CA1177810A - Physical mixture of catalysts - Google Patents
Physical mixture of catalystsInfo
- Publication number
- CA1177810A CA1177810A CA000397298A CA397298A CA1177810A CA 1177810 A CA1177810 A CA 1177810A CA 000397298 A CA000397298 A CA 000397298A CA 397298 A CA397298 A CA 397298A CA 1177810 A CA1177810 A CA 1177810A
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- cracking catalyst
- accordance
- zeolite
- fluorided
- 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.)
- Expired
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/12—Fluorides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
An improved cracking catalyst prepared by treating a metallic reforming catalyst with an aqueous solution containing a fluorine compound, drying and calcining the fluorided catalyst, and then physically mixing the fluorided catalyst with a zeolite-containing cracking catalyst. The composite yields higher octane products than conventional cracking catalysts.
An improved cracking catalyst prepared by treating a metallic reforming catalyst with an aqueous solution containing a fluorine compound, drying and calcining the fluorided catalyst, and then physically mixing the fluorided catalyst with a zeolite-containing cracking catalyst. The composite yields higher octane products than conventional cracking catalysts.
Description
PHYSICAL MIXTURE OF CATALYSTS
Background of the_Invention This invention relates to an improved cracking catalyst.
More particularly, this invention relates to a composite of a zeolite-containing cracking catalyst and a fluorided reforming catalyst.
Cracking reactionc are used to convert heavier hydro-carbons into products having a lower average molecular weight useful in the production of motor fuels. Cracked products generally have a lower octane number than that , desir~d for gasoline blending components. Catalytic reforming is a process which increases the octane number of cracked products by converting low octane hydrocarbons, such as paraffins and naphthenes, into aromatic-rich products. To minimize further processing, such as catalytic reforming operations, it is desirable that the gasoline componènts of ~he products of the cracking operation have as high an octane number as possible.
It is known in the art that catalytic activity of solid contact catalysts may be enhanced by incorporating into the catalyst acid activators, such as fluorine. See generally Choudhary, Ind. Eng. Chem., Prod. Res. Div~, 16, 12 (1977). Prior to the advent of zeolite cracking catalysts, amorphous-type catalysts, for example, alumina and silica-alumina catalysts, were enhanced by treatment with various fluorine compounds under anhydrous or aqueous conditions. For example, U.S. Patent Nos.
Background of the_Invention This invention relates to an improved cracking catalyst.
More particularly, this invention relates to a composite of a zeolite-containing cracking catalyst and a fluorided reforming catalyst.
Cracking reactionc are used to convert heavier hydro-carbons into products having a lower average molecular weight useful in the production of motor fuels. Cracked products generally have a lower octane number than that , desir~d for gasoline blending components. Catalytic reforming is a process which increases the octane number of cracked products by converting low octane hydrocarbons, such as paraffins and naphthenes, into aromatic-rich products. To minimize further processing, such as catalytic reforming operations, it is desirable that the gasoline componènts of ~he products of the cracking operation have as high an octane number as possible.
It is known in the art that catalytic activity of solid contact catalysts may be enhanced by incorporating into the catalyst acid activators, such as fluorine. See generally Choudhary, Ind. Eng. Chem., Prod. Res. Div~, 16, 12 (1977). Prior to the advent of zeolite cracking catalysts, amorphous-type catalysts, for example, alumina and silica-alumina catalysts, were enhanced by treatment with various fluorine compounds under anhydrous or aqueous conditions. For example, U.S. Patent Nos.
2,336,165 (Connolly), 2,483,131 (Garrison), 2,694,674 tStarr et al.), and 2,848,380 (Thomas) all describe the preparation of improved alumina and silica-alumina crack-ing catalysts by treatment with various fluorine compounds.
, ~7'7~-2-More recent patents disclose fluorided reforming and dual-function catalysts. Some of these catalysts contain a zeolite component. For example, U.S. Patent No.
4,191,638 (Plank et al.) describes a reforming catalyst which comprises a mixture of a zeolite and a conventional reforming catalyst, such as a metallic reforming catalyst.
Both the zeolite component and the metallic reforming catalyst contain a halogen component, ~uch as chloride or fluoride. The patent does not disclose a method for fluoriding the metallic reforming catalyst.
U.S~ Patent No. 3,702,312 (Wilson) discloses a dual-function catalyst comprising a fluoxided zeolite and a hydrogenative metal component prepared by a sequence of steps to incorporate f luorine into the crystalline structure of the zeolite. Attempts to fluoride crystalline alumino-silicate by conventional halide impregnation with an aqueous solution of hydrogen fluoride destroyed the crystalline stxucture of the zeolite.
U.S. Patent Nos. 4,097,368 (Hayes) and 4,098,679 (Hayes) describe dual-function composite catalysts comprising a combination of three or four metals on a porous carrier which may comprise a zeolite. Halogen may be added to the carrier material in any suitable manner, for example, by treatment of the carrier material with an aqueous solution of hydrogen f luoride.
:
The present invention relates to a fluorided cracking catalyst comprising a physical mixture of a fluorided reforming catalyst and a zeolite-containing cracking catalyst. The improved cracking catalyst of the present invention is prepared by treating a metallic reforming catalyst with an aqueous solution containing a fluorine ~, .
.
~1~7'~
compound, and then physically mixing the fluorided reformlng catalyst with a zeolite-containing cracking catalyst. Use of the catalyst of this invention in cracking reactions yields higher octane products than can be obtained with conventional cracking catalyst.
Summary and Detailed Description of the Invention According to the present invention there is provided an improved cracking catalyst comprising a composite of zeolite, a carrier material and about 5 to about 10 percent by weight of a metallic reforming catalyst comprising 0.01 to about 2 percent by weight of platinum on an alumina support, said re-forming catalyst also comprising between about 0.5 to about 5 percent by weight of fluorine, said improved cracking catalyst having been prepared by treating the platinum containing metallic reforming catalyst with an aqueous solution containing a fluorine compound dissolved therein, followed by drying and cal-cining the resulting fluorided reforming catalyst and physically mixing the fluorided reforming catalyst with a zeolite-containing cracking catalyst.
In one embodiment of the invention, the zeolite-containing cracking catalyst is itself fluorided. In another embodiment of the invention, the zeolite-containing catalyst is unf]uorided.
The metallic reforming catalyst of the present invention comprises about 0.01 to about 2 percent by weight of platinum on an alumina support, preferably gamma alumina. Optionally, the reforming catalyst also contains about 0.01 to about 5 percent by weight of a metal selected from the group consisting of germanium, tin, and rhenium. A reforming catalyst containing 0.375 percent by weight of Pt and 0.25 percent by weight of Ge on a gamma alum-ina support commercially sold under the trade name of UOP R-22 by UOP, Inc., Des Plaines, Illinois, is suitable.
~ 7'7~ 3 Although the pracise form in which fluorine combines with ~he reforming catalyst i5 not entirely known, it is customary in the art to refer to the fluorine as being present in the form of fluoride. The present invention, however, is not limited to fluorides but embraces all forms of fluorine incorporated into the metallic reform-ing catalyst when prepared as described above.
Hydrogen fluoride is the preferred fluoriding agent for this invention although other fluorine compounds, such as ammonium fluoride, ammonium bifluoride, boron trifluoride, ammonium fluoborate, and ammonium fluosilicate, are also suitable. Fluoriding of the metallic reforming catalyst may be accomplished by an incipient wetness impregnation technique carried out a~ 32F. Other fluoriding methods, especially impregnation methods, may also be suitable.
Following the fluoriding step, the metallic reforming catalyst should contain about 0.5 to about 5 percent by weight of fluoride, most preferably, about 1 percent by weight. The fluorided metallic reforming catalyst is then dried a~ a temperature of about 200F to about 600F, preferably about 300F, for about 2 to about 24 hours.
The fluorided metallic reforming catalyst is then calcined for about 0.5 to about 10 hours at a temperature of about 700F to about 1100F, preferably at about 1000F.
Finally, the fluorided reforming catalyst is physically mixed with a zeolite-containing cracking catalyst.
.
~ 30 The zeolite which may be used in the practice of this i invention may be a naturally occurring or synthetically prepaxed Y zeolite. Preferably, the zeolite is associated with an alumina-silica matrix that may contain free alumina or free silica. The zeolite-containing cracking catalyst which is used in the practices of this invention may be fluorided. Fluoriding may be accomplished by any known technique, such as by a technique similar to the one in accordance with this invention.
Cracking is achieved by placing a hydrocarbon charge stock in contact with the improved cracking catalyst described herein. The contacting may be accomplished by any conventional technique, for example, by using the catalyst in a fixed bed system, a moving bed system, a fluidized bed system, or in a batch type operation.
The conditions under which the improved cracking catalyst may be used are those customarily used in the art for cracking reactions. Thus, temperatures from about 850F to about 1025~F and pressures of about 10 to about 25 psig are ordinarily usedL
`:
The following examples are presented to illustrate more fully the nature and manner of practicing the invention.
` Examples , An improved cracking catalyst was prepared in accordance with the present invention. Catalyst A comprised a metallic reforming catalyst having 0.375 percent by weight platinum and 0.25 percent by weight germanium on a gamma alumina support. Catalyst A was ground to 50 to 200 mesh particle size and was then fluorided with aqueous hydrogen fluoride by an incipient wetness impreg-nation technique. The aqueous solution containing 0.014gm of HF per cc was prepared by diluting 4 gm of concen-trated HF acid with 136 ml of distilled water. 70 ml of the HF solution was added to 100 gm of Catalyst A at 32F with mixing in order to distribute the solution on the catalyst. The nominal loadiny of the fluoride was ~ 6-1 percent by weight. After contacting Catal~st A with the HF solution ~or periods o~ either 3 or 1~ hours, moisture was removed by drying the catalyst at 30QP~
The fluor;ded reforming catalyst was tfien ca`lci`ned at 1000F for three hours.
:;
In examples 2 through 6, Catalyst A was physically ~ixed with a commercial zeolite-contaïning cracki~ catalyst, Catalyst B. Catalyst B compris~d a Y zeolite in an alumina-silica matrix. Catalyst B had previously been used in a commercial cracking operation and had the following characteristics: surface area = 98 m2/gm, pore volume = 0.36 cc/gm, density (loose) = 48.0 lbs/cu. ft., alumina = 38.1 wt.%, average par~icle size = 55 microns.
~ In examples 5 and 6, Catalyst B was fluorided by the ; method described above prior to mixing with Catalyst A.
Nominal loading of Catalyst B with fluoride was 1 -~ percent by weight. Table 1 sets out the catalysts used ~ 20 in the examples, the period of contact with the fluoriding ;~; solution, and the calcining conditions.
:
HF Contact Calcination Calcination 25 ~ Catalyst Tlme, hrs. ~ Time, hrs.
2 10%A~ 0 - -90%B 0 - -
, ~7'7~-2-More recent patents disclose fluorided reforming and dual-function catalysts. Some of these catalysts contain a zeolite component. For example, U.S. Patent No.
4,191,638 (Plank et al.) describes a reforming catalyst which comprises a mixture of a zeolite and a conventional reforming catalyst, such as a metallic reforming catalyst.
Both the zeolite component and the metallic reforming catalyst contain a halogen component, ~uch as chloride or fluoride. The patent does not disclose a method for fluoriding the metallic reforming catalyst.
U.S~ Patent No. 3,702,312 (Wilson) discloses a dual-function catalyst comprising a fluoxided zeolite and a hydrogenative metal component prepared by a sequence of steps to incorporate f luorine into the crystalline structure of the zeolite. Attempts to fluoride crystalline alumino-silicate by conventional halide impregnation with an aqueous solution of hydrogen fluoride destroyed the crystalline stxucture of the zeolite.
U.S. Patent Nos. 4,097,368 (Hayes) and 4,098,679 (Hayes) describe dual-function composite catalysts comprising a combination of three or four metals on a porous carrier which may comprise a zeolite. Halogen may be added to the carrier material in any suitable manner, for example, by treatment of the carrier material with an aqueous solution of hydrogen f luoride.
:
The present invention relates to a fluorided cracking catalyst comprising a physical mixture of a fluorided reforming catalyst and a zeolite-containing cracking catalyst. The improved cracking catalyst of the present invention is prepared by treating a metallic reforming catalyst with an aqueous solution containing a fluorine ~, .
.
~1~7'~
compound, and then physically mixing the fluorided reformlng catalyst with a zeolite-containing cracking catalyst. Use of the catalyst of this invention in cracking reactions yields higher octane products than can be obtained with conventional cracking catalyst.
Summary and Detailed Description of the Invention According to the present invention there is provided an improved cracking catalyst comprising a composite of zeolite, a carrier material and about 5 to about 10 percent by weight of a metallic reforming catalyst comprising 0.01 to about 2 percent by weight of platinum on an alumina support, said re-forming catalyst also comprising between about 0.5 to about 5 percent by weight of fluorine, said improved cracking catalyst having been prepared by treating the platinum containing metallic reforming catalyst with an aqueous solution containing a fluorine compound dissolved therein, followed by drying and cal-cining the resulting fluorided reforming catalyst and physically mixing the fluorided reforming catalyst with a zeolite-containing cracking catalyst.
In one embodiment of the invention, the zeolite-containing cracking catalyst is itself fluorided. In another embodiment of the invention, the zeolite-containing catalyst is unf]uorided.
The metallic reforming catalyst of the present invention comprises about 0.01 to about 2 percent by weight of platinum on an alumina support, preferably gamma alumina. Optionally, the reforming catalyst also contains about 0.01 to about 5 percent by weight of a metal selected from the group consisting of germanium, tin, and rhenium. A reforming catalyst containing 0.375 percent by weight of Pt and 0.25 percent by weight of Ge on a gamma alum-ina support commercially sold under the trade name of UOP R-22 by UOP, Inc., Des Plaines, Illinois, is suitable.
~ 7'7~ 3 Although the pracise form in which fluorine combines with ~he reforming catalyst i5 not entirely known, it is customary in the art to refer to the fluorine as being present in the form of fluoride. The present invention, however, is not limited to fluorides but embraces all forms of fluorine incorporated into the metallic reform-ing catalyst when prepared as described above.
Hydrogen fluoride is the preferred fluoriding agent for this invention although other fluorine compounds, such as ammonium fluoride, ammonium bifluoride, boron trifluoride, ammonium fluoborate, and ammonium fluosilicate, are also suitable. Fluoriding of the metallic reforming catalyst may be accomplished by an incipient wetness impregnation technique carried out a~ 32F. Other fluoriding methods, especially impregnation methods, may also be suitable.
Following the fluoriding step, the metallic reforming catalyst should contain about 0.5 to about 5 percent by weight of fluoride, most preferably, about 1 percent by weight. The fluorided metallic reforming catalyst is then dried a~ a temperature of about 200F to about 600F, preferably about 300F, for about 2 to about 24 hours.
The fluorided metallic reforming catalyst is then calcined for about 0.5 to about 10 hours at a temperature of about 700F to about 1100F, preferably at about 1000F.
Finally, the fluorided reforming catalyst is physically mixed with a zeolite-containing cracking catalyst.
.
~ 30 The zeolite which may be used in the practice of this i invention may be a naturally occurring or synthetically prepaxed Y zeolite. Preferably, the zeolite is associated with an alumina-silica matrix that may contain free alumina or free silica. The zeolite-containing cracking catalyst which is used in the practices of this invention may be fluorided. Fluoriding may be accomplished by any known technique, such as by a technique similar to the one in accordance with this invention.
Cracking is achieved by placing a hydrocarbon charge stock in contact with the improved cracking catalyst described herein. The contacting may be accomplished by any conventional technique, for example, by using the catalyst in a fixed bed system, a moving bed system, a fluidized bed system, or in a batch type operation.
The conditions under which the improved cracking catalyst may be used are those customarily used in the art for cracking reactions. Thus, temperatures from about 850F to about 1025~F and pressures of about 10 to about 25 psig are ordinarily usedL
`:
The following examples are presented to illustrate more fully the nature and manner of practicing the invention.
` Examples , An improved cracking catalyst was prepared in accordance with the present invention. Catalyst A comprised a metallic reforming catalyst having 0.375 percent by weight platinum and 0.25 percent by weight germanium on a gamma alumina support. Catalyst A was ground to 50 to 200 mesh particle size and was then fluorided with aqueous hydrogen fluoride by an incipient wetness impreg-nation technique. The aqueous solution containing 0.014gm of HF per cc was prepared by diluting 4 gm of concen-trated HF acid with 136 ml of distilled water. 70 ml of the HF solution was added to 100 gm of Catalyst A at 32F with mixing in order to distribute the solution on the catalyst. The nominal loadiny of the fluoride was ~ 6-1 percent by weight. After contacting Catal~st A with the HF solution ~or periods o~ either 3 or 1~ hours, moisture was removed by drying the catalyst at 30QP~
The fluor;ded reforming catalyst was tfien ca`lci`ned at 1000F for three hours.
:;
In examples 2 through 6, Catalyst A was physically ~ixed with a commercial zeolite-contaïning cracki~ catalyst, Catalyst B. Catalyst B compris~d a Y zeolite in an alumina-silica matrix. Catalyst B had previously been used in a commercial cracking operation and had the following characteristics: surface area = 98 m2/gm, pore volume = 0.36 cc/gm, density (loose) = 48.0 lbs/cu. ft., alumina = 38.1 wt.%, average par~icle size = 55 microns.
~ In examples 5 and 6, Catalyst B was fluorided by the ; method described above prior to mixing with Catalyst A.
Nominal loading of Catalyst B with fluoride was 1 -~ percent by weight. Table 1 sets out the catalysts used ~ 20 in the examples, the period of contact with the fluoriding ;~; solution, and the calcining conditions.
:
HF Contact Calcination Calcination 25 ~ Catalyst Tlme, hrs. ~ Time, hrs.
2 10%A~ 0 - -90%B 0 - -
3 10%A(1%HF)~ 16 1000 3 ~ ' TABLE 1 (cont'd.) HF Contact Calcination Calcination Example Catalyst Time, hrs. Temp., F Time, hrs.
4 10%A(1%HF)+ 3 1000 3 - %B ~ _ 10%Atl%HF)~16 1000 3 90%B(l~HF) 3 1100 16 6 10%A(1%HF)+ 3 1000 3 90%B(l~HF) 16 1000 3 Tests were conducted in a pulsed feed, fixed bed micro-xeactor unit designed to evaluate cracking catalysts.
. The tests were conducted at 900F with a hydrocarbon - charge stock having the following properties:
~ravity, API 36.7 Viscosity at 100F, cs. 4.3 Vis~osity at 210 DF, CS . 1 . 5 25 Pour Point, F Z0 Sulfux wt.% 0.08 Conradson Carbon Residue, wt.~ None Bromine No. 3 ASTM Distillation (D-2887) F
Initial Boiling Point 318 : - 5% 435 10%. 465 20% 498 30% 522 40% 543 ~' 50% 566 TABLE 2 (cont'd.~
60% S86 70% 610 80% 645 90% 692 95% 735 End Point 856 In each of the test runs of the examples~ 4 grams of catalyst were contacted with 1~3 grams of the test feed during a 75 second pulse at 1 atmosphere pressure. The catalyst to oil weight ratio was 3 and the Weight Hourly - Space Velocity (WHSV) was 16.
The liquid products from the tests were collected in a receiver cooled in an ice-water bath and analyzed on a chromatograph. Conversion, naphtha and gas oil were determined by ASTM Method D-2887-73. The naphtha was the liquid product fraction with a boiling point below 421F. The gas oil was the fraction with a boiling point above 421F. Conversion was calculated as the percentage of the original charge with a boiling point - below 421F $ollowing cracking.
Research Octane Numbers (RON) were calculated by analyzing the naphtha fraction into specific groups and assigning an octane factor to each group. The octane numbers of the products are based upon the amount of each specific group in the product and the octane factor assigned to each group. See P. C. Anderson~ J. M. Sharkey, and R. P.
Walsh, J. Inst. Pet., 58, 83 (1972) .
_g_ ~i~ferences between similar preparations are attributed to the different fluoriding conditions shown in Table 1.
For instance, the contact period was 16 hours for example 3 and 3 hours for example 4. Results of the test runs are summarized in Table 3 below.
~ t'7~
~ ~ o u~ ~ ~r o oo ~ a .
o 1~ c~
~i ~ t` ~ o ~ a: ~ +
o'P d~
o o a~ Lno ~ I` o ~3 co co :` ~ o +
.. ~ ~, .~ +
:. _ :~ m ~) r-l O ~ G _I O O
+
O
~~ ~ t~cn o In ~g ~r co o o o a~ .
O C~ Q l` ~D
N ~r O W ~ i~
.o ~ ~P
~1 0 ~ Z ~ S o o X ~ z ~ ~0 ~ P P
1~1 00 11~ 0 ~ /~
c~ Z ~ a t~ 3 z 3 ~ 3 '7~:~t) The test runs demonstrate that a fluorided metallic reforming catalyst mixed with a zeolite-containing cracking catalyst yields a higher octane product than is produced by unfluorided catalysts. A simple mixture of unfluorided A and unfluorided B produces a higher octane product than unfluorided B alone. However, the : best results are produced by a composite of fluorided A
and either fluorided or unfluorided B. In most cases, the fluorided composites of A and B increase the octane number more than ~wice as much as the unfluorided com-posite of A and B. The improvement in octane number demonstrated in these test runs may be attributed to the enhanced aromatization and dehydrogenation activity of fluorided reforming catalyst.
While the invention has been described by reference to specific examples, these examples were for purposes of illustration only. They should not be construed to limit the spirit or scope of the invention.
. The tests were conducted at 900F with a hydrocarbon - charge stock having the following properties:
~ravity, API 36.7 Viscosity at 100F, cs. 4.3 Vis~osity at 210 DF, CS . 1 . 5 25 Pour Point, F Z0 Sulfux wt.% 0.08 Conradson Carbon Residue, wt.~ None Bromine No. 3 ASTM Distillation (D-2887) F
Initial Boiling Point 318 : - 5% 435 10%. 465 20% 498 30% 522 40% 543 ~' 50% 566 TABLE 2 (cont'd.~
60% S86 70% 610 80% 645 90% 692 95% 735 End Point 856 In each of the test runs of the examples~ 4 grams of catalyst were contacted with 1~3 grams of the test feed during a 75 second pulse at 1 atmosphere pressure. The catalyst to oil weight ratio was 3 and the Weight Hourly - Space Velocity (WHSV) was 16.
The liquid products from the tests were collected in a receiver cooled in an ice-water bath and analyzed on a chromatograph. Conversion, naphtha and gas oil were determined by ASTM Method D-2887-73. The naphtha was the liquid product fraction with a boiling point below 421F. The gas oil was the fraction with a boiling point above 421F. Conversion was calculated as the percentage of the original charge with a boiling point - below 421F $ollowing cracking.
Research Octane Numbers (RON) were calculated by analyzing the naphtha fraction into specific groups and assigning an octane factor to each group. The octane numbers of the products are based upon the amount of each specific group in the product and the octane factor assigned to each group. See P. C. Anderson~ J. M. Sharkey, and R. P.
Walsh, J. Inst. Pet., 58, 83 (1972) .
_g_ ~i~ferences between similar preparations are attributed to the different fluoriding conditions shown in Table 1.
For instance, the contact period was 16 hours for example 3 and 3 hours for example 4. Results of the test runs are summarized in Table 3 below.
~ t'7~
~ ~ o u~ ~ ~r o oo ~ a .
o 1~ c~
~i ~ t` ~ o ~ a: ~ +
o'P d~
o o a~ Lno ~ I` o ~3 co co :` ~ o +
.. ~ ~, .~ +
:. _ :~ m ~) r-l O ~ G _I O O
+
O
~~ ~ t~cn o In ~g ~r co o o o a~ .
O C~ Q l` ~D
N ~r O W ~ i~
.o ~ ~P
~1 0 ~ Z ~ S o o X ~ z ~ ~0 ~ P P
1~1 00 11~ 0 ~ /~
c~ Z ~ a t~ 3 z 3 ~ 3 '7~:~t) The test runs demonstrate that a fluorided metallic reforming catalyst mixed with a zeolite-containing cracking catalyst yields a higher octane product than is produced by unfluorided catalysts. A simple mixture of unfluorided A and unfluorided B produces a higher octane product than unfluorided B alone. However, the : best results are produced by a composite of fluorided A
and either fluorided or unfluorided B. In most cases, the fluorided composites of A and B increase the octane number more than ~wice as much as the unfluorided com-posite of A and B. The improvement in octane number demonstrated in these test runs may be attributed to the enhanced aromatization and dehydrogenation activity of fluorided reforming catalyst.
While the invention has been described by reference to specific examples, these examples were for purposes of illustration only. They should not be construed to limit the spirit or scope of the invention.
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An improved cracking catalyst comprising a composite of zeolite, a carrier material and about 5 to about 10 percent by weight of a metallic reforming catalyst comprising 0.01 to about 2 percent by weight of platinum on an alumina support, said reforming catalyst also comprising between about 0.5 to about 5 percent by weight of fluorine, said improved cracking catalyst having been prepared by treating the platinum containing metallic reforming catalyst with an aqueous solution containing a fluorine compound dissolved therein, followed by drying and calcining the resulting fluorided reforming catalyst and physically mixing the fluorided reforming catalyst with a zeolite-containing cracking catalyst.
2. An improved cracking catalyst in accordance with Claim 1 wherein said carrier material is alumina-silica containing free alumina.
3. An improved cracking catalyst in accordance with Claim 2 wherein said free alumina is gamma alumina.
4. An improved cracking catalyst in accordance with Claim 1 wherein said fluorine compound is selected from a group consisting of hydrogen fluoride, ammonium fluoride, ammonium bifluoride, boron trifluoride, ammonium fluoborate, and ammonium fluosilicate.
5. An improved cracking catalyst in accordance with Claim 4 wherein said fluorine compound is hydrogen fluoride.
6. An improved cracking catalyst in accordance with Claim 1 wherein said zeolite is a Y zeolite.
7. An improved cracking catalyst in accordance with claim 1 wherein said zeolite-containing cracking catalyst is fluorided by treatment with an aqueous solution containing a fluorine compound.
8. An improved cracking catalyst in accordance with claim 1 wherein said metallic reforming catalyst also contains a cataly-tically effective amount of a metal selected from the group consisting of tin, germanium, and rhenium on said support.
9. An improved cracking catalyst in accordance with claim 1 or 8 wherein said support is gamma alumina.
10. An improved cracking catalyst in accordance with claim 1 wherein said fluorided reforming catalyst contains about 1 percent by weight of fluoride.
11. In a process where hydrocarbons are cracked by contact with a cracking catalyst under hydrocarbon cracking conditions, the improvement which comprises contacting said hydrocarbons with a cracking catalyst in accordance with claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000397298A CA1177810A (en) | 1982-03-01 | 1982-03-01 | Physical mixture of catalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000397298A CA1177810A (en) | 1982-03-01 | 1982-03-01 | Physical mixture of catalysts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1177810A true CA1177810A (en) | 1984-11-13 |
Family
ID=4122186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000397298A Expired CA1177810A (en) | 1982-03-01 | 1982-03-01 | Physical mixture of catalysts |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1177810A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0373741A1 (en) * | 1988-12-16 | 1990-06-20 | Exxon Research And Engineering Company | Wax isomerization process using a catalyst with small particles and low fluoride content. |
| US4992159A (en) * | 1988-12-16 | 1991-02-12 | Exxon Research And Engineering Company | Upgrading waxy distillates and raffinates by the process of hydrotreating and hydroisomerization |
-
1982
- 1982-03-01 CA CA000397298A patent/CA1177810A/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0373741A1 (en) * | 1988-12-16 | 1990-06-20 | Exxon Research And Engineering Company | Wax isomerization process using a catalyst with small particles and low fluoride content. |
| US4992159A (en) * | 1988-12-16 | 1991-02-12 | Exxon Research And Engineering Company | Upgrading waxy distillates and raffinates by the process of hydrotreating and hydroisomerization |
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