WO2024069636A1 - A catalyst composition for catalytic cracking of paraffin rich feed into light olefins - Google Patents

A catalyst composition for catalytic cracking of paraffin rich feed into light olefins Download PDF

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Publication number
WO2024069636A1
WO2024069636A1 PCT/IN2022/051152 IN2022051152W WO2024069636A1 WO 2024069636 A1 WO2024069636 A1 WO 2024069636A1 IN 2022051152 W IN2022051152 W IN 2022051152W WO 2024069636 A1 WO2024069636 A1 WO 2024069636A1
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Prior art keywords
zeolite
zsm
catalyst
composition
beta zeolite
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PCT/IN2022/051152
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French (fr)
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Lavanya Meesala
Kumaresan Loganathan
Pramod Kumar
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Hindustan Petroleum Corporation Limited
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Publication of WO2024069636A1 publication Critical patent/WO2024069636A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80Mixtures of different zeolites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084Y-type faujasite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007Zeolite Beta
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28Phosphorising
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04Oxides
    • C10G11/05Crystalline alumino-silicates, e.g. molecular sieves
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/18After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions

Definitions

  • the present invention relates to a catalyst composition comprising ultra-stabilized zeolites, alkaline earth (AE) metal ion modified phosphatized-ZSM-5 and beta zeolites. Specifically, the present invention relates to usage of the catalyst composition for cracking paraffin rich feed having boiling point in the range of 150-350°C to light olefins, gasoline products.
  • AE alkaline earth
  • kerosene fraction which is a paraffin rich feed. Part of this fraction is refined into Aviation Turbine Fuel (ATF) and the excess kerosene is blended into diesel stream.
  • ATF Aviation Turbine Fuel
  • kerosene is not fully absorbed into diesel stream.
  • kerosene is also used as a fuel for heating and cooking. But when burning kerosene, it usually produces considerable smoke and an unpleasant odor. The smoke and odor not only reduce the heat efficiency but also pollute the air. Due to availability of more clean fuels the demand for kerosene is decreasing day by day. Accordingly, it is observed that the kerosene needs to be converted into more valuable products such as light olefins and gasoline.
  • the catalytic cracking is employed to convert the heavier hydro feed into light olefins and gasoline.
  • Catalytic cracking is a conversion process that can be applied to a variety of feedstocks ranging from gas oil to heavy crude oil and residue.
  • the concept of catalytic cracking is basically the same as thermal cracking, but it differs by the use of a catalyst that is not consumed in the process, and it is one of several practical applications used in a refinery that employs a catalyst to improve process efficiency and product state.
  • Catalytic cracking in the usual commercial process involves contacting a feedstock (usually a gas oil fraction) with a catalyst under suitable conditions of temperature, pressure, and residence time. By this means, a substantial part (>50%) of the feedstock is converted into gasoline and lower boiling products, usually in a single-pass operation.
  • US20220081624 relates to methods for upgrading a hydrocarbon feed, the method includes introducing the hydrocarbon feed to a separation unit, where the separation unit separates the hydrocarbon feed to produce at least a greater boiling point effluent and a lesser boiling point effluent, and the greater boiling point effluent has an American Petroleum Institute gravity less than 30 degrees. Then passing the greater boiling point effluent to a first downflow fluid catalytic cracking unit downstream of the separation unit, where the first downflow fluid catalytic cracking unit contacts the greater boiling point effluent with a multicomponent catalyst.
  • the contact results at least a portion of the greater boiling point effluent to undergo catalytic cracking and produce a first spent multicomponent catalyst and a first cracked effluent having one or more olefins.
  • the multicomponent catalyst includes from 0 weight percent to 10 weight percent ZSM-5, from 10 weight percent to 40 weight percent zeolite Beta, and from 10 weight percent to 30 weight percent USY zeolite based on the total weight of the multicomponent catalyst, and where one or more transition metals are substituted into the framework of the USY zeolite.
  • CN102019200B discloses a high-activity catalytic pyrolysis catalyst and a preparation method thereof, which is characterized in that: the catalytic pyrolysis catalyst is a solid composition which is formed by high-activity phosphorus modified ZSM-5 zeolite, high-activity rare earth modified Y zeolite, an alumina-based bonder, nickel tetracarbonyl vapor deposition modified porous silicide and filler clay, is in multiple pore diameter distribution and has different types of catalytic active centers; the catalytic pyrolysis catalyst has another important characteristic: the pore capacity provided by the mesoporous ZSM-5 zeolite in the catalytic pyrolysis catalyst should be approximately equal to the pore capacity provided by the macroporous Y zeolite, that is to say, the ratio is in a range of 0.9-1.1.
  • the total amount of the zeolite is 30-60% of the total amount of the solid composition by weight; the alumina-based bonder formed by acidified pseudoboehmite and/or alumina sol is 5-30% of the total amount by weight; the porous silicide which is 0.01-0.5% of the nickel tetracarbonyl vapor deposition nickeliferous oxide by weight is 1-20% of the total amount by weight; and the balance is the filler clay.
  • the slurry of the solid composition is spray-dried to form the microsphere catalytic pyrolysis catalyst which has extraordinarily high activity and selectivity when being used in a catalytic pyrolysis device and can effectively transform the heavy feeding and improve the yield of the low-carbon olefins such as ethylene, propylene and the like.
  • US20220001362A1 discloses a fluid catalytic cracking catalyst composition (FCC catalyst composition) which includes a framework- substituted ultra-stable Y-type zeolite (USY zeolite) having one or more transition metals substituted into the framework of a USY zeolite and a FCC zeolite cracking additive.
  • a method for upgrading a hydrocarbon feed includes contacting the hydrocarbon feed with the FCC catalyst composition of the present disclosure at reaction conditions sufficient to upgrade at least a portion of the hydrocarbon feed.
  • a method for upgrading a hydrocarbon feed includes passing the hydrocarbon feed to a fluid catalytic cracking unit, contacting the hydrocarbon feed with a FCC catalyst composition in the fluid catalytic cracking unit under reaction conditions sufficient to cause at least a portion of the hydrocarbon feed to undergo cracking reactions to produce a cracking reaction mixture comprising a used FCC catalyst composition and a cracked effluent comprising one or more olefins.
  • KR101566185B1 discloses that gasoline and diesel oil are obtained in high yields, and at the same time provides a bottom-catalytic cracking, low-coke yield hydrocarbon catalytic cracking catalyst.
  • the present invention relates to a catalyst composition
  • a catalyst composition comprising ultra-stabilized zeolites, AE metal ion modified phosphatized-ZSM-5 and beta zeolites. Further, the catalyst composition is utilized for cracking kerosene molecule into light olefins and gasoline.
  • the present invention provides a catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the composition includes (a) 5-30 wt.% of an ultra-stabilized Y-zeolite, (b) 20-60 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite, (c) 20-40 wt.% of a filler; and (d) 5-10 wt.% of a binder.
  • AE alkaline earth
  • the present invention provides catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the composition includes (a) 5-20 wt.% of an ultra-stabilized Y-zeolite, (b) 20-50 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite, (c) 20-40 wt.% of a filler, and (d) 5-10 wt.% of a binder.
  • the ultra-stabilized Y-zeolite is selected from a rare earth exchanged USY (RE-USY) with rare earth (RE) content 2-3.5 wt.%.
  • the alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite is selected from a ZSM-5/Beta zeolite having mono magnesium hydrogen phosphate, di-magnesium hydrogen phosphate, tri-magnesium phosphate, strontium phosphate, calcium phosphate, or barium phosphate.
  • the filler is clay, the binder is alumina and the beta zeolite have silicon to alumina ratio in a range of 30-50.
  • the present invention provides a process for preparation of the catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the process includes preparing a magnesium hydrogen phosphate by treating magnesium nitrate hexahydrate with ortho-phosphoric acid and ammonium hydroxide. Then preparing alkaline- earth metal (AE) ion modified phosphated ZSM-5 zeolite by reacting the magnesium hydrogen phosphate with a ZSM-5 zeolite. Then preparing alkaline-earth metal (AE) ion modified phosphated beta zeolite by reacting the magnesium hydrogen phosphate with Beta zeolite.
  • AE alkaline- earth metal
  • a ZSM-5/Beta zeolite composite catalyst by combining the AE ion modified phosphated ZSM-5 zeolite and the AE ion modified phosphated Beta zeolite. Finally, mixing 5- 30 wt.% of an ultra-stabilized Y-zeolite, 20-60 wt.% of the ZSM-5/Beta zeolite composite catalyst, 20-40 wt.% of clay, and 5-10 wt.% of alumina.
  • the catalyst composition provides cracking of kerosene into valuable products like gasoline about >50%, liquefied petroleum gas (LPG) about >25% with higher C3+C4 olefin selectivity in LPG (>70%).
  • LPG liquefied petroleum gas
  • Pre-phosphate modification of ZSM-5 and combination with Beta zeolite stabilizes the zeolites framework as shape selective functionality to develop a composite catalyst.
  • It is a primary objective of the present invention to provide a catalyst composition comprising ultra-stabilized zeolites, AE metal ion modified phosphatized-ZSM-5 and beta zeolites.
  • the present invention relates to a catalyst composition
  • a catalyst composition comprising: (a) 5-30 wt.% of an ultrastabilized Y-zeolite; (b) 20-60 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5 zeolite and beta zeolite; (c) 20-40 wt.% of a filler; and (d) 5-10 wt.% of a binder.
  • AE alkaline earth
  • the present invention provides catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the composition includes (a) 5-20 wt.% of an ultra-stabilized Y-zeolite, (b) 20-50 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite, (c) 20-40 wt.% of a filler, and (d) 5-10 wt.% of a binder.
  • AE alkaline earth
  • the ultra-stabilized Y-zeolite is selected from rare earth exchanged USY (RE-USY) with RE content 1-3.5 wt.%.
  • the alkaline earth (AE) metal ion modified phosphated ZSM-5/ Beta zeolites is selected from Mono Magnesium hydrogen phosphate, di-magnesium hydrogen phosphate, Tri-magnesium phosphate, strontium phosphate, calcium phosphate, or barium phosphate.
  • the silicon to alumina ratio of the ZSM-5 & beta zeolite is selected from 25-50.
  • the filler is clay
  • the binder is alumina
  • the catalyst composition is utilized for cracking kerosene to light olefins.
  • the process comprises cracking kerosene molecule with boiling range of 200-350°C in a temperature range of 540-650°C to convert into valuable products.
  • the pre-phosphate modification of ZSM-5 stabilizes and combines with beta zeolite as shape selective functionality to develop a catalyst composition.
  • the present invention provides a process for preparation of the catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the process includes preparing a magnesium hydrogen phosphate by treating magnesium nitrate hexahydrate with ortho-phosphoric acid and ammonium hydroxide. Then preparing alkaline-earth metal (AE) ion modified phosphated ZSM-5 zeolite by reacting the magnesium hydrogen phosphate with a ZSM-5 zeolite. Then preparing alkaline-earth metal (AE) ion modified phosphated beta zeolite by reacting the magnesium hydrogen phosphate with Beta zeolite.
  • AE alkaline-earth metal
  • a ZSM-5/Beta zeolite composite catalyst by combining the AE ion modified phosphated ZSM-5 zeolite and the AE ion modified phosphated Beta zeolite. Finally, mixing 5-30 wt.% of an ultra-stabilized Y-zeolite, 20-60 wt.% of the ZSM-5/Beta zeolite composite catalyst, 20-40 wt.% of clay, and 5-10 wt.% of alumina.
  • Preparing the modified magnesium hydrogen phosphate includes dissolving 256 g of magnesium nitrate hexahydrate with 800 g of demineralized water to get a solution. Adding 196 g of orthophosphoric acid to the solution, then adding 300 g of ammonium hydroxide under stirring at 30°C to obtain white precipitates. Filtering the white precipitates, washing the white precipitates with hot DM water for three times to remove excess ammonium, and drying the white precipitates.
  • Preparing the alkaline-earth metal (AE) ion modified phosphated ZSM-5 zeolite includes mixing 500 g of ZSM-5 zeolite with magnesium hydrogen phosphate having phosphate ion loading concentration of 10 wt.% to obtain a zeolite mixer. Adding 5000 g of DM water into the prepared zeolite mixer to get a zeolite slurry, mixing the zeolite slurry, and heating the zeolite slurry at 70°C for 3 hours. Then filtering and washing the zeolite slurry with DM water for 2 times to obtain a wet cake. Finally, drying the wet cake at 120°C for 10 hours and calcinating at 700°C for 3 hours.
  • AE alkaline-earth metal
  • Preparing the alkaline-earth metal (AE) ion modified phosphated Beta zeolite includes mixing 500 g of Beta zeolite with magnesium hydrogen phosphate having phosphate ion loading concentration of 10 wt.% to obtain a zeolite mixer. Adding 5000 g of DM water into the prepared zeolite mixer to get a zeolite slurry, mixing the zeolite slurry, and heating the zeolite slurry at 70°C for 3 hours. Filtering and washing the zeolite slurry with DM water for 2 times to obtain a wet cake. Drying the wet cake at 120oC for 10 hours and calcinating at 700°C for 3 hours.
  • AE alkaline-earth metal
  • Preparing the ZSM-5/Beta zeolite composite catalyst includes mixing 85 g of ortho-phosphoric acid, 447 g of clay, 333 g of ammonium poly silicate and 69 g of alumina to prepare a uniform slurry, milling the uniform slurry with the help of a wet ball for 5 hours to get a milled slurry. Then mixing the milled slurry with 316 g of AE ion modified phosphated ZSM-5 zeolite and 112 g of AE ion modified phosphated Beta zeolite to produce a final slurry.
  • spherical catalyst microspheres After spray drying the final slurry in a co-current spray dryer unit having an inlet temperature of 450°C and an outlet temperature of 150°C to form spherical catalyst microspheres. Calcinating the spherical catalyst microspheres at 590°C for 4 hours to form a final composite ZSM-5/Beta zeolite catalyst.
  • the spherical catalyst microspheres have an average particle size of 75-80 micron, an ABD above 0.9 g/cc, and an attrition less than 6.
  • the present invention also provides a process for cracking paraffin rich feed such as kerosene, naphtha, or VGO into light olefins by using the catalyst composition as discloses herein, wherein the process includes cracking paraffin rich feed with boiling range of 200-350°C in a temperature range of 540-650°C and maintaining the pressure in a range of 1.5-5 bar.
  • alkaline earth metal ion based hydrogen phosphate salts were prepared with different AE/P ratios.
  • the prepared phosphate salts were impregnated on the surface of zeolites and calcined at 500-700°C to establish the formation of stable Al-O-P with AE ion without affecting crystallinity of the zeolites.
  • These P-modified zeolites were incorporated into the catalyst formulation with different composition along with binder, matrix components for shaping the catalyst to make microsphere of final catalyst.
  • the final catalyst was calcined at temperature above 500°C and subjected for testing for cracking of kerosene.
  • Example-2 Preparation of AE ion modified phosphated zeolites:
  • 500 g of ZSM-5 (CBV-3024, Zeolyst) zeolite was mixed with above magnesium hydrogen phosphate having phosphate ion loading concentration of 10 wt.%.
  • 5000 g of DM water was added to the prepared zeolite mixer to get a zeolite slurry.
  • the zeolite slurry was mixed and heated at 70°C for 3 hours. After 3 hours, zeolite slurry was filtered and washed with DM water for 2 times and a wet cake was obtained. The wet cake was dried at 120°C for 10 hours and calcined at 700°C for 3 hours.
  • 500 g of beta zeolite CP814C, Zeolyst
  • was treated with magnesium hydrogen phosphate was dried and calcined at 700°C for 3hours.
  • Example -3 Preparation of ZSM-5/beta zeolite composite catalyst
  • Example-4 Preparation of ZSM-5/Beta zeolite composite catalyst without pre-phosphate modification:
  • 121 g of ortho-phosphoric acid, 411 g of clay, 333 g of ammonium polysilicate and 69 g of alumina (Pural SB grade, Sasol) were mixed into make uniform slurry and milled at wet ball for 5 hours.
  • the milled slurry was mixed with 341 g of ZSM-5 and 117 g of beta zeolites to make final slurry.
  • the slurry was spray dried at inlet temperature of 450°C and outlet temperature of 150°C to form spherical microsphere of have ABD above 0.85 g/cc and Attrition index less than 6, average particle size of 75-80 micron in co-current spray dryer unit.
  • the spray dried catalyst was calcined at 590°C for 4 hours to form final composite ZSM-5/Beta zeolite catalyst without pre-phosphate modification.
  • Example-5 Preparation of ZSM-5/Beta zeolite composite catalyst without pre-phosphate modification with promoter:
  • 121 g of ortho-phosphoric acid, 191 g of magnesium nitrate, 376 g of clay, 333 g of ammonium polysilicate and 69 g of alumina (Pural SB grade, Sasol) were mixed into make uniform slurry and milled at wet ball for 5 hours.
  • the milled slurry was mixed with 341 g of ZSM-5 and 117 g of beta zeolites to make final slurry.
  • the slurry was spray dried at inlet temperature of 450°C and outlet temperature of 150°C to form spherical microsphere of have ABD above 0.85 g/cc and Attrition index less than 6, average particle size of 75-80 micron in co-current spray dryer unit.
  • the spray dried catalyst was calcined at 590°C for 4 hours to form final composite ZSM-5/Beta zeolite catalyst without pre-phosphate modification.
  • UOPK factor which signifies cracking potential of Kerosene stream
  • VGO vacuum gas oil
  • UOPK 11.44
  • catalytic cracking experiments were carried out with Kerosene as feed in ACE R+MM unit using FCC E-CAT and in combination of ZSM-5 additive.
  • Table 2 provides the list of the results of these experiments.
  • the product yields from kerosene and VGO were compared and in presence of ZSM-5 additive kerosene molecules undergoes alkylation and form LCO range products.
  • CLO from kerosene cracking the developed ZSM-5/beta zeolites composite catalyst was studied. During cracking of kero feedstock molecules, the molecules undergoes dimerization reaction, produces heavier molecules and increasing yield of LCO and CLO.
  • Example 7 Catalyst composition with phosphate modification prepared from Example-3
  • Table 3 discloses that the catalyst composition with phosphate modification provides higher C2- C4 olefins, lower LCO & CLO and higher conversion.
  • the composite catalyst was evaluated at 600 and 630°C in different Cat/oil ratio. It was observed from the results, the modified catalyst composition provides higher conversion with minimum LCO and nil CLO.
  • Example 8 Catalyst composition as prepared from Example-4 & 5 Table 4 discloses that the catalyst composition with no prephosphate modification of zeolites provides lower C2-C4 olefins.
  • Catalyst composition with phosphate modification provides higher conversion rate with minimum LCO and nil CLO.

Abstract

The present invention discloses a catalyst composition comprising ultra-stabilized zeolites, alkaline earth (AE) metal ion modified phosphatized-ZSM-5/ Beta zeolites. Further, the catalyst composition is utilized for cracking paraffin rich feed into light olefins, wherein, the paraffin rich feed is selected from a kerosene, naphtha, or VGO.

Description

A CATALYST COMPOSITION FOR CATALYTIC CRACKING OF PARAFFIN RICH FEED INTO LIGHT OLEFINS
FIELD OF THE INVENTION:
The present invention relates to a catalyst composition comprising ultra-stabilized zeolites, alkaline earth (AE) metal ion modified phosphatized-ZSM-5 and beta zeolites. Specifically, the present invention relates to usage of the catalyst composition for cracking paraffin rich feed having boiling point in the range of 150-350°C to light olefins, gasoline products.
BACKGROUND OF THE INVENTION:
In a crude oil, 180-300°C fraction is considered as kerosene fraction which is a paraffin rich feed. Part of this fraction is refined into Aviation Turbine Fuel (ATF) and the excess kerosene is blended into diesel stream. With expected reducing demand in kerosene and other fossil fuels, kerosene is not fully absorbed into diesel stream. Further, it is well known that kerosene is also used as a fuel for heating and cooking. But when burning kerosene, it usually produces considerable smoke and an unpleasant odor. The smoke and odor not only reduce the heat efficiency but also pollute the air. Due to availability of more clean fuels the demand for kerosene is decreasing day by day. Accordingly, it is observed that the kerosene needs to be converted into more valuable products such as light olefins and gasoline. Generally, the catalytic cracking is employed to convert the heavier hydro feed into light olefins and gasoline.
Catalytic cracking is a conversion process that can be applied to a variety of feedstocks ranging from gas oil to heavy crude oil and residue. The concept of catalytic cracking is basically the same as thermal cracking, but it differs by the use of a catalyst that is not consumed in the process, and it is one of several practical applications used in a refinery that employs a catalyst to improve process efficiency and product state. Catalytic cracking in the usual commercial process involves contacting a feedstock (usually a gas oil fraction) with a catalyst under suitable conditions of temperature, pressure, and residence time. By this means, a substantial part (>50%) of the feedstock is converted into gasoline and lower boiling products, usually in a single-pass operation. Below are some of the prior know documents which discloses the catalytic conversion of different type of hydrocarbon feeds into more valuable and lighter hydrocarbon products. US20220081624 relates to methods for upgrading a hydrocarbon feed, the method includes introducing the hydrocarbon feed to a separation unit, where the separation unit separates the hydrocarbon feed to produce at least a greater boiling point effluent and a lesser boiling point effluent, and the greater boiling point effluent has an American Petroleum Institute gravity less than 30 degrees. Then passing the greater boiling point effluent to a first downflow fluid catalytic cracking unit downstream of the separation unit, where the first downflow fluid catalytic cracking unit contacts the greater boiling point effluent with a multicomponent catalyst. The contact results at least a portion of the greater boiling point effluent to undergo catalytic cracking and produce a first spent multicomponent catalyst and a first cracked effluent having one or more olefins. Wherein, the multicomponent catalyst includes from 0 weight percent to 10 weight percent ZSM-5, from 10 weight percent to 40 weight percent zeolite Beta, and from 10 weight percent to 30 weight percent USY zeolite based on the total weight of the multicomponent catalyst, and where one or more transition metals are substituted into the framework of the USY zeolite.
CN102019200B discloses a high-activity catalytic pyrolysis catalyst and a preparation method thereof, which is characterized in that: the catalytic pyrolysis catalyst is a solid composition which is formed by high-activity phosphorus modified ZSM-5 zeolite, high-activity rare earth modified Y zeolite, an alumina-based bonder, nickel tetracarbonyl vapor deposition modified porous silicide and filler clay, is in multiple pore diameter distribution and has different types of catalytic active centers; the catalytic pyrolysis catalyst has another important characteristic: the pore capacity provided by the mesoporous ZSM-5 zeolite in the catalytic pyrolysis catalyst should be approximately equal to the pore capacity provided by the macroporous Y zeolite, that is to say, the ratio is in a range of 0.9-1.1. The total amount of the zeolite is 30-60% of the total amount of the solid composition by weight; the alumina-based bonder formed by acidified pseudoboehmite and/or alumina sol is 5-30% of the total amount by weight; the porous silicide which is 0.01-0.5% of the nickel tetracarbonyl vapor deposition nickeliferous oxide by weight is 1-20% of the total amount by weight; and the balance is the filler clay. The slurry of the solid composition is spray-dried to form the microsphere catalytic pyrolysis catalyst which has extraordinarily high activity and selectivity when being used in a catalytic pyrolysis device and can effectively transform the heavy feeding and improve the yield of the low-carbon olefins such as ethylene, propylene and the like.
US20220001362A1 discloses a fluid catalytic cracking catalyst composition (FCC catalyst composition) which includes a framework- substituted ultra-stable Y-type zeolite (USY zeolite) having one or more transition metals substituted into the framework of a USY zeolite and a FCC zeolite cracking additive. A method for upgrading a hydrocarbon feed includes contacting the hydrocarbon feed with the FCC catalyst composition of the present disclosure at reaction conditions sufficient to upgrade at least a portion of the hydrocarbon feed. A method for upgrading a hydrocarbon feed includes passing the hydrocarbon feed to a fluid catalytic cracking unit, contacting the hydrocarbon feed with a FCC catalyst composition in the fluid catalytic cracking unit under reaction conditions sufficient to cause at least a portion of the hydrocarbon feed to undergo cracking reactions to produce a cracking reaction mixture comprising a used FCC catalyst composition and a cracked effluent comprising one or more olefins.
KR101566185B1 discloses that gasoline and diesel oil are obtained in high yields, and at the same time provides a bottom-catalytic cracking, low-coke yield hydrocarbon catalytic cracking catalyst. A zeolite and a binder, and a catalyst composition B containing aluminum compound, a binder of 10 to 30% by weight of a catalyst composition A and zeolite, and a binder containing silica-based binder of 10 to 30% by weight of the weight of the catalyst composition by A W A, catalyst and the mass ratio (W A : W B ) of the composition B was set to W B in the range of 10:90 to 90: 10.
The above disclosed prior art documents provide catalytic process and catalyst to crack the different types of hydrocarbon feeds into lighter hydrocarbons. However, the prior art document does not disclose converting the paraffin rich feed such as kerosene, naphtha, or VGO into more valuable products like light olefins and gasoline. Further, the prior art does not provide any disclosure related to the catalyst which can be utilized to convert the kerosene into more valuable products. Accordingly, there is a need for a catalyst and a process for converting the kerosene into more valuable products such as light olefins, or gasoline products. SUMMARY OF THE PRESENT INVENTION:
The present invention relates to a catalyst composition comprising ultra-stabilized zeolites, AE metal ion modified phosphatized-ZSM-5 and beta zeolites. Further, the catalyst composition is utilized for cracking kerosene molecule into light olefins and gasoline.
Specifically, the present invention provides a catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the composition includes (a) 5-30 wt.% of an ultra-stabilized Y-zeolite, (b) 20-60 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite, (c) 20-40 wt.% of a filler; and (d) 5-10 wt.% of a binder.
Specifically, the present invention provides catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the composition includes (a) 5-20 wt.% of an ultra-stabilized Y-zeolite, (b) 20-50 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite, (c) 20-40 wt.% of a filler, and (d) 5-10 wt.% of a binder. The ultra-stabilized Y-zeolite is selected from a rare earth exchanged USY (RE-USY) with rare earth (RE) content 2-3.5 wt.%. The alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite is selected from a ZSM-5/Beta zeolite having mono magnesium hydrogen phosphate, di-magnesium hydrogen phosphate, tri-magnesium phosphate, strontium phosphate, calcium phosphate, or barium phosphate. The filler is clay, the binder is alumina and the beta zeolite have silicon to alumina ratio in a range of 30-50.
Further, the present invention provides a process for preparation of the catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the process includes preparing a magnesium hydrogen phosphate by treating magnesium nitrate hexahydrate with ortho-phosphoric acid and ammonium hydroxide. Then preparing alkaline- earth metal (AE) ion modified phosphated ZSM-5 zeolite by reacting the magnesium hydrogen phosphate with a ZSM-5 zeolite. Then preparing alkaline-earth metal (AE) ion modified phosphated beta zeolite by reacting the magnesium hydrogen phosphate with Beta zeolite. Then preparing a ZSM-5/Beta zeolite composite catalyst by combining the AE ion modified phosphated ZSM-5 zeolite and the AE ion modified phosphated Beta zeolite. Finally, mixing 5- 30 wt.% of an ultra-stabilized Y-zeolite, 20-60 wt.% of the ZSM-5/Beta zeolite composite catalyst, 20-40 wt.% of clay, and 5-10 wt.% of alumina.
TECHNICAL ADVANTAGES OF THE INVENTION:
The present invention has the following advantages over the cited prior arts:
(i) The catalyst composition provides cracking of kerosene into valuable products like gasoline about >50%, liquefied petroleum gas (LPG) about >25% with higher C3+C4 olefin selectivity in LPG (>70%).
(ii) It provides more than 90% conversion of kerosene during the cracking process.
(iii) It provides very low light cycle oil (LCO) and less than 1% heavier products of hydrocarbon with boiling point above 540°C.
(iv) Pre-phosphate modification of ZSM-5 and combination with Beta zeolite stabilizes the zeolites framework as shape selective functionality to develop a composite catalyst.
OBJECTIVES OF THE PRESENT INVENTION:
It is a primary objective of the present invention to provide a catalyst composition comprising ultra-stabilized zeolites, AE metal ion modified phosphatized-ZSM-5 and beta zeolites.
It is a further objective of the present invention to provide a catalyst composition for cracking kerosene molecule into light olefins and gasoline.
It is a further objective of the present invention to provide a process for preparation of the catalyst composition.
DESCRIPTION OF THE INVENTION:
Those skilled in the art will be aware that the present disclosure is subject to variations and modifications other than those specifically described. It is to be understood that the present disclosure includes all such variations and modifications. The disclosure also includes all such components of the composition, features of composition, referred to or indicated in this specification, individually or collectively and any and all combinations of any or more of such components or features.
Definitions
For convenience, before further description of the present disclosure, certain terms employed in the specification, and examples are collected here. These definitions should be read in the light of the remainder of the disclosure and understood as by a person of skill in the art. The terms used herein have their meanings recognized and known to those of skill in the art, however, for convenience and completeness, particular terms and their meanings are set forth below.
The articles “a”, “an” and “the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.
The terms “comprise” and “comprising” are used in the inclusive, open sense, meaning that additional elements may be included. It is not intended to be construed as “consists of only”.
Throughout this specification, unless the context requires otherwise the word “comprise”, and variations such as “comprises” and “comprising”, will be understood to imply the inclusion of a stated element or step or group of element or steps but not the exclusion of any other element or step or group of element or steps.
The term “including” is used to mean “including but not limited to”. “Including” and “including but not limited to” are used interchangeably.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosure, the preferred methods, and materials are now described. All publications mentioned herein are incorporated herein by reference. The present disclosure is not to be limited in scope by the specific embodiments described herein, which are intended for the purposes of exemplification only. Functionally equivalent products and processes are clearly within the scope of the disclosure, as described herein.
The present invention relates to a catalyst composition comprising: (a) 5-30 wt.% of an ultrastabilized Y-zeolite; (b) 20-60 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5 zeolite and beta zeolite; (c) 20-40 wt.% of a filler; and (d) 5-10 wt.% of a binder.
Specifically, the present invention provides catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the composition includes (a) 5-20 wt.% of an ultra-stabilized Y-zeolite, (b) 20-50 wt.% of an alkaline earth (AE) metal ion with phosphorus modified ZSM-5/Beta zeolite, (c) 20-40 wt.% of a filler, and (d) 5-10 wt.% of a binder.
In yet another embodiment, the ultra-stabilized Y-zeolite is selected from rare earth exchanged USY (RE-USY) with RE content 1-3.5 wt.%.
In another embodiment, the alkaline earth (AE) metal ion modified phosphated ZSM-5/ Beta zeolites is selected from Mono Magnesium hydrogen phosphate, di-magnesium hydrogen phosphate, Tri-magnesium phosphate, strontium phosphate, calcium phosphate, or barium phosphate.
In another embodiment, the silicon to alumina ratio of the ZSM-5 & beta zeolite is selected from 25-50.
In another embodiment, the filler is clay, and the binder is alumina.
In yet another embodiment, the catalyst composition is utilized for cracking kerosene to light olefins. The process comprises cracking kerosene molecule with boiling range of 200-350°C in a temperature range of 540-650°C to convert into valuable products. Further, the pre-phosphate modification of ZSM-5 stabilizes and combines with beta zeolite as shape selective functionality to develop a catalyst composition.
In yet another embodiment, the present invention provides a process for preparation of the catalyst composition for cracking of paraffin rich feed such as kerosene, naphtha, or VGO into light olefins, wherein the process includes preparing a magnesium hydrogen phosphate by treating magnesium nitrate hexahydrate with ortho-phosphoric acid and ammonium hydroxide. Then preparing alkaline-earth metal (AE) ion modified phosphated ZSM-5 zeolite by reacting the magnesium hydrogen phosphate with a ZSM-5 zeolite. Then preparing alkaline-earth metal (AE) ion modified phosphated beta zeolite by reacting the magnesium hydrogen phosphate with Beta zeolite. Then preparing a ZSM-5/Beta zeolite composite catalyst by combining the AE ion modified phosphated ZSM-5 zeolite and the AE ion modified phosphated Beta zeolite. Finally, mixing 5-30 wt.% of an ultra-stabilized Y-zeolite, 20-60 wt.% of the ZSM-5/Beta zeolite composite catalyst, 20-40 wt.% of clay, and 5-10 wt.% of alumina.
Preparing the modified magnesium hydrogen phosphate includes dissolving 256 g of magnesium nitrate hexahydrate with 800 g of demineralized water to get a solution. Adding 196 g of orthophosphoric acid to the solution, then adding 300 g of ammonium hydroxide under stirring at 30°C to obtain white precipitates. Filtering the white precipitates, washing the white precipitates with hot DM water for three times to remove excess ammonium, and drying the white precipitates.
Preparing the alkaline-earth metal (AE) ion modified phosphated ZSM-5 zeolite includes mixing 500 g of ZSM-5 zeolite with magnesium hydrogen phosphate having phosphate ion loading concentration of 10 wt.% to obtain a zeolite mixer. Adding 5000 g of DM water into the prepared zeolite mixer to get a zeolite slurry, mixing the zeolite slurry, and heating the zeolite slurry at 70°C for 3 hours. Then filtering and washing the zeolite slurry with DM water for 2 times to obtain a wet cake. Finally, drying the wet cake at 120°C for 10 hours and calcinating at 700°C for 3 hours. Preparing the alkaline-earth metal (AE) ion modified phosphated Beta zeolite includes mixing 500 g of Beta zeolite with magnesium hydrogen phosphate having phosphate ion loading concentration of 10 wt.% to obtain a zeolite mixer. Adding 5000 g of DM water into the prepared zeolite mixer to get a zeolite slurry, mixing the zeolite slurry, and heating the zeolite slurry at 70°C for 3 hours. Filtering and washing the zeolite slurry with DM water for 2 times to obtain a wet cake. Drying the wet cake at 120oC for 10 hours and calcinating at 700°C for 3 hours.
Preparing the ZSM-5/Beta zeolite composite catalyst includes mixing 85 g of ortho-phosphoric acid, 447 g of clay, 333 g of ammonium poly silicate and 69 g of alumina to prepare a uniform slurry, milling the uniform slurry with the help of a wet ball for 5 hours to get a milled slurry. Then mixing the milled slurry with 316 g of AE ion modified phosphated ZSM-5 zeolite and 112 g of AE ion modified phosphated Beta zeolite to produce a final slurry. Then spray drying the final slurry in a co-current spray dryer unit having an inlet temperature of 450°C and an outlet temperature of 150°C to form spherical catalyst microspheres. Calcinating the spherical catalyst microspheres at 590°C for 4 hours to form a final composite ZSM-5/Beta zeolite catalyst. The spherical catalyst microspheres have an average particle size of 75-80 micron, an ABD above 0.9 g/cc, and an attrition less than 6.
Specifically, the present invention also provides a process for cracking paraffin rich feed such as kerosene, naphtha, or VGO into light olefins by using the catalyst composition as discloses herein, wherein the process includes cracking paraffin rich feed with boiling range of 200-350°C in a temperature range of 540-650°C and maintaining the pressure in a range of 1.5-5 bar.
In the present invention, alkaline earth metal ion based hydrogen phosphate salts were prepared with different AE/P ratios. The prepared phosphate salts were impregnated on the surface of zeolites and calcined at 500-700°C to establish the formation of stable Al-O-P with AE ion without affecting crystallinity of the zeolites. These P-modified zeolites were incorporated into the catalyst formulation with different composition along with binder, matrix components for shaping the catalyst to make microsphere of final catalyst. The final catalyst was calcined at temperature above 500°C and subjected for testing for cracking of kerosene.
Having described the important aspects of the present invention, the following non-limiting examples illustrate specific embodiments thereof. Those skilled in the art will appreciate that many modifications may be made in the invention without changing the essence of the invention.
EXAMPLES:
Example- 1: Preparation of magnesium hydrogen phosphate
256 g of magnesium nitrate hexahydrate was dissolved with 800 g of demineralized water. 196 g of ortho-phosphoric acid (50% concentration) was added to the solution. 300 g of ammonium hydroxide was added slowly under stirring at 30°C. The white precipitate was filtered and washed with hot DM water for three times to remove excess ammonium. The solid precipitate was dried used for modification of zeolites.
Example-2: Preparation of AE ion modified phosphated zeolites:
500 g of ZSM-5 (CBV-3024, Zeolyst) zeolite was mixed with above magnesium hydrogen phosphate having phosphate ion loading concentration of 10 wt.%. 5000 g of DM water was added to the prepared zeolite mixer to get a zeolite slurry. The zeolite slurry was mixed and heated at 70°C for 3 hours. After 3 hours, zeolite slurry was filtered and washed with DM water for 2 times and a wet cake was obtained. The wet cake was dried at 120°C for 10 hours and calcined at 700°C for 3 hours. Similarly, 500 g of beta zeolite (CP814C, Zeolyst) was treated with magnesium hydrogen phosphate, dried and calcined at 700°C for 3hours.
Example -3: Preparation of ZSM-5/beta zeolite composite catalyst
85 g of ortho-phosphoric acid, 447 g of clay, 333 g of ammonium polysilicate and 69 g of alumina (Pural SB grade, Sasol) were mixed into make uniform slurry and milled at wet ball for 5 hours. The milled slurry was mixed with AE modified zeolites i.e., 316 g of ZSM-5 and 112 g of modified beta zeolites to make final slurry. The slurry was spray dried at inlet temperature of 450°C and outlet temperature of 150°C to form spherical microsphere having ABD above 0.9 g/cc and Attrition less than 6, average particle size of 75-80 micron in a co-current spray dryer unit. The spray dried catalyst was calcined at 590°C for 4 hours to form final composite ZSM- 5/Beta zeolite catalyst.
Example-4: Preparation of ZSM-5/Beta zeolite composite catalyst without pre-phosphate modification:
121 g of ortho-phosphoric acid, 411 g of clay, 333 g of ammonium polysilicate and 69 g of alumina (Pural SB grade, Sasol) were mixed into make uniform slurry and milled at wet ball for 5 hours. The milled slurry was mixed with 341 g of ZSM-5 and 117 g of beta zeolites to make final slurry. The slurry was spray dried at inlet temperature of 450°C and outlet temperature of 150°C to form spherical microsphere of have ABD above 0.85 g/cc and Attrition index less than 6, average particle size of 75-80 micron in co-current spray dryer unit. The spray dried catalyst was calcined at 590°C for 4 hours to form final composite ZSM-5/Beta zeolite catalyst without pre-phosphate modification.
Example-5: Preparation of ZSM-5/Beta zeolite composite catalyst without pre-phosphate modification with promoter:
121 g of ortho-phosphoric acid, 191 g of magnesium nitrate, 376 g of clay, 333 g of ammonium polysilicate and 69 g of alumina (Pural SB grade, Sasol) were mixed into make uniform slurry and milled at wet ball for 5 hours. The milled slurry was mixed with 341 g of ZSM-5 and 117 g of beta zeolites to make final slurry. The slurry was spray dried at inlet temperature of 450°C and outlet temperature of 150°C to form spherical microsphere of have ABD above 0.85 g/cc and Attrition index less than 6, average particle size of 75-80 micron in co-current spray dryer unit. The spray dried catalyst was calcined at 590°C for 4 hours to form final composite ZSM-5/Beta zeolite catalyst without pre-phosphate modification.
Example 6: Cracking experiment with kerosene
Table 1 below lists properties of Kerosene.
Table- 1: Properties of kerosene
Figure imgf000012_0001
Figure imgf000013_0001
As can be seen from the Table 1 above, UOPK factor, which signifies cracking potential of Kerosene stream, is comparable to the typical vacuum gas oil (VGO) feedstock (UOPK = 11.44). Furthermore, catalytic cracking experiments were carried out with Kerosene as feed in ACE R+MM unit using FCC E-CAT and in combination of ZSM-5 additive. Table 2 provides the list of the results of these experiments. The product yields from kerosene and VGO were compared and in presence of ZSM-5 additive kerosene molecules undergoes alkylation and form LCO range products. In order to reduce the formation of LCO, CLO from kerosene cracking, the developed ZSM-5/beta zeolites composite catalyst was studied. During cracking of kero feedstock molecules, the molecules undergoes dimerization reaction, produces heavier molecules and increasing yield of LCO and CLO.
Table 2: Cracking experiments with kerosene and compared with VGO feedstock Catalyst: 50% FCC E-Cat+ 50% ZSM-5 additive
Figure imgf000013_0002
Figure imgf000014_0001
Example 7: Catalyst composition with phosphate modification prepared from Example-3
Table 3 discloses that the catalyst composition with phosphate modification provides higher C2- C4 olefins, lower LCO & CLO and higher conversion. The composite catalyst was evaluated at 600 and 630°C in different Cat/oil ratio. It was observed from the results, the modified catalyst composition provides higher conversion with minimum LCO and nil CLO.
Table 3 : Results with catalyst composition with phosphate modification
Figure imgf000014_0002
Example 8: Catalyst composition as prepared from Example-4 & 5 Table 4 discloses that the catalyst composition with no prephosphate modification of zeolites provides lower C2-C4 olefins.
Table 4: Results with catalyst composition with no phosphate modification
Figure imgf000015_0001
Accordingly, it is clear that the Catalyst composition with phosphate modification provides higher conversion rate with minimum LCO and nil CLO.

Claims

We Claim:
1. A catalyst composition for cracking of paraffin rich feed into light olefins, wherein the composition comprises:
(a) 5-30 wt.% of an ultra-stabilized Y-zeolite;
(b) 20-60 wt.% of an alkaline earth (AE) metal ion modified phosphated ZSM-5/Beta zeolite;
(c) 20-40 wt.% of a filler; and
(d) 5-10 wt.% of a binder.
2. The catalyst composition as claimed in claim 1, wherein the composition comprises:
(a) 5-20 wt.% of an ultra-stabilized Y-zeolite;
(b) 20-50 wt.% of an alkaline earth (AE) metal ion modified phosphated ZSM-5/Beta zeolite;
(c) 20-40 wt.% of a filler; and
(d) 5-10 wt.% of a binder.
3. The composition as claimed in claim 1, wherein the ultra-stabilized Y-zeolite is selected from a rare earth exchanged USY (RE-USY) with rare earth (RE) content 1-3.5 wt.%.
4. The composition as claimed in claim 1, wherein the alkaline earth (AE) metal ion modified phosphated ZSM-5/Beta zeolite is selected from a ZSM-5/Beta zeolite having mono magnesium hydrogen phosphate, di-magnesium hydrogen phosphate, trimagnesium phosphate, strontium phosphate, calcium phosphate, or barium phosphate.
5. The composition as claimed in claim 1, wherein the filler is clay.
6. The composition as claimed in claim 1, wherein the binder is alumina.
7. The composition as claimed in claim 1, wherein the beta zeolite comprises silicon to alumina ratio in a range of 30-50.
8. A process for preparation of the catalyst composition as claimed in claim 1, wherein the process comprises:
(i) preparing a magnesium hydrogen phosphate by treating magnesium nitrate hexahydrate with ortho-phosphoric acid and ammonium hydroxide;
(ii) preparing alkaline-earth metal (AE) ion modified phosphated ZSM-5 zeolite by reacting the magnesium hydrogen phosphate with a ZSM-5 zeolite;
(iii) preparing alkaline-earth metal (AE) ion modified phosphated beta zeolite by reacting the magnesium hydrogen phosphate with an AE ion modified phosphated Beta zeolite;
(iv) preparing a ZSM-5/Beta zeolite composite catalyst by combining the AE ion modified phosphated ZSM-5 zeolite and the AE ion modified phosphated Beta zeolite;
(v) mixing the 5-30 wt.% of an ultra-stabilized Y-zeolite, 20-60 wt.% of the ZSM- 5/Beta zeolite composite catalyst, 20-40 wt.% of clay, and 5-10 wt.% of alumina to get a slurry;
(vi) spray drying the slurry to form spherical catalyst microspheres, spray drying is performed in a co-current spray dryer unit having an inlet temperature of 450°C and an outlet temperature of 150°C; and
(vii) calcinating the spherical catalyst microspheres at 590°C for 4 hours to get the catalyst composition.
9. The process as claimed in claim 8, wherein, the spherical catalyst microspheres have an average particle size of 75-80 micron, an ABD above 0.9 g/cc, and an attrition less than 6.
10. A process for cracking a paraffin rich feed into light olefins by using the catalyst composition as claimed in claim 1-9, wherein the process comprises cracking the paraffin rich feed in a temperature range of 540-650°C and maintaining the pressure 1.5-5 bar.
11. The process as claimed in claim 10, wherein, the paraffin rich feed has a boiling point in a range of 200-540°C.
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