CA1171054A - Hydrocarbon conversion catalysts and processes utilizing the same - Google Patents
Hydrocarbon conversion catalysts and processes utilizing the sameInfo
- Publication number
- CA1171054A CA1171054A CA000382018A CA382018A CA1171054A CA 1171054 A CA1171054 A CA 1171054A CA 000382018 A CA000382018 A CA 000382018A CA 382018 A CA382018 A CA 382018A CA 1171054 A CA1171054 A CA 1171054A
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- CA
- Canada
- Prior art keywords
- catalyst
- zeolite
- weight percent
- alumina
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
Abstract
ABSTRACT OF THE DISCLOSURE
A catalyst, having a specified amount of rare earth metal content and a specified amount of alkali metal content, suitable for conversion of hydrocarbon oils to lower boiling products comprises a crystalline alumino-silicate zeolite, such as zeolite Y, an inorganic oxide matrix and, optionally discrete particles of alumina dis-persed in the matrix. The zeolite prior to being compos-ited with the matrix has a unit cell size above about 24.5 Angstroms. A cracking process utilizing the catalyst is also provided.
A catalyst, having a specified amount of rare earth metal content and a specified amount of alkali metal content, suitable for conversion of hydrocarbon oils to lower boiling products comprises a crystalline alumino-silicate zeolite, such as zeolite Y, an inorganic oxide matrix and, optionally discrete particles of alumina dis-persed in the matrix. The zeolite prior to being compos-ited with the matrix has a unit cell size above about 24.5 Angstroms. A cracking process utilizing the catalyst is also provided.
Description
-- 1 ~
: 3ACKGROUND _ OF THE I NVENTI ON
: 3ACKGROUND _ OF THE I NVENTI ON
2 1. Field of_the Invention
3 The pre~ent invention relates to a catalyst and
4 its use in a catalytic cracking process. More particularly, the present invention relates to a catalytic cracking cata-6 lyst having improved acti~ity and selectivity for producing 7 high octane number naphtha.
8 2. Description of the Prior Art 9 Hydrocarbon conversion catalysts comprising a zeolite dispersed in a siliceous matrix are kn~wn. See, 11 for example U.S. Patent 3,140,249 and U.S. Patent 3,352,796.
12 A catalyst comprising a zeolite, an inorganic 13 oxide matrix and i~ert fines, which may be alpha alumina, 14 is known. See U.S. Patent 3,312,615.
A catalyst comprising an amorphous silica-aluminar 16 separately added alumina and a zeolite i~ kn~wn. See U.S.
17 Patent 3,542~670.
18 A catalyst comprising a zeolite, an amorphous 19 hydrous alumina and alumina monohydrate is known. See U.S.
Patent 3,428,550.
21 To improve the steam and therma} stability of 22 zeolites, it is known to produce zeolites having a low level 23 of alkali metal content and a unit cell size less than 24 about 24.45 Angstroms. See U.S. Patents 3,293,192 and Re 28,629 (Reissue of U.S. Patent 3,402,996).
26 It is also known to treat hydrogen or ammonium 27 zeolite with H2O at a temperature ranging from about 800 28 to about 1500F, and subsequently cation exchanging the 29 steam and water treated zeolite with cations which may be rare earth metal cations. The method increases the silica 31 to alumina mole ratio of the zeolite. See U.S. Patent 32 3,591,488.
33 U.S. Patent 3,676,368 discloses a rare earth ex-34 changed-hydrogen faujasite containing from 6 to 14 percent rare earth oxides.
~ ~ ~7~
1 U.S. Patent 3,957,623 discloses a rare earth ex-2 changed zeolite ha~ing a total of 1 to 10 weight percent 3 rare earth metal oxide.
4 U.S. Patent 3,607,043 discloses a process for pxeparing a zeolite having a rare earth content of 0.3 to 6 10 w~ight percent.
7 U.S. Patent 4,036,739 discloses hydrothermally 8 stable and ammonia stable Y zeolite in which a sodium Y
9 zeolite is ion exchanged to partially exchange sodium ions for ammonium ions, followed by steam calcination and a 11 further ion exchange with ammonium to reduce the final 12 sodium oxide content to below 1 weight percent, followed 13 by calcination of the reexchanged product, or according to 14 U.S. Patent 3,781,199, the second calcination may be con-ducted after the zeolite is admixed with a refractory oxide.
16 SUMMARY O~ THE INVENTION
17 In accordance with the invention there isprovided, 18 a catalyst comprising:
19 . (a) a crystalline aluminosilicate zeolite having uniform pore diameters ranging from about 6 to about 15 21 Angstroms and a silica to alumina mole ratio of at least 22 about 3;
23 - (b) an inorganic oxide matrix; and 24 (c) discrete particles of alumina;
said zeolite prior to being composited with (b) 26 having a unit cell size greater than about 24.5 Angstroms, 27 and said catalyst having an alkali metal content such that 28 the ratio o~ weigh~ percent alkali metal, calculated as 29 the alkali metal oxide, based on the total catalyst, di-vided by the weight percent zeolite based on the total 31 catalyst is not greater than 0.024 and a rare earth metal 32 content such that the ratio of weight percent rare earth 33 metal, calculated as the rare earth metal oxide, based on 34 the total catalyst, divided by the weight percent æeolite based on the total catalyst ranges from about 0~01 to about 36 0O08~
6~
1 In accordance with the invention there is further 2 provided a catalytic cracking process utilizing the above 3 stated cataly~t.
The catalyst of the present invention must have 6 (1) an alkali metal content such that the ratio of weight 7 percent alkali metal oxide based on the total catalyst 8 divided by the weight percent zeolite based on the total 9 catalyst is not more than about 0.024, pre~erably not more than about 0.013 and (2) a rare earth content such that 11 the ratio of weight percent rare earth metal oxide based 12 on the total catalyst divided by the weight percent zeo-13 lite based on the total catalyst ranges from about 0.01 14 to 0.08, preferably from about 0.01 to about 0.06, moxe preferably from about 0.01 to about 0.04.
16 The alkali metal in the catalyst can be a single 17 alkali metal or a mixture of alkali metals. The rare earth 18 metal may be a single rare earth metal or a mixture of rare 19 earth metals of elements having atomic numbers ranging from 57 to 71.
21 The required amount of rare earth metal and alkali 22 metal can be incorporated into the catalyst either by pre 23 paring a æeolite having the required rare earth content and 24 alkali metal content and then compositing the zeolite with a conventional matrix or the required amount of rare earth 26 an~ alkali metal in the catalyst can be obtained by util-27 i ing a zeolite having essentially no rare earth metal 28 cations, that is, less than 1 weight percent rare earth 29 oxide based on the zeolite, or le~s than the required amount o~ rare earth metal and subsequently treating the composite 31 catalyst (that is, zeolite dispersed in a ~latrix~ with a 32 solution comprising rare earth metal components to 33 incorporate the required amount of rare eaxth metal com-34 ponents into the catalyst.
The Zeolite Component 36 The initial zeolite component of the catalyst of 37 the present invention prior to being composited with the , ~ ~'7~
1 other components can be any of the large pore crystalline 2 aluminosilicate zeolites having uniform pore openings rang-3 ing from about 6 to about 15 Angstroms and a silica to 4 alumina mole ratio of at least about 3. Examples of these ; zeolites are æeolites designated by the Linde Division of - 6 Union Carbide by the letter Y (this zeolite has the struc-7 ture of a faujasite and is descrlbed in U.S. Patent 8 3,120,017)a~ well as naturally occurring faujasites. The 9 preferred initial zeolite is a Y-type zeolite. The unit cell size of the initial zeolite used prior to compositing 11 it with the other components is greater than 24.S Angstroms, 12 preferably g~eater than about 24.6 Angstroms.
13 The zeolite may comprise rare earth metal cations 14 and may additionally comprise hydrogen cations and cations of Group IB to VILI metals of the Periodic Table of Elements.
16 The Periodic Table referred to herein is given in Handbook 17 of Chemistry and Physics, published by the Chemical ~ubber 18 Company, Cleveland, Ohio, 45th Edition, 1964. When addi-19 tional cations are present other than rare earth metals and alkali metals, the preferred additional cations are calcium, 21 magnesium, hydrogen and mixtures thereof. The concentra-22 tion of hydrogen present in the finished zeolite will be 23 that concentration equivalent to the difference between the 24 theoretical cation concentration of the particular zeolite in question and the amount of cation present in the form of, 26 for example, rare eaxth and residual ion.
27 When the rare earth content and low alkali metal 28 of the catalyst are controlled by utilizing a zeolite which 29 has been treated to comprise at least a portion of the re-quired rare earth metal, for example, as rare earth met~l 31 cations, the zeolite having the desired rare earth metal 32 component can be obtained by various methods~
33 One method of producing a required zeolite having 34 only a limited amount of rare earth metal cations and low alkali metal content is to staxt with ~ sodium Y-type zeo-36 lite having a unit cell size greater than 24.5 Angstroms 37 and ion exchange it with an ammonium ion by a conventional method known in the art such as for example, by utilizing an ammonium salt in an aqueous or non-aqueous fluid medium.
Ion exchange methods are described, for example, in U.S.
Patent 3,140,249; U.S. Patent 3~140,251; U.S. Patent 3,140,253.
Although a wide varlety of salts can be employed, particular preference is given to chlorides, nitrates, and sulfates.
The ion exchange treatment is conducted for a time sufficient to replace enough of the alkali metal cation by ammonium to decrease the alkali metal conten~ of the zeolite to a desired value. The ammonium treatment may be a single treatment or a successive number of trea~ents. If desired, the treated zeolite can be washed between successive ammonium treatments.
The resulting ammonium exchanged zeolite is recovered, for example, by filtration. The recovered zeolite is washed with water to remove soluble matter. The ammonium exchanged Y
zeolite is contacted with a fluid medium comprising rare eaxth metal cations of a single rare earth metal or cations o~ a mixture of rare eart~ metals. The ion exchange is conducted in a con~entional way such as by utilizing salts of the desired rare earth metals. The rare earth metal treatment additionally replaces some of the remaining alkali metal cations of the zeolite and may replace some of the ammonium ions~
The amount of rare earth metal used is such that it does not exceed the limits of the range required for the catalyst of th~ present inventionv The total amount of re-quired rare earth may be exchanged into the zeolite itself or only a portion of the amount required by the catalyst of the present invention may be exchanged into the zeolite and the balance of the desired requiredjamount may be composited with the finished catalyst, for example, by posttreating the finished ca~alyst with a solution comprising rare earth metal components that become associated with the finished catalyst.
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1 The rare earth-exchanged zeolite is recovered, 2 for example, by filtration, and washed with water to re-3 move soluble matter and calcined, for example, at a temp-4 erature ranging from about 1300F to 1600F for about 0~5 to 6 hours, preferably from about 1400F to 1500F for 6 about 1 to 3 hours in the absence or in the presence of 7 H2O which may be steam or water.
8 The final zeolite may be composited with other 9 catalytic metal components, such as metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB, and VIII of the Periodic 11 Table of ElementsO
12 The particle size of the zeolite component will 13 generally range from about 0.1 to 10 microns, preferably 14 from about 0.5 to 3 microns. Suitable amounts of the zeo-lite component in the total cakalyst will range from about 16 1 to 60, preferably from about 1 to 40, more preferably 17 from about 5 to 40, most preferably from about 8 to 35 18 weight percent, based on the total catalyst.
19 ~ .
The catalyst of the pre~;ent invention, optionallyr 21 comprises a porous al~umina component. The porous alumina 22 component is present in the preferred catalyst of the 23 present invention.
24 The porous alumina component of the catalyst of the present invention comprises discrete particles of var~
26 ious porous aluminas, preferably crystalline alumina, which 27 are known and commercially available. In general, the por-28 ous alumina component of the eatalyst of the present in-29 vention are discrete particles having a total surface area, as mea ured by the method of Brunauer, Emmett and Teller 31 (BET) greater than about 20 square meter~ per gram (m2/g), 32 preferably greater than 145 m2/g, for example, ~rom about 33 145 to 300 m2/g. Preferably ~he pore volume (BET) of the 34 alumina will be greater than 0.35 cc/g. The average particle size of the alumina particles would generally be 36 less than 10 microns, prefarably less than 3 microns.
37 Pre~erably, the porous alumina will be a material having .'7~
1 initially, if used alone, prior to being composited with 2 the other components, inherently less catalytic cracking 3 activity of its own than the inorganic matrix component 4 of the catalyst. Preferably, the porous alumina will be a bulk alumina. The term "bulk" with reference to the 6 porous alumina is intended herein to designate a material 7 which has been preformed and placed in a physical form such 8 that its surface area and pore structure are stabilized so 9 that when it i5 added to an impure, inorganic gel contain-ing considerable amounts of residual soluble salts, the 11 salts will not alter the surface and pore characteristics 12 measurably nor will they promote chemical attack on the 13 preformed porous alumina which could undergo change. For 14 example, addition of "bulk" alumina will mean use of a material which has been formed by suitable chemic~l reac-16 tion, the slurry aged, filtered, dried, washed free of 17 residual salt and then heated to reduce its ~olatile con-18 tent to less th n about 15 weight percent. The porous 19 alumina component may suitably be present in the catalyst of the present invention in an amount ranging from about 5 21 to about 40 weight percent, pre~erably from about 10 to 22 about 30 weight percent based on the total catalyst.
23 Alternatively and optionally, an alumina hydrosol or 24 hydrogel or hydrous alumina slurry may be used inltially in the catalyst preparation as precursor of tke discrete Z6 particles of~alumina in the final catalyst.
27 The Inorganic Oxide M ix Component 28 The inorganic oxide matrices suitable as compo-29 nent o~ the catalyst of the present invention are amorphous catalytic inorganic oxides, such as silica, alumina, silica-31 alumina, silica-zirconia, silica-magnesia, alumina-boria, 32 alumina-titania and the like and mixtures thereof Prefer-33 ably, the inorganic oxide matrix is a silica-containing gel;
34 more preferably the inorganic oxide gel is an amorphous silica-alumina component such as a conventional silica-36 alumina cracking catalyst, several types and com~ositions of 37 which are commercially available. l'hese materials are .... . .
-- ~ --1 generally prepared as a cogel of silica and alumina or as 2 alumina precipitated on a preformed and preaged hydrogel.
3 In general, the silica is present as a major component in 4 the catalytic solids present in said gels, being present in amounts ranging from about 55 to 100 weight percent;
6 preferably the silica will be present in amounts ranging 7 from about 70 to about 90 weight percent. Particularly 8 preferred are two cogels, one comprising about 75 weight ~ percent silica and 25 weisht percent alumina and the other comprising about 87 weight percent silica and 13 weight 11 percent alumina. The inorganic oxide matrix component may 12 suitably be present in the catalyst of the present inven-13 tion in an amount ranging from about 40 to about 99 weight 14 percent, preferably from about 50 to about 80 weight per-cent, based on the total catalyst. It is also within the 16 scope of this invention to incorporate in the catalyst 17 other materials, to be employed in cracking catalysts such 18 as various other types of ~eolites, clays, carbon monoxide 19 oxidation promoters, etc.
2~ The catalyst of the present invention may be 21 pxepared by any one of several methods. The preferred 22 method of preparing one of the catalysts of the present 23 invention, that is, a catalyst comprising silica-alumina 24 and porous alumina, is to react sodium silicate with a solution of aluminum sulfate to fonm a silica/alumina 26 hydrogel slurry which is thPn aged to give the desired 27 pore properties, filtered ~o remove a considerable amount 28 of the extraneous and undesired sodium and sulfate ions 29 and then reslurried in water. Separately, the bulk alumina is made, ~or example, by reacting solutions of sodium 31 aluminate and aluminum sulfate under suitable conditions 32 aging the slurry to give the desired pore properties of 33 the al~mina, filtering, drying, reslurry in water to re-34 move sodium and sulfate ions and drying to reduce volatile matter content to less than 15 weight percent. The alumina 36 is then slurried in water and blended in proper amounts, 37 with a ~lurry of impure silica-alumina hydrogel.
~'7~
1 The zeolite component is added to this blend. A
2 sufficient amount of each component is utilized to give the 3 desired final composition~ The resulting mixture is then 4 filtered to remove a portion of the remaining extraneous soluble salts therefrom. The filtered mixture is then dried 6 to produce dried solids. The dried solids are subsequently 7 reslurried in water and washed substantially free of the 8 undesired soluble salts. The catalyst is then dried to a 9 residual water content of less than about 15 weight percent.
The catalyst is recovered after calcination for 6 hours at 11 1000F in air. The catalyst of the present invention i5 12 particularly suited for use in catalytic cracking of hydro-13 carbons.
14 Catalytic cracking with the catalyst of the pres-ent invention can be conducted in any conventional catalytic 16 cracking manner. Suitable catalytic cracking conditions 17 include a temperature ranging rom about 700F to about 18 1300F and a pressure ranging from about subatmospheric 19 to several hundreds of atmospheres, typically from about atmospheric to about 100 psig. The process may be carried 21 out in a fixed bed, moving bed, ehullating bed, slurry, 22 transferline, or fluidized bed operation. The catalyst of 23 the present invention can be used to convert any of the 24 conventional hydrocarbon feeds used in catalytic cracking, that is, it can be used to cxack naphthas, gas oil and 26 residual oils having a high content of metal contaminants.
27 It is especially suited for cracking hydrocarbons boiling 28 in the gas oil range, that is, hydrocarbon oils having an 29 atmospheric pressure boiling point ranging from about 450 ts about 1100F to naphthas to yield not only products 31 having a lower boiling point than the initial feed but 32 also products having an improved octane number.
33 DESCRIPTION OF THE PREFERRED EMBO~IMENT
_ . ~ . ,. - ~
34 The following examples are presented to illus-trate the invention.
36 Preparation o~ ~h i-A~3~!~onent 37 A zeolite suitable as component of the catalyst , .
, 1 of the present in~ention was m~de as follows:
2 (1) In a mixing tank, slurry 22 lbs of sodium 3 Y zeolite in 100 lbs of water heated to 135F.
4 (~) With stirring and continued heating, add 5 lbs of (NH4)2SO4. Continue to heat and stir at 135F for 6 2 hours, filter and rinse the filter cake with 2 gallons 7 of hot water. (A portion of the material was analyzed and 8 showed 7.06 percent residual sodium oxide).
9 (3) In a mixing vessel, 100 lbs of water are heated to 135F and S lbs of ammonium sulfate dissolv~d 11 in it. The pH of the solution was lowered to 4.0 by addi-12 t.ion of sulfuric acid. With stirring and heating continued 13 at 135F, the wet filter cake was added and contacted for 14 2 hours, filtered and rinsed with 2 gallons of hot water.
A sample of this material analyzed 4.60 weight percent 16 sodium oxide.
I7 (4) In a separate vessel charged 75 lbs of water, 18 slurry the wet filter cake of (3) and heat the slurry to 19 135F. With continued heating and stirring, add 850 cc of a solution of mixed rare earth chlorides (equivalent 21 to 360 grams ~E2O3). Cont~ct time was 1 hour. Filter and 22 rinse with 3 gallons of hot water. A sample of this mat-23 erial analyzed 4.48 weight percent sodium oxide and 5.37 24 weight percent RE2O3.
8 2. Description of the Prior Art 9 Hydrocarbon conversion catalysts comprising a zeolite dispersed in a siliceous matrix are kn~wn. See, 11 for example U.S. Patent 3,140,249 and U.S. Patent 3,352,796.
12 A catalyst comprising a zeolite, an inorganic 13 oxide matrix and i~ert fines, which may be alpha alumina, 14 is known. See U.S. Patent 3,312,615.
A catalyst comprising an amorphous silica-aluminar 16 separately added alumina and a zeolite i~ kn~wn. See U.S.
17 Patent 3,542~670.
18 A catalyst comprising a zeolite, an amorphous 19 hydrous alumina and alumina monohydrate is known. See U.S.
Patent 3,428,550.
21 To improve the steam and therma} stability of 22 zeolites, it is known to produce zeolites having a low level 23 of alkali metal content and a unit cell size less than 24 about 24.45 Angstroms. See U.S. Patents 3,293,192 and Re 28,629 (Reissue of U.S. Patent 3,402,996).
26 It is also known to treat hydrogen or ammonium 27 zeolite with H2O at a temperature ranging from about 800 28 to about 1500F, and subsequently cation exchanging the 29 steam and water treated zeolite with cations which may be rare earth metal cations. The method increases the silica 31 to alumina mole ratio of the zeolite. See U.S. Patent 32 3,591,488.
33 U.S. Patent 3,676,368 discloses a rare earth ex-34 changed-hydrogen faujasite containing from 6 to 14 percent rare earth oxides.
~ ~ ~7~
1 U.S. Patent 3,957,623 discloses a rare earth ex-2 changed zeolite ha~ing a total of 1 to 10 weight percent 3 rare earth metal oxide.
4 U.S. Patent 3,607,043 discloses a process for pxeparing a zeolite having a rare earth content of 0.3 to 6 10 w~ight percent.
7 U.S. Patent 4,036,739 discloses hydrothermally 8 stable and ammonia stable Y zeolite in which a sodium Y
9 zeolite is ion exchanged to partially exchange sodium ions for ammonium ions, followed by steam calcination and a 11 further ion exchange with ammonium to reduce the final 12 sodium oxide content to below 1 weight percent, followed 13 by calcination of the reexchanged product, or according to 14 U.S. Patent 3,781,199, the second calcination may be con-ducted after the zeolite is admixed with a refractory oxide.
16 SUMMARY O~ THE INVENTION
17 In accordance with the invention there isprovided, 18 a catalyst comprising:
19 . (a) a crystalline aluminosilicate zeolite having uniform pore diameters ranging from about 6 to about 15 21 Angstroms and a silica to alumina mole ratio of at least 22 about 3;
23 - (b) an inorganic oxide matrix; and 24 (c) discrete particles of alumina;
said zeolite prior to being composited with (b) 26 having a unit cell size greater than about 24.5 Angstroms, 27 and said catalyst having an alkali metal content such that 28 the ratio o~ weigh~ percent alkali metal, calculated as 29 the alkali metal oxide, based on the total catalyst, di-vided by the weight percent zeolite based on the total 31 catalyst is not greater than 0.024 and a rare earth metal 32 content such that the ratio of weight percent rare earth 33 metal, calculated as the rare earth metal oxide, based on 34 the total catalyst, divided by the weight percent æeolite based on the total catalyst ranges from about 0~01 to about 36 0O08~
6~
1 In accordance with the invention there is further 2 provided a catalytic cracking process utilizing the above 3 stated cataly~t.
The catalyst of the present invention must have 6 (1) an alkali metal content such that the ratio of weight 7 percent alkali metal oxide based on the total catalyst 8 divided by the weight percent zeolite based on the total 9 catalyst is not more than about 0.024, pre~erably not more than about 0.013 and (2) a rare earth content such that 11 the ratio of weight percent rare earth metal oxide based 12 on the total catalyst divided by the weight percent zeo-13 lite based on the total catalyst ranges from about 0.01 14 to 0.08, preferably from about 0.01 to about 0.06, moxe preferably from about 0.01 to about 0.04.
16 The alkali metal in the catalyst can be a single 17 alkali metal or a mixture of alkali metals. The rare earth 18 metal may be a single rare earth metal or a mixture of rare 19 earth metals of elements having atomic numbers ranging from 57 to 71.
21 The required amount of rare earth metal and alkali 22 metal can be incorporated into the catalyst either by pre 23 paring a æeolite having the required rare earth content and 24 alkali metal content and then compositing the zeolite with a conventional matrix or the required amount of rare earth 26 an~ alkali metal in the catalyst can be obtained by util-27 i ing a zeolite having essentially no rare earth metal 28 cations, that is, less than 1 weight percent rare earth 29 oxide based on the zeolite, or le~s than the required amount o~ rare earth metal and subsequently treating the composite 31 catalyst (that is, zeolite dispersed in a ~latrix~ with a 32 solution comprising rare earth metal components to 33 incorporate the required amount of rare eaxth metal com-34 ponents into the catalyst.
The Zeolite Component 36 The initial zeolite component of the catalyst of 37 the present invention prior to being composited with the , ~ ~'7~
1 other components can be any of the large pore crystalline 2 aluminosilicate zeolites having uniform pore openings rang-3 ing from about 6 to about 15 Angstroms and a silica to 4 alumina mole ratio of at least about 3. Examples of these ; zeolites are æeolites designated by the Linde Division of - 6 Union Carbide by the letter Y (this zeolite has the struc-7 ture of a faujasite and is descrlbed in U.S. Patent 8 3,120,017)a~ well as naturally occurring faujasites. The 9 preferred initial zeolite is a Y-type zeolite. The unit cell size of the initial zeolite used prior to compositing 11 it with the other components is greater than 24.S Angstroms, 12 preferably g~eater than about 24.6 Angstroms.
13 The zeolite may comprise rare earth metal cations 14 and may additionally comprise hydrogen cations and cations of Group IB to VILI metals of the Periodic Table of Elements.
16 The Periodic Table referred to herein is given in Handbook 17 of Chemistry and Physics, published by the Chemical ~ubber 18 Company, Cleveland, Ohio, 45th Edition, 1964. When addi-19 tional cations are present other than rare earth metals and alkali metals, the preferred additional cations are calcium, 21 magnesium, hydrogen and mixtures thereof. The concentra-22 tion of hydrogen present in the finished zeolite will be 23 that concentration equivalent to the difference between the 24 theoretical cation concentration of the particular zeolite in question and the amount of cation present in the form of, 26 for example, rare eaxth and residual ion.
27 When the rare earth content and low alkali metal 28 of the catalyst are controlled by utilizing a zeolite which 29 has been treated to comprise at least a portion of the re-quired rare earth metal, for example, as rare earth met~l 31 cations, the zeolite having the desired rare earth metal 32 component can be obtained by various methods~
33 One method of producing a required zeolite having 34 only a limited amount of rare earth metal cations and low alkali metal content is to staxt with ~ sodium Y-type zeo-36 lite having a unit cell size greater than 24.5 Angstroms 37 and ion exchange it with an ammonium ion by a conventional method known in the art such as for example, by utilizing an ammonium salt in an aqueous or non-aqueous fluid medium.
Ion exchange methods are described, for example, in U.S.
Patent 3,140,249; U.S. Patent 3~140,251; U.S. Patent 3,140,253.
Although a wide varlety of salts can be employed, particular preference is given to chlorides, nitrates, and sulfates.
The ion exchange treatment is conducted for a time sufficient to replace enough of the alkali metal cation by ammonium to decrease the alkali metal conten~ of the zeolite to a desired value. The ammonium treatment may be a single treatment or a successive number of trea~ents. If desired, the treated zeolite can be washed between successive ammonium treatments.
The resulting ammonium exchanged zeolite is recovered, for example, by filtration. The recovered zeolite is washed with water to remove soluble matter. The ammonium exchanged Y
zeolite is contacted with a fluid medium comprising rare eaxth metal cations of a single rare earth metal or cations o~ a mixture of rare eart~ metals. The ion exchange is conducted in a con~entional way such as by utilizing salts of the desired rare earth metals. The rare earth metal treatment additionally replaces some of the remaining alkali metal cations of the zeolite and may replace some of the ammonium ions~
The amount of rare earth metal used is such that it does not exceed the limits of the range required for the catalyst of th~ present inventionv The total amount of re-quired rare earth may be exchanged into the zeolite itself or only a portion of the amount required by the catalyst of the present invention may be exchanged into the zeolite and the balance of the desired requiredjamount may be composited with the finished catalyst, for example, by posttreating the finished ca~alyst with a solution comprising rare earth metal components that become associated with the finished catalyst.
'~f -. .
~ 3~
1 The rare earth-exchanged zeolite is recovered, 2 for example, by filtration, and washed with water to re-3 move soluble matter and calcined, for example, at a temp-4 erature ranging from about 1300F to 1600F for about 0~5 to 6 hours, preferably from about 1400F to 1500F for 6 about 1 to 3 hours in the absence or in the presence of 7 H2O which may be steam or water.
8 The final zeolite may be composited with other 9 catalytic metal components, such as metals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB, and VIII of the Periodic 11 Table of ElementsO
12 The particle size of the zeolite component will 13 generally range from about 0.1 to 10 microns, preferably 14 from about 0.5 to 3 microns. Suitable amounts of the zeo-lite component in the total cakalyst will range from about 16 1 to 60, preferably from about 1 to 40, more preferably 17 from about 5 to 40, most preferably from about 8 to 35 18 weight percent, based on the total catalyst.
19 ~ .
The catalyst of the pre~;ent invention, optionallyr 21 comprises a porous al~umina component. The porous alumina 22 component is present in the preferred catalyst of the 23 present invention.
24 The porous alumina component of the catalyst of the present invention comprises discrete particles of var~
26 ious porous aluminas, preferably crystalline alumina, which 27 are known and commercially available. In general, the por-28 ous alumina component of the eatalyst of the present in-29 vention are discrete particles having a total surface area, as mea ured by the method of Brunauer, Emmett and Teller 31 (BET) greater than about 20 square meter~ per gram (m2/g), 32 preferably greater than 145 m2/g, for example, ~rom about 33 145 to 300 m2/g. Preferably ~he pore volume (BET) of the 34 alumina will be greater than 0.35 cc/g. The average particle size of the alumina particles would generally be 36 less than 10 microns, prefarably less than 3 microns.
37 Pre~erably, the porous alumina will be a material having .'7~
1 initially, if used alone, prior to being composited with 2 the other components, inherently less catalytic cracking 3 activity of its own than the inorganic matrix component 4 of the catalyst. Preferably, the porous alumina will be a bulk alumina. The term "bulk" with reference to the 6 porous alumina is intended herein to designate a material 7 which has been preformed and placed in a physical form such 8 that its surface area and pore structure are stabilized so 9 that when it i5 added to an impure, inorganic gel contain-ing considerable amounts of residual soluble salts, the 11 salts will not alter the surface and pore characteristics 12 measurably nor will they promote chemical attack on the 13 preformed porous alumina which could undergo change. For 14 example, addition of "bulk" alumina will mean use of a material which has been formed by suitable chemic~l reac-16 tion, the slurry aged, filtered, dried, washed free of 17 residual salt and then heated to reduce its ~olatile con-18 tent to less th n about 15 weight percent. The porous 19 alumina component may suitably be present in the catalyst of the present invention in an amount ranging from about 5 21 to about 40 weight percent, pre~erably from about 10 to 22 about 30 weight percent based on the total catalyst.
23 Alternatively and optionally, an alumina hydrosol or 24 hydrogel or hydrous alumina slurry may be used inltially in the catalyst preparation as precursor of tke discrete Z6 particles of~alumina in the final catalyst.
27 The Inorganic Oxide M ix Component 28 The inorganic oxide matrices suitable as compo-29 nent o~ the catalyst of the present invention are amorphous catalytic inorganic oxides, such as silica, alumina, silica-31 alumina, silica-zirconia, silica-magnesia, alumina-boria, 32 alumina-titania and the like and mixtures thereof Prefer-33 ably, the inorganic oxide matrix is a silica-containing gel;
34 more preferably the inorganic oxide gel is an amorphous silica-alumina component such as a conventional silica-36 alumina cracking catalyst, several types and com~ositions of 37 which are commercially available. l'hese materials are .... . .
-- ~ --1 generally prepared as a cogel of silica and alumina or as 2 alumina precipitated on a preformed and preaged hydrogel.
3 In general, the silica is present as a major component in 4 the catalytic solids present in said gels, being present in amounts ranging from about 55 to 100 weight percent;
6 preferably the silica will be present in amounts ranging 7 from about 70 to about 90 weight percent. Particularly 8 preferred are two cogels, one comprising about 75 weight ~ percent silica and 25 weisht percent alumina and the other comprising about 87 weight percent silica and 13 weight 11 percent alumina. The inorganic oxide matrix component may 12 suitably be present in the catalyst of the present inven-13 tion in an amount ranging from about 40 to about 99 weight 14 percent, preferably from about 50 to about 80 weight per-cent, based on the total catalyst. It is also within the 16 scope of this invention to incorporate in the catalyst 17 other materials, to be employed in cracking catalysts such 18 as various other types of ~eolites, clays, carbon monoxide 19 oxidation promoters, etc.
2~ The catalyst of the present invention may be 21 pxepared by any one of several methods. The preferred 22 method of preparing one of the catalysts of the present 23 invention, that is, a catalyst comprising silica-alumina 24 and porous alumina, is to react sodium silicate with a solution of aluminum sulfate to fonm a silica/alumina 26 hydrogel slurry which is thPn aged to give the desired 27 pore properties, filtered ~o remove a considerable amount 28 of the extraneous and undesired sodium and sulfate ions 29 and then reslurried in water. Separately, the bulk alumina is made, ~or example, by reacting solutions of sodium 31 aluminate and aluminum sulfate under suitable conditions 32 aging the slurry to give the desired pore properties of 33 the al~mina, filtering, drying, reslurry in water to re-34 move sodium and sulfate ions and drying to reduce volatile matter content to less than 15 weight percent. The alumina 36 is then slurried in water and blended in proper amounts, 37 with a ~lurry of impure silica-alumina hydrogel.
~'7~
1 The zeolite component is added to this blend. A
2 sufficient amount of each component is utilized to give the 3 desired final composition~ The resulting mixture is then 4 filtered to remove a portion of the remaining extraneous soluble salts therefrom. The filtered mixture is then dried 6 to produce dried solids. The dried solids are subsequently 7 reslurried in water and washed substantially free of the 8 undesired soluble salts. The catalyst is then dried to a 9 residual water content of less than about 15 weight percent.
The catalyst is recovered after calcination for 6 hours at 11 1000F in air. The catalyst of the present invention i5 12 particularly suited for use in catalytic cracking of hydro-13 carbons.
14 Catalytic cracking with the catalyst of the pres-ent invention can be conducted in any conventional catalytic 16 cracking manner. Suitable catalytic cracking conditions 17 include a temperature ranging rom about 700F to about 18 1300F and a pressure ranging from about subatmospheric 19 to several hundreds of atmospheres, typically from about atmospheric to about 100 psig. The process may be carried 21 out in a fixed bed, moving bed, ehullating bed, slurry, 22 transferline, or fluidized bed operation. The catalyst of 23 the present invention can be used to convert any of the 24 conventional hydrocarbon feeds used in catalytic cracking, that is, it can be used to cxack naphthas, gas oil and 26 residual oils having a high content of metal contaminants.
27 It is especially suited for cracking hydrocarbons boiling 28 in the gas oil range, that is, hydrocarbon oils having an 29 atmospheric pressure boiling point ranging from about 450 ts about 1100F to naphthas to yield not only products 31 having a lower boiling point than the initial feed but 32 also products having an improved octane number.
33 DESCRIPTION OF THE PREFERRED EMBO~IMENT
_ . ~ . ,. - ~
34 The following examples are presented to illus-trate the invention.
36 Preparation o~ ~h i-A~3~!~onent 37 A zeolite suitable as component of the catalyst , .
, 1 of the present in~ention was m~de as follows:
2 (1) In a mixing tank, slurry 22 lbs of sodium 3 Y zeolite in 100 lbs of water heated to 135F.
4 (~) With stirring and continued heating, add 5 lbs of (NH4)2SO4. Continue to heat and stir at 135F for 6 2 hours, filter and rinse the filter cake with 2 gallons 7 of hot water. (A portion of the material was analyzed and 8 showed 7.06 percent residual sodium oxide).
9 (3) In a mixing vessel, 100 lbs of water are heated to 135F and S lbs of ammonium sulfate dissolv~d 11 in it. The pH of the solution was lowered to 4.0 by addi-12 t.ion of sulfuric acid. With stirring and heating continued 13 at 135F, the wet filter cake was added and contacted for 14 2 hours, filtered and rinsed with 2 gallons of hot water.
A sample of this material analyzed 4.60 weight percent 16 sodium oxide.
I7 (4) In a separate vessel charged 75 lbs of water, 18 slurry the wet filter cake of (3) and heat the slurry to 19 135F. With continued heating and stirring, add 850 cc of a solution of mixed rare earth chlorides (equivalent 21 to 360 grams ~E2O3). Cont~ct time was 1 hour. Filter and 22 rinse with 3 gallons of hot water. A sample of this mat-23 erial analyzed 4.48 weight percent sodium oxide and 5.37 24 weight percent RE2O3.
(5) ~ portion of the filter cake was dxied and Z6 calcined 6 hours at lOOO~F. It had a unit cell size of 27 24.63 Angstroms and showed a crystallini~y of 144 percent.
28 (6) The we~ filter cake was placed in a furnace 29 already at 1000F and the temperature raised to 1500F
maintaining 1500F for 30 minutes and then allowed to cool 31 to 300F. A portion of the material was analyzed. It had 32 a unit cell size of ~4.60 Angstroms and at a crystallinity 33 of 141 percent. This material is suitable as a zeolite 34 component of the catalyst of the present invention.
EXA~PLE
__ 36 Comparative cracking experiments were made util-~7 izing catalysts A, B, C, D, E, F and G. Catalysts A, B, C
~7~
1 and G are not catalysts in accordance with the invention.
2 Catalysts D, E and F are catalyst of the invention with 3 catalysts D and E being preferred catalysts of the present 4 invention. The compositions of the catalysts are shown in S Table I. Catalysts A, B, C, D, E and F comprised about 20
28 (6) The we~ filter cake was placed in a furnace 29 already at 1000F and the temperature raised to 1500F
maintaining 1500F for 30 minutes and then allowed to cool 31 to 300F. A portion of the material was analyzed. It had 32 a unit cell size of ~4.60 Angstroms and at a crystallinity 33 of 141 percent. This material is suitable as a zeolite 34 component of the catalyst of the present invention.
EXA~PLE
__ 36 Comparative cracking experiments were made util-~7 izing catalysts A, B, C, D, E, F and G. Catalysts A, B, C
~7~
1 and G are not catalysts in accordance with the invention.
2 Catalysts D, E and F are catalyst of the invention with 3 catalysts D and E being preferred catalysts of the present 4 invention. The compositions of the catalysts are shown in S Table I. Catalysts A, B, C, D, E and F comprised about 20
6 weight percent of a Y-type zeolite, about 20 weight percent
7 of discrete particles of a porous al~nina dispersed in
8 abou~ 60 weight percent silica-alumina gel matrix. The
9 Y-type zeolite in catalyst C was an ultrastable ~ype Y
zeolite. The s~ne porous alumina and silica-alumina gel 11 were used in the preparation of catalysts A, B, C, D, E
1~ and F. Catalyst G was a standard commercially available 13 cracking catalyst comprising about 16 weight percent rare 14 earth metal exchanged Y-type zeolite, dispersed in a mixed matrix of silica-alumina gel and kaolin. The rare earth 16 metal content, calculated as rare earth metal oxide, based 17 on total catalyst of catalyst G was about 3.74 weight per-18 cent. Catalyst A, which is not a catalyst of the present 19 invention, was prepared by utilizing NaNH4Y zeolite which was neither rare earth exchanged nor calcined prior to 21 being composited with the remaining catalyst components.
22 Catalyst B, which is not a catalyst of the present inven-23 tion~ was prepared by utilizing a zeolite prepared from a 24 sodium Y zeolite by direct exchange with rare~earth chlor-ides without a~prior ammonium exchange. Catalyst C, which 26 ~ i:s not a catalyst o~ the present inventionl was prepared 27 ~rom a sodium ~ zeolite by ammonium exchange followed by 28 a 1500F calcination, followed by another ammonium ion 2g exchange. The resulting zeolite wa~s an ul~rastable Y type zeolite. The zeolite of catalyst C was not subjected to 31 rare earth exchange treatrnent.
32 Catalysts D, E and F, which are catalysts in 33 accordance with the present invention, were each prepared by 34 utilizing a sodium Y type zeolite which was subjected to amrnoniwn exchange, followed by rare earth metal ion ex-36 change and calcination at 1500F. Catalysts ~, B, C, D, 37 E, and F were post washed, that is, the composite catalysts .
1 were washed in the same manner as is well known in the art, 2 to remove residual salts.
3 Catalysts A, B, C, D, E, F and G were each steamed 4 16 hours at 1400F and 0 psig. The steamed catalysts were then evaluated for cracking activity by a standard micro-6 activity test (M~T). The results of the5e tests are shown 7 in Table II. The steamed catalyst~ were also evaluated for 8 cracking performance in a full cycle cracking operation.
9 The unit was operated in a once-through manner, that is, there was no recycle oil mixed with fresh feed. ~he reed-11 stock used was a 450 to 1100F vacuum gas oil. The unit 12 was operated at a constant catalys~ to oil ratio of 4.
13 The reactor temperature was 925F and the regenerator 14 temperature was 1105F. The catalysts were compared at a constant feed rate of 10 grams per minute. The results 16 are summarized in Table II.
17 ~As can be seen from the data in Table II, the 18 octane number of the naphtha product falls sharply when 19 a catalyst is used in which the rare earth metal oxide content o~ the catalyst is 0.072 where the rare earth metal 21 content is calculated as the rare earth metal oxide of the 22 total catalyst divided by the weight percent zPolite on 23 total catalyst.
24 Catalyst G contained a fully rare earth exchanged Y type zeolite, that is, all the exchange~ble cationic 26 positions were occupied by rare earth metal cations. Cata-27 lysts D, E and~F, which are ~atalysts i~ accordance with 28 the present invention~, had a defined limited amount of rare 29 earth metal components in the total composite catalyst, and exhibited superior activity.
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zeolite. The s~ne porous alumina and silica-alumina gel 11 were used in the preparation of catalysts A, B, C, D, E
1~ and F. Catalyst G was a standard commercially available 13 cracking catalyst comprising about 16 weight percent rare 14 earth metal exchanged Y-type zeolite, dispersed in a mixed matrix of silica-alumina gel and kaolin. The rare earth 16 metal content, calculated as rare earth metal oxide, based 17 on total catalyst of catalyst G was about 3.74 weight per-18 cent. Catalyst A, which is not a catalyst of the present 19 invention, was prepared by utilizing NaNH4Y zeolite which was neither rare earth exchanged nor calcined prior to 21 being composited with the remaining catalyst components.
22 Catalyst B, which is not a catalyst of the present inven-23 tion~ was prepared by utilizing a zeolite prepared from a 24 sodium Y zeolite by direct exchange with rare~earth chlor-ides without a~prior ammonium exchange. Catalyst C, which 26 ~ i:s not a catalyst o~ the present inventionl was prepared 27 ~rom a sodium ~ zeolite by ammonium exchange followed by 28 a 1500F calcination, followed by another ammonium ion 2g exchange. The resulting zeolite wa~s an ul~rastable Y type zeolite. The zeolite of catalyst C was not subjected to 31 rare earth exchange treatrnent.
32 Catalysts D, E and F, which are catalysts in 33 accordance with the present invention, were each prepared by 34 utilizing a sodium Y type zeolite which was subjected to amrnoniwn exchange, followed by rare earth metal ion ex-36 change and calcination at 1500F. Catalysts ~, B, C, D, 37 E, and F were post washed, that is, the composite catalysts .
1 were washed in the same manner as is well known in the art, 2 to remove residual salts.
3 Catalysts A, B, C, D, E, F and G were each steamed 4 16 hours at 1400F and 0 psig. The steamed catalysts were then evaluated for cracking activity by a standard micro-6 activity test (M~T). The results of the5e tests are shown 7 in Table II. The steamed catalyst~ were also evaluated for 8 cracking performance in a full cycle cracking operation.
9 The unit was operated in a once-through manner, that is, there was no recycle oil mixed with fresh feed. ~he reed-11 stock used was a 450 to 1100F vacuum gas oil. The unit 12 was operated at a constant catalys~ to oil ratio of 4.
13 The reactor temperature was 925F and the regenerator 14 temperature was 1105F. The catalysts were compared at a constant feed rate of 10 grams per minute. The results 16 are summarized in Table II.
17 ~As can be seen from the data in Table II, the 18 octane number of the naphtha product falls sharply when 19 a catalyst is used in which the rare earth metal oxide content o~ the catalyst is 0.072 where the rare earth metal 21 content is calculated as the rare earth metal oxide of the 22 total catalyst divided by the weight percent zPolite on 23 total catalyst.
24 Catalyst G contained a fully rare earth exchanged Y type zeolite, that is, all the exchange~ble cationic 26 positions were occupied by rare earth metal cations. Cata-27 lysts D, E and~F, which are ~atalysts i~ accordance with 28 the present invention~, had a defined limited amount of rare 29 earth metal components in the total composite catalyst, and exhibited superior activity.
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Claims (26)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A catalyst comprising:
(a) a crystalline aluminosilicate zeolite having uniform pore diameters ranging from about 6 to about 15 Angstroms, and a silica to alumina mole ratio of at least about 3;
(b) an inorganic oxide matrix, and (c) discrete particles of alumina, said zeolite prior to being composited with (b) having a unit cell size greater than about 24.5 Angstroms, and said catalyst having an alkali metal content such that the ratio of weight percent alkali metal, calculated as the alkali metal oxide, based on the total catalyst, divided by the weight percent zeolite based on the total catalyst is not greater than 0.024 and a rare earth metal content such that the ratio of weight percent rare earth metal, calcu-lated as the rare earth metal oxide, based on the total catalyst, divided by the weight percent zeolite based on the total catalyst ranges from about 0.01 to about 0.08.
(a) a crystalline aluminosilicate zeolite having uniform pore diameters ranging from about 6 to about 15 Angstroms, and a silica to alumina mole ratio of at least about 3;
(b) an inorganic oxide matrix, and (c) discrete particles of alumina, said zeolite prior to being composited with (b) having a unit cell size greater than about 24.5 Angstroms, and said catalyst having an alkali metal content such that the ratio of weight percent alkali metal, calculated as the alkali metal oxide, based on the total catalyst, divided by the weight percent zeolite based on the total catalyst is not greater than 0.024 and a rare earth metal content such that the ratio of weight percent rare earth metal, calcu-lated as the rare earth metal oxide, based on the total catalyst, divided by the weight percent zeolite based on the total catalyst ranges from about 0.01 to about 0.08.
2. The catalyst of claim 1 wherein said alkali metal oxide ratio is not greater than about 0.013.
3. The catalyst of claim 1 or claim 2 wherein said rare earth metal oxide ratio ranges from about 0.01 to about 0.06.
4. The catalyst of claim 1 or claim 2 wherein said rare earth metal oxide ratio ranges from about 0.01 to about 0.04.
5. The catalyst of claim 1 wherein said zeolite prior to being composited with (b) has a unit cell size greater than about 24.6 Angstroms.
6. The catalyst of claim 1 wherein said zeolite is present in an amount ranging from about 1 to about 60 weight percent.
7. The catalyst of claim 1 wherein said zeolite is a Y-type zeolite.
8. The catalyst of claim 1 wherein said parti-cles of alumina have a surface area greater than about 20 m2/g and a pore volume greater than about 0.35 cc/g.
9. The catalyst of claim 1 wherein said parti-cles of alumina in themselves have less cracking activity than said inorganic oxide matrix.
10. The catalyst of claim 1 wherein said parti-cles of alumina are present in an amount ranging from about 5 to about 40 weight percent, said zeolite is present in an amount ranging from about 1 to about 40 weight percent and said inorganic oxide matrix is present in an amount ranging from about 40 to about 90 weight percent, each based on the total catalyst.
11. A process for the catalytic cracking of a hydrocarbon feedstock, which comprises: contacting said feedstock at catalytic cracking conditions with a catalyst comprising:
(a) a crystalline aluminosilicate zeolite having uniform pore diameters ranging from about 6 to about 15 Ang-stroms, and a silica to alumina mole ratio of at least about 3;
(b) an inorganic oxide matrix, said zeolite prior to being composited with (b) having a unit cell size greater than about 24.5 Angstroms, and said catalyst having an alkali metal content such that the ratio of weight percent alkali metal, calculated as the alkali metal oxide, based on the total catalyst, divided by the weight percent zeolite based on the total catalyst is not greater than 0.024 and a rare earth metal content such that the ratio of weight percent rare earth metal oxide, based on the total catalyst, divided by the weight percent zeolite based on the total catalyst ranges from about 0.01 to about 0.08.
(a) a crystalline aluminosilicate zeolite having uniform pore diameters ranging from about 6 to about 15 Ang-stroms, and a silica to alumina mole ratio of at least about 3;
(b) an inorganic oxide matrix, said zeolite prior to being composited with (b) having a unit cell size greater than about 24.5 Angstroms, and said catalyst having an alkali metal content such that the ratio of weight percent alkali metal, calculated as the alkali metal oxide, based on the total catalyst, divided by the weight percent zeolite based on the total catalyst is not greater than 0.024 and a rare earth metal content such that the ratio of weight percent rare earth metal oxide, based on the total catalyst, divided by the weight percent zeolite based on the total catalyst ranges from about 0.01 to about 0.08.
12. The process of claim 11 wherein said alkali metal oxide ratio is not greater than about 0.013.
13. The process of claim 11 or claim 12 wherein said rare earth metal oxide ratio ranges from about 0.01 to about 0.06.
14. The process of claim 11 or claim 12 wherein said rare earth metal oxide ratio ranges from about 0.01 to about 0.04.
15. The process of claim 11 wherein said zeolite prior to being composited with (b) has a unit cell size greater than about 24.6 Angstroms.
16. The process of claim 11 wherein said zeolite is present in an amount ranging from about 1 to about 60 weight percent.
17. The process of claim 11 wherein said zeolite is a Y-type zeolite.
18. The process of claim 11 wherein said catalyst additionally comprises discrete particles of alumina dis-persed in said matrix.
19. The process of claim 18 wherein said parti-cles of alumina have a surface area greater than about 20 m2/g and a pore volume greater than about 0.35 cc/g.
20. The process of claim 18 wherein said parti-cles of alumina in themselves have less cracking activity than said inorganic oxide matrix.
21. The process of claim 18 wherein said parti-cles of alumina are present in an amount ranging from about 5 to about 40 weight percent, said zeolite is present in an amount ranging from about 1 to about 40 weight percent and said inorganic oxide matrix is present in an amount ranging from about 40 to about 90 weight percent, each based on the total catalyst.
22. The process of claim 11 wherein said cata-lytic cracking conditions include a temperature ranging from about 700 to about 1300°F.
23. The process of claim 11 wherein said hydro-carbon feedstock is a gas oil.
24. The process of claim 11 wherein a naphtha product having an increased octane number is recovered.
25. The catalyst of claim 1 wherein said inor-ganic oxide matrix comprises silica-alumina.
26. The process of claim 11 wherein said inor-ganic oxide matrix comprises silica alumina.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US196,191 | 1980-10-10 | ||
| US06/196,191 US4339354A (en) | 1980-10-10 | 1980-10-10 | Hydrocarbon conversion catalysts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1171054A true CA1171054A (en) | 1984-07-17 |
Family
ID=22724398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000382018A Expired CA1171054A (en) | 1980-10-10 | 1981-07-20 | Hydrocarbon conversion catalysts and processes utilizing the same |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4339354A (en) |
| JP (1) | JPS5791741A (en) |
| BE (1) | BE890679A (en) |
| BR (1) | BR8106564A (en) |
| CA (1) | CA1171054A (en) |
| DE (1) | DE3140076A1 (en) |
| FR (1) | FR2491776B1 (en) |
| GB (1) | GB2084891B (en) |
| IT (1) | IT1140456B (en) |
| NL (1) | NL8104635A (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288396A (en) * | 1979-10-15 | 1994-02-22 | Union Oil Company Of California | Hydrocracking process using a catalyst selective for making middle distillates |
| US4565621A (en) * | 1981-12-04 | 1986-01-21 | Union Oil Company Of California | Hydrocracking with rare earth-containing Y zeolite compositions |
| US4604187A (en) * | 1981-12-04 | 1986-08-05 | Union Oil Company Of California | Hydrocracking with rare earth-containing Y zeolite compositions |
| US4584287A (en) * | 1981-12-04 | 1986-04-22 | Union Oil Company Of California | Rare earth-containing Y zeolite compositions |
| US4480047A (en) * | 1983-04-07 | 1984-10-30 | Ashland Oil, Inc. | High performance catalysts for carbometallic oil conversion and their manufacturing and use |
| US4561968A (en) * | 1983-04-07 | 1985-12-31 | Ashland Oil, Inc. | Carbometallic oil conversion with zeolite y containing catalyst |
| EP0135317B1 (en) * | 1983-08-12 | 1988-09-07 | Engelhard Corporation | A fluid catalytic cracking catalyst for cracking sulfur containing petroleum feedstocks and a process for using it |
| DE3390537C2 (en) * | 1983-10-20 | 1995-08-10 | Stone & Webster Eng Corp | Catalytic cracking of residual oils |
| US4681747A (en) * | 1984-11-16 | 1987-07-21 | The Standard Oil Company | Process for the preparation of metallosilicates of tetravalent lanthanide and actinide series metals using heterpoly metallates |
| US4567152A (en) * | 1984-12-13 | 1986-01-28 | Exxon Research And Engineering Co. | Co-matrixed zeolite and p/alumina |
| FR2582665B1 (en) * | 1985-06-04 | 1988-08-05 | Inst Francais Du Petrole | CATALYTIC CRACKING PROCESS |
| US5037531A (en) * | 1986-08-15 | 1991-08-06 | Mobil Oil Corporation | Catalytic cracking process |
| US4891164A (en) * | 1986-08-28 | 1990-01-02 | The Standard Oil Company | Method for separating and immobilizing radioactive materials |
| US4921824A (en) * | 1988-06-30 | 1990-05-01 | Mobil Oil Corp. | Metal passivating catalyst composition for cracking hydrocarbons |
| US6248684B1 (en) | 1992-11-19 | 2001-06-19 | Englehard Corporation | Zeolite-containing oxidation catalyst and method of use |
| CN100357399C (en) * | 2005-03-31 | 2007-12-26 | 中国石油化工股份有限公司 | Process for preparing cracking catalyst |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2882244A (en) * | 1953-12-24 | 1959-04-14 | Union Carbide Corp | Molecular sieve adsorbents |
| US3140253A (en) * | 1964-05-01 | 1964-07-07 | Socony Mobil Oil Co Inc | Catalytic hydrocarbon conversion with a crystalline zeolite composite catalyst |
| US3312615A (en) * | 1965-04-09 | 1967-04-04 | Mobil Oil Corp | Catalyst composition containing a crystalline alumino-silicate, a siliceous matrix and inerts for the conversion of hydrocarbons |
| US3210267A (en) * | 1965-04-20 | 1965-10-05 | Socony Mobil Oil Co Inc | Catalytic cracking of hydrocarbons with the use of a crystalline zeolite catalyst containing rare earths and a porous matrix |
| US3402996A (en) * | 1966-12-19 | 1968-09-24 | Grace W R & Co | Ion exchange of crystalline zeolites |
| US3607043A (en) * | 1969-11-19 | 1971-09-21 | Grace W R & Co | Cation and thermal stabilization of a faujasite-type zeolite |
| US3676368A (en) * | 1970-08-26 | 1972-07-11 | Grace W R & Co | Rare earth-hydrogen exchanged zeolites |
| US3930987A (en) * | 1973-04-12 | 1976-01-06 | Mobil Oil Corporation | Catalyst and method of preparing same |
| JPS5643782B2 (en) * | 1973-11-24 | 1981-10-15 | ||
| US3957623A (en) * | 1974-04-24 | 1976-05-18 | W. R. Grace & Co. | Stable, catalytically active and coke selective zeolite |
| US4259212A (en) * | 1978-06-07 | 1981-03-31 | Exxon Research And Engineering Co. | Octane improvement cracking catalyst |
| FR2427843B1 (en) * | 1978-06-07 | 1987-09-18 | Exxon Research Engineering Co | COMPOSITION FOR CATALYTIC CRACKING BASED ON ALUMINA, ULTRA STABLE Y ZEOLITE AND A POROUS OXIDE MATRIX |
| US4242237A (en) * | 1979-05-31 | 1980-12-30 | Exxon Research & Engineering Co. | Hydrocarbon cracking catalyst and process utilizing the same |
-
1980
- 1980-10-10 US US06/196,191 patent/US4339354A/en not_active Expired - Lifetime
-
1981
- 1981-07-20 CA CA000382018A patent/CA1171054A/en not_active Expired
- 1981-10-08 DE DE19813140076 patent/DE3140076A1/en not_active Ceased
- 1981-10-08 FR FR8118987A patent/FR2491776B1/en not_active Expired
- 1981-10-09 IT IT24441/81A patent/IT1140456B/en active
- 1981-10-09 BR BR8106564A patent/BR8106564A/en unknown
- 1981-10-09 GB GB8130532A patent/GB2084891B/en not_active Expired
- 1981-10-09 BE BE2/59409A patent/BE890679A/en not_active IP Right Cessation
- 1981-10-09 JP JP56160400A patent/JPS5791741A/en active Granted
- 1981-10-12 NL NL8104635A patent/NL8104635A/en active Search and Examination
Also Published As
| Publication number | Publication date |
|---|---|
| FR2491776A1 (en) | 1982-04-16 |
| IT1140456B (en) | 1986-09-24 |
| FR2491776B1 (en) | 1987-04-30 |
| US4339354A (en) | 1982-07-13 |
| IT8124441A0 (en) | 1981-10-09 |
| BE890679A (en) | 1982-04-09 |
| BR8106564A (en) | 1982-06-29 |
| JPS5791741A (en) | 1982-06-08 |
| DE3140076A1 (en) | 1982-05-13 |
| NL8104635A (en) | 1982-05-03 |
| GB2084891B (en) | 1984-06-27 |
| GB2084891A (en) | 1982-04-21 |
| JPH0239306B2 (en) | 1990-09-05 |
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