WO2002018045A1 - Crystalline microporous oxide catalysts having increased lewis acidity and methods for the preparation thereof - Google Patents
Crystalline microporous oxide catalysts having increased lewis acidity and methods for the preparation thereof Download PDFInfo
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- WO2002018045A1 WO2002018045A1 PCT/US2001/025939 US0125939W WO0218045A1 WO 2002018045 A1 WO2002018045 A1 WO 2002018045A1 US 0125939 W US0125939 W US 0125939W WO 0218045 A1 WO0218045 A1 WO 0218045A1
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- aluminum
- crystalline microporous
- promoter metal
- acetylacetonate
- microporous oxide
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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
- C10G11/14—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
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- 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
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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
- 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 ethoxides, tris[2,2,6,6-tetramethyl-3-5, heptanedianoto] aluminum-Ill [A1(TMHD)3], aluminum acetate, aluminum nitrate, aluminum propoxide, magnesium acetylacetonate, chromium acetylacetonate,
- 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 olefms 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 24.40 A.
- 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 densities, 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, ⁇ -alumina, ⁇ -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 paraffmic and naphthenic compounds in a hydrocarbon feed stream to form olefinic 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 2 O 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 olefms as a result of the paraffins having contacted the crystalline microporous oxide.
- the olefms are then preferably converted into smaller paraffin molecules, olefinic 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.
- such 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 5 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 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
- Hydrocarbons which may be isomerized by the process of the present invention include paraffinic and olefinic 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 hydrogena and an appropriate catalyst in fixed-bed reactors. Typically, 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.
- EXAMPLE 1 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). 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. Table 1
- 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.
- 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 NH_ ⁇ + according to the method of Dyer; and ultrastabilized 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. Vol. 58, Ed.
- 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 sorption 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.
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Application Number | Priority Date | Filing Date | Title |
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CNB018149898A CN1319647C (en) | 2000-08-31 | 2001-08-17 | Crystalline microporous oxide catalysts having increased lewis acidity and methods for the preparation thereof |
CA002419668A CA2419668A1 (en) | 2000-08-31 | 2001-08-17 | Crystalline microporous oxide catalysts having increased lewis acidity and methods for the preparation thereof |
AU2001285090A AU2001285090B2 (en) | 2000-08-31 | 2001-08-17 | Crystalline microporous oxide catalysts having increased lewis acidity and methods for the preparation thereof |
AU8509001A AU8509001A (en) | 2000-08-31 | 2001-08-17 | Crystalline microporous oxide catalysts having increased lewis acidity and methods for the preparation thereof |
JP2002523011A JP2004507347A (en) | 2000-08-31 | 2001-08-17 | Crystalline microporous oxide catalyst with enhanced Lewis acidity and method for its preparation |
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US09/653,135 US6482313B1 (en) | 1994-10-03 | 2000-08-31 | FCC process incorporating crystalline microporous oxide catalysts having increased Lewis acidity |
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 |
US09/653,135 | 2000-08-31 |
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PCT/US2001/025940 WO2002018516A1 (en) | 2000-08-31 | 2001-08-17 | Fcc process incorporating crystalline microporous oxide catalysts having increased lewis acidity |
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CN (2) | CN1288225C (en) |
AU (4) | AU8509101A (en) |
CA (2) | CA2419253A1 (en) |
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- 2001-08-17 JP JP2002524019A patent/JP2004507608A/en active Pending
- 2001-08-17 WO PCT/US2001/025939 patent/WO2002018045A1/en active IP Right Grant
- 2001-08-17 CN CN 01814855 patent/CN1288225C/en not_active Expired - Fee Related
- 2001-08-17 AU AU8509101A patent/AU8509101A/en active Pending
- 2001-08-17 JP JP2002523011A patent/JP2004507347A/en active Pending
- 2001-08-17 AU AU2001285090A patent/AU2001285090B2/en not_active Ceased
- 2001-08-17 CA CA002419668A patent/CA2419668A1/en not_active Abandoned
- 2001-08-17 CN CNB018149898A patent/CN1319647C/en not_active Expired - Fee Related
- 2001-08-17 AU AU2001285091A patent/AU2001285091B2/en not_active Ceased
- 2001-08-17 WO PCT/US2001/025940 patent/WO2002018516A1/en active IP Right Grant
- 2001-08-17 AU AU8509001A patent/AU8509001A/en active Pending
- 2001-08-22 TW TW90120661A patent/TW583021B/en not_active IP Right Cessation
- 2001-08-22 TW TW90120655A patent/TW592816B/en not_active IP Right Cessation
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US20210221679A1 (en) * | 2011-12-22 | 2021-07-22 | Iogen Corporation | Method for producing renewable fuels |
US11873220B2 (en) * | 2011-12-22 | 2024-01-16 | Iogen Corporation | Method for producing renewable fuels |
CN107837819A (en) * | 2017-11-20 | 2018-03-27 | 运城学院 | A kind of MnY catalyst for indoor formaldehyde catalytic elimination and preparation method thereof |
CN107837819B (en) * | 2017-11-20 | 2020-07-24 | 运城学院 | MnY catalyst for indoor formaldehyde catalytic removal and preparation method thereof |
Also Published As
Publication number | Publication date |
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CN1319647C (en) | 2007-06-06 |
TW592816B (en) | 2004-06-21 |
CN1531582A (en) | 2004-09-22 |
JP2004507347A (en) | 2004-03-11 |
AU8509101A (en) | 2002-03-13 |
CN1288225C (en) | 2006-12-06 |
JP2004507608A (en) | 2004-03-11 |
AU2001285091B2 (en) | 2005-11-10 |
CN1449306A (en) | 2003-10-15 |
AU8509001A (en) | 2002-03-13 |
AU2001285090B2 (en) | 2005-11-10 |
TW583021B (en) | 2004-04-11 |
CA2419253A1 (en) | 2002-03-07 |
WO2002018516A1 (en) | 2002-03-07 |
CA2419668A1 (en) | 2002-03-07 |
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