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Title:
HIGH ACTIVITY, HIGH GASOLINE YIELD AND LOW COKE FLUID CATALYTIC CRACKING CATALYST
Document Type and Number:
WIPO Patent Application WO/2018/201046
Kind Code:
A1
Abstract:
A method of treating a microspherical fluid catalytic cracking catalyst includes contacting in a zeolite crystallization liquor for 12 to 24 hours. The microspherical fluid catalytic cracking catalyst includes zeolite and provides superior hydrocarbon cracking properties compared to non-treated or non-contacted catalysts.

Inventors:
WEI JUNMEI (US)
KHARAS KARL (US)
GILBERT CHRISTOPHER (US)
DORAZIO LUCAS (US)
GAO XINGTAO (US)
Application Number:
PCT/US2018/029950
Publication Date:
November 01, 2018
Filing Date:
April 27, 2018
Export Citation:
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Assignee:
BASF CORP (US)
International Classes:
B01J29/08; B01J37/00; B01J37/04; B01J37/06; B01J37/10; B01J37/30; C10G11/05
Foreign References:
CN102125872A2011-07-20
CN104888840A2015-09-09
US20150174559A12015-06-25
US20040235642A12004-11-25
US20040220046A12004-11-04
Attorney, Agent or Firm:
LOMPREY, Jeffrey, R. et al. (US)
Download PDF:
Claims:
WHAT IS CLAIMED IS:

1. A method of treating a fluid catalytic cracking (FCC) catalyst, the method

comprising:

contacting a zeolitic microsphere material in a crystallization liquor for a time period of from about 6 to about 50 hours.

2. The method of claim 1, wherein the contacting is carried out for a time period of from about 12 to about 24 hours.

3. The method of any one of claims 1 or 2, wherein the contacting is carried out at a temperature of about 180 °F to about 240 °F.

4. The method of any one of claims 1-3, wherein the contacting is carried out at a temperature of about 190 °F to about 230 °F.

5. The method of claim 4, wherein the contacting is carried out at a temperature of about 200 °F to about 220 °F.

6. The method of claim 1, wherein the contacting is carried out with agitation of the crystallization liquor.

7. The method of any one of claims 1-6, further comprising isolating the catalyst.

8. The method of any one of claims 1-7, further comprising washing the catalyst.

9. The method of claim 1, wherein the zeolitic microsphere material is prepared by a process comprising:

pre-forming a precursor microsphere comprising a non-zeolitic material and

alumina;

in situ crystallizing a zeolite on the pre-formed microsphere to provide the zeolitic microsphere material.

10. The method of claim 9, further comprising calcining the zeolitic microsphere material.

11. A method of treating a fluid catalytic cracking (FCC) catalyst, the method

comprising: contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the Y zeolite exhibits less than 0.35% strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data, or

until the catalyst provides at least 10% lower coke at 92.5% bottoms conversion.

12. The method of claim 11, wherein the contacting occurs for a time period such that the Y zeolite exhibits less than 0.35% strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.

13. The method of claim 11, wherein prior to the contacting, the Y zeolite exhibits greater than 0.35% strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.

14. The method of claim 11, wherein the contacting occurs for a time period such that the catalyst provides at least 10% lower coke at 92.5% bottoms conversion.

15. A method of treating a fluid catalytic cracking (FCC) catalyst comprising:

contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the zeolite exhibits an increase in stability of at least about 8%.

16. The method of claim 15, wherein prior to the contacting, the Y zeolite exhibits a stability of about 35%.

17. The method of claim 15 or 16, wherein after the contacting, the Y zeolite exhibits a stability of about 42%.

18. A method of treating a fluid catalytic cracking (FCC) catalyst, the method

comprising:

contacting a zeolitic microsphere material comprising a zeolitic component

comprising Y-zeolite in a crystallization liquor for a time period such that the zeolitic component comprises no more than about 5% zeolite P.

19. The method of claim 18, wherein the zeolitic component comprises no more than about 1%) zeolite P.

20. A microspherical FCC catalyst as prepared by any one of claims 1-19.

21. A microspherical FCC catalyst comprising Y-zeolite, wherein the Y zeolite

exhibits less than 0.35% strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data, or

wherein the catalyst provides at least 10% lower coke at 92.5% bottoms conversion.

22. The microspherical FCC catalyst according to claim 21, wherein the Y zeolite exhibits less than 0.35% strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.

23. The microspherical FCC catalyst according to 21 or 22, wherein the catalyst

provides at least 10% lower coke at 92.5% bottoms conversion.

24. The catalyst of any one of claims 20-23, wherein the catalyst has a phase

composition comprising at least about 30 wt.% Y-zeolite.

25. The catalyst of any one of claims 20-23, wherein the catalyst has a phase

composition comprising at least about 40 wt.% Y-zeolite.

26. The catalyst of any one of claims 20-23, wherein the phase composition further comprises at least about 30 wt.% amorphous material.

27. The catalyst of any one of claims 20-26, wherein the Y-zeolite is crystallized as a layer on the surface of a porous alumina-containing matrix.

28. The catalyst of claim 27, wherein the matrix is derived from a kaolin calcined through the exotherm.

29. The catalyst of any one of claims 20-28, wherein the zeolitic microsphere material exhibits a mesoporosity that is about 10% greater than the mesoporosity of a catalyst wherein the zeolitic microspheric material has not been contacted with the crystallization liquor.

30. The catalyst of any one of claims 20-24, wherein the Y zeolite on the surface of the zeolitic microsphere material exhibits less than 0.35% strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.

1. The catalyst of any one of claims 20-30, wherein the catalyst provides at least 10% lower coke at 92.5% bottoms conversion.

Description:
HIGH ACTIVITY, HIGH GASOLINE YIELD AND LOW COKE FLUID

CATALYTIC CRACKING CATALYST

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Application No. 62/491,914, filed on April 28, 2017, the contents of which are incorporated herein in their entirety.

FIELD

[0002] The present technology is generally related to petroleum refining catalysts. More specifically, the technology is related to microspherical fluid catalytic cracking (FCC) catalysts including zeolite, and methods of preparing and using such catalysts.

BACKGROUND

[0003] Catalytic cracking is a petroleum refining process that is applied commercially on a very large scale. Catalytic cracking, and particularly fluid catalytic cracking (FCC), is routinely used to convert heavy hydrocarbon feedstocks to lighter products, such as gasoline and distillate range fractions. In FCC processes, a hydrocarbon feedstock is injected into the riser section of a FCC unit, where the feedstock is cracked into lighter, more valuable products upon contacting hot catalyst circulated to the riser-reactor from a catalyst regenerator.

[0004] Excessive coke and hydrogen are undesirable in commercial catalytic cracking processes. Even small increases in the yields of these products relative to the yield of gasoline can cause significant practical problems. For example, increases in the amount of coke produced can cause undesirable increases in the heat that is generated by burning off the coke during the highly exothermic regeneration of the catalyst. Conversely, insufficient coke production can also distort the heat balance of the cracking process. In addition, in commercial refineries, expensive compressors are used to handle high volume gases, such as hydrogen. Increases in the volume of hydrogen produced, therefore, can add substantially to the capital expense of the refinery. [0005] Since the 1960s, most commercial fluid catalytic cracking catalysts have contained zeolites as an active component. Such catalysts have taken the form of small particles, called microspheres, containing both an active zeolite component and a non- zeolite component in the form of a high alumina, silica-alumina (aluminosilicate) matrix. The active zeolitic component is incorporated into the microspheres of the catalyst by one of general techniques known in the art, such as those in U.S. Patent No. 4,482,530, or U.S. Pat. No. 4,493,902 incorporated herein by reference in its entirety. Another technique is in situ technique, microspheres are first formed and then zeolite component is then crystallized in the microspheres themselves to provide microspheres containing both zeolitic and non-zeolitic components.

SUMMARY

[0006] In one aspect, the present technology provides a method of treating a fluid catalytic cracking (FCC) catalyst, the method including: contacting a zeolitic microsphere material in a crystallization liquor for a time period of from about 6 to about 50 hours. In some embodiments, the contacting is carried out at a temperature of about 180 °F to about 240 °F. In some embodiments, the contacting is carried out with agitation of the crystallization liquor. In further embodiments, the catalyst is isolated. In yet further embodiments, the catalyst is washed with a suitable solvent, such as water.

[0007] In some embodiments, the FCC catalyst may be further calcined.

[0008] In one aspect, the present technology provides a method of treating an FCC catalyst, wherein the zeolitic microsphere material is prepared by a process including: preforming a precursor microsphere comprising a non-zeolitic material and alumina; and in situ crystallizing a zeolite on the pre-formed microsphere to provide the zeolitic microsphere material.

[0009] In one aspect, the present technology provides a method of treating a fluid catalytic cracking (FCC) catalyst including, contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the Y zeolite exhibits less than 0.35% strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data. In some embodiments, prior to the contacting, the Y zeolite exhibits greater than 0.35% strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.

[0010] In one aspect, the present technology provides a method of treating a fluid catalytic cracking (FCC) catalyst including contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the zeolitic component comprises no more than about 5% zeolite P or zeolite ANA, no more than about 3 % zeolite P or zeolite ANA, no more than about 2% zeolite P or zeolite ANA, or no more than about 1% zeolite P or zeolite ANA. In some embodiments, the contacting occurs for a time period such that the Y-zeolite comprises no more than about 4% zeolite P or zeolite ANA. In specific embodiments, the contacting occurs for a time period such that the Y-zeolite comprises no detectable zeolite P or zeolite ANA.

[0011] In one aspect, the present technology provides a method of treating a fluid catalytic cracking (FCC) catalyst including contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the zeolitic component comprises no more than about 5% zeolite P. In some embodiments, the contacting occurs for a time period such that the Y-zeolite comprises no more than about 4% zeolite P, no more than about 3 % zeolite P, no more than about 2% zeolite P, or no more than about 1% zeolite P. In specific embodiments, the contacting occurs for a time period such that the Y-zeolite comprises no detectable zeolite P.

[0012] In one aspect, the present technology provides a method of treating a fluid catalytic cracking (FCC) catalyst including contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the zeolite exhibits an increase in stability of at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, or at least about 10%. In some embodiments, prior to the contacting, the Y zeolite exhibits a stability of about 35%. In some embodiments, the stability is measured after steaming of the FCC catalyst.

[0013] In some embodiments, the process provides for further calcining the zeolitic microsphere material.

[0014] In one aspect, the present technology is a microspherical FCC catalyst as prepared by the described process. [0015] In one aspect, the present technology is a microspherical FCC catalyst, wherein the Y zeolite on the surface of the zeolitic microsphere material exhibits less than about 0.35% strain, less than about 0.34% strain, less than about 0.33% strain, less than about 0.32%) strain, less than about 0.31% strain, or less than about 0.30%> strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data and wherein the catalyst provides at least 10%> lower coke at 92.5% bottoms conversion.

[0016] In some embodiments, the catalyst has a phase composition comprising at least about 30 wt.%) Y-zeolite. In further embodiments, the catalyst has a phase composition comprising at least about 40%, at least about 50%, or at least about 60% Y-zeolite. In additional and alternative embodiments, the phase composition further comprises at least about 30 wt.%) amorphous material.

[0017] In some embodiments of the described FCC catalyst, the Y-zeolite is crystallized as a layer on the surface of a porous alumina-containing matrix. In some embodiments, the matrix is derived from a kaolin calcined through the exotherm.

[0018] In some embodiments, described herein is a the zeolitic microsphere material that exhibits a mesoporosity that is about 10%> greater than the mesoporosity of a catalyst wherein the zeolitic microspheric material has not been contacted with the crystallization liquor.

[0019] In some embodiments, described herein is a zeolitic microsphere material, wherein the Y zeolite on the surface of the zeolitic microsphere material exhibits less than about 0.35%) strain, less than about 0.34%> strain, less than about 0.33%> strain, less than about 0.32%) strain, less than about 0.31% strain, or less than about 0.30%> strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.

[0020] In some embodiments, described herein is an FCC catalyst, wherein the catalyst provides at least 10%> lower coke at 92.5% bottoms conversion.

BRIEF DESCRIPTION OF THE DRAWINGS

[0021] FIG. 1 provides scanning electron microscope images of control, 12 hour, and 24 hour treated samples at the NaY form. [0022] FIG. 2 A and 2B are scanning electron microscope images of NaY samples treated for 48 hours.

[0023] FIG. 3 is a chart of the zeolite surface area of catalyst at the NaY form, after first calcination, after second calcination, or after steaming, each in comparison with the 24 hour contacting or the 48 hour contacting.

[0024] FIG. 4a and FIG. 4b illustrates gasoline yield and heavy cycle oil yield, respectively, of catalysts as prepared by 12 hour and 24 hour treating method, in comparison with a control sample.

[0025] FIG. 5 illustrates the heavy cycle oil yield of catalysts as prepared by 12 hour and 24 hour treating method, in comparison with a control sample.

DETAILED DESCRIPTION

[0026] Various embodiments are described hereinafter. It should be noted that the specific embodiments are not intended as an exhaustive description or as a limitation to the broader aspects discussed herein. One aspect described in conjunction with a particular embodiment is not necessarily limited to that embodiment and can be practiced with any other embodiment(s).

[0027] As used herein, "about" will be understood by persons of ordinary skill in the art and will vary to some extent depending upon the context in which it is used. If there are uses of the term which are not clear to persons of ordinary skill in the art, given the context in which it is used, "about" will mean up to plus or minus 10% of the particular term.

[0028] The use of the terms "a" and "an" and "the" and similar referents in the context of describing the elements (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is

incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., "such as") provided herein, is intended merely to better illuminate the embodiments and does not pose a limitation on the scope of the claims unless otherwise stated. No language in the specification should be construed as indicating any non-claimed element as essential.

[0029] It has been unexpectedly found that contacting the zeolitic microsphere in the crystallization liquor (mother liquor) at a temperature of about 200 °F to about 220 °F for a time period of from about 12 to about 24 hours improves zeolite stability, produces crystals having decreased strain, and results in increased gasoline yield and lower coke yields in the refining process.

[0030] In one aspect, disclosed herein are methods of making the FCC catalysts described herein.

[0031] The method of treating a fluid catalytic cracking (FCC) catalyst may include contacting a zeolitic microsphere material in a crystallization liquor for a time period of from about 6 to about 50 hours. In some embodiments, the time period of contacting may be about 8 to about 36 hours, or about 10, about 12, or about 24 hours. In some embodiments, the method may include contacting in the crystallization liquor at a temperature of about 180 °F to about 240 °F. In some embodiments, the temperature of the crystallization liquor is about 180 °F, about 190 °F, about 200 °F, about 210 °F, about 212 °F, about 220 °F, about 230 °F, or about 240 °F. In some embodiments, prior to contacting, the microspheres include zeolite crystallized as a layer on the surface of a porous alumina-containing matrix. In some embodiments, the contacting is carried out after an about 12 to 16 hour crystallization period. In some embodiments, the zeolitic microspheric material is prepared by mixing together microspheres, seeding zeolite crystals, sodium silicate, and caustic (NaOH), and water, and stirring the resultant slurry at a temperature of about 210 °F, followed by a 4-6 hours induction period, during which a small amount of zeolite Y is detected. This may be followed by a crystallization period of about 8-16 hours or about 8-12 hours, during which the yield of zeolite Y increases. Thus, in some embodiments, the contacting is carried out after the zeolite is crystallized to greater than 90%, greater than about 95%, or greater than about 98%, or about 100% of the theoretical yield. [0032] In some embodiments, the contacting is conducted at a temperature at a temperature of about 200 °F to about 220 °F. In some embodiments, the contacting is conducted at about 210 °F. In some embodiments, the contacting is conducted for about 12 to about 24 hours. In specific embodiments, the contacting is stopped by isolation of the FCC catalyst after about 24 hours.

[0033] In some embodiments, the method of treating a fluid catalytic cracking (FCC) catalyst may include contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the Y zeolite exhibits less than about 0.35% strain, less than about 0.34% strain, less than about 0.33% strain, less than about 0.32%) strain, less than about 0.31% strain, or less than about 0.30%> strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data. In some embodiments, prior to the contacting, the Y zeolite exhibits greater than 0.35%> strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.

[0034] In some embodiments, the method of treating a fluid catalytic cracking (FCC) catalyst may include contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the resulting catalyst provides at least 10%) lower coke at 92.5% bottoms conversion.

[0035] In some embodiments, the method of treating a fluid catalytic cracking (FCC) catalyst may include contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the zeolitic component comprises no more than about 5% zeolite P or zeolite ANA. In some embodiments, the contacting occurs for a time period such that the Y-zeolite comprises no more than about 4% zeolite P or zeolite ANA, no more than about 3 % zeolite P or zeolite ANA, no more than about 2% zeolite P or zeolite ANA, or no more than about 1% zeolite P or zeolite ANA. In specific embodiments, the contacting occurs for a time period such that the Y-zeolite comprises no detectable zeolite P or zeolite ANA.

[0036] In some embodiments, the method of treating a fluid catalytic cracking (FCC) catalyst may include contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the zeolite exhibits an increase in stability of at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, or at least about 10%. In some embodiments, prior to the contacting, the Y zeolite exhibits a stability of about 35%. In some embodiments, the stability is measured after steaming of the FCC catalyst.

[0037] In some embodiments, the contacting is carried out with agitation of the crystallization liquor. In specific embodiments, the agitation may be stirring by an impeller.

[0038] In some embodiments, the FCC catalyst may be isolated or separated from the crystallization liquor after contacting. The isolation may be carried out by commonly used methods such as filtration. In further embodiments, the FCC catalyst may be washed or contacted with water or other suitable liquid to remove residual crystallization liquor.

[0039] In some embodiments, the method may further include mixing the microspheres with an ammonium solution prior to or subsequent to contacting with the crystallization liquor, wherein the microspheres include Y-zeolite in the sodium form prior to the mixing with the ammonium solution. In some embodiments, the mixing with the ammonium solution is conducted at acidic pH conditions. In some embodiments, the mixing with the ammonium solution is conducted at pH of about 3 to about 3.5. In some embodiments, the mixing with the ammonium solution is conducted at a temperature above room

temperature. In some embodiments, the mixing with the ammonium solution is conducted at a temperature of at least about 80 °C to about 100 °C, including increments therein.

[0040] In some embodiments, the ammonium exchanged microspheric material is further ion exchanged with a rare earth ion solution. In some embodiments, the rare earth ion are nitrates of lanthanum, cerium, praseodymium, and neodymium. In some embodiments, the microspheres are contacted with solutions of lanthanum nitrate. In one or more embodiments, the ion exchange step or steps are carried out so that the resulting catalyst contains less than about 0.5% by weight Na 2 0, or about 0.2%, by weight Na 2 0. After ion exchange, the microspheres are dried. Rare earth levels in the range of 0.1% to 12%) by weight, specifically 1-5% by weight, and more specifically 2-3% by weight are contemplated. In certain embodiments, the amount of rare earth added to the catalyst as a rare earth oxide will range from about 1 to 5%, typically 2-3 wt.% rare earth oxide (REO). [0041] In some embodiments, the method may further include conducted an additional sodium exchange of the microspheres with ammonium. The second or additional sodium exchange may be carried out in the same manner as for the first sodium exchange.

[0042] In some embodiments, the FCC catalyst is further calcined. Calcination conditions are commonly known to those of skill in the art. For example, the calcining may be conducted at a temperature of from about 500 °C to about 750 °C.

[0043] In some embodiments of the described method, the microspheres include zeolite. In some embodiments of the method, the microspheres include Y-zeolite crystallized as a layer on the surface of a porous alumina-containing matrix. In further embodiments of the method, prior to or subsequent to the contacting, the microspheres are pre-treated to exchange sodium with ammonium ions.

[0044] In some embodiments of the method, the microspheres including Y-zeolite crystallized as a layer on the surface of a porous alumina-containing matrix undergo mixing in an ammonium solution and a first calcination and a second calcination.

[0045] In another aspect, disclosed herein are microspherical FCC catalysts as prepared by any of the methods disclosed herein.

[0046] In some embodiments, the FCC catalyst has a phase composition including at least 35 wt.% Y-zeolite. In some embodiments, the FCC catalyst has a phase composition including at least 60 wt.% Y-zeolite. In some embodiments, the FCC catalyst has a phase composition including at least 65 wt.% Y-zeolite.

[0047] The FCC catalyst has a phase composition that may also include an amorphous material. Illustrative amorphous materials include, but are not limited to, silica-alumina. In further embodiments, the amorphous material may be derived from the disintegration of crystalline zeolite. In still further embodiments, the amorphous material may be derived from the disintegration of crystalline Y-zeolite.

[0048] The FCC catalyst may have a phase composition further including at least about 40 wt.%) amorphous material.

[0049] The FCC catalyst has a phase composition that may further include mullite. In some embodiments, the phase composition further includes at least about 20 wt.%> mullite. [0050] The FCC catalyst may have a phase composition including zeolite, mullite, and amorphous material. In some embodiments, the FCC catalyst has a phase composition including zeolite, mullite, and amorphous material.

[0051] The FCC catalyst may have a phase composition including Y-zeolite, mullite, and amorphous material. In some embodiments, the FCC catalyst has a phase composition including Y-zeolite, mullite, and amorphous material.

[0052] The FCC catalyst average particle size may be from about 60 to about 100 micrometers. In some embodiments, the FCC catalyst has an average particle size of about 60 to about 90 micrometers.

[0053] In some embodiments, the zeolite is incorporated into an amorphous binder. In some embodiments, the zeolite is Y-zeolite. Suitable binders include, but are not limited to, silica, silica-alumina, alumina, clay (e.g., kaolin) or other known inorganic binders. In some embodiments, a transitional alumina, such as γ-Α1 2 03, η-Α1 2 0 3 , δ-Α1 2 0 3 , Θ-Α1 2 0 3 , κ- Α1 2 0 3; χ-Α1 2 0 3 , or any combination thereof, is included in the composition. In some embodiments, a slurry containing zeolite and one or more binders is made and spray-dried to yield microspheres whose average particle size is from about 60 to about 100 micrometers. In some embodiments, the slurry further contains alumina. In some embodiments, the slurry further contains clay. In some embodiments, the slurry further contains alumina and clay. Any effective binder may be used; particularly effective binders include, but are not limited to, aluminum chlohydrol sol, silica sol, and aluminum phosphates.

[0054] The Y-zeolite may be produced into high zeolite content microspheres by the in situ procedure described in U.S. Patent No. 4,493,902 ("the '902 Patent"), the teachings of which are incorporated by reference in their entirety. The '902 Patent discloses FCC catalysts including attrition-resistant, high zeolitic content, catalytically active

microspheres containing more than about 40%, preferably 50-70% by weight Y faujasite and methods for making such catalysts by crystallizing more than about 40% sodium Y- zeolite in porous microspheres composed of a mixture of metakaolin (kaolin calcined to undergo a strong endothermic reaction associated with dehydroxylation) and kaolin calcined under conditions more severe than those used to convert kaolin to metakaolin, i.e., kaolin calcined to undergo the characteristic kaolin exothermic reaction, sometimes referred to as the spinel form of calcined kaolin. The microspheres containing the two forms of calcined kaolin could also be immersed in an alkaline sodium silicate solution, which is heated, preferably until the maximum obtainable amount of Y faujasite is crystallized in the microspheres.

[0055] In carrying out the invention described in the '902 Patent, the microspheres composed of kaolin calcined to undergo an exotherm, and the metakaolin is reacted with a caustic enriched sodium silicate solution in the presence of a crystallization initiator (seeds) to convert silica and alumina in the microspheres into synthetic sodium faujasite (Y-zeolite). The microspheres are separated from the sodium silicate mother liquor, ion- exchanged with rare earth, ammonium ions or both to form rare earth or various known stabilized forms of catalysts. The technology of the '902 Patent provides means for achieving a desirable and unique combination of high zeolite content associated with high activity, good selectivity and thermal stability, as well as attrition-resistance.

[0056] In general, the zeolitic microspheric material is separated from the crystallization liquor after completion of crystallization. In some embodiments of the present technology, however, the synthetic sodium faujasite of the '902 patent is contacted with the crystallization liquor for further 12 to 40 hours at about 200 °F to about 220 °F even after completion of crystallization for to form the Y-zeolite of the FCC catalyst of the present invention.

[0057] The Y-zeolite may be produced as zeolite microspheres, generally disclosed in U.S. Patent Nos. 6,656,347 ("the '347 Patent") and 6,942,784 ("the '784 Patent"), both of which are incorporated by reference herein in their entirety. These zeolite microspheres are macroporous, have sufficient levels of zeolite to be very active and are of a unique morphology to achieve effective conversion of hydrocarbons to cracked gasoline products with improved bottoms cracking under short contact time FCC processing. These zeolite microspheres are produced by novel processing, which is a modification of technology described in the '902 Patent. It had been found that if the non-zeolite, alumina-rich matrix of the catalyst was derived from an ultrafine hydrous kaolin source having a particulate size such that 90 wt. % of the hydrous kaolin particles were less than 2 microns, and which was pulverized and calcined through the exotherm, then a macroporous zeolite

microsphere was produced. More generally, the FCC catalyst matrix useful to achieve FCC catalyst macroporosity was derived from alumina sources, such as kaolin calcined through the exotherm, that have a specified water pore volume, which distinguished over prior art calcined kaolin used to form the catalyst matrix. The water pore volume was derived from an Incipient Slurry Point (ISP) test, which is described in the patent.

[0058] The morphology of the microsphere catalysts of '347 and '784 Patents which were formed is unique relative to the in situ microsphere catalysts formed previously. Use of a pulverized, ultrafine hydrous kaolin calcined through the exotherm yields in-situ zeolite microspheres having a macroporous structure in which the macropores of the structure are essentially coated or lined with zeolite subsequent to crystallization.

Macroporosity as defined herein means the catalyst has a macropore volume in the pore range of greater than 50θΑ, of at least 0.07 cc/gm mercury intrusion, or at least about 0.10 cc/gm mercury intrusion. This catalyst is optimal for FCC processing, including the short contact time processing in which the hydrocarbon feed is contacted with a catalyst for times of about 3 seconds or less.

[0059] In some embodiments, the described catalyst exhibits a mesoporosity that is about 10% greater than the mesoporosity of a catalyst wherein the zeolitic microspheric material has not been contacted with the crystallization liquor.

[0060] In the broadest sense, zeolitic catalysts described in the '347 patent and the '784 patent is not restricted to macroporous catalysts having a non-zeolite matrix derived solely from kaolin. Thus, any alumina source which has the proper combinations of porosity and reactivity during zeolite synthesis and can generate the desired catalyst macroporosity and morphology can be used. The desired morphology includes a matrix which is well dispersed throughout the catalyst, and the macropore walls of matrix are lined with zeolite and are substantially free of binder coatings.

[0061] In some embodiments, the FCC catalyst includes an alkali metal ion-exchanged zeolite. In some embodiments, the FCC catalyst includes a lanthanum-exchanged zeolite. In some embodiments, the FCC catalyst includes a lanthanum-exchanged zeolite crystallized in situ in a porous kaolin matrix. In some embodiments, the zeolite is crystallized as a layer on the surface of a porous alumina-containing matrix. In further embodiments, the matrix is derived from a kaolin calcined through the exotherm.

[0062] In some embodiments, the FCC catalyst includes an alkali metal ion-exchanged Y-zeolite. In some embodiments, the FCC catalyst includes a lanthanum-exchanged Y- zeolite. In some embodiments, the FCC catalyst includes a lanthanum-exchanged Y- zeolite crystallized in situ in a porous kaolin matrix. In some embodiments, the Y-zeolite is crystallized as a layer on the surface of a porous alumina-containing matrix. In further embodiments, the matrix is derived from a kaolin calcined through the exotherm.

[0063] In some embodiments, the Y-zeolite has a unit cell parameter of less than or equal to 24.70 A. In some embodiments, the unit cell size after second calcination is 24.50-24.65A. In some embodiments, the unit cell size after steaming is 24.28-24.35A.

[0064] In some embodiments, the Y-zeolite on the surface of the zeolitic microsphere material exhibits after steaming less than about 0.35% strain, less than about 0.34% strain, less than about 0.33% strain, less than about 0.32% strain, less than about 0.31% strain, or less than about 0.30% strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.

[0065] Catalysts were evaluated after deactivation and blending with inert microspheres in an Advanced Catalytic Evaluation (ACE) micro-scale fixed fluidized bed (FFB) reactor. Cracking tests were conducted at 1020° F, constant 60 s time on stream (CTOS), and 575 s stripping on standard gas oil (4350) injected at 1.2 g/min for 60 s, where the space velocity was varied by changing the percentage of active catalyst contained in a 9 g charge of active/inert blend. The oil injector height was 2.125" so the bed height had to be maintained constant to prevent systematic bias in the results. This was done by choosing the ratios of active component, a high density inert and low density inert to maintain constant ABD in the blends.

[0066] Catalyst performance was also evaluated using a Circulating Riser pilot Unit (CRU). The riser inlet and outlet temperatures were 65 Γ C (1185° F) and 531° C (988° F), the catalyst/oil (C/O) ratio was about 6 and the riser superficial velocity about 3.4 ft/s, and the riser residence time was 2.0 seconds.

Methods of Use

[0067] In another aspect, disclosed herein are methods to produce gasoline in an FCC system, wherein the methods include using an FCC catalyst described herein. [0068] In another aspect, disclosed herein are methods to improve gasoline yield in an FCC system, wherein the methods include using an FCC catalyst described herein.

[0069] In another aspect, disclosed herein are methods to lower coke production in an FCC system, wherein the methods include using an FCC catalyst described herein. In some embodiments, the catalyst may provide at least 10% lower coke at 92.5% bottoms conversion.

[0070] The present invention, thus generally described, will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present invention.

EXAMPLES

[0071] Example 1: Preparation of NaY intermediate. A microsphere was prepared containing 40 parts of hydrous clay, 60 parts of clay calcined beyond 1050°C. To this mixture, 8 parts of sodium silicate (on the basis of the silicate mass) was added. The slurry for spray dried microspheres was formed by mixing two component slurry in a Cowles mixer. The material was spray dried with in-line injection of sodium silicate as described in patent US 6,942,784. The microsphere was calcined at 1500 °F for 2h before crystallization. The microsphere was crystalized for 12-16 hours to form zeolite Y by the conventional procedures. See e.g., U.S. pat. 4,493,902. The crystalized material was separated from crystallization mother liquor by filtration. The crystallized material was dried in an oven at 100°C overnight, then following the procedure described in

US6,942,784 to do ion-exchange and calcination. Sample was then steamed at 1500°F/24h with 100%) steam before testing. The resultant FCC catalyst provided the control sample.

[0072] The NaY intermediate can also be prepared by a general procedure of U.S. Pat. No. 4,493,902. Microspheres composed of kaolin calcined to undergo the characteristic exotherm and uncalcined hydrous clay are spray dried and then calcined to convert hydrous clay to metakaolin. Microspheres are mixed with caustic soda, crystallization seeds and sodium silicate solution and then heated to 99°C (210 °F) with agitation to grow Na-Y in situ under the conditions of H 2 0/Na 2 0=9 to 13, Si0 2 /Al 2 0 3 =6.5 to 9.5,

Seeds=0.001 to 0.004, The growth rates are optimized by altering Si0 2 /Na 2 0 for a 12-16 hour termination time. After the crystallization, the zeolite-containing microspheres or powder are filtered and washed, and then ion exchanged. NaY can be ion exchanged with ammonium nitrate between two and five times (typically twice) at 82 °C (180 °F), rare earth (RE) exchanged at 82° C and pH of 3 for a rare earth loading on the zeolitic component equivalent to 3% Na, followed by first calcination at temperatures between 950° F and 1450 °F (typically 621 °C, 1150 °F; covered with 25% moisture for 2 hours), then ion exchanged with ammonium nitrate three or four more times at 82 °C (180 F), and then normally calcined again, typically at 1150 °F. The pH is kept constant at 3 using nitric acid or ammonium hydroxide during these ion exchanges.

[0073] Example 2: Preparation of treated samples, Investigation of Zeolite

Properties and Stability: After regular crystallization as described in example 1, a NaY in situ intermediate was not separated from mother liquor, was contacted with the mother liquor at 210° F for 12 hours or 24 hours after the completion of crystallization. The samples were subsequently separated by filtration, dried, and the ammonium exchange and calcination carried out as described in US Pat. No. 6,942,784. Some samples were also steamed at 1450 °F for 24 hours. The resultant FCC catalyst was analyzed as described below.

[0074] Rietveld refinement: Rietveld analysis of the steamed product reveals little change in volume-averaged Y zeolite crystallite size, but shows a decrease in Y zeolite strain. Results of the Rietveld analysis are shown in Table 1. Strain was determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data. For example, the General Structure Analysis System (GSAS) manual provides for calculation of as determined from profile function 2 parameter LY as follows:

S = ( /18000)*(LY-LYi)100%

See Larson, A.C. et al. General Structure Analysis System (GSAS), Los Alamos Natinoal Laboratory Report LAUR p. 163 (2004). It was determined that in this particular instance, and for the diffractometer used in the analysis, LYi is zero. That is, the instrument used does not contribute to parameter LY.

[0075] Table 1: Rietveld refinement and strain calculation of control, 12-hour, and 24- hour contact samples. volume-averaged

729 ± 15 A 714±13 A 769±15 A crystallite size (1σ)

Strain 0.365±0.028 % 0.309±0.028 % 0.293 ±0.024 %

[0076] These X-ray diffraction results, which average over a large number of microspheres, are consistent with SEM results (discussed below) indicating a larger Y zeolite crystal near the exterior surface of microspheres in the NaY form.

[0077] Without being bound by theory, it is hypothesized that the decrease in strain in the crystallization liquor contacted samples is caused by a more homogeneous distribution of tetrahedral Al Bronsted sites in the zeolites. It is further hypothesized that a more homogeneous distribution of acid sites results in a decrease in coke selectivity (discussed below).

[0078] The samples were further tested for porosity, surface area, and stability as shown in Table 2

[0079] Table 2: Properties of Control, 12 hour, and 24 hour mother liquor treated samples before and after steaming. HgPV provides the mercury pore volume in cc/g, MSA provides the matrix surface area, and ZSA provides the zeolite surface area, SUCS provides the steamed unit cell size in angstroms. The BET method provides a

measurement of the specific surface area. The matrix surface area is calculated using the t- plot method from the BET surface area; zeolite surface area is obtained by difference.

[0080] FIG. 1 shows scanning electron microscope images of control, 12 hour, and 24 hour treated samples at the NaY form. FIG. 1 shows that the zeolite crystal size after contacting is 2-3 times as bigger as the control. Without being bound by theory, it is believed that the zeolite surface area at NaY stage of treated samples is lower than control because some metastable zeolite may dissolve in mother liquor during hot contacting, then recrystallized to form bigger zeolite crystal.

[0081] In contrast, as seen in FIG. 2, for samples treated for 48 hours in the

crystallization liquor, zeolite P covered all of the microsphere surface and eventually totally destroys the microsphere. Zeolite P is undesirable for an FCC catalyst. Thus, longer contacting periods of 48 hours do not further improve the catalyst. Further evidence of the damage done by longer contacting periods is shown in FIG. 3, provides a chart of the zeolite surface area of catalyst at the NaY form in comparison with the 24 hour contacting or the 48 hour contacting. As seen in FIG. 3, the NaY surface area was reduced after 24 and 48h contacting. The 48 hour contacting reduced surface area at NaY by 27%. Without being bound by theory, it is believed that the reduction in zeolite surface area reduction after 48 hour contacting is apparently due to zeolite P formation. Thus, unlike 24 hour contacting, 48 hour contacting did not improve zeolite stability.

[0082] Samples subjected to 12 hours and 24 hour treatment exhibited higher pore volume than the control sample. The mesopore volume (5-20nm in radii) of final product increased 35% after 24h treatment. These properties further demonstrate that the described FCC catalyst is structurally different from the control catalyst.

[0083] Example 3: Catalytic Properties in ACE™ reactor. Catalysts were evaluated after deactivation and blending with inert microspheres in an Advanced Catalytic

Evaluation (ACE) micro-scale fixed fluidized bed (FFB) reactor. Cracking tests were conducted at 1020° F, constant 60 s time on stream (CTOS), and 575 s stripping on standard gas oil (4350) injected at 1.2 g/min for 60 s, where the space velocity was varied by changing the percentage of active catalyst contained in a 9 g charge of active/inert blend. The oil injector height was 2.125" so the bed height had to be maintained constant to prevent systematic bias in the results. This was done by choosing the ratios of active component, a high density inert and low density inert to maintain constant ABD in the blends.

[0084] As seen in FIG. 4a and FIG. 4b, samples subjected to the 12-hour or 24 hour contacting exhibited higher amounts of gasoline yield to lower amounts of coke. Both the 12 hour and 24 hour treated samples showed 1 1 and 19% lower coke respectively at 92.5% bottoms conversion and 24h treated sample showed 2% absolute lower bottoms at 4% coke. Samples treated for 24 hours also showed 2% higher gasoline yield at 4% coke. Thus, the catalyst described above performs better than a conventional catalyst that has not been subjected to the contacting in crystallization liquor. The novel fluid catalytic cracking catalyst has higher activity, obtains higher gasoline yield, lower coke yield, and higher LCO (light cycle oil)/bottoms ratio as a function of gasoline conversion.

[0085] Without being bound by theory, it is hypothesized that the contacting process resulted in a catalyst with greater mesopore volume, larger zeolite crystals at the microsphere surface (e.g. a 2x to 3x increase), less zeolite strain (about 15% lower on a relative basis) and higher zeolite stability (44% v. 34%). The growth of larger crystals appears to be the result of a ripening process occurring during the contacting period. The increase in mesoporosity is attributed to the packing of the larger crystals. During the ripening process, it is also believed some metastable zeolite is removed.

[0086] The zeolite surface area of treated samples after first calcination is much higher than the control. Without being bound by theory, it is also believed that metastable zeolite in the control may collapse during the first calcination, leaving non-framework alumina in catalyst, which is considered to be coke formation sites. However, in the treated samples, the metastable zeolite dissolves in the crystallization liquor to participate the

recrystallization during contacting, thus no metastable zeolite collapses during first calcination and fewer coke formation sites are left behind.

[0087] Example 4: Catalytic Properties in CRU unit. FCC catalysts described above was scaled up and tested in a circulating riser unit (CRU). All samples were prepared in the 25-gal pilot plant reactor and worked up. Samples were also steamed at 1450 °F (about 788 °C) for 24 hours using a fluid-bed steamer. Catalyst performance in the CRU was evaluated on Garyville feed. The riser inlet and outlet temperatures were 651° C (1 185° F) and 531° C (988° F), the catalyst/oil (C/O) ratio was about 6 and the riser superficial velocity about 3.4 ft/s, and the riser residence time was 2.0 seconds.

[0088] Results from the CRU tests are shown in Table 3 and FIG. 5. CRU test results indicated that the catalyst performance of 24 hour treated sample is very similar to 12 hour treated. Both 12 hour and 24 hour treated samples demonstrated about 10% lower coke at 92.5 % bottoms conversion and 1% higher absolute bottoms conversion at 5% coke.

[0089] Table 3: Catalytic Performance of FCC catalysts in CRU unit

[0090] The present invention, thus generally described, will be understood more readily by reference to the following examples, which are provided by way of illustration and are not intended to be limiting of the present invention.

[0091] While certain embodiments have been illustrated and described, it should be understood that changes and modifications can be made therein in accordance with ordinary skill in the art without departing from the technology in its broader aspects as defined in the following claims.

[0092] The embodiments, illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms "comprising," "including," "containing," etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the claimed technology. Additionally, the phrase "consisting essentially of will be understood to include those elements specifically recited and those additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of excludes any element not specified.

[0093] The present disclosure is not to be limited in terms of the particular embodiments described in this application. Many modifications and variations can be made without departing from its spirit and scope, as will be apparent to those skilled in the art.

Functionally equivalent methods and compositions within the scope of the disclosure, in addition to those enumerated herein, will be apparent to those skilled in the art from the foregoing descriptions. Such modifications and variations are intended to fall within the scope of the appended claims. The present disclosure is to be limited only by the terms of the appended claims, along with the full scope of equivalents to which such claims are entitled. It is to be understood that this disclosure is not limited to particular methods, reagents, compounds compositions or biological systems, which can of course vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.

[0094] In addition, where features or aspects of the disclosure are described in terms of Markush groups, those skilled in the art will recognize that the disclosure is also thereby described in terms of any individual member or subgroup of members of the Markush group.

[0095] As will be understood by one skilled in the art, for any and all purposes, particularly in terms of providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations of subranges thereof. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, tenths, etc. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc. As will also be understood by one skilled in the art all language such as "up to," "at least," "greater than," "less than," and the like, include the number recited and refer to ranges which can be subsequently broken down into subranges as discussed above. Finally, as will be understood by one skilled in the art, a range includes each individual member.

[0096] All publications, patent applications, issued patents, and other documents referred to in this specification are herein incorporated by reference as if each individual publication, patent application, issued patent, or other document was specifically and individually indicated to be incorporated by reference in its entirety. Definitions that are contained in text incorporated by reference are excluded to the extent that they contradict definitions in this disclosure. [0097] Other embodiments are set forth in the following claims.