33.0% TPV 
in pores having diameters of greater than 250 .ANG.. 
In related copending U.S. application Ser. No. 08/425,971 (D# 
92,030-C1-D1), now U.S. Pat. No. 5,545,602, which is a divisional of U.S. 
Pat. No. 5,435,908 (to Texaco as assignee of Nelson et al.) there is 
disclosed a hydrotreating process employing, as catalyst, a porous alumina 
support with pellet diameters of 0.032-0.038 inches bearing 2.5-6 w % of a 
Group VIII non-noble metal oxide, 13-24 w % of a Group VIB metal oxide, 
less than or equal to 2.5 w % of silicon oxide, typically about 1.9-2 w % 
of intentionally added silica oxide, and 0-2 w % of a phosphorus oxide, 
preferably less than about 0.2 w % of a phosphorus oxide, with no 
phosphorus-containing components intentionally added during the catalyst 
preparation, said catalyst having a Total Surface Area of 165-210 m.sup.2 
/g, a Total Pore Volume of 0.75-0.95 cc/g, and a Pore Diameter 
Distribution whereby 14-22% of the Total Pore Volume is present as 
macropores of diameter .gtoreq.1000 .ANG., 22-32% of the Total Pore Volume 
is present as pores of diameter .gtoreq.250 .ANG., 68-78% of the Total 
Pore Volume is present as pores of diameter .ltoreq.250 .ANG., 26-35% of 
the Total Pore Volume is present as mesopores of diameters .gtoreq.200 
.ANG., 34-69% of the Total Pore Volume is present as secondary micropores 
of diameters 100-200 .ANG., 5-18% of the Total Pore Volume is present as 
primary micropores of diameter .ltoreq.100 .ANG., and .gtoreq.57% of the 
micropore volume is present as micropores of diameter .+-.20 .ANG. about a 
pore mode by volume of 100-145 .ANG.. The instant case employs as 
catalyst, a porous alumina support with pellet diameters of 0.032-0.044 
inches, preferably 0.039-0.044 inches, bearing 2.2-6 w % of a Group VIII 
non-noble metal oxide, 7-24 w % of a Group VIB metal oxide, less than or 
equal to 2.5 w % of silicon oxide, preferably 1.3-2.5 w % of intentionally 
added silica oxide, and 0.3-2 w % of a phosphorus oxide, preferably 
0.5-1.5 w % of a phosphorus oxide, with phosphorus-containing components 
intentionally added during the catalyst preparation, said catalyst having 
a Total Surface Area of 175-205 m.sup.2 /g, a Total Pore Volume of 
0.82-0.98 cc/g, and a Pore Diameter Distribution whereby 29.6-33.0% of the 
Total Pore Volume is present as macropores of diameter greater than 250 
.ANG., 67.0-70.4% of the Total Pore Volume is present as micropores of 
diameter less than 250 .ANG., .gtoreq.65% of the micropore volume is 
present as micropores of diameter .+-.25 .ANG. about a pore mode by volume 
of 110-130 .ANG., and less than or equal to 0.05 cc/g of micropore volume 
is present in micropores with diameters less than 80 .ANG.. 
A recent approach to developing improved catalysts for the hydroconversion 
of feedstock components having a boiling point greater than 1000.degree. 
F. to products having a boiling point less than 1000.degree. F. has 
involved the use of catalysts having micropores intermediate between the 
above described monomodal HDS and HDM catalysts with pore volumes in the 
HDS type of range and with macroporosities sufficient to overcome the 
diffusion limitations for conversion of feedstock components having 
boiling points greater than 1000.degree. F. into products having boiling 
points less than 1000.degree. F. but limited macroporosities so as to 
limit poisoning of the interiors of the catalyst particles. Such catalysts 
are described in U.S. Pat. No. 5,397,456 (To Texaco as assignee of Dai et 
al.) and copending U.S. application Ser. No. 08/130,472 (D# 92,067), now 
U.S. Pat. No. 5,514,273, discussed herein. 
U.S. Pat. No. 5,397,456 (to Texaco as assignee of Dai et al.) discloses a 
catalyst composition useful in the hydroconversion of a sulfur- and 
metal-containing feedstock comprising an oxide of a Group VIII metal and 
an oxide of a Group V-IB metal and optionally phosphorus on a porous 
alumina support, the catalyst having a Total Surface Area of 240-310 
m.sup.2 /g, a Total Pore Volume of 0.5-0.75 cc/g, and a Pore Diameter 
Distribution whereby 63-78% of the Total Pore Volume is present as 
micropores of diameter 55-115 .ANG. and 11-18% of the Total Pore Volume is 
present as macropores of diameter greater than 250 .ANG.. The heavy 
feedstocks are contacted with hydrogen and with the catalyst. The catalyst 
is maintained at isothermal conditions and is exposed to a uniform quality 
of feed. The process of Dai et al. is particularly effective in achieving 
desired levels of hydroconversion of feedstock components having a boiling 
point greater than 1000.degree. F. to products having a boiling point less 
than 1000.degree. F. The instant invention is distinguished from U.S. Pat. 
No. 5,397,456 in that Dai et al. requires a catalyst with a Pore Diameter 
Distribution wherein 63-78% of the Total Pore Volume is present as 
micropores of diameter 55-115 .ANG. and 11-18% of the Total Pore Volume is 
present as macropores of diameter greater than 250 .ANG., whereas, the 
catalysts employed in the instant invention have only about 20-25% of the 
Total Pore Volume present as micropores of diameter 55-115 .ANG. and 
29.6-33.0% of the Total Pore Volume is present as macropores of diameter 
greater than 250 .ANG.. 
In related copending U.S. application Ser. No. 08/130,472 (D# 92,067), now 
U.S. Pat. No. 5,514,273, there is disclosed a hydrotreating process and 
catalyst wherein 50-62.8% of the TPV is present in micropores of diameter 
55-115 .ANG. and 20-30.5% of the TPV is present as macropores of diameter 
greater than 250 .ANG.. In the instant case, the catalyst preferably has 
only about 20-25% of the TPV present in pores having diameter of 55-115 
.ANG.. 
None of the above-identified catalyst types in the art have been found to 
be effective for achieving all of the desired improved process needs. 
Early catalysts in the art addressed the need for improved 
hydrodesulfurization and/or hydrodemetallation as measured in the total 
liquid product. One recent line of catalyst development, as typified by 
U.S. Pat. Nos. 4,941,964 and 5,047,142, has been to develop improved 
catalysts for petroleum bottoms HDS (i.e., selective sulfur removal from 
the unconverted hydrocarbon product having a boiling point greater than 
1000.degree. F. from a hydroprocess operating with significant 
hydroconversion of feedstocks components [e.g., petroleum resids] having a 
boiling point greater than 1000.degree. F. to products having a boiling 
point less than 1000.degree. F.). More recent developments of petroleum 
bottoms HDS catalysts, as typified by U.S. Pat. No. 5,399,259 and 
copending U.S. application Ser. No. 08/425,971 (D# 92,030-C1-D1), now U.S. 
Pat. No. 5,545,602, which is a divisional of U.S. Pat. No. 5,435,908, have 
been to develop petroleum bottoms HDS catalysts with a degree of sediment 
control allowing the use of higher temperatures and reducing sediment 
make. However, none of the above-described petroleum bottoms HDS catalysts 
give improved levels of hydroconversion of feedstocks components having a 
boiling point greater than 1000.degree. F. to products having a boiling 
point less than 1000.degree. F. while, at the same time, reducing sediment 
make. 
A second line of catalyst development, as typified by U.S. Pat. No. 
5,397,456 and copending U.S. application Ser. No. 08/130,472 (D# 92,067), 
now U.S. Pat. No. 5,514,273 has been to develop hydroconversion catalysts 
for the improved hydroconversion of feedstocks components having a boiling 
point greater than 1000.degree. F. to products having a boiling point less 
than 1000.degree. F. The most recent developments of hydroconversion 
catalysts, as typified by U.S. application Ser. No. 08/130,472 (D# 
92,067), now U.S. Pat. No. 5,514,273 have been to develop hydroconversion 
catalysts with slightly improved bottoms HDS activities and some slight 
degree of sediment control allowing the use of some higher temperatures 
and reducing sediment make. Although the above-described hydroconversion 
catalysts give improved levels of hydroconversion of feedstocks components 
having a boiling point greater than 1000.degree. F. to products having a 
boiling point less than 1000.degree. F., they do not give the desired 
levels of sulfur removal obtained from the above-described petroleum 
bottoms HDS catalysts and these hydroconversion catalysts still make some 
amount of sediment. 
It would be desirable if a catalyst were available which provided improved 
hydroconversion, improved bottoms HDS, and no sediment make and which 
could also withstand operation at higher temperatures, so that it would be 
possible to attain an even higher level of hydroconversion without the 
undesirable formation of sediment. Undesirable low levels of 
hydroconversion represent a problem which is particularly acute for those 
refiners who operate vacuum resid hydroprocessing units at their maximum 
heat and/or temperature limits. Such limits often exist when refiners are 
operating at maximum charge rates.

It is an object of this invention to provide a process for hydroconverting 
a charge hydrocarbon feed, particularly, to hydroconvert feedstock 
components having boiling points greater than 1000.degree. F. into 
products having boiling points less than 1000.degree. F. while 
simultaneously removing high amounts of sulfur from the unconverted 
1000.degree. F.+ product stream. It is also an object of this invention to 
provide improved conversion at low Existent IP Sediment values in the 
650.degree. F.+ boiling point product (Discussed below under "Sediment 
Measurement"). It is also an object of this invention to allow the use of 
higher operating temperatures with reduced sediment make. Other objects 
will be apparent to those skilled in the art. 
STATEMENT OF THE INVENTION 
In accordance with certain of its aspects, this invention is directed to a 
process for hydroprocessing a charge hydrocarbon feed containing 
components boiling above 1000.degree. F., and sulfur, metals, and carbon 
residue which comprises 
contacting said charge hydrocarbon feed with hydrogen at isothermal 
hydroprocessing conditions in the presence of, as catalyst, a porous 
alumina support containing .ltoreq.2.5 wt % of silica and bearing 2.2-6 wt 
% of a Group VIII metal oxide, 7-24 wt % of a Group VIB metal oxide, and 
0.3-2 wt % of a phosphorus oxide, said catalyst having a Total Surface 
Area of 175-205 m.sup.2 /g, a Total Pore Volume of 0.82-0.98 cc/g, and a 
Pore Diameter Distribution whereby 29.6-33.0% of the Total Pore Volume is 
present as macropores of diameter greater than 250 .ANG., 67.0-70.4% of 
the Total Pore Volume is present as micropores of diameter less than 250 
.ANG., .gtoreq.65% of the micropore volume is present as micropores of 
diameter .+-.25 .ANG. about a pore mode by volume of 110-130 .ANG., less 
than 0.05 cc/g of micropore volume is present in micropores with diameters 
less than 80 .ANG., thereby forming hydroprocessed product containing 
decreased content of components boiling above 1000.degree. F. and sulfur, 
metals, and carbon residue; and 
recovering said hydroprocessed product containing decreased content of 
components boiling above 1000.degree. F., and of sulfur, metals, and 
carbon residue, 
recovering said hydroprocessed product containing decreased content of 
sulfur in the portion of the hydroprocessed product boiling above 
1000.degree. F., and 
recovering said hydroprocessed product containing decreased content of 
sediment in the portion of the hydroprocessed product boiling above 
650.degree. F. 
The catalyst of the instant invention allows operation at about +10.degree. 
F. and about +8 wt % 1000.degree. F. conversion compared to operations 
with a first generation H-OIL catalyst. This constitutes a substantial 
economic advantage. 
DESCRIPTION OF THE INVENTION 
Feedstock 
The hydrocarbon feed which may be charged to the process of this invention 
may include heavy, high boiling petroleum cuts typified by gas oils, 
vacuum gas oils, petroleum cokes, residual oils, vacuum resids, etc. The 
process of this invention is particularly useful to treat high boiling 
oils which contain components boiling above 1000.degree. F. to convert 
them to products boiling below 1000.degree. F. The charge may be a 
petroleum fraction having an initial boiling point of above 650.degree. F. 
characterized by presence of an undesirable high content of components 
boiling above 1000.degree. F., and sulfur, carbon residue and metals; and 
such charge may be subjected to hydrodesulfurization (HDS). In particular, 
the charge may be undiluted vacuum resid. 
A typical charge which may be utilized is an Arabian Medium/Heavy Vacuum 
Resid having the following properties: 
TABLE I 
______________________________________ 
Property Value 
______________________________________ 
API Gravity 4.8 
1000.degree. F.+, vol % 87.5 
1000.degree. F.+, wt % 88.5 
1000.degree. F.- wt % 11.5 
Sulfur, wt % 5.1 
Total Nitrogen, wppm 4480 
Hydrogen, wt % 10.27 
Carbon, wt % 84.26 
Alcor MCR, wt % 22.2 
Kinematic Viscosity, cSt 
@ 212.degree. F. 2430 
@ 250.degree. F. 410 
@ 300.degree. F. 117 
Pour Point, .degree. F. 110 
n-C.sub.5 Insolubles, wt % 28.4 
n-C.sub.7 Insolubles, wt % 9.96 
Toluene Insolubles, wt % 0.02 
Asphaltenes, wt % 9.94 
Metals, wppm 
Ni 49 
V 134 
Fe 10 
Cu 3 
Na 49 
Total Metals wppm 245 
Chloride, wppm 28 
______________________________________ 
It is a particular feature of the process of this invention that it may 
permit treating of hydrocarbon charge, particularly those containing 
components boiling above about 1000.degree. F., to form product which is 
characterized by an increased content of components boiling below 
1000.degree. F. and by decreased content of undesirable components 
typified by sulfur, metals, and carbon residue. It is another feature of 
the process of the instant invention that it provides improved sulfur 
removal from the unconverted 1000.degree. F. products. It is another 
feature of the process of the instant invention that it provides the above 
mentioned improvements with little or no sediment formation as measured by 
the Existent IP Sediment values of the 650.degree. F.+ boiling point 
product. It is another feature of the process of the instant invention 
that it allows operations at higher temperatures with consequent higher 
levels of 1000.degree. F.+ to 1000.degree. F.- than may be achieved with 
the use of first generation catalysts. 
Sediment Measurement 
It is a particular feature of the catalyst of this invention that it 
permits operation to be carried out under conditions which yield a 
substantially decreased content of sediment in the product stream leaving 
hydrotreating. 
The charge to a hydroconversion process is typically characterized by a 
very low sediment content of 0.01 weight percent (wt %) maximum. Sediment 
is typically measured by testing a sample by the Shell Hot Filtration 
Solids Test (SHFST). See Jour. Inst. Pet. (1951) 37 pages 596-604 Van 
Kerknoort et al.--incorporated herein by reference. Typical 
hydroprocessing processes in the art commonly yield Shell Hot Filtration 
Solids of above about 0.17 wt % and as high as about 1 wt % in the 
650.degree. F.+ product recovered from the bottoms flash drum (BFD). 
Production of large amounts of sediment is undesirable in that it results 
in deposition in downstream units which in due course must be removed. 
This of course requires that the unit be shut down for an undesirable long 
period of time. Sediment is also undesirable in the products because it 
deposits on and inside various pieces of equipment downstream of the 
hydroprocessing unit and interferes with proper functioning of e.g. pumps, 
heat exchangers, fractionating towers, etc. 
Very high levels of sediment formation (e.g., 1 wt %), however, are not 
usually experienced by those refiners who operate vacuum resid 
hydroprocessing units at or near their maximum heat and feedstock charge 
rates. Such units are generally operating at moderate conversion levels of 
feedstock components having boiling points greater than 1000.degree. F. 
into products having boiling points less than 1000.degree. F. (say, 40-65 
volume percent--vol %--conversion) and at relatively low but still 
undesirable values of sediment (e.g., 0.17 wt %). 
In the instant invention the IP 375/86 test method for the determination of 
total sediment has been very useful. The test method is described in ASTM 
Designation D 4870-92--incorporated herein by reference. The IP 375/86 
method was designed for the determination of total sediment in residual 
fuels and is very suitable for the determination of total sediment in our 
650.degree. F.+ boiling point product. The 650.degree. F.+ boiling point 
product can be directly tested for total sediment which is designated as 
the "Existent IP Sediment value." We have found that the Existent IP 
Sediment Test gives essentially equivalent test results as the Shell Hot 
Filtration Solids Test described above. 
We have noted, however, that even 650.degree. F.+ boiling point products 
which give low Existent IP Sediment values, may produce additional 
sediment upon storage. Thus, we have developed a more severe test for 
sediment. In this modified test, 50 grams of 650.degree. F.+ boiling point 
product are heated to about 90.degree. C. and mixed with about 5 
milliliters of reagent grade hexadecane. The mixture is aged for about one 
hour at about 100.degree. C. The resultant sediment is then measured by 
the IP 375/86 test method. The values obtained from this modified test are 
designated the "Accelerated IP Sediment values." 
As it is recommended that the IP 375/86 test method be restricted to 
samples containing less than or equal to about 0.4 to 0.5 wt % sediment, 
we reduce sample size when high sediment values are observed. This leads 
to fairly reproducible values for even those samples with very large 
sediment contents. 
It will be noted that catalysts of this invention, characterized by (i) 
about 0.15-0.20 cc/g of pores in the .gtoreq.1200 .ANG. range, (ii) about 
21-27% of TPV in pores in the .gtoreq.600 .ANG. range, (iii) 29.6-33.0% of 
the TPV in pores having a diameter of .gtoreq.250 .ANG., (iv) 67.0-70.4% 
of the TPV in micropores of diameter less than 250 .ANG., (v) .gtoreq.65% 
of the micropore volume in micropores of diameter .+-.25 .ANG. about a 
pore mode by volume of 110-130 .ANG., (vi) about 20-25% of the TPV in 
pores having a diameter of 55-115 .ANG., and (vii) less than 0.05 cc/g 
micropore volume in micropores with diameters less than 80 .ANG..--are 
particularly advantageous in that they permit attainment of product 
hydrocarbon streams containing the lowest content of sediment at highest 
conversion, while producing product characterized by low sulfur, carbon 
residue and metals contents. It is a feature of the catalyst of this 
invention that it permits attainment of hydrotreated product with &lt;0.15 wt 
% sediment, as measured by the Existent IP Sediment test in the portion of 
the hydroprocessed product boiling above 650.degree. F., typically as low 
as 0.0-0.1 wt %, preferably 0.0-0.05 wt %, say 0.05 wt %. 
Reaction Conditions 
In the practice of the process of this invention (as typically conducted in 
a single-stage Robinson reactor in pilot plant operations), the charge 
hydrocarbon feed is contacted with hydrogen at isothermal hydrotreating 
conditions in the presence of catalyst. Pressure of operation may be 
1500-10,000 psig, preferably 1800-2500 psig, say 2250 psig. Hydrogen is 
charged to the Robinson Reactor at a rate of 2000-10,000 SCFB, preferably 
3000-8000, say 7000 SCFB. Liquid Hourly Space Velocity (LHSV) is typically 
0.1-1.5, say 0.56 volumes of oil per hour per volume of liquid hold-up in 
the reactor. Temperature of operation is typically 700-900.degree. F., 
preferably 750-875.degree. F., say 760.degree. F. Operation is essentially 
isothermal. The temperature may typically vary throughout the bed by less 
than about 20.degree. F. 
In another more preferred embodiment of the process of the instant 
invention, the liquid and gaseous effluent from the previously described 
first-stage Robinson reactor is routed to a second-stage Robinson reactor 
containing the same weight of catalyst as had been loaded to the 
first-stage Robinson reactor and which is operated at essentially the same 
temperature and pressure as the first-stage Robinson reactor. The 
difference in average temperature between the first- and second-stage 
reactors is 0.degree. F.-30.degree. F., preferably 0.degree. F.-15.degree. 
F., say 0.degree. F. No additional hydrogen is normally injected to the 
second-stage Robinson reactor. The liquid effluent passes through the 
second-stage Robinson reactor at a similar LHSV to that of the first-stage 
Robinson reactor. The liquid effluent from the first-stage Robinson 
reactor is uniformly contacted with the hydrogen-containing gaseous 
effluent and the second loading of catalyst at isothermal conditions in 
the second-stage Robinson reactor. No attempt is made to maintain constant 
catalytic activity by periodic or continuous withdrawal of portions of 
used catalyst and replacement of the withdrawn material with fresh 
catalyst in the two-stage Robinson reactor system. The catalyst begins as 
fresh catalyst and accumulates catalyst age generally expressed in barrels 
per pound. The average temperature is defined as the average of the 
temperatures of the first- and second-stage reactors. Average temperature 
of operation is typically 700-900.degree. F., preferably 750-875.degree. 
F., say 760.degree. F. Overall, the hydrocarbon charge passes through the 
entire process system (i.e., the first- and second-stage Robinson 
reactors) at an overall LHSV of 0.05-0.75, say 0.28 volumes of oil per 
hour per volume of liquid hold-up in the reactor. 
In general, reaction may be carried out in one or more continuously stirred 
tank reactors (CSTR's), such as Robinson reactors, in which the catalyst 
is exposed to a uniform quality of feed. 
In one particularly preferred embodiment of the process of the instant 
invention, a sulfur-and metal-containing hydrocarbon feedstock is 
catalytically hydroprocessed using the H-OIL (TM) Process configuration. 
H-OIL is a proprietary ebullated bed process (co-owned by Hydrocarbon 
Research, Inc. and Texaco Development Corporation) for the catalytic 
hydrogenation of residua and heavy oils to produce upgraded distillate 
petroleum products and an unconverted bottoms product particularly suited 
for blending to a low sulfur fuel oil. The ebullated bed system operates 
under essentially isothermal conditions and allows for exposure of 
catalyst particles to a uniform quality of feed. 
In the H-OIL Process, a catalyst is contacted with hydrogen and a sulfur- 
and metal-containing hydrocarbon feedstock by means which insures that the 
catalyst is maintained at essentially isothermal conditions and exposed to 
a uniform quality of feed. Preferred means for achieving such contact 
include contacting the feed with hydrogen and the catalyst in a single 
ebullated bed reactor, or in a series of 2-5 ebullated bed reactors, with 
a series of two ebullated bed reactors being particularly preferred. This 
hydroprocessing process is particularly effective in achieving high levels 
of hydrodesulfurization with vacuum residua feedstocks. 
In the H-OIL Process, the hydrocarbon charge is admitted to the first-stage 
reactor of a two-stage ebullated bed H-OIL unit in the liquid phase at 
650.degree. F.-850.degree. F., preferably 700.degree. F.-825.degree. F. 
and 1000-3500 psia, preferably 1500-3000 psia. Hydrogen gas is admitted to 
the first-stage reactor of a two-stage ebullated bed H-OIL unit in amount 
of 2000-10,000 SCFB, preferably 3000-8000 SCFB. The hydrocarbon charge 
passes through the first-stage ebullated bed reactor at a LHSV of 0.16-3.0 
hr.sup.-1, preferably 0.2-2 hr.sup.-1. During operation, the catalyst bed 
is expanded to form an ebullated bed with a defined upper level. Operation 
is essentially isothermal with a typical maximum temperature difference 
between the inlet and outlet of 0.degree. F.-50.degree. F., preferably 
0.degree. F.-30.degree. F. The liquid and gaseous effluent from the 
first-stage reactor is then routed to the second-stage reactor of the 
two-stage H-OIL unit which is operated at essentially the same temperature 
and pressure as the first-stage reactor. The difference in average 
temperature between the first- and second-stage reactors is 0.degree. 
F.-30.degree. F., preferably 0.degree. F.-15.degree. F. Some additional 
hydrogen may optionally be injected to the second-stage reactor to make up 
for the hydrogen consumed by reactions in the first-stage reactor. 
In the H-OIL process, constant catalytic activity is maintained by periodic 
or continuous withdrawal of portions of used catalyst and replacement of 
the withdrawn material with fresh catalyst. Fresh catalyst is typically 
added at the rate of 0.05-1.0 pounds per barrel of fresh feed, preferably 
0.20-0.40 pounds per barrel of fresh feed. An equal volume of used 
catalyst is withdrawn and discarded to maintain a constant inventory of 
catalyst on the volume basis. The catalyst replacement is performed such 
that equal amounts of fresh catalyst are added to the first-stage reactor 
and the second-stage reactor of a two-stage H-OIL unit. 
Catalyst Support 
The catalyst support may be alumina. Although the alumina may be alpha, 
beta, theta, or gamma alumina, gamma alumina is preferred. 
The charge alumina which may be employed in practice of this invention may 
be available commercially from catalyst suppliers or it may be prepared by 
variety of processes typified by that wherein 85-90 parts of 
pseudoboehmite alumina is mixed with 10-15 parts of recycled fines. Silica 
(SiO.sub.2) may be incorporated in small amounts typically up to about 2.5 
wt % on the finished catalyst basis, and preferably 1.3-2.5 wt % on the 
finished catalyst basis. Acid is added and the mixture is mulled and then 
extruded in an Auger type extruder through a die having cylindrical holes 
sized to yield a calcined substrate having a diameter of 0.032-0.044 
inches, preferably 0.039-0.044 inches. Extrudate is air-dried to a final 
temperature of typically 250-275.degree. F. yielding extrudates with 
20-25% of ignited solids. The air-dried extrudate is then calcined in an 
indirect fired kiln for 0.5-4 hours in an atmosphere of air and steam at 
typically about 1000.degree. F.-1150.degree. F. 
Catalysts of the Instant Invention--Pore Size Distribution 
The catalyst which may be employed is characterized by Total Surface Area 
(TSA), Total Pore Volume (TPV), and (Pore Diameter Distribution (Pore Size 
Distribution PSD). The Total Surface Area is 175-205 m.sup.2 /g, 
preferably 175-195 m.sup.2 /g, say 178 m.sup.2 /g. The total Pore Volume 
(TPV) may be 0.82-0.98, preferably 0.82-0.90, say 0.83 cc/g. 
Less than 0.05 cc/g of micropore volume is present in micropores with 
diameters less than 80 .ANG.. 
Micropores of diameter in the range of less than 250 .ANG. are present in 
an amount of about 67.0-70.4% of the Total Pore Volume, preferably 
67.0-69.1% TPV, say 67.0% TPV. Preferably greater than or equal to 65% of 
the micropore volume is present as micropores of diameter .+-.25 .ANG. 
about a pore mode by volume of 110-130 .ANG.. 
The amount of Total Pore Volume in the range of 55-115 .ANG. is only about 
20-25% and preferably 20.8%. 
The Pore Size Distribution is such that 29.6-33% of the Total Pore Volume, 
and preferably about 33.0% is present as macropores of diameter greater 
than 250 .ANG.. 
The amount of Total Pore Volume in pores with a diameter greater than 600 
.ANG. is only about 21-27% and preferably 26.6% TPV. 
The amount of Total pore Volume in pores having a diameter greater than 
1200 .ANG. is only about 0.15-0.20 cc/g and preferably 0.20 cc/g. 
It should be noted that the percentages of the pores in the finished 
catalyst are essentially the same as in the charge gamma alumina substrate 
from which it is prepared--although the Total Surface Area of the finished 
catalyst may be 75-85%, say 80% of the charge gamma alumina substrate from 
which it is prepared (i.e., 75-85% of a support surface area of 205-275 
m.sup.2 /g, say 221 m.sup.2 /g). It should also be noted that the Median 
Pore Diameter by Surface Area from mercury porosimetry of the finished 
catalyst is essentially the same as that of the charge gamma alumina 
substrate from which it is prepared. 
It is also noted that the Pore Size Distribution (percent of total) in the 
finished catalyst may be essentially the same as in the charge alumina 
from which it is prepared (unless the majority of the pore volume 
distribution in a given range is near a "break-point"--e.g. 80 .ANG. or 
250 .ANG., in which case a small change in the amount of pores of a stated 
size could modify the reported value of the pore volume falling in a 
reported range). The Total Pore Volume, of the finished catalyst may be 
75%-98%, say 80% of the charge alumina from which it is prepared. 
Catalysts of the Instant Invention--Metals Loadings 
The alumina charge extrudates may be loaded with metals to yield a product 
catalyst containing a Group VIII non-noble oxide in amount of 2.2-6 wt %, 
preferably 3.0-3.5 wt %, say 3.3 wt % and a Group VIB metal oxide in 
amount of 7-24 wt %, preferably 12.5-15.5 wt %, say 14.4 wt %. 
The Group VIII metal may be a non-noble metal such as iron, cobalt, or 
nickel. This metal may be loaded onto the alumina typically from a 
10%-30%, say 15% aqueous solution of a water-soluble salt (e.g. a nitrate, 
acetate, oxalate etc.). The preferred metal is nickel, employed as about a 
11.3 wt % aqueous solution of nickel nitrate hexahydrate 
Ni(NO.sub.3).sub.2.6H.sub.2 O. 
The Group VIB metal can be chromium, molybdenum, or tungsten. This metal 
may be loaded onto the alumina typically from a 10%-40%, say 20% aqueous 
solution of a water-soluble salt. The preferred metal is molybdenum, 
employed as about a 15.5 wt % aqueous solution of ammonium molybdate 
tetrahydrate (NH.sub.4).sub.6 Mo.sub.7 O.sub.24.4H.sub.2 O. 
It is a feature of the catalyst of the invention that it contains about 
0.3-2 wt % of P.sub.2 O.sub.5 and preferably about 0.5-1.5 wt %. This 
level of phosphorus oxide loading is very small representing only 
0.13-0.87 wt % of elemental phosphorus and preferably 0.22-0.87 wt % of 
elemental phosphorus. The phosphorus component may be loaded onto the 
alumina as a 0-4 wt %, say 1.1 wt % aqueous solution of 85 wt % phosphoric 
acid H.sub.3 PO.sub.4 in water. 
As described above, silica SiO.sub.2 may be incorporated into the catalyst 
supports prior to impregnation and may therefore be present in small 
amounts typically up to about 2.5 wt %, and preferably 1.3-2.5 wt %, 
although the benefits of the invention may be attained without addition of 
silica. 
These catalyst metals and phosphorus may be loaded onto the alumina support 
by impregnating the latter with a solution of the former. Although it is 
preferred to load the metals simultaneously, it is possible to load each 
separately. Small amounts of H.sub.2 O.sub.2 may be added to stabilize the 
impregnating solution. It is preferred that the catalyst be impregnated by 
filling 90-105%, preferably 97-98%, say 97% of the substrate pore volume 
with the solution containing the requisite amounts of metals and 
phosphorus. Loading is followed by drying and calcining at 900.degree. 
F.-1250.degree. F., preferably 1150.degree. F.-1210.degree. F., say 
1180.degree. F. for 0.5-5 hours, say 1.0 hour. 
Another feature of the catalyst composition of the instant invention is 
that the ratio of the measured hydrodesulfurization (HDS) microactivity 
rate constant k of the catalyst of the instant invention to the measured 
HDS microactivity rate constant k of a standard hydroprocessing catalyst 
(namely, Criterion HDS-1443B, a commercially available, state-of-the-art 
catalyst for use in hydroprocessing resid oils), has a value of 0.5-1.0, 
preferably 0.6-0.85. As used in this description, the phrase "HDS 
microactivity" means the intrinsic hydrodesulfurization activity of a 
catalyst in the absence of diffusion, as measured according to the HDS 
Microactivity (HDS-MAT) Test, described as follows. In the HDS-MAT Test, a 
given catalyst is ground to a 30-60 mesh fraction and presulfided at 
750.degree. F. with a gas stream containing 10% H.sub.2 S/90% H.sub.2. The 
catalyst is then exposed to a sulfur-containing feed, namely 
benzothiophene, which acts as a model sulfur compound probe, at reaction 
temperature and with flowing hydrogen for approximately 4 hours. Samples 
are taken periodically and analyzed by gas chromatography for the 
conversion of benzothiophene to ethylbenzene, thereby indicating the 
hydrodesulfurization properties of the catalyst being tested. The activity 
is calculated on both a catalyst weight and catalyst volume basis to 
account for any density differences between catalysts. The conditions for 
a typical HDS-MAT Test are as follows: 
Temperature: about 550.degree. F. 
Pressure: about atmospheric 
Feedstock: about 0.857 molar Benzothiophene in reagent grade normal heptane 
Space Velocity: 4 hr.sup.-1 
Catalyst Charge: 0.5 gram 
The kinetics of the reactor used in the HDS-MAT Test are first order, plug 
flow. At the above stated temperature and space velocity, the rate 
constant, k, may be expressed as 
EQU k=ln (1/1-HDS) 
where HDS is the fractional hydrodesulfurization value obtained for a given 
catalyst at the above-stated conditions. A commercially available, 
state-of-the-art catalyst sold for use in hydroprocessing resid oils 
(Criterion HDS-1443B catalyst) was evaluated with the HDS-MAT Test under 
the above stated conditions and was found to have a % HDS value of 73% on 
a weight basis and a corresponding rate constant k value of 1.3093. 
Additional details of the HDS-MAT Test can be found in U.S. Pat. No. 
5,047,142 to Texaco as assignee of Dai et al., supra, incorporated herein 
by reference. The catalysts of the instant invention require that the 
ratio of the measured HDS-MAT rate constant k, relative to that obtained 
with Criterion HDS-1443B, have values of 0.5-1.0, preferably 0.6-0.85, 
whereas the catalysts of U.S. Pat. No. 5,047,142 are required to have 
values &gt;1.0, preferably &gt;1.5. 
It is another feature of the catalyst composition of the instant invention 
that the oxide of molybdenum, preferably MoO.sub.3, is distributed on the 
above described porous alumina support in such a manner that the 
molybdenum gradient is about 1.0. As used in this description, the phrase 
"molybdenum gradient" means the ratio of molybdenum/aluminum atomic ratio 
observed on the exterior surfaces of catalyst pellets relative to the 
molybdenum/aluminum atomic ratio observed on surfaces of a sample of the 
same catalyst which has been ground to a fine powder, the atomic ratios 
being measured by X-Ray photoelectron spectroscopy (XPS), sometimes 
referred to as Electron Spectroscopy for Chemical Analysis (ESCA). It is 
theorized that the molybdenum gradient is strongly affected by the 
impregnation of molybdenum on the catalyst support and the subsequent 
drying of the catalyst during its preparation. ESCA data were obtained on 
an ESCALAB MKII instrument available from V. G. Scientific Ltd., which 
uses a 1253.6 electron volt magnesium X-Ray source. Additional details of 
the determination of molybdenum gradient can be found in U.S. Pat. No. 
5,047,142 to Texaco as assignee of Dai et al., supra, incorporated herein 
by reference. 
Generally the finished catalysts of this invention will be characterized by 
the properties set forth in Table II wherein the columns show the 
following: 
1. The first column lists the broad ranges for the catalysts of this 
invention and the second column lists the preferred ranges for the 
catalysts of this invention, including: Total Pore Volume in cc/g; Pore 
Volume occupied by pores falling in designated ranges--as a volume % of 
Total Pore Volume (% TPV) or as a volume % of the Pore Volume in pores 
with diameters less than 250 .ANG. (i.e., % of Pore Volume in the 
micropores) or in cc of Pore Volume per gram of catalyst; Pore Mode by 
volume from mercury porosimetry (dV/dD); Pore Volume falling with .+-.25 
.ANG. from the dV/dD peak in the less than 250 .ANG. region; and, Surface 
Area in m.sup.2 /g. 
2. The third column lists specific properties of the best known mode 
catalyst, Example I. The fourth column lists specific properties of a 
second sample, Example II, made by the same formula as Example I. 
3. The remaining columns list properties for other hydroprocessing 
catalysts in the art. 
TABLE II 
__________________________________________________________________________ 
Texaco R&D-PA Analyses of Catalyst Samples* 
Instant Invention Selected U. S. Pat. No./ 
Broad Preferred 
Example 
Example 
Art Application Serial No. 
Ranges Ranges I II Ranges 
Reference 
__________________________________________________________________________ 
Metals 
Molybdenum (as MoO.sub.3) 7-24 12.5-15.5 14.4 14.1 
Nickel (as NiO) 2.2-6 3.0-3.5 3.3 3.4 
Silicon (as SiO.sub.2) .ltoreq.2.5 1.3-2.5 1.7 1.3 
Phosphorus (as P.sub.2 O.sub.5) 0.3-2.0 0.5-1.5 0.7 0.8 No phosphorus 
is added 5,435,908; 08/425,971 
(Preferably &lt;0.2 wt %) 
Surface Area (N.sub.2, BET) m.sup.2 /g 
175-205 
175-195 
178 187 140-190 4,395,328 
&gt;220 5,221,656 
240-310 5,397,456 
Pore Size Distribution (Hg)** 
TPV cc/g 0.82-0.98 0.82-0.90 0.83 0.85 0.4-0.65 4,089,774 
0.5-0.75 4,941,964 
0.5-0.75 5,047,142 
0.5-0.75 5,397,456 
0.5-0.8 5,399,259 
PV, cc/g &gt;1200.ANG. .about.0.15-0.20 .about.0.15-0.20 0.20 0.17 
0.23-0.31 5,221,656 
PV, cc/g &gt;600.ANG., % of TPV .about.21-27 .about.21-27 26.6 23.8 35-55 
4,395,329 
PV, cc/g &gt;250.ANG., % of TPV 29.6-33.0 29.6-33.0 33.0 30.9 5.5-22.0 
4,941,964 
1.0-15.0 5,047,142 
11-18 5,397,456 
22-29 5,399,259 
22-32 5,435,908, 08/425,971 
PV, cc/g &lt;80.ANG. &lt;0.05 &lt;0.05 0.01 0.02 
Pore Mode (dV/dD MAX 110-130 110-130 121 121 40-100 5,221,656 
from Hg) 
PV, .+-.25.ANG. from dV/dD MAX, .gtoreq.65 .gtoreq.65 72.6 65.0 
% of PV &lt;250.ANG. 
PV, cc/g 55-115 .ANG., .about.20-25 20-25 20.8 23.5 63-78 5,397,456 
% of TPV 50-62.8 
08/130,472 
PV, cc/g &gt;1000.ANG., % of TPV .about.20-25 20.9-24.4 24.4 20.9 14-22 
5,435,908; 08/425,971 
Median Pore Diameter (by 
.about.115-130 .about.115-130 
121 120 
Surface Area from Hg), .ANG. 
Impregnation characteristics 
HDS-MAT C 0.5 g @ 49-73 49-73 55 67 
550.degree. F. 
HDS-MAT, Relative k*** 0.5-1.0 0.5-1.0 0.61 0.85 
Nickel Extraction, wt % 10-14.7 10-14.7 (12.0) (NA) 15-30 5,047,142 
ESCA Molybdenum Gradient &lt;5 
&lt;5 1.4 1.2 
Average Pellet Diameter, 0.032-0.044 0.039-0.044 0.042 0.043 0.032-0.038 
5,435,908; 08/425,971 
Inches 
__________________________________________________________________________ 
*Values in parentheses obtained at Cytec Industries Stamford Research 
Laboratories. 
**Contact angle 130.degree.; surface tension = 484 dynes/cm. 
***As described in U. S. Pat. No. 5,047,142. 
The catalyst may be evaluated in a two-stage Robinson Reactor, a 
Continuously Stirred Tank Reactor (CSTR) which evaluates catalyst 
deactivation at conditions simulating those of a two-stage H-OIL ebullated 
bed Unit. The feedstock is an Arabian Medium/Heavy Vacuum Resid of the 
type set forth above. Evaluation is carried out for four or more weeks to 
a catalyst age of 1.86 or more barrels per pound. 
Preferred Embodiment 
In practice of the process of this invention, the catalyst, preferably in 
the form of extruded cylinders of 0.039-0.044 inch diameter and about 0.15 
inch length may be placed within the first- and second-stage reactors of a 
two-stage H-OIL Unit. The hydrocarbon charge is admitted to the lower 
portion of the first-stage reactor bed in the liquid phase at 650.degree. 
F.-850.degree. F., preferably 700.degree. F.-825.degree. F. and 1000-3500 
psia, preferably 1500-3000 psia. Hydrogen gas is admitted to the 
first-stage reactor of the two-stage ebullated bed H-OIL unit in amount of 
2000-10,000 SCFB, preferably 3000-8000 SCFB. The hydrocarbon charge passes 
through the first-stage ebullated bed reactor at a LHSV of 0.16-3.0 
hr.sup.-1, preferably 0.2-2 hr.sup.-1. During operation, the first stage 
reactor catalyst bed is expanded to form an ebullated bed with a defined 
upper level. Operation is essentially isothermal with a typical maximum 
temperature difference between the inlet and outlet of 0.degree. 
F.-50.degree. F., preferably 0.degree. F.-30.degree. F. The liquid and 
gaseous effluent from the first-stage reactor is admitted to the lower 
portion of the second-stage reactor of the two-stage H-OIL unit which is 
operated at essentially the same temperature and pressure as the 
first-stage reactor. The difference in average temperature between the 
first- and second-stage reactors is 0.degree. F.-30.degree. F., preferably 
0.degree. F.-15.degree. F. Some additional hydrogen may optionally be 
injected to the second-stage reactor to make up for the hydrogen consumed 
by reactions in the first-stage reactor. During operation, the 
second-stage reactor catalyst bed is also expanded to form an ebullated 
bed with a defined upper level. Constant catalytic activity is maintained 
by periodic or continuous withdrawal of portions of used catalyst and 
replacement of the withdrawn material with fresh catalyst. Fresh catalyst 
is typically added at the rate of 0.05-1.0 pounds per barrel of fresh 
feed, preferably 0.20-0.40 pounds per barrel of fresh feed. An equal 
volume of used catalyst is withdrawn and discarded to maintain a constant 
inventory of catalyst on the volume basis. The catalyst replacement is 
performed such that equal amounts of fresh catalyst are added to the 
first-stage reactor and the second-stage reactor of a two-stage H-OIL 
unit. 
In a less preferred embodiment, the reaction may be carried out in one or 
more continuously stirred tank reactors (CSTR) which also provides 
essentially isothermal conditions. 
During passage through the reactor, preferably containing an ebullated bed, 
the hydrocarbon feedstock is converted to lower boiling products by the 
hydrotreating/hydrocracking reaction. 
Practice of the Instant Invention 
In a typical embodiment, employing a two-stage Robinson reactor pilot Unit, 
a charge containing 60 wt %-95 wt %, say 88.5 wt % boiling above 
1000.degree. F. may be converted to a hydrotreated product containing only 
28 wt %-45 wt %, say 42 wt % boiling above 1000.degree. F. The sulfur of 
the original charge is 3-7 wt %, typically 5.1 wt %; the sulfur content of 
the unconverted 1000.degree. F.+ component in the product is 0.5-3.5 wt %, 
typically 1.6 wt %. In another embodiment, employing a two-stage Robinson 
reactor pilot Unit operating at +10.degree. F. over normal operating 
temperatures and at a larger value of catalyst age, a charge containing 60 
wt %-95 wt %, say 88.5 wt % boiling above 1000.degree. F. may be converted 
to a hydrotreated product containing only 24 wt %-38 wt %, say 35.4 wt % 
boiling above 1000.degree. F. The sulfur content of the unconverted 
1000.degree. F.+ component in the product is 0.5-3.5 wt %, typically 2.2 
wt %. In both embodiments, the Existent IP sediment values of the 
650.degree. F.+ product leaving the reactor are extremely small; 
.ltoreq.0.05 wt %. 
ADVANTAGES OF THE INVENTION 
It will be apparent to those skilled in the art that this invention is 
characterized by advantages including the following: 
(i) It permits attainment of increased yield of hydrocarbon products 
boiling below 1000.degree. F.; 
(i) It permits the attainment of the above mentioned increased yield with 
little or no sediment as measured by the Existent IP Sediment values of 
the 650.degree. F.+ boiling point product; 
(iii) It permits an improved level of sulfur removal as seen in the 
observed hydrodesulfurization (HDS) of the total liquid product and the 
substantially improved, lower level of sulfur in the unconverted 
1000.degree. F. stream; and, 
(iv) It permits improved levels of carbon residue reduction and nickel and 
vanadium removal. 
Practice of the process of this invention will be apparent to those skilled 
in the art from the following wherein all parts are parts by weight unless 
otherwise stated. 
DESCRIPTION OF SPECIFIC EMBODIMENTS 
Best Known Mode Reactor Data 
Equal amounts of Example I catalyst are placed within the reaction vessels 
(the first-stage and second-stage Robinson Reactors). The hydrocarbon 
charge (i.e., the undiluted Arabian Medium/Heavy vacuum resid, described 
in Table I, supra) is admitted in liquid phase to the first-stage Robinson 
reactor at 760.degree. F. and 2250 psig. Hydrogen gas is admitted to the 
first-stage Robinson reactor in the amount of 7000 SCFB. The hydrocarbon 
charge passes through the first-stage Robinson reactor at a Liquid Hourly 
Space Velocity (LHSV) of 0.56 volumes of oil per hour per volume of liquid 
hold up. This is equivalent to a Catalyst Space Velocity (CSV) of 0.130 
barrels of hydrocarbon charge per pound of catalyst per day. The 
hydrocarbon feed is uniformly contacted with hydrogen and catalyst at 
isothermal conditions in the first-stage Robinson reactor. The liquid and 
gaseous effluent from the first-stage Robinson reactor is then routed to 
the second-stage Robinson reactor which is operated at essentially the 
same temperature and pressure as the first-stage Robinson reactor. The 
difference in average temperature between the first- and second-stage 
reactors is nominally 0.degree. F. No additional hydrogen is injected to 
the second-stage Robinson reactor. The liquid effluent passes through the 
second-stage Robinson reactor at a Liquid Hourly Space Velocity (LHSV) of 
0.56 volumes of liquid effluent per hour per volume of liquid hold up. 
This is equivalent to a Catalyst Space Velocity (CSV) of 0.130 barrels of 
liquid effluent per pound of catalyst per day. The liquid effluent from 
the first-stage Robinson reactor is uniformly contacted with the 
hydrogen-containing gaseous effluent and the second loading of catalyst at 
isothermal conditions in the second-stage Robinson reactor. No attempt is 
made to maintain constant catalytic activity by periodic or continuous 
withdrawal of portions of used catalyst and replacement of the withdrawn 
material with fresh catalyst in the two-stage Robinson reactor system. The 
catalyst begins as fresh catalyst and accumulates catalyst age generally 
expressed in barrels per pound. The average temperature is defined as the 
average of the temperatures of the first- and second-stage reactors. 
Overall, the hydrocarbon charge passes through the entire process system 
(i.e., the first- and second-stage Robinson reactors) at an overall LHSV 
of 0.28 volumes of oil per hour per volume of liquid hold up. This is 
equivalent to an overall CSV of 0.065 barrels of hydrocarbon charge per 
pound of catalyst per day. As will be discussed below, the temperatures of 
the first- and second-stage reactors may be raised to higher levels with 
the catalyst of the instant invention. 
Product is collected and analyzed over a range of catalyst age of 0.195 
through 1.08 barrels per pound (corresponding approximately to the 3rd 
through 16th days of the evaluation) to yield the following averaged data: 
TABLE III 
______________________________________ 
Property Value 
______________________________________ 
% Sulfur Removal 79.6 
% Carbon Residue Reduction 58.0 
% Ni Removal 73.0 
% V Removal 94.9 
% Hydroconversion of 1000.degree. F.+ 52.6 
to 1000.degree. F.- Materials (wt % Basis) 
% Kinetically Adjusted Hydroconversion 52.6 
(to 0.0650 bbl/lb/day and 760.0.degree. F.) 
of 1000.degree. F.+ to 1000.degree. F.- Materials- 
wt % Basis) 
______________________________________ 
From the above Table III, it is apparent that the process of the instant 
invention permits increasing the conversion of materials boiling above 
1000.degree. F. by 52.6 wt %; and sulfur, carbon residue, and metals are 
removed. 
Upon distillation to recover (i) a first cut from the initial boiling point 
to 650.degree. F., (ii) a second cut from 650.degree. F. to 1000.degree. 
F., and (iii) a third cut above 1000.degree. F., the following is noted: 
TABLE IV 
______________________________________ 
Product 
______________________________________ 
Cut 1: up to 650.degree. F. 
Specific Gravity, g/cc 0.85 
Sulfur, wt % 0.1 
Cut 2: 650.degree. F.-1000.degree. F. 
Specific Gravity, g/cc 0.93 
Sulfur, wt % 0.6 
Cut 3: 1000.degree. F.+ 
Specific Gravity, g/cc 1.02 
Sulfur, wt % 1.6 
______________________________________ 
From the above Table IV, it is apparent that the Sulfur content is 
decreased in all of the product fractions (from 5.1 wt % in the feed). 
Upon distillation to recover (iv) a cut which boils at temperatures of 
about 650.degree. F. and higher, the following is noted: 
TABLE V 
______________________________________ 
Product 
______________________________________ 
Cut 4: 650.degree. F.+ 
Existent IP Sediment, wt % 0.00 
Accelerated IP Sediment, wt % 0.00 
______________________________________ 
From the above Table, it is apparent that the process of the instant 
invention can operate at about 52.6 wt % conversion of feed components 
with boiling points greater than 1000.degree. F. to products with boiling 
points less than 1000.degree. F. without making any sediment. 
EXAMPLE A 
Comparison To First Generation Catalyst 
Comparative data between the Example I catalyst of the instant invention 
and a first generation nickel/molybdenum H-OIL catalyst (Criterion 
HDS-1443B), collected under virtually identical reactor conditions, are 
given in Table VI. The process of the instant invention is superior in 
that it gives: 
(i) No sediment versus an undesirable level with a commercially available 
first generation nickel/molybdenum H-OIL catalyst; 
(ii) An improved level of 1000.degree. F.+ to 1000.degree. F.- wt % 
conversion once the data from both catalysts are kinetically adjusted to 
the target CSV and temperature; 
(iii) An improved level of sulfur removal as seen in the observed 
hydrodesulfurization (HDS) of the total liquid product and the 
substantially improved, lower level of sulfur in the unconverted 
1000.degree. F. stream; and, 
(iv) Improved levels of carbon residue reduction and nickel and vanadium 
removal. 
TABLE VI 
______________________________________ 
EXAMPLE A 
Two-Stage Robinson Reactor Catalyst Test Results 
Single-Pass, Pure Resid, No Diluent, Once Through Hydrogen 
Age = 0.195 to 1.08 Barrels Per Pound 
1st Generation 
Catalyst Example I (HDS-1443B*) 
______________________________________ 
CSV (Bbl/Lb/Day) 0.0668 0.0638 
Temperature (.degree.F.) 759.9 760.3 
(Average both stages) 
Cut 4: (650.degree. F.+) 
Existent IP Sediment (wt %) 0.00 0.17 
Accelerated IP Sediment (wt %) 0.00 0.76 
Total Liquid Product 
% Sulfur Removal 79.6 78.2 
% Carbon Residue Reduction 58.0 54.8 
% Nickel Removal 73.0 65.4 
% Vanadium Removal 94.9 90.8 
% Hydroconversion of 1000.degree. F.+ 52.6 53.7 
to 1000.degree. F.- Materials (wt %) 
Kinetically Adjusted (CSV and T) 
% Hydroconversion of 1000.degree. F.+ 53.5 52.8 
to 1000.degree. F.- Materials (wt %) 
Cut 1: up to 650.degree. F. 
Specific Gravity (g/cc) 0.85 0.85 
Sulfur (wt %) 0.1 0.1 
Cut 2: 650.degree. F.-1000.degree. F. 
Specific Gravity (g/cc) 0.93 0.93 
Sulfur (wt %) 0.6 0.6 
Cut 3: 1000.degree. F.+ 
Specific Gravity (g/cc) 1.02 1.02 
Sulfur (wt %) 1.6 1.9 
______________________________________ 
*Criterion HDS1443B HOIL catalyst. 
**1st order CSTR kinetics (assuming equal rate constants for the 1st and 
2nd stage reactors); Activation Energy = 65 kcal/mole. 
EXAMPLE B 
Data At Higher Temperatures 
In the evaluation of the Example I catalyst of the instant invention, 
reactor temperatures were raised about 10.degree. F. over a period of 2.5 
days to a final temperature of approximately 770.degree. F. (i.e., the 
first-stage, second-stage, and average temperatures). Product was 
collected and analyzed over a range of catalyst age of 1.28 through 1.86 
barrels per pound (corresponding approximately to the 19th through 28th 
days of the evaluation). Comparative data between the catalyst of the 
instant invention operating at about +10.degree. F. compared to the first 
generation nickel/molybdenum H-OIL catalyst (Criterion HDS-1443B) at the 
same catalyst ages are given in Table VII. The process of the instant 
invention is superior in that it gives: 
(i) Low sediment at 60 wt % 1000.degree. F.+ to 1000.degree. F.- conversion 
versus an undesirable level with the first generation nickel/molybdenum 
H-OIL catalyst operating at only 52 wt % 1000.degree. F.+ to 1000.degree. 
F.- conversion; 
(ii) An improved level of 1000.degree. F.+ to 1000.degree. F.- wt % 
conversion by the observed data and once the data from both catalysts are 
kinetically adjusted to the target CSV; 
(iii) An improved level of sulfur removal as seen in the observed 
hydrodesulfurization (HDS) of the total liquid product and the 
substantially improved, lower level of sulfur in the unconverted 
1000.degree. F.+ stream; and 
(iv) Improved levels of carbon residue reduction and nickel and vanadium 
removal. 
It was noted that the sulfur levels of the 650.degree. F.+-1000.degree. F.+ 
bp boiling cut (approximating the composition of a vacuum gas oil) were 
slightly higher with the Example I catalyst of the instant invention 
operating at about +10.degree. F. compared to the level obtained with the 
first generation catalyst when both were at catalyst ages of 1.28 through 
1.86 barrels per pound. 
The catalyst of the instant invention, besides giving low sediment results 
for the 650.degree. F.+ boiling cut, also showed improved operability. The 
evaluation went smoothly at both 760.degree. F. and 770.degree. F. On the 
other hand, the first generation catalyst evaluation showed evidence of 
plugging due to accumulated sediment during the course of the run. 
Operations became somewhat erratic with the first generation catalyst at 
about 1.54 bbl/pound catalyst age and the unit had to be shut down and 
partially cleaned out before we could complete the evaluation of the first 
generation catalyst. With so much trouble due to sediment, it was felt 
that temperatures could not be raised any higher with the first generation 
catalyst. 
TABLE VII 
______________________________________ 
EXAMPLE B 
Two-Stage Robinson Reactor Catalyst Test Results 
Single-Pass, Pure Resid, No Diluent, Once Through Hydrogen 
Age = 1.28 to 1.86 Barrels Per Pound 
(We have now raised temperature .sup..about. 10.degree. F. for Example 
I) 
1st Generation 
Catalyst Example I (HDS-1443B*) 
______________________________________ 
CSV (Bbl/Lb/Day) 0.0651 0.0643 
Temperature (.degree.F.) 770.3 760.7 
(Average both stages) 
Cut 4: (650.degree. F.+) 
Existent IP Sediment (wt %) 0.05 0.15 
Accelerated IP Sediment (wt %) 0.33 0.559 
Total Liquid Product 
% Sulfur Removal 75.9 71.7 
% Carbon Residue Reduction 57.3 52.5 
% Nickel Removal 73.9 62.7 
% Vanadium Removal 94.8 88.3 
% Hydroconversion of 1000.degree. F.+ 60.0 52.0 
to 1000.degree. F.- Materials (wt %) 
Kinetically Adjusted (CSV ONLY) 
% Hydroconversion of 1000.degree. F.+ 60.0 51.7 
to 1000.degree. F.- Materials (wt %) 
Cut 1: up to 650.degree. F. 
Specific Gravity (g/cc) 0.84 0.84 
Sulfur (wt %) 0.2 0.2 
Cut 2: 650.degree. F.-1000.degree. F. 
Specific Gravity (g/cc) 0.93 0.93 
Sulfur (wt %) 0.9 0.8 
Cut 3: 1000.degree. F.+ 
Specific Gravity (g/cc) 1.03 1.03 
Sulfur (wt %) 2.2 2.5 
______________________________________ 
*Criterion HDS1443B HOIL catalyst. 
**1st order CSTR kinetics (assuming equal rate constants for the 1st and 
2nd stage reactors).