CA1194465A - Zeolite catalyst manufacture - Google Patents

Abstract

CATALYST MANUFACTURE
Attract Zeolite containing catalysts are prepared by forming and drying an aqueous slurry of zeolite, aluminum chlorhydrol and clay to obtain particulate composites that contain in excess of about 1 percent by weight alkali metal oxide. The particulate composites are calcined and subsequently ion exchanged to obtain hard, attrition resistant catalyst particles which have an alkali metal oxide content of less than 1 percent by weight.

Description

The present invention relates to the manufacture of catalysts, and more specifically to the preparation oi hard, attrition resistant zeolite containing catalysts which are highly active for the catalytic conversion of 5 hyd r ocarbons.
Hydrocarbon conversion catalysts such as fluid cracking catalysts (FCC) which comprise crystalline zeolites dispersed in 3n inor~anic oxide matrix are typically prepared by spray drying an aqueous slurry of zeolite, clay and a suitable binder such as silica-al~mina hydrogel, silica sol or alumina sol.
The spray dried catalyst particles may be calcine~ and ion exchanged to remove undesirable alkali metal impurities.
Canadian 967,136 to LRngade issued May 6/75 descrlbes hydrocarbon conversion catalyst which cc~pri~es zeolite, clay and an alumlna sol binder. The catalysts are prepared by spray dryin~
a mixture of low soda ion exchanged zeolite, clay, and alumina sol (chlorhydrol), and calcining the spray dried particles to obtain hard, attrition resistant catalysts.
U.S~3,425956 to Baker et al issued Feb.4/69 descr ~ s a me~ for preparating a zeolite containing cracking catalyst wherem a spray dried composite of partially ion exchanged zeolite and silica-alumina hydrogel is calcined and subsequently ion exchanged. The calcination step stabilizes ~eolite and enhances alkali metal oxide removal.
In recent years the cracking c~talyst ind~stry has been particularly conGerned with regard to the production of catalysts which are highly attrition resistant, active and selective for the production of gasoline fractions.
It is therefore an cbject of the present invention to provide a process by which highly active, attrition ~;

resistant catalysts may be economically prepared.
It is another object to provide a zeolitic hydrocarbon conversion catalyst preparation method wherein the need for multiple high temperature calcination steps may be eliminated.
It is yet another object to produce thermally stable catalytic cracking catalysts which are capable of producing a high level of gasoline fraction~.
It is stiall a further object to provide zeolite containing fluid cracking catalysts which are selective for the preparation of high octane gasoline fractionsO
These and other objects of the present invention will become readily apparent to one skilled in the art following the detailed description and drawing wherein the figure comprises a block flow diagram which outlines a process which incorporates the teaching of our invention.
Broadly, our invention contemplates a process for the production of alumina bound zeolite containing catalysts in which a dried particulate composite comprising an alkali metal containing zeolite and an aluminum chlorhydrol binder is calcined and subsequently ion e~changed to lower the alkali metal content to below about 1 percent by weight.
More specifically, we have found that by calcining an aluminum chlorh~drol bound particulate catalyst composite which includes an alkali metal containing zeolite, the catalyst composite may be simultaneously hardened by conversion of the aluminum chlorhydrol to 30` a]umina binder, an~ activated for sodium removal by subsequent ion exchange.
A more clear understanding of our invention may be obtained by reference to the drawing which outlines a catalyst preparation method which may be used in tne practice of our invention.

As shown in the figure, sources of aluminum chlorhy(rol solution, zeolite slurry and clay slurry are combined in a mixer device to obtain a ~niform aqueous slurry. As indicated in the Eigure/ the mixed chlorhydrol/~eolite/clay slurry is conducted to a spray drying step wherein the slurry is converted to particulate solid composites that comprise zeolite and clay particles bound by aluminum chlorhydrolO These composites are calcined to obtain hard, attrition resistant particles. During the calcination step, the aluminum ch]orhydrol is converted to a strong alumina binder and acid chloride by-products, which are removed from the composite. The calcination step also renders the alkali metal oxide, which is present in the zeolite component, more readily available for removal by subsequent ion exchange.
As shown in the drawing~ the calcined catalyst composite is ion exchanged and/or washed to remove excess alkali metal oxide and any other soluble impurities which may be present. The ion exchange step may be conducted using an ammonium salt solution such as ammonium sulfate and/or rare earth chloride solution. The ion exchanged composite is washed with water to remove soluble impurities. Subsequent to ion exchanging and washing, the catalyst composite, which at this point contains less than about l percent, preferably less than .5 percent by weight alkali metal oxide, is dried to a level of about 5 to 25 by weight moisture~
The aluminum chlorhydrol solution used in the practice of the present invention is readily available from commercial souces and typically possesses the

2+m (OH)3m 16 wherein m has a value of about 4 to 12.

The al~minum chlorhydrol solutions are also frequent'y referred ~o in the art as polymeric cationic hydroxy aluminum complexes or aluminum chlorhydroxides which are polymers formed from a monomeric precursor haviny the ~eneral formula A12(OH)5Cl.2~2O~ For the purpose of the present application, the binder component will be referred to as alumin~m chlorhydrol.
The preparation of the aluminum chlorhydrol solution is typically disclosed m U.S. 2,196,016 to Huehn issued ~pril 2/40, C~nadian 967,136 and in U.S. 4,176,090 to ~auqh~n issued Nov.27/79. Typically, preparation of aluminum chlorhydrol involves reacting al~num metal and hydrochloric acid in amounts which will produce a composition having the formula indicated above~ Furthermore, the aluminum chlorhydrol may be obtained using various sources of aluminum such as alumina (A12O3), clay and/or mixtures of alumina and/or clay with aluminum metal, Preferably, the aqueous al~minum chlorhydrol solutions used in the practice of the present invention will have a solids content of from about 15 to 30 percent by weight A12O3.
The zeolite component used in our invention is typically a synthetic faujasite zeolite such as sodium Type Y zeolite ~NaY~ which contains from about 10 to 15 percent by weignt by weight Na2OD It is also contemplated that the zeolites may be partially ion exchanged to lower the soda level thereof prior to incorporation in the catalyst. Typically, the zeolite component may comprise a partially ammonium exchanged type Y zeolite (NH~NaY) which will contain about 3 to 4 percent by weight Wa2O. Furthermore, the zeolite may be partially exchanged with polyvalent metal ions such as rare earth metal ions, calcium and magnesium.
The zeolite component may also be exchanged with a s combination of metal and ammonium and/or acid ions. It is also contemplated that the zeolite component may comprise a mixture of zeolites such as synthetic fau~asite in combination with mordenite and the ZSM
type zeolites. Preferably the zeolite is combined with the aluminum chlorhydrol and a clay componen~ as an aqueous slurry which contains from about 20 to 60 weight percent solids.
The catalysts of the present invention may contain substantial quantities of clay such as kaolin. The clay component, however, i5 optional and comprises from about 0 to about 30 weight percent ~dry basis~ of the overall catalyst composition~ While kaolin is the preferred clay component, it is also contemplated that therm?lly modified kaolin such as metakaolin may be included in the catalyst composition.
During the mixing step, aS shown in the figure, a spray-dryer feed slurry is obtained which contains from about 20 to 60 weight percent solids, of which fcom ~o about 5 to 25 weight percent comprises aluminum chlorhydrol tdry basis) as Al203/ 0 to 60 weight percent zeoli~e, and from about 0 to 90 weight percent clay. While the drawing illustrates a process by which fluid cracking catalysts are obtained by spray drying the catalyst preparation slurry, it is also contemplated that particulate catalysts of larger particle size, i~e. on the order of From about l/~ to 2 mm may be obtained by forming beads or pills oE the present compositions which are particularly useful for the preparation of hydroprocesslng catalysts such as hydrocracking/ hydrodesulfurization and hydrodenitrogenation, and demetallization catalystsO
The spray drying step is conducted using inlet temper~tures in the range of from about 300 to 400 C
and outlet gas temperatures of from about lO0 to 200C. During the spray drying step, the moisture content of the particles is reduced to about 10 ~o 30 percen~ by ~ei~ht. Catalyst composites nav~ a particle size on the order of 20 to 150 microns.
After spray drying the c~talyst composites are calcined at temperatures on the order of from about 300 to 700C for a period of from about 1/~ to 3 hours, and prefer~bly about /2 to 2 ho~rs. During the calcination step the aluminum chlorhydrol i5 converted to solid aluminum binder and volatile acid ~hlorides, which are removed from the calcination zone as part of the off-gas stream. The removal of the aci~ chlorides at high temperatures converts the aluminum chlorhydrol to an aluminum oxide binder which produces a tough, attrition resistant catalyst particleO Furthermore, ~he calcination step activates~ i.e. loosens, the residual alkali metal oxide present in the zeolite component which is readily removed by subsequent ion exchange and/or washing steps~
The ion exchange step which reduces tlle alKali metal oxide level of the catalyst composites to less than about 1 percent by weight is conducted using water and/or aqueous ammonium salt solutions such as ammonium sulfate solution and/or solutions of polyvalent metals such as rare earth chloride solutions. Typically, these ion exchange solutions contain from about 1 to 10 weight percent dissolved salts. Frequently~ i~ is found that multiple exchanges are beneficial to achieve the desired degree of alkali metal oxide removal~
Typically the exchanges are conducted at temperatures on the order of from 5Q to 100C. Subsequent to ion exchanging~ the catalyst components are washed, typically with water, to lower the soluble impurity level to a desirable ]evel.

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Subseq~ent to ion exchange and washing, ~he catalyst composites are dried, typically at temperatures ranging from about 100 ~o 200C to lower the moisture content thereof to a level of preferably below about 15 percent by weight~
Cracking catalysts obtained by our process are highly active for the catalytic cracking of hydrocarbons. Typically, it is found that ~he activity of these catalysts range from about 60 to 90 volume percent conversion subsequent to deactivation and eleva~ed temperatures. Furthermore, it is found that the catalysts are highly selective for the production of gasoline, and in particular, selective or the production of cracked ga~oline fractions which have a high octane rating. Furthermore, the catalysts are extremely tough and attrition resistant.
While the primary components of the catalyst comprise zeolite, aluminum chlorhydrol and op~ionally, clay, it is also understood that other components such ~o as particulate alumina and rare ear~h impregnated alumina may be added for the purpose of enhancing the Sx control capabilities of the catalyst.
Furthermore, it is understood tha~ the catalyst may be combined with minor yuantities (1 to 100 ppm) of platinum and palladium which are added for khe purpose of enhancing the CO oxidation characteristics of the catalyst. The attrition properties of the catalyst are expressed in terms of the Davison Index (DI) and the Jersey Index (JI) which are determined as set forth in U.S. 4,247,420 to Dumoulin issued Jan. 27/81.
Having described the basic aspects of the present invention, the following examples are given to illustrate specific embodiments thereof~

EX~1PLE 1 The following ingredients were combined in a lO
gallon stainless steel mix.ing kettle: 3,404 g of aluminum chlorhydrol solution possessing the formula Al2Cl(O~1)5 and containing 23.5 percent by weight Al2O3; 7500 g (dry basis) kaolin; 1500 g (dry basis) calcined rare earth exchanged type Y zeolite (CREY); and sufficient water to obtain a slurry which c~ntained 25 weight percent solids. The calcined, rare earth exchanged type Y zeolite was obtained by exchange with aqueous mixed rare earth chloride solution a~ pH=5 of NaY followed by calcination for 3 hours at 1000F
and contained 15.02 wei,ght percent RE203 and 3O8 weight percent Na2OO The slurry was thoroughly agitated and spray dried using a gas inlet temperature oE 320~ and a gas outlet tempera~ure of 150Co The spray dried catalyst particles which contained about 25 weight percent water and 0.5 weight percent Na20 were : calcined (i.eO heated) in a muffle furnace at a temperature of lO00F for l hour. Subsequent to calcination the catalyst was dried at a temperature of 150C. The chemical analysis of this catalyst as well as its cracking properties are set forth in Table I.

The preparation method of Example l was repeated, However, 3000 g of the calcined catalyst particles were ion exchanged by contact with 9000 ml of ammonium sulfate solution which contained 3 weight percent by weight ammonium sulfate. The analysis and properties of this catalyst is set forth in Table I.

The preparation me~hod of Example l was repeated.
However, the zeolite comprised an ammonium exchanged, calcined type Y zeolite which contained 12.5 weight percent RE203, and 0.5 weight percent Na20. The catalyst was not ion exchanged subseguent to calcination. The properties of this catalyst sample are set forth in Table I.

EX~MPLE 4 The preparation procedure of Example l was repeated. However, a non-calcined rare earth exchanged Y zeolite was utilized (REY) which contained 13.4 weight percent Re203 and 3.2 weight percent Na20- This catalyst sample was not ion exchanged subsequent to calcination. The properties of this catalyst are set forth in Table I.

The catalyst preparation method of E~ample 4 was repeated" ~owever, 3000 9 of the calcined catalyst was exchanged with 9000 ml of ammonium sulfate solution containing solution containing 3 weight percent by weight ammonium sulfate subsequent to calcination. The properties of this catalyst are set forth in Table I.

EX~PLE 6 The catalyst preparation method of Example l was repeated. However, the finished catalyst contained 25 weight percent of a sodium ammonium Y zeolite which contained 3.8 weight percent Na20 which was obtained by exchanging a sodium Y zeolite with ammonium sulfate. 3000 g of this catalyst was washed with 9000 ml of water subseguent to calcination. The properties of this catalyst are set forth in Table II~

3~1b ~

The catalyst preparation procedure of Example 6 was repeated. However, subsequent to calcination 3000 g of the catalyst was exchanged with 9000 ml of ammonium sulfate sclution which contained 3 wei~ht percent by weight ammonium sulfate, The properties of these catalysts is described in Table II.

The catalyst preparation me~hod of Example 1 was repeated. ~owever, the zeolite comprised 25 weight percent by weight oE an ammonium exchanged, calcined, stabilized Type Y zeolite ~Z14US zeolite) which was prepared in accordance with the pro~ess set forth in U.S.
3,449,070 to McDaniel issued June 10~69. The Z14US zeolite, at the time of incorporation in the catalyst, contained about 308 weight percent Na20. 3000 9 of the catalyst subsequent to calcination was exchanged with 9000 ml of ammonium sulfate solution. Tne properties of this catalyst are set forth in Table II.

The catalyst preparation method of Example 1 was followedO Howe~er, a catalyst was prepared which contained 40 weight percent ammonium exchanged type Y
æeolite which con~ained 3.3 weight percent Na20.
Furthermore, the quantity oE chlorhydrol was adjusted to provide an alumina binder content of 15 weight percent and the kaolin content was adjusted ~o 45 weight percentO This catalyst was not washed subsequent to calcination. The properties of the catalyst are set forth in Table III.

.. ..

The catalyst preparation method of Example 9 was repeated. However, subsequen~ to calcination 3000 9 of the catalyst was washed with 9000 ml of water. The properties of this catalyst are set forth in Table IIIo EXAMPLE_ll The catalyst preparation me~hod of Example 9 was repeatedO ~owever, subsequent to calcination 3000 g of the catalyst was washed with 9000 ml of ammonium sulfate solution which contained 3 weight percent of ammonium sulfate. The properties of this catalyst are set forth in Tables III and IV.

A com~ercial comparison ca~alyst which contained 40 weigh~ percent ~14US zeolite, 23 weight percent of a silica sol binder, and 37 weight percent kaolin clay was prepared by the me~hod set forth in U.S. 3,957,689 to Cste~e~ issued Mhy 18/76. This catalyst was washed wi~h a~n sulfate and the properties thereof are described in Table lV.

A catalyst was prepared by the method set forth in Example 9. ~owever, the zeolite component comprised 40 weight percent of a Z14US type zeolite which had been exchan~ed with ammonium sulfate to a level of abo~t 0.2 percent by weiyht Na20. This catalyst was not ion exchanged or washed subsequent to calcination. The properties of this catalyst are set orth in Table IVo -12~

EXAMPLE l4 In this example the properties of the catalysts prepared in Examples l through 5 were determine~ and tabulated in Table I below:
\

TABLE I

Catalyst of Example No. 1 2 3 4 5 Analyses Wt. ~ Na2O 0.51 0.14 0.18 0.44 0.18 Wt~ % RE2O3 2.26 2033 2.43 2.77 2.74 Wt. % SO4 0.1~ 1.31 0.15 0.13 9.67 S~rface Area m2/g 133 133 148 14~ 146 Density g/cm2 0.84 0.84 0.84 0.87 0.87 10 Davison Index/
Jersey Index 6/0.336/3.5 3/0.1 3/0.9 16/1.7 Microactivity (Vol. % Conv.) Deactivation 15 (5-13.5) (1) 72 73 71 76 /6 Deact.ivation (1500~ (2) 54 68 S5 62 72 (1) S-13.5: 3 nours at 1000F in air followed by 8 ho~rs at 1350F in 100% steam at 15 psig.

20 (2) 1500: 5 hours at 1500E in 100~ steam at 0 psig.

It is noted from the data set forth in Table I that the activity of catalysts which contained the non calcined Y zeolite (Examples 4 and 5) are superior to those which contained the precalcined zeolite (Examples 1l 2 and 3) 3 EXAMPI,E 15 In this e~ample the properties of the catllysts prepared in Examples 6, 7 and 8 were determined and are compared in Table II belowO

TABLE II
"
Catalyst of Example No. 6 7 8 Wt. % Na2O 0.58 0,13 0.27 Unit Cell ~A) 24.62 24~62 24.50 Microactivity (Vol. %
Conversion after S-13.5 ~ deactivation) 60 59 57 Pilot Unit Data Microactivity ~Vol. ~
Conversion) after S-20 deactivation (3) 58.~ 62.0 60.5 Research Octane No. 89.5 90.3 90.6 Motor Octane No. 78.2 79.0 79.3 (3) S~20: 1~ hours at 1520F, 20% steam, 80~ air, 0 psig.

It is noted from the data set forth in Table II
that the octane selectivity for the catalysts prepared in accordance with the teachings of the present invention (Examples 6 and 7) are almost equal to the catalyst which contained the precalcined Z14US type zeolite (Example 8).

In this example the properties of the catalysts obtained in Exam~les 9, 1~ and 11 are compared, as set forth in Table III below.

TABLE III

Catalyst Example No. 9 10 11 No Wash/Exchange Water Wash Ammonium Sulfate Exchange Wt. % Na20 2.11 O~9l 0.54 Microactivity after S-13.5 Deactivation 16 50 67 ; The above data indicates that substantial soda removal may be obtained through use of the practice of the present invention, even though only water ~Example 10) is used in lieu of ammonium sulfate solution tExample 11).

The peoperties of the ca~alysts descrlbed in Examples 11, 12 and 13 are compared and summari~ed in Table IV below.

1'ABLE IV

Catalyst Example No. 11 12 13 Wt. ~ Na2O 0.22 0.54 0.04 Microactivity after S-13.5 ~eactivation 69 6-/ 69 Microactivity (Yol~ %
Conversion) after 1400 Deactivation (4) 55.0 68.0 71.0 Research Octane No. 92.8 92.7 93.0 Motor Octane No. 81.3 80.2 81.8 * USY exchanged to 0O20% Na2O

(4) 1400: 16 hours at 1000F in air followed by 16 hours at 1400~, 100% steaml 0 psigO

The above data indicate that use of the process described in the present invention (Examples 11 and 13) provides catalysts of high activity and good octane selectivity when compared to a prior art catalyst (Example 12).

SUPPLF.MENTARY DISCLOSURE

In accordance with the teachings of the Principal Disclosure there is provided a process for preparing catalyst compo~itions which comprises preparing an aqueous mixture of an alkali metal containing zeolite and aluminum chlorllydrol;
S forming the mixture to obtain particulate zeolite/aluminum in excess of about 1 percent by weight alk~li metal o~ideO
Calcining the composites at a temp2rature in excess of about 500C; and ion exchanging and washing the calcined composites to obtain catalyst particles having an alkali metal oxide content of below abou~ 0.5 weight percent.
It is an object of the present teachings to provid~ a process by which highly active, attxition resistant catalysts 6upports may be economically prepared~
Broadly, our invention contemplates methods for preparing alumina bound zeolite containing c~talyst composites wherein a zeolite component which contains more than 1 percent by weight alkali metal oxide (typically Na~O) is combined with aqueous aluminum chlorhydrol solution, and, in some ins~ances, particulate components such as clay and/or alumlna, fo~med into particula~e composites, calclned, and, when required, ion~exchanged and/or washed to remove excess alkali me~al ions~
More specifically we have found that valuable zeolite containing catalysts and catalyst supports may be obtained by ~he process which is outlined as follows-(1) An alkali metal containing ~eolite which contains more than 1 percent by w~ight alkali metal oxide is mixed with aluminum chlorhydrol, water, andl if desired, a particulate component such as clay and/or alumina to obtain a mixture that is plastlc or fluid in consistency.
(2) The mixture is then formed into particles of desired shape and size and dried to obtain solid particulate zeolite-chlorhydrol containing composites.
(3) The particulate composites are then calcined to convert the aluminum chlorhydrol component into a strong alumina binder and impart physical strengtn to tne particles and in ~ome instances "activate" the alkali metal ions for removal ~y ion exchange and~or washing.
T;~e aluminum chlorhydrol solu~ion i5 as previously taugilt and the ~eolite component used in our inventlon is typically a syntnetic faujasite zeolite such as sodium ~ype Y zeoli~e (NaY) which contalns from about 10 to l percent by weight Na2O. It is also contemplated tnat the zeolites may be partially ion exchanged ~o lower the soda level thereof prior to incorporation in th~
catalyst. Typically, ~he ~eolite component may comprise a partially ammonium exchanged type Y zeolite (N~NaY) which will contain in excess of 1 percent and more frequently frvm about 3 to 6 percent by weight Na2O. Furthermore, the zeolite may be partially exchanged with polyvalent metal ions such as rare ear~h metal ions, calcium and magnesium. The zeolite component may also be exchanged with a combination of metal and ammonium and/or acid ions. It is al50 contemplated that the zeolite component may comp~ise a mixture of zeolites such 2S synthetic faujasite in combination wlth mordenite and ~he ZSM type zeolites, Preferably the zeolite is comb1ned witn the alumln~m -SDl9-.~, . ~, 6~

chlorhydrol and a clay component as an aqueous slurry whch contains from about 20 to bO wei~nt percent solids.
The catalysts of the present invention may contaln subs~antlal quan~ities of a par~lculate component such as clay and/or alumina. ~hile kaolin is the preferre~
clay component, it is also contemplated that t~ermally modified kaolin such as metakaolin may be included in the catalyst composition.
During the mixing step, as shown in the fiyure, a spray-dryer feed slurry is obtained which contains from about 20 to 60 weight percent solids/ of which from about 5 to 25 parts by weight comprises aluminum chlorhydrol (dry basis) as A1203, 1 to 60 parts by weight zeolite, and ~rom about O to 90 weight percent clay. While the drawing illustrates a process by which fluid cracking catalysts are obtained by spray dryin~
the catalyst preparation slurry, it is also contemplated that particulate catalysts of larger particle size, i.eO on the order of from about 1/~ to mm may be obtained by for~ing beads or pills of the presen~ compositions which are ~artirularly useful for the preparation of hydroprocessing catalysts such as hydrocracking, hydrodesulfurization, hydrodenitrogena~lon~ and demetallization catalysts.
The spray drying step is conduc~ed using inlet temperatures in the ran~e of from about 300 to 400C
and outlet gas temperatures of from about 100 to 200C~ During tne spray drying step, the moisture content of the particles is reduced ~o about lU ~o 30 percen~ by weight. 5pray dried catalyst composi~es have a particle size on the order of 20 to 150 microns~
After spray drying the catalyst composites are calcined at temperatures on the order of from about 300 to 700C for ~ period of from about 1/4 ~o 3 hours, and S~20~

preferably about 1/2 to 2 hours. During ~he calcination step the aluminum chlorhydrol ls converted to solid alumina binder and volatile acid chlorldes, which are removed from the calcination zone as part of the off-gas stream~ The removal of the acid chlorides at high temperatures converts ~he aluminum chlorhydrol to an aluminum oxide binder which produces a tough, attrition resistan~ catalyst particle. Furthermore, the calcinatlon step when conducted at temperatures of 10 about 300 to 600C and preferably 400 to 550C
"activates" the residual alkali metal ions present in the zeolite componen~ for subsequent removal ~y washing and/or ion exchange. The activated alkali metal ions are then readily removed by subsequen~ ion exchange and/or washing steps. It is noted tnat when the calcination temperature exceeds abou~ 550 ~o 600~ the sodium ions tend to become more diffi~ult to remove ~y ion exchange. ~owever, it is found that at higher calcination temperatures of 600 to 700C satisfactory catalysts may be pro~uce~ wi~hout washing or ion exchan~e if the Na2O content of the initial composite does not exceed about 0.6 percen~ by weignt. It appears in some instances that the calcination step ln some way renders the sodium ions less active for subsequent deactivation of th2 cataly~t during use a~
elevated temperature.
The ion exchange step which reduces ~he alkali metal oxide level of the catalyst composites to less than akout 1 and preferably less than 0.5, and more preferakly below 0.2 percent by weight is conducte~
using water and/or aqueous ammonium salt solutions such as ammonium sulfate solution and/or solutions of polyvalent metals such as rare earth chloride solutions. Typically, these ion exchange solutions -S~21-. .
.
.
.. ~ . . , . , ,,-, -, . - - - -~3~

contain from about 1 to 10 weight percent dissolved sal~s. Frequently, it is found that multiple exchanges are beneficial to achieve the desired degree of alkali metal oxide removal~ Typically the exchanges are conducted at temperatures on the order of from 50 to 100C~ Subsequent to ion exchanging, ~he catalyst components are washed, ~ypically wi~h water, to lower the soluble impurity level to a desirable level.
Subsequent to ion exchange and washing, the catalyst composites are dried, typically at temperatures ranging from about 100 to 200~ to lower the moisture content thereof to a level of preferAbly below about 15 percen~ by weight.
Cracking catalysts o~tained by our process are highly active for the catalytic cracking ot nydrocarbons. Typically, it is founQ that tne activity of these catalysts range ~rom about 60 to 90 volume percent conversion subsequerlt to deactivation at elevated temperatures when ~ested in accordance wit~
the standard activity test procedures set forth in As-rM
test procedure D 3907~ Furthermore, it is found that the catalysts are highly selective for ~he produc~ion of gasoline, and in particular, selective for the production of cracked gasoline fractions which have a high octane rating. Furthermore, the ca~alys~s are extremely tough and attrition resistant.

--S~
:

... .. .... . . ... . . .. .. . . . .

In considering table 1 it is fur~hermore noted that ~he catalysts of Examples 1 and 4 are not exchanged after calcination and which contain relatively high levels of Na2Of possess a relatively high level of stability and activity.
In considering table ll it is furthermore noted that the atalyst of ~xample 6, which was not exchanged wi~h ammonium sulfate solution and which contains a high level of Na2O7 pos~es~es a reasonably high level of activity and octane selectivity.
~ h respect to table 111 it is furthermore noted that the catalysts of Examples 10 and 11 which have Na2O levels of above 0.5 weight percent s~ill pos~ess a fairly high level of activity.
The following additional example i8 provided~

A spray dried catalyst composite was prepare~ wnlcn contained 16 weight percent rare ear~h exchanged t~pe Y
zeolite (302 wt. % Na2O), 10 weight percent a~umina (as chlorhydrol binder) and 74 weight percent kaolin clay. Three samples of the catalyst composites ~-ere calcined at 800, 1000 and 1200F for ~wo hours, respectively. The calcine~ catalyst samples were exchanged with dilute amm~nium sulfa~e ~olution. The properties of the ~amples are set forth in Table V.
TABLE V
Sample No. 1 2 3 Calcination temperature (F/C) 800/427 1000/538 1200/649 Na2O (wt. %) 0O07 0.19 0.3 DI/JI 16/1.1 2/O.g 8/0.
RE2O3 (~t- %) 3.66 3.g2 3.8 The above data indicate tha~ as the calcination temperature increases from 800 to 1000 to i200~ the amount of Na2O removed by ion exchange progxessively decreases, i'S
~ .. . ..

Claims (39)

WE CLAIM:

1. A method for preparing catalyst compositions which comprises:
(a) preparing an aqueous mixture of an alkali metal containing zeolite and aluminum chlorhydrol;
(b) forming said mixture to obtain particulate zeolite/aluminum chlorhydrol composites which contain in excess of about 1 percent by weight alkali metal oxide;
(c) calcining said composites at a temperature in excess of about 500°C; and (d) ion exchanging and washing the calcined composites to obtain catalyst particles having an alkali metal oxide content of below about 0.5 weight percent.

2. The method of claim 1 wherein said aluminum chlorhydrol has the formula Al2+m(OH)3m Cl6 wherein m has a value of about 4 to 12.

3. The method of claim 1 wherein the zeolite is a type Y zeolite.

4. The method of claim 1 wherein said aqueous mixture prepared in step (a) includes clay.

5. The method of claim 1 wherein said mixture is formed at step (b) by spray drying.

6. The method of claim 1 wherein said ion exchange step (d) includes contacting the calcined particles with a solution which includes ammonium ions and/or rare earth ions.

7. A catalyst composition prepared by the method of claim 1.

8. A fluid cracking catalyst composition prepared by the method of claim 5.

9. The composition of claim 8 wherein said zeolite is present in an amount up to 60 weight percent, 5 to 25 weight percent alumina binder, and up to about 90 weight percent clay.

10. The catalyst composition of claim 9 wherein said zeolite is type Y zeolite.

11. The composition of claim 10 wherein said zeolite is exchanged with rare earth and/or ammonium ions.

CLAIMS SUPPORTED BY THE SUPPLEMENTARY DISCLOSURE

12. In a process for preparing catalyst compositions wherein (a) a zeolite is mixed with an aluminum chlor-hydrol binder, (b) the mixture is formed into particles, and (c) the particles are calcined to obtain hard, attrition resistant catalysts, the improvement comprising;
combining a zeolite which contains in excess of about one percent by weight alkali metal oxide with the chlor-hydrol, calcining the particles at a temperature of about 300° to 600°C., and ion exchanging and washing the formed calcined particles to obtain a catalyst containing less than about one percent by weight alkali metal oxide.

13. The method of claim 12 wherein said catalyst parti-cles have an alkali metal oxide content of below about 0.5 weight percent.

14. The method of claim 12 wherein said aluminum chlorhydrol has the formula Al2+m(OH)3mCl6 wherein m has a value of about 4 to 12.

15. The method of claim 12 wherein the zeolite is a type Y zeolite which contains about 3 to 6 percent by weight Na2O.

16. The method of claim 12 wherein said aqueous mixture prepared in step (a) includes clay.

17. The method of claim 12 wherein said mixture is formed at step (B) by spray drying.

18. The method of claim 12 wherein said ion exchange step includes contacting the calcined particles with a solution which includes ammonium ions and/or rare earth ions.

19. The method of claim 12 wherein said particles are calcined at a temperature of 500° to 550°C. and is ion exchanged and/or washed to lower the alkali metal oxide content thereof to below about 0.5 percent by weight.

20. The method of claim 19 wherein said alkali metal oxide content is lowered to below about 0.2 percent by weight.

21. A catalyst composition prepared by the method of claim 12.

22. A fluid cracking catalyst composition prepared by the method of claim 17.

23. The composition of claim 21 wherein said catalyst contains from about 1 to 60 percent by weight zeolite, 5 to 25 parts by weight alumina binder, and up to about 90 parts by weight of a particulate component selected from the group consisting of alumina, rare-earth impregnated alumina, clay and mixtures thereof.

24. The catalyst composition of claim 23 wherein said zeolite is type Y zeolite.

25. The catalyst composition of claim 24 wherein said zeolite is exchanged with rare earth and/or ammonium ions.

26. A hydroprocessing catalyst support prepared in accordance with the method set forth in claim 12.

27. In a method for preparing catalyst compositions wherein (a) a zeolite is mixed with an aluminum chlor-] binder, (b) the mixture is formed into particles, and (c) the particles are calcined to obtain hard, attrition resistant catalysts, the improvement consisting essentially of;
mixing a zeolite containing about 3 to 6 percent by weight alkali metal oxide in amounts to provide active catalysts which contain less than about 0.6 percent by weight alkali metal oxide.

28. The method of claim 27 wherein said particles are calcined at a temperature of 500° to 700 C.

29. The method of claim 28 wherein said particles contain below about 0.5 percent by weight alkali metal oxide.

30. The method of claim 27 wherein said aluminum sheller-hydrol has the formula Al2+m(OH)3mCl6 wherein m has a value of about 4 to 12.

31. The method of claim 27 wherein the zeolite is a type Y zeolite.

32. The method of claim 27 wherein the mixture prepared in step (a) includes clay.

33. The method of claim 27 wherein said ion exchange step (d) includes contacting the calcined particles with a solution which includes ammonium ions and/or rare earth ions.

34. A catalyst composition prepared by the method of claim 27.

35. A fluid cracking catalyst composition prepared by the method of claim 32.

36. The composition of claim 34 wherein said catalyst contains from about 1 to 60 parts by weight zeolite, 5 to 25 parts by weight alumina binder, and up to about 90 parts by weight of a particulate component selected from the group consisting of alumina, rare-earth impregnated alumina, clay and mixtures thereof.

37. The catalyst composition of claim 36 wherein said zeolite is type Y zeolite.

38. The catalyst composition of claim 37 wherein said zeolite is exchanged with rare earth and/or ammonium ions.

39. A hydroprocessing catalyst support prepared in accordance with the method set forth in claim 27.