JPH0275697A - Method for cracking of hydrocarbon and catalyst used therein - Google Patents

Abstract

PURPOSE: To lower a harmful action on a catalyst because of a metal contaminant by performing catalytic cracking of a hydrocarbon supply material in the presence of a solid composition including a specific metal constituent and a catalyst containing a molecular sieve.

CONSTITUTION: In catalytic cracking of a hydrocarbon supply material carried out in a catalytic area in the presence of a solid composition including a catalyst, which contains a molecular sieve and can promote cracking of the hydrocarbon supply material under an efficient condition for decomposing it into constituents with lower boiling points, this catalytic cracking is carried out in the presence of at least one kind of metal constituent selected from barium, chromium, zirconium, and tin in addition to the catalyst. The metal constituent may exist in a particle other than a solid particle containing the catalyst, however, the metal constituent is favorably contained in the solid particle. For a useful molecular sieve, a zeolite series molecular sieve or zeolite, a non-zeolite series molecular sieve or NZMS, and a mixture of them are available.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydrocarbon cracking process and a catalyst composition suitable for use in the process. More particularly, the present invention provides a molecular sieve containing one or more predetermined metal components useful for reducing the deleterious effects of contaminant metals, such as those present in hydrocarbon feedstocks. This invention relates to a hydrocarbon decomposition method using a catalyst.

Catalytic hydrocarbon cracking is a major process commercially practiced by, for example, petroleum refiners to produce gasoline and other relatively low boiling hydrocarbon products. Such decomposition is often carried out in the presence of fixed particles containing molecular sieve-containing decomposition catalysts. Most conventional catalytic cracking processes that crack hydrocarbon feedstocks to produce gasoline and other light distillates experience a gradual decline in the cracking capacity or performance of the molecular sieve-containing catalyst. It is often the case that at least some of the degradation can be due to contaminant metals from the feedstock adhering to the solid particles. The deposition of these contaminants, including nickel, vanadium, and iron, tends to adversely affect the cracking process by, for example, reducing gasoline production and undesirably increasing hydrogen and coke yields.

vanadium oxide or vanadia penetrates and interacts with the structure of the molecular sieve to form a low-melting eutectic mixture, which neutralizes and irreversibly destroys the acid sites of the molecular sieve crystals; Vanadium is of particular concern since it leads to amorphous materials with low activity and low surface area.

Many attempts have been made to reduce the adhesion of such contaminant metals to solid 9-catalyst particles. For example, numerous US patents for Phillips Petroleum Company use antimony as a nickel passivating agent (p
It discloses that it can be used as an assivation agent). Several US patents to Galfoil Corporation disclose the use of tin as a metal passivating agent. U.S. Pat. No. 4,451,355 to Galfoil Corporation describes calcium-titanium, calcium-zirconium, calcium-titanium-zirconium oxide, and mixtures thereof as catalyst additives useful for cracking hydrocarbonaceous oils containing vanadiram. It is disclosed that it can be used as Other passivating metal components such as gallium, indium, zinc, tellurium,
A number of proposals have been made, including aluminum, cadmium, and arsenic. U.S. Patent 4.324°648:4.348.273
．． 4.504.381.4.415.440.4.16
7,471.

4, 363.720: 4.326.990 and 4.39
See No. 6.496.

The use of various barium compounds to passivate contaminant metals on hydrocarbon cracking catalysts is described in U.S. Pat. No. 4,473,4.
No. 63 and No. 4.377.494.

These patents teach that useful barium compounds can be organic or inorganic, and that oil-soluble or water-soluble barium compounds are preferred. Suitable inorganic barium compounds include barium salts of mineral acids such as barium nitrate, barium sulfate, barium halides, barium oxyhalides; basic barium compounds such as barium hydroxide, barium hydrosulfide and barium carbonate, as disclosed in European Patent Publication Box 0194536 discloses the use of barium titanium oxide, particularly barium titanate, in combination with a zeolitic molecular sieve cracking catalyst to crack metal-containing hydrocarbon feedstocks.

U.S. Pat. No. 4,432,890 discloses a number of metal additives that immobilize vanadia onto zeolite-containing cracking catalysts. Such metal additives include the following metals, their oxides and salts and their organometallic compounds: Mg, Ca
, Sr, Ba, Sc, Y, La, Ti, zn, Hf, N
b, Ta, Mn, Fe, In, T1. Bi, Te, rare earth, actinide and lanthanide series elements. This patent specifies that Group IA or alkaline earth metals such as Mg, C
Mixtures of these additive metals other than a, Sr, and Ba with vanadia appear to form high melting point ternary, quaternary, or higher component reaction mixtures, such as vanadium titanium zirconate (VO-Tin□-ZiO□ ). This patent also states that Group 1A metals and other metals are substituted for vanadia by high melting point immobile substances such as Ba.
aVTi20i, BaO- to 2O-TiOi-Vz0
4 and 3aQ-Na20-TiO□-VtOi, but these metals can lead to excessive neutralization of acidic sites on the catalyst and usually cause vanadia to become immobilized on the zeolite-containing cracking catalyst. It states that it cannot be used as a metal additive.

However, there continues to be a need for metal, particularly vanadium passivating agents for zeolite-containing cracking catalysts.

The following additional US patents were reviewed while preparing this application: 3.446.730.4.450.241.4
．． 425.25'l;4, 412.914:4.149
．． 998;4.418.008.4.089.810.
4.293.445.3.360.330. and 3,3
17,439.

We have discovered a new method for decomposing hydrocarbons. This method is suitable for hydrocarbon feedstocks, especially those containing contaminant amounts of metals, such as vanadium, nickel, iron, and mixtures thereof, especially carbonized layers containing vanadium. The contacting preferably comprises contacting the hydrogen feedstock in the contacting zone in the presence of a solid composition, preferably solid particles, containing a molecular sieve-containing catalyst capable of promoting hydrocarbon feedstock decomposition. Conditions are effective to crack the hydrocarbon feedstock to lower boiling components of l+ffi or higher in the absence of substantially free molecular hydrogen. According to the invention, this contact is carried out in a very special manner in the presence of barium and at least one other metal component selected from the group consisting of chromium, zirconium and tin, preferably oxygen. Do it effectively. Another preferred metal is chromium. In one embodiment, the metal component reduces the deleterious effects of contaminant metals on the catalyst.
□ Present in effective amounts. Metal components may be combined with, eg, incorporated into, solid compositions to form new compositions.

The invention provides considerable advantages. For example, currently available metal components have been found to be effective in reducing the deleterious effects on molecular sieve-containing cracking catalysts caused by contaminant metals, particularly vanadium, often present in hydrocarbon feedstocks to be cracked. In many cases, these metal components reduce these deleterious effects more effectively than the barium compounds disclosed in various patents, such as those discussed above. Additionally, these metal components can be used without substantially adversely affecting the solid composition, the molecular sieve-containing catalyst, and the hydrocarbon cracking operation. Additionally, currently available metal components are relatively inexpensive and can be used in a cost effective manner, for example, in attempting to reduce vanadium contamination. In particular with respect to barium and chromium containing components, particularly barium chromate, these materials are relatively or substantially inert towards sulfur oxides which are often present in hydrocarbon cracking operations contemplated by the present invention. I understand. This inert nature leaves the barium, chromium-containing components free to reduce the harmful effects of contaminating metals, rather than being consumed in the formation of often useless and possibly harmful sulfates. It's advantageous.

The barium-containing metal component is present in an amount effective to reduce the deleterious effects of contaminant metals, particularly vanadium, on the catalyst during contact with the feedstock/solid composition. To,
Particularly effective. Although the metal component may be present in a separate particle from the catalyst-containing solid particles, it is preferred that the metal component is in the solid particles, preferably from about 0.1 to about 40% by weight of the solid composition. , -layer preferably present in an amount ranging from about 0.1 to about 25% by weight. Even more preferably, the metal component is present in an amount ranging from about 1% to about 20% by weight of the solid composition.

In one embodiment, it is preferred that the metal component further contains or includes oxygen. In this embodiment, the metal component can be characterized as a mixed metal oxide. Preferably, the amount of oxygen introduced is that necessary to meet the stoichiometric requirements of the particular metal component used, the metal component being preferably fed to the water and hydrocarbon feedstock at ambient conditions. Particularly useful monometallic components, preferably substantially insoluble under the conditions of raw material/solid composition contact, are selected from the group consisting of barium chromate, barium zirconate, barium stannate, and mixtures thereof, particularly chromate. It's barium.

Currently useful metal components can be prepared using conventional techniques. For example, one or more barium compounds and one or more other metal compounds, namely chromium, zirconium and tin, are combined and exposed to high temperature in air or other oxygen-containing gaseous medium; For example, the metal component is formed by exposure to a temperature ranging from about 700°C or about 00°C to about 1200°C or more for a period of time ranging from about 1 to about 24 hours or more. Preferred barium compounds and other metal compounds are oxides, oxide precursors, ie compounds that form oxides at elevated temperatures and in the presence of an oxygen-containing gaseous medium. Barium chromate can be prepared, for example, by baking barium carbonate and dichromium oxide at high temperatures, such as in the range of about 900° to about 1100°C. In preparation, after triblending the barium carbonate and dichromic oxide, a calcination step is performed for a period of about 5 to about 20 hours.

Solid compositions useful in the invention, such as solid particles, include
1 that can facilitate catalytic cracking of a hydrocarbon feedstock into one or more lower boiling products;
Contains one or more molecular sieves.

Molecular sieves useful in the present invention can be selected from zeolitic molecular sieves or zeolites, non-zeolitic molecular sieves or NZMS, and mixtures thereof. However, the proviso is that the molecular sieve is capable of promoting hydrocarbon decomposition.

Zeolites that can be used in the practice of this invention include both natural and synthetic zeolites. These naturally occurring zeolites include gmelinite, chapazite, datiardite, clinoptilolite, faujasite, hyulantite, analcite, levinite, erionite, sodalite, canclinite, nepheline, luxzuite, scaracite, nitrolite, offretite, mesolite, mordenite,
Contains bluestellite, ferrierite, etc. Suitable synthetic zeolites that can be used in this method include
Y, A%L, Zk-4,8% E, F, H, J, M, Q
%T, W, Z, Fulfill, Beta, Omega, ZSM-type, ultrastable Y zeolite, etc.0. It is preferable because it is easier to prepare than commercially produced zeolite.

Alkali metals, such as sodium, tend to reduce the catalytic effectiveness of zeolites. It is therefore preferred to remove most or substantially all of the alkali metals that may be present in the zeolite or to replace them with other metal cations, such as calcium or aluminum ions or rare earth metal ions. Means for removing/replacing alkali metals and procedures to render zeolites advantageous for hydrocarbon cracking are known for the time being. For example, U.S. Patent 3.140
, 253 and reissued U.S. Pat. No. 27,659.

Currently useful NZMS include molecular sieves encompassed by the experimental chemical composition represented by the following formula on an anhydrous basis: (1) mR: (QwAlxP,S+z)Oz where Q is a framework oxide unit with charge n rQo2'J
(n can be -3, -2, -1,0 or +1); "R" represents at least one element present in the intracrystalline pore system; !
represents the organic template agent of J; “m” is (Qw
Al-PyS+,) represents the number of moles of rRJ present per 21 moles and has a value of 0 to about 0.3 = "W", r
xJ, “y” and rzJ are QOzll, AlO□-1PO□”, SiO, which exist as framework oxide units, respectively
Represents the mole fraction of □. rQJ is characterized as an element having an average rT-OJ spacing of about 1.51 to about 2.06 people in a tetrahedral oxide structure.

rQJ has a cation electronegativity of about 125 to about 310 kcal/g atom and rQJ has a cation electronegativity of greater than about 59 kcal/g atom at 298"K.
Stable Q-0-P, Q-0-A1 or Q-0- in a crystalline three-dimensional oxide structure with J bond dissociation energy
Q-bonds can be formed (8a, 8b of EPc Publication No. 0159624 published on October 30, 1985).
and discussion of rELJ and rMJ characterization on page 8c. (as used herein), r w J, rxJ, ryJ and rzJ are respectively "Q" present as a framework oxide, aluminum,
represents the mole fraction of phosphorus and silicon, which mole fractions are within the following limiting composition values or points: W is equal to 0 to 99 mol%; y is equal to 1 to 99 mol% : X is equal to 1-99 mol%: Z is equal to 0-99 mol%.

rQJ of the rQAPSOJ molecular sieve in formula (1)
may be defined as representing at least one element capable of forming a framework tetrahedral oxide and may be one of the following elements: arsenic, beryllium,
boron, chromium, cobalt, gallium, germanium,
Iron, lithium, magnesium, manganese, titanium, vanadium and zinc. Combinations of elements are intended to represent Q and such combinations, to the extent present in the structure of QAPSO, may be present in the mole fraction of the Q component ranging from 1 to 99%. (It should be noted that Equation 11 is intended for the case where Q and Si are not present. In such a case, the working structure is that of aluminophosphate or AlPO4. In this case, the operative structure is that of silicoaluminophosphate or 5APO. Hence, the term QAPSO does not necessarily indicate the presence of the elements Q and S (actually Si). , in which case the elements present, to the extent contemplated by the present invention, the structure of the implementation is ELAPSO or ELAPO or M e A P as discussed herein.
O or MeAPSO structure. However, Q
If it is intended to invent molecular sieves of QAPSO variants in which QAPSO is another element, we intend to include them as molecular sieves suitable for carrying out the present invention.

An illustrative example of QAPSO composition and structure is provided by Lai. Murakami, Ni, Shijima, J, W, Ward (J, W,
``Aluminophosphate molecular sieves and The various compositions and structures described in the paper entitled ``Xaviariodic Table''. A variety of such compositions and structures are described in: (1) U.S. Pat. No. 4.567.029.
, 4.440.871.4.500.651.4,55
No. 4,143.4.310.440, (2) European Patent Publication 0159, published October 30, 1985.
No. 624; European Patent Publication 0161488.0161489゜0, published on November 21, 1985
No. 161490.0161491; each October 1985
European Patent Publication 015897 published on 23rd of May
5 and 0158'976: October 16, 1985, respectively.
European Patent Publications Nos. 0158348 and 0158350 published on

The effective pore diameter of presently useful molecular sheets preferably ranges from about 6 to about 15 angstroms.

Compositions of solid compositions particularly useful in the present invention include molecular sieves in an amount effective to promote the desired hydrocarbon cracking, e.g., in a catalytically effective amount, e.g. It is a porous matrix material that includes an amorphous material that may or may not be oxidized. Included among such matrix materials are clays and amorphous compositions such as alumina, silica, silica-alumina, magnesia, zirconia, and mixtures thereof. Molecular sieves are incorporated into the matrix material from about 1 to about 75% by weight of the total solids composition, preferably from about 2 to about 5 -layers.
Preferably, it is included in an amount within the range of 0% by weight. Catalytically active molecular sieves formed during the production of the solid composition and/or as part of the process for producing the solid composition are within the scope of the present invention.

The form, eg particle size, of the solid composition is not critical to the invention and can vary depending on, eg, the type of reaction-regeneration system employed. Such compositions may be formed using conventional methods into any desired particles, such as buildings, cakes, extrudates, powders, granules, spheres, etc. For example, if the final particles are intended to be used as a fixed bed, The solid composition has a minimum dimension of at least about 0.01 inch (
0.25 mm) and maximum dimension approximately 1.8 inches (1.8 cm)
It may be preferable to form particles up to 1 inch (2.5 cm) or larger. Diameter 0.
0.03 to about 0.125 inches (0,08 to 6.4 mm), preferably about 0.03 to about 0.15 inches (O,OS to 3
．． Spherical particles having a diameter of 8 mm) are often useful, especially in fixed bed or moving bed operations. For fluidized bed systems, solid particles by weight are approximately 10
Preferably, the layer has a diameter in the range from about 20 to about 150 microns, preferably from about 20 to about 150 microns.

The solid compositions of the invention can be prepared by any one of several conventional methods. One method involves creating a sol containing the matrix material and/or a precursor of the material and another aqueous slurry containing the molecular sieve component and the metal component. The slurry can be milled to achieve the desired particle size distribution. Mix the sol and slurry together. The resulting mixture can be spray dried and the resulting microspheres can be washed free of attached soluble salts using, for example, dilute ammonium sulfate solution and water. Rare earth metal ions may also be exchanged into microspheres. After such washing/ion exchange, the microspheres are fired.

If the metal component is intended to be in separate particles from the molecular sieve-containing particles, it is preferred that the metal component is combined with a porous matrix material, eg as described above, into said separate particles. In one embodiment, the size and/or shape of the other particles is substantially the same as the size and/or shape of the molecular sieve-containing particles. Preferably, the metal component comprises from about 1% to about 75% by weight of the separate particles. Other presently useful particles can be made using any one of several conventional techniques. For example, an aqueous slurry of metal components can be milled to achieve the desired particle size distribution. This milled slurry is combined with an aqueous slurry containing matrix material. The milled slurry is then spray dried and the resulting microspheres are fired.

The solid compositions, such as solid particles, of the present invention are preferably used in the cracking of hydrocarbon feedstocks to lower boiling products such as gasoline and light distillate cuts. Hydrocarbon feedstocks often include gas oil fractions, such as those derived from petroleum, shale oil, tar sands oil, coal, and the like. Such feedstocks are straight run,
For example, it may contain a mixture of virgin, gas oil. Such gas oil fractions are primarily from about 400 to about 1000'F (2
It often boils in the range 04° to 538°C). Other hydrocarbon feedstocks, such as petroleum naphtha,
High boiling or heavy fractions, petroleum residues, shale oil, tar sands oil, coal, etc. can be cracked using the catalyst and method of the present invention. Such hydrocarbon feedstocks often contain small amounts of other elements such as sulfur, nitrogen, oxygen, etc.

The present methods and compositions are particularly useful for converting hydrocarbon feedstocks containing contaminant amounts of at least one metal selected from the group consisting of vanadium, nickel, iron, and mixtures thereof, particularly vanadium. About 10 to about 30,00 by weight, calculated as vanadium element
Hydrocarbon feedstocks containing amounts in the range of 0 ppm or more can be effectively processed. The catalyst-containing solid particles contain about 2% by weight of vanadium, calculated on elemental beige.
Preferably, the layer contains less, preferably about 1% by weight or less.

Hydrocarbon cracking conditions are well known and approximately 850
This often involves temperatures ranging from about 1100'F (454° to 593°C), preferably from about 900" to about 1050 degrees Fahrenheit (482° to 596°C). Other reaction conditions include about 100 psia (7 kg/ cm'' A) or higher; catalyst to oil ratio of 1:2 to about 25:1, preferably from about 3:1 to about 15:1: weight hourly space velocity (WH3
V) typically from about 3 to about 60. These hydrocarbon cracking conditions may vary depending on, for example, the feedstock used, the solid particles or combined particles, the reactor-regenerator system employed, such as a fluidized bed or moving bed catalytic cracking system, and the desired products. Can be done. Preferably, the contacting of the hydrocarbon feedstock/solid composition is conducted in the substantial absence of added free molecular hydrogen.

In addition, the catalytic hydrocarbon cracking system includes a regeneration zone that restores the catalytic activity of the solid composition previously used to promote hydrocarbon cracking to the carbonaceous deposit-containing solid composition from the zero reaction zone. A free oxygen-containing gaseous medium is contacted with the solid composition under conditions that remove, or burn, at least a portion of the carbonaceous material from the solid composition, thereby restoring or maintaining the activity of the catalyst. The conditions under which such free oxygen gas contact is carried out are:
For example, it can vary over a conventional range. The temperature within the catalyst regeneration zone of the hydrocarbon cracking system ranges from about 900" to about 15"
00"F (482'-816C), preferably about 1
100' to about 1350 below (593° to 732°C), preferably about 11oo'' to about 1300 below (593° to 7
04°C) range. Other conditions within such a regeneration zone are, for example, about 100 psia (7k
g/cm2A) or above and about 3 to about 7
Includes average catalyst contact time within 5 minutes. The amount of carbonaceous material deposited on the solid composition in the reaction zone is preferably such that there is enough oxygen in the regeneration zone to completely burn out the carbon and hydrogen of the carbonaceous deposits to carbon dioxide and water. preferably ranges from about 0.005 to about 15% by weight of the solid composition, preferably from about 0.1 to about 5%.

The following examples illustrate some aspects and advantages of the invention and are not intended to limit the invention.

The composition used for the test was prepared as follows.

531 grams of barium chromate and 38 grams of amorphous alumina
A slurry of 0 grams, 885 grams of sodium Y zeolite (on silica/alumina basis), and 6900 grams of water was prepared. The slurry was sand milled to reduce particle size. 8850 grams of the milled slurry was mixed with 5900 grams of silica sol binder and 1741 grams of 61% by weight kaolin clay/water slurry in a collarless mixer. This mixed slurry was then spray dried at an exit temperature of 325°F (163°C).

A slurry containing 1000 grams of spray-dried microspheres (dried beige) and 4000 grams of water was prepared and collected on a Buchner funnel.
140 for 400 grams of ammonium sulfate in 000 grams
It was ion-exchanged at 60°C, washed with 6000 grams of water, and ion-exchanged with a solution containing 43.2 grams of mixed rare earth chloride hydrate and 1528.8 grams of water. The cake was then washed with 4000 grams of water and 2
Oven dried at 12°F (100°C) and baked at 1000°C (538°C) for 1 hour. After firing, the microspheres were re-exchanged with 133 grams of ammonium sulfate in 1330 grams of water, washed with 6000 grams of water, and heated under 300 grams (14
It was dried in an oven at 9°C. The final composition is Zeolite 2
The microspheres contained 5% by weight and 15% by weight of barium chromate.

Example 1 was repeated except that in Example 2 barium zirconate was replaced by barium chromate and in Example 3 barium stannate was replaced by barium chromate. Each of the final compositions were microspheres containing 25% by weight zeolite and 15% by weight barium zirconate (Example 2) or barium stannate (Example 3).

Example 1 except that barium titanate was replaced with barium chromate.
repeated. The composition was microspheres containing 25% by weight zeolite and 5% by weight barium titanate.

9 l Barium titanate 30 instead of 459 grams of titanate
6 grams, 214 grams and 153 grams, respectively, and 1643 grams of the kaolin clay/water slurry instead of 1490 grams of the kaolin clay-water slurry;
Example 4 was repeated three times, except using 1753 grams and 1796 grams, respectively. Each of the final compositions were microspheres containing 25% by weight of zeolite and the following weight% of barium titanate: Examples 5 - 10 Examples 6-7 Examples 7 - 5° Takumi and Barium Titanate Example 1 was repeated five times, but with different metal components. Each of the final compositions were microspheres containing 25% by weight zeolite and 15% by weight of the following metal components: Example 8 Ca5nOs Example 9 BaCl2 Example 10 BaSO4 Example 11 BaCO5- Example 1 2 BaCl2/Ti (OCsLL
The compositions used for testing were prepared as follows.

A slurry containing 2.500 grams of barium titanate in 7,500 grams of water was sand milled to reduce particle size. 7,000 grams of the milled slurry was mixed in a colorless mixer with 8,500 grams of peptized pseudoboehmite slurry containing 10% by weight alumina, 300 grams of 50% by weight silica sol, and 61% by weight kaolin clay/water. 3,688 grams of slurry was mixed.

The mixed slurry was spray dried at an exit temperature of 300°C (149°C).

The spray-dried microspheres were calcined at 1.000° C. (538° C.) for 1 hour. The calcined microspheres contained 35% by weight barium titanate, 17% by weight alumina, and no zeolite.

A blend of these microspheres and commercially available decomposition catalyst particles (Katalystiks, a decomposition catalyst sold by Incorporated under the trade name SI GMA 600) was added to the final mixture. Alternatively, a composition was prepared containing 15% barium titanate.

Koigami A Each of the compositions prepared in Examples 1-13 was impregnated with various levels of vanadium to artificially simulate the deposition of vanadium on cracking catalyst particles during a hydrocarbon cracking operation. These impregnations are described in [n.d.

Eng, Chem, Proc, Res, Dev,,
19 (1980) 209 B, R, Mitchell (B, l'l.

The experiment was carried out using the industrially recognized metal (vanadium) nathanate described in the paper by J. Mitchell.

The hydrocarbon catalytic cracking performance of each of the compositions prepared in Examples 1-13 and the vanadium-impregnated composition prepared in Example 4 was determined using a standard microactivity test or MAT (AST).
MD3907-80). Prior to microactivity testing, the composition was subjected to normal MA
Hydrothermally aged under 1,400° C. (760° C.) for 5 hours in a 100% steam environment under T-steamer dynamics. Standard space velocity, catalyst/oil pores, product identification and M
Using AT charging material, the hydrocarbon decomposition performance was reduced to 900% (
487°C). The MAT results are shown in Tables 1-4.

These results demonstrate that barium chromate, barium zirconate, and barium stannate are effective in reducing the deleterious effects of vanadium on molecular sieve-containing catalytic cracking catalyst compositions. These metal components, especially barium chromate, are particularly effective when the vanadium content of the catalyst composition is less than 2% by weight. For example, barium chromate surprisingly performs as well as or better than barium titanate at such catalytic vanadium concentrations. is unexpectedly effective in reducing the harmful effects of

Although the invention has been described with respect to various specific examples and embodiments, it is to be understood that the invention is not limited thereto and may be practiced in various ways within the scope of the claims.

Claims (1)

Claims: 1. Supplying the hydrocarbon feedstock in a contacting zone at conditions effective to decompose the hydrocarbon feedstock into one or more lower boiling point components; A catalytic cracking process comprising contacting in the presence of a solid composition containing a molecular sieve-containing catalyst capable of promoting the cracking of a feedstock, the contacting comprising, in addition to the catalyst, a mixture of barium and chromium, zirconium and tin. A method characterized in that it is carried out in the presence of at least one metal component containing at least one other metal selected from the group consisting of: 2. The feedstock comprises an amount of at least one contaminant metal, and the metal component is present in an amount effective to reduce the deleterious effects of the contaminant metal on the catalyst. the method of. 3. The method according to claim 2, wherein the contaminating metal is vanadium. 4. The method according to claim 1, wherein the metal component further contains oxygen. 5. The method according to claim 2, wherein the metal component further contains oxygen. 6. The method according to claim 1, wherein said other metal is chromium. 7. The method according to claim 4, wherein the other metal is chromium. 8. The method according to claim 7, wherein the metal component is barium chromate. 9. The method of claim 1, wherein said metal component is present in an amount ranging from 0.1 to 25% by weight of said solid composition. 10. The method of claim 1, wherein said metal component is present in an amount ranging from 1 to 20% by weight of said solid particles. 11. The method of claim 1, wherein the catalyst is present in solid particles and the metal component is present in at least a portion of the solid particles. 12. The method of claim 1, wherein said catalyst is present in solid particles and said metal component is present separately from said solid particles. 13. Periodically contacting the solid particles with an oxygen-containing gaseous medium to remove at least a portion of the carbonaceous deposits formed during the feedstock/solid composition contact, and the periodic contacting A method according to claim 1, which is carried out in the presence of the components. 14. A molecular sieve-containing catalyst capable of promoting the decomposition of vanadium-contaminated hydrocarbon feedstocks and an amount of barium and at least one other metal effective to reduce the deleterious effects of vanadium on the catalyst. A composition comprising at least one metal component containing chromium, zirconium, and tin. 15. The composition according to claim 14, wherein the metal component further contains oxygen. 16. Claim 1, wherein the other metal is chromium.
Composition according to item 4. 17. The composition according to claim 14, wherein the metal component is barium chromate. 18. The composition of claim 14, wherein said metal component is present in an amount ranging from 0.1 to 25% by weight of said catalyst. 19. The composition of claim 14, wherein the catalyst is present in solid particles and the metal component is present in the solid particles. 20. The composition of claim 14, wherein the catalyst is present in solid particles and the metal component is separate from the solid particles.