Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
5~
HETTINGER-B~.CK
- CARBO ME~ALLIC OIL CONV~RSION PROCESS AND CATALYSTS
This invention i8 concerned with characterizing a
select group o hydrocarbon conversion catalysts
suitable for converting carbo~me~allic oil containing
S hydrocarbons such a~ reduced crudesl residual oils,
topped crude~ and high boiling hydrocarbon~ such as
vacuum gas oils boiling above about 650F and
comprising re~idue material boiling in exce~s of
1025F to low boiling transportation fuels. The
~elect group of catalysts o this invention and method
o~ preparation possess a high concentration of at
least one select high activity crystalline zeolite of
high lanthanum exchange content or ~tability
dispersed in a matrix of high pore volume of at least
0.35 cc/gm~ and pore siz~ to particularly implement
liquid and gasiform material di~fusion contact with
the catalyst particle3 A hiyh pore volume and
relatively large pore size matrix material complex is
provided with and/or without acidic cracking activity
but preferably prepared ~o provide at least ~ome
acidic cracking activity for catalytic eracking of
some deposited liquid components o the high boiling
feed~ More particularly the matrix material of large
pore si~e and high pore volume promotes the
~5 accumulation and passiv~tion of metals deposited by
the high boiling feed and particularly immobilizatior
o~ deposited vanadia at temperatures encountered in a
hydrocarbon conYersion process ~uch as the
regeneration ~ection thereof.
Background of he Invention
The cataly~ts utllized in conventional gas oil
fluid catalytic cracking (FCC3 operations are ~ailored
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~nd prepared with less than 20 wt% zeolite for use
other than in high carbon and metals deposition~
reduced crude cracking operations, The fact tha~
the~e k~own catalysts may be used to crack residual
oils and reduced crudes in a marginal short .time
operation does not mean they are economically suitable
for processing liquid carbo-metallic oil contributing
~aterials such as asphaltenes, polynuclear aromatics,
polar molec~le~, naphthenes and porphyrins found in
the residue of vacuum distillation and boiling above
1025F or more usually above 1050F~ ~enerally, a
conventional gas oil FCC ~ystem employs a catalyst of
relatively low crystalline zeolite content less than
20 wt~ llO-15 wt%) which h s a rela~ively low
hydrothermal stabili~y due ~o a low silica to alumina
ratio zeolite; comprise6 a high cerium to lanthanum
ratio exchanged crystalline zeolite dispersed in a
matrix material of low pore volume usually not above
about 0~22 cc/gm; and comprises a pore size opening of
less than 500 angstroms. Generally, the matrix is
merely a binder material of little or no acidic
cracking activity~
The processing of gas oils ~atmospheric and
vacuum) and boiling below about 1025F with
crystalline ~.eolite~ containing cracking ~atalysts has
been available to the petroleum refiner since the
early 60~s and used considerably in the 70's.
~enerally such gas oil feeds are relatively low in
metal contaminants and Conradson carbon value because
of the feed purity sources selected~ In additiont
high ~ulfur or sour crudes and those comprising hiyh
levels of metal contaminants were not used in FCC
operation in the absence of severe treating processes
to remove or substantially reduce these undesired
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components. Such processe~ include hydrogenation,
propane deasphalting, coking, hydrocracking,
visbreaking and vacuum distilla~ion. These processes
are expensive and çonsiderably reduce the volume of
the crude oil upgraded to transportation fue~s.
The catalysts developed for gas oil FCC process~
ing have been developed to provide a high conversion
and high ~electivity to particularly gasoline boiling
range product~ and light cy~le oilfi since higher boil-
ing product material i~ normally recycled to thecracking operation. In this gas oil processing
environment, the deposition of metal~ is relatively
low because of feed composition a~ well as the
Conradson carbsn level being generally below about 1
w~ ~nd more u~ually ~uch Conradson carbon deposi~ion
is within the range of 0~1~0.2 w~. The feeds used in
~uch gas oil operations are rea~ily vaporized a~ ~he
cra~king reaction conditions and thu5 deposition o
large amounts o~ uids on the catalyst is minimized
i~ not avoided. In FCC ga~ oil cracking operations,
diffu~ion of the gas oil feed in ~he 1uid particle
size catalyst is not a major problem and pore blockage
by excessive metal deposition by high boiling liquid
hydrocarbons and by high coke deposition is not
encountered as a ma~or problem in the operating
environment, Since deposition of undesired metal
components and carbon i~ normally of a low order of
magnitude there ha~ been le~s need to provide a matrix
material particularly de~igned or tailored to
a~cumulate metal to the exclusion of sub~antially
disturbing the catalyst cracking activity. Further
more, and much more importantly~ there has ~een no
recognition by others of the need to particularly
immobilize vanadia (vanadium pentoxide) because the
level of depos.iton of vanadia encountered in yas oil
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35~
cra~king did not trigger recognition of particle
sintering and coalescence due to li~uefaction of this
material at regeneration ~e~perature condi~ions in the
range of 12Q0 ~o 1600DF~
In contrast tb ~he gas oil FCC operation as it is
now known t~day~ a reduced crude conver~ion operation
proce~sing much poorer ~uality feeds which have not
been subjected to vacuum distillation~ propane
deasphalting and other contaminant removal processes
as by hydrogenation, cQntain high levels of metal
contaminants, sulfur and nitrogen compQunds and a high
Conradson carbon value, This high boilin~ dirty feed
which we have chosen to define as earbo-metallic feed,
composition ~h3racterization is par~icularly
representative by much of the very poor qualtity feeds
available to the refiner todayr
The use of a c~onven~ional low æeolite content,
les than 20 wt~ zeolite containing FCC conversion
catalyst as known toclay in a r~duced crude conversion
process leads to rapid catalyst dea~tivati3n by metals
and hi~h carbon deposits which can be corrected only
by using very high catalyst replacement rates contri
buting to a highly unattractive economic operationO
The rapid deactivation of the low zeolite containing
catalyst i5 due to a rapid loss in zeolite activity
and selectivity by metals deposition and relatively
lo~ hydrothermal ~tabi~ity for handling high levels of
carbon depo~itiGn during regeneration thereof. Our
studies have shown khat high temperature regeneration
in the presence o~ ~team and especially vanadium and
oxygen, rapidly clestroys the activity of the zeoli~e
cracking component of ~he catalyst and the ~eolite
cracking component of the catalyst and ~hi~ condi~ion
i~ aggravated by using low silica-alumina ra~ioO
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5 ~5~
higher ~odium ~ontaining zeolites in conjunction with
high metals depositicn comprising vanadium, sodium and
nickel, leading to rapid zeolite ~racking activity
neutralization. In addition the activi~y of ~he
5 catalyst is affected by the large amount of hea~y high
boilin~ hydrocarbons ~n reduced crudes tha~ are not
vaporized and rapidly coat the catalyst particles with
tacky liquid material also eausins particle
coalescence and agglomeration because of materials
10 such as asphaltenes in the feed. Fur'chermore, the
~orbed heavy hydrorarbons contribute to pore blockage,
both in the matrix, and espe~ially zeolite pore~, and
aggravate diffusion problems because of low pore
volume~ and effect acid site neutrali~ation by
adsorption o basic nitrogen compounds in ~he high
boiling reduced crude feed~
The problems above reported with respect ~o
cracking activity, acidity~ hydr~thermal stability,
diffusion and pore blockage, ~odium content of the
zeolite, acid site neutralization, metals accumulation
and vanadia immobilization are reduced or circumvented
in substantial measure by employing the special cata-
lyst compositions of the present inven~ion for u9e in
a Reduced Crude Conversion Process.
Brief Description of Drawing
Figure l :is a ~chematic diagram of a preferred
embodiment of this inventionO
Summary of the Invention
This invention i~ directed to the identif.ica~ion
and characteriæation of an improv2d and novel class of
cataly~t compositions particularly ~uitable for
converting high boiling hydrocarbons or heavy oil
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feeds recovered as atmospheric bottom of an atmospher-
ic distillation tower and comprising asphaltenes~
polynuclear aromatics, polars, naphthen~s, porphyrins,
nitrogen and sulfur ~ompounds boiling above 1O25OF
~he present invention is concerned with ~he y~tiliza-
~ion ~f the~e unique catalysts, and identiication of
one or more unique methods for preparing a select
group of these catalyst compositions. The catalyst
compositions thereof are particularly adapted and
suita~le for the convPrsion of one or more high
boiling feeds herein identified and known by ~ne or
more terms such as a combination of materials in heavy
oils ~omprising ~omponents boiling above 1050F7 as
reduced crudes, topped crudes, residual oils, shale
oils, oil produc~s from coal liquefaction~ tar sand~
oil products and resids all of which comprise some
carbo-me~alli~ oil comp~nents in the form of metals,
asphaltenes, refractory aromatic and polar compounds,
naphthenes and porphyrins. The special catalysts of
this invention are useful for proce~sing Conradson
carbon producing feed materials in the range of ~ to 8
Conradson carbon and comprising up to 75 ppm or more
of vanadium~, The catalyst composltions of ~his inven-
tion are particularly useful for processing high boil-
25 ing ~eeds above identified when carrying an accumulat-
ed metal~ level of Ni ~ v in excess c~f 6000 ppm of
which either nickel or vanadium is in a major
proportion~ In yet a further aspect, the present
invention is concerned with providing an improved
metals tolerant catalyst composition of high eracking
activity whereby the catalyst particle service i~
extended and the catalyst inventory of the proce~sing
system is kept at a desired low level oE magni~ude
contributing significantl~ to the economic efficiency
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of a reduced crude cracking operation. The provision
for low catalyst inv~ntories is desirable since it
permits reducing the size of costly regenera~ion
equipment, reduces the relative kime the high vanadium
containin~ catalys~ i8 e~posed to ~ime and temperature
in the regenerator relatiYe to the time it is engaged
in riser ~racking. The longer the time that a high
vanadium containing catalyst is at high temperature in
the presence of steam and 2 has been found to be very
detrimental to ~atalyst life. ~ow catalyst inventor-
ies reduce catalyst makeup invelltory for mainta ning a
prede~ermined and desired cataly~t activity selectiv-
ity characterizati~n in a circulating catalys~ system
compri~ing hydrocarbon ~onver~ion to form de~ire~
products and regeneration of catalyst used in such an
operation.
The high boiling reduced crude conversion
operation contemplated by this invention relies upvn a
maintained catalyst inventory which will permit the
use of catalyst o oil feed ratios in the rang~ of
~ - 20 to 1 in a short contact time tempera~ure
res~ricted cracking zone such as att.ained in a riser
cracking ~one. Al50 of low or restricted inventory is
an associated catalyst stripping zone and intercon-
2$ necting catalyst transfer conduits in combinationwi~h a catalyst regeneration operation compri~ing at
least two stages of catalyst regeneration in sequence
to achieve the removal of deposited hydrocarbonaceous
materials~ Thus by providing a catalyst compositi~n
which will accept a greater metals accumulation at
desired retained activity and ~electivity thereby
permitting a ~onyer on ~tream operation with a higher
activity-equilibrium metals level catalyst will
greatly reduce ~atalyst replacement rate and th~s
3S improve the process operating efficiency.
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8 ~ 8
The improved high aetivity metals tolerant
catalysts of this inven~ion are special microspherical
particle compositions of fluidizable particulate size
in the range of 20 o 200 microns ~ize comprising a
higher than normal percentage of high activi~y
cry~talline aluminosillcate of large pore size
dimensions~ ion exchanged to provide a lan~hanum rich
crystalline zeolite of low residual ~odium, less than
0.25 wt% in the finished catalyst and preferably less
than n . 1 wt~ sodium oxide di~persed in a special
matrix ~omposition and comprising a clay which may
provide some cracking activity with or witho~t acidic
modifiers dispersed in a s.ilica or ~ilica-alumina of
gelaceous or colloidal ancestraryO The ~atalyst is
prepared under conditions to provide a pore volume
greater than 0c22 cc/g and preferably at least about
0~32 cc~g. A cal:alyst par~icle with a pore volume o
at least 0.4 cc/g i5 particularly desirableO The
zeolite-clay mixture i5 prepared in combination with a
binder material initially comprising one or more
refractory metal oxides providing desired hardness in
the final ~icrospherical particle5 The refractory
metal oxide or vxides suitable for this purpose may be
selected from the group consisting of silica3 alumina~
silica-alumina, silica~magnesia~ ~ilica~alumina-
magnesia, silica-titania, si ica-zirconia, titania~
~irconia and mixture~ and combinations thereofO The
special catalysts of this invention are based on form-
in~ a silica ~ol (colloidal3 matrix material by one or
more proce~ing routes i~cluding .~tarting with a
sodium silicate to form gelaceous or colloidal
suspension with additions ~hereto a~ herein provided.
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g
Zeolites or cry~talline aluminosilicates ICAS) of
aeceptable pore dimen~ion~ and particle size suitable
for the preparation of cracking catalyst composition
usable according to thi~ invention are micron size
three dimensional structures containing a large number
of uni~orm opening~ or cavi~ies interconnected by
~maller, relatiYely uniform holes or channels.
Some zeolites which may be used with varying
degrees o ~uccess include mordenite, gmelinite,
10 zeolite ~L", ZSM 4" faujasite and dealuminized
fauja~ite of at least 5.5/1 silica to ~lumina ratio.
A ~Y" type crystalline faujasite is particularly
preferred in pre~aring the catalyst of this invention.
Some characteristics of these ~rystalline ~eoli~e are
15 as follows~
Summary of Some Zeolite Pore Sizes
Pore Pcre Free
Dimension~Area ~A2 ~Si/Al Ratio
Faujasite7.4 x 7c4 55.0 ~.8
ZSM4 7a3 x 7~3 53~i 3~1
~L~ 701 x 7~1 5005 3.6
Gmelinite7~3 x 7.0 49D0 2.5
Mordenite607 x 7.0 46.8 6 D O
The preferred zeolite for preparing ~he metals
t~lerant catalyst o~ ~his invention is a cataly~ically
active faujasite crystalline zeolite providing a
silica to alumina ratio greater than 5 and which has
been ion exchanged ~everal times before and after
calcination ~o include rare earths and par~icularly
provide a lanthanum to cerium rati~ of at least 1/1
and preferably at least 2/l:La/Ce or more. It is
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9~
known that zeolite ~tability is directly propor ioned
to the lanthanum or neodymium content and inversely
proportional to the ~erium con~ent. Thus in commer-
cial applications~ ~ome lanthanum rich exchange ~olu-
~icns have been used for zeolite exchange, ~he faujasite type zeolites known as "X~ and ~Y~ crystalline
~eolites are regularly shaped, discrete particles gen-
erally of a particle size in the ran~e of 0.05 to 10
microns, preferably less ~han 5 microns when synthe-
tically prepared and used in ~he ~atalyst preparationconcepts of this invention. The especially preferred
zeolite is the ~Y" type crystalline zeolite, and the
hiyher the ~ilica to alumina ratio; the better its
~tability. Generally speaki~q, ~he preferred ~yN
zeolite will contain a s;li~a-alumina ratio of 4O5 or
greater, ~ore usually one containing 5/1 silica to
alumina ratio and preferably at least 5O5 to 1 silica
to alumina molar ratio.
The zeolites are catalyti~ally activa~ed and sta-
biliæed by ion exchange to replace ~odium to a desired
low level with hydrogen and/or rare earth metal to
provide a final ~atalyst particle composition ~ompris-
in~ less than 0O25 wt~ sodium oxideO The removal of
sodium ions to a very low level and provi~ion of a
rare earth exchanged ~yll faujasite characterlzed as
herein provided is much more ~table than the hydrogen
form of zeolite an3 this is particularl~ optimi2ed by
providing a high lanthanum content zeolite exchanged
before and ater calcination of a high silica content
zeolite. In particular9 when dealing with vanadia, a
high lanthanum content crystalline zeoli~e o~ a~ leas~
7 wt% is especially desirable, These catalytically
modified rare earth coAtaining cryst~line zeolites
are highly active catalytic compos.itions and most
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usually require ~ome further modif ication as by high
temperature 6teaming and dilution in a ~upport or
matrix material to restrict the overall cataly~t
particle activity ~hereof wi~hin acceptable catalytic
S eracking limits.
In the pri<~r art, catalyst c:ompositions have been
prepared so 'chat the matrix comprises silica, alumina
or mixtures thereof comprising at least 25 wt~ alumina
and more usually at lea~t 50 wt% alumina. The matrix
material is also known to c:omprise a clay in an amoun~
of about 10 to 65 wt% of the f inished catalyst . Clays
such as kaolin~ halloysite, montmorillonite and others
have been used in the prior art~, Also heat and
chemically modii.ed clays ~u~h as Isletakaolin and acid
treated halloysite can be used. On the other hand, a
colloidal dispersion of silica and/or alumina par~
cles (10 to 10 ,OOOA) may be added to a preformed
catalyst or catalyst gel to provide a catalyst compo-
sition of improved resistance to metal poisonirlg, as
in ~1~, S. Paten~ 4,198,320. Furthermore V. S~, Pa~en~
3,944,~82 proposes cracking of a high metals con~ent
hydrocarbon iEeed~tock in the presence of a catalyst
comprising from 1 to 40 wt% of a zeolite dispersed in
a refractory metal oxide matrix providing a pore size
distribution in the range of 5D-100 Angstroms. U~ S~
Patents 3 ,972, 835; 3, 957, 689 and 3 ~ 867, 308 prepare
catalysts by neutralizing silicates by adjustirlg their
p~l and then adding clay and zeolites t~ ~orm cracking
catalyst J
The imp~oved metal tolerant catalysts of this
invention are o a composition comprising at least 35
w~6 and more usually about 40 wt% c: f a ~elect
;anthanum rich crystalline æeolite of small particle
~ize in the range of about 0.05 to 5 microns par~icle
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12 ~ 8
size dispe~sed in ~ gel or colloidal ~uspension of
silica~ alumina or a combination ~hereof to form a
matrix material providing desired intimacy ~f
admixture ~ith the small particles of khe select
S crystalline zeolite herein iden~ified. Preferably a
kaolinite clay characterized by a small particle sixe
of a~ou~ icron si2e~ more or le~s and providing a
pore volume in the catalyst particle complex in excess
of .30 cc/g. It is preferred that the pore volume be
at least 0.32 cc/g and more desirably in the range of
0.4 to 0.8 ~c/g.
In one particul~r aspect of this invention
microspherical catalys~ particles prepared by the
technique ~f this invention are observed to include
hollow shell particles some of which include at least
one large major pa~sageway to the interior of the
particle shell. Thus the improved and novel catalyst
composition of high lanthanum rich zeolite content
provides a metals tolerant ~pherical ca~alyst parti-
cle çomposition prepared as herein provided which
appear to be ~ubstantially less diffusion limited and
thus remains e~fective catalytically even with high
levels of metal contaminant for a much extended
operating period over that heretofore experienced~
It will be recognized by those skilled in the art
that the catalyst compositions of this invention are
much more highly active catalytically than known prior
art compositions because of the high concentr~tion of
a select rare earth rich crystallinic zeolite composi-
3Q tion of about 40 weight percent dispersed in a select
matrix material preferably colloidal as herein
identified and providing a high pore volume preferably
greater ~han 0.30 ~c~g. That is, a hi~h percentage of
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13 ~ ~ ~ 5 ~ ~ ~
a lanthanum rich rare earth exchanged~ high ~ilica tv
alumina ratio CREY*zeolite eatalyst composition
(calcined rare ear~h ~xchanged crystalline wy~
zeolite) of high h~drothermal ~ability is prepared
S and provided in a high por~ volume select ma~rix
material of colloidal ~ncestrary chara~terization~
The catalyst composition comprises at least 40% of its
pore openings being greater than 5DO Angstroms; and at
least 25% grea$er ~han 1000 Angstroms. This
characterizaiton ~tatistically provldes a catalyst
particle composition comprising at least 6~ and
preferably at least 7~ rare ear~hs for more available
active cracking ~ites even in the presence o$ high
metal~ loading for conver~ing high CRC (Conradson
carbon) precursor hydrocarbon feed materials in
contact therewithD The u~e of microspherical catalyst
compositions comprising colloidal matrix component~ -
and prepared as herein provided is operationally
enhanced in the cracking of catalytic hydrocarbon
conversion opera'cion by selecting catalyst o oil
ratios ~uficiently high which will exclude filling
more than 2/3 bu~ at lea~t 1/4 to 1/2 of the catalyst
particle ~ore volume with reactant oil feed material
as herein identified.
The known li.terature and prior patent art, teach
that metals, such as Ni, V~ Fe, Cu and Na are
deposited on a cracking catalyst when processing
reduced crudesO The~e metals, particularly Na, are
known to effect cataly~t activity and ~electivity.
The prior art al~o teache~ that nickel and to ~ome
degree vanadium are especially harmful with regard to
producing coke and hydrogen, and thus the metal
contaminant level is expressed in terms of nickel
* Trade Mark
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equivalents. This i~ evident from the following
equations:
Ni equivalents = 4 Ni ~ V + Fe
Ni equivalents - Ni + V/4 + Fe~5
In an investigation ~o identify catalyst oomposi-
tions most suitable for converting reduced crudes
in the presence of lar~e amounts of metal, vanadia was
id~ntified as by far the most de~truc~ive of the me~al
contaminant~, followed by sodium. Ni~kel appeared ~o
be the least de~tr~ctive. Vanadia; a~ vanadium
pentoxide, causes irrever~able destruction of the
crystalline zeolite structure, rapidly producing a
much lower activi~y material of or approaching
amorphous nature. Sodium does lead to permanent
~eutralization of the zeoli~e acid cracking sites.
Nickel leads primarily ~o temporary neutrali~ation o
the cracking ~ites by promoting dehydrogenation and
deposition o~ carbonaoeous materials~
The catalyst oompositions of this invention may
be employed in a number of different appara~us
arrangement~ known in the art or yet to be devised
which permits lo~ reactant residence time less than 3
seconds and more usually in the ran~e of 0.5 to 2
seconds between a hydrocarbon feed, vaporous colver-
sion products and oatalyst particles at temperatures
providing desired catalytic hydrocarbon cracking or
conversion to more u~eful products. The product
vapors are recovered at a ~emperature within the range
of 950 to 1150F but more usually no~ above about
1100F. In cooperation with the hydrocarbon ~onver~
sion operation i5 a regeneration system or operation
designed to restri~t cataly~t regeneratio~ time and
temperatures below 1500F and more usually below
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i8
1400F so as to produce a recoverable CO rich flue
gas~ The c~talyst regeneration operation is designed
to provid a regenerated catalyst of low re~idual car-
bon content and preferably less than 0~1 wt~ In a
more particular aspect it i~ preferred emplo.ying a~
least two ~tages of temperature restricted catalyst
regeneration operations in combination with one or
more catalyst ~tripping opera~ions which will opera~e
in conjunction with one another to reduce the exother
mic temperature rise encoun~ered during the xemoval of
relatively large deposits of hydrocarhonaceous materi-
als and some metal contamina~ts contributed by crack-
ing reduced crudes. More particularly a two stage
oxygen containing gas regeneration operation is
contemplated or one stage ~hereof may be replaced by
using CO2 to remove hydrocarbonaceous component
material in combination with a relatively high temper~
ature ~tripping operation to remove hydrogen, sulur
and nitrogenO In this catalyst regeneration operation
~0 and sequence of temperature restEicted contact step~,
it is contemplated in one particular embodiment of
relying upon high temperature CO2 to remove some
hydrogen and some carbonaceous depo~its in one or more
stages and such an operation may be intercepted by
oxygen combustion removal of a portion of the
deposited carbonaceous materlal by burning to produce
a CO or CO2 rich flue ~as recovered from the
operation. In any of these regeneration combinatlons
it is particularly desirable to restrict the
~emperatures of oxygen combustion tG relatively low
levels, preferably below about 1450F, which will
provide recovera~le CO rich or CO2 rich f lue gases .
Removing hydrogen in hydrocarbonaceou~3 ~eposits with
C2 as well as carbon to produce recoverable CO
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16 ~
~ improve~ measurably the overall heat balance of the
combination operation and reduces potential
temperature excursion changes to the ~atalyst under
elevated temperatlire hydrothermal conditions.
Discussion of Speciic Embodiments
The present invention parti~ularly relates to the
preparation and method of use of ~ovel ca~alyst compo-
sitions and is particul~rly suitable for the conver-
sion of high boiling hydro~arbons comprising carbo-
metallic oil component of a~phaltenes, naphthenes and
and porphyrins. More particularly, the present inven-
tion is dir2cted to the characterization and prepara-
tion o~ a select novel class of high activity hydro-
carbon conversion catalyst eompositions 6uitable for
u~e in converting high boilir.g hydrocarbons compri~ing
components boiling above 1025F~
The flexibility of this invention permits the
preparation of catalyst~ incorpora~ing the following
features especially suitable for these ~atalysts
utîlized in redu~ed crude ~onversion. Ranges o
special interest are indicated as ollows:
1~ Cracking Activity - providing at least 20 wt~ up
to 45 wt% of a hydrogen or rare ear~h [exchanged
before and/or after calcination of a] ~Y" faujasite
crystalline aluminosilicate or crystallin~ zeoli~e of
high silica to alumina ratio at least equal to 4~5/1
and preferably greater than 5.0/1 silica-alumina molar
ratio.
2) Cracking Activity - preparing a final catalyst
composition of low sodium content from 18w ~odium
ingredient material and compri~ing less than about
0.40 wt% 60dium oxide and more preferably no more than
about 0~25 w~% thereof.
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17
3~ ~ydrothermal Stability - improving the catalyst
hydrothermal stablili~y with either a hydrog~n
exchanged ~Y~ or a combination of rare earth exchanges
to provide a high lanthanium to cerium r~tio in excess
5 of 1/1 in the catalyst composition and particularly
the zeolite component ther~of~ and preferably greater
than 3/1, and provide a ~atalyst particle composition
comprising a rare earth oxide ~ontent of at least 3
wt% and preferably greater than 5 wt% rare earth
oxides.
4) Diffusion and Pore ~lock~ge - employing a matrix
material compositi~n comprisiny one or mor~ components
of colloidal ance~try or conYertable ~o c~lloidal
su~pensionsO Prefer~bly the matrix is of a composi
tion providing ~ ~u~stantial portion of its pore ~ize
openings comprising 40 or more percent thereof at
least a~out 500 Angstroms; at least 25% greater than
1000 Angstroms of sufficient large pore ~ize openings
so that the highest molecular weight components of ~he
2~ feed will be adsorbed without caus.ing undesired pore
blockage; so that diffusiQn problems associated with
the escape of cracked m~terial are minimized, and so
that the deposit~ of me~als in the large pores al~o do
not cause substantial pore blockage or diffusion
problems. Thu~ it i~ also contemplated employing
different amount~ of at least two different pore ~ize
providing colloidal ~uspensions of different particl~
size in forming the matrix composition of the catalyst
par icle compositiQn of this invention. Thi~
variation in pore size openings as well as pore volume
i~ used as a ba~is ~or varying particle porosity and
at~ri~ion resistance properties of a spray dried
micro~pherical catalyst particle compositionu Thus~
colloidal suspensions of diferent size silica colloid
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18
or alumina c~lloid or a combination thereof may be
employed to achieve a binder matrix material for the
zec~1ite componerlt e)f desired porosi~y and hardne~s.,
5 ) High Boiling Oil Componen'c Absorption - the matrix
5 materi 1 of the catalyst composition7 whether acidic
or neutral, is lpreerably of large pore volume greater
than O . 30 cc/g and comprising ~ubstantial pore size
openings vf at lea~'c 500 Angs~roms up to and including
1000 An~stroms so that the highest boiling componerlts
10 of a reduced crude feed not completely vaporized upon
contact with freshly regenerated catalyst at tempera-
tures up to 1350'3~ can crac:k and a product of cracking
enter the select zeolite pores for catalytic upgradin~
in preference to coating the catalyst particl surface
15 and causing undesired particle agglomeration. It is
also important to encourage condensation products of
reduced crude cracking to deposit on the catalyst
rather than parts of the apparatus employed and ~uch
deposition is particularly influenced by employing the
20 catalyst to oil ratio hereîn defined in conjunc~ion
with the large pore size opening and pore volume
def ined O The catalyst rompositions of this invention
therefore are provided with a high pore volume
preferably greater than 0.30 cc/g.
6) Matrix Material ~ the matrix material of the
catalyst compositions vf thi5 invention can be either
relatively inert or active with respect to cracking
activity~ Preferably the matrix composition is an
acidic acting material which will en~ure that both
3Q thermal and catalytic crackin~ of absorbed and
adsorb~d high boiling hydrocarbon componen~ are
accomplished. Thermal or catalytic conversion-of high
mc~lecular compvnen'cs to form lower molecular weight
P~I5156
19 ~ &3~
component material~ ~7hlch may be further eonverted
under more selective erystalline æecli~e cracking
ccnditions in a reaction zone is an impor~ant aspec~
in the utilization of the ~elect lanthanum rich high
zeolite content catalyst of this invention. Thus in
reduced crude conversion ~he combination of high pore
volume - large pore ~ize when combined with
catalytically active matrix material i~ relied upon in
substantial measure to thermally and catalytically
convert high molecular weight high ~oiling
metallo-porphyrin~ and asphal~ene~ or Conradson carbon
precursQrs so that metal components therecf are
deposited preferably on the matrix surface rather ~han
on ~he select cry~talline zeolite component of the
catalysta In addition, the matrix acidi~y may be
particularly desired ~o selectivity adsorb the basic
heavy nitrogen compounds ~o ~ha~ they also are
res~rained from enterin~ ~he 2eolite s~ruc~ure,
whereby neutr31izing the ~pecial ~eolite cracki.ng
sites can be more de~irably restEained over an
ex~ended period of use. The matrix material of this
invention may be provided with added acidity by the
addition Gf one or more material~ ~uch as sulfonates,
phosphates, a halogen con~ributing material,
~5 phosphoric acid, boric acid, acid ac~ivated clay,
silica-alumina, silica-titania, silica zirconia and
other such acid contributiny materials~
7) Matrix and Metals Control - one of the impor~ant
unctions of the catalyst composi~ions of this
inven~ion i~ related to effecting a control on th2
met~ls deposited from cracking reduced crude
containing portions of crude oils and comprising
carbo~-metallic componentsO As discu~sed herein, thes~
carbo metallic components comprising Conradson carhon
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contributors and deposited metals including particu-
larly ~i~ V~ ~e, and Na of which vanadiu~ has been
identified as contributing greater damage to the cata-
~yst zeollte component than either ~odium, iron or
S nickel with ~odium being the second most damaging~
Thus ~he special matrix material or cvmpositions cvm~-
prising the cataly~t compositi~n of ~hi~ invention and
prepared from 1 ow s~dium materials~ because o its
provided pore volume and substantial pore size open
ings of at least 5~0 to 1000 ~ng~roms, entraps me~als
and accumulates them to a much higher order of magni-
tude heretofore not possible wi~h much lower pore
volume ma~rix ~ontaining catalyst of the order of
about 0.22 cc/gm, This me~al en~rapment provision of
the catalysts prepared according to this inven~ion is
made even more effective and novel by ~he employmen~
of one or more vanadia immobill~a~ion material~ which
will complex therewith ~o form compositions which melt
at a tempera~ure above the temperature normally
2.0 encountered in the catalyst regeneration operat.ion in
which employed. Thus ~he matrix material or comp~si-
tion contemplated by this invention prepared from gels
and/or colloids of silica/ alumina or a combina~ion
thereof a~ identified herein in admixture with small
~5 particles of clay material or a second metals entrap-
ment zeolite material identified herein ties up ~he
deposited metal~ ~e~ore they can reach and/or react
with the ~pecial or select zeolite structure de~ined
above to destroy it or cause catalyst particle
coalescence and agglomera~ion as herein discussed~
Materials suitable for acting a~ a me~als accumula~or
and vanadia immobilization agent part~cularly includes
an alumina m~terial incorporated in ~he matrix~ a
pillared interlayered clay material ar,d selected metal
RI6156
21
additives which complex ~ith ~anadia to form highe~
melting mixture~ than encountered during re~enerat~on
such as identified in appli~ants copending application
Serial Number 399,612 filed March 29, 1982 and Serial
S Nu~ber 400,612 filed April 7, 198~.
The above ranges of parameters are particularly
suited to reduced crude conversion ~RCC), bu~ the
invention is not limited to such ranges.
The select noYel class of catalyst compositions
identified by this invention serve a mul~iplicity of
functions as herein identified when prepared to
incl~de the compositional parameters and components
herein identified~ The preparation of such catalytic
materials also embodies or contemplates the inclusion
of cheap filler and~or binder material as required,
but more importantly a material which permits
achievemenf of m2tals entrapment and enhancement of
the desired pore size openin~ and volume s~ructure in
~he manner above identified~ Some materials suit.able
for this purpose include carbon black such as
identified in applican~s Unl-ted States
Patent 4 431 749 a high p~rity vexy fine
kaolin clay, alumina and certain ball clays. In this
regard an acid leached montmorillonite, bentonite, or
halloysite are al~o possible candidates and can also
serve to provide acidity in ~he ma~rix as well as
being used as a binder material.
Advanta~es of Using a Colloid Binder Mater-al
I~ is known from the literature that colloidal
silica and colloidal alumina are stable dispersion~ of
mill;micron-si~ed particles in water or other suitable
liquid medium~ The tiny particles are generally
spherical in shape and may be uniform or varied in
RI6156
22
size~ 8ecause the particles are so small their
collective ~urface area i~ extremely large~ This
combination of par~icle size colloidal material and
large 5urface area provides unique intimacy ~roper~ies
desired in ~he preparation of catalysts of this inven-
tion and make them commercially unique in a wide
variety of applications as herein briefly discussed~
Colloidal par~icles represent a ubdivision state
between a course su~pension and a truly di~solved one.
Colloids exhibit propertie~ more like ~he dispersing
medium rather than ~he dispersed phase. Colloidal
particle sizes are usually expressed in millimicrons
~one-millionth of a millimeter~ and a colloidal size
range i~ between 1 and 1000 millimicrons. To more
particularly identify ps~en~ial in~imacy with 5uch
materials, the ~mall quantity of seven grams o~ ~ilica
sol (colloid) with a particle si~.e of 5 m~ have a
surface area about equal to that of a football field.
The catalyst compositions cf this inventiun xely
particularly upon the intimacy of contact between
ingredient~ (Z--M A~ zeolite matrix-additive identified
herein and prepared as herein provided for the follow~
ing reasons:
(1) The desirability of a catalyst preparation proce-
dure of ~tarting with low or no sodium compcnent
ingredients (Z - zeolite, PV - pore volume addi-
tive, C - clay filler~ M -- matrix material~ A -
metal additiveO ZS - sacrificial sieve~ B bind-
er, G - getter of the attached table and fi~ure) r
allows one to ~imply mix ~uspensions or a ~lurry
of the ingredients and ~pray dry to obtain useful
sa~alyst par~icles. Thus it is now recogniz.ed
that there is no need to go to the long drawn out
5tep5 and expense of washing~ exchanging9 dxying
and calcining formed ~pray dried ~olids ~o remove
RI615~
23
undesired levels of ~odium~ Th~s~ the simplified
catalyst preparation method6 contemplated by this
particular invention eliminate subs~antial cost
to a refiner and catalyst preparer as well the
~ime, equipment and labor required for ~atrix
preparation and catalyst component mixing, parti-
cle formation and optional treating steps associ-
ated therewith, and the costly post formation
~teps of rewetting dried ~articles, washing
extensively and redrying for ~hipmen~0 It even
contemplate~ elimination of shipment, i~ ~eing
vi~ualized that catalysts of highly valued indus~
trial application can be manufactured at point of
use. A150 ~he inYentiOn eliminates the need o~
heating the ca~alyst preparation in order ~o
control gel time. This method of prepara~ion
allows flexibility in variation of ca~alyst com~
position ingredients to optimize the variation iJl
feedstock qualtiy parameters such as metal
content~ Conradson carbon, amount 3f material
boiling above 1025F and the likeO
(2) The special catalyst preparation procedure
associated with colloidal suspensions allows each
starting component (2-M-A) to be purchased or
p~epared individually and separately stored until
u~e is required thus eliminating 2xpensive
gellation time, washings to re~ove sodium salts
and c~mplicated~ time consuming treatments on the
final ~pray dried eataly~t micro~pheres~ Further
treatmen~ of ~he spray dried micro~pheres may
have some beneficial effects on some of the
catalyst components thereof but they may also
have some har~ful results on other components of
the catalyst composition. For example~ i one
exchanges the catalyst microspheres to put
RI6156
additional rare earths into the zeolite~ one
would also exchange and adsorh rare earths into
any clays, sacrifi~ial sie~es~ selective adsorb~
ents, matrix acid sites which are presentO Unless
S one intends to have these rare earth cations
adsorbed in this manner, cons~mption and eo~ts of
these exchanged rare earths may ~e undesirably
increased~ H~wever by starting with little or no
sodium in individual ca~alys~ ingredients or by
first separa~ely exchanging each ingredien~ Z M~
of the catalyst composition for optimum Na
removal, preferred exchange condi~ions may be
provided for each compGnen~ before ultima~e mix-
ing as by homogeniYation of the ingredients to
form a slurry mix f~r ~pray drying ollowing the
varied catalyst preparation techniques of this
invention,
~3) Excess electrolytes (mainly Na~ are ~3esirably
removed from low sod~um starting colloidal sus-
pensions, ~o that higher p~'~ approaching a pH of
5.5 may be used for an acidic colloidal suspen-
sion without causing the colloids ~o gel~ A
colloidal cuspension thu~ formed may be more
concentrated, and can be mlxed more vigorously in
a homogeniæer and/or even heated to a hiyher
~emperature without causing gellation to occur~
The ~lexibility of the desired microspherical
catalyst manufacturing process of this invention
is thus greatly increased. The use of a pH
between 3OS and 5~5 will elimina~e sub~tantial
acid destruction of th~ zeolite crysta~ ~tructure
normally found in other catalyst prepara~ion
procedures~ Also of more significant importance
i5 he recogniti3n that the low electrolyte
~I6156
colloidal suspension i5 also more ~table over an
extended 'cime again~ gelling or gel formation.
The ~ols (colloidal ~uspen~ions) th~s prepared
can be made before ~ime while quali~y con~rol
S testing thereo~ is conduc~ed or they cah be
purchased on the open market rom ~ number of
suppliers, thu~ eliminating all need or related
manufacturing equipment. The u~timate financial
value of such an approach is readily perceivec3 by
one skilled in ~he art. Thus a more uniform
ultimate ~pray dried catalyst composition will
result and ean be relied up~n or varied as
de~ired between preparationsO
(4) The par~icle ~ize of he binding colloid may be
preselected ~n an in~ividual batch basis so that
one can vary the physical proper~ies of the ~inal
catalysts. Thus different amoun~s of two or more
colloidal ~uspensions of the ~ame or different
average particle ~izes and compo~ition may also
be used ~o vary porosi~, acidi~y and attrition
of an ultimate catalyst eomposition prepared from
the selected colloidal suspensionO
(S) The cata1ysts prepared by the procedre and ~ech~
niques of thl~ inven~ion from low sodium or no
sodium ~olloids will have a desired very low
sodium content ~o ~hat any sol~ble sodium coming
in contact with the special low scdium rare ear~h
exchanged crystalline zeolite c~mposi~lon hexein
identified and particularly preferr~d will not ~e
subjected to a back exchange of ~odium in~o the
zeolite~
~53 Since silica sols ~coiloids) are most s~able in
two ranges of pH on either ~ide of abou~ 5 0 5 to
7 pH, acidic in the range of 305 to 5A5 and basic
3~ ~ol in the r~nge of 7 to 13 such colloidal
RI6l56
2~
suspensions may be used wi~h consider~ble
adv~nt~ge~ For exarnple, this procedure permits
preparation of cataly~ts on ~he high pH ~ide as
well, by replacing ~odium or other poisonous and
destructive cations with non~harmful cat-ions such
as ~mmonium ion, ~onome~hyl~ dime~hyls trime~hyl
and tetramethyl ammonium ions; and other organic
ba~es of a similar nature~ Since N~4~ or H~
ca~ions are used to ~tabilize such sols, ~ome
].0 ~dditional exchange o ~odium ou~ of a zeolite
may be expexienced in some selected cases. When
employing eatalyst composi~ions prepared from
acidic sol~ ~ome rare earth~ may be added to the
~pray dryer feed to achieve a f inal rare earth
exchange even during the catalyst forming
sequenceO
(7) The catalyst preparaticn technique and me~hod of
this invention will allo~ one ~o u~e or
incorporate TiO2 9 2rO2~ A1203~ and 5b203 ~ols and
~0 gels for preparing carbo-me~alllc reduced crude
conver~ion cataly~ts.
( 8 ) The catalyst preparation ~echnique also permits
one to u~e metal oxide coated sols ~uch as TiO~,
2rO2, Re~03, Cr~03, Fe203 or A1203 coating on a
2S ~ilica and/or alumina par~icle ~o prepare reduced
crude conversion catalysts.
(9) The catalyst preparation techrlique of ~his
invention al~;o permits one ~o place rel~tively
uniform coatings of the sol material on the clay
and zeolite particle~
(~0) Fur~hermore, it i~ also speculate~ ~hat the
higher surface ~rea of the colloid used ~
prepare the matrix material will improve ~he ra~e
of deposition and adsorp~ion of me~als from ~he
hydr~carbon feed onto the colloid ~urf~ce.
RI61~6
~ (
Figure 1 is a ~chema~ic drawing on one embodiment
of the proce~s and apparatus of the in~ention. In
Figure 1~ a series of agitated mixin~ vessels 10-17
prepare various in~redient~ for fee~ing to mixing and
homogenizing tank 18,
Zeolites: Z~olites purch'ased from any of ~he usual
~uppliers, ecg~ Davison t DiVis ion o W. R. Grace,
UniGn Carbide Corporation Philadelphia Quartz or
other suppliers with the sodium having been
substantially removed b~ ion exchange ~w;~h hydrogen,
ammoniump or rare earths~ e~cD) is mixed with
demineralized water to form a slur~y which i~
transferred ~through sui~able pipes, valves~ and
instrumentation~ into mixing and homogenizing tank 18.
Suitable commercial ~eolites include CREY* R~CREY*
~l~ra-stable Yc HY, ZSM-5, ~igh 5ili~a Zeoli~e (HSZ)
and othersO
Clay- Clay obtained from any clay manufacturer is
mixed with demineralized wa~er and ~lurried in mi~ing
tank 11 and thereafter transf2rred to mixing and
homogenizing tank :L8, Suitable clays include kaolin,
halloysite~ acid leached mon~morillonite~ synthetic
montmorillonite and others. In most cases~ the clays
are shipped we~ and require only minor amounts of
additional water to form a pumpable slurry~
2~ Sols: Low~sodium s015 are mixed wi~h deminerali~ed
water and slur~ied in mixing tank 1~ and ~hereafter
transferred to m.ixing and homogenizing tank 18~
Suitable sols may be purchased rom ~alco~ ~upont and
other manuacturers or ~he sols can be made by we~l-
known technique~ and washed witn sodium-fre2 acids
llow pH) or ammoniurn Gr QtheE ba5e~ Ihigh pH3 t;o
remove ~odium~ Suitable sols include alumina~
*Trade Marks
RI6156
28
~ilica-alumlna~ titania~ zirconia, antimony trioxide.
These can be purcha~ed sodium-free or purchased with
sodium content which is removed by leaching tank 12~
Pore Formers: In mixing vessel 13 under our prepared
~lurries of pore formers, preferably carbon black,
carbon ~lack ~ho~ld be selected ~o give the desired
pore size a~d thermal furnace or other blacks may be
employed as desired~ The finished slurry i5
transferred to mixing and homogenizing ~ank 180
S~crificial Sieves~ Slurries are formed with
demineralized water as before utilizing~ in mixing
vessel 14~ zeoli~es, for example, thos~ available
commercially from the Da~i~on~ Division of W. R~
Grace, PPG, Proctor ~ Gamble ~ompany, Suitable
zeolites include zeolite A, ZSM~5, mordenite,
chabazite, co-gelled SiO2-Al2O3 all ~uitable washed
to remove ~odium2 The contents of tank 14 are, as
with the other ingredients, tran~ferred by suitable
lines and pumps to mixing and homogenizing ~ank 18 for
the preparation of the ca~alys~0
Acid Matrix Subs~ances~ In mixing tank 15~
demineralized water i5 used to prepare slurries of
acid matrix substances such a finely ground gel~
e.g. silica gel, silica-al.umina qel~ titania-silica,
etcl These acid ma~rix substances can be purchased
from Davison or PPG as aforementionedO The finished
acid matrix slurry is transferred to mixing and
homogenizing tank 18, as above described for other
slurriesO
Binderso In mïxiny tank 16, demineralized water i~
used per a slurry of ~cid lea~hed bentonite~ acid
leached halloysite, pseudoboehmite, silicic acid,
RI6156
~9
synthetic montmorillonite or other suitable catalyst
hinder well known to ~hose skilled in ~he catalys~
arts. The resulting slurry is tran~fer~ed to mixing
and homogenizing tank 18c
S Getters: In tank 17, ~here are prepared slurrie5 of
demi~eralized water and suitable getters9 e.g.
compounds which will immobilize metals, e~g. vanadia
and/or nickel, sodium or iron, by trapping the
foregoing metals by reac~ion or association~ Sultable
getters include ~itania, alumina, ~i~conia, indium
oxide r manganese dioxide, lanthanium oxide and others
known to the art~ These are slurried with
demineralized water and fed ~o mixing and homogenizing
tank 18,
In each of the above di~cussions~ by low-sodium
is meant that ~he ingredient should have a sodium
con~ent after washing and at time of feeding ~o mixing
and homogenizing ~ank 18 such that the aggregate
~odium eon~ent of the mixture in tank 18 contains more
than about D~5 weight percen~, or preferably 002
weight percent and most preferably below about Ool
percent.
The mixing vessels, as with the plumbing and
instrumentation, employed in the above schematic
~5 description of the inventions, may be of any s~i~able
composition and configuration. The single mixing
vessel may be used for successively producing a
~eri~s of batches of the ~arious ingredients, The
process may be practiced con~inuou~ly with flow mixers
being employed in lieu of mixing vesselsO Tempera-
tures and pre~sures will not be narrowly critical and
will be ~hose whlch are convenient for ~he economic
preparation of the desired pumpable sl-lrries. The
RI6156
vessels may~ in some instances, be compartment~ of a
tran~port vehicle, e.g., a compar~mented tank ~ruck or
rail c~ which prepared ~lurries can be shipped for
custom blending at or near the point of use of the
catalyst. ~-
In fact, it i~ an important feature of ~he
pre~ent inven~ion ~ha~ by s~ocking ingredients a~ or
near the point ~f use~ ~hP usual delays involved in
ordering and delivery of cataly~ts can be avoided and
catalysts can be custom blended to optimize their
compositions to acco~nodate variations in feedstock,
e.g., those noted in a pipeline which is delivering
~uccessive batches o varying composition whi~h would
most desirably be converted by means of cataly~t of
different composi~ion.
Of course~ converslon operation~ or certain
feedstocks and under certain conditions will permi~
the toleration 3f higher amoun~s of sodium and in such
instances deionized water be substituted for
demineralized water and higher sodium con~ents may be
accepted in the mixing and homogenizing tank and in
the final catalyst~
The percentage of each of the above ingredients
will vary with the zeolite content being preferably in
~he rAnge of about 10 to about 60, more preferably
from about 15 to about 50 and mo~t preferably from
about 20 to about 43 9 the clay content being from
about 0 to about 60~ more preferably from about 0 to
about 45, and most preferably from abou~ 10 ~o about
35; the sol conten~ being from about 0 to about 40,
more preferably from about 10 to about 30 9 and most
preferably from abou~ 20 to about 25, ~he pore former
content being from about 0 to about 259 more
RI6156
31
p~eferably from about 0 to about 20, and most prefer-
ably r~m ahout 0 ~o abou~ 15 as meas~red on ~he
volatile free ~inished catalyst~ the sacrificial
~ieves content being from ~bout 0 to about 20, mor2
preferably from about 0 to about 15, and most preer-
ably from about 0 to about 10; the acld matri~
substance eontent ~rom about 0 to about S0, more
preferably from about 0 to 35~ and most preferably
from about 0 to about 20; ~he binders content being
rom about 0 to about 60, and, dependiny on the
physical and temperature conditions which the finished
~ataly5t must undergo, more preferably from about 0 to
about 45, and most pref~rably from about 10 to about
35; and the getter ~ontent may be from about 0 to
about 20, more preEerably from about 0 to abou~ 15~
and most preferably from about 0 ~o about 1~ percent
~y weight based on weight of the finished catalyst~
The composite o slurries will be thorGughly
mixed and homo~enized in tank 1~ to obtain a highly
uniform composition which is then transferred by
suitable pumps, piping and in~trumentation to spray
c3rier 19 through sui~ab3.e nozzles to ~orm catalyst
pellets of the recluired size. Spray drying techniques
will be those well-known as conventional to tho~e
skilled in ~he catalyst preparation art~ In
specializ.ed circumstances, pelletizing may be ~ubsti-
tuted for ~he spray drier and in other circumstances,
the slurrie~ may be spray dried in ~itu by injecting
them into one or more ~tages of the catalyst
regeneration system in a normal RCC or FCC uni~.
RI6156
32 g~
Catal~st ~Preparations
Example 1
A reduced crlJde conversion catalyst comprising
about e~o w~c~ of a ~elec~ ~eolite comprisins~ a ~alcined
rare earth exchanged ~Y" zeolite known as CREY which
5 is iEurther rare earth ~RE) e~schanged af~cer ~::alcination
will provide a particularly de~ired lan~hanum rich
(La/Ce = 3~1~ zeolite~ This material iden~ified as a
RECREY zeolite hereinl has a sodium content of abou~c
O.q7 wt~ or less. This special ~.eoli~e composition of
10 desired small particle ~ize i5 in~imately mixed with
about 25 wt% of a ~ilica sol ~colloid ? binder material
to form a suspensicn thereof~ The initial ilica
(SiO2) ~;ol su~;pension of this example is provided in
the form of a ~tabilized acidic ~ol with a p~ up to
15 about 5~ The speclf ic cataly~t preparation i~ as
f oll~ws:
(1~ To 4.0 L ~ ers~ of 4O0 pH demineralized ~a~er
prepared with EICl is mixed 4 . 30 k~ of coTnmercial
~ydrite UF Kaolinite def ined below to :IEorm a
suspension thereofO The kaolinite clay is added to the
acidic wa~er in at least two pcrtlons with vig~rous
agitation to obtain a slurry or suspension o~
relatively high viscosity~ A dispersant may be added
with the clay in an amount in the range of 0,25 to
about 2 D 0 wt~ and more usually a~ least about 0O5 w~
RI6156
33 i~
o the clay~ The alkali me'al content of the clay is
considered to be relatively tightly bound and thus
does not n~rmally appear to provide a significant
level of free alkali metal or ionizable metal or
exchange into the special zeoli~e identified- above
when added toge~her. However~ when desired, the clay
may be exchanged or washed before use wi~h such
~a~ions as NH4~ to lower its ~odium content.
~2~ A slurry of the ~pecial RECREY ~eolite above
identified and preferably of low ~odium content is
prepared by mixing 3O0 L of 4.0 pH water wi~h 4.2 ~g
of well disper~ed and inely ground RECREY ~a rare
earth exchanged caleined rare earth exchanged wy..
faujasite cry~t~lline zeoli~e). The special zeoli~e
is finely ground to particles of less than 5 Tnicron5
and preferably ~o at least 1 micron to aid in
obtaining a well dispersed zeolite,
(3) The kaolinite slurry obtained in step (1) is
placed in a homogenizing mixer with 4.8 L of Nalcols
1034~A colloidal silica defined below and comprising
less than 0.05 wt~ Na~O and mixed thorou~hly for abou~
5 minutes.
(4) After mixing the colloidal silica with the clay,
the wetted zeolite slurry prepared i.n (2~ abo~e is
added slowly to the silica-clay ~lurry in the
homogenizer. The rate of addition and dilution when
required is adjusted to obtain and maintain a sm~oth
slurry suitable for ~pray drying to form
microspherical. solids. The solids thus combined are
blended for about 15 minutes in the homogeni~er or
under sufficiently long mixing conditions to ob~ain a
slurry of about 4~0 pH with a viscosity o:f 900 ~ps at
100Fo
RY6156
3~
~5) The ~lurry thus obtained in step (4) and
comprising silica colloid, clay and crystalline
zeolite is then ~pray dried to form microspherical
catalyst par~icles comprising about 25 w~ ~ilica, 35
wt% clay and about 40 wt~ of the special La rich
RECREY zeoli~eO Apparatus suitable for this spray
drying purpose inelude a Niro atomizer maintained a~
an inlet temperature of about 400C (752F) and an
outlet temperature of about 120C ~248F). Other
known spray drier apparatus suitable for the purpose
may be employed and the vi~co ity of the ~lurry may be
adjusted as required to optimize the spray drier
operation, Microspherical cataly~t particles of
fluidizable particle size are recovered from this
spray dry operation which may then be used for
hydrocarbon ~onversion as herein provided.
When it is de~ired to incorporate rare earth
components with the matrix as well as the zeolite, a
further step of water washing and rare earth exchange
one or more times i5 contemplated. Rare earth salts
can also be added directly to the slurry and then run
to the ~pray ~rier. In the event that such is
desired, it is proposed to employ in a specific
example about 5 L of 65~C water for each kilogram of
~5 catalyst solids, The washed catalyst particles are
exchanged several times, ~hree for example, with 4 L
of a 0.15N rare earth chloride solution which contains
a La/Ce ratio greater than about ~0 The exchanged
catalyst ~olids are then water washed several times to
provide solids eompri~ing le~s than 0~1 wt% sodium
which is then dried at a temperature of about 1.~0C
~302F) for several hours or as lons as required.
RI6156
~,~
A Hyd~ite UF kaolinite clay~ commercially
available i8 identified as provld.ing a medium micron
particle size of abou~ 0.20, a pH in ~he range of
402 ~.2~ a 325 mesh residue maximum ~ of 0~209 and an
5 oil adsorption of 471 The w~% composition is~
Aluminum oxide 38038 Calcium oxide ~05
Silicon dioxide 45.30 Magnesium oxide o25
Iron oxide 0~30 So~ium oxide 0027
Titanium oxide 1044 Potassium oxide ,D4
The elements of Tio Ca, ~g~ Na and K appear to be
so tightly bound in the clay ~hat no detectable
exchan~e of these ma~erials into ~he high lanthanum
containing CREY zeolite initially prepared as above
defined for low residual ~odium content is observed.
Thus, any free sodium content of the formed
microspherical catalyst particles is thu~ essen~ially
restri~ted to ~hat contained in the zeoli~e or added
by the oil ~eed during hydrocarbon conversion~
Nalco*lO34A colloidal silica or silica sol is 2
colloidal dispersion of subm1cron size silica
particles, in the form of ti~y spheres of SiO2 in an
aqueous mediumO It is an acidic pH aqueous colloidal
~ilica product commercially available~ A genera~
description of this material is as followss
Colloidal Silica, ~iO~ 34%
p~ 3~1 ~ 0~5
Average Particle Size lÇ-22 m~
~verage Surface Area l35-l90m~gram
Specific Gravity ~ 68F l~230
Yisc~it~ @ 77D~ <~n ~p
Na2~ ~0~05
*~rade Marks
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36
~he sodium content of this ~ilica colloid is 50
low that ~he percentage of ~ilica in ~he microspheri-
cal catalyst particles does not materially infl~ence
the sodium content of the catalys~ particles.
It will be recognîzed by ~ho~e ~killed in the art
from tAe deseription herein presented~ that the
preparation of fluidizable ~icrosp~erical particles
may be varied considerably in composition employing
the basic procedure o~ Example 1 and will produce as
desired a high activity high zeolite content cracking
catalyst of desired very low sodium content. The
basic operating procedures of this example may be
varied by inclusion of diferent additive materials
and by employing one or more colloidal materials ~uch
as an alumina colloid with the silica colloid or
different p~rticle size silica colloids may be
employed as ~iscussed above.
Example 2
The zeolite cracking catalyst of this example i5
prepared in a manner ~imilar to ~hat ~f ~xample 1
except for u~ing at least one basic ammonium ~tabil-
ized SiO~ sol (colloid~ ~o produce microspherical
catalyst particles con~aining about 40 wt~ of the
special RECREY zeolite which i5 lanthanum rieh and
prepared as defined above in combina~ion with about 35
wt~ of a fine kao:Linite clay of less than 5 micron
par~icle size above defined and ~bou~ 25 wt% of a
colloidal silica binder material defined below~
(1) 2 L (liters) of a 10 pH wateE i~ prepared ~sing
ammonia hydroxide and demineralized wa~er~ rr~ ~his
basic water solution is mi~ed 4.7 Kg of RECREY zeolite
(La/Ce 3/1) o~ained as provided in Example 1 in two
or more portions to obtain a smookh wetted powder
mixture.
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37
~23 4.5 L of Nalco9s 2327 (an ammonia ~tabilized)
colloidal ~ilica (defined below) is added to a
homogenizing mixer as a slurry suspension and while
mixing, 3,8 ~g o ~ydri~e UF kaolini~e clay above
5 defined is added to the silica sol (colloid) slurry
suspension in the mixer. The ra~e of addition is
adjusted to maintain a well blended and smooth slurry.
(3~ Next the wetted finely ground RECREY zeolite or
slurry obtained by ~tep ~ added to the well
blended slurry above obtained in s~ep (2) while mixing
to obtain ~ further well blended slurry mixture
comprising the special RECREY ~eoli~e, finely ~rou~d
clay and colloidal silicaO The ~lurry mixture thus
formed is mixed for an addi~ional ~ime as re~uired
to form a smooth slurry with water adju~men~ as
required to obtaln a sprayable slurry o~ about 9 pH
and providing a viscosity o abou~ 200 centipoise
(cps) at a temperature of 140Fo
(4) The 61urry formed in step (3) above is ~hereafter
spray dried in one speciic embodiment in a manner
s.imilar to that described in Example 1 to form
microspherioal partic~es employing a ~pray drier inlet
temperature of about 400C and a 120C outlet
temperature~ The spray dried catalyst microspheres
~5 thus obtained may be further treated or exchanged if
desired with a rare earth chloride solution ~s
described with respect to Example 1 when it i~ desired
to incorporate more rare earth material in the
cataly~t microsphere and particularly the matrix
component thereofD
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~`~
~8
Nalco 2327 ~mmonia Stabi~ized Colloidal Silica i~
described ~s comprising:
Colloidal Silica as SiO2 40~
p~ 9~2
Average Particle Si~e 20 m~ ~
Average Surface Area 1~0 m2/gram
Na2O ~0~1%
NH3 0.2
Example 3
1~ In ~his examplel ca~alys~ parti~les comprising
the special lanth num rich zeolite ~uch as RECREY pre-
pared as described in E~ample 1 is mixed with islands
of alumina (aluminum oxide) ~upplied as Catapal alumi-
na and a Hydrite UF kaQlinite clay to produc~ a catal-
yst composit;on comprising abou~ 40% ~ECREY; 25% 8ili-
ca; 25~ of clay and 10% of Catapal alumina. Ca~apal
alumina is an alumina gel-like material which upon
dispersion is returned to a colloidal like suspension.
This colloidal ma~erial can also be used to prepare
similar catalysts and will be described in later
examplesO The preparation proced~re is as followso
(1) Add 5.~ Kg of finely ground Hydrite UF kaolinite
to ln L of Nalco 2321 colloidal sili a ~ammonia
stabilized) defined in Example 2 in a homogenizing
mixer ~o form ~ slurry and agitate for several minutes
up to about 5 minutes to obtain a ~mooth ~lurry,
(2) Add about 250 ml or ~ufficient eoncentrated
ammonium hydroxide ts the ~lurry product ~f ~tep ~1
to obtain a 10 p~ ~lurry comprising finely divided
kaGlinite and colloidal ~ilica~
~3j With continued mixing9 add about ~,1 Rg of a com~
mercially available and finely ground Catapal~alumlna
powder (defined below) to the colloidal silica~clay
~lurry of ~tep ~2~. The rate of addition of the
* Trade Mark
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S~
39 ~ ~ ~ ~ ~ ~
Catapal alumina and mixing thereof i~ selected to
obtain a well blended ~lurry of the ~hree components.
Catapal SB alumi~a i~ identi~ied as an ultra hi~h
puri~y alpha alumina mon~hydrate ~Boehmi~e3 prepared
as a white spray dried powderO X~ i5 o~en ~ilized
as a high purity catalyst support ma~erial. It i~
converted to ga~ma alumina by calcination at gOOF for
about 3 hours. A typical chemical analyfiis ~wt~ is
as follows
~12~3 74.2 N~2O .004
SiO~ .008 Sulfur CoOl
Fe2~3 o005
Particle size di~tribu~ion is id2ntiied as:
48~ <45 microns
12~ >90 micron~
~4) The ~lurry o~tained in 8~ep ~ 3) above i5 adjusted
to a pH of 10 with concen~rated ammonium hydroxide.
(5) To ~he pH adjusted slurry of s~ep (4~ i~ added
finely ground zeolite in an amount of a~ou~ 8.3 Kg of
~0 ~he special RECREY powder ob~ained as deflned in
Example 1 with careful mixing durlng addition at a
ra~e to obtain a well~blended ~lurryO Water may be
add~d to this ~lurry mix to adjus~ the viscosi~y
thereof for ~u~sequent efficient spray drying oF the
~lurry mix as herein discussed~
(6) The slurry mix formed in step (5) is in one
cxample ~pray dried using a 400~C inlet temperature
and a 120C outlet temperature similarly to ~ha~
described in Example ~ to form fluidi~able
microspheri~al catalys~ particles.
(7) The spray dried microspherical cataly~t particles
obtained are of a ~odium content less than 0.25 wt%
and may be used as obtained in a reduced crude
cra~king operation~ However~ one may also ~ubject the
spray dried particles to additional water washing and
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~o ~o5~
rare earth ex~hange as discu~sed with respect to
Example 1 when it i~ desired to particularly
incorporate rare ear~h ma~erial also in the ma~xix.
Example 4
The pro~edure of ~his example is ollowed for
producing a catalyst that difers from Example 3 in
that an acid sol i~ u~ed and Catapal alumina is al~o
included in the cataly~t particle~
(1) Add ~0 ml of concentrated ~Cl ~o 7 L of H2O and
thereafter add 7.4 L of Nalco 1034A silica sol
~colloid~ above identified to produce a ailica scl
with about a 2O5 pH,
(2) Next Mix 3.1 Kg of finely ground ~ydri~e UF
kaolin and 30 gm of a low sodium dispersant ~o the
silica sol of Step 1,
(3) Add 1.2 ~g of finely ground Catapal alumina to
the mixture of step (2) and continue to mi~ several
minutes suf~icient to obtain a smooth slurry mix~ure
~0 of ~he ingredient~.
(4) The pH of the resulting slurry of atep (3) is pH
adjusted to about 3,0 by adc~ing 150 ml o~ eoncentrated
HCl before carefully mixing 5.0 Kg of finely ground
RECREY identi~ied in Example 1 into the ~lurry, The
~5 resulting pH is adjusted to be about 3O50> ~he slurry
mixture thus obtained is mixed for an additional time
suficient ~o produce a smooth slurry surface for
~pray drying to form micxospherical catalyst
particles,
(5) The thoroughly mixed slurry of step (4j and
adjusted as required o a suitable vi5cosity i~ then
spray dried to form fluidizable mlcro~pherical
catalyst particles in the manner part1cularly deined
as Example 1
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~3~
~1 -
~6) It is al50 con~emplated further treating the
spray dried microspherical ca~aly~ par~icle~ of this
example with additiona~ water wash and rare earth
exchange for the rea~ons particularly discussed in the
a~ove examples~
~xample 5
AD Rare Earth Exchanged CREY
(1) CREY ~29.6 kg~ ~lurried with B4 L of water was
exchan~ed with 1.7 L o REC13 ~olution a~ 140F for
1 1/2 h~urs. The ratio of equivalen~ o~ rare earths
to sodium was ab~ut 1~1~ The ~lurry was filtered a~
the end of the exchange~
(2) The C~EY fil~ercake from ~1) was slurried with 64
L of water and exchanged ayain with 1~7 L REC13
solutioll at 140F for 1~1/2 hours~ ~f~er this peri~d
of time~ the exchansed CREY was filtered.
(3~ Step (2) was repeatedO
(4) The RE exchanged CREY ~o form (RECR~Y) from S~ep
(3) was washed three ~imes 9 Each wash u~ilized 64 L
of water and was carried out at 1408F for 30 minutes.
After each wa~h, the RECREY was filtered.
(5) The washed RECREY was dried overnight at 150QFo
B. Ammonium Exchanged Hydrite UF Clay
~1) Hydrite VF clay (23 kg) was e~changed with 1.15
kg of ammonium chloride in 96 L w~ter at 140F fox 3
hours. The pH of the slurxy was 4~5. The rati~ of
equivalen~s o~ ammonium ion to metals on ~he clay was
~6~ ~he clay was filtered at the end of ~he
exchange.
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42
~2) The ammonium exchanged clay wa5 wa5hed with 6~ L
of water at 140bF for one hour. The water-clay ~lurry
was fil~ered in approximately 5 gallon portionsç
After filtering each porticn~ the clay was ~lurried
with 3 gallon~ of water and filtered again.
(3) The exchanged and washed clay was dried overnight
at 150F.
C. Preparation of Spray Dried Catalys~ Con~aining
40~ RECREY~ 35% NH4~ Exchanged Hydrite UF, and
25~ Silica as Acidic Silica Sol
(1) Nalco 1034A l632 L~ 2.6 kg SiO2~ and 25 ml
hydrochloric acid were mixed in a 5 gallon pail. The
pH of the HCl - silica ~ol was 2 31~
(2) Ammonium ion exchanged hydri~e UF ~3.6 kg) and S
L of water were a~ded ~o ~he ~ol from Step (11. The
slurry was mixed or five minutes! tran~ferred to ~he
Kady mill and mixed for an additional 5 minutes at
lOO~F. The pH of the ~lurry was 3.4.
(3) RECREY ~396 kg) was added ~o the ~ilica ~ clay
slurry and mixed for 5 minutes3 Approximately 8 L of
water were added o the slurry to reduce its
viscosity. The slurry was then mixed for 15 minutes
at 125F. The pH of the slurry wa~ 335. Its
viscosity was about 800 cpsO
(~) The ~lurry from Step (3) was spray dried,
Example 6
D. Spray Dried Catalyst Containing 40~ RECREY, 25%
Ammoniu~ Exch~nged Hydrite l]F, 25~ Silica as
Silica Sol~ and 10~ Catapal Alumina
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(
43
~lj Nalco 2327 ~6 L, 3~1 kg SiO~3 ilica ~ol, 6 L of
~2~ and 50 ml of ammonium hydroxide were added ~o the
Kady mill. They were mixed brie1y~ The pH was 9~5
(2~ Hydrite UF (3~1 kg) was added ~o the sol ~rom
Step (1~. The slurry was mixed for 5 minute~ at
125F~ The pH of the slurry was 9~1~
~3) RECREY ~5~0 kg) was added batchwise ~o the slurry
from Step (2~1 About ~8 L of water and 350 ml
~mmonium hydroxide were added duriny ~he RECREY
addition for vi~cosity and pH con~rol~ The larger
amount of water was added to reduce the viscosity of
the gel that formed during RECREY addition. The
~lurry wa~ mixed for 15 min~tes at 13~F. The pH and
visocity of the sluxry after mixing were 8.8 and 1500
cps, respectively D
~4~ The catalyst was spray dried at inlet temperature
of 400~C, an outlet temperatur~ of 120~Cy and a
pressure of 26 psig.
Example 7
E. Spray Dried Catalyst Containing 40% RECREY, 35~
Ammonium Ion ~xchanged Hydrite UF~ 25% 5ilica as
Silica Sol and 10% Carbon Black
(1) Nalco 2327 t6 L~ 3.1 kg SiO2) silica ~ol~ 5 L o~
water, and 50 ml of ammonium hydroxide were added to
the Kady mill~ They were mixed for abou~ 1 min~te at
100Fa The pH o the silica sol was 9~7~
~2~ Dispersant Norlig NH*~37~5 ~3 was added to the
~ilica ~ol from Step il~o The ~ol and Norlig NH were
mixed or about 2 minutes.
(3) Carbon black M 347 (1027 kgj was added to the
product from Step (2) and mixed for about 1 minute.
The paste that was produced was treated with 8 L o~
water and 25 90 o~ Norlig NH. The slurry ~ha~
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resulted was mixed for 5 minutes at 125Fo The p~ of
the slurry was 125DF~
~ 4 ~ Ammonium ion exchanged hydrite t~F ~ 4 . O kg ~ and
100 ml NH40H were added to ~he pro~luc~ from S~ep ~3)~
The ~lurry wa5 mixed for 5 minu~es at 1~5F. The pH
of the slurry was 9 . 3 O
~ 5) REC~EY ( 5 kg ) was added batchwi~e to product from
Step (43~ Approximately 6 L of ~aterl S0 9 ~f Norlig
NH, and 600 ml NH4O~ were added d~ring the RECREY
addi tion for vi~co~ity and pH control O The slurry ~as
mixed for 15 minutes at 125Fo The pH and viscosity
of the slurry were 8~8 and 700 cps, respectively~
( 6 ) ~he catalyst was spray driea a'~ an inlet:
temperature o~ J100C9 an outlet temperaJcure s~f 120DC,
and at a pressure of 26 psig~
( 71 The cetalyst f rom Step ( 6 ~ was heat 'created at
850F for ~bou~ 60 hours and at 1100F :Eor 2 hours to
burn of the carbon blackO
The ca'calyst preparation ~echniques of this
inven'cior- are par~icularly sui~able or preparing a
special ~lass of cry~talllne ~eolite contalning
catalysts broadly referred ~o as reduced crude
conversion ~atalyst o the following compositiono
1 - Zeolite content 10-60 wt%
SiO2~A12O3 (molar) >5
La/Ce (molar) >3
2 - Total Rare Earths tRE~03~ >3 wt~
3 ~ To~al Na~O C0O~ wt~
4 - Pore Volume (H2O) >~ c /9
5 ABD ~0~7 g~cc
6 - Surface Area
(a) Total >200 m2/g
RI6156
7 - Particle Size Distribution
(a) 0-40 microns ~10 wtg
~b) AP5 70 microns
8 ~- ~ydro~hermal S~ability, MAT >80
(1450F for 5 hours, 100% H~O)
9 ~ Attrition Resistance
~a) DI <15
~b) JI ~2c0
Numerous variations on the above examples of
basic ingredien~s in ~he catalyst particles can be
made by mi~ing numerous dlfferent addltive materials
herein identiied into the various formed slurries.
The purpose of these addi~iYes can be to passivate
metals, alter selectiviti2s, immobilize metals~ or add
a dual ca~alytic func~ion ~o the final ca~alyst~
These additives may be included as ine solids~
colloidal particle~s gels or soluable solutions at one
or more of th2 steps in the described catalys~
preparat ion procedures. Furthermore 9 a titania,
alumina or zircorlia gel may be combined with the
~lurry jU5t before spray drying to produce a catalys~
with improved metal tolerance, Other additives which
may provide beneficial effect~ ~uch as sacrificial
sieves, are more particularly discus~ed below~
The new and novel catalysts described and
prepared according to Example 1 through 4 were
evaluated for their activity characteristics and
compared to a high ~ctivity catalyst described in ~he
pa~ent literature, A catalyst was prepared aecording
to the procedure outl~ned in ~. S~ Patent No~
3~957,689 (Ostermaier-Elliott) and compared to ~he
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~ ~6~ 5 ~ ~ ~
eatalysts of this invention~ The activity of these
catalysts was measured by ~he ~S~ micro-ac~ivity test
procedure D-3907-~0 and the re~ul~s given below~
The catalysts were pr2conditioned by steaming in
100% ~team for 5 hours at 1450Fo
Catalyst
Preparation Example Example Example
Method UO S. 3,957~689 1 2 3
MAT Conv. Vol% 80 91.8 86.5 92
10Rel. Activity 175 668 368 699
The catalyst prepared as above identified Example
1 t 2 and 3 are 2-4 times more active than that
descri~ed in ~he pa~ent literature~
The m~st common crystalline zeolite utilized is a
naturally occurring or syn~hetic 50dium ~Y" faujasite
which upon a first series of exchange with a rare
earth chloride (Ce/La 2~1~ solution yields a lower
sodium rare earth exchange zeolite called REY
(Na-1-2~). A common cataly~t preparaticn practice is
to add this crystalline REY of relatively high sodium
content to the ~lurry and then spray dry (a form of
calcination) to form catalyst particlesO The ~odlum
content of the spray dried catalyst particles is
further lowered by water wa~h and treated wi~h a rare
ear~h salt solution to lower the sodium content of
the particles to a range of about 1-2~ Ma down to Oe7~
1,2 wt% Na in the REY component of the catalyst4 This
type o catalyst preparation ~REY-spray drying~RE
exchange to yield REY) does reduce cost~ on ~he
~onversion of REY to the calcined material CREY as
shown schematically below~
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~7
11 NaY ~ E -~ REY into catalyst sllJrry~-> ~pray
dry~-~ RE exchange-~> CREY in eatalyst
2) NaY ~ RE=-~> REY=-~ calcination~ R~ e~schange-->
RECREY-~ slurry--~ spray dry
5 Elcwever, ~he fur~:her RE exchange o a spray dried and
formed FCC cataly~t par~icle containing REY does put a
considerable amount of RE ~alts ir~tc) the matrix~
As to the matrix Inater ials ~ ~odium sal~cs such as
Na alumina'ce and Na ~ilicate are tradi'clonally
10 utilized f~r synthesi~ of the ma'Lrix which also
contributes a high Na content. This can be reduced by
u~ing an acid ~ Ql: ~lkaline ~NH4~ wa~h, but a high
sodium content ~ithin the matrix ~till remains and
will require ~everal repea~ed washings ~o reduce this
15 to an acceptable level q Fur~hermore 7 ~he use of
deionized water is useless sin~e it also has a high Na
content and thus would require using a demineralized
w;lter. If a clay i8 u~illzed as a part of ~r the sole
matrix rnaterial r the clay also introduces ~ome Na plus
other alkallrle metals such as K, Ca, My and the like~
However clay materials ~uitable for catalyst
preparation normally contain these materials ~ightly
bound to the extent that they do not re-exchange into
the crystalline zeolite present~ The methods of
catalyst preparation of the prior art do not yield ~he
optimum vr an idealized RCC catalyst as particularly
related to the catalyst hydrothermal stabilityr its
metal~ tolerance and it~ activity-selectivi~y
characteristic~ ~æeolite an2 matrix acidi~y)~
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The cataly~t preparation techniques of thi~
invention are particularly directed ~o ~he elimina~ion
of a maximum amount of sodium from the speci~l
catalyst ingredients before they are slurried a~
5 herein provided and spray driedO The treatment of a
NaY crystalline faujasi~e by ~he par~icular ~equence
comprising rare earth exchange of the zeolite with or
without ammonia exchan~e~ calcinatior, and a further
rare earth exchanse maximi2es Na removal from the
crystalline zeolite withou~ des~roying i~s crystal
struct~re~ Rare earth (RE) inclusion into the zeoli~e
is however ~ubstantially increased by calcination of
the zeoli~e between rare ear~h exchange steps which
will yield the particularly desired ~pecial zeolites
used in this invention of catalyst prepara~ion and
comprising sufffciently low sodium that the fLnal
catalyst composition will be less ~han 0~3 w~% Na2O~
pre~erably below 0~25 wt~o ~he lower the sodium
content~ the better the catalyst i5 for reduced crude
cracking.
The use of sodium free ingredients ~uch as
colloidal alurninat colloidal silica, tit~nia and
zirconia and mixture~ thereof ensure that little or no
sodium i5 contributed by the matrix material. When a
25 special kaolin c:lay is utilized as herein def ined ~ as
part of the matr:ix material, the æcdium present
therein is so tightly bound ini:o the clay that i~ does
not appear to migrate such as tc~ a zeolite mixed
therewithO However, even thi~ tightly bound sodium
30 san be par~ially removed by an acid ~rea~cmen~ or ~y
exchanging with NH~ or rare earth 5altsO
The catalyst compositions prepared by the
techniques of this inv2ntion m~y be modified to some
considerable extent with respect to pore size, matrix
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~9
-cracking activity and metals adsorbing capability.
That is, it is also contempla~ed increasing the pore
size openings of the spray dried particles by incor-
porat~ng, for example t carbon black or other ~uitable
S re~oval material in the ~lurry composition beEore
spray drying thereof or in one or more wetted mixes of
clay or colloidal materials and prior ko forming a
61urry thereof with the ~elect high lan~hanum rich low
~odium content crystalline zeolite obtained as herein
defined. On the other hand, the metals adsorbing
capacity of the catalyst particle may be incr~ased by
incorporating yet another me~al entrapm2n~ material in
the catalyst composition and compri~ing one or more
added materials selected ~r~m the group consisting of
lS zeolite A, mordeni~e, chabazi~e, a cheap naturally
occurring faujaslte material, a pillared clay materlal
or combinations thereof. The addition of these metals
adsorbing material~ is limited however to avoid
undesired addition of sodium to the catalys~ particle
in conjunction ~ith preparation of a less expensive
catalyst without upsetting desired activity-selectiv-
ity characteristics thereof~
In yet another aspect~ the primary catalyst
~omposi~ion components of this invention comprising a
25 select lanthanum rich ~rystalline zeolite~ colloidal
matrix component and clay component~ of a particle
size con~ributin~ to intima~e admixture of the
par~icles may be modiied by the additiorl of one or
more acidic promoters ko the matrix ma~erial ~uch as
by adding nitrates, sulfatesO phosphates~ a halogen
contributing material or an a~idic ~ilica con~aining
~omponent ~uch a5 silica-alumina, silica-magne~ia~
silica-z.irconia~ silica-kitania and others herein
identified material~ ~uitable for the purpose,
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5~
~o
The catalyst preparation techniques of this
invention al~o encompass some minor v~riation~ thereof
a~ iden~ified above wi~h respect to additive ~a~erials
for passivating accumulated metals in cooperation ~i~h
the basic catalyst co~position ingredients.
In a particular nvvel embodiment of this
invention the ~lur~ied catalyst composi~ions prepared
as above defined can be used to contribute several
advantages to the catalyst preparation techniques
herein identified by spray drying a homogenized slurry
composition comprising from 2 to 55% solids ~omprising
the desired ingredients. Spray drying of the
homogenized slurried composi~ion in an a~idic or basic
condition may be accamplished i~ a conventional manner
known in the artO How~ver~ more importantly, in
accordance with one embodiment of thi~ invention~
the homogenized slurry mixture of desired ingredien~s
is spray dried in~o the dilute or above a d2nse bed
catalyst phase in a flue catalys~ conversion or
reduced erude conversion regeneration zone wherein
relatively high eombus~ion temperatures are en~ounter-
ed. The high temperature of this dilute ca~alyst
phase ~an be relied upon to dry the sprayed micro-
~pherical catalyst particles for .in situ preparation
in the presence of regeneration combustion product
flue gase~ which carry away formed steam from the
major mass of catalyst particles therein undergQing
regeneration. In ~his di~persed catalyst phase high
temperature environment in the range o 1200 ~o l~OO~F
30 the sprayed slurry forms microspher.ical particles and
ormed steam is removed before causing hydrothermal
degradation of the mass of dense phase cataly~t
particles being regenerated~ Xn this manner e~cess
heat from regeneration can be economically utili~ed ~o
further reduce the cost of catalyst prepara~iorl. It
RI6156
51
will be rec~gnized by those ~killed in the art that
~he homo~eni7ed ~lurry may be considerably Shickened
during homogenization thereof and sprayed into ~he
dllute catalyst phase~ The dispersed ~atalyst phase
temperature will be reduced and generally below CO
combustion temperatures therein should they exi5~0
This ne~ and novel combination technique of forming
spray dried eatalyst particle~ can be used to some
con~iderable advantage, particularly when incorporat~
10 ing carbon black in the homogenized slurry mix to form
a large pore distribution in the eatalyst part icle
abovP identifiedO Since the spray dlried particle
formed in the dispersed phase will be heated to a high
tempera~ure and will fall into the dense fluid bed o
zatalyst ~here below being regenerated, the added
carbon black will he removed by combustionO This
particular in situ catalyst preparation or novel
operating technique of this invention offer~ consider-
able flexibility and economy to the combination of
catalyst preparations~ That i~, the slurry components
comprising the catalyst eompositiorl may be varied at
will, if not daily, ~he catalyst may be prepared in
situ a~ needed and the heat available in the dispersed
catalyst phase of the regenerator is available for
~5 drying the sprayed materlal which combination
contributes measurably to the economics of the
operation part.icularly associated with catalyst
prepara~ion~ In this atmosphere of operating novelty
it is further recognized that the refiner is now able
to vary compositiun o the catalyst par~icle~ as the
oil feed ~upplied and processed i5 ~aried and as new
catalyst technology is uncoYerec3 ~uch fle~ibili~y in
operation benefits considerab~y with respect to
RX6156
~2
reduced cost~ to manufacture catalyst, reduces capital
investment and more particularly permits adjustment of
catalyst composition and activity essentially at will
t~ optimize conver~ion of a given oil charge. It is
even visualized ~hat micropxocessor control can be
util~zed ~o vary ca~alyst composition daily. Other
advantages to this operating technique will be
recognized by ~hose ~killed in the art particularly
whe~ a given reduced erude conversion operation
requires variation in ~ataly~t replacement due to
attrition and changes in Gatalyst replacement rates as
metals accumulation increases to e~uilibrium ~tatus to
achieve particularly de~ired re~ul~ requiring changes
in catalyst activity-selectivity characteristics,
The benefi~s derived by using ca~alysts prepared using
the colloidal and ~he preparation techniques of this
invention are manifold:
1) Reduced crudes contain high Yanadium (v~ levels
which upon depo~ition on the RCC catalyst in the ri~er
cracking operation followed by catalyst re~eneration
yields v2os. V2Os melt~ ~1275F) below RCC regenera
tion temperatures, flows through the cataly~t destroy-
ing sieve and thus destroys catalytic activity. The
reaction of any sodium present wi~h V~s yields sodium
vanadate, also a low melting ~olid (1240CF)~ This
melting point of sodi~m vanadate is also below
normal RCC regeneration temperatures ~1250 to 1500~F`~,
Thus either of these metal composition species are
capable of migr~tion or 1Ow as a 1iquid across and
through catalyst particle~ causing irrev~rsible
destruction of the zeolite crystalline structure ~o
form an amorphous material resulting in a substantial
loss in catalyst activity and ~electivity~ In
addition, the flow of vanadia caus~s matrix slntering,
~615~
pore blockage and particle roalescence sufficient to
cause defluidiza~ion in the operating environment in
which employed.
To counteract the liq~id migration effects of
5 V259 immobilization agents such as Ti, Zr, and In are
added to ~he catalys~ particle composi~ion durlng or
after preparatlo~ there~. A slurry mixture of the
catalyst ingredients may be provided with one or more
vanadia immobilization agents to form stable~high
melting solids with deposited vanadia as it occurs
while encountering high tem~eratures in the
regenerator, The formed high melting solids would
indicate vanadium titanate, vanad:ium zirconate,
vanadium indiate titanate, vanadium zirconate~ vanadi~
um indiate or other sui~able added complex forming
materials ~11 of which will not melt at regeneration
temperatures. The presence of ~odium in the hydrocar-
bon feed, however, will form high melting sodium
derivatives of Ti, Zr, In, such as Na titanate, Na
zirconate, Na indiate and thus reduce the effectiYe
ness of ~ r, and In as V immobilization agents.
2) Sodium in the catalyst particle will also migrate
and react with and tie up acid cracking sites present
in the zeol.ite and matrix material and thus reduce the
activity-~electivi~y characteristics of the catalystO
This necessarily also reduces the desired cracki~g
activity o~ the catalyst matrix or the conversion of
the large non-volatile molecules present in reduced
crude to provide ~maller volatile molecules that can
en~er ~he zeolite pore structure for further eracking
to gaseous and liguid fuels sueh as gasoline and
hea~ing uels.
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54
By having litkle or substantially no mobile ~odium
presen~ in ~he catalyst as prepared by the concepts
and seguence of steps of ~his invention and by
operating ~n efficien~ desalter on the raw crude 5il
eed we ensure ~hat ~he effec~iveness of vanadia
immobilization additives are maximized and ~odium
deactivation is minim.i~ed~
3) By having little or no mobile sodium prese~t in
the ma~rix materials including the sol binding
matrix material and the clay ~btained by acid treat-
ing and exchanging sodium out of any clay material
utilized or by u6ing the particular kaolini~e clay
above identified, a large number of acid si~es can
be provided and maintained in the catalyst matrix.
One can ~hus tolerate a somewha~ higher sodium level
in the feed, since khe matrix can react with or
immobilize sodium present in the feed, maintain
matrix cracking activity for a longer on stream time
period and ensure thak very li~tle~ if any~ ~odium
reaches the crystalline zeolite catalyst componen~
and thus neutraliæe zeolite cracking activity,
4~ The calcination of a (RE~) rare earth exchanged
~Y" zeolite followed by ~RE) rare eax~h exchange
ater calcination ensures high sodium removal and
provides the low sodium content special crystalline
zeoli~e composikion particularly desired. Furkher-
more, a better temperature control of zeolite cal~
cination is po~sible and a ~etter rare earth
exchan~e environmenk is provided ko obtain a lantha
num rich rare earth exchanged zeolite~ Secondly~
the rare e~rths are more easily exchanged in~o ~.he
crystalline zeolite to replace sodiu~ and/ox hydro
ogen therein as opposed to (RE) exchanging a final
RI61S6
catalyst particle composikion or complex comprising
a r~re earth exchanged ~Y~ zeoli~e (REY) containiny
catalyst particle ~ompositionO The rare earth
exchanging of ~pray dried REY con~aining catalyst
particles puts ~ome RE in~o ~he matrix wi~hou~
assuring maximum exchange with ~odium in ~he zeolike
component of the particle and this will neutralize
~ome previously established acid si~es in ~he matrix
thus reducing the ma~rix cracking acidity~ ~odium
neutralization level of the feed and lastly; this
method o remc>ving ~odium from a ca~21yst particles
requires ~ubstantially more rare arth ~olution to
o~tain (RE~ rare earth at a desired l~vel in the
crystalline zeolite componen~ so as ~o reduce i~s
sodium and/or hydrogen level~
The novel catalyst preparation procedure of
this invention is designed to considerably reduce
khe C05t of oatalysts, especially but not necessari-
ly limited 'co processing caa~bo~metallic :Eee2s~ocks.
The procedure al50 considerably reduces the other
above undesired impediments/ derogat3ry resul~s and
particularly ensure~ obtaining a low COStJ a 1OW
sodium, hi~h activity if desiredy matrix material in
combination with the special crystalline zeoli.te
composition which characteristics are considered
particularly clesirable and more appropriately
u~ilized when coupled wi~h the other desirable
catalyst ingredient and preparational features
particulrly iden~ified aboveO
Having thus generally described the improved
techniques ~f this invention and discussed specifie
RI615S
3~
56
examples in ~upport thereof~, it is ~o be understood
that no undue restrictions are to be imposed by
reasons thereo:E except a~ def ined by ~he ollowing
claims .
S When providing catalysts o.r carbc>-metallic
feedsto~s conversion, cos~ becomes an exceedingly
important factor, as catalyst :requirement~ for
processing of high metals containing feeds tocks are
many times that required for processing of vacuum
gas oil. The con~iderable advantages of thi~ method
of catalyst preparation will be obvious to one
skilled in the ar~,
RI6156
