CA1195968A - Carbo-metallic oil conversion process and catalysts - Google Patents

Abstract

Abstract of The Invention Commercial catalysts are prepared combining the various ingredients into a catalytic binder system which has been freed of sodium so that the catalyst ingredients can be preferably spray dried and used in Fluid Catalytic Cracking or Reduced Crude Conversion hydrocarbon conversion operations without subsequent washing or drying. Catalysts can even be prepared on site, e.g., in spray drier operations performed in the FCC/RCC regenerator. Low-sodium slurries of any or all of the following ingredients can be employed in the manufacture: zeolites, clays, sols, carbon blacks, sacrificial sieves, acid matrix substances, and getters.

Description

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 ~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 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 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

-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 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 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.

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.

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 RI6.156 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 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 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 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 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 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

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.

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 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 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 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 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~

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 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 ~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, ~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 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 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~.

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~

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 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.

~,~

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 RI6l56 ~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.

~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

~`~

~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 Rl6156 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 ~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 ~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.

~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 ( ~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~
* Trade Mark 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 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 ~ ~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~

~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)~

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 ~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, 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 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 ~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.

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 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 3~

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~,

Claims (61)

The embodiments of the invention in which an exclusive property of privilege is claimed, are defined as follows:

1. A method for preparing a hydrocarbon conversion catalyst comprising a crystalline zeolite, a clay, and a colloid binder material, said catalyst being prepared from catalyst ingredients selected from the group consisting of binders, crystalline zeolites, sols, clays, pore formers, sacrificial crystalline zeolites, acidic matrix substances, and metal getters and being suitable for use in converting heavy oil feeds, which method comprises:
(a) forming separate liquid slurries of two or more of said ingredients;
(b) preparing each of said liquid slurries from low-sodium content material and low-sodium content water so that the total sodium content of a spray dried composite of said liquid slurries when used alone or in combination with one or more of said ingredients added to a slurry as a powder is less than about 0.25 wt%
sodium oxide;
(c) thoroughly mixing two or more of said liquid slurries alone or in combination with one or more of said ingredients added to a slurry as a powder to form a slurry mixture; and (d) spray drying said slurry mixture to provide fluidizable catalyst particles suitable for use in catalytic cracking of heavy oil feeds and having a low-sodium content of less than 0.25 wt% sodium oxide.

2. The process of Claim 1 wherein said spray dried catalyst is prepared in the vicinity of a hydrocarbon conversion process in which said catalyst is to be employed.

3. The process of Claim 1 wherein said catalyst is formed by spraying drying said mixed slurries into the dilute phase of a catalyst regenerator of a hydrocarbon conversion unit.

4. The method of Claim 1 wherein the spray dried catalyst particles are used in a reduced crude conversion process in which carbo-metallic hydrocarbons are cracked into lower molecular weight products in the presence of at least about 5 ppm by weight of vanadia in the hydrocarbon feedstock.

5. The catalyst preparation method of Claim 1 wherein the sol is an alumina sol.

6. The catalyst preparation method of Claim 1 wherein the sol is an alumina coated silica sol.

7. The catalyst preparation method of Claim 1 wherein the sol is a combination of silica and alumina sol.

8. The catalyst preparation method of Claim 1 wherein the sol is a colloidal titania sol.

9. The catalyst preparation method of Claim 1 wherein the sol is a colloidal zirconia sol.

10. The catalyst preparation method of Claim 1 in which the sol is an alumina colloid which is contacted with one or more of TiO2, ZrO2, CrO23, Fe203 or Al203 to form a coating on the colloid particle before admixture with a slurry comprising a mixture of crystalline zeolite particles and clay particles.

11. The catalyst preparation method of Claim 1 in which the sol is a mixture of silica and alumina colloid which is contacted with one or more of TiO2, ZrO2, Cr203, Fe203 or A1203 to form a coating on the colloid particle before admixture with a slurry comprising a mixture of crystalline zeolite particles and clay particles.

12. The catalyst preparation method of Claim 1 wherein an alpha alumina monohydrate is added to an aqueous slurry of a sol of colloidal silica.

13. The catalyst preparation of Claim 1 wherein an aqueous slurry comprising an alumina sol is adjusted to a basic pH before adding a powder of crystalline zeolite thereto which has been rare earth exchanged before and after calcination to provide a high ratio of La/Ce.

14. The catalyst preparation method of Claim 1: wherein the sacrificial crystalline zeolite material of acceptable sodium content is selected from the group consisting of zeolite A, mordenite, chabazite, a cheap faujasite and a pillared clay material .

15. The catalyst preparation method of Claim 1 wherein the acidity of the matrix material is increased by the addition of one or more materials which are volatile in the regenerator such as phosphates, a halogen contributing material and one of phosphoric, sulfuric or boric acid.

16. The catalyst preparation method of Claim 1 wherein the acidity of the matrix material is increased by the addition of one or more materials such as silica-alumina, silica-titania, silica zirconia, acid activated clay, mordenite, chabzite, erionite and the like.

17. The catalyst preparation method of Claim 1 wherein the pore size distribution of the spray dried microspherical particles is increased by the addition of carbon black to one of the component slurries of colloid, a mixed clay-colloid slurry or a final slurry homogenized mix of all slurry components before spray drying thereof.

18. The method of Claim 1 wherein the heavy oil feed is selected from the group consisting of residual oils, topped rudes, reduced crudes, heavy oils comprising components boiling above 1050°F, shale oils, oil products of coal liquefaction, tar sands oil products and combinations thereof.

19. A method of preparing a fluidizable microspherical cracking catalyst composition suitable for use in converting a heavy oil feed comprising carbo-metallic impurities which comprises:
a) preparing a colloidal silica slurry of basic or acidic pH level which will avoid gel formation, b) preparing an aqueous slurry of micro size clay particles adjusted to a pH above or below the range 5.5 to 7, c) preparing an aqueous slurry of a calcined rare earth exchanged crystalline "Y" zeolite (RECREY) which is rare earth exchanged to provide a lanthanum to cerium ratio of at least 2:1 and a sodium content below 0.3 wt%, d) mixing the colloidal silica and clay slurries of steps (a) and (b), adding the slurry of crystalline zeolite of step (c) to the slurry mixtures of step (d) with homogenous mixing to obtain a smooth slurry thereafter spray dried to form microspherical catalyst particles comprising about silica, from 5 to about 60 wt% of a lanthanum rich special RECRAY crystalline zeolite, up to about 35 wt% of the kaolin clay, and e) recovering the spray dried microspherical catalyst particles for use in converting a heavy oil feed into transportation fuels.

20. The catalyst preparation method of Claim 19 wherein the spray dried particles are recovered and further rare earth exchanged to increase the lanthanum to cerium ratio thereof.

21. The method of Claim 19 wherein the colloidal silica is in combination with one of alumina, magnesia, zirconia, titania or a combination thereof and is maintained above or below a pH
in the range of 5.5 to 7 during preparation of the suspension.

22. The method of Claim 19 wherein the spray dried catalyst comprises a pore volume of at least 0.35 cc/g and a separate material such as carbon black is added to the slurry before spray drying to provide substantial pore size openings of at least 500 Angstroms up to 40% and at least 25% greater than 1000 Angstroms upon calcination of the spray dried particles.

23. The method of Claim 19 wherein the crystalline zeolite is one providing a silica to alumina ratio of at least 4.5/1.

24. The method of Claim 19 wherein the clay component is one selected from the group consisting of kaolin, kaolinite, metakaolin, ball clays, montmorillonite, bentonite, halloysite acid leached clays and combinations thereof.

25. The catalyst preparation method of Claim 19 which is thereafter further rare earth exchanged and calcined sufficiently to reduce the sodium content thereof below 0.1 weight percent and provide rare earths in the silica clay matrix component of the catalyst.

26. The catalyst preparation method of Claim 19 wherein two or more colloidal dispersions of different particle size are used to vary the porosity and attrition resistance of the catalyst composition particles.

27. The method of Claim 19 wherein the silica clay slurry comprises a material selected from the group consisting of Fe203, Cr203 and Sb203 as a part of the catalyst matrix.

28. The method of Claim 19 wherein the colloidal silica is coated with one of TiO2, ZrO2, Re203, Cr2O3, Fe2O3 or A12O3.

29. A method for preparing a catalyst comprising a calcined rare earth exchanged "Y" crystalline zeolite provided with a lanthanum to cerium ratio of at least 3/1 which comprises:

a) preparing a relatively high viscosity liquid slurry mixture of micro-size kaolinite clay particles, b) preparing a liquid slurry comprising a lanthanum-rich "Y" crystalline zeolite of less than 0.47 wt% residual sodium by rare earth exchanges and calcinations, c) mixing the clay slurry of step (a) with colloidal silica to form a mixture comprising less than 0.05 weight percent Na2O, d) mixing the crystalline zeolite slurry of step (b) with the clay-colloidal silica slurry of step (c) under conditions to obtain a smooth homogenized slurry mixture at a pH avoiding gelling thereof, and thereafter e) spray drying the slurry mixture of step (d) after homogenization to form microspherical catalyst particles comprising about 10-50 weight percent silica, 5-50 weight percent clay and about 15-85 weight percent of said La rich rare earth exchanged crystalline "Y" zeolite

30. The preparation of Claim 29 wherein the slurry mixture of step (d) comprises from 2 to 55% solids.

31. The preparation of Claim 29 wherein the homogenizing temperature of step (d) is restricted to within the range of 90 to 150°F.

32. The preparation of Claim 29 wherein the crystalline zeolite of the spray dried microspherical catalyst particles of step (e) comprise at least 6 wt% and preferably at least 7 wt%
rare earths.

33. The method of Claim 29 wherein said lanthanum rich crystalline zeolite of step (b) is in combination with one or more crystalline zeolites selected from the group consisting of zeolite A, ZSM4, zeolite L, gmelinite, mordenite and a cheap faujasite of low sodium content.

34. A method for preparing a catalyst composition suitable for converting hydrocarbon feeds which comprises:

a) preparing a liquid slurry of micro-size clay particles;

b) preparing a liquid slurry of a crystalline zeolite selected from the group consisting of CREY, RECREY, ultra-stable "Y", HY, ASM-5, and high silica zeolites, c) mixing the clay slurry of (a) with a colloidal silica to form a low sodium mixture thereof;

d) mixing the crystalline zeolite of (b) with the clay-silica mixture of (c) under conditions to form a smooth slurry at a pH avoiding gelling thereof;

e) spray drying the slurry mixture of (d) under conditions to form microspherical catalyst particles comprising from 10 to 50 wt.% silica; 5-50 wt.% clay and from 10 to 50 wt.% of said crystalline zeolite.

35. The method of claim 34 wherein the crystalline zeolite is ultra-stable "Y" zeolite.

36. The method of Claim 34 wherein the crystalline zeolite is HY zeolite.

37. The method of Claim 34 wherein the spray dried particles are prepared to comprise lanthanum.

38. The method of Claim 34 wherein the catalyst comprises an ultra-stable "Y" crystalline zeolite in admixture with a zeolite selected from the group consisting of zeolite A, ZSM4, zeolite L, gmelinite, mordenite, chabazite, erionite or a low sodium, faujasite zeolite.

39. The method of Claim 34 wherein an alumina sol contacted with one or more of TiO2, ZrO2, Cr203, Fe203 and Al203 is formed for admixture with the formed slurry of crystalline zeolite-clay-silica mixture of step (d).

40. The method of Claim 34 wherein the catalyst particle comprises one or more of silica-alumina, silica-titania, silica-zirconia.

41. The method of Claim 34 wherein the pore size distribution of the spray dried particles is increased by adding carbon black to the mixed slurries before spray drying.

42. The method of Claim 34 wherein the mixed slurries are sprayed into the dilute phase of a catalyst regeneration operation to form microspherical catalyst particles.

43. The method of Claim 34 wherein the micro-size clay particles is one selected from the group consisting of kaolin, kaolinite, ball clays, montmorillonite, bentonite, halloysite, acid leached clays and combinations thereof.

44. A continuous process for the conversion of residual hydrocarbon feedstocks into lower molecular weight hydrocarbon transportation fuels wherein said residual hydrocarbon feedstocks comprise metal contaminants, fractions boiling above 1025°F
comprising asphaltenes, polynuclear aromatics, polars, naphthenes and porphyrins and wherein the level of such metals and materials boiling above 1025°F in such hydrocarbon feedstock varies from time to time; said process comprising and adapting the catalyst to optimize catalyst parameters comprising porosity, metals content, rare earth content and zeolite content, with respect to composition of hydrocarbon feedstock and related regenerator temperature while simultaneously maintaining low levels of catalyst inventory; said process comprising in combination the steps of:

A. providing a first supply of aqueous slurry of the hydroxy form of a colloidal matrix material selected from the group consisting of silica colloid, alumina colloid and mixtures thereof at a pH in the range selected from the group of ranges consisting of (1) about 3.5 to about 5.5 and (2) about 7 to about 13, said pH being selected to retard gelation of said colloidal matrix material;

B. providing a second supply of an aqueous slurry of micro size clay particles adjusted to a pH substantially the same as that of said colloidal matrix materials;

C. providing a third supply of an aqueous slurry comprising calcined crystalline zeolite;

D. preparing each of said aqueous slurries from low-sodium content ingredients and low-sodium content water so that the total sodium content of a spray dried composite of any combination of said slurries is less than about 0.25 percent by weight sodium;

E. thoroughly mixing 2 or more of said slurries with or without other ingredients having the above low-sodium content to provide mixture;

F. feeding said mixture into a spray drier to provide a low-sodium fluidizable catalyst suitable for fluid catalyst cracking;

G. contacting said fluidizable catalyst with said hydrocarbon feedstock under hydrocarbon conversion conditions to produce lower molecular weight hydrocarbon transportation fuels;

H. determining the analysis of said hydrocarbon feedstock sometime in advance of its contact with a catalyst to be produced by the above steps; and I. varying the ratio of said liquid slurries and other ingredients to optimize the porosity, rare earth content, zeolite content and/or other parameter of the catalyst for optimum conversion of the particular hydrocarbon feedstock which is to contact the particular catalyst being manufactured.

45. In a process for effecting the catalytic conversion of oil feeds boiling above gasoline to form gasoline, light and heavy cycle oils wherein the composition of the charged oil feed varies periodically in carbon producing components and metal contaminants, the improved method of operation which comprises:

A . maintaining separate low sodium content slurries comprising: a one micron clay particle slurry; a faujasite slurry of catalytically activated "Y" faujasite zeolite particles of less than 5 microns containing at least one of hydrogen and exchanged rare earth wherein a La/Ce ratio is at least 1; a carbon particle slurry comprising suspended particles of a carbon black, thermal furnace black or other high surface area blacks; a sacrifical sieve slurry comprising micron sized particles of a sacrificial sieve selected from the group consisting of zeolite A, ZSM/5 mordenite, gmelinites, chabazite and co-gelled SiO2-A1203; a matrix slurry of colloidal particles of an acidic matrix substance selected from the group consisting of finely ground gels, silica-alumina gel, titania-silica; a slurry of fine powder of a binder substance selected from the group consisting of acid leached bentonite, acid leached halloysite, pseudoboehmite, silicic acid and montmorillonite, and a slurry of fine powders of metal getters selected from the group consisting of titania, alumina, zirconia, indium oxide, manganese dioxide and lanthanum oxide;

B. maintaining the sodium content of each of the slurries:

(a) sufficiently low so that at the time of mixing three or more of such slurries in a homogenizing zone, the sodium content of the mixture will be less than 0.2 wt.%, (b) charging a mixture of said slurries to said homogenizing zone in amounts selected to provide spray dried catalyst particles suitable for effecting catalytic conversion of any one of the oil feeds of different composition charged to the same catalytic conversion zone, and (c) spray drying the slurry mixture formed in (b) to form catalyst particles of desired composition.

46 . The process of Claim 45 wherein the crystalline faujasite zeolite comprises a silica to alumina ratio greater than 5/1, a La/Ce ratio greater than 3/1 and a rare earth oxide content greater than 5 wt.% rare earths.

47. The process of Claim 45 wherein a formed matrix composition slurry is provided by one or more components of colloidal ancestry which provide pore size openings in the spray dried particles of at least 500 Angstroms in an amount of 40 or more percent with at least 25% thereof being greater than 1000 Angstroms.

48. The process of Claim 47 wherein the formed matrix composition of the catalyst particle is an acidic acting material which is supplemented by the addition of one or more materials selected from sulfonates, phosphates a halogen contributing material, phosphoric acid, boric acid, acid activated clay, silica alumina, silica titania and silica zirconia.

49. The process of Claim 48 wherein the spray dried slurry is provided with a metal accumulator material and a vanadia immobilization agent by the addition there to of a material selected from alumina, pillared interlayered clay material and a metal additive which will complex with vanadia to effect collection and immobilization thereof.

50. The process of Claim 45 wherein two or more colloidal suspensions of the same or different average particle size and composition are used in the slurry to vary the spray dried catalyst particle porosity, acidity and attrition resistance of the catalyst particle.

51. The process of Claim 45 wherein the matrix forming inorganic oxide colloid slurry is maintained during storage at a pH
outside the range of 5.5 to 7.

52. The process of Claim 45 wherein the spray dried catalyst particle compositions are formed from a slurry comprising silica and/or alumina sols coated with one or more of TiO2, ZrO2, Re203, Fe203 and Al03.

53. The process of Claim 45 wherein the separate slurry pools are used to form catalyst particles comprising a zeolite content of 10 to 60 weight percent; a clay particle content of 10 to 60 weight percent; a matrix forming sol content from 10 to 40 weight percent; a pore forming additive up to 25 weight percent; a sacrificial sieve content up to 20 weight percent; an acid matrix particle substance up to 50 weight percent; a binder material particle content up to 60 weight percent and a metal getter particle material content up to 20 weight percent of the finished spray dried catalyst particle.

54. The process of Claim 45 wherein a catalyst composition suitable for the catalytic conversion of a reduced crude is prepared by:

A. forming a very low sodium content slurry of kaolinite clay micron sized particles in demineralized water of about 4.0 pH, B. forming a low sodium micron sized particles of Recrey "Y"
faujasite crystalline zeolite of high lanthanum content in 4.0 pH demineralized water, C. charging the kaolinite slurry of (A) to a homogenizing mixer with a slurry of low sodium colloidal silica and said zeolite slurry of (B), D. thoroughly mixing the slurries of (C) to obtain a slurry of about 4.0 pH with a viscosity of 900 cps at 100°F, and E. spray drying the mixed slurry comprising silica colloid, clay and crystalline zeolite in a catalyst regenerator to obtain microspherical fluidizable catalyst particles comprising the La rich crystalline zeolite component of slurry (B).

55. The process of Claim 54 wherein an alumina powder is added to the kaolinite slurry and comprising colloidal silica prior to mixing with the zeolite slurry, the pH of the slurry comprising alumina powder without zeolite component is adjusted to a pH of 10 by addition of ammonium hydroxide and thereafter adding the Recrey "Y" faujasite zeolite particles as a powder to the slurry comprising alumina and adjusting the viscosity of the slurry mixture with water to form a slurry suitable for said spray drying.

56. A method for preparing a catalyst composition suitable for effecting catalytic cracking of an oil feed boiling above 650°F which comprises:

A. preparing a slurry comprising a silica colloid in water of a pH of about 2.5, B. adding powdered kaolin clay and dispersant to the silica colloid slurry with mixing and thereafter adding powdered alumina with mixing to obtain a smooth slurry mixture of the ingredients, C. adjusting the pH of the slurry mixture of (B) to about 3.0 and thereafter mixing a desired amount of fine powder, less than 5 microns, Recrey crystalline "Y"
zeolite of high La to Ce ratio greater than 1/1 and with adjustment of the slurry mixture to a pH of about 3.5 to provide a smooth slurry mixture of adjusted viscosity by water addition suitable for spray drying, and D. spray drying the viscosity adjusted slurry into a heated zone of a fluid catalytic cracking-catalyst regeneration operation of a temperature sufficient to provide spray dried microspherical catalyst particles of said slurry.

57. The method of Claim 56 wherein carbon black is added to the slurry during formation and before spray drying thereof.

58. The method of Claim 56 wherein sodium free ingredients selected from colloidal silica, colloidal alumina, titania, zirconia and mixtures thereof are used in preparing said slurry.

59. The method of Claim 56 wherein the metal adsorbing capacity of the catalyst particles is increased by incorporating in the slurry one or more materials selected from the group consisting of zeolite A, mordenite, chabazite, a cheap naturally occurring zeolite, a pillared clay material and combinations thereof.

60. The method of Claim 59 wherein the formed slurry is modified by the addition of one or more acidic promoters selected from nitrates, sulfates, phosphates, a halogen contributing material, or an acid silica containing component selected from silica alumina, silica magnesia, silica zirconia and silica titania.

61. A process according to claim 45 wherein the spray drying is accomplished in the dispersed phase of a catalyst regeneration zone.