WO2000021661A1 - A soft chemistry resynthesis route to faujasitic and related fcc catalyst promoters - Google Patents
A soft chemistry resynthesis route to faujasitic and related fcc catalyst promoters Download PDFInfo
- Publication number
- WO2000021661A1 WO2000021661A1 PCT/US1999/023204 US9923204W WO0021661A1 WO 2000021661 A1 WO2000021661 A1 WO 2000021661A1 US 9923204 W US9923204 W US 9923204W WO 0021661 A1 WO0021661 A1 WO 0021661A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- molecular sieve
- metal
- coke
- sites
- Prior art date
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Classifications
-
- 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
-
- 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
- B01J29/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
-
- 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
- B01J29/88—Ferrosilicates; Ferroaluminosilicates
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
Definitions
- the present invention relates to an improved fluidized-bed catalytic cracking (FCC) catalyst.
- FCC fluidized-bed catalytic cracking
- the catalyst produces less coke than prior art catalysts, imparting improved selectivity in the products and facilitating a higher conversion operation.
- the catalyst particles become covered with coke as the oil feed is degraded to lighter fuel products on one hand and condensation of less reactive polymeric coke products on the other.
- the fresh feed and recycle streams are preheated by heat exchangers or a furnace and enter the unit at the base of the feed riser where they are mixed with the hot regenerated catalyst.
- the heat from the catalyst vaporizes the feed and brings it up to the desired reaction temperature.
- the mixture of catalyst and hydrocarbon vapor travels up the riser into the reactors.
- the cracking reactions start when the feed contacts the hot catalyst in the riser and continues until the oil vapors are separated from the catalyst above the riser.
- the hydrocarbon vapors are sent to the synthetic crude fractionator for separation into liquid and gaseous products, and the catalyst proceeds to the stripper.
- the catalyst leaving the reactor is called spent catalyst and contains hydrocarbons adsorbed on its internal and external surfaces as well as the coke deposited by the cracking reactions. Some of the adsorbed hydrocarbons are removed by steam stripping before the catalyst enters the regenerator. In the regenerator, coke is burned from the catalyst with air. Both process and catalysts are complex, and have been reviewed in a recent publication (J. S. Magee and M. M. Mitchell, Jr., "Fluid Catalytic Cracking: Science and Technology", Studies in Surf. Sci. Catal., v. 76 (Elsevier, Amsterdam (1993)).
- the present invention is a coke selective catalyst and process for using it in a fluidized-bed catalytic cracking unit.
- the catalyst(s) is a metal deficient framework having a substantially ordered distribution of reaction sites.
- the catalyst is contacted with a hydrocarbon feedstream in fluidized-bed catalytic cracking unit which provides superior carbon selectivity thereby minimizing coke production and maximizing conversion efficiency. While not to be bound by particular theories or mechanisms, it is believed that the superior performance is related to the ordered state of the residual Al acid sites, whereas in conventional materials the Al aggregates into oxide clusters in the large mesopores, so forming non-selective Lewis acid centers which promote coke formation.
- Figure 1 compares the typical pore size distribution of the materials of this invention compared with prior art commercial samples. The maintenance of micropores and a high proportion of super-micropores is clearly visible in the materials of this invention.
- the present invention requires a catalyst zeolite component having a substantially ordered distribution of reaction sites, a low number of sites (preferably less than 10% based on total T (tetrahedral sites)), and a pore volume in "super micropores” equal or greater than the pore volume in mesopores.
- the term "super micropores” means pores having diameters in the range of 15 to 50 A and mesopores are pores having diameters in the range 50-500 A, as measured by conventional gas sorption methods well known in the art (e.g. ASTM Method D4641 is a typical method). Such values relate to the zeolite and not to the matrix components, the latter being independently varied.
- the catalyst may be prepared by substituting a metal, M, into the framework sites (T-sites) of a crystalline metal molecular sieve material during its synthesis and then demetallating it as described in U.S. 5,308,813. Surprisingly, these materials have superior coke selectivity in FCC processing.
- the process comprises the following steps:
- Diluent or matrix binder components may include those well known in the art, such as naturally occurring or synthetic inorganic oxides (typically, silica, umina titania, zirconia, boria, P 2 O 5 , and mixtures thereof) and hydroxides in the form of particulates, sols, gels or cogels of same, and virgin or modified clays, and pillared layered compounds as reviewed by Vaughan (Amer. Chem. Soc. Symp. Ser. #368, p. 308-323 (1988)) and Ohtsuka (Chem. Materials, v. 9, p. 2039-50 (1997)), included herein by reference.
- rare-earths include elements having atomic numbers between 57 (La) and 71 (Lu)
- lower cost commercial rare-earth solutions comprise mainly mixtures of these with La, Ce and Nd being the major components. If used individually La 3+ may be the preferred exchange rare-earth cation. Zeolites may also be used as binder or cocatalysts with these materials.
- the catalyst may be formed by any of the methods well known in the art, but spray drying is the preferred method as it is the cheapest way to make the desired 20-150 micron particles used in FCC.
- faujasite commercial products include US- Y, LZ-210, LZY-82, CBV types
- zeolites is a long established practice in the catalyst industry to enhance the stability and moderate the catalytic activity of zeolite catalysts, particularly promoters in the faujasite family of FCC and hydrocracking catalysts (see Scherzer, Amer. Chem. Soc. Symp. Ser. #248, Ch. 10 (1984): Catal. Rev., 3_i, 215 (1989), for an extensive review of this subject).
- the aluminosilicate form of the Y zeolite is used as the starting material and the objective in preparing US-Y materials is to enhance the stability of the zeolite, and to moderate its catalytic activity which is generally proportional to the level of Al 3+ in the framework sites of the zeolite.
- mesopores caused by the random and uncontrolled hydrolysis of aluminum from the zeolite lattice, followed by collapse and solubilization of parts of the zeolite crystals during a high temperature stearning process. These pores are further expanded by sequential de umination treatments, such as post acid washes, and catalyst regeneration involving high temperature steam.
- the resulting materials have a random distribution of mesoporosity in the form of pores and channels in the crystals up to tens of nanometers in diameter (Dai et al, Amer. Chem. Soc. Petr. Prepr., 38(31 594 (1993); Addison et al, Appl. Catal., 45, 307 (1988); Lohse and Mildebrath, Z. anorg. Allg. Chemie, 476, 126 (1981)) in addition to retained zeolitic microporosity.
- detrital Al species (A10 + , Al(OH) ⁇ (3"x)+ , A1 2 0 3 clusters, etc.) deposited throughout the retained crystalline and non-crystalline pore structure which act as non-selective catalytic sites and block micropores.
- the new method described in this report produces a demetallated material with ordered defects (which can be filled later if desired) and acid sites and negligible detrital uminum.
- the demetallation procedures described below result in a preponderance of small mesopores or large micropores (designated "super-micropores" for the purpose of this invention), in the range of 15 A to 5 ⁇ A.
- This pore size range has been shown to have desirable mid-distillate selectivities in amorphous sUica-alumina materials (British Patent 1483466).
- Figure 1 compares the typical pore size distribution of the materials of this invention compared with prior art commercial samples. The maintenance of micropores and a high proportion of super-micropores is clearly visible in the materials of this invention.
- a Fe-ECR-32 with .25 Fe:(Al + Fe) ratio was prepared using modified well known synthesis procedures (Vaughan et al., U.S. Patent 4,931,267).
- This process had not only removed almost all of the Fe but also half of the Al .
- This sample sorbed 18.6% n-hexane at 50 torr and 23°C after outgassing at 400°C under vacuum.
- a portion of this EDTA treated material was steamed (100% steam) at 1250°F for 5 hours.
- This steamed sample sorbed 12.5% n-hexane at 50 torr and 23°C after outgassing at 400°C under vacuum.
- This sample was subsequently converted into a cracking catalyst containing 30% wt. zeolite by mixing together into a thick slurry: 2.1 gm. zeolite (dry basis), 3.8 gm.
- colloidal silica DuPont Ludox HS-40
- 3.55 gm. kaolin clay Ga Kaolin Hydrite UF grade
- 30 gm. distilled water This was de-watered on a hot plate with stirring until it formed a paste, then it was oven dried in flowing air at 120°C followed by calcination for three hours at 350°C.
- the hard composite was then crushed and sieved to -100 to +40 mesh.
- This FCC catalyst was then tested in a standard FCC micro-activity test (ASTM D3907; 3C/0; 16 WHSV; 980°F) after steaming at 1400°F for 5 hours in 100% stream and using a high sulfur gasoil as feed (Table 1).
- a gallium aluminosilicate faujasite of the Y type was prepared using modified well known synthesis procedures (Vaughan et al, Proc. 7th Intl. Zeolite Conf, p. 207, (1989); Amer. Chem. Soc, Symp. Ser. #218, p. 231 (1983)).
- the thimble was charged with 9.5 g H t EDTA(.032 moles) and allowed to slowly extract into the zeolite mixture for a period of 48 hours.
- This material was then ammonium exchanged as described in Example 1. This sample adsorbed 23.8% n-hexane at 50 torr and 23°C after outgassing at 400°C under vacuum.
- the pore size distribution was measured using the method of Barrett, Joyner and Halenda (J. Amer. Chem. Soc, 73, p. 373-380, 1951) which is based upon applying the Kelvin equation of capillary condensation to the nitrogen desorption isotherm.
- the mesopore size distribution along with the micropore volume (radii ⁇ lOA) was determined from analysis of the T-plot (Lippens and de Boer, J. Catalysis, 4, p. 319-323, 1965).
- Figure 1 compares the nitrogen pore size distribution of this example with a typical steamed commercial US-Y (LZY-82 from UOP/Union Carbide Corp.), the former showing a strong graded component in the mesopore range in addition to the retained zeolite micropore volume.
- LZY-82 from UOP/Union Carbide Corp.
- Both the product of this example and a sample of commercial LZY-82 were converted to identically loaded catalysts as described in Example 1, steamed at 1400°F for 5 hours, then microactivity tested using the ASTM D3907 procedure (3 C/O; 16 WHSV; 980°F) and the high sulfur gas oil feedstock described in Table 1.
- the results presented in Table 3 show that at comparable activity levels the product of this invention has a 17% improved light olefin and coke selectivities, that can be translated to higher barrels/day processed or lower catalyst additions.
- This material was then exchanged with ammonium ion to a low sodium level as described in Example 1.
- This sample sorbed 16.9% n-hexane at 50 torr at 23°C after outgassing at 400°C under vacuum.
- the pore size distribution was measured using the desorption branch of the nitrogen isotherm at -77°C.
- the mesopore size distribution along with the micropore volume (radii ⁇ 10 A) dete ⁇ riined from analysis of the T-plot is shown in Figure 1 and clearly shows the increased super microporosity of the EDTA treated FeFAU material over a conventional LZ-Y82 material.
- the product of this example was converted to a 30% zeolite loaded catalyst in the manner described in Example 1, steamed at 1400°F for 5 hours, then microactivity tested using the ASTM D3907 procedure (3 C/O; 16 WHSV; 980°F) and the high sulfur gasoil feedstock described in Table 1.
- the results presented in Table 4 compare it with a US-Y commercial catalyst (Grace/Davison Octacat D) steam deactivated to a similar conversion level. They again show that the product of this invention has improved coke and light olefin selectivities.
- the 30% improvement in coke selectivity can be converted to higher unit throughput or lower catalyst addition.
- TOTAL C4 WT% 5.401 5.453
- the products of this invention show improved coke and light olefin and gas selectivities whilst retaining gasoline and distillate selectivities over a range of conversion levels.
- the ability to make these catalysts at low temperature without steaming provides an important control on the pore distribution and degree of demetallation of the catalyst promoter.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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Abstract
Description
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99954752A EP1137485A4 (en) | 1998-10-09 | 1999-10-05 | A soft chemistry resynthesis route to faujasitic and related fcc catalyst promoters |
AU11028/00A AU1102800A (en) | 1998-10-09 | 1999-10-05 | A soft chemistry resynthesis route to faujasitic and related fcc catalyst promoters |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US16965298A | 1998-10-09 | 1998-10-09 | |
US09/169,652 | 1998-10-09 |
Publications (1)
Publication Number | Publication Date |
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WO2000021661A1 true WO2000021661A1 (en) | 2000-04-20 |
Family
ID=22616597
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/023204 WO2000021661A1 (en) | 1998-10-09 | 1999-10-05 | A soft chemistry resynthesis route to faujasitic and related fcc catalyst promoters |
Country Status (4)
Country | Link |
---|---|
US (1) | US20010044372A1 (en) |
EP (1) | EP1137485A4 (en) |
AU (1) | AU1102800A (en) |
WO (1) | WO2000021661A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8932454B2 (en) | 2008-09-18 | 2015-01-13 | Exxonmobile Research And Engineering Co. | Mesoporous Y hydrocracking catalyst and associated hydrocracking processes |
US20110224068A1 (en) * | 2010-03-11 | 2011-09-15 | W.R. Grace & Co.-Conn. | Low small mesoporous peak cracking catalyst and method of using |
CN102464327A (en) * | 2010-11-04 | 2012-05-23 | 中国石油化工股份有限公司 | Method for modifying molecular sieve |
EP2990463B1 (en) | 2014-08-27 | 2018-07-11 | Indian Oil Corporation Limited | A catalyst additive composition for catalytic cracking, a process of preparation thereof and cracking processes of using thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3442795A (en) * | 1963-02-27 | 1969-05-06 | Mobil Oil Corp | Method for preparing highly siliceous zeolite-type materials and materials resulting therefrom |
US4961836A (en) * | 1986-05-23 | 1990-10-09 | Exxon Research And Engineering Company | Synthesis of transition metal alumino-silicate IOZ-5 and use of it for hydrocarbon conversion |
US5308813A (en) * | 1993-02-01 | 1994-05-03 | Exxon Research & Engineering Company | Selective demetallation of zeolites and related materials |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3133747A1 (en) * | 1981-08-26 | 1983-03-17 | Hoechst Ag, 6000 Frankfurt | "ALUMOSILICATES AND SILICONE GELS WITH A LOW CONTENT OF TRANSITION ELEMENTS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE" |
US4734539A (en) * | 1986-10-29 | 1988-03-29 | Exxon Research And Engineering Company | Naphtha isomerization using a medium pore zeolite catalyst |
US4788375A (en) * | 1987-11-27 | 1988-11-29 | Mobil Oil Corporation | Olefin conversion to lubricant range hydrocarbons |
-
1999
- 1999-10-05 WO PCT/US1999/023204 patent/WO2000021661A1/en not_active Application Discontinuation
- 1999-10-05 AU AU11028/00A patent/AU1102800A/en not_active Abandoned
- 1999-10-05 EP EP99954752A patent/EP1137485A4/en not_active Withdrawn
-
2001
- 2001-05-11 US US09/853,766 patent/US20010044372A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3442795A (en) * | 1963-02-27 | 1969-05-06 | Mobil Oil Corp | Method for preparing highly siliceous zeolite-type materials and materials resulting therefrom |
US4961836A (en) * | 1986-05-23 | 1990-10-09 | Exxon Research And Engineering Company | Synthesis of transition metal alumino-silicate IOZ-5 and use of it for hydrocarbon conversion |
US5308813A (en) * | 1993-02-01 | 1994-05-03 | Exxon Research & Engineering Company | Selective demetallation of zeolites and related materials |
Non-Patent Citations (1)
Title |
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See also references of EP1137485A4 * |
Also Published As
Publication number | Publication date |
---|---|
US20010044372A1 (en) | 2001-11-22 |
AU1102800A (en) | 2000-05-01 |
EP1137485A4 (en) | 2002-03-27 |
EP1137485A1 (en) | 2001-10-04 |
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