Immobilization of Vanadia Deposited on Catalytic Materials During Carbo-Metallic Oil Conversion

This invention relates to an improved catalyst, one or more methods for its preparation, and a process for its use in the conversion of carbo-metallic oils to liquid transportation and/or heating fuels. More particularly, the invention is related to a catalyst composition comprising a catalytically active crystalline aluminosilicate zeolite uniformly dispersed within a matrix containing a metal additive as a free metal, its oxides or its salts to immobilize vanadium oxides deposited on the catalyst during the conversion reaction. The metal additive for vanadia immobilization may be added during catalyst manufacture, after manufacture by impregnation of virgin catalyst, or at any point in the catalyst cycle for conversion of the oil feed.

The introduction of catalytic cracking to the petroleum industry in the 1930's constituted a major advance over previous techniques with the object of increasing the yield of gasoline and its quality. Early fixed bed, moving bed, and fluid bed catalytic cracking FCC processes employed vacuum gas oils (VGO) from crude sources that were considered sweet and light. The terminology of sweet refers to low sulfur content and light refers to the amount of material boiling below approximately 1000.degree.-1025.degree. F.

The catalysts employed in early homogeneous fluid dense beds were of an amorphous siliceous material, prepared synthetically or from naturally occurring materials activated by acid leaching. Tremendous strides were made in the 1950's in FCC technology in the areas of metallurgy, processing equipment, regeneration and new more-active and more stable amorphous catalysts. However, increasing demand with respect to quantity of gasoline and increased octane number requirements to satisfy the new high horsepower-high compression engines being promoted by the auto industry, put extreme pressure on the petroleum industry to increase FCC capacity and severity of operation.

A major breakthrough in FCC catalysts come in the early 1960's with the introduction of molecular sieves or zeolites. These materials were incorporated into the matrix of amorphous and/or amorphous/kaolin materials constituting the FCC catalysts of that time. These new zeolitic catalysts, containing a crystalline aluminosilicate zeolite in an amorphous or amorphous/kaloin matrix of silica, alumina, silica-alumina, kaolin, clay or the like were at least 1,000-10,000 times more active for cracking hydrocarbons than the earlier amorphous or amorphous/kaolin containing silica-alumina catalysts. This introduction of zeolitic cracking catalysts revolutionized the fluid catalytic cracking process. New innovations were developed to handle these high activities, such as riser cracking, shortened contact times, new regeneration processes, new improved zeolitic catalyst developments, and the like.

The new catalyst developments revolved around the development of various zeolites such as synthetic types X and Y and naturally occuring faujasites; increased thermalsteam (hydrothermal) stability of zeolites through the inclusion of rare earth ions or ammonium ions via ionexchange techniques; and the development of more attrition resistant matrices for supporting the zeolites. These zeolitic catalyst developments gave the petroleum industry the capability of greatly increasing throughput of feedstock with increased conversion and selectivity while employing the same units without expansion and without requiring new unit construction.

After the introduction of zeolitic containing catalysts the petroleum industry began to suffer from a lack of crude availability as to quantity and quality accompanied by increasing demand for gasoline with increasing octane values. The world crude supply picture changed dramatically in the late 1960's and early 1970's. From a surplus of light, sweet crudes the supply situation changed to a tighter supply with an ever increasing amount of heavier crudes with higher sulfur contents. These heavier and higher sulfur crudes presented processing problems to the petroleum refiner in that these heavier crudes invariably also contained much higher metals and Conradson carbon values, with accompanying significantly increased asphaltic content.

Fractionation of the total crude to yield cat cracker charge stocks also required much better control to ensure that metals and Conradson carbon values were not carried overhead to contaminate the FCC charge stock.

The effects of heavy metals and Conradson carbon on a zeolite containing FCC catalyst have been described in the literature as to their highly unfavorable effect in lowering catalyst activity and selectivity for gasoline production and their equally harmful effect on catalyst life.

As mentioned previously, these heavier crude oils also contained more of the heavier fracitons and yielded less or a lower volume of the high quality FCC charge stocks which normally boil below about 1025.degree. F. and are usually processed so as to contain total metal levels below 1 ppm, preferably below 0.1 ppm, and Conradson carbon values substantially below 1.0.

With the increasing supply of heavier crudes, which meant lowered yields of gasoline, and the increasing demand for liquid transportation fuels, the petroleum industry began a search for processing schemes to utilize these heavier crudes in producing gasoline. Many of these processing schemes have been described in the literature. These include Gulf's Gulfining and Union Oil's Unifining processes for treating residuum, UOP's Aurabon process, Hydrocarbon Research's H-Oil process, Exxon's Flexicoking process to produce thermal gasoline and coke, H-Oil's Dynacracking and Phillip's Heavy Oil Cracking (HOC) processes. These processes utilize thermal cracking or hydrotreating followed by FCC or hydrocracking operations to handle the higher content of metal contaminants (Ni-V-Fe-Cu-Na) and high Conradson carbon values of 5-15. some of the drawbacks of these types of processing are as follows: coking yields thermally cracked gasoline which has a much lower octane value than cat cracked gasoline and is unstable due to the production of gum from diolefins and requires further hydrotreating and reforming to produce a high octane product; gas oil quality is degraded due to thermal reactions which produce a product containing refractory polynuclear aromatics and high Conradson carbon levels which are highly unsuitable for catalytic cracking; and hydrotreating requires expensive high pressure hydrogen, multi-reactor systems made of special alloys, costly operations, and a separate costly facility for the production of hydrogen.

To better understand the reasons why the industry has progressed along the processing schemes described, one must understand the known and established effects of contaminant metals (Ni-V-Fe-Cu-Na) and Conradson carbon on the zeolite containing cracking catalysts and the operating parameters of a FCC unit. Metal content and Conradson carbon are two very effective restraints on the operation of a FCC unit and may even impose undesirable restraints on a Reduced Crude Conversion (RCC) unit from the standpoint of obtaining maximum conversion, selectivity and life. Relatively low levels of these contaminants are highly detrimental to a FCC unit. As metals and Conradson carbon levels are increased still further, the operation capacity and efficiency of a RCC unit may be adversely affected or made uneconomical. These adverse effects occur even though there is enough hydrogen in the feed to produce an ideal gasoline consisting of only toluene and isomeric pentenes (assuming a catalyst with such ideal selectivity could be devised).

The effect of increased Conradson carbon is to increase that portion of the feedstock converted to coke deposited on the catalyst. In typical VGO operations employing a zeolite containing catalyst in a FCC unit, the amount of coke deposited on the catalyst averages around about 4-5 wt. % of the feed. This coke production has been attributed to four different coking mechanisms, namely, contaminant coke from adverse reactions caused by metal deposits, catalytic coke caused by acid site cracking, entrained hydrocarbons resulting from pore structure adsorption and/or poor stripping, and Conradson carbon resulting from pyrolytic distillation of hydrocarbons in the conversion zone. There has been postulated two other sources of coke present in reduced crudes in addition to the four present in VGO. They are: (1) adsorbed and absorbed high boiling hydrocarbons which do not vaporize and connot be removed by normally efficient stripping, and (2) high molecular weight nitrogen containing hydrocarbon compounds adsorbed on the catalyst's acid sites. Both of these two new types of coke producing phenomena add greatly to the complexity of resid processing. Therefore, in the processing of higher boiling fractions, e.g., reduced crudes, residual fractions, topped curde, and the like, the coke production based on feed is the summation of the four types present in VGO processing (the Conradson carbon value generally being much higher than for VGO), plus coke from the higher boiling unstrippable hydrocarbons and coke associated with the high boiling nitrogen containing molecules which are adsorbed on the catalyst. Coke production on clean catalyst, when processing reduced crudes, may be estimated as approximately 4 wt. % of the feed plus the Conradson carbon value of the heavy feedstock.

The coked catalyst is brought back to equilibrium activity by burning off the deactivating coke in a regeneration zone in the presence of air, and the regenerated catalyst is recycled back to the reaction zone. The heat generated during regeneration is removed by the catalyst and carried to the reaction zone for vaporization of the feed and to provide heat for the endothermic cracking reaction. The temperature in the regenerator is normally limited because of metallurgical limitations and the hydrothermal stability of the catalyst.

The hydrothermal stability of the zeolite containing catalyst is determined by the temperature and steam partial pressure at which the zeolite begins to rapidly lose its crystalline structure to yield a low activity amorphous material. The presence of steam is highly critical and is generated by the burning of adsorbed and absorbed (sorbed) carbonaceous material which has a significant hydrogen content (hydrogen to carbon atomic ratios generally greater than about 0.5). This carbonaceous material is principally the high boiling sorbed hydrocarbons with boiling points as high as 1500.degree.-1700.degree. F. or above that have a modest hydrogen content and the high boiling nitrogen containing hydrocarbons, as well as related porphyrins and asphaltenes. The high molecular weight nitrogen compounds usually boil above 1025.degree. F. and may be either basic or acidic in nature. The basic nitrogen compounds may neutralize acid sites while those that are more acidic may be attracted to metal sites on the catalyst. The porphyrins and asphaltenes also generally boil above 1025.degree. F. and may contain elements other than carbon and hydrogen. As used in this specification, the term "heavy hydrocarbons" includes all carbon and hydrogen compounds that do not boil below about 1025.degree. F., regardless of whether other elements are also present in the compound.

The heavy metals in the feed are generally present as porphyrins and/or asphaltenes. However, certain of these metals, particularly iron and copper, may be present as the free metal or as inorganic compounds resulting from either corrosion of process equipment or contaminants from other refining processes.

As the Conradson carbon value of the feedstock increases, coke production increases and this increased load will raise the regeneration temperature; thus the unit may be limited as to the amount of feed that can be processed because of its Conradson carbon content. Earlier VGO units operated with the regenerator at 1150.degree.-1250.degree. F. A new development in reduced crude processing, namely, Ashland Oil's "Reduced Crude Conversion Process", as described in the pending U.S. application referenced below, can operate at regenerator temperatures in the range of 1350.degree.-1400.degree. F. But even these higher regenerator temperatures place a limit on the Conradson carbon value of the feed at approximately 8, which represents about 12-13 wt. % coke on the catalyst based on the weight of feed. This level is controlling unless considerable water is introduced to further control temperature, which addition is also practiced in Ashland's RCC processes.

The metal containing fractions of reduced crudes contain Ni-V-Fe-Cu in the form of porphyrins and asphaltenes. These metal containing hydrocarbons are deposited on the catalyst during processing and are cracked in the riser to deposit the metal or are carried over by the coked catalyst as the metallo-porphyrin or asphaltene and converted to the metal oxide during regeneration. The adverse effects of these metals as taught in the literature are to cause non-selective or degradative cracking and dehydrogenation to produce increased amounts of coke and light gases such as hydrogen, methane and ethane. These mechanisms adversely affect selectivity, resulting in poor yields and quality of gasoline and light cycle oil. The increased production of light gases, while impairing the yield and selectivity of the process, also puts an increased demand on gas compressor capacity. The increase in coke production, in addition to its negative impact on yield, also adversely affects catalyst activity-selectivity, greatly increases regenerator air demand and compressor capacity, and may result in uncontrollable and/or dangerous regenerator temperatures.

These problems of the prior art have been greatly minimized by the development at Ashland Oil, Inc., of its Reduced Crude Conversion (RCC) Processes described in Ser. No. 094,092 (U.S. Pat. No. 4,332,673) and the other co-pending applications referenced below and incorporated herein by reference. The new process can handle reduced crudes or crude oils containing high metals and Conradson carbon values previously not susceptible to direct processing. Normally, these crudes require expensive vacuum distillation to isolate suitable feedstocks and produce as a by-product, high sulfur containing vacuum still bottoms. Ashland's RCC process avoids all of these prior art disadvantages.

This invention provides an improved catalyst and method for the conversion of petroleum oil feeds containing significant levels of vanadium (at least about 0.1 ppm). More particularly, metal additives are porvided on the catalyst to reduce the deactivation of catalytically active crystalline alumino-silicate zeolites by the vanadium contaminants in oil feeds--of all types utilized in FCC and/or RCC operations. The invention is particularly useful in the processing of carbo-metallic oil feeds in RCC units.

It has long been known that reduced crudes with high nickel levels present serious problems as to catalyst deactivation at high metal on catalyst contents, e.g., 5,000-10,000 ppm and elevated regenerator temperatures. It has now been recognized that when reduced crudes with high vanadium to nickel levels are processed over zeolite containing catalysts, especially at high vanadium levels on the catalyst, rapid deactivation of the zeolite can occur. This deactivation manifests itself as a loss of zeolitic structure. This loss has been observed at vanadium levels of 1,000 ppm or less. The loss of zeolitic structure becomes more rapid and severe with increasing levels of vanadium and at vanadium levels about 5,000 ppm, particularly at levels approaching 10,000 ppm complete destruction of the zeolite may occur. Prior to the present invention, it was believed impossible to operate economically at vanadium levels higher than 10,000 ppm because of this phenomena. Previously, vanadium deactivation at vanadium levels of less than 10,000 ppm has been retarded by lowering regenerator temperatures and increasing the addition rate of virgin catalyst. Lowering regenerator temperatures has the disadvantage of requiring higher catalyst to oil ratios which increase the amount of coke produced and adversely affect yields. Increasing catalyst addition rates is costly and can result in an uneconomical operation.

Some crude oils and some FCC charge stocks from the distillation of crude oils contain significant amounts (greater than 0.1 ppm) of heavy metals such as Ni, V, Fe, Cu, Na. Residual fractions from curde oil distillation have even greater amounts of heavy metals and may also have high Conradson carbon values. According to the present invention, these oils are converted to liquid transportation and distillate heating fuels by contact with a zeolitic catalyst containing a metal additive to immobilize vanadium oxides deposited on the catalyst during the conversion reaction. As used throughout the specification, "vanadia" refers collectively to the oxides of vanadium.

It has been found that vanadium is especially detrimental to catalyst life. As the vanadium oxide level builds up on the catalyst, the elevated temperatures encountered in the catalyst regeneration zone cause vanadium pentoxide (V.sub.2 O.sub.5) to melt and this liquid vanadia to flow. Among other things, this vanadia enters the zeolite structure leading to neutralization of acid sites and more significantly to irreversible destruction of the crystalline aluminosilicate structure so as to form a less active amorphous material. In addition, this melting and flowing of vanadia can, at high levels and for catalyst materials with low surface area, also coat the outside of catalyst microspheres with liquid and thereby cause coalescence between catalyst particles which adversely affects its fluidization properties. The select metal additives of this invention were chosen so as to form compounds or complexes with vanadia which have melting points above the temperatures encountered in the regeneration zone, thus avoiding zeolite destruction, surface sintering and particle fusion.

The select additives were also chosen for the purpose of immobilizing vanadia while simultaneously avoiding neutralization of acidic sites. Many additional additives which do affect the melting point of vanadia were eliminated due to their negative effect on catalyst activity. Titania and zirconia not only tie up the vanadia but, in combination with silica, form acidic catalysts with cracking activity in their own right.

The method of addition of the metal additive can be during catalyst manufacture or at any point in the reduced crude processing cycle. Addition during manufacture may be made either to the catalyst slurry before particle formation or by impregnation after catalyst particle formation, such as after spray drying of the catalyst slurry to form microspheres. It is to be understood that the catalyst particles can be of any size, depending on the size approprate to the conversion process in which the catalyst is to be employed. Thus, while a fluidizable size is preferred, the metal additives may be employed with larger particles, such as those for a moving catalyst bed in contact with unvaporized feeds.

The problems of the prior art caused by vanadium containing contaminants are overcome by employing the catalyst and select metal additive of this invention. Although FCC operations are also contemplated, this invention is especially effective in the processing of reduced crudes and other carbo-metallic feeds with high metals, high vanadium to nickel ratios and high Conradson carbon values. This RCC feed having high metal and Conradson carbon values is preferably contacted in a riser with a zeolite containing catalyst of relatively high surface area at temperatures above about 950.degree. F. Residence time of the oil in the riser is below 5 seconds, preferably 0.5-2 seconds. The preferred catalyst is spray dried composition in the form of microspherical particles generally in the size range of 10 to 200 microns, preferably 20 to 150 microns and more preferably between 40 and 80 microns, to ensure adequate fluidization properties.

The RCC feed is introduced at the bottom of the riser and contacts the catalyst at a temperature of 1275.degree.-1450.degree. F. to yield a temperature at the exit of the riser in the catalyst disengagement vessel of approximately 950.degree.-1100.degree. F. Along with the RCC feed, water, steam, naphtha, flue gas, or other vapors or gases may be introduced to aid in vaporization and act as a lift gas to control residence time and provide the other benefits described in Ashland's co-pending RCC applications.

Coked catalyst is rapidly separated from the hydrocarbon vapors at the exit of the riser by employing the vented riser concept developed by Ashland Oil, Inc., and described in U.S. Pat. Nos. 4,066,533 and 4,070,159 to Myers, et al, which patents are incorporated herein by reference. During the course of the reaction in the riser, the metal and Conradson carbon compounds are deposited on the catalyst. After separation in the vented riser, the coked catalyst is deposited as a dense but fluffed bed at the bottom of the disengagement vessel, transferred to a stripper and then to the regeneration zone. The coked catalyst is there contacted with an oxygen containing gas to remove the carbonaceous material through combustion to carbon oxides to yield a regenerated catalyst containing less than 0.1 wt. % carbon, preferably less than 0.05 wt. % carbon. The regenerated catalyst is then recycled to the bottom of the riser where it again joins high metal and Conradson carbon containing feed to repeat the cycle.

At the elevated temperatures encountered in the regeneration zone, the vanadium deposited on the catalyst in the riser is converted to vanadium oxides, in particular, vanadium pentoxide. The melting point of vanadium pentoxide is much lower than the temperatures encountered in the regeneration zone. Thus, it can become a mobile liquid and flow across the catalyst surface, causing pore plugging, particule coalescence, and more importantly, entering the pores of the zeolite, where it catalyzes irreversible crystalline collapse of zeolite to form an amorphous material.

This application describes a new approach to offsetting the adverse effects of vanadium pentoxide by the incorporation of select free metals, their oxides or their salts into the catalyst matrix during manufacture, either by addition to the undried catalyst composition or by impregnation techniques after spray drying or other particle forming techniques, or during FCC or RCC processing by introducing these additives at select points in the FCC or RCC unit to affect vanadium immobilization through compound, complex, or alloy formation. These metal additives serve to immobilize vanadia by creating complexes, compounds or alloys of vanadia having melting points which are higher than the temperatures encountered in the regeneration zone.

The metal additives for immobilizing vanadia includes the following metals, their oxides and salts, and their organo-metallic compounds: Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Nb, Ta, Mn, Fe, In, Tl, Bi, Te, the rare earths, and the Actinide and Lanthanide series of elements. These metal additives based on the metal element content may be used in concentration ranges from about 0.5 to 20 percent, more preferably about 1 to 8 percent by weight of virgin catalyst. If added instead during the conversion process, the metal elements may build up to these concentrations on equilibrium catalyst and maintain at these levels by catalyst replacement.

The catalytically active promoter in the preferred catalyst composition is a crystalline aluminosilicate zeolite, commonly known as molecular sieves. Molecular sieves are initially formed as alkali metal aluminosilicates, which are dehydrated forms of crystalline hydrous siliceous zeolites. However, since the alkali form does not have appreciable activity and alkali metal ions are deleterious to cracking processes, the aluminosilicates are ion exchanged to replace sodium with some other ion such as, for example, ammonium ions and/or rare earth metal ions. The silica and alumina making up the structure of the zeolite are arranged in a definite crystalline pattern containing a large number of small uniform cavities interconnected by smaller uniform channels or pores. The efective size of these pores is usually between about 4A.degree. and 12A.degree..

The zeolites which can be employed in accordance with this invention include both natural and synthetic zeolites. The natural occurring zeolites including gmelinite, clinoptiloite, chabazite, dechiardite, faujasite, heulandite, erionite, analcite, levynite, sodalite, cancrinite, nephelite, lcyurite, scolicite, natrolite, offertite, mesolite, mordenite, brewsterite, ferrierite, and the like. Suitable synthetic zeolites include zeolites Y, A, L, ZK-4B, B, E, F, H, J, M, Q, T, W, X, Z, ZSM-types, alpha, beta and omega. The term "zeolites" as used herein contemplates not only aluminosilicates but substances in which the aluminum is replaced by gallium and substances in which the silicon is replaced by germanium and also the so called pillared clays more recently introduced into the art.

The matrix material for the catalyst of this invention should possess good hydro-thermal stability. Examples of materials exhibiting relatively stable pore characteristics are alumina, silica-alumina, silica, clays such as kaolin, meta-kaolin, halloysite, anauxite, dickite and/or macrite, and combinations of these materials. Other clays, such as montmorillonite, may be added to increase the acidity of the matrix. Clay may be used in natural state or thermally modified.

The invention may be further understood by reference to the description of the best mode taken in conjunction with the accompanying drawings in which:

FIG. 1 is a schematic diagram of an apparatus for carrying out the process of the invention.

FIG. 2 is a graph showing the change in catalytic activity with increasing amounts of vanadium on the catalyst.

FIG. 3 is a graph showing changes in catalytic activity with increasing amounts of nickel on the catalyst.

FIG. 4 is a graph showing the loss of crystalline aluminosilicate zeolite with increasing amounts of vanadium on the catalyst.

FIG. 5 is a graph showing the loss of crystalline aluminosilicate zeolite with increasing amounts of nickel on the catalyst.

FIG. 6 is a table giving catalyst parameters and conversion data relative to the amount of nickel or vanadium on a catalyst of relatively low surface area.

FIG. 7 is a table giving catalyst parameters and conversion data relative to the amount of nickel or vanadium on a catalyst of relatively high surface area.

FIG. 8 is a table illustrating the effectiveness of titanium in immobilizing vanadium.

FIG. 9 is a graph showing the change in catalyst relative activity with decreasing vol. % MAT conversion.

FIG. 10 is a graph showing the time required to buildup metals on a catalyst at varying metals level in feed and a catalyst addition rate of 3% of inventory.

FIG. 11 is a graph showing the time required to buildup metals on a catalyst at varying metals level in feed and a catalyst addition rate of 4% of inventory.

It is not proposed to define the exact mechanism for the immobilization of vanadia but the metal additives of this invention will form compounds, complexes or alloys with vanadia that have higher melting points than the temperatures encountered in the regeneration zone. The preferred minimum atomic ratio of additive metal to vanadium to be maintained on the catalyst is at least 0.5 or 1.0, depending on the number of additive metal atoms in the oxide of the additive metal, e.g. TiO.sub.2 or In.sub.2 O.sub.3, forming a stable, high melting binary oxide material with vanadium pentoxide (V.sub.2 O.sub.5). Thus, at the preferred ratio, the melting point of the binary oxide material should be generally well above the operating temperatures of the regenerator. Although initially, the amount of additive metal will be considerably above the preferred minimum ratio if it is incorporated in the catalyst prior to use, the ratio of additive metal to vanadium on the catalyst will decrease as vanadium is deposited on the catalyst. Alternatively, the metal additive may be added to the process at a preferred minimum rate equivalent to either 50% or 100% of the metal content of the feed, depending on whether a 0.5 or 1.0 minimum ratio is to be maintained. This latter approach was employed to identify and confirm suitable metal additives which can form binary mixtures with vanadium pentoxide so as to yield a solid material that has a melting point of at least about 1600.degree. F., preferably at least about 1700.degree. F., more preferably 1800.degree. F. or higher, at the preferred ratio. This high melting point product ensures that vanadia will not melt, flow and enter the zeolite cage structure to cause destruction of the zeolite's crystalline sieve structure as previously described.

The additive metals of this invention include those elements from the Periodic chart of elements shown in Table A. The melting points of Table A are based on a 1:1 mole ratio of the metal additive oxide in its stable valence state under regenerator conditions to vanadium pentoxide.

This invention also recognizes that mixtures of these additive metals with vanadia may occur to form high melting ternary, quaternary, or higher component reaction mixtures, such as vanadium titanium zirconate (VO-TiO.sub.2 -Zr O.sub.2). In addition, binary, ternary and/or quaternary reaction mixtures can occur with metals not covered in the Groups above. Thus, although Group IIA metals and certain other metals that are not specified in Table A are capable of tying up vanadia in high melting immobile materials, those metals may result in excessive neutralization of acidic sites on the catalyst and generally should not be used in the method of the present invention.

Examples of such additional ternary and quaternary compounds are shown in Table B.

Further, in this invention we have covered the lower oxidation states of vanadium as well as vanadium pentoxide. However, in processing a sulfur containing feed and regeneration in the presence of an oxygen containing gas, vanadium will also likely form compounds, such as vanadium sulfides, sulfates, and oxysulfides, which may also form binary, ternary, quaternary or higher component reaction mixtures with the metal additives of this invention.

While not intending to be bound by any one theory or mechanism, it is believed that a reaction of the metal additive with vanadia generally yields a binary reaction product. In the case of manganese acetate reacting with vanadium pentoxide, the compound formed was tentatively identified as Mn.sub.2 V.sub.2 O.sub.7. When titania was reacted with vanadium pentoxide, no true compound could be identified because the reaction is believed to involve the substitution of Ti.sup.+4 in the crystalline structure by V.sup.+4. Thus, the disappearance of the titania X-ray pattern and the vanadium pentoxide X-ray pattern was observed, indicating vanadium substitution.

The preferred metal additives are compounds of titanium, zirconium, manganese, indium, lanthanum, or a mixture of the compounds of these metals. Where the additive is introduced directly into the conversion process, that is into the riser, into the regenerator or into any intermediate components, the metal additives are preferably organo-metallic compounds of these metals soluble in the hydrocarbon feed or in a hydrocarbon solvent miscible with the feed. Examples of preferred organo-metallic compounds are tetraisopropyltitanate, Ti (C.sub.3 H.sub.7 O).sub.4, available as TYZOR from the Du Pont Company; methylcyclopentadienyl manganese tricarbonyl (MMT), Mn (CO).sub.3 C.sub.6 H.sub.7 ; and zirconium isopropoxide, Zr (C.sub.3 H.sub.7 O).sub.4 ; Indium 2,4 pentanedionate--In (C.sub.5 H.sub.7 O.sub.2).sub.3 ; Tantalum ethoxide--Ta (C.sub.2 H.sub.5 O).sub.5 ; and zirconium 2,4-pentanedionate - Zr (C.sub.5 H.sub.7 O.sub.2).sub.4. These organo-metallics are only a partial example of the various types available and others would include alcoholates, esters, phenolates, naphthenates, carboxylates, dienyl sandwich compounds, and the like. The invention therefore is not limited to the examples given. Other preferred process additives include titanium tetrachloride and manganese acetate, both of which are relatively inexpensive.

The organo-metallic additives are preferably introduced directly into the hydrocarbon conversion zone, preferably near the bottom of the riser, so that the metal additive will be deposited on the catalyst along with the heavy metals in the feed. When the additive metal of the invention reaches the regenerator, its oxide is formed, either by decomposition of the additive directly to the metal oxide or by decomposition of the additive to the free metal which is then oxidized under the regenerator conditions. This provides an intimate mixture of metal additive and heavy metals and is believed to be one of the most effective means for tying up vanadium pentoxide as soon as it is formed in the regenerator. The metal additive is introduced into the riser by mixing it with the feed in an amount sufficient to give an atomic ratio between the metal in the additive and the vanadium in the feed of at least 0.25, preferably in the range of 0.5 to 3.0, more preferably in the range of 0.75 to 1.5, and most preferably 100 to 200 percent of the preferred minimum ratios previously defined.

If the metal additive is added directly to the catalyst during catalyst manufacture or at some other time before the catalyst is introduced into the conversion system, the metal additives are preferably water soluble inorganic salts of these metals, such as the acetate, halide, nitrate, sulfate, sulfite and/or carbonate. These additive compounds are soluble in the catalyst slurry or in a water impregnating solution. If the metal additive is not added to the catalyst before or during particle formation, then it can be added by impregnation techniques to the dried catalyst particles, which are preferably spray dried microspheres. Impregnation after drying may be advantageous in some cases where sites of additive metal are likely to be impaired by catalyst matrix material which might partially cover additive metal sites introduced before spray drying or before some other particle solidification process. Inorganic metal additives may also be introduced into the conversion process along with water containing steams, such as used to cool the regenerator or to lift, fluidize or strip catalyst.

A preferred matrix material is a semi-synthetic combination of clay and silica-alumina as described in U.S. Pat. No. 3,034,994. Preferably the clay is mostly a kaolinite and is combined with a synthetic silica-alumina hydrogel or hydrosol. This synthetic component forms preferably about 15 to 75 percent, more preferably about 20 to 25 percent, of the formed catalyst by weight. The proportion of clay is such that the catalyst preferably contains after forming, about 10 to 75 percent, more preferably about 30 to 50 percent, clay by weight. The most preferred composition of the matrix contains approximately twice as much clay as synthetically derived silica-alumina. The synthetically derived silica-alumina should contain 55 to 95 percent by weight of silica (SiO.sub.2), preferably 65 to 85 percent, most preferably about 75 percent. Catalysts wherein the gel matrix consists entirely of silica gel or alumina gel are also included.

Various processes may be used in preparing the synthetic silica-alumina matrix, such as those described in U.S. Pat. No. 3,034,994, which patent is incorporated herein by reference. One of these processes involves gelling an alkali metal silicate with an inorganic acid while maintaining the pH on the alkaline side. An aqueous solution of an acidic aluminum salt is then intimately mixed with the silica hydrogel so that the aluminum salt solution fills the silica hydrogel pores. The aluminum is thereafter precipitated as a hydrous slumina by the addition of an alkaline compound.

As a specific example of this method of preparation, a silica hydrogel is prepared by adding sulfuric acid with vigorous agitation and controlled temperature, time and concentration conditions to a sodium silicate solution. Aluminum sulfate in water is then added to the silica hydrogel with vigorous agitation to fill the gel pores with the aluminum salt solution. An ammonium solution is then added to the gel with vigorous agitation to precipitate the aluminum as hydrous alumina which combines with silica at the surface of the silica hydrogel pores. The hydrous gel is then porcessed, for instance, by separating a part of the water on vacuum filters and then drying, or more preferably, by spray drying the hydrous gel to produce microspheres. The dried porduct is then washed to remove sodium and sulfate ions, either with water or a very weak acid solution. The resulting product is then dried to a low moisture content, usually less than 25 percent by weight, e.g., 10 percent to 20 percent by weight, to provide the finished catalyst product.

The silica-alumina hydrogel slurry may be filtered and washed in gel form to affect purification of the gel by the removal of dissolved salts. This may enhance the formation of a continuous phase in the spray dried microspherical particles. If the slurry is prefiltered and washed and it is desired to spray dry the filter cake, the latter may be reslurried with enough water to produce a pumpable mixture for spray drying. The spray dried product may then be washed again and given a final drying in the manner previously described.

The zeolite materials utilized in the preferred embodiments of this invention are synthetic faujasites which possess silica to alumina ratios in the range from about 2.5 to 7.0, preferably 3.0 to 6.0 and most preferably 4.5 to 6.0. Synthetic faujasites are widely known crystalline aluminosilicate zeolites and common examples of synthetic faujasites are the X and Y types commercially available from the Davison Division of W. R. Grace and Company and the Linde Division of Union Carbide Corporation. The ultrastable hydrogen exchanged zeolites, such as Z-14XS and Z-14US from Davison, are also particularly suitable. In addition to faujasites, other preferred types of zeolitic materials are mordenite and erionite.

The preferred synthetic faujasite is zeolite Y which may be prepared as described in U.S. Pat. Nos. 3,130,007 and 4,010,116, which patents are incorporated herein by reference. The aluminosilicates of this latter patent have high silica (SiO.sub.2) to alumina (Al.sub.2 O.sub.3) molar ratios, preferably above 4, to give high thermal stability.

The following is an example of a zeolite produced by the silication of clay. A reaction composition is produced from a mixture of sodium silicate, sodium hydroxide, and sodium chloride formulated to contain 5.27 mole percent SiO.sub.2, 3.5 mole percent Na.sub.2 O, 1.7 mole percent chloride and the balance water. 12.6 parts of this solution are mixed with 1 part by weight of calcined kaolin clay. The reaction mixture is held at about 60.degree. F. to 75.degree. F. for a period of about four days. After this low temperature digestion step, the mixture is heated with live steam to about 190.degree. F. until crystallization of the material is complete, for example, about 72 hours. The crystalline material is filtered and washed to give a silicated clay zeolite having a silica to alumina ratio of about 4.3 and containing about 13.5 percent by weight of Na.sub.2 O on a volatile free basis. Variation of the components and of the times and temperatures, as is usual in commercial operations, will produce zeolite having silica to alumina mole ratios varying from about 4 to about 5. Mole ratios above 5 may be obtained by increasing the amount of SiO.sub.2 in the reaction mixture. The sodium form of the zeolite is then exchanged with polyvalent cations to reduce the Na.sub.2 O content to less than about 1.0 percent by weight, and preferably less than 0.1 percent by weight. Procedures for removing alkali metals and putting the zeolite in the proper form are well-known in the art as described in U.S. Pat. Nos. 3,293,192; 3,402,996; 3,446,727; 3,449,070; and 3,537,816; which patents are incorporated herein by reference.

The amount of zeolitic material dispersed in the matrix based on the final fired product should be at least about 10 weight percent, preferably in the range of about 20 to 50 weight percent, most preferably about 20 to 40 weight percent.

Crystalline aluminosilicate zeolites exhibit acidic sites on both interior and exterior surfaces with the largest proportion to total surface area and cracking sites being internal to the particles within the crystalline micropores. These zeolites are usually crystallized as regularly shaped, discrete particles of approximately 0.1 to 10 microns in size and, accordingly, this is the size range normally provided by commercial catalyst suppiers. To increase exterior (portal) surface area, the particle size of the zeolites for the present invention should preferably be in the lower portion of this size range. The preferred zeolites are thermally stabilized with hydrogen and/or rare earth ions and are steam stable to about 1650.degree. F.

As one preferred embodiment of the invention, the metal additive may be incorporated directly into the matrix material. To an aqueous slurry of the raw matrix material and zeolite is mixed the metal additive in amount of yield approximately 1 to 20 wt. % concentration on the finished catalyst. The metal additive can be added in the form of a water soluble compound such as the nitrate, halide, sulfate, carbonate, or the like, and/or as an oxide or hydrous gel, such as titania or zirconia gel. Other active gelatinous precipitates or other gel like materials may also be used. This mixture may be spray dried to yield the finished catalyst as a microspherical particle of 10 to 200 microns in size with the active metal additive deposited within the matrix and/or on the outer surface of the catalyst particle. Since the concentration of vanadium on spent catalyst can be as high as 4 wt. % of particle weight, the concentration of additive metal is preferably in the range of 1 to 8 wt. % as the metal element. More preferably, there is sufficient metal additive to maintain at least the preferred atomic ratio of additive metal to vanadium at all times.

The zeolites and/or the metal additive can be suitably dispersied in the matrix materials for use as cracking catalysts by methods well-known in the art, such as those disclosed, for example, in U.S. Pat. Nos. 3,140,249 and 3,140,253 to Plank, et al.; U.S. Pat. No. 3,660,274 to Blazek, et al.; U.S. Pat. No. 4,010,116 to Secor, et al.; U.S. Pat. No. 3,944,482 to Mitchell, et al.; and U.S. Pat. No. 4,079,019 to Scherzer, et al.; which patents are incorporated herein by reference.

After introduction of the zeolite and/or metal additive, the composition is preferably slurried and spray dried to form catalyst microspheres. The particle size of the spray dried matrix is generally in the range of about 10 to 200 microns, preferably 20 to 150 microns, more preferably 40 to 80 microns. The finished catalyst should contain from 5 to 50% by weight zeolite, preferably rare earth or ammonia exchanged sieve of either or both the X and Y variety and preferably about 15 to 45% by weight, most preferably 20 to 40% by weight. To further enhance the catalyst, rare earth exchanged sieve may be calcined and further exchanged with rare earth or ammonia to create an exceptionally stable sieve.

The following is one example of a spray dryable composition. A silica sol component is prepared by mixing sodium silicate with water and rapidly mixing with acid to provide a sol which comprises from about 0.5 to 0.6% by weight Na.sub.2 O and sufficient acid to provide a pH of between about 0.5 to 3.3 and preferably of between 1.0 and 3.0. Typically, the sol is prepared by combining commercially available 40.degree. Baume 3.25 Na.sub.2 O.SiO.sub.2 solution with sulfuric acid solution having a concentration of 9 to 36% by weight H.sub.2 SO.sub.4. Optionally, the sol may be combined with from about 15 to 45% by weight total solids and the remainder water. The metal additive may be added to this sol and/or to the zeolite slurry component below.

A basic zeolite slurry component is then made up by mixing the desired quantities of zeolite in the sodium form with a sufficient quantity of sodium silicate solution (typically 40.degree. Baume) and water to give a product having the desired pH. Clay may be added to the basic zeolite slurry component if desired. The pH of the zeolite slurry component is maintained above about 10 and preferably at between 10.5 and 14. The slurry component will contain from about 10 to 17% by weight sodium silicate, from about 10 to 17% by weight zeolite and optionally from about 15 to 40% by weight clay and the balance water. The total solids content of the zeolite containing basic slurry ranges from about 33 to 46% by weight.

In the next step of this process, the two streams are mixed instantaneously and homogeneously in amount such from about 1.5 to 7.5 parts by weight of the above defined sol component is mixed with each part by weight of the zeolite slurry component. The mixture is immediately atomized, i.e. sprayed, into a heated gaseous atmosphere, such as air and/or steam having a temperature of 25.degree. to 300.degree. F., using a commercially available spray drier, such as a Model V Production Minor unit made by Niro Atomizer, Inc., of Columbia, Maryland, U.S.A. A water slurry of the spray formed microspherical particles has a pH of about 3.0 to 10.0.

It is critical to successful operation of this process that the mixing and subsequent spraying take place rapidly to prevent premature setting of the gel. The air atomizer used should feed the two components into the nozzle at pressures of about 90 to 150 psi and maintain the air in the nozzle at about 80 to 90 psi, preferably about 81-83 psi. As an alternative to premixing with either component, the metal additive may also be fed separately to the nozzle via a separate line operated at pressures of about 90 to 150 psi.

This catalyst was prepared to study vanadium immobilization effects of titania as shown in Run 4 of FIG. 8.

345 grams of vanadyl naphthenate is added to 1800 ml of a hydrocarbon solution (1000 ml toluene--800 ml cyclohexane) and heated to 60.degree. C. with stirring to solubilize the vanadyl naphthenate. 2,000 g. of a reduced crude conversion catalyst (containing 40% zeolite in a silica bound matrix) is added to a flask, heated and evacuated to 30 mm Hg pressure. The vanadyl naphthenate solution is added slowly with vibration to cover the catalyst. The pressure is increased to ambient conditions to thoroughly fill the catalyst pores. The vanadium impregnated catalyst is dried at 300.degree. F. for three hours and a portion calcined at 900.degree. F. for 7 hours. This yielded a catalyst containing 0.52 wt. % vanadium.

75 grams of the vanadium impregnated catalyst (not calcined) is dried at 100.degree. C. under vacuum for two hours. 2.4 ml of Du Pont's Tyzor TPT (tetra isopropyl titanate) is dissolved in 75 ml of cyclohexane. Utilizing a Roto-Vap apparatus, the titanium solution is added to the vacuum dried catalyst and allowed to contact with agitation for 30 minutes. Excess solution was then stripped from the impregnated catalyst to yield dried solid particles. The catalyst was then humidified in a dessicator (50% relative humidity) for 24 hours.

The catalyst was then regenerated (organic moieties burned off) as a shallow bed in a furnace at 900.degree. F. for 6 hours. The regenerated catalyst was then steamed at 1450.degree. F. for 5 hours according to the procedure outlined in this invention. This procedure yielded a catalyst containing 0.53 wt. % V and 0.53 wt. % Ti in a 1/1 weight ratio.

The select catalysts of this invention include solids of high catalytic activity such as zeolites in a matrix of clays, kaolin, silica, alumina, smectites and other 2-layered lamellar silicates, silica-alumina, and the like. The surface area of these catalysts are preferably above 100 m.sup.2 /g and they have a pore volume preferably in excess of 0.2 cc/g and a micro-activity (MAT) value in volume percent conversion as measured by ASTM Test Method No. D-3908-80 of at least 60, and preferably in the range of 65 to 90.

In general, it is preferred to employ a catalyst having a relatively high level of cracking activity, providing high levels of conversion and selectivity at low residence times. The conversion capabilities of the catalyst may be expressed in terms of the conversion produced during actual operation of the process and/or in terms of conversion produced in standard catalyst activity tests.

For example, it is preferred to employ a catalyst which, in the course of extended operation under prevailing process conditions is sufficiently active for sustaining a level of conversion of at least about 50% and more preferably at least about 60%. In this connection, conversion is expressed in liquid volume percent based on fresh feed.

Also, for example, the preferred catalyst may be defined as one which, in its virgin or equilibrium state, exhibits a specified activity expressed as a percentage in terms of MAT (micro-activity test) conversion. For purposes of the present invention, the foregoing percentage is the volume percentage of standard feedstock which a catalyst under evaluation will convert to 430.degree. F. end point gasoline, lighter products and coke at 900.degree. F., 16 WHSV (weight hourly space velocity calculated on a moisture free basis using clean catalyst which has been dried at 1100.degree. F., weighted and then conditioned for a period of at least 8 hours at about 25.degree. C. and 50% relative humidity, until about one hour or less prior to contacting the feed), and 3 C/O (catalyst to oil weight ratio) by ASTM D-32 MAT test D-3907-80, using an appropriate standard feedstock, e.g. a sweet light primary gas oil, such as that used by Davison Division of W. R. Grace and defined as follows.

The gasoline end point and boiling temperature-volume percent relationships of the produced in the MAT conversion test may for example be determined by simulated distillation techniques, for example by modification of the gas chromatographic "Sim-D" technique of ASTM D-2887-73. The results of such simulations are in reasonable agreement with the results obtained by subjecting larger samples of material to standard laboratory distillation techniques. Conversion is calculated by subtracting from 100 the volume percent (based on fresh feed) of those products heavier than gasoline which remain in the recovered product.

On pages 935-937 of Hougen and Watson, "Chemical Process Principles", John Wiley & Sons, Inc., N.Y. (1947), the concept of "Activity Factors" is discussed. This concept leads to the use of "relative activity" to compare the effectiveness of an operating catalyst against a standard catalyst. Relative activity measurements facilitate recognition of how the quantity requirements of various catalysts differ from one another. Thus, relative activity is a ratio obtained by dividing the weight of a standard or reference catalyst which is or would be required to produce a given level of conversion, as compared to the weight of an operating catalyst (whether proposed or actually used) which is or would be required to produce the same level of conversion in the same or equivalent feedstock under the same or equivalent conditions. Said ratio of catalyst weights may be expressed as a numerical ratio, but preferably is converted to a percentage basis. The standard catalyst is preferably chosen from among catalysts useful for conducting the present invention, such as for example, zeolite fluid cracking catalysts, and is chosen for its ability to produce a predetermined level of conversion in a standard feed under the conditions of temperature, WHSV, catalyst to oil ratio and other conditions set forth in the preceding description of the MAT conversion test and in ASTM D-32 MAT test D-3907-80. Conversion is the volume percentage of feedstock that is converted to 430.degree. F. endpoint gasoline, lighter products and coke. For standard feed, one may employ the above-mentioned light primary gas oil, or equivalent.

For purposes of conducting relative activity determinations, one may prepare a "standard catalyst curve", a chart or graph of conversion (as above defined) vs. reciprocal WHSV for the standard catalyst and feedstock. A sufficient number of runs is made under ASTM D-3907-80 conditions (as modified above) using standard feedstock at varying levels of WHSV to prepare an accurate "curve" of conversion vs. WHSV for the standard feedstock. This curve should traverse all or substantially all of the various levels of conversion including the range of conversion within which it is expected that the operating catalyst will be tested. From this curve, one may establish a standard WHSV for test comparisons and a standard value of reciprocal WHSV corresponding to that level of conversion which has been chosen to represent 100% relative activity in the standard catalyst. For purposes of the present disclosure the aforementioned reciprocal WHSV and level of conversion are, respectively, 0.0625 and 75%. In testing an operating catalyst of unknown relative activity, one conducts a sufficient number of runs with that catalyst under D-3907-80 conditions (as modified above) to establish the level of conversion which is or would be produced with the operating catalyst at standard reciprocal WHSV.

Then, using the above-mentioned standard catalyst curve, one establishes a hypothetical reciprocal WHSV contitituting the reciprocal WHSV which would have been required, using the standard catalyst, to obtain the same level of conversion which was or would be exhibited by the operating catalyst at standard WHSV. The relative activity may then be calculated by dividing the hypothetical reciprocal WHSV of the standard catalyst by the actual reciprocal WHSV of the test catalyst. The result is relative activity expressed in terms of a decimal fraction, which may then be multiplied by 100 to convert to % relative activity (relative activity may also be expressed as follows: relative activity at constant conversion is equal to the ratio of the WHSV of the test catalyst divided by the WHSV of the standard catalyst). To simplify this calculation, a MAT conversion vs. relative activity curve was developed utilizing a standard catalyst of 75 vol. % conversion to represent 100% relative activity. One such curve is shown in FIG. 9. In applying the results of this determination a relative activity of 0.5, or 50%, means that it would take twice the amount of the operating catalyst to give the same conversion as the standard catalyst, i.e., the production catalyst is 50% as active as the reference catalyst.

The catalyst may be introduced into the process in its virgin form or, as previously indicated, in other than its virgin form; e.g., one may use equilibrium catalyst withdrawn from another unit, such as catalyst that has been employed in the cracking of a different feed. Whether characterized on the basis of MAT activity or relative activity, the preferred catalysts may be described on the basis of their activity "as introduced" into the process of the present invention, or on the basis of their "as withdrawn" or equilibrium activity in the process of the present invention, or on both of these bases.

A preferred activity level of virgin and non-virgin catalyst "as introduced" into the process of the present invention is at least about 60% by MAT conversion and preferably at least about 20%, more preferably at least about 40% and still more preferably at least about 60% in terms of relative activity. However, it will be appreciated that, particularly in the case of non-virgin catalysts supplied at high addition rates, lower activity levels may be acceptable. An acceptable "as withdrawn" or equilibrium activity level of catalyst which has been used in the process of the present invention is at least about 20% or more, but about 40% or more and preferably about 60% or more is preferred on a relative activity basis, and an activity level of 60% or more on a MAT conversion basis is also contemplated. More preferably, it is desired to employ a catalyst which will, under the conditions of use in the unit, establish an equilibrium activity at or above the indicated level. The catalyst activities are determined with catalyst having less than 0.01 coke, e.g. regenerated catalyst.

Representative feedstocks contemplated for use with the invention include whole crude oils; light fractions of crude oils such as light gas oils, heavy gas oils, and vacuum gas oils; and heavy fractions of crude oils such as topped crude, reduced crude, vacuum fractionator bottoms, other fractions containing heavy residua, coal-derived oils, shale oils, waxes, untreated or deasphalted residua, and blends of such fractions with gas oils and the like. A high vanadium feed for FCC processing is one having more than 0.1 ppm vanadium, preferably 1.0 to 5.0 ppm where a relatively small amount of reduced crude (5-25%) is mixed with VGO to provide an FCC feedstock. A high vanadium feed for RCC processing is one having more than 1.0 ppm vanadium, preferably more than about 5.0 ppm. In either case, the preferred weight ratio of vanadium to nickel in feed without additive nickel is in the range of from about 1:3 to 5:1, more preferably greater than about 1:1.

The vanadia immobilization catalysts and/or methods described in this specification are preferably employed in combination with the processes and apparatuses for carbo-metallic oil conversion described in co-pending U.S. applications Ser. Nos. 94,091 (4,299,687); 94,092 (4,332,673); 94,216 (4,341,624); 94,217 (4,347,122); and 94,227 (4,354,923); each of said co-pending applications having been filed on Nov. 14, 1979, and being expressly incorporated herein by reference. The preferred feeds capable of being cracked by these methods and apparatuses are comprised of 100% or less of 650.degree. F.+ material of which at least 5 wt. %, preferably at least 10 wt. %, does not boil below about 1025.degree. F. The terms "high molecular weight" and/or "heavy" hydrocarbons refer to those hydrocarbon fractions having a normal boiling point of at least 1025.degree. F. and include non-boiling hydrocarbons, i.e., those materials which may not boil under any conditions.

A carbo-metallic feed for purposes of this invention is one having a heavy metal content of at least about 4 ppm nickel equivalents (ppm total metals being converted to nickel equivalents by the formula: Ni Eq.=Ni+V/4.8+Fe/7.1+Cu/1.23), a Conradson carbon residue value greater than about 1.0, and a vanadium content of at least 1.0 ppm. The feedstocks for which the invention is particularly useful will have a heavy metal content of at least about 5 ppm of nickel equivalents, a vanadium content of at least 2.0 ppm, and a Conradson residue of at least about 2.0. The greater the heavy metal content and the greater the proportion of vanadium in that heavy metal content, the more advantageous the metal additives and processes of this invention becomes. A particularly preferred feedstock for treatment by the process of the invention includes a reduced crude comprising 70% or more of a 650.degree. F.+ material having a fraction greater than 20% boiling about 1025.degree. F. at atmospheric pressure, a metals content of greater 5.5 ppm nickel equivalents of which at least 5 ppm is vanadium, a vanadium to nickel atomic ratio of at least 1.0, and a Conradson carbon residue greater than 4.0. This feed may also have a hydrogen to carbon ratio of less than about 1.8 and coke precursors in an amount sufficient to yield about 4 to 14% coke by weight based on fresh feed. The feed is preferably pretreated to remove sodium to a level less than 1 ppm.

Sodium vanadates have low melting points and may also flow and destroy the crystalline zeolites in the same manner as vanadium pentoxide. Although it is desirable to maintain low sodium levels in the feed in order to minimize neutralization of acid sites, as well as to avoid sodium vanadates on the catalyst, the metal additives of the present invention are also effective in forming compounds, alloys, or complexes with sodium vanadates so as to prevent these compounds from destroying the zeolite.

With respect to the tolerance levels of heavy metals on the catalyst itself, such metals may accumulate on an FCC catalyst to levels in the range of 100 to 10,000 ppm total metals, preferably 500-5,000 ppm, of which 5 to 100%, preferably 20 to 80%, is vanadium. Such metals may accumulate on RCC catalysts to levels in the range of from about 3,000 to about 70,000 ppm of total metals, preferably 10,000 to 30,000 ppm, of which 5 to 100%, preferably 20 to 80% is vanadium.

The feed may contain nickel in controlled amounts so that the oxides of nickel may help tie up vanadium pentoxide in a high melting complex, compound or alloy. The invention therefore contemplates controlling the amounts of nickel in the feed by introducing nickel additives or feedstocks with high nickel to vanadium ratios so that the compounds of this metal, either alone or in combination with other additives, comprise the metal additive of the invention. Similarly, a nickel containing catalyst may also be made by first using virgin catalyst, with or without another metal additive, in a conversion process employing a feedstock with a high nickel to vanadium ratio; and then using the resulting equilibrium catalyst as make-up catalyst in the process of the present invention. In these embodiments, the atomic ratio of nickel to vanadium on the catalyst should be greater than 1.0, preferably at least about 1.5.

The cracking reaction according to the methods disclosed in the above co-pending applications (Ashland's RCC processes) is sufficiently severe to convert 50 to 90 percent of the carbo-metallic oil feed to gasoline per pass and produce coke in amounts of 4 to 14 percent by weight based on weight of fresh feed. This coke is laid down on the catalyst in amounts in the range of about 0.3 to 3 percent by weight of catalyst, depending upon the catalyst to oil ratio (weight of catalyst to weight of feedstock) in the riser.

The feed, with or without pretreatment, is introduced as shown in FIG. 1 into the bottom of the riser along with a suspension of hot cracking catalyst prepared in accordance with this invention. Steam, naphtha, water, flue gas and/or some other diluent is preferably introduced into the riser along with the feed. These diluents may be from a fresh source or may be recycled from a process stream in the refinery. Where recycle diluent streams are used, they may diluent specified includes the amount of water used. Extra diluent would further increase the vapor velocity and further lower the feed partial pressure in the riser.

As the feed travels up the riser, it is catalytically cracked to form basically five products known in the industry as dry gas, wet gas, cat naphtha, light cycle oil, heavy cycle oil and/or slurry oil. At the upper end of the riser, the catalyst particles are ballistically separated from product vapors as previously described. The catalyst which then contains the coke formed in the riser is sent to the regenerator to burn off the coke and the separated product vapors are sent to a fractionator for further separation and treatment to provide the five basic products indicated.

The invention may be utilized in FCC processes. Preferred riser conditions for an FCC process employing the invention are summarized in Table C-1. The preferred conditions for the riser conversion reaction of Ashland's RCC processes are summarized in Table C-2. In these tables, the abbreviations used have the following meanings: "Temp." for temperature, "Dil." for diluent, "pp" for partial pressure, "wgt" for weight, "V" for vapor, "Res." for residence, "C/O" for catalyst to oil ratio, "Cat." for catalyst, "bbl" for barrel, "MAT" for micro-activity by the MAT test using a standard Davison feedstock, "Vel." for velocity, "cge" for charge, "d" for density and "Reg." for regenerated.

In cracking carbo-metallic feedstocks in accordance with Ashland's RCC processes, the regenerating gas may be any gas which can provide oxygen to convert carbon to carbon oxides. Air is highly suitable for this purpose in view of its readily availability. The amount of air required per pound of coke for combustion depends upon the desired carbon dioxide to carbon monoxide ratio in the effluent gases and upon the amount of other combustible materials present in the coke, such as hydrogen, sulfur, nitrogen and other elements capable of forming gaseous oxides at regenerator conditions.

The regenerator is operated at temperatures in the range of about 1000.degree. to 1600.degree. F., preferably 1275.degree. to 1450.degree. F., to achieve adequate combustion while keeping catalyst temperatures below those at which significant catalyst degradation can occur. In order to control these temperatures, it is necessary to control the rate of burning which in turn can be controlled at least in part by the relative amounts of oxidizing gas and carbon introduced into the regeneration zone per unit time. With reference to FIG. 1, the rate of introducing carbon into the regenerator may be controlled by regulating the rate of flow of coked catalyst through valve 40 in conduit 39, the rate of removal of regenerated catalyst by regulating valve 41 in conduit 16, and the rate of introducing oxidizing gas by the speed of operation of blowers (not shown) supplying air to the conduit 14. These parameters may be regulated such that the ratio of carbon dioxide to carbon monoxide in the effluent gases is equal to or less than about 4.0, preferably about 1.5 or less. In addition, water, either as liquid or steam, may be added to the regenerator to help control temperatures and to influence the carbon dioxide to carbon monoxide ratio.

The regenerator combustion reaction is carried out so that the amount of carbon remaining on regenerated catalyst is less than about 0.25, preferably less than about 0.05 percent and most preferably less than about 0.01 percent on a substantially moisture-free weight basis. The residual carbon level is ascertained by conventional techniques which include drying the catalyst at 1100.degree. F. for about four hours before actually measuring the carbon content so that the carbon level obtained is on a moisture-free basis.

When the metal additive is introduced as an aqueous or hydrocarbon solution or as a volatile compound during the processing cycle, it may be added at any point of catalyst travel in the processing apparatus. With reference to FIG. 1, this would include, but not be limited to, addition of the metal additive solution at the riser wye 17, along the riser length 4, to the dense bed 9 in the reactor vessel 5, to the strippers 10 and 15, to regenerator air inlet 14, to regenerator dense bed 12, and/or to regenerated catalyst standpipe 16.

The catalyst of this invention with or without the metal additive is charged to a FCC unit of the type outlined in FIG. 1 or to a Reduced Crude Conversion (RCC) unit of the type disclosed in Ashland's said RCC applications. Catalyst particle circulation and operating parameters are brought up to process conditions by methods well-known to those skilled in the art. The equilibrium catalyst at a temperature of 1100.degree.-1500.degree. F. contacts the oil feed at riser wye 17. The feed can contain steam and/or flue gas injected at point 2 or water and/or naphtha injected at point 3 to aid in feed vaporization, catalyst fluidization and controlling contact time in riser 4. The catalyst and vaporous hydrocarbons travel up riser 4 at a contact time of 0.1-5 seconds, preferably 0.5-3 seconds. The catalyst and vaporous hydrocarbons are separated in vented riser outlet 6 at a final reaction temperature of 900.degree.-1100.degree. F. The vaporous hydrocarbons are transferred to a multistage cyclone 7 where any entrained catalyst fines are separated and the hydrocarbon vapors are sent to a fractionator (not shown) via transfer line 8. The coked catalyst is then transferred to stripper 10 for removal of entrained hydrocarbon vapors and then to regenerator vessel 11 to form a dense fluidized bed 12. An oxygen containing gas such as air is admitted to the bottom of dense bed 12 in vessel 11 to combust the coke to carbon oxides. The resulting flue gas is processed through cyclones 22 and exists from regenerator vessel 11 via line 23. The regenerated catalyst is transferred to stripper 15 to remove any entrained combustion gases and then transferred to riser wye 17 via line 16 to repeat the cycle.

At such time that the metal level on the catalyst becomes intolerably high such that catalyst activity and selectivity declines, additional catalyst can be added and deactivated catalyst withdrawn at addition-withdrawal point 18 into the dense bed 12 of regenerator 11 and/or at addition-withdrawal point 19 into regenerated catalyst standpipe 16. Addition-withdrawal points 18 and 19 can be utilized to add virgin catalysts containing one or more metal additives of the invention. In the case of a virgin catalyst without additive, the metal additive as an aqueous solution or as an organo-metallic compound in aqueous or hydrocarbon solvents can be added at points 18 and 19, as well as at addition points 2 and 3 on feed line 1, addition point 20 in riser 4 and addition point 21 near the bottom of vessel 5. The addition of the metal additive is not limited to these locations, but can be introduced at any point in the oil catalyst processing cycle.

As an example of additive addition to such commercial cracking processes, TPT is diluted with heavy gas oil (HGO) to form a solution of 1 part TPT to 1 part HGO. This solution is added to riser feed line 1 in an amount sufficient to yield 1 part titanium by weight to 1 part vanadium in the feed. The feed is a reduced crude processed at 600,000 lb. per day with a vanadium content of 200 ppm. Based on the vanadium content and the molecular weight of the TPT, this equates to adding 420 lbs. of TPT per day to 600,000 lbs. of reduced crude feed per day.

Another example of commercial application of the metal additive of this invention is the use of methylcyclopentadienyl manganese tricarbonyl (MMT). Two drums of this material is added over a two hour period to partially immobilize the vanadium on the catalyst. Each drum weighs 410 lbs. and contains 25 wt. % MMT in a hydrocarbon solvent. Based on a manganese concentration of 28.3 wgt. % Mn in MMT and a circulating catalyst inventory of 42 tons, approximately 700 ppm Mn is deposited on the catalyst. Both the TPT and MMT additions improve the circulating efficiency of the catalyst.

In a FCC or RCC unit, the rate of metals buildup on the circulating catalyst is a function of metals in the feed, the catalyst circulating inventory, the catalyst addition and withdrawal rates (equal), and the catalyst to oil ratio. FIGS. 10 and 11 give the rate of metal buildup on a circulating catalyst at constant inventory, constant catalyst addition and withdrawal rate and varying metals content in the feed. These figures show that for feed metals levels of 20-70 ppm, total metal levels on the catalyst equilibrate after about 90-150 days. Thereafter, the metals level on catalyst remained constant with time. By utilizing these figures, or similar figures that can be developed for higher metals levels, higher addition rates and higher circulating inventories, the required concentrations of the metal additives of this invention on the catalyst can be calculated so as to yield the preferred atomic ratio of metal additive to vanadium.

For example, in FIG. 10, the unit has 9,000 lbs. of catalyst inventory, a catalyst addition rate of 1.35 lb./bbl. of feed per day, and a feed rate of 200 bbl./day. Assuming the metals content is all vanadium, Curve 1 in FIG. 10 would be utilized to show total vanadium after 150 days of continuous operation with 70 ppm vanadium in the feed. The vanadium level on the catalyst would equilibrate at about 17,000 ppm and then remains constant with time. Thus, in making a catalyst containing a titania additive according to this invention, the catalyst would be prepared such that it would contain at least 8,500 ppm titanium to ensure at least a 0.5 atomic ratio of titanium to vanadium was maintained at equilibrium conditions. Similar calculations can be performed for lower and higher equilibrium vanadium values using the other curves or multiples of those curves (120 ppm metals on catalyst would equilibrate at about 30,000 ppm under the conditions of FIG. 10).

In processing feeds of varying vanadium content, the rate of vanadium buildup on the catalyst and the equilibrium or steady state of vanadium on the catalyst is a function of vanadium content of the feed and especially the catalyst addition and withdrawal rates which are equal to equilibrium conditions. Table E presents a typical case for a 40,000 bbl./day unit in which the vanadium content of the feed is varied from 1 ppm (FCC operations with VGO containing 5-20% of a heavy hydrocarbon fraction) up to 25-400 ppm (RCC operations). In order to maintain various levels of vanadium on the catalyst at the equilibrium state after long term operation (50-150 days), the catalyst addition rate can be varied to yield equilibrated vanadium values of from 5,000 to 30,000 ppm. As stated and explained elsewhere, vanadium, as vanadium pentoxide on the catalyst, causes irreversible zeolite destruction and especially manifests this phenomena at the higher vanadium levels. For example, at 5,000 ppm vanadium, the zeolite content can be reduced by at least 50%, and at 10,000 ppm, complete destruction of the zeolite crystalline structure is apparent. By applying the additive of this invention, one can now operate in the upper ranges of vanadium levels (20,000-30,000 ppm) without the vanadium destroying the zeolite and causing particle coalescence.

Table F presents the economic advantage of introducing the additive of this invention into the riser as an aqueous or hydrocarbon solution. Table F shows the economic differential (savings in $/day) that can be realized by utilizing the additives of this invention and operating at the 20,000 ppm level versus the 10,000 ppm level of vanadium. These savings can be higher by a factor of about two (2) if one considers operation at the 5,000 ppm level versus the 20,000 ppm level of vanadium. A cheaper additive (titanium tetrachloride instead of TPT) will also improve these economics. Thus, where as TPT costs $12/lb. of titanium content, titanium tetrachloride costs only $1.50/lb. of titanium content.

As shown in Table F, a FCC operation (1 ppm vanadium in feed) would show a savings of at least $490/day with TPT as the additive and a RCC operation (25-100 ppm vanadium in feed) would show a savings of at least $12,000-$48,000/day.

The regenerator vessel as illustrated in FIG. 1 is a simple one zone-dense bed type. The regenerator section is not limited to this example but can consist of two or more zones in stacked or side by side relation and with internal and/or external circulation transfer lines from zone to zone. Such multistage regenerators are described in more detail in Ashland's above RCC applications.

Having thus described above the observed detrimental effects of vanadium and nickel and the catalyst, metal additives and processes of this invention, the following tests illustrate the effects of vanadia flow and catalyst deactivation through destruction of the zeolite's crystalline structure. It was determined that vanadia deposited on a zeolitic cracking catalyst would, under the conditions of elevated temperatures in the regenerator zone, enter the zeolite and cause destruction of its crystalline structure so as to form a less active amorphous material, with subsequent low activity and selectivity.

This phenomena was evaluated in the laboratory by depositing vanadium and nickel, singly, on a specially chosen candidate catalyst to study its resistance to severe thermal and steaming conditions according to a test sequence designated as calcining, impregnation and steaming (CIS). The test measures the effects of nickel and vanadium deposition on fluid cracking catalysts under severe conditions of hydrothermal treatment. According to the CIS test, fresh catalyst is calcined at 1200.degree. F. for 3 hours in a shallow bed, 100 gms of the dried material is then vacuum impregnated with 0.25, 0.5, 1.0 and 2.0 wt. % of added nickel or vanadium. Either aqueous solutions of the sodium sulfate or pentane solutions of metal organic complex are employed. Excess solvent is removed at 0.1 mm Hg pressure. The impregnated catalyst is oxidized at 1000.degree. F. for 3 hours using a shallow bed and muffle furnace. After oxidation, the oxidized material is steamed at 1450.degree. F. for 5 hours according to the Steaming Torture Test of Table D. Samples are then tested for MAT activity, selectivities, surface area, zeolite and metal concentrations.

As shown in FIGS. 2 through 7, the overall effect of nickel is to neutralize acid sites and increase coke and gas production, but little or no destruction of the zeolite crystalline cage structure was observed. Vanadium, on the other hand, was irreversibly destructive. At suitably severe conditions, as the vanadia content was increased, zeolite content decreased proportionally to the point that at approximately the 1 wt. % vanadium level, the zeolite crystalline structure was completely destroyed after 5 hours contact at 1450.degree. F. with 100% steam, leading to a completely deactivated catalyst. In FIGS. 6 and 7, "CPF" stands for Carbon Producing Factor and is defined as the ratio of the amount of coke produced by the test catalyst to the amount of coke produced by the standard catalyst at the same conversion level. "HPF" stands for Hydrogen Producing Factor and is defined as the ratio of the amount of hydrogen produced by the test catalyst to the amount of hydrogen produced by the standard catalyst at the same combustion level.

The determination that vanadia deposited on a catalyst would flow and cause coalescence between catalyst particles at regenerator temperatures, and the selection of those elements and their salts which would prevent this process were studies by three methods, namely: the clumping or lump formation technique, vanadia diffusion from or compound formation with a metal additive in an alumina-ceramic crucible, and through spectroscopic studies and differential thermal analyses of vanadia metal additive mixtures.

A clay, spray dried to yield microspherical particles in the 20 to 150 micron size, had vanadia deposited upon it in varying concentrations. Clay free of vanadia and clay containing varying vanadia concentrations were placed in individual ceramic crucibles and calcined at 1400.degree. F. in air for two hours. At the end of this time period, the crucibles were withdrawn from the muffle furnace and cooled to room temperature. The surface texture and flow characteristics of these samples were noted and the results are reported in Table X.

As shown in Table X, the clay free of vanadia does not form any crust or clumps or fused particles at temperatures encountered in the regnerator section of the process described in this invention. At vanadia concentrations of 1,000-5,000 ppm clumping was observed but the crusts binding particles could be readily broken into free flowing, crusty particles. At vanadia concentrations above 5,000 ppm, the clay begins to clump and bind badly and does not flow at all even with moderate impact. While liquid at operating temperature, manifestation of this phenomenum is demonstrated by the finding that when these coalesed particles are cooled down below their solidification point in a crucible, or in an operating unit cooled down in order to facilitate entrance to the unit for cleaning out plugged diplegs and other repairs, a solid mass of catalyst is formed which must be forcibly removed. This phenomena makes turn-around lengthy and complex for an operating unit as this material must be chipped out.

An extension of the clumping test is the use of a ceramic-alumina crucible to determine whether vanadia reacts with a given metal additive. If vanadia does not react with the metal additive or only a small amount of compound formation occurs, then the vanadia diffuses through and over the porous alumina walls and deposits as a yellowish to orange deposit on the outside wall of the crucible. On the other hand, when compound formation occurs, there are little or no vanadaia deposits formed on the outside of the crucible wall. Two series of tests were performed. In the first series shown in Table Y, a 1:1 mixture by weight of vanadium pentoxide and the metal additive was placed in the crucible and heated to 1500.degree. F. in air for 12 hours. Compound formation or vanadia diffusion was as noted in Table Y.

In the second series of tests, a vanadia containing material was tested in a similar manner. A one to one ratio by weight of vanadium pentoxide and the metal additive were heated to 1500.degree. F. in air for 12 hours. The results are shown in Table Z. The material reported in Table Z as containing 24,000 ppm vanadia on clay with no metal additive was fired at 1500.degree. F. and then studied in a scanning electron microscope (SEM). The fused particles initially gave a picture of fused particles. However, as the material was continuously bombarded, the fused particles separated due to the heat generated by the bombarding electrons. One was able to observe the melting and flowing of vanadia as the initial single fused particles separated into two or more distinct microspherical particles.

The study of the capability of certain elements to immobilize vanadium pentoxide was extended by use of Du Pont differential thermal analyses (DTA), X-ray diffraction (XRD) and scanning electron microscope (SEM) instruments. The metal additives studies on the DTA showed that titania, barium oxide, calcium oxide, the lanthanide series, magnesium oxide and indium oxide all were excellent additives for the formation of high melting metal vanadates, with melting points of 1800.degree. F. or higher. Copper gave intermediate results with compounds melting at approximately 1500.degree. F. Poor results were obtained with materials such as lead oxide, molybdena, tin oxide, chromia, zinc oxide, cobalt oxide, and cadmium oxide.

An example of the effectiveness of the metals of this invention to immobilize vanadium and reduce its destructiveness towards the crystallinity of the zeolite structure is shown in FIG. 8. A standard FCC catalyst was steamed with and without vanadia, as shown in Runs 1 and 2. The presence of vanadium reduces the zeolite content from an intensity of 9.4 down to 3.1. Runs 3 and 4 illustrate the effectiveness of titania and the preference for the titania to be present as the vanadia is being deposited on the catalyst in the riser and before regeneration. As shown in run 4, the titanium and vanadium are deposited as organo-metallics, oxidized to remove the hydrocarbon portion of the organo-metallic compounds and to oxidize the elements to their corresponding oxides of highest valence. This is then followed by steaming at 1450.degree. F. for 5 hours. During the oxidation and steaming, the titanium was present in a one to one atomic ratio relative to vanadium for the formation of titanium vanadate which is a high melting solid as shown in Table A.

The invention is useful in catalytic conversion of both FCC and RCC feeds as described above. The present invention is particularly useful in the catalytic cracking of high boiling carbo-metallic feedstocks to lower boiling hydrocarbon fractions in the liquid fuel range. Examples of these oils are reduced crudes and other crude oils or crude oil fractions containing residua as above defined.

Although the catalytic cracking process is preferably conducted in the riser reactor of the vented type, other types of risers and other types of reactors with either upward or downward flow may be employed. Thus, the cracking operation may be conducted with a moving bed of catalyst which moves in countercurrent relation to liquid (unvaporized) feedstock under suitable contact conditions of pressure, temperature and weight hourly spaced velocity. Alternatively, the feedstock may be passed through alternating fixed beds of catalyst with cycling cracking and regeneration.

Although the preferred contacting operation is catalystic cracking, the catalyst and processes of the invention may be employed in various other types of hydrocarbon conversion operations, such as dehydrocyclization, hydrocracking, hydroforming of naphthene hydrocarbons and the like, polymerization of olefins, depolymerization of polymers, alkylation, dealkylation, disproportionation, reforming of naphthas, isomerization of paraffins and the like, aromatization of paraffins and the like, hydrogenation, dehydrogenation, various types of hydrofining operations in which one or more characteristics of the feedstock are improved by treatment with hydrogen in the presence of a catalyst, and like types of other contacting and/or conversion processes.