CA2179380A1 - A catalytic cracking process - Google Patents
A catalytic cracking processInfo
- Publication number
- CA2179380A1 CA2179380A1 CA002179380A CA2179380A CA2179380A1 CA 2179380 A1 CA2179380 A1 CA 2179380A1 CA 002179380 A CA002179380 A CA 002179380A CA 2179380 A CA2179380 A CA 2179380A CA 2179380 A1 CA2179380 A1 CA 2179380A1
- Authority
- CA
- Canada
- Prior art keywords
- zsm
- zeolite
- catalyst
- pore
- catalytic cracking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
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
- B01J29/80—Mixtures of different 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
Heavy oils are subjected to catalytic cracking in the absence of added hydrogen using a catalyst containing a zeolite having the structure of ZSM-12 and a large-pore crystalline zeolite having a Constraint Index less than about 1. The process is able to effect a bulk conversion of the oil while at the same time yielding a higher octane gasoline and increased light olefin content.
Description
WO 951~9~06 2 1 7 9 3 8 0 PCr/lJsg~/oo~z7 A C~T YTIC rR7 . ~ PROCE88 This invention relates to a process for the catalytic cracking of hydrocarbon oils.
Catalytic cracking of hydrocarbon oils utilizing 5 crystalline zeolites is a known process, practiced for example, in fluid-bed catalytic cracking (FCC) units, moving bed or thermofor catalytic cracking ~TCC) reactors, and f ixed-bed crackers .
Crystalline zeolites, particularly large pore 10 zeolites having a pore size in excess of 7 Angstom, and especially zeolite Y, have been found to be particularly effective for the catalytic cracking of a gas oil to produce motor fuels, and have been described and claimed in many patents, including U . S .
Patents 3,140,249; 3,140,251; 3,140,252; 3,140,253;
and 3,271,418. It is also known in the prior art to incoL~Jr clte the large pore crystalline zeolite into a matrix for catalytic cracking, and such disclosure appears in one or more of the above-identified U.S.
Catalytic cracking of hydrocarbon oils utilizing 5 crystalline zeolites is a known process, practiced for example, in fluid-bed catalytic cracking (FCC) units, moving bed or thermofor catalytic cracking ~TCC) reactors, and f ixed-bed crackers .
Crystalline zeolites, particularly large pore 10 zeolites having a pore size in excess of 7 Angstom, and especially zeolite Y, have been found to be particularly effective for the catalytic cracking of a gas oil to produce motor fuels, and have been described and claimed in many patents, including U . S .
Patents 3,140,249; 3,140,251; 3,140,252; 3,140,253;
and 3,271,418. It is also known in the prior art to incoL~Jr clte the large pore crystalline zeolite into a matrix for catalytic cracking, and such disclosure appears in one or more of the above-identified U.S.
2 0 patents .
It is also known that; ~vt:d results can be obtained in the catalytic cracking of gas oils if a crystalline zeolite having a pore size of less than 7 Angstrom units is included with the large pore 25 crystalline zeolite with or without a matrix. A
disclosure of this type is found in U. S . Patent 3,769,202. Although the incorporation of a crystalline zeolite having a pore size of less than 7 Angstrom units into a catalyst composite comprising a 30 large-pore size crystalline zeolite has been very effective with r~spect to raising the octane number of the gasoline product, nevertheless it has done so at the expense of the overall yield of g~col ;n~.
T .,v~:d results in catalytic cracking with 35 respect to both octane number and overall yield were WO 95/l 91,(\fi PCT/uss~l~P~7 achieved in U . S . Patent 3, 758, 4 03, in which the cracking catalyst comprised a large-pore size crystalline zeolite (pore size greater than 7 Angstrom units) in admixture with a ZSM-5 zeolite, wherein the ratio of ZSM-5 zeolite to large-pore size crystalline zeolite was in the range of 1:10 to 3:1.
The use of ZSM-5 zeolite in conjunction with a zeolite cracking catalyst of the X or Y faujasite variety is described in U.S. Patents 3,894,931;
3,894,933; and 3,894,934. The former two patents disclose the use of a ZSM-5 zeolite in amounts of about 5-10 wt. %; the latter patent discloses the weight ratio of ZSM-5 zeolite to large-pore size crystalline zeolite within the range of 1:10 to 3:1.
The addition of a separate additive or composite catalyst comprising ZSM-5 has been found to be tUL~L- ly efficient as an octane and total yield improver, when used in very small amounts, in conjunction with a conventional cracking catalyst.
Thus, in U.S. Patent 4,309,279, it was found that only 0.1 to 0.5 wt.9~ of a ZSM-5 catalyst, added to a conventional cracking catalyst under conventional cracking operations, could increase octane by about 1-3 RON + O (Research Octane Number Without Lead).
U.S. Patent 4,309,280 also teaches ZSM-5 and other zeolites in conjunction with a conventional cracking catalyst.
U.S. Patent 4,740,292 discloses catalytic cracking with a mixture of zeolite Beta and a faujasite zeolite.
U.S. Patents 4,309,279; 4,309,280; and 4,521,298 disclose catalytic cracking processes characterized by the addition of very small amounts of additive promoter comprising a class of zeolites having a WO 95/I9.t06 2 1 7 9 3 8 0 PCTIUS9 1/0~27 Constraint Index of about l to 12 to cracking catalysts .
U.S. Patent 4,416,765 discloses catalytic cracking using a catalyst comprising an amorphous cracking catalyst and a minor amount of a class of crystalline zeolites characterized by a silica to alumina ratio greater than about 12 and a Constraint Index of 1 to 12.
In accordance with the present invention, there has now been discovered an improved process for upgrading the total yield and octane number of gasoline boiling range product, while also increasing the yields of C3, C4 and C5 olefins and isobutane.
This desirable result is obtained by the use of a catalyst composition comprising ZSM-12 and one or more large-pore crystalline zeolites having a Constraint Index less than about 1.
Accordingly, the present invention resides in a catalytic cracking process which comprises contacting a hydrocarbon feed in the absence of added 11YdLU~
with a cracking catalyst comprising a zeolite having the structure of ZSM-12 and a large-pore, crystalline zeolite having a Constraint Index less than 1, the weight ratio of the zeolite having the structure of ZSN-12 to the large-pore crystalline zeolite component being in the range 1:10 to 10 :1.
The process enables heavy feedstocks, such as gas oils boiling above 215C (420-F), to be converted to gasoline range pIvdu~L~ boiling below 215-C
(420-F) and distillates in the 215 to 343-C (420 to 650 F range) . Use of the catalyst composition of this invention results in; ~JVC:d cracking activity over the base REY catalyst, increased octane numbers of the product gasoline and increased gasoline plus WO 95/l9~OG PCTIUS9~/OO~t7 2~ 79380 alkylate yield relative to the base REY catalyst alone .
The present hydrocarbon conver6ion process is an ~,ved catalytic cracking process which involves 5 converting a hydrocarbon feed over a cracking cataly6t. The catalyst used in the process comprises a zeolite having the structure of ZSM-12 and a large-pore, crystalline zeolite having a Constraint Index less than 1, such as REY, USY and REUSY.
ZSM-12 i5 described in U.S. Patent No.
3,832,449, which is incorporated herein by reference.
The weight ratio of the zeolite having the structure of ZSr~1-12 to the large-pore, crystalline zeolite having a Constraint Index less than 1 is in the range 1:10 to 10:1, preferably in the range 1:10 to 3:1 and most prefably in the range 1:10 to 10:7.
As stated previously, another _ ^~t of the catalyst mixture of the invention is a large-pore, crystalline zeolite having a Constraint Index less 20 than 1. The method by which Constraint Index is det-nm1 ned is described fully in U. 5 . Patent No .
It is also known that; ~vt:d results can be obtained in the catalytic cracking of gas oils if a crystalline zeolite having a pore size of less than 7 Angstrom units is included with the large pore 25 crystalline zeolite with or without a matrix. A
disclosure of this type is found in U. S . Patent 3,769,202. Although the incorporation of a crystalline zeolite having a pore size of less than 7 Angstrom units into a catalyst composite comprising a 30 large-pore size crystalline zeolite has been very effective with r~spect to raising the octane number of the gasoline product, nevertheless it has done so at the expense of the overall yield of g~col ;n~.
T .,v~:d results in catalytic cracking with 35 respect to both octane number and overall yield were WO 95/l 91,(\fi PCT/uss~l~P~7 achieved in U . S . Patent 3, 758, 4 03, in which the cracking catalyst comprised a large-pore size crystalline zeolite (pore size greater than 7 Angstrom units) in admixture with a ZSM-5 zeolite, wherein the ratio of ZSM-5 zeolite to large-pore size crystalline zeolite was in the range of 1:10 to 3:1.
The use of ZSM-5 zeolite in conjunction with a zeolite cracking catalyst of the X or Y faujasite variety is described in U.S. Patents 3,894,931;
3,894,933; and 3,894,934. The former two patents disclose the use of a ZSM-5 zeolite in amounts of about 5-10 wt. %; the latter patent discloses the weight ratio of ZSM-5 zeolite to large-pore size crystalline zeolite within the range of 1:10 to 3:1.
The addition of a separate additive or composite catalyst comprising ZSM-5 has been found to be tUL~L- ly efficient as an octane and total yield improver, when used in very small amounts, in conjunction with a conventional cracking catalyst.
Thus, in U.S. Patent 4,309,279, it was found that only 0.1 to 0.5 wt.9~ of a ZSM-5 catalyst, added to a conventional cracking catalyst under conventional cracking operations, could increase octane by about 1-3 RON + O (Research Octane Number Without Lead).
U.S. Patent 4,309,280 also teaches ZSM-5 and other zeolites in conjunction with a conventional cracking catalyst.
U.S. Patent 4,740,292 discloses catalytic cracking with a mixture of zeolite Beta and a faujasite zeolite.
U.S. Patents 4,309,279; 4,309,280; and 4,521,298 disclose catalytic cracking processes characterized by the addition of very small amounts of additive promoter comprising a class of zeolites having a WO 95/I9.t06 2 1 7 9 3 8 0 PCTIUS9 1/0~27 Constraint Index of about l to 12 to cracking catalysts .
U.S. Patent 4,416,765 discloses catalytic cracking using a catalyst comprising an amorphous cracking catalyst and a minor amount of a class of crystalline zeolites characterized by a silica to alumina ratio greater than about 12 and a Constraint Index of 1 to 12.
In accordance with the present invention, there has now been discovered an improved process for upgrading the total yield and octane number of gasoline boiling range product, while also increasing the yields of C3, C4 and C5 olefins and isobutane.
This desirable result is obtained by the use of a catalyst composition comprising ZSM-12 and one or more large-pore crystalline zeolites having a Constraint Index less than about 1.
Accordingly, the present invention resides in a catalytic cracking process which comprises contacting a hydrocarbon feed in the absence of added 11YdLU~
with a cracking catalyst comprising a zeolite having the structure of ZSM-12 and a large-pore, crystalline zeolite having a Constraint Index less than 1, the weight ratio of the zeolite having the structure of ZSN-12 to the large-pore crystalline zeolite component being in the range 1:10 to 10 :1.
The process enables heavy feedstocks, such as gas oils boiling above 215C (420-F), to be converted to gasoline range pIvdu~L~ boiling below 215-C
(420-F) and distillates in the 215 to 343-C (420 to 650 F range) . Use of the catalyst composition of this invention results in; ~JVC:d cracking activity over the base REY catalyst, increased octane numbers of the product gasoline and increased gasoline plus WO 95/l9~OG PCTIUS9~/OO~t7 2~ 79380 alkylate yield relative to the base REY catalyst alone .
The present hydrocarbon conver6ion process is an ~,ved catalytic cracking process which involves 5 converting a hydrocarbon feed over a cracking cataly6t. The catalyst used in the process comprises a zeolite having the structure of ZSM-12 and a large-pore, crystalline zeolite having a Constraint Index less than 1, such as REY, USY and REUSY.
ZSM-12 i5 described in U.S. Patent No.
3,832,449, which is incorporated herein by reference.
The weight ratio of the zeolite having the structure of ZSr~1-12 to the large-pore, crystalline zeolite having a Constraint Index less than 1 is in the range 1:10 to 10:1, preferably in the range 1:10 to 3:1 and most prefably in the range 1:10 to 10:7.
As stated previously, another _ ^~t of the catalyst mixture of the invention is a large-pore, crystalline zeolite having a Constraint Index less 20 than 1. The method by which Constraint Index is det-nm1 ned is described fully in U. 5 . Patent No .
4,016,218. Constraint Index (CI) for some typical zeolites including some which are suitable as catalyst . ~s in the catalytic cracking process 25 of this invention are as follows:
W095119~06 2 1 7q380 PCTIUS9110PJ27 CI (at test t~ ^rature) ZSM-4 0.5 (316-C) ZSM-5 6-8.3 (371-C-316-C) 5 ZSM-ll 5-8.7 (371~C-316-C) ZSM-12 2.3 (316-C) ZSM-20 0.5 (371-C) ZSM-22 7.3 (427-C) ZSM-23 9.1 (427-C) ZSM-34 50 (371-C) ZSM-35 4.5 (454-C) ZSM-48 3 . 5 (538 C) ZSM--50 2.1 (427-C) MCM--22 1.5 (454-C) TMA Offretite 3.7 (316-C) TEA Mordenite 0.4 (316-C) Clinoptilolite 3. 4 (510 C) Mordenite 0.5 (316-C) REY 0.4 (316-C) Dealll~;ni 70~ y 0.5 (510-C) Erion ite 3 8 ( 316 C ) Zeolite Beta 0.6-2.0 (316-C-399-C) The large-pore, crystalline zeolites having a CI
le6s than about 1 which are useful in the process of 25 this invention are well known in the art and have a pore size sufficiently large to admit the vast majority of, ~^,nonts normally found in the feedstock. The zeolites are generally stated to have a pore size in excess of 7 Any-LL~ and are 30 represented by zeolites having the structure of, e.g., ZSM-4, ZSM-20, Mordenite, Zeolite Beta, Dealuminized Y, ~EY, USY and REUSY. A crystalline silicate zeolite well known in the art and useful in the present invention is faujasite. The ZSM-20 35 zeolite resembles faujasite in certain aspects of wo 95ll9~oG PCTIUS94/~0~27 structure but has a notably higher silica/alumina ratio than faujasite, as does Dealuminized Y.
ZSM-4 is described in U.S. Patent 3,642,434.
ZSM-20 is described in U.S. Patent 3,972,983.
Mordenite is described in U.S. Patent 4,503,023.
Dealuminized Y zeolite is described in U.S.
Patent 3, 442, 795 .
Zeolite Beta is described in U . S . Patent 3,308,069 and RE 28,341.
Zeolites of particular use include REY, USY, and REUSY .
REY is described in U.S. Patents 3,595,611 and 3,607,043.
Low sodium Ultrastable Y molecular sieve (USY) is described in U.S. Patents 3,293,192 and 3,449,070.
REUSY is described in U.S. Patent 3,957,623.
It may be desirable to incorporate the zeolites into a material resistant to the temperature and other conditions employed in the process. Such matrix materials include synthetic and naturally occurring substances, such as inorganic materials, e.g., clay, silica, and metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels, including mixtures of silica and metal oxides. Naturally occurring clays can be composited with the zeolites, including those of the -- t _illonite and kaolin families.
These clays can be used in the raw state as originally mined or initially subj ected to calcination, acid treat, ~, or chemical modif ication .
The zeolites may be composited with a porous matrix material, such as alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary WO 95/19 106 2 1 7 9 3 ~ ~ PC'r/US9 1/OO~Z7 c4mpositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia. The matrix may be in the form of a cogel or sol. The relative proportions of zeolite - ~ and inorganic oxide gel matrix on an anhydrous basis may vary widely with the zeolite content ranging from 5 to 99, more usually 10 to 65, wt. % of the dry composite. The matrix itself may possess catalytic properties, generally of an acidic nature, and may be impregnated with a combustion promoter, such as platinum, to enhance a carbon combustion.
The matrix material may include rho~rhorus that is derived from a water soluble phosphorus c _u.-d including phosphoric acid, ammonium dihydrogen phosphate, ~1;; ;um llydL~ phosphate, ammonium phosphate, ammonium hypophosrh~te, ammonium phosphite, ammonium l~y~ l h~ ; te and i l~m dillydL~ or~hnphnsphite.
The zeolite having the structure of ZSM-12 and the large-pore, crystalline zeolite having a Constraint Index less than 1 may be used on separate catalyst particles , i . e ., a mixture of the catalysts .
The ZSM-12 zeolite and the large-pore, crystalline zeolite may also be used as a composite, i.e., catalyst particles containing both zeolites in the same particle.
The ZSM-12 and the large-pore, crystalline zeolite may be combined, blended, dispersed, or otherwise intimately admixed or composited with a porous matrix in such proportions that the resulting product cnnt lin~: 1 to 95 wt%, and preferably 10 to 70 wt. 96 of the total zeolites in the final composite.
In a moving bed process, the use of a composite ..
WO 95/19.S06 2 1 7 9 3 8 0 PCT/I~S9 J100~27 catalyst may be preferred; but in a fluid process a mixture is satisfactory.
The feedstock of the present conversion process comprises a heavy hydrocarbon oil, such as gas oil, coker tower bottoms fraction reduced crude, vacuum tower bottoms, tlpAcrhAlted vacuum resids, FCC tower bottoms, and cycle oils. Oils derived from coal, shale or tar sands may also be treated in this way.
Oils of this kind generally boil about 650'F t343 C) although this process is also useful with oils which have initial boiling points as low as 500-F t260C).
These heavy oils comprises high molecular weight long-chain paraf f ins, naphthenes and high molecular weight aromatics with a large proportion of fused ring aromatics. The heavy hydrocarbon oil feedstock will normally contain a substantial amount boiling above 230-C t450F) and will normally have an initial boiling point of about 550-F t288-C), more usually about 650F t343-C). Typical boiling ranges will be 650 to 1050-F t343 to 566-C), or 650 to 950-F t343 to 510-C), but oils with a narrower boiling range may, of course, be p~,cessed, for example, those with a boiling range of about 650 to 850-F t343 to 454-C).
Heavy gas oils are often of this kind, as are cycle oils and other nonresidual materials. It is possible to co-process materials boiling below 500-F (288-C), but the degree of conversion will be lower for such - ~ ~s. Feedstocks containing lighter ends of this kind will normally have an initial boiling point above about 300-F tl49-C).
The processing is carried out under conditions similar to those used for conventional catalytic cracking. Process temperatures of 750 to 1200-F (400 to 650-C) may conveniently be used, although 35 temperatures above 1050 F t565 C) will normally not ..h'O 9S~19-106 2 1 7 9 38 0 PCT/Us9~100~27 g be employed. Generally, temperatures of 840 to 1050F (450 to 565'C) will be employed. The space velocity of the feedstock will normally be from 0.1 to 20 LHSV, preferably 0.1 to 10 LHSV.
The conversion may be conducted by contacting the feedstock with a fixed stationary bed of catalyst, a fluidized bed, or with a transport bed.
The catalyst may be regenerated by burning in air or other oxygen-containing ga6.
A pr-~l ;m;nAry hydL~JL- l:ating step to remove the nitrogen and sulfur and to saturate aromatics to naphthenes without substantial boiling range conversion will usually~improve catalyst performance and permit lower temperatures, higher space velocities, or combinations of these conditions to be employed .
The invention will now be more particularly .1.~5.';h~ with reference to the following examples and the A~ ying drawings, in which:
Figure lA is a plot illustrating the relat;nn~h;r of C5+ ~A~:olin~ yield to activity t%
conversion) .
Figure lB is a plot illustrating the relat;~nchi~ of octane number of C5+ gasoline to activity (% conversion).
Figure 2A is a plot illustrating the relati~n~h;~ of total C4's yield to activity (%
conversion) .
Figure 2B is a plot illustrating the relationship of dry gas (C3-) yield to activity (%
conversion).
Figure 2C is a plot illustrating the relationship of coke yield to activity (%
conversion) .
Wo 95/l9~0C PCT~S9~/00~27 21 793~ -lo- ~
Figure 3A i8 a plot illustrating the relationship of % pentenes/pentanes yield to activity (% conversion).
Figure 3B is a plot illustrating the 5 relation6hip of % butenes/butanes yield to activity ( % conversion) .
Figure 3C is a plot illustrating the relationship of % propenes/propanes yield to activity (% conversion).
Figure 4A is a plot illustrating the relationship of C5+ gasoline + alkylate yield to activity (% conversion).
Figure 4B is a plot illustrating the relationship of octane number of C5+ gasoline +
15 alkylate to activity t % conversion) .
Figure 5A is a plot illustrating the relationship of coke yield to crackability.
Figure 5B is a plot illustrating the relation~hip of catalyst/oil ratio to crackability.
~S--VPT,~
Catalyst A
A commercially available FCC catalyst which comprises about 15 wt% REY is used as the base catalyst. This catalyst is withdrawn from a 25 commercial FCC unit after oxidative regeneration.
The catalyst contains 560 ppm V, 260 ppm Ni and 1. 7 wt% rare earth oxide. The catalyst has a unit cell size of 24.41 Al~y~r and is henceforth referred to as Catalyst A.
Cat~lyst B t A catalyst for use in the present process is prepared by spray drying an aqueous slurry containing 25 wt . % ZSM-12, synthesized in accordance with U. S .
Patent 3, 832, 449, in a SiO2-A1203 gel/clay matrix.
W095119~06 2 1 7q380 PCTIUS9110PJ27 CI (at test t~ ^rature) ZSM-4 0.5 (316-C) ZSM-5 6-8.3 (371-C-316-C) 5 ZSM-ll 5-8.7 (371~C-316-C) ZSM-12 2.3 (316-C) ZSM-20 0.5 (371-C) ZSM-22 7.3 (427-C) ZSM-23 9.1 (427-C) ZSM-34 50 (371-C) ZSM-35 4.5 (454-C) ZSM-48 3 . 5 (538 C) ZSM--50 2.1 (427-C) MCM--22 1.5 (454-C) TMA Offretite 3.7 (316-C) TEA Mordenite 0.4 (316-C) Clinoptilolite 3. 4 (510 C) Mordenite 0.5 (316-C) REY 0.4 (316-C) Dealll~;ni 70~ y 0.5 (510-C) Erion ite 3 8 ( 316 C ) Zeolite Beta 0.6-2.0 (316-C-399-C) The large-pore, crystalline zeolites having a CI
le6s than about 1 which are useful in the process of 25 this invention are well known in the art and have a pore size sufficiently large to admit the vast majority of, ~^,nonts normally found in the feedstock. The zeolites are generally stated to have a pore size in excess of 7 Any-LL~ and are 30 represented by zeolites having the structure of, e.g., ZSM-4, ZSM-20, Mordenite, Zeolite Beta, Dealuminized Y, ~EY, USY and REUSY. A crystalline silicate zeolite well known in the art and useful in the present invention is faujasite. The ZSM-20 35 zeolite resembles faujasite in certain aspects of wo 95ll9~oG PCTIUS94/~0~27 structure but has a notably higher silica/alumina ratio than faujasite, as does Dealuminized Y.
ZSM-4 is described in U.S. Patent 3,642,434.
ZSM-20 is described in U.S. Patent 3,972,983.
Mordenite is described in U.S. Patent 4,503,023.
Dealuminized Y zeolite is described in U.S.
Patent 3, 442, 795 .
Zeolite Beta is described in U . S . Patent 3,308,069 and RE 28,341.
Zeolites of particular use include REY, USY, and REUSY .
REY is described in U.S. Patents 3,595,611 and 3,607,043.
Low sodium Ultrastable Y molecular sieve (USY) is described in U.S. Patents 3,293,192 and 3,449,070.
REUSY is described in U.S. Patent 3,957,623.
It may be desirable to incorporate the zeolites into a material resistant to the temperature and other conditions employed in the process. Such matrix materials include synthetic and naturally occurring substances, such as inorganic materials, e.g., clay, silica, and metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels, including mixtures of silica and metal oxides. Naturally occurring clays can be composited with the zeolites, including those of the -- t _illonite and kaolin families.
These clays can be used in the raw state as originally mined or initially subj ected to calcination, acid treat, ~, or chemical modif ication .
The zeolites may be composited with a porous matrix material, such as alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, as well as ternary WO 95/19 106 2 1 7 9 3 ~ ~ PC'r/US9 1/OO~Z7 c4mpositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia. The matrix may be in the form of a cogel or sol. The relative proportions of zeolite - ~ and inorganic oxide gel matrix on an anhydrous basis may vary widely with the zeolite content ranging from 5 to 99, more usually 10 to 65, wt. % of the dry composite. The matrix itself may possess catalytic properties, generally of an acidic nature, and may be impregnated with a combustion promoter, such as platinum, to enhance a carbon combustion.
The matrix material may include rho~rhorus that is derived from a water soluble phosphorus c _u.-d including phosphoric acid, ammonium dihydrogen phosphate, ~1;; ;um llydL~ phosphate, ammonium phosphate, ammonium hypophosrh~te, ammonium phosphite, ammonium l~y~ l h~ ; te and i l~m dillydL~ or~hnphnsphite.
The zeolite having the structure of ZSM-12 and the large-pore, crystalline zeolite having a Constraint Index less than 1 may be used on separate catalyst particles , i . e ., a mixture of the catalysts .
The ZSM-12 zeolite and the large-pore, crystalline zeolite may also be used as a composite, i.e., catalyst particles containing both zeolites in the same particle.
The ZSM-12 and the large-pore, crystalline zeolite may be combined, blended, dispersed, or otherwise intimately admixed or composited with a porous matrix in such proportions that the resulting product cnnt lin~: 1 to 95 wt%, and preferably 10 to 70 wt. 96 of the total zeolites in the final composite.
In a moving bed process, the use of a composite ..
WO 95/19.S06 2 1 7 9 3 8 0 PCT/I~S9 J100~27 catalyst may be preferred; but in a fluid process a mixture is satisfactory.
The feedstock of the present conversion process comprises a heavy hydrocarbon oil, such as gas oil, coker tower bottoms fraction reduced crude, vacuum tower bottoms, tlpAcrhAlted vacuum resids, FCC tower bottoms, and cycle oils. Oils derived from coal, shale or tar sands may also be treated in this way.
Oils of this kind generally boil about 650'F t343 C) although this process is also useful with oils which have initial boiling points as low as 500-F t260C).
These heavy oils comprises high molecular weight long-chain paraf f ins, naphthenes and high molecular weight aromatics with a large proportion of fused ring aromatics. The heavy hydrocarbon oil feedstock will normally contain a substantial amount boiling above 230-C t450F) and will normally have an initial boiling point of about 550-F t288-C), more usually about 650F t343-C). Typical boiling ranges will be 650 to 1050-F t343 to 566-C), or 650 to 950-F t343 to 510-C), but oils with a narrower boiling range may, of course, be p~,cessed, for example, those with a boiling range of about 650 to 850-F t343 to 454-C).
Heavy gas oils are often of this kind, as are cycle oils and other nonresidual materials. It is possible to co-process materials boiling below 500-F (288-C), but the degree of conversion will be lower for such - ~ ~s. Feedstocks containing lighter ends of this kind will normally have an initial boiling point above about 300-F tl49-C).
The processing is carried out under conditions similar to those used for conventional catalytic cracking. Process temperatures of 750 to 1200-F (400 to 650-C) may conveniently be used, although 35 temperatures above 1050 F t565 C) will normally not ..h'O 9S~19-106 2 1 7 9 38 0 PCT/Us9~100~27 g be employed. Generally, temperatures of 840 to 1050F (450 to 565'C) will be employed. The space velocity of the feedstock will normally be from 0.1 to 20 LHSV, preferably 0.1 to 10 LHSV.
The conversion may be conducted by contacting the feedstock with a fixed stationary bed of catalyst, a fluidized bed, or with a transport bed.
The catalyst may be regenerated by burning in air or other oxygen-containing ga6.
A pr-~l ;m;nAry hydL~JL- l:ating step to remove the nitrogen and sulfur and to saturate aromatics to naphthenes without substantial boiling range conversion will usually~improve catalyst performance and permit lower temperatures, higher space velocities, or combinations of these conditions to be employed .
The invention will now be more particularly .1.~5.';h~ with reference to the following examples and the A~ ying drawings, in which:
Figure lA is a plot illustrating the relat;nn~h;r of C5+ ~A~:olin~ yield to activity t%
conversion) .
Figure lB is a plot illustrating the relat;~nchi~ of octane number of C5+ gasoline to activity (% conversion).
Figure 2A is a plot illustrating the relati~n~h;~ of total C4's yield to activity (%
conversion) .
Figure 2B is a plot illustrating the relationship of dry gas (C3-) yield to activity (%
conversion).
Figure 2C is a plot illustrating the relationship of coke yield to activity (%
conversion) .
Wo 95/l9~0C PCT~S9~/00~27 21 793~ -lo- ~
Figure 3A i8 a plot illustrating the relationship of % pentenes/pentanes yield to activity (% conversion).
Figure 3B is a plot illustrating the 5 relation6hip of % butenes/butanes yield to activity ( % conversion) .
Figure 3C is a plot illustrating the relationship of % propenes/propanes yield to activity (% conversion).
Figure 4A is a plot illustrating the relationship of C5+ gasoline + alkylate yield to activity (% conversion).
Figure 4B is a plot illustrating the relationship of octane number of C5+ gasoline +
15 alkylate to activity t % conversion) .
Figure 5A is a plot illustrating the relationship of coke yield to crackability.
Figure 5B is a plot illustrating the relation~hip of catalyst/oil ratio to crackability.
~S--VPT,~
Catalyst A
A commercially available FCC catalyst which comprises about 15 wt% REY is used as the base catalyst. This catalyst is withdrawn from a 25 commercial FCC unit after oxidative regeneration.
The catalyst contains 560 ppm V, 260 ppm Ni and 1. 7 wt% rare earth oxide. The catalyst has a unit cell size of 24.41 Al~y~r and is henceforth referred to as Catalyst A.
Cat~lyst B t A catalyst for use in the present process is prepared by spray drying an aqueous slurry containing 25 wt . % ZSM-12, synthesized in accordance with U. S .
Patent 3, 832, 449, in a SiO2-A1203 gel/clay matrix.
6 2 1 7 9 3~0 PCT/U594/00~27 The 6pray dried catalyst i5 ~n;~ Yrh;~n~-~tl and calcined. The calcination is carried out at 1000-F
t540-C) for 2 hours in air followed by steaming the catalyst for 4 hours at 1200-F (650-C) in a 45%
steam/55% air mixture at 0 psig (100 kPa). One part by weight ZSM-12 catalyst is then blended with 3 parts by weight REY catalyst (Catalyst A) to provide a cracking catalyst having 6.25 wt% ZSM-12/11.25 wt%
REY and is henceforth referred to as Catalyst B.
CatalYst C
A catalyst for use in the process of the present invention is prepared by spray drying an aqueous slurry containing 40 wt. % ZSN-12, synthes; Psd in accordance with U.S. Patent 3,832,449, in a SiO2-A12O3-H3PO4 sol/clay matrix. The spray dried catalyst is ammonium ~yrh~n~ed and calcined. The calcination is carried out at 1000-F (540-C) for 2 hours in air. One part by weight ZSM-12 catalyst is then blended with 3 parts by weight REY catalyst (Catalyst A) to provide a cracking catalyst having 8 . O wt~ ZSN-12/11. 25 wt% REY and is henceforth referred to as Catalyst C.
CatAlvst D
This is a catalyst blend used for comparative purposes comprising ZSM-5 and Catalyst A to show that the ZSM-12/large-pore, crystalline zeolite catalysts of the present invention selectively enhance the yield of C4 olefins over the ZSM-5/large-pore, crystalline zeolite catalyst. A ~ ;ially available ZSM-5 fluid catalyst which comprises about 25 wt. % ZSM-5 in a SiO2-A12O3-clay matrix is calcined at 1000-F (540-C) for 2 hours in air followed by steaming the catalyst for 4 hours at 1200-F (650-C) in a 4596 stean/ 55% air mixture at 0 psig (100 kPa).
One part by weight ZSM-5 catalyst is then blended Wo 95/19406 PCT/U594Mn427 21 7q380 -12-with 3 parts by weight REY catalyst (Catalyst A) to provide a cracking catalyst having 6 . 25 wt . % ZSM-5/
11.25 wt.% REY and is henceforth referred to as Catalyst D.
Catalysts A, B, C, and D were evaluated in a fixed-fluidized bed (FFB) unit at a t~ c.Lul~: of 960F (515-C), a 1.0 minute contact time and a' , ~^r ic plc:S~-ULe: (100 kPa) using a Sour Heavy Gas oil (SHGO) having the properties as shown in Table 1.
Tabla 1 ~rop~rtias of Joliat Sour ~vy GA8 oil Pour Point, F(-C) 95(35) Conradson Coke Residue, wt. 9~ 0 . 56 Rinematic Viscosity @ 40C 104.8 15Kinematic Viscosity e lOO-C 7.95 Aniline Point, F(-C) 168.5(76) Bromine Number 6 . 9 Gravity, API 2 0 .1 Carbon, wt. % 85 .1 20Hydrogen, wt. % 12 .1 Sulfur, wt.% 2.6 Nitrogen, wt. 96 0 . 2 ~otal, wt.% 100.0 Basic Nitrogen, ppm 465 25Nickel, ppm 0 . 5 Vanadium, ppm 0 . 3 Iron, ppm 1. 2 Copper, ppm < 0. 1 Sodium, ppm 0 . 8 Wo gs/l9406 2 1 7 q 3 ~3 0 Pcrl[rss4loo~27 A range of conversions were scanned by varying the catalyst to oil ratio. The fixed-fluidized bed results, after interpolation to 65 vol96 conversion, 21re summarized in Tables 2 and 3 below.
!l~ 2 Catalyst Cataly$ Catalyst Catalyst A B C D
C5+ Gasoline, vol.% 52.4 - 49.9 40.0 37.4 Gasoline + allylate, 10 vol.% 71.2 72.4 74.4 73.8 Alkylate, vol.% 18.8 22.6 34.4 36.5 RON, C5+ Gasoline 90.5 91.4 93.2 93.6 RON, C5+ Gasoline +
Alkylate 91.4 92.2 93.5 93.6 15 Coke, wt.% 6.2 5.3 6.0 5.8 LightFuel Oil wt.% 29.3 29.0 28.3 28.9 Heavy Fuel Oil ~vt.% 7.8 8.3 9.5 8.8 G+D, wt.% 71.9 69.8 60.9 59.7 Total C3, vol.% 7.7 8.9 15.8 18.8 20 Total C4, vol.% 11.7 14.7 19.9 19.4 n-C~;, vol.% 0.4 0.3 o.5 0.3 N-C'4, vol.% 0.8 0.2 0.2 0.1 C, vol.% 1.9 2.9 4.5 4.9 i-~, vol.% 5.3 6.1 5.0 5.0 25 i-C4, vol.% 5.5 7.2 10.4 11.1 Outside i-CA for Alkylate, vol.% 7.3 8.1 13.2 14.0 Light Gases Light Gas, wt.% 2.5 2.5 25 3.2 30 C2, wt.% 0.5 0.4 0-5 0-5 C2=, wt.% 0.5 0.3 0.5 0-9 Cl, w~ % 05 0.4 0.5 0.6 H~, wt.% 0.17 0.11 0.13 0.17 H~S, wt.% 0.93 1.26 0.78 0.99 35 H~drogen Factor 146 107 94 95 Wo 95tl940~ PCTrUSs4/00427 21 7~380 Table 3 Catalyst Catalyst Catalyst Catalyst A B C D
Olefin Yield 5Propylene, vol% 5.8 6.0 11.3 13.9 Butenes, vol.% 5.4 7.5 93 8.2 Pentenes, vol.~fo 4.2 5.3 5.0 3.9 Total, vol.% 15.4 18.8 25.6 26.0 Olefin/Paraffin Selectivity 10 Propylene/Propane 3.1 2.1 25 2.8 Butenes/Butanes 0.9 1.0 0.9 0.7 Pentenes/Pentanes 0.7 0.8 0.9 0.7 Olefin Selectivity 15 C~=/Total (C3 + Cd + C5 ) 0.38 0.32 0.44 0.53 C,~=/rotal tC~3=+ C4=+ C5=) 0.35 0.40 0.36 0.32 C5=/Total 20 (C3 + C4 + C5 ) 0.27 0.28 0.20 0.15 Figures lA and lB compare the C5 catalytically cracked gasoline yield and RON as a function of 650-F+(343 C+) conversion. Figures L~ and lB show the use of ZSM-12 ~L~,~uces a si~nif1~-Ant drop in gasoline yield and a concomitant increase in RON. The ZS~-12/REY catalysts (Catalysts B and C) show ~-nhAn~ activity as measured by RON as compared to the base REY catalyst alone (Catalyst A). The RON
boosts are in the 1-2 range.
Figures 2A, 2B and 2C compare the C4, dry gas and coke yields as a function of 650-F+(343-C+) conversion. Figures 2A and 2B show the use of ZSM-12/REY catalysts (Catalysts B and C) increase the amount of C4's (butenes + butanes) ~nluced while increasing dry gas (H2S + H2 + Cl + C2 + C3 ) only wo 9SII9l0~ 2 1 7 ~ 3 8 0 PcT/uss4mn~27 marginally. C4's are more desirable than dry gas.
The use of ZSM-12/REY catalysts also re6ult in no change in coke make.
Figures 3A, 3B and 3C compare the olefin to 5 paraffin ratio for the light gases (C3 through C5) as a function of 650 F (343-C+) conversion. Figure 3C
shows that the ZSM-12/REY catalysts (Catalyst B and C) reduce the olefinicity of the C3, -nts while increasing the olefinicity of the C4 and C5 10 ~ ^-,ts, as shown in Figures 3A and 3B. C4 and C5 olefins are valuable for methyl tert butyl ether (MTBE) and tertiary amyl methyl ether (TAME) production which are maj or, ts in u~-yy~ ated gasol ine .
Figure 3B in conjunction with Table 3 further shows that ZSM-12/REY catalysts (Catalysts B and C) are also more selective toward C4 olefins (butenes) than the ZSM-5/REY catalyst (Catalyst D). Butenes are the preferred feedstock for alkylation and for MTBE production.
Figures 4A and 4B compare the C5+ catalytically cracked ~colin~ + alkylate, which equals the net gasoline from the process, and RON as a function of 650-F (343 C) conversion. Figure 4A shows that the ZSM-12/REY catalysts (Catalysts B and C) make more net ~col in~ than REY (Catalyst A) alone. Figure 4B
shows that the ZSM-12/REY catalysts (Catalysts B and C) also produce a higher octane gasoline product as measured by RON.
Figures 5A and 5B compare the coke make and the res~uired catalyst to oil ratio versus crackability.
Crackability is a kinetic parameter that reflects the global second order kinetics of the cracking reaction. Higher crackabilities correspond to higher wo 95119~06 --16- PCTIUSg~/00~27 conversions. Figure 5A shows that at the same crackability ( - conversion), the addition of the ZSM-12 (Catalysts B and C) has little effect on coke make. At equivalent crackabilities higher catalyst 5 to oil ratios ~uLL~o~.d to lower catalyst activity.
Figure 5B shows that the unsteamed ZSM-12 (Catalyst C) produces a slightly more active catalyst while the stea~ned ZSM-12 (Catalyst B) is marginally less active than the base REY (Catalyst A) with which it is 10 co~bined.
t540-C) for 2 hours in air followed by steaming the catalyst for 4 hours at 1200-F (650-C) in a 45%
steam/55% air mixture at 0 psig (100 kPa). One part by weight ZSM-12 catalyst is then blended with 3 parts by weight REY catalyst (Catalyst A) to provide a cracking catalyst having 6.25 wt% ZSM-12/11.25 wt%
REY and is henceforth referred to as Catalyst B.
CatalYst C
A catalyst for use in the process of the present invention is prepared by spray drying an aqueous slurry containing 40 wt. % ZSN-12, synthes; Psd in accordance with U.S. Patent 3,832,449, in a SiO2-A12O3-H3PO4 sol/clay matrix. The spray dried catalyst is ammonium ~yrh~n~ed and calcined. The calcination is carried out at 1000-F (540-C) for 2 hours in air. One part by weight ZSM-12 catalyst is then blended with 3 parts by weight REY catalyst (Catalyst A) to provide a cracking catalyst having 8 . O wt~ ZSN-12/11. 25 wt% REY and is henceforth referred to as Catalyst C.
CatAlvst D
This is a catalyst blend used for comparative purposes comprising ZSM-5 and Catalyst A to show that the ZSM-12/large-pore, crystalline zeolite catalysts of the present invention selectively enhance the yield of C4 olefins over the ZSM-5/large-pore, crystalline zeolite catalyst. A ~ ;ially available ZSM-5 fluid catalyst which comprises about 25 wt. % ZSM-5 in a SiO2-A12O3-clay matrix is calcined at 1000-F (540-C) for 2 hours in air followed by steaming the catalyst for 4 hours at 1200-F (650-C) in a 4596 stean/ 55% air mixture at 0 psig (100 kPa).
One part by weight ZSM-5 catalyst is then blended Wo 95/19406 PCT/U594Mn427 21 7q380 -12-with 3 parts by weight REY catalyst (Catalyst A) to provide a cracking catalyst having 6 . 25 wt . % ZSM-5/
11.25 wt.% REY and is henceforth referred to as Catalyst D.
Catalysts A, B, C, and D were evaluated in a fixed-fluidized bed (FFB) unit at a t~ c.Lul~: of 960F (515-C), a 1.0 minute contact time and a' , ~^r ic plc:S~-ULe: (100 kPa) using a Sour Heavy Gas oil (SHGO) having the properties as shown in Table 1.
Tabla 1 ~rop~rtias of Joliat Sour ~vy GA8 oil Pour Point, F(-C) 95(35) Conradson Coke Residue, wt. 9~ 0 . 56 Rinematic Viscosity @ 40C 104.8 15Kinematic Viscosity e lOO-C 7.95 Aniline Point, F(-C) 168.5(76) Bromine Number 6 . 9 Gravity, API 2 0 .1 Carbon, wt. % 85 .1 20Hydrogen, wt. % 12 .1 Sulfur, wt.% 2.6 Nitrogen, wt. 96 0 . 2 ~otal, wt.% 100.0 Basic Nitrogen, ppm 465 25Nickel, ppm 0 . 5 Vanadium, ppm 0 . 3 Iron, ppm 1. 2 Copper, ppm < 0. 1 Sodium, ppm 0 . 8 Wo gs/l9406 2 1 7 q 3 ~3 0 Pcrl[rss4loo~27 A range of conversions were scanned by varying the catalyst to oil ratio. The fixed-fluidized bed results, after interpolation to 65 vol96 conversion, 21re summarized in Tables 2 and 3 below.
!l~ 2 Catalyst Cataly$ Catalyst Catalyst A B C D
C5+ Gasoline, vol.% 52.4 - 49.9 40.0 37.4 Gasoline + allylate, 10 vol.% 71.2 72.4 74.4 73.8 Alkylate, vol.% 18.8 22.6 34.4 36.5 RON, C5+ Gasoline 90.5 91.4 93.2 93.6 RON, C5+ Gasoline +
Alkylate 91.4 92.2 93.5 93.6 15 Coke, wt.% 6.2 5.3 6.0 5.8 LightFuel Oil wt.% 29.3 29.0 28.3 28.9 Heavy Fuel Oil ~vt.% 7.8 8.3 9.5 8.8 G+D, wt.% 71.9 69.8 60.9 59.7 Total C3, vol.% 7.7 8.9 15.8 18.8 20 Total C4, vol.% 11.7 14.7 19.9 19.4 n-C~;, vol.% 0.4 0.3 o.5 0.3 N-C'4, vol.% 0.8 0.2 0.2 0.1 C, vol.% 1.9 2.9 4.5 4.9 i-~, vol.% 5.3 6.1 5.0 5.0 25 i-C4, vol.% 5.5 7.2 10.4 11.1 Outside i-CA for Alkylate, vol.% 7.3 8.1 13.2 14.0 Light Gases Light Gas, wt.% 2.5 2.5 25 3.2 30 C2, wt.% 0.5 0.4 0-5 0-5 C2=, wt.% 0.5 0.3 0.5 0-9 Cl, w~ % 05 0.4 0.5 0.6 H~, wt.% 0.17 0.11 0.13 0.17 H~S, wt.% 0.93 1.26 0.78 0.99 35 H~drogen Factor 146 107 94 95 Wo 95tl940~ PCTrUSs4/00427 21 7~380 Table 3 Catalyst Catalyst Catalyst Catalyst A B C D
Olefin Yield 5Propylene, vol% 5.8 6.0 11.3 13.9 Butenes, vol.% 5.4 7.5 93 8.2 Pentenes, vol.~fo 4.2 5.3 5.0 3.9 Total, vol.% 15.4 18.8 25.6 26.0 Olefin/Paraffin Selectivity 10 Propylene/Propane 3.1 2.1 25 2.8 Butenes/Butanes 0.9 1.0 0.9 0.7 Pentenes/Pentanes 0.7 0.8 0.9 0.7 Olefin Selectivity 15 C~=/Total (C3 + Cd + C5 ) 0.38 0.32 0.44 0.53 C,~=/rotal tC~3=+ C4=+ C5=) 0.35 0.40 0.36 0.32 C5=/Total 20 (C3 + C4 + C5 ) 0.27 0.28 0.20 0.15 Figures lA and lB compare the C5 catalytically cracked gasoline yield and RON as a function of 650-F+(343 C+) conversion. Figures L~ and lB show the use of ZSM-12 ~L~,~uces a si~nif1~-Ant drop in gasoline yield and a concomitant increase in RON. The ZS~-12/REY catalysts (Catalysts B and C) show ~-nhAn~ activity as measured by RON as compared to the base REY catalyst alone (Catalyst A). The RON
boosts are in the 1-2 range.
Figures 2A, 2B and 2C compare the C4, dry gas and coke yields as a function of 650-F+(343-C+) conversion. Figures 2A and 2B show the use of ZSM-12/REY catalysts (Catalysts B and C) increase the amount of C4's (butenes + butanes) ~nluced while increasing dry gas (H2S + H2 + Cl + C2 + C3 ) only wo 9SII9l0~ 2 1 7 ~ 3 8 0 PcT/uss4mn~27 marginally. C4's are more desirable than dry gas.
The use of ZSM-12/REY catalysts also re6ult in no change in coke make.
Figures 3A, 3B and 3C compare the olefin to 5 paraffin ratio for the light gases (C3 through C5) as a function of 650 F (343-C+) conversion. Figure 3C
shows that the ZSM-12/REY catalysts (Catalyst B and C) reduce the olefinicity of the C3, -nts while increasing the olefinicity of the C4 and C5 10 ~ ^-,ts, as shown in Figures 3A and 3B. C4 and C5 olefins are valuable for methyl tert butyl ether (MTBE) and tertiary amyl methyl ether (TAME) production which are maj or, ts in u~-yy~ ated gasol ine .
Figure 3B in conjunction with Table 3 further shows that ZSM-12/REY catalysts (Catalysts B and C) are also more selective toward C4 olefins (butenes) than the ZSM-5/REY catalyst (Catalyst D). Butenes are the preferred feedstock for alkylation and for MTBE production.
Figures 4A and 4B compare the C5+ catalytically cracked ~colin~ + alkylate, which equals the net gasoline from the process, and RON as a function of 650-F (343 C) conversion. Figure 4A shows that the ZSM-12/REY catalysts (Catalysts B and C) make more net ~col in~ than REY (Catalyst A) alone. Figure 4B
shows that the ZSM-12/REY catalysts (Catalysts B and C) also produce a higher octane gasoline product as measured by RON.
Figures 5A and 5B compare the coke make and the res~uired catalyst to oil ratio versus crackability.
Crackability is a kinetic parameter that reflects the global second order kinetics of the cracking reaction. Higher crackabilities correspond to higher wo 95119~06 --16- PCTIUSg~/00~27 conversions. Figure 5A shows that at the same crackability ( - conversion), the addition of the ZSM-12 (Catalysts B and C) has little effect on coke make. At equivalent crackabilities higher catalyst 5 to oil ratios ~uLL~o~.d to lower catalyst activity.
Figure 5B shows that the unsteamed ZSM-12 (Catalyst C) produces a slightly more active catalyst while the stea~ned ZSM-12 (Catalyst B) is marginally less active than the base REY (Catalyst A) with which it is 10 co~bined.
Claims (10)
1. A catalytic cracking process which comprises contacting a hydrocarbon feed in the absence of added hydrogen with a cracking catalyst comprising a zeolite having the structure of ZSM-12 and a large-pore, crystalline zeolite having a Constraint Index less than 1, the weight ratio of the zeolite having the structure of ZSM-12 to the large-pore crystalline zeolite component being in the range 1:10 to 10:1.
2. A process according to claim 1 in which the weight ratio of the zeolite having the structure of ZSM-12 to the large-pore, crystalline zeolite is from 1:10 to 3:1.
3. A process according to claim 1 in which the weight ratio of the zeolite having the structure of ZSM-12 to the large-pore, crystalline zeolite is from 1:10 to 7:10.
4. A process according to claim 1 wherein in which the large-pore, crystalline zeolite is selected from REY, USY, REUSY, ZSM-4, ZSM-20, Mordenite, Dealuminized Y and Zeolite Beta.
5. A process according to claim 1 in which the large-pore, crystalline zeolite is selected from REY, USY and REUSY.
6. A process according to claim 1 in which the the cracking catalyst comprises a composite of the zeolite having the structure of ZSM-12 and the large-pore, crystalline zeolite.
7. A process according to claim 1 in which the cracking catalyst comprises the zeolite having the structure of ZSM-12 and the large-pore, crystalline zeolite as separately matrixed components of a mixture.
8. A process according to claim 7 in which the mixture comprises about 25 wt% of the component comprising the zeolite having the structure of ZSM-12 and about 75 wt.% of the component comprising the large-pore, crystalline zeolite.
9. A process according to claim 1 in which the catalytic cracking is carried out as a fluid catalytic cracking process.
10. A process according to claim 1 in which the catalytic cracking process is carried out a a temperature in the range of 750 to 1050°F (400 to 565°C).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002179380A CA2179380A1 (en) | 1994-01-12 | 1994-01-12 | A catalytic cracking process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA002179380A CA2179380A1 (en) | 1994-01-12 | 1994-01-12 | A catalytic cracking process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2179380A1 true CA2179380A1 (en) | 1995-07-20 |
Family
ID=4158437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002179380A Abandoned CA2179380A1 (en) | 1994-01-12 | 1994-01-12 | A catalytic cracking process |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2179380A1 (en) |
-
1994
- 1994-01-12 CA CA002179380A patent/CA2179380A1/en not_active Abandoned
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| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |