Production of valuable chemicals from co-liquefaction of bioliquor and biomass

Abstract

The present invention relates to a solvothermal process for producing high quality fuels and chemicals from biomass feedstocks using lignin-containing bioliquor as a solvent for hydrothermal liquefaction. The lignin-containing bioliquor of the present invention is obtained as a waste stream from a 2G-ethanol production plant.

Description

[Technical field]

[0001] The present invention relates generally to processes for preparing hydrocarbons and chemicals. In particular, the present invention relates to a solvothermal process for producing high quality fuels and valuable chemicals from biomass feedstocks using lignin-containing bioliquor as a solvent for hydrothermal liquefaction with a catalyst. The lignin-containing bioliquor of the present invention is produced as a waste stream from a 2G-ethanol production plant. [Background technology]

[0002] The Background Description contains information that may be helpful in understanding the present invention. No admission is made that any information provided herein is prior art or related to the presently claimed invention, nor is any admission made that any publication referenced herein, either expressly or implicitly, is prior art.

[0003] With the dwindling reserves of fossil fuels and renewed interest in renewable energy due to climate change concerns, extensive research has been conducted towards the production of gaseous and liquid fuels from renewable energy sources such as biomass and waste. Biomass is being investigated globally as a feedstock for the preparation of hydrocarbon liquid biofuels due to its low cost and wide availability. Various studies are ongoing on the conversion of biomass to hydrocarbon liquid biofuels via hydrothermal liquefaction in laboratory scale reactors and autoclaves.

[0004] Hydrothermal liquefaction (HTL) is a thermochemical depolymerization process for the conversion of biomass to liquid fuels in the presence of a solvent at elevated temperature and pressure. Hydrothermal liquefaction of lignocellulosic materials including bagasse has been studied using different solvents and process conditions to identify its potential for bio-oil synthesis. The effectiveness of HTL with different types of biomass depends on various process parameters such as reaction temperature, reaction pressure, solvent, biomass / solvent ratio, and type of reactor.

[0005] Biofuel, Bioprod. Bioref. 9:630 638 (2015) discloses hydrothermal liquefaction (HTL) of sugarcane bagasse using ethanol and black liquor as solvents. However, the oil yields are low and HTL does not utilize a catalyst.

[0006] Although there are various studies on hydrothermal liquefaction that focus on oil yields and products from biomass under few isolated hydrothermal liquefaction conditions, optimization of hydrothermal liquefaction temperature and other parameters to achieve high oil yields is still required.

[0007] As an alternative to current non-renewable energy resources such as oil and natural gas, biofuels produced from different biomasses have been studied by scientists around the world. Depending on the resource and technological impact, three generations of biofuels have been identified. The first generation was produced from food resources such as sugarcane, corn, soybeans, etc., through techniques such as fermentation, transesterification, and distillation, and was used for several decades. The downside of this first generation fuel is that the feedstock is a food resource, and further technological advances in this field will lead to an imbalance in the world's food supply and demand. On the other hand, second generation biofuels are produced from biomasses that are not food resources. For example, switchgrass, corn stover, wheat straw, rice straw, rice husk, municipal solid waste, etc. The advantage of using this second generation fuel production is the availability of large quantities of this feedstock, as most of the feedstock is biological waste. In this 2G ethanol production process, a waste stream of bioliquor rich in lignin is extracted. Several studies worldwide have included processing techniques to upgrade this liquor, and some of these studies also describe the separation of lignin to be used as a combustible fuel.

[0008] Therefore, there is a need to provide a method for producing high yield fuels and valuable chemicals from biosolvents utilizing biomass feedstocks that results in ease of conversion, energy recovery and oil content for different applications. Summary of the Invention [Problem to be solved by the invention]

[0009] It is an object of the present invention to provide a solvothermal processing method for producing high quality fuels and valuable chemicals from biomass feedstocks using lignin-containing liquor as a solvent for hydrothermal liquefaction.

[0010] Another object of the present invention is to provide a solvothermal processing method for producing high quality fuels and chemicals from biomass feedstocks using lignin-containing liquor as a solvent for liquefaction, the lignin-containing bioliquor resulting from acid / base pretreatment of the waste stream of a 2G-ethanol plant.

[0011] Another object of the present invention is to provide a solvothermal processing method for producing high quality fuels and chemicals from biomass feedstocks using lignin-containing liquor as a solvent for hydrothermal liquefaction utilizing a catalyst resulting in very good oil yields. [Means for solving the problem]

[0012] The present invention relates to a solvothermal process for producing high quality fuels and chemicals from biomass feedstocks using lignin-containing bioliquor as a solvent for hydrothermal liquefaction. The lignin-containing bioliquor of the present invention is produced as a waste stream from a 2G-ethanol production plant.

[0013] The present invention refers to utilizing bioliquor, a lignin-containing waste stream from 2G-ethanol production plants, as an alternative solvent to water for the liquefaction of biomass into valuable bio-oil consisting of valuable chemicals. Furthermore, transition metal-based oil-soluble catalysts are used during the process of hydrothermal liquefaction to enhance the decomposition of biomass and improve the oil yield.

[0014] In one aspect, the present invention provides a method for producing (a) mixing a biomass feedstock in a feedstock vessel and introducing the biomass feedstock into a hydrothermal liquefaction reactor; (b) treating the lignocellulose in a biomass processor to obtain a treated lignocellulosic biomass and a bioliquor, and fermenting the treated lignocellulosic biomass in a fermenter to obtain ethanol; (c) introducing the bioliquor stream into a hydrothermal liquefaction reactor containing the feedstock to obtain a mixture; (d) hydrothermally liquefying the mixture 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 gas product and a gas-free product stream; (f) separating the gas-free product stream into an oil stream containing valuable fuels and chemicals, a solid phase, and an aqueous phase; (g) optionally refining the oil stream to obtain a refined oil stream; (h) optionally upgrading the refined oil stream to obtain fuels and chemicals; The present invention relates to a method for producing valuable fuels and chemicals, comprising:

[0015] In another embodiment of the present invention, the biomass feedstock is selected from rice straw, rice husk, sawdust, corn stover, and combinations thereof.

[0016] In another embodiment of the invention, treating lignocellulosic biomass comprises treating lignocellulosic biomass with acid or base and C5-C6 sugars.

[0017] In another embodiment of the present invention, the acid is selected from organic or inorganic acids, the base is sodium hydroxide, potassium hydroxide and the C5-C6 sugar is xylose, arabinose, glucose, fructose or lignin.

[0018] In another embodiment of the invention, the bioliquor stream comprises sodium hydroxide and lignin.

[0019] In another embodiment of the invention, the hydrothermal liquefaction is carried out at a temperature in the range of 120° C. to 400° C. and a pressure in the range of 2 to 30 MPa.

[0020] In another embodiment of the invention, the hydrothermal liquefaction is carried out at a temperature in the range of 180° C. to 350° C. and a pressure in the range of 10 to 20 MPa.

[0021] In another embodiment of the present invention, the hydrothermal liquefaction is carried out for a time range of 5 minutes to 120 minutes.

[0022] In another embodiment of the invention, the gaseous product obtained from the liquefied product is sent for heat integration with the feed heating.

[0023] In another embodiment of the invention, separation of the gas-free product stream comprises separation of the extraction stream and the charge liquid associated with the bioliquor for further processing.

[0024] In another aspect of the present invention, the present invention provides a method for producing a method for treating a cancer cell comprising the steps of: (a) purifying the solid phase to obtain a purified solid phase; and (b) sending the purified solid phase to a solid bone char upgrading section to obtain the final product; The present invention relates to the purification of a solid phase obtained from a gas-free product stream, comprising:

[0025] In another aspect of the invention, the invention relates to a method for upgrading an oil stream, the method comprising: (a) mixing an oil stream with a petroleum fraction in a co-treatment process to obtain hydrocarbons; (b) hydrotreating the oil stream in a hydrotreater to obtain a diesel or jet range fuel; (c) cracking the oil stream in the presence of a catalyst using a fluid catalytic cracking unit to obtain light olefins and gasoline additive compounds; and (d) cracking the oil stream into ethylene and propylene using a stream cracker; is selected from.

[0026] 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 combinations thereof.

[0027] Various objects, features, aspects and advantages of the invention will become more apparent from the following detailed description of preferred embodiments. Effect of the Invention

[0028] The present invention provides a method for the conversion of biomass feedstocks to fuels and chemicals that provides high yields of oil streams.

[0029] The present invention relates to a C8-C 13 A method for the conversion of biomass feedstocks to fuels and chemicals useful for obtaining aromatics is provided.

[0030] The present invention provides the feasibility of utilizing the waste stream from a 2G-ethanol plant to produce bioliquor, with good oil yields, thereby totally eliminating the dependency on pure water as a solvent.

[0031] The present invention allows for the use of extremely low catalyst loadings per required biomass to provide high yields of multiple oil streams including hydrocarbons and phenols. [Brief description of the drawings]

[0032] [Figure 1] FIG. 1 shows the process flow for catalytic hydrothermal liquefaction of biomass feedstock using bioliquor as a solvent. [Diagram 2] Figure 2 shows a process flow for upgrading oil streams into useful chemicals. [Diagram 3] FIG. 3 shows the relative oil yields of Examples 1 and 2 of the present invention and the Comparative Example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0033] The following is a detailed description of the embodiments of the present disclosure. The embodiments are detailed to clearly communicate the present disclosure. However, the amount of detail provided is not intended to limit the variations of the embodiments contemplated, but rather to cover all variations, equivalents, and alternatives within the spirit and scope of the present disclosure as defined by the appended claims.

[0034] Throughout the following specification, unless the context requires otherwise, the term "comprise" and variations thereof, such as "comprises" and "comprising" are to be interpreted in their open, inclusive sense, such as "including, but not limited to."

[0035] References throughout this specification to "one embodiment" or "an embodiment" mean that a particular feature, structure, or characteristic described in connection with that 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.

[0036] 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 used in its sense to include "and / or" unless the content clearly dictates otherwise.

[0037] In some embodiments, the numbers expressing properties such as amounts and concentrations of ingredients, reaction conditions, and the like, used to describe and claim certain embodiments of the invention should be understood to be modified in some cases by the term "about". Accordingly, in some embodiments, the numerical parameters set forth in the written description are approximations that may vary depending on 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 possible.

[0038] Recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of referring individually to each individual value falling within the range, and unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein.

[0039] All processes described herein can be performed in any suitable order unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "etc.") provided with respect to specific embodiments herein is intended merely to better illustrate the invention and does not limit the scope of the invention as otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

[0040] The headings and abstracts provided herein are for convenience only and do not interpret the scope or meaning of the embodiments.

[0041] The following discussion provides a number of exemplary embodiments of the subject matter of the present invention. Although each embodiment represents a single combination of the elements of the present invention, the subject matter of the present invention is considered to include all possible combinations of the elements disclosed. Thus, if one embodiment includes elements A, B, and C, and a second embodiment includes elements B and D, the subject matter of the present invention is considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.

[0042] All publications herein are incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated to be incorporated by reference. In the event that a definition or use of a term in an incorporated reference contradicts or is contrary to a definition of that term provided herein, the definition of that term provided herein shall apply and the definition of that term in the reference shall not apply.

[0043] Grouping of alternative elements or embodiments of the invention disclosed herein should not be construed as limiting. Each group member may be referenced 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 may be included in or deleted from a group for reasons of convenience and / or patentability. When such inclusion or deletion occurs, the specification is considered to include the modified group and thus meets the following written description, and the embodiments described herein are provided to illustrate one or more examples of specific embodiments of the principles and aspects of the present disclosure. These examples are provided for purposes of illustration, not limitation of those principles and disclosures.

[0044] It should also be understood that the present invention can be implemented in numerous ways, including as a system, a method, or a device. These implementations, or other forms that the present invention may take, may be referred to herein as processes. In general, the order of steps in a disclosed process may be varied within the scope of the present invention.

[0045] Various terms used in this specification are set forth below. Unless a term used in the claims is defined below, it should be given the broadest definition given to that term by a practitioner of the relevant art as reflected in the printed publication and issued patent at the time of filing.

[0046] The term "hydrothermal liquefaction reactor" as used herein refers to a reactor in which a solvent is used in supercritical conditions for hydrothermal liquefaction to convert any organic matter to crude oil and chemicals at moderate temperatures and pressures. Typically, the hydrothermal liquefaction process is carried out in a batch-type autoclave reactor capable of sustaining temperatures up to 500°C and pressures up to 32 MPa and equipped with an electrically heated furnace, high temperature thermocouple, stirrer, and pressure gauge. The reactor material is stainless steel (SS316) and the reactor volume can range from 0.5 to 1.2 L. The reactor used in this study was a 0.5 L high temperature, high pressure stirred reactor (Parr 4575) with a Parr 4848B reactor controller obtained from Parr Instrument Co., Moline, Illinois, USA.

[0047] The term "transition metal catalyst" as used herein refers to the catalysts prepared in patent applications US 2021 / 0339235 and WO 2018 / 235094. The transition metal catalyst may be an oil-soluble catalyst or a water-soluble catalyst and may be in the form of a powder.

[0048] In a general embodiment, the present invention relates to a solvothermal process for producing high quality fuels and chemicals from biomass feedstocks using lignin-containing bioliquor as a solvent for hydrothermal liquefaction. The lignin-containing bioliquor of the present invention can be obtained as a waste stream from a 2G-ethanol production plant.

[0049] In a first embodiment, the present invention provides a method for producing a method for treating a cancer cell comprising the steps of: (a) mixing a biomass feedstock in a feedstock vessel and introducing the biomass feedstock into a hydrothermal liquefaction reactor; (b) treating the lignocellulose in a biomass processor to obtain a treated lignocellulosic biomass and a bioliquor, and fermenting the treated lignocellulosic biomass in a fermenter to obtain ethanol; (c) introducing the bioliquor stream into a hydrothermal liquefaction reactor containing the feedstock to obtain a mixture; (d) hydrothermally liquefying the mixture 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 gas product and a gas-free product stream; (f) separating the gas-free product stream into a fuel and chemical containing oil stream, a solid phase, and an aqueous phase; (g) optionally refining the oil stream to obtain a refined oil stream; (h) optionally upgrading the refined oil stream to obtain fuels and chemicals; The present invention relates to a method for producing valuable fuels and chemicals, comprising:

[0050] In another embodiment of the present invention, FIG. 1 shows a flow diagram for catalytic hydrothermal liquefaction of biomass in the presence of a solvent and a transition metal catalyst to obtain valuable chemicals and fuels according to the present disclosure. According to the present invention, the biomass feedstock is stored and mixed in a feed hopper combined with a feeder and a feedstock container (3). The biomass feedstock is introduced into a hydrothermal liquefaction reactor (HTL) (4). Lignocellulosic biomass is first treated in a biomass pretreatment section (1) resulting in an acid / base pretreatment and then sends the C5-C6 sugars constituting cellulose and hemicellulose to a fermenter (2) where ethanol (c) is the main product along with a lignocellulosic containing liquor stream (d). This bioliquor (d) is composed of sodium hydroxide and lignin. The bioliquor stream (d) is sent to the HTL reactor (4). A transition metal catalyst (e) is added to the fresh biomass feed (10-20 wt. % in solvent) in the HTL reactor. The hydrothermal liquefaction is carried out at a temperature ranging from 120°C to 400°C and a pressure ranging from 2 to 30 MPa for a time ranging from 5 to 120 minutes to obtain a liquefied product stream (mixture of solid bone char, aqueous phase and oil phase) (f). This liquefied product stream (f) obtained during the hydrothermal liquefaction is sent to a product recovery vessel (5) where the gaseous product (g) is recovered and can be sent to an outlet or sent to thermal integration with feed heating. The gas-free product stream (i) is sent to a solid-liquid separator (6) where it undergoes a single or multi-stage separation process. The biocrude stream (j) is separated from the solid phase (n) and the aqueous phase (k). The extraction stream (l) and the charge liquid (h) are also separated.

[0051] In another embodiment of the invention, the oil phase (j) can be refined or processed in (7) and the final oil (m) is sent to a refinery section such as a fluid catalytic cracker or hydrocracker / hydrotreater for upgrading or blending into droplets for fuel / co-processing.

[0052] In another embodiment of the invention, the solid phase (n) is sent to a purification section (8) where the solid phase is sent to a solid bone char upgrading section for purification into an end product that can be used as a catalyst support (p) or for bioremediation aids (q). The solid bone char upgrading section can utilize potassium hydroxide or other activating agents to improve the surface area and physical properties of the raw bone char stream (o).

[0053] In one embodiment of the present invention, the load liquid (h) may be integrated with the bioliquor stream.

[0054] In one embodiment of the present invention, the feedstock biomass is selected from any of the different lignocellulosic biomass categories: hardwood, softwood, grass and surface waste. Examples of such biomass are poplar, oak, eucalyptus, pine, Douglas fir, spruce, wheat straw, barley husk, barley straw, rice straw, rice husk, oat straw, ray straw, corn cob, corn stalk, sugarcane bagasse, sorghum straw, grass, switch grass, etc. or combinations thereof. Preferably, the feedstock biomass is rice straw, rice husk, sawdust, corn stover or combinations thereof.

[0055] In one embodiment of the present invention, C8-C olefins are beneficial in biocrude oil yields and as a Research Octane Number (RON) improving additive to the gasoline pool. 13 As a solvent for the process to facilitate in the production of aromatics having the above properties, a bioliquor stream is formed from the acid / base pretreatment of a 2G-ethanol plant waste stream.

[0056] In one embodiment of the present invention, the biomass used for the preparation of the bioliquor is selected from perennial grasses (miscanthus, switchgrass), poplar trees, willow trees, or waste materials such as rice straw, corn stover, wheat straw, etc.

[0057] In one embodiment of the invention, the solids loading of the biomass is present in a concentration range of 10-30% by weight.

[0058] In one embodiment of the present invention, the transition metal catalyst based oil-soluble catalyst or powder catalyst has a solid loading in the concentration range of 0.1-10 wt % for improving the quality of fuel oil and lubricating oil.

[0059] In another embodiment of the present invention, the transition metal catalyst may be a Fe, Mo, Ni, or Co based catalyst, or an iron powder, Ni powder, or Fe rich red mud powder catalyst.

[0060] In another embodiment of the invention, the bioliquor stream contains 1%-10% by weight sodium hydroxide (NaOH) and about 1-40% by weight lignin and may be associated with a lignin concentration step using multiple effect evaporation to obtain a high concentration of lignin.

[0061] In one embodiment of the present invention, the hydrothermal liquefaction is carried out at a temperature in the range of 120°C to 400°C, preferably in the range of 180°C to 350°C, and more preferably in the range of 300°C to 350°C.

[0062] In one embodiment of the present invention, the hydrothermal liquefaction is carried out at a pressure in the range of 2 to 30 MPa, preferably at a pressure in the range of 15 to 25 MPa, and more preferably at a pressure in the range of 20 to 25 MPa.

[0063] In another embodiment of the present invention, the hydrothermal liquefaction is carried out for a time range of 5 minutes to 120 minutes, preferably for a time range of 10 minutes to 60 minutes, and more preferably for a time range of 10 minutes to 20 minutes.

[0064] In one embodiment of the present invention, the catalyst used in the liquefaction is present in a concentration range of 0.1-10 wt % solids loading to improve the quality of fuel oils and lubricants.

[0065] According to the present invention, a process for converting biomass feedstocks to fuels or chemicals provides an oil stream with a yield in the range of 40% to 60%.

[0066] In another embodiment of the present invention, the oil stream produced by the process may have a higher heating value (HHV) in the range of 25-40 MJ / Kg.

[0067] In one embodiment of the present invention, the process for converting biomass feedstocks to fuels or chemicals produces valuable fuel compounds, olefins, aromatics, and more preferably aromatic group compounds.

[0068] In another embodiment of the invention, the process for converting biomass feedstocks to fuels or chemicals produces valuable compounds such as alcohols, alkenes, aromatics, cycloalkanes, ketones and phenols.

[0069] In one embodiment of the present invention, the method for converting biomass feedstocks into fuels or chemicals is particularly 13 In addition, the process also promotes the formation of specialty chemicals such as xylenes, ethylbenzene, etc.

[0070] In one embodiment of the present invention, the process for converting biomass feedstocks to fuels or chemicals produces significantly greater amounts of aromatic compounds.

[0071] In another aspect, the present invention relates to a method for upgrading a crude oil stream, the method comprising: (a) mixing an oil stream with a petroleum fraction in a co-treatment process to obtain hydrocarbons; (b) hydrotreating the oil stream in a hydrotreater to obtain a diesel or jet range fuel; (c) cracking the oil stream in the presence of a catalyst using a fluid catalytic cracking unit to obtain light olefins and gasoline additive compounds; and (d) cracking the oil stream into ethylene and propylene using a stream cracker; is selected from.

[0072] According to the present invention, FIG. 2 shows a flow diagram of an upgrading technology for products obtained from the hydrothermal liquefaction of biomass in the presence of a bioliquor solvent. The oil stream (j) is refined or processed in unit (2a). Unit (2a) is a co-processing unit where the oil stream is mixed with petroleum fractions such as vacuum gas oil or heavy gas oil and processed to obtain upgraded fuels or chemicals. Unit (2a) can also be a hydrotreater for converting the biocrude into diesel / jet range fuels. Unit (2a) can also be a fluid catalytic cracker, capable of cracking the biocrude into light olefins and gasoline additive compounds in the presence of a catalyst such as a zeolite (ZSM-5, beta zeolite, y-zeolite, etc.). Unit (2a) can also be a stream where the oil stream is cracked to produce ethylene or propylene.

[0073] In another embodiment of the present invention, the upgrading of oil stream (j) comprises: (a) refining oil stream (j) in unit (2a) to obtain a refined oil stream; and (b) carrying out a phenolic compounds purification in unit (3a) to obtain a purified phenol-rich stream (c1); Equipped with.

[0074] In one embodiment of the present invention, the upgrading of oil stream (j) comprises: (c) refining the oil stream (j) in unit (2a) to obtain a refined oil stream; and (d) carrying out aromatics purification in unit (4a) to produce purified C8-C 15 obtaining a rich aromatic stream (d1); Equipped with.

[0075] In one embodiment of the present invention, the upgrading of oil stream (j) comprises: (a) refining oil stream (j) in unit (2a) to obtain a refined oil stream; and (b) carrying out paraffin purification in unit (4a) to obtain a purified paraffin stream (e1); Equipped with.

[0076] While the above describes various embodiments of the present disclosure, other and further embodiments of the present disclosure may be devised without departing from the basic scope of the present disclosure. The scope of the present invention is determined by the claims. The present invention is not limited to the described embodiments, versions, or examples, which, when combined with information and knowledge available to those skilled in the art, are included to enable those skilled in the art to make and use the present invention. EXAMPLES

[0077] The present invention will be further described in the form of the following examples. However, it should be understood that the following examples are merely illustrative and are not intended to limit the scope of the present invention.

[0078] The biomass used in the present invention is obtained from a local animal feed market in Devangonshi, Bengaluru.

[0079] Preparation Example 1 - Bioliquor Solvent Preparation Bioliquor is produced as a waste stream from the 2G-ethanol plant, which is sent further to enrich the lignin content in the stream.

[0080] Sulfuric acid (2 g) is taken in 100-200 ml of raw bioliquor. This solution is made up to 500-600 ml with water. Approximately 100-150 g of biomass (rice straw) is added to this solution and soaked for 30 min-1 hr. The soaked liquor is heated in a reactor at a temperature of 100-200 °C for 15-30 min. Then, after cooling, the remainder is manually squeezed to produce about 300-400 ml of waste liquor. Now, a solid residue containing about 100-200 ml of liquor is taken and about 2% sodium hydroxide solution is added to it. For one equivalent of solid residue, the same amount of sodium hydroxide is added and left for some time. Further manual squeezing process is carried out to neutralize the solid residue and reduce the water content below 100 g. Now, a 3% solution is prepared and 200-300 ml of sodium hydroxide is added to it. This solution is heated at a temperature of 200-200 °C for 3-0 min to 1 h to obtain the final bioliquor solution.

[0081] The resulting bioliquor solution can be used as a low-cost fuel, but in this innovation, it is used as a solvent for hydrothermal liquefaction of biomass, as the lignin content of the liquor aids in forming highly valuable bio-crude oil that can be further utilized as a diesel or gasoline blend.

[0082] Preparation Example 2 - Synthesis of transition metal catalyst A solution was prepared by taking about 100 g of molybdic acid as the metal precursor. To this, 100 g of 2-ethylhexanoic acid (first additive) solution was added and refluxed at 180°C for 4 hours to obtain a black salt. The salt was cooled and redissolved in 150 g of 2-ethylhexanol (second additive) and refluxed at 180°C for 12 hours to obtain Mo(O),(2-ethyl hexanoate)2-ethyl hexanolate catalyst. About 340 g was produced with approximately 14% Mo.

[0083] Preparation Example 3 - Synthesis of transition metal catalyst To a solution of iron(III) nitrate (1 equiv.) in water and hexane (1:2 ratio, 5 ml per nmol of Fe salt) was added dropwise an aqueous solution of sodium 2-ethylhexanoate (3 equiv.) (1 mmol solution in 1 ml water) at 70°C, and the solution was refluxed at 80°C for 3 h. The resulting reaction mixture was cooled and partitioned between a water / hexane layer. The organic layer was washed with water. The organic layer was dried (Na2NO3) and concentrated in vacuo to provide the catalyst iron ethylhexanoate as a sticky solid.

[0084] Example 1 Solvothermal liquefaction of biomass as feed in the presence of lignin-containing liquor solvent and molybdenum oil-soluble catalyst was carried out in a high-temperature and high-pressure 500 ml autoclave (Parr 4848B model, USA) equipped with a pressure gauge, a J thermocouple and an external electric furnace with a heating device controlled by PID control. 20 g of feedstock, lignin-containing bioliquor solvent (80 g) and 0.2 g of molybdenum oil-soluble catalyst are charged into the reactor. The reactor is purged with nitrogen gas to maintain an inert and homogenous atmosphere. A pressure test is performed to make the reactor safe, the lines are tightly sealed and no leaks are found. The initial pressure of the conveying device is maintained at atmospheric pressure and the stirrer speed is adjusted to 350 rpm. The reactor is then allowed to reach the desired reaction temperature of 593 degrees Kelvin with an increment of 10 degrees Kelvin / min. Once that temperature is reached, the reactor is maintained at the desired temperature, 23-25 ​​MPa, for a residence time of 15 minutes. At the end of the reaction, the autoclave is immediately cooled to room temperature in an external cooling bath. After collecting gas samples for analysis using a gas bulb, the pressure is released from the reactor through a vent. As a separate step, the reactor contents and the stirrer are thoroughly washed several times with the solvent ethyl acetate. The mixture was filtered with the help of Büchner funnel to remove the solids from the liquid phase. Two layers are observed in the separatory funnel where the oil stream is separated from the water stream. The oil stream is extracted from the liquid sample by separating the solvent in a rotary vacuum evaporator (Buchi Rotavapor). The compounds obtained in the oil stream are given in Tables 1 and 1a below. [Table 1]

[0085] [Table 2]

[0086] The following examples and comparative examples were prepared using the above experimental procedures under appropriate conditions and starting materials as given in the table below with non-critical variations. [Table 3]

[0087] [Table 4]

[0088] [Table 5]

[0089] [Table 6]

[0090] [Table 7]

[0091] [Table 8]

[0092] [Table 9]

[0093] [Table 10]

[0094] [Table 11]

[0095] [Table 12]

[0096] [Table 13]

[0097] [Table 14]

[0098] [Table 15]

[0099] [Table 16]

[0100] Results: GC-MS analysis was performed on each sample and it was found that aromatics were formed. The yield of oil stream obtained from the process of the present invention is given in Table 6 below and Figure 3. The results in the table and Figure 3 showed that the process of the present invention gives a higher yield of oil stream when compared to the comparative example.

[0101] The yield of solid residue and oil formed is calculated from the following reaction: X SR % = (weight of solid residue × 100) / weight of feedstock (1) X OIL % = (weight of oil × 100) / weight of feedstock (2)

[0102] [Table 17]

[0103] [Table 18]

[0104] A skilled artisan will understand that the types and amounts of each ingredient may be used in different combinations or alone, and all such variations and combinations are within the scope of this disclosure.

[0105] The above examples are merely illustrative and do not limit the scope of the present invention. Various modifications and improvements to the disclosed embodiments will be apparent to those skilled in the art. Such modifications and improvements can be made without departing from the scope of the present invention.

Claims

1. (a) mixing a biomass feedstock in a feedstock vessel and introducing the biomass feedstock into a hydrothermal liquefaction reactor; (b) treating lignocellulose in a biomass treatment unit to obtain treated lignocellulosic biomass and a bioliquor, and fermenting the treated lignocellulosic biomass in a fermenter to obtain ethanol; (c) introducing the bioliquor stream into a hydrothermal liquefaction reactor containing a biomass feedstock to obtain a mixture; (d) hydrothermally liquefying the mixture 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 gas product and a gas-free product stream; (f) separating the gas-free product stream into a fuel and chemical containing oil stream, a solid phase, and an aqueous phase; (g) optionally refining the oil stream to obtain a refined oil stream; (h) optionally upgrading the refined oil stream to obtain fuels and chemicals; A method for producing fuels and chemicals from biomass feedstocks comprising:

2. 2. The method as claimed in claim 1, wherein the biomass feedstock is selected from rice straw, rice husk, sawdust, corn stover, and combinations thereof.

3. The treatment of the lignocellulosic biomass comprises treating the biomass with an acid or base and C ５ -C ６ The method as claimed in claim 1 , comprising the step of treating the lignocellulosic biomass with sugars.

4. The acid is selected from organic acids or inorganic acids, the base is sodium hydroxide, potassium hydroxide, ５ -C ６ 4. The method as claimed in claim 3, wherein the sugar is xylose, arabinose, glucose, fructose or lignin.

5. 2. The method as claimed in claim 1, wherein the bioliquor stream comprises sodium hydroxide and lignin.

6. 2. The process as claimed in claim 1, wherein the hydrothermal liquefaction of step (d) is carried out at a temperature in the range of 120° C. to 400° C. and a pressure in the range of 2 to 30 MPa.

7. 2. The process as claimed in claim 1, wherein the hydrothermal liquefaction of step (d) is carried out at a temperature in the range of 180° C. to 350° C. and a pressure in the range of 10 to 20 MPa.

8. 2. The method as claimed in claim 1, wherein the hydrothermal liquefaction of step (d) is carried out for a time range of 5 minutes to 120 minutes.

9. 2. The process as claimed in claim 1, wherein the gaseous product obtained in step (e) is sent to heat integration with feed heating.

10. 10. The method as claimed in claim 1, wherein separating the gas-free product stream further comprises separating a gas extraction stream and a charge liquid associated with the bioliquor for further processing.

11. (a) purifying the solid phase to obtain a purified solid phase; and (b) sending the purified solid phase to a solid bone char upgrading section to obtain the final product; The method of claim 1 , further comprising subjecting the solid phase to purification comprising:

12. 13. A method for upgrading an oil stream resulting from the method of claim 1, comprising the steps of: The method for upgrading, (a) mixing said oil stream with a petroleum fraction in a co-processor to obtain hydrocarbons; (b) hydrotreating the oil stream in a hydrotreater to obtain a diesel or jet range fuel; (c) cracking the oil stream in the presence of a catalyst using a fluid catalytic cracking unit to obtain light olefins and gasoline additive compounds; and (d) cracking the oil stream into ethylene and propylene using a stream cracker; A method selected from the group consisting of

13. The method as claimed in claim 13, wherein the catalyst of the fluid catalytic cracking unit is selected from ZSM-5, beta zeolite, y-zeolite, or combinations thereof.

14. 2. The process as claimed in claim 1, wherein the transition metal catalyst is an Fe, Mo, Ni, or Co based catalyst, or an iron powder, Ni powder, or Fe-rich red mud powder catalyst.

15. 2. The method as claimed in claim 1, wherein the transition metal catalyst is present in a concentration range of 0.1 to 10 wt. % solids loading.

16. 2. The method as claimed in claim 1, wherein the solids loading of the biomass is present in a concentration range of 10-30% by weight.

17. 2. The method as claimed in claim 1, wherein the fuels and chemicals are selected from alcohols, alkenes, aromatic compounds, cycloalkanes, ketone compounds and phenolic compounds.

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