FIELD OF THE INVENTION

[0001] The present invention generally relates to a process for preparing hydrocarbons and chemicals. Specifically, the present invention relates to a solvothermal process for producing high quality fuels and chemicals from a waste plastics feedstock using lignin containing bioliquor as a solvent for hydrothermal liquefactionalong with transisition metal catalysts. The lignin containing bioliquor of the present invention isproduced as a waste stream from 2G- ethanol manufacturing plants.

BACKGROUND OF THE INVENTION

[0002] Background description includes information that may be useful in understanding the present invention. It is not an admission that any of the information provided herein is prior art or relevant to the presently claimed invention, or that any publication specifically or implicitly referenced is prior art.

[0003] Energy demands and the supply-demand imbalance have always intrigued the scientists across the world to focus on making use of unconventional fuels, and non-fossilized sources as the future of energy.

[0004] Plastics like polyethylene, polypropylene, teflon, nylon, polyester, polyvinyl chloride, thermoplastic polyurethane, etc., have emerged as the most fundamental commodity for human-life due to the convenience of moulding into different shapes and sizes, low cost, and durability. Several hundred tons of plastic waste is produced each year and being non- biodegradable, this waste is adding up to the already existing pollution and hence posing to be a huge threat to the environment. Studies report that over 6-7 billion tons of plastic waste was generated few years back and most of that (nearly 75%) ended up as landfill, with only about 10% that was incinerated.

[0005] Pyrolysis of plastics has been the common practice for re-using or utilizing plastic waste. As such literature on hydrothermal liquefaction of waste plastic is scarce. Since the municipal solid waste contains a blend of plastics comprising of polyvinyl chloride (PVC), polypropylene (PP), polyethylene terephthalate (PET), low density and high density polyethylene (LDPE, HDPE) and polystyrene (PS), various research groups focused on liquefying these to useful chemicals (Seshasayee M.S. et.al, Applied Energy 278 (2020): 115673, Souza dos Passos et. al., ACS Sustainable Chemistry & Engineering 8.51 (2020): 19051-19061, Wu X et. al., RSC advances 7.23 (2017): 13768- 13776).

[0006] Currently, at several places, this plastic waste is pyrolysed at very high temperatures of about 450 deg C - 500 deg C and higher reaction times of 60 to 120 min which results in higher energy consumption and production costs. Moreover, few of the studies also included a co-processing method together with polypropylene where algae or perennial grass was used as feedstock, but the oil yield was found to be very low at 10 - 20%. There lies a need to conduct the reaction at milder conditions with good amount of oil yield. Moreover, there is no evidence of previous work that involved co-processing of plastic along with liquor waste from second generation ethanol plants.

[0007] Another commonly found plastic waste, (PET bottles) was also employed in hydrothermal liquefaction to produce fuel (Seshasayee MS, Applied Energy 278 (2020): 115673, Pedersen TH, Waste Management 68 (2017): 24-31, Wang B, Journal of Analytical and Applied Pyrolysis 110 (2014): 382-389). Most of these reported very low amount of oil yields of about 9% to 27% with high amount of solids (60 to 75%) at relatively supercritical temperatures (over 400 deg C). Hence, there is a need to improve the oil yield and also using milder reaction conditions.

[0008] In contrast, hydrothermal liquefaction (or solvothermal synthesis in presence of liquor solvent) offers the advantage of low temperatures (may be 120 deg C to 400 deg C), and the convenience of using wet waste to form plastic crudeoil, that can be conveniently used as a fuel blend with simple upgradation processes.

[0009] Biofuel, Bioprod. Bioref. 9:630-638 (2015) discloses hydrothermal liquefaction (HTL) of sugarcane bagasse using ethanol and black liquor as solvents. However, the oil yield is less and HTL does not utilize a catalyst. And the publication silent on waste plastic as feedstcoks for the HTL process.

[0010] Although there are various studies of hydrothermal liquefaction that emphasis on oil yields and products from various plastic materials at a few isolated hydrothermal liquefaction conditions, still there requires an optimisation on hydrothermal liquefaction process parameters. Recent studies has focused on polyolefins and much less is known about hydrothermal liquefaction of other materials such as polypropylenes, polyethylene Terephthalate (PET), polyestersand so on.

[0011] Therefore, there is a need to provide a method of producing high quality fuels and chemical from different set of plastics wastes which results in ease of conversion, energy recovery, and oil compositions, for different applications. OBJECTS OF THE INVENTION

[0012] An object of the present invention is to provide a method of solvothermal process for producing high quality fuels and chemicals from a waste plastics feedstock of using lignin containing liquor as a solvent for liquefaction.

[0013] Another object of the present invention is to provide a method of solvothermal process for producing high quality fuels and chemicals from a waste plastics feedstock using lignin containing liquor as a solvent for liquefaction wherein the lignin containting liquor is formed from the acid/base pre-treatment of 2G-ethanol plant waste stream.

[0014] Another object of the present invention is to provide a method of solvothermal process for producing high quality fuels and chemicals from a waste plastics feedstock using lignin containing liquor as a solvent for liquefaction yielding very good oil yield with assistance of catalyst.

SUMMARY OF THE INVENTION

[0015] The present invention relates to a solvothermal process for producing high quality fuels and chemicals from a waste plastics feedstock using lignin containing bioliquor as a solvent for hydrothermal liquefactionalong with oil soluble transisition metal catalysts. The lignin containing bioliquor of the present invention is produced as a waste stream from 2G- ethanol manufacturing plants.

[0016] In one aspect, the present invention relates to a method of producing valuable fuels and chemicals comprising the steps of:

(a) mixing a waste plastic feedstock in a feedstock vessel and introducing the waste plastic feedstock into a hydrothermal liquefaction reactor;

(b) processing a lignocellulose biomass in a biomass treatment unit to obtain a processed lignocellulose biomass and bio liquor and fermenting the processed lignocellulose biomass in a fermenter to obtain ethanol;

(c) introducing the bioliquor stream into the hydrothermal liquefaction reactor comprising the waste plastic feedstock to obtain a mixture;

(d) subjecting the mixuture to hydrothermal liquefaction by adding a transition-metal catalyst to obtain a liquefied product;

(e) collecting the liquefied product in a collection vessel and separating the liquefied product into a gaseous product and a gas-free product stream;

(f) separating the gas-free product stream into oil stream comprising fuels and chemicals, a solid phase and an aqueous phase; (g) optionally purifying the oil stream to obtain purified oil stream; and

(h) optionally updgrading the purified oil stream to obtain fuels and chemicals.

[0017] In an embodiment of the present invention, optionally the slurry oil streams in combination with plastics can be used instead of the bio liquor heavy oil.

[0018] In an embodiment of the present invention, the waste plastic feedstock is selected from low density polyethylene (LDPE), high density polyethylene (HDPE), linear LDPE, polypropylene (PP), Teflon, nylon, polyester, thermoplastic polyurethane and combination thereof.

[0019] In another embdoiment of the present invention, the lignocellulose biomass is selected from rice straw, rice husk, saw dust, com stover, bagasse, wheat straw and combination thereof.

[0020] In another embodiment of the present invention, the processing of lignocellulose biomass comprises the step of treating lignocellulose biomass with acid or base and C5-C6 sugars.

[0021] In another embodiment of the present invention, the acid is inorganic acids like sulphuric acid, hydrochloric acid, phosphoric acid, and organic acids like acetic acid, formic acid, oxalic acid, maleic acid, or citric acid;the base is selected from sodium hydroxide, KOH or ammonia, and C5-C6 sugar is xylose, arabinose, glucose, fructose.

[0022] In another embodiment of the present invention, the bioliquor stream comprises of sodium hydroxide and lignin.

[0023] In another embodiment of the present invention, the hydrothermal liquefaction reaction is carried out at a temperature in the range of 120 deg C to 400 deg C and at a pressure in the range of 2 to 30 MPa.

[0024] In another embodiment of the present invention, the hydrothermal liquefaction reaction is carried out at a temperature in the range of 180 deg C to 350 deg C and at a pressure in the range of 10 to 20 MPa.

[0025] In another embodimentof the present invention, the hydrothermal liquefaction reaction is carried out in a time ranging from 5 minutes to 120 minutes.

[0026] In another embodiment of the present invention, the gaseous product obtained is routed for heat integration with feedstock heating.

[0027] In another embodiment of the present invention, the separating gas-free product stream comprises of bleed stream and make-up liquid which is connected with the bio-liquor for further processing. [0028] In another aspect, the present invention relates to a purification of solid phase obtained from the gas-free product stream comprising the step of:

(a) purifying the solid phase to obtain purified solid product; and

(b) sending the purified solid product to solid char upgradation unit to obtain a final product.

[0029] In another aspect, the present invention relates to amethod of upgradation oil stream, wherein the upgradation methods are selected from:

(a) mixing the oil stream with petroleum fractions in co-processing unit to obtain the hydrocarbons;

(b) hydrotreating the oil stream in a hydrotreating unit to obtain diesel or jet range fuels;

(c) cracking the oil stream using a fluid catalytic cracking unit in present of a catalyst in presence of a catalysts to obtain light olefins and gasoline additive compounds;

(d) cracking the oil stream using a steam cracking unit to ethylene and propylene; and

(e) co-processing the oil stream with used cooking oil and vegetable oil in fixed bed hydrotreater or hydrotreating followed by catalytic cracking to obtain fuel and chemical feedstock.

[0030] In another embodiment of the present invention, the catalyst used in the fluid catalytic cracking unit is selected from ZSM-5, beta zeolite, y- zeolite or combination thereof.

[0031] In another embodiment of the present invention, the catalyst used inthe hydrotreating unit catalyst can be of NiMo, CoMo, NiW or supported on AI2O3 or ZrCh- [0032] Various objects, features, aspects and advantages of the inventive subject matter will become more apparent from the following detailed description of preferred embodiments.

BRIEF DESCRIPTION OF THE FIGURES

[0033] Figure 1 represents process flow for the catalytic hydrothermal liquefaction of waste plastic biomass.

[0034] Figure 2 represents process flow for upgradation of oil stream to valuable chemicals.

[0035] Figure 3 shows the comparative oil yield for the examples 1-2 of the present invention and comparative examples. DETAILED DESCRIPTION OF THE INVENTION

[0036] 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.

[0037] 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.”

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] The headings and abstract of the invention provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] It should also be appreciated that the present invention can be implementedin 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.

[0048] 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.

[0049] The term, “hydrothermal liquefaction reactor” as used herein refers to a reactor in which a solvent is used at its super critical conditions for hydrothermal liquefaction to convert any organic substance to crude oil and chemicals at moderate temperature and pressure. Generally, the hydrothermal liquefaction process is conducted in a batch type autoclave reactor, that can sustain temperatures upto 500 deg C and pressures upto 32MPa, fitted with an electrically heated furnace, high temperature thermocouple, stirrer, and pressure gauge. The reactor material can be stainless steel (SS3316) and the volume of reactor is anywhere between 0.5 to 1.2 L. The reactor used in this study was a 0.5 L high temperature and high pressure stirred reactor (Parr 4575) with Parr 4848B reactor controller obtained from Parr Instrument Co., Moline, IL, US.

[0050] The term “transition metal catalyst” as used herein refers to a catalyst as prepared in the the patent applications, US20210339235A1 and WO2018235094 Al. The transition metal catalyst can be oil soluble catalyst or water soluble catalyst and in the form of powder.

[0051] The presentinvention points toward the determination that bio-liquor, a waste stream containing lignin from the 2G-ethanol plants can be made use as a solvent instead of water for the liquefaction of waste plastic feedstock (may be low density polyethylene (LDPE), high density polyethylene (HDPE) or linear LDPE, or polypropylene (PP), or Teflon, or nylon, or polyester, or polyvinyl chloride, or thermoplastic polyurethane etc.), into useful bio-oil consisting of valuable chemicals. Furthermore, a transition-metal based catalyst is added during the process to enhance the degradation of plastics and improve the oil yield. Effect of catalyst on product distribution is observed in both water and bio liquor as solvent.

[0052] In first embodiment, the present invention relates to a method of producingvaluable fuels and chemicals comprising the steps of:

(a) mixing a waste plastic feedstock in a feedstock vessel and introducing the waste plastic feedstock into a hydrothermal liquefaction reactor;

(b) processing a lignocellulose biomass in a biomass treatment unit to obtain a processed lignocellulose biomass and bio liquor and fermenting the processed lignocellulose biomass in a fermenter to obtain ethanol; (c) introducing the bioliquor stream into the hydrothermal liquefaction reactor comprising the waste plastic feedstock to obtain a mixture,

(d) subjecting the mixuture to hydrothermal liquefaction by adding a transition-metal catalyst to obtain a liquefied product;

(e) collecting the liquefied product in a collection vessel and separating the liquefied product into a gaseous product and a gas-free product stream;

(f) separating the gas-free product stream into oil stream comprising fuels and chemicals, a solid phase and an aqueous phase;

(g) optionally purifying the oil stream to obtain purified oil stream; and

(h) optionally updgrading the purified oil stream to obtain fuels and chemicals.

[0053] In another embodiment of the present invention, the figure 1 shows the flow scheme for the catalytic hydrothermal liquefaction of waste plastic biomass in the presence of solvent and a transition metal oil-soluble catalyst to valuable chemicals and fuels in accordance with the present disclosure. According to the present invention, the waste plastic feedstock is stored or mixed in the feedstock vessel (3) which is introduced into the hydrothermal liquefaction reactor (HTL) reactor (4). The lignocellulosic biomass is initially processed in the biomass pretreatment unit (1) where acid/base pre-treatment occurs and then, the C5-C6 sugars (b), constituting cellulose and hemicellulose are sent into a fermenter (2), where the ethanol (c) is the main product along with a lignin containing liquor stream (d). This bio-liquor(d) is composed of sodium hydroxide and lignin. Bio-liquor stream, along with waste plastic feedstock are sent to a HTL reactor (4). A transition-metal catalyst stream (e)is added to the feedstock in HTL reactor.The liquefaction takes place at a temperature in the range of 120 deg C to 400 deg C and at a pressure in the rang of 2 to 30 MPa, and for a residence time 5 min to 120 min to obtain a liquefied product (mixture of solid char, aqueous phase and oil phase) (f).This liquefied stream (f), obtained during the hydrothermal liquefaction are sent into a product collector vessel (5), where the gaseous product (g) may be collected, may be sent to vent, may be routed for heat integration with feedstock heating. The gas-free product stream (i) is sent into a liquid-solid separator (6), where there may be a single stage or multi-stage separation procedures. The plastic crude stream (j) is separated from the solid phase (n) and the aqueous phase (k). A bleed stream (1) and make-up liquid (h) are also separated.

[0054] In another embodiment of the present invention, the oil phase (j) can be purified or processed in (7) and final oil (m) can be sent for upgradation or blending into drop in fuel/ coprocessed in refinery units like fluid catalytic cracking or hydrocracking/ hydrotreater. [0055] In another embodiment of the present invention, the solid phase (n) is sent into a purification unit (8), where the solid phases is purified and sent into an solid char upgradation unit (9) to a final product which can be used as a catalyst support (p) or for bio -remediation aid(q). The solid char upgradation unit can use steam, KOH, steamor any other activation agent for improving surface area and physical propertirs of raw char stream (o).

[0056] In an embodiment of the present invention, the feedstock of waste plastics can be selected from any of the different kinds of plastic derived from agriculture waste, packaging waste, construction waste, electric waste or household waste and can be a mixture of two or more of these plastics - polyethylene terephthalate (PET), polystyrene (PS), polyethylene, high density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low density polyethylene (LLPDE), styrene-acrylonitrile resin (SAN), styrene methyl methacrylate (SMMA), poly (methyl methacrylate) PMMA, acrylic styrene acrylonitrile (ASA), expanded polystyrene (EPS), extruded polystyrene (XPS), polycarbonate (PC), polyoxymethylene (POM), poly butylene terephthalate (PBT), polyvinyl chloride (PVC), polysulfone (PSU), polyphenyl (PPSU), polyphenylene sulfide (PPS), poly vinylidene fluoride (PVDF), polyurethane (PUR) and so on or a combination thereof. Preferably, the feedstock of waste plastics can be polypropylene (PP), Polyethylene Terephthalate (PET), Teflon, nylon, polyester, or combination thereof.

[0057] In an embodiment of the present invention, the lignocellulose biomassis selected from any of the different kinds of lignocellulosic biomass categories - hardwood, softwood, grasses and agricultural wastes. Examples of such biomass are poplar, oak, eucalyptus, pine, douglas fir, spruce, wheat straw, barley hull, barley straw, rice straw, rice husks, oat straw, ray straw, corn cobs, corn stalks, sugarcane bagasse, sorghum straw, grass, switch grass and so on or combination thereof. Preferably, it is selected from rice straw, rice husk, saw dust, com stover and combination thereof.

[0058] In an embodiment of the present invention, the bioliquor streamcan be formed from the acid/base pre-treatment of 2G-ethanol plant waste stream, as a solvent for the process, that aids in improving the plastic crude oil yield, and also producing alcohols, olefins, naphthenes and paraffins in ranges that are useful for being used for lube oil preparation, bitumen blending, surfactants, detergents and so on.

[0059] In another embodiment of the present invention, the lignocellulosic biomass is a complex material comprising of hemicellulose (16-35%), cellulose (25 to 50%), and lignin (<25%) and it can be decomposed during the pre-treatment stages and later can produce sugars in the C5-C6 range (like xylose, mannose, glucose, fructose, arabinose, galactose, rhamnose, and so on) when subjected to hydrolysis. The pre-treatment of the bio-mass can be carried out using different techniques such as physical (like pyrolysis treatment, microwave treatment, ultrasonic treatment, or mechanical comminution), biological (fungal treatments, bacterial treatments), and chemical (acid/alkali/organo- solvent/ ionic liquid/deep-eutectic solvent/ sulfite treatments, or steam explosion, ammonia fiber explosion, oxidative treatment, supercritical fluid treatment).

[0060] In an embodiment of the present invention, the waste plastic is loaded in an amount ranges from 5% to 30% by total weight percentage.

[0061] In an embodiment of the present invention, the transition metal based oil-soluble catalyst or powdered catalyst is in the concentration of 0.1-10 wt% of solids loading for enhancing the quality of the plastic crude towards fuel oils and lubricating oils.

[0062] In another embodiment of the present invention, the bio-liquor stream comprises of 1% to 10 wt % sodium hydroxide (NaOH) and lignin about 1 to 30 wt% and can be associated with lignin concentration step using multi effect evaporation.

[0063] In an embodiment of the present invention, the liquefaction takes place at a temperature in the range of 120 deg C to 400 deg C. Preferably, at a temperature in the range of 180 deg C to 350 deg C. More preferably, at a temperature in the range of 300 deg C to 350 deg C.

[0064] In an embodiment of the present invention, the liquefaction takes place at apressure in the range of 2 to 30 MPa. Preferably, at a pressure in the range of 15 to 25MPa. More preferably, at apressure in the range of 20 to 25MPa.

[0065] In another embodiment of the present invention, the reacting bio-liquor stream in the hydrothermal liquefaction reactor is carried out in a time ranging from 5 minutes to 120 minutes. Preferably, in a time ranging from 10 minutes to 60 minutes. More preferably, in a time ranging from 10 minutes to 20 minutes.

[0066] In an embodiment of the present invention, the catalyst used in the liquefaction can be present in the concentration range of 0.1-10 wt% of solids loading for enhancing the quality of the plastic crude towards fuel oils and lubricating oils.

[0067] According to the present invention, the method of converting of mixed feedstock of biomass to fuels and chemicals provides oil stream in range of 50% to 70% yield.

[0068] In an embodiment of the present invention, the method of converting of mixed feedstock of biomass to fuels and chemicals produces valuable fuel compounds, olefins and aromatics. [0069] In an embodiment of the present invention, the method of converting of mixed feedstock of biomass to fuels and chemicals produces alcohols, olefins, naphthenes and paraffins that are useful for lube oil preparation, bitumen blending, surfactants, detergents, fuels and the like.

[0070] In an embodiment of the present invention, the method of converting of waste plastic feedstock to fuels and chemicals produces valuable benzene and benzene derivatives along with its precursor chemical benzoic acid in significantly higher quantity.

[0071] In another embodiment of the present invention, the fuels and chemicals can be selected from carboxlic acid, aromatic, benzene and benzene derivatives, alcohol, alkane, alkene, cycloalkane, and ketonic compounds.

[0072] In another embodiment of the present invention, the PET waste feedstock gives majorly benzoic acid upto 60 wt% as valuable compounds.

[0073] In antoher aspect, the present invention relates to a method of upgrading the crude oil stream, wherein the upgradation methods are selected from:

(a) mixing the oil stream with petroleum fractions in co-processing unit to obtain the hydrocarbons;

(b) hydrotreating the oil stream in a hydrotreating unit to obtain diesel or jet range fuels;

(c) cracking the oil stream using a fluid catalytic cracking unit in present of a catalyst in presence of a catalysts to obtain light olefins and gasoline additive compounds;

(d) cracking the oil stream using a steam cracking unit to ethylene and propylene; and

(e) co-processing the oil stream with used cooking oil and vegetable oil in fixed bed hydrotreater or hydrotreating followed by catalytic cracking to obtain fuel and chemical feedstock.

[0074] According to the present invention, figure 2 shows the flow scheme of upgradation techniques for the products obtained from the solvothermal synthesis of waste plastics in the presence of bio-liquor solvent. The oil stream (j) can be purified or processed in unit (2a) . Unit (2a) can be a coprocessing unit, where the oil stream mixed with petroleum fractions like vacuum gas oil and heavy gas oil and processed to obtain the upgraded fuels or chemicals. Also, unit (2a) can be a hydrotreating unit for converting plastic crude into diesel/jet range fuels. Unit (2a) can also be a fluid catalytic cracking unit, where plastic crude can be cracked in presence of catalysts like zeolites (ZSM-5, beta-zeolite, y-zeolite etc) to light olefins and gasoline additive compounds. Unit 2a can also be a steam cracking unit, where plastic crude can be steam cracked to produce ethylene and propylene [0075] In an embodiment of the present invention, the updgradation of oil stream (j) comprising the steps of:

(a) purifiying oil stream (j) in unit (2a) to obtain purified oil stream; and

(b) carrying out benzoic acid purification in unit (3a) to obtain purified benzoic acid (cl).

[0076] In an embodiment of the present invention, the updgradation of oil stream (j) comprising the step of purifiying oil stream (j) in unit (2a) to obtain purified oil stream.

[0077] In an embodiment of the present invention, the updgradation of oil stream (j) comprising the steps of:

(a) purifiying oil stream (j) in (2a) to obtain purified oil stream; and

(b) carrying out paraffins purification in unit (5a) to obtain paraffin stream (el).

[0078] 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 scope of the invention is determined by the claims that follow. The invention is not limited to the described embodiments, versions or examples, which are included to enable a person having ordinary skill in the art to make and use the invention when combined with information and knowledge available to the person having ordinary skill in the art.

EXAMPLES

[0079] 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.

[0080] The biomass used in the present invention is procured from the local animal feed market in Devangonthy, Bengaluru.

[0081] Preparation 1 - Synthesis of transition-metal catalyst

[0082] For the metal precursor, about 100g molybdic acid is taken and a solution is prepared. To this, 100g of 2-ethyl hexanoic acid (first additive) solution was added and refluxed at 180 °C for 4 hours to obtain the dark black color salt. The salt was cooled and redissolved in 150 g of 2-ethyl hexanol (second additive) and heated with reflux at 180 °C for 12 hours to obtain the Mo(O), (2-ethyl hexanoate)2-ethyl hexanolate catalyst. About 340g was produced with the Mo percentage around 14 %.

[0083] Preparation 2 - Synthesis of transition-metal catalyst

[0084] To a solution of iron (III) nitrate (1 eq.) in water and hexane (1:2 ratio; 5 ml per 1 mmol of Fe salt), sodium 2-ethyl hexanoate (3 eq.) in water (solution of 1 mmol in ImL water) was added drop wise at 70 °C and the solution was refluxed for 3 h at 80 °C. The resulting reaction mixture was cooled and fractionated between water/hexane layers. The organic layer was washed with the water. The organic phase was dried (Na2NOs), concentrated in vacuo to afford the catalyst, iron ethyl-hexanoate as a gummy solid.

[0085] Example 1:

[0086] Solvothermal liquefaction of polyproylene (PP) plastics as feedin presence of lignin containing liquor solvent and molybdenum oil- soluble catalyst were performed in a high pressure high temperature 500 mL autoclave (Parr 4848B model, USA) equipped with a pressure sensor, J-type thermocouple and an external electric furnace, where the heating system is controlled by a PID controller

20g of waste polypropylene (solid to solvent ratio of 1:4) of feedstock is mixed withlignin containing bio-liquorsolvent (80g) and 0.2g of Molybdenum oil-soluble catalyst are loaded into the reactor. The reactor was purged with nitrogen gas to maintain an inert homogeneous atmosphere. A pressure test was carried out to ensure the reactors and lines are securely sealed and no leak was observed. Initial pressure of the reactor was kept at atmospheric pressure, and stirrer speed was adjusted to 350 rpm. Reactor was then allowed to reach the desired reaction temperature of 593 deg K with increments of 10 deg K/min. Once the temperature is reached, the reactor is kept at the desired temperature for residence time of 15 minutesat the pressures of 23-25 MPa. On the completion of the reaction, the autoclave is immediately cooled to room temperature with an external cooling bath. After the gas samples were collected for analysis using gas bags, the pressure was released from the reactor through vent. For the separation process, the contents of the reactor and the stirrer are washed thoroughly with dichloromethane, several times. The mixture was filtered with the help of buchner filter funnel, to remove the solids from the liquid phase. Two layers are observed in the separating funnel, where the oil stream is separated from the aqueous stream. Oil stream is extracted from the liquid samples by separating the solvent in a rotary vacuum evaporator (Buchi Rotavapor). The compounds obtained in the oil stream is given in the table below.

Table 1: List of Compounds

[0087] The following Examples and comparative examples were produced using the above experimental procedures with appropriate conditions, and starting material as given in the table below with non-critical variations. [0088] Example 2:

Table 2: List of Compounds

[0089] Comparative Example - 1 (CE-1):

Table 3: List of Compounds:

[0090] Comparative Example - 2 (CE-2)

Table 4: List of compounds [0091] Comparative Example - 3 (CE-3)

Table 5: List of compounds

[0092] Results:GC-MS analysis was conducted for each plastic crude-oil sample and was seen that 60% of benzoic acid was formed along with aromatics and alkanes. On adding bioliquor, the plastic crude included good amount of benzoic acid, along with high amounts of useful aromatics that can be distilled and processed to be used in gasoline blending. The yield of the oil stream obtained from the method of the present invention is provided in the table 6and figure 3. The results in the table and figures 3-4 clearly demonstrated that the process of present invention provides high yield of the oil stream when compared to the comparative examples. The yields of the solid residue and oil formed were calculated from the below reactions:

XSR % = (Weight of Solid Residue x 100) / Weight of feedstock — (1) XQIL %= (Weight of Oil x 100) / Weight of feedstock - (2)

Table 6: Comparative table.

-Temperature, P-Pressure

[0093] A skilled artisan will appreciate that the quantity and type of each ingredient ingredients can be used in different combinations or singly. All such variations and combinations would be falling within the scope of present disclosure

[0094] 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. ADVANTAGES OF THE PRESENT INVENTION

[0095] The present invention provides a method of producing valuable fuels and chemicals usingwaste plastic feedstock that gives high yield of oil stream.

[0096] The present invention provides a method of producing valuable fuels and chemicals using waste plastic feedstock that is useful in semi segegrated waste to biocrude.

[0097] The present invention minimizes the dependence on pure water as solvent, by replacing with a waste stream (bio-liquor, from 2G ethanol plant), to produce high yield of biocrude oil.

[0098] The present invention provides the advantage of producing valuable olefns, benzene derivatives and alcohols from waste plastic biomass.