Description:FIELD OF THE INVENTION
[0001] The present disclosure relates to a method for preparation of a demetallization nanocatalyst for residue upgradation. The present disclosure also relates to the development of demetallization nanocatalyst. The present disclosure also discloses a process for demetallizing a hydrocarbon feed by treating the hydrocarbon feed with a demetallization nanocatalyst.

BACKGROUND OF THE INVENTION
[0002] With the deterioration and heaviness of crude oil, the efficient conversion of heavy oil and the improvement of the yield of light oil products become an important trend in the development of oil refining technology. The residue fixed bed hydrogenation technology is an effective means for realizing the high-efficiency conversion of heavy oil. By adopting the technical route, the impurities such as metal, sulfur, nitrogen, carbon residue and the like in the residual oil can be effectively removed, high-quality feed is provided for catalytic cracking, and the strict environmental protection regulation requirements are met while the yield of light oil products is increased.
[0003] The amount of metals in crude oil usually varies from a few parts per million to more than 1000 ppm. The metals found are sodium, potassium, lithium, calcium, strontium, copper, silver, vanadium, manganese, tin, lead, cobalt, titanium, gold, chromium and nickel. The metals are usually in combination with naphthenic acid as soaps and in the form of complex organometallic compounds such as metalloporphyrins. Among these metals the most abundant and undesirable are vanadium and nickel. Depending on the origin of crude oil, the concentration of the vanadium varies from as low as 0.1 ppm to as high as 1200 ppm, while that of nickel commonly varies from trace to 150 ppm. Crude oils containing large proportions of metals are frequently treated for their removal, as these substances tend to accumulate in the residuum during distillation and affect its properties adversely. Some of the organometallic compounds may also volatilize at refinery distillation temperatures in the higher-boiling distillates.
[0004] The presence of metal contaminants in FCC feeds presents another and potentially more serious problem because although sulfur can be converted to gaseous forms which can be readily handled in an FCC unit, the nonvolatile metal contaminants tend to accumulate in the unit and during the cracking process they are deposited on the catalyst together with the coke. Because both nickel and vanadium exhibit dehydrogenation activity, their presence on the catalyst particles tends to promote dehydrogenation reactions during the cracking sequence and this result in increased amounts of coke and light gases at the expense of gasoline production. Vanadium and nickel seriously affect cracking, when they accumulate on the particles of the catalyst over time, causing alteration in the catalyst structure. Also, small amounts of nickel and vanadium in the charge stocks poison clay and synthetic catalysts. To mitigate these effects, there have been several attempts towards preparation of effective demetallization catalysts. A few of them are discussed below.
[0005] CN109504423A discloses a crude oil metal removers and preparation method thereof, the crude oil metal remover is made of by weight percentage following components: citric acid 30-50%, 2- hydroxyethylidene diphosphonic acid guanidine-acetic acid 2-3%, hexamethylenetetramine 1-2%, sodium lignin sulfonate 3-5%, chitosan nano ball suspension 1-2%, water surplus.
[0006] US3052627A discloses process for treating a distilled fraction of crude petroleum substantially composed of constituents boiling above about 300° C. and containing type I metalloporphyrin complexes in amounts of above about 10 parts per million to remove type I metalloporphyrin complexes which process comprises in combination contacting said distilled fraction with a mixture of a liquid 2-pyrrollidone compound and an aliphatic alcohol containing 1 to 3 carbon atoms at a temperature between about 25 and 150° C., separating the extracted petroleum hydrocarbon from the 2-pyrrolidone compound-alcohol mixture, removing extracted metalloporphyrin complexes from the 2-pyrrolidone compound-alcohol mixture and reusing the 2-pyrrolidone compound for further extraction of said petroleum distillate fraction containing metalloporphyrin complexes.
[0007] CN110882684A discloses an alumina carrier with a secondary pore structure and a preparation method and application thereof relate to the field of catalyst carriers. The alumina carrier comprises microspheres assembled by needle-shaped nanocrystals, the microspheres are stacked to form mutually communicated macropores, the length of the needle-shaped nanocrystals is 8-12 nm, the diameter of the microspheres is 1-3 µm, the diameter of the macropores is 100-500 nm, and the diameter of the mesopores is 10-25 nm.
[0008] Despite the developments in the state of the art, minimizing the amount of metals in the feedstock, particularly heavy oil, remains a challenge. Moreover, there is always a need to provide a catalyst having improved characteristics such as surface area, pore volume, particle size, etc. which in turn affects the overall catalyst activity towards demetallization and enhances the life of the catalyst. Furthermore, scalability of catalyst is also a challenge in the state of the art.
[0009] Thus, there is a need to remove metal contaminants from hydrocarbon feedstock and design a novel demetallization nanocatalyst effective in mitigating one or more of the challenges in the state of the art.

OBJECTS OF THE INVENTION
[0010] An objective of the present invention is to provide a method for preparation of a demetallization nanocatalyst for residue upgradation.
[0011] Another objective of the present invention is to provide a demetallization nanocatalyst.
[0012] Yet another objective of the present invention is to provide a process for demetallizing a hydrocarbon feed by treating the said hydrocarbon feed with a demetallization nanocatalyst.
[0013] Another objective of the present invention is to provide use of a demetallization nanocatalyst for treating a hydrocarbon feed.

BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 showed XRD images of demetallization nanocatalyst without surfactant (a) and with surfactant (b).
[0015] FIG. 2 showed HRTEM images of demetallization nanocatalyst without surfactant (a) and with surfactant (b).
[0016] FIG. 3 showed Temperature Program Reduction (TPR) analysis of demetallization nanocatalyst with and without surfactant.
[0017] FIG. 4 showed Mo 3d XPS analysis of demetallization nanocatalyst with and without surfactant.

SUMMARY OF THE INVENTION
[0018] 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.
[0019] The present disclosure discloses a method for preparation of a demetallization nanocatalyst for residue upgradation, the method comprising the steps of: a) impregnating 2-30 w/w % of at least one transition metal on an alumina extrudates to obtain a metal supported extrudates; b) adding 1-20 w/w% of at least one polymeric surfactant and 1-10 w/w % of at least one structure directing agent to the metal supported extrudates; and c) drying and calcining the metal supported extrudates of step (b) to obtain a demetallization nanocatalyst, wherein the structure directing agent is a nitrogen-containing organic compound, and the polymeric surfactant contains at least one monomer unit derived from vinylpyrrolidone, wherein the w/w % is based on the total weight of the demetallization nanocatalyst.
[0020] The present disclosure discloses a demetallization nanocatalyst comprising: 60 to 85 w/w % of alumina extrudates; 2 - 30 w/w % of at least one transition metal; and 1 - 20 w/w % of at least one polymeric surfactant and 1 - 10 w/w % of at least one structure directing agent, wherein the structure directing agent is a nitrogen-containing organic compound, and the polymeric surfactant contains at least one monomer unit derived from vinylpyrrolidone, wherein the w/w % is based on the total weight of the demetallization nanocatalyst.
[0021] The present disclosure also discloses a process for demetallizing a hydrocarbon feed by treating the said hydrocarbon feed with a demetallization nanocatalyst comprising: 65 - 80 w/w % of alumina extrudates; 4 - 25 w/w % of at least one transition metal; and 2 – 18 w/w % of at least one polymeric surfactant and 2 - 8 w/w % of at least one structure directing agent, wherein the structure directing agent is a nitrogen-containing organic compound, and the polymeric surfactant contains at least one monomer unit derived from vinylpyrrolidone, wherein the w/w % is based on the total weight of the demetallization nanocatalyst.
[0022] The present disclosure also discloses the use of a demetallization nanocatalyst for treating a hydrocarbon feed, said demetallization nanocatalyst comprising: 60 - 85 w/w % of alumina extrudates; 2 - 30 w/w % of at least one transition metal; and 1 - 20 w/w % of at least one polymeric surfactant and 1 - 10 w/w % of at least one structure directing agent, wherein the structure directing agent is a nitrogen-containing organic compound, and the polymeric surfactant contains at least one monomer unit derived from vinylpyrrolidone, wherein the w/w % is based on the total weight of the demetallization nanocatalyst.
[0023] 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
[0024] 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.
[0025] 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.”
[0026] 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.
[0027] 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.
[0028] 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.
[0029] 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.
[0030] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.
[0031] 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.
[0032] 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.
[0033] 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.
[0034] 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.
[0035] 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.
[0036] An aspect of the present disclosure relates to a method for preparation of a demetallization nanocatalyst for residue upgradation.
[0037] In an embodiment of the present disclosure, the method comprises the steps of: a) impregnating 2-30 w/w % of at least one transition metal on an alumina extrudates to obtain a metal supported extrudates; b) adding 1 - 20 w/w % of at least one polymeric surfactant and 1 - 10 w/w % of at least one structure directing agent to the metal supported extrudates; and c) drying and calcining the metal supported extrudates of step (b) to obtain a demetallization nanocatalyst, wherein the structure directing agent is a nitrogen-containing organic compound, and the polymeric surfactant contains at least one monomer unit derived from vinylpyrrolidone, wherein the w/w % is based on the total weight of the demetallization nanocatalyst. The preferred range of alumina extrudates is 65-80 w/w % total weight of the demetallization nanocatalyst. The preferred range of at least one transition metal is 4-25 w/w % of total weight of the demetallization nanocatalyst. The preferred range of at least one polymeric surfactant is 2-18 w/w % of total weight of the demetallization nanocatalyst. The preferred range of at least one structure directing agent is 2-8 w/w% of total weight of the demetallization nanocatalyst.
[0038] In an embodiment of the present disclosure, the alumina extrudates are gamma alumina extrudates.
[0039] In an embodiment of the present disclosure, the transition metal is molybdenum and/or nickel.
[0040] In an embodiment of the present disclosure, the nitrogen-containing organic compound is selected from the group consisting of diethylamine, methylamine, ethylmethylamine, hexamethylene tetramine, and aminopropane. Preferably, the nitrogen-containing organic compound is ethylmethylamine, hexamethylene tetramine, and aminopropane. More preferably, the nitrogen-containing organic compound is hexamethylene tetramine.
[0041] In an embodiment of the present disclosure, the polymeric surfactant is selected from the group consisting of polyvinyl pyrrolidone, poly(1-vinylpyrrolidone-co-styrene), and poly(1-vinylpyrrolidone-co-vinyl acetate. Preferably, the polymeric surfactant is polyvinyl pyrrolidone and poly(1-vinylpyrrolidone-co-styrene). More preferably, the polymeric surfactant is polyvinyl pyrrolidone.
[0042] In an embodiment, the present disclosure discloses that the polymeric surfactant has an average molecule weight (Mw) ranging between 5x103 g/mol to 2x106 g/mol, or 1x104 g/mol to 1x106 g/mol, or 3x104 g/mol to 8x104 g/mol.
[0043] In an embodiment of the present disclosure, the demetallization nanocatalyst has a particle size ranging between 3 to 9 nm. In the present context, the particle size is determined by transmission electron microscopy (HRTEM, JEOL JEM-2200FS) and supported by particle size analyser Zetasizer Nano ZS (DLS, Malvern ZEN3600).
[0044] In an embodiment of the present disclosure, the drying in step c) is carried out at a temperature in the range of 100-200°C for a period in the range of 5-8 hrs and calcination at a temperature in the range of 450-550°C for a period in the range of 4-5 hrs.
[0045] The alumina extrudates can be obtained using techniques known to a person skilled in the art. In an embodiment, the process for preparing alumina extrudates includes the following steps: i) mixing 75 - 95 w/w % of a boehmite with 5 - 25 w/w % of a solvent to obtain a paste; ii) extruding the paste to obtain pellets; and iii) drying the pellets followed by calcination to obtain the alumina extrudates. Herein, the w/w % is based on the total weight of the alumina extrudates.
[0046] In an embodiment of the present disclosure, the solvent is deionized water.
[0047] In an embodiment of the present disclosure, the paste further comprises a zeolite. Suitable amounts of zeolite in the paste can be added. For instance, the zeolite can be present in an amount ranging between 5-25 w/w % based on the total weight of the alumina extrudates.
[0048] In an embodiment of the present disclosure, the pellets of step iii) are dried at a temperature in the range of 100-200°C for a period in the range of 5-8 hrs and calcined at a temperature in the range of 450-550°C for a period in the range of 4-5 hrs.
[0049] In an embodiment of the present disclosure, the gamma alumina extrudates is impregnated in step b) with the precursor ammonium heptamolybdate and nitrate salts of nickel transition metal.
[0050] Another aspect of the present disclosure relates to the demetallization nanocatalyst, as described above. Accordingly, the embodiments described hereinabove in respect of the method for preparing the demetallization nanocatalyst are applicable here as well.
[0051] In an embodiment of the present disclosure, the demetallization nanocatalyst comprises: 60 to 85 w/w % of alumina extrudates; 2 - 30 w/w % of at least one transition metal; and 1 - 20 w/w % of at least one polymeric surfactant and 1 - 10 w/w % of at least one structure directing agent, wherein the structure directing agent is a nitrogen-containing organic compound, and the polymeric surfactant contains at least one monomer unit derived from vinylpyrrolidone, wherein the w/w % is based on the total weight of the demetallization nanocatalyst.
[0052] The preferred range of alumina extrudates is 65-80 w/w % based on the total weight of the demetallization nanocatalyst. The preferred range of at least one transition metal is 4-25 w/w % based on the total weight of the demetallization nanocatalyst. The preferred range of at least one polymeric surfactant is 2-18 w/w % of total weight of the demetallization nanocatalyst. The preferred range of at least one structure directing agent is 2-8 w/w% of total weight of the demetallization nanocatalyst.
[0053] Yet another aspect of the present disclosure relates to a process for demetallizing a hydrocarbon feed by treating the said hydrocarbon feed with the demetallization nanocatalyst, as described above. Accordingly, the embodiments described hereinabove in respect of the demetallization nanocatalyst are applicable here as well.
[0054] In an embodiment of the present disclosure, the process for demetallizing the hydrocarbon feed by treating the said hydrocarbon feed with demetallization nanocatalyst comprises: 65 - 80 w/w % of alumina extrudates; 4 - 25 w/w % of at least one transition metal; and 2 – 18 w/w % of at least one polymeric surfactant and 2 - 8 w/w % of at least one structure directing agent, wherein the structure directing agent is a nitrogen-containing organic compound, and the polymeric surfactant contains at least one monomer unit derived from vinylpyrrolidone, wherein the w/w % is based on the total weight of the demetallization nanocatalyst.
[0055] In an embodiment of the present disclosure, the hydrocarbon feed is selected from vacuum residue, bitumen, and heavy oil.
[0056] Another aspect of the present disclosure relates to the use of the demetallization nanocatalyst for treating the hydrocarbon feed, as described above. Accordingly, the embodiments described hereinabove in respect of the demetallization nanocatalyst are applicable here as well.
[0057] In an embodiment of the present disclosure, the demetallization nanocatalyst comprises: 60 - 85 w/w % of alumina extrudates; 2 - 30 w/w % of at least one transition metal; and 1 - 20 w/w % of at least one polymeric surfactant and 1 - 10 w/w % of at least one structure directing agent, wherein the structure directing agent is a nitrogen-containing organic compound, and the polymeric surfactant contains at least one monomer unit derived from vinylpyrrolidone, wherein the w/w % is based on the total weight of the demetallization nanocatalyst.
[0058] 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.
ADAVATAGES OF THE PRESENT INVENTION
[0059] It has been observed that the properties of the prepared demetallization nanocatalyst were improved by addition of the surfactant. The surface area increases substantially due to the presence of micropores. The particle size deceases with inclusion of surfactant in the reaction system, which leads to increase in surface area along with the presence of micropores. The demetallization nanocatalyst of the present invention shows improved demetallization (HDM) activity. Parallelly, desulphurization (HDS) activity decreases which indicate comparatively less chances of conversion of sulfur to gaseous forms which is a drawback of the prior art documents. Furthermore, the conversion activity of the demetallization nanocatalyst of the present invention is better than the state of the art.
EXAMPLES
[0060] 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.
[0061] General synthesis of catalyst
• Alumina extrudates were prepared by using pseudoboehmite powder or by precipitation method using ammonia,
• Extrudates were dried and calcined,
• Metal impregnation and addition of surfactant (PVP and HMTA) on the extrudates, and
• Drying and calcination of the catalyst.
Example 1:
[0062] Alumina supports were synthesized from commercial boehmite (details about commercial support is mentioned in Table 1) as follows: First, a paste (binder) was prepared with the total boehmite (15 gm) and deionized water incorporated in a mortar pestel until a homogeneous paste was obtained. In few cases 5-25 wt% of zeolite was added to the boehmite while preparing the paste. This paste was extruded into 1 mm diameter cylindrical pellets. The extrudates were dried 5-8 hrs in an oven kept at 100-200 °C and then calcined at 450-550 °C for 4-5 hrs to obtain γ-Al2O3 extrudates. The molybdenum and Ni supported catalysts were prepared by the wet impregnation method using the required amount of ammonium heptamolybdate and nitrate salts of Nickel transition metal. After impregnation, the samples were dried at 100-200 °C for 5-8 hrs and calcined at 450-550 °C for 4-5 hrs.
Example 2:
[0063] A demetallization nanocatalyst was prepared by impregnating 7 w/w % of the molybdenum metal and 2 w/w % of the nickel metal on 76 w/w % of an alumina extrudates to obtain a metal supported extrudates. 10 w/w % of a polyvinyl pyrrolidone and 5 w/w % of hexamethylene tetramine was added to the metal supported extrudates which were dried at 150°C for 6 hrs and then calcined at 500°C for 5 hrs to obtain demetallization nanocatalyst.
Example 3:
[0064] A demetallization nanocatalyst was prepared by impregnating 10 w/w % of the nickel metal on 80 w/w % of an alumina extrudates to obtain a metal supported extrudates. 5 w/w % of a polyvinyl pyrrolidone and 5 w/w % of hexamethylene tetramine was added to the metal supported extrudates which were dried at 200°C for 6 hrs and then calcined at 550°C for 5 hrs to obtain demetallization nanocatalyst.
Example 4:
[0065] A demetallization nanocatalyst was prepared by impregnating 5 w/w % of the molybdenum metal on 75 w/w % of an alumina extrudates to obtain a metal supported extrudates. 10 w/w % of a Poly(1-vinylpyrrolidone-co-styrene and 10 w/w % of diethylamine was added to the metal supported extrudates which were dried at 150°C for 5 hrs and then calcined at 450°C for 4 hrs to obtain demetallization nanocatalyst.
Example 5:
[0066] A demetallization nanocatalyst was prepared by impregnating 15 w/w % of the molybdenum metal on 60 w/w % of an alumina extrudates to obtain a metal supported extrudates. 15 w/w % of a polyvinyl pyrrolidone and 10 w/w % of hexamethylene tetramine was added to the metal supported extrudates which are dried at 150°C for 5 hrs and then calcined at 450°C for 4 hrs to obtain demetallization nanocatalyst.
Example 6:
[0067] A demetallization nanocatalyst was prepared by impregnating 30 w/w % of the molybdenum metal on 60 w/w % of an alumina extrudates to obtain a metal supported extrudates. 5 w/w % of a Poly(1-vinylpyrrolidone-co-vinyl acetate and 5 w/w % of methylamine was added to the metal supported extrudates which were dried at 150 °C for 6 hrs and then calcined at 500°C for 5 hrs to obtain demetallization nanocatalyst.
Characterization of the designed nanocatalyst
[0068] Surface characterization data such as surface area, pore size, pore volume is tabulated for the designed catalyst in Table 1 which shows an increase in the surface area after surfactant addition. XRD images of the above-mentioned catalyst (Example 2) confirms the formation of the gamma alumina phase of the catalysts. Also, the metals are uniformly distributed throughout the catalyst as no prominent peaks corresponding to Mo or Ni is detected in the XRD pattern. Characteristic XRD peaks detected with 2θ value of 36.99, 45.42, 66.8 corresponds to (311), (400) and (440) plane for the synthesized catalyst which were matching with the gamma alumina phase precedent literature indicating the support phase was formed (FIG. 1). Surface characteristics of the catalyst depend on the support character. It is clearly observed in the HRTEM images that without addition of any surfactant the size of the transition metals are in the 120-140 nm range whereas after addition of surfactant size of the active metals confined in the 6-9 nm range. In the TPR profile (in the temperature range from 100-900 oC), the nanocatalyst with surfactant shows a broad single peak with a peak center at 480 oC which is the reaction temperature for demetallization whereas for the catalyst without surfactant shows two peaks centered at 360 and 720 oC. Crushing strength of these extruded were measured and it was noticed that the crushing strength value is in the range of 15-17 kg. FIG. 4 shows high resolution Mo 3d spectra for demetallization nanocatalyst for both the samples with and without surfactant. The XPS spectra for Mo 3d reveal peaks at binding energy of 232.1 eV and 235.6 eV assigned to Mo3d5/2 and Mo3d3/2 molybdenum oxide, respectively. The differences in shape and position of Mo 3d XPS spectra suggest a change in chemistry of Mo cations before and after the use of surfactant. A detailed analysis on the binding energy revealed the Mo peaks for Mo oxides to be mainly Mo6+ with a small amount of Mo4+. This suggests that the presence of a mixture of MoO3 and MoO2 phases. After addition of surfactant, a third peak was observed at 229.8 eV in FIG. 2b, corresponding to the formation of Moδ+ (0<δ<4). The Moδ+ peak can be attributed to the formation bond between Mo and Ni. For the nanocatalyst with surfactant, the peak position for Mo3d5/2 and Mo3d3/2 shifts towards high binding energy confirm there is transfer of electrons from Mo to the Ni ion species which will take part in the demetallization reaction.
Table 1: Surface properties of Nanocatalysts with and without surfactant
Sample Name Surface Area (m2/gm) Mesoporous Surface Area (m2/gm) Micro pore Surface Area
(m2/gm) Pore Volume (cc/gm) APD (Average Pore Diameter) Crushing Strength (Kg) Synthesis details
Without Surfactant 162 162 0 0.63 14 15.15 Regular fabrication technique
With Surfactant 264 232 32 0.45 3.9 16.4 With surface controlling reagent

[0069] It can be observed from the above table that with the addition of the surfactant, the surface area increases substantially due to the presence of micropores. As shown in Figure 2, it is clear that the particle size decreases with inclusion of surfactant in the reaction system, which leads to increase in surface area along with the presence of micropores. The optimized particle size also helps to constrain the reduction temperature very much close to the reaction temperature as presented in TPR in Figure 3. Crushing strength is evaluated in bulk crushing strength tested and presented in above table, is comparable to the commercial catalysts.
Table 2: Demetallization reaction activity of Nanocatalysts with and without surfactant
EB Demetallization Catalyst Development
Catalyst % HDM % HDS Conversion %
Without Surfactant 69.4 84.5 71.6
With Surfactant 85 77.3 78.8

[0070] It can be observed from Table 2 that the demetallization (HDM) activity of the designed ebulated bed nanocatalyst is 85%. Increased desulphurization (HDS) and conversion activity of 77.3% and 78.8%, respectively, can be further observed. Thus, the present disclosure catalyst provides for enhanced demetallization and desulphurization in comparison to the state-of-the-art catalyst.
[0071] 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.
[0072] 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 method for preparation of a demetallization nanocatalyst for residue upgradation, said method comprising the steps of:
a) impregnating 2-30 w/w % of at least one transition metal on 60 to 85 w/w % of an alumina extrudates to obtain a metal supported extrudates;
b) adding 1 - 20 w/w % of at least one polymeric surfactant and 1 - 10 w/w % of at least one structure directing agent to the metal supported extrudates; and
c) drying and calcining the metal supported extrudates of step (b) to obtain a demetallization nanocatalyst,
wherein the structure directing agent is a nitrogen-containing organic compound, and the polymeric surfactant contains at least one monomer unit derived from vinylpyrrolidone,
wherein the w/w % is based on the total weight of the demetallization nanocatalyst.

2. The method as claimed in claim 1, wherein the alumina extrudates are gamma alumina extrudates.

3. The method as claimed in claim 1 or 2, wherein the transition metal is molybdenum and/or nickel.

4. The method as claimed in claim one or more of claims 1 to 3, wherein the nitrogen-containing organic compound is selected from the group consisting of diethylamine, methylamine, ethylmethylamine, hexamethylene tetramine, and aminopropane.

5. The method as claimed in one or more of claims 1 to 4, wherein the polymeric surfactant is selected from the group consisting of polyvinyl pyrrolidone, Poly(1-vinylpyrrolidone-co-styrene), and Poly(1-vinylpyrrolidone-co-vinyl acetate).
6. The method as claimed in one or more of claims 1 to 6, wherein the demetallization nanocatalyst has a particle size ranging between 3 to 9 nm.

7. A demetallization nanocatalyst comprising:
60 to 85 w/w % of alumina extrudates;
2 - 30 w/w % of at least one transition metal; and
1 - 20 w/w % of at least one polymeric surfactant and 1 - 10 w/w % of at least one structure directing agent,
wherein the structure directing agent is a nitrogen-containing organic compound, and the polymeric surfactant contains at least one monomer unit derived from vinylpyrrolidone,
wherein the w/w % is based on the total weight of the demetallization nanocatalyst.

8. A process for demetallizing a hydrocarbon feed by treating the said hydrocarbon feed with a demetallization nanocatalyst comprising:
65 - 80 w/w % of alumina extrudates;
4 - 25 w/w % of at least one transition metal; and
2 – 18 w/w % of at least one polymeric surfactant and 2 - 8 w/w % of at least one structure directing agent,
wherein the structure directing agent is a nitrogen-containing organic compound, and the polymeric surfactant contains at least one monomer unit derived from vinylpyrrolidone,
wherein the w/w % is based on the total weight of the demetallization nanocatalyst.

9. The process as claimed in claim 8, wherein the hydrocarbon feed is selected from vacuum residue, bitumen, and heavy oil.

10. Use of a demetallization nanocatalyst for treating a hydrocarbon feed, said demetallization nanocatalyst comprising:
60 - 85 w/w % of alumina extrudates;
2 - 30 w/w % of at least one transition metal; and
1 - 20 w/w % of at least one polymeric surfactant and 1 - 10 w/w % of at least one structure directing agent,
wherein the structure directing agent is a nitrogen-containing organic compound, and the polymeric surfactant contains at least one monomer unit derived from vinylpyrrolidone,
wherein the w/w % is based on the total weight of the demetallization nanocatalyst.