WO2002018516A1 - Procede de craquage catalytique fluide a base de catalyseur a l'oxyde cristallin microporeux presentant une acidite de lewis accrue - Google Patents

Procede de craquage catalytique fluide a base de catalyseur a l'oxyde cristallin microporeux presentant une acidite de lewis accrue Download PDF

Info

Publication number
WO2002018516A1
WO2002018516A1 PCT/US2001/025940 US0125940W WO0218516A1 WO 2002018516 A1 WO2002018516 A1 WO 2002018516A1 US 0125940 W US0125940 W US 0125940W WO 0218516 A1 WO0218516 A1 WO 0218516A1
Authority
WO
WIPO (PCT)
Prior art keywords
crystalline microporous
oxide
zeolite
catalyst
microporous oxide
Prior art date
Application number
PCT/US2001/025940
Other languages
English (en)
Inventor
William L. Schuette
Albert E. Schweizer
Original Assignee
Exxonmobil Research And Engineering Company
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
Priority claimed from US09/653,135 external-priority patent/US6482313B1/en
Priority claimed from US09/653,136 external-priority patent/US6673734B1/en
Application filed by Exxonmobil Research And Engineering Company filed Critical Exxonmobil Research And Engineering Company
Priority to AU8509101A priority Critical patent/AU8509101A/xx
Priority to AU2001285091A priority patent/AU2001285091B2/en
Priority to CA002419253A priority patent/CA2419253A1/fr
Priority to JP2002524019A priority patent/JP2004507608A/ja
Publication of WO2002018516A1 publication Critical patent/WO2002018516A1/fr

Links

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
    • C10G11/14—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
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
    • 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

Definitions

  • This invention relates to catalyst components and compositions and methods of making and using the composition which comprises a crystalline microporous oxide having a promoter metal compound that promotes dehydrogenation and increases Lewis acidity without increasing the unit cell size of the crystalline microporous oxide.
  • Crystalline microporous oxides such as zeolitic materials
  • zeolitic materials have been in commercial use in a variety of industries for many years. These materials are especially valuable for their fluid separation ability as molecular sieves, as well as for their ability to act as a catalyst.
  • Crystalline microporous oxides are particularly useful as catalysts which convert the large paraffin molecules of a hydrocarbon mixture into smaller more unsaturated molecules such as olefins and aromatics.
  • Typical conversion processes include fluid catalytic cracking and hydrocracking.
  • many structural properties of the catalyst have to be balanced, such as pore size, pore volume, Lewis acidity, and Br ⁇ nsted acidity. If the structural properties of the conversion catalyst are not properly balanced, conversion of the hydrocarbon mixture to product may be low, product quality may be poor, or the conversion catalyst may be rapidly deactivated.
  • One embodiment of the present invention comprises a catalyst comprising (i) a matrix material, and (ii) a crystalline microporous oxide incorporated into/with the matrix material.
  • the crystalline microporous oxide comprises a non-framework portion and has a unit cell size.
  • the non-framework portion comprises a promoter metal compound incorporated only into the non-framework portion of the crystalline microporous oxide.
  • the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide.
  • the crystalline microporous oxide comprises a Y zeolite incorporated into the matrix material.
  • the Y zeolite comprises a non-framework portion, has a unit cell size greater than about 24.30A, and comprises aluminum oxide incorporated only into the non-framework portion of the crystalline microporous oxide, such that the aluminum oxide increases Lewis acidity but does not substantially increasing the unit cell size of the zeolite.
  • the crystalline microporous oxide comprises a non-framework portion comprising a promoter metal compound capable of increasing Lewis acidity incorporated only into the non-framework portion of the crystalline microporous oxide, such that the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide.
  • the embodiments of the catalyst can be used in an FCC unit, an isomerization unit, or a hydrocracker by contacting the catalyst with a suitable feedstock.
  • Another embodiment of the present invention comprises a process for making a catalyst. The process comprises (a) contacting a crystalline microporous oxide and a promoter precursor comprising a promoter metal capable of forming a promoter metal compound, said crystalline microporous oxide comprising a non-framework portion and having a unit cell size; and, (b) heating the mixture of step (a) to a temperature between 150°C and 550°C; wherein a promoter metal compound comprising said promoter metal is incorporated only into the non-framework portion of the crystalline microporous oxide and wherein the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide.
  • Another embodiment of the present invention is a process comprising: (a) contacting a crystalline microporous oxide and a promoter precursor, the crystalline microporous oxide comprising a non-framework portion and having a unit cell size and the promoter precursor comprising a promoter metal capable of forming a promoter metal compound; (b) decomposing said promoter precursor thereby forming a promoter metal compound comprising an oxide form of said promoter metal; (c) dispersing said promoter metal compound only into the non-framework portion of said crystalline microporous oxide; wherein the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide.
  • Another embodiment of the present invention is a process comprising: (a) calcining a zeolite comprising a non-framework portion and having a unit cell size; (b) contacting the zeolite with a promoter precursor comprising a promoter metal capable of forming a promoter metal compound, wherein said promoter metal is selected from the group consisting of magnesium, chromium, iron, lanthanum, gallium, manganese and aluminum and wherein said promoter precursor is selected from the group consisting of aluminum acetylacetonate, aluminum isopropyloxide, aluminum hexafluoroacetylacetonate, aluminum dichlorohydrol, aluminum efhoxides, tris[2,2,6,6-tetramethyl-3-5, heptanedianoto]aluminum-III[Al(TMHD)3], aluminum acetate, aluminum nitrate, aluminum propoxide, magnesium acetylacetonate, chromium acetylacet
  • Another embodiment of the present invention is a process comprising: (a) contacting a calcined crystalline microporous oxide and a promoter precursor comprising a promoter metal capable of forming a promoter metal compound, said crystalline microporous oxide comprising a non-framework portion and having a unit cell size; and, (b) activating said promoter metal compound, wherein said promoter metal compound is incorporated only into the non-framework portion of the crystalline microporous oxide and wherein the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide.
  • Another embodiment of the present invention is a process comprising: (a) calcining a crystalline microporous oxide, the crystalline microporous oxide comprising a non-framework portion and having a unit cell size; (b) contacting an aluminum alkyl selected from the group consisting of trimethylaluminum, triethylaluminum, tri(t-butyl)aluminum, and tri(i-butyl)aluminum; (c) treating the product of step (b) with an oxygen-containing material to form a promoter metal compound, wherein the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide.
  • inventions of the present invention include the products produced by the processes of the present invention. These products may or may not be incorporated into a matrix material, but are preferably incorporated into a matrix material before used in a process unit.
  • the catalytic activity of a crystalline microporous oxide can be improved by effectively incorporating a promoter metal compound that promotes dehydrogenation and increases Lewis acidity of the crystalline microporous oxide without increasing its unit cell size.
  • a crystalline microporous oxide can be used as a catalyst alone, the crystalline microporous oxide is preferably incorporated into a matrix material, preferably an inorganic oxide. Other catalytic or non-catalytic components can also be present in the matrix material.
  • the crystalline microporous oxide of this invention can be used to catalyze the breakdown of primary products from the catalytic cracking reaction into clean products such as naphtha for fuels and olefins for chemical feedstocks.
  • the crystalline microporous oxide is preferably selected from the group consisting of crystalline aluminosilicate zeolites (hereafter zeolites), tectosilicates, tetrahedral aluminophophates (ALPOs) and tetrahedral silicoaluminophosphates (SAPOs). More preferably, the crystalline microporous oxide is a zeolite. Suitable zeolites include both natural and synthetic zeolites.
  • Suitable natural zeolites include gmelinite, chabazite, dachiardite, clinoptilolite, faujasite, heulandite, levynite, erionite, cancrinite, scolecite, offretite, mordenite, and ferrierite.
  • Suitable synthetic zeolites are zeolites X, Y, L, ZK-4, ZK-5, E, H, J, M, Q, T, Z, alpha and beta, ZSM-types and omega. Faujasites are preferred, particularly zeolite Y and zeolite X having a unit cell size greater than or equal to 24.30A, more preferably greater than or equal to about 24.40A.
  • the aluminum in the zeolite, as well as the silicon component, can be substituted for other framework components.
  • the aluminum portion can be replaced by boron, gallium, titanium or trivalent metal compositions which are heavier than aluminum. Germanium can be used to replace the silicon portion.
  • the crystalline microporous oxide is preferably included within an inorganic oxide matrix material that binds the catalyst components together so that the final catalyst is hard enough to survive interparticle and reactor wall collisions.
  • An inorganic oxide matrix material can be made from an inorganic oxide sol or gel which is dried to "glue" the catalyst components together.
  • the inorganic oxide matrix material comprises oxides of silicon and aluminum.
  • the inorganic oxide matrix material can further comprise an active porous inorganic oxide catalyst component and an inert catalyst component.
  • each component of the catalyst is held together by attachment with the inorganic oxide matrix material.
  • An active porous inorganic oxide catalyst component typically catalyzes the formation of primary products by cracking hydrocarbon molecules that are too large to fit inside the crystalline microporous oxide.
  • An active porous inorganic oxide catalyst component which can be incorporated into the cracking catalyst is preferably a porous inorganic oxide that cracks a relatively large amount of hydrocarbons into lower molecular weight hydrocarbons as compared to an acceptable thermal blank.
  • a low surface area silica e.g., quartz
  • the extent of cracking can be measured in any of various ASTM tests such as the MAT (microactivity test, ASTM # D3907-8). Compounds such as those disclosed in Greensfelder, B. S., et al, Industrial and Engineering Chemistry, pp. 2573-83, Nov. 1949, are desirable.
  • Alumina, silica-alumina and silica-alumina-zirconia compounds are preferred.
  • An inert catalyst component typically densifies, strengthens and acts as a protective thermal sink.
  • An inert catalyst component which can be incorporated into the cracking catalyst of this invention preferably has a cracking activity that is not significantly greater than the acceptable thermal blank.
  • Kaolin and other clays as well as ⁇ -alumina, titania, zirconia, quartz and silica are examples of suitable inert components.
  • the discrete alumina phases are preferably incorporated into the inorganic oxide matrix material.
  • Species of aluminum oxyhydroxides- ⁇ -alumina, boehmite, diaspore, and transitional aluminas such as ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, K-alumina, and p-alumina can be employed.
  • the alumina species is an aluminum trihydroxide such as gibbsite, bayerite, nordstrandite, or doyelite.
  • the crystalline microporous oxide catalyst component includes a compound for promoting dehydrogenation and increasing Lewis acidity, referred to herein as a promoter metal compound.
  • a promoter metal compound for promoting dehydrogenation and increasing Lewis acidity
  • the promoter metal compound is preferably in a chemical state to effectively promote the dehydrogenation of paraffinic and naphthenic compounds in a hydrocarbon feed stream to form olefmic compounds.
  • aluminum oxide (A1 2 0 3 )
  • aluminum a suitable promoter metal
  • the oxide of aluminum is in such an effective chemical state.
  • the crystalline microporous oxide includes a framework portion and a non- framework portion.
  • Lewis acidity of the crystalline microporous oxide is increased by increasing the number of effective metal cation sites of the non-framework portion of the crystalline microporous oxide without increasing the unit cell size.
  • the unit cell size will be increased.
  • the promotor materials are preferably incorporated only into the non-framework portion of the crystalline microporous oxide material.
  • metal cation refers to either a metal ion or the metal ion plus oxide ion species.
  • One embodiment of the present invention is a process for making an activated catalytic component.
  • Other embodiments are the activated catalytic component produced by the process and a final catalyst product that includes a matrix material.
  • One embodiment of the processes of the present invention comprises contacting, by mixing or by other suitable methods, a crystalline microporous oxide and a promoter precursor capable of forming a promoter metal compound.
  • mixing means combining components and does not necessarily require any mechanical agitation.
  • Contacting the promoter precursor with the crystalline microporous oxide causes the promoter precursor to disperse within the non- framework portion of the crystalline microporous oxide.
  • the promoter metal compound is then activated, preferably by decomposing the promoter precursor, resulting in a residual organic portion and a promoter metal compound sorbed or dispersed into the non-framework portion of the crystalline microporous oxide.
  • the promoter metal compound sorbs to the crystalline microporous oxide by a liquid or gas phase reaction, such as vapor phase transfer.
  • the promoter precursor and crystalline microporous oxide are contacted for an amount of time sufficient for the crystalline microporous oxide to retain between 40 and 60 wt%, preferably about 50 wt%, of the promoter metal oxide resulting from decomposition of the promoter precursor.
  • the degree of retention can be measured by measuring the weight of the crystalline microporous oxide/promoter precursor mixture during the activation/heating step.
  • the crystalline microporous oxide and promoter precursor are mixed in a weight ratio of crystalline microporous oxide:promoter precursor is between 100:15 to 100:200, preferably 100:15 to 100:100.
  • the aluminum acetylacetonate will yield about 15.7% Al 2 O 3 upon decomposition/reaction. Assuming that about 55 wt% of the Al 2 O 3 from the aluminum acetylacetonate disperses into the non-framework portion of the zeolite upon decomposition/reaction and is retained by the zeolite, to get 15 grams of Al 2 O 3 onto 100 grams of zeolite (15% Al O 3 added), 100 grams of zeolite are mixed with about 175 grams of aluminum acetylacetonate:
  • the residual organic portion may be removed by contacting it with a suitable oxygen containing gas to combust the organic portion.
  • a suitable oxygen containing gas to combust the organic portion.
  • Other suitable methods known in the art are also acceptable.
  • the promoter metal compound is preferably multivalent metal compound.
  • the multivalent metal compound is a compound containing a di-valent or tri-valent metal, preferably selected from the group consisting of magnesium, chromium, iron, lanthanum, gallium, manganese and aluminum.
  • the promoter precursor is stable in the gas phase and preferably has a boiling point less than about 550°C, more preferably less than about 500°C.
  • preferred promoter precursors include, but are not limited to, aluminum acetylacetonate, aluminum isopropyloxide, aluminum hexafluoroacetylacetonate, aluminum dichlorohydrol, aluminum ethoxides, tris[2,2,6,6-tetramethyl-3-5, heptanedianoto]aluminum-III[Al(TMHD)3], aluminum alkyls such as trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum, aluminum acetate, aluminum nitrate, aluminum propoxide, gallium acetylacetonate, manganese acetylacetonate, magnesium acetylacetonate, chromium acetylacetonate, iron acetylacetonate, and lanthanide acetylaceton
  • the crystalline microporous oxide is preferably calcined by methods known in the art before contacting it with a promoter precursor that may include, but is not limited to aluminum acetylacetonate, aluminum isopropyloxide, aluminum hexafluoroacetylacetonate, aluminum dichlorohydrol, aluminum ethoxides, tris[2,2,6,6-tetramethyl-3-5, heptanedianotojaluminum- III[A1(TMHD)3], aluminum acetate, aluminum nitrate, aluminum propoxide, magnesium acetylacetonate, chromium acetylacetonate, iron acetylacetonate, manganese acetylacetonate, gallium acetylacetonate, and lanthanide acetylacetonate, which upon activation, form the promoter metal compounds.
  • a promoter precursor may include, but is not limited to aluminum acetylacetonate, aluminum iso
  • the promoter metal compound is activated by heating the crystalline microporous oxide/promoter precursor mixture to between about 150°C and about 550°C.
  • the heating step decomposes the promoter precursor into a residual organic portion and a promoter metal compound that is dispersed in the non-framework portion of the crystalline microporous oxide.
  • the resulting activated crystalline microporous oxide catalyst component can then be combined with a suitable matrix material and used as a catalytst.
  • the preferred promoter precursors include
  • the crystalline microporous oxide is a zeolite, preferably Y zeolite, and the promoter precursor is aluminum acetylacetonate, resulting in an aluminum oxide promoter metal compound of aluminum oxide.
  • the crystalline microporous oxide is preferably calcined by methods known in the art before contacting it with the promoter precursor comprising an aluminum alkyl.
  • Suitable aluminum alkyls include, but are not limited to trimethylaluminum, triethylaluminum, tri(t-butyl)aluminum, tri(i-butyl)aluminum.
  • the promoter metal compound is activated by contacting the crystalline microporous oxide/promoter precursor mixture with an oxygen containing material.
  • Suitable oxygen containing materials include, but are not limited to air, oxygen gas, water, and alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, and butyl alcohol.
  • the oxygen-containing material reacts with the aluminum alkyl, thereby activating the promoter metal compound by forming aluminum oxide and a residual organic portion.
  • the reaction step decomposes the promoter precursor into a promoter metal compound that is dispersed in the non-framework portion of the crystalline microporous oxide and into a residual organic portion that can be removed if necessary as described above.
  • the resulting activated crystalline microporous oxide catalyst component can then be combined with a suitable matrix material and used as a catalytst.
  • the promoter metal comprises aluminum and the crystalline microporous oxide comprises a zeolite.
  • the product of the process of the preceeding paragraph comprising crystalline microporous oxide material and promoter metal compound incorporated into the non- framework portion of the crystalline microporous oxide material can be added to an inorganic oxide matrix material as described above to form a catalyst, preferably to form a fresh non-contaminated catalyst.
  • the catalyst is then passed to a process unit for suitable use as described below.
  • the matrix material may constitute the balance of the final catalyst composition, although other catalyst components and materials can be incorporated into the catalyst.
  • the matrix material comprises about 40 to about 99 wt%, more preferably from about 50 to about 80 wt% of the catalyst based on the total catalyst weight. It is also within the scope of the invention to incorporate into the catalyst other types of microporous oxides, clays, and carbon monoxide oxidation promoters.
  • the catalyst of the present invention is preferably fresh when passed into the cracking process, that is, it is substantially free from the metals that may contaminate the catalyst during a catalytic cracking process. Such metals include but are not limited to, nickel, vanadium, sodium and iron.
  • the catalysts of the present invention can be used is various petroleum and chemical processes, particularly those in which dehydrogenation of paraffins is desired. For example, they can be used to catalyze reactions in fluid catalytic cracking, hydrocracking, and isomerization.
  • the promoter metal compound sorbs to the crystalline microporous oxide portion of the catalyst in such a manner as to promote the dehydrogenation of paraffins and naphthenes.
  • large paraffins are converted to olefins as a result of the paraffins having contacted the crystalline microporous oxide.
  • the olefins are then preferably converted into smaller paraffin molecules, olefmic molecules, and aromatic molecules in ratios desired for fuels products.
  • Fluid catalytic cracking is used to convert high boiling petroleum oils to more valuable lower boiling products, including gasoline and middle distillates, such as kerosene, jet fuel and heating oil.
  • Typical feeds to a catalytic cracker have a high boiling point an include residuum, either on its own, or mixed with other high boiling fractions.
  • the most common feeds are gas oils with an initial boiling point usually above about 230°C, more commonly above about 350°C, with end points of up to about 620°C.
  • Typical gas oils include straight run (atmospheric) gas oil, vacuum gas oil, and coker gas oils.
  • hydrocarbon fractions are difficult to precisely define by initial boiling point since there are so many different types of compounds present in a petroleum hydrocarbon fraction.
  • Hydrocarbon fractions in this range include gas oils, thermal oils, residual oils, cycle stocks, topped and whole crudes, tar sand oils, shale oils, synthetic fuels, heavy hydrocarbon fractions derived from coking processes, tar, pitches, asphalts, and hydrotreated feed stocks derived from any of the foregoing.
  • Fluid catalytic cracking units will typically contain a reactor where the feedstock contacts a hot powdered catalyst heated in a regenerator. Transfer lines connect the two vessels for moving catalyst particles back and forth.
  • the cracking reaction will preferably be carried out at a temperature from about 450° to about 680°C, more preferably from about 480° to about 560°C; pressures from about 5 to 60 psig, more preferably from about 5 to 40 psig; contact times (catalyst in contact with feed) of about 0.5 to 15 seconds, more preferably about 1 to 6 seconds; and a catalyst to oil ratio of about 0.5 to 10, more preferably from about 2 to 8.
  • the catalyst particles During the cracking reactions, lower boiling products are formed and some hydrocarbonaceous material and non-volatile coke are deposited on the catalyst particles.
  • the hydrocarbonaceous material is removed by stripping the catalyst, preferably with steam.
  • the non- volatile coke is typically comprised of highly condensed aromatic hydrocarbons.
  • the catalyst particles can recover a major proportion of their original activity by removing most of the hydrocarbonaceous material by stripping and removing the coke by a suitable oxidative regeneration. Consequently, the catalyst particles are sent to a stripper and then to a regenerator.
  • Catalyst regeneration is accomplished by burning the coke deposits from the catalyst surface with an oxygen-containing gas such as air. Catalyst temperatures during regeneration may range from about 560°C to about 760°C. The regenerated catalyst particles are then transferred back to the reactor via a transfer line and, because of their heat, are able to maintain the reactor at the temperature necessary for the cracking reactions. Coke burn-off is an exothermic reaction; therefore, in a conventional fluid catalytic cracking unit with conventional feeds, no additional fuel needs to be added.
  • the feedstocks used in the practice of the present invention primarily because of their low levels of aromatics, and also due to the relatively short contact times in the reactor or transfer line, may not deposit enough coke on the catalyst particles to achieve the necessary temperatures in the regenerator.
  • an additional fuel to provide increased temperatures in the regenerator so the catalyst particles returning to the reactor are hot enough to maintain the cracking reactions.
  • suitable additional fuel include C 2 - gases from the catalytic cracking process itself, natural gas, and torch oil. The C 2 - gases are preferred.
  • Hydrocarbons which may be isomerized by the process of the present invention include paraffinic and olefmic hydrocarbons typically having 4-20, preferably 4-12, more preferably about 4-6 carbon atoms; and aromatics such as xylene.
  • the preferred chargestock is comprised of paraffinic hydrocarbons typified by butanes, pentanes, hexanes, heptanes, etc.
  • Isomerization conditions include temperatures from about 80°C to about 350°C, preferably from about 100°C to 260°C; a pressure from about 0 to 1,000 psig, peferably from about 0 to 300 psig; a liquid hourly space velocity of about 0.1 to 20, preferably about 0.1 to 2; and a hydrogen rate, in standard cubic feet per barrel of about 1,000 to 5,000, preferably from about 1,500 to 2,500.
  • Operating temperatures and catalyst activity are correlated with space velocity to give reasonably rapid processing of the feedstock at catalyst deactivation rates which insure maximum on-stream time of the catalyst between periods of regeneration.
  • the catalysts of the present invention may also be used in hydrocracking processing. Hydrocracking increases the overall refinery yield of quality gasoline- blending components.
  • Hydrocracking can take a relatively low-quality gas oil feed that otherwise would be blended into distillate fuel and converts it, in the presence of hy rogena and an appropriate catalyst in fixed-bed reactors.
  • the feedstock is mixed with hydrogen vapor, heated to about 140°C to 400°C, pressurized to about 1,200 to 3,500 psi, and charged to a first-stage reactor where about 40 to 50% of the feedstock reacts to remove nitrogen and sulfur compounds that inhibit the cracking reactions and make lower quality products.
  • the stream from the first stage is cooled, liquefied, and run through a separator where butanes and lighter gases are taken off.
  • the bottoms fraction is passed to a second-stage reactor a cracked at higher temperatures and pressures wherein additional gasoline-blending components and a hydrocrackate are produced.
  • Standard MAT tests (e.g., microactivity test, ASTM # D3907-8) were run on three separate commercially available crystalline microporous oxides: USY (obtained from W.R. Grace, Davison Division, as Z14USY or UOP as LZY 82 or LZY 84); LZ- 210 (available from Katalystiks, Inc.); and calcined rare earth exchanged Y (CREY, available from W.R. Grace, Davison Division).
  • the crystalline microporous oxides Prior to running the MAT test, the crystalline microporous oxides were combined with matrix material (Ludox, available from DuPont) and steamed at 1400°F for 16 hours to produce a cracking catalyst. Each catalyst tested comprised 20 wt% zeolite and 80 wt% matrix material. The results are indicated in Table 1 below.
  • the crystalline microporous oxides of EXAMPLE 1 were metal ion exchanged according to the method of cation exchange in zeolites as described in A. Dyer, An Introduction to Zeolite Molecular Sieves, Chapter 6, "Zeolites as Ion Exchangers", John Wiley & Sons, 1988, which chapter is incorporated herein by reference. After the crystalline microporous oxides were ion exchanged, they were combined with matrix material and steamed as in EXAMPLE 1, and run according to a standard MAT test. The results are shown in Table 2. Table 2
  • the metal ion exchanged crystalline microporous oxides have a significant reduction in conversion to product compared to the non- exchanged crystalline microporous oxides of EXAMPLE 1. This indicates that the metal ion exchange procedure results in the loss of effective metal cation sites of the non-framework portion of the crystalline microporous oxides in that the balance between Br ⁇ nsted sites and Lewis sites is not favorable for the desired activity.
  • rare earth exchanged CREY (RECREY) made by ' exchanging a portion of the CREY of Example 1 with a rare earth ion solution by the method of Dyer; hydrogen calcined rare earth exchanged Y (HCREY) made by exchanging the approximately 4 wt% Na + of the CREY with NH4 + according to the method of Dyer; and ulfrastabilized calcined exchanged rare earth Y (USCREY) made by calcining NH4CREY according to the method described in references 6-13 of R. Szostak, "Modified Zeolites" (Chapter 5), Introduction to Zeolite Science and Practice, Nol.
  • Each of the crystalline microporous oxides of EXAMPLE 3 was blended in a separate container with aluminum acetylacetonate (ratio of zeolite to aluminum acetylacetonate approximately 1 : 1.4; decomposition temperature of aluminum acetylacetonate slightly greater than 320°C).
  • Each container was placed in an oven and heated to 150°C, held for one hour, and the oven was purged with an amount of nitrogen sufficient to flush out the potentially flammable decomposition products of the acetylacetone decomposition. After purging, the oven was heated to 500°C, held for one hour, and allowed to cool. The oven was then heated in air for 2 hours at 500°C.
  • Example 3 If after steaming as in Example 3 hereof, pyridine is adsorbed onto the catalysts, then heated to 250°C under vacuum to desorb any pyridine from the more weakly acidic at non-acidic sites, infrared spectroscopy can be used to measure the relative amounts of pyridine adsorbed as the pyrindinium ion onto Br ⁇ nsted acidic sites, and the amount sorbed as coordinated pyridine on the strong Lewis sites. When this is done on the catalysts as desorbed, the following band intensities of the adsorbed pyridine on the three catalysts is observed.
  • RECREY a rare-earth exchanged zeolite of the FAU structure type. This is the starting material for the next two samples of this table.
  • RECREY + added alumina -I is a sample of the RECREY to which alumina has been added by the methods taught herein, as effective added alumina.
  • RECREY + added alumina -II is a sample of the RECREY to which alumina has been added in a way that is not effective as additional Lewis acid.
  • Table 5 shows that only in the case of the effectively added alumina (I) is the weak acidity increased, along with the total acidity.
  • the other example (II) shows that simply increasing the amount of alumina does not necessarily increase the acidity.
  • Example 3 Each of the zeolite samples described above are used to prepare catalysts as described in Example 3, and then these composite catalysts are steamed to deactivate them at the same conditions described in Example 3.
  • each catalyst sample was then pressed into a thin disk. Each disk was weighed and its' diameter and thickness measured. Each disk was then placed in a vacuum chamber and heated to remove any water or other sorbed gases. It was then " cooled to 50°C and exposed to pyridine vapor for a short period. The sample was then held in vacuum for several hours and its infrared spectrum obtained, particularly between 1400cm “1 and 1600cm “1 . The sample was then heated to 250°C and held for several hours, and the spectrum was again obtained. This increased temperature and high vacuum removed any pyridine that was physically sorbed.
  • the infrared spectrum between 1400cm “1 and 1600cm “1 was measured on the material before the pyridine so ⁇ tion and the spectrum was subtracted from the spectrum of the sample containing the pyridine. The resulting spectrum was that due to the pyridine interacting with the acidic sites of the catalyst.
  • Table 6 lists the intensities observed for the bands due to the presence of Br ⁇ nsted and Lewis sites on the catalysts.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un composant catalytique, un catalyseur, et un procédé relatif à l'élaboration du composant catalytique et du catalyseur. L'invention concerne également un procédé de craquage catalytique fluide permettant de convertir des charges de pétrole en produits à point d'ébullition inférieur, qui consistent à mettre ces charges en contact avec le catalyseur. Le composant catalytique est un catalyseur à l'oxyde cristallin microporeux auquel on ajoute efficacement un composé favorisant la déshydrogénation et augmentant l'acidité de Lewis. Ce composant peut être intégré à un matériau à matrice d'oxyde inorganique et utilisé comme catalyseur. De préférence, le composé qui favorise la déshydrogénation et augmente l'acidité de Lewis est ajouté efficacement à une partie de l'oxyde cristallin microporeux ne constituant pas l'édifice structural de cet oxyde.
PCT/US2001/025940 2000-08-31 2001-08-17 Procede de craquage catalytique fluide a base de catalyseur a l'oxyde cristallin microporeux presentant une acidite de lewis accrue WO2002018516A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
AU8509101A AU8509101A (en) 2000-08-31 2001-08-17 Fcc process incorporating crystalline microporous oxide catalysts having increased lewis acidity
AU2001285091A AU2001285091B2 (en) 2000-08-31 2001-08-17 FCC process incorporating crystalline microporous oxide catalysts having increased lewis acidity
CA002419253A CA2419253A1 (fr) 2000-08-31 2001-08-17 Procede de craquage catalytique fluide a base de catalyseur a l'oxyde cristallin microporeux presentant une acidite de lewis accrue
JP2002524019A JP2004507608A (ja) 2000-08-31 2001-08-17 ルイス酸性が増加した結晶性微孔質酸化物触媒を組み入れた流動接触分解方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US09/653,135 US6482313B1 (en) 1994-10-03 2000-08-31 FCC process incorporating crystalline microporous oxide catalysts having increased Lewis acidity
US09/653,135 2000-08-31
US09/653,136 2000-08-31
US09/653,136 US6673734B1 (en) 1994-10-03 2000-08-31 Crystalline microporous oxide catalysts having increased Lewis acidity and methods for the preparation thereof

Publications (1)

Publication Number Publication Date
WO2002018516A1 true WO2002018516A1 (fr) 2002-03-07

Family

ID=27096445

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/US2001/025939 WO2002018045A1 (fr) 2000-08-31 2001-08-17 Catalyseurs a base d'oxyde microporeux cristallin possedant une acidite de lewis accrue, et procedes de preparation associes
PCT/US2001/025940 WO2002018516A1 (fr) 2000-08-31 2001-08-17 Procede de craquage catalytique fluide a base de catalyseur a l'oxyde cristallin microporeux presentant une acidite de lewis accrue

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/US2001/025939 WO2002018045A1 (fr) 2000-08-31 2001-08-17 Catalyseurs a base d'oxyde microporeux cristallin possedant une acidite de lewis accrue, et procedes de preparation associes

Country Status (6)

Country Link
JP (2) JP2004507608A (fr)
CN (2) CN1288225C (fr)
AU (4) AU2001285090B2 (fr)
CA (2) CA2419253A1 (fr)
TW (2) TW592816B (fr)
WO (2) WO2002018045A1 (fr)

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010023456A1 (fr) * 2008-08-29 2010-03-04 Petróleo Brasileiro S A - Petrobas Procédé de production d'oléfines de faible poids moléculaire dans des unités de craquage catalytique avec une déficience en énergie
CN106179388A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢处理催化剂的制备方法
CN106179378A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢处理催化剂的制法
CN106179390A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢处理催化剂及其制备方法
CN106179384A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢精制催化剂的制法
CN106179379A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢处理催化剂的制法
CN106179389A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢精制催化剂及其制备方法
CN106179387A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢精制催化剂组合物的制备方法
CN106179464A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢裂化催化剂的制法
CN106179466A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢裂化催化剂的制备方法
CN106179381A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢精制催化剂的制法
CN106179391A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢裂化催化剂及其制备方法
CN106179465A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢裂化催化剂的制法
CN106179377A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢精制催化剂组合物的制备方法
CN106179386A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢精制催化剂的制备方法
CN106179383A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢处理催化剂的制备方法
CN106179382A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种体相加氢处理催化剂的制备方法
CN106179461A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢裂化催化剂的制备方法
CN106179385A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢精制催化剂的制备方法

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002018045A1 (fr) * 2000-08-31 2002-03-07 Exxonmobil Research And Engineering Company Catalyseurs a base d'oxyde microporeux cristallin possedant une acidite de lewis accrue, et procedes de preparation associes
WO2008026635A1 (fr) * 2006-08-31 2008-03-06 Nippon Oil Corporation Procédé de craquage catalytique fluide
WO2008026681A1 (fr) * 2006-08-31 2008-03-06 Nippon Oil Corporation Procédé de craquage catalytique fluide
RU2548362C2 (ru) 2009-06-25 2015-04-20 Чайна Петролеум & Кемикал Корпорейшн Катализатор каталитического крекинга и способ повышения селективности катализатора(варианты)
EP2463028A1 (fr) * 2010-12-11 2012-06-13 Umicore Ag & Co. Kg Procédé de production de zéolites et zéotypes dopés en métal et application associée à l'élimination catalytique d'oxydes d'azote
US8945373B2 (en) * 2011-12-22 2015-02-03 Iogen Corporation Method for producing renewable fuels
JP6203910B2 (ja) * 2016-06-28 2017-09-27 住友化学株式会社 非水電解液二次電池用絶縁性多孔質層および非水電解液二次電池用積層セパレータ
CN107837819B (zh) * 2017-11-20 2020-07-24 运城学院 一种用于室内甲醛催化去除的MnY催化剂及其制备方法
CN109061778B (zh) * 2018-09-12 2020-04-24 江西泰华光电科技股份有限公司 一种手机镜头加工方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3013987A (en) * 1958-09-24 1961-12-19 Union Carbide Corp Metal loading of molecular sieves
US3354078A (en) * 1965-02-04 1967-11-21 Mobil Oil Corp Catalytic conversion with a crystalline aluminosilicate activated with a metallic halide
US3644220A (en) * 1969-11-13 1972-02-22 Exxon Research Engineering Co Metal halide containing zeolites and method for their preparation
US4259175A (en) * 1978-10-10 1981-03-31 Union Oil Company Of California Process for reducing sox emissions from catalytic cracking units
US4357265A (en) * 1980-10-28 1982-11-02 W. R. Grace & Co. Catalytic cracking catalyst
US4624936A (en) * 1984-03-21 1986-11-25 Catalysts & Chemicals Industries Co., Ltd. Method for preparing hydrocarbon catalytic cracking catalyst compositions
US4728629A (en) * 1980-08-05 1988-03-01 Phillips Petroleum Company Cracking catalyst restoration with aluminum compounds
US4874729A (en) * 1987-04-14 1989-10-17 Shell Oil Company Process for the preparation of modified zeolites
US5159128A (en) * 1990-08-31 1992-10-27 Shell Oil Company Process for cracking paraffins to olefins
US5576258A (en) * 1994-02-09 1996-11-19 Petroleo Brasileiro S.A. Petrobras Modified Y-zeolite, process for the preparation thereof, and modified Y-zeolite-containing FCC catalyst

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1167071A (fr) * 1980-03-15 1984-05-08 William J. Ball Methode de production d'hydrocarbures aromatiques
CA1161019A (fr) * 1980-08-05 1984-01-24 Brent J. Bertus Regeneration d'un catalyseur de fractionnement a l'aide de composes alumines
US4415439A (en) * 1980-10-28 1983-11-15 W. R. Grace & Co. Catalytic cracking catalyst
NL8103069A (nl) * 1980-10-28 1982-05-17 Grace W R & Co Werkwijze voor de bereiding van katalytische kraakkatalysatoren.
DE3373671D1 (en) * 1983-07-04 1987-10-22 Mobil Oil Corp Process for converting propane to aromatics over zinc-gallium zeolite
JPS6042228A (ja) * 1983-08-15 1985-03-06 モビル　オイル　コ−ポレ−シヨン ゼオライト類の処理法
US5294332A (en) * 1992-11-23 1994-03-15 Amoco Corporation FCC catalyst and process
US6482313B1 (en) * 1994-10-03 2002-11-19 Exxonmobil Research And Engineering Company FCC process incorporating crystalline microporous oxide catalysts having increased Lewis acidity
CA2177293C (fr) * 1995-06-23 2003-12-09 William Lee Schuette Oxyde microporeux cristallise possedant une acidite de lewis plus grande; procede de craquage catalytique fluide utilisant cet oxyde
WO2002018045A1 (fr) * 2000-08-31 2002-03-07 Exxonmobil Research And Engineering Company Catalyseurs a base d'oxyde microporeux cristallin possedant une acidite de lewis accrue, et procedes de preparation associes

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3013987A (en) * 1958-09-24 1961-12-19 Union Carbide Corp Metal loading of molecular sieves
US3354078A (en) * 1965-02-04 1967-11-21 Mobil Oil Corp Catalytic conversion with a crystalline aluminosilicate activated with a metallic halide
US3644220A (en) * 1969-11-13 1972-02-22 Exxon Research Engineering Co Metal halide containing zeolites and method for their preparation
US4259175A (en) * 1978-10-10 1981-03-31 Union Oil Company Of California Process for reducing sox emissions from catalytic cracking units
US4728629A (en) * 1980-08-05 1988-03-01 Phillips Petroleum Company Cracking catalyst restoration with aluminum compounds
US4357265A (en) * 1980-10-28 1982-11-02 W. R. Grace & Co. Catalytic cracking catalyst
US4624936A (en) * 1984-03-21 1986-11-25 Catalysts & Chemicals Industries Co., Ltd. Method for preparing hydrocarbon catalytic cracking catalyst compositions
US4874729A (en) * 1987-04-14 1989-10-17 Shell Oil Company Process for the preparation of modified zeolites
US5159128A (en) * 1990-08-31 1992-10-27 Shell Oil Company Process for cracking paraffins to olefins
US5576258A (en) * 1994-02-09 1996-11-19 Petroleo Brasileiro S.A. Petrobras Modified Y-zeolite, process for the preparation thereof, and modified Y-zeolite-containing FCC catalyst

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010023456A1 (fr) * 2008-08-29 2010-03-04 Petróleo Brasileiro S A - Petrobas Procédé de production d'oléfines de faible poids moléculaire dans des unités de craquage catalytique avec une déficience en énergie
US20110266197A1 (en) * 2008-08-29 2011-11-03 Petroleo Brasileiro S.A. - Petrobras Method of production of light olefins in catalytic cracking units with energy deficiency
CN106179388A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢处理催化剂的制备方法
CN106179378A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢处理催化剂的制法
CN106179390A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢处理催化剂及其制备方法
CN106179384A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢精制催化剂的制法
CN106179379A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢处理催化剂的制法
CN106179389A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢精制催化剂及其制备方法
CN106179387A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢精制催化剂组合物的制备方法
CN106179464A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢裂化催化剂的制法
CN106179466A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢裂化催化剂的制备方法
CN106179381A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢精制催化剂的制法
CN106179391A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢裂化催化剂及其制备方法
CN106179465A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢裂化催化剂的制法
CN106179377A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢精制催化剂组合物的制备方法
CN106179386A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢精制催化剂的制备方法
CN106179383A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 加氢处理催化剂的制备方法
CN106179382A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种体相加氢处理催化剂的制备方法
CN106179461A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢裂化催化剂的制备方法
CN106179385A (zh) * 2015-04-30 2016-12-07 中国石油化工股份有限公司 一种加氢精制催化剂的制备方法
CN106179465B (zh) * 2015-04-30 2018-12-21 中国石油化工股份有限公司 加氢裂化催化剂的制法
CN106179378B (zh) * 2015-04-30 2018-12-21 中国石油化工股份有限公司 加氢处理催化剂的制法

Also Published As

Publication number Publication date
CN1531582A (zh) 2004-09-22
JP2004507347A (ja) 2004-03-11
AU8509001A (en) 2002-03-13
JP2004507608A (ja) 2004-03-11
CN1449306A (zh) 2003-10-15
AU2001285091B2 (en) 2005-11-10
AU2001285090B2 (en) 2005-11-10
WO2002018045A1 (fr) 2002-03-07
TW583021B (en) 2004-04-11
TW592816B (en) 2004-06-21
CA2419253A1 (fr) 2002-03-07
AU8509101A (en) 2002-03-13
CN1288225C (zh) 2006-12-06
CA2419668A1 (fr) 2002-03-07
CN1319647C (zh) 2007-06-06

Similar Documents

Publication Publication Date Title
AU2001285091B2 (en) FCC process incorporating crystalline microporous oxide catalysts having increased lewis acidity
AU2001285091A1 (en) FCC process incorporating crystalline microporous oxide catalysts having increased lewis acidity
AU2001285090A1 (en) Crystalline microporous oxide catalysts having increased lewis acidity and methods for the preparation thereof
EP1966350B1 (fr) Procede fcc avec catalyseur basique
US20090000984A1 (en) Catalytic Cracking Process For High Diesel Yield With Low Aromatic Content And/Or High Propylene Yield
CA2643099C (fr) Catalyseur de craquage, son procede de preparation et procede de craquage catalytique d'hydrocarbure liquide
US6482313B1 (en) FCC process incorporating crystalline microporous oxide catalysts having increased Lewis acidity
EP0749781B1 (fr) Oxydes cristallins microporeux ayant une acidité accrue et procédé de craquage catalytique en lit fluidisé les utilisant
US20090045099A1 (en) Catalytic Cracking And Hydroprocessing Process For High Diesel Yield With Low Aromatic Content And/Or High Propylene Yield
US6673734B1 (en) Crystalline microporous oxide catalysts having increased Lewis acidity and methods for the preparation thereof
EP2055760B1 (fr) Procédé de craquage catalytique fluide pour la maximisation d'oléfines légères dans des opérations de faible gravité
US20140235429A1 (en) Process for enhancing nickel tolerance of heavy hydrocarbon cracking catalysts
US20080308454A1 (en) Basic Cracking Compositions Substantially Free Of Large Pore Zeolites
Shen et al. The determination of acidity in fluid cracking catalysts (FCCs) from adsorption microcalorimetry of probe molecules
Chia Fluid catalytic cracking catalyst deactivation: impact on selectivity for complex feeds
WO2009087576A2 (fr) Procédé de craquage catalytique fluide employant des compositions de craquage basiques

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2419253

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2001285091

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 2002524019

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 018148557

Country of ref document: CN

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
WWG Wipo information: grant in national office

Ref document number: 2001285091

Country of ref document: AU