Molecular sieve abstract
Method of activating a catalyst composite comprising particles
of a catalytic metals-free crystalline zeolitic molecular sieve
dispersed in a gel matrix comprising silica-alumina, a Group VI
hydrogenating component and a Group VIII hydrogenating component,
which method comprises heating said catalyst composite in an oxygen-containing
gas stream at 1200.degree. to 1600.degree.F. for 0.25 to 48 hours,
and the catalyst composite so activated.
Molecular sieve claims
What is claimed is:
1. A catalyst composite comprising:
A. a gel matrix comprising:
a. at least 15 weight percent silica,
b. alumina, in an amount providing an alumina-to-silica weight
ratio of 15/85 to 80/20
c. nickel or cobalt, or the combination thereof, in the form of
metal, oxide, sulfide, or any combination thereof, in an amount
of 1 to 10 weight percent of said matrix, calculated as metal,
d. molybdenum or tungsten, or the combination thereof, in the form
of metal, oxide, sulfide, or any combination thereof, in an amount
of 5 to 25 weight percent of said matrix, calculated as metal;
B. a crystalline zeolitic molecular sieve substantially in the
ammonia or hydrogen form, substantially free of any catalytic loading
metal or metals, said sieve further being in particulate form and
being dispersed through said matrix;
said catalyst composite being further characterized by an average
pore diameter below 100 Angstroms and a surface area above 200 square
meters per gram;
said catalyst composite being further characterized by hydrocracking
activities and stabilities developed therein by heating said catalyst
composite in an oxygen-containing gas stream at temperatures in
the range 1200.degree.F. to 1600.degree.F. for 0.25 to 48 hours.
2. A catalyst composite as in claim 1 wherein said gel matrix further
comprises titania.
3. A catalyst comprising a silica-alumina matrix having dispersed
in it particles of a low-sodium molecular sieve zeolite, the silica-alumina
matrix having dispersed in it a Group VI metal or metal compound
and a Group VIII metal or metal compound and the zeolite being substantially
free of chemically or physically bonded metals or metal compounds
having appreciable catalytic activity for hydrogenation; said catalyst
being further characterized by hydrocracking activities and stabilities
developed therein by heating said catalyst in an oxygen-containing
gas stream at temperatures in the range 1200.degree. to 1600.degree.F.
for 0.25 to 48 hours.
4. A catalyst comprising a crystalline zeolitic molecular sieve
of the ammonia or hydrogen form and substantially free of metals
or metal compounds having catalytic activity for hydrogenation dispersed
in a hydrocracking catalyst matrix comprised of silica-alumina having
dispersed in it 1 to 10% by weight of nickel in the formm of metal,
metal oxide or metal sulfide and 5 to 25% by weight of molybdenum
or tungsten in the form of metal, metal oxide or metal sulfide,
said catalyst being further characterized by hydrocracking activities
and stabilities developed therein by heating said catalyst in an
oxygen-containing gas stream at temperatures in the range 1200.degree.
to 1600.degree.F. for 0.25 to 48 hours.
Molecular sieve description
INTRODUCTION
In Joseph Jaffe copending application Ser. No. 749836 filed Aug.
2 1968 for "Hydrotreating Catalyst and Process," there
is described a novel and unusually effective hydrofining-hydrocracking
catalyst. Said catalyst comprises a crystalline zeolitic molecular
sieve component substantially free of any catalytic metal or metals,
a silica-containing gel component, a Group VI hydrogenating component,
and a component selected from titanium, zirconium, thorium, hafnium,
and compounds thereof. It has now been found that catalysts of this
general type, either with or without a Group IV component, can be
even further improved in various respects by a novel heat treatment
procedure, which serves both to activate and stabilize the catalyst.
Said heat treatment procedure, hereinafter for convenience called
an activation or thermactivation treatment or procedure, is applied
to the total catalyst composite, following dispersion of the crystalline
zeolitic molecular sieve component in the gel matrix.
STATEMENT OF INVENTION
In accordance with the present invention catalysts of the aforesaid
type are thermactivated in an oxygen-containing gas stream at temperatures
in the range 1200.degree. to 1600.degree.F., preferably 1250.degree.
to 1400.degree.F., for 0.25 to 48 hours. The oxygen-containing
gas stream, which may be air, preferably is as dry as practicable.
The improved results obtainable with the process of the present
invention are optimized as the gas stream becomes extremely dry;
although for most practical purposes the gas stream need be only
as dry as ambient air, greater dryness is preferred. Those skilled
in the art will be aware of various methods for drying the gas stream
to any desired extent.
Although the process of the present invention is applicable to
activation of catalysts of the aforesaid type with a wide range
of silica content, it is especially useful with such catalysts that
contain less than 40 weight percent silica in the total catalyst,
and less than 35 weight percent silica in the catalyst matrix.
Further in accordance with the present invention there is provided
the method of activating a catalyst composite comprising:
A. A gel matrix comprising:
A. at least 15 weight percent silica,
B. alumina, in an amount providing an aluminum-to-silica weight
ratio of 15/85 to 80/20
C. nickel or cobalt, or the combination thereof, in the form of
metal, oxide, sulfide or any combination thereof, in an amount of
1 to 10 weight percent of said matrix, calculated as metal,
D. molybdenum or tungsten, or the combination thereof, in the form
of metal, oxide, sulfide or any combination thereof, in an amount
of 5 to 25 weight percent of said matrix, calculated as metal;
B. A crystalline zeolitic molecular sieve substantially in the
ammonia or hydrogen form, substantially free of any catalytic loading
metal or metals, said sieve further being in particulate form and
being dispersed through said matrix;
said catalyst composite being further characterized by an average
pore diameter below 100 Angstroms and a surface area above 200 square
meters per gram;
which method comprises heating said catalyst composite in an oxygen-containing
gas stream at temperatures in the range 1200.degree. to 1600.degree.F.
for 0.25 to 48 hours.
Further in accordance with the present invention there is provided
a catalyst composite comprising:
A. A gel matrix comprising:
a. at least 15 weight percent silica,
b. alumina, in an amount providing an alumina-to-silica weight
ratio of 15/85 to 80/20
c. nickel or cobalt, or the combination thereof, in the form of
metal, oxide, sulfide or any combination thereof, in an amount of
1 to 10 weight percent of said matrix, calculated as metal,
d. molybdenum or tungsten, or the combination thereof, in the form
of metal, oxide, sulfide or any combination thereof, in an amount
of 5 to 25 weight percent of said matrix, calculated as metal;
B. A crystalline zeolitic molecular sieve substantially in the
ammonia or hydrogen form, substantially free of any catalytic loading
metal or metals, said sieve further being in particulate form and
being dispersed through said matrix;
said catalyst composite being further characterized by an average
pore diameter below 100 Angstroms and a surface area above 200 square
meters per gram; said catalyst composite being further characterized
by hydrocracking activities and stabilities developed therein by
heating said catalyst composite in an oxygen-containing gas stream
at temperatures in the range 1200.degree.to 1600.degree.F. for 0.25
to 48 hours.
The gel matrix of the aforesaid catalyst composite additionally
may comprise titanium, zirconium, thorium, hafnium, or any combination
thereof, in the form of the metal, oxide, sulfide or any combination
thereof, in an amount of 1 to 10 weight percent of said matrix,
calculated as metal.
The reference to a crystalline zeolitic molecular sieve "substantially
free of any catalytic loading metal or metals" means that the
molecular sieve contains no more than 0.5 weight percent of catalytic
metal or metals, based on the sieve. The catalytic metal or metals
include the Group VI and VIII metals, excluding sodium.
|