JPS6128376B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to catalyst compositions and their use in catalytic cracking processes. More particularly, this invention relates to fluid cracking catalysts with improved activity and selectivity for producing high octane gasoline fractions from petroleum gas oil feedstocks. As is well known, catalytic cracking of heavy petroleum fractions is one of the major refining operations used to convert crude oil into desired fuel products such as kerosene and high octane gasoline. An example of a "fluid" catalytic conversion process is fluid catalytic cracking. In this process, suitably preheated high molecular weight hydrocarbon liquids and vapors are contacted with hot fine solid catalyst particles in a fluidized bed reactor or an elongated riser reactor to form suitable gasoline fractions in a fluidized or dispersed state. The elevated temperature is maintained long enough to achieve the desired degree of cracking to yield low molecular weight hydrocarbons. A wide variety of petroleum cracking catalysts are described in the literature and commercially available for use in fluid cracking processes. Industrial cracking catalysts currently in use generally contain a crystalline aluminosilicate zeolite cracking component in combination with an inorganic oxide matrix component. Typical zeolites in combination with inorganic oxide matrices include hydrogen and/or rare earth metal exchanged synthetic haujasites (X or Y types).
The matrix material generally includes an amorphous silica alumina gel and/or a clay material such as kaolin. Cracking catalysts used industrially in the production of gasoline must have good activity and selectivity. The activity of a catalyst is commonly referred to as the catalyst's ability to convert heavy petroleum fractions to lower molecular weight fractions. Under given operating conditions, the extent to which a catalyst converts feedstock to low molecular weight materials is a measure of catalyst activity. Thus, two or more catalysts can have activities that are compared by the degree of cracking product produced by each catalyst under the same process conditions. Catalyst selectivity refers to a particular or molecular weight range, such as a fraction of cracking products such as C ₅ /430〓 (221° C.) naphtha, C ₃ carbon gas, carbon, etc. A more specific guideline for selectivity is C ₅ /(430
〓) It is the octane rate of naphtha (hereinafter referred to as octane productivity). However, what is most desirable for a preferred cracking catalyst are high cracking activity, high selectivity to gasoline ( _C5 /430〓) boiling range materials and high octanization productivity (purifying gasoline boiling range materials with high octane percentages). It is to demonstrate the ability to Unfortunately, catalysts with very high activity do not produce very high octane naphtha products, and vice versa. As an example, amorphous silica-alumina cracking catalysts used prior to the advent of today's zeolite cracking catalysts were less active than current gas oil feedstock cracking zeolite catalysts and were used for _C5 /430 naphtha refining. Purifies octanized naphtha with lower but higher selectivity than conventional zeolite cracking catalysts. The components of the catalyst composition of the present invention are described in the literature. It is believed that the special combination of components of the present invention to produce a catalyst with high activity and selectivity for the production of high octane gasoline has not been demonstrated in the prior art. For example, U.S. Pat.
No. 3,312,615 describes an acid group catalyst system comprising a crystalline aluminosilicate, a substantially inert fine powder, and an inorganic oxide matrix therefor. Crystalline aluminosilicates can be found in a wide variety of zeolites, such as zeolites X, Y, A, L, D, R,
S, T, Z, E, F, Q, B, ZK-4, ZK-5
These include natural zeolites such as chiabazite, hojiasite, mordenite, etc. Substantially inert fine powders include alpha alumina, barites,
Contains zircon, zirconia, canite, and luteil fine powder. U.S. Pat. No. 3,542,670 discloses a contact structure that combines a silica-alumina hydrogel with a boehmite amorphous hydrated hydras alumina and a crystalline aluminosilicate (having pores in the 8-15 Å range and a silica to alumina molar ratio greater than 3:1). Describes cracking catalysts. Crystalline aluminosilicates include various zeolites that have been exchanged with various ions such as hydrogen and non-toxic metals such as rare earth metals. U.S. Pat. No. 3,816,342 is directed to a method for making a fluid catalytic cracking catalyst containing a highly active crystalline aluminosilicate and a relatively less active matrix material. The patentee of the same patent proposed the general formula in the salt state: M _2/o OAl ₂ O ₃ YSiO ₂ ×ZH ₂ O (n is the valence of the metal cation M, Y is the number of moles of silica, and _ZH2O is water of hydration)
A patent is claimed for a crystalline aluminosilicate material having the following properties: Zeolites Y and X are described as belonging to the most suitable synthetic crystalline aluminosilicates. As matrix materials, inorganic oxide gels such as silica-zirconia, alumina, magnesia and their combinations with each other and with clays, alumina, metals and refractory substances are mentioned. U.S. Pat. No. 3,930,987 describes a catalytic cracking catalyst comprising a composite of crystalline aluminosilicate containing rare earth metal cations dispersed in an inorganic oxide matrix (at least 50% by weight of the inorganic oxide is silica). and/or alumina). The matrix is preferably made from silica-alumina, silica-zirconia, or silica-zirconia alumina, preferably in the presence of a weighting agent, preferably clay and/or alumina. If alumina is used, alpha alumina is preferred. U.S. Pat. No. 3,717,587 describes a method for making cracking catalyst compositions containing a wide variety of crystalline aluminosilicates dispersed in an inorganic oxide gel matrix containing a weighting agent. This patent specifically states that the most preferred weighting agent is kaolin clay. Other suitable weighting agents include zirconia, alpha alumina, mullite, alumina monohydrate, alumina trihydrate, halloysite, sand, and metals such as aluminum and titanium. U.S. Pat. No. 3,788,977 relates to a cracking catalyst for increasing the amount of aromatic gasoline groups from gas oil feedstocks. As cracking catalysts, compositions containing a number of zeolite components in combination with small amounts of reforming additives (consisting of uranium oxide and/or platinum metal impregnated on an inorganic oxide support) have been described. . Zeolites contemplated in this patent include hydrogen and/or rare earth metal exchanged synthetic Houjasites, type X and Y Houjasites, with silica to alumina ratios of 2.5 to about 6. In addition to rare earth metal-exchanged houjasites, low soda content zeolites are also mentioned. Cracking catalysts with improved activity and selectivity for converting hydrocarbon feedstocks to high octane gasoline fractions include (a) ultrastable Y zeolite, (b) alumina, and (c) inorganic porous oxide matrix materials. Contains. The zeolite component of the catalyst of the present invention is a crystalline aluminosilicate zeolite, commonly known as "stable" or "ultrastable" Y-type haujasite. These types of zeolites are well known. For example, these are U.S. Patent Nos.
3293192 and 3402996, and the Society of Chemical Engineering (London) Monograph by CVMCDANIEL and PKMAHER. (London)
Monograph Molecular Sieves), 1968, page 186. As used herein, the term "ultrastable" means highly resistant to deterioration of crystallinity by high temperature and steam treatment, less than about 4% by weight;
R ₂ O content (R is Na ₁ K or other alkali metal ion) preferably less than about 1 weight percent;
and a unit cell size of less than about 24.50 Å and a unit cell size of 3.5 to
It refers to Y-type zeolites characterized by a SiO ₂ /Al ₂ O ₃ molar ratio in the range of 7 or more. In a preferred embodiment of the invention, the unit cell size of the ultrastable Y zeolite is less than 24.40 Å. The ultrastable form of Y zeolite is mainly obtained by highly depleting alkali metal ions and reducing the unit cell size after the alkali metal removal step. In other words, ultrastable zeolites are characterized by both a relatively small unit cell in their crystal structure and a low alkali metal content. An ultra-stable form of Y zeolite can be obtained, for example, by preparing Y zeolite or Y-type horsiyaite in an aqueous solution of an ammonium salt such as ammonium nitrate so that the alkali metal content of Y zeolite is approximately 4% by weight R ₂ O (R refers to an alkali metal such as sodium). ) can be produced by continuous base exchange until lower. The base-exchanged zeolite is then calcined, for example, for a period of 0.5 to 5 hours, at a temperature of 538°C (1000°) to 816°C (1500°) to produce an ultrastable zeolite. If desired, steam may be added during baking. Preferably, the ultrastable Y zeolite is then continuously base exchanged again with an aqueous solution of an ammonium salt until the alkali metal content is reduced to less than 1% R ₂ O by weight. More preferably, the ultrastable Y zeolite is then reconstituted at a temperature of 538-816°C (1000-1500°), again with water vapor added if desired.
Calcined to purify an ultrastable Y zeolite with a unit cell size of less than about 24.40 Å. Due to this ion exchange and heat treatment step, the alkali metal content of the original zeolite is greatly reduced and the unit cell is also reduced. It is thought that this makes the obtained Y zeolite highly stable. The particle size of these zeolites usually ranges from 0.1 to 10 microns, more typically from 0.5 to 3 microns. In a preferred embodiment, the ultrastable Y zeolite components of the present invention include, for example, cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erubium, ythtrium, thorium, scandium, lutetium, and mixtures thereof. Contains substantially no rare earth metals. Substantially free means that the zeolite has a rare earth metal content of less than about 1% by weight as metal oxides (RE ₂ O ₃ ). Similarly, Mg or other metal ions such as Ca can be introduced into the zeolite by base exchange up to about 1% by weight. The alumina component of the catalyst of the present invention comprises discrete particles of a variety of known and often commercially available alumina particles. These aluminas are anhydrous and/or hydrated. A more detailed explanation of alumina can be found in the Encyclopedia of Chemical Technology.
Technology), Kirk Osmer (Kirk−
Othmer) 2nd edition, Volume 2, Interscience Publishers, pages 41-55. Some of the aluminas useful for preparing the catalysts of the invention have a total surface area of greater than 20 m ² /g, preferably greater than 145 ^{m 2 /} g, e.g. ,
The Van Nostrand Chemist Dictionary
Dictionary (1953 edition) is a discrete particle of alumina. Preferably the alumina pore volume (BET
law) is greater than 0.35cc/g. The average particle size of the alumina is generally less than 10 microns, preferably less than 3 microns. The discrete particles of alumina used to make these catalysts are often referred to as "bulk" alumina. The term "bulk" is used herein to refer to alumina that has been preformed to have a physical structure that stabilizes its surface area and pore structure. When the bulk alumina is added to an impure organic gel containing significant amounts of residual soluble salts, the salts not only do not measurably alter the surface area and pore properties of the alumina, but also the preformed alumina. (which may then change) undergoes only a very small chemical reaction. For example, the addition of bulk alumina involves the addition of bulk alumina to a material that has been purified by appropriate chemical reactions, aged, filtered, dried, washed free of residual salts, and then reduced to less than about 25% by weight of its volatile content. means dried slurry. In addition to the bulk porous preformed alumina described above, it is also conceivable to prepare the catalyst using an aqueous slurry of dispersed hydrated alumina in a particular crystalline structure or amorphous or a mixture thereof. These hydrates are alumina α-hydrate, α-trihydrate, β
Includes trihydrates and to a lesser extent β-hydrates. These are generally made from solutions of aluminum salts or alkaline aluminates. Depending on the reaction conditions, purified alumina has a wide range of physical properties. Furthermore, the alumina slurry can be made into a gel. Alumina gels generally have a dry solids content of about 2-12% by weight. Upon drying, the alumina gel gradually loses water and as the temperature increases, the first dislocation layer (non-hydrated) is either η or γ alumina. The presence of discrete particles of crystalline alumina in the catalysts of the present invention is demonstrated in Advances in Ex-Ray Refractometry and Ex-Ray Spectrography.
in X-ray Refractometory and X-ray
Spectrography), edited by William Parrish, 1962
It can be observed by X-ray diffraction using well-known techniques such as those described by Centerx Publishing Company-Eindhoven. Inorganic porous oxides used as matrices in the catalyst compositions of the present invention include readily available porous materials such as alumina, silica, boria, chromia, magnesia, zirconia, titania, silica-alumina, etc., and mixtures thereof. Either is fine. These substances can also be used as one or two types.
It includes several types of well-known clays, such as montmorillonite, kaolin, halloysite, bentonite, and the like. Preferably, the inorganic porous oxide is one or more conventional silicon-based variants containing a large amount of silica and a small amount of an oxide of at least one metal of Groups -A, -A and -B of the Periodic Table. Typical silica-containing matrix materials include silica-alumina, silica-magnesia, silica-zirconia,
Includes silica-solia, silica-titania, silica-alumina-zirconia, silica-alumina-magnesia, and the like. In a more preferred embodiment of the invention, the inorganic porous oxide matrix material is an amorphous silica alumina gel. As is commonly known,
These materials are typically made from silica hydrogels or hydrosols that are mixed with an alumina source, typically an aluminum salt solution, to maintain the desired silica-alumina composition. The alumina content of the silica alumina matrix typically ranges from about 5 to 40% by weight, although preferred compositions have an alumina content of about 10 to 35% by weight alumina. Various methods of producing silica alumina are described in the literature. (For example, U.S. Patent No. 2908635 and
See No. 2844523. ) The catalyst composition of the present invention contains 5 to 40% by weight, preferably 10 to 30% by weight of the ultrastable Y zeolite,
It contains 5 to 40% by weight alumina, preferably 10 to 30% by weight, and 40 to 90% by weight, preferably 50 to 80% by weight of a porous oxide matrix.
It is also within the scope of this invention for the catalyst to contain other materials commonly used in cracking catalysts, such as various zeolites, clays, metal CO oxidation promoters, and the like. In a preferred embodiment, the ratio of weight percent Na ₂ O in the gold catalyst to weight percent zeolite in the total catalyst is less than or equal to 0.013 in the catalyst of the invention. The catalyst of the present invention can be manufactured by well-known methods. For example, a preferred method of making the catalysts of the present invention involves reacting sodium silicate with an aluminum sulfate solution to produce a silica-alumina hydrogel slurry, which is then aged under controlled conditions to provide the desired pore characteristics and then filtered. , which removes large amounts of excess undesired sodium and sulfate ions and then reslurrying in water. Separately, bulk alumina can be prepared, for example, by reacting sodium aluminate and aluminum sulfate solutions under appropriate conditions, aging the slurry to give the desired pore characteristics of the alumina, filtering, drying, and reslurrying in water. , by removing sodium and sulfate ions and drying to a volatile content of less than 25% by weight. The alumina is then slurried in water and blended with an appropriate amount of impure silica alumina hydrogel slurry. The ultrastable zeolites of this invention can be added to this blend using sufficient amounts of each component of the catalyst to obtain the desired final composition. If desired, the resulting mixture is filtered to remove some of the remaining excess soluble salt therefrom and reduce the amount of liquid present in the slurry. The filtered mixture is dried to obtain a dry solid. The dried solids are then reslurried in water and washed substantially free of undesired soluble salts using a pH controlled ammonium sulfate solution followed by a water wash. The catalyst is then dried until the residual moisture is less than about 15% by weight. Other methods of obtaining the components of the invention are known to those skilled in the art and are included within the scope of the invention. Suitable feedstocks for the conversion process of the present invention also include the well-known feedstocks conventionally used in catalytic cracking processes. Usually petroleum, but shale oil,
It does not exclude other sources such as tar sands oil coal. Typical of these feedstocks are heavy and light virgin naphtha solvent extracted gas oils, coked gas oils, steam cracked gas oils, cycle oils, residues, deasphalted residues, hydrotreated residues, stopped crude oils, etc., and mixtures thereof. be. The catalyst of the present invention can be used in the catalytic cracking of the above-mentioned feedstocks by well-known techniques. Generally cracking conditions are approximately 454-566℃ (850-1050℃)
〓) temperature range, 0~3.5Kg/ ^cm2 (0~50psig)
pressure and a feed rate of 1 to 200 W/Hr/W. The catalyst can be regenerated under temperature conditions ranging from 593 to 816°C (1100 to 1500°), preferably from 635 to 732°C (1175 to 1350°). The invention will be further illustrated by the following examples. Unless stated otherwise, all proportions are expressed in weight percentages. Example 1 A catalyst of the present invention was produced as follows. A dilute sodium silicate solution containing approximately 50 g of silica was contacted with CO ₂ to gel. The impure silica hydrosol was aged and then blended with aluminum sulfate granules. After filtering the impure silica/alumina to remove some extraneous soluble salts, the material had a dry solids content of 15.7%. The dry solid content was determined to be 57.3 by analysis.
% _SiO2 and 20.2 _{% Al2O3} . 15.8 Kg (35 lbs) of water in the mixing tank to 44.4 Kg (98.75 lbs.
6.8 lbs.) of the above impure silica/alumina hydrogel in a second mixing tank.
Kg (15 lbs.) of water and 1824 g (dry basis) of alumina (Conoco Chemical Division of
Continental Oil Company)
(CONOCO Chemical Division of Continental
(sold under the trade name Catapal HP Grades) by the Oil Company). Then, with stirring, 1824 g (dry basis) of low soda content Hojiasite (Union Carbide Corporation) was added.
It is sold under the trade name Linde 33-200 grade. ) was blended. The composite slurry was added to the gel slurry, homogenized twice by colloid milling, and spray dried. The impure material was slurried in warm water to about 18% solids by weight and filtered. The filter instrument was treated with a 3% by weight ammonium sulfate solution, brought to a pH of 8 with ammonia, and finally rinsed with aqueous ammonia (approximately 5 pounds of solution per pound of catalyst) to remove residual soluble salts, and finally rinsed with water. Washed with. The resulting catalyst has a Na ₂ O content of 0.17% by weight
approximately 20% ultra-stable Y zeolite, 20%
It contained _Al2O2 and ₆₀ % _{SiO2 / Na2O3} .
This is indicated by "A" in the example below. EXAMPLE 2 The catalyst of Example 1 was tested for activity and selectivity for the production of high octane catnaphtha, compared with commercially available or
A comparison was made with various cracking catalysts (designated "B", "C" and "D") which are typical cracking catalysts currently used in the petroleum industry. Catalyst B is a widely used industrial catalyst, containing about 14-16% hawkiasite (Y-type), about 28
Contains ~30% kaolin clay and approximately 55-60% silica alumina gel matrix. The precatalyst is approx.
Contains 2.8-3.5% rare earths (as oxides). Catalyst C is a commercially available catalyst and consists of about 5% Houjasite (Y type) and about 95% silica alumina gel. The haujasite in C was replaced with a mixed rare earth and calcined before mixing with the matrix gel. Catalyst C contains about 1.0-1.2% rare earths (as oxides). Catalyst D is about 8
~9% Hojiasite (Y type) and approx. 91-92%
silica alumina gel matrix.
Catalyst D is believed to contain houjasite that has been preexchanged with rare earth elements and calcined prior to mixing with the matrix. Catalyst D is approximately 1.8 according to analysis.
Contains ~2.2% rare earths (as oxides).
Therefore, the comparative catalysts in the following examples are 5-
Contains 16% haujasite (Y type), 1.0-3.5% rare earths (as oxides) and silica alumina gel matrix (with or without bulk kaolin addition). Example 3 of these catalysts
The cracking performance will be compared with Catalyst A of the present invention. Each of these catalysts compared in Example 3 was 0 Kg/cm ² at 760°C (1400〓) for 16 hours.
(0 psig) to simulate deactivation in industrial operations prior to testing. Example 3 Each of the catalysts described in the two examples above was tested in a circulating fluidized bed catalytic cracking unit (comprising a reactor and a regenerator) under the following conditions. The raw materials used in these experiments are listed in the table. The results of these experiments are listed in the table. Table Raw materials Specific gravity 27.5 API degree Sulfur 0.812% by weight Nitrogen 618 ppm Conradson carbon 0.27% by weight Aniline point 77.2 °C (171〓) Distillation range ^* °C IBM/5% 249/263 10/20% 276/298 30/ 40% 317/341 50/60% 366/382 70/80% 416/441 90/95% 475/504 FBP 513 * Atmospheric pressure

TABLE The relative activity and octane productivity of the catalysts tested in this example is shown in the figure. 1/2 in drawing
Octane productivity, measured by (RONC+MONC), is plotted against catalyst activity, measured by conversion (% by volume) under the same cracking conditions. In general, it can be seen from the drawing that the octane productivity of the catalyst increases as the catalyst activity decreases, and vice versa. However, contrary to expectations, it has been discovered that the catalyst of the present invention has a much higher octane productivity for the same activity than the prior art catalyst. At the same time, 430 by volume% of naphtha
It was found that its selectivity to naphtha, measured as fraction conversion, was equal to the prior art catalyst. In fact, when considering the potential alkylates (i.e. propylene and butylene refined products) produced by any catalyst, the potential gasoline selectivity of catalyst A (catalyst naphtha +
latent alkylate) was somewhat better than prior art catalysts. This is shown in the table.

[Table] Alkylate Selectivity Example 4 Another catalyst of the present invention was prepared as follows. (a) 9.9 Kg (22 lb) of Hoziersite (commercially available as Linde LZ-Y52 grade by Union Carbide Corporation) in 45 Kg (100 lb) of water at 57°C.
(135〓) was made into a slurry. In a separate vessel, dissolve 4.05 Kg (9 lbs) of ammonium sulfate in 22.5 Kg (50 lbs) of water, then
200 c.c. of H ₂ SO ₄ was added. The acidic ammonium sulfate solution was then added to the houjasite slurry and the mixture was heated to 57°C (135°C) and
Stir for hours. The PH4.5 slurry was filtered, washed with warm water, and oven dried at approximately 107°C (225°C) for 16 hours. (b) The oven-dried material from step (a) was placed in a shallow tray and heated under an atmosphere of flowing steam in an oven preheated to 677°C (1250°C). Fire the Hojia site at 677℃ (1250〓) for 1 hour,
Before unloading, the furnace is heated to 260℃ (500℃) in flowing steam.
cooled down to. The calcined material had a Na ₂ O content of 5.7% and a unit cell size of 24.62 Å. (c) The calcined Houjasite zeolite obtained from step (b) was reprocessed as described in step (a). After drying in the oven, Hojiasite was heated to 482℃ (900℃).
〓) for 1 hour in ambient air.
After cooling, the produced Hojiasite contains 2.15% _Na2O
content, and the unit cell size was 24.50 Å. This is a stabilized low soda content houjasite (zeolite Y). (d) In a mixing tank, add impure silica-alumina hydrogel prepared as in Example 1.
36Kg (80 lbs) (11.3% catalyst solids dry basis)
was slurried with 18 Kg (40 lb) of water. In the second mixing tank, 1850g (1360g when dry)
The commercially available alumina of g) was slurried with 11.3 Kg (25 lbs) of water. Part of alumina pre-538
℃ (1000〓) for 6 hours, surface area (BET) 523 m ² /g and pore volume (diameter
pores between 90 and 200 Å have a pore volume of 0.21 cc/g)
It was made to have. This alumina slurry is subjected to the above process after ball milling in ambient air.
1648g of calcined stabilized Hojiasite obtained from (c)
(1360 g when dry) was added. The slurry was combined and spray dried at approximately 122°C (250°C). The composite material was washed free of extraneous soluble salts, filtered, washed with water, and dried as described in Example 1 above. Production catalyst is 0.24%
Ultra-stable Y zeolite containing about 20% Na ₂ O,
Contains 20% alumina and 60% silica-alumina gel. This is used as catalyst E in the following examples.
Name it. Example 5 This example describes the preparation of a preferred catalyst of the invention. (a) A portion of the stabilized zeolite obtained from step (c) of Example 4 above was placed in a dish and inserted into a furnace at 538°C (1000°C). Raise the temperature to 816℃ (1500〓),
It was held at that temperature for 1 hour and then cooled. The resulting material had 2.15% Na ₂ O and its unit cell size was 24.38 Å. The unit cell size was reduced from 24.50 Å to 24.38 Å by heat treatment. (b) 1.35 Kg (3.0 lb) of calcined stabilized Hojia site (dry) obtained in step (a) of this example was slurried with 9 Kg (20 lb) of water. Next, 1.35 Kg (3.0 lbs) of alumina (dry) from Run 4 was added. This mixed slurry was then blended with 4.1 Kg (9.0 lbs) of the impure silica-alumina hydrogel of Example 4 (on a dry catalyst solids basis), spray dried, and
Extraneous soluble salts were washed away as in Example 4. This total composite catalyst, named "F", is approximately 20%
of precalcined ultra-stable Y zeolite, 20% Al ₂ O ₃ and 60% silica-alumina gel. this is
Contained 0.23% _Na2O and 0.46% sulfate. Example 6 The catalyst of this example is the catalyst of the present invention. This catalyst was produced as follows. (a) Commercially available stable low soda content with 80.3% dry solids content, 0.12% soda as Na ₂ O, SiO ₂ /Al ₂ O ₃ molar ratio of 5.5 and unit cell size of 24.15 Å Hoziersite (Linde LZ from Union Carbide Corporation)
- Sold under the trade name Y82 grade) is ball milled and its 1.35 kg (3.0 lb)
(on a dry basis) was slurried with 9 Kg (20 lbs) of water. Approximately 1.35 Kg (3.0 lb) of the alumina described in Example 4 (dry basis) was added to this slurry.
was added. (b) In a separate mixing tank, 31.95 Kg (71.0 lb) of the crude silica-alumina hydrogel described in Example 1 [equal to 4.05 Kg (9 lb) catalyst solids] was slurried with 18 Kg (40 lb) of water. The slurry prepared in step (a) of this example was added to the silica-alumina hydrogel slurry with mixing. The composite slurry was colloid milled as in Example 1, spray dried, washed of extraneous soluble salts, and dried. Catalyst is 0.08%
of _Na2O and 0.11% _SO4 , and had a composition of approximately 20% ultrastable Y zeolite, 20% alumina, and 60% silica-alumina gel. This was named "G" in the following example. Example 7 The catalyst of this example is another catalyst of the present invention. This was produced as follows. (a) The stabilized low soda content Y zeolite described in Example 6 above was placed in a dish and placed in a furnace at 538°C (1000°C). The temperature was raised to 816°C (1500°C), held for 1 hour, and then cooled. 538 substances
It was taken out from the furnace below ℃ (1000〓). This calcined ultra-stable Houjasite had a unit cell size of 24.34 Å compared to 24.51 Å before this calcining process. (b) In the mixing tank, the crude silica-alumina hydrogel described in Example 1 above [4.05Kg
(9.0 lbs) of catalyst solids] equal to 31.95Kg
(71.0 lbs.) was slurried with 18 Kg (40 lbs.) of water. In the second mixing tank, 1400 g (1.35 Kg (3.0 lb) dry basis) of the ball-milled, precalcined houjasite obtained in step (a) of this example was slurried with 9 Kg (20 lb) water. To this slurry was added 1.35 Kg (3.0 lbs) (dry basis) of the ball milled alumina of Example 4. (c) The slurry obtained from step (b) of this example was combined, colloid milled, spray dried, washed of foreign salts, and dried as in Example 1. The resulting catalyst was named "H". It contained 0.07% _Na2O and 0.40% _SO4 .
Catalyst "H" had a composition of 20% precalcined ultrastable zeolite Y, 20% alumina, and 60% silica-alumina gel. Example 8 Catalysts "B", "E", "F", "G" and "H" were each calcined at 538°C (1000〓) for 6 hours and then at 760°C.
(1400〓) for 16 hours at a vapor pressure of 0 Kg/cm ² (0 psig) to stimulate the performance of a commercially available equilibrium cracking catalyst. Each catalyst was then measured for cracking performance in one complete cycle of operation. The unit used was a circulating flow catassembler with a regenerator and a reactor/withdrawal vessel. The reactor and regenerator temperatures are 496℃ (925〓) and 596℃ (1105℃), respectively.
〓) It was. Feed materials are listed in the table
It was 450/593℃ (1100〓) vacuum light oil. The apparatus was operated at a catalyst to oil weight ratio of 4.0 and a pressure of 0 kg/cm ² (0 psig). The results shown in the table are constant
Comparable to catalyst at 70% conversion by volume. Table Raw materials Specific gravity 22.9 API degree Sulfur 1.245% by weight Nitrogen 705 ppm Conradson carbon 0.43% by weight Aniline point 84.2 ℃ (183.5〓) Distillation range ^* ℃ IBP/5% 298/334 10/20% 349/378 30/ 40% 395/412 50/60% 432/457 70/80% 482/499 90/95% 523/543 FBP 565 * Atmospheric pressure

[Table] The results show that Catalysts E, F, G, and H all significantly increased the octane number of cracked naphtha compared to Reference Catalyst B. Catalysts F and H of the invention
It can be seen that octanes are increased compared to Catalysts E and G. This is the size of the unit cell
This is due to the pre-calcination treatment applied to the ultra-stable Y zeolite in order to reduce the thickness to 24.38 Å or less. Example 9 Six types of catalysts having the compositions shown in the table were prepared according to a conventional method.

[Table] Among the above catalysts, No. 5 corresponds to the catalyst of the present invention. All catalysts were tested for 16 hours at 750
The activity of a commercially available equilibrium cracking catalyst was simulated by steam treatment at ℃ and normal pressure. These steam-treated catalysts were evaluated for cracking activity using the well-known microactivity test (MAT). This MAT is, for example, Oil and Gas Journal, published in 1966, Volume 64.
Pages 7, 84 and 85 of No. 39 and the same magazine.
It is described on pages 60 to 68 of the November 22, 1971 issue. The results of this test were also expressed in terms of relative catalytic activity (RCA) defined by the following formula:

[Table] The MAT and RCA of each catalyst are shown in the table.

[Table] From the above results, it can be seen that catalyst No. 5 corresponding to the present invention has considerably higher catalytic activity than other catalysts. Example 10 Catalysts Nos. 3, 4, 5 and 6 of Example 9 were evaluated for cracking ability in a circulating flow catalytic cracking unit consisting of a reactor, a regenerator and a stripping tower. The unit operated in batch mode with no recycled oil being mixed with fresh feedstock. The temperatures inside the reactor and regenerator are 496°C and 596°C, respectively. The feedstock was the same as that used in Example 3 (Table) and the catalyst to oil weight ratio was maintained at 4.0. This unit has a feed rate of 10 g/min under normal pressure.
Operated in minutes. The results of this test are shown in the table.

[Table] From the table, catalyst No. 5 has an extremely high yield of gasoline (C ₅ /221℃ naphtha) compared to other catalysts.
The average values of RONC and MONC, which indicate actual octane quality, are also higher than other catalysts. Therefore, it can be seen that catalyst No. 5 exhibits extremely superior performance compared to other catalysts.

[Brief explanation of the drawing]

The figure is a graph showing the activity and selectivity characteristics of various cracking catalysts, which are comparatively described in detail in each example herein. In the same figure,
The vertical axis shows naphtha octane (RONC+MONC/2), and the horizontal axis shows conversion rate (volume %).

Claims (1)

[Scope of Claims] 1. Containing loose particles of ultra-stable Y zeolite and loose particles of alumina dispersed in a porous oxide matrix, wherein the ultra-stable Y zeolite is 5-40% by weight and the alumina is 5-40% by weight. 40% by weight of the porous oxide matrix and 40-90% by weight of the porous oxide matrix. 2. The cracking catalyst composition of claim 1, wherein the porous oxide matrix includes silica. 3. The cracking catalyst composition of claim 1 or 2, wherein the porous oxide matrix includes silica-alumina gel. 4. The cracking catalyst composition according to any one of claims 1 to 3, wherein the alumina includes alumina gel. 5. The cracking catalyst composition according to any one of claims 1 to 4, wherein the ultrastable Y zeolite has a unit cell diameter of less than 24.40 Å. 6. The cracking catalyst composition according to any one of claims 1 to 5, wherein the ultra-stable Y zeolite contains less than 1% of rare earth metal oxide (Re ₂ O ₃ ). . 7 The ultra-stable Y zeolite contains less than 1% by weight
The cracking catalyst composition according to any one of claims 1 to 6, characterized in that it contains Na ₂ O. 8. Any one of claims 1 to 7, characterized in that the ratio of the weight percent of Na ₂ O on the total catalyst to the weight percent of zeolite on the total catalyst is less than or equal to 0.013. The cracking catalyst composition described in . 9 (a) (a) porous oxide, (b) alumina particles, and (c)
producing an aqueous slurry mixture containing ultrastable Y zeolite particles; (b) drying said mixture to form loose particles of ultrastable Y zeolite and loose particles of alumina dispersed in said porous oxide matrix; (c) washing the catalyst complex to remove foreign salts soluble in an aqueous ammonium salt solution; and (d) drying the washed catalyst complex to remove water. 15
1. A method for producing a cracking catalyst composition, characterized by a combination of steps for reducing the percentage by weight. 10. The method according to claim 9, characterized in that in step (c), the catalyst composite is continuously washed with an ammonium salt solution and water.