JPS5832691A - Akushitabanajianofudoka - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides improved catalysts, one or more methods of preparation thereof, one or more processing methods thereof, and the conversion of prefixed crude oil or crude oil to liquid transportation and/or heating fuels. It relates to a method for this purpose. More particularly, the present invention provides for the use of catalysts with uniformly dispersed catalytic activity in a matrix containing selected metals as metal additives, their oxides or salts, to immobilize vanadium oxide deposited on the catalyst during processing. The present invention relates to a catalyst composition comprising a crystalline, aluminosilicate zeolite. Another embodiment of the invention provides that during catalyst production, by impregnation after spray drying,
or the addition of metal additives for panagia immobilization at any point in the processing cycle of the prefixed crude oil.

The introduction of catalytic cracking to the petroleum industry in the 1930s was a major advance over previous technology aimed at increasing the yield of ganlin and its quality. Early fixed-bed, moving-bed, and fluidized-bed catalytic cracking FCO processes involved vacuum gas oil obtained from crude oils that were considered to be sweet and light.
oils, VGO) f was used. The term sweet refers to a low sulfur content; the term light refers to a sulfur content of approximately 1.000 to 1.
．． It relates to the amount of material that boils below 0.25F.

Early homogeneous fluid dense bed
The catalysts used in Bed) were of amorphous siliceous materials made from natural materials activated synthetically or by acid leaching. Significant advances were made in FCC technology during the 1950's in metallurgy, processing equipment, regeneration, and new, more active and more stable amorphous catalysts. However, increasing demands on gasoline quality to meet the new high-horsepower, high-compression engines subsidized by the auto industry, as well as increased demands on octane, have resulted in stricter production capacity and operation requirements under the FCC Act. Significant pressure was placed on the petroleum industry to increase productivity.

A major advance in FCC catalysis was achieved in the early 11960s with the introduction of molecular sieves or zeolites. These were incorporated into the matrix of amorphous and/or amorphous/kaolin materials that constituted the FCC catalysts of the time. These new zeolite catalysts containing crystalline aluminosilicate zeolites in a matrix of amorphous materials, amorphous/kaolin materials, silica, alumina, silica-alumina, kaolin, etc., are superior to earlier ones containing silica-alumina catalysts. The amorphous material was at least 1,000 times more active for cracking hydrocarbons than the amorphous/kaolin material.

The introduction of this zeolite cracking catalyst brought about a revolution in fluid catalytic cracking. New modifications have been made to handle these high activities, such as riser cracking, reduced contact times, new regeneration methods, and the development of new and improved zeolite-based catalysts.

The overall economic result of the development of these zeolite-based catalysts is to significantly increase feedstock throughput using the same unit without the need for expansion or the construction of new units; This provided the petroleum industry with the possibility of increasing ion, e-ion and selectivity.

Newer catalysts have been developed, centering on the development of various zeolites such as X, Y, and faujasite types.

Matrixes with increased thermal-steam stability and greater wear resistance have been developed by incorporating rare earth ions or ammonium through ion exchange techniques.

After the introduction of catalysts containing zeolitic materials, the petroleum industry began to struggle with the availability of crude oil in terms of quantity and quality as the demand for higher octane gasoline increased. The world's number one crude oil supply situation changed from the late 1960s to the early 1970s. The supply situation has changed from an abundance of light-swede crude oil to a more scarce supply situation with constant increases in heavier crude oils with higher sulfur content. These heavier and higher sulfur content crude oils differ from petroleum oil in that these heavier crude oils always also have higher amounts of metals and Conradson carbon numbers, with a chewy increase in asphalt content. Raised processing issues to refiners.

The fractionation of the total crude oil to obtain the catalytic cracking feedstock also needed to be better (controlled) to ensure that the metals and Conradson carbon numbers were not migrated throughout and mixed into the FCC feedstock.

The effect of metals and Konrad Son carbon on FCC catalysts containing zeolitic materials has been shown to have a significant adverse effect on catalyst activity and selectivity for gasoline production, as well as on the lifetime of the catalyst. It has been documented in the literature that they have harmful effects. In particular, we have found that the presence of vanadia in high concentrations in the feedstock is particularly detrimental to catalyst life.

As noted above, these heavier crude oils also contained higher amounts of heavier fractions, resulting in lower amounts of good quality FCC feedstocks. FCC feedstock oil is usually 1025F.
It is usually processed to have a metal content of less than 1 ppm, preferably less than 0.1 ppm, and a Conradson carbon number of substantially less than 1.

This increased supply of heavier crude oils means lower gasoline yields and increased demand for liquid transportation fuels, leading the oil industry to use these heavier crudes for gasoline. We began to pursue a processing plan for use in generation. These processing plans are mostly described in the literature. These include Gulf's Galfining process and Union Oil's Unifying process for treating bottoms; UOP's Aurabon process for producing pyrolysis gasoline and coke;
These include Hydrocarbon Research's H-oil method, Exxon's 7-lexi coking method, or H-Oil's Guichi cracking method and Philips' heavy oil cracking method (Hoc'). These methods employ pyrolysis or hydrotreating and subsequent (FCC or hydrocracking operations) to remove relatively high metal contents (
N1-V-Fe-Cu-Na) and a high Conradson carbon number of 5-15. The disadvantages of this type of processing method are as follows. The coking method yields a hot gasoline with a significantly lower octane number than catalytic cracking gasoline, and the coking method is unstable due to the formation of rubber from qualefin and yields a product with a high octane number. This requires further hydrogen treatment and reforming. The thermal reaction degrades the quality of moth oil, devalues the product containing refractory polynuclear aromatic compounds, and the high Conradson carbon number is highly unsuitable for catalytic cracking.

Also, high-pressure hydrogen is expensive for hydrogen treatment9. It requires a multi-reactor system made of bamboo special alloy, expensive operation, and expensive separate equipment for hydrogen production.

In order to better understand why the industry has advanced with the above processing schemes['], we have compared the contaminant metals (Nl-V-F6-Cu-Na) and the operating parameters of zeolite-containing cracking catalysts and FCC units The known effects of Conradson carbon must be understood. Metal content and Conradson carbon are F
CC unit or prefixed crude oil conversion (Redu
These are two very significant restraints on operating the ced Crude Convection unit for maximum conversion, selectivity and longevity.

Although there is only enough hydrogen to produce only toluene and tanthane if highly selective catalysts are devised, the operating capacity and efficiency of FCC units decreases with increasing metals and carbon. is severely affected and ultimately becomes adversely affected or rendered inoperable.

The effect of increasing Conradson carbon is that there is more feed oil that can be converted to carbon that is deposited on the catalyst. F
In a typical GO operation using a zeolide-containing catalyst in a CC unit, the amount of coke deposited on the catalyst averages about 4 to 5 times the feed rate. This coke formation was due to four types of coking mechanisms. These are contaminated coke (from metal deposits), catalytically cracked coke (cracking in acidic sites), entrained hydrogen chloride (poor structure adsorption - poor stripping) and Conradson carbon. High-boiling fractions, such as prefixed crude oil (redu
ced crudea topped crude),
When processing the residual fraction, etc., the amount of coke produced relative to the supply amount is the same as the above four types that exist during VGO processing,
It is the sum of the high Conradson carbon number, unstripped high-boiling hydrocarbons, and coke associated with nitrogen-rich molecules irreversibly adsorbed on the catalyst. Therefore, when processing a prefixed crude oil, the amount of coke produced on a clean catalyst is about 4 parts by weight plus the Conradson carbon number of the feedstock.

Therefore, in addition to the four present in VGO, it has been hypothesized that there are two other coking sources in the prefixed crude oil. These are: 1) adsorbed and absorbed high boiling hydrocarbons that cannot be removed by stripping at normal capacity; and 2) high molecular weight hydrocarbon compounds containing nitrogen adsorbed on the acidic sites of the catalyst. These two new types of coke formation phenomena significantly increase the complexity of kettle bottom processing.

The spent catalyst that produced coke is brought back to equilibrium activity by burning off the inactivated coke in the presence of air in a regeneration zone and recycled to the reaction zone. The heat generated during regeneration is removed by the catalyst and transported to the reaction zone for vaporization of the feedstock and to provide heat for the endothermic nature of the cracking reaction. The temperature in the regeneration zone is kept within conventional limits due to metallurgical limitations and thermal-steam stability of the catalyst.

The thermal-steam stability of zeolite-containing catalysts is determined by the temperature and water vapor partial pressure at which the zeolite rapidly begins to lose its crystalline structure to an amorphous material of low activity. The presence of water vapor is very significant and is generated by the combustion of adsorbed carbonaceous material with a high hydrogen atomic content. This carbonaceous material mainly has a boiling point of 150°C with a moderate hydrogen content.
Adsorbed high boiling hydrocarbons from 0 to 1700'F or higher and nitrogen-containing high boiling hydrocarbons and associated porphyrins and asphaltenes.

Coke production increases as the Conradson carbon number of the feedstock increases, and this increased loading will increase regeneration temperatures. The unit is therefore limited in terms of the amount of feedstock it can process due to its Conradson carbon content.

Relatively early VGO units had a regenerator of 1150
Operated at ~1250F. A newly developed method in the processing of prefixed crude oil, namely Ashland-Osh 11
The company's "Prefixed Crude Oil Conversion Method" (patent application under examination USSN 094.216) is 1350-1400F.
Can be operated at regenerator temperatures in the range of .

However, even this high regenerator temperature is limited to a Conradson carbon number of about 8 for the feedstock. This level will be the regulation unless significant amounts of water are introduced to further control the temperature (which the RCC method does).

The metal-bearing fraction of the prefixed crude oil contains Ni-V7Fe-Cu present in porphyrins and asquartene. These metal-containing hydrocarbons can be deposited on the catalyst during processing, cracked in the riser to deposit metals, or used as metal-porphyrins or asphaltenes and left behind by the catalyst to form metal oxides during regeneration. be changed. - According to the literature, the adverse effects of these metals result in non-selective or degradative racking and dehydrogenation, increasing the production of coke and light gases (e.g. hydrogen, methane and ethane) that affect selectivity. resulting in lower yields and quality of gasoline and diesel oil. Increased production of light gases compromises the yield and selectivity structure of the process, while also increasing demands on compressor capacity. In addition to its negative impact on yield, increased coke production also affects catalyst activity and selectivity, significantly reducing regenerator air demand and compressor capacity, and potentially uncontrollable and dangerous regenerator temperatures. increase to

These problems of the prior art have been greatly reduced by the development of the prefixed crude conversion process at Assurant 9 Oil Company (see pending patent applications USSN 094,092 and 094°216). This new method allows handling of prefixed crude oils or crude oils with high metal content and Conradson carbon numbers that previously could not be processed directly. Thus, these crude oils require expensive vacuum distillation to separate the appropriate feedstocks and produce vacuum still bottoms with high sulfur content as a by-product. The RCC method avoids all of these.

Prefixed crude oil with high nickel to vanadium levels has a high metal content relative to the catalyst (e.g. 5,000 to 10,0
It was recognized early on that catalyst deactivation presented fewer problems at elevated regeneration temperatures (00 ppm). However, it was recognized early on that crude oils prefixed with high levels of vanadium to nickel were used over zeolite-containing catalysts, especially for catalysts. Rapid deactivation of zeolite-containing catalysts is observed when processed at relatively high vanadium contents. This deactivation occurs at elevated regeneration temperatures at vanadium levels ranging from 5.000 ppm to 10,000 ppm. It has been shown that zeolite structure is rapidly lost.Published commentary reports that it is not possible to operate at vanadium levels above 10,000 ppm due to this factor. To date, this rapid inactivation by vanadium at high vanadium levels has only been suppressed by lowering the regenerator temperature and increasing the rate of fresh catalyst addition.

These problems of the prior art are solved in a process using the catalyst and selected metal additives according to the invention, whereby a prefixed crude oil with high metal content (high vanadium/nickel ratio) and high Conradson carbon number is Or crude oil can be processed. A prefixed crude oil or crude oil having a high metal content and a high Conradson carbon number is contacted with a zeolitic material-containing catalyst at a high temperature region of about 950F or higher. Hara in the rising pipe? The residence time of - is 5 seconds or less, preferably 0.5 to 2 seconds. The particle size of the catalyst is
Approximately 20-150 mi to ensure proper liquidity. - Ron's dimensions.

Exhaust - Crude oil - Introduce crude oil to the bottom of the riser pipe, 12 () 0 ~
Contacting the catalyst at a temperature of 1400F results in a temperature of about 950-1.1'007' at the exit of the reactor riser. Prefixed crude oil or crude oil together with water, steam, naphtha,
Flue gas or the like may also be introduced to assist in the evaporation and act as a lift gas to control residence time to obtain other advantages as shown in patent application USSN 094.216.

The spent catalyst is rapidly separated from the hydrocarbon vapors at the exit of the riser by employing an Indian riser mechanism developed by Ashland Oil Company.

During the reaction in the riser, metals and Conradson carbon compounds are deposited on the catalyst. The spent catalyst is separated in the Indian riser and deposited in a dense but fluffy layer at the bottom of the reactor, transferred to the IJ horn and then to the regeneration zone. . The used catalyst is brought into contact with an oxygen-containing gas and burned to form carbon oxides, thereby removing carbonaceous material and regenerating the carbon content to 0.1% by weight or less, preferably 0.05% by weight or less. A catalyst is obtained. The regenerated catalyst is then recycled to the bottom of the riser where it is once again combined with the high metal content and conradone carbon content feedstock to repeat the cycle.

Vanadium deposited on the catalyst converts to oxides of vanadium, particularly vanadium pentoxide, at the elevated temperatures encountered in the regeneration zone. The melting point of vanadium pentoxide is much lower than the temperature encountered in the regeneration zone, so it becomes mobile and flows over the surface of the catalyst, plugging the pores, coalescing the particles and, more importantly, forming the zeolite fines. It enters the pores, where our research has shown that the crystal irreversibly collapses, mediating the formation of an amorphous material.

The present invention provides that specific metals, metal oxides or their salts are incorporated into the catalyst matrix during production or by impregnation after spray drying, or added at specific points in the unit during processing. This represents a new means for immobilizing vanadium by forming compounds or complexes and counteracting the adverse effects of vanadium pentoxide. These compounds or complexes of vanadia and metal additives act to immobilize the vanadia by forming a complex or compound of vanadia with a melting point higher than the temperatures encountered in the regeneration zone.

Particular catalysts of the invention include clays, kaolins, silicas, aluminas, smectites, and other bilayer plate silicates,
Included are solids with high catalytic activity, such as zeolites, in matrices such as silica-alumina. The surface area of these catalysts is preferably 100 m”/9
The porosity is 0.
2 me/11 or higher, and ASTM test method AD
3907-80 has a microactivity value or conversion of only at least 60 or more, preferably 65 or more.

The metal additives are mixed into the aqueous slurry of raw matrix material and zeolite to a concentration of about 1-20% by weight relative to the final catalyst. Metal additives are present in the form of water-soluble compounds such as nitrates, halides, sulfates, carbonates, etc.1. and/or can be added as an oxide or water gel. Spray drying this mixture provides the promoted final catalyst as microspherical particles with dimensions of 10 to 200 microns containing active metal additives deposited within the matrix and/or on the outer surface of the catalyst particles. Since the concentration of panagia in the used catalyst may be up to 4% by weight of the weight of the particles, the metal additives should be added as metallic elements in order to maintain at least a 1:1 atomic ratio of vanadium to metal additives at all times. It will be in the range of 1 to 6 weight units. Touch
The medium may be impregnated with metal additives after spray drying using techniques well known in the art, or an active gelatinous precipitate (e.g. titania or zirconia gel or other gel) may be formed prior to spray drying as described above. ) can be added to the matrix gel.

Although there is no intent to determine the exact mechanism of vanadium immobilization, it is likely that the metal additives of the present invention form compounds or complexes with vanadia that have higher melting points than those encountered in the regeneration zone. A 1:1 atomic ratio is chosen as the minimum. However, if the catalyst is to be loaded with metal prior to use, the metal additive may initially be significantly higher than this ratio. The ratio of additive to vanadium will then decrease as vanadium is deposited on the catalyst. Therefore, in this 1:1 ratio (50% vanadium - 50% metal additive) the melting point of the two-component reaction product is generally well above the operating conditions. Alternatively, metal additives can be added in proportions equal to the metal content of the feedstock to maintain a 1:1 atomic ratio. This experimental method uses vanadium pentoxide as well as
The components form a reaction mixture in this 1:1 ratio of about 180
A practical approach was taken to find and identify suitable metal-metal oxides that could give solid compounds with melting points above 0F. The search for this high melting point reaction product was initiated to gain confidence that vanadia would not melt and flow and enter the zeolite cage structure and disrupt the zeolite crystal structure as described above. The metal-metal oxides in the present invention include the Queen group of the Periodic Table of Elements and their active elements. - Table A Melting point of 1/1 mixture Group IA MR, Ca, Sr, Ba 1740
-1900 Seal B Group Sc, Y, La
1800-2100 ■ Group B Ti, Zr, H
f 1700-2000VB group Nl)
, T6 1800-20 [ ] 0 ■ B group
Mn' 1750 ■ Family Fe, G
o, Ni 1600-1800 Seal A group
In, Tt 1800VA Group B
i 1800 VIA Te
1500 lanthanide series G e r
P r a etc. 2100 actinide series T
)1. U etc. - Reaction of vanadia with metal additives generally results in a two-component reaction mixture. According to the present invention, mixtures of vanadia with these additives can produce high melting point ternary and quaternary reaction mixtures (including barium vanadium titanate), and these six and quaternary components. It has also been recognized that reaction mixtures can occur with metals not included in the above groups. Additionally, the present invention includes vanadium pentoxide as well as lower oxidation states of vanadium. However, during processing of sulfur-containing feedstocks and regeneration in the presence of oxygen-containing gases, vanadium is thought to form compounds such as vanadium sulfides, sulfates, and oxysulfides. However, these may also form binary, ternary, etc. reaction mixtures in the form of mixed oxides and mixed sulfides together with the metal additives in the present invention.

If the metal additive is not added to the catalyst during manufacture, it can be added to the spray-dried microspherical catalyst particles by an impregnation method. Additionally, metal additives can be added as aqueous solutions, hydrocarbon solutions, or volatile compounds at any point during the processing cycle as the catalyst moves through the processing unit. This includes the riser 7 junction 17 along the riser length 4, the dense catalyst bed (den
9. Adding an aqueous solution of an inorganic metal salt or a hydrocarbon solution of an organometallic compound to the Stritz groups 10 and 15, the regenerator inlet 14, the dense catalyst bed 12 of the regenerator, or the pipe 16 in the regenerated catalyst chamber. including, but not limited to.

The specific catalyst of the present invention (with or without metals), the prefixed crude oil conversion (as outlined in FIG. 1)
Rce) type unit. Catalyst particle circulation and operating parameters are adapted to process conditions in a manner well known to those skilled in the art. The equilibrium catalyst contacts the high metal content and Conradson carbon number prefixed crude oil in riser 7 junction 17 at a temperature of 1100-1400F. The prefixed crude oil is injected with steam and/or flue gas in section 2, water and/or injected in section 6, to aid in evaporation, fluidization of the catalyst, and control the contact time in the riser 4. Alternatively, it may contain naphtha. The catalyst and vaporous hydrocarbons rise in the riser 4 for a contact time of 0.5 to 5 seconds, preferably 1 to 2 seconds.

The catalyst and vaporous hydrocarbons have a final reaction temperature of 950-110
At 0'F, it is separated at the Indian riser exit B. The vaporous hydrocarbons are transferred to a cyclone 7 where any entrained catalyst fines are separated and the hydrocarbon vapors are sent via a transfer line 8 to a rectifier. The used catalyst is then removed from the IJ tube for removal of entrained hydrocarbon vapors.
10 and then to a regenerator 11 to form a dense, catalyst bed 12. An oxygen-containing gas, such as air, can enter the bottom of the dense catalyst bed 12 of the regenerator 11 and is cokely combusted to form oxides of carbon.

The resulting flue gas is processed through a cyclone and exits the regenerator 11 via line 13. The regenerated catalyst is
After being transferred to the IJ collar 15 to remove all the entrained combustion gas, it is transferred to the riser pipe 17 via the line 16, and this suction process is repeated.

At this point the metal level on the catalyst becomes too high and the activity and selectivity of the catalyst decreases, so additional catalyst is added and the deactivated catalyst is removed at the add-deposit point 18 to remove the dense catalyst. '' into the bed 12 and removed at the add-out position 19 and transferred to the regenerated catalyst chamber into the tube 16. Addition positions '18 and 19 can also be used for the addition of catalyst promoted with metal additives. In the case of unpromoted catalysts, metal additives in the form of aqueous solutions or organometallic compounds in aqueous or hydrocarbon solvents are added at addition points 18 and 19 and in charge line 1.
dosing positions 2 and 6 above, dosing position 20 in riser 4;
Dense catalyst bed 9 at the bottom of reactor 5 at addition point 21
Can be added to the inside. Addition of the metal additive is not limited to these locations (it can be made at any point in the prefixed crude-catalyst processing cycle).

The regenerator shown in FIG. 1 is a simple, single zone, dense catalyst bed type. The regenerator section is not limited to this example, but may be of two or more zones, in an overlapping or side-by-side manner, with internal and/or external circulation transfer lines from zone to zone. But that's fine.

Low levels of metal impurities in some of the conventional prefixed crude oil processing methods? Using a prefixed crude oil with a high nickel/vanadium ratio as a feedstock, acceptable catalyst life and selectivity could be obtained. However, as the vanadium content of the catalyst increases, or the use of prefixed crude oils with high Nadium/Nickel ratios, the activity and selectivity of the catalyst decreases rapidly to an economically unacceptable extent. can only be corrected by increasing the rate of tactile addition. The observed deleterious effects of vanadium and nickel, the catalyst of the present invention, the promoter metal additive, and the method of the present invention have been described above. The following specific examples are presented to illustrate the action of vanadia to flow and deactivate the catalyst by disrupting the crystalline structure of the zeolite, and the steps taken to prevent this from occurring.

Example: Vanadia deposited on a fluidized catalytic cracking catalyst enters the zeolite under elevated temperature conditions in the regeneration zone, destroying its crystal structure and forming an amorphous material with lower activity.
Determinations of differential mediating (with associated low activity and selectivity) were observed in our prefixed crude demonstration unit.

This phenomenon was then determined in the laboratory by individually depositing vanadium and nickel on specific canadidate catalysts to examine the catalyst's resistance to harsh temperature and cooking conditions. As seen in Figures 2-5 and W, Tables 1 and 2, the overall action of nickel is to neutralize acidic sites and increase coke and gas production, resulting in a zeolite cage structure. Little or no destruction was observed. Vanadium, on the other hand, was irreversibly destructive. As the vanadium content increases under moderately harsh conditions, the crystalline structure of the zeolite changes to 5 at 1450'F in steam at about 1 weight scale vanadium level.
The zeolite content decreased proportionately to the point where it was destroyed after 1 minute, resulting in a completely inactivated catalyst.
・We conducted research using six methods to determine that vanadium deposited on the catalyst flows and causes fusion between catalyst particles at the regenerator temperature, and which elements and their salts prevent this process. Ta.

agglomeration or agglomeration methods, diffusion of vanadium with metal additives in alumina-ceramic crucibles or formation of compounds with metal additives, as well as spectroscopic studies and differential thermal analysis of vanadium-metal additive mixtures. be.

Agglomeration Test Various concentrations of di-Na were deposited on clay that had been spray dried into microspherical particles ranging in size from 20 to 150 microns. The vanadium-free clay and the clay containing various concentrations of vanadium were placed in separate ceramic crucibles and fired in air at 1400F for 2 hours. At the end of this period, the crucible was removed from the Matsufuru furnace and cooled to room temperature. The surface texture and fluidity of these samples were confirmed and the results are shown in Table 3.

Table V2O5 concentration (ppm) Surface texture Flow
Gender 0 Independent Free Flow 1.00
0-5.000 surface flocculation Partial shell - free flowing 5.000-20,000 surface flocculation Total flocculation - no flowability wl, As shown in Table 3, the vanadia-free clay is the regenerator in the present invention. Hull or agglomerates or fused particles at the temperatures encountered in the part?
5. Does not occur. At vanadia concentrations above D This is explained by the finding that the freezing point in the crucible or operating unit is lowered to facilitate entry into the unit for repair. Since this material has to be scraped away, this phenomenon also causes double-track changes of direction in time.

Diffusion in the Crucible - Compound Formation □ The extended flocculation test uses a ceramic aluminum crucible to determine whether vanadia reacts with certain metal additives. If the vanadia does not react with the metal additive or only a small amount of the compound is formed, the vanadia will diffuse through the porous alumina wall onto the wall and deposit as a yellow to orange deposit on the outer wall of the crucible. It was approved to do so. On the other hand, when the compound is formed, there is little or no vanadia deposit on the external surface of the crucible outer wall. Two series of tests were conducted. Fourth
In the first series shown in the table, a 1:1 (by weight) mixture of vanadium pentoxide and metal additives was placed in a crucible and
Heat to 500F for 12 hours. Formation of compounds or diffusion of vanadia was observed.

Table 4 V2O5'I, parts 10 Metal additives 1 part 1501 - Air - 12 hours Titania None Yes Magnesium oxide None Yes Lanthanum oxide None Yes Alumina Yes
No Barium acetate No Yes Copper oxide
Yes In a partial second series of tests, vanadia-containing materials were tested in a similar manner. Vanadia-containing material and metal additives (1:1 weight ratio) in air at 1500F
The mixture was heated for 12 hours. The results are shown in Table 5.

Table 5 V2O5 - 1 part catalyst 1,000 Metal additive 1500°F - Air - 12 hours Vanadia concentration (ppm) Metal additive Particle formation 24.000 Without Yes 24.00
0 Calcium oxide None24.000
Magnesium Oxide None 24,000 Manganese Oxide None DuPont Differential Thermal Analysis (D
It has expanded to include equipment such as TA, X-ray diffraction (XRD), and scanning electron microscopy (SEM). D.T.A.
In examining metal additives based on It was shown that copper and manganese formed compounds that melted at about 1500F, giving intermediate results.Lead oxide,
Poor results were obtained for some of the following: morizodena, tin oxide, chromia, zinc oxide, conolate oxide, cadmium oxide, and rare earths.

1500 ppm of vanadia on the product shown in Table 5, i.e. clay containing no metal additives.
After combustion at F, it was examined by SEM.

The fused particles initially exhibited the state of fused particles. However, as the material continued to be bombarded, the fused particles separated due to the heat generated by the bombarded electrons.

The Panasia was observed to melt and "flow" with the initial single fused particle separating into two separate microspherical particles.

An example of an XRD study is the identification of the compound formed when manganese acetate reacts with vanadium pentoxide. This compound has been tentatively identified as Mn2V207.

M) The IJ sock material for the catalyst of the invention must have good hydrothermal stability. Examples of materials exhibiting relatively stable pore characteristics are alumina, silica-alumina, silica, clays such as kaolin, metakaolin, halloysite, dietskiite, and macrite.
, and combinations of these substances. other clays,
For example, montmorillonite can be added to increase the acidity of the matrix. Clays can be used in their natural state or in their heat-modified state. The preferred matrix of U.S. Pat. No. 3,034,994 is a semi-synthetic combination of clay and silica-alumina.

Preferably, the clay is predominantly kaolinite, combined with a synthetic silica-alumina hydrogel or a human 50 sol. The synthesis components preferably account for about 10% of the product catalyst.
~75% by weight, more preferably about 20-25%. The proportion of clay is preferably between about 10 and 10 after the catalyst is formed.
It contains 75% by weight of clay, more preferably 60-50% by weight. The most preferred matrix compositions contain about twice as much clay as synthetically derived silica-alumina. Synthetically derived silica-alumina contains 55-95% by weight, preferably 65-85% by weight, most preferably about 75% by weight of silica (Si02).
'l should be included. However, catalysts whose gel matrix is entirely composed of silica gel are included. After introducing the zeolite and/or metal additives, the composition is preferably slurried and spray dried into catalyst microspheres.

The spray-dried IJ Lux particle size is generally about 5 to 1
60 microns, preferably in the range of 4 o to so microns.

Generally, the final catalyst is a molecular sieve of both type X or Y (exchanged with rare earth or ammonia) from 5 to 50 parts by weight or from 15 to 45 parts by weight, most preferably from 20 to
It will also contain 40% by weight t. To further increase the catalytic activity, the rare earth exchanged sieve can be calcined and further exchanged with rare earth or ammonia to produce an extremely stable molecular sieve.

Various methods can be used to synthetically produce silica-alumina, such as those described in U.S. Pat. No. 6,834,994. One of these methods is to gel alkali metal silicates with inorganic acids while maintaining the pH on the alkaline side. An aqueous solution of acidic aluminum salt is then intimately mixed with the silica hydrogel;
Fill the pores of the silica hydrogel with an aluminum salt solution.

The aluminum is then precipitated as water alumina by addition of an alkali compound.

As a special example of this method of preparation, silica hydrogels are prepared by adding sulfuric acid to a sodium silicate solution under vigorous stirring and under controlled temperature, time and Q conditions. Aluminum sulfate in water is then added to the silica hydrogel under vigorous stirring, filling the gel with the porous aluminum salt solution. An ammonium solution is then added to the gel under vigorous stirring to precipitate aluminum as hydrated alumina into the pores of the silica hydrogel.

The aquarium gel is then processed, for example by removing some of the water on a vacuum filter and drying, or more preferably by spray drying the aquarium gel to form microspheres. The dried product is then washed with water or a very weak acid solution to remove sodium and sulfate ions. The resulting product is then dried to a low moisture content, usually less than 25% by weight, for example 10-20% by weight, to yield the final catalyst product.

Silica hydrogel slurries with or without alumina in the hydrated state can be purified into gels by filtering and washing to remove dissolved salts.

This will promote the formation of a continuous phase in the spray dried microspherical particles. If the slurry has been previously filtered and washed and it is desired to spray dry the filtered mass, reslurry it with sufficient water to form a pumpable mixture for spray drying. You can also do that. The spray-dried product can then be washed again and finally dried by the means described above.

Metal additives for vanadium immobilization include M, 9, and C.
a, Sr, Ba, Sc, Y, La, Ti,
Zr, )(f, Nb, Ta, Mn, Fe,
n, T/, Bi, Te, rare earths, and metals such as actinide and lanthanide series elements, their oxides and salts, or organometallic compounds. These promoters or elemental metal additives can be used in concentrations ranging from about 0.5 to 20 parts by weight of the final catalyst, preferably about 1 to 5 parts by weight of the final catalyst.

The catalytically active promoter in the preferred catalyst composition is a crystalline aluminosilicate zeolite, commonly known as a molecular sieve. Molecular sieves are initially formed as alkali metal aluminosilicates. It is a dehydrated form of crystalline siliceous zeolite. However, is the activity of the alkaline type measurable? Since alkali metal ions are harmful to the cranking process, the aluminosilicate is ion-exchanged to replace the sodium with any other ion, such as ammonium and/or
Or substitute with rare earth metal ions.

The silica and alumina that form the structure of zeolites are arranged in a regular crystalline pattern that includes a large number of uniform pores interconnected by smaller uniform grooves or pores. The pore size of these pores is typically about 4A to 12A.

Zeolites that can be used in accordance with the present invention include both natural and synthetic zeolites. Natural zeolites include damerisite, clinoptilolite, chabazite, dechiar-dite, faujasite, hyurandite, erionite, analcite, levynite, sodalite, cancrinite, nepheline, lcyurite,
Includes scol 1cite, natrolite, offretite, menrite, mordenite, bluesterite, ferrierite, etc. Suitable synthetic zeolites include zeolide, Y, A, L%ZK-4B,
B, E, F, H, J, M, Q, T%W%X
, Z, ZSM-type, alpha, beta and omega. The term "zeolite" as used in the present invention refers not only to aluminosilicates, but also to substances in which aluminum is replaced by gallium, and silicon is replaced by germanium, as well as so-called pillares (pillares<1 ) Also means clay.

The zeolide-based materials used in preferred embodiments of the invention are about 2.5 to 7. O1 is preferably a synthetic porgysite with a silica/alumina ratio ranging from 3.0 to 6.0 and most preferably from 4.5 to 6.0. Synthetic faujasite is a widely known crystalline aluminosilicate zeolite, and common examples of synthetic faujasite are W, R,
Grace, &, Kanhoney Divinn Department & Union. Types X and Y are commercially available from Linde Division of Carbide Corporation. Ultrastable hydrogen-substituted zeolites such as Z −1,4,,X S
and z-14US (Divison) are also particularly suitable.

Besides faujasite, other preferred types of zeolite materials are mordenite and erionite.

A preferred synthetic faujasite is zeolite Y, which is described in U.S. Pat.
No. 10,116, and these patents? It is quoted here for reference. The latter patent's aluminosilicate is a high silica (SiO2)/alumina (At2
03) Molar ratio (preferably 4 or more)? It has high thermal stability.

Below are examples of zeolites produced by silicification of clays. 5i025', 27-Ele%, Na2O3,
A reaction mixture is obtained from a mixture of sodium silicate, sodium hydroxide and sodium chloride prepared to contain 5 mole %, 1.7 mole % chloride and water (the balance). 12.6 parts of this solution are mixed with 1 part of calcined kaolin clay. The reaction mixture is held at about 60-75F for about 4 days. After this low temperature aging step, the mixture is heated to about 190F with active steam until crystallization of the material is complete (eg, about 72 hours). After filtering and washing, this crystalline material has a silica/alumina ratio of about 4.3 and about 13.5% Na2O by weight in the volatile free state.
A silicified crezeolite containing is obtained. Varying the ingredients and time and temperature as is commonly practiced in commercial operations will produce zeolites with silica/alumina molar ratios varying between about 4 and 5. Molar ratios greater than about 5 can be obtained by increasing the amount of 8102 in the reaction mixture. The NB20 content is then reduced to below about 5% by weight (preferably 1.0% by weight) by exchanging the zeolite with sodium-type polyvalent cations. Methods for removing alkali metals and forming zeolites into appropriate types are described in U.S. Pat. CI, 7-0 and 23.537,816, which are well known in the art and are incorporated herein by reference.

Zeolites and/or metal additives are dispersed in the matrix used as cracking catalyst by methods well known in the art. These methods are described, for example, in US Pat. Nos. 3,140,249 and 3.140.2.
No. 53 (Blank et al.), U.S. Patent No. 5,660,274
(Prazek et al.), U.S. Patent No. 4,010,116 (
Secor et al.), U.S. Pat. No. 3,944,482 (Mitchell et al.), and U.S. Pat. .

For the heated final product, the amount of zeolite aggregate dispersed in the matrix should be small (approximately 10% by weight, preferably about 25-50% by weight, most preferably about 25-50% by weight). 50 quantity.

Crystalline aluminosilicates exhibit acidic sites on both the inner and outer surfaces and have the largest proportion to the total surface area. The cranking site is within the crystalline microspheres inside the particle. These zeolites are usually crystallized as discrete particles of regular shape from about 0.1 to 10 microns in size, and thus this is the size range commonly offered by catalyst suppliers.

In order to increase the portal surface area, the particle size of the zeolite for the present invention should preferably be in the range of 0.1 to 1 micron or less, more preferably 0.1 micron or less. Preferred zeolites are heat treated with hydrogen and/or rare earth ions;
Steam resistant up to approximately 1.650F.

Examples of the effectiveness of the metals of this invention in immobilizing vanadium and reducing its destructive effect on the crystallinity of the zeolite structure are shown in Table 6. FCC catalyst as shown in experiments 1 and 2? Steamed in the presence and absence of vanadia. The presence of vanadium reduces the zeolite content from 9.4 to 6.10 strength. Experiments 3 and 4 demonstrate the effectiveness of titania and the necessity of its presence as vanadia is deposited on the catalyst. As shown in Experiment 4, titanium and sodium are deposited as organometallic compounds, oxidized to remove the hydrocarbon portion of these organometallic compounds, and elemental oxidized to their corresponding oxides. Then steam at 1'450F for 5 hours. During oxidation and cooking, titanium is absorbed in small quantities due to the formation of titanium vanadate (see Table A), a high-melting solid.
Present in a ratio of 1 to 1.

Table 6 V: Ti as vanadium naphthenate: Standard catalyst as trizolobyl titanate V Ti Ti Zeolite 1 0' O-9,4 255000-3,1 355005soio v Ti after regeneration 3.
5 added 4 5500 5500 with V compound 8
．． Add 2Ti, then regenerate

[Brief explanation of the drawing]

Figure 1 shows the prefixed crude oil conversion (
An example of a RCC) type unit is shown below. FIG. 2 is a graph showing the change in catalytic activity as the concentration of vanadium on the catalyst increases. FIG. 6 is a graph showing the change in catalyst activity as the amount of nickel on the catalyst increases. FIG. 4 is a graph showing the loss of crystalline aluminosilicate zeolite as the amount of vanadium on the catalyst increases. FIG. 5 is a graph showing the loss of crystalline aluminosilicate zeolite as the amount of nickel on the catalyst increases. w, 1 The symbols in the figure are as follows."f04---Rising pipe 5-m-Reactor 6---Rising pipe outlet 7---Cyclone 8---Transfer line 9-m-High Density catalyst bed 1n, 15--Stritz tool-11 regenerator 12--High density catalyst bed 1
4-11 Regenerator population 15-11 Stripper 16--Regenerated catalyst standpipe 17--Rising pipe Y-junction is, 19--1 Addition and take-out position 20.21--1 Addition position day 4 -'i (no change to i'5'i) 7 people E-63 Ill, 11. - 203 Russell Meadowlark Road, Kentucky, 41169, United States Inventor: Stephen M. Kovatch 3430 Yuma Drive, Ashland, Kentucky, United States of America 41169 Inventor: James El Balmer 41139 Flatt's Botter Street, Kentucky, United States of America 1707 0 Inventor Oliver Jay Zandona 11 Ashulared the Oaks Drive, Kentucky 41101, United States of America Procedural Amendment June 1980/1llil Commissioner of the Patent Office Shima 1) Haruki Tono 1, Indication of the Case 1981 Patent Application No. 44455 of 1957 2, Name of the invention Prefix: Immobilization of vanadia deposited on catalyst material during processing of crude oil 3, Relationship with the case of the person making the amendment Patent applicant address name Name Ashland Oil Inc. Holley Ted 4, Agent (Attachment) (1,) @ Corrects section of request to read: ``(I) Transportation of prefixed crude oil or crude oil in liquid form having a substantial metal and carbon content. A method for converting said feedstock into a petroleum fuel for industrial and light heating purposes, comprising: converting said feedstock into a petroleum fuel of at least 50 g
, the vanadium compound is immobilized by contacting it with a catalyst having a catalytic cracking microactivity value of preferably 60 or more,' then the gaseous product and the spent catalyst are immediately separated, and the spent catalyst is exposed to a gas containing oxygen. and recirculating the regenerated catalyst to the riser transfer zone for conversion of new crude oil or crude oil. (2) The prefixed crude oil or crude oil contains 200 pprn or less of a metal consisting of nickel, vanadium, iron or copper, and has a Conrad 9son carbon number of 10% by weight or less. A method according to claim 1. (3) Prefixed crude oil or crude oil contains 200 ppm vanadium
Contains the following, and has a Conrad Ison carbon number of 12% by weight or less. ! ￥f The method according to claim 1. (4) Prefixed crude oil or crude oil contains vanadium 100 ppm
Contains the following and has a Conradson carbon number of 10% by weight or less. A method according to claim 1. (5) The method according to claim 1, wherein the prefixed crude oil or crude oil contains 75 ppm or less of vanadium and has a Conradson carbon number of 10% by weight or less. (6) Crystalline aluminosilicate zeolite 10-4 in which the catalyst is dispersed in an amorphous inert solid oxide matrix containing metal additives for vanadium compound immobilization.
A method according to claim 1, comprising 0% by weight. (The metal additive is a water-soluble inorganic metal salt or a hydrocarbon-soluble organometallic compound. The method described in item 1 of the scope of patent claims. (8) Metal addition to immobilize the vanadium compound deposited on the catalyst. The objects are Mf, Ca, Sr, Ba, Sc, Y,
La. Ti, Zr, Hf, Nb, Te, MFL, Fe, If
2. The method of claim 1, comprising elements of the lanthanide series and actinide series: L, Tt, Bl, Te. (9) Metal additives can react with vanadium compounds to form binary vanadate metal salts and react with mixtures thereof to form ternary and quaternary compounds or complexes. A method according to claim 1. 01lI) metal additives about 1-20% by weight of the final catalyst;
2. A process according to claim 1, wherein it is present in the catalyst in an amount preferably from 1 to 6% by weight. (II) The method according to claim 1, wherein the vanadium compounds deposited on the catalyst include vanadium oxides, sulfides, sulfites, sulfates and oxysulfides. 2. The method of claim 1, wherein a metal additive is added to the aqueous slurry of O2 catalyst components prior to spray drying. 0 (Process according to claim 1, characterized in that the metal additive is introduced into the spray-dried catalyst by an impregnation process.0) The metal additive is incorporated into the crystalline aluminosilicate zeolite by ion exchange.Claim range 1
The method described in section. θ The process according to claim 1, paragraph 1, word i'', which features metal additives in the production of crystalline silica-metal zeolites.00 Crystalline silica-titanate zeolites or crystals using titanium or zirconium. Claim 1F characterized by a silica-zirconate zeolite
How to put it on. (17) Adding the metal additive as an aqueous solution of a metal salt or a hydrocarbon solution of an organometallic compound at any point in the prefixed crude oil catalyst processing cycle. A method according to claim 1. 08 The vanadium concentration of the catalyst is 0.1 to 5 of the catalyst weight
% by weight. 09 The vanadium/nickel ratio in the prefixed crude oil or crude oil is in the range of ~%. A method according to claim 1(e). (a) The method according to claim 1, wherein the proportion of vanadium in the total metal content in the raw material pot residual oil is greater than 50%. 01) The atomic ratio of the metal additives added to the processing cycle is at least 0.0% of the vanadium present in the feedstock.
5. 2. A method according to claim 1, preferably in a ratio of at least 1:1. (2. Water-soluble metal additives) - Rogenides, nitrates. The method according to claim 1, wherein the salt is a sulfate, a sulfite, or a carbonate. (23I Hydrocarbon-soluble metal additives are alcoholates, esters, felts, naphthinates, carboxylates, :) enyl-based sandinth compounds. A method according to claim 1. (24) The method according to claim 1, wherein the metal additive for immobilizing the vanadium compound is tetraisopropyl titanate. ■ Titanium tetrachloride is a metal additive used to immobilize vanadium compounds. A method according to claim 1. (c) The metal additive for immobilizing the vanadium compound is MMT. A method according to claim 1. (c) The metal additive for immobilizing the vanadium compound is titanium-containing clay. A method according to claim 1. (To) The titanium-containing clay has a titania content of at least 1.
5. The method of claim 1, wherein the kaolin is 5% by weight. 2. The method of claim 1, wherein 0.1 to 20% by weight of the metal additive is contained as a gelatinous precipitate in the spray-dried gel within the pores. (to) The catalyst promoted with metal additives contains up to 40% by weight of crystalline aluminosilicate zeolites consisting of one or more different zeolites. A method according to claim 1. C31) A patent in which the catalyst composition consists of silica-alumina, kaolin clay and crystalline aluminosilicate zeolite, which further features 1-5% titania gel. 02. The method according to claim 1, wherein the catalyst composition used in the processing of feedstock residues with high metal content comprises silica or silica-alumina, kaolin clay and crystalline aluminosilicate zeolite, which further comprises zirconia. The method according to claim 1, characterized in that the catalyst composition used for processing the raw kettle residue with a high metal content is silica or silica-alumina, kaolin clay and crystalline clay. ``The method described in claim 1, which is an aluminosilicate zeolite, which further features 1 to 5% alumina gel.'' Kazuo Wakasugi, Commissioner of the Patent Office, 1, Indication of Case, 1982, Patent Application No. 44455 No. 3, Relationship with the case of the person making the amendment Applicant Address Name Ashland Oil Incorporated 4, Agent 5 Date of amendment order June 29, 1980 (shipment date) 6, Target of correction -

Claims (1)

[Claims] +11 A method for converting prefixed crude oil or crude oil into liquid transportation and light heating petroleum fuels having a substantial metal content and Conradson carbon content, said feedstock being heated at an elevated temperature. In the riser flow transfer zone, at least 50
．． The vanadium compound is immobilized by contacting with a catalyst having a catalytic cracking microactivity value of preferably 60 or more, followed by immediate separation of the gaseous products and the spent catalyst and regeneration of the spent catalyst in the presence of an oxygen-containing gas. and recirculating the regenerated catalyst to the riser transfer zone for fresh crude oil or crude oil conversion. (2) Prefixed crude oil and tconic crude oil contain nickel, vanadium,
2. The method according to claim 1, wherein the method contains 200 ppm or less of a metal consisting of aluminum or copper and has a Conradson carbon number of 10% by weight or less. (3) Prefixed crude oil or crude oil contains 200 ppm vanadium
The method according to claim 1, wherein the method comprises: and has a Conradson carbon number of 12% by weight or less. (4) Prefixed crude oil or crude oil contains vanadium 100 ppm
σ) Method according to claim 1, which contains the following and has a Conradson carbon number of 10% by weight or less. (5) The prefix crude oil or crude oil is vanadium 75 pl) m
The method according to claim 1, wherein the method comprises: and has a Conradson carbon number of 10% by weight or less. (6) Crystalline aluminosilicate zeolite 10-4 in which the catalyst is dispersed in an amorphous inert solid oxide matrix containing metal additives for vanadium compound immobilization.
A method according to claim 1, comprising 0% by weight. (7) The method according to claim 1, wherein the metal additive is a water-soluble inorganic metal salt or a hydrocarbon-soluble organometallic compound. (8) The metal additives that immobilize the vanadium compound deposited on the catalyst are M9, Ca, Sr, Ba, Sc, Y
, La, Ti, Zr, Hf, Nb, Ta,
The method of claim 1, comprising Mn, Fe, In, Tz, Bi, Te, elements of the lanthanide series and the actinide series. (9) The metal additive can react with vanadium compounds to form binary vanadate metal salts, and react with mixtures thereof to form hexacomponent and quaternary compounds or complexes. The method described in Scope 1. Ql Metal additive is present in the catalyst in an amount of about 1 to 20%, preferably 1 to 6% by weight of the final catalyst! ! The method described in Section 1. 0υ The method of claim 1, wherein the vanadium compounds deposited on the catalyst include oxides, sulfides, sulfites, sulfates and oxysulfides of vanadium. 2. The method of claim 1, wherein the aqueous slurry of Q2+ catalyst components includes a metal additive prior to spray drying. 0 (method according to claim 1, characterized in that the metal additive is introduced into the spray-dried catalyst by an impregnation method; 04) method according to claim 1, characterized in that the metal additive is incorporated into the crystalline aluminosilicate zeolite by ion exchange. Range 1
The method described in section. 05) The method according to claim 1, characterized in that metal additives are used during the production of the crystalline silica-metal zeolite, Ω. (16) The method according to claim 1, characterized in that the crystalline silica-titanate zeolite or the crystalline silica-zirconate zeolite is produced using titanium or zirconium. 07) The method described in Patent No. 1" (i) in which the metal additive is added as an aqueous solution of a metal salt or a hydrocarbon solution of an organometallic compound at any point in the prefixed crude oil catalyst processing cycle. 0 The method according to claim 1, wherein the vanadium concentration in the catalyst is in the range from 0.1 to 5% by weight of the catalyst weight. Claim 1 within the scope
The method described in section. (2) The method according to claim 1, wherein the proportion of vanadium in the total metal content in the raw material pot residual oil is greater than 50 parts. Process according to claim 1, wherein the atomic ratio of the metal additive added to the processing cycle is at least 0.5, preferably a 1:1 ratio of the vanadium present in the feedstock. (2) The method according to claim 1, wherein the water-soluble metal additive is a salt consisting of a halide, a nitrate, a sulfate, a sulfite, or a carbonate. (c) The method according to claim 1, wherein the hydrocarbon-soluble metal additive is an alcoholate, an ester, a ferulate, a naphthinate, a carboxylate, or a genyl-based sanderutsch compound. 2. The method of claim 1, wherein the metal additive for immobilizing the Ca vanadium compound is tetraisopropyl titanate. (c) The method according to claim 1, wherein the metal additive for immobilizing the vanadium compound is titanium tetrachloride. (a) The method according to claim 1, wherein the metal additive for immobilizing the vanadium compound is MMT. (5) The method according to claim 1, wherein the metal additive for immobilizing the vanadium compound is a titanium-containing clay. Q81 Claims where the titanium-containing clay is kaolin with a titania content of at least 1.5% by weight! The method described in Section 1. A method according to claim 1, wherein from 0.1 to 20% by weight of the metal additive is contained as a gelatinous precipitate in the spray-dried gel within the pores. 7. The method of claim 1, wherein the metal additive-promoted catalyst contains up to 40% by weight of crystalline aluminosilicate zeolite consisting of one or more different zeolites. c31) The catalytic composition used for the processing of raw yarn resid with high metal content consists of silica-alumina, kaolin clay and crystalline aluminosilicate zeolite, which is further characterized by 1-5% titania gel. The method described in Section 1. ■ Claims in which the catalytic composition used for processing raw yarn residues with high metal content consists of silica or silica-alumina, kaolin clay and crystalline aluminosilicate, further characterized by 1 to 5% of zirconia gel. The method described in paragraph 1. (to) A patent in which the catalyst composition used in the processing of raw yarn resid with high metal content is silica or silica-alumina, kaolin clay and crystalline aluminosilicate zeolite, which further features 1-5% alumina gel. The scope of the claims! The method described in Section 1.