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WO1986003218A1 - Catalyseur de craquage et procede utilisant des filtres moleculaires de silicoaluminophosphates - Google Patents

Catalyseur de craquage et procede utilisant des filtres moleculaires de silicoaluminophosphates Download PDF

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Publication number
WO1986003218A1
WO1986003218A1 PCT/US1985/002324 US8502324W WO8603218A1 WO 1986003218 A1 WO1986003218 A1 WO 1986003218A1 US 8502324 W US8502324 W US 8502324W WO 8603218 A1 WO8603218 A1 WO 8603218A1
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WO
WIPO (PCT)
Prior art keywords
sapo
silicoaluminophosphate
catalyst
molecular sieve
percent
Prior art date
Application number
PCT/US1985/002324
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English (en)
Inventor
Regis Joseph Pellet
Peter Kevin Coughlin
Mark Thomas Staniulis
Gary Norman Long
Jule Anthony Rabo
Original Assignee
Union Carbide Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Union Carbide Corporation filed Critical Union Carbide Corporation
Publication of WO1986003218A1 publication Critical patent/WO1986003218A1/fr
Priority to FI863822A priority Critical patent/FI863822A/fi
Priority to DK486486A priority patent/DK486486D0/da
Priority to NO864592A priority patent/NO864592L/no

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]

Definitions

  • the present invention relates to cracking catalysts formed from specific sllicoaluminophosphate molecular sieves described in U.S. Patent No. 4,440,871.
  • blended matrix components e.g., a catalyst comprising a zeolite, an inorganic oxide matrix and inert fines, which may be alpha alumina
  • a catalyst comprising a zeolite, an inorganic oxide matrix and inert fines which may be alpha alumina
  • Catalysts comprising an amorphous silica-alumina, separately added alumina and a zeolite are disclosed in U.S. Pat. No. 3,542,670
  • catalyst comprising a zeolite, an amorphous hydrous alumina and alumina monohydrate are disclosed in U.S. Pat. No. 3,428,550.
  • the hydrogen or ammonium form of a zeolite may be treated with H-0 at a temperature ranging from about 800° to about 1500°F, or then subsequently cation exchange the steam and water treated zeolite with cations which may be rare earth metal cations.
  • the method increases the silica to alumina mole ratio of the zeolite and also the defect structure.
  • U.S. Pat. No. 3,676,368 discloses a rare earth exchanged-hydrogen faujasite containing from 6 to 14 percent rare earth oxides.
  • 3,957,623 discloses a rare earth exchanged zeolite having a total of 1 to 10 weight percent rare earth metal oxide.
  • U.S. Pat. No. 3,607,043 discloses a process for preparing a zeolite having a rare earth content of 3 to 10 weight percent.
  • U.S. Pat. No. 4,036,739 discloses hydrothermally stable and ammonia stable Y zeolite in which a sodium Y zeolite is ion exchanged to partially exchange sodium ions for ammonium ions, followed by steam calcination and a further ion exchange with ammonium to reduce the final sodium oxide content to below 1 weight percent, followed by calcination of the reexchanged product, or according to U.S. Pat. No. 3,781,199, the second calcination may be conducted after the zeolite is admixed with a refractory oxide.
  • the instant invention relates to cracking catalysts and to fluid catalytic cracking processes.
  • the catalysts comprise a specific class of sllicoaluminophosphate molecular sieves disclosed in U.S. Patent No. 4,440,871 having particular pore sizes and are preferably employed with at least one inorganic oxide present as a binder and/or matrix component.
  • the instant invention relates to the catalytic cracking of crude oil feedstocks to produce lower boiling hydrocarbons.
  • the process of this invention is carried out by contacting said feedstock with a specific class of the sllicoaluminophosphate molecular sieves of U.S. Patent No. 4,440,871.
  • silicoaluminophosphates employable herein are described in U.S. Patent No. 4,440,871, issued April 3, 1984 and are characterized in their calcined' form by an adsorption of isobutane of at least 2 percent by weight at a pressure of 500 torr and a temperature of 20°C.
  • such silicoaluminophosphates are also characterized in their calcined form by an adsorption of triethylamine of greater than 5 percent by weight at a pressure of 2.6 torr and a temperature of 22°C.
  • the present invention relates to new catalytic cracking catalysts containing sllicoaluminophosphate molecular sieves and to the process of their use in catalytic cracking processes.
  • the catalytic cracking catalysts of the instant invention are derived from the novel silicoaluminophosphates disclosed in U.S. Patent No. 4,440,871, incorporated herein by reference thereto.
  • the silicoaluminophosphates employed in the present invention will be referred to herein, solely for the purpose of reference herein, as "SAPO" molecular sieves as a short hand notation consistent with that employed in U.S. Patent No. 4,440,871.
  • Catalysts employing SAPOs contain certain of the sllicoaluminophosphate catalysts of U.S. Patent No. 4,440,871, discussed hereinafter, and are generally employed in conjunction with at least one inorganic oxide matrix component.
  • SAPO is employed herein as denominating the "SAPO” molecular sieves of U.S. Patent No. 4,440,871.
  • SAPO molecular sieves of U.S. Patent No.
  • 4,440,871 are disclosed as being microporous ' crystalline silicoaluminophosphates the pores of which are uniform and have nominal diameters of greater than about 3 Angstroms and whose essential empirical chemical composition in the as-synthesized and anhydrous form is: mR: (Si ⁇ Al y P z )0 2 wherein "R” represents at least one organic templating agent present in the intracrystalline pore system; "m” has a value of from 0.02 to 0.03; “m” represents the moles of "R” present per mole of (Si Al P )0,; "x", "y” and “z” represent the mole fractions of silicon, aluminum and phosphorus respectively, present as tetrahedral oxides, said mole fractions being such that they are w ' ithin the pentagonal compositional area defined by points A,B,C,D and E which is FIG.
  • the molecular sieves of U.S. Patent No. 4,440,871 are also characterized as sllicoaluminophosphate material having a three-dimensional microporous framework structure of PO-, A10 2 and Si0 2 tetrahedral units, and whose essential empirical chemical composition on an anhydrous basis is: mR:(Si ⁇ Al y P 2 )0 2 wherein R represents at least one organic templating agent present in the intracrystalline pore system; "m” represents the moles of "R” present per mole of (Si Al P )0, and has a value of from zero to 0.3; "x", y” and “z” represent respectively, the mole fractions of silicon, aluminum and phosphorus present in the oxide moiety, said mole fractions being within the compositional area bounded by points A, B, C, D and E on the ternary diagram which is FIG.
  • said silcoaluminophosphate having a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth below in any one of Tables, I, III, V, VII, IX, XIII, XVII, XXI, XXIII or XXV of U.S. Patent No. 4,440,871.
  • the SAPO molecular sieves may be calcined at a temperature sufficiently high to remove at least some of the organic templating agent present in the intracrystalline pore system.
  • SAPOs employable herein include SAPO-5, SAPO-11, SAPO-31, SAPO-37, SAPO-40 and SAPO-41.
  • SAPO catalysts of the instant invention are prepared by the use of tread the silicoaluminophosphates of U.S. Patent No. 4,440,871, as hereinbefore described, which are further characterized in its calcined form by an adsorption of isobutane of at least 2 percent by weight at a pressure of 500 torr and a temperature of 20°C.
  • such SAPOs are also characterized in its calcined form by an adsorption of triethylamine of greater than 5 percent by weight at a pressure of 2.6 torr and a temperature of 22°C.
  • the above characterization of the silicoaluminophosphates (SAPOs) employed in the instant invention relates to an adsorption characterization that is carried out on a SAPO which has been subjected to a post synthesis treatment, e.g., calcination or chemical treatment, to remove a substantial portion of the template "R" which is present as a result of synthesis.
  • a post synthesis treatment e.g., calcination or chemical treatment
  • SAPO SAPO in its calcined form
  • the instant invention necessarily includes the use of a non-calcined SAPO which is characterized by such adsorption in its calcined form, since upon use of such a non-calcined SAPO in the instant process at catalytic cracking conditions the SAPO will be calcined or hydrothermally treated iji situ so as to have the characteristic adsorption of isobutane or triethylamine.
  • the SAPO will be rendered in situ to a form characterized by the aforementioned adsorption of isobutane due to the presence of template "R" which is present as a result of synthesis, although the calcined form of SAPO-11 is characterized by the aforementioned" adsorption of isobutane or triethylamine.
  • reference to a SAPO having a particular adsorption characteristic in its calcined form is not intended to exclude the use of the SAPO in its as-synthesized form which upon calcination, hydrothermal treatment or other treatment , e.g., ion exchange, would have such adsorption characteristics.
  • thermal treatment is employed here to denominate both a thermal calcination in the presence of air or inert gas, e.g., nitrogen, and a hydrothermal calcination (thermal calcination in the presence of steam).
  • Thermal treatment is typically carried out at a temperature in excess of 300°C for a period in excess of 0.25 hours and when the thermal treatment is a hydrothermal treatment it is typically carried out in the presence of at least about 20 percent steam by volume in air.
  • the source of the steam is not important and may be provided from an external source or may be generated in situ at the temperatures employed for the hydrothermal treatment.
  • a SAPO may also be employed in the instant process in its as-synthesized form since an in situ hydrothermal treatment will be provided upon introduction of the as-synthesized SAPO to the process under catalytic cracking conditions.
  • the SAPOs may also be ion- exchanged by contacting the sllicoaluminophosphate molecular sieve (with or without the presence of an inorganic oxide matrix component) with a solution of at- least one hydrogen-forming cation, such as NH-, and H and quaternary ammonium.
  • a solution of at- least one hydrogen-forming cation such as NH-, and H and quaternary ammonium.
  • the selected SAPO(s) may also include cations selected from the group " consisting of cations of Group IIA, Group IIIA, Groups IIIB to VII B and rare earth cations selected from the group consisting of cerium, lanthanum, praseodymium, neodytnium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and mixtures thereof.
  • rare earth cations selected from the group " consisting of cations of Group IIA, Group IIIA, Groups IIIB to VII B and rare earth cations selected from the group consisting of cerium, lanthanum, praseodymium, neodytnium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, y
  • the silicoaluminophosphates may contain at least one cation, e.g., hydrogen-forming cation, which is different from the cations initially associated with the silicoaluminophosphates molecular sieves as a result of their synthesis.
  • the cation present as a result of ion exchange is preferably present in an effective amount between about 0.1 weight percent and about 20 percent, based on the weight of the starting silicoaluminophosphate molecular sieve and is typically present in an effective amount between about 0.5 weight percent and about 10 weight percent.
  • the ion-exchange is generally carried out by preparing a slurry of the silicoaluminophosphate catalyst by adding about 5 to 15 volumes of water per volume of catalyst, after which a solution of a selected cation is added.
  • the ion exchange is generally carried out at room temperature and the resulting solution is then heated to above about 50°C and stirred at this temperature for about 0.5 to 3 hours. This mixture is then filtered and water washed to remove excess anion present as a result of the solution of the cation salt.
  • the silicoaluminophosphate molecular sieve is typically employed with at least one inorganic oxide matrix component, such inorganic oxide matrix components typically employed heretofore in formulating FCC catalysts, including: amorphous catalytic inorganic oxides such as catalytically active silica/aluminas, clays, silicas, aluminas, silica-aluminas, silica-zirconias, silica-magnesias, alumina-borias, alu ina-titanias and the like and mixtures thereof.
  • amorphous catalytic inorganic oxides such as catalytically active silica/aluminas, clays, silicas, aluminas, silica-aluminas, silica-zirconias, silica-magnesias, alumina-borias, alu ina-titanias and the like and mixtures thereof.
  • the matrix may be in the form of a sol, hydrogel or gel and is typically an alumina, silica or silica-alumina component such as a conventional silica-alumina cracking catalyst, several types and compositions of which are commercially available.
  • the matrix may itself provide a catalytic effect, such as that observed for catalytically active silica/aluminas, or it may be essentially inert.
  • the matrix may act as a "binder" in some instances although in some instances the final catalyst may be spray dried or formed without the need of a binder.
  • These matrix materials may be prepared as a cogel of ' silica and alumina or as alumina precipitated on a preformed and preaged hydrogel.
  • Silica may be present as a major matrix component in the solids present in the matrix e.g. present in an amount between about 5 and about 40 weight percent and preferably between about 10 and about 30 weight percent.
  • the silica may also be employed in the form of a cogel comprising about 75 weight percent silica and about 25 weight percent alumina or comprising about 87 weight percent silica and about 13 weight percent alumina.
  • the inorganic oxide matrix component will typically be present in the final catalyst in an amount between about 0 and about 99 weight percent, preferably between about 5 and about 90 weight percent, based on the total catalyst. It is also within the scope of the instant invention to employ other materials with the silicoaluminophosphates in the final cracking catalysts, including clays, carbon monoxide oxidation promoters, etc.
  • the catalysts of the present invention may be employed with a matrix component and this may be a silica or alumina component.
  • the alumina component which may comprise discrete particles of various aluminas, e.g., pseudobeohmite.
  • the alumina component may be in the form of discrete particles having a total surface area, as measured by the method of Brunauer, Emmett and Teller (BET), greater than about 20 square
  • the pore volume of the alumina component is typically be greater than 0.35 cc/g.
  • the average particle size of the alumina particles is generally less than 10 microns and preferably less than 3 microns.
  • the alumina may be employed alone as the matrix or composited with the other matrix components.
  • the alumina component may be any alumina and has preferably been preformed and placed in a physical form such that its surface area and pore structure are stabilized so that when the alumina is added to an impure, inorganic gel containing considerable amounts of residual soluble salts, the salts will not alter the surface and pore characteristics measurably nor will they promote chemical attack on the preformed porous alumina which could undergo change.
  • the alumina is typically an alumina which has been formed by suitable chemical reaction, the slurry aged, filtered, dried, washed free of residual salt and then heated to reduce its volatile content to less than about 15 weight percent.
  • the alumina component may be present in the final catalyst in an amount ranging between about 5 and about 95 weight percent, preferably between about 10 and about 30 weight percent based on the total catalyst.
  • an alumina hydrosol or hydrogel or hydrous alumina slurry may be used in the catalyst preparation.
  • Mixtures of one or more silicoalumino ⁇ phosphate molecular sieves and one or more inorganic matrix components may be formed into a final form for the catalyst by standard catalyst forming techniques including spray-drying, pelleting, extrusion and other suitable conventional means.
  • spray drying procedures is the preferred means by which catalysts are prepared and such procedures are well known in the art.
  • the catalyst is formed as extruded pellets and dried in an air such are typically crushed and sized to a size less than 150 microns.
  • Catalysts containing SAPOs may be prepared by any conventional method.
  • One method of preparing such catalysts employing silica-alumina and porous alumina is to react sodium silicate with a solution of aluminum sulfate to form a silica/alumina hydrogel slurry which is then aged to give the desired pore properties, filtered to remove a considerable amount of the extraneous and undesired sodium and sulfate ions and then reslurried in water.
  • the alumina may be prepared by reacting solutions of sodium aluminate and aluminum sulfate under suitable conditions, aging the slurry to give the desired pore properties of the alumina, filtering drying, reslurry in water to remove sodium and sulfate ions and drying to reduce volatile matter content to less than 15 weight percent.
  • the alumina may then be slurried in water and blended in proper amounts, with a slurry of impure silica-alumina hydrogel.
  • the SAPO molecular sieve component may then be added to this blend. A sufficient amount of each component is utilized.to . give the desired final composition.
  • the resulting mixture is then filtered to remove a portion of the remaining extraneous soluble salts therefrom.
  • the filtered mixture is then dried to produce dried solids.
  • the dried solids are subsequently reslurried in water and washed substantially free of the undesired soluble salts.
  • the catalyst is then dried to a residual water content of less than about 15 weight percent.
  • the catalyst is typically employed after a calcination which may be an n. situ calcination in the process under catalytic cracking conditions.
  • Catalytic cracking with the catalyst of the present invention can be conducted in any conventional catalytic cracking manner under effective catalytic cracking conditions.
  • Suitable catalytic cracking conditions include a temperature ranging between about 400 ⁇ F and about 1600 ⁇ F, preferably between about 700°F and about 1600°F, and a pressure ranging from about subatmospheric to several atmospheres, typically between about atmospheric (14.7 psia) and about 100 psia.
  • the process may be carried out in fixed bed, moving bed, ebullating bed, slurry, transferline, riser reactor or fluidized bed operation.
  • the catalyst of the present invention can be used to convert any of the conventional hydrocarbon feeds used in catalytic cracking, that is, it can be used to crack naphthas, gas oil and residual oils having a high content of metal contaminants. It is especially suited for cracking hydrocarbons boiling in the gas oil range, that is, hydrocarbon oils having an atmospheric pressure boiling point ranging from about 420°F to about 1800°F to naphthas to yield not only products having a lower boiling point than the initial feed but also products having an improved octane number.
  • Crude oil feed is used herein to denominate any full range crude oil from primary, secondary or tertiary recovery from conventional or offshore oil fields and feedstocks derived therefrom.
  • "Crude oil feeds” may include any full range “syncrude” such as those that can be derived from coal, shale oil, tar sands and bitumens.
  • the crude may be virgin (straight run) or generated synthetically by blending. It is generally desirable, however, to first desalt the crude since sodium chloride is known to be a poison for most cracking operations.
  • crude oil derived feed is meant to include component parts of the crude which are generally employed as catalytic cracking feeds or potential feeds therefor and include: feeds such as distillate gas oils, heavy vacuum gas oils, atmospheric and vacuum resids, syncrudes (from shale oil, tar sands, coal), feed derived from hydrocrackers, hydrotreaters, cokers, pyrolysis processes and high boiling FCC product recycle fractions; and fractions boiling above the traditional end of the gasoline boiling range which generally includes compounds containing greater than about eleven carbon atoms and combinations thereof.
  • feeds such as distillate gas oils, heavy vacuum gas oils, atmospheric and vacuum resids, syncrudes (from shale oil, tar sands, coal), feed derived from hydrocrackers, hydrotreaters, cokers, pyrolysis processes and high boiling FCC product recycle fractions; and fractions boiling above the traditional end of the gasoline boiling range which generally includes compounds containing greater than about eleven carbon atoms and combinations thereof.
  • the instant catalyst can be effectively used in an FCC (fluid catalytic cracking) process wherein a carbon-hydrogen fragmentation compound (CHFC) employed in admixture with the crude oil feed.
  • FCC fluid catalytic cracking
  • CHFC carbon-hydrogen fragmentation compound
  • carbon-hydrogen fragmentation compound(s) is employed herein to mean materials comprising a lesser number of carbon atoms than found in materials within the gasoline boiling range, preferably those materials containing 5 or less carbon atoms, that fit into any of the categories of: a) Hydrogen-rich molecules, i.e. molecules with wt. % hydrogen ranging from about
  • This may include light paraffins, i.e., CH4, , C2H6r , C3,H8_ and other materials.
  • Molecules whose chemical structure permits or favors the transfer of carbon-hydrogen fragments may be employed. This includes CH-OH, other low boiling alcohols such as ethanol, n-propanol, isopropanol, n-butanol, isobutanol, etc., aliphatic ethers, ' e.g. , dimethyl ether, and other oxygen compounds (acetals, aldehydes, ketones).
  • the preferred carbon-hydrogen fragmentation compounds are methanol, dimethyl ether and C 2 ⁇ C 5 olefins, with methanol and dimethyl ether being the most preferred.
  • the FCC-CHFC process is believed to involve combination reactions which are believed to be effective, at least in part, in removing sulfur, oxygen, nitrogen and metal contaminants found in a whole crude or a heavy hydrocarbon portion thereof.
  • an FCC-CHFC type process is generally carried out at temperatures within the range of 400°F up to about 1400°F and more usually within the range of 700°F to about 1200°F at pressures selected from within the range of below atmospheric up to several hundred pounds per square inch gauge (psig) but normally less than 200 psig.
  • Preferred conditions include a temperature within the range of about 800°F to about 1150°F and pressures within the range of atmospheric to about 100 psig and higher.
  • the carbon-hydrogen fragmentation compound may be provided to the process in most any way so long as it is present when contact with the catalyst material is effected, i.e. in situ generation is suitable.
  • an FCC-CHFC process methanol is used in combination with a gas oil type of hydrocarbon charge stock.
  • the weight percent of methanol in the hydrocarbon charge passed to the cracking or conversion operation will vary considerably and may be selected from within the range of between about 11. and about 25 percent by weight, it being preferred to maintain the ratio within the range between about 5% and about 20, based on the weight of the feed. However, this may vary depending upon the hydrogen deficiency of the high molecular weight hydrocarbon charge, the amount of sulfur, nitrogen and oxygen in the oil charge, the amount of polycyclic aromatics, the type of catalyst employed, and the level of conversion desired. It is preferred to avoid providing any considerable or significant excess of methanol with the charge because of its tendency to react with itself under some conditions.
  • the FCC-CHFC process preferably employs a fluidized catalyst system at low pressures without the need for high pressure hydrogen gas.
  • a fluidized catalyst system promotes the highly efficient contact of relatively inexpensive carbon-hydrogen fragmentation compounds with heavy, refractory molecules in the presence of high-surface area cracking catalyst.
  • Intermolecular hydrogen-transfer interactions e.g., methylatihg reactions, and catalytic cracking reactions are effected in the presence of fluidized catalyst particles and act to minimize problems due to diffusion/mass transport limitations and/or heat transfer.
  • the FCC-CHFC process can make use of the relatively cheap carbon-hydrogen fragmentation compounds readily available in petroleum refineries, such as light gas fractions, light olefins, low boiling liquid streams, etc., and, in particular, can employ methanol, a product which is readily available in quantity, either as a transportable product from overseas natural gas conversion processes, or as a product from large scale coal, shale, or tar sand gasification. It also can utilize carbon monoxide (in combination with contributors such as water or methanol), which gas is readily available from refinery regeneration flue gas (or other incomplete combustion processes), or from coal, shale, or tar sand gasification. Highly efficient recycle of carbon-hydrogen fragmentation compounds can also be effected.
  • Example 1 Two catalysts were prepared for evaluation according to ASTM test method D-3907 (Microactivity Test). The two catalysts were prepared using the non-zeolitic molecular sieve SAPO-5 and the zeolite
  • SAPO-5 was prepared according to U.S.
  • Patent 4,440,871 was " employed after air calcination.
  • LZ-210 Si0 2 to A1 2 0 3 ratio of
  • LZ-210 containing 9.9 weight percent rare earth expressed as the oxide.
  • the rare earth exchange was carried out with a rare earth chloride solution containing 46.01 by weight rare earth, expressed as the oxides with the rare earth component comprising
  • a matrix for the SAPO-5 and LZ-210 was prepared by mixing 90 percent by weight of a silica/alumina, sold by the Davison Division of W.R. Grace under the trade designation MS13/110, and 10 percent by weight of a microcrystalline cellulose extrusion aid. The mixture was extruded in the form of 1/16 inch pellets and dried in air at 110°C for about 16 hours and then steam deactivated in 100 percent steam at 760°C for 2 hours. The steam deactivated material was then crushed and sized to 60 to 200 mesh (U.S. Standard). The SAPO-5 and LZ-210 catalysts were each prepared by mixing 15 percent by weight of the selected material with 85 percent by weight of the matrix.
  • the LZ-210 was steam deactivated in 1001 steam at 760°C for 2 hours prior to use in the preparation of the catalyst.
  • the final catalyst mixtures were then calcined at 590°C in air for 3 hours.
  • Each catalyst was evaluated in a single run according to ASTM test method D-3907 with the following four modifications of ASTM test method D-3907.
  • ASTM test method D-3907 the end boiling point of the products identified as gasoline products was 431°F.
  • the nitrogen post stripping of the catalyst was at 30 milliliters/min. for a period of 23 minutes to 27 minutes.
  • the conversion is the measured conversion and not the standardized conversion of the ASTM test method.
  • the feedstock employed in the test method had an API gravity of 24.0°, and IBP (Initial Boiling Point) of 354°F, FBP (Final Boiling Point) of 1077°F and a UOP Factor K of 11.8.
  • the "Wt. 1 Conversion” is the measured weight percent conversion.
  • Wt. 1 Gasoline is the weight percent of hydrocarbons in the product from C, hydrocarbons to hydrocarbons boiling below 431°F.
  • Wt. 1 Gas is defined as those hydrocarbons boiling below C. in the product, as a weight percent of feed.
  • the "Wt. 1 Coke” is defined as the residue left on the used catalyst after post stripping as set forth in ASTM test method D-3907, as a weight percent of the feed.
  • Wt. 1 C.s is, defined as the weight percent of isobutane, n-butane - 21 -
  • SAPO-5 is active as a cracking catalyst giving substantially the same conversion as catalysts containing the zeolitic alumninosilicate LZ-210 while providing a different product distribution.
  • Example 2 An FCC-CHFC process is carried out using a gas oil feed comprising a heavy vacuum gas oil in a cracking operation.
  • the vacuum gas oil is characterized by the API gravity (60°F) of 20.7, an average molecular weight of about 400 + 10 and a boiling range between about 700°F and about 1100°F.
  • the carbon-hydrogen fragmentation compound is methanol and is present in an amount of 10 percent by weight.
  • the catalyst contains SAPO-5 and is introduced to a riser FCC unit after heating the catalyst to about 1000°F + 20°F.
  • the hydrocarbon products show improved selectivity to motor fuel (hydrocarbon) products by addition of methanol as characterized by the presence of hydrocarbon fuels boiling below the boiling range of the gas oil feed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Des catalyseurs de craquage contenant des filtres moléculaires de silicoaluminophosphates sont dérivés des filtres moléculaires spécifiques de silicoaluminophosphates. Lors de leur utilisation pour convertir des hydrocarbures, ils produisent des mélanges différents de ceux qui sont obtenus lorsque l'on utilise des catalyseurs à base d'aluminosilicates.
PCT/US1985/002324 1984-11-27 1985-11-26 Catalyseur de craquage et procede utilisant des filtres moleculaires de silicoaluminophosphates WO1986003218A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
FI863822A FI863822A (fi) 1984-11-27 1986-09-22 Krackningskatalysatorer foer katalytisk krackning och krackningsfoerfarande med silikoaluminofosfatmolekylsaoll.
DK486486A DK486486D0 (da) 1984-11-27 1986-10-10 Krakningskatalysator og krakningsfremgangsmaade, hvori der anvendes siliciumaluminiumphosphatmolekylsigter
NO864592A NO864592L (no) 1984-11-27 1986-11-18 Spaltningskatalysator og fremgangsmaate med anvendelse av molekylarsikter av silisiumaluminiumfosfat.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US67527984A 1984-11-27 1984-11-27
US675,279 1984-11-27

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WO1986003218A1 true WO1986003218A1 (fr) 1986-06-05

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PCT/US1985/002324 WO1986003218A1 (fr) 1984-11-27 1985-11-26 Catalyseur de craquage et procede utilisant des filtres moleculaires de silicoaluminophosphates

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EP (1) EP0203160A1 (fr)
CN (1) CN1004357B (fr)
AU (1) AU5203586A (fr)
DK (1) DK486486D0 (fr)
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WO (1) WO1986003218A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN103272557B (zh) * 2013-06-13 2018-01-19 河北民海化工有限公司 一种有机含硫化合物和有机含氮化合物双效吸附剂

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
EP0111748A2 (fr) * 1982-11-16 1984-06-27 Hoechst Aktiengesellschaft Silicates d'aluminium à structure de zéolite et procédé pour leur préparation
EP0124119A1 (fr) * 1983-05-02 1984-11-07 Union Carbide Corporation Procédé de conversion de pétroles bruts avec composés de fragmentation contenant du carbone et de l'hydrogène sur des catalyseurs non-zéolitiques
EP0124122A1 (fr) * 1983-05-02 1984-11-07 Union Carbide Corporation Catalyseur et procédé pour le craquage catalytique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
EP0111748A2 (fr) * 1982-11-16 1984-06-27 Hoechst Aktiengesellschaft Silicates d'aluminium à structure de zéolite et procédé pour leur préparation
EP0124119A1 (fr) * 1983-05-02 1984-11-07 Union Carbide Corporation Procédé de conversion de pétroles bruts avec composés de fragmentation contenant du carbone et de l'hydrogène sur des catalyseurs non-zéolitiques
EP0124122A1 (fr) * 1983-05-02 1984-11-07 Union Carbide Corporation Catalyseur et procédé pour le craquage catalytique

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CN1004357B (zh) 1989-05-31
EP0203160A1 (fr) 1986-12-03
DK486486D0 (da) 1986-10-10
AU5203586A (en) 1986-06-18
FI863822A0 (fi) 1986-09-22
CN85109362A (zh) 1986-08-27
FI863822A (fi) 1986-09-22

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