CATALYST COMPOSITION FOR ENHANCING YIELD OF OLEFINS IN FLUID CATALYTIC CRACKING PROCESS (FCC)

Abstract

The present invention provides a catalyst composition comprising rare earth exchanged USY zeolite (REUSY); pentasil zeolite; phosphorous compound; clay, silica, alumina, and spinel to enhance the catalytic activity and selectivity for light olefins in FCC operation conditions. The present invention also provides a process for the preparation of Light olefin enhancing catalyst composition with high propylene yield and coke selectivity.

Claims

1. A composite catalyst composition, comprising: about 10-25 wt % rare earth exchanged USY zeolite (REUSY); about 5-20 wt % stabilized pentasil zeolite; about 2-8 wt % phosphorous compound; about 20-45 wt % clay; about 5-25 wt % silica; about 10-35 wt % alumina; and about 0.5 to 3 wt % mixed metal oxide selected from a group consisting of at least one of Group XI and XIII metals, and the wt % being based on total weight of the catalyst composition.

2. The composition as claimed in claim 1, wherein the mixed metal oxide is a spinel.

3. The composition as claimed in claim 1, wherein the mixed metal oxide comprises of oxides of metals selected from at least one of copper, nickel, zinc, aluminium, and mixtures thereof.

4. The composition as claimed in claim 1, wherein the pentasil zeolite is selected from a group consisting of ZSM-5, ZSM-11, mordenite, and beta.

5. The composition as claimed in claim 1, wherein the REUSY comprises of 0.1 to 5 wt % of rare earth oxide.

6. The composition as claimed in claim 1, wherein the phosphorous compound is sourced from a group consisting of at least one of mono-ammonium phosphate, di-ammonium phosphate, and phosphoric acid.

7. The composition as claimed in claim 1, wherein the clay is selected from a group consisting of at least one of bentonite, attapulgite, and kaolinite.

8. The composition as claimed in claim 1, wherein the silica is selected from at least one of sodium and ammonium stabilized colloidal silica with silica content varying in the range of 20-50 wt %.

9. The composition as claimed in claim 1, wherein the alumina is selected from a group consisting of pseudoboehmite, boehmite, aluminum trihydrate, and gamma.

10. The composition as claimed in claim 1, wherein the catalyst composition enhances light olefin yield by about 1.5%, selectivity of propylene in LPG in the range of about 39-52%, retention of gasoline in the range of about 19-22 wt % and retention of diesel in the range of about 23-26 wt %.

11. The composition as claimed in claim 1, wherein the composition is suitable for at least one of fixed bed or fluid bed catalytic cracking operation.

12. The composition as claimed in claim 1, wherein the composite catalyst composition in the form of at least one of pellet, extrude, tablet, and microsphere.

13. A process for preparing a composite catalyst composition for selective catalytic cracking of heavy oils in petroleum processing industry, wherein the process comprises the steps of: (a) preparing a slurry of clay, alumina and phosphorous compound; (b) dispersing pentasil zeolite in the clay-alumina-phosphate slurry obtained in step (a) to obtain another slurry; (c) milling, spray drying, and calcining the slurry obtained in step (b) to obtain a zeolite-clay-phosphate powder; (d) preparing a binder comprising of at least one of alumina and polysilicate; (e) sequentially dispersing the zeolite-clay-phosphate powder, mixed metal oxide selected from a group consisting of at least one of Group XI and XIII metals, REUSY zeolite, and silica into the binder to obtain a precursor slurry; (f) milling and spray drying the precursor slurry to obtain a spray dried product; and (g) calcining the spray dried product to obtain composite catalyst composition.

14. The process as claimed in claim 13, wherein the REUSY zeolite is prepared by exchanging USY zeolite with salts of rare earth selected from a group consisting of at least one of hydroxides, chlorides, nitrates, sulphates, oxalates, carbonates, acetates, formats, and hydrates.

15. The process as claimed in claim 13, wherein the REUSY zeolite is prepared by exchanging USY zeolite with the salts of lanthanum rich compound.

16. The process as claimed in claim 13, wherein the spinel is prepared by dispersing Group XI metal oxide with alumina in demineralized water followed by spray drying and calcination.

17. A catalytic cracking process for selective conversion of heavy hydrocarbons to light olefins, wherein the process comprises of contacting the heavy hydrocarbons with a light olefin selective composite catalyst composition according to claim 1 at a temperature of about 510 to 530 C.; and wherein the catalyst enhances production of total olefin by about to 1-2 wt %, propylene selectivity by about 1-3%, gasoline yield by about 1-3 wt %, and diesel yield by about 1-2 wt %.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0038] While the invention is susceptible to various modifications and/or alternative processes and/or compositions, specific embodiment thereof has been shown by way of example in tables and will be described in detail below. It should be understood, however that it is not intended to limit the invention to the particular processes and/or compositions disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and the scope of the invention as defined by the appended claims.

[0039] The tables and protocols have been represented where appropriate by conventional representations, showing only those specific details that are pertinent to understanding the embodiments of the present invention so as not to obscure the disclosure with details that will be readily apparent to those of ordinary skill in the art having benefit of the description herein.

[0040] The following description is of exemplary embodiments only and is not intended to limit the scope, applicability or configuration of the invention in any way. Rather, the following description provides a convenient illustration for implementing exemplary embodiments of the invention. Various changes to the described embodiments may be made in the function and arrangement of the elements described without departing from the scope of the invention.

[0041] Any particular and all details set forth herein are used in the context of some embodiments and therefore should not be necessarily taken as limiting factors to the attached claims. The attached claims and their legal equivalents can be realized in the context of embodiments other than the ones used as illustrative examples in the description below.

[0042] Accordingly, the present invention provides a Fluid Catalytic Cracking (FCC) catalyst composition comprising REUSY, pentasil zeolite with a stabilizer, silica, alumina, clay and spinel. The catalyst composition of the present invention possesses enhanced catalytic activity and selectivity towards production of light end olefins in total yield of slabs. It may be known to those involved in preparation and performance evaluation of FCC catalysts along with pentasil zeolite, that every enhancement in yield of light end is associated with loss in yield of high value gasoline, heavy naphtha and LCO. Limitations encountered in conventional FCC catalysts and additive system is being addressed in catalyst composition described in the present invention.

[0043] According to a preferred feature, the present invention provides an olefin selective catalyst composition comprising: 10-25 wt % rare earth exchanged USY zeolite (REUSY); 5-20 wt % stabilized pentasil zeolite; 2-8 wt % phosphorous compound; 20-45 wt % clay; 5-25 wt % silica; 10-35 wt % alumina; and 0.5 to 3 wt % mixed metal oxide selected from a group consisting of at least one of Group XI and XIII metals, and the wt. % being based on total weight of the catalyst.

[0044] According to another preferred feature, the present invention provides a process for preparing a composite catalyst composition for selective catalytic cracking of heavy oils in petroleum processing industry, wherein the process comprises: [0045] (a) preparing a slurry of clay, alumina and phosphorous compound; [0046] (b) dispersing pentasil zeolite in the clay-alumina-phosphate slurry obtained in step (a) to obtain another slurry; [0047] (c) milling, spray drying, and calcining the slurry obtained in step (b) to obtain a zeolite-clay-phosphate powder; [0048] (d) preparing a binder comprising of at least one of alumina and polysilicate; [0049] (e) sequentially dispersing the zeolite-clay-phosphate powder, mixed metal oxide selected from a group consisting of at least one of Group XI and XIII metals, REUSY zeolite, and silica into the binder to obtain a precursor slurry; [0050] (f) milling and spray drying the precursor slurry to obtain a spray dried product; and [0051] (g) calcining the spray dried product to obtain composite catalyst composition.

[0052] According to another feature of the present invention, the process for preparing olefin selective catalyst composition comprises the following sequence of steps: [0053] (a) preparing a rare earth exchanged USY zeolite; [0054] (b) preparing binder, selected from alumina and polysilicate; [0055] (c) preparing spinel; [0056] (d) preparing stabilized pentasil zeolite; [0057] (e) sequentially dispersing clay, REUSY zeolite, stabilized pentasil zeolite and spinel in silica-alumina binder; [0058] (f) passing the precursor slurry through colloid mill to ensure homogenization of all the components of catalyst; [0059] (g) spray drying the slurry of step (f); and [0060] (h) calcining the spray dried product of step (g) and cooling to room temperature to produce composite catalyst composition.

[0061] According to another embodiment, the present invention provides a catalytic cracking process for selective conversion of heavy hydrocarbons to light olefins, wherein the process comprises of contacting the heavy hydrocarbons with a light olefin selective composite catalyst of the present invention at lower reaction temperature of around 510 to 530 C. In a preferred feature, the said process is carried out at around 529 C. The composite catalyst enhances production of total olefin by about 1-2 wt %, propylene selectivity by about 1-3%, gasoline yield by about 1-3 wt %, and diesel yield by about 1-2 wt %. In a preferred feature, the composite catalyst of the present invention enhances production of total olefin by about 1.5 wt %, propylene selectivity by about 2%, gasoline yield by about 2.5 wt %, and diesel yield by about 1.6 wt %.

[0062] According to a feature of the present invention, the clay is selected with diluents and fillers to have minimum impurities such as sodium, Fe.sub.2O.sub.3, TiO.sub.2, MgO, and quartz.

[0063] According to a feature of the present invention, the composite catalyst composition of the present invention is in the form of, but not limited to, at least one of pellet, extrude, tablet, or microsphere.

[0064] According to an aspect of the present invention, the catalyst composition is suitable for at least one of fixed bed or fluid bed catalytic cracking operation.

[0065] According to an aspect of the present invention, the REUSY is prepared by exchanging USY zeolite with salts of rare earth compounds. The salts are selected from at least one of hydroxides, chlorides, nitrates, sulphates, oxalates, carbonates, acetates, formates, and hydrates but free from sodium. In addition, the REUSY comprises of 0.1 to 5 wt % of rare earth oxide.

[0066] According to another aspect of the present invention, the REUSY is prepared preferably by exchanging USY zeolite with salts of Lanthanum rich compound.

[0067] According to yet another feature of the present invention, the silica is selected from at least one of sodium and ammonium stabilized colloidal silica with silica content varying in the range of 20-50 wt %. The alumina is selected from a group consisting of pseudoboehmite, boehmite, aluminum trihydrate, and gamma.

[0068] According to another feature of the present invention, the silica and alumina are taken in judicious weight, so that taken quantity is just enough to bind REUSY, clay, and spinel. According to another feature of the present invention, the pentasil zeolite is selected from a group consisting of ZSM-5, ZSM-11, mordenite, and beta. In addition, the phosphorous compound is sourced from a group consisting of at least one of mono-ammonium phosphate, di-ammonium phosphate, and phosphoric acid. The clay is selected from a group consisting of at least one of bentonite, attapulgite, and kaolinite.

[0069] According to yet another feature of the present invention, the mixed metal oxide may be selected from a group consisting of at least one of Group X, XI, XII, XIII metals. Preferably, the mixed metal oxide is selected from Groups XI and XIII metals.

[0070] According to another feature of the present invention, the mixed metal oxide comprises of metal selected from at least one of copper, nickel, zinc, aluminium, and mixtures thereof. More preferably, the mixed metal oxides comprises of copper and aluminium metals. In a preferred feature, the mixed metal oxide is copper aluminate.

[0071] According to an aspect of the present invention, the mixed metal oxide in the catalyst composition is a spinel. In a preferred feature, the spinel is a copper aluminate spinel.

[0072] A typical cracking process involves conversion of heavy hydrocarbons to desired olefins, especially light olefins in the presence of heterogeneous catalysts with large surface area and porosity. Metal oxides with solid supports, such as copper oxides are widely used as catalysts. However, the copper oxides are inherently crystalline in form of large crystals due to their cubic structure. This leads to lower dispersion of the copper oxide particles in catalysts and affects thermal and mechanical properties of the catalyst.

[0073] Therefore, the present invention utilizes copper aluminate spinel in the catalyst composition. The copper aluminate spinel in the catalyst composition enables effective exploitation of catalytic functionality of the copper aluminate spinel to control reaction network during cracking process, which further enhances yields of high value hydrocarbons in FCC.

[0074] Without being bound by the theory, the inventors of the present invention believe that the effective conversion of the heavy hydrocarbons to the desired olefins is attributed to the structural features of copper aluminate. The spinel structure of the copper aluminate enables effective dispersion of the active components of copper aluminate in the catalyst, thereby improving the overall surface area, porosity, and thermal/mechanical stability of the catalyst.

[0075] According to an aspect of the present invention, the spinel, preferably copper aluminate spinel, present in the catalyst composition helps to reduce the formation of coke with selectivity of propylene in LPG of around 40 wt % with minimum loss in Gasoline (around 21.6%), and distillate yield (around 25%) while cracking the heavier hydrocarbon molecules.

[0076] According to another aspect, the present invention provides the catalyst composition with improved light olefin selectivity in the range of 35-40%.

[0077] According to yet another aspect of the present invention, fine dispersion of the spinel at low concentrations in the range of 0.5 to 3 wt % in conjunction with other components such as alumina matrix, ZSM-5 zeolite and Re-USY results in the high distillate and gasoline yield.

[0078] According to a feature of the present invention, the spinel is prepared by co-precipitation method. More specifically, the spinel is prepared by dispersing Group XI metal oxide and alumina in demineralized (DM) water followed by spray drying and calcination.

[0079] According to yet another feature of the present invention, the spinel is preferably prepared by dispersing metal oxides of copper compound, preferably copper hexanitrate, and alumina in DM water followed by spray drying and calcination.

[0080] According an embodiment the catalyst may be a composite of FCC catalyst, ZSM-5 additive, residue up-gradation additive and a spinel additive with desired particle size in the range of 80-90 micron, ABD in the range of 0.78 to 0.85 g/cc, attrition index (AI) of around 3%. A preferred catalyst composition of the present invention comprises about 15 wt % rare earth exchanged USY zeolite (REUSY), about 12 wt % stabilized pentasil zeolite, about 4.2 wt % phosphorous compound, about 37.8 wt % clay, about 11.5 wt % silica, about 18.05 wt % alumina, and about 1.5 wt % copper aluminate spinel.

[0081] According to another feature, the present invention provides the catalyst composition, comprising introducing the REUSY, stabilized pentasil zeolite, silica, and clay along with the spinel to an alumina binder and shaping the mixture obtained to microspheroidal form and further calcination to harden the microspheres suitable for fluidization and circulation.

[0082] Further, according to yet another feature, the present invention provides a process for the preparation of catalyst composition for catalytic cracking of hydrocarbons to provide higher conversion, higher yield of light end olefins, naphtha yield and lower bottoms.

[0083] According to yet another feature, the present invention provides a composite catalyst composition, which enhances light olefin yield in an amount of about 1.5%, selectivity of propylene in LPG in the range of 35-40%, retention of gasoline in the range of 19-22 wt % and retention of diesel in the range of 23-26 wt %.

[0084] According to an aspect, the present invention provides a composite catalyst composition that enables improved selective catalytic cracking of heavy oils in petroleum processing industry at cat/oil ratio of about 6 and riser outlet temperature of about 529 C.

EXAMPLES

[0085] The present invention is exemplified by following non-limiting examples:

Example-1: Preparation of RE-USY

[0086] This example illustrates the process for preparation of rare earth exchange Y zeolite. Hydrothermally stable, large crystallite sized USY zeolite was taken as the starting zeolite. REUSY was prepared as per Example 2 of U.S. Pat. No. 6,528,447B1, which is incorporated herein by reference, having surface area 720 m.sup.2/g unit cell size (UCS) 24.55 A, rare earth content 4 wt % by rare earth exchange with 1% rare earth chloride solution.

Example-2: Preparation of FCC Catalyst

[0087] FCC catalyst was prepared as per example 3 of U.S. Pat. No. 6,528,447B1, which is incorporated herein by reference, employing rare earth exchanged USY of example 1, ammonium polysilicate, pseudo-boehmite alumina and kaolin clay. The final catalyst product had following composition: REUSY 25 wt %, alumina 30 wt %, kaolin clay 40 wt % and silica 5 wt % having properties, surface area 240 m.sup.2/g, ABD 0.76 g/cc, AI<6, average particle size 80 micron.

Example-3: Preparation of Residue Up Gradation (RUA) Catalyst

[0088] Residue up-gradation catalyst was prepared as per example 3 of co-pending U.S. Ser. No. 14/857449, which is incorporated herein by reference, free of any zeolite. Final catalyst possesses ABD of 0.8 g/cc, surface area of 50 m.sup.2/g, average particle size 82 micron.

Example-4: Preparation of ZSM-5 Additive

[0089] 98.63 gm of Pural SB grade alumina (having loss on ignition of 23.96 wt %) was made into a slurry with 425 gm of DM water. The slurry was peptised with 21.52 gm of formic acid (85% concentration). 750 gm of ZSM-5 zeolite (loss on ignition 12.12 wt %) having silica to alumina molar ratio of 30 was made into a slurry with 862 gm of 10% ammonical solution followed by addition of 27.7 g phosphoric acid (85%) to produce a zeolite slurry having pH of 7.5. 635 gm of kaolin clay (having loss on ignition 14.91 wt %) was made into a slurry with 685 gm DM water and kept under vigorous stirring while 191.53 gm of ortho-phosphoric acid (concentration 85 wt %) was added. To clay-phosphate slurry earlier prepared alumina sol and zeolite slurry were added one after another under vigorous stirring. Final slurry having pH of 2.53 was spray dried similar to slurry of example 1 and the product was processed further. Spray dried product showed ABD of 0.79 with attrition index of 2.2. This catalyst has shown LPG yield of 18.2 wt % with a conversion of 60.2%. Final catalyst had surface area 155 m.sup.2/g, ABD 0.79 g/cc, average particle size 85 micron.

Example-5: Preparation of Copper Aluminate Spinel

[0090] Copper aluminate spinel was prepared by co-precipitation method. Copper nitrate hexahydrate 242 g and aluminium sulphate 630 g was dissolved in 5000 ml DM water. 320 g Sodium hydroxide was dissolved in 1000 g DM water. Sodium hydroxide solution was sequentially added into acidic solution till pH of the reaction mixture reach to 10.5. The reaction was conducted at 35-45 C. under constant stirring condition. After an hour, the precipitate was filtered, washed with hot DM water five times to remove sodium salt. The final washed material was dried at 120 C. for 10 hours, and then calcined at 850 C. for 2 hour.

Example-6: Preparation of Composite Catalyst (Present Invention)

[0091] This example illustrates a process of preparing composite catalyst of present invention as an alternate composition. 140 gm of ZSM-5 zeolite, silica to alumina ratio 29 was dispersed in clay-alumina-phosphate slurry prepared by mixing 110.55 gm of clay and 33.37 gm of PSB alumina in 502 gm di-ammonium hydrogen phosphate solution (72.25 DAHP in 430 gm of DM water). Final slurry was ball milled and spray dried and the resulting powder after calcination at 510 C., was pulverized to particle size below 5 microns. 142.5 gm PSB alumina was dispersed in 1300 gm of DM water and the slurry was acidified with 42 gm of 85% formic acid. To the alumina gel, 237 gm of clay was added, followed by addition of 375 gm of pulverized stabilized ZSM-5-clay-phosphate powder prepared as above, 37.5 gm of milled spinel (prepared by dispersing 9.1 gm Cu(OH).sub.2 and 30 gm of alumina in 47 gm of DM water followed by spray drying and calcination), added 125 gm of REUSY powder prepared as per example-1. Finally, 125 gm of silica (as ammonium polysilicate) was added under stirring to obtain catalyst precursor slurry. Green catalyst of present invention was prepared by spray drying at outlet temperature 120 C., inlet 375 C. Spray dried product was calcined to 550 C. for one hr to yield final olefin maximization catalyst microspheres. The catalyst was steam deactivated at 810 C. for 5 hrs and performance evaluation was carried in a fluid bed MAT unit at cat:oil ratio 6.

[0092] The above weights are volatile free basis.

Example-7: Performance of Catalyst Comprising FCC Catalyst, RUA, ZSM-5 and Spinel

[0093] This example illustrates performance of composite catalyst prepared as per example 2, 3, 4, and 5. In general, according to the present invention, the catalyst comprises FCC catalyst, RUA, ZSM-5, and spinel in a ratio of 60 to 70:1 to 10:20 to 30:1 to 10, respectively. For this specific example, the catalyst was prepared comprising FCC catalyst, RUA, ZSM-5, and spinel in the ratio of 60:5:30:5, respectively.

[0094] The composite catalyst was steam deactivated at 810 C. for 5 hrs and performance evaluation was carried in a fluid bed MAT unit at cat:oil ratio 6. The performance of the catalyst is given below in Table 2.

Example-8: Performance of Catalyst Comprising FCC Catalyst, RUA and ZSM-5

[0095] This example illustrates performance of composite catalyst comprising catalyst of example 2, 3 and 4. In general, according to the present invention, the catalyst comprises FCC catalyst, RUA and ZSM-5 in a ratio 60 to 70:1 to 10:20 to 30, respectively. For this specific example, the catalyst was prepared comprising FCC catalyst, RUA and ZSM-5 in the ratio of 65:5:30, respectively.

[0096] The composite catalyst was steam deactivated at 810 C. for 5 hrs and performance evaluation was carried in a fluidized bed MAT unit at cat:oil ratio 6. The performance of the catalyst is given in below Table 2.

[0097] Properties of feed where all the above additives prepared as per examples-3 to 7 are evaluated are given in below Table-1, and Physico-chemical properties of final catalyst and steam deactivated product is shown in Table-2:

TABLE-US-00001 TABLE 1 Feed properties Sr. No. Attributes Unit Value 1 Density @ 15 C. g/cc 0.89 2 Distillation, D-1160 3 IBP C. 250.0 4 5% C. 321.0 5 30% C. 397.0 6 50% C. 428.0 7 70% C. 459.0 8 Sulphur wt % 0.4 9 CCR wt % 0.2 10 V ppm 1 11 Ni ppm 1 12 Na ppm 2

TABLE-US-00002 TABLE 2 Performance of catalyst of examples 6-7 Present Invention Catalyst of Physical example 6 mixture Catalyst Single Catalyst of composition microsphere example 7 Catalyst of Catalyst similar to of Physical example 8 without describe in U.S. Alumina, ZSM- mixture of Physical RUA, ZSM- Pat. Nos. 5, Z-Y FCC, RUA, ZSM- mixture of 5 and 5,846,402 and Cu- 5 and Cu- FCC, RUA, copper FCC + BCA + ZSM-5 aluminate aluminate ZSM-5 aluminate Cracking 529.0 529.0 529.0 529.0 529.0 Temperature, *c. Injection 30.0 30.0 30.0 30.0 30.0 Time, sec Catalyst strip 360 360 360 360 360 Time, sec Recovery, 99.1 95.6 98.2 98.7 98.7 wt % Catalyst-to- 6.00 6.00 6.00 6.0 6.0 oil, wt/wt Conv., wt % 71.43 70.63 72.7 72.06 Yields, wt % Coke 6.488 3.86 6.7 6.62 5.76 Dry gas 2.825 2.74 3.19 3.01 0.82 Ethylene 2.279 2.25 2.50 2.43 0.04 Propane 2.816 2.32 3.11 2.96 0.67 propylene 13.376 13.86 13.64 13.51 4.5 n-Butane 1.563 1.26 1.60 1.58 0.53 Isobutene 3.948 3.01 3.71 3.83 2.61 C4 Olefins 13.591 14.04 13.28 13.48 8.32 1-butene 2.102 2.20 2.06 2.08 1.48 Isobutylene 5.581 5.79 5.54 5.56 3.02 C-2 Butene 2.496 2.56 2.44 2.47 1.61 Total light 42.8 44.0 42.9 42.8 42.8 olefin t-2-Butene 3.394 3.45 3.33 3.36 2.17 Gasoline (C5 19.118 21.60 18.76 18.94 35.0 to 160 C.) HN (160 to 7.708 7.96 8.52 8.12 13.2 216 C.) LCO (216 to 16.045 17.43 13.35 14.70 18.9 370 C.) Diesel 23.753 25.39 21.87 22.81 32.1 (HN + LCO) Bottoms 12.522 11.93 13.97 13.25 10.0 Total 100.00 100.00 100.00 100.0 Propylene in 37.898 40.19 38.5 38.2 27.0 LPG (%) LPG 35.295 34.48 35.44 35.3 16.6 LPG/(Gasoline + 1.87 0.73 0.88 0.84 0.25 Diesel)

Performance Evaluation as Per Results Shown in Table-2

[0098] It is evident from the Table-2 that performance of the composite catalyst comprising copper aluminates spinel (as illustrated in example-6) enhances the total olefin by +1.2 wt % and propylene selectivity in LPG by 2% along with enhancing gasoline and diesel by 2.5 wt % and 1.6 wt %, respectively.

[0099] The superior performance is attributed to close proximity of the copper aluminate spinel with ZSM-5 in combination with the method of preparation and the synergistic effect of alumina, ZSM-5 zeolite and Re-USY in the composition. This in-turn results in the high distillate and gasoline yield.