Description:FIELD OF THE INVENTION
The present invention relates to the technical field of slurry residue hydrocracking. Particularly, the present disclosure provides a catalyst composition and a method for hydroconversion of hydrocarbonaceous feed in a slurry hydrocracking process.

BACKGROUND
Slurry hydrocracking process, a process for upgrading vacuum residue or heavy oil (hydrocarbonaceous feed), involves relatively high temperature and pressures and allows conversion of hydrocarbonaceous feed to obtain lighter distillate product, which are of increased value. However, the conventional processes do not provide higher liquid yield as desired, furthermore, the conventional processes tend to produce side-products such as coke and gas to a great extent.
In a continuous slurry hydrocracking process, frequent operability issues are encountered due to choking of coke material all over the reactor systems and valves. Reduced coke formation in the slurry hydrocracking process has been the most sought after aspect of the slurry hydrocracking process in the recent past, inasmuch as, reduction of even a few extra percentages of coke formation leads to significantly improved operation feasibility.
In view of the above, there is a long felt need to develop catalytic composition for conversion of hydrocarbonaceous feed (such as vacuum residues and heavy oils) in a slurry hydrocracking process to obtain valuable distilled product(s) without excessive production of undesirable products (coke and gases), in a manner, which does not significantly increase the cost of obtaining the desired end product(s). The present disclosure alleviates the aforesaid shortcomings, amongst others, and provides an improved catalyst composition and method for hydroconversion of hydrocarbonaceous feed in a slurry hydrocracking process.

OBJECTS
An object of the present disclosure is to provide an improved catalyst composition for hydroconversion of hydrocarbonaceous feed in a slurry hydrocracking process.
Another object of the present disclosure is to provide a catalyst composition that affords enhanced yield of liquid product(s) while reducing the gas and coke yields.
Another object of the present invention is to provide a catalyst composition that increases the hydrogenation efficiency in a hydrocracking process.
Another object of the present invention is to provide a catalyst composition that reduces the time for achieving desired pre-operating process conditions such as catalyst activation during the hydrocracking process.
Further object of the present invention is to provide an improved method for hydroconversion of hydrocarbonaceous feed in a slurry hydrocracking process that affords enhanced yield of distillate product(s) while reducing the formation of gas and coke.
Still further object of the present invention is to provide a method for hydroconversion of hydrocarbonaceous feed in a slurry hydrocracking process that is economical and environment friendly.

SUMMARY
The present disclosure is, in part, on the premise of a surprising discovery by inventors of the present disclosure that during the hydrocracking process, high molecular weight asphaltene and resins (present in the hydrocarbonaceous feedstock) have a tendency to undergo phase separation over time, and thermal cracking leads to increased coke and gas formation; incorporation/usage of asphaltene dispersant(s) along with the oil soluble sulfurized metal compound(s) aids in increasing solubility/dispersibility of high molecular weight asphaltene and resins in the reaction medium, while the oil soluble sulfurized metal compound(s) upon being exposed to a hydrocracking temperature (e.g. in excess of 300°C) and a hydrocracking pressure (e.g. in excess of 100 bar hydrogen atmosphere) result in in-situ conversion to active metal sulfide specie(s) that act as catalyst affording enhanced hydroconversion of heavy hydrocarbonaceous feed resulting in reduction of coke formation and increase in yield of the liquid product(s). Accordingly, asphaltene dispersant(s) and oil soluble sulfurized metal compound(s) exhibit excellent functional reciprocity therebetween reducing the formation of coke and gases while enhancing the yield of liquid product(s) in the slurry hydrocracking process. In-situ conversion of oil soluble sulfurized metal compound(s) to active metal sulfide specie(s) precludes the need of any separate pre-activation process(es) and the need of addition of sulfur and/or solvent during the hydrocracking process.
Accordingly, an aspect of the present disclosure provides a catalyst composition for hydroconversion of hydrocarbonaceous feed in a slurry hydrocracking process, said composition comprising: (a) an oil soluble sulfurized metal compound in an amount ranging from 60% to 95% w/w, said metal being selected from molybdenum, cobalt or combinations thereof; and (b) an asphaltene dispersant in an amount ranging from 5% to 40% w/w.
In an embodiment, the composition includes the oil soluble sulfurized metal compound and the asphaltene dispersant in a weight ratio ranging from 20:1 to 2:1. In an embodiment, the asphaltene dispersant is selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof. In an embodiment, the oil soluble sulfurized metal compound is a reaction product of: a secondary amine, carbon disulfide, and a cobalt compound and/or a molybdenum compound. In an embodiment, the oil soluble sulfurized metal compound is selected from an alkyl thio molybdenum compound, an alkyl thio cobalt compound and mixtures thereof, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof.
In an embodiment, the composition comprises: (a) an alkyl thio cobalt compound, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof in an amount ranging from 60% to 95% w/w; and (b) an asphaltene dispersant in an amount ranging from 5% to 40% w/w, said asphaltene dispersant being selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof.
In an embodiment, the composition comprises: (a) a combination of an alkyl thio cobalt compound and an alkyl thio molybdenum compound, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof in an amount ranging from 60% to 95% w/w; and (b) an asphaltene dispersant in an amount ranging from 5% to 40% w/w, said asphaltene dispersant being selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof, wherein the composition comprises the alkyl thio cobalt compound and the alkyl thio molybdenum compound in molar ratio ranging from 9:1 to 1:9. In an embodiment, the composition comprises the alkyl thio cobalt compound and the alkyl thio molybdenum compound in molar ratio of 3:1.
Another aspect of the present disclosure relates to a method for hydroconversion of a hydrocarbonaceous feed in a slurry hydrocracking process, said method comprising contacting the hydrocarbonaceous feed with hydrogen in presence of a catalyst composition at a hydrocracking temperature and hydrocracking pressure to obtain lighter distillate, gas and metal sulfide doped coke, wherein the catalyst composition comprises: (a) an oil soluble sulfurized metal compound in an amount ranging from 60% to 95% w/w, said metal being selected from molybdenum, cobalt or combinations thereof; and (b) an asphaltene dispersant in an amount ranging from 5% to 40% w/w.
In an embodiment, the hydrocracking temperature ranges from 420°C to 440°C, and wherein the hydrocracking pressure ranges from 80 bar to 175 bar. In an embodiment, the catalyst composition is present in an amount ranging from 0.1 wt. % to 1.0 wt. % by weight of the hydrocarbonaceous feed. In an embodiment, the oil soluble sulfurized metal compound is a reaction product of: a secondary amine, carbon disulfide, and a cobalt compound and/or a molybdenum compound, further wherein the oil soluble sulfurized metal compound is selected from an alkyl thio molybdenum compound, an alkyl thio cobalt compound and mixtures thereof, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof. In an embodiment, the hydrocarbonaceous feed comprises heavy, asphaltene containing, hydrocarbenoeus liquid(s) such as, but not limited to, petroleum vacuum residues, tar sand oils, coal oils, shale oils and mixtures thereof.

BRIEF DISCRIPTION OF DRAWINGS
The accompanying drawings are included to provide a further understanding of the present disclosure and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments of the present disclosure and together with the description, serve to explain the principles of the present disclosure.
FIG. 1 illustrates an exemplary graph showing variation in gas product yields with respect to catalysts composition and temperature.
FIG. 2 illustrates an exemplary graph showing variation in liquid product yields with respect to catalysts composition and temperature.
FIG. 3 illustrates an exemplary graph showing variation in coke product yields with respect to catalysts composition and temperature.
FIG. 4 illustrates an exemplary graph showing variation in total residue conversion with respect to catalysts composition and temperature.

DETAILED DESCRIPTION
The present invention relates to the technical field of slurry hydrocracking. Particularly, the present disclosure provides a catalyst composition and a method for hydroconversion of hydrocarbonaceous feed in a slurry hydrocracking process.
The following is a detailed description of embodiments of the disclosure depicted in the accompanying drawings. 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.
Each of the appended claims defines a separate invention, which for infringement purposes is recognized as including equivalents to the various elements or limitations specified in the claims. Depending on the context, all references below to the "invention" may in some cases refer to certain specific embodiments only. In other cases it will be recognized that references to the "invention" will refer to subject matter recited in one or more, but not necessarily all, of the claims.
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.”
Reference throughout this specification to “one embodiment” or “an embodiment” means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment. Thus, the appearances of the phrases “in one embodiment” or “in an embodiment” in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
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.
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. 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 were individually recited herein. All methods 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.
The following description provides different examples and 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.
All percentages, ratios, and proportions used herein are based on a weight basis unless otherwise specified.
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.
The term “hydrocarbonaceous feed”, “feed” and “feedstock”, as used herein, throughout the present disclosure, synonymously and interchangeably, denotes heavy asphaltene containing hydrocarbonaceous liquids stocks. The heavy asphaltene containing hydrocarbonaceous oils/liquids mainly contains higher percentage of metal contaminants (such as Ni, Fe and V), high contents of sulfur and nitrogen compounds and a high Condradson carbon residue. The metal content of such oils may be 1000 ppm or even more and the sulfur content may range upto 5-7 percentage. The API gravity of such feed may range from about -5 to about 10o API and the Condradson carbon residue of the heavy feeds may range from about 10 to about 50 weight percentages. Exemplary heavy asphaltene containing hydrocarbonaceous liquids stocks includes, but not limited to, petroleum crude oils including heavy crude oils; residual oils such as petroleum atmospheric distillation tower resid (boiling above 360oC), and a petroleum vacuum distillation tower resid (boiling above 565oC); tars; bitumen; tar sand oils, coal oils; shale oils and mixtures thereof.
The term “oil soluble” appearing in the context of sulfurized metal compound(s), throughout the present disclosure, denotes sulfurized metal compound(s), which are generally hydrophobic in nature and are soluble in oil or hydrocarbon.
An aspect of the present disclosure provides a catalyst composition for hydroconversion of hydrocarbonaceous feed in a slurry hydrocracking process, said composition comprising: (a) an oil soluble sulfurized metal compound, said metal being selected from molybdenum, cobalt or combinations thereof; and (b) an asphaltene dispersant.
In an embodiment, the composition includes the oil soluble sulfurized metal compound in an amount ranging from 10% to 95% w/w and the asphaltene dispersant in an amount ranging from 5% to 90% w/w. In an embodiment, the composition includes the oil soluble sulfurized metal compound in an amount ranging from 30% to 95% w/w and the asphaltene dispersant in an amount ranging from 5% to 70% w/w. In an embodiment, the composition includes the oil soluble sulfurized metal compound in an amount ranging from 40% to 95% w/w and the asphaltene dispersant in an amount ranging from 5% to 60% w/w. In an embodiment, the composition includes the oil soluble sulfurized metal compound in an amount ranging from 50% to 95% w/w and the asphaltene dispersant in an amount ranging from 5% to 50% w/w. Preferably, the composition includes the oil soluble sulfurized metal compound in an amount ranging from 60% to 95% w/w and the asphaltene dispersant in an amount ranging from 5% to 40% w/w.
In an embodiment, the composition includes the oil soluble sulfurized metal compound and the asphaltene dispersant in a weight ratio ranging from about 20:1 to about 2:1. In an embodiment, the composition includes the oil soluble sulfurized metal compound and the asphaltene dispersant in a weight ratio ranging from about 15:1 to about 2:1, preferably, ranging from about 10:1 to about 2:1, more preferably, ranging from about 7:1 to about 2:1.
In an embodiment, the asphaltene dispersant is selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof.
In an embodiment, the oil soluble sulfurized metal compound is a reaction product of: a secondary amine, carbon disulfide, and a cobalt compound and/or a molybdenum compound. In an embodiment, the secondary amine is selected from diethyl amine, di-n-propyl amine, di-n-butyl amine, piperidine, pyrrolidine and mixtures thereof.
In an exemplary embodiment, the oil soluble sulfurized metal compound is obtained by a process including the steps of: (a) mixing the secondary amine and NaOH in water in a reactor; (b) cooling the amine solution to a temperature ranging from about 2-20°C (preferably, about 5-15°C, more preferably, about 5-7°C); (c) adding carbon disulfide to the cooled amine solution while stirring; (d) adding cobalt and/or molybdenum salt solution to the solution of step (c); and (e) stirring the reaction mixture from step (d) for a suitable time period (such as for about 5 minutes to about 120 minutes or more) maintaining temperature in the range of about 2-20°C (preferably, about 5-15°C, more preferably, about 5-7°C) to obtain the precipitates of oil soluble sulfurized metal compound. In an embodiment, the process further includes a step of acidification after the step of stirring the reaction mixture, such as by addition of nitric acid to the precipitates of oil soluble sulfurized metal compound. The precipitates may then be subjected to filtration, washing with water and/or methanol and drying to obtain the oil soluble sulfurized metal compound that acts as catalysts in slurry hydrocracking process.
In an embodiment, the oil soluble sulfurized metal compound is selected from an alkyl thio molybdenum compound, an alkyl thio cobalt compound and mixtures thereof, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof.
In an embodiment, the oil soluble sulfurized metal compound is selected from thio carbamide cobalt compound, thio carbamide molybdenum compound and mixtures thereof, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof.
In an embodiment, the composition comprises: (a) an alkyl thio molybdenum compound, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof in an amount ranging from 60% to 95% w/w; and (b) an asphaltene dispersant in an amount ranging from 5% to 40% w/w, said asphaltene dispersant being selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof.
In an embodiment, the composition comprises: (a) an alkyl thio molybdenum compound, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof in an amount ranging from 70% to 95% w/w; and (b) an asphaltene dispersant in an amount ranging from 5% to 30% w/w, said asphaltene dispersant being selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof.
In an embodiment, the composition comprises: (a) an alkyl thio cobalt compound, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof in an amount ranging from about 60% to about 95% w/w; and (b) an asphaltene dispersant in an amount ranging from about 5% to about 40% w/w, said asphaltene dispersant being selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof.
In an embodiment, the composition comprises: (a) an alkyl thio cobalt compound, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof in an amount ranging from about 70% to about 95% w/w; and (b) an asphaltene dispersant in an amount ranging from about 5% to about 30% w/w, said asphaltene dispersant being selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof.
In an embodiment, the composition comprises: (a) a combination of an alkyl thio cobalt compound and an alkyl thio molybdenum compound, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof in an amount ranging from about 60% to about 95% w/w; and (b) an asphaltene dispersant in an amount ranging from about 5% to about 40% w/w, said asphaltene dispersant being selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof, wherein the composition comprises the alkyl thio cobalt compound and the alkyl thio molybdenum compound in molar ratio ranging from about 9:1 to about 1:9.
In an embodiment, the composition comprises: (a) a combination of an alkyl thio cobalt compound and an alkyl thio molybdenum compound, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof in an amount ranging from about 70% to about 95% w/w; and (b) an asphaltene dispersant in an amount ranging from about 5% to about 30% w/w, said asphaltene dispersant being selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof, wherein the composition comprises the alkyl thio cobalt compound and the alkyl thio molybdenum compound in molar ratio ranging from about 9:1 to about 1:9.
In an embodiment, the composition comprises the alkyl thio cobalt compound and the alkyl thio molybdenum compound in molar ratio ranging from about 5:1 to about 1:5, preferably, about 5:1 to about 1:3, more preferably, ranging from about 5:1 to about 1:1, still more preferably, ranging from about 5:1 to about 2:1. In an embodiment, the composition comprises the alkyl thio cobalt compound and the alkyl thio molybdenum compound in molar ratio of about 3:1.
Another aspect of the present disclosure relates to a method for hydroconversion of a hydrocarbonaceous feed in a slurry hydrocracking process, said method comprising contacting the hydrocarbonaceous feed with hydrogen in presence of a catalyst composition at a hydrocracking temperature and hydrocracking pressure to obtain lighter distillate, gas and metal sulfide doped coke, wherein the catalyst composition comprises: (a) an oil soluble sulfurized metal compound in an amount ranging from 60% to 95% w/w, said metal being selected from molybdenum, cobalt or combinations thereof; and (b) an asphaltene dispersant in an amount ranging from 5% to 40% w/w.
In an embodiment, the catalyst composition comprises: (a) an oil soluble sulfurized metal compound in an amount ranging from 60% to 95% w/w, said metal being selected from molybdenum, cobalt or combinations thereof; and (b) an asphaltene dispersant in an amount ranging from 5% to 40% w/w realized in accordance with embodiments of the present disclosure.
In an embodiment, the hydrocracking temperature ranges from about 420°C to about 440°C. In an embodiment, the hydrocracking pressure ranges from about 80 bar to about 175 bar.
In an embodiment, the catalyst composition is present in an amount ranging from about 0.1 wt. % to about 1.0 wt. % by weight of the hydrocarbonaceous feed. In an embodiment, the catalyst composition is present in an amount ranging from about 0.25 wt. % to about 0.75 wt. % by weight of the hydrocarbonaceous feed.
In an embodiment, the oil soluble sulfurized metal compound is a reaction product of: a secondary amine, carbon disulfide, and a cobalt compound and/or a molybdenum compound, wherein the oil soluble sulfurized metal compound is selected from an alkyl thio molybdenum compound, an alkyl thio cobalt compound and mixtures thereof, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof.
In an embodiment, the hydrocarbonaceous feed comprises heavy, asphaltene containing, hydrocarbenoeus liquid(s) such as, but not limited to, petroleum vacuum residues, tar sand oils, coal oils, shale oils and mixtures thereof.
The present disclosure is further explained in the form of following examples. However, it is to be understood that the 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 and spirit of the present invention.
EXAMPLES
Example 1: Synthesis of oil soluble molybdenum compound
Di-n-Propyl amine (0.28 mol) and sodium hydroxide (0.28 mol) were mixed in 400 ml of distilled water in a glass reactor using overhead stirrer. The mixture was cooled to about 5-7 oC using cooler while stirring. To the reaction mixture, carbon disulfide (0.28 mol) was added at once while vigorously stirring. After 15 min, sodium molybdate dehydrate (0.14 mol) was added to the reaction mixture, and stirred for 1.5 h at 5-7 oC. To this reaction mixture, 500 ml of 0.5 N Nitric acid was added drop-wise using peristaltic pump. During the addition of nitric acid, black color precipitate was formed and sticking over wall of the reactor and impeller. Further, the reaction mixture was allowed to stir for 20 min at 5-7 oC. After completion of the reaction, it was filtered and gummy black coloured product was separated by filtration. The sticky product was dissolved in minimum amount of toluene and dried over anhydrous sodium sulfate. To this solution, petroleum ether (60-80 oC) was slowly added, resulting in orange color product, which was precipitated and removed by filtration, and dried to afford oil soluble molybdenum compound for slurry hydrocracking process.
Example 2: Synthesis of oil soluble cobalt compound
Di-n-Propyl amine (0.28 mol) and sodium hydroxide (0.28 mol) were mixed in 400 ml of distilled water in a glass reactor using overhead stirrer. The mixture was cooled to about 5-7 oC using cooler while stirring. To the reaction mixture carbon disulfide (0.28 mol) was added at once while vigorously stirring. To this reaction mixture freshly prepared cobalt salt solution (0.14 mol of CoCl2.6H20 in 500 ml of Distilled water) was added drop wise using peristaltic pump for 40 minutes duration. During the addition of solution, green color precipitate was formed and further, the reaction mixture was allowed to stir for 20 mints at 5-7 oC. After completion of the reaction, the green color product was precipitated and removed by filtration, washed with water and methanol, and dried to afford oil soluble cobalt compound for slurry hydrocracking process.
General experimental process for slurry hydrocracking process
All the experiments in the examples were performed in CSTR (continuously stirred tank reactor) having 1 litre capacity. The reaction mixture comprising Arab mix vacuum residue (VR) (565 oC) as a feed, oil soluble metal compounds and/or an asphaltene dispersant were introduced into the autoclave. The autoclave was sealed, purged to remove air and pressurized with hydrogen and heated to the required temperature, such as 400 oC - 450 oC, more precisely 420 oC - 440 oC. Since, the vacuum bottom (VR) residue was solid in nature at room temperature, the reactor was heated to 100oC and thereafter stirring was initiated. The reactor was stirred at 500 rpm at required reaction temperature and a reaction was carried out for 60-240 minutes. The reactor was cooled off to 30 deg C by removing external furnace jacket around the reactor. The product mixture was then decanted from the reactor and processed further by separating different fractions as per boiling range.
Table 1 below provides properties of Arab mix vacuum tower bottom used in the examples.
Table 1: Properties of Arab mix vacuum residue (VR)
Properties Arab mix vacuum residue (VR)
Density at 15°C 1.0416 gm/cc
Specific Gravity at 60/60ºF 1.0425
API Gravity 4.23
Total Sulphur 5.5405 wt. %
Pour Point 60 °C
Total acid no. (TAN) 4.1810 mg KOH/gm
Carbon, C 82.98 wt. %
Hydrogen, H 9.86 wt. %
Nitrogen, N 0.17 wt. %
Sulphur, S 5.29 wt. %
Saturates 13.01 wt. %
Aromatics 40.75 wt. %
Resins 28.74 wt. %
Asphaltenes 17.50 wt. %
Vanadium Content 125 ppm
Nickel Content 35 ppm
Iron Content 55 ppm
Copper Content 1.36 ppm
Micro Carbon Residue 25.74 wt. %
Kin. Viscosity, 100°C 5868.75 cSt
Penetration 39 dmm
Softening point 52 °C

In catalyst evaluations process, required amount of catalysts i.e. the oil soluble metal compounds (1000 ppm of metal content) along with feed (250 g) was loaded into the autoclave and fitted to the reactor system. The reactor vessel was pressurized with hydrogen at room temperature and then heated to 430oC at stirring of 500 rpm. During experiments, required amount of hydrogen was introduced into the reactor when there was pressure drop due to consumption of hydrogen.
After completion of reaction, the gaseous components were released into the air through an alkali wash bottle. The liquid contents in the autoclave was transferred to a bottle and used for further analysis. SIMDIST analysis and D1160 distillation method was used to analyze the liquid products. The distilled liquid products were categorized based on initial boiling point (IBP) and final boiling point (FBP) range as naphtha (30oC- 150oC), middle distillate (150oC -350 oC) vacuum gas oil (350oC - 565oC) and residue (565+ oC). Finally, the left over coke material along with absorbed heavy liquids was recovered from reactor. The absorbed heavy liquid was separated through toluene distillation method. The filtered coke materials was dried in oven at 110 oC for 2h. Mostly, the toluene-insoluble fraction was coke and sulfurized dispersed catalyst. The total residue conversion was calculated by the following equations:
Residue Conversion = ((565?+in feed)-(565?+in product+Coke))/((565?+in feed))×100
Example 3 (Comparative Example): Effect of standalone oil soluble molybdenum metal compound in slurry hydrocracking process (devoid of asphaltene dispersant)
The reactor vessel was charged with 250 g of Arab mix vacuum bottom residue, followed by 1000 ppm metal equivalent oil soluble molybdenum compound prepared in example 1 was added and pressurized with hydrogen. The reactor vessel was initially pressurized with 80 bar pressure hydrogen and the content was heated at 430oC for 240 minutes and the final reaction pressure was maintained at 150 bar pressure as mentioned in the reaction process.
Example 4 (Comparative Example): Effect of standalone oil soluble cobalt metal compound in slurry hydrocracking process (devoid of asphaltene dispersant)
The reactor vessel was charged with 250 g of Arab mix vacuum bottom residue, followed by 1000 ppm metal equivalent oil soluble cobalt compound mentioned in example 2 was added and pressurized with hydrogen. The reactor vessel was initially pressurized with 80 bar pressure hydrogen and the content was heated at 430oC for 240 minutes and the final reaction pressure was maintained at 150 bar pressure as mentioned in the reaction process.
The results corresponding to Examples 3 and 4 are provided in the Table 2 below:
Table 2: Effect of oil soluble Co and Mo compounds
Experiment test condition: 430oC, 150 bar reaction pressure, 240 min, 500 rpm
Experiment No Example 3
(with Mo Cat.) Example 4
(with Co Cat.)
Yields
(with respect to feed wt.)
Gas, wt.% 14.5 16.8
C5-150 oC, wt.% 11.2 16.1
150-350 oC, wt.% 38.4 33.0
350-565 oC, wt.% 25.3 21.3
565 oC+, wt.% 5.2 6.9
Coke, wt.% 3.9 5.8
Residue conversion, % 89.4 87.1
Liquid product Selectivity (C5-565 oC+), wt.% 74.7 70.4

Effect of a combination of an oil soluble molybdenum compound and oil soluble cobalt compound in slurry hydrocracking process (devoid of asphaltene dispersant)
Examples 5-7 illustrates the synergy effect between oil soluble molybdenum compound and oil soluble cobalt compound in slurry hydrocracking experiments. Varying ratio of oil soluble molybdenum compound (from Example 1) and oil soluble cobalt compound were mixed (from Example 2) and studied their catalytic activity in slurry hydrocracking experiments. Three experiments were undertaken with the ratio of 1:1 of Co/Mo, 3:1 of Co/Mo and 9:1 of Co/Mo to analyse the product profile.
Example 5 (Comparative Example): Effect of a combination of an oil soluble molybdenum compound and oil soluble Cobalt compound (ratio of 1:1 of Co/Mo) in slurry hydrocracking process (devoid of asphaltene dispersant)
To the reactor vessel, 250 g of Arab mix vacuum bottom residue, 500 ppm metal equivalent oil soluble molybdenum compound prepared in example 1 and 500 ppm metal equivalent oil soluble cobalt compound prepared in example 2 were charged (i.e. ratio of 1:1 of Co/Mo) and pressurized with hydrogen. The reactor vessel was initially pressurized with 80 bar pressure hydrogen and the content was heated at 420oC for 240 minutes and the final reaction pressure was maintained at 150 bar as mentioned in the reaction process.
Example 6 (Comparative Example): Effect of a combination of an oil soluble molybdenum compound and oil soluble Cobalt compound (ratio of 3:1 of Co/Mo) in slurry hydrocracking process (devoid of asphaltene dispersant)
The reaction undertaken in this example was same as Example 5, except a combination comprising 250 ppm metal equivalent oil soluble molybdenum compound prepared in example 1 and 750 ppm metal equivalent oil soluble cobalt compound prepared in example 2 was used.
Example 7 (Comparative Example): Effect of a combination of an oil soluble molybdenum compound and oil soluble Cobalt compound (ratio of 9:1 of Co/Mo) in slurry hydrocracking process (devoid of asphaltene dispersant)
The reaction undertaken in this example was same as Example 5, except a combination comprising 100 ppm metal equivalent oil soluble molybdenum compound prepared in example 1 and 900 ppm metal equivalent oil soluble cobalt compound prepared in example 2 was used.
The results corresponding to Examples 5-7 are provided in the Table 3 below:

Table 3: Effect of varying ratio of oil soluble Co and Mo compounds
Experiment test condition: 430oC, 150 bar reaction pressure, 240 min, 500 rpm
Experiment No Example 5
(1:1 ratio of oil soluble Co and Mo Catalyst) Example 6
(3:1 ratio of oil soluble Co and Mo Catalyst) Example 7
(9:1 ratio of oil soluble Co and Mo Catalyst)
Yields
(with respect to feed wt.)
Gas, wt.% 14.8 15.8 16.6
C5-150 oC, wt.% 15.3 15.5 16.5
150-350 oC, wt.% 34.2 32.5 33.1
350-565 oC, wt.% 24.7 25 21.5
565 oC+, wt.% 7.3 7.1 7
Coke, wt.% 3.6 3.9 5.1
Residue conversion, % 89.0 88.8 87.7
Liquid product Selectivity (C5-565 oC+), wt.% 74.2 73.0 71.1

Effect of catalyst composition including oil soluble molybdenum compound and asphaltene dispersant
Example 8:
This example illustrates the effect of oil soluble metal compound along with an asphaltene dispersant in slurry hydrocracking process at 420oC. To the reactor vessel, 250 g of Arab mix vacuum bottom residue, 1000 ppm metal equivalent oil soluble molybdenum compound prepared in example 1 and 250 ppm of n-butyl catechol were charged and pressurized with hydrogen. The reactor vessel was initially pressurized with 80 bar pressure hydrogen and the content was heated at 420oC for 240 minutes and the final reaction pressure was maintained at 150 bar as mentioned in the reaction process.
Example 9:
The reaction undertaken in this example was same as Example 8, except the reaction temperature was 430oC.
Example 10:
The reaction undertaken in this example was same as Example 8, except the reaction temperature was 435oC.
Example 11:
The reaction undertaken in this example was same as Example 8, except the reaction temperature was 440oC.
The results for the examples 8-11 are shown in Table 4 below.
Table 4: Comparison between oil soluble Mo compound and a composition having oil soluble Mo compound and asphaltene dispersant
Process Temperature Product yield Oil soluble Mo Cat. alone Oil soluble Mo cat. with asphaltene dispersant
420 oC
(Example 8)
Gas, wt.% 10.9 9.6
C5-150 oC, wt.% 8.4 8.8
150-350 oC, wt.% 34.0 36.0
350-565 oC, wt.% 31.5 31.0
565 oC+ 12.0 11.3
Coke, wt.% 2.0 1.6
Residue conversion, % 84.8 85.4
Liquid product Selectivity (C5-565 oC+), wt.% 73.9 75.8
430 oC
(Example 9)
Gas, wt.% 14.5 12.5
C5-150 oC, wt.% 11.2 13.1
150-350 oC, wt.% 38.4 39.8
350-565 oC, wt.% 25.3 26.2
565 oC+ 5.2 5.0
Coke, wt.% 3.9 3.1
Residue conversion, % 89.4 91.6
Liquid product Selectivity (C5-565 oC+), wt.% 74.7 79.1
435 oC
(Example 10)
Gas, wt.% 17.3 14.5
C5-150 oC, wt.% 13.0 14.8
150-350 oC, wt.% 37.2 38.8
350-565 oC, wt.% 20.9 21.2
565 oC+ 4.6 4.1
Coke, wt.% 5.1 4.6
Residue conversion, % 88.4 89.3
Liquid product Selectivity (C5-565 oC+), wt.% 71.1 74.8
440 oC
(Example 11)
Gas, wt.% 21.5 19.8
C5-150 oC, wt.% 15.3 16.3
150-350 oC, wt.% 35.6 37.2
350-565 oC, wt.% 14.3 14.5
565 oC+ 3.3 3.0
Coke, wt.% 8.3 7.7
Residue conversion, % 86.6 87.8
Liquid product Selectivity (C5-565 oC+), wt.% 65.1 68.0

Effect of catalyst composition including oil soluble cobalt compound and asphaltene dispersant
Example 12:
This example illustrates the effect of oil soluble cobalt catalyst (compound) along with an asphaltene dispersant in slurry hydrocracking process at 420oC. To the reactor vessel, 250 g of Arab mix vacuum bottom residue, 1000 ppm metal equivalent oil soluble cobalt catalyst (compound) prepared in Example 2 above and 250 ppm of n-butyl catechol were charged and pressurized with hydrogen. The reactor vessel was initially pressurized with 80 bar pressure hydrogen and the content was heated at 420oC for 240 minutes and the final reaction pressure was maintained at 150 bar as mentioned in the reaction process.
Example 13: The reaction undertaken in this example was same as Example 12, except the reaction temperature was 430oC.
Example 14: The reaction undertaken in this example was same as Example 12, except the reaction temperature was 435oC.
Example 15: The reaction undertaken in this example was same as Example 12, except the reaction temperature was 440oC.
The results for the examples 12-15 are shown in Table 4 below.
Table 5: Comparison of oil soluble Co compound with composition having oil soluble Co compound and asphaltene dispersant
Process Temperature Product yield Oil soluble Co Cat alone Oil soluble Co cat with asphaltene dispersant
420 oC
(Example 12)
Gas, wt.% 13.4 12.1
C5-150 oC, wt.% 14.5 15.4
150-350 oC, wt.% 28.3 31.1
350-565 oC, wt.% 20.5 22.0
565 oC+ 18.8 16.1
Coke, wt.% 4.3 3.2
Residue conversion, % 76.7 80.6
Liquid product Selectivity (C5-565 oC+), wt.% 63.3 68.5
430 oC
(Example 13) Gas, wt.% 16.8 15.4
C5-150 oC, wt.% 16.1 16.7
150-350 oC, wt.% 33.0 34.2
350-565 oC, wt.% 21.3 22.5
565 oC+ 6.9 6.2
Coke, wt.% 5.8 4.9
Residue conversion, % 87.1 88.8
Liquid product Selectivity (C5-565 oC+), wt.% 70.4 73.4
435 oC
(Example 14) Gas, wt.% 18.5 17.0
C5-150 oC, wt.% 15.2 15.8
150-350 oC, wt.% 30.0 32.2
350-565 oC, wt.% 23.1 23.2
565 oC+ 4.3 4.1
Coke, wt.% 8.8 7.6
Residue conversion, % 86.8 88.2
Liquid product Selectivity (C5-565 oC+), wt.% 68.3 71.2
440 oC
(Example 15) Gas, wt.% 23.7 23.2
C5-150 oC, wt.% 13.2 13.7
150-350 oC, wt.% 28.1 29.5
350-565 oC, wt.% 20.6 20.8
565 oC+ 3.8 3.0
Coke, wt.% 10.5 9.7
Residue conversion, % 85.6 87.2
Liquid product Selectivity (C5-565 oC+), wt.% 61.9 64.0

FIG. 1 illustrates an exemplary graph showing variation in gas product yields with respect to catalysts composition and temperature. FIG. 2 illustrates an exemplary graph showing variation in liquid product yields with respect to catalysts composition and temperature. FIG. 3 illustrates an exemplary graph showing variation in coke product yields with respect to catalysts composition and temperature. FIG. 4 illustrates an exemplary graph showing variation in total residue conversion with respect to catalysts composition and temperature. Based on the experimental data provided hereinabove, it could be concluded that the catalyst composition and method of the present disclosure affords hydroconversion of hydrocarbonaceous feed in a slurry hydrocracking process with enhanced yield of distillate product(s) while reducing the formation of gas and coke, making the process economical and environment friendly. It precludes the need of any separate pre-activation process(es) and the need of addition of sulfur and/or solvent during the hydrocracking process.

ADVANTAGES
The present disclosure provides a catalyst composition that increases the hydrogenation efficiency in a hydrocracking process.
The present disclosure provides a catalyst composition and a method for hydroconversion of hydrocarbonaceous feed in a slurry hydrocracking process that eliminates or otherwise reduces the coke formation during the process and thereby reduces system shutdown time and productivity loss owing to requirement of cleaning and/or replacing coke deposited equipments.
The present disclosure provides a catalyst and a method for hydroconversion of hydrocarbonaceous feed in a slurry hydrocracking process that is industrially applicable, economical and environment friendly.
, Claims:1. A catalyst composition for hydroconversion of hydrocarbonaceous feed in a slurry hydrocracking process, said composition comprising:
a. an oil soluble sulfurized metal compound in an amount ranging from 60% to 95% w/w, said metal being selected from molybdenum, cobalt or combinations thereof; and
b. an asphaltene dispersant in an amount ranging from 5% to 40% w/w.
2. The catalyst composition as claimed in claim 1, wherein the composition comprises said oil soluble sulfurized metal compound and said asphaltene dispersant in a weight ratio ranging from 20:1 to 2:1.
3. The catalyst composition as claimed in claim 1, wherein the asphaltene dispersant is selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof.
4. The catalyst composition as claimed in claim 1, wherein the oil soluble sulfurized metal compound is a reaction product of: a secondary amine, carbon disulfide, and a cobalt compound and/or a molybdenum compound.
5. The catalyst composition as claimed in claim 1, wherein the oil soluble sulfurized metal compound is selected from an alkyl thio molybdenum compound, an alkyl thio cobalt compound and mixtures thereof, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof.
6. The catalyst composition as claimed in claim 1, wherein the composition comprises:
a. an alkyl thio molybdenum compound, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof in an amount ranging from 60% to 95% w/w; and
b. an asphaltene dispersant in an amount ranging from 5% to 40% w/w, said asphaltene dispersant being selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof.
7. The catalyst composition as claimed in claim 1, wherein the composition comprises:
a. an alkyl thio cobalt compound, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof in an amount ranging from 60% to 95% w/w; and
b. an asphaltene dispersant in an amount ranging from 5% to 40% w/w, said asphaltene dispersant being selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof.
8. The catalyst composition as claimed in claim 1, wherein the composition comprises:
a. a combination of an alkyl thio cobalt compound and an alkyl thio molybdenum compound, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof in an amount ranging from 60% to 95% w/w; and
b. an asphaltene dispersant in an amount ranging from 5% to 40% w/w, said asphaltene dispersant being selected from n-butyl catechol, t- butyl catechol, catechol and mixtures thereof,
wherein the composition comprises the alkyl thio cobalt compound and the alkyl thio molybdenum compound in molar ratio ranging from 9:1 to 1:9.
9. The catalyst composition as claimed in claim 8, wherein the composition comprises the alkyl thio cobalt compound and the alkyl thio molybdenum compound in molar ratio of 3:1.
10. A method for hydroconversion of a hydrocarbonaceous feed in a slurry hydrocracking process, said method comprising contacting the hydrocarbonaceous feed with hydrogen in presence of a catalyst composition at a hydrocracking temperature and hydrocracking pressure to obtain lighter distillate, gas and metal sulfide doped coke, wherein the catalyst composition comprises: (a) an oil soluble sulfurized metal compound in an amount ranging from 60% to 95% w/w, said metal being selected from molybdenum, cobalt or combinations thereof; and (b) an asphaltene dispersant in an amount ranging from 5% to 40% w/w.
11. The method as claimed in claim 10, wherein the hydrocracking temperature ranges from 420°C to 440°C, and wherein the hydrocracking pressure ranges from 80 bar to 175 bar.
12. The method as claimed in claim 10, wherein the catalyst composition is present in an amount ranging from 0.1 wt. % to 1.0 wt. % by weight of the hydrocarbonaceous feed.
13. The method as claimed in claim 10, wherein the oil soluble sulfurized metal compound is a reaction product of: a secondary amine, carbon disulfide, and a cobalt compound and/or a molybdenum compound, further wherein the oil soluble sulfurized metal compound is selected from an alkyl thio molybdenum compound, an alkyl thio cobalt compound and mixtures thereof, the alkyl group being selected from ethyl, propyl, butyl, piperidinyl, pyrrolidinyl and mixtures thereof.