Description:FIELD OF THE INVENTION
[0001] The present disclosure relates to a regenerable non-halogenated heavy naphtha reforming catalyst. The present disclosure also relates to a method of synthesizing a regenerable non-halogenated heavy naphtha reforming catalyst. Present disclosure discloses development of composite solid support that combines use of an unconventional promoter atom for making this novel formulation. The solid support along with the promoter atom avoids the active metal agglomeration during the reaction, unlike in the conventional chlorinated catalyst where the active metal undergo agglomeration during the reaction and needs chlorination to re-disperse the agglomerated active metal. The developed catalyst of the present disclosure is halogen free catalyst and is regenerable without any conventional oxychlorination step

BACKGROUND OF THE INVENTION
[0002] US7569508 discloses a reforming nanocatalyst particles are formed using a dispersing agent having at least one functional group selected from the group of a hydroxyl, a carboxyl, a carbonyl, an amide, an amine, a thiol, a sulfonic acid, sulfonyl halide, an acyl halide, an organometallic complex, and combinations of these. The dispersing agent is particularly useful for forming multicomponent catalysts comprising an alloy, combination, mixture, decoration, or interspersion of platinum and one or more of tin, rhenium or iridium. The formation of the nanoparticles may include a heat treating process performed in an inert or oxidative environment to maintain the catalyst atoms in a non-zero oxidation state to thereby maintain a stronger bond between the dispersing agent and the catalyst atoms. US7569508 discloses advantageous treatment of support material with a halogen to impart acidity. US7569508 cites in general use of silica, alumina, zeolites, or a metal oxide as support material. It requires dispersing agent to be essentially present in the catalyst system.
[0003] CA2586727C discloses a catalyst and a process for using the catalyst are disclosed generally for the conversion of hydrocarbons. The catalyst has an increased average bulk density and a decreased mass ratio of platinum-group metal. The process using the catalyst obtains unexpected high activity and stability for the reforming of naphtha range hydrocarbons. Mössbauer spectroscopy is used to characterize the extent of tin association with platinum and determine an effective molar tin ratio appropriate for alumina supports with densities above 0.6 g/cc. CA2586727C cites optional incorporation of halogen component in the catalyst and Sn as essential component. CA2586727C cites in general use of alumina, magnesia, zirconia, chromia, titania, boria, thoria, phosphate, zinc oxide, silica and mixtures thereof as support material.
[0004] GB2483994 discloses a catalyst for hydrogenation of unsaturated hydrocarbons, comprises an active metal, selected from palladium, platinum, nickel, copper and ruthenium, and is supported on a carrier and a silane group, and the silane group is grafted by silylation, and makes up 0.05 wt%-25 wt% of the total weight of the catalyst. The carrier is chosen from the group consisting of Al2O3, TiO2, V2O5, SiO2, ZnO, SnO2, ZrO2, MgO, activated carbon, kaolin and diatomite. The catalyst further comprises a metallic promoter, which makes up 0.01-10 wt% of the total weight of the catalyst, and comprises more than one metal chosen from sodium, potassium, caesium, calcium, magnesium, barium, gallium, indium, lead and bismuth. The process for preparing the catalyst involves supporting an active metallic component on the carrier, reducing the active metallic component to a metallic state, such as with hydrogen, or vulcanising it to a vulcanised state and silanising the catalyst using an organic silane, siloxane, silazane chlorosilane or mixtures thereof, to graft the silane group. GB2483994 discloses silane group grafted on catalyst carrier as essential component of the catalyst system. GB2483994 cites optional incorporation of halogens as non-metallic promoter in the catalyst system. GB2483994 cites an unsaturated hydrogenation catalyst system.
[0005] WO2020219311 relates to a method and system for the conversion of sulfur-containing feedstock, in particular, naphtha feedstock, into high-octane gasoline and chemical products (benzene, toluene, and xylenes) while minimizing catalyst deactivation. Provided herein are methods and systems for converting hydrocarbons that include providing a modified zeolitic catalyst that is substantially free of rhenium, the modified zeolitic catalyst comprising a zeolite, transition metal, and optionally a binder, and contacting a hydrocarbon feed stream having a sulfur content optionally in excess of about 0.5 ppm with a modified zeolitic catalyst under conditions effective to convert the hydrocarbon feed stream to a hydrocarbon product stream comprising a high-octane gasoline, xylenes, benzene, toluene, or a blend thereof, wherein when the RON of the C5+ fraction of the product stream is 95, the C5+ fraction yield is at least 75 wt. %. WO2020219311 cites incorporation of Tungsten Oxide as Extra framework metal oxides on the zeolite.
[0006] US8882992 discloses relates to a multistage reforming process to produce a high octane product. A naphtha boiling range feedstock is processed in a multi-stage reforming process, in which the process involves at least 1) a penultimate stage for reforming the naphtha feedstock to produce a penultimate effluent 2) a final stage for further reforming at least a portion of the penultimate effluent 3) a regeneration step for the final stage catalyst. The severity of the penultimate stage can be increased during final stage catalyst regeneration in order to maintain the target RON of the reformate product and avoid reactor downtime. US8882992 cites replacement of Si/Al atoms in molecular sieve catalyst by Ga to modify its catalytic activity. US8882992 also cites optional addition of halogen in the catalyst system.
[0007] Jawad et al. [2020 IOP Conf. Ser.: Mater. Sci. Eng. 928 022103] discloses nano gamma-alumina support was prepared successfully by Sol-gel method using aluminum nitrate without and with carbon nanotubes as a template at different calcination temperatures (600, 650, and 700°C) and then loaded with 0.3% of platinum and 0.3% of tungsten by the wet- impregnation method. X-ray diffraction (XRD), thermal gravimetric analysis (TGA), atomic force microscope (AFM), field emission scanning electron microscopy (FE-SEM) and (BET) surface area were used to characterize the prepared nano catalyst. The best results obtained were 389.34 m2/gm surface area, 0.468 cm3 /gm pore volume, 8.07 nm pore size and 42.71 nm average particle size for the prepared nana gamma-alumina at a calcination temperature of 600°C. Thus, Jawad et al. cites loading of Platinum and Tungsten on nano gamma-alumina support.
[0008] Vadi et al. discloses mono-metallic and bi-metallic catalysts have been prepared by impregnating with solutions containing a compound of H2PtCl6, WO3 and 1 ml HCl (0.1 mol). It should be noted that the catalysts’ activity and selectivity have been determined under these conditions: 450–500°C, and 15–25 atm by H2. For converting n-heptane, the molar ratio H2/C7H16 is 5, and LHSV is 1.5 ml/h. It has been proved that, under these experimental conditions, the conversion of n-heptane into branched aliphatic isomers is catalyzed by a bifunctional mechanism. The results indicate that in the presence of W, the catalysts have much higher selectivity and stability for isomerization reaction. At a given conversion, the bi-metallic catalysts produce much lower concentrations of cracked products. According to the tests, W modifies the support acidity resulting to the higher selectivity for isomerization and the lower one for cracking, and it also modifies the Pt properties. Thus, Vadi et al. cites loading of Platinum and Tungsten on gamma-alumina support.
[0009] However, the halogen containing conventional catalysts poses disadvantages such as use of high corrosive halogen, need of expensive metallurgy which is corrosive free, downstream halogen guard beds which adds to overall expenditure of the plant and also possible formation of ammonium halides which may choke downstream units. Thus, to overcome the drawbacks of the prior arts, there is a need to develop a halogen-free catalyst system which is regenerable without addition of the halogen.

OBJECTS OF THE INVENTION
[0010] An objective of the present invention is to provide a composite solid support along with a suitable promoter atom.
[0011] Another objective of the present invention is to provide a regenerable non-halogenated heavy naphtha reforming catalyst.
[0012] Yet another objective of the present invention is to provide a process of synthesizing a regenerable non-halogenated heavy naphtha reforming catalyst.
SUMMARY OF THE INVENTION
[0013] This summary is provided to introduce a selection of concepts in a simplified form that are further described below in Detailed Description section. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.
[0014] The present disclosure discloses a regenerable non-halogenated heavy naphtha reforming catalyst comprising: 95-98.5 w/w % of a composite solid support; 0.1-0.5 w/w % of an active metal; 0.1-0.5 w/w % of a first promoter; and 0.1-0.5 w/w % of a second promoter.
[0015] The present disclosure also discloses a composite solid support comprising: 90-98 w/w % of a non-acidic support having combination of a metal oxide and a spinel oxide; 1-10 w/w % of a first zeolite; 1-10 w/w % of a second zeolite; and 1-10 w/w % of a binder.
[0016] The present disclosure also discloses a process of synthesizing a regenerable non-halogenated heavy naphtha reforming catalyst comprising: a) exchanging of protons of a 1-10 w/w % of first zeolite with ammonium precursor to obtain an ammonia containing first zeolite; b) adding 0.1-0.5 w/w % aqueous solution of a first active metal precursor to the ammonia containing first zeolite to obtain a metal containing first zeolite; c) impregnating 0.1-0.5 w/w % of a first promoter precursor on 1-10 w/w % of a second zeolite to obtain a promoter containing second zeolite; d) mixing of the metal containing first zeolite, the promoter containing second zeolite, 90-98 w/w % of a non-acidic support having combination of metal oxide and spinel oxide and 1-10 w/w % of a binder to obtain a mixture; e) extruding the mixture with a peptizing agent followed by drying and calcination to obtain a composite solid support; f) impregnating 0.1-0.5 w/w % of an aqueous solution of a second active metal precursor and 0.1-0.5 w/w % of a second promoter on 95-98.5 w/w % of the composite solid support of step e) followed by drying and calcination to obtain a regenerable non-halogenated heavy naphtha reforming catalyst.
[0017] Various objects, features, aspects and advantages of the inventive subject matter will become more apparent from the following detailed description of preferred embodiments.

DETAILED DESCRIPTION OF THE INVENTION
[0018] The following is a detailed description of embodiments of the disclosure. The embodiments are in such detail as to clearly communicate the disclosure. However, the amount of detail offered is not intended to limit the anticipated variations of embodiments; on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the present disclosure as defined by the appended claims.
[0019] Unless the context requires otherwise, throughout the specification which follow, the word “comprise” and variations thereof, such as, “comprises” and “comprising” are to be construed in an open, inclusive sense that is as “including, but not limited to.”
[0020] As used in this specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the content clearly dictates otherwise. It should also be noted that the term “or” is generally employed in its sense including “and/or” unless the content clearly dictates otherwise.
[0021] In some embodiments, the numbers expressing quantities of ingredients, properties such as concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term “about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable.
[0022] The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it is individually recited herein.
[0023] All processes described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g. “such as”) provided with respect to certain embodiments herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.
[0024] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0025] The following discussion provides many example embodiments of the inventive subject matter. Although each embodiment represents a single combination of inventive elements, the inventive subject matter is considered to include all possible combinations of the disclosed elements. Thus if one embodiment comprises elements A, B, and C, and a second embodiment comprises elements B and D, then the inventive subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.
[0026] All publications herein are incorporated by reference to the same extent as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. Where a definition or use of a term in an incorporated reference is inconsistent or contrary to the definition of that term provided herein, the definition of that term provided herein applies and the definition of that term in the reference does not apply.
[0027] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member can be referred to and claimed individually or in any combination with other members of the group or other elements found herein. One or more members of a group can be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is herein deemed to contain the group as modified thus fulfilling the written description that follows, and the embodiments described herein, is provided by way of illustration of an example, or examples, of particular embodiments of the principles and aspects of the present disclosure. These examples are provided for the purposes of explanation, and not of limitation, of those principles and of the disclosure.
[0028] It should also be appreciated that the present invention can be implemented in numerous ways, including as a system, a method or a device. In this specification, these implementations, or any other form that the invention may take, may be referred to as processes. In general, the order of the steps of the disclosed processes may be altered within the scope of the invention.
[0029] Various terms as used herein are shown below. To the extent a term used in a claim is not defined below, it should be given the broadest definition persons in the pertinent art have given that term as reflected in printed publications and issued patents at the time of filing.
[0030] An embodiment of the present disclosure discloses a regenerable non-halogenated Continuous Catalytic Reforming (CCR) catalyst development, wherein the catalyst has been designed to have solid acid support along with an unconventional promoter atom in place of conventional chlorinated alumina to provide acidity to the catalyst and to avoid active metal agglomeration during the reaction. Metal functionality is attained through incorporation of noble metal along with the two promoter atoms.
[0031] An embodiment of the present disclosure discloses a regenerable non-halogenated heavy naphtha reforming catalyst comprising: 95-98.5 w/w % of a composite solid support; 0.1-0.5 w/w % of an active metal; 0.1-0.5 w/w % of a first promoter; and 0.1-0.5 w/w % of a second promoter. The composite solid support having a non-acidic support that composed of a metal oxide and a spinel oxide.
[0032] Another embodiment of the present disclosure discloses the active metal is selected from a group consisting of Pt, Pd, Ru, Rh, Os and Ir. The preferable active metal is Pt. The active metal comprises a first active metal precursor and a second active metal precursor. The first active metal precursor and the second active metal precursor are selected from H2PtCl6.6H2O and Pt(NH3)4(NO3)2.
[0033] Another embodiment of the present disclosure discloses the first promoter is selected from a group consisting of W, Sn, Re, Ge, Ir, In, Tl, Pb and Ga. The preferable first promoter is Ga. The second promoter is selected from a group consisting of W, Sn, Re, Ge, Ir, In, Tl, Pb and Ga. The preferable second promoter is W. The first promoter and the second promoter is different.
[0034] Another embodiment of the present disclosure, the metal may further include alkali or alkaline earth metals and transition metals. The alkali or alkaline earth metal is selected from a group consisting of Na, K, Mg, Be, Ca, Sr and Ba. The alkali or alkaline earth metal is present in the range of 0.1-0.5 w/w %. The transition metal is present in the range of 0.1-0.5 w/w %.
[0035] Another embodiment of the present disclosure that the reforming catalyst disclosed here is a multimetallic catalyst system. Following table shows a list of metals which can be used in the catalysts.
S.No. List of metals which can be used wt% ranges
1 Active Metal: Pt, Pd, Ru, Rh, Os, Ir 0.1 – 0.5
2 For bimetallic
1st Promoter Atom: W, Sn, Re, Ge, Ir, In, Tl, Pb, Ga 0.1 – 0.5
3 For trimetallic
2nd Promoter Atom: W, Sn, Re, Ge, Ir, In, Tl, Pb, Ga 0.1 – 0.5
4 Alkali or alkaline earth metals:
Na, K, Mg, Be, Ca, Sr, Ba
0.1 – 0.5
Transition metals 0.1 – 0.5

[0036] Another embodiment of the present disclosure discloses composite solid support comprising:
90-98 w/w % of a non-acidic support having combination of a metal oxide and a spinel oxide;
1-10 w/w % of a first zeolite;
1-10 w/w % of a second zeolite; and
1-10 w/w % of a binder.
[0037] Another embodiment of the present disclosure discloses that the metal oxide and the spinel oxide are selected from a group consisting of Al2O3 (preferably γ phase), SiO2, titania, zirconia, zinc oxide, MgAl2O4, and FeAl2O4.
[0038] Another embodiment of the present disclosure discloses that the first zeolite is selected from a group consisting of TS1, GaZSM5, zeolites covering ZSM-5, ZSM-11, ZSM-12, ZSM-20, X-zeolite, Y-zeolite, L-zeolite, mordenite, beta, MCM-22 and boron containing large pore zeolites. The second zeolite is selected from a group consisting of TS1, GaZSM5, zeolites covering ZSM-5, ZSM-11, ZSM-12, ZSM-20, X-zeolite, Y-zeolite, L-zeolite, mordenite, beta, MCM-22 and boron containing large pore zeolites. The first zeolite and the second zeolite are different.
[0039] Another embodiment of the present disclosure discloses that the binder is selected from the group consisting of boehmite, pseudoboehmite, SiO2 and Al2O3.
[0040] Another embodiment of the present disclosure discloses that the support is typically a composite of alumina with spinel oxide and two or more zeolites. The composition of the composite with wt% are given below:

S.No. Support material wt% ranges
1 Non-acidic support: Composition of metal oxide and a spinel oxide
Al2O3 (preferably γ phase), SiO2, Titania, Zirconia, zinc oxide,spinel structures such as MgAl2O4, FeAl2O4, 90 – 98 wt%
2 Zeolite-1:
TS1, GaZSM5, zeolites covering ZSM-5, ZSM-11, ZSM-12, ZSM-20, X-zeolite, Y-zeolite, L-zeolite, mordenite, beta, MCM-22, boron containing large pore zeolites 1 – 10 wt%
3 Zeolite – 2:
TS1, GaZSM5, zeolites covering ZSM-5, ZSM-11, ZSM-12, ZSM-20, X-zeolite, Y-zeolite, L-zeolite, mordenite, beta, MCM-22, Boron containing large pore zeolites 1 – 10 wt%
4 Binder
Boehmite, pseudoboehmite, SiO2, Al2O3 1 – 10 wt%

[0041] In another embodiment of the present disclosure discloses a process of synthesizing a regenerable non-halogenated heavy naphtha reforming catalyst comprising:
a) exchanging of protons of a 1-10 w/w % of first zeolite with ammonium precursor to obtain an ammonia containing first zeolite;
b) adding 0.1-0.5 w/w % aqueous solution of a first active metal precursor to the ammonia containing first zeolite to obtain a metal containing first zeolite;
c) impregnating 0.1-0.5 w/w % of a first promoter precursor precursor on 1-10 w/w % of a second zeolite to obtain a promoter containing second zeolite;
d) mixing of the metal containing first zeolite, the promoter containing second zeolite, 90-98 w/w % of a non-acidic support having combination of metal oxide and spinel oxide and 1-10 w/w % of a binder to obtain a mixture;
e) extruding the mixture with a peptizing agent followed by drying and calcination to obtain a composite solid support;
f) impregnating 0.1-0.5 w/w % of an aqueous solution of a second active metal precursor and 0.1-0.5 w/w % of a second promoter on 95-98.5 w/w % of the composite solid support of step e) followed by drying and calcination to obtain a regenerable non-halogenated heavy naphtha reforming catalyst.
[0042] Another embodiment of the present disclosure discloses that the ammonia precursor is ammonium acetate.
[0043] Another embodiment, the present invention discloses that the exchanging of proton of first zeolite of step a) is carried out at a temperature in the range of 80-100 °C for a period in the range of 2-4 hrs, followed by drying at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs.
[0044] Another embodiment, the present invention discloses that the first active metal precursor and the second active metal precursor are selected from H2PtCl6.6H2O and Pt(NH3)4(NO3)2.
[0045] Another embodiment, the present invention discloses that the addition of the active metal precursor aqueous solution in step b) is carried out at a temperature in the range of 80-100 °C for a period in the range of 2-4 hrs, followed by drying at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs.
[0046] Another embodiment, the present invention discloses that the promoter containing second zeolite of step c) is dried at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs and calcination at a temperature in the range of 450-550 °C for a period in the range of 2-4 hrs.
[0047] Another embodiment, the present invention discloses that the first promoter is Ga. The precursor of Ga is Ga(NO3)3.
[0048] Another embodiment, the present invention discloses that the peptizing agent is selected from a group consisting of nitric acid and acetic acid. Nitric acid is present in an amount in the range of 0.5-2.0 M and the acetic acid is present in an amount in the range of 1-15%.
[0049] Another embodiment, the present invention discloses that the composite solid support of step e) dried at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs and calcination at a temperature in the range of 450-550 °C for a period in the range of 3-5 hrs.
[0050] Another embodiment, the present invention discloses that the impregnation in step f) is followed by drying at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs and calcination at a temperature in the range of 450-550 °C for a period in the range of 3-5 hrs.
[0051] Another embodiment, the present invention discloses that the impregnating in step c) is selected from wet and incipient impregnation or spray impregnation. The impregnating in step f) is selected from sequential impregnation, spray impregnation and wet impregnation. Water is used as a solvent in the metal impregnation.
[0052] General procedure for the synthesis of a regenerable non-halogenated heavy naphtha reforming catalyst.
a) exchanging of protons of a 1-10 w/w % of first zeolite with ammonium precursor at a temperature in the range of 80-100 °C for a period in the range of 2-4 hrs, followed by drying at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs to obtain an ammonia containing first zeolite;
b) adding 0.1-0.5 w/w % aqueous solution of a first active metal precursor to the ammonia containing first zeolite at a temperature in the range of 80-100 °C for a period in the range of 2-4 hrs, followed by drying at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs to obtain a metal containing first zeolite;
c) impregnating 0.1-0.5 w/w % of a first promoter precursor on 1-10 w/w % of a second zeolite to obtain a promoter containing second zeolite followed by drying at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs and calcination at a temperature in the range of 450-550 °C for a period in the range of 2-4 hrs.;
d) mixing of the metal containing first zeolite, the promoter containing second zeolite, 90-98 w/w % of a non-acidic support having combination of metal oxide and spinel oxide and 1-10 w/w % of a binder to obtain a mixture;
e) extruding the mixture with a peptizing agent followed by drying at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs and calcination at a temperature in the range of 450-550 °C for a period in the range of 3-5 hrs to obtain a composite solid support;
f) impregnating 0.1-0.5 w/w % of an aqueous solution of a second active metal precursor and 0.1-0.5 w/w % of a second promoter on 95-98.5 w/w % of the composite solid support of step e) followed by drying at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs and calcination at a temperature in the range of 450-550 °C for a period in the range of 3-5 hrs to obtain a regenerable non-halogenated heavy naphtha reforming catalyst.
[0053] While the foregoing describes various embodiments of the disclosure, other and further embodiments of the disclosure may be devised without departing from the basic scope thereof. The invention is not limited to the described embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the invention when combined with information and knowledge available to the person having ordinary skill in the art.
EXAMPLES
[0054] The present invention is further explained in the form of following examples. However, it is to be understood that the following examples are merely illustrative and are not to be taken as limitations upon the scope of the invention.
[0055] Example 1:
[0056] A regenerable non-halogenated heavy naphtha reforming catalyst is synthesized by exchanging of protons of a zeolite beta with 1M ammonium acetate solution maintaining solution to zeolite wt ratio at 10 and temperature of 90 °C for a period of 3 hrs, followed by drying at 120 °C for 8 hrs to obtain an ammonia containing zeolite beta. The ammonium ions of the zeolite are further exchanged with Pt(NH3)4(NO3)2 at 90 °C for 3 hrs followed by drying at 120 °C for 8 hrs to obtain a Pt containing zeolite beta. TS1 zeolite is wet impregnated with Ga(NO3)3 solution to obtain 1wt% of Ga in the final catalyst formulation, followed by drying at 120 °C for 8hrs and calcination at 500 °C for 3 hrs. Mixing of 2 wt% Pt containing zeolite beta and 3 wt% Ga containing TS1 zeolite with 95 w/w % of γ-Al2O3 containing 5% spinel oxide and 10% pseudoboehmite to achieve final composition solid support. The support is made into extrudates using 0.75 M HNO3. The support is dried at 120 °C for 8 hrs and calcined at 500 °C for 4 hrs. Aqueous solution of ammonium tungstate and H2PtCl6.6H2O are sequentially impregnated on the final composite support to obtain a regenerable non-halogenated heavy naphtha reforming catalyst with mole ratio of W/Pt at 1 with Pt loading of 0.25 wt%. The catalyst is dried at 120 °C for 8 hrs followed by calcination at 500 °C for 4 hrs.
Chloride free Catalyst without W addition
[0057] Example 2: Fresh Catalyst
[0058] Similar catalyst described in Example 1 is prepared, however without addition of promoter atom W to study the effect of W addition on regeneration capability.
[0059] Example 3: Regeneration 1
[0060] Catalyst after reaction is regenerated by a simple calcination process, where the spent catalyst is heated at 500 °C for 4 hours under heating rate at 1 °C/min, to completely burn the coke deposited on the catalyst and re-tested under the similar conditions of a fresh catalyst.
Chloride free Catalyst with W addition
[0061] Example 4: Fresh Catalyst
[0062] Procedure described in Example 1
[0063] Example 5: Regeneration 1
[0064] Procedure described in Example 3
[0065] Example 6: Regeneration 2
[0066] Procedure described in Example 3
[0067] Example 7: Regeneration 3
[0068] Procedure described in Example 3
[0069] Example 8: Regeneration 4
[0070] Procedure described in Example 3

Table 1: Result of catalytic activity with or without W addition
Catalyst W/Pt Naphthenes i-Par n-Par Aromatics RON
Feed 26.14 29.80 28.30 15.70
Chloride free Catalyst without W addition (NEGATIVE DATA)
Fresh Catalyst 0 0.61 5.80 3.34 89.19 105.6
Regeneration 1 0 14.68 15.8 11.0 56.30 96
Chloride free Catalyst with W addition
Fresh Catalyst 1 1.16 6.76 4.11 87.46 105.0
Regeneration 1 1 1.27 5.06 2.70 90.50 105.8
Regeneration 2 1 1.32 10.01 5.94 81.70 103.5
Regeneration 3 1 1.82 8.25 4.64 83.86 102.8
Regeneration 4 1 2.30 10.24 5.14 81.38 103.7

[0071] The results in the above Table 1 clearly indicate the influence of W addition on the catalyst regeneration activity. The active metal Pt is responsible for dehydration reaction involved in naphthenes conversion. In the case of catalyst without W, as the Pt undergo agglomeration under high temperature reaction conditions, the Pt activity is very poor during 1st regeneration cycle for naphthenes conversion. Also, as this is a chloride free catalyst, no addition of chlorine maintains Pt in agglomerated state and responsible for poor activity of the regenerated catalyst. However, with addition of W it was very clear that the catalyst activity can be regenerated through a simple calcination process and without the need of adding any chlorinating agent. This along with dispersion data shown in Table 2 confirms that the addition of W maintains Pt in dispersed state even during high temperature reaction and does not require any chlorination for its re-dispersion. The present invention discloses the addition of spinel oxide in maintaining the Pt dispersion even during the high temperature reaction.
[0072] The catalyst formulation of the present invention maintains active metal dispersion even at high temperature reaction and does not require any chlorination for acidity and for recovering active metal dispersion, during regeneration cycles.
Table 2: Results of Pt dispersion
S.No. Catalyst %Pt Dispersion
1 Fresh Catalyst 78
Without W addition
2 Regeneration-1 40
With W Addition
3 Regeneration -1 76
4 Regeneration – 2 75
5 Regeneration – 3 71

[0073] A skilled artisan will appreciate that the quantity and type of each ingredient can be used in different combinations or singly. All such variations and combinations would be falling within the scope of present disclosure.
[0074] The foregoing examples are merely illustrative and are not to be taken as limitations upon the scope of the invention. Various changes and modifications to the disclosed embodiments will be apparent to those skilled in the art. Such changes and modifications may be made without departing from the scope of the invention.
, Claims:1. A regenerable non-halogenated heavy naphtha reforming catalyst comprising:
95-98.5 w/w % of a composite solid support;
0.1-0.5 w/w % of an active metal;
0.1-0.5 w/w % of a first promoter; and
0.1-0.5 w/w % of a second promoter.
2. The catalyst as claimed in claim 1, wherein the active metal is selected from a group consisting of Pt, Pd, Ru, Rh, Os and Ir.
3. The catalyst as claimed in claim 1, wherein the active metal comprises a first active metal precursor and a second active metal precursor.
4. The catalyst as claimed in claim 3, wherein the first active metal precursor and the second active metal precursor are selected from H2PtCl6.6H2O and Pt(NH3)4(NO3)2.
5. The catalyst as claimed in claim 1, wherein the first promoter and the second promoter is selected from a group consisting of W, Sn, Re, Ge, Ir, In, Tl, Pb and Ga, the first promoter and the second promoter is different.
6. A composite solid support comprising:
90-98 w/w % of a non-acidic support having combination of a metal oxide and a spinel oxide;
1-10 w/w % of a first zeolite;
1-10 w/w % of a second zeolite; and
1-10 w/w % of a binder.
7. The composite solid support as claimed in claim 6, wherein the metal oxide and the spinel oxide are selected from a group consisting of Al2O3, SiO2, titania, zirconia, zinc oxide, MgAl2O4, and FeAl2O4.
8. The composite solid support as claimed in claim 6, wherein the first zeolite and the second zeolite is selected from a group consisting of TS1, GaZSM5, zeolites covering ZSM-5, ZSM-11, ZSM-12, ZSM-20, X-zeolite, Y-zeolite, L-zeolite, mordenite, beta, MCM-22 and Boron containing large pore zeolites, the first zeolite and the second zeolite is different.
9. The composite solid support as claimed in claim 6, wherein the binder is selected from the group consisting of boehmite, pseudoboehmite, SiO2 and Al2O3.
10. A process of synthesizing a regenerable non-halogenated heavy naphtha reforming catalyst comprising:
a) exchanging of protons of a 1-10 w/w % of first zeolite with ammonium precursor to obtain an ammonia containing first zeolite;
b) adding 0.1-0.5 w/w % aqueous solution of a first active metal precursor to the ammonia containing first zeolite to obtain a metal containing first zeolite;
c) impregnating 0.1-0.5 w/w % of a first promoter precursor on 1-10 w/w % of a second zeolite to obtain a promoter containing second zeolite;
d) mixing of the metal containing first zeolite, the promoter containing second zeolite, 90-98 w/w % of a non-acidic support having combination of metal oxide and spinel oxide and 1-10 w/w % of a binder to obtain a mixture;
e) extruding the mixture with a peptizing agent followed by drying and calcination to obtain a composite solid support;
f) impregnating 0.1-0.5 w/w % of an aqueous solution of a second active metal precursor and 0.1-0.5 w/w % of a second promoter on 95-98.5 w/w % of the composite solid support of step e) followed by drying and calcination to obtain a regenerable non-halogenated heavy naphtha reforming catalyst.
11. The process as claimed in claim 10, wherein the ammonia precursor is ammonium acetate.
12. The process as claimed in claim 10, wherein the process condition includes:
i) the exchanging of proton of first zeolite of step a) is carried out at a temperature in the range of 80-100 °C for a period in the range of 2-4 hrs, followed by drying at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs.
ii) the addition of the active metal precursor aqueous solution in step b) is carried out at a temperature in the range of 80-100 °C for a period in the range of 2-4 hrs, followed by drying at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs.
iii) the promoter containing second zeolite of step c) is dried at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs and calcination at a temperature in the range of 450-550 °C for a period in the range of 2-4 hrs.
iv) the composite solid support of step e) dried at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs and calcination at a temperature in the range of 450-550 °C for a period in the range of 3-5 hrs.
v) the impregnation in step f) is followed by drying at a temperature in the range of 110-130 °C for a period in the range of 7-9 hrs and calcination at a temperature in the range of 450-550 °C for a period in the range of 3-5 hrs.
13. The process as claimed in claim 10, wherein the peptizing agent is selected from a group consisting of nitric acid and acetic acid.
14. The process as claimed in claim 10, wherein the impregnating in step c) is selected from wet and incipient impregnation or spray impregnation.
15. The process as claimed in claim 10, wherein the impregnating in step f) is selected from sequential impregnation, spray impregnation and wet impregnation.