Catalyst compositions
Catalytic compositions comprising up to about 50 weight percent ZSM-5 zeolite dispersed in an attrition resistant, porous inorganic oxide matrix selected from silica-alumina cogels, silica, alumina and silica alumina sol bound clay. The compositions are combined with zeolitic containing catalytic cracking catalysts and used to convert residual and/or gas oil hydrocarbon feedstocks into lower molecular weight products that include high octane gasoline fractions.
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Having described the basic aspects of the invention, the following examples are given to illustrate specific embodiments thereof.
EXAMPLE IAn octane enhancing catalyst was prepared which contained 25% ZSM-5, 20% SiO.sub.2.Al.sub.2 O.sub.3 sol binder, 55% kaolin (oxide basis) as follows:
1. A 25% solids slurry was prepared with 5.0 pounds of dry oxide basis ZSM-5 in sufficient water to constitute the desired 25% slurry.
2. The slurry in "1" above was acidified to 4.0-4.5 pH using 20% H.sub.2 SO.sub.4.
3. The silica-alumina sol was prepared
containing 4.0 lbs of SiO.sub.2 by reacting continuously a stream of 18.degree. Be' sodium silicate at 70.degree. F. in a centrifugal mix pump with 70.degree. F. acid alum containing 35 g/l Al.sub.2 O.sub.3 and 235 g/l H.sub.2 SO.sub.4 at a discharge pH of 3.0-3.1.
4. The silica-alumina sol was collected in a 10 gallon vessel under a high shear mixer.
5. The slurry in "2" was added and mixed with the silica-alumina sol in "4".
6. To the slurry in "5" was added with mixing 13.0 lbs of dry powered kaolin. The kaolin was allowed to fully disperse to a smooth slurry.
7. The slurry from "6" was spray dried to give a 60-70 micron average particle size at 12-16% moisture using a wheel atomized parallel flow 10' diameter spray dryer.
8. The spray dried catalyst is reslurried in 120.degree.-150.degree. F. water containing 0.1 lb ammonium sulfate per pound of oxide basis catalyst.
9. The catalyst slurry from "8" is dewatered and rinsed first with a 5% ammonium sulfate solution at 120.degree. F. and then with sufficient 150.degree. F. water to rinse the cake sulfate free.
10. The catalyst cake from "9" is oven dried at 400.degree. to 12-16% H.sub.2 O to obtain the desired product.
EXAMPLE IIAn octane enhancing catalyst was prepared which contained 25% ZSM-5, 78% silica-alumina cogel (25% SiO.sub.2, 75% Al.sub.2 O.sub.3) as follows:
1. A ZSM-5 slurry was prepared as in Example I.1. containing 5.0 lbs dry basis.
2. A silica-alumina cogel was prepared which contained 11.25 lbs Al.sub.2 O.sub.3 and 3.75 lbs SiO.sub.2 by continuously reacting a 4% SiO.sub.2 sodium silicate solution in a centrifugal mix pump with 4% Al.sub.2 O.sub.3 1.4 mole ratio sodium aluminate and further reacting this product in a second continuous mixer with acid alum (35 g/l Al.sub.2 O.sub.3, 235 g/l H.sub.2 SO.sub.4) to obtain a cogel slurry having a 10.3-10.5 pH. All solutions were maintained at 80.degree.-90.degree. F.
3. The slurry from "2" was collected and combined with the slurry from "1" and mixed well.
4. The slurry from "3" was dewatered on a belt filter.
5. The dewatered cake from "4" was reslurried with water to facilitate pumping.
6. The slurry from "5" was spray dried, washed, and dried as in Example I, steps 7, 8, 9 and 10.
EXAMPLE IIIAn octane enhancing catalyst was prepared which contained 25% ZSM-5, 15% Al.sub.2 O.sub.3 binder from aluminum chlorhydrol, 60% kaolin (dry oxide basis) as follows:
1. A ZSM-5 slurry containing 5.0 lbs dry basis was prepared as in Example I.1.
2. The slurry in "1" was acidified to 4.0-4.3 pH with 10% HCl.
3. A slurry was prepared by adding first 13.0 lbs of aluminum chlorhydrol containing 3.0 lbs Al.sub.2 O.sub.3 to a 10 gallon bucket with a high shear agitator and then adding the slurry from "2".
4. To the slurry in "3" was added 14.1 lbs of dry powdered kaolin and allowed to mix until smooth about 5 minutes.
5. The slurry from "4" was spray dried as in Example I, step 7.
6. A portion of the catalyst from "5" was activated for 2 hours at 1000.degree. F. in a muffle furnace to remove volatiles and fix the binder.
EXAMPLE IVTo illustrate the octane increasing properties of the additive compositions of the present invention, an additive composition of the type described in Example I (Additive 0) was combined with a commercially available FCC cracking catalyst (Octacat) which comprises about 40 percent Ultrastable Type Y zeolite combined with asilica-alumina sol binder and kaolin matrix and used to catalytically crack gas oil having a boiling range of about 400.degree. to 1000.degree. F. A summary of the test results including "Base Case" results obtained using Octacat without Additive 0 is set forth in Table A below:
TABLE A
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BASE CASE
TEST #1 TEST #2
OCTACAT
OCTACAT/ADDITIVE "O"
OCTACAT/ADDITIVE
__________________________________________________________________________
"O"
OPERATIONS SUMMARY
CATALYST
Gas Oil Feed Rate, BPD
5551 5514 5500
Slurry Recycle, BPD
750 600 750
Combined Feed Temp., .degree.F.
510 506 431
Reactor Temp., .degree.F.
920 920 928
Pegen. Dense Temp., .degree.F.
1290 1275 1264
Regen. Dilute Temp., .degree.F.
1310 1300 1287
Flue Gas Temp., .degree.F.
1290 1258 1320
Est. Additive "O"in Inv., wt. %
0 6 5
Equilibrium Microactivity
65 60.sup.(1) 62
YIELD SUMMARY
Conversion, vol. %
69.0 64.7.sup.(1) 68.4
YIELDS
C.sub.2 minus, wt. %
1.7 1.2 1.2
C.sub.3, vol. % 1.4 1.1 2.0
C.sub.3 =, vol. %
5.8 6.9 6.6
iC.sub.4, vol. % 3.7 2.8 3.4
nC.sub.4, vol. % 0.5 0.9 1.1
C.sub.4 =, vol. %
7.0 7.9 8.3
C.sub.5 + gasoline (430.degree. F. E.P.) vol. %
57.3 53.1 55.4
Octane Number, Research
90.7 93.0 92.6
Total Gasoline + 77.8 76.8 79.2
Potential Alkylate, vol. %
LCO (650.degree. F. E.P.), vol. %
17.6 19.1 17.3
Slurry, vol. % 13.4 16.2 14.3
Coke, wt. % 5.1 5.0 5.7
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.sup.(1) The activity loss, which resulted from lower than typical fresh
catalyst additions, was responsible for the lower conversion.
The above examples clearly indicate that the catalytic compositions of the present invention which comprise octane enhancing FCC additives containing ZSM-5 zeolite may be used to produce significantly improved yields of high octane gasoline fractions.
Claims
1. A catalytic cracking composition which comprises a separate particulate octane-enhancing additive component comprising ZSM-5 dispersed in an inorganic oxide matrix, and a particulate Y zeolite containing catalytic cracking catalyst component, comprising 15 to 60 percent by weight ultrastable y zeolite dispersed in an inorganic oxide matrix.
2. The composition of claim 1 wherein the inorganic oxide matrix for said additive component and said cracking catalyst component is selected from the group consisting of silica-alumina cogels, silica, alumina, silica-alumina sol bound clay.
3. The composition of claim 1 wherein the matrix of said ZSM-5 component comprises alumina sol and clay containing less than about 0.10 percent by weight Na.sub.2 O.
4. The composition of claim 1 wherein the ZSM-5 component comprises from about 5 to 50 weight percent of said composition.
5. The composition of claim 1 wherein said composition has an average particle size ranging from about 50 to 85 micrometer.
6. The composition of claim 1 wherein said matrix possesses a surface area of from about 20 to 400 m.sup.2 /g and a pore volume of from about 0.15 to 0.60 cc/g.
Type: Grant
Filed: Jul 31, 1987
Date of Patent: Mar 1, 1988
Assignee: W. R. Grace & Co. (New York, NY)
Inventor: John A. Rudesill (Baltimore, MD)
Primary Examiner: John F. Terapane
Assistant Examiner: J. E. Thomas
Attorney: Arthur P. Savage
Application Number: 7/81,554
International Classification: B01J 2906; B01J 2908; C10G 1105;
