AU2011202519B2

AU2011202519B2 - Additives for metal contaminant removal

Info

Publication number: AU2011202519B2
Application number: AU2011202519A
Authority: AU
Inventors: Albert A. Vierheilig
Original assignee: Intercat Inc
Current assignee: Johnson Matthey Process Technologies Inc
Priority date: 2004-09-08
Filing date: 2011-05-30
Publication date: 2012-03-29
Anticipated expiration: 2025-09-07
Also published as: AU2011202519A1

Abstract

The present invention is directed to catalytic cracking additives comprising a metals trapping material; and a high activity catalyst. The present invention is directed to processes for the catalytic cracking of feedstock comprising contacting said feedstock under catalytic cracking conditions with a composition comprising a bulk catalyst and a catalytic cracking additive, wherein the catalytic cracking additive comprises a metals trapping material; and a high activity catalyst. The invention is also directed to processes for increasing the performance of a bulk catalyst in the presence of at least one metal comprising contacting a feedstock with a catalytic cracking additive comprising a metals trapping material; and a high activity catalyst. WO 20061029129 PCTUS200IO31 649 tN 2 p an SRO Buh~lk cat ayst in i . La*4 T Fitro1

Description

AUSTRALIA Regulation 3.2 Patents Act 1990 COMPLETE SPECIFICATION DIVISIONAL APPLICATION APPLICANT: Intercat, Inc. Invention Title: ADDITIVES FOR METAL CONTAMINANT REMOVAL The following statement is a full description of this invention, including the best method of performing it known to me: P:\CommonWord97 34001-34500\4013INT\20110 52 3 APO - File Falent Application doc WO 20061029129 PCT/ S2005/031649 Additives for Metal Contaminant Removal Throughout this application, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by referene into this application in order to more fully describe the state of the art as known to those skilled 5 therein as of the date of the invention described and claimed herein. The disclosure of this patent document contains material which is s bject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as it appears in t e Patent and Trademark Office patent file or records, but otherwise reserves all copyrigh rights 10 whatsoever. Field of the Invention The invention provides compositions and methods for mitigating the deleterious effect of metal contaminants on catalytic cracking. 15 Background of the Invention Catalytic cracking is a petroleum refining process that is applied commercially on a very large scale. A majority of the refinery gasoline blending pool in the United States is produced by this process, with almost all being produced using the fluid catalytic 20 cracking ("FCC") process. In the FCC process, heavy hydrocarbon fraction are converted into lighter products by reactions taking place at high temperature in the presence of a catalyst, with the majority of the conversion or cracking occur ing in the gas phase. The FCC feedstock is thereby converted into gasoline, distillate and other liquid cracking products as well as lighter gaseous cracking products of four or fe er carbon 25 atoms. These products, liquid and gas, consist of saturated and unsaturated hydrocarbons. In FCC processes, feedstock is injected into the riser section of a FCC reactor, where it is cracked into lighter, more valuable products by contacting hot ca alyst that has been circulated to the riser-reactor from a catalyst regenerator. As the endothermic cracking reactions take place, heavy carbon is deposited onto the catalyst. Tais heavy 30 carbon, known as coke, reduces the activity of the catalyst and the catalyst rust be regenerated to revive its activity. The catalyst and hydrocarbon vapors are carried up the riser to the disengagement section of the FCC reactor, where they are separate ed. 1 WO 20061029129 PCT/US2005/031649 Subsequently, the catalyst flows into a stripping section, where the hydrocarbon vapors entrained with the catalyst are stripped by steam injection. Following removal of occluded hydrocarbons from the spent cracking catalyst, the stripped catalyst flows through a spent catalyst standpipe and into the catalyst regenerator. 5 Typically, catalyst is regenerated by introducing air into the regenerator and burning off the coke to restore catalyst activity. These coke combustion reactions are highly exothermic and as a result, heat the catalyst. The hot, reactivated catalyst flows through the regenerated catalyst standpipe back to the riser to complete the catalyst cycle. The coke combustion exhaust gas stream rises to the top of the regenerator through the 10 regenerator flue. The exhaust gas generally contains nitrogen oxides (NOx), sulfur oxides (SOx), carbon monoxide, carbon dioxide, ammonia, nitrogen, and oxygen. The performance of a fluid catalytic cracking unit can be measured by the conversion of crude hydrocarbon feedstock into useable products such as gasoline. With the addition of a catalytic cracking catalyst, conversion will increase, but so will the 15 production of undesirable side products including coke and hydrogen gas. It is desirable to increase the conversion of an FCC unit while minimizing the increase in coke and H 2 byproducts. The presence of metal contaminants in feedstock presents a serious problem. Common metal contaminants include iron, nickel, sodium, and vanadium. Some of these 20 metals can promote dehydrogenation reactions during the cracking sequence, which can result in increased amounts of coke and light gases at the expense of gasoline production. Metal contaminants can also have a detrimental effect on cracking products. Metal contaminants can deposit on the catalyst and affect its stability and crystallinity. In some cases, the catalyst can be deactivated by the metal contaminants. During the regeneration 25 step, metals present within the catalyst can volatize under the hydrothermal conditions and re-deposit on the catalyst. For example, vanadium contaminants in feedstock can poison the cracking catalyst and reduce its activity. One theory to explain this poisoning mechanism is that vanadium compounds in the feedstock can become incorporated into the coke deposited on the 30 cracking catalyst, and are then oxidized to vanadium pentoxide in the regenerator as the coke is burned off. Vanadium pentoxide can react with water vapor in the regenerator to form vanadic acid, which can then react with the cracking catalyst to destroy its crystallinity and reduce its activity. 2 WO 2006/029129 PCT/US2005/031649 Because compounds containing vanadium and other metal contaminants cannot generally be removed from the FCC unit as volatile compounds, the usual approach has been to passivate these compounds under the conditions encountered during the cracking process. Passivation can involve incorporating additives into the cracking catalyst or 5 adding separate additive particles into the FCC unit along with the cracking catalyst. These additives can preferentially combine with the metal contaminants and act as "traps" or "sinks" so that the active component of the cracking catalyst is protected. Metal contaminants can then be removed along with the catalyst that is withdrawn from the unit during its normal operation. Fresh metal passivating additives can then be added to the 10 unit, along with makeup catalyst, in order to affect a continuous withdrawal of the detrimental metal contaminants during operation of the FCC unit. Depending on the level of metal contaminants in the feedstock, the quantity of additive can be varied relative to the makeup catalyst in order to achieve the desired degree of metals passivation. Industrial facilities are continuously trying to find new and improved methods to 15 increase the conversion of an FCC unit while minimizing the increase in coke and H 2 byproducts. The invention is directed to these and other important ends. Summary of the Invention The present invention is directed to catalytic cracking additives comprising a 20 metals trapping material; and a high activity catalyst. The present invention is directed to processes for the catalytic cracking of feedstock comprising contacting said feedstock under catalytic cracking conditions with a composition comprising a bulk catalyst and a catalytic cracking additive, wherein the catalytic cracking additive comprises a metals trapping material; and a high activity catalyst. The invention is also directed to processes 25 for increasing the performance of a bulk catalyst in the presence of at least one metal comprising contacting a feedstock with a catalytic cracking additive comprising a metals trapping material; and a high activity catalyst. 3 WO 2006/029129 PCT/US2005/031649 Brief Description of the Figures Figure 1 shows X-ray diffraction ("XRD") patterns of a high activity catalyst and a bulk catalyst. Figure 2 shows XRD patterns of fresh and deactivated bulk catalyst. 5 Figure 3 shows XRD patterns of fresh bulk catalyst, deactivated bulk catalyst, and bulk catalyst in the presence of a catalytic cracking additive of the present invention. Detailed Description of the Invention The present invention is directed to catalytic cracking additives comprising a 10 metals trapping material; and a high activity catalyst. The present invention is directed to processes for the catalytic cracking of feedstock comprising contacting said feedstock under catalytic cracking conditions with a composition comprising a bulk catalyst and a catalytic cracking additive, wherein the catalytic cracking additive comprises a metals trapping material; and a high activity catalyst. The invention is also directed to processes 15 for increasing the performance of a bulk catalyst in the presence of at least one metal comprising contacting a feedstock with a catalytic cracking additive comprising a metals trapping material and a high activity catalyst. The term "XRD" as used herein means x-ray diffraction. The term "FCC" as used herein means fluid catalytic cracking. 20 The term "Re" as used herein means rare earth. Applicant has surprisingly discovered that the catalytic cracking additives of the invention can increase catalytic conversion but without increased coke or gas production. Applicant has recognized that catalytic cracking is a two-step process with respect 25 to metal contaminants that can be present in feedstock, wherein 1) metal contaminants are deposited on catalyst particles, along with byproducts including coke, under the riser/reactor conditions in an FCC unit; and 2) catalyst particles containing metals are exposed to steam in order to regenerate the catalyst particles. Without wishing to be bound by theory, applicant believes that metal contaminants 30 should be removed from the catalyst particles in order to preserve their catalytic abilities. This physical removal of metal contaminants is needed regardless of whether traditional metals passivating agents that can prevent metals contamination of the catalyst particles are present in the riser/reactor. Applicant further believes that metal contaminants are volatile and can migrate within or from catalyst particles in the presence of steam and high 4 WO 2006/029129 PCT/US2005/031649 temperature, such as under conditions that are effective to regenerate the catalyst particles. Applicant believes that in the presence of steam and high temperature, the catalytic cracking additives herein can function by preferentially adsorbing volatilized metal contaminants, which had been deposited on the catalyst particles. 5 I. Catalytic Cracking Additives In one embodiment is provided a catalytic cracking additive comprising a metals trapping material and a high activity catalyst. In one embodiment, the metals trapping material and the high activity catalyst 10 comprise separate particles. In one embodiment, the metals trapping material and the high activity catalyst particles are added concurrently to the catalytic cracking unit. In another embodiment, the metals trapping material and the high activity catalyst are within the same particle. 15 a) Metals Trapping Material In one embodiment, the metals trapping material comprises a calcium-containing compound, a magnesium-containing compound, or a combination thereof In one embodiment, the metals trapping material is a low-density material. In one embodiment, the metals trapping material has a density that is from about 0.50 g/cc to 20 about 1.0 g/cc. In another embodiment, the density is from about 0.7 to about 0.9 g/cc. In one embodiment, the density is from about 0.50 g/cc to about 0.70 g/cc. In another embodiment, the metals trapping material has a density that is less than about 0.70 gce; less than about 0.69 g/cc; less than about 0.68 g/cc; less than about 0.67 g/cc; less than about 0.66 g/ce; less than about 0.65 g/ce; less than about 0.60 g/cc; or less than about 25 0.55 g/cc. In one embodiment, the metals trapping material is a porous material. In one embodiment, the metals trapping material has a porosity that is greater than about 0.40 cc/g as determined by a water sorption technique. In another embodiment, the metals trapping material has a porosity that is greater than about 0.45 cc/g; greater than about 30 0.50 cc/g; greater than about 0.55 cc/g; or greater than about 0.60 cc/g. In one embodiment, the metals trapping material is a low-density and high porosity material. In one embodiment, the metals trapping material has a density that is less than about 0.70 g/ce, and a porosity that is greater than about 0.40 cc/g. Applicant believes that a metals trapping material that is low-density and high porosity can preferentially absorb WO 2006/029129 PCT/US2005/031649 volatile metal contaminants in the presence of steam and high temperature. One of skill in the art will recognize that the porosity of a material can be a function of the density of the material. In one embodiment, the metals trapping material comprises a hydrotalcite-like 5 compound, a silica- and alumina-containing compound, a mixed metal oxide, or a combination thereof i) Hydrotalcite-like Compounds In one embodiment, the metals trapping material is a hydrotalcite-like compound. Hydrotalcite-like compounds are characterized by structures having positively charged 10 layers that are separated by interstitial anions and/or water molecules. Exemplary natural minerals that are hydrotalcite-like compounds include meixnerite, pyroaurite, sjogrenite, hydrotalcite, stichtite, reevesite, eardleyite, mannaseite, barbertonite and hydrocalumite. Other hydrotalcite-like compounds and methods for making them are described by Cavani et al, Catalysis Today, 11:173-301 (1991), the disclosure of which is incorporated by 15 reference herein in its entirety. In other embodiments, the hydrotalcite-like compound can be a compound of formula (1), (II), (III) and/or (IV):

(X

2 mY 3 n(OH) 2 m+ 2 n)Aia."~- bH2O (I) (Mg2mAl'+(OH)2m+2n)An/a"- bH 2 Q (II) 20 (X 2 mY 3 +n(OH) 2 m+ 2 )OH. - bH 2 0 (III) (Mg2mAl'n(OH)2m+2.)OHn - bH 2 0 (IV) where X is magnesium, calcium, zinc, manganese, cobalt, nickel, strontium, barium, copper or a mixture of two or more thereof; Y is aluminum, manganese, iron, cobalt, nickel, chromium, gallium, boron, lanthanum, cerium or a mixture of two or more thereof; 25 A is CO 3 , NO 3 , SO 4 , Cl, OH, Cr, I, SiO 3 , HPO 3 , MnO 4 , HGaO 3 , HVO 4 , C10 4 , B0 3 or a mixture of two or more thereof; a is 1, 2 or 3; b is between 0 and 10; and in and n are selected so that the ratio of n/n is about 1 to about 10. In one embodiment, the hydrotalcite-like compound is hydrotalcite, i.e., Mg 6 Al 2

(OH)

16 CO3-4H 2 0. In another embodiment, the hydrotalcite-like compound is 30 Mg 6 Al 2

(OH)

1 -4.5H 2 0. The hydrotalcite-like compounds, compositions and/or shaped bodies of the invention can be made by the methods described in U.S. Patent No. 6,028,023. In one embodiment, the hydrotalcite-like compound is a solid solution comprising magnesium and aluminum in a ratio of about 1:1 to about 6:1. 6 WO 2006/029129 PCT/US2005/031649 ii) Silica- and Alumina-containing Compounds In one embodiment, the metals trapping material is an alurninosilicate material. In one embodiment, the aluminosilicate material is a crystalline material, a quasi crystalline material, an amorphous material, or a combination thereof 5 In another embodiment, the aluminosilicate material contains calcium, and the predominant metals trapping capability is performed by the calcium component. In one embodiment, the aluminosilicate material contains no zeolitic component. iii) Mixed Metal Oxides In one embodiment, the metals trapping material is a mixed metal oxide. As used 10 herein the tenn "mixed metal oxide" means a chemical compound in which oxygen is combined with two or more metals. In one embodiment, the mixed metal oxide is a magnesium aluminate. Mixed metal oxide compounds contemplated in one embodiment of the present invention are described, for example, in co-pending U.S. Serial Nos. 60/527,258 and 15 60/576,146. In one embodiment, the mixed metal oxide is a solid solution magnesium aluminate comprising magnesium and aluminum in a ratio of about 1:1 to about 6:1, wherein the calcined form of the solid solution magnesium aluminate has an X-ray diffraction pattern displaying at least a reflection at a two theta peak position at about 43 degrees and about 62 degrees, and wherein the mixed metal oxide is a magnesium- and 20 aluminum-containing compound that has not been derived from a hydrotalcite-like compound. In one embodiment, the mixed metal oxide is a spinel. In another embodiment, the mixed metal oxide is a magnesium aluminate spinel. In another embodiment, the mixed metal oxide is derived from a hydrotalcite-like 25 compound, for example by collapsing the hydrotalcite-like compound. The mixed metal oxide compounds, compositions and/or shaped bodies in one embodiment of the invention can be made by the methods described in U.S. Patent No. 6,028,023. iv) Form of Metals Trapping Materials 30 In one embodiment, the metals trapping material is in the form of a solid solution. In one embodiment, the metals trapping material is used per se in the catalytic cracking additive. In one embodiment, the metals trapping material is in the form of a shaped body. In one embodiment, the shaped bodies are dried, calcined or a mixture thereof In one embodiment, the metals trapping materials can further comprise one or 7 WO 21)06/029129 PCT/US2005/031649 more other metal components such as metals of antimony, bismuth, cadmium, calcium, cerium, chromium, cobalt, copper, dysoprosium, erbium, europium, gadolinium, germanium, gold, holmium, iridium, iron, lanthanum, lead, magnesium, manganese, molybdenum, neodymium, nickel, niobium, osmium, palladium, platinum, praseodymium, 5 promethium, rhenium, rhodium, ruthenium, samarium, scandium, selenium, silicon, silver, sulfur, tantalum, tellurium, terbium, tin, titanium, tungsten, thulium, vanadium, ytterbium, yttrium, zinc, or a mixture of two or more thereof The metals can be in an elemental state and/or can be in the form of metal oxides, metal hydroxides, metal sulfides, metal halides, or mixtures of two or more thereof Some or all of the metal components can also be 10 present as organic or inorganic salts, including, for example, metal nitrate salts and/or metal acetate salts. In one embodiment, the aqueous reaction mixture further comprises calcium (e.g., CaO, Ca(OH) 2 , or CaCO 3 ), magnesium (e.g., MgO, Mg(OH) 2 , or MgCO 3 ), or a combination thereof The one or more metal components (or oxides, sulfides, and/or halides thereof) can be present in the metals trapping material in an amount up to about 15 50% by weight; up to about 40% by weight; up to about 30% by weight; or from about 1% to about 25% by weight; or from about 2% to about 20% by weight, calculated as the oxide equivalent. The one or more other metal components can be added to the metals trapping material at the same time as the components of the metals trapping material. In another embodiment, the invention provides shaped bodies comprising metals 20 trapping materials and one or more metal components. In another embodiment, the metals trapping material is in the form of a solid solution. In one embodiment, the metal in the metal component is antimony, bismuth, cadmium, calcium, cerium, chromium, cobalt, copper, dysoprosium, erbium, europium, gadolinium, germanium, gold, holmium, iridium, iron, lanthanum, lead, magnesium, manganese, molybdenum, neodymium, nickel, 25 niobium, osmium, palladium, platinum, praseodymium, promethium, rhenium, rhodium, ruthenium, samarium, scandium, selenium, silicon, silver, sulfur, tantalum, tellurium, terbium, tin, titanium, tungsten, thulium, vanadium, ytterbium, yttrium, zinc, or a mixture of two or more thereof In another embodiment, the metal in the metal component is calcium, magnesium, or a mixture thereof In one embodiment, the shaped bodies are 30 dried, calcined or a mixture thereof In another embodiment, the invention provides one or more shaped bodies comprising metals trapping material and a support. In another embodiment, the metals trapping material is in the form of a solid solution. In one embodiment, the support is a spinet, hydrotalcite-like compound, magnesium acetate, magnesium nitrate, magnesium 8 WO 2006/029129 PCT/US2005/031649 chloride, magnesium hydroxide, magnesium carbonate, magnesium formate, aluminum titanate, zinc titanate, zinc aluminate, zinc titanate/zinc aluminate, aluminum zirconate, calcium oxide, calcium aluminate, aluminum nitrohydrate, aluminum hydroxide compound, aluminum-containing metal oxide compound (e.g., other than alumina or 5 aluminum hydroxide compounds), aluminum chlorohydrate, titania, zirconia, clay (e.g., halloysite, rectorite, hectorite, montmorillinite, synthetic montmorillinite, sepiolite, activated sepiolite, kaolin), clay phosphate material, zeolite, or a mixture of two or more thereof In one embodiment, the support is zinc titanate, zinc alurninate, or zinc titanate/zinc aluminate. Methods for making such compositions are described, for 10 example, in WO 99/42201. In one embodiment, the shaped bodies can are dried, calcined or a mixture thereof. In another embodiment, the invention provides shaped bodies comprising metals trapping material; one or more metal components; and a support. In another embodiment, the metals trapping material is in the form of a solid solution. In one embodiment, the 15 shaped bodies are dried, calcined or a mixture thereof. In some embodiments of the invention described herein, the metal components are present in an amount of up to about 50% by weight; from about 0.1% by weight to about 40% by weight; from about 1% by weight to about 30% by weight; from about 1% by weight to about 25% by weight; from about 1% by weight to about 20% by weight; from 20 about 1% by weight to about 15% by weight; or from about 1% by weight to about 10% by weight, calculated as the oxide equivalent. In one embodiment, the solid support is present in an amount up to about 50% by weight; from about 1% by weight to about 30% by weight; from about I % by weight to about 20% by weight; from about 1% by weight to about 15% by weight; from about 1% by weight to about 10% by weight; or from about 25 1% by weight to about 5% by weight v) Amount of Metals Trapping Materials In one embodiment, the metals trapping material comprises from about 2% to about 98% of the catalytic cracking additive by weight. In one embodiment, the metals trapping material comprises from about 30% to about 95% of the catalytic cracking 30 additive by weight. In one embodiment, the metals trapping material comprises from about 30% to about 60%; or from about 40% to about 60% of the catalytic cracking additive by weight. In another embodiment, the metals trapping material comprises from about 60% to about 95%; or from about 70% to about 90% of the catalytic cracking additive by weight. 9 WO 2006/029129 PCT/US2005/031649 b) High Activity Catalysts As used herein, the term "high activity catalyst" means a catalyst that has a higher percentage of zeolite and/or a higher overall surface area and/or a higher overall 5 crystallinity than a bulk catalyst. In one embodiment, the high activity catalyst has at least about 1.5 times the percentage of zeolite and/or 1.5 times the overall surface area and/or 1.5 times overall crystallinity than a bulk catalyst. In another embodiment, the high activity catalyst has at least about 2.0 times the percentage of zeolite and/or overall surface area and/or overall crystallinity than a bulk catalyst; or at least about 2.5 times the 10 percentage of zeolite and/or overall surface area and/or overall crystallinity than a bulk catalyst; or at least about 3.0 times the percentage of zeolite and/or overall surface area and/or overall crystallinity than a bulk catalyst; or at least about 3.5 times the percentage of zeolite and/or overall surface area and/or overall crystallinity than a bulk catalyst; or at least about 4.0 times the percentage of zeolite and/or overall surface area and/or overall 15 crystallinity. As an example, Figure 1 shows a conventionally prepared Y zeolite bulk catalyst (bottom trace) compared with a high activity Y zeolite catalyst component of the present invention (top trace). Comparing the Y zeolite XRD peak at about 6.3 degrees shows significantly more diffracted intensity with the high activity catalyst. More diffracted 20 intensity is indicative of the increased crystallinity of the high activity catalyst of the top trace. More diffractive intensity also indicates a higher zeolite content of the high activity catalyst, and can be indicative of the subsequent higher activity of the high activity catalyst. i) Zeolites 25 In one embodiment, the high activity catalyst is a zeolite. In one embodiment, the high activity catalyst is an in situ synthesized zeolite. The zeolites can be stabilized with rare earths, for example, in an amount of from about 0.1 to about 10% by weight. Catalysts including zeolites can contain varying amounts of rare earth compounds. These rare earth compounds can be present during the synthesis of the zeolite, or can be 30 exchanged onto the zeolite following its synthesis. Rare earth-stabilized zeolites are typically denoted "REY". The zeolites can also be stabilized with steam, including, for example, steam stabilized Y zeolite, known as "USY". In one embodiment, the zeolite is zeolite X, Y zeolite, zeolite A, zeolite L, zeolite 10 WO 2006/029129 PCT/US2005031649 ZK-4, beta zeolite, faujasite, or a combination thereof In another embodiment, the high activity catalyst is a large pore zeolite. In one embodiment, the high activity catalyst is beta zeolite, Y zeolite, faujasite, or a combination thereof In another embodiment, the high activity catalyst is rare-earth stabilized beta zeolite, rare-earth stabilized Y zeolite, 5 rare-earth stabilized faujasite, or a combination thereof In one embodiment, the high activity catalyst has an overall surface area of greater than about 350 m 2 /gr; or greater than about 400 m 2 /gr; or greater than about 450 m 2 /gr. In one embodiment, the high activity catalyst has an overall surface area of about 400 m 2 /gr. Exemplary high activity catalysts according to the present invention include, for 10 example, catalysts available commercially from Engelhard Corporation under the trade name Converterm ii) Amount of High Activity Catalysts In one embodiment, the high activity catalyst comprises from about 5% to about 60% of the catalytic cracking additive by weight. In one embodiment, the high activity 15 catalyst comprises from about 5% to about 40%; or from about 10% to about 30% of the catalytic cracking additive by weight. In another embodiment, the high activity catalyst comprises from about 40% to about 60% of the catalytic cracking additive by weight. 11 WO 2006/029129 PCT/US2005/031649 I. Processes for Catalytic Cracking In one embodiment is provided a circulating inventory of catalyst particles in a fluid catalytic cracking process, wherein from about 2% to about 80% by weight of said circulating inventory comprises the catalytic cracking additives as described above. 5 In one embodiment is provided processes for the catalytic cracking of feedstock comprising contacting said feedstock under catalytic cracking conditions with a composition comprising a bulk catalyst and a catalytic cracking additive, wherein the catalytic cracking additive comprises a metals trapping material and a high activity catalyst. 10 In another embodiment is provided processes for improving FCC catalyst performance from a fluid catalytic cracking unit by adding the additives described herein to an FCC unit. In one embodiment is provided processes for increasing the performance of a bulk catalyst in the presence of at least one metal comprising contacting a feedstock with a 15 catalytic cracking additive, wherein the catalytic cracking additive comprises a metals trapping material and a high activity catalyst. In another embodiment, the catalytic cracking additive increases the catalytic conversion of feedstock. In one embodiment, the catalytic cracking additive increases gasoline production from feedstock. In one embodiment, the catalytic cracking additive increases LPG production from feedstock. In 20 another embodiment, the catalytic cracking additive decreases LCO production from feedstock. In one embodiment, the catalytic cracking additive decreases the bottoms production from feedstock. In another embodiment, the catalytic cracking additive decreases the coke production from feedstock. In one embodiment, the catalytic cracking additive decreases hydrogen gas production from feedstock. 25 In one embodiment, the catalytic cracking additive mitigates the decrease in crystallinity of the bulk catalyst. In one embodiment, the catalytic cracking additive mitigates the reduction in the peak area of the 2-theta peak at 6.3 degrees of the bulk catalyst. In one embodiment, the catalytic cracking additive mitigates the reduction in the surface area of the bulk catalyst. 30 a) Feedstock Any conventional FCC feedstock can be used in the FCC unit. The feedstock can range from the typical, such as petroleum distillates or residual stocks, either virgin or partially refined, to the atypical, such as coal oils and shale oils. The feedstock can 12 WO 2006/029129 PCT/US2005/031649 contain recycled hydrocarbons, such as light and heavy cycle oils which have already been subjected to cracking. Exemplary feedstocks include gas oils, vacuum gas oils, atmospheric resids, and vacuum resids. 5 b) Catalytic Cracking Conditions In one embodiment, the catalytic cracking additives can be added to the riser or regenerator of an FCC unit. In another embodiment, the catalytic cracking additives are added to the regenerator of an FCC unit. In one embodiment, the catalytic cracking additives are added to an FCC unit containing bulk catalyst. 10 The catalytic cracking additives and bulk catalysts can be introduced into the FCC unit by manually loading via bags or.drums. The catalytic cracking additives and bulk catalysts can also be introduced into the FCC unit by automated addition systems, as described, for example, in U.S. Patent No. 5,389,236. To introduce the catalytic cracking additives to an FCC unit, the catalytic cracking additives can be pre-blended with bulk 15 catalysts and introduced into the unit as one system. Alternatively, the catalytic cracking additives and bulk catalysts can be introduced into the FCC unit via separate injection systems. In another embodiment, the catalytic cracking additives can be added in a varying ratio to the bulk catalyst. A varying ratio can be determined, for example, at the time of addition to the FCC unit in order to optimize the rate of addition of the catalytic 20 cracking additives. Conventional riser cracking conditions can be used. Typical riser cracking reaction conditions include catalyst/oil ratios of about 0.5:1 to about 15:1 and a catalyst contact time of about 0.1 to about 50 seconds, and riser top temperatures of from about 900'F to about 1050'F. In one embodiment, good mixing of feedstock with catalyst in the 25 base of the riser reactor is provided using conventional techniques such as adding large amounts of atomizing steam, use of multiple nozzles, use of atomizing nozzles and similar technology. The base of the riser can comprise a riser catalyst acceleration zone. In one embodiment, the riser reactor can discharge into a closed cyclone system for rapid and efficient separation of cracked products from spent catalyst. 30 The additives of the invention can be added to any conventional reactor regenerator systems, to ebullating catalyst bed systems, to systems which involve continuously conveying or circulating catalysts/additives between reaction zone and regeneration zone and the like. In one embodiment, the system is a circulating bed system. Typical of the circulating bed systems are the conventional moving bed and 13 WO 2006/029129 PCT/US2005/031649 fluidized bed reactor-regenerator systems. Both of these circulating bed systems are conventionally used in hydrocarbon conversion (e.g., hydrocarbon cracking) operations. In one embodiment, the system is a fluidized catalyst bed reactor-regenerator system. Other specialized riser-regenerator systems that can be used herein include deep 5 catalytic cracking (DCC), millisecond catalytic cracking (MSCC), and resid fluid catalytic cracking (RFCC) systems. c) Bulk Catalysts As used herein, the term "bulk catalyst" means any catalyst which can be used for 10 operating an FCC unit under standard catalytic cracking conditions, including those discussed in more detail above. Any commercially available FCC catalyst can be used as the bulk catalyst. The bulk catalyst can be 100% amorphous, but in one embodiment, can include some zeolite in a porous refractory matrix such as silica-alumina, clay, or the like. The zeolite is usually 15 from about 5 to about 40% of the catalyst by weight, with the rest being matrix or diluent. Conventional zeolites such as Y zeolites, or aluminum deficient forms of these zeolites, such as dealuminized Y, ultrastable Y and ultrahydrophobic Y, can be used. The zeolites can be stabilized with rare earths, for example, in an amount of from about 0.1 to about 10% by weight. 20 The zeolites that can be used herein include both natural and synthetic zeolites. Relatively high silica zeolite containing catalysts can be used in the invention. They can withstand the high temperatures usually associated with complete combustion of CO to CO 2 within the FCC regenerator. Such catalysts include those containing about 10 to about 40% ultrastable Y or rare earth ultrastable Y. 25 In one embodiment, the bulk catalyst has a surface area of less than about 300 m 2 /gr. In another embodiment, the bulk catalyst has a surface area of about 250 m 2 /gr. A suitable bulk catalyst can also include a catalyst that has been synthesized by an in situ technique and then blended with a diluent. This can include, for example, a high activity catalyst, as defined herein, and a diluent. In one embodiment, the bulk catalyst 30 includes from about 5% to about 70% of a high activity catalyst by weight. In another embodiment, the bulk catalyst includes from about 5% to about 40% of a high activity catalyst by weight. d) Catalytic Cracking Additives 14 WO 2016/029129 PCT/US2005/031649 The catalytic cracking additives comprise a metals trapping material and a high activity catalyst, as set forth in more detail above. In one embodiment, the catalytic cracking additive comprises from about 2% to about 80% of the composition by weight. In one embodiment, the catalytic cracking 5 additive comprises from about 20% to about 60% of the composition by weight. In one embodiment, the catalytic cracking additive comprises from about 40% to about 60% of the composition by weight. In another embodiment, the catalytic cracking additive comprises from about 5% to about 20%; or about 10% of the composition by weight. 10 e) Other Components The catalyst inventory can also contain one or more additives in addition to the bulk catalyst and the catalytic cracking additive of the present invention, either present as separate additive particles, or mixed in with each particle of the cracking catalyst. Additives can be added to enhance octane, such as medium pore size zeolites, e.g., ZSM-5 15 and other materials having a similar crystal structure. Additives can also be added to promote CO combustion; to reduce SOx emissions, NOx emissions and/or CO emissions; to promote catalysis; or to reduce gasoline sulfur. In one embodiment, the catalytic cracking additive of the present invention also serves to enhance octane, promote CO combustion, reduce SOx emissions, NOx emissions 20 and/or CO emissions, to promote catalysis, or to reduce gasoline sulfur. Examples The following examples are for purposes of illustration only and are not intended to limit the scope of the claims appended hereto. 25 15 WO 2006/029129 PCT/US2005/031649 Example 1: Hydrotalcite-like Compounds Hydrotalcite compounds were prepared following the methods described herein and in U.S. Patent No. 6,028,023. MgO powder (having a surface area of about 100 m 2 /g) (MAGOX@, Premier 5 Chemicals, Cleveland, OH) is slurried in water at a solids level of about 14%. Thereafter, 5.2% technical grade acetic acid is added to the MgO slurry. Separately, pseudoboehmite (P2@ Condea) is dispersed in water at a solids level of 8% to produce an alumina sol. The MgO slurry and alumina sol are mixed in a container such that the molar ratio 10 of Mg/Al of the preparation was 4:1. Additional water is added to the mixture to adjust the solids content of the mixture to about 9%. The mixture is heated to about 214*F over period of about 5 hours. Once heated, 8 dry basis parts of the resulting slurry was mixed with 2 dry basis parts of technical grade calcium hydroxide along with sufficient water to give a final solids content of about 10%. The mixture is then spray dried under standard 15 conditions to produce microspheroidal particles with an average particle size of about 75 80 microns. The product is then calcined in a rotary calciner at an approximate equivalent temperature of about 600*C for 1 hour. The substance is further hydrated with water to produce a hydrotalcite-like phase. The x-ray diffraction pattern shows that the predominant magnesium aluminum phase was most closely represented by 20 Mg 6 A1 2 OHi8-4.5H 2 0, as depicted in ICDD card 35-965. This substance is referred to herein as "Metals Trap A". The hydrotalcite-like compound is then collapsed by heating at about 500*C until a solids content of about 8% is reached. Attrition resistant microspheres with an ASTM 2 hour attrition of about 2.1, apparent bulk density of about 0.72 g/cc, a surface area of about 65 rn 2 /g, and a pore volume of about 0.45 ce/g were 25 obtained. Example 2: Silica- and Alumina-containing Compounds A metals trapping additive containing a calcium oxide active component was prepared by mixing, on an ignited basis, 3 parts calcium hydroxide, 3 parts 30 pseudoboehmite alumina gel, 0.5 parts silica sol and 4 parts kaolin clay. Sufficient excess water was included such that the final solids was approximately 20 weight percent. The resulting slurry was spray dried to an average particle size of about 100 microns and calcined to a final LOI of about 5 weight percent. Attrition resistant microspheres with an ASTM 2 hour attrition of about 1.2, apparent bulk density of about 0.64 g/cc, a surface 16 WO 2006/029129 PCTUS2005/031649 area of about 60 m 2 /g, and a pore volume of about 0.54 cc/g were obtained. This substance is referred to herein as "Metals Trap B". Example 3: Mixed Metal Oxides 5 Magnesium aluminate was prepared following the methods described herein and in U.S. Patent No. 6,028,023. MgO powder (having a surface area of about 100 m 2 /g) (MAGOX@, Premier Chemicals, Cleveland, OH) is slurried in water at a solids level of about 14%. Thereafter, 5.2% technical grade acetic acid is added to the MgO slurry. 10 Separately, pseudoboehmite (P2@ Condea) is dispersed in water at a solids level of 8% to produce an alumina sol. The MgO slurry and alumina sol are mixed in a container such that the molar ratio of Mg/Al of the preparation was 4:1. Additional water is added to the mixture to adjust the solids content of the mixture to about 9%. The mixture is heated to about 214"F over a 15 period of about 5 hours. Once heated, 8 dry basis parts of the resulting slurry was mixed with 2 dry basis parts of technical grade calcium hydroxide along with sufficient water to give a final solids content of about 10%. The mixture is then spray dried under standard conditions to produce microspheroidal particles with an average particle size of about 75 100 microns. The product is then calcined in a rotary calciner at an approximate equivalent 20 temperature of about 600'C for 1 hour to.produce a mixed metal oxide of magnesium, calcium and aluminum. Example 4: Improved FCC Catalyst Performance To evaluate the performance of the additives, feedstock was catalytically cracked 25 under FCC reactor-like conditions with various bulk catalyst/additive combinations. The bulk catalyst was comparable to commercially available catalysts and formulated with 25% rare earth exchanged Y zeolite in an active matrix of about 30% pseudoboehmite alumina gel and silica sol. The catalyst slurry was spray dried to form microspheroidal particles and then calcined. The catalyst surface area was measured to be about 250 m 2 /g 30 and the rare earth content on a Re 2 0 3 basis was about 1.3wt%. The high activity catalyst used was a Y zeolite prepared via an in situ technique from clay microspheres, available commercially from Engelhard Corporation under the trade name Converterm The surface area was approximately 400m 2 /g with a total rare earth content on a Re 2 03 basis of about 5%, and the pore volume was about 0.54 cc/g. 17 WO 2006/029129 PCT/US2005/031649 Each catalyst mixture (with or without additive components) was first calcined individually at 732*C for one hour and then deactivated according to protocol. Vanadium and nickel naphthanates were cracked onto each specific catalyst mixture using a commercially available automated deactivation unit (Kayser Technologies Model D-100). 5 Then the metal contaminated catalyst was steam treated at 800'C with about 50% steam for about 9 hours. The catalyst mixtures had a final vanadium concentration of about 10,000 ppm and nickel concentration of about 900 ppm. For comparison, a fresh bulk catalyst was also deactivated under the same protocol as the catalyst mixture. An XRD pattern comparison of a bulk catalyst, with and without deactivation, is shown in Figure 2. 10 Figure 2 demonstrates that the deactivation process has a significant impact on the crystal structure of the Y zeolite contained within the bulk catalyst. To measure catalytic performance, deactivated catalyst mixtures were then loaded into a commercially available, laboratory-scale FCC test unit (Kayser Technology ACE model R+). ACE conditions included a reactor temperature of about 985 0 F, catalyst to oil 15 ratio of about 7, weighted hourly space velocity of about 8, and using a standard US Gulf Coast feedstock. In Test Run IA, no additive was used. In Test Runs 1B-IF, the additive was Metals Trap A as described in Example 1 and/or the high activity catalyst Y Zeolite, sold under the trade name ConverterT". In Test Runs I B- 1 F, the additive made up 10% of the 20 total catalyst mixture. Performance results for Metals Trap A as the metals trapping material are given in Table 1, below. All data is given as weight percentages. 18 WO 2006/029129 PCT/US20051031649 Table 1. FCC Catalyst Performance Results for Metals Trap A Test % Additive Conversion LPG Gasoline LCO Bottoms Coke Hz Run Additive (%) Yield Yield Yield Yield Yield Yield in Catalyst Mixture 1A 0 None 60.9 14.5 30.9 21.6 17.5 12,2 1.0 1B 10% High 60.1 13.8 31.3 21.4 18.5 11.8 0.9 activity catalyst iC 10% Metals 70.5 20.3 38.8 15.6 13.9 8.5 0.7 Trap A 1D 10% 90% 71.4 22.1 37,5 18A 10.2 8.9 0.6 Metals Trap A 10% high activity catalyst 1E 10% 80% 68.4 21.0 36.5 19.1 12.4 8.2 0.5 Metals Trap A 20% high activity catalyst IF 10% 70% 69.2 20.4 36.3 19.4 11.4 9.3 0.8 Metals Trap A 30% high activity catalyst In Test Runs 2A-2D, conditions were as above for Test Runs 1A-IF, except that catalyst mixtures had a final vanadium concentration of about 5000 ppm and nickel 5 concentration of 2000 ppm, the catalyst to oil ratio was about 6.0, and using a Mexican Mayan crude feedstock. In Test Run 2A, no additive was used. In Test Runs 2B-2D, the additive was Metals Trap A as described in Example 1 and the high activity catalyst Y Zeolite, sold under the trade name Converter . In Test Runs 28-2C, the additive made up 25% of the total catalyst mixture. In Test Run 2D, the additive made up 50% of the 10 total catalyst mixture. Additional performance results for Metals Trap A as the metals trapping material are given in Table 2, below. All data is given as weight percentages. 19 WO 2006/029129 PCT/US2005/031649 Table 2. FCC Catalyst Performance Results for Metals Trap A Test % Additive Conversion LPG Gasoline LCO Bottors Coke H, Run Additive (%) Yield Yield Yield Yield Yield Yield in Catalyst Mixture 2A 0 None 56.8 13.3 26.4 22.2 21.0 13.6 1.2 2B 25% 50% 66.1 18.7 35.7 20.0 13.5 9.0 0.6 Metals Trap A 50% high activity catalyst 2C 25% 40% 65.9 18.4 35.0 20.5 13.5 9.6 0.8 Metals Trap A 60% high activity catalyst 2D 50% 40% 68.1 17.4 39.7 19.7 12.2 8-3 0.6 Metals Trap A 60% high activity catalyst In Test Runs 3A-3F, conditions were as above for Test Runs 1A-IF, except for the additive. In Test Run 3A, no additive was used. In Test Runs 3B-3F, the additive was 5 Metals Trap B as described in Example 2 and/or the high activity catalyst Y Zeolite, sold under the trade name ConverterTM. In Test Runs 3B-3F, the additive made up 10% of the total catalyst mixture. Performance results for Metals Trap B as the metals trapping material are given in Table 3, below. All data is given as weight percentages. 10 20 WO 2006/029129 PCT/JUS20051031649 Table 3. FCC Catalyst Performance Results for Metals Trap B Test % Additive Conversion LPG Gasoline LCO Bottoms Coke Hz Run Additive (%) Yield Yield Yield Yield Yield Yield in Catalyst Mixture 3A 0 None 60.9 14.5 30.9 21.6 17.5 12.2 1.0 313 10% High 60.1 13.8 31.3 21.4 18,5 11.7 0.9 activity catalyst 3C 10% Metals 63.7 16.4 33.4 21.3 15.0 10.6 0.9 Trap B 3D 10% 90% 66.6 18.9 34.4 20.0 13.3 10.4 0.8 Metals Trap B 10% high activity catalyst 3E 10% 80% 66.0 18.5 34.8 20.3 13,6 9.6 0.8 Metals Trap B 20% high activity catalyst 3F 10% 70% 66.7 18.0 35.1 20.6 12.7 10.3 0.9 Metals Trap B 30% high activity catalyst The results reported in Tables 1, 2, and 3 demonstrate a synergistic effect from using an additive that contains both a high activity catalyst and a metals trapping material. 5 Essentially no benefit is seen from using the high activity catalyst alone as an additive, but the benefits of high activity catalyst in combination with a metals trapping material in the additive is generally greater than the benefit of metals trapping material alone. The combination of a high activity catalyst and metals trapping material in an additive increases conversion, increases LPG yield, increases gasoline yield, decreases LCO yield, 10 decreases bottoms yield, and decreases coke yield, and decreases hydrogen gas yield. 21 WO 2006/029129 PCT/US2005/031649 Example 5: Crystallinity of Fresh Catalysts Powder x-ray diffraction using Cu Ka radiation and surface area measurements (single point BET) were first taken of the fresh bulk catalyst and fresh high activity catalyst as described in Example 4. These results are given in Table 4, below. 5 Table 4. Crystallinity of Fresh Catalysts Peak (6.3* 2-0) Area Fresh Bulk Catalyst 4236 Fresh High Activity Catalyst 14554 The results reported in Table 4 demonstrate the distinction between a bulk catalyst and a high activity catalyst of the present invention. The area of this XRD pattern peak is 10 a metric that generally indicates the degree of crystallinity of a catalyst. The greater the peak area, the more crystalline the catalyst. Example 6: Mitigate Loss of Bulk Catalyst Crystallinity To further evaluate the performance of the instant invention, XRD and surface area 15 measurements were taken of FCC catalysts that had been mixed with Metals Trap A and then deactivated. In Test Run 1A, no catalytic cracking additive was used. Test Run 1D used the catalytic cracking additive Metals Trap A and high activity catalyst of the present invention. The results are given in Table 5 below. 20 Table 5. Improved Bulk Catalyst Characteristics Test Run Catalyst Mixture Peak Area Surface Area (6.3* 2-0) (n'/g) IA Bulk catalyst 438 68 ID Bulk Catalyst with 10% 4713 102 catalytic cracking additive (90% Metals Trap A and 10% high activity catalyst) The results reported in Table 5 show that the present invention increases the area of the XRD pattern peak at about 6.3 degrees 2-theta. Generally, the area of this XRD 22 pattern peak is a metric that indicates the degree of crystallinity of the bulk catalyst. The greater the peak area, the more crystalline the catalyst. The actual x-ray diffractogram is shown in Figure 3. In Figure 3, the bottom trace shows the diffraction pattern of the fresh, bulk catalyst subjected to no deactivation. Following deactivation, severe loss in crystallinity is observed as shown in the center trace (Test Run 1A). Upon reacting with a catalytic cracking additive of the present invention (Test Run ID), a significant portion of the crystallinity is preserved as shown in the top trace. Surface area of the catalyst is another indicator of crystallinity. The results also show that the reduction of the surface area of the bulk catalyst is decreased by catalytic cracking additive of the present invention. Example 7: Metals Trapping Scanning Electron Microscopy utilizing Energy Dispersive Spectroscopy (SEM/EDS) was performed on the catalytic cracking additives used in Example 4, above. FCC catalyst/catalytic cracking additive mixtures were deactivated by being metallated and steamed as described in Example 4. The additive particles were found to contain one or more of the following elements: vanadium, sulfur, silicon, cerium. Various modifications of the invention, in addition to those described herein, will be apparent to one skilled in the art from the foregoing description. Such modifications are understood to fall within the scope of the appended claims. Throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", and variations such as "comprises" and "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. The reference to any prior art in this specification is not, and should not be taken as, an acknowledgement or any form of suggestion that the prior art forms part of the common general knowledge in Australia.

Claims

1. A process for the catalytic cracking of feedstock comprising contacting said feedstock under catalytic cracking conditions with a composition comprising a bulk catalyst comprising a zeolite, wherein the bulk catalyst has a surface area of less than about 300 m 2 /g, and a catalytic cracking additive, wherein the catalytic cracking additive comprises: a) a metals trapping material; and b) a high activity catalyst, wherein the high activity catalyst has a surface area of greater than 350 m 2 /g.

2. The process of Claim 1, wherein the catalytic cracking additive comprises from about 2% to about 80% of the composition by weight.

3. The process of Claim 1, wherein the catalytic cracking additive comprises from about 20% to about 60% of the composition by weight.

4. The process of Claim 1, wherein the catalytic cracking additive comprises from about 5% to about 20% of the composition by weight.

5. The process of Claim 1, wherein the metals trapping material comprises from about 2% to about 98% of the additive by weight.

6. The process of Claim 1, wherein the metals trapping material comprises from about 60% to about 95% of the additive by weight.

7. The process of Claim 1, wherein the metals trapping material comprises from about 70% to about 90% of the additive by weight.

8. The process of Claim 1, wherein the high activity catalyst comprises from about 5% to about 40% of the additive by weight. 24

9. The process of Claim 1, wherein the metals trapping material and the high activity catalyst comprise separate particles.

10. The process of Claim 1, wherein the metals trapping material and the high activity catalyst are within the same particle.

11. The process of Claim 1, wherein the metals trapping material comprises a calcium containing compound, a magnesium-containing compound, or a combination thereof

12. The process of Claim 1, wherein the metals trapping material comprises a non-anionic magnesium- and aluminum-containing compound that has not been derived from a hydrotalcite-like compound, a hydrotalcite-like compound, a silica- and alumina-containing compound, or a combination thereof

13. The process of Claim 1, wherein the high activity catalyst comprises a zeolite.

14. The process of Claim 1, wherein the high activity catalyst comprises an in situ synthesized zeolite.

15. The process of Claim 13, wherein the zeolite is zeolite X, Y zeolite, zeolite A, zeolite L, zeolite ZK-4, beta zeolite, ZSM-5 zeolite, faujasite, or a combination thereof

16. The process of Claim 13, wherein the zeolite is Y zeolite, beta zeolite, or a combination thereof

17. The process of Claim 1, wherein the metals trapping material is a vanadium trapping material.

18. The process of Claim 1, wherein the bulk catalyst is about 5% to about 40% zeolite. 25