DESC:FIELD
The present disclosure relates to a process for the preparation of an FCC catalyst additive composition.
BACKGROUND
The background information herein below relates to the present disclosure but is not necessarily prior art.
Fluid Catalytic Cracking Unit (FCCU) is a primary unit that converts heavier hydrocarbon to lighter hydrocarbon. The FCCU has the ability to convert different types of feed into more valuable products thereby making the FCC process extremely versatile and profitable. The profitability of the FCCU depends primarily on two factors, i.e. firstly the type of feed being processed and secondly the product targeted which is directly related to the catalyst and additives used.
From the FCCU, a high value product obtained is propylene. Typically, there are two ways to improve the selectivity towards propylene, one is by increasing the temperature of the cracking and another is adding “small pore” zeolites such as ZSM-5 based additive along with the main catalyst. Although, by increasing the temperature of the cracking, the yield of light olefins increases with an increase in conversion, its formation is also controlled by an equilibrium thermodynamic mechanism. The change in the thermodynamic equilibrium by increasing the temperature leads to the formation of more dry gas due to the over-cracking of light olefins. This is an unselective process leading to the formation of huge low-value products like dry gas. Further, the addition of small pore zeolites additive into the main catalyst favors the secondary cracking of gasoline range products to propylene predominantly. Hence, it is always a challenge to improve the light olefin yield, while minimizing the dry gas formation to increase refinery profit.
FCC additive is basically composed of four components; namely the active material which is a zeolite, matrix, filler, and binder. Generally, by altering the pore size and acidity of the zeolite, the selectivity to the final product can be fine-tuned. However, zeolites are not hydrothermally stable and lose their structural integrity under FCC conditions, thus, to stabilize the zeolite various methods are followed, one such method to stabilize ZSM-5 zeolite is to use phosphorous. The second component in the FCC additive is the matrix, usually alumina based, silica based, or a mixture of both, which provides “molecular highways” for the larger hydrocarbon to reach the zeolite and is also responsible for primary cracking. The third component in the FCC additive is the filler, which is usually clay that provides the required density and acts as a heat sink. The fourth component is the alumina based binder or silica based binder that binds all together.
It is well known in the art that the addition of a medium-sized porous material such as ZSM-5 type microporous zeolites to large pore zeolite enhances the light olefin yield in FCC. Further, it is well known in the prior art that the zeolite can be stabilized by using a clay phosphate which is obtained by treating phosphorous with clay and binder. However, it would be difficult to bind zeolite with only a clay phosphate to obtain desired attrition rate.
Therefore, there is felt a need for a process for the preparation of an FCC catalyst additive composition that can mitigate the drawbacks mentioned hereinabove or at least provide an alternative solution.
OBJECTS
Some of the objects of the present disclosure, which at least one embodiment herein satisfies, are as follows.
An object of the present disclosure is to ameliorate one or more problems of the background or to at least provide a useful alternative.
Another object of the present disclosure is to provide a process for the preparation of an FCC catalyst additive.
Still another object of the present disclosure is to provide a process for the preparation of an FCC catalyst additive composition that provides higher yields of propylene and liquified petroleum gas (LPG).
Yet another object of the present disclosure is to provide a process for the preparation of an FCC catalyst additive composition that has comparatively high surface area.
Still another object of the present disclosure is to provide a simple and economical process for the preparation of an FCC catalyst additive.
Another object of the present disclosure is to provide an FCC catalyst additive composition.
Other objects and advantages of the present disclosure will be more apparent from the following description, which is not intended to limit the scope of the present disclosure.
SUMMARY
A process for the preparation of FCC catalyst additive composition, comprises the steps of mixing at least one alumina precursor, at least one phosphorous compound, with water at a first predetermined temperature for a first predetermined time period followed by aging for a time period in the range of 1 hour to 4 hours to obtain an aluminophosphate (AlPO) slurry. The aluminophosphate (AlPO) slurry is mixed with a group IVB metal oxide solution at a second predetermined temperature for a second predetermined time period to obtain a metal incorporated aluminophosphate (M-AlPO) slurry. At least one clay is mixed with at least one silica precursor and water to obtain a binder slurry. Separately, at least one zeolite, at least one phosphorous compound and water are mixed followed by aging for a time period in the range of 30 minutes to 90 minutes to obtain a zeolite-phosphate slurry. The zeolite-phosphate slurry is added to the binder slurry under stirring to obtain a homogeneous zeolite-binder slurry. The M-AlPO slurry is added to the homogeneous zeolite-binder slurry under stirring followed by aging for a time period in the range of 30 minutes to 90 minutes to obtain a resultant slurry. The resultant slurry is spray dried to obtain micro spherical particles. The spray dried micro spherical particles are calcined at a third predetermined temperature for a third predetermined time period to obtain the FCC catalyst additive composition.
The silica precursor is optionally treated with a monoprotic acid at a pH in the range of 3 to 4 to obtain acidified silica.
The alumina precursor is selected from the group consisting of colloidal alumina, crystalline alumina, amorphous alumina, colloidal hydrous alumina, boehmite, pseudoboehmite, alumina hydrate, and ? phase of alumina.
The phosphorous compound is selected from the group consisting of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hypophosphate, ammonium orthophosphate, ammonium dihydrogen orthophosphate, ammonium hydrogen orthophosphate, triammonium phosphate, phosphines, and phosphites.
The first predetermined temperature is in the range of 30 ºC to 60 ºC.
The first predetermined time period is in the range of 1 hour to 4 hours.
The group IVB metal oxide solution is selected from an aqueous titanium oxide solution and an aqueous zirconium oxide solution.
The group IVB metal oxides in the group IVB metal oxide solution having a crystal size in the range of 10 nm to 25 nm.
The second predetermined temperature is in the range of 30 ºC to 60 ºC.
The second predetermined time period is in the range of 30 minutes to 180 minutes.
The silica precursor is selected from the group consisting of colloidal silica, fumed silica, sodium silicate and silica gel.
The monoprotic acid is selected from formic acid and acetic acid.
The clay is selected from the group consisting of kaolin, montmorillonite, sapiolite, hallosite, and bentonite.
The zeolite is selected from the group consisting of ZSM-5, ZSM-11, ZSM-22, beta zeolite, mordenite, and rare earth Y (REY) zeolite.
The molar ratio of silica to alumina (SAR) in the zeolite is in the range of 10:1 to 45:1.
The average particle size of the spray-dried spherical particles is in the range of 80 µm to 110 µm.
The third predetermined temperature is in the range of 400 ºC to 750 ºC.
The third predetermined time period is in the range of 1 hour to 8 hours.
The molar ratio of aluminium to phosphorus in the aluminophosphate slurry is in the range of 0.5 to 1.2.
An FCC catalyst additive composition comprises at least one zeolite in an amount in the range of 30 mass% to 60 mass% with respect to the total amount of the composition, at least one binder in an amount in the range of 5 mass% to 20 mass% with respect to the total amount of the composition, at least one phosphorus compound in an amount in the range of 5 mass% to 15 mass% with respect to the total amount of the composition, at least one Group IVB metal compound in an amount in the range of 0.1 mass% to 10 mass% with respect to the total amount of the composition and at least one clay in an amount in the range of 5 mass% to 40 mass% with respect to the total amount of the composition.

The zeolite is selected from the group consisting of ZSM-5, ZSM-11, ZSM-22, beta zeolite, mordenite, and rare earth Y (REY) zeolite.
A molar ratio of silica to alumina (SAR) in the zeolite is in the range of 10:1 to 45:1.
The binder is selected from aluminophosphate and silica aluminophasphate.
A molar ratio of aluminium to phosphorus in the binder is in the range of 0.5 to 1.2.
The phosphorous compound is selected from the group consisting of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hypophosphate, ammonium orthophosphate, ammonium dihydrogen orthophosphate, ammonium hydrogen orthophosphate, triammonium phosphate, phosphines, and phosphites.
The IVB metal oxide is selected from titanium oxide solution and zirconium oxide.
The clay is selected from the group consisting of kaolin, montmorillonite, sapiolite, hallosite, and bentonite.
The amount of components a) to e) provided in the composition are prior to subjecting to a hydrothermal treatment.
A process for cracking hydrocarbon feed by using a mixture of a FCC catalyst and a FCC catalyst additive in a ratio in the range of 70 to 85: 15 to 30 at a temperature in the range of 450 °C to 650 °C for a time period in the range of 10 seconds to 40 seconds to obtain cracked hydrocarbons containing LPG and propylene.
The feed comprises olefins containing naphtha (C5 to C12), C4 to C6 paraffin, heavier hydrocarbons consisting of gas oil, vacuum gas oil, atmospheric oil/vacuum residue, slurry oil, heavy crude, biomass pyrolysis oil, waste plastic pyrolysis oil or combination thereof.
The FCC catalyst is rare-earth-containing ultrastable Y zeolite (ReUSY).
The FCC catalyst is hydrothermally deactivated by using 100% steam under atmospheric pressure at a temperature in the range of 750 °C to 850 °C for a time period in the range of 15 hours to 25 hours.
The FCC catalyst additive is hydrothermally deactivated by using 100% steam under atmospheric pressure at a temperature in the range of 750 °C to 900 °C for a time period in the range of 30 hours to 120 hours.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWING
The present disclosure will now be described with the help of the accompanying drawing, in which:
Figure 1 illustrates the X-ray diffraction (XRD) patterns of a) FCC catalyst additive obtained in example 1 which is calcined; b) FCC catalyst additive obtained in example 1 which is hydrothermally deactivated (steamed); c) FCC catalyst additive obtained in example 2 which is calcined; d) FCC catalyst additive obtained in example 2 which is hydrothermally deactivated (steamed); and e) pure ZSM-5 zeolite.
Figures 2, 3 and 4 illustrate the pore size distribution curves of fresh FCC catalyst additives of examples 4, 5 and 6 respectively; and
Figures 5, 6 and 7 illustrate the pore size distribution curves of hydrothermally deactivated catalyst additives of examples 4, 5 and 6 respectively.
DETAILED DESCRIPTION
The present disclosure relates to a process for the preparation of an FCC catalyst additive composition.
Embodiments, of the present disclosure, will now be described with reference to the accompanying drawings.
Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail.
The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure. As used in the present disclosure, the forms "a,” "an," and "the" may be intended to include the plural forms as well, unless the context clearly suggests otherwise. The terms "comprises," "comprising," “including,” and “having,” are open ended transitional phrases and therefore specify the presence of stated features, integers, steps, operations, elements, modules, units and/or components, but do not forbid the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The particular order of steps disclosed in the method and process of the present disclosure is not to be construed as necessarily requiring their performance as described or illustrated. It is also to be understood that additional or alternative steps may be employed.
As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed elements.
The terms first, second, third, etc., should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.
Fluid Catalytic Cracking Unit (FCCU) is a primary unit that converts heavier hydrocarbon to lighter hydrocarbon. The FCCU has the ability to convert different types of feed into more valuable products thereby making the FCC process extremely versatile and profitable. The profitability of the FCCU depends primarily on two factors, i.e. firstly the type of feed being processed and secondly the product targeted which is directly related to the catalyst and additives used.
From the FCCU, a high-value product obtained is Propylene. Typically, there are two ways to improve the selectivity towards propylene, one is by increasing the temperature of the cracking and another is adding “small pore” zeolites such as ZSM-5 based additive along with the main catalyst. Although, by increasing the temperature of the cracking, the yield of light olefins increases with an increase in conversion, its formation is also controlled by an equilibrium thermodynamic mechanism. The change in the thermodynamic equilibrium by increasing the temperature leads to the formation of more dry gas due to the over-cracking of light olefins. This is an unselective process leading to the formation of huge low-value products like dry gas. Further, the addition of small pore zeolites additive into the main catalyst favors the secondary cracking of gasoline range products to propylene predominantly. Hence, it is always a challenge to improve the light olefin yield, while minimizing the dry gas formation to increase refinery profit.
FCC additive is basically composed of four components; namely the active material which is a zeolite, matrix, filler, and binder. Generally, by altering the pore size and acidity of the zeolite, the selectivity to the final product can be fine-tuned. However, zeolites are not hydrothermally stable and lose their structural integrity under FCC conditions, thus, to stabilize the zeolite various methods are followed, one such method to stabilize ZSM-5 zeolite is to use phosphorous. The second component in the FCC additive is the matrix, usually alumina based, silica based, or a mixture of both, which provides “molecular highways” for the larger hydrocarbon to reach the zeolite and is also responsible for primary cracking. The third component in the FCC additive is the filler, which is usually clay that provides the required density and acts as a heat sink. The fourth component is the alumina-based binder or silica based binder that binds all together.
It is well known in the prior art that the addition of a medium-sized porous material such as ZSM-5 type microporous zeolites to large pore materials enhances the light olefin yield in FCC. Further, it is well known in the prior art that the zeolite can be stabilized by using a clay phosphate which is obtained by treating phosphorous with clay and binder. However, it would be difficult to bind zeolite with only a clay phosphate to obtain desired attrition rate.
The present disclosure relates to a process for the preparation of an FCC catalyst additive composition. The process of the present disclosure provides higher yields of propylene and liquified petroleum gas (LPG).
The process for the preparation of FCC catalyst additive composition comprises the following steps:
i. mixing at least one alumina precursor, at least one phosphorous compound, and water at a first predetermined temperature for a first predetermined time period followed by aging for a time period in the range of 1 hour to 4 hours to obtain an aluminophosphate (AlPO) slurry;
ii. mixing the aluminophosphate (AlPO) slurry and a group IVB metal oxide solution at a second predetermined temperature for a second predetermined time period to obtain a metal incorporated aluminophosphate (M-AlPO) slurry;
iii. mixing at least one clay and at least one silica precursor with water to obtain a binder slurry;
iv. separately, mixing at least one zeolite, at least one phosphorous compound and water followed by aging for a time period in the range of 30 minutes to 90 minutes to obtain a zeolite-phosphate slurry;
v. adding the zeolite-phosphate slurry to the binder slurry under stirring to obtain a homogeneous zeolite-binder slurry;
vi. adding the M-AlPO slurry to the homogeneous zeolite-binder slurry under stirring followed by aging for a time period in the range of 30 minutes to 90 minutes to obtain a resultant slurry;
vii. spray drying the resultant slurry to obtain spray dried micro spherical particles; and
viii. calcining the spray dried micro spherical particles at a third predetermined temperature for a third predetermined time period to obtain the FCC catalyst additive composition.
The process is described in detail as given below.
i. Preparation of an aluminophosphate (AlPO) slurry:
In a first step, at least one alumina precursor and at least one phosphorous compound, are mixed with water at a first predetermined temperature for a first predetermined time period to obtain an aluminophosphate (AlPO) slurry.
In an embodiment of the present disclosure, the alumina precursor is selected from the group consisting of colloidal alumina, crystalline alumina, amorphous alumina, colloidal hydrous alumina, boehmite, pseudoboehmite, alumina hydrate, and ? phase of alumina. In the exemplary embodiments, the alumina precursor is a mixture of pseudoboehmite and colloidal alumina.
In an embodiment of the present disclosure, the phosphorous compound is selected from the group consisting of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hypophosphate, ammonium orthophosphate, ammonium dihydrogen orthophosphate, ammonium hydrogen orthophosphate, triammonium phosphate, phosphines, and phosphites. In an exemplary embodiment, the phosphorus compound is phosphoric acid.
In accordance with the present disclosure, the phosphorous compound has a covalent or ionic constituent capable of reacting with hydrogen ion.
In an embodiment of the present disclosure, at least one alumina precursor, at least one phosphorous compound, optionally a complexing organic agent are mixed with water at a first predetermined temperature for a first predetermined time period to obtain an aluminophosphate (AlPO) slurry.
In an embodiment of the present disclosure, the complexing organic agent is selected from the group consisting of urea, acetamide, citric acid, oxalic acid, glucose, and a combination thereof.
The complexing organic agent improves the dispersion of active zeolite in the matrix component and also improves the matrix surface area.
In an embodiment of the present disclosure, the first predetermined temperature is in the range of 30 ºC to 60 ºC. In an exemplary embodiment, the first predetermined temperature is 45 ºC.
In accordance with an embodiment of the present disclosure, the first predetermined time period is in the range of 1 hour to 4 hours. In an exemplary embodiment, the first predetermined time period is 2 hours.
In accordance with an embodiment of the present disclosure, the aluminophosphate (AlPO) slurry is aged for a time period in the range of 1 hour to 4 hours. In an exemplary embodiment, the aluminophosphate (AlPO) slurry is aged for 2 hours.
A molar ratio of aluminium to phosphorus in the binder is in the range of 0.5 to 1.2.
ii. Preparation of metal incorporated aluminophosphate (M-AlPO) slurry:
In a second step, the aluminophosphate (AlPO) slurry is mixed with a group IVB metal oxide solution at a second predetermined temperature for a second predetermined time period to obtain a metal incorporated aluminophosphate (M-AlPO) slurry. The pH of so obtained M-AlPO slurry is less than 3.
In an embodiment of the present disclosure, the group IVB metal oxide solution is selected from an aqueous titanium oxide solution and an aqueous zirconium oxide solution. In an exemplary embodiment of the present disclosure, the group IVB metal oxide solution is an aqueous titania solution.
In an embodiment of the present disclosure, the group IVB metals in group IV B metal oxide solution are selected from titanium and zirconium. In an exemplary embodiment, the group IVB metal is titanium.
In an embodiment of the present disclosure, the group IVB metal oxides in the group IVB metal oxide solution have a crystal size in the range of 10 nm to 25 nm.
In accordance with an embodiment of the present disclosure, the second predetermined temperature is in the range of 30 ºC to 60 ºC. In an exemplary embodiment, the second predetermined temperature is 45 ºC.
In accordance with an embodiment of the present disclosure, the second predetermined time period is in the range of 30 minutes to 180 minutes. In an exemplary embodiment, the second predetermined time period is 60 minutes.
iii. Preparation of a binder slurry:
In a third step, at least one of, the silica precursor or the acidified silica is mixed with at least one clay and water to obtain binder slurry.
In an embodiment of the present disclosure, at least one silica precursor is treated with monoprotic acid (monomerized by acidification) at a pH in the range of 3 to 4 to obtain an acidified silica.
In an embodiment of the present disclosure, the silica precursor is selected from the group consisting of colloidal silica, fumed silica, sodium silicate and silica gel. In an exemplary embodiment, the silica precursor is colloidal silica.
In accordance with an embodiment of the present disclosure, the monoprotic acid is selected from formic acid and acetic acid. In an exemplary embodiment, the monoprotonic acid is acetic acid.
In an embodiment of the present disclosure, the clay is selected from the group consisting of kaolin, montmorillonite, sapiolite, hallosite, and bentonite.
iv. Preparation of a zeolite-phosphate slurry:
In a fourth step, at least one zeolite and at least one phosphorous compound and water are mixed followed by aging for a time period in the range of 1 hour to 4 hours to obtain a zeolite-phosphate slurry.
In an embodiment of the present disclosure, the zeolite is selected from the group consisting of ZSM-5, ZSM-11, ZSM-22, beta zeolite, mordenite, and REY zeolite. In an exemplary embodiment, the zeolite is ZSM-5.
In accordance with the present disclosure, the zeolite content has the effect on activity of FCC catalyst additive as zeolite is the major active component in the FCC catalyst additive for gasoline cracking to propylene.
In accordance with an embodiment of the present disclosure, a molar ratio of silica to alumina (SAR) in the zeolite is in the range of 10:1 to 45:1. In an exemplary embodiment, the molar ratio of silica to alumina (SAR) in the zeolite is 30:1.
In accordance with an embodiment of the present disclosure, the phosphorous compound is selected from the group consisting of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hypophosphate, ammonium orthophosphate, ammonium dihydrogen orthophosphate, ammonium hydrogen orthophosphate, triammonium phosphate, phosphines, and phosphites. In an exemplary embodiment, the phosphorus compound is phosphoric acid.
In accordance with an embodiment of the present disclosure, the zeolite-phosphate slurry is aged for a time period in the range of 30 minutes to 90 minutes. In an exemplary embodiment, the zeolite-phosphate slurry is aged for 60 minutes.
v. Preparation of zeolite-binder slurry:
In a fifth step, the zeolite-phosphate slurry is slowly added to the binder slurry under stirring to obtain a homogeneous zeolite-binder slurry.
vi. Preparation of a resultant slurry:
In a sixth step, the M-AlPO slurry is slowly mixed with the zeolite-binder slurry under stirring to obtain a resultant slurry.
In accordance with an embodiment of the present disclosure, the pH of the resultant slurry is in the range of 1 to 5.
In accordance with an embodiment of the present disclosure, the resultant slurry is aged for a time period in the range of 30 minutes to 90 minutes. In an exemplary embodiment, the resultant slurry is aged for 60 minutes.
vii. Preparation of a spray-dried micro spherical particles:
In a seventh step, the resultant slurry is subjected to spray drying to obtain a spray-dried micro spherical particles.
In accordance with an embodiment of the present disclosure, the inlet temperature is in the range of 300° C to 500° C. In an exemplary embodiment, the inlet temperature is 400° C.
In accordance with an embodiment of the present disclosure, the outlet temperature is in the range of 120°C to 180°C. In an exemplary embodiment, the outlet temperature is 160° C.
In accordance with an embodiment of the present disclosure, the average particle size of the spray-dried spherical particles is in the range of 80 µm to 110 µm.
viii. Preparation of an FCC catalyst additive composition:
In a final step, the spray-dried micro spherical particles are calcined at a third predetermined temperature for a third predetermined time period to obtain the FCC catalyst additive composition.
In an embodiment of the present disclosure, the third predetermined temperature is in the range of 400 ºC to 750 ºC. In an exemplary embodiment, the third predetermined temperature is 600 ºC.
In an embodiment of the present disclosure, the third predetermined time period is in the range of 1 hour to 8 hours. In an exemplary embodiment, the third predetermined time period is 5 hours.
An FCC catalyst additive composition comprises at least one zeolite in an amount in the range of 30 mass% to 60 mass% with respect to the total amount of the composition, at least one binder in an amount in the range of 5 mass% to 20 mass% with respect to the total amount of the composition, at least one phosphorus compound in an amount in the range of 5 mass% to 15 mass% with respect to the total amount of the composition, at least one Group IVB metal compound in an amount in the range of 0.1 mass% to 10 mass% with respect to the total amount of the composition and at least one clay in an amount in the range of 5 mass% to 40 mass% with respect to the total amount of the composition.
The zeolite is selected from the group consisting of ZSM-5, ZSM-11, ZSM-22, beta zeolite, mordenite, and rare earth Y (REY) zeolite. In an exemplary embodiment, the zeolite is ZSM-5.
A molar ratio of silica to alumina (SAR) in the zeolite is in the range of 10:1 to 45:1. In an exemplary embodiment, a molar ratio of silica to alumina (SAR) in the zeolite is 30:1.
The binder is selected from aluminophosphate and silica aluminophasphate. In an exemplary embodiment, the binder is aluminophosphate.
A molar ratio of aluminium to phosphorus in the binder is in the range of 0.5 to 1.2. In an exemplary embodiment, a molar ratio of aluminium to phosphorus in the binder is 0.67. In another exemplary embodiment, a molar ratio of aluminium to phosphorus in the binder is 0.83. In yet another exemplary embodiment, a molar ratio of aluminium to phosphorus in the binder is 1.0.
The phosphorous compound is selected from the group consisting of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hypophosphate, ammonium orthophosphate, ammonium dihydrogen orthophosphate, ammonium hydrogen orthophosphate, triammonium phosphate, phosphines, and phosphites. In an exemplary embodiment, the phosphorous compound is phosphoric acid.
The IVB metal oxide is selected from titanium oxide and zirconium oxide. In an exemplary embodiment, the IVB metal oxide is titanium oxide
The clay is selected from the group consisting of kaolin, montmorillonite, sapiolite, hallosite, and bentonite. In an exemplary embodiment, the clay is kaolin.
The amount of components a) to e) provided in said composition are prior to subjecting to a hydrothermal treatment.
A process for cracking hydrocarbon feed by using a mixture of a FCC catalyst and a FCC catalyst additive in a ratio in the range of 70 to 85:15 to 30 at a temperature in the range of 450 °C to 650 °C for a time period in the range of 10 seconds to 40 seconds to obtain cracked hydrocarbons containing LPG and propylene.
The hydrocarbon feed comprises olefins containing naphtha (C5 to C12), C4 to C6 paraffins and heavier hydrocarbons consisting of gas oil, vacuum gas oil, atmospheric oil/vacuum residue, slurry oil, heavy crude, biomass pyrolysis oil, waste plastic pyrolysis oil or combination thereof. In an exemplary embodiment, the hydrocarbon feed is vaccum gas oil(VGO).
The FCC catalyst is rare-earth-containing ultrastable Y zeolite (ReUSY).
The FCC catalyst is hydrothermally deactivated by using 100% steam under atmospheric pressure at a temperature in the range of 750 °C to 850 °C for a time period in the range of 15 hours to 25 hours. In an exemplary embodiment, the FCC catalyst is hydrothermally deactivated by using 100% steam under atmospheric pressure at 800 °C for 20 hours.
The FCC catalyst additive is hydrothermally deactivated by using 100% steam under atmospheric pressure at a temperature in the range of 750 °C to 900 °C for a time period in the range of 30 hours to 120 hours. In an exemplary embodiment, the FCC catalyst additive is hydrothermally deactivated by using 100% steam under atmospheric pressure at 800 °C for 20 hours.
The so obtained FCC catalyst additive composition of the present disclosure enhances the conversion and yield of propylene while lowering the dry gas yield in the fluid catalytic cracking of hydrotreated vacuum gas oil (HT-VGO). This is due to the improved retention of zeolite framework aluminum by bonding with phosphorous and elements from transition metals of Group IVB. The direct stabilization of zeolite by phosphorous is used along with other materials like other zeolites, silica-alumina, a mixture of colloidal and or crystalline/amorphous alumina, unlike the conventional clay-phosphorous interaction. The present disclosure effectively uses the ‘phosphorus (P)’ to form aluminophosphate (AIPO) to stabilize the zeolite. By the addition of transition metals in the catalyst additive composition of the present disclosure, facilitates additional stability and enhances dehydrogenation to form more olefins. The presence of AIPO imparts higher matrix surface area apart from improving binding, this further enhanced surface area. The enhanced surface area improves the diffusion and increases the conversion, which in turn maximizes propylene formation. Further, the synergic effect of metal aluminophosphate (M-AlPO), silica binder, clay, zeolite-phosphorous, and added silica-alumina interactions led to high stability and improved propylene yields in FCC.
The foregoing description of the embodiments has been provided for purposes of illustration and not intended to limit the scope of the present disclosure. Individual components of a particular embodiment are generally not limited to that particular embodiment but are interchangeable. Such variations are not to be regarded as a departure from the present disclosure, and all such modifications are considered to be within the scope of the present disclosure.
The present disclosure is further described in light of the following experiments which are set forth for illustration purpose only and not to be construed for limiting the scope of the disclosure. The following experiments can be scaled up to industrial/commercial scale and the results obtained can be extrapolated to industrial scale.
EXPERIMENTAL DETAILS
Experiment-1: General process for the preparation of the FCC catalyst additive composition
Examples 1-3: A process for the preparation of an FCC catalyst additive composition, in accordance with the present disclosure.
The alumina precursor(s) and phosphorous compound, were mixed in water at 45 ºC for 2 hours followed by aging for 2 hours to obtain an aluminophosphate (AlPO) slurry.
Step-ii: Preparation of a metal incorporated aluminophosphate (M-ALPO) slurry
The so obtained aluminophosphate (AlPO) slurry was mixed with IVB metal solution at 45 °C for 1 hour to obtain a metal incorporated aluminophosphate (M-AlPO).
The colloidal silica (silica precursor) was monomerized by acidification with a acetic acid at a pH in the range of 3 to 4 to obtain an acidified silica.
Step-iii: Preparation of a binder slurry:
Clay was mixed with acidified silica and water to obtain a binder slurry.
Step-iv: Preparation of a zeolite-phosphate slurry:
Zeolite, phosphorous compound and water were mixed followed by aging for 60 minutes to obtain a zeolite phosphate slurry.
Step-v: Preparation of zeolite-binder slurry:
The zeolite-phosphate slurry was slowly added to the binder slurry under stirring to obtain a homogeneous zeolite-binder slurry.
Step-vi: Preparation of a resultant slurry:
The M-AlPO slurry was slowly added to the zeolite-binder slurry under stirring followed by aging for 1 hour to obtain a resultant slurry having a pH in the range of 1 to 5.
Step-vii: Preparation of spray dried micro spherical particles:
The resultant slurry was subjected to spray drying at an inlet temperature of 400 °C and at an outlet temperature of 160 °C to obtain spray-dried micro spherical particles having a particle size in the range of 70 µm to 100 µm.
Step-viii: Preparation of FCC catalyst additive composition:
The spray-dried micro spherical particles were calcined at a temperature of 600 ºC for 5 hours to obtain the FCC catalyst additive composition. The FCC catalyst additive has a particle size in the range of 70 µm to 100 µm.
The amounts of the ingredients and specific catalyst additive composition for examples 1 to 3 are provided in Table 1.
Table 1: Amounts of the ingredients used in the catalyst additive composition of examples 1-3
Ingredients Example-1 Example-2 Example-3
ZSM-5 (g) (zeolite) 1075 1183 1075
Pseudoboehmite (alumina precursor)(g) 59 59 59
Colloidal alumina (g) (alumina precursor) 60 60 69
P2O5 (g) (phosphorous compound) 292 292 292
Colloidal silica (g) (silica precursor) 333 333 533
Titania (g) (Nano TiO2) 111 111 111
Clay (g) 694 576 624
The ingredients for catalyst composition are mentioned in Table 1 are used to prepare respective slurries using water.
Experiment-2: Hydrothermal deactivation of the FCC catalyst additive (Steaming):
The FCC catalyst additive compositions obtained in examples 1-3 were hydrothermally deactivated to match the activity equivalent to Equilibrium Catalyst (ECAT) from the FCC unit. Deactivation was carried out at a temperature in the range of 800 ºC to 850 ºC in presence of 100% steam for a time period in the range of 20 hours to 100 hours. The steam deactivated catalyst additives were tested for their FCC performance activity in Advanced Cracking Evaluation (ACE unit).
The properties of the FCC catalyst additive compositions of the present disclosure in Table 1 were compared with the commercial FCC catalyst additive, which is provided in Table 2.
Physical properties of the FCC catalyst additive obtained in examples 1-3:
The physical properties namely total surface area (TSA), zeolite surface area (ZSA), matrix surface area (MSA), total pore volume (TPV), zeolite pore volume (ZPV), apparent bulk density (ABD), average particle size (APS), and attrition index (AI) as per ASTM D5757 are mentioned in Table 2.
Table 2: Physical properties of Examples 1 - 3
Catalyst additive Example-1 Example-2 Example-3 Conventional additive
TSA(F), m2/g 136 175 139 151
ZSA(F), m2/g 112 146 118 133
MSA(F), m2/g 24 29 21 18
TPV, cc/g 0.096 0.102 0.106 0.092
ZPV, cc/g 0.051 0.066 0.05 0.061
ABD, g/cc 0.74 0.73 0.74 0.75
APS, (µ) 88 80 90 95
Attrition Index (AI) 9 11 8 5
From table 2 it is observed that by increasing the zeolite content from 50% to 55%, both zeolite surface area, as well as matrix surface area, has increased. This suggests zeolite is uniformly distributed in the composition even in higher zeolite content. Further, the matrix surface area was higher than the commercial additive which shows improved diffusion and accessibility of the matrix for this additive, which in turn would provide better cracking and olefin yields. In general, increasing the zeolite content improves the zeolite surface area by reducing the matrix surface area. In contrast, in the existing composition, both zeolite and matrix surface area increased by increasing the zeolite content from 50% to 55% in Example 2.
The physical properties of the hydrothermally deactivated catalyst additives (Example-1 to Example-3) are shown in Table 3.
Table 3: Physical properties of the catalyst composition of Examples 1-3 (after hydrothermally deactivated)
Catalyst additive Example-1 Example-2 Commercial additive Example-3 Commercial additive
Hydrothermal deactivation time 40 hours 100 hours
Zeolite % 50 55 50 50 50
TSA, m2/g 168 183 162 175 160
ZSA, m2/g 76 91 87 69 76
MSA, m2/g 92 92 75 106 85
TPV, CC/g 0.113 0.114 0.109 0.145 0.108
ZPV, CC/g 0.036 0.041 0.037 0.032 0.037
Table 3 shows the surface area, pore volume, and pore size results of the hydrothermally deactivated catalysts at different deactivation times. With increasing the deactivation time, there was a loss in zeolite surface area but an increase in matrix surface area. The catalyst in Example-3 showed the highest matrix surface area of 106 m2/g vs 85 m2/g in a commercial catalyst. The increase in matrix surface area was attributed to the presence of aluminum phosphate in the matrix and also due to the de-blocking of phosphorus species or phosphorous migration from the zeolite pores during hydrothermal deactivations. It can thus be suggested that the changes in porosity of the P/ZSM-5 additive upon steaming at FCC conditions were mainly attributed to the changes of the zeolitic crystals, i.e., the decrease of microporosity, and the formation of the secondary meso/macropore network.
Examples 1-3 are prepared in the manner as explained earlier with varying zeolite and silica content by balancing the rest with clay. The catalyst in Example-1 consists of 50% by weight of zeolite and 5% by weight of silica with Al/P molar ratio of 0.67 in aluminophosphate slurry. Catalyst in Example-2 is prepared in a similar manner as Example 1 with the exception of 55 wt% of zeolite content. The catalyst in Example-3 consists of 50 wt% by weight of zeolite, 8 wt% by weight of silica with an Al/P molar ratio of 0.83. Examples 1-2 are deactivated at 800 ºC in presence of 100% steam for a time period of 40 hours, while Example-3 is deactivated at 800 ºC in presence of 100% steam for a time period of 100 hours.
X-ray diffraction studies
XRD patterns of the catalyst additives of the present disclosure of example-1 and example-2 (both calcined and steamed) are illustrated in Figure 1. The XRD patterns of pure ZSM-5 zeolite (SAR 30) and commercial catalysts additive were also analyzed for comparison. The XRD patterns of all the catalyst additive compositions showed similar diffractions which suggests the majority of the crystallinity coming from the ZSM-5 zeolite which was around 50 to 55% in the overall composition. Other than the zeolite, silica, alumina, and clay components were highly amorphous and has not shown any corresponding reflections in XRD which is evident from Fig.1. Similarly, diffractions corresponding to titania were also not visible due to well dispersed nanoparticles in the matrix. Aluminophosphates (AlPO) were similar to zeolite materials and were essentially built from ordered framework structures as of zeolites but with weaker or no acidity. However, by substituting a few Al3+ or P5+ ions with Si4+ ions, they generate more number of acid sites (Bronsted) which takes part in cracking and isomerization reactions.
Due to the framework structure of AlPO, they exhibited highly crystalline in nature. AlPO tends to show diffraction in XRD which is evident from a small diffraction at 2? = 21.6 degrees in all AlPO containing additives. However, the presence of very weak diffraction signals of AlPO in XRD suggested the stable well dispersed Silica-AlPO framework in the additive. This provided additional acidity to crack LCO/gasoline range hydrocarbon fraction and also provided improved hydrothermal stability to achieve greater tolerance to loss of activity during several reaction-regeneration cycles.
Examples 4-6: Effect of Al/P ratio of Aluminophosphate binder (slurry) on physical properties and activity of the catalyst additive

The base formulation in examples 4 to 6 was prepared in a similar manner as in example 1 except the change in Al/P ratios as shown in table 4 below:
Table 4: Physical properties of the catalyst composition of Examples 4-6 (fresh
catalyst and hydrothermally deactivated catalyst.
Parameter Example 4 Example 5 Example 6
Final slurry viscosity, cp 2750 1133 850
Mole ratio of Al/P in AlPO 0.67 0.83 1.0
ABD 0.66 0.72 0.70
PSD, microns 112 106 108
Fresh catalyst
TSA, m2/g 140 139 136
ZSA, m2/g 116 118 113
MSA, m2/g 24 21 22
TPV, cc/g 0.100 0.106 0.105
ZPV, cc/g 0.05 0.05 0.05
Hydrothermally deactivated catalyst
TSA, m2/g 169 175 172
ZSA, m2/g 53 69 71
MSA, m2/g 116 106 101
TPV, cc/g 0.108 0.145 0.115
ZPV, cc/g 0.025 0.032 0.033

Physical properties
The physical properties of examples 4 to 6 were analyzed in Accelerated Surface Area and Porosimetry System (ASAP) N2 porosimeter. It was seen that after hydrothermal deactivation, the zeolite surface area in examples 4 to 6 was reduced while the matrix area was significantly improved. Due to severe hydrothermal deactivation, partial loss of framework alumina from zeolite and extra framework aluminium and phosphorous from the matrix were removed, thereby generating larger pores as shown in figures 2 to 4. The Catalyst additive in example 5 showed optimium combination of zeolite retention and matrix accessibility which is evident from it’s TSA, while catalyst in example 4 showed higher matrix accessibility with lower zeolite retention which was reflected in pore size distribution in figures 2 to 4. Based on the surface area data, catalyst in Ex-5 with Al/P ratio of 0.83 shows improved activity and hydrothermal stability.
Al/P ratio of Aluminophosphate binder (slurry) affects the matrix activity and diffusion of gasoline and LCO molecules.

Experiment-III:
Example 7: A fluid catalytic cracking process carried out by using a commercial FCC catalyst (ReUSY based) and the FCC catalyst additives, in accordance with of examples 1-3 of the present disclosure
The base FCC catalyst (RE USY based) and the catalyst additives of examples 1-3 of the present disclosure were hydrothermally deactivated by using 100 % steam under atmospheric pressure at 800 °C. The deactivation for RE USY commercial catalyst was carried out for 20 hours. The deactivation for catalyst additives in examples 4-5 was carried out for 40 hours and the deactivation for catalyst additives in example 6 was carried out for 100 hours. Admixture of the hydrothermally deactivated RE USY based catalyst and the hydrothermally deactivated additive with a predetermined ratio (78:22) was loaded in a fixed fluid bed ACE microreactor. The microreactor was electrically heated to maintain the catalyst bed temperature at 545 °C. The hydro treated Vacuum Gas Oil (VGO) was injected into the fluidized bed for 30 seconds to generate the cracking data at various catalysts to oil ratios. The properties of VGO are shown in Table 5 . The product yields at constant conversion are compiled in Table 6 .
Table 5 : The properties of the VGO feed
Properties Value
VGO specific gravity 0.907
Viscosity (at 99 °C) 6.8 cSt
Sulfur 0.25 wt%
CCR (Carbon) 0.12 wt%
Total Nitrogen 800 wt ppm
UOP K 11.85
wt% of hydrocarbons distilled out at different temperatures (SIM Dist D2887) in °C
5 wt% 327
10 wt% 350
30 wt% 401
50 wt% 433
70 wt% 470
90 wt% 518
Table 6 : Product yields of FCC process at constant conversion
FCC product
yields wt% Example-1 Example-2 Commercial additive Example-3 Commercial additive
Hydrothermal deactivation time 40 hours 100 hours
C/O ratio 7.0 6.7 7.06 7.28 7.58
Dry gas, wt% 4.4 4.05 5.72 3.43 2.87
Total LPG (incl. propylene), wt% 35.12 32.74 35.58 32.3 33.35
Propylene, wt% 15.3 13.9 14.7 13.78 13.65
Gasoline, wt% 29.5 32.41 27.8 35.18 34.58
LCO, wt% 17.9 17.94 18.4 17.6 17.34
CSO, wt% 8.1 8.06 7.6 6.4 6.66
Coke, wt% 4.98 4.8 4.9 5.09 5.2
Total 100 100 100 100 100
Conversion 74 74 74 76 76
The higher matrix surface area of additive in example -1 before and after steaming in comparison to commercial additive was expected to facilitate better diffusion of hydrocarbon molecules and thereby better cracking yields, which was evident from higher propylene yield, lower dry gas, and lower LCO of example -1. The presence of a stable AlPO matrix provides additional acidity which facilitates the cracking of LCO to gasoline and propylene maximization compared to commercial additive as shown in Table 6 .
In addition, example-1 also showed a slightly improved conversion and lower dry gas yield. Example-2 with 55% zeolite content however shows marginally lower propylene yield and higher bottoms. This can be attributed to lower matrix activity owing to higher zeolite content.
The catalyst in example 3 has achieved 76 wt% conversion at a lower catalyst-to-oil (C/O) ratio, which shows improved catalytic activity in comparison to the commercial sample. In addition, gasoline yield is higher than commercial catalyst additive. Thus, the composition of example 1 of the present disclosure is optimum to have better gasoline and bottoms cracking and higher propylene yield.
Example 8: A fluid catalytic cracking process carried out by using a commercial FCC catalyst and the FCC catalyst additives of examples 4-6, in accordance with the present disclosure
The base FCC catalyst (RE USY based) and the catalyst additives of examples 1-3 of the present disclosure were hydrothermally deactivated by using 100 % steam under atmospheric pressure at 800 °C. The deactivation for RE USY commercial catalyst was carried out for 20 hours. The deactivation for catalyst additives in examples 4-5 was carried out for 40 hours and the deactivation for catalyst additives in example 6 was carried out for 100 hours. Admixture of the hydrothermally deactivated RE USY based catalyst and the hydrothermally deactivated additive with a predetermined ratio (78:22) was loaded in a fixed fluid bed ACE microreactor. The microreactor was electrically heated to maintain the catalyst bed temperature at 545 °C. The hydro treated Vacuum Gas Oil (VGO) was injected into the fluidized bed for 30 seconds to generate the cracking data at various catalysts to oil ratios. The product yields at are compiled in Table 8.
Table 8: Product yields of FCC process using conventional FCC catalysts and FCC catalyst additives of examples 4 to 6
Sample Description Commercial
ReUSY Example 4 Example 5 Example 6
Dry gas 2.1 2.07 2.08 2.1
Ethylene 2 2.18 2.32 2.03
Propylene 10.37 10.32 10.47 10.33
LPG 18.38 18.11 18.28 18.22
Gasoline 35.88 36.18 36.14 36.02
LCO 18.22 18.22 17.97 18.56
CSO 7.4 7.23 7.05 7.1
Coke 5.66 5.69 5.69 5.66
Conversion 74.38 74.75 74.78 74.35
Total 100 100 100 100
Regen dense bed Temp °C 696.3 694.3 695 695.2
ROT °C 540.9 541 541.9 540.9
C/O 10.3 10.3 10.3 10.3
Regen air total, knm3/hr 777 782 782 777
Figures 2-7 show retention of external pores. The improvement in these intra particle voids provide better accessibility for the cracking of heavier fractions which lead to better CSO and LCO cracking leading to more conversion and propylene yield. The isotherms in figures 2-7 show a significant loss of micropore volume but improvement in the external surface area, which is evident from isotherms in figures 2-7 and BJH PSD cruves. After steaming, the total pore volume of the fresh catalyst was also improved.
This was due to the fact that the phosphorus-containing zeolites have their zeolitic micropores blocked partially by phosphorus species, while the steaming procedure induced the removal of phosphorus species from micropores. It was observed that the changes in porosity of the P/ZSM-5 additive upon steaming at FCC relevant conditions are mainly attributed to the changes of the zeolitic crystals, i.e., the decrease of microporosity, and the formation of secondary meso/macropore network.
From table 8 it is observed that the optimum Al/P ratio of AlPO binder in example 5 has provided improved diffusion of larger hydrocarbon molecules (CSO & LCO) in the matrix and thereby improving conversion and providing higher propylene yield. Along with facilitating the diffusion, the presence of stable SAPO matrix provides additional Bronsted acidity in the matrix and facilitates cracking of LCO to gasoline and propylene maximization compared to commercial additives. Eventhough the yield of propylene obtained in the FCC process using catalyst additives of the present disclosure is comparable with the yield of propylene using conventional catalyst additives FCC, the CSO yield is lower than commercial catalyst, which suggests improved activity of catalyst additive prepared in accordance with the present disclosure.
Experiment IV: Stability study of the FCC catalyst additives
To study the stability of the catalyst additive under severe hydrothermal FCC conditions, the catalyst activity was tested for four cycles of reaction and regenerations by using a proprietary method. After each ACE evaluation, the catalysts (commercial and catalyst of example 1) were regenerated by burning the coke on the catalyst and reused for the next cycle. This study was required to understand the loss of activity in commercial FCC units over a period of time. This would further provide insights on the rate of addition of ZSM-5 additive to the catalyst. Table 9 shows conversion and propylene loss during four reaction-regeneration cycles.
It can be seen from table 9 that loss of conversion was comparable in commercial and additive from Example 1. However, the propylene loss was more in commercial catalyst additive in comparison to the additive prepared as given in Example 1. This shows improved zeolite retention activity and matrix stability in the current composition.
Table 9 : Reaction-regeneration cycle data of additive given in Example-1.
Cycle No. 1 2 3 4 Delta of 4th and 1st cycle 1 2 3 4 Delta of 4th and 1st cycle
Catalyst Name Commercial additive Example-1
Feed Hydro treated VGO
Conversionwt% 72.4 71.8 71.0 70.7 -1.7 72.6 71.1 71.0 70.6 -2.0
Propylene, wt% 14.25 13.68 12.97 12.90 -1.35 14.00 13.48 13.20 13.4 -0.55

TECHNICAL ADVANCEMENTS
The present disclosure described herein above has several technical advantages including, but not limited to, the realization of a process for the preparation of an FCC catalyst additive composition:
• that is simple and economical;
• that provides higher yields of propylene and liquefied petroleum gas (LPG); and
• that has a comparatively high zeolite and matrix surface area in obtained FCC catalyst additive and also after hydrothermal deactivations; and
• that has improved zeolite retention properties over several reaction-regeneration cycles.
The embodiments herein and the various features and advantageous details thereof are explained with reference to the non-limiting embodiments in the following description. Descriptions of well-known components and processing techniques are omitted so as to not unnecessarily obscure the embodiments herein. The examples used herein are intended merely to facilitate an understanding of ways in which the embodiments herein may be practiced and to further enable those of skill in the art to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein.
The foregoing description of the specific embodiments so fully reveal the general nature of the embodiments herein that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. Therefore, while the embodiments herein have been described in terms of preferred embodiments, those skilled in the art will recognize that the embodiments herein can be practiced with modification within the spirit and scope of the embodiments as described herein.
The use of the expression “at least” or “at least one” suggests the use of one or more elements or ingredients or quantities, as the use may be in the embodiment of the disclosure to achieve one or more of the desired object or results.
Any discussion of documents, acts, materials, devices, articles or the like that has been included in this specification is solely for the purpose of providing a context for the disclosure. It is not to be taken as an admission that any or all of these matters form a part of the prior art base or were common general knowledge in the field relevant to the disclosure as it existed anywhere before the priority date of this application.
The numerical values mentioned for the various physical parameters, dimensions or quantities are only approximations and it is envisaged that the values higher/lower than the numerical values assigned to the parameters, dimensions or quantities fall within the scope of the disclosure, unless there is a statement in the specification specific to the contrary.
While considerable emphasis has been placed herein on the components and component parts of the preferred embodiments, it will be appreciated that many embodiments can be made and that many changes can be made in the preferred embodiments without departing from the principles of the disclosure. These and other changes in the preferred embodiment as well as other embodiments of the disclosure will be apparent to those skilled in the art from the disclosure herein, whereby it is to be distinctly understood that the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation. ,CLAIMS:WE CLAIM:
1. A process for the preparation of an FCC catalyst additive composition, said process comprising the following steps:
i. mixing at least one alumina precursor, at least one phosphorous compound, and water at a first predetermined temperature for a first predetermined time period followed by aging for a time period in the range of 1 hour to 4 hours to obtain an aluminophosphate (AlPO) slurry;
ii. mixing said aluminophosphate (AlPO) slurry and a group IVB metal oxide solution at a second predetermined temperature for a second predetermined time period to obtain a metal incorporated aluminophosphate (M-AlPO) slurry;
iii. mixing at least one clay and at least one silica precursor with water to obtain a binder slurry;
iv. separately, mixing at least one zeolite, at least one phosphorous compound and water followed by aging for a time period in the range of 30 minutes to 90 minutes to obtain a zeolite-phosphate slurry;
v. adding said zeolite-phosphate slurry to said binder slurry under stirring to obtain a homogeneous zeolite-binder slurry;
vi. adding said M-AlPO slurry to said homogeneous zeolite-binder slurry under stirring followed by aging for a time period in the range of 30 minutes to 90 minutes to obtain a resultant slurry;
vii. spray drying said resultant slurry to obtain a spray dried micro spherical particles; and
viii. calcining the spray dried micro spherical particles at a third predetermined temperature for a third predetermined time period to obtain said FCC catalyst additive composition.

2. The process as claimed in claim 1, wherein at least one silica precursor is optionally treated with a monoprotic acid at a pH in the range of 3 to 4 to obtain an acidified silica.

3. The process as claimed in claim 1, wherein said alumina precursor is selected from the group consisting of colloidal alumina, crystalline alumina, amorphous alumina, colloidal hydrous alumina, boehmite, pseudoboehmite, alumina hydrate, and ? phase of alumina.

4. The process as claimed in claim 1, wherein said phosphorous compound is selected from the group consisting of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hypophosphate, ammonium orthophosphate, ammonium dihydrogen orthophosphate, ammonium hydrogen orthophosphate, triammonium phosphate, phosphines, and phosphites.

5. The process as claimed in claim 1, wherein said first predetermined temperature is in the range of 30 ºC to 60 ºC.

6. The process as claimed in claim 1, wherein said first predetermined time period is in the range of 1 hour to 4 hours.

7. The process as claimed in claim 1, wherein said group IVB metal oxide solution is selected from an aqueous titanium oxide solution and an aqueous zirconium oxide solution.

8. The process as claimed in claim 7, wherein said group IVB metal oxides in said group IVB metal oxide solution have a crystal size in the range of 10 nm to 25 nm.

9. The process as claimed in claim 1, wherein said second predetermined temperature is in the range of 30 ºC to 60 ºC.

10. The process as claimed in claim 1, wherein said second predetermined time period is in the range of 30 minutes to 180 minutes.

11. The process as claimed in claim 1, wherein said silica precursor is selected from the group consisting of colloidal silica, fumed silica, sodium silicate, and silica gel.

12. The process as claimed in claim 2, wherein said monoprotic acid is selected from formic acid and acetic acid.

13. The process as claimed in claim 1, wherein said clay is selected from the group consisting of kaolin, montmorillonite, sapiolite, hallosite, and bentonite.

14. The process as claimed in claim 1, wherein said zeolite is selected from the group consisting of ZSM-5, ZSM-11, ZSM-22, beta zeolite, mordenite, and rare earth Y (REY) zeolite.

15. The process as claimed in claim 14, wherein a molar ratio of silica to alumina (SAR) in said zeolite is in the range of 10:1 to 45:1.

16. The process as claimed in claim 1, wherein the average particle size of said spray-dried micro spherical particles is in the range of 80 µm to 110 µm.

17. The process as claimed in claim 1, wherein said third predetermined temperature is in the range of 400 ºC to 750 ºC.

18. The process as claimed in claim 1, wherein said third predetermined time period is in the range of 1 hour to 8 hours.

19. The process as claimed in claim 1, wherein a molar ratio of aluminium to phosphorus in said aluminophosphate slurry is in the range of 0.5 to 1.2.

20. An FCC catalyst additive composition comprising
a) at least one zeolite in an amount in the range of 30 mass% to 60 mass% with respect to the total amount of said composition;
b) at least one binder in an amount in the range of 5 mass% to 20 mass% with respect to the total amount of said composition;
c) at least one phosphorus compound in an amount in the range of 5 mass% to 15 mass% with respect to the total amount of said composition;
d) at least one Group IVB metal compound in an amount in the range of 0.1 mass% to 10 mass% with respect to the total amount of said composition; and
e) at least one clay in an amount in the range of 5 mass% to 40 mass% with respect to the total amount of said composition.

21. The composition as claimed in claim 20, wherein said zeolite is selected from the group consisting of ZSM-5, ZSM-11, ZSM-22, beta zeolite, mordenite, and rare earth Y (REY) zeolite.

22. The composition as claimed in claim 20, wherein a molar ratio of silica to alumina (SAR) in said zeolite is in the range of 10:1 to 45:1.

23. The composition as claimed in claim 20, wherein said binder is selected from aluminophosphate and silica aluminophasphate.

24. The composition as claimed in claim 20, wherein a molar ratio of aluminium to phosphorus in said binder is in the range of 0.5 to 1.2.

25. The composition as claimed in claim 20, wherein said phosphorous compound is selected from the group consisting of phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium hypophosphate, ammonium orthophosphate, ammonium dihydrogen orthophosphate, ammonium hydrogen orthophosphate, triammonium phosphate, phosphines, and phosphites.

26. The composition as claimed in claim 20, wherein said IVB metal oxide is selected from titanium oxide solution and zirconium oxide.

27. The composition as claimed in claim 20, wherein said clay is selected from the group consisting of kaolin, montmorillonite, sapiolite, hallosite, and bentonite.

28. The composition as claimed in claim 20, wherein the amount of components a) to e) provided in said composition are prior to subjecting to a hydrothermal treatment.

29. A process for cracking hydrocarbon feed by using a mixture of a FCC catalyst and a FCC catalyst additive as claimed in claim 1 in a ratio in the range of 70 to 85: 15 to 30 at a temperature in the range of 450 °C to 650 °C for a time period in the range of 10 seconds to 40 seconds to obtain cracked hydrocarbons containing LPG and propylene.

30. The process as claimed in claim 29, wherein said hydrocarbon feed comprises olefins containing naphtha (C5 to C12), C4 to C6 paraffins and heavier hydrocarbons consisting of gas oil, vacuum gas oil, atmospheric oil/vacuum residue, slurry oil, heavy crude, biomass pyrolysis oil, waste plastic pyrolysis oil or combination thereof.

31. The process as claimed in claim 29, wherein FCC catalyst is rare-earth-containing ultrastable Y zeolite (ReUSY).

32. The process as claimed in claim 29, wherein said FCC catalyst is hydrothermally deactivated by using 100% steam under atmospheric pressure at a temperature in the range of 750 °C to 850 °C for a time period in the range of 15 hours to 25 hours.

33. The process as claimed in claim 29, wherein said FCC catalyst additive is hydrothermally deactivated by using 100% steam under atmospheric pressure at a temperature in the range of 750 °C to 900 °C for a time period in the range of 30 hours to 120 hours.

Dated this 30th day of May, 2024

_______________________________
MOHAN RAJKUMAR DEWAN, IN/PA – 25
OF R. K. DEWAN & CO.
AUTHORIZED AGENT OF APPLICANT

TO,
THE CONTROLLER OF PATENTS
THE PATENT OFFICE, AT MUMBAI