EP0073874A1 - Immobilisation d'oxyde de vanadium déposé sur des catalyseurs pendant la conversion d'huiles contenant des précurseurs de coke et des métaux lourds - Google Patents

Immobilisation d'oxyde de vanadium déposé sur des catalyseurs pendant la conversion d'huiles contenant des précurseurs de coke et des métaux lourds Download PDF

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EP0073874A1
EP0073874A1 EP82101625A EP82101625A EP0073874A1 EP 0073874 A1 EP0073874 A1 EP 0073874A1 EP 82101625 A EP82101625 A EP 82101625A EP 82101625 A EP82101625 A EP 82101625A EP 0073874 A1 EP0073874 A1 EP 0073874A1
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Prior art keywords
catalyst
vanadia
metal
metal additive
vanadium
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EP82101625A
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German (de)
English (en)
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EP0073874B1 (fr
Inventor
Wayne H. Beck
James D. Carruthers
Edward B. Cornelius
William P. Hettinger, Jr.
Stephen M. Kovach
James L. Palmer
Oliver J. Zandona
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Ashland LLC
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Ashland Oil Inc
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Priority claimed from US06/277,751 external-priority patent/US4432890A/en
Priority claimed from PCT/US1981/000356 external-priority patent/WO1982003225A1/fr
Application filed by Ashland Oil Inc filed Critical Ashland Oil Inc
Priority to AT82101625T priority Critical patent/ATE29150T1/de
Publication of EP0073874A1 publication Critical patent/EP0073874A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique

Definitions

  • This invention relates to an improved catalyst, one or more methods for its preparation, one or more methods for treatment, and a process for its use in the conversion of reduced crude or crude oil to liquid transportation and/or heating fuels. More particularly, the invention is related to a catalyst composition comprising a catalytically active crystalline alumino- silicate zeolite uniformly dispersed within a matrix containing a metal additive as a select metal, its oxide or salts to immobilize the vanadium oxide deposited on the catalyst during processing.
  • a further embodiment of this invention is the addition of the metal additive for vanadia immobilization during catalyst manufacture, after spray drying by impregnation, or at any point in the reduced crude processing cycle.
  • VGO vacuum gas oils
  • 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 as to metallurgy, processing equipment, regeneration and new more-active and more stable amorphous catalysts.
  • 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.
  • the newer catalyst developments revolved around the development of various zeolites such as type X, Y, faujasite; increased thermal-steam stability through the inclusion of rare earth ions or ammonium via ion-exchange techniques and the development of more attrition resistant matrices.
  • these heavier crude oils also contained more of the heavier fractions and yielded less or a lower volume of the high quality FCC charge stocks which normally boils below 1025°F, and usually is so processed, as to contain metal contents below 1 ppm, preferably 0.1 ppm and Conradson carbon values substantially below 1.
  • Conradson carbon The effect of increasing Conradson carbon is to increase that portion of the feedstock converted to carbon deposited on the catalyst.
  • the amount of coke deposited on the catalyst averages around about 4-5 wt% of feed.
  • This coke production has been attributed to four different coking mechanisms, namely, contaminant coke (from metal deposits), catalytic coke (acid site cracking), entrained hydrocarbons (pore structure adsorption - poor stripping) and Conradson carbon.
  • the coke production based on feed is the summation of the four types present in VGO processing plus the higher Conradson carbon value, higher boiling unstrippable hydrocarbons and coke associated with high nitrogen containing molecules which irreversibly adsorb on the catalyst.
  • coke production on clean catalyst when processing reduced crudes, is approximately 4 wt% plus the Conradson carbon value of the feedstock.
  • the spent-coked catalyst is brought back to equilibrium activity by burning off the deactivating coke in a regeneration zone in the presence of air and 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 nature of the cracking reaction.
  • the temperature in the regenerator is normally limited because of metallurgy limitations and the thermal-steam stability of the catalyst.
  • the thermal-steam 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 carboneceous material which has a high hydrogen content.
  • This carboneceous material is principally the high boiling adsorbed hydrocarbons with boiling points as high as 1500-l700°F or above that have a modest hydrogen content and the high boiling nitrogen containing hydrocarbons as well as related porphyrins and asphaltenes.
  • the metal containing fractions of reduced crudes contain Ni-V-Fe-Cu, present in 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 carried over by the spent 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 coke and light gases such as hydrogen, methane and ethane which affects selectivity, resulting in and poor yield and quality of gasoline and light cycle oil.
  • a reduced crude or crude oil having a high metal and Conradson carbon value is contacted with a zeolitic containing catalyst of high area at tempertures above about 950°F. Residence time of the oil in the riser is below 5 seconds, preferably 0.5 - 2 seconds.
  • the particle size of the catalyst is approximately 20 to 150 microns in size to ensure adequate fluidization properties.
  • the reduced crude - crude oil is introduced at the bottom of the riser and contacts the catalyst at a temperature of 1200-1400 * F to yield a temperature at the exit of the riser in the reactor vessel of approximately 950-1100°F.
  • water, steam, naphtha, flue gas, etc. may be introduced to aid in vaporization and act as a lift gas to control residence time and provides other benefits described in applications #094,216.
  • Spent 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. U. S. Patent No. 4,066,533.
  • the metal and Conradson carbon compounds are deposited on the catalyst.
  • the spent catalyst is deposited as a dense but fluffed bed at the bottom of the reactor vessel, transferred to a stripper and then to the regeneration zone.
  • the spent catalyts is contacted with an oxygen containing gas to remove the carboneous 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.
  • vanadium deposited on the catalyst is converted to vanadium oxides, in particular, vanadium pentoxide.
  • the melting point of vanadium pentoxide is much lower than temperatures encountered in the regeneration zone. Thus, it can become mobile, flow across the catalyst surface, cause pore plugging, particle coalescence, and more importantly, enter the pores of the zeolite, where our studies have shown that it catalyzes irreversible crystalline collapse to an amorphous material.
  • This application describes a new approach to offsetting the adverse effect of vanadium pentoxide by the incorporation of select metals, metal oxides or their salts into the catalyst matrix during manufacture, by impregnation techniques after spray drying, or added during processing at select points in the unit to affect vanadium immobilization through compound or complex formation.
  • select metals, metal oxides or their salts into the catalyst matrix during manufacture, by impregnation techniques after spray drying, or added during processing at select points in the unit to affect vanadium immobilization through compound or complex formation.
  • the select catalysts of this invention will 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, etc.
  • the surface area of these catalysts would preferably be above 100 m 2 /g, have a pore volume in excess of 0.2 cc/g and a micro-activity or conversion value as measured by the ASTM test method No. D3907-80 of at least or greater than 60, and preferably above 65.
  • the metal additive To an aqueous slurry of the raw matrix matrix material and zeolite is mixed the metal additive to yield approximately 1-20 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, etc., and/or as the oxide or hydrous gel. This mixture is spray dried to yield the finished promoted catalyst as a microspherical particle of 10-200 microns in size with the active metal additive deposited within the matrix and/or the outer surface of the catalyst particle.
  • the concentration of vanadia on the spent catalyst can be as high as 4 wt% of particle weight, the concentration of metal additive will be in the range of 1-6 wt% as the metal element to maintain at least a one to one atomic ratio of vanadium to metal additive at all times.
  • the catalyst can be impregnated with the metal additive after spray drying, employing techniques well known in the art, or as metioned above, an active gelatinous precipitate, such as titania or zirconia gel, or other gels can be added to the matrix gel prior to spray drying.
  • the metal additives of this invention will for- compounds or complexes with vanadia that have higher melting points than the temperatures encountered in the regeneration zone.
  • the one to one atomic ratio was chosen as minimum, although initially, the metal additive may be considerably above this ratio if it is incorporated in the catalyst prior to use, after which the ratio of additive to vanadia will decrease as vanadia is deposited on the catalyst.
  • the melting point of the binary reaction product is generally well above operating conditions.
  • the metal additive may be added at the same rate as the metal content of the feed to maintain a one to one atomic ratio.
  • metal-metal oxides of this invention include the following groups and their active elements from the Periodic chart of the elements:
  • the reaction of the metal additive with vanadia generally yields a binary reaction mixture.
  • This invention also recognizes that mixtures of these additive metals with vanadia can occur to form high melting ternary and quaternary reaction mixtures, e.g., Barium vanadium titanate, and in addition, these ternary and quaternary reaction mixtures can occur with metals not covered in the Groups above. Further, in this invention we have covered the lower oxidation states of vanadium as well as vanadium pentoxide.
  • vanadium in processing a sulfur containing feed and regeneration in the presence of an oxygen containing gas vanadium will also likely form such compounds as vanadium sulfides, sulfates, and oxysulfides which can also form binary, ternary, etc., reaction mixtures with the metal additives of this invention as mixed oxides and sulfides.
  • the metal additive can be added by impregnation technques to the spray dried microspherical catalyst particles.
  • the metal additive can be added as an aqueous or hydrocarbon solution or volatile compound during the processing cycle at any point of catalyst travel in the processing unit. This would include but not be limited to addition of an aqueous solution of the inorganic metal salt or a hydrocarbon solution of organo-metallic compounds at the riser wye 17, along the riser length 4, the dense bed 9 in the reactor vessel 5, stripper 10 and 15, regenerator inlet 14, regenerator dense bed 12, or regenerated catalyst standpipe 16.
  • the selective catalyst of this invention with or without the metal additive is charged to a Reduced Crude Conversion (RCC) type unit as outlined in Figure 1.
  • RRC Reduced Crude Conversion
  • 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 1100-1400°F contacts the reduced crude of high metals and Conradson carbon values at riser wye 17.
  • the reduced crude can contain steam and/or flue gas injected at point 2, water and/or naphtha injected at point 3 to aid in vaporization, catalyst fluidization, and controlling contact time in riser 4.
  • the catalyst and vaporous hydrocarbons travel up riser 4 at a contact time of 0.5-5 seconds, preferably 1-2 seconds.
  • the catalyst and vaporous hydrocarbons are separated in vented riser outlet 6 at a final rection temperature of 950-l100°F.
  • the vaporous hydrocarbons are transferred to cyclone 7 where any entrained catalyst fines are separated and the hydrocarbon vapors are sent to the fractionator via transfer line 8.
  • the spent catalyst is then transferred to stripper 10 for removal of entrained hydrocarbon vapors and then to regenerator vessel 11 to form dense 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 and exits from regenerator vessel 11 via line 13.
  • 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.
  • Additions point 18 and 19 can also be utilized to add metal additive promoted catalyst.
  • the metal additive as an aqueous solution or an organo-metallic compound in aqueous or hydrocarbon solvents can be added at addition points 18 and 19 as well as at addition points 2 and 3 on feed line 1, addition point 20 in riser 4, addition point 21 to the bottom of vessel 5 into dense bed 9.
  • the addition of the metal additive is not limited to these locations but can be practiced at any point in the reduced crude - catalyst processing cycle.
  • the regenerator vessel as illustrated in Figure 1, is a simple one zone-dense bed type.
  • the regenerator section is not limited to this example but can exist of two or more zones, stacked or side by side arrangement, with internal and/or external circulation transfer lines from zone to zone.
  • the clay, free of vanadia, and those containing varying vanadia concentrations were placed in individual ceramic crucibles and calcined at 1400°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 3.
  • the clay free of vanadia does not form any crust or clumps or fused particles at temperatures encountered in the regenerator section of the process described in this
  • An extension of the clumping test is the use of a ceramic- alumina crucible to determine whether vanadia react with given metal additive. If vanadia does not react with the metal additive or only a small amount of compound formation occurs, then the vanadia has been observed to diffuse through and over the porous alumina walls and deposit as a yellowish to orange deposit on the outside wall of the crucible. On the other hand, when compound formation occurs, there is little or no vanadia deposits on the outside of the crucible wall.
  • Two series of tests were performed. In the first series shown in Table 4, a 1/1 mixture by weight of vanadia pentoxide and the metal additive was placed in the crucible and heated to 1500°F in air for 12 hours. Compound formation or vanadia diffusion was noted. In the second series of tests a vanadia containing material was tested in a similar manner. A one to one ratio by weight of the vanadia containing material and the metal additive were heated to 1500°F in air for 12 hours. The results are shown in Table 5.
  • the matrix material for the catalyst of this invention should possess good hydro-thermal stability.
  • materials exhibiting relatively stable pore characteristics are alumina, silica-alumina, silica, clays such as kaolin, meta-kaolin, hal- loysite, 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 preferred matrix of U. S. Patent No. 3,034,994 is a semisynthetic combination of clay and silica-alumina.
  • 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 (Si0 2 ), preferably 65 to 85 percent, most preferably about 75 percent.
  • catalysts wherein the gel matrix consists entirely of silica gel are also to be included.
  • 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 5 to 160 microns, preferably 40 to 80 microns.
  • the finished catalyst will also contain from 5 to 50% by weight of rare earth or ammonia exchanged sieve of both X or Y variety, preferably about 15-45% by weight and most preferably 20-40% by weight.
  • rare earth exchanged sieve may be calcined and further exchanged with rare earth or ammonia to create an exceptionally stable sieve.
  • Various processes may be used in preparing the synthetically silica-alumina, such as those described in U. S. Patent No. 3,034,994.
  • 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 alumina by the addition of an alkaline compound.
  • 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 in the pores of the silica hydrogel, after which the hydrous gel is processed, 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 product 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 hydrogel slurry with or without alumina in hydrous form may be filtered and washed in gel form to affect purification of the gel by the removal of dissolved salts.
  • the slurry may be 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 mixure for spray drying. The spray dried product may then be washed again and given a final drying in the manner previously described.
  • the metal additives to immobilize vanadia includes the metals, their oxides and salts, or organo-metallic compounds of such metals as Mg, Ca, Sr, Ba, Sc, Y, La, Ti, Zr, Hf, Nb, Ta, Mn, Fe, In, Tl, Bi, Te, the rare eaths, and the actinide and Lanthanide series of elements.
  • These promoters or metal additives in the metal element state may be used in concentration ranges from about 0.5 to 20 percent, more preferably about 1 to 5 percent by weight of finished catalyst.
  • 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.
  • 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 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 effective size of these pores is usually between about 4A and 12A.
  • the zeolites which can be employed in accordance with this invention include both natural and synthetic zeolites.
  • the natural occurring zeolites include gmelinite, clinoptilolite, chabazite, dechiardite, faujasite, heulandite, erionite, anal- cite, levynite, sodalite, cancrinite, nepheline, lcyurite, scolicite, natrolite, offertite, mesolite, mordenite, brewster- ite, 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.
  • 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.
  • the zeolite materials utilized in the preferred embodiments of this invention are synthetic faujasites which possess silica to alumina ratios inthe 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 W. R. Grace and Company and the Linde Division of Union Carbon Corporation.
  • the ultrastable hydrogen exchanged zeolites, such as Z-14XS and Z-14US from Davison, are also particularly suitable.
  • 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. Patent No. 3,130,007 and U. S. Patent No. 4,010,116, which patents are incorporated hereby by reference.
  • the aluminosilicates of this latter patent have high silica (Si0 2 ) to alumina (A1 2 0 3 ) molar ratios, preferably above 4, to give high thermal stability.
  • a reaction composition is produced from a mixture of sodium silicate, sodium hydroxide, and sodium chloride formulated to contain 5.27 mole percent Si0 2 , 3.5 mole percent Na 2 0, 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°F to 75°F for a period of about four days. After this low temperature digestion step, the mixture is heated with live steam to about 190°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 about 13.5 percent by weight of Na 2 0 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 Si0 2 in the reaction mixutre. The sodium form of the zeolite is then exchanged with polyvalent cations to reduce the Na 2 0 content to less than about 5 percent by weight, and preferably less than 1.0 percent by weight.
  • the zeolites and/or the metal additive can be suitably dispersed in matrix materials for use as cracking catalysts by methods well-known in the art, such as those disclosed, for example, in U. S. Patent Nos. 3,140,249 and 3,140,253 to Plank, et al.; U. S. Patent No. 3,660,274 to Blazek, et al.; U. S. Patent No. 4,010,116 to Secor, et al.; U. S. Patent No: 3,944,482 to Mitchell, et al.; and U. S. Patent No. 4,079,019 to Scherzer, et al.; 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 25 to 50 weight percent, most preferably about 35 to 45 weight percent.
  • Crystalline aluminosilicate zeolites exhibit acidic sites on both interior and exterior surface 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, discreet particles of approximtely 0.1 to 10 microns in size and, accordingly, this is the size range normally provided by commercial catalyst suppliers. To increase exterior (portal) surface area, the particle size of the zeolites for the present invention should preferably be in the range of less than 0.1 to 1 micron and more preferably in the range of less than 0.1 micron.
  • the preferred zeolites are thermally stabilized with hydrogen and/or rare earth ions and are steam stable to about 1,650°F.

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EP19820101625 1981-03-19 1982-03-03 Immobilisation d'oxyde de vanadium déposé sur des catalyseurs pendant la conversion d'huiles contenant des précurseurs de coke et des métaux lourds Expired EP0073874B1 (fr)

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Application Number Priority Date Filing Date Title
AT82101625T ATE29150T1 (de) 1981-03-19 1982-03-03 Immobilisierung von vanadinoxid, das bei der umwandlung von koksvorlaeufer und schwermetalle enthaltenden oelen auf katalysatoren abgelagert wurde.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US06/277,751 US4432890A (en) 1981-03-30 1981-03-19 Immobilization of vanadia deposited on catalytic materials during carbo-metallic oil conversion
WOPCT/US81/00356 1981-03-19
PCT/US1981/000356 WO1982003225A1 (fr) 1981-03-19 1981-03-19 Immobilisation de composes de vanadium deposes sur des materiaux catalytiques pendant la conversion d'une huile carbometallique
US277751 1981-03-30

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EP0073874A1 true EP0073874A1 (fr) 1983-03-16
EP0073874B1 EP0073874B1 (fr) 1987-08-26

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0140007A2 (fr) * 1983-09-15 1985-05-08 Ashland Oil, Inc. Passivation de vanadium accumulé sur des particules solides fluidisables, inertes ou catalytiques
EP0189267A2 (fr) * 1985-01-14 1986-07-30 Engelhard Corporation Composition fluidifiable pour le craquage catalytique
EP0194536A2 (fr) * 1985-03-12 1986-09-17 Akzo N.V. Composition catalytique fluidisable pour le craquage, contenant de titanate de barium
EP0201152A2 (fr) * 1985-01-14 1986-11-12 Engelhard Corporation Composition fluidifiable de catalyseur de craquage
AU579688B2 (en) * 1984-12-27 1988-12-01 Betz International, Inc. Passivation of vanadium contaminants of catalytic cracking catalysts
GB2245001A (en) * 1990-06-11 1991-12-18 Unilever Plc Catalyst compositions containing metal ion-exchanged zeolites

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
US9266101B2 (en) 2010-07-08 2016-02-23 Indian Oil Corporation Ltd. Value added spent fluid catalytic cracking catalyst composition and a process for preparation thereof

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US3696025A (en) * 1970-11-09 1972-10-03 Chevron Res Catalytic cracking by addition of titanium to catalyst
US3977963A (en) * 1975-04-17 1976-08-31 Gulf Research & Development Company Method of negating the effects of metals poisoning on cracking catalysts
FR2335582A1 (fr) * 1975-12-19 1977-07-15 Standard Oil Co Procede de craquage catalytique avec degagement reduit de gaz nocifs
US4083807A (en) * 1976-01-13 1978-04-11 Gulf Research & Development Company Method for preparing crystalline aluminosilicate cracking catalysts
US4141858A (en) * 1976-03-29 1979-02-27 Phillips Petroleum Company Passivating metals on cracking catalysts
GB2007107A (en) * 1977-11-02 1979-05-16 Grace W R & Co Cracking catalyst composition
WO1979001170A1 (fr) * 1978-06-01 1979-12-27 Phillips Petroleum Co Procede et catalyseur de cracking
EP0009819A1 (fr) * 1978-10-06 1980-04-16 Phillips Petroleum Company Catalyseur de craquage, procédé pour le craquage d'hydrocarbures et procédé de passivation de métaux contaminants sur des catalyseurs de craquage d'hydrocarbures
US4218337A (en) * 1978-03-13 1980-08-19 Phillips Petroleum Company Passivating metals on cracking catalysts with tellurium
US4256564A (en) * 1979-04-03 1981-03-17 Phillips Petroleum Company Cracking process and catalyst for same containing indium to passivate contaminating metals

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Publication number Priority date Publication date Assignee Title
US3696025A (en) * 1970-11-09 1972-10-03 Chevron Res Catalytic cracking by addition of titanium to catalyst
US3977963A (en) * 1975-04-17 1976-08-31 Gulf Research & Development Company Method of negating the effects of metals poisoning on cracking catalysts
FR2335582A1 (fr) * 1975-12-19 1977-07-15 Standard Oil Co Procede de craquage catalytique avec degagement reduit de gaz nocifs
US4083807A (en) * 1976-01-13 1978-04-11 Gulf Research & Development Company Method for preparing crystalline aluminosilicate cracking catalysts
US4141858A (en) * 1976-03-29 1979-02-27 Phillips Petroleum Company Passivating metals on cracking catalysts
GB2007107A (en) * 1977-11-02 1979-05-16 Grace W R & Co Cracking catalyst composition
US4218337A (en) * 1978-03-13 1980-08-19 Phillips Petroleum Company Passivating metals on cracking catalysts with tellurium
WO1979001170A1 (fr) * 1978-06-01 1979-12-27 Phillips Petroleum Co Procede et catalyseur de cracking
EP0009819A1 (fr) * 1978-10-06 1980-04-16 Phillips Petroleum Company Catalyseur de craquage, procédé pour le craquage d'hydrocarbures et procédé de passivation de métaux contaminants sur des catalyseurs de craquage d'hydrocarbures
US4256564A (en) * 1979-04-03 1981-03-17 Phillips Petroleum Company Cracking process and catalyst for same containing indium to passivate contaminating metals

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0140007A2 (fr) * 1983-09-15 1985-05-08 Ashland Oil, Inc. Passivation de vanadium accumulé sur des particules solides fluidisables, inertes ou catalytiques
EP0140007A3 (en) * 1983-09-15 1985-12-11 Ashland Oil, Inc. Passivation of vanadium accumulated on inert or catalytic solid fluidizable particles
AU579688B2 (en) * 1984-12-27 1988-12-01 Betz International, Inc. Passivation of vanadium contaminants of catalytic cracking catalysts
EP0189267A2 (fr) * 1985-01-14 1986-07-30 Engelhard Corporation Composition fluidifiable pour le craquage catalytique
EP0201152A2 (fr) * 1985-01-14 1986-11-12 Engelhard Corporation Composition fluidifiable de catalyseur de craquage
EP0201152A3 (fr) * 1985-01-14 1987-06-03 Engelhard Corporation Composition fluidifiable de catalyseur de craquage
EP0189267A3 (fr) * 1985-01-14 1987-06-10 Engelhard Corporation Composition fluidifiable pour le craquage catalytique
EP0194536A2 (fr) * 1985-03-12 1986-09-17 Akzo N.V. Composition catalytique fluidisable pour le craquage, contenant de titanate de barium
EP0194536A3 (en) * 1985-03-12 1986-12-03 Akzo N.V. Barium titanium oxide-containing fluidizable cracking catalyst composition
GB2245001A (en) * 1990-06-11 1991-12-18 Unilever Plc Catalyst compositions containing metal ion-exchanged zeolites

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