CA1131193A - Octane improvement cracking catalyst - Google Patents
Octane improvement cracking catalystInfo
- Publication number
- CA1131193A CA1131193A CA329,201A CA329201A CA1131193A CA 1131193 A CA1131193 A CA 1131193A CA 329201 A CA329201 A CA 329201A CA 1131193 A CA1131193 A CA 1131193A
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- CA
- Canada
- Prior art keywords
- alumina
- catalyst
- zeolite
- ultra
- stable
- 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.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A cracking catalyst comprising discrete particles of ultra-stable Y-type zeolite and discrete particles of alumina, which particles are dispersed in a porous oxide matrix to produce a catalyst comprising 5 - 40 wt. %
ultra-stable Y-type zeolite, 5 - 40 wt. % alumina and 40 - 90 wt. %
of porous oxide matrix. The cracking catalyst has unusually high activity and selectivity for the production of high octane gasoline fractions from higher boiling point feedstocks.
A cracking catalyst comprising discrete particles of ultra-stable Y-type zeolite and discrete particles of alumina, which particles are dispersed in a porous oxide matrix to produce a catalyst comprising 5 - 40 wt. %
ultra-stable Y-type zeolite, 5 - 40 wt. % alumina and 40 - 90 wt. %
of porous oxide matrix. The cracking catalyst has unusually high activity and selectivity for the production of high octane gasoline fractions from higher boiling point feedstocks.
Description
BACKG~OUND OF lHE INVENTION
2 Field of the Invention
3 This invention relates to a catalyst composi-
4 tion and its use in catalytic cracking processes. More particularly, the invention is concerned with a fluid 6 cracking catalyst which has improved activity and selec-7 tivity for producing high octane gasoline fractions from 8 petroleum gas oil feedstocks.
9 DescriPtion of the Prior Art As is well known, the catalytic cracking of 11 heavy petroleum fractions is one of the msjor refining 12 operations employed in the conversion of crude petroleum 13 oils to desirable fuel products such as heating oils and 14 high octane gasoline. Illustrative of "fluid" catalytic conversion processes is the fluid catalytic cracking pro-16 cess wherein suitably preheated high molecular weight 17 hydrocarbon liquids and vapors are contacted with hot, 18 finely-divided, solid catalyst particles, either in a 19 fluidized bed reactor or in an elongated riser reactor, and maintained at an elevated temperature in a fluidized 21 or dispersed state for a period of time sufficient to ef-22 fect the desired degree of cracking to lower molecular weight 23 hydrocarbons suitable as gasoline fractions.
24 A wide variety of petroleum cracking catalysts are described in the literature and are commercially avail-26 able for use in fluidized cracking processes. Commercial 27 cracking catalysts currently in use generally comprise a 28 crystalline aluminosilicate zeolite cracking component in 29 combination with an inorganic oxide matrix component.
Typical zeolites combined with the inorganic oxide matrix 31 include hydrogen and/or rare earth metal-exchanged synthetic 32 faujasite of the X or Y-type. The matrix materials gen-33 erally include amorphous silica-alumina gel and/or a clay 34 material such as, for example, kaolin.
Cracking catalysts which are commercially used 36 for the production of gasoline must exhibit good activity 37 and selectivity. The activity of a catalyst is generally 38 referred to as the ability of the catalyst to convert heavy . .
petroleum fractions to lower molecular weight fractions.
2 Under a given set of operating conditions, the degree to 3 which the catalyst converts the Eeed to lower molecular 4 weight materials is a measure of the catalyst activity.
9 DescriPtion of the Prior Art As is well known, the catalytic cracking of 11 heavy petroleum fractions is one of the msjor refining 12 operations employed in the conversion of crude petroleum 13 oils to desirable fuel products such as heating oils and 14 high octane gasoline. Illustrative of "fluid" catalytic conversion processes is the fluid catalytic cracking pro-16 cess wherein suitably preheated high molecular weight 17 hydrocarbon liquids and vapors are contacted with hot, 18 finely-divided, solid catalyst particles, either in a 19 fluidized bed reactor or in an elongated riser reactor, and maintained at an elevated temperature in a fluidized 21 or dispersed state for a period of time sufficient to ef-22 fect the desired degree of cracking to lower molecular weight 23 hydrocarbons suitable as gasoline fractions.
24 A wide variety of petroleum cracking catalysts are described in the literature and are commercially avail-26 able for use in fluidized cracking processes. Commercial 27 cracking catalysts currently in use generally comprise a 28 crystalline aluminosilicate zeolite cracking component in 29 combination with an inorganic oxide matrix component.
Typical zeolites combined with the inorganic oxide matrix 31 include hydrogen and/or rare earth metal-exchanged synthetic 32 faujasite of the X or Y-type. The matrix materials gen-33 erally include amorphous silica-alumina gel and/or a clay 34 material such as, for example, kaolin.
Cracking catalysts which are commercially used 36 for the production of gasoline must exhibit good activity 37 and selectivity. The activity of a catalyst is generally 38 referred to as the ability of the catalyst to convert heavy . .
petroleum fractions to lower molecular weight fractions.
2 Under a given set of operating conditions, the degree to 3 which the catalyst converts the Eeed to lower molecular 4 weight materials is a measure of the catalyst activity.
5 Thus two or more catalysts can have their activities com-
6 pared by the level of cracked products msde by each cata-
7 lyst under the same process conditions. The selectivity
8 of a catalyst refers to the fraction of the cracked products
9 in a particular boiling or molecular weight range; e.g., C5/430F. naphtha, C3- dry gas, carbon, etc. A more speclal 11 measure of selectivity is the octane rating of the C5/430F.
12 naphtha hereafter referred to as octane producibility.
13 Hence it is most desirable for a preferred cracking cata-14 lyst to exhibit both high cracking activity, a high selec-lS tivity to gasoline (C5/430F.) boiling range material, and 16 of high octane number producibility, that is the ability 17 to produce gasoline boiling range material with a high oc-18 tane rating. Unfortunately, catalysts having the highest 19 activity do not produce the highest octane naphtha products and vice versa. As an example, the amorphous silica-21 alumina cracking catalyst used prior to the advent of the 22 present day zeolite cracking catalyst is less active than 23 the present day zeolite cracking catalysts for cracking 24 the gas oil feedstock, is less selective in the yield of C5/430F. naphtha, but produces a higher octane number 26 naphtha than conventional zeolite cracking catalysts.
27 The individual components of the catalyst composi-28 tion of this invention are described in the literature.
29 The specific combination of the components of the invention to produce a highly active and selective catalyst for the 31 production of high octane gasoline is not believed to be 32 shown in the prior art. For example, U.S. Patent No.
33 3,312,615 describes a three component catalyst system 34 comprising a crystalline aluminosilicate, substantially inert fines and an inorganic oxide matrix therefor. The 36 crystalline aluminosilicate includes a wide variety of 37 zeolites such as zeolites X, Y, A, L, D, R, S, T, Z, E, 38 F, Q, B, ZR-4, ZK-5 as well as naturally occurring zeolites 39 including chabazite, faujasite, mordenite, and the like.
~1~1193 1 The substantially inert fines include alpha-alumina, 2 barytes, zircon, zirconia, kyanite, and rutile fines.
3 U.S. Patent No. 3,542,670 describes a cracking 4 catalyst made by combining a silica-alumina hydrogel with a boehmite amorphous hydrous alumina, and a crystalline 6 aluminosilicate having pores in the 8 - 15~ range and 7 a silica-to-alumina mol ratio greater than 3:1. The 8 crystalline aluminosilicate includes a variety of zeolites 9 which are exchanged with various ions including hydrogen, and nonpoisoning metals such as rare earth metals.
11 U.S. Patent No. 3,816,342 is directed to a 12 process for preparing a fluid catalytic cracking catalyst 13 containing a highly act$ve crystalline aluminosilicate 14 and a relatively less active matrix material. The patentee claims the crystalline aluminosilicate materials having 16 the general formula:
17 M2/nO A1203 YSiO2 ZH20 18 in the salt form, wherein n is the valence of the metal 19 cation M, Y is the number of moles of silica, and ZH20 is the water of hydration. Zeolites Y and X are described 21 as being among the most suitable synthetic crystalline 22 aluminosilicates. The matrix materials are described as 23 inorganic oxide gels, such as those of silica-zirconia, 24 alumina, magnesia, and combinations thereof with one another, clays, alumina, metals and refractory materials.
26 U.S. Patent No. 3,930,987 describes a cracking 27 catalyst comprising a composite of crystalline alumino-28 silicates containing rare earth metal cations dispersed 29 in an inorganic oxide matrix wherein at least 50 wt. %
of the inorganic oxide is silica and/or alumina. The 31 matrix preferably is made up of silica-alumina, silica-32 zirconia, or silica-zirconia alumina, desirably along 33 with a weighting agent preferably clay and/or alumina.
34 Alpha alumina is preferred in the event alumina is em-ployed.
36 U.S. Patent No. 3,717,587 describes the prepara-37 tion of a cracking catalyst composition containing 8 wide 38 variety of crystalline aluminosilicates dispersed in an 39 inorganic oxide gel matrix containing a weighting agent.
11;~3 The patent specifies that the most preferred weiyhting agent is kaolin clay. Other suitable weighting agents include zirconia, alpha alumina, mullite, alumina monohydrate, alumina trihydrate, halloysite, sand, metals such as aluminum and titanium, etc.
U.S. Patent No. 3,788,977 relates to a cracking catalyst for increasing the amount of aromatic gasoline fractions from gas oil feedstocks. The cracking catalyst is described as a composition comprising a number of zeolite components in combination with minor amounts of a reforming-like additive which consists of uranium oxide and/or platinum metal impregnated upon an inorganic oxide support. The zeolites contemplated by patentee include hydrogen and/or rare earth metal exchanged synthetic faujasites which have silica to alumina ratios on the order of 2.5 up to about 6, including type X or Y faujasties.
In addition to rare earth metal exchanged faujasites, patentee contemplates the use of low soda content zeolites.
SVMMARY OF THE INVENTION
A cracking catalyst which has improved activity and selectivity for the conversion of hydrocarbon feedstocks to high octane gasoline fractions, which comprises (a) the ultra-stable variety of Y zeolite, (b) alumina, and (c) an inorganic porous oxide matrix material.
DETAILED DESCRIPTION OF THE INVENTION
The zeolitic component of the catalyst of the invention comprises a crystalline aluminosilicate zeolite which is com-monly known as "stabilized" or "ultra-stable" Y-type faujasite.
These types of zeolites are well known. They are described, for example, in U.S. Patent Nos. 3,293,192 and 3,402,996 and in the publication, Society of Chemical Engineering (London) Monograph Molecular Sieves, pp. 186 (1968) by C.V. McDaniel and P.K. Maher. As used herein, "ultra-stable" refers to a Y zeolite which is highly resistant to degradation of crystallinity by high temperatures and steam treatment and is characterized by an R2O content (where R is Na, K, ~L~ 9~
1 or any other alkali metal ion) of less than about 4 weight 2 %, preferably less than about 1 weight %, and a unit cell 3 size less than about 24.50 angstrom units (A) and an 4 SiO2/A1203 mol ratio in the range of 3.5-7 or higher.
In a preferred embodiment of the invention, the unit cell 6 size of the ultra-stable Y zeolite will be }ess than 24.40 7 ~. The ultra-stable form of the Y zeolite is obtained 8 primarily by the substantial reduction of the alkali metal 9 ion content and the unit cell size reduction subsequent to the alkali metal removal steps. In other words, the 11 ultra-stable zeolite is identified both by the smaller 12 unit cell and the low alkali metal content in the crystal 13 structure.
14 The ultra-stable form of the Y zeolite can be prepared, for example, by successively base-exchanging a 16 Y zeolite, i.e., Y-type faujasite, with an aqueous solution 17 of an ammonium salt, such as ammonium nitrate, until the 18 alkali metal content of the Y zeolite is reduced to less 19 than about 4 wt. %, R20 (where R refers to an alkali metal such as sodium). The base-exchanged zeolite is 21 then calcined at a temperature of 1000F. to 1500F. over 22 a period of time ranging, for example, from 0.5 to 5 hours, 23 to produce an ultra-stable Y zeolite. If desired, steam 24 may be added to the system during the calcination.
Preferably, the ultra-stable Y zeolite is thereafter again 26 successively base-exchanged with an aqueous solution of 27 an ammonium salt until the alkali metal content is re-28 duced to less than 1 wt. % R20. More preferably, the 29 ultra-stable Y zeolite is then again calcined at a temp-erature of 1000 to 1500F. with added steam, if desired, 31 to produce an ultra-stable Y zeolite having a unit cell 32 size less than about 24.40 A. This sequence of ion ex-33 change and heat treatment results in the substantial reduc-34 tion of the alkali metal content of the original zeolite and results in unit cell shrinkage which are believed to 36 lead to the ultra high stability of the resultant Y zeo-37 lite. The particle size of these zeolites is usually in 38 the range of 0.1 - 10 microns, more typically in the 39 range 0.5 - 3 microns.
In a preferred embodiment, the ultra-stable Y-type zeolite component of the invention will be substantially free of rare earth metals such as, for example, cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gado-linium, terbium, dysprosium, holmium, erbium, yttrium, thulium, scandium, lutecium and mixtures thereof. By substantially free is meant that the rare earth metal content of the zeolite will be less than about 1 wt. ~ as metal oxide (~e2O3). Similarly, up to about 1 wt. ~ of other metal ions such as magnesium or calcium may be base exchanged into the zeolite.
The alumina component of the catalyst of the invention comprises discrete particles of various aluminas which are known and, in many instances, commercially available. These aluminas include the anhydrous and/or the hydrated forms. A rather comprehensive description of aluminas is given in "Encyclopedia of Chemical Technology", Kirk-Othmer, Second Edition, Volume 2 (Interscience Publishers) at pages 41-55.
Among the aluminas useful in preparing the catalyst of this invention are discrete alumina particles having a total surface area (B.E.T. method - Brunauer, Emmett and Teller;
The Van Nostrand Chemist's Dictionary (1953 Edition)) greater than 20 square meters per gram (m2/g), preferably greater than 145 m2/g, for example, 145 - 300 m2/g. Preferably the pore volume (B.E.T. method) of the alumina will be greater than 0.35 cc/g. The average particle size of the alumina will generally be less than 10 microns, more preferably less than 3 microns. These discrete alumina particles used in preparing the catalyst are sometimes designated as "bulk" alumina.
The term "bulk" is intended herein to designate an alumina which has been preformed and placed in a physical form such that its surface area and pore structure is stabilized so that when it is added to an impure inorganic gel containing considerable amounts of residual soluble salts, the salts will not alter the surface and pore characteristics measurably nor will they promote more than minimal chemical ,, 1 attack on the preformed alumina which could then under-2 go change. For example, addition of "bulki' alumina will 3 mean a material which has been formed by suitable chemical 4 xeaction, the slurry aged, filtered, dried, washed free of residual salts and then dried to reduce its volatile 6 contents to less than about 25 wt. %.
7 In addition to the above described bulk, 8 porous, preformed aluminas, it is also envisioned to pre-9 pare the catalyst by using hydrous slurries of diverse hydrated aluminas which may be a particular crystalline 11 form, or amorphous, or mixtures. These hydrates include 12 alpha-monohydrate, alpha-trihydrate, beta-trihydrate, and 13 to a lesser de~ree, beta-monohydrate forms of alumina.
14 These are generally made from solutions of aluminum salts or of alkaline aluminates. Depending on reaction condi-16 tions, the product aluminas can have a wide range of 17 physical properties. In addition to the foregoing, the 18 alumina slurry can be a gel. Alumina gels generally have 19 a dried solids content of about 2 - 12% by weight. On drying, the alumina gels lose water progressively and 21 with increasing temperatures the first transision phase 22 (nonhydrated) can be either eta- or gamma- alumina.
23 The presence of discrete particles of crystalline 24 alumina in the catalyst of this invention can be observed by x-ray diffraction in accordance with well known tech-26 niques such as described in Advances in X-Ray Diffractometry 27 and X-Ray Spectrographyedited by William Parrish (1962), 28 Centrex Published Company - Eindhoven.
29 The inorganic porous oxide which is used as the matrix in the catalyst composition of the invention 31 may include any of the readily available porous materials 32 such as alumina, silica, boria, chromia, magnesia, zir-33 conia, titania, silica-alumina, and the like, and mixtures 34 thereof. These materials may also include one or more of the various well known clays such as montmorillonite, 36 kaolin, halloysite, bentonite, and the like. Preferably, 37 the inorganic porous oxide will be one or more of the 38 conventional siliceous varieties containing a major amount 39 of silica and a minor amount of an oxide of at least one 1 metal in Croups II-A, III-A and IV-B of the Periodic 2 Table (Handbook of Chemistry and Physics, 38th Ed., 1957).
3 Representative silica-containing matrix materials include 4 silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-titania, silica-fllumina-zirconia, silica-6 alumina-magnesia, etc.
7 In a more preferred embodiment of the invention, 8 the inorganic porous oxide matrix material will be an 9 amorphous silica-alumina gel. As is generally known, these materials are typically prepared from silica hydro-11 gel or hydrosol, which is mixed with an alumina source, 12 generally an aluminum salt solution, to secure the desired 13 silica-alumina composition. The alumina content of the 14 silica-alumina matrix will typically range from about 5 to 40 wt. % with the preferred composition having an alumina 16 content of about 10 to 35 wt. %. Various procedures are 17 described in the literature for making silica-alumina, 18 e.g., U.S. Patent Nos. 2,908,635 and 2,844,523.
19 The catalyst composition of the invention will comprise 5 - 40 wt. %, preferably 10 - 30 wt. %, of the 21 aforedescribed ultra-stable Y zeolite; 5 - 40 wt. %, 22 preferably 10 - 30 wt. %, of alumina; and 40 - 90 wt. %, 23 prefersbly 50 - 80 wt. %, of the porous oxide matrix. It 24 is also within the scope of this invention to lncorporate in the catalyst other materials commonly employed in 26 cracking catalysts such as various zeolites, clays, metal 27 C0 oxidation promoters, etc.
28 In a preferred embodiment, the catalyst of the inven-29 - . Wei~ht % Na 0 on total catalyst tion will have the ratlo Weight % ze~lite in total catalyst 31 equal to or less than 0.013.
32 The catalysts of the present invention may be 33 prepared in accordance with well known techniques. For 34 example, a preferred method of preparing a catalyst of the invention is to react sodium silicate with a solution 36 of aluminum sulfate to form a silica-alumina hydrogel 37 slurry which is then aged under controlled conditions to 38 give the desired pore properties, filtered to remove a 39 considerable amount of the extraneous and undesired sodium and sulfate ions and then reslurried in water. Separately, 2 a bulk alumins is made, for example, by reacting solu-3 tions of sodium aluminate and aluminum sulfate, under 4 suitable conditions, aging the slurry to give the desired 5 pore properties of the alumina, filtering, drying, re-6 slurrying in water to remove sodium and sulfate ions and 7 drying to reduce volatile matter content to less than 25 8 weight percent. The alumina is then slurried in water and 9 blended, in proper amount, with the slurry of impure
12 naphtha hereafter referred to as octane producibility.
13 Hence it is most desirable for a preferred cracking cata-14 lyst to exhibit both high cracking activity, a high selec-lS tivity to gasoline (C5/430F.) boiling range material, and 16 of high octane number producibility, that is the ability 17 to produce gasoline boiling range material with a high oc-18 tane rating. Unfortunately, catalysts having the highest 19 activity do not produce the highest octane naphtha products and vice versa. As an example, the amorphous silica-21 alumina cracking catalyst used prior to the advent of the 22 present day zeolite cracking catalyst is less active than 23 the present day zeolite cracking catalysts for cracking 24 the gas oil feedstock, is less selective in the yield of C5/430F. naphtha, but produces a higher octane number 26 naphtha than conventional zeolite cracking catalysts.
27 The individual components of the catalyst composi-28 tion of this invention are described in the literature.
29 The specific combination of the components of the invention to produce a highly active and selective catalyst for the 31 production of high octane gasoline is not believed to be 32 shown in the prior art. For example, U.S. Patent No.
33 3,312,615 describes a three component catalyst system 34 comprising a crystalline aluminosilicate, substantially inert fines and an inorganic oxide matrix therefor. The 36 crystalline aluminosilicate includes a wide variety of 37 zeolites such as zeolites X, Y, A, L, D, R, S, T, Z, E, 38 F, Q, B, ZR-4, ZK-5 as well as naturally occurring zeolites 39 including chabazite, faujasite, mordenite, and the like.
~1~1193 1 The substantially inert fines include alpha-alumina, 2 barytes, zircon, zirconia, kyanite, and rutile fines.
3 U.S. Patent No. 3,542,670 describes a cracking 4 catalyst made by combining a silica-alumina hydrogel with a boehmite amorphous hydrous alumina, and a crystalline 6 aluminosilicate having pores in the 8 - 15~ range and 7 a silica-to-alumina mol ratio greater than 3:1. The 8 crystalline aluminosilicate includes a variety of zeolites 9 which are exchanged with various ions including hydrogen, and nonpoisoning metals such as rare earth metals.
11 U.S. Patent No. 3,816,342 is directed to a 12 process for preparing a fluid catalytic cracking catalyst 13 containing a highly act$ve crystalline aluminosilicate 14 and a relatively less active matrix material. The patentee claims the crystalline aluminosilicate materials having 16 the general formula:
17 M2/nO A1203 YSiO2 ZH20 18 in the salt form, wherein n is the valence of the metal 19 cation M, Y is the number of moles of silica, and ZH20 is the water of hydration. Zeolites Y and X are described 21 as being among the most suitable synthetic crystalline 22 aluminosilicates. The matrix materials are described as 23 inorganic oxide gels, such as those of silica-zirconia, 24 alumina, magnesia, and combinations thereof with one another, clays, alumina, metals and refractory materials.
26 U.S. Patent No. 3,930,987 describes a cracking 27 catalyst comprising a composite of crystalline alumino-28 silicates containing rare earth metal cations dispersed 29 in an inorganic oxide matrix wherein at least 50 wt. %
of the inorganic oxide is silica and/or alumina. The 31 matrix preferably is made up of silica-alumina, silica-32 zirconia, or silica-zirconia alumina, desirably along 33 with a weighting agent preferably clay and/or alumina.
34 Alpha alumina is preferred in the event alumina is em-ployed.
36 U.S. Patent No. 3,717,587 describes the prepara-37 tion of a cracking catalyst composition containing 8 wide 38 variety of crystalline aluminosilicates dispersed in an 39 inorganic oxide gel matrix containing a weighting agent.
11;~3 The patent specifies that the most preferred weiyhting agent is kaolin clay. Other suitable weighting agents include zirconia, alpha alumina, mullite, alumina monohydrate, alumina trihydrate, halloysite, sand, metals such as aluminum and titanium, etc.
U.S. Patent No. 3,788,977 relates to a cracking catalyst for increasing the amount of aromatic gasoline fractions from gas oil feedstocks. The cracking catalyst is described as a composition comprising a number of zeolite components in combination with minor amounts of a reforming-like additive which consists of uranium oxide and/or platinum metal impregnated upon an inorganic oxide support. The zeolites contemplated by patentee include hydrogen and/or rare earth metal exchanged synthetic faujasites which have silica to alumina ratios on the order of 2.5 up to about 6, including type X or Y faujasties.
In addition to rare earth metal exchanged faujasites, patentee contemplates the use of low soda content zeolites.
SVMMARY OF THE INVENTION
A cracking catalyst which has improved activity and selectivity for the conversion of hydrocarbon feedstocks to high octane gasoline fractions, which comprises (a) the ultra-stable variety of Y zeolite, (b) alumina, and (c) an inorganic porous oxide matrix material.
DETAILED DESCRIPTION OF THE INVENTION
The zeolitic component of the catalyst of the invention comprises a crystalline aluminosilicate zeolite which is com-monly known as "stabilized" or "ultra-stable" Y-type faujasite.
These types of zeolites are well known. They are described, for example, in U.S. Patent Nos. 3,293,192 and 3,402,996 and in the publication, Society of Chemical Engineering (London) Monograph Molecular Sieves, pp. 186 (1968) by C.V. McDaniel and P.K. Maher. As used herein, "ultra-stable" refers to a Y zeolite which is highly resistant to degradation of crystallinity by high temperatures and steam treatment and is characterized by an R2O content (where R is Na, K, ~L~ 9~
1 or any other alkali metal ion) of less than about 4 weight 2 %, preferably less than about 1 weight %, and a unit cell 3 size less than about 24.50 angstrom units (A) and an 4 SiO2/A1203 mol ratio in the range of 3.5-7 or higher.
In a preferred embodiment of the invention, the unit cell 6 size of the ultra-stable Y zeolite will be }ess than 24.40 7 ~. The ultra-stable form of the Y zeolite is obtained 8 primarily by the substantial reduction of the alkali metal 9 ion content and the unit cell size reduction subsequent to the alkali metal removal steps. In other words, the 11 ultra-stable zeolite is identified both by the smaller 12 unit cell and the low alkali metal content in the crystal 13 structure.
14 The ultra-stable form of the Y zeolite can be prepared, for example, by successively base-exchanging a 16 Y zeolite, i.e., Y-type faujasite, with an aqueous solution 17 of an ammonium salt, such as ammonium nitrate, until the 18 alkali metal content of the Y zeolite is reduced to less 19 than about 4 wt. %, R20 (where R refers to an alkali metal such as sodium). The base-exchanged zeolite is 21 then calcined at a temperature of 1000F. to 1500F. over 22 a period of time ranging, for example, from 0.5 to 5 hours, 23 to produce an ultra-stable Y zeolite. If desired, steam 24 may be added to the system during the calcination.
Preferably, the ultra-stable Y zeolite is thereafter again 26 successively base-exchanged with an aqueous solution of 27 an ammonium salt until the alkali metal content is re-28 duced to less than 1 wt. % R20. More preferably, the 29 ultra-stable Y zeolite is then again calcined at a temp-erature of 1000 to 1500F. with added steam, if desired, 31 to produce an ultra-stable Y zeolite having a unit cell 32 size less than about 24.40 A. This sequence of ion ex-33 change and heat treatment results in the substantial reduc-34 tion of the alkali metal content of the original zeolite and results in unit cell shrinkage which are believed to 36 lead to the ultra high stability of the resultant Y zeo-37 lite. The particle size of these zeolites is usually in 38 the range of 0.1 - 10 microns, more typically in the 39 range 0.5 - 3 microns.
In a preferred embodiment, the ultra-stable Y-type zeolite component of the invention will be substantially free of rare earth metals such as, for example, cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gado-linium, terbium, dysprosium, holmium, erbium, yttrium, thulium, scandium, lutecium and mixtures thereof. By substantially free is meant that the rare earth metal content of the zeolite will be less than about 1 wt. ~ as metal oxide (~e2O3). Similarly, up to about 1 wt. ~ of other metal ions such as magnesium or calcium may be base exchanged into the zeolite.
The alumina component of the catalyst of the invention comprises discrete particles of various aluminas which are known and, in many instances, commercially available. These aluminas include the anhydrous and/or the hydrated forms. A rather comprehensive description of aluminas is given in "Encyclopedia of Chemical Technology", Kirk-Othmer, Second Edition, Volume 2 (Interscience Publishers) at pages 41-55.
Among the aluminas useful in preparing the catalyst of this invention are discrete alumina particles having a total surface area (B.E.T. method - Brunauer, Emmett and Teller;
The Van Nostrand Chemist's Dictionary (1953 Edition)) greater than 20 square meters per gram (m2/g), preferably greater than 145 m2/g, for example, 145 - 300 m2/g. Preferably the pore volume (B.E.T. method) of the alumina will be greater than 0.35 cc/g. The average particle size of the alumina will generally be less than 10 microns, more preferably less than 3 microns. These discrete alumina particles used in preparing the catalyst are sometimes designated as "bulk" alumina.
The term "bulk" is intended herein to designate an alumina which has been preformed and placed in a physical form such that its surface area and pore structure is stabilized so that when it is added to an impure inorganic gel containing considerable amounts of residual soluble salts, the salts will not alter the surface and pore characteristics measurably nor will they promote more than minimal chemical ,, 1 attack on the preformed alumina which could then under-2 go change. For example, addition of "bulki' alumina will 3 mean a material which has been formed by suitable chemical 4 xeaction, the slurry aged, filtered, dried, washed free of residual salts and then dried to reduce its volatile 6 contents to less than about 25 wt. %.
7 In addition to the above described bulk, 8 porous, preformed aluminas, it is also envisioned to pre-9 pare the catalyst by using hydrous slurries of diverse hydrated aluminas which may be a particular crystalline 11 form, or amorphous, or mixtures. These hydrates include 12 alpha-monohydrate, alpha-trihydrate, beta-trihydrate, and 13 to a lesser de~ree, beta-monohydrate forms of alumina.
14 These are generally made from solutions of aluminum salts or of alkaline aluminates. Depending on reaction condi-16 tions, the product aluminas can have a wide range of 17 physical properties. In addition to the foregoing, the 18 alumina slurry can be a gel. Alumina gels generally have 19 a dried solids content of about 2 - 12% by weight. On drying, the alumina gels lose water progressively and 21 with increasing temperatures the first transision phase 22 (nonhydrated) can be either eta- or gamma- alumina.
23 The presence of discrete particles of crystalline 24 alumina in the catalyst of this invention can be observed by x-ray diffraction in accordance with well known tech-26 niques such as described in Advances in X-Ray Diffractometry 27 and X-Ray Spectrographyedited by William Parrish (1962), 28 Centrex Published Company - Eindhoven.
29 The inorganic porous oxide which is used as the matrix in the catalyst composition of the invention 31 may include any of the readily available porous materials 32 such as alumina, silica, boria, chromia, magnesia, zir-33 conia, titania, silica-alumina, and the like, and mixtures 34 thereof. These materials may also include one or more of the various well known clays such as montmorillonite, 36 kaolin, halloysite, bentonite, and the like. Preferably, 37 the inorganic porous oxide will be one or more of the 38 conventional siliceous varieties containing a major amount 39 of silica and a minor amount of an oxide of at least one 1 metal in Croups II-A, III-A and IV-B of the Periodic 2 Table (Handbook of Chemistry and Physics, 38th Ed., 1957).
3 Representative silica-containing matrix materials include 4 silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-titania, silica-fllumina-zirconia, silica-6 alumina-magnesia, etc.
7 In a more preferred embodiment of the invention, 8 the inorganic porous oxide matrix material will be an 9 amorphous silica-alumina gel. As is generally known, these materials are typically prepared from silica hydro-11 gel or hydrosol, which is mixed with an alumina source, 12 generally an aluminum salt solution, to secure the desired 13 silica-alumina composition. The alumina content of the 14 silica-alumina matrix will typically range from about 5 to 40 wt. % with the preferred composition having an alumina 16 content of about 10 to 35 wt. %. Various procedures are 17 described in the literature for making silica-alumina, 18 e.g., U.S. Patent Nos. 2,908,635 and 2,844,523.
19 The catalyst composition of the invention will comprise 5 - 40 wt. %, preferably 10 - 30 wt. %, of the 21 aforedescribed ultra-stable Y zeolite; 5 - 40 wt. %, 22 preferably 10 - 30 wt. %, of alumina; and 40 - 90 wt. %, 23 prefersbly 50 - 80 wt. %, of the porous oxide matrix. It 24 is also within the scope of this invention to lncorporate in the catalyst other materials commonly employed in 26 cracking catalysts such as various zeolites, clays, metal 27 C0 oxidation promoters, etc.
28 In a preferred embodiment, the catalyst of the inven-29 - . Wei~ht % Na 0 on total catalyst tion will have the ratlo Weight % ze~lite in total catalyst 31 equal to or less than 0.013.
32 The catalysts of the present invention may be 33 prepared in accordance with well known techniques. For 34 example, a preferred method of preparing a catalyst of the invention is to react sodium silicate with a solution 36 of aluminum sulfate to form a silica-alumina hydrogel 37 slurry which is then aged under controlled conditions to 38 give the desired pore properties, filtered to remove a 39 considerable amount of the extraneous and undesired sodium and sulfate ions and then reslurried in water. Separately, 2 a bulk alumins is made, for example, by reacting solu-3 tions of sodium aluminate and aluminum sulfate, under 4 suitable conditions, aging the slurry to give the desired 5 pore properties of the alumina, filtering, drying, re-6 slurrying in water to remove sodium and sulfate ions and 7 drying to reduce volatile matter content to less than 25 8 weight percent. The alumina is then slurried in water and 9 blended, in proper amount, with the slurry of impure
10 silica-alumina hydrogel.
11 The ultra-stable Y zeolite of the invention may
12 then be added to this blend, with a sufficient amount of
13 each component of the catalyst being utilized to give the
14 desired final composition. If desired, the resulting mix-ture is filtered to remove a portion of the rem~ining ex-16 traneous soluble salts therefrom and to reduce the amount 17 of liquid present in the slurry. The filtered mixture is 18 then dried to produce dried solids. The dried solids are 19 subsequently reslurried in water and washed substantially free of the undesired soluble salts using a pH controlled 21 ammonium sulfate solution followed by a water rinse. The 22 catalyst may then be dried to a residual water content of 23 less than about 15 wt. %. Other methods for compositing 24 the components of the invention are known to those skilled in the art and are meant to be included within the scope 26 of this invention.
27 The feedstocks suitable for conversion in accor-28 dance with the invention include any of the well known 29 feeds conventionally employed in catalytic cracking pro-cesses. Usually, they will be petroleum derived, although 31 other sources such as shale oil, tar sands oil, and coal 32 are not to be excluded. Typical of such feeds are heavy 33 and light virgin gas oils, heavy and light virgin naphthas, 34 solvent extracted gas oils, coker gas oils, steam-cracked gas oils, cycle oils, residua, deasphalted residua, hydro-36 treated residua, topped crudes, etc. and mixtures thereof.
37 The catalyst of the invention may be employed 38 for the catalytic cracking of the aforementioned feedstocks 39 in accordance with well known techniques. In general, the g3 1 cracking conditions will include a temperature in the 2 range of about 850 to 1050F., l pressure of O to 50 3 psig. and a feed rate of 1 to 200 W/Hr/W. The catalyst 4 may be regenerated at conditions which include a tempera-ture in the range of 1100 to 1500F., preferably 1175 6 to 1350F.
8 The Figure is a graph illustrating the activity 9 and selectivity characteristics of various cracking cata-lysts which are compared and described in detail in the 11 examples hereinafter.
12 DESCRIPTION OF THE PREFERRED EMBODrMENTS
13 The following examples further illustrate the 14 present invention. Unless otherwise stated, all percentages refer to weight percentages.
16 Example 1 17 A catalyst of the invention was prepared as 18 follows:
19 A dilute sodium silicate solution containing 20 about 50 g. silica/liter was contacted with C02 to effect 21 gelation, the impure silica hydrosol aged and then blended 22 with a stream of aluminum sulfate. After filtering the 23 impure silica/alumina to remove some of the extraneous 24 soluble salts, the material had a dry solids content of
27 The feedstocks suitable for conversion in accor-28 dance with the invention include any of the well known 29 feeds conventionally employed in catalytic cracking pro-cesses. Usually, they will be petroleum derived, although 31 other sources such as shale oil, tar sands oil, and coal 32 are not to be excluded. Typical of such feeds are heavy 33 and light virgin gas oils, heavy and light virgin naphthas, 34 solvent extracted gas oils, coker gas oils, steam-cracked gas oils, cycle oils, residua, deasphalted residua, hydro-36 treated residua, topped crudes, etc. and mixtures thereof.
37 The catalyst of the invention may be employed 38 for the catalytic cracking of the aforementioned feedstocks 39 in accordance with well known techniques. In general, the g3 1 cracking conditions will include a temperature in the 2 range of about 850 to 1050F., l pressure of O to 50 3 psig. and a feed rate of 1 to 200 W/Hr/W. The catalyst 4 may be regenerated at conditions which include a tempera-ture in the range of 1100 to 1500F., preferably 1175 6 to 1350F.
8 The Figure is a graph illustrating the activity 9 and selectivity characteristics of various cracking cata-lysts which are compared and described in detail in the 11 examples hereinafter.
12 DESCRIPTION OF THE PREFERRED EMBODrMENTS
13 The following examples further illustrate the 14 present invention. Unless otherwise stated, all percentages refer to weight percentages.
16 Example 1 17 A catalyst of the invention was prepared as 18 follows:
19 A dilute sodium silicate solution containing 20 about 50 g. silica/liter was contacted with C02 to effect 21 gelation, the impure silica hydrosol aged and then blended 22 with a stream of aluminum sulfate. After filtering the 23 impure silica/alumina to remove some of the extraneous 24 soluble salts, the material had a dry solids content of
15.7% and the dry solids analyzed 57.3% SiO2 and 20.2%
26 A1203.
27 In a mixing tank, 35 pounds water were blended 28 with 98. 75 pounds of the above impure silica/alumina 29 hydrogel. In a second mixing tank, 15 pounds of water were blended with 1824 grams (dry basis) alumina (sold p~31 under the trade ~ Catapal HP grade by Conoco Chemical 32 Division of Continental Oil Company) and then with stirring 33 1824 grams (dry basis) of low soda content faujasite (sold 34 under the trade ~ Linde 33-200 grade by Union Carbide Corporation) blended therein. The composite slurry was 36 added to the gel slurry, homogenized by colloid milling 3 7 twice, and then spray dried.
38 The impure material was slurried in warm water 39 to about an 18 wt. % solids content and then filtered.
~ 9 3 1 The filter cake was treated with a 3 wt. % ammonium 2 sulfate solution brought to a pH of 8 with ammonia and 3 finally rinsed with ammoniated water (about 5 lb. solution 4 per lb. catalyst) to remove residual soluble salts and finally rinsed with water. The resultant catalyst had 6 an Na20 content of 0.17 wt. % and contained about 20%
7 ultra-stable Y zeolite,20% A1203 and 60% (SiO2/A1203) 8 and is designated "A" in subsequent examples.
9 Example 2 The catalyst of Example 1 was compared in activity 11 and selectivity for the production of high octane cat 12 naphthas with various cracking catalysts designated as 13 "B", "C" and "D" which are commercially avsilable or which 14 are representative of cracking catalysts presently employed in the petroleum industry.
26 A1203.
27 In a mixing tank, 35 pounds water were blended 28 with 98. 75 pounds of the above impure silica/alumina 29 hydrogel. In a second mixing tank, 15 pounds of water were blended with 1824 grams (dry basis) alumina (sold p~31 under the trade ~ Catapal HP grade by Conoco Chemical 32 Division of Continental Oil Company) and then with stirring 33 1824 grams (dry basis) of low soda content faujasite (sold 34 under the trade ~ Linde 33-200 grade by Union Carbide Corporation) blended therein. The composite slurry was 36 added to the gel slurry, homogenized by colloid milling 3 7 twice, and then spray dried.
38 The impure material was slurried in warm water 39 to about an 18 wt. % solids content and then filtered.
~ 9 3 1 The filter cake was treated with a 3 wt. % ammonium 2 sulfate solution brought to a pH of 8 with ammonia and 3 finally rinsed with ammoniated water (about 5 lb. solution 4 per lb. catalyst) to remove residual soluble salts and finally rinsed with water. The resultant catalyst had 6 an Na20 content of 0.17 wt. % and contained about 20%
7 ultra-stable Y zeolite,20% A1203 and 60% (SiO2/A1203) 8 and is designated "A" in subsequent examples.
9 Example 2 The catalyst of Example 1 was compared in activity 11 and selectivity for the production of high octane cat 12 naphthas with various cracking catalysts designated as 13 "B", "C" and "D" which are commercially avsilable or which 14 are representative of cracking catalysts presently employed in the petroleum industry.
16 Catalyst "B" is a widely used commercial catalyst
17 and contains about 14 - 16% faujasite (Y-type), about 28 -
18 30% kaolin clay and about 55 - 60% silica/alumina gel
19 matrix. The total catalyst contains about 2.8 - 3.5%
rare earths (as oxides). Catalyst "C" is a commercial 21 catalyst and consists of about 5% faujasite (Y-type) and 22 about 95% silica/alumina gel. The faujasite in "C" was 23 exchanged with mixed rare earths and calcined before 24 compositing with the matrix gel. Catalyst "C" contains about 1.0 - 1.2% rare earths (as oxides). Catalyst "D"
26 contains about 8 - 9% faujasite (Y-type) and about 91 -27 92% silica/alumina gel matrix. It is believed to contain 28 faujasite pre-exchanged with rare earths and calcined 29 before mixing with the matrix. Catalyst "D" analyzes about 1.8 - 2.2% rare earths (as oxides). Thus the 31 catalysts of comparison in the following example contain 32 from 5 - 16% faujasite (Y-type), from 1.0 - 3.5% rare 33 earths (as oxides), and a matrix of silica/alumina gel 34 with or without added bulk kaolin. These catalysts are compared in cracking performance with the catalyst of the 36 invention "A" in Example 3 hereof. Each of these catalysts 37 compared in Example 3 were steamed for 16 hours at 1400F.
38 and 0 psig. to simulate commercial deactivation before 39 testing.
11~1193 1 Example 3 2 Each of the catalysts described in the previous 3 two examples were tested under conditions listed below in 4 a circulating, fluidized bed cat,alytic cracking unit with reactor and regenerator vessels. The feed used for these 6 experiments is described in Table I. The results of these 7 experiments are listed in Table II.
9 Feed Gravity 27.5 API
11 Sulfur .812 wt. 70 12 Nitrogen 618 ppm 13 Conradson Carbon 0.27 wt. %
14 Aniline Point 171F.
Distillation Range*, C.
16 rBP/5% 249/263 17 10/20% 276/298 18 30/40% 317/341 19 50/60% 366/382 70/80% 416/441 21 90/95% 475/504 23 * Atmospheric Pressure . .
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~ 0 ~ ~C ~ CO ~ ~ ~ 0~ 0 P' ~ ~ ~; ~ ~;t C
JJ ~ 0 4 0 ~ C ~ ~ P~
g ~ g g ., :' 1 The relative activities and octane producibilities 2 of the catalysts tested in this example are shown in the 3 figure wherein octane producibil:ity as measured by 1/2 4 (RONC + MONC) is plotted against catalyst activity as mea-sured by volume percent conversion at the same cracking 6 conditions. In general, it is seen from the figure that 7 catalyst octane producibility is greater for state of the 8 art catalysts having lower actlvity and vice versa. Un-9 expectedly, however, the catalyst of this invention was found to have much higher octane producibility for its 11 activity than prior art catalysts. At the same time, its 12 selectivity for naphtha as measured by volume percent 13 naphtha as a fraction of 430F. conversion yield was found 14 to be equivalent to the prior art catalysts. In fact, when the potential aLkylate (i.e., propylenes and butylenes 16 yields) produced by all catalysts was considered, the 17 potential gssoline selectivity (cat naphtha plus potential 18 alkylate per unit of conversion) of catalyst A was somewhat 19 better than the state of the art catalysts. This is shown by Table III.
22 Catalyst A B C D
23 C /430F. Naphtha .89 .89 .90 .88 24 5Selectivity C /430F. Naphtha + 1.21 1.18 1.20 1.18 26 5Alkylate Selectivity 27 ExamPle 4 28 Another catalyst of this invention was prepared 29 as follows:
(a) 22 pounds of faujasite (sold under the trade 31 name Linde T7-Y52 grade by Union Carbide Corporation) were 32 slurried into 100 pounds of water at 135F. In a 33 separate vessel, 9 pounds of ammonium sulfate were dis-34 solved in 50 pounds of water, followed by the addition of 200 cc H2S04. The acidified ammonium sulfate solution 36 was then added to the faujasite slurry and the mixture 37 heated to 135F. and stirred for 2 hours. The slurry, 38 which had a pH of 4.5, was then filtered, rinsed with 1 hot water and oven dried at about 225F. for 16 hours.
2 (b) The oven dried material from step (a) was 3 placed in shallow trays and heated in a furnace preheated 4 at 1250F. in an atmosphere of flowing steam. The faujasite was calcined 1 hour at 1250F. and the furnace cooled to 6 500F. in flowing steam before removing. The calcined 7 material had a Na20 content of 5.7% and a unit cell size 8 of 24.62A.
9 (c) The calcined faujasite zeolite from step (b) was re-treated as described above in step (a). After 11 oven drying, the faujasite was calcined 1 hour at 900F.
12 in ambient air. After cooling, the resultant faujasite 13 had a Na20 content of 2.15% and a unit cell size of 24.50A.
14 It is a stabilized low soda content faujasite (zeolite Y).
(d) In a mixing tank, 40 pounds of water were 16 slurried with 80 pounds of impure silica-alumina hydrogel 17 prepared in the manner of Example 1 (11.3% catalytic solids 18 dry basis). In a second mixing tank, 25 pounds of water 19 were slurried with 1850 grams (1360 grams dry basis) of a commercial grade alumina. A portion of the alumina was 21 previously calcined at 1000F. for 6 hours and had a sur-22 face area (BET) of 523 M2/g and a pore volume of 1.08 23 cc/gram with a pore volume of 0.21 cc/gram in pores having 24 diameters in the range of 90 - 200A. To this alumina slurry was added 1648 grams (1360 grams dry basis) of 26 the calcined stabilized faujasite from step (c) above 27 after ball milling in ambient air. The slurries were 28 combined and then spray dried at about 250F. The com-29 posite material was washed free of extraneous soluble salts, filtered, rinsed and dried as described hereinabove 31 in Example 1. The resultant catalyst contained 0.24%
32 Na20 and comprised about 20% ultra-stable Y zeolite, 20%
33 alumina, and 60% silica-alumina gel. It is designated as 34 catalyst "E" in subsequent examples.
Example 5 36 This example illustrates the preparation of a 37 preferred catalyst of the invention.
38 (a) A portion of the stabilized zeolite Y from 39 step (c) of Example 4 above was placed in a dish and ~131~'93 1 charged to a furnace at 1000F. The temperature was2 raised to 1500F., held there for 1 hour, and then allowed 3 to cool. The material analyzed 2.15V/o Na20 and had a unit 4 cell size of 24.38A. The heat treatment reduced the cell size from 24.50A to 24.38A.
6 (b) 3.0 pounds (dry basis) of the calcined, 7 stabilized faujasite from step (a) of this Example were 8 then slurried in 20 pounds of water. This was followed 9 by the addition of 3.0 pounds (dry basis) of the alumina from Example 4. The mixed slurry was then blended with 11 9.0 pounds (dry catalytic solids basis) of the impure 12 silica-alumina hydrogel of Example 4, spray dried, and 13 washed free of extraneous soluble salts in the manner of 14 Example 4. The total composite catalyst, designated "F", had a composition of about 20% precalcined ultra-stable 16 Y zeolite, 20% A1203, and 60% silica-alumina gel. It 17 analyzed 0.23% Na20 and 0.46% sulfate.
18 Example 6 l9 The catalyst of this example is a catalyst of this invention. It was made as follows:
21 (a) Commercially available stabilized low soda 22 content faujasite (sold under the trade ~ e of Linde LZ-23 Y82 grade by Union Carbide Corporation) having a dry solids 24 content of 80.3%, a soda content of 0.12% as Na20, a SiO2/A1203 mol ratio of 5.5 and a unit cell size of 24.5L~
26 was ball milled and 3.0 pounds ~dry basis) thereof slurried 27 in 20 pounds of water. To this slurry were added 3.0 28 pounds (dry basis) of the alumina described in Example 4 29 above.
(b) In a separate mixing tank, 40 pounds of water 31 were slurried with 71.0 pounds of the impure silica-alumina 32 hydrogel described in Example 1 (equivalent to 9.0 lbs.
33 catalytic solids). The slurry prepared in step (a) of 34 this Example was then added with mixing to the slurry of silica-alumina hydrogel. The composite slurry was then 36 colloid milled, spray dried, washed free of extraneous 37 soluble salts, and dried in the manner of Example 1. The 38 catalyst analyzed 0.08% Na20 and 0.11% S04 and had a 39 composition of about 20% ultra-stable Y zeolite, 20%
1131~93 1 alumina, and 60% silica-alumina gel. It is designated 2 "G" in subsequent examples.
3 Example 7 4 The catalyst of this example is another catalyst of the inventlon. It was made as follows:
6 (a) The stabilized, low soda content Y zeolite 7 as described in Example 6 above was placed in a dish and 8 charged to a furnace at 1000F. The temperature was 9 raised to 1500F. and held for 1 hour and then allowed to cool. The material was discharged from the furnace below 11 1000F. This precalcined ultra-stable faujasite had a 12 unit cell size of 24.34~ compared to 24.5LA before this 13 calcination step.
14 (b) In a mixing tank, 40 pounds of water were slurried with 71.0 pounds of the impure silica-alumina 16 hydrogel (equivalent to 9.0 pounds catalytic solids) 17 described in Example 1 above. In a second mixing tank, 18 20 pounds of water were slurried with 1400 grams of ball 19 milled precalcined faujasite (3.0 pounds dry basis) from step (a) of this Example. To this slurry were added 3.0 21 pounds (dry basis) of the ball milled alumina of Example 22 4.
23 (c) The slurries from step ~b) of this Example 24 were combined, colloid milled, spray dried, washed free of extraneous salts, and dried in the manner of Example 1.
26 The resultant catalyst is designated "H" and contains 27 0.07% Na20 and 0.40% S04. Catalyst "H" has a composition 28 of 20% precalcined ultra-stable zeolite Y, 20% alumina 29 and 60% silica-alumina gel.
Example 8 31 Catalysts "B", "E", "F", "G" and "H" were each 32 calcined 6 hours at 1000F. and then steamed at 1400F.
33 for 16 hours and 0 psig steam pressure to simulate commer-34 cial equilibrium cracking catalyst performance. The catalysts were then each evaluated for cracking performance 36 in a full cycle cracking operation. The unit employed is 37 a circulating, fluidized cat cracking unit with a regen-38 erator and reactor/stripper vessels. The temperatures in 39 the reactor and regenerator were 925F. and 1105F., 1 respectively. The feed stock was a 450/1100F. vacuum 2 g8S oil described below in Table IV. The unit was oper-3 ated at a catalyst to oil weight ratio of 4.0, a pressure 4 of 0 psig. The results given below in Table V compare the catalysts at constant 70 vol.ume % conversion.
Feed 8 Gravity 22.9 API
9 Sulfur 1.245 wt. %
Nitrogen 705 ppm 11 Conradson Carbon 0.43 wt. %
12 Aniline Point 183.5F.
13 Distillation Ran~e*, C.
14 IBP/5% 298i334 10/20% 349/378 16 30/40% 395/412 17 50/60% 432/457 18 70/80% 482/499 19 90/95% 523/543 21 * Atmospheric pressure :
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rare earths (as oxides). Catalyst "C" is a commercial 21 catalyst and consists of about 5% faujasite (Y-type) and 22 about 95% silica/alumina gel. The faujasite in "C" was 23 exchanged with mixed rare earths and calcined before 24 compositing with the matrix gel. Catalyst "C" contains about 1.0 - 1.2% rare earths (as oxides). Catalyst "D"
26 contains about 8 - 9% faujasite (Y-type) and about 91 -27 92% silica/alumina gel matrix. It is believed to contain 28 faujasite pre-exchanged with rare earths and calcined 29 before mixing with the matrix. Catalyst "D" analyzes about 1.8 - 2.2% rare earths (as oxides). Thus the 31 catalysts of comparison in the following example contain 32 from 5 - 16% faujasite (Y-type), from 1.0 - 3.5% rare 33 earths (as oxides), and a matrix of silica/alumina gel 34 with or without added bulk kaolin. These catalysts are compared in cracking performance with the catalyst of the 36 invention "A" in Example 3 hereof. Each of these catalysts 37 compared in Example 3 were steamed for 16 hours at 1400F.
38 and 0 psig. to simulate commercial deactivation before 39 testing.
11~1193 1 Example 3 2 Each of the catalysts described in the previous 3 two examples were tested under conditions listed below in 4 a circulating, fluidized bed cat,alytic cracking unit with reactor and regenerator vessels. The feed used for these 6 experiments is described in Table I. The results of these 7 experiments are listed in Table II.
9 Feed Gravity 27.5 API
11 Sulfur .812 wt. 70 12 Nitrogen 618 ppm 13 Conradson Carbon 0.27 wt. %
14 Aniline Point 171F.
Distillation Range*, C.
16 rBP/5% 249/263 17 10/20% 276/298 18 30/40% 317/341 19 50/60% 366/382 70/80% 416/441 21 90/95% 475/504 23 * Atmospheric Pressure . .
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g ~ g g ., :' 1 The relative activities and octane producibilities 2 of the catalysts tested in this example are shown in the 3 figure wherein octane producibil:ity as measured by 1/2 4 (RONC + MONC) is plotted against catalyst activity as mea-sured by volume percent conversion at the same cracking 6 conditions. In general, it is seen from the figure that 7 catalyst octane producibility is greater for state of the 8 art catalysts having lower actlvity and vice versa. Un-9 expectedly, however, the catalyst of this invention was found to have much higher octane producibility for its 11 activity than prior art catalysts. At the same time, its 12 selectivity for naphtha as measured by volume percent 13 naphtha as a fraction of 430F. conversion yield was found 14 to be equivalent to the prior art catalysts. In fact, when the potential aLkylate (i.e., propylenes and butylenes 16 yields) produced by all catalysts was considered, the 17 potential gssoline selectivity (cat naphtha plus potential 18 alkylate per unit of conversion) of catalyst A was somewhat 19 better than the state of the art catalysts. This is shown by Table III.
22 Catalyst A B C D
23 C /430F. Naphtha .89 .89 .90 .88 24 5Selectivity C /430F. Naphtha + 1.21 1.18 1.20 1.18 26 5Alkylate Selectivity 27 ExamPle 4 28 Another catalyst of this invention was prepared 29 as follows:
(a) 22 pounds of faujasite (sold under the trade 31 name Linde T7-Y52 grade by Union Carbide Corporation) were 32 slurried into 100 pounds of water at 135F. In a 33 separate vessel, 9 pounds of ammonium sulfate were dis-34 solved in 50 pounds of water, followed by the addition of 200 cc H2S04. The acidified ammonium sulfate solution 36 was then added to the faujasite slurry and the mixture 37 heated to 135F. and stirred for 2 hours. The slurry, 38 which had a pH of 4.5, was then filtered, rinsed with 1 hot water and oven dried at about 225F. for 16 hours.
2 (b) The oven dried material from step (a) was 3 placed in shallow trays and heated in a furnace preheated 4 at 1250F. in an atmosphere of flowing steam. The faujasite was calcined 1 hour at 1250F. and the furnace cooled to 6 500F. in flowing steam before removing. The calcined 7 material had a Na20 content of 5.7% and a unit cell size 8 of 24.62A.
9 (c) The calcined faujasite zeolite from step (b) was re-treated as described above in step (a). After 11 oven drying, the faujasite was calcined 1 hour at 900F.
12 in ambient air. After cooling, the resultant faujasite 13 had a Na20 content of 2.15% and a unit cell size of 24.50A.
14 It is a stabilized low soda content faujasite (zeolite Y).
(d) In a mixing tank, 40 pounds of water were 16 slurried with 80 pounds of impure silica-alumina hydrogel 17 prepared in the manner of Example 1 (11.3% catalytic solids 18 dry basis). In a second mixing tank, 25 pounds of water 19 were slurried with 1850 grams (1360 grams dry basis) of a commercial grade alumina. A portion of the alumina was 21 previously calcined at 1000F. for 6 hours and had a sur-22 face area (BET) of 523 M2/g and a pore volume of 1.08 23 cc/gram with a pore volume of 0.21 cc/gram in pores having 24 diameters in the range of 90 - 200A. To this alumina slurry was added 1648 grams (1360 grams dry basis) of 26 the calcined stabilized faujasite from step (c) above 27 after ball milling in ambient air. The slurries were 28 combined and then spray dried at about 250F. The com-29 posite material was washed free of extraneous soluble salts, filtered, rinsed and dried as described hereinabove 31 in Example 1. The resultant catalyst contained 0.24%
32 Na20 and comprised about 20% ultra-stable Y zeolite, 20%
33 alumina, and 60% silica-alumina gel. It is designated as 34 catalyst "E" in subsequent examples.
Example 5 36 This example illustrates the preparation of a 37 preferred catalyst of the invention.
38 (a) A portion of the stabilized zeolite Y from 39 step (c) of Example 4 above was placed in a dish and ~131~'93 1 charged to a furnace at 1000F. The temperature was2 raised to 1500F., held there for 1 hour, and then allowed 3 to cool. The material analyzed 2.15V/o Na20 and had a unit 4 cell size of 24.38A. The heat treatment reduced the cell size from 24.50A to 24.38A.
6 (b) 3.0 pounds (dry basis) of the calcined, 7 stabilized faujasite from step (a) of this Example were 8 then slurried in 20 pounds of water. This was followed 9 by the addition of 3.0 pounds (dry basis) of the alumina from Example 4. The mixed slurry was then blended with 11 9.0 pounds (dry catalytic solids basis) of the impure 12 silica-alumina hydrogel of Example 4, spray dried, and 13 washed free of extraneous soluble salts in the manner of 14 Example 4. The total composite catalyst, designated "F", had a composition of about 20% precalcined ultra-stable 16 Y zeolite, 20% A1203, and 60% silica-alumina gel. It 17 analyzed 0.23% Na20 and 0.46% sulfate.
18 Example 6 l9 The catalyst of this example is a catalyst of this invention. It was made as follows:
21 (a) Commercially available stabilized low soda 22 content faujasite (sold under the trade ~ e of Linde LZ-23 Y82 grade by Union Carbide Corporation) having a dry solids 24 content of 80.3%, a soda content of 0.12% as Na20, a SiO2/A1203 mol ratio of 5.5 and a unit cell size of 24.5L~
26 was ball milled and 3.0 pounds ~dry basis) thereof slurried 27 in 20 pounds of water. To this slurry were added 3.0 28 pounds (dry basis) of the alumina described in Example 4 29 above.
(b) In a separate mixing tank, 40 pounds of water 31 were slurried with 71.0 pounds of the impure silica-alumina 32 hydrogel described in Example 1 (equivalent to 9.0 lbs.
33 catalytic solids). The slurry prepared in step (a) of 34 this Example was then added with mixing to the slurry of silica-alumina hydrogel. The composite slurry was then 36 colloid milled, spray dried, washed free of extraneous 37 soluble salts, and dried in the manner of Example 1. The 38 catalyst analyzed 0.08% Na20 and 0.11% S04 and had a 39 composition of about 20% ultra-stable Y zeolite, 20%
1131~93 1 alumina, and 60% silica-alumina gel. It is designated 2 "G" in subsequent examples.
3 Example 7 4 The catalyst of this example is another catalyst of the inventlon. It was made as follows:
6 (a) The stabilized, low soda content Y zeolite 7 as described in Example 6 above was placed in a dish and 8 charged to a furnace at 1000F. The temperature was 9 raised to 1500F. and held for 1 hour and then allowed to cool. The material was discharged from the furnace below 11 1000F. This precalcined ultra-stable faujasite had a 12 unit cell size of 24.34~ compared to 24.5LA before this 13 calcination step.
14 (b) In a mixing tank, 40 pounds of water were slurried with 71.0 pounds of the impure silica-alumina 16 hydrogel (equivalent to 9.0 pounds catalytic solids) 17 described in Example 1 above. In a second mixing tank, 18 20 pounds of water were slurried with 1400 grams of ball 19 milled precalcined faujasite (3.0 pounds dry basis) from step (a) of this Example. To this slurry were added 3.0 21 pounds (dry basis) of the ball milled alumina of Example 22 4.
23 (c) The slurries from step ~b) of this Example 24 were combined, colloid milled, spray dried, washed free of extraneous salts, and dried in the manner of Example 1.
26 The resultant catalyst is designated "H" and contains 27 0.07% Na20 and 0.40% S04. Catalyst "H" has a composition 28 of 20% precalcined ultra-stable zeolite Y, 20% alumina 29 and 60% silica-alumina gel.
Example 8 31 Catalysts "B", "E", "F", "G" and "H" were each 32 calcined 6 hours at 1000F. and then steamed at 1400F.
33 for 16 hours and 0 psig steam pressure to simulate commer-34 cial equilibrium cracking catalyst performance. The catalysts were then each evaluated for cracking performance 36 in a full cycle cracking operation. The unit employed is 37 a circulating, fluidized cat cracking unit with a regen-38 erator and reactor/stripper vessels. The temperatures in 39 the reactor and regenerator were 925F. and 1105F., 1 respectively. The feed stock was a 450/1100F. vacuum 2 g8S oil described below in Table IV. The unit was oper-3 ated at a catalyst to oil weight ratio of 4.0, a pressure 4 of 0 psig. The results given below in Table V compare the catalysts at constant 70 vol.ume % conversion.
Feed 8 Gravity 22.9 API
9 Sulfur 1.245 wt. %
Nitrogen 705 ppm 11 Conradson Carbon 0.43 wt. %
12 Aniline Point 183.5F.
13 Distillation Ran~e*, C.
14 IBP/5% 298i334 10/20% 349/378 16 30/40% 395/412 17 50/60% 432/457 18 70/80% 482/499 19 90/95% 523/543 21 * Atmospheric pressure :
o 0 ~ ~ ~ o ~ ~ ~o :S: ~i r~ ~ ~~O ~
0..o. ~
o oo ~C~l~ ~ ~ o ,`
~1 ~ a~
O C`l --IO~ ~1 ~o ~1 ~ r~
~, ,~ ~ ~ . o ~
' :, ~ ~ _I 0 0 ~ ~ ` o C`~ O 1~
0_1 0 0 ~'~ 0 a~ o ~o ~ ~u~ ~ O o~
`D ~i ~ l~ 0 ~ 0 _~ o 3 g ~ ~ g e c~ ~
^ ~ ê ~5 ~ o z; t~ o ~ ~ ~ J' O ~ ~ 3 ~C~ _I ~ ~ s~
u ~ ~ 0~ ~ + ~ ~) o o o ~ 0 ~ z _~
1 1 3 ~ 3
- 20 -1 The data show that catalysts E, F, G and H all 2 show significant increases in octane nu~bers of the 3 cracked naphtha over reference catalyst B. Catalysts F
4 and H of this invention show increased octanes over catalysts E and G, due to the precalcining treatment 6 given the ultra-stable Y zeolite to reduce the unit cell 7 size to 24.38~ and lower.
4 and H of this invention show increased octanes over catalysts E and G, due to the precalcining treatment 6 given the ultra-stable Y zeolite to reduce the unit cell 7 size to 24.38~ and lower.
Claims (11)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A cracking catalyst composition characterized by comprising discrete particles of ultra-stable Y zeolite and dis-crete particles of alumina dispersed in a porous oxide matrix, said catalyst comprising 5 - 40 wt. % ultra-stable Y zeolite, 5 -40 wt. % alumina and 40 - 90 wt. % of porous oxide matrix.
2. A cracking catalyst composition according to claim 1 further characterized in that the said porous oxide matrix comprises silica.
3. A cracking catalyst composition according to claim 1 further characterized in that the said porous oxide matrix comprises silica-alumina gel.
4. A cracking catalyst composition according to any one of claims 1-3 further characterized in that the said alumina comprises alumina gel.
5. A cracking catalyst composition according to any one of claims 1-3 further characterized in that the said ultra-stable Y zeolite has a unit cell size of less than 24.40 .ANG..
6. A cracking catalyst composition according to any one of claims 1-3 further characterized in that the said ultra-stable Y zeolite contains less than 1% rare earth metal oxides (Re2O3 ).
7. A cracking catalyst composition according to any one of claims 1-3 said ultra-stable Y zeolite contains less than 1 wt. % NA2O.
8. A cracking catalyst composition according to any one of claims 1-3 further characterized by having the ratio weight percent Na2O on total catalyst/weight percent zeolite in total catalyst equal to or less than 0.013.
9. A method for preparing the cracking catalyst com-position of claim 1 characterized by the following steps in combination:
(1) forming an aqueous slurry mixture containing (a) said porous oxide, (b) said particles of alumina, and (c) said particles of ultra-stable Y zeolite;
(2) drying said mixture to form a catalyst composite comprising said discrete particles of ultra-stable Y zeolite and said discrete particles of alumina which are dispersed in said porous oxide matrix;
(3) washing said catalyst composite to remove extran-eous salts soluble in an aqueous ammonium salt solution; and (4) drying the washed catalyst composite to reduce the moisture content thereof below 15 wt. %.
(1) forming an aqueous slurry mixture containing (a) said porous oxide, (b) said particles of alumina, and (c) said particles of ultra-stable Y zeolite;
(2) drying said mixture to form a catalyst composite comprising said discrete particles of ultra-stable Y zeolite and said discrete particles of alumina which are dispersed in said porous oxide matrix;
(3) washing said catalyst composite to remove extran-eous salts soluble in an aqueous ammonium salt solution; and (4) drying the washed catalyst composite to reduce the moisture content thereof below 15 wt. %.
10. A method according to claim 9 further characterized in that the said catalyst composite is successively washed in step (3) thereof with an ammonium salt solution and water.
11. A process for the catalytic cracking of a hydrocar-bon feedstock characterized by contacting said feedstock under catalytic cracking conditions with the catalyst composition of any one of claims 1-3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US91348078A | 1978-06-07 | 1978-06-07 | |
| US913,480 | 1978-06-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1131193A true CA1131193A (en) | 1982-09-07 |
Family
ID=25433311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA329,201A Expired CA1131193A (en) | 1978-06-07 | 1979-06-06 | Octane improvement cracking catalyst |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS54161593A (en) |
| BE (1) | BE876820A (en) |
| BR (1) | BR7903584A (en) |
| CA (1) | CA1131193A (en) |
| DE (1) | DE2923117A1 (en) |
| FR (1) | FR2427843B1 (en) |
| GB (1) | GB2022439B (en) |
| IT (1) | IT1121278B (en) |
| MX (1) | MX5819E (en) |
| NL (1) | NL188395B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4339354A (en) * | 1980-10-10 | 1982-07-13 | Exxon Research & Engineering Co. | Hydrocarbon conversion catalysts |
| CA1171055A (en) * | 1980-10-10 | 1984-07-17 | Lloyd A. Pine | Hydrocarbon conversion catalysts and processes utilizing the same |
| US4440868A (en) * | 1981-12-07 | 1984-04-03 | Ashland Oil, Inc. | Carbo-metallic oil conversion catalysts |
| FR2521155B1 (en) * | 1982-02-08 | 1986-04-18 | Engelhard Corp | PROCESS FOR THE MANUFACTURE OF HIGH-INDEX OCTANE GASOLINE USING A CATALYTIC CRACKING UNIT |
| US4636484A (en) * | 1983-09-22 | 1987-01-13 | Catalysts & Chemicals Industries Co., Ltd. | Method for the preparation of catalyst composition for use in cracking hydrocarbons |
| WO1985001740A1 (en) * | 1983-10-20 | 1985-04-25 | Total Engineering And Research Company | A method for catalytically converting residual oils |
| FR2582665B1 (en) * | 1985-06-04 | 1988-08-05 | Inst Francais Du Petrole | CATALYTIC CRACKING PROCESS |
| US4762537A (en) * | 1985-11-07 | 1988-08-09 | Aluminum Company Of America | Adsorbent for HCl comprising alumina and acid-treated Y zeolite |
| FR2673385B1 (en) * | 1991-03-01 | 1994-07-22 | Inst Francais Du Petrole | CATALYST FOR CRACKING HYDROCARBON FILLERS RICH IN NAPHTHENIC COMPOUNDS AND / OR PARAFFINS COMPRISING A Y ZEOLITE AND A MATRIX. |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3816342A (en) * | 1963-05-14 | 1974-06-11 | Mobil Oil Corp | Process for preparing a crystalline aluminosilicate zeolite |
| US3425956A (en) * | 1964-03-26 | 1969-02-04 | Grace W R & Co | Process for preparing molecular sieve containing cracking catalysts |
| 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 |
| US3542670A (en) * | 1965-05-21 | 1970-11-24 | Sinclair Research Inc | Catalyst comprising silica-alumina,separate phase alumina and crystalline alumino silicate |
| CA983464A (en) * | 1970-03-26 | 1976-02-10 | Hanson L. Guidry | Zeolite promoted hydrocarbon conversion catalysts |
| CA984368A (en) * | 1971-10-08 | 1976-02-24 | W.R. Grace And Co. | Hydrocarbon cracking catalyst |
| US4036739A (en) * | 1971-10-20 | 1977-07-19 | Union Oil Company Of America | Catalytic cracking process using ammonia-stable zeolite catalyst |
| JPS563148B2 (en) * | 1973-08-13 | 1981-01-23 | ||
| US4072600A (en) * | 1974-02-08 | 1978-02-07 | Mobil Oil Corporation | Catalytic cracking process |
| US3994800A (en) * | 1975-02-19 | 1976-11-30 | W. R. Grace & Co. | Catalytic cracking with catalyst of improved Y zeolite |
-
1979
- 1979-06-05 FR FR7914347A patent/FR2427843B1/en not_active Expired
- 1979-06-06 CA CA329,201A patent/CA1131193A/en not_active Expired
- 1979-06-06 IT IT23334/79A patent/IT1121278B/en active
- 1979-06-06 BR BR7903584A patent/BR7903584A/en not_active IP Right Cessation
- 1979-06-07 DE DE19792923117 patent/DE2923117A1/en active Granted
- 1979-06-07 BE BE2/57854A patent/BE876820A/en not_active IP Right Cessation
- 1979-06-07 MX MX798055U patent/MX5819E/en unknown
- 1979-06-07 GB GB7919862A patent/GB2022439B/en not_active Expired
- 1979-06-07 JP JP7216979A patent/JPS54161593A/en active Granted
- 1979-06-07 NL NLAANVRAGE7904493,A patent/NL188395B/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| GB2022439B (en) | 1983-05-18 |
| NL188395B (en) | 1992-01-16 |
| DE2923117C2 (en) | 1991-01-31 |
| BE876820A (en) | 1979-12-07 |
| MX5819E (en) | 1984-07-27 |
| IT1121278B (en) | 1986-04-02 |
| IT7923334A0 (en) | 1979-06-06 |
| GB2022439A (en) | 1979-12-19 |
| JPS54161593A (en) | 1979-12-21 |
| DE2923117A1 (en) | 1979-12-13 |
| FR2427843B1 (en) | 1987-09-18 |
| JPS6128376B2 (en) | 1986-06-30 |
| BR7903584A (en) | 1980-01-22 |
| FR2427843A1 (en) | 1980-01-04 |
| NL7904493A (en) | 1979-12-11 |
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