WO2019180734A1

WO2019180734A1 - Hydrocarbon-soluble formulation for thermal cracking process

Info

Publication number: WO2019180734A1
Application number: PCT/IN2019/050210
Authority: WO
Inventors: Pramod Kumar; Naresh KOTTARI; Madankumar KUMARAVELAN; Siva Kesava Raju CHINTALAPATI; Subhash Kumar; Ramkumar MANGALA; Peddy VENKAT CHALAPATHI RAO; Gandham SRIGANESH
Original assignee: Hindustan Petroleum Corporation Limited
Priority date: 2018-03-20
Filing date: 2019-03-15
Publication date: 2019-09-26

Abstract

The present disclosure relates to a catalyst formulation comprising: (a) at least one metal carboxylate; and (b) at least one additive is selected from radical initiator or radical quencher, wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001. It also relates to the process of preparation of said catalyst formulation. The instant disclosure further relates to the process of thermal cracking in the presence of said catalyst formulation.

Description

HYDROCARBON-SOLUBLE FORMULATION FOR THERMAL CRACKING

PROCESS

TECHNICAL FIELD

[0001] The present disclosure is in the field of petroleum refining. In particular, it pertains to visbreaking and coker processes.

BACKGROUND OF THE INVENTION

[0002] Industrialization has a heavy reliance on constant energy supply. As major nations jostle over gaining global dominance, the ability of a nation to position itself as a heavyweight in terms of meeting the global energy-demand would be a key factor in determining the global standing. Accordingly, petroleum sector world-over has focused on introducing improvements in the refining process in order to cater to the ever-increasing demand.

[0003] Thermal cracking processes, such as, visbreaking and coker are well-known processes for upgradation of heavy vacuum residue in order to obtain light olefins. These processes have been traditionally carried out with temperatures in excess of 450 °C commonly being utilized. In spite of its energy-intensive nature, the utility of this process has ensured its continued existence (Speight, J. G. Sci. Iran. C, 2012, 19(3), 569). It would however, be useful to make the modifications to the process such that the efficiency is enhanced.

[0004] Several attempts have been made in this regard. A well-recognized approach would be to employ catalysts to reduce energy costs of the reaction. US5057204 reveals a selenium dioxide catalyst impregnated on a porous support. Alternatively, US 4233138 attempts to use alkali and alkaline earth metal sulfides for the process. An important criterion for a catalyst for thermal cracking process would be its hydrocarbon solubility.

[0005] The thermal cracking such as visbreaking process is a free-radical reaction, with the high temperatures being needed for radical initiation. However, an uncontrolled radical initiation may lead to low product stability. On the flip-side low temperatures can lead to lower radical initiation and low reaction rates. It is hence, important to obtain a formulation that can suitably tackle low product stability or low reaction rates, while being hydrocarbon- soluble as well as introducing the severity in thermal cracking process that is necessary for increased conversion of heavy oil. SUMMARY OF THE INVENTION

[0006] The instant disclosure relates to a catalyst formulation comprising: a) at least one metal carboxylate; and b) at least one additive selected from a radical initiator or a radical quencher, wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0007] The instant disclosure also relates to a process for the preparation of the catalyst formulation comprising: a) at least one metal carboxylate; and b) at least one additive, said process comprising the steps of: a) obtaining at least one metal carboxylate; b) obtaining at least one additive; and c) contacting the at least one metal carboxylate and at least one additive with at least one solvent to obtain the catalyst formulation.

[0008] The instant disclosure relates to a thermal cracking process in the presence of the catalyst formulation comprising: a) at least one metal carboxylate; and b) at least one additive, the process comprising : contacting the catalyst formulation with a resid fuel selected from the various ranges of feed stocks vacuum residue, atmospheric residue, bitumen, sand tar, FCC resid, and combinations thereof to obtain a downstream product selected from the group consisting of fuel gas, liquefied petroleum gas, naphtha, gas oil, heavy gas oil, residual oil, coke, and combinations thereof.

[0009] These and other features, aspects and advantages of the present subject matter will be better understood with reference to the following description and appended claims. This summary is provided to introduce a selection of concepts in a simplified form. This summary is not intended to be used to limit the scope of the claimed subject matter.

DETAILED DESCRIPTION

[0010] Those skilled in the art will be aware that the present disclosure is subject to variations and modifications other than those specifically described. It is to be understood that the present disclosure includes all such variations and modifications. The disclosure also includes all such steps, features, compositions and compounds referred to or indicated in this specification, individually or collectively and any and all combinations of any or more of such steps or features.

Definitions

[0011] For convenience, before further description of the present disclosure, certain terms employed in the specification, and examples are collected here. These definitions should be read in the light of the remainder of the disclosure and understood as by a person of skill in the art. The terms used herein have the meanings recognized and known to those of skill in the art, however, for convenience and completeness, particular terms and their meanings are set forth below.

[0012] The articles“a”,“an” and“the” are used to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article.

[0013] The terms“comprise” and“comprising” are used in the inclusive, open sense, meaning that additional elements may be included. Throughout this specification, unless the context requires otherwise the word“comprise”, and variations, such as“comprises” and“comprising”, will be understood to imply the inclusion of a stated element or step or group of element or steps but not the exclusion of any other element or step or group of element or steps.

[0014] The term“including” is used to mean“including but not limited to”.“Including” and “including but not limited to” are used interchangeably.

[0015] The term“halo” refers to halogen groups ordinarily known to the person skilled in the art. Halo groups for the purpose of the present disclosure may be selected from the group consisting of chloro, iodo, fluoro, bromo, and combinations thereof.

[0016] The term“alkyl” refers to a saturated hydrocarbon chain having the specified number of carbon atoms. For example, which are not limited, C1-20 alkyl refers to an alkyl group having from 1 - 20 carbon atoms, or 1 - 10 carbon atoms. Alkyl groups may be straight or branched chained groups. Representative branched alkyl groups have one, two, or three branches. Preferred alkyl groups include, without limitation, methyl, ethyl, n-propyl, isopropyl, butyl, and isobutyl.

[0017] The term“aryl” refers to aromatic ring having a specified number of carbon atoms. For example, C5-20 aryl refers to aryl group having 5 or 6 member atoms, or 6 member atoms, or 7 member atoms, or 9 member atoms, 10 member atoms, or 12 member atoms, 14 member atoms, 16 member atoms, 18 member atoms, 20 member atoms. Preferred aryl groups include, without limitation, phenyl, and the like.

[0018] The term“between” should be understood as being inclusive of the limits.

[0019] The term "haloalkyl" embraces radicals wherein any one or more of the C1-16 alkyl carbon atoms is substituted with halo as defined above. [0020] The term“cycloalkyl” refers to non-aromatic mono or polycyclic ring system of about 3 to 12 carbon atoms, which may be optionally substituted by one or more substituents. The polycyclic ring denotes hydrocarbon systems containing two or more ring systems with one or more ring carbon atoms in common, i.e., a spiro, fused or bridged structures. Preferred cycloalkyl groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctanyl, perhydronaphthyl, adamantyl, noradamantyl and norbornyl groups, bridged cyclic groups or spirobicyclic groups e.g. spiro [4.4] non-2-yl and the like.

[0021] The term“heteroaryl” refers to a heteroaromatic carbocyclic group of 1 to 20 carbon atoms having a single ring (e.g. pyridine) or multiple rings (e.g. isoquinoline), or multiple condensed (fused) rings. Preferred heteroaryls include thiophene, pyrazole, thiazole, pyridine and the like. The groups may be optionally substituted.

[0022] Furthermore, the term“heterocyclyl” refers to at least one stable 3 to 6 membered heterocyclic ring, which consists of 1 - 20 carbon atoms and from one to five heteroatoms selected from nitrogen, phosphorus, oxygen and sulfur. For purposes of this invention the heterocyclic ring may be monocyclic, bicyclic or tricyclic ring systems, and the nitrogen, phosphorus, carbon, oxygen or sulfur atoms in the heterocyclic ring may be optionally oxidized to various oxidation states. In addition, the nitrogen atom may be optionally quaternized; and the heterocyclic ring may be partially or fully saturated. Preferred heterocyclyl groups, without limitation, include azetidinyl, acridinyl, benzodioxolyl, benzodioxanyl, benzofuranyl, carbazolyl, cinnolinyl, dioxolanyl, indolizinyl, naphthyridinyl, perhydroazepinyl, phenazinyl, phenothiazinyl, phenoxazinyl, phthalazinyl, pyrazolyl, pyridyl, pteridinyl, purinyl, quinazolinyl, qunioxalinyl, quinolinyl, isoquinolinyl, tetrazolyl, imidazolyl, tetrahydroisoquinolinyl, piperidinyl, piperazinyl, homopiperazinyl, 2-oxoazepinyl, azepinyl, pyrrolyl, 4-piperidonyl, pyrrolidinyl, pyrazinyl, pyrimidinyl, pyridazinyl, oxazolyl, oxazolinyl, triazolyl, indanyl, isoxazolyl, isoxazolidinyl, thiazolyl, thiazolinyl, thiazolidinyl, isothiazolyl, quinuclidinyl, isothiazolidinyl, indolyl, isoindolyl, indolinyl, isoindolinyl, octahydroindolyl, octahydroisoindolyl, quinolyl, isoquinolyl, decahydroisoquinolyl, benzimidazolyl, thiadiazolyl, benzopyranyl, benzothiazolyl, benzooxazolyl, thienyl, morpholinyl, thiomorpholinyl, thiamorpholinyl sulfoxide, furyl, tetrahydrofuryl, tetrahydropyranyl, chromanyl and isochromanyl. The groups may be optionally substituted. [0023] The term“alkanediyl” refers to a divalent saturated aliphatic group having 1 - 16 carbon atoms, with one or two saturated carbon atom(s) as the point(s) of attachment. The groups - CH_2— (methylene),— CH₂CH_2— ,— CH₂C(CH₃)₂CH_2— ,— CH₂CH₂CH_2— are non-limiting examples of alkanediyl groups. The groups may be optionally substituted.

[0024] The term "arylene" refers to an aromatic group where two hydrogen atoms are removed allowing for a group to be substituted at the position where the two hydrogen atoms were removed, and having 5 to 20 carbon atoms. The groups may be optionally substituted.

[0025] The term“haloalkanediyl” refers to a divalent saturated aliphatic group having 1 - 16 carbon atoms, with one or two saturated carbon atom(s) as the point(s) of attachment, and wherein any one or more of the Ci-i₆ alkyl carbon atoms is substituted with‘halo’ as defined above. The groups may be optionally substituted.

[0026] The term“cycloalkanediyl” refers to a diradical saturated monocyclic or polycyclic hydrocarbon group. Examples of “cycloalkanediyl” include, without limitation, ‘cyclopropanediyT, and‘cyclobutanediyT . The groups may be optionally substituted.

[0027] The term“heteroarenediyl” refers to a divalent heteroaromatic carbocyclic group of 1 to 20 carbon atoms having a single ring (e.g. pyridine) or multiple rings (e.g. isoquinoline), or multiple condensed (fused) rings. The groups may be optionally substituted.

[0028] The term“heterocyclicdiyl” refers to a divalent, stable 2 to 6 membered rings radical, which consists of 1 - 20 carbon atoms and from one to five heteroatoms selected from nitrogen, phosphorus, oxygen and sulfur. For purposes of this invention the heterocyclicdiyl ring radical may be monocyclic, bicyclic or tricyclic ring systems, and the nitrogen, phosphorus, carbon, oxygen or sulfur atoms in the heterocyclic ring radical may be optionally oxidized to various oxidation states. In addition, the nitrogen atom may be optionally quaternized; and the ring radical may be partially or fully saturated. The groups may be optionally substituted.

[0029] The terms“catalyst” and“catalyst formulation” have been used interchangeably in the present disclosure to define the oil-soluble metal carboxylate formulations that have been employed for thermal cracking process described herein.

[0030] The term“hydrocarbon-soluble” or“oil-soluble” is used to refer to the catalyst compounds that are essentially“dissolved” or completely dissociated from other catalyst compounds or molecules in a heavy oil or hydrocarbon feedstock, without any presence of suspended residue. [0031] The metal carboxylates could be“bimetallic” or“multimetallic”. The molar fractions of metals in the catalyst formulation can be varied from 0.1 to 0.9. For example, the combinations such as Feo_.5Coo_.5A_y, Feo_.1Coo_.9A_y, Coo_.1Nio_.9A_y, Moo_.9Wo_.1A_y, Fe_xCo_yAlo_.5A2o_.5, Fe_xCo_yAlo_.2A2o_.8, Co_xNi_yAlo_.9A2o_.i are under the scope of the present disclosure; Al and A2 are mono or di-carboxylic aliphatic and/or aromatic acids; x and y are in the range of 1-4.

[0032] The metal compounds used for the preparation of hydrocarbon soluble catalyst formulation are water-soluble metal salts and Group II metal salts, for example, Fe, Mg, Co, Ni, Mo, W, Cu, V and Zn salts. The term“metal salts” means a compound in which metal in positive state with the negative counter ion. The preferred salts are metal halides, metal nitrates and metal sulfates.

[0033] The term“organic phase” means the hydrocarbon solvent layer, such as, hexane, toluene, xylene, diesel, kerosene, naphtha and the like. The hydrocarbon layer is separated after the completion of the reaction and concentrated to afford the oil soluble metallic catalyst.

[0034] The term“resid” or“vacuum oil” or“vacuum resid fuel” or“vacuum residue” refer to heavier hydrocarbons with molecular weights ranging from 5000 - 10000. These terms may be used interchangeably throughout the specification.

[0035] The term“downstream product” refers to products obtained after thermal cracking of heavy hydrocarbons. The downstream products are selected from the group consisting of fuel gas, liquified petroleum gas (LPG), naphtha (boiling point of C5 - 150 °C), gas oil (boiling point- 150 - 370 °C), heavy gas oil (boiling point- 370 - 540 °C), residual oil (boiling point > 540 °C), coke, and combinations thereof.

[0036] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the disclosure, the preferred methods, and materials are now described. All publications mentioned herein are incorporated herein by reference.

[0037] Molar equivalent ratios of metals and organic agents may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a temperature range of about 60°C to about 90°C should be interpreted to include not only the explicitly recited limits of about 60°C to about 90°C, but also to include sub ranges, such as 65°C to 75°C, 80°C to 85°C, and so forth, as well as individual amounts, including fractional amounts, within the specified ranges, such as 62.2°C, 60.6°C, and 6l.3°C, for example.

[0038] The present disclosure is not to be limited in scope by the specific embodiments described herein, which are intended for the purposes of exemplification only. Functionally equivalent products, compositions, and methods are clearly within scope of the disclosure, as described herein.

[0039] With regards to the problems discussed in the background section, the present disclosure furnishes a catalyst formulation comprising metal carboxylate salt and an additive comprising radical initiator or radical quencher, for efficient heavy oil upgradation.

[0040] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate; and b) at least one additive selected from a radical initiator or a radical quencher, wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001. In another embodiment of the present disclosure, the catalyst formulation comprises: a) at least one metal carboxylate; and b) at least one additive being a radical initiator, wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001. In yet another embodiment of the present disclosure, the catalyst formulation comprises: a) at least one metal carboxylate; and b) at least one additive being a radical quencher, wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0041] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate; and b) at least one additive selected from a radical initiator or a radical quencher, wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.015- 1:0.0005. In another embodiment of the present disclosure, the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.01- 1:0.001. In yet another embodiment of the present disclosure, the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.008- 1:0.002. [0042] In an embodiment of the present disclosure, there is provided a catalyst formulation as described herein, wherein the radical initiator is an organic radical initiator or an inorganic radical initiator.

[0043] In an embodiment of the present disclosure, there is provided a catalyst formulation as described herein, wherein the radical initiator is selected from the group consisting of alkyl hydroperoxide, aryl hydroperoxide, ketone peroxides, diacyl peroxides, peroxy esters, peroxy acetals, peroxy dicarbonates, sodium persulfate, ammonium persulfate, and combinations thereof. In another embodiment of the present disclosure, the radical initiator is an organic radical initiator. In another embodiment of the present disclosure, the radical initiator is an inorganic radical initiator.

[0044] In an embodiment of the present disclosure, there is provided a catalyst formulation as described herein, wherein the radical initiator is selected from the group consisting of benzoyl peroxide, azobisisobutyronitrile, and combinations thereof. In another embodiment of the present disclosure, the radical initiator is benzoyl peroxide.

[0045] In an embodiment of the present disclosure, there is provided a catalyst formulation as described herein, wherein the radical quencher is selected from the group consisting of hydroquinone, butyl phenol, alkyl hydroquinone, alkyl phenols, and combinations thereof. In another embodiment of the present disclosure, the radical quencher is hydroquinone.

[0046] In an embodiment of the present disclosure, there is provided a catalyst formulation as described herein, wherein the at least one metal carboxylate is a combination of a) at least one metal selected from the group consisting of group IIA metals, I-B metals, II-B metals, V-B metals, VIII-B metals, and combinations thereof; and b) at least one carboxylate selected from the Formula: Rl(COO )_a, wherein‘a’ is in the range of 1-2; when‘a’ is 1, Rl is selected from the group consisting of C_1-20 alkyl, C_5-20 aryl, C_1-16 haloalkyl, C_3-12 cycloalkyl, C_1-20 heteroaryl, and Ci -₂₀ heterocyclyl; when ‘a’ is 2, Rl is selected from the group consisting of C_1-20 alkanediyl, C_5-20 arylene, C_1-16 haloalkanediyl, C_3-12 cycloalkanediyl, C_1-20 heteroarenediyl, and Ci -₂₀ heterocyclicdiyl.

[0047] In an embodiment of the present disclosure, there is provided a catalyst formulation as described herein, wherein the at least one metal carboxylate is a combination of a) at least one metal selected from the group consisting of group IIA metals, I-B metals, II-B metals, V-B metals, VIII-B metals, and combinations thereof; and b) at least one carboxylate selected from the Formula: Rl(COO^~)_a, wherein‘a’ is in the range of 1-2; when‘a’ is 1, Rl is selected from the group consisting of Ci-is alkyl, C5-15 aryl, Ci-io haloalkyl, C3-10 cycloalkyl, C1-15 heteroaryl, and Ci -₁₅ heterocyclyl; when ‘a’ is 2, Rl is selected from the group consisting of C_1-15 alkanediyl, C_5-15 arylene, Ci-io haloalkanediyl, C_3-10 cycloalkanediyl, C_1-15 heteroarenediyl, and Ci-is heterocyclicdiyl.

[0048] In an embodiment of the present disclosure, there is provided a catalyst formulation as described herein, wherein the at least one metal is selected from the group consisting of Fe, Co, Ni, Mg, Mo, Cu, Zn, Ca, V, and combinations thereof. In another embodiment of the present disclosure, the at least one metal is Fe. In yet another embodiment of the present disclosure, the at least one metal is Ni. In an alternate embodiment of the present disclosure, the at least one metal is Co. In a further embodiment of the present disclosure, the at least one metal is Mo. In a further alternative embodiment of the present disclosure, the at least one metal is W.

[0049] In an embodiment of the present disclosure, there is provided a catalyst formulation as described herein, wherein the at least one metal is a combination of Fe and Co. In another embodiment of the present disclosure, the at least one metal is a combination of Ni and Co. In yet another embodiment of the present disclosure, the at least one metal is a combination of Mo and W. In a further embodiment of the present disclosure, the at least one metal is Mg. In a further alternative embodiment of the present disclosure, the at least one metal is a combination of Mg and Fe.

[0050] In an embodiment of the present disclosure, there is provided a catalyst formulation as described herein, wherein the at least one carboxylate is selected from the group consisting of C_5-20 monocarboxylic acids, C_5-20 dicarboxylic acids, and combinations thereof. In another embodiment of the present disclosure, the at least one carboxylate is selected from C_5-20 monocarboxylic acids. In yet another embodiment of the present disclosure, the at least one carboxylate is selected from C_5-15 monocarboxylic acids. In a further embodiment of the present disclosure, the at least one carboxylate is selected from C_5-10 monocarboxylic acids.

[0051] In an embodiment of the present disclosure, there is provided a catalyst formulation as described herein, wherein the at least one metal carboxylate is a combination of a) at least one metal selected from the group consisting of Fe, Co, Ni, Mg, Mo, Cu, Pd, Pt, Zn, Ca, V, and combinations thereof; and b) at least one carboxylate is selected from the group consisting of C_5-20 monocarboxylic acids, C_5-20 dicarboxylic acids, and combinations thereof. [0052] In an embodiment of the present disclosure, there is provided a catalyst formulation as described herein, wherein the at least one metal carboxylate is a combination of a) at least one metal selected from the group consisting of Fe, Co, Ni, Mg, Mo, and combinations thereof; and b) at least one carboxylate is selected from the group consisting of C5-15 monocarboxylic acids, C5-15 dicarboxylic acids, and combinations thereof.

[0053] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of Fe; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0054] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of Ni; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0055] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of Co; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0056] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of Mo; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0057] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of W; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001. [0058] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of a combination of Fe and Co; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0059] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of a combination of Ni and Co; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0060] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of a combination of Mo and W; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0061] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of a combination of Mg and Fe; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0062] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid of Fe; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0063] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid acid of Ni; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001. [0064] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid acid of Co; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0065] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid acid of Mo; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0066] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid of W; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0067] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid of a combination of Fe and Co; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0068] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid of a combination of Ni and Co; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0069] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid of a combination of Mo and W; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001. [0070] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid acid of a combination of Mg and Fe; and b) at least one additive is a radical initiator, wherein the radical initiator is benzoyl peroxide wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0071] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of Fe; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0072] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of Ni; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0073] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of Co; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0074] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of Mo; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0075] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of W; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001. [0076] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of a combination of Fe and Co; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0077] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of a combination of Ni and Co; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0078] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of a combination of Mo and W ; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0079] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-10 monocarboxylic acid of a combination of Mg and Fe; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0080] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid of Fe; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0081] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid acid of Ni; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001. [0082] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid acid of Co; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0083] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid acid of Mo; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0084] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid of W; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0085] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid of a combination of Fe and Co; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0086] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid of a combination of Ni and Co; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0087] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid of a combination of Mo and W ; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001. [0088] In an embodiment of the present disclosure, there is provided a catalyst formulation comprising: a) at least one metal carboxylate is selected from C5-15 dicarboxylic acid of a combination of Mg and Fe; and b) at least one additive is a radical quencher, wherein the radical quencher is hydroquinone wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

[0089] In an embodiment of the present disclosure, there is provided a process for the preparation of the catalyst formulation comprising: a) at least one metal carboxylate; and b) at least one additive, said process comprising the steps of: a) obtaining at least one metal carboxylate; b) obtaining at least one additive; and c) contacting the at least one metal carboxylate and the at least one additive with at least one solvent to obtain the catalyst formulation.

[0090] In an embodiment of the present disclosure, there is provided a process for the preparation of the catalyst formulation as described herein, wherein obtaining at least one metal carboxylate comprises the steps of: a) contacting the at least one metal with the at least one carboxylate at a temperature in the range of 60 - 90 °C for a period in the range of 0.1 - 10 hours to obtain a first mixture; and b) processing the first mixture to obtain the metal carboxylate. In another embodiment of the present disclosure, obtaining at least one metal carboxylate comprises the steps of: a) contacting the at least one metal with the at least one carboxylate at a temperature in the range of 65 - 85 °C for a period in the range of 0.1 - 3.2 hours to obtain a first mixture; and b) processing the first mixture to obtain the metal carboxylate. In yet another embodiment of the present disclosure, processing the first mixture is selected from the group consisting of filtration, evaporation, solvent extraction, chromatography, recrystallization, precipitation, and combinations thereof.

[0091] In an embodiment of the present disclosure, there is provided a process for the preparation of the catalyst formulation as described herein, wherein contacting the at least one metal carboxylate and at least one additive with the at least one solvent is carried at a temperature in the range of 20 - 35 °C for a period in the range of 0.1 - 4.0 hours to obtain the catalyst formulation. In another embodiment of the present disclosure, contacting the at least one metal carboxylate and at least one additive with the at least one solvent is carried at a temperature in the range of 22 - 32 °C for a period in the range of 0.1- 3.5 hours to obtain the catalyst formulation. [0092] In an embodiment of the present disclosure, there is provided a process for the preparation of the catalyst formulation comprising: a) at least one metal carboxylate; and b) at least one additive, said process comprising the steps of: a) obtaining at least one metal carboxylate comprises the steps of: i) contacting the at least one metal with the at least one carboxylate at a temperature in the range of 60 - 90 °C for a period in the range of 0.1 - 10 hours to obtain a first mixture; and ii) processing the first mixture to obtain the metal carboxylate; b) obtaining at least one additive; and c) contacting the at least one metal carboxylate and at least one additive with the at least one solvent is carried at a temperature in the range of 20 - 35 °C for a period in the range of 0.1 - 4.0 hours to obtain the catalyst formulation.

[0093] In an embodiment of the present disclosure, there is provided a process for the preparation of the catalyst formulation as described herein, wherein the at least one solvent is selected from the group consisting of toluene, benzene, hexane, petroleum ether, and combinations thereof. In another embodiment of the present disclosure, the at least one solvent is toluene.

[0094] In an embodiment of the present disclosure, there is provided a thermal cracking process in the presence of the catalyst formulation comprising: a) at least one metal carboxylate; and b) at least one additive, the thermal cracking process comprising steps of: a) contacting the catalyst formulation with a resid fuel selected from the various ranges of feed stocks vacuum residue, atmospheric residue, bitumen, sand tar, FCC resid, and their combinations thereof to obtain a downstream product selected from the group consisting of fuel gas, liquefied petroleum gas, naphtha, gas oil, heavy gas oil, residual oil, coke, and combinations thereof.

[0095] In an embodiment of the present disclosure, there is provided a thermal cracking process in the presence of the catalyst formulation as described herein, wherein contacting the catalyst formulation with a resid fuel is carried out at a temperature in the range of 350 - 500 °C and pressure in the range of 0.1 - 30 bar with a residence time in the range of 0.1 - 24 hours. In another embodiment of the present disclosure, contacting the catalyst formulation with a resid fuel is carried out at a temperature in the range of 380 - 480 °C and pressure in the range of 5.0 - 25 bar with a residence time in the range of 0.1 - 20 hours. In yet another embodiment of the present disclosure, contacting the catalyst formulation with a resid fuel is carried out at a temperature in the range of 400 - 460 °C and pressure in the range of 10.0 - 20 bar with a residence time in the range of 0.1 - 20 hours.

[0096] In an embodiment of the present disclosure, there is provided a thermal cracking process in the presence of the catalyst formulation comprising: a) at least one metal carboxylate; and b) at least one additive, the thermal cracking process comprising steps of: a) contacting the catalyst formulation with a resid fuel selected from the various ranges of feed stocks vacuum residue, atmospheric residue, bitumen, sand tar, FCC resid, and their combinations thereof to obtain a downstream product selected from the group consisting of fuel gas, liquefied petroleum gas, naphtha, gas oil, heavy gas oil, residual oil, coke, and combinations thereof, wherein contacting the catalyst formulation with a resid fuel is carried out at a temperature in the range of 350 - 500 °C and pressure in the range of 0.1 - 30 bar with a residence time in the range of 0.1 - 24 hours.

[0097] In an embodiment of the present disclosure, there is provided a thermal cracking process in the presence of the catalyst formulation as described herein, wherein the catalyst formulation comprising at least one additive selected from radical initiator or radical quencher to increase distillate yield and conversion without leading to unstable fuel oil. In another embodiment of the present disclosure, there is provided a thermal cracking process in the presence of the catalyst formulation as described herein, wherein the catalyst formulation comprises radical initiator. In yet another embodiment of the present disclosure, there is provided a thermal cracking process in the presence of the catalyst formulation as described herein, wherein the catalyst formulation comprises radical quencher.

[0098] In an embodiment of the present disclosure, there is provided a thermal cracking process in the presence of the catalyst formulation as described herein, wherein the catalyst formulation comprising at least one additive selected from a radical initiator or a radical quencher to enhance the fuel oil stability and conversion. In another embodiment of the present disclosure, the radical initiator is part of the formulation in order to enhance the conversion. In yet another embodiment of the present disclosure, the radical quencher is part of the formulation in order to enhance the fuel oil stability.

[0099] In an embodiment of the present disclosure, there is provided a thermal cracking process in the presence of the catalyst formulation as described herein, wherein the catalyst formulation is introduced along with feed stock prior to pre-heating section or along with feedstock prior to heating furnace or along with feedstock downstream of the heating furnace in transfer line or soaker drum.

[00100] Although the subject matter has been described in considerable details with reference to certain preferred embodiments thereof, other embodiments are possible.

EXAMPLES

[00101] The following examples are given by way of illustration of the present disclosure and should not be construed to limit the scope of the present disclosure. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the claimed subject matter.

[00102] Few representative examples for the preparation of catalyst formulation are described below in Example 1 and 2.

Example 1

[00103] The solution of Iron (III) chloride (1 eq) in butanoic acid (5 eq) was stirred at 80 °C for 6 hours. The solution (first mixture) turned reddish brown color. The excess acid was removed to obtain iron carboxylate as a gummy solid. Yield: 92 % (based on FeCb); WD-XRF 18 % Fe. Subsequently 1 wt % of benzoyl peroxide was mixed with the above gummy solid in toluene and the excess solvent was removed to obtain the catalytic formulation.

Example 2

[00104] To a solution of Ni (II) nitrate (1 eq) in water and hexane (1:2 ratio; 5 ml per 1 mmol of Ni salt), 2-ethyl hexyl carboxylate (3 eq) in water (solution of lmmol in 1 mL water) was added drop wise at 70 °C and the solution was refluxed for 3 hours at 80 °C. The resulting reaction mixture (first mixture) was cooled and fractionated between water/hexane layers. The organic layer was washed with the water. The organic phase was dried (Na₂S0₄), concentrated in vacuum to afford the nickel carboxylate as a gummy solid. Yield: 93 %; ICP-OES: 8.5 % Ni. Subsequently 1 wt % of hydroquinone was mixed with the above gummy solid in toluene and the solvent was removed to obtain the catalytic formulations.

Example 3

[00105] Known quantity of resid fuel (i.e. 400 gm) was taken in a reactor with/without catalyst formulation and heated at a temperature in the range of 350 - 500 °C and pressure in the range of 0.1 - 30 bar with a residence time in the range of 0.1 - 24 hours till desired set temperature was attained. After attaining the set temperature, the reactor was kept for desired residence time of l5mins. Immediately after completing the reaction time the reactor content was cooled down to 80-l00°C and reactor pressure was reduced to 0.5-1 Kg/cm². g. The liquid product obtained was analyzed for SIMDIS (Simulated Distillation) and S-value for measuring the material balance and assessing the product quality. The results obtained are recorded in Table 1 below:

Table 1:

*IBP= Initial boiling point; **FBP= Final boiling point

[00106] It is inferred from the Table 1, that the conversion is high with catalytic formulation of the present disclosure in comparison with the base case. The S-Value determines the stability of asphaltenes in residual oil using ASTM-D7157. This clearly indicates that the stability of fuel oil is maintained in spite of high conversion.

Example 4

[00107] Known quantity of heavy residue sample (i.e. 80 gm) was taken in the microwave reactor (1700 W) with/without catalyst formulation and heated for desired residence time of 15 mins. Immediately after completing the reaction, the coke and liquid separated and analyzed for SIMDIS. The results obtained are recorded in Table 2 below:

Table 2

[00108] Table 2 depicts the reduced percentage of coke in the presence of the catalytic formulation of the present disclosure which comprises radical quencher. The radical quencher arrests the formation of coke by condensation of asphaltene radicals.

[00109] Known quantity of heavy residue sample (i.e. 80 gm) was taken in the microwave reactor (1700 W) with/without catalyst formulation and heated for desired residence time of 15 mins. Immediately after completing the reaction, the coke and liquid separated and analyzed for SIMDIS. The results obtained are recorded in Table 2 below:

Table 2

[00110] Table 2 depicts the reduced percentage of coke in the presence of the catalytic formulation of the present disclosure which comprises radical quencher. The radical quencher arrests the formation of coke by condensation of asphaltene radicals.

Example 5 [00111] Known quantity of heavy residue sample (i.e. 80 gm) was taken in with/without catalyst formulation and heated at 410 °C for desired residence time of 60 mins. Immediately after completing the reaction, the coke and liquid separated and analyzed for SIMDIS. The results obtained are recorded in Table 3 below:

Table 3

[00112] Table 3 depicts the reduced percentage of coke in the presence of the catalytic formulation of the present disclosure which comprises radical quencher. The radical quencher arrests the formation of coke by condensation of asphaltene radicals.

Advantages of the present disclosure

[00113] The catalyst formulation of the present disclosure tackles low product stability and low reaction rates, while being hydrocarbon-soluble as well as introducing the severity in thermal cracking process that is necessary for increased conversion of heavy oil.

[00114] Although the subject matter has been described in considerable details with reference to certain examples and embodiments, this description is not meant to be construed in a limiting sense. Various modifications of the disclosed embodiments, as well as alternate embodiments of the subject matter, will become apparent to persons skilled in the art upon reference to the description of the subject matter. It is therefore contemplated that such modifications can be made without departing from the present subject matter as defined.

Claims

I/We Claim:

1. A catalyst formulation comprising:

(a) at least one metal carboxylate; and

(b) at least one additive selected from a radical initiator or a radical quencher, wherein the at least one metal carboxylate to the at least one additive weight ratio is in the range of 1:0.02- 1:0.0001.

2. The catalyst formulation as claimed in claim 1, wherein the radical initiator is selected from an organic radical initiator or an inorganic radical initiator.

3. The catalyst formulation as claimed in claim 1, wherein the radical initiator is selected from the group consisting of alkyl hydroperoxide, aryl hydroperoxide, ketone peroxides, diacyl peroxides, peroxy esters, peroxy acetals, peroxy dicarbonates, sodium persulfate, ammonium persulfate, and combinations thereof.

4. The catalyst formulation as claimed in claim 3, wherein the radical initiator is selected from the group consisting of benzoyl peroxide, azobisisobutyronitrile, and combinations thereof.

5. The catalyst formulation as claimed in claim 1, wherein the radical quencher is selected from the group consisting of hydroquinone, butyl phenol, alkyl hydroquinone, alkyl phenols, and combinations thereof.

6. The catalyst formulation as claimed in claim 1, wherein the at least one metal carboxylate is a combination of a) at least one metal selected from the group consisting of group IIA metals, I-B metals, II-B metals, V-B metals, VTTT-B metals, and combinations thereof; and b) at least one carboxylate selected from the Formula: Rl(COO^~)_a, wherein‘a’ is in the range of 1-2; when‘a’ is 1, Rl is selected from the group consisting of C_1-20 alkyl, C_5-20 aryl, C_1-16 haloalkyl, C_3-12 cycloalkyl, C_1-20 heteroaryl, and C_1-20 heterocyclyl; when‘a’ is 2, Rl is selected from the group consisting of Ci -₂₀ alkanediyl, C_5-20 arylene, C_1-16 haloalkanediyl, C_3-12 cycloalkanediyl, C_1-20 heteroarenediyl, C_1-20 heterocyclicdiyl.

7. The catalyst formulation as claimed in claim 6, wherein the at least one metal is selected from the group consisting of Fe, Co, Ni, Mg, Mo, Cu, Pt, Pd, Zn, Ca, V, and combinations thereof.

8. The catalyst formulation as claimed in claim 6, wherein the at least one carboxylate is selected from the group consisting of C5-20 monocarboxylic acids, C5-20 dicarboxylic acids, and combinations thereof.

9. A process for preparing the catalyst formulation as claimed in any of the claims 1-8, the process comprising steps of:

(a) obtaining at least one metal carboxylate;

(b) obtaining at least one additive; and

(c) contacting the at least one metal carboxylate and the at least one additive with the at least one solvent to obtain the catalyst formulation.

10. The process for preparing the catalyst formulation as claimed in claim 9, wherein obtaining at least one metal carboxylate comprises the steps of: a) contacting the at least one metal with the at least one carboxylate at a temperature in the range of 60 - 90 °C for a period in the range of 0.1 - 10 hours to obtain a first mixture; and b) processing the first mixture to obtain the metal carboxylate.

11. The process for preparing the catalyst formulation as claimed in claim 9, wherein contacting the at least one metal carboxylate and the at least one additive with the at least one solvent is carried at a temperature in the range of 20 - 35 °C for a period in the range of 0.1 - 4.0 hours to obtain the catalyst formulation.

12. The process for preparing the catalyst formulation as claimed in claim 9 or 11, wherein the at least one solvent is selected from the group consisting of toluene, benzene, hexane, petroleum ether, and combinations thereof.

13. A thermal cracking process in the presence of the catalyst formulation as claimed in any of the claims 1-8 or the catalyst formulation as obtained from the process as claimed in any of the claims 9-12, the process comprising:

contacting the catalyst formulation with a resid fuel selected from the various ranges of feed stocks vacuum residue, atmospheric residue, bitumen, sand tar, FCC resid, and combinations thereof to obtain a downstream product selected from the group consisting of fuel gas, liquefied petroleum gas, naphtha, gas oil, heavy gas oil, residual oil, coke, and combinations thereof.

14. The thermal cracking process as claimed in claim 13, wherein contacting the catalyst formulation with a resid fuel is carried out at a temperature in the range of 350 - 500 °C and pressure in the range of 0.1 - 30 bar with a residence time in the range of 0.1 - 24 hours.

15. The thermal cracking process as claimed in claim 13, wherein the catalyst formulation comprising at least one additive selected from radical initiator or radical quencher leads to an increase in distillate yield and conversion without leading to unstable fuel oil.