Note: Descriptions are shown in the official language in which they were submitted.
\
HYDROCARBON CONVERSION CATALYSIS
BACKGROUND OF THE INVENTION
This invention relates to improved catalytic
compositions having utility in hydrocarbon conversion
processes. In a specific aspect, the invention
relates to improved catalytic compositions having
utility in hydrogen treating of hydrocarbon feed
materials.
Catalytic compositions containing a catalytically
active metallic component deposed on a non zeolitic,
refractory inorganic oxide support are well known
as are numerous uses therefore Familiar examples
include petroleum and synthetic crude oil hydrotreating
and hydrocracking catalysts comprising a Group VIM
and/or VIII metal such as cobalt, nickel, molybdenum
and/or tungsten deposed on a non-zeolitic, refractory
inorganic oxide such as alumina, silica, magnesia,
etc. and olefin polymerization catalysts comprising
a Group VIM metal deposed on silica or silica-alur.lina
supports.
It also is known that the activity or performance
of catalysts of the type described hereinabove for
reactions such as hydrocracking, disproportionation
and oligomeri~ation can be improved or modified by
inclusion in the catalyst of a crystalline molecular
sieve zealot component. Thus U.S. 3,649l523
~Bertolacini et at.) discloses a hydrocarbon convert
soon process, and particularly hydrocracking and
disproportionation of petroleum hydrocarbon feed
materials, carried out in the presence of improved
catalysts comprising a metallic component having
hydrogenating activity deposed on a support component
comprising a large pore crystalline aluminosilicate
and a porous support material such as alumina, silica
or aluminum phosphate. U.S. 3,894,930 and U.S.
4,054,539 (both ensoul) disclose hydrocracking in
the presence of improved catalysts comprising a
metallic hydrogenating component and a support
component comprising ultra stable large pore crystal-
line aluminosilicate and silica alumina U.S.
3,876,522 (Campbell et at,) discloses preparation
of lube oils by a process that includes a hydra-
cracking step in which there are employed catalysts
containing a composite of a crystalline alumina-
silicate zealot component and a porous refractory
Lo oxide component such as alumina or silica, such
composite containing deposited or exchanged catalytic
metals. U.S. 4,029,601 (Wise) discloses oligomeri-
ration of alikeness using a cobalt oxide-active carbon
composite supported on a refractory oxide such as
silica or alumina and/or crystalline aluminosilicate
zealots. Other processes in which catalysts comprise
in catalytically active metals and a support combo-
next comprising a porous oxide and a crystalline
molecular sieve zealot are useful include isomer-
ration of alkylaromatics and alkylation of aromatics
and paraffins.
It also is known that the performance of various
catalysts containing catalytically active metals
deposed on a non-zeolitic, refractory inorganic
oxide support component can be improved or modified
by inclusion of phosphorus in the catalytically
active metallic component or through the use of
phosphorus compounds in catalyst preparation For
example, U.S. 3,287,280 (Colgan et at.) discloses
that the use of phosphoric acid solutions of nickel
and/or molybdenum salts to impregnate non-zeolitic
supports such as alumina or silica leads to improved
dispersion of catalytically active metals on the
support surface and improved results in hydrodesul~
furization of petroleum hydrocarbon feeds. The
patentee also discloses that phosphoric acid residues
remaining in the catalyst impart thermal stability
thereto. U.S. 3,840~472 (Colgan) contains a similar
disclosure with respect to the use of phosphoric
acid impregnating solutions of active metal salts.
U.S. 4,165,274 (Kant) discloses a two step process
for hydrotreating and hydrocracking tar sands oils
wherein hydrotreating takes place in a first stage
in the presence of an alumina-supportedl fluorine
and phosphorus-containing nickel-molybdenum catalyst,
lo after which hydrocracking is conducted in the presence
of a catalyst-containing nickel and tungsten supported
on a low-sodium, Y type molecular sieve support
component. U.S. 3,985,676 (Refers et at.) discloses
catalysts for polymerization of olefins prepared by
deposition of various organophosphorus compounds of
chromium onto high surface area non-zeolitic supports
such as silica or silica-alumina followed by thermal
activation of the result.
Notwithstanding similarities in the basic gala-
lyric composition catalytically active metal come
potent deposed on non-zeolitic refractory inorganic
oxide support component into which phosphorus or
crystalline molecular sieve zealot components have
been incorporated according to the above-described
proposals, the reported effects of the zealot and
phosphorus components are, in many respects, surf-
ficiently unrelated as to mitigate against attempting
to combine the effects of the components into a
single catalyst. For example, the improved hydra-
cracking activity of the above-described zealot-
containing catalysts typically would not be desired
in a hydrodesulfurization or hydrodenitrogenation
catalyst because in typical hydxotreating processes
employing such catalysts it is preferred to limit
cracking. Similarly, the improved hydrodesulfuri-
ration activity of phosphorus-promoted catalysts
--4--
such as those of Colgan et at. would be of little
consequence within the context of a cracking, alkali-
lion, isomerization or disproportionation process.
On the other hand, we have previously found what a
phosphorus component incorporated into the hydra-
jointing component of certain hydrotreating catalyst
exerts a promotional effect with respect to donator-
genation of high nitrogen feeds while crystalline
molecular sieve zealot components incorporated
into catalysts containing similar active metals but
free of phosphorus exerts a promotional effect with
respect to denitrogenation and hydrocracking react
lions.
It also is known from Rob, Zealot Chemistry
no Catalysis, AS Monograph 171, American Chemical
Society, pages 294-297 (1976), that many crystalline
molecular sieve zealots possess only limited stab-
lily with respect to strong acids such as the pros-
phonic acid used according to Colgan et at. Accord-
tingly, it can be speculated that attempts to combine the promotional effects of phosphoric acid and cry-
stalling molecular sieve zealots have been limited
by concern over destruction of the zealot component.
U.S. 3,617,S28 (Hilfman), which is directed to
preparation of supported nickel-containing catalysts
by coextrusion of a phosphoric acid solution of
nickel or nickel and Group VIM metal compounds and
an alumina-containing carrier, suggests the use of
carriers containing silica and alumina that are
amorphous or zeolitic in nature Column lines
39-43. Crystalline aluminosilicate zealots specify
icily disclosed by Hilfman are mordant, faujasite
and Types A and U molecular sieves Column 3 lines
42-46. Hilfman does not address the effect of the
acid on zealot integrity or crystallinity, nor is
there any disclosure or suggestion as to whether
I
any zealot employed in the disclosed preparations
would remain intact in the final catalyst. In fact,
none of the disclosed crystalline aluminosi:Licate
zeolikes, or any other for that matter, is employed
in the patentee's examples. Further, U.S. 3,706,6~3
(Michelson et at. '693) and U.S. 3,725,243 (sass eke
alp) teach that exposure of zealots to strong acids
such as phosphoric acid destroys zealot crystallinity
and integrity. In fact, both Michelson et at. '693
and Hess et alp are directed specifically to catalyst
preparations in which impregnation of crystalline
aluminosilicate-containing supports with phosphoric
acid solutions of salts of hydrogenating metals
results in destruction ox zealot crystallinity.
Further, three of the four crystalline aluminosilicate
zealots specifically disclosed by Hilfman (faujasite,
mordant and Type A molecular sieve) are included
among the crystalline aluminosilicate zealots that
are preferred for use in Michelson et Allis and
Hess et Allis zeolite-destructive preparations.
The aforesaid Rob publication teaches that among
Zealot A, faujasite and mordant, only the latter
exhibits appreciable acid stability.
U.S. 3,905,914 (Juries et at.) is directed
to preparation of oxidation catalysts by mixing a
vanadium compound, zirconium salt and hydrogen halide,
and then adding phosphoric acid or a compound hydra-
losable to phosphoric acid. The result is reflexed
to form a gel which then is dried, or loused to impreg-
Nate a suitable carrier, such as alumina, alundum,
silica, silicon carbide, silica-alumina, zircon,
zirconium phosphate and/or a zealot." Column 2
lines 47-51. Juries et at. does not identify any
zealots nor do the patentee's examples illustrate
preparation of a supported catalyst. Also, no con-
side ration is given to acid stability of zealots
I
and there is no indication whether any zealot used
in the disclosed catalyst preparation would remain
intact.
Similar to the Michelson et at. '693 and Hess
et at. patents discussed hereinabove, U.S. 3,749,663,
3,749,664 and 3,755,150 (all ~ickelson) are directed
Jo impregnation of support materials with phosphoric
acid solutions of salts of catalytically active
metals. Although none of these patents discloses
10 impregnation of support materials containing a zoo-
file component, each patent expressly cautions against
exposure of supports containing aluminum ions to
phosphoric acid at relatively low pi stating that
reaction of the acid and aluminum degrades the sup-
15 port, fouls the impregnation solution and results
in formation of undesirable chemical forms in the
finished catalyst. (See Michelson '663 at Column 8
lines 60-69, Michelson '664 at Column 8 lines 6-15,
Michelson '150 at Column 9 lines 12-21.)
U.S. 3,836,561 (Young) also deals with acid
treatment of crystalline aluminosilicate zealots.
According to Young, alumina-containing compositions,
including those containing crystalline aluminosilicate
zealots, are reacted with aqueous acids including
25 hydrochloric, sulfuric, nitric, phosphoric and
various organic acids, at a pi below about 5 in the
presence of an ionizable salt that is soluble in
the aqueous phase, and then the result is washed,
dried and calcined. The result of such treatment
30 is removal of aluminum from the alumina-containing
composition, replacement thereof with metallic cations
if the ionizable salt is one containing cations
that can be exchanged into the zealot, increased
porosity and decreased bulk volume of the catalyst.
35 The resulting compositions are said to have utility
as absorbents, ion exchange resins, catalysts and
1 1.9~ ?~,
catalyst supports. Acid-stable zealots and the
effects of acid treatment on zealot crystallinity
are discussed at Column 2 lines 61-68. Of course,
Young's acid treatment differs from the use of pros-
phonic acid according to the patents discussed here-
in above in that Young's purpose is to remove aluminum
from the composition rather than to incorporate
phosphorus into it. It also differs from the patents
discussed hereinabove in that the disclosed compost-
lions lack a catalytically-active metallic component
deposed on the alumina-containing carrier.
Other patents and publications that may be of
interest to the present invention in disclosing
treatment of crystalline molecular sieve zealots
or compositions containing the same with phosphoric
acid and other phosphorus compounds to incorporate
phosphorus into the zealot are U.S. 3,962,364 (Young)
and U.S. 4,274,982, 4,276,437 and 4,276,438 (all
Chum). According to these patents, suitable phosphorus
compounds include halides, oxyhalides, oxyacids, and
organophosphorus compounds such as phosphines, pros-
whites and phosphates. Incorporation of phosphorus
according to these patents is reported to improve
para-selectivity in alkylation reactions. Chum '982
further discloses treatment of the phosphorus-
containing zealots with magnesium compounds. Chum
'437 discloses impregnation of the phosphorus treated
compositions with solutions of gallium, iridium or
thallium compounds. Chum '438 contains a similar
disclosure with respect to impregnation of compounds
of silver, gold and copper. Both patents disclose
use of acid solutions of the metals as impregnating
solutions, with hydrochloric, sulfuric and nitric
as well as various organic acids being disclosed.
None of these patents discloses or suggests the use
of phosphoric acid impregnating solutions nor is
there any suggestion of a catalyst containing an
active metallic component which contains phosphorus.
Rather, the respective patentees' phosphorus is
incorporated into the zealot
British 1,555,928 (Convene et aloe discloses
crystalline silicates of specified formula having
utility in a wide range of hydrocarbon conversiorls~
Impregnation of the silicates with catalytic petals
is disclosed as is promotion or modification with
halogens, magnesium, phosphorus, boron, arsenic or
antimony, (Page 6 lines 33-54); with incorporation
of phosphorus into the silicate to improve alkylation
selectivity, as in the above-described Chum patents,
being specifically disclosed.
It also is known that phosphine or other organ-
phosphorus complexes of various metal salts can be
employed in preparation of various supported catalyst
compositions. or example, U.S. 3,703,561 (Kubicek
et aloe discloses catalysts for olefin disproportional
lion comprising a reaction product of (1) an organ-
aluminum halide, aluminum halide or combination
thereof with each other or with another organometallic
halide and (2) a mixture of a salt of copper, silver
or gold with a completing agent which may be an
organophosphine. Reaction of components I and
(2) is conducted in the presence of a solvent for
the reactants, in the substantial absence of air
and at temperatures low enough to avoid decomposition
ox the reactants. It also is disclosed to provide
the catalysts in supported form by impregnating a
support such as a non-zeolitic, refractory inorganic
oxide or a elite with the reaction product, or by
impregnation with one of the reactants followed by
addition of the other. Kubicek et at. also states
that if such supported catalysts are to be activated
by calcination the calcination should take place
I
prior to impregnation with the active species, i.e.,
the reaction product of components (1) and 12)~ It
is unclear whether residues of any or~anophosphine
compound used in preparation of the catalysts of
Kubicek et at. would remain in association with the
active metallic species In any event, the catalyst
preparation according to this patent is conducted
under conditions designed to avoid conversion ox
any such organophosphine residues to an oxygenated
phosphorus component such as that required according
to the present invention.
U.S. 3,721,718 (Hughes et at.) and U.S.
4,010,217 (Zuech) contain disclosures similar to
that of Kubicek et at. with respect to use of organ-
phosphorus complexes of various metal salts in prepay
ration of olefin disproportinativn catalysts. Like
- Kubicek et at., both Hughes et at. and Zuech contem-
plate supported catalysts; however, both patentees
also state that if activation by calcination is
desired, it should be accomplished by calcination
of support prior to incorporation of active metals.
Another patent disclosing the use of metal
complexes in catalyst preparation is U.S. 3,~49,457
(Haag et at.) which is directed to preparation of
carboxylic acids by hydrogenolysis of esters The
catalysts of Haag et at. comprise a hydrogenating
metal component and a solid acid component such as
a zealot which components may be employed as a
loose physical admixture or ho combining the two
components into a single particle Various methods
for combining the two components into a single part-
ale are disclosed at Column 6 line 64-Column 7 line
OWE One of these involves mixing a solution of a
metal pi-complex with the acid solid and then deco-
posing the complex to form elemental metal and depositing the elemental metal onto the acid solid.
-10-
A specific metal complex employed in this preparative
scheme is tetra(triphenylphosphine)palladium(II)
dibromide. Another preparative method useful with
respect to zeolitic acid solid components involves
incorporation of the hydrogenation component by
conventional methods such as ion exchange or impreg-
nation. None of the disclosed methods would Rosetta
in association of an oxygenated phosphorus component
with the metallic component of the patentees' gala-
lust.
U.S. 4,070,403 Homier discloses a hydra-
formulation catalyst comprising a cobalt compound
and a zeolite-alumina hydrosol dispersion. The
cobalt compound is chemically bonded to the alumina
zealot dispersion by a vapor-phase impregnation
technique Suitable cobalt components of the disk
closed catalysts include various salts such as
halides, nitrate and various carboxylates as well
as organophosphine complexes. Homier does not disk
close or suggest the presence ox an oxygenated pros-
chorus component in the final catalyst, nor does
the patentee attribute any promotional effect to
phosphorus.
It can be appreciated from the foregoing that
efforts to include both a crystalline molecular
sieve zealot component and a phosphorus component
in catalysts comprising an active metal component
deposed on a non-zeolitic refractory inorganic oxide
component in such a manner that the promotional
effects of both the phosphorus and the zealot are
retained have been largely unsuccessful. In those
instances in which an attempt has been made to incur-
prorate a promoting phosphorus component through the
use of phosphoric acid impregnating solutions of
compounds of active metals, such use of phosphoric
acid in conjunction with a crystalline aluminosilicate
zeolite-containing composition often results in
destruction of the crystalline aluminosilicate zealot
component. Other proposals such as those involving
use of organophosphorus complexes of various metal
5 salts to aid impregnation or deposition of active
metals into or onto support result in only incidental,
if any, incorporation of phosphorus into the final
catalyst, and phosphorus so incorporated appears
lacking in promotional effect.
It would be desirable to provide an improved
catalytic composition in which both phosphorus and
crystalline molecular sieve zealot components are
present in a form capable of exerting a promotional
effect. It is an object of this invention to provide
an improved catalytic composition A further object
of the invention is to provide for the use of such
catalytic compositions in hydrocarbon conversion
processes. A still further object is to provide
for the preparation of catalysts in which improved
performance is attained through incorporation of
crystalline molecular sieve zealot and phosphorus
components. Other objects of the invention will be
apparent to persons skilled in the art from the
following description and the appended claims.
We have now found that the objects of this
invention can be attained by incorporation of an
oxygenated phosphorus component into the catalytically
active metallic component of a catalytic composition
and incorporation of selected crystalline molecular
sieve zealot components into the support component
of the composition. Advantageously, the crystalline
molecular sieve zealot components of the invented
catalysts are derived from acid-tolerant crystalline
molecular sieve zealots, and accordingly, phosphorus
component can be incorporated without substantial
destruction of zealot integrity or crystallinity.
I
Further, the phosphorus component is incorporated
into the metallic component in a Norm capable of
exerting a promotional effect. Thus, as demonstrated
in the examples appearing hereinbelow, the catalysts
ox the invention, wherein an oxygenated phosphorus
component is incorporated into a catalytically active
metallic component which it deposed on or associated
with a support component comprising at least one
crystalline molecular sieve Zulu component and a
non-zeoliticl refractory inorganic oxide matrix
component, are superior to catalyst compositions
that are identical but for the inclusion of a pros-
chorus component, or but for inclusion of the zealot
component, in a variety of catalytic processes.
Accordingly, the overall effect of the phosphorus
and zealot components on performance of the basic
catalytically active composition comprising a metallic
component and a non-zeolitic, refractory inorganic
oxide component is greater than the effect of either
component alone in a variety of reactions.
In addition to the patents and publications
discussed hereinabove, U.S. 4,228,036 (Swift et
at.) and U.S. 4,277,373 (Sawyer et at.) may be of
interest to the present invention in disclosing
catalytic compositions containing phosphorus and
zealot components. Specifically, Swift et at.
discloses an improved catalytic cracking catalyst
comprising an alumina-aluminum phosphate-silica
matrix composite with a zealot component having
cracking activity, such as a rare earth-exchanged
Y-type crystalline alllminosilicate zealot Swift
et at. does not disclose inclusion of an active
metallic component into such catalysts. Further,
in contrast to the catalysts of the present invention,
wherein an oxygenated phosphorus component is
included in an active metallic component, the pros-
lo
-13-
chorus component of Swift et Allah catalysts is
included in a refractory oxide material.
Sawyer et at. discloses hydroprocessing kowtow
lusts comprising a Group VIM and/or Viol metal combo-
Nina composite with an ultrastahle Taipei crystal-
line aluminosilicate zealot and an alumina-aluminum
fluorophospha~e component. The catalyst also may
contain an alumina gel-containing matrix although
an essential component of Sawyer et Allis catalyst
is he aluminum fluorophosphate component of the
support, it also is to be noted that patentee disk
cloves use of phosphomolybdic acid to impregnate a
support containing a Y-type crystalline aluminosil-
irate and alumina-aluminum fluorophosphate in
Example 1 (see Column 5 lines 21-25). According to
the example, however, it appears that there was no
incorporation of a phosphorus component into the
active metal component of the catalyst because the
table at Column 5 lines 42-52 fails to report pros-
chorus content other than that contained in the
aluminum fluorophosphate component of the support.
Table 2 of Sawyer et at. also reports on a compare-
live catalyst C containing specified levels of alum
mine, Y-type zealot, nickel oxide, molybdenum oxide,
and phosphorus peroxide For catalyst C to have
been a fair comparator for the calcites of Sawyer
et Allis invention, the phosphorus pent oxide component
must have been present in a Mann r similar Jo the
fluorophosphate component of the patentees' catalysts,
i.e., as part of the support. As such, Sawyer et
at. fails to discos or suggest a catalyst containing
phosphorus as an essential part of the active metal
component.
DESCRIPTION OF THE INVENTION
35 Briefly, the catalyst composition of this invent
lion comprises (1) an active metallic component
us
-14-
comprising at least one metal having hydrocarbon
conversion activity and at least one oxygenated
phosphorus component; and (2) a support component
comprising a least one non-zeolitic, refractory
inorganic oxide matrix component and at least one
crystalline molecular sieve zealot component.
According to a further aspect of the invention,
such catalytic compositions are prepared by a method
comprising (1) impregnating a support component
comprising at least one non-~eolitic, refractory
inorganic oxide matrix component and at least one
acid-tolerant, crystalline molecular sieve zealot
component with precursors to an active metallic
component comprising a least one metal having hydra-
carbon conversion activity and at least one oxygen-
axed phosphorus component under conditions effective
to retain substantial zealot crystallinity; and
(2) calcining the result to convert active metallic
component precursors to active form. According to
a still further aspect of the invention, the above-
described catalytic compositions are employed in
hydrocarbon conversion processes in which a hydra-
carbon-containi~g charge stock is contacted with the
catalytic composition under hydrocarbon conversion
conditions.
In another aspect the invention provide a process
for denitrogenation of high nitrogen content hydrocarbon
feeds comprising contacting the feed with hydrogen under
denitrogenation conditions in the presence of a catalyst
comprising an active metallic component comprising at
least one metal having hydrogenation activity and at least
one oxygenated phosphorus compoIIent~ and a support come
potent comprising at least one non~zeolitic, porous
refractory inorganic oxide matrix component and at least
one crystalline molecular sieve zealot component. In
preferred embodiments of such process the denitrogenation
-aye-
conditions are denitroyenation hyd.rotreating conditions
and comprise a temperature of about 650 to about 760F,
hydrogen pressure ox about 1000 to about 2500 pal, LHSV
of about 0.2 to about 4 and hydrogen addition rate ox
S about 200Q to about 20,000 SCAB.
On treater detail, the invented catalytic come
position comprises an active metallic component and
a support component. Rowley proportions of these
are not critical so long a the active metallic
component is present in at least a catalytically
effective amount. Optimum proportions for a given
catalyst will vary depending on intended use. Use-
f ugly, the active metallic component constitutes
about 5 to about 50 wit% and the support constitutes
about 50 to about 95 wit%, such weight percentages
-15-
being based upon total weight of the catalytic come
position.
The active metallic component of the invented
catalyst comprises at least one metal having hydra-
carbon conversion activity and at least one oxygenated phosphorus component. Suitable metals hiving hydra-
carbon conversion activity include any of the metals
typically employed to catalyze hydrocarbon conversion
reactions such as those of Groups IBM II, IIIB-VIIB
and VIII. These can be present in the catalyst in
elemental form, as oxides, as sulfides, or in other
active forms. Combinations also are contemplated.
The Group VIM metals exhibit a high degree of siesta-
ability to promotion by oxygenated phosphorus combo-
next. Accordingly, preferred compositions are those in which the active metallic component comprises at
least one Group VIM metal.
For a given catalyst, the preferred metal or
combination of metals of the active metallic component
will vary depending on end use. For example, in
hydrogen processing of hydrocarbon feed materials
such as petroleum or synthetic crude oils, coal or
Bahamas liquids, or fractions thereof, preferred
metals are those of Groups VIM and VIII such as
chromium, molybdenum, tungsten, nickel, cobalt,
iron, platinum, rhodium, palladium, iridium and
combinations thereof. Oxides and sulfides of these
are most preferred from the standpoint of catalytic
performance. In processes for denitrogenation hydra-
treating or denitrogenation hydrocracking, combine-
lions of nickel or cobalt with molybdenum and cry-
mum give particularly good results. Particularly
good results in hydrocracking processes are attained
using catalysts containing combinations of cobalt
and molybdenum, nickel and molybdenum, or nickel
and tungsten as the metals of the active metallic
I
-16-
component. In mild hydrocracking processes such as
catalytic dew axing and catalytic cracker feed hydra-
cracking processes, preferred metals of the metallic
component are combinations of nickel and molybdenum.
In addition to the above described catalytically
active metal component, the active metallic component
of the invented composition contains at least one
oxygenated phosphorus component which ma be present
in a variety of forms such as one or more simple
oxides, phosphate anions, complex species in which
phosphorus is linked through oxygen to one or more
metal or metals of the active metallic component or
compounds of such metal or metals, or combinations
of these. The specific form of the oxygenated pros-
chorus component is not presently known; accordingly,
for purposes hereof, phosphorus contents are cowlick-
fated and expressed in terms of Pros.
Content of the metal and phosphorus components
of the active metallic component is not critical
although phosphorus component preferably is present
in at least an amount effective to promote hydrocarbon
conversion activity of the metal or metals of the
metallic component. In general, the metal or metals
of the metallic component, calculated as oxide of
the metal or metals in a common oxidation state,
e.g., Cry, Moo, WOW, No, Coo make up about 3
-17-
to about 45 White of the total catalyst weight while
phosphorus component, expressed as Pros, makes up
about 0.1 to about 20 wt.% of the total catalyst.
Within these broad ranges, preferred levels of metal
and phosphorus component will vary clependiny on end
use. For example, catalysts useful in hydrogen
processing of petroleum or synthetic crude oils,
coal or Bahamas liquids, or fractions thereof prefer-
by contain about 5 to about 35 wt.% Group VIM and/or
VIII metal expressed as common metal oxide, and
about 0.5 to about 15 wt.% oxygenated phosphorus
component expressed as POW. Of course, higher
and lower levels of metal Andre phosphorus component
can be present; however, below about 5 White metal
oxide, hydrogenation activity can suffer while above
about 35 White, improvements in activity typically
do not compensate for the cost of the additional
metal. Similarly, below about 0.5 wt.% phosphorus
component, calculated as Pros, promotional effect
may be insignificant while above about 15 White, the
phosphorus component may adversely affect hydrogen-
lion activity or performance For high nitrogen
feed stocks, the hydrogenating metal preferably makes
up about 10 to 40 White of overall catalyst while
phosphorus content as Pros makes up about 0.5 to
about 15% of overall catalyst weight. For mild
hydrocracking r hydrogenating metal preferably makes
up about 5 to about 30 wt.% of overall catalyst
weight while phosphorus content as Pros makes up
about 0.1 to about 10 wt.% of overall catalyst weight.
The support component of the invented catalytic
composition comprises a non-zeolitic, refractory
inorganic oxide matrix component and at least one
crystalline molecular sieve zealot component. Suit-
able non-zeolitic, refractory inorganic oxide matrix
components are well known to persons skilled in the
-18-
art and include alumina, silica, silica-alumina,
alumina silica, magnesia, zircon, titanic, etch,
and combinations thereof. The matrix component
also can contain adjutants such as phosphorus oxides,
boron oxides, fluorine and/or chlorine. Matrix
components that are preferred are those comprising
alumina, owing to the availability and strength
thereof. More preferably the matrix component is
alumina, or a combination of alumina and silica.
The support component of the invented catalytic
composition also comprises at least one crystalline
molecular sieve zealot component. This component
of the support component is derived from at least
one acid-tolerant crystalline molecular sieve zealot.
For purposes hereof, an acid-tolerant crystalline
molecular sieve zealot is defined as one that retains
substantial crystallinity on exposure to phosphoric
acid at pi down to about 3 to 4 and contains surf-
ficiently low levels of cations capable of reacting
with aqueous phosphoric acid to form insoluble metal
phosphates capable of plugging the zealots pores
as to avoid substantial plugging. Both naturally
occurring and synthetic zealots are contemplated.
As with the metals of the metallic component of the
invented catalysts, the specific zealot component
to be included in a given catalyst will vary depending
on intended use ox the catalytic composition.
Examples of acid tolerant, crystalline molecular
sieve zealots include faujasite-type crystalline
aluminosilicate zealots selected from the ultra stable
Y-type crystalline aluminosilicate zealots in
acid and ammonium forms/ AMS-type crystalline boron
silicate zealots, ZSM~type crystalline aluminosili-
gate zealots and mordenite-type crystalline alumina-
silicate zealots.
I
--19--
The ultra stable crystalline aluminosilicate
zealots typically are faujasite~type zealots that
exhibit improved stability at elevated temperatures,
such stability being imparted by exchanging original
alkali metal cations with ammonium salt, calcining
Jo convert the zealot to hydrogen form, steaming
or calcining again, exchanging with ammonium salt
once again and finally calcining. Specific examples
of ultra stable Y type crystalline aluminosilicate
lo zealots include zealot ZEUS, which it described
in detail in U.S. 3,293,192 (Maker et at.) and U.S.
3,44~,070 (McDaniel et Allah
Y-type crystalline
aluminosilicate zealots in hydrogen or ammonium
form also exhibit sufficient acid-tolerance as to
be suitable for purposes of the present invention.
When used in preparation of catalysts, Y-type zealots
in ammonium form are converted to acid form.
Crystalline borosilicate zealots of the AS-
type are described in detail in commonly assigned
U.S. 4,269,813 clout).
A specific example of this material
is crystalline borosilicate zealot RMS-lB which
corresponds to the formula:
owe 0.2 M2/nO:B2O3 ysio2 ZOO
wherein M is at least one cation having a valence of
n, Y ranges from 4 to about 600 and Z ranges from 0
to about 160. AS lo provides an X-ray pattern
that comprises the following X-ray diffraction lines
and assigned strengths:
-20-
d (A) Assigned Strength
11.2 _ 0.2 WIVES
10~0 0.2 W-MS
5 97 0 07 W-M
30~2 0.05 US
3.70 0.05 MS
3.S2 0.05 M-MS
2.97 0.02 W-M
1.99 -I 0.02 VW-M
Crystalline aluminosilicate zealots of the
ZSM-type are well known and typically contain silica
and alumina in a molar ratio of at least 12-1
(Sue) and have average pore diameters of at
least about 5 I. Specific examples ox crystalline
aluminosilicate zealots of the ZSM type include
crystalline aluminosilicate zealot ZSM-5, which is
described in detail in U.S. 3l702,886; crystalline
aluminosilicate ZSM-ll, which is described in detail
in U.S. 3,709,979; crystalline aluminosilicate zealot
ZSM-12, which is described in detail in U.S.
3,832,449; crystalline aluminosilicate elite ZSM-
35, which is described in detail in U.S. 4,016,245;
and crystalline aluminosilicate zealot ZSM~38,
which is described in detail in U.S. 4,046.859.
Mordenite-type crystalline aluminosilicate
zealots also can be present in the catalytic combo-
session of the present invention. Suitable mordant-
type crystalline aluminosilicate zealots are disk
closed in U.S. 3,247,098 (Timberline), U.S. 3,281,483
(Buoyancy et at.) and U.S. 3,299,153 (Adams et at.).
Synthetic mordenite-~tructure crystalline aluminosil-
Jo
-21-
irate zealots, such as whose designated Zillion and
available from the Norton Company of Worcester,
Massachusetts, also are contemplated according to
the invention.
Synthetic crystalline molecular sieve zealots
often are synthesized in alkali metal form, i.e.,
having alkali metal cations associated with framework
species. For purposes of the present invention,
the original form as well as various exchanged forms
such as the hydrogen (acid), ammonium and metal-
exchanged forms are suitable. Crystalline molecular
sieve zealots can be converted to acid form by
exchange with acids or by indirect means which typic
gaily involve contacting with ammonium or amine salts
to form ammonium-exchanged intermediate species
which can be calcined to acid form. Metal exchanged
zealots are well known as are methods for preparation
thereof. Typically, zealot is contacted with a
solution or solutions containing metal cations capable
of associating with framework metallic species As
noted hereinabove, crystalline molecular sieve zealot
components present in the catalysts of the present
invention contain only insubstantial levels of metals
capable of reacting with aqueous phosphoric acid to
form insoluble metal phosphates capable of plan
the pores of the support component. Accordingly,
preferred metal-exchanged crystalline molecular
sieve zealots are those in which the exchanged
metals are nickel, cobalt, iron or a Group VIII
noble metal. In catalysts intended for use in hydra-
gun processing of petroleum or synthetic crude oils,
coal or Bahamas liquids, or fractions thereof, pro-
furred crystalline molecular sieve zealot combo-
newts of thy invented catalysts are those in acid
or polyvalent metal ion exchanged form, and especially
the former.
* Trade mark.
-22-
Content of non-zeolitic, porous refractory
inorganic acid matrix component and crystalline
molecular sieve zealot component in the support
component of the invented composition are not
critical. Broadly, the matrix component constitutes
about 5 to about 95 White of the support, and likewise,
the zealot component can constitute about 5 to
about 95 White of the support. Preferably, the content
of the non~zeolitic matrix component is at least
about 10 wit% in order to ensure that the support
component will exhibit sufficient strength and pry-
steal integrity to allow shaping of the component
or final catalyst into a form suitable for intended
use. Of course, even at less than about 10 White
matrix component, suitable catalytic performance
can be attained in applications amenable to use of
catalyst in finely divided form.
In terms of overall catalyst weight of the
invented catalytic composition, preferred matrix
content ranges from about 10 to about 90 wit% and
preferred zealot content ranges from about 5 to
about 90 wit%. Within these ranges, precise levels
of matrix and zealot components that are more pro-
furred for a given catalyst will vary depending on
intended use. For use in mild hydrocracking, the
matrix component content preferably ranges from 40
to about 95 wt.% of the support while zealot content
ranges from about 5 to about 60 White of the support
component.
The support component of the invented catalytic
composition can be prepared by any suitable method.
A preferred method comprises blending acid-tolerant
zeolitic component, preferably in finely divided
form, into a sol, hydrosol or hydrogen of at least
one inorganic oxide and adding a golfing medium
such as ammonium hydroxide with stirring to produce
-23~
a gel. It also is contemplated to add the zealot
component to a slurry of the matrix component, In
either case, the result can be dried, shaped I
desired, and then calcined to firelight the support come
pennant Suitable drying temperatures Lange frornabout 80 to about 350F (about 27 to about 177C)
and suitable drying times range from seconds to
several hours. Calcination preferably is conducted
at a temperature of about 800 to about 1,200F (about
lo 427 to about ~49C) for about l/2 to about 16 hours.
Shaping of the support component can be conducted
if desired, preferably after drying or calcining.
Another suitable method for preparing the support
component of the invented composition comprises
physically mixing particles of the matrix and zealot
components, each preferably in finely divided form,
followed by thorough blending of the mixture.
The invented catalytic composition is prepared
by a method comprising (l) impregnating the above-
described support component with precursors to the active metallic component under conditions effective
to retain substantial elite crystallinity; and
(2) calcining the result.
Impregnation of support component with precursors
to the active metallic component can be conducted
in a single step or in a series of separate steps
which may be separated by drying and/or calcination
steps, provided that impregnation with at least one
metal precursor takes place prior to or simultaneously
with impregnation with phosphorus component precursor.
If the active metallic component contains more than
one metal, precursors can be impregnated simultan-
easily, in sequence or by various combinations of
simultaneous and sequential impregnations. Phosphorus
component precursor or precursors can be included
with one or more of the metal precursors, or one or
-24-
more separate phosphorus component precursor impreg-
nation steps can be included between or after the
metal precursor impregnation steps It also it
contemplated to impregnate either the porous refract
tory inorganic oxide matrix component or the zeoliticcomponent with precursors to the active metallic
component and blend the result with the other combo-
next.
The mechanics of impregnating a support with
metallic component precursors are well known to
persons skilled in the art and typically involve
contacting a support with one or more solutions of
one or more precursors in amounts and under conditions
effective to yield a final composition containing
the desired amount of metal or metals. Suitable
solvents for the impregnating solution or solutions
include water and various low boiling alcohols in
which the precursors are soluble. Water is preferred
over alcohols from the standpoint of cost. In the
case of simultaneous impregnations of metal and
phosphorus component precursors a more preferred
solvent is aqueous phosphoric acid.
Metal precursors useful in preparation of the
invented catalytic compositions are well known to
persons skilled in the art and include a wide range
of salts and compounds of the metals that are soluble
in the impregnating solvent and convertible to the
desired form on calcination. Examples of useful
salts include organic acid salts such as acetates,
formats and preappoints; nitrates; androids;
sulfates; and ammonium salts.
Useful precursors to the oxygenated phosphorus
component en materials capable of reaction with
the metal or metals of the metallic component or
compounds of such metal or metals, or precursors
thereto, so as to incorporate into the metallic
-25-
component or metallic component precursor a phosphorus
containing species what can be converted to an
oxygenated phosphorus component. From the standpoint
of maximizing the promotional effect of the oxygenated
phosphorus component, the preferred phosphorus come
potent precursor is one containing or capable of
liberating phosphate anions as these are sufficiently
reactive with the metal or metal precursors to yield
the desired promotional effect. Specific examples
of such phosphorus anion sources include phosphoric
acid and salts thereof such as ammonium dihydrogen
phosphate and diammonium hydrogen phosphate. Other
phosphorus component precursors contemplated according
to the invention, though less preferred from the
standpoint ox attaining maximum promotional effect,
include organophosphorus compounds such as partial
and full esters of the aforesaid oxyacids such as
organophosphates and organophosphites; other organ-
phosphorus compounds such as phosphines, and other
phosphoric oxyacids such as phosphorus and phosphinic
acids.
Impregnation of the support component with pro-
cursors to the metallic component is conducted
under conditions effective to avoid substantial
destruction of crystallinity of the crystalline
molecular sieve zealot component. Preferably,
such conditions include a temperature that is high
enough to maintain the metal and/or phosphorus come
potent precursors in solution in the impregnating
solvent though not so high as to decompose sup h
precursors or have substantial adverse effects on
the support component. More preferably, impregnating
temperatures range from about 40 to about 200F.
pi of the impregnating solution or solutions to be
used also is important from the standpoint of insuring
retention of substantial zealot crystallinity when
I
phosphoric acid or other phosphate anion source is
employed as a phosphorus component precursor and/or
impregnating solvent. In such cases, pi preferably
is sufficiently high that only insubstantial destruct
lion of zealot crystallinity takes place during the preparation. Of course, the precise pi at which
substantial decomposition of crystallinity will
occur will vary somewhat depending upon the choice
of zealot component. In general, however, pi should
be above about 2 in order to insure retention of
sufficient zealot crystallinity to insure desirable
catalytic performance. Most preferably, pal ranges
from about 2.5 to about 6 in order to insure retention
of a high degree of zealot crystallinity while
also insuring the desired association of the pros-
chorus and metal components of the active metallic
component.
Following impregnation of the support component
with metallic component precursors, it is preferred
to dry the impregnated support. It also is contem-
plated to dry the support subsequent to any interim-
dilate impregnating steps in a multi step impregnation.
Preferred drying temperatures range from about I
to about 350F (about 27 to about 177C), with pro-
furred drying times ranging from a few seconds inspire drying operations to several hours in convent
tonal driers.
Following impregnation of the support with
precursors to the metallic component and any optional
drying steps, the impregnated support is subjected
to calcination in order to convert at least a portion
of the metal or metals of the metallic component to
the active form and to convert phosphorus precursors
to oxygenated phosphorus component. Calcination is
conducted in an atmosphere containing molecular
oxygen at a temperature and for a period of time
effective to attain the desired conversion. Prefer
ably, calcination temperatures range from about 800
to about 1,200F (about 427 to about 649C). Pro-
furred calcination times range from about 1/2 to
about 16 hours.
As a result of the above-described preparation,
there is attained a catalytic composition comprising
(l) a metallic component comprising at least one
metal having hydrocarbon conversion activity and at
lo least one oxygenated phosphorus component, and I
a support component comprising at least one Nan
zeolitic, refractory inorganic oxide matrix component
and at least one crystalline molecular sieve zealot
component. Preferred compositions are those in
which the zealot component exhibits at least about
40% crystallinity as compared to compositions identi-
eel but for inclusion of phosphorus component More
preferably, such relative crystallinity is at least
about 75% in order to ensure desirable catalyst
performance.
The compositions of this invention have utility
in a wide range of hydrocarbon conversion processes
in which a charge stock comprising hydrocarbon is
contacted with the catalyst under hydrocarbon convert
soon conditions. The invented catalysts are paretic-
ularly useful in processes for hydrogen processing
of hydrocarbon feed materials such as whole petroleum
or synthetic crude oils, coal or Bahamas liquids,
and fractions thereof. The process of the invention
is described in further detail with reference to
hydrogen processing of such feed materials.
Petroleum and synthetic crude oil feeds that
can be hydrogen processed according to this aspect
of the invention include whole petroleum, shale and
tar sands oils, coal and Bahamas liquids and fractions
-28-
thereof such as distillates, gas oils and residuals
fractions.
Such feed materials are contacted with the
catalyst of the invention under hydrogen processing
conditions which will vary depending upon the specific
feed to be processed as well as the type of processing
desired. Broadly, hydrogen treating temperatures
range from about 350 to about 850F (about 177 to
about 455C), hydrogen pressures range from about
100 to about 3,000 prig (about 7 to about 210 kg/m2)
and feed linear hourly space velocities range from
about 0.1 to about 10 volumes of feed per volume of
catalyst per hour. hydrogen addition rate generally
ranges from about 200 to about 25,000 standard cubic
feet per barrel (SCAB).
Hydrocarbon feed materials treated under mild
hydrocracking conditions are whole petroleum or
synthetic crude oils, coal or Bahamas liquids, or
fractions thereof. Substantial levels of impurities
such as nitrogen, sulfur, oxygen and/or waxy combo-
newts may be present in the feeds. Typical feeds
contain up to about 1.5 wt.% nitrogen and/or oxygen,
up to about 12 wit% sulfur and/or sufficient waxy
components, e.g., n-paraffins and isoparaffins, to
exhibit pour points of at least about 30F. Specific
examples of useful feeds include heavy and light
vacuum gas oils, atmospheric and vacuum distillates
and disaffiliated and hydrotrPated residual fractions.
Mild hydrocracking conditions vary somewhat
depending on the choice of feed as well as the type
of processing to be conducted. Dew axing mild hydra
cracking conditions are employed when it is desired
to reduce n paraffin and isoparaffin content of the
feed without substantial cracking of desirable art-
mattes, naphthenes and branched paraffins. Dewaxingmild hydrocracking conditions preferably include a
temperature of about 650 to about 800F, hydrogen
-29-
pressure of about B00 to about 2500 psi, linear
hourly space velocity (LHSV) of about 0.2 to about
5 and hydrogen addition rate of about 1000 to aback
20,000 standard cubic feet per barrel (SCAB).
The catalytic dew axing mild hydrocracking process
can be included as part of a multi step process for
preparation of lube oils wherein catalytic dew axing
is conducted in combination with other conventional
processing steps such as solvent extraction, solvent
dew axing, hydrocracking or hydrotreating to obtain
lube oil base stocks of relatively low pour point
and high viscosity index and stability According
to a preferred aspect of the invention, however,
there is provided an improved process for preparation
of lube oil base stocks of high viscosity index
low pour point and sufficiently low sulfur and/or
nitrogen content to exhibit good stability consisting
essentially of catalytically dew axing a feed, and
preferably a petroleum or synthetic crude oil
distillate fraction having a pour point of about 50
to about 150F and containing up to about 5 White
sulfur, 0.5 wt.% oxygen and/or 0.5 White nitrogen in
the presence of the aforesaid catalyst. Conditions
according to this aspect of the invention typically
are somewhat more severe than those in catalytic
dew axing operations conducted as part of a multi step
process. Preferred conditions according to this
aspect of the invention include temperature ranging
from about 700 to about 800F, hydrogen pressure of
about 1200 to about 2000 psi, LHSV of about 0.2 to
about 2 reciprocal hours and hydrogen addition rate
of about 2000 to about 10,000 SCAB. A preferred
catalyst according to this aspect of the invention
is one in which the shape selective zeolitic cracking
component is a crystalline borosilicate component
of the AMS-lB type in hydrogen form, and the hydra-
yenating metal of the active metallic component
-30-
comprises a molybdenum component and a nickel come
potent.
Catalytic cracking feed mild hydra racking
conditions are employed when it is desired to remove
nitrogen and/or sulfur from the feed as well as
crack hydrocarbon components thereof to lower boiling
components. Such conditions include temperatures
ranging from about 650 to about 760~F, hydrogen
pressures ranging from about 500 to about 2000 psi,
LHSV ranging from about 0.2 to about 4 reciprocal
hours and hydrogen addition rates ranging from about
1000 to about 20,000 SCAB. Preferred catalytic
cracking feed mild hydrocracking conditions include
a temperature ranging from about 690 to about 740F,
hydrogen pressure of about 800 to about 1600 psi,
LHSV of about 0.5 to about 1 reciprocal hour and
hydrogen addition rate of about 1000 to about 15,000
SCAB.
The process can be conducted in either fixed
or expanded bed operations using a single reactor
or series thereof as desired.
Catalysts that are preferred for use in the
mild hydrocracking process of the present invention
are those in which the active metallic component
comprises at least one metal of Group VIM or VIII,
the non-zeolitic matrix component comprises alumina
or silica-alumina and the shape selective crystalline
molecular sieve elite component comprises a crystal-
line aluminosilicate zealot of the ZSM-type or a
crystalline borosilicate zealot of the Mistype
as these exhibit high activity for hydrogenation
and cracking. More preferably, the hydrogenation
metal of the active metallic component is nickel,
cobalt, chromium, molybdenum or tungsten or a comb-
nation thereof and is present in an amount ranging from about 10 to about 30 wit% calculated as metal
oxide and based on total catalyst weight Preferred
-31-
support compositions contain about 60 to about 90
wit% alumina or silica-alwnina having dispersed therein
about 1.0 to about 40 wit% shape selective crystalline
molecular ivy zealot.
Most preferably, the hydrogenating metal of
the active metallic component of the catalyst employed
comprises a combination of nickel and molybdenum.
Best results in terms of mild hydrocracking are
attained using catalysts contain about 1 to about
7 wit% No, about 10 to about 20 wit% Moo, about 0.1
to about 5 White oxygenated phosphorus component,
calculated as POW, and a support comprising about
65 to about 85 wit% alumina having dispersed therein
about 15 to about 35 White crystalline borosilicate
zealot of the AMS-type, especially HAMS-lB.
hydrocarbon feed materials treated under hydra-
cracking conditions are gas oil boiling range hydra-
carbons derived from petroleum or synthetic crude
oils, coal liquids or Bahamas liquids. Preferred
feeds are those boiling from about 400 to about
1000F and containing up to about 0.1 White nitrogen
and/or up to about 2 White sulfur. Specific examples
of preferred gas oil boiling range feeds include
petroleum and synthetic crude oil distillates such
as catalytic cycle oils, virgin gas oil boiling
range hydrocarbons and mixtures thereof.
Hydrocracking conditions vary somewhat depending
on the choice of feed and severity of hydrocracking
desired. Broadly, conditions include temperatures
ranging from about 650 to about 850F, total pressures
ranging from about 1000 to about 3000 psi, hydrogen
partial pressures ranging from about 300 to about
2500 psi, linear hourly space velocities (LHSV)
ranging from about 0.2 to about 10 reciprocal hours
and hydrogen recycle rates ranging from about 5,000
to about 20,000 standard cubic feet per barrel of
feed (SKIFF). Hydrogen consumption broadly ranges
from about 500 to about 3000 SCAB under such condo-
lions. Preferred conditions in hydrocracking of
catalytic cycle oils, virgin gas oils, and kimono-
lions thereof to gasoline boiling range products
include a temperature ranging from about 675 to
about 775F, total pressure of about 1500 to about
2500 psi, hydrogen partial pressure of about 1000
to about 1500 psi, space velocity of about 0.5 to
about 4 reciprocal hours and hydrogen recycle rate
of about 10,000 to about 15,000 SAAB, with hydrogen
consumption ranging from about 1000 to about 2000
SCAB.
The process can be conducted in either fixed
or expanded bed operations using a single reactor
or series thereof as desired.
Catalysts that are preferred for use in the
hydrocracking process of the present invention are
those in which the active metallic component comprises
at least one metal of Group VIM or VIII, the non-
zeolitic matrix component comprises alumina, orsilica-alumina and the crystalline molecular sieve
zealot component comprises a low sodium, ultra stable
Y-type crystalline aluminosilicate zealot, as these
exhibit high activity for hydrogenation and cracking
over prolonged periods of time. More preferably,
the hydrogenation metal of the active metallic come
potent is nickel, cobalt, chromium, molybdenum or
tungsten or a combination thereof and is present in
an amount ranging from about 8 to about 25 wit%,
calculated as metal oxide and based on total catalyst
weight. Preferred support compositions contain
about 40 to about 80 wit% alumina or silica-alumina
having dispersed therein about 20 to about 60 wit%
low sodium, ultra stable Y-type crystalline alumina-
silicate zealot.
Most preferably, the hydrogenating metal of the active metallic component of the catalyst employed
comprises a combination of cobalt and molybdenum,
nickel and molybdenum or nickel and tungsten, jest
results are attained using catalysts containing
about 0.5 to about 6 White oxygenated phosphorus
component, calculated as Pros and a hydrogenatlny
component containing about l to about 4 wit%, Coo or
No and about 3 to about 15 wit% Moo; or about l to
about 4 wit% No and about 15 to about 25 wit% WOW;
and a support comprising about 50 to about 70 White
alumina or silica-alumina having dispersed therein
about 30 to about 50 wit% low sodium ultra stable
Y type crystalline aluminosilicate zealot component,
such weight percentages of hydrogenating metal oxides
being based on total catalyst weight, and such matrix
and zealot weight percentages being based on support
weight.
Hydrocarbon feeds treated under denitrogenation,
hydrotreating or hydrocracking conditions are those
containing substantial levels of nitrogen compounds.
Preferred feeds are those containing at least about
0.4 White nitrogen. Specific examples of preferred
high nitrogen feeds include whole shale oils and
fractions thereof such as shale oil resins, vacuum
and atmospheric distillates and naphtha fractions.
Whole petroleum crude oils, tar sands oils, coal
and Bahamas liquids suitably high in nitrogen, as
well as various fractions thereof, also are par-
titularly well suited for use.
Denitrogenation conditions vary somewhat depend-
in on the choice of feed as well as the type of
processing to be conducted. Denitrogenation hydra-
treating conditions are employed when it is desired
to reduce nitrogen content of the feed without sub-
staunchly cracking thereof and include a temperature
of about 650 to about 760F, hydrogen pressure of
about 1000 to about 2500 psi, linear hourly space
velocity (LHSV) of about 0.2 to about 4 volumes of
-34-
feed per volume of catalyst per hour (Herr) and
hydrogen addition rate of about 2U00 to about 20,000
standard cubic feet per barrel (SKIFF). Preferred
denitrogenation hydrotreatiny conditions include a
temperature ranging from about 6B0 to about 750F,
hydrogen pressure of about 1400 to about 2200 psi,
LO of about 0~3 to about 3 and hydrogen rate of
about 4000 to about 10,000 SCAB as these result in
desirable reductions in product nitrogen while avoid-
in exposure of the catalyst to conditions so severe
as to adversely affect catalyst lifetime.
Denitrogenation hydrocracking conditions are
employed when it is desired to remove nitrogen from
the feed as well as crack higher boiling Components
thereof to lower boiling components. Denitrogenation
hydrocracking temperature ranges from about 720 to
about 8~0~F, hydrogen pressure ranges from about
1000 to about 2500 psi, LHSV ranges from about 0.2
to about 3 and hydrogen addition rate ranges from
about 4,000 to about 20,000 SCAB. A particularly
preferred application in which denitrogenation hydra-
cracking conditions are employed is in conversion
of whole shale oils or fractions thereof to jet
fuel. Preferred conditions for such an application
include a temperature ranging from about 750 to
about 82QF, hydrogen pressure of about 1200 to
about 2200 psi, LHSV of about 0.3 to about 1 and
hydrogen addition rate of about 5000 to about 10,000
SCAB.
The process can be conducted in either fixed
or expanded bed operations using a single reactor
or series thereof as desired.
Catalysts that are preferred for use in the
denitrogenation hydrotreating or hydrocracking
process are those in which the hydrogenating metal
of the active metallic component is nickel, cobalt,
chromium, molybdenum, tungsten or a combination
-35-
thereof, the non-zeolitic matrix component comprises
alumina or silica-alumina and the crystalline molecular
sieve zealot component comprises an ultra stable I-
type crystalline aluminosilicate zealot, a crystal
line aluminosilicate zealot ox the ZSM-type or a
crystalline borosilicake zealot of the Mistype
as these exhibit high activity for denitrogenation
hydrotreating and hydrocracking. More preferably,
the hydrogenation metals of the active metallic
component comprise a combination of nickel and Malibu-
denim or a combination of cobalt or nickel, chromium
and molybdenum and are present in an amount ranging
from about 10 to about 30 White calculated as metal
oxide and based on total catalyst weight, and the
support component contains about 40 to about 80 wit%
alumina or silica-alumina having dispersed therein
about 20 to about 60 White crystalline molecular sieve
zealot component, such weight percentages being
based on support weight.
Most preferably, the catalyst employed in the
denitrogenation process contains about 1 to about 5
wit% No and about 12 to about 20 wit% Moo; or about
1 to about 5 White Coo or No, about 2 to about 10
wit% Cry and about 12 to about 20 White Moo; and
about 0.5 to about 8 White oxygenated phosphorus come
potent, expressed as Pros; and a support containing
a dispersion of about 30 to about 60 wit% ultra stable
Y-type crystalline aluminosilicate zealot, AS-
type crystalline borosilicate zealot or ZSM-type
crystalline aluminosilicate zealot in about 40 to
about 70 wit% alumina or silica alumina Ultra stable
Y-type crystalline aluminosilicate zealots give
best results in denitrogenation hydrocracking applique-
anions.
-36-
The present invention is described in further
detail in the hollowing examples, it being understood
that the same are for purposes of illustration and
not limitation.
EXAMPLE 1
A support component containing 30 wt.% ultra stable
Y-type crystalline aluminosilicate zealot obtained
from the Davison Chemical Division of W. R. Grace
and Co. dispersed in 70 wt.% alumina was prepared
by mixing 15,890 g alumina sol Lowe wt.% alumina
dry weight) with 681 g ultra stable Taipei zealot.
To the result was added a solution of 400 ml water
and 400 ml concentrated N~40H while stirring rapidly
to form a gel. The resulting gel was dried overnight
at 250F in air, ground to lo mesh, mulled with
water, extruded to 5/64" particles, dried overnight
at 250F in air and calcined at 1000 in air for
three hours.
A solution prepared by dissolving 8.30 g
(N~4)2Cr2O7 in 49 ml water was added to 72.77 9 of
support component and allowed to stand for 1 hour
after which the result was dried in air at 250F
for l hour.
Subsequently, 18.40 g (NH4)6Mo70~4 OWE, 5.85 9
Cowan 6H20 and 8.6 g 85% phosphoric acid (H3PO4)
were dissolved in 35 ml water to form an impregnating
solution having a pi of about 3. The impregnating
solution was added to the chromia-impregnated support
and the mixture was allowed to stand for l hour
after which the result was dried in air at 250F
for l hour and calcined in air at 1000F for l hour.
The resulting catalyst contained 5.0 wit% Cry,
15.0 White% Molly 1.5 wt.% Coo and 5.5 wt.% oxygenated
phosphorus component, calculated as PRO.
EXAMPLE 2
A support component containing 50 White ultra-
stable Y-type crystalline aluminosilicate zealot
-37-
Davison) dispersed in 50 wt.% alumina was prepared
substantially according is the procedure of Example
1 using 3863 g alumina sol (10 White alumina) and
386.5 9 ultra stable Y-type zealot.
solution prepared by dissolving 16.6 g
(NH~)2Cr~O7 in 90 ml water was added to 148.98 y of
the support component and allowed to stand for 1
hour. The result was dried in air at 250F for 1
hour and calcined in air at 1000F for 1 hour.
Subsequently, 36.8 g (NH4)Mo7O~4 4H20, 11.70 g
Cowan and 13.02 g 85~ H3PO4 were dissolved
in 67 ml water to form an impregnating solution
having a pi of about 3. This solution was added to
the Crimea impregnated support and the result was
allowed to stand for 1 hour after which the result
was dried in air at 250F for 1 hour and calcined
in air at 1000F for 1 hour.
The resulting catalyst contained 5.0 White% Cry,
15.0 wt.% Moo, 1.5 wt.% Coo and 4.0 wt.% oxygenated
phosphorus component, calculated as P25.
EXAMPLE 3
An impregnating solution having a pi of about
5.0 was prepared by dissolving 34.80 g cobalt nitrate,
42.45 9 ammonium molybdate and 16.63 g phosphoric
acid in 600 ml distilled water r after which total
volume of the solution was brought to 660 ml with
distilled water. The impregnating solution was
added to 331 g of a premixed support component con-
twining 41 wt.% ultra stable Y-type crystalline alum-
no silicate zealot and 59 wt.% silica-alumina and
stirred vigorously for a short time The result
was dried in air at 250F for several hours, ground
to pass a 28 mesh screen, formed into 1/8" pellets
and calcined in air for 1 hour at FOE for 1 hour
at 750F and for 5 hours at 1000F.
-38-
The resulting catalyst contained 9.13 White%
Moo, 2.36 wt.% Coo and 2.3 wt.% phosphorus component,
calculated as Pros.
EXAMPLE 4
A support component containing 35 wt.% ultra
stable Y-type crystalline aluminosilicate zealot
Davison) dispersed in 65 wit,% silica alumina con-
twining 71.7 wt.% silica was prepared in two batches
by blending 4160 g of silica-alumina slurry containing
about 2.5 wt.% solid with 54.4 g of the elite
component for about 5 to 10 minutes and then filter-
in, drying the solid in air at 250F overnight,
grinding the dried solid to pass through a 3Q-mesh
screen and calcining in air at 1000F for 3 hours.
lo An impregnating solution was prepared by disk
solving 35.4 9 cobalt nitrate, 41~6 g ammonium Malibu-
date and 4.6 y phosphoric acid in 472 ml distilled
water, 290 g of the support component were contacted
with the impregnating solution after which the result
was dried in air at 250F overnight, ground to 28
mesh, formed into 1/8" pills and calcined in air at
500F for 1 hour, at 700F for 1 hour and at EYE
for 5 hours.
The resulting catalyst contained 2.6 wt.% Coo
9.6 wt.% Moo and 0.6 White oxygenated phosphorus
component, calculated as Pus
EXAMPLE 5
147.84 g support component containing 20 wt.%
Mistype crystalline borosilicate zealot dispersed
in 80 wt.% alumina was impregnated with a solution
prepared by dissolving 22.09 9 (NH4)2Mo7O2~ OWE
and 13.63 g Nina in 68 ml distilled water
and adding drops 7~44 g 85% H3PO~ thereto while
stirring. A small amount of water was added to the
impregnation mixture and the result was allowed to
stand for 1 hour. The result was dried in air at
250F overnight, and then impregnated with 22.09 g
-39-
(NH4)2Mo7O24.4H2O, 13.63 g Nina, and 7.44 9
85~ H3PO~ in 68 ml distilled water. The result was
allowed to stand for 2 hours, dried in air at 250F
and calcined at 1000F.
The resulting catalyst contained 17.70 White%
Moo, 3.44 wt.% No and 4.35 White oxygenated pros-
chorus component, calculated as Pros, and had a
surface area of 242 mug and pore volume of 004802
cc/g.
EXAMPLE 6
The catalysts prepared in Examples 1 and 2
were tested for denitrogenation and hydrocracking
activity in an automated processing unit that included
a vertical, tubular downfall reactor having a length
of 32" and inner diameter of 1/4". The unit included
automatic controls to regulate hydrogen pressure
and flow, temperature and feed rate. Catalyst was
ground to 14-20 mesh and loaded into a 10-12" segment
of the reactor and sulfide therein by passing, 8
vowel HIS in hydrogen over the catalyst at 300 psi
for 1 hour at 300F followed by 1 hour at 400F and
then 1 hour at 700F. The reactor then was heated
to operating temperature, pressured with hydrogen
and a high nitrogen feed generated in situ from oil
shale was pumped into the reactor using a Rusks
pump. The feed had the following properties:
APT Gravity I 23.8
Nitrogen (wt.%) 1.27
Sulfur (wt.%) 0.65
Oxygen (wt.%) 1.40
Pour Point (OF) 60
Simulated Distillation (~)
IBP--360F 2.0
360--650~' 42.5
650F~ 55.5
operating conditions and results for each run
are shown in Table I. In addition to runs with the
I
-40-
catalysts from Examples 1 and 2, comparative runs
were conducted using comparative catalysts A-C which
were prepared according to the general procedure of
Examples 1 and 2 but without the use of phosphoric
acid in the case of A and B and without a zealot
component in the case of C. Compositions of catalysts
A-C were as hollows:
A) :L0.0 White Cry, 15.0 wt.% Moo and 1.5
wt.% Coo supported on a dispersion of 30 White ultra-
stable Y-type crystalline aluminosilicate elite
(Davison) in 70 White alumina;
B) 10.0 wit n Cry, 15.0 wt.% Moo and 1.5
wt.% Coo supported on a dispersion of 50 White ultra-
stable Y-type crystalline aluminosilicate zealot
dispersed in 50 wt.% alumina;
C) 5.0 White Cry, 15.0 wt.% Moo, 1.5 wt.%
Coo and 4.6 wt.% oxygenated phosphorus component,
calculated as Pros, supported on alumina.
TABLE 1
Catalyst 1 A 2 B C
Tempt (OF) 760 760 780 780 760
Pressure tPsi~ 1800 1800 18001300 1800
LHSV (Harley 0.5 0.5 0.50.5 0.5
Days on Oil 6 9 7 6 6
Liquid Product (9)184 239 124190 198
APT gravity I 40.0 36.5 49.449.6 37.0
Pour Point (OF) 70 80 40 15 75
Sulfur (ppm) 2 110 6 26~ 57
Nitrogen (ppm) 1.7 173 0.7 3 85
Simulated
Distillation (~)
IMP -350F 14.5 lQ.7 44.5 42.0 9.0
350--~5~ 60.0 54.3 53.~520~ 55.0
650F+ 2505 35.0 2.55.4 36.0
As can be seen from the table, catalysts 1 and
2 according to the invention exhibited superior
denitrogenation and desulfurization activity as
I
compared to all three comparative catalysts. Further,
cracking activities of catalysts 1 and 2 were superior
to those of comparative catalyst A and B, respective-
lye as evidenced by the simulated distillation data
showing reduced 650F~ content. Cracking activities
of 1 and 2 also were superior to that of catalyst C
which lacked a zealot component.
EXAMPLE 7
The catalysts prepared in Examples 3 and 4
were -tested for hydrocracking activity in a vertical,
tubular, downfall reactor having a length of 19-1/2"
and inner diameter of 0.55" and equipped with a
pressure gauge and DO cell to control hydrogen flow
and a high pressure separator for removal of products.
The reactor was loaded with 18.75 g catalyst, immersed
in a molten salt-containing heating jacket at 500F
and pressured to 1250 pi with hydrogen. Temperature
was held at 500F for two hours and then feed was
pumped to the reactor with a Milton Roy pump.
Temperature was slowly increased to 680F, held
there overnight and then raised to operating tempera-
lure of 710-730F. Feed rate (LHSV) was 1-2 hurl
Runs were conducted for two weeks with periodic
sampling.
The feed used in all runs was a mixture of 70
White light catalytic cycle oil and 30 White% light
virgin gas oil having the following properties:
APT Gravity to) 25.3
Nitrogen (ppm) 304
Sulfur two.%) 1.31
Initial Boiling Point tF~ 404
Final Boiling Point (OF) 673
In addition to the runs conducted using the
catalysts of Examples 3 and 4, comparative runs
were conducted using comparative catalysts A C which
are described below:
-42-
A) 2.5 wt.% Coo and 10.2 wt.% Moo supporter
on a dispersion of 35 White ultra stable Y-type crystal-
line aluminosilicate zealot in 65 White alumina
prepared substantially according to the procedure
of Example 3;
B) commercial hydrocracking catalyst containing
2.63 wt.% Coo and 10.5 wt.% Moo supported on the
base used in Example 3 obtained from the Davison
Chemical Division of W. R. Grace and Co.;
C) 2.6 wt.% Coo and 10.0 wt.% Moo supported
on a dispersion of 35 wt.% ultra stable Y-type crystal-
line aluminosilicate zealot (Davison) in 65 White
alumina and prepared substantially according to the
procedure of Example 4.
~ydrocracking activities of the catalysts were
determined on the basis of temperature required to
convert 77 wt.% of the feed to gasoline boiling
range products (up to 380F). Activities relative
to comparative catalyst C are reported in Table 2.
I TABLE 2
CATALYST RELATIVE ACTIVITY INCREASE ( % )
102 2
B 126 26
3 14ds 44
C 100
4 138 I
As can be seen from the table, the phosphorus-
promoted, ~eolite-containing catalysts of the invent
lion exhibited significantly improved hydrocracking0 activity as compared to the comparative catalysts.
EXAMPLE 8
Activity of the catalyst of Example 5 for mild
hydrocracking was tested in an automated pilot plant
consisting of a downfall, vertical pipe reactor of
about 30" length and 3/8" inner diameter equipped
with four independently wired and controlled heaters,
a pressure step down and metering device for introduce
-43-
lion of hydrogen and an outlet pressure control
loop to control withdrawal of hydrogen. The catalyst
of Example 5 was calcined in air at luff for about
2 hours and then screened to 14-20 mesh. The reactor
was loaded to a height of twelve inches with glass
balls after which about ten inches were loaded with
16 cm3 of catalyst. lass balls were added to fill
the reactor.
The reactor was heated 300F and a gaseous
mixture of 8 volt HIS in hydrogen was passed over
the catalyst at 200 psi and 0~8 ft3/hr. After an
hour, temperature was raised to 400F, and after
another hour, to 700F. After one hour at 700F,
flow of the gaseous mixture was discontinued and a
hydrogen flow of 12,000 SCAB at 1200 psi was begun.
Heavy vacuum gas oil was pumped to the reactor at
10.2 cc/hr using a positive displacement pump. After
passage through the reactor, product exited the
reactor through a high pressure gas-liquid separator
via a valve with a control loop designed to maintain
a constant liquid level in the high pressure swooper-
ion. Feed properties were as follows:
-44-
APT Gravity I 18.6
Pour Point (OF) 110
Viscosity (cyst at 100~C) 11.~8
Carbon (wt.%) 84.94
Hydrogen (White 11.63
Nitrogen (White) 0.166
Sulfur (wt.%) 2.98
Simulated Distillation I
IMP
I 671
10% 727
20% 788
40% 863
I 918
80% 977
90~ 1000 -I
Paraffins (wt.%) 19.7
Naphthenes (wt.%) 34.7
Monoaromatics (White) 12.6
Polyaromatics and 33.0
Heterocyclics (White)
In addition to the catalyst from Example 5, a
comparative catalyst (A) containing 3.5 wt.% Nil
10 wt.% Cry and 15 wt.% Moo supported on a dispel-
soon of I woo% rare earth-exchanged ultra stable Y-
type zealot in 80 White alumina was tested. Another
run was conducted using a catalyst (B) containing
20 wt.% Moe 3.5 wt.% No and 3.0 White oxygenated
phosphorus component, calculated as Pros, supported
on alumina
Operating conditions and results are shown in
Table 3.
-45-
TABLE 3
RUN NO SAMPLE NO. 1/1 1/2 1/3
CATALYST 5 5 5
TEMPT (OF) 700 740 740
PRESSURE (psi) 1200 1200 1200
LHSV (Harley) 0.625 0.625 0.625
HYDROGEN (SCAB) 12000 12000 12000
HOURS ON OIL. 136 352 496
APT GRAVITY I 28.0 33.6 32.9
POUR POINT (OF) 80 -70 ~60
VISCOSITY (cyst it 100C) 4.71 2.51 2.55
CARBON (wt.%) 87~00 86.90 87.05
HYDROGEN (White) 12.93 13.09 12.94
SULFUR (ppm) 633 137 86
NITROGEN (ppm) 135 8.8 14
SIMULATED DISTILLATION
IMP 114 0 -15
5% 329 165 168
I 631 ~27 448
50% 797 696 707
80% 907 860 863
95% g90 967 961
% DESULFURIZATION 97.9 99.5 99.7
% DENITROGE~ATION 91.9 99.5 99.2
HYDROGEN CONSUMED (SCAB) 795 1045 940
YIELD (wt.%)
IBP-360F 5.5 14.8 13.6
360-650F 17.9 25.7 24.7
650F+ 75.4 53.9 55.3
';~
-46-
ABLE 3 (Continued)
RUN NO SAMPLE NO. 1/4 1/5 1/6
_
CATALYST 5 5 5
TEMPT (OF) 690 730 730
PRESSURE (psi) 1200 1200 800
LHSV (Harley) 0.625 0.625 0.625
HYDROGEN (SCAB) 12000 12000 12000
HOURS ON OIL 808 976 1312
APT GRAVITY I 26.6 30.3 28.2
POUR POINT (OF) 95 30 55
VISCOSITY (cyst at 100C) 6.07 3.88 3.89
CARBON (wt.%) 87.09 87~02 87~26
HYDROGEN to 12.80 OWE 12.66
SULFUR (ppm) 660 88 368
NITROGEN (ppm) 409 29 338
SIMULATED DISTILLATION
IMP 409 ND* ND
5% 584 ND ND
20~ 716 ND ND
50% 830 ND ND
80% 928 ND ND
95% 999 ND ND
DESULFURIZATION 97.7 99.7 98.7
% DENITROGENATION 60.2 98~2 79.6
HYDROGEN CONSUMED (SCAB) 700 930 635
YIELD (White)
IBP-360F 0 ND ND
360-650F 10.4 ND ND
650F+ 88.9 ND ND
*ND stands for not determined.
-47-
TABLE 3 (Continued)
RUN NO SAMPLE NO. 2/1 2/2 2/3
___ _
CATALYST B B e
TEMPT (OF) 740 780 780
PRESSURE (psi) 1200 1200 1200
LM~V (Harley) 0.68 0.68 0.68
HYDROGEN (SCAB) 12000 12000 12000
HOW'S ON OIL 128 320 488
APT GRAVITY I ND* 32.5 33.2
POUR POINT (OF) 100 100 90
VISCOSITY (cyst at 100C~ND 2.10 2.30
CARBON two.%) 86.78 86.97 87.06
HYDROGEN White) 13.19 13.02 12.93
SULFUR (ppm) 240 70 16
NITROGEN (ppm) 22 3
SIMULATED DISTILLATION
IMP 187 97 147
5% 343 244 267
20% 572 440 462
50% 769 656 67~
80~ 869 827 841
95% 985 931 941
% DESULFURIZATION 99.2 99.8 99.9
% DENITROGENATION 98.7 99.8 99.9
HYDROGEN CONSUMED (SCFB)990 940 870
YIELD (wt.%)
IBP-360F 5.6 12.0 11.4
360-659F 22.9 37.2 34.3
650F+ 70.1 48.0 51.6
*ND stands for not determined.
I
-48-
TABLE 3 (Continued)
RUN NO SAMPLE NO. 3/1 3/2
_ _
CATALYST A A
TEMPT (OF) 740 780
PRESSURE (psi) 1200 1200
LHSV (Harley) 0.625 0.625
HYDROGEN (SCAB) 12000 12000
HOURS ON OIL 110 158
APT GRAVITY I 29.7 30.3
POUR POINT (OF) 105 100
VISCOSITY (cyst at 100C)3.84 2.98
CARBON (wt.%) 87.01 87.16
HYDROGEN (wt.%) 12.97 12.82
SULFUR (ppm) 102 79
NITROGEN (ppm) 76 137
SIMULATED DISTILLATION
IMP 9 151
5% 36~ 322
20% 606 558
I 786 753
80~ 905 882
95~ 990 969
DESULFURIZATION 99.7 99.1
DENITROGENATION 95.3 91. 6
HYDROGEN CONSUMED (SCFB)82 5 890
YIELD (wt.%)
IBP-360F 4.8 6.0
360-650F 20.1 23.3
650F~ 74.0 64.9
*ND stands for not determined
-49-
As can be seen from the table, all three
catalysts exhibited high desulfurization activity
and catalysts 5 and B showed good denitrogenation.
Cracking activity, as indicated by the yield data,
was generally comparable for catalysts 5 and B,
both of which were superior to eatalysks A.
Catalyst 5 was superior to both comparative catalysts
in terms of selective cracking of waxy eompon~nts
as evidenced by the reductions in pour point in runs
using catalyst 5. Catalyst 5 also was superior in
terms of overall performance in that comparable or
better results were achieved with that catalyst at
lower temperatures than those used in the comparative
runs.
EXAMPLE 3
A series of catalyst compositions was prepared
from various erys~alline molecular sieve zealot and
matrix components and aqueous phosphoric acid soul-
lions of various metal salts (pi about 3) according
to the general procedure of Examples 1-5. A second
series of catalysts was prepared in similar fashion
to entwine identical levels of metals and support
components but no phosphorus (pi about I
Samples of the catalysts were analyzed by X-
I ray diffraction to determine the effect of phosphorieaeid on retention of zealot erystallinity. For
each pair of catalysts (with and without phosphoric
and impregnation) of identical metals and support
content, intensity of one or more X-ray bands err-
touristic of the zealot component and not subjeetto interference by the metals of the catalysts
were measured.
For each pair of catalysts, composition and
crystallinity of the phosphorus eomponent-eontaining
catalyst relative to that of the phosphorus free
composition is reported in Table 4.
-50-
TALE 4
RELATIVE
CRYSTAL-
SAMPLE COMPOSITION (wt.%) LUNATE
(%~
A 3.5% No, 18~ Moo, 3.4% Pros/ 86
50 US, 50~ AYE
B 3~5% No, 18~ Moo, 3-4% P2s/ 78
50% v, 50% AYE
C 3.5% No, 18% Moo, 3-4% P2s/ 86
50~ ZSM-5~3), 50% AYE
D 1.5~ Coo 10% Cry, 15% Moo, 79
4.6~ Pus HAMS-lB(4),
60~ AYE
E 1.5~ Coo 10% Cry, 15% Moo, 88
4.6~ P20s/30~ US, 70% Aye
.
(1) Ultra stable Y-type crystalline aluminosiLicate
zealot.
(2) Y-type crystalline aluminosilicate zealot.
(3) Crystalline aluminosilicate zealot ZSM-5.
(4) Crystalline borosilicate zealot HAMS-lB.
As can be seen, crystallinity of the compositions
according to the invention was quite high relative
to compositions identical but for inclusion of pros-
phonic acid in preparation. 3.5% No, 18.0% Moo,
3.5~ P20s/30% US, 70~ AYE exhibited 66~ crystal-
tinily relative to a dispersion of 30% US in 70~
Aye .
