Catalytic hydrocracking, hydrodesulfurization, and/or hydrodenitrogenation of organic compounds employing promoted zinc titanate and a zeolite as the catalytic agent

The catalytic hydrocracking, hydrodesulfurization, and/or hydrodenitrogenation of organic compounds is carried out in the presence of a catalyst composition comprising zeolite, zinc, titanium, and at least one promoter selected from the group consisting of vanadium, chromium, cobalt, nickel, molybdenum, tungsten, rhenium, platinum, palladium, rhodium, ruthenium and compounds thereof.

This invention relates to a process for hydrocracking a feedstock which 
contains at least one hydrocrackable organic compound and a catalyst 
therefor. In another aspect, this invention relates to a process for the 
hydrodesulfurization of organic sulfur compounds or hydrodenitrogenation 
of organic nitrogen compounds, and a catalyst therefor. In still another 
aspect, this invention relates to a one-stage process for hydrocracking a 
feedstock which contains at least one hydrocrackable organic compound, for 
hydrodesulfurizing any organic sulfur compounds and for 
hydrodenitrogenating any organic nitrogen compounds contained in the 
feedstock, and a catalyst therefor. 
Hydrodesulfurization is a process intended primarily to convert the sulfur 
in organic sulfur compounds to hydrogen sulfide. Hydrodenitrogenation is a 
process intended primarily to convert the nitrogen in organic nitrogen 
compounds to ammonia. Hydrodesulfurization and hydrodenitrogenation will 
generally occur at the same time under similar process conditions if both 
organic sulfur compounds and organic nitrogen compounds are present in the 
feed stream. The hydrogen sulfide and/or ammonia can be removed from the 
feed stream after the hydrodesulfurization and/or hydrodenitrogenation 
process. Hydrodesulfurization and hydrodenitrogenation are processes which 
are typically utilized to remove sulfur and nitrogen from a 
hydrocarbon-containing feedstock which also contains organic sulfur 
compounds and/or organic nitrogen compounds to produce fuels which, when 
burned, will meet environmental standards. The processes may be applied to 
feed streams other than hydrocarbon-containing feeds if organic sulfur 
compounds and/or organic nitrogen compounds are present and the removal of 
sulfur and/or nitrogen is desired. 
Hydrocracking refers to the process of breaking carbon-carbon bonds in the 
presence of hydrogen. The most general application of hydrocracking is to 
convert gas oils to gasoline. However hydrocracking can be utilized to 
convert naphtha to liquefied petroleum gas, convert residuum to a 
distillate, etc. 
Usually the feed for a hydrocracking process must first be passed through a 
hydrodesulfurization and/or hydrodenitrogenation process to remove sulfur 
and nitrogen to avoid poisoning the hydrocracking catalyst. Obviously, it 
would be desirable to avoid a two-stage process if catalyst poisoning 
could be avoided. 
It is thus an object of this invention to provide a one-stage process for 
hydrocracking a feedstock which contains at least one hydrocrackable 
organic compound, for hydrodesulfurizing any organic sulfur compounds 
contained in the feedstock, and for hydrodenitrogenating any organic 
nitrogen compounds contained in the feedstock. It is a further object of 
this invention to provide a catalyst composition which is useful for 
hydrocracking, hydrodesulfurization, and/or hydrodenitrogenation. 
In accordance with the present invention, a catalyst composition comprising 
zeolite, zinc, titanium and a promoter is utilized as a catalyst for a 
hydrocracking process, hydrodesulfurization process and/or 
hydrodenitrogenation process. The promoter is at least one member selected 
from the group consisting of vanadium, chromium, cobalt, nickel, 
molybdenum, tungsten, rhenium, platinum, palladium, rhodium, ruthenium, 
and compounds thereof. 
The catalyst composition is extremely resistant to poisoning by ammonia or 
hydrogen sulfide. The catalyst composition also exhibits a low coke 
formation rate which allows the use of long process cycles without 
regeneration and low operating temperatures. 
The catalyst composition may be utilized for hydrocracking only, if no 
organic sulfur compounds or organic nitrogen compounds are present in the 
feedstock. The catalyst composition may be utilized only for 
hydrodesulfurization and/or hydrodenitrogenation if desired. While the 
invention is particularly directed towards hydrocarbon-containing 
feedstreams, organic sulfur compounds and/or organic nitrogen compounds 
contained in any suitable gaseous stream may be hydrodesulfurized and/or 
hydrodenitrogenated in accordance with the present invention. Thus, while 
preferably the catalyst composition of the present invention is utilized 
in a hydrocracking process in which it is also desired to hydrodesulfurize 
organic sulfur compounds or hydrodenitrogenate organic nitrogen compounds, 
the catalyst composition of the present invention is also applicable to 
hydrocracking, hydrodesulfurization, or hydrodenitrogenation singly, or in 
any combination. 
Other objects and advantages of the invention will be apparent from the 
foregoing brief description of the invention and the appended claims, as 
well as from the detailed description of the invention which follows. 
Any suitable hydrocarbon containing feedstream can be hydrocracked in 
accordance with the present invention. Feedstreams which are considered to 
be advantageously and efficiently hydrocracked in accordance with the 
process of this invention include petroleum products and products from 
extraction and/or liquefaction of coal and lignite, products from tar 
sands, products from shale oil and similar products. Suitable hydrocarbons 
include naphtha, distillates, gas oil having a boiling range from about 
205.degree. to about 538.degree. C., topped crude having a boiling range 
in excess of about 343.degree. C. and residuum. In general, residuum and 
topped crude may be hydrocracked to produce a distillate or a naphtha 
while gas oils are generally hydrocracked to produce gasoline range 
materials and naphtha and distillates are hydrocracked to produce LPG. 
Organic sulfur compounds and/or organic nitrogen compounds contained in the 
hydrocarbon-containing feedstreams which are being hydrocracked may be 
hydrodesulfurized and/or hydrodenitrogenated in accordance with the 
present invention. It is again noted that while the invention is 
particularly directed to hydrocarbon-containing feedstreams which also 
contain organic sulfur compounds and/or organic nitrogen compounds, the 
invention is applicable to hydrocarbon-containing feedstreams which do not 
contain organic sulfur compounds and/or organic nitrogen compounds. The 
invention is also applicable to hydrodesulfurizing organic sulfur 
compounds and/or hydrodenitrogenating organic nitrogen compounds contained 
in any suitable fluid stream. Suitable fluid streams include not only the 
hydrocarbon-containing feeds previously mentioned but also include light 
hydrocarbons such as methane, ethane, ethylene and natural gas, gases such 
as hydrogen and nitrogen, gaseous oxides of carbon, steam, and the inert 
gases such as helium and argon. 
Any suitable organic sulfur compound can be hydrodesulfurized in accordance 
with the present invention. Suitable organic sulfur compounds include 
sulfides, disulfides, mercaptans, thiophenes, benzothiophenes, 
dibenzothiophenes and the like and mixtures of any two or more thereof. 
Any suitable organic nitrogen compound can be hydrodenitrogenated in 
accordance with the present invention. Suitable organic nitrogen compounds 
include amines, diamines, pyridines, quinolines, porphyrins, 
benzoquinolines and the like and mixtures of any two or more thereof. 
The catalyst employed in the process of the present invention is a 
composition comprising zeolite, zinc, titanium and a promoter. At least 
one member of the promoter is selected from the group consisting of 
vanadium, chromium, cobalt, nickel, molybdenum, tungsten, rhenium, 
platinum, palladium, rhodium, ruthenium, and compounds thereof. The 
preferred promoters are cobalt, nickel, molybdenum, tungsten and rhenium. 
The promoting elements are generally present on the catalyst as the oxide 
or the sulfide except for platinum which will generally be present as the 
element. The zinc and titanium are generally present as zinc titanate. 
The zinc titanate portion of the catalyst composition may be prepared by 
intimately mixing suitable portions of zinc oxide and titanium dioxide, 
preferably in a liquid such as water, and calcining the resulting mixture 
in a gas containing molecular oxygen at a temperature in the range of 
about 650.degree. C. to about 1050.degree. C., preferably in the range of 
about 675.degree. C. to about 975.degree. C. A calcining temperature in 
the range of about 800.degree. C. to about 850.degree. C. is most 
preferred because the surface area of the catalyst is maximized in this 
temperature range thus producing a more active catalyst. The titanium 
dioxide used in preparing the zinc titanate preferably has extremely fine 
particle size to promote intimate mixing of the zinc oxide and titanium 
dioxide. This produces a rapid reaction of the zinc oxide and titanium 
dioxide which results in a more active catalyst. Preferably the titanium 
dioxide has an average particle size of less than 100 millimicrons and 
more preferably less than 30 millimicrons. Flame hydrolyzed titanium 
dioxide has extremely small particle size and is particularly preferred in 
preparing the catalyst. The atomic ratio of zinc to titanium can be any 
suitable ratio. The atomic ratio of zinc to titanium will generally lie in 
the range of about 1:1 to about 3:1 and will preferably lie in the range 
of about 1.8:1 to about 2.2:1 because the activity of the catalyst is 
greatest for atomic ratios of zinc to titanium in this range. The term 
"zinc titanate" is used regardless of the atomic ratio of zinc to 
titanium. 
The zinc titanate portion of the catalyst composition may also be prepared 
by coprecipitation from aqueous solutions of a zinc compound and a 
titanium compound. The aqueous solutions are mixed together and the 
hydroxides are precipitated by the addition of an alkali metal hydroxide. 
The precipitate is then washed, dried and calcined, as described in the 
preceding paragraph, to form zinc titanate. This method of preparation is 
less preferred than the mixing method because the zinc titanate prepared 
by the coprecipitation method is softer than the zinc titanate prepared by 
the mixing method. 
The promoter, at least one member of which is selected from the group 
consisting of vanadium, chromium, cobalt, nickel, molybdenum, tungsten, 
rhenium, platinum, palladium, rhodium, ruthenium and compounds thereof, is 
generally present on the catalyst in the oxide or sulfide form except for 
platinum which will generally be present in the elemental form. The 
promoter can be added to the zinc titanate by any method known in the art. 
The promoter can be added to the zinc titanate as powdered oxide and 
dispersed by any method known in the art such as rolling, shaking or 
stirring. For ease of preparation, the preferred method of adding the 
promoter is by impregnating the preformed zinc titanate with a solution of 
a compound of the promoting element that becomes converted to the oxide 
during the subsequent preparation of the catalyst. The impregnated 
catalyst is dried to remove solvent and is then heated in the presence of 
molecular oxygen at a temperature in the range of about 500.degree. C. to 
about 650.degree. C., preferably about 540.degree. C. If more than one of 
the promoting elements is to be used in the catalyst composition, the 
catalyst composition is preferably dried and calcined after each addition 
of a promoting element. 
The concentration of the promoter can be any suitable concentration. The 
concentration of the total promoter, expressed as an element, will 
generally range from about 0.1 to about 24 weight percent based on the 
weight of the catalyst composition. The concentration of the vanadium, 
chromium, cobalt, nickel, molybdenum, or tungsten as individual promoting 
elements, expressed as an element, if present, will preferably be in the 
range of about 0.1 to about 16 weight percent based on the weight of the 
catalyst composition and will more preferably be in the range of about 1.6 
to about 8 weight percent. The concentration of rhenium, palladium, 
rhodium, ruthenium or platinum as individual promoting elements, expressed 
as the element, if present, will preferably be in the range of about 0.2 
to about 1.6 weight percent. 
Either the elemental form of the promoters or any suitable compound of the 
promoters may be used to form the catalyst composition. 
Vanadium compounds suitable for use as a promoter include di-, tri-, 
tetra-, and pentavalent vanadium oxides, vanadium (III) sulfide, vanadium 
(IV) oxide sulfate, ammonium metavanadate, sodium metavanadate, and the 
like and mixtures of any two or more thereof. 
Chromium compounds suitable for use as a promoter include ammonium chromate 
and ammonium dichromate, chromic nitrate, chromium (III) oxide, chromium 
(VI) oxide, chromic sulfate, potassium chromate and potassium dichromate, 
chromic acetate, and the like and mixtures of any two or more thereof. 
Cobalt compounds suitable for use as a promoter include cobalt acetate, 
cobalt carbonate, cobalt nitrate, cobalt oxide, cobalt sulfate, cobalt 
thiocyanate, and the like and mixtures of any two or more thereof. 
Nickel compounds suitable for use as a promoter include nickel acetate, 
nickel carbonate, nickel nitrate, nickel oxide, nickel sulfate ammonium 
nickel sulfate, nickel sulfamate, and the like and mixtures of any two or 
more thereof. 
Molybdenum compounds suitable for use as a promoter include ammonium 
molybdate, ammonium heptamolybdate, molybdenum oxides such as molybdenum 
(IV) oxide and molybdenum (VI) oxide, molybdenum sulfide, and the like and 
mixtures of any two or more thereof. 
Tungsten compounds suitable for use as a promoter include ammonium 
tungstates such as ammonium metatungstate and ammonium paratungstate, 
tungsten oxides such as tungsten (IV) oxide and tungsten (VI) oxide, 
tungsten sulfides such as tungsten (IV) sulfide and tungsten (VI) sulfide, 
heteropoly acids such as tungstophosphoric acid and tungstosilicic acid, 
and the like and mixtures of any two or more thereof. 
Rhenium compounds suitable for use as a promoter include perrhenic acid, 
ammonium perrhenate, rhenium oxides such as rhenium (VI) oxide and rhenium 
(VII) oxide, rhenium sulfide, and the like and mixtures of any two or more 
thereof. 
Platinum compounds suitable for use as a promoter include dihydrogen 
hexachloroplatinate, diamineplatinum (II) nitrate, tetraamineplatinum (II) 
nitrate, and the like and mixtures of any two or more thereof. 
Ruthenium, rhodium, and palladium nitrates are a suitable form for the 
addition of these elements as catalyst promoters. 
Halogen-containing compounds of the promoting elements can be used as 
promoters. However, the user should be aware of the possibility of 
corrosion caused by their presence. 
Any suitable zeolite may be utilized in the catalyst composition. The 
preferred zeolite is a Y-type zeolite which has a low sodium content 
preferably not greater than about 0.5 weight percent and more preferably 
not greater than about 0.2 weight percent. Linde LZ-Y82, a zeolite 
commercially available from the Linde Division of Union Carbide 
Corporation, is a suitable zeolite. Y-type zeolites and removal of sodium 
are described in the Kirk-Othmer Encyclopedia of Chemical Technology, 
Second Edition, Volume 18, pages 157-158. 
The zeolite may be present in the catalyst composition in any suitable 
concentration. Preferably, the concentration of the zeolite will be in the 
range from about 1 to about 60 weight percent of the total catalyst 
composition and will more preferably be in the range of about 10 to about 
40 weight percent of the total catalyst composition. 
Preferably, the promoter is added to the zinc titanate prior to combining 
the promoted zinc titanate with the zeolite. The promoted zinc titanate 
may be combined with the zeolite in any suitable manner. One method of 
combining the promoted zinc titanate with the zeolite is to mix the solid 
powders and then add sufficient distilled water to produce a slurry. The 
resulting slurry is dried and then calcined in the presence of molecular 
oxygen at a temperature in the range of about 500.degree. C. to about 
650.degree. C., preferably about 540.degree. C., for two or more hours. 
The thus calcined material may be pilled, extruded, or crushed and 
screened to an appropriate size. 
The most preferred catalyst composition comprises a low sodium Y-type 
zeolite, zinc titanate, cobalt and molybdenum. The concentration of the 
low sodium Y-type zeolite in the preferred catalyst composition is in the 
range of about 10 to about 40 weight percent. The atomic ratio of cobalt 
to molybdenum in the preferred catalyst composition is in the range of 
about 0.6:1 to about 0.8:1. 
The catalyst may become sulfided during the hydrocracking process if 
organic sulfur compounds or hydrogen sulfide is present in the feedstream 
or may be presulfided. The catalyst is preferably presulfided even if the 
catalyst is to be used only for hydrocracking or hydrodenitrogenation. The 
presulfiding of the catalyst is preferred before the catalyst is initially 
used and after each regeneration of the catalyst. Preferably, the catalyst 
is presulfided in two steps. The catalyst is first treated with a mixture 
of hydrogen sulfide in hydrogen at a temperature in the range of about 
175.degree. C. to about 225.degree. C., preferably about 205.degree. C. 
The temperature in the catalyst composition will rise during this first 
presulfiding step and the first presulfiding step is continued until the 
temperature rise in the catalyst has substantially stopped or until 
hydrogen sulfide is detected in the effluent flowing from the reactor. The 
mixture of hydrogen sulfide and hydrogen preferably contains in the range 
of about 5 to about 20 mole percent hydrogen sulfide, preferably about 10 
mole percent hydrogen sulfide. 
The second step in the presulfiding process consists of repeating the first 
step at a temperature in the range of about 350.degree. C. to about 
400.degree. C., preferably about 370.degree. C. It is noted that other 
mixtures containing hydrogen sulfide or other sulfur-containing compounds 
may be utilized to presulfide the catalyst. Also the use of hydrogen 
sulfide is not required. In a commercial operation, it is common to 
utilize a light naphtha containing sulfur to presulfide the catalyst. 
The pre-sulfided form is the most active state of the catalyst. However, 
since the zinc titanate portion of the catalyst becomes sulfided up to 
about 25 weight percent of the zinc titanate, the presulfiding time as 
described above might be too lengthy to be practical in a commercial 
operation. An alternative method is sulfiding with the feed to be 
processed at mild conditions where coke formation on the catalyst is 
minimal. The feed is preferably recycled until the desired sulfur content 
is reached, and the gaseous effluent containing hydrogen sulfide is also 
recycled. When the desired catalyst activity is reached the recycle 
operation is discontinued. 
The process of this invention can be carried out by means of any apparatus 
whereby there is achieved a contact with the catalyst of the organic 
compounds to be hydrocracked, hydrodesulfurized and/or 
hydrodenitrogenated. The process is in no way limited to the use of a 
particular apparatus. The process of this invention can be carried out 
using a fixed catalyst bed, fluidized catalyst bed, or moving catalyst 
bed. Presently preferred is a fixed catalyst bed. 
Any suitable temperature for hydrocracking, hydrodesulfurization and/or 
hydrodenitrogenation over the catalyst composition of the present 
invention can be utilized. The temperature will generally be in the range 
of about 260.degree. C. to about 482.degree. C. and will more preferably 
be in the range of about 316.degree. C. to about 399.degree. C. In the 
upper end of the preferred range (about 371.degree. C. to about 
399.degree. C.), hydrocracking, hydrodenitrogenation and 
hydrodesulfurization all occur at a high level. In the lower end of the 
preferred range (about 316.degree. C. to about 343.degree. C.) 
hydrodenitrogenation occurs at a high level, hydrodesulfurization occurs 
at a moderate level, and hydrocracking occurs at a low level. 
Any suitable pressure for the hydrocracking, hydrodesulfurization and/or 
hydrodenitrogenation process over the catalyst composition of the present 
invention can be utilized. In general, the pressure will be in the range 
of about 200 to about 2500 psig total system pressure for the process. The 
total system pressure is the sum of the partial pressure of the feedstock 
plus the partial pressure of the added hydrogen. Preferably, the total 
system pressure will range from about 500 to about 1500 psig for the 
process. 
Any suitable quantity of hydrogen can be added to the hydrocracking, 
hydrodesulfurization and/or hydrodenitrogenation process. The quantity of 
hydrogen used to contact the feedstock being hydrocracked, 
hydrodesulfurized and/or hydrodenitrogenated in terms of standard cubic 
feet (SCF)/barrel (bbl) will be in the range of about 100 to about 10,000 
SCF/bbl. and will more preferably be in the range of about 500 to about 
3000 SCF/bbl. 
Any suitable residence time for the feedstock in the presence of the 
catalyst composition of the present invention can be utilized. In general, 
the residence time in terms of liquid hourly space velocity, i.e. the 
volumes of liquid per volume of catalyst per hour (LHSV), can range from 
about 0.1 to about 10 and will more preferably range from about 0.5 to 
about 3. 
To maintain the activity of the catalyst composition, the process 
temperature is generally gradually increased to compensate for loss of 
catalyst activity due to fouling of the catalyst. When the temperature of 
the process cannot conveniently be increased further, the catalyst is 
typically regenerated by terminating the flow of feed to the reactor, 
purging with an inert fluid such as nitrogen to remove combustibles and 
then introducing a free oxygen-containing fluid to oxidize the 
carbonaceous deposits which have formed on the catalyst during the 
process. The catalyst will generally be utilized for a year or longer 
before being regenerated but may have to be regenerated sooner if a 
particularly heavy feedstock is being hydrocracked. 
Any suitable purge time may be utilized. The purge duration will generally 
be of sufficient duration to remove all hydrocarbons and hydrogen from the 
system. Any suitable flow rate of the purge gas may be utilized. Presently 
preferred is a purge fluid flow rate in terms of gas hourly space velocity 
(GHSV) in the range of about 800 GHSV to about 1200 GHSV. 
The amount of oxygen, from any source, supplied during the regeneration 
step, will be sufficient to remove carbonaceous materials from the 
catalyst and will preferably be in 1-5 mol percent concentration. The 
regeneration step is conducted at generally the same pressure recited for 
the hydrocracking, hydrodesulfurization and/or hydrodenitrogenation 
process but can be carried out at lower pressure if desired. The 
temperature for the regeneration step is preferably maintained in the 
range of about 425.degree. C. to about 540.degree. C. in order to remove 
any carbonaceous deposits on the catalyst within a reasonable time, 
although the temperature can be as high as 620.degree. C. Regeneration 
will also partially convert the sulfided catalyst to the oxide form and 
the presulfiding step is preferably repeated. 
Any suitable time for the regeneration of the catalyst composition can be 
utilized. The regeneration effluent should be substantially free of carbon 
dioxide at the end of the regeneration period.

The following examples are presented in further illustration of the 
invention. 
EXAMPLE I 
Zinc titanate was prepared by combining Mallinckrodt zinc oxide with 
Cab-O-Ti titanium dioxide in water and mixing for 10 minutes in a blender. 
The resulting slurry was dried in an oven at 105.degree. C. and then 
calcined by heating in air at 816.degree. C. for three hours. After 
cooling, the calcined solid was crushed and screened. A &lt;40 mesh portion 
of the thus screened zinc titanate was utilized to prepare catalyst A. The 
atomic ratio of zinc to titanium in the zinc titanate was 1.8:1. 
Cobalt and molybdenum promoters were added to the thus prepared zinc 
titanate by first covering the zinc titanate with an aqueous solution of 
cobalt as Co(NO.sub.3).sub.2.6H.sub.2 O. After standing one hour at 
25.degree. C., excess solution was removed by decanting or filtering and 
the wet zinc titanate was dried with occasional stirring. The thus dried 
zinc titanate was calcined in air in a muffle furnace for 3-4 hours at 
538.degree. C. and cooled in a dessicator. The cobalt promoted zinc 
titanate was then covered with an aqueous solution of molybdenum as 
(NH.sub.4).sub.6 Mo.sub.7 O.sub.24.4H.sub.2 O. After standing one hour at 
25.degree. C., excess solution was removed by decanting and the wet 
promoted zinc titanate was dried with occasional stirring. The thus dried 
zinc titanate promoted with cobalt and molybdenum was calcined in air in a 
muffle furnace for 3-4 hours at 538.degree. C. and cooled in a dessicator. 
The resulting cobalt and molybdenum promoted zinc titanate was combined 
with Linde zeolite LZ-Y82 (a type Y zeolite) by slurrying the cobalt and 
molybdenum-promoted zinc titanate and the Linde zeolite LZ-Y82 in 
distilled water. The resulting slurry was dried and heated to 1000.degree. 
F. The thus dried combination of zeolite, zinc titanate, cobalt and 
molybdenum was then crushed and screen to 16-40 mesh size and hereinafter 
is designated as catalyst A. 
An analysis of catalyst A is as follows: bulk density 0.75 3 g/cc; surface 
area 49.5 m.sup.2 /g; wt. % Zn 44.2; wt. % Ti 17.2; wt. % CoO 0.51; wt % 
MoO.sub.3 1.56. The wt. % Y zeolite was calculated to be 14.22. X-ray 
diffraction showed the major zinc component present to be zinc titanate. 
ZnO and ZnTiO.sub.3 were also present in minor amounts. 
The hydrodesulfurization and hydrodenitrogenation activity of catalyst A 
was compared with Shell 344, which is a commercial cobalt 
molybdate/alumina hydrotreating catalyst. Analysis of Shell 344 is as 
follows: bulk density, 0.79 g/cc; pore volume, 0.5 cc/g; surface area 186 
m.sup.2 /g; wt. % CoO, 2.99; wt. % MoO.sub.3 14.42. For the comparison the 
feedstock was a blend of a 70 percent straight run distillate and a 30 
percent light cycle oil. The feedstock had a boiling range of 
99.degree.-382.degree. C., contained 0.75 weight percent sulfur and 187 
parts per million nitrogen. The comparison was made using a 316 stainless 
steel reactor having a 1-inch outside diameter, a 0.8-inch inside diameter 
and a length of 5 inches. Catalyst volume in the reactor was 10 cc diluted 
with inert alundum to make 25 cc total volume. The feedstock was fed to 
the reactor at a rate of 2.5 LHSV. Hydrogen was fed to the reactor at a 
rate of 5000 standard cubic feet/bbl. The reaction effluent passed from 
the reactor to a high pressure liquid-vapor separator. Total system 
pressure in the reactor was 500 psig. 
Prior testing the catalyst, the reactor containing the catalyst was purged 
with an inert gas and the catalyst was pretreated with the feedstock for a 
time sufficient for the catalyst to become sulfided. After the catalyst in 
the reactor had been presulfided, a temperature survey was made in the 
sequence of 750.degree., 800.degree., 600.degree., 650.degree., 
700.degree., and 750.degree. F. During the temperature survey, liquid 
product was removed from the high pressure liquid-vapor separator for 
analysis for sulfur, nitrogen, carbon, hydrogen and hydrocarbon type. 
Both hydrogen sulfide and ammonia were removed from the liquid product 
prior to analysis for sulfur and nitrogen by a caustic wash (10% KOH). The 
analysis for sulfur was done by X-ray fluorescence. The analysis for 
nitrogen was carried out by chemiluminescence techniques. A standard 
combustion analysis was utilized to analyze for carbon and hydrogen. A 
mass spectrometer structural analysis was utilized to analyze for 
hydrocarbon type. 
Table I summarizes test results for the comparison of catalyst A and Shell 
344: 
TABLE I 
______________________________________ 
% HDS % HDN 
Temp. (.degree.F.) 
Catalyst A 
Shell-344 Catalyst A 
Shell-344 
______________________________________ 
600 (346.degree. C.) 
55.3 90.7 99.5 82.2 
650 (343.degree. C.) 
81.3 96.0 100 73.4 
700 (371.degree. C.) 
98.4 97.3 100 71.0 
750 (399.degree. C.) 
97.5 98.8 100 74.3 
800 (427.degree. C.) 
97.9 97.3 100 82.7 
______________________________________ 
Table I illustrates that catalyst A was superior to Shell 344 for 
hydrodenitrogenation at all temperatures and closely corresponded to the 
hydrodesulfurization activity of Shell 344 at the higher temperatures 
tested. 
EXAMPLE II 
The hydrocracking activity of catalyst A was illustrated using the reactor, 
feedstock and process conditions of Example I. A time survey was made at 
650.degree. F. and 750.degree. F. Prior to the time survey of 650.degree. 
F., catalyst A was presulfided by exposing catalyst A to the feedstock at 
a flow rate of 2.5 LHSV and a temperature of 750.degree. F. for about 18 
hours. 
TABLE II 
__________________________________________________________________________ 
Reactor Temp. 650.degree. F. (343.degree. C.) 
750.degree. F. (399.degree. C.) 
Feed 
__________________________________________________________________________ 
Time on stream (hrs.)* 
26 56 94 35 62 100 
Conv. of 400.degree. F. + (204.degree. C.) 
Feed (wt. %) 31.0 
20.3 
8.2 87.6 
67.9 
73.7 
Conv. of 500.degree. F. + (204.degree. C.) 
Feed (wt. %) 43.9 
31.4 
23.4 
92.1 
78.3 
87.9 
% HDS 81.3 
65.3 
64.4 
97.5 
94.9 
98.0 
% HDN 100 100 100 100 100 100 
Yields (wt. %)** 
C.sub.1 -C.sub.4 (Gas product) 
9.7 9.4 3.7 33.3 
17.1 
25.4 
0 
C.sub.5 -400.degree. F.(204.degree. C.) 
gasoline Liquid Product 
33.6 
23.8 
20.1 
56.4 
56.0 
58.2 
17.1 
400.degree. + (204.degree. C.) 
56.6 
66.8 
76.2 
9.9 26.9 
16.4 
82.9 
Liquid Product 
S (wt. %) 0.140 
0.260 
0.267 
0.019 
0.038 
0.015 
0.75 
N (ppm) 0 0 0 0 0 0 187 
.degree.API.sub.60 
43.7 
40.1 
39.7 
59.8 
52.6 
56.6 
36.1 
% C 86.33 
86.40 
-- 86.24 
86.37 
86.81 
86.41 
% H 13.36 
13.25 
-- 13.03 
13.18 
13.26 
12.93 
Paraffin 39.6 
36.3 
-- 42.4 
43.2 
-- 35.1 
Naphthenes 33.2 
34.8 
-- 23.4 
28.0 
-- 33.9 
Aromatics 27.2 
28.9 
-- 32.4 
28.8 
-- 31.0 
__________________________________________________________________________ 
*Catalyst was presulfided by 18 hours exposure to feed at 2.5 LHSV at 
750.degree. F. 
**Calculated on an H.sub.2 S free basis. 
Significant hydrocracking activity is indicated by the conversion of the 
500.degree. F. and 400.degree. F. fractions to lower boiling materials. 
Hydrodesulfurization activity and hydrodenitrogenation activity are 
indicated by the %HDS, %HDN, lower wt % of sulfur and lower parts per 
million of nitrogen. 
EXAMPLE III 
Linde zeolite LZ-Y82 was impregnated with an aqueous solution of molybdenum 
as (NH.sub.4).sub.6 Mo.sub.7 O.sub.24.4H.sub.2 O and an aqueous solution 
of cobalt as Co(NO.sub.3).sub.2.6H.sub.2 O at the same time. The thus 
impregnated Linde zeolite 33-200 was then dried and calcined in air at a 
temperature of 1000.degree. F. The resulting cobalt and molybdenum 
promoted zeolite is designated hereinafter as catalyst B. The weight 
percent of cobalt as cobalt oxide was 1.8 while the weight percent of 
molybdenum as molybdenum oxide was 6.3. 
Catalyst A and B were compared using the reactor, feedstock and process 
conditions of Example I. Table III indicates that the presence of zinc 
titanate generally improved hydrodesulfurization and hydrodenitrogenation 
and also provided an impoved hydrocracking catalyst. 
TABLE III 
__________________________________________________________________________ 
Catalyst A Catalyst B Feed 
__________________________________________________________________________ 
Reactor Temp. (.degree.F.) 
750 650 750 750 650 750 
Time on stream (hrs) 
23 32 58 23 32 58 
Conv. of 400.degree. F. + (204.degree. C.) 
73.7 
5.6 24.5 
58.6 
4.1 19.2 
(wt. %) 
Conv. of 500.degree. F. + (260.degree. C.) 
87.9 
22.5 
32.1 
76.3 
18.8 
40.2 
(wt. %) 
% HDS 98.0 
64.4 
73.9 
92.0 
55.2 
70.8 
% HDN 100 100 100 100 93.0 
95.7 
Yields (wt. %)* 
C.sub.1 -C.sub.4 (gas product) 
25.4 
3.4 7.1 27.1 
2.3 8.5 0 
C.sub.5 -400.degree. F. gasoline 
58.2 
20.1 
24.8 
47.6 
19.2 
31.0 
16.2 
400 .degree. F. + 
16.4 
76.2 
68.1 
25.3 
78.5 
54.8 
83.8 
Liquid Product 
S (wt. %) 0.015 
0.267 
0.196 
0.082 
0.336 
0.219 
0.75 
N (ppm) 0 0 0 0 13 8 187 
.degree.APL.sub.60 
56.6 
39.7 
41.7 
50.6 
38.6 
42.6 
36.1 
% C 86.81 
-- -- 87.16 
-- -- 86.91 
% H 13.26 
-- -- 13.02 
-- -- 12.93 
Paraffin -- -- -- 43.7 
-- -- 35.1 
Naphthenes -- -- -- 21.1 
-- -- 33.9 
Aromatics -- -- -- 35.1 
-- -- 31.0 
__________________________________________________________________________ 
*Calculated on an H.sub.2 S free basis. 
EXAMPLE IV 
Zinc titanate was prepared by combining Mallinckrodt zinc oxide with 
Degussa flame hydrolyzed titanium dioxide in water and mixing for 10 
minutes in a blender. The resulting slurry was dried in an oven at 
105.degree. C. and then calcined by heating in air at 816.degree. C. for 
three hours. After cooling, the calcined solid was crushed and screened. A 
&lt;40 mesh portion of the thus screened zinc titanate was utilized to 
prepare catalyst C. The atomic ratio of zinc to titanium in the zinc 
titanate was 1.8:1. 
Cobalt and molybdenum promoters were added to the thus prepared zinc 
titanate by first covering the zinc titanate with an aqueous solution of 
cobalt as Co(NO.sub.3).sub.2.6H.sub.2 O. After standing one hour at 
25.degree. C., excess solution was removed by decanting or filtering and 
the wet zinc titanate was dried with occasional stirring. The thus dried 
zinc titanate was calcined in air in a muffle furnace for 3-4 hours at 
538.degree. C. and cooled in a dessicator. The cobalt promoted zinc 
titanate was then covered with an aqueous solution of molybdenum as 
(NH.sub.4).sub.6 Mo.sub.7 O.sub.24.4H.sub.2 O. After standing one hour at 
25.degree. C., excess solution was removed by decanting and the wet 
promoted zinc titanate was dried with occasional stirring. The thus dried 
zinc titanate promoted with cobalt and molybdenum was calcined in air in a 
muffle furnace for 3-4 hours at 538.degree. C. and cooled in a dessicator. 
The resulting cobalt and molybdenum promoted zinc titanate was combined 
with Linde zeolite LZ-Y82 by slurrying the cobalt and molybdenum-promoted 
zinc titanate and the Linde zeolite LZ-Y82 in distilled water. The 
resulting slurry was dried and heated to 1000.degree. F. The thus dried 
combination of zeolite, zinc titanate, cobalt and molybdenum was then 
crushed and screened to 16-40 mesh size. 
The fines left after screening the resulting zeolite, zinc titanate, cobalt 
and molybdenum catalyst composition were slurried with additional Linde 
LZ-Y82 zeolite. The resulting slurry was dried and heat calcined in air 
for about 4 hours at 1000.degree. F. The resulting calcined composition 
was crushed and screened to give 10-30 mesh particles and is hereinafter 
designated as catalyst C. Catalyst C contained 37 weight percent zeolite 
which was a significantly larger concentration of zeolite than was present 
in catalyst A. The surface area of catalyst C was 200 m.sup.2 /g; the wt % 
CoO was 2.7 and the wt % MoO.sub.3 was 2.6. 
Catalyst C was tested using the reactor, feedstock, and process conditions 
of Example I. A time survey was made at 750.degree. F. The results of the 
test are presented in Table IV. 
TABLE IV 
______________________________________ 
750 
Reactor temp. (.degree.F.) 
(399+ C.) 
750 750 FEED 
______________________________________ 
Time on stream (hrs)* 
17 70 166 
Conv. of 500.degree. F. + (wt. %) 
70.2 54.3 55.6 
% HDS 86.8 85.5 78.5 
% HDN 100 100 100 
Yields (wt. %)** 
C.sub.1 -C.sub.4 (gas product) 
10.4 16.1 12.6 0 
C.sub.5 -400.degree. F. gasoline 
50.0 35.2 36.7 13.2 
400.degree. F. + 
39.6 48.7 50.7 86.8 
Liquid Product 
S (wt. %) 0.099 0.109 0.161 0.75 
N (ppm) 0 1 0 222 
.degree.API.sub.60 
48.7 48.7 45.1 36.1 
______________________________________ 
*catalyst not presulfided 
**calculated on an H.sub.2 S free basis 
Comparing the data of Table IV to the data of Table III catalyst A at 23 
and 58 hours showed 87.9% and 32.1% conversion of the 500.degree. F.+ 
fraction respectively while catalyst C at 17 and 70 hours showed 70.2% and 
54.3% conversion of the 500.degree. F.+ respectively. This, while catalyst 
C is initially not as active as catalyst A, catalyst C maintained higher 
activity over a long period of time. This illustrates that the higher 
zeolite content in catalyst C imparts longer life to the catalyst. 
Reasonable variations and modifications are possible within the scope of 
the disclosure and the appended claims to the invention.