Method and system for producing a low carbon intensity oil

Abstract

The invention relates to a method for producing a low carbon intensity oil, where the method comprises the steps of providing a feed mixture comprising: a carbonaceous material; a primary solvent comprising phenolics in a concentration of at least 3 % by weight and one or more alcohols and / or polyols in a concentration of at least 5 % by weight; water in a concentration from 1 to 40 % by weight; converting the feed mixture by treating it at a pressure in the range 10 bar to 220 bar and at a temperature in the range 280 °C to 410 °C in a predefined time and recovering oil from the converted feed mixture.

Description

[0001] Method and system for producing a low carbon intensity oil

[0002] Field of the invention

[0003] The present invention relates to the area of production of liquid fuels and chemicals having a low carbon intensity. More specifically the invention relates to an improved method and system for producing a low carbon intensity oil from a carbonaceous material.

[0004] Background of the invention

[0005] The carbon intensity of advanced liquid biofuels and chemicals is a key feature determining the amount of greenhouse gases avoided by substitution of fossil fuels and chemicals and therefore to a large extent contributes to the value of such advanced liquid biofuels and chemicals. Hence, advanced liquid biofuels and chemicals having a low carbon intensity produced at least partly from renewable carbonaceous materials such as biomass and residue streams have become a central focus to mitigate global climate change arising from greenhouse gas emissions to develop sustainable circular economies.

[0006] Several processes to convert biomass into advanced biofuels are being applied and developed including biological decomposition to produce liquids (e.g. ethanol) and gases (e.g. methane), and thermochemical conversion processes to produce advanced liquid biofuels. The thermochemical processes use temperature and pressure to break down biomass at the cellular level. Thermochemical conversion processes include gasification, pyrolysis as well as hydrothermal liquefaction (HTL) and solvothermal liquefaction (STL). Whereas the moisture content shall be below a certain level for gasification and pyrolysis processes, the HTL and STL processes allow for direct processing of wet carbonaceous materials and saves a significant amount of energy that would otherwise be required for dehydrating / drying prior to the processing of these materials.

[0007] Despite these disclosures and many other studies of hydrothermal and solvothermal pathways, hydrothermal and solvothermal processes for advanced liquid biofuels are still on a demonstration stage and yet to be commercialized. There are still several requirements for improvements of the technologies, including improvement of yields, reduction of carbon intensity, improved product characteristics such as more stable oil products, higher process efficiency e.g., by using less severe process conditions, easier controllable processes, increased on-stream factor e.g. by reduced fouling and / or clogging, and reduced charring in processes.

[0008] Objective of the invention

[0009] Hence, the object of the present invention is therefore to provide an improved method for producing oil from carbonaceous materials that is more efficient and therefore may achieve lower carbon intensity than the prior art.

[0010] The improvements may, dependent on choice of process parameters, be one or more of the following: higher oil yield, less char production, easier controllable process, easier downstream product separation, less severe operating conditions meaning cheaper / more cost-effective installation and operations.

[0011] The improved process may further lead to an improved product meaning one or more of the following: a more stable and less reactive oil product having a higher heating value, lower oxygen content, being less corrosive (lower acid number), more valuable by-products meaning a more cost-effective process, better resource utilization through increase process efficiency, meaning increased circularity, lower energy consumption for heating due to lower heat capacity, which again means an advantage in the process efficiency due to processing in organic solvents.

[0012] Description of the invention

[0013] According to one aspect of the present invention the objective of the invention is achieved through a method for producing a low carbon intensity oil oil produced comprising the steps of a. providing a feed mixture comprising i. a carbonaceous material being at least partly renewable ii. a primary organic solvent comprising phenolics in a concentration of at least 3 % by weight, and one or more alcohols and / or polyols in a concentration of at least 5 % by weight; iii. water in a concentration from 1 to 40 % by weight including moisture added with the carbonaceous material; b. converting the feed mixture by treating it at a pressure in the range 10 bar to 220 bar and at a temperature in the range of 280 °C to 410 °C in a predefined time; c. recovering oil from the converted feed mixture.

[0014] The low carbon intensity oil according to the present invention results in a substantial decarbonization effect due to avoided greenhouse gas emissions when used instead of fossil oils and / or chemicals. The low carbon intensity may be obtained as a result of efficient use of renewable carbonaceous materials and / or efficient processing with high carbon efficiency e.g. high oil yields and / or high circularity and / or efficient processing with a minimum paracetic losses e.g. efficient heat recovery and / or low consumptions and / or use of renewable resources such as renewable electricity and / or solvents having a renewable origin. In one embodiment of the present invention the carbon intensity of the oil produced is below 30 g CO2 / MJ oil produced such as below 20 g CO2 / MJ oil produced. Preferably the carbon intensity of the oil produced is below 15 g CO2 / MJ oil produced such as below 10 g CO2 / MJ oil produced. In some advantageous embodiments of the invention, the carbon intensity of the oil may even be carbon neutral or carbon negative such as having a carbon intensity equal to or less than 0 g CO2 / MJ oil produced such as equal to or less than -10 g CO2 / MJ oil produced.

[0015] A carbonaceous material according to the present invention is generally a carbon containing material e.g. organic matter. The carbonaceous material used in the present invention often comprises a renewable carbonaceous material, whereby the carbon intensity is reduced. Examples of renewable carbonaceous materials are biomass and / or residue materials. Carbonaceous materials according to the invention are further described in the detailed description.

[0016] In contrast to hydrothermal liquefaction processes where water is the primary solvent, the primary solvent in the feed mixture according to the present invention is an organic solvent comprising an aromatic solvent in the form of at least 3 % by weight phenolics and one or more alcohols and / or polyols in a concentration of at least 5 % by weight i.e. the present invention is a solvothermal process rather than a hydrothermal process. Additionally, the feed mixture comprises water such as a water in a concentration from 1 to 40 % by weight including eventual moisture contained in carbonaceous material.

[0017] The solvent combination may enhance the oil yield by providing improved solubilization of the biomass compounds particularly at low temperature and minimization of undesirable side reactions e.g. reactions leading to repolymerization and char formation reactions by stabilization of reactive intermediate compounds. Hereby an improved method for producing oil from carbonaceous materials that is more efficient and have lower carbon intensity than the prior art is provided. Hereby a major objective of the invention is fulfilled. The char formation may be less than 20% and in most circumstances less than 15% or 10% on a carbon basis, which is a result of the efficiency of the process meaning that the carbon present in the feedstock primarily is found in the oil and gas produced.

[0018] The weight ratio of alcohol to water in the feed mixture according to the invention is often maintained in the range 4:1 to 1 :2 such as in the range 4:1 to 1 :1. Advantageously the weight ratio of alcohol to water in the feed mixture according to the present invention is in the range 2:3 to 3:2 including water contained in the carbonaceous feedstock.

[0019] In a preferred embodiment according to the present invention the water may constitute up to 30 % by weight of the feed mixture such as up to 25 % by weight of the feed mixture. In many advantageous embodiments the water content of the feed mixture is up 20 % by weight such as up to 15 % by weight or up to 10 % by weight of the feed mixture.

[0020] Phenolics in the present context is used to describe chemical compounds consisting of one or more hydroxyl groups (-OH) bonded directly to an aromatic hydrocarbon group.

[0021] The step of providing the feed mixture may in an embodiment of the present invention comprise adding phenolics in a concentration of at least 5 % by weight such as at least 7,5 % by weight. Preferred embodiments of the invention include embodiments, where the concentration of phenolics in the feed mixture is at least 10 %, at least 12,5 % by weight, at least 15 % by weight and at least 20 % by weight. The ratio of the weight of phenolics to the dry ash free weight of the carbonaceous material is in many embodiments at least 0,2 such as at least 0,3; Preferred embodiments include embodiments where the ratio of the weight of phenolics to the dry ash free weight of the carbonaceous material at least 0,4, at least 0,5, at least 0,6, at least 0,7 such as at least 0,8. In further preferred embodiments the ratio of weight of phenolics to the dry ash free weight of carbonaceous material is at least 0,9, at least 1 ,0 and at least 1 ,5.

[0022] In an advantageous embodiment the phenolics added to the feed mixture comprises phenol and / or an alkylated phenol and / or an alkoxy phenol in a concentration of at least 2 % by weight such as in a concentration of at least 4 % by weight. In further advantageous embodiments the feed mixture comprises phenol and / or an alkylated phenol and / or an alkoxy phenol in a concentration of at least 6 % by weight, at 8 % by weight, at least 10 % by weight, at least 12 % by weight, at least 15 % by weight, at least 18 % by weight such as at least 20 % by weight.

[0023] The phenolics added to the feed mixture according to particularly preferred embodiments of the present invention is produced from a renewable source, whereby the carbon footprint of the oil is reduced.

[0024] In an advantageous embodiment, the phenolics in the feed mixture are at least partly produced by the process.

[0025] In one embodiment, the phenolics in the feed mixture is at least partly provided by recycling at least of the oil produced by the process such as a phenolics enriched fraction of the oil.

[0026] In a preferred embodiment the weight of recycled oil produced by the process to the dry ash free weight of the carbonaceous material is at least 1 ,5 such as least 2,0; preferably the ratio of the weight of recycled oil to the dry ash free weight of the carbonaceous material is at least 2,5 such as at least 3,0. In other preferred embodiments the ratio of the weight of renewable oil to the dry ash free weight of the carbonaceous material is at least 4 such as least 5.

[0027] In one embodiment, the concentration of the one or more alcohols and / or polyols is at least 10 % by weight such as at least 15 % by weight. In other preferred embodiments the concentration of the one or more alcohols and / or polyols is at least 20 % by weight, at least 25 % by weight, at least 30 % by weight, at least 35 % by weight, at least 40 % by weight.

[0028] In one embodiment, the ratio of the weight of the one or more alcohols and / or polyols to the dry ash free weight of the carbonaceous material is at least 0,5 such as at least 1. In other preferred embodiments the ratio of the weight of the one or more alcohols and / or polyols to the dry ash free weight of the carbonaceous material is at least 1 ,5, at least 2,0, at least 2,5, at least 3,0.

[0029] In a preferred embodiment the one or more alcohols and / or polyols according to the invention comprises methanol, ethanol, propanol, isopropanol, buthanol, isobuthanol, pentanol, glycerol, ethylene glycol, polyethylene glycol, propylene glycol, catechol’s or a combination thereof.

[0030] In one embodiment of the invention the one or more alcohols and / or polyols comprises methanol and / or ethanol.

[0031] The conversion of the carbonaceous material in the presence of a primary organic solvent comprising at least one aromatic compound in the form of phenolics and alcohol(-s) according to the present invention represents an advantageous combination of organic solvents that improves the yield and quality of the oil. The solvent combination in the present invention is efficient in solubilizing the biomass components particularly at low temperature, and are acting as efficient hydrogen donors for the conversion of the biomass, provide increased solubility of oily products, favor deoxygenation and hydrogenolysis reactions, and stabilize the reactive intermediate products e.g. by forming acetals with carbonyl groups such as ketones and aldehydes and esters with carboxylic acids. Thereby the solvent composition retards repolymerization reactions that may lead to high molecular weight products often called solid residues or char formation and lower oil quality.

[0032] In an advantageous embodiment the one or more alcohols and / or polyols have a renewable origin. Thereby they assist or further assist in reducing the carbon intensity of the produced oil.

[0033] The conversion process according to the present invention is in many applications advantageously carried out under moderately acidic conditions i.e. the pH value e.g. measured in the aqueous phase after recovering oil from the product is maintained below 7, such as in the range 2 to 6 or 3 to 5.

[0034] By carrying out the conversion process according to the present invention under acidic conditions stabilizing reactions such as acetal formation with carbonyl and ester formation with carboxylic acids are favored.

[0035] In some applications it is not necessary to introduce additional acidic compounds to maintain the pH in desired range due to formation of acidic byproducts.

[0036] In a preferred embodiment the pH value during the conversion process is controlled by adding one or more carboxylic acids and / or a salt of a carboxylic acid and / or an ester of a carboxylic acid in a concentration from 0,1 to 30 % by weight to the feed mixture such as in the range 0,5 to 10 % by weight such as in the range 1 ,0 to 8,0 % by weight. In an advantageous embodiment, the carboxylic acid added comprises formic acid, acetic acid, citric acid, levulinic acid, lactic acid and / or salts and / or esters thereoff.

[0037] In another advantageous embodiment according to the invention sulphuric acid is added to the feed mixture to maintain the desired pH during the conversion process. The sulphuric acid added may in many applications be in the range from 0,1 wt % to 5 wt %.

[0038] In yet another advantageous embodiment according to the invention, the pH value during the conversion step is controlled by at least partly recycling acids recovered from product separation.

[0039] The pressure during the conversion of the feed mixture is often at least 20 bar such as at least 40 bar; preferably the pressure during the conversion of the feed mixture is at least 60 bar such as at least 70 bar; more preferably the pressure during the conversion of the feed mixture is at least 80 bar such as at least 90 bar; even more preferably the pressure during the conversion of the feed mixture is at least 100 bar such as at least 110 bar.

[0040] In many applications the pressure during the conversion of the feed mixture is maintained below 220 bar such as below 200 bar. Often the pressure during the conversion of the feed mixture is maintained below 180 bars such as below 160 bar. In some embodiments the pressure during the conversion of the feed mixture is below 150 bars such as below 140 bar. In further embodiments the pressure during the conversion of the feed mixture is maintained below 130 bar such as below 120 bar.

[0041] In one preferred embodiment according to the present invention the pressure is maintained in the range from about 30 bar to about 120 bar such as in the range 40 to 120 bar or 50 to 100 bar. In many embodiments the pressure during the conversion process is maintained in the range from 20 bar below to 20 bar above the critical pressure of the fluid mixture.

[0042] Advantageously the pressure during the conversion of the feed mixture is maintained above the boiling point pressure of the fluid mixture so as to maintain the fluid mixture in a liquid or supercritical state such as a pressure in the range 80 to 180 bar or in the range 100 to 160 bar.

[0043] The conversion of the feed mixture is often performed at a temperature of at least 300 °C such as a temperature of at least 310 °C. In some embodiments the conversion of the feed mixture is performed at a temperature of at least 320 °C such as at a temperature of at least 330 °C. In other embodiments the conversion of the feed mixture is performed at a temperature of at least 340 °C such as a temperature of at least 350 °C. In further embodiments the conversion of the feed mixture is performed at a temperature of at least 360 °C such as a temperature of at least 370 °C.

[0044] Preferred embodiments include converting the feed mixture at a temperature of less than 400 °C such as a temperature of less than 390 °C. Often the conversion of the feed mixture is performed at a temperature of less than 385 °C such as at a temperature of less than 380 °C. In some embodiments the conversion of the feed mixture is performed at a temperature of less than 374 °C such as at a temperature of less than 370 °C.

[0045] Advantageously the pressure and temperature during the conversion of the feed mixture is maintained above the boiling point pressure of the fluid mixture so as to maintain the fluid mixture in a liquid or supercritical state such as a pressure in the range 330 to 400 °C such as in the range 350 to 385 °C or in the range 360 to 380 °C.

[0046] By maintaining the temperature in the ranges above a high degree of conversion, deoxygenation and resulting low Total Acid Number (TAN) and high heating value is obtained i.e. an improved product is obtained, whereby an objective of the present invention is obtained. It is further believed that the solvent acts as an alkylation agent with the oil, when the temperature is sufficiently high. Hereby both the oil yield and the miscibility of the oil with petroleum fractions may be enhanced.

[0047] The process gas produced by the conversion process of the carbonaceous material(-s) comprises carbon oxides such as carbon mono oxide as the main compounds. In an advantageous embodiment the alcohol(-s) and / or polyols added to the feed mixture in the step of providing the feed mixture comprises one or more alcohols produced from the gas produced in the conversion process of carbonaceous material(-s).

[0048] An aspect of the present invention relates to producing alcohol(-s) from the process gas by reacting the gas with hydrogen in a catalytic reaction step. Often said catalytic reaction step is performed at pressures in the range 30 to 150 bar and temperatures in the range 200 to 450 °C such as at pressures in the range 50 to 100 bar and temperatures in the range 200 to 300 °C.

[0049] Suitable catalysts for use in the catalytic reaction step for alcohol synthesis from process gas by reaction by hydrogen include copper zinc oxide catalysts, copper zinc chromium catalysts, copper mixed oxides catalysts, iron oxide catalysts on an alumina, zirconia carrier or zeolite carrier material. Other metal promotors and modifications may be added to the catalyst structure for activity and selectivity enhancement. In a preferred embodiment the hydrogen used in the catalytic reaction step for production of alcohol from the process gas is comprises green hydrogen such as produced by electrolysis using renewable electricity, e.g. produced from wind, solar and / or geothermal.

[0050] In some preferred embodiments the catalytic reaction step to produce alcohol from the process gas further comprises a syngas preparation step prior to the alcohol synthesis step to adjust the H2 to CO ratio to the desired level for the alcohol synthesis.

[0051] In an advantageous embodiment, the syngas preparation step comprises a reverse water gas shift step.

[0052] By at least partly producing the alcohol from the carbon oxide containing process gas from the conversion process the oil yield and the overall process efficiency are improved. By using green hydrogen such as produced by electrolysis using renewable electricity the carbon footprint and carbon intensity of the produced oil are further reduced.

[0053] It shall further be noted that producing alcohol from the process gas produced according to process conditions according to the present invention the capital and operating cost intensive carbon capture step is avoided and further the relative high ratio of carbon mono oxide to total carbon oxides results in a lower hydrogen demand for the alcohol synthesis. Often the hydrogen consumption for the alcohol synthesis is at least 20 % lower than the hydrogen consumption for production of methanol from carbon dioxide such as at least 30 % lower. In some embodiments the hydrogen consumption for the alcohol synthesis is at least 40 % lower than the hydrogen consumption for production of methanol from carbon dioxide. An aspect of the present invention comprises at producing phenolics from one or more carbonaceous material(-s) in a separate conversion step at less severe conditions, and at least partly providing said phenolics to the feed mixture in the step of providing the feed mixture.

[0054] A preferred embodiment comprises producing the phenolics by conversion of lignocellulosic material in a pre-conversion zone in the presence of phenolics, one or more alcohols and / or polyols and one or more acid catalysts at temperatures in the range 150 to 240 °C and at pressures from 5 to 90 bar.

[0055] An advantageous embodiment of the present invention is where the acid catalyst comprises sulphuric acid in a concentration of 1 to 5 % by weight of feed mixture added to the pre-conversion zone.

[0056] By producing the phenolics added to the process from a carbonaceous material in the form of a lignocellulosic material the overall carbon footprint and carbon intensity of the produced oil is reduced as it is produced from a renewable source (biogenic carbon).

[0057] Further by producing the phenolics in a separate conversion step it is obtained that the process conditions in the pre-conversion step can be optimized for production of phenolics and the conversion step optimized for yield and quality of the oil produced. Hereby the overall efficacy of the process is improved.

[0058] Brief description of the drawings

[0059] The invention will be described in more detail in the following detailed description, with reference to embodiments shown in the drawings where:

[0060] FIG. 1 shows a schematic overview of a process according to the invention for converting carbonaceous material into an oil, a carbon oxides rich gaseous product, a water phase and a solid phase in the presence of alcohol / polyols and phenolics;

[0061] FIG. 2 shows a schematic overview of another preferred embodiment of a process according to the invention, where phenolics are at least partly provided by recycling the at least part of the crude oil such as a phenolics rich fraction produced by the process to the step of providing the feed mixture, and / or where alcohol / polyol is at least partly recovered and recycled to the step of providing the feed mixture;

[0062] FIG. 3 shows a schematic drawing of a system of an embodiment of a process according to the invention, where phenolics are at least partly produced in a separate conversion step prior to the step of providing the feed mixture;

[0063] FIG 4 shows a schematic overview of a preferred embodiment according to the invention comprising a system for production of alcohol from the carbon oxides rich gas produced in the conversion process, and at least partly recycling the alcohol produced to the step of providing the feed mixture in the conversion step;

[0064] FIG. 5 shows a schematic overview of an advantageous embodiment according to the invention comprising a system for producing methanol from the carbon oxides rich gas produced in the conversion process using hydrogen produced by electrolysis and recycling at least part of the methanol to the step of providing the feed mixture to the conversion process;

[0065] FIG. 6 shows a schematic overview of another advantageous embodiment of a system for producing methanol from the gas produced in the conversion process according to the invention further comprising using low carbon intensity electricity such as electricity produced from wind, solar, hydro, geothermal and / or nuclear energy. Description of a preferred embodiment

[0066] FIG. 1 shows a preferred embodiment of a production process for conversion of carbonaceous material such as biomass and waste in the presence of alcohol / polyols and phenolics to 1. a low carbon intensity oil product, 2. a gaseous product comprising carbon oxides such as carbon mono oxides and carbon dioxide, 3. a solid product, and 4. a mixture of alcohol / polyol and water.

[0067] The conversion process according to the present invention is performed by treating the carbonaceous material at a pressure in the range 10 bar to 220 bar and a temperature of 280 to 410 °C in the presence of a primary organic solvent comprising phenolics in a concentration of at least 3 % by weight and one or more alcohols and / or polyols in a concentration of at least 5 % by weight, and water in a concentration from 1 to 40 % by weight including moisture added with the carbonaceous material in a predefined time and separating the converted feed mixture to recover oil from the converted feed mixture.

[0068] A carbonaceous material according to the present invention is generally a carbon containing material e.g. organic matter such as biomass and / or waste materials. Often the carbonaceous material added to the feed mixture according to the present invention is carbon neutral or renewable i.e. it releases the same amount CO2 when combusted as its uptake during its growth period. Hence, at least partly processing of renewable carbonaceous materials contribute to reducing the carbon intensity or carbon footprint of the oilproduced according to the present invention.

[0069] Nonlimiting examples of carbonaceous materials according to the present invention include lignin, cellulose, hemicellulose, lignocellulosics, proteins, starch, saccharides, lipids, woody biomass such as residues from forestry or pulp & paper operations e.g. wood chips, hog fuel, sawdust, prunings, thinnings and waste, bark, leaves, park and garden waste and weeds, road cuttings, wine trash etc.; Residues, byproducts and waste streams from agricultural production such as grasses, straw, stems, stover, husk, cobs, hulls, shells, kernels, leaves, pulp from e.g. wheat, barley, oat, rye, corn, rice, sunflowers, rapeseed, flax, nut shells, cotton; empty fruit bunches from palm oil production, oil manufacturers effluent (e.g. Palm Oil Manufacturers Effluent (POME) from palm oil manufacturing), pressing residues from vegetable oil production, manures and beddings from animal production, green / organic household wastes, greenhouse waste etc.; energy crops like short rotation coppice, willow, jatropha, sorghum, switchgrass and miscanthus; such as aquatic biomass such as water hyacinth, duck weed, azoIla, water fem; such as red, green and brown macroalgae / seaweed such as sargassum, genus, caulerpaf, euglena, ucus, gracelaria, laminaria, macrocystis, monostroma, porphyra, pleurochrysis etc.; microalgae such as ankistrodemus, botryococcus, chlorella, chlorophyta, cryptophyte, dictyophaerium, dinophyta, chlorophyta, cryptophyte, crypthecodinum, cyclotella, dunaliella, glaucophyta, haematococus, hydrodictyon, hantzschia, microcystis, nannochloris, nannochloropsis, neochloris, nitsschia, nodularia, oscillatoria, phaeophyta, phaedactylum, rhodophyta, scenedesmus, spirogyra, spirulina, scenedesmus, schizacytrium, stichococcus, tetraselmis, thalassiosira, tribophyta; bacteria such as cyanobacteria, industrial waste, residues and by-products such as residues, byproducts and waste streams from vegetable oil production, residues and byproducts from juice production, residue from wine production, residues, byproducts and waste streams from vegetable oil production; residues, byproducts and waste from food production such as brewers spent grains and yeast; residues and byproducts from fruit and vegetable processing such as pulp; residues, by-products and waste streams from coffee production, residues, byproducts and waste stream from cocoa production, residues and by products sugar production such as bagasse, molasses, vinasses, residues and byproducts from fermentation processes such as distillers grains, brewers grains, residues and waste streams paper production such as paper sludges, black liquor, green liquor, white liquor; digestate from aerobic and anaerobic digestion; primary and / or secondary sludge from wastewater cleaning, leachate, clarifier sludges, paper waste, organic fraction of household waste, restaurant wastes, slaughter house wastes, municipal solid waste, pulped household and / or municipal solid wastes, used and recycle cooking oils, fats, glycerine, plastic and polymers, and combinations thereof.

[0070] In many applications of the invention the carbonaceous material comprises lignin in a concentration of at least 5 % of the dry ash free weight of the carbonaceous material such as at least 10 %, at least 15 %, at least 20 % of the dry ash free weight of the carbonaceous material.

[0071] In one embodiment of the present invention, the carbonaceous material comprises lignin in a concentration of up 60 % of the dry ash free weight of the carbonaceous material such as up to 50 %, up to 40 %, up to 30 % of the dry ash free weight of the carbonaceous material.

[0072] In one preferred embodiment according to the present invention, the carbonaceous material comprises a combination of a lignocellulosic material and a plastic material. The plastic material constitutes in some embodiments up to 50 % of the dry ash free weight of the carbonaceous material such as up to 40 %, whereas in other applications of the invention the plastic material may constitute up to 35 %, up to 30 %, up to 25 %, up 20 %, up to 15 % by weight of the dry ash free carbonaceous material.

[0073] The carbonaceous material may according to the present invention be in a solid form and / or liquid form or a combination thereof, and may be contained in one or more feedstock. Further the carbonaceous material(-s) may be received in various sizes and shapes. In many embodiments according to the present invention the step of providing the feed mixture include a pretreatment step prior to further processing.

[0074] In a preferred embodiment according to the present invention, the pretreatment step includes a size reduction step for homogenization and / or mixing of the carbonaceous material. The specific size reduction depends on the character of the specific feedstock and may comprise one or more cutting, crushing, grinding, attriting and / or milling operations. Non limiting examples of size of suitable size reduction techniques according to the present invention include chippers, macerators, shredders, hammer mills, knife mills, shear mills, roller mills, disc mills, pin mills, ball mills, colloidal mills, stone mills and combinations thereof.

[0075] In many embodiments according to the present invention the carbonaceous material is size reduced to a maximum particle size of 30 mm, 15 mm, 10 mm, 5 mm, 3 mm, 2 mm, 1 ,5 mm, 1 mm, 0,5 mm or 0,1 mm.

[0076] In a preferred embodiment according to the present invention the carbonaceous material is sized reduced to an average particle size of less than 2 mm, 1 ,5 mm, 1 ,25 mm, 1 ,0 mm, 0,75 mm, 0,5 mm, 0,25 mm, 0,1 mm or 0,05 mm.

[0077] Advantageously the carbonaceous material has a bimodal size distribution i.e. is comprised of two particle size distributions each having an average particle size.

[0078] In a preferred embodiment the first particle size distribution of the carbonaceous material has an average particle size of less than 200 micron (0,2 mm) with a standard deviation of up to 50 micron such as an average particle size of less than 100 micron with a standard deviation of up to 30 micron, and the second particle size distribution of the carbonaceous material has an average particle size of up to 1500 micron (1 ,5 mm) with a standard deviation of up to 500 micron (0,5 mm) such as an average particle size of up to 1200 micron with an average particle size distribution of up to 300 micron (0,3 mm).

[0079] Control of maximum particle size, average particle size and particle size distribution of the carbonaceous material is important for the rheological properties of the feed mixture as well as for the mass- and heat transfer within the particles during the step of converting.

[0080] The pretreatment of the step of providing the carbonaceous material may according to many applications of the present invention further comprise measures for removal of contaminants from the carbonaceous material prior to processing. Such contaminant removal may comprise means removal of surface dirt, metallic and non-metallic contaminants by washing, magnetic separators, eddy current separators and combinations thereof. By the removal of such contaminants in the pretreatment step of wear of equipment and pipes such as by erosion is reduced. A further effect may be easier down-stream processing such as easier product separation, and purification, a higher overall yield of desired product.

[0081] An advantage of the primary organic solvent combination according to the present invention is an easier preparation of a pumpable feed mixture with high dry matter content of the carbonaceous material possibly due to a better affinity to the carbonaceous material and / or less sweeling of the carbonaceous material than for water.

[0082] In many applications of the present invention the dry carbonaceous material constitutes at least 15 % by weight of the feed mixture such as at least 17,5 % by weight of the feed mixture. Preferably the the dry carbonaceous material constitutes at least 20 % by weight of the feed mixture such as at least 22,5 % by weight of the feed mixture or at least 25 % weight of the feed mixture.

[0083] The pressure during the conversion of the feed mixture is often at least 20 bar such as at least 40 bar; preferably the pressure during the conversion of the feed mixture is at least 60 bar such as at least 70 bar; more preferably the pressure during the conversion of the feed mixture is at least 80 bar such as at least 90 bar; even more preferably the pressure during the conversion of the feed mixture is at least 100 bar such as at least 110 bar.

[0084] In many applications the pressure during the conversion of the feed mixture is maintained below 220 bar such as below 200 bar. Often the pressure during the conversion of the feed mixture is maintained below 180 bars such as below 160 bar. In some embodiments the pressure during the conversion of the feed mixture is below 150 bars such as below 140 bar. In further embodiments the pressure during the conversion of the feed mixture is maintained below 130 bar such as below 120 bar.

[0085] In one preferred embodiment according to the present invention the pressure is maintained in the range from about 30 bar to about 120 bar such as in the range 40 to 120 bar or 50 to 100 bar.

[0086] In many embodiments the pressure during the conversion process is maintained in the range from 20 bar below to 20 bar above the critical pressure of the fluid mixture at the conversion temperature.

[0087] Advantageously the pressure during the conversion of the feed mixture is maintained above the boiling point pressure of the fluid mixture or the critical pressure of the fluid mixture so as to maintain the fluid mixture in a liquid or supercritical state such as a pressure in the range 80 to 180 bar or in the range 100 to 160 bar. Hereby a more efficient method having a lower carbon intensity may be obtained as addition of the latent heat of evaporation of the evaporated fraction is avoided. A further advantage of maintaining the pressure above the boiling point pressure or the critical pressure of the fluid mixture may be that the risk of cavitation and / or liquid hammering due to two phase flow is reduced.

[0088] The conversion of the feed mixture is often performed at a temperature of at least 300 °C such as a temperature of at least 310 °C. In some embodiments the conversion of the feed mixture is performed at a temperature of at least 320 °C such as at a temperature of at least 330 °C. In other embodiments the conversion of the feed mixture is performed at a temperature of at least 340 °C such as a temperature of at least 350 °C. In further embodiments the conversion of the feed mixture is performed at a temperature of at least 360 °C such as a temperature of at least 370 °C.

[0089] Preferred embodiments include converting the feed mixture at a temperature of less than 400 °C such as a temperature of less than 390 °C. Often the conversion of the feed mixture is performed at a temperature of less than 385 °C such as at a temperature of less than 380 °C. In some embodiments the conversion of the feed mixture is performed at a temperature of less than 374 °C such as at a temperature of less than 370 °C.

[0090] Advantageously the pressure and temperature during the conversion of the feed mixture is maintained above the boiling point pressure of the fluid mixture so as to maintain the fluid mixture in a liquid or supercritical state such as a temperature in the range 330 to 400 °C such as in the range 330 to 385 °C or in the range 350 to 380 °C. A further advantage of the method according to the present invention is that the energy required for heating is significantly reduced as the heat capacity of organic solvents like phenolics and alcohols are approximately half of the heat capacity of water. Thereby the overall efficiency and the carbon intensity is improved.

[0091] The predefined time or residence time at the conversion temperature and pressure is generally at least 2 minutes such as at least 4 minutes. In some embodiments the residence time at the conversion temperature and pressure is at least 6 minutes such as at least 7,5 minutes. In other embodiments the residence time at the conversion temperature and pressure is at least 10 minutes such as at least 12,5 minutes. In further embodiments the residence time at the conversion temperature and pressure is at least 15 minutes such as at least 20 minutes.

[0092] The residence time at the conversion temperature and pressure is generally less than 120 minutes such as less than 60 minutes. Often the residence time at the conversion temperature and pressure is below 30 minutes such as below 25 minutes. In some embodiments more preferably the residence time at the conversion temperature and pressure is below 20 minutes such as below 15 minutes. In other embodiments the residence time at the conversion temperature and pressure is below 12,5 minutes such as below 10 minutes.

[0093] The residence is generally selected as long enough to achieve the desired conversion of the feed mixture and short enough to minimize repolymerization of the oil produced. In an advantageous embodiment of the predefined time or residence time at conversion pressure and temperature is maintained relatively short such as in the range 4 to 20 minutes such as in the range 6 to 15 minutes. In a preferred embodiment the process according to the invention is continuous.

[0094] In an aspect of the invention the feed mixture comprises one or more acids selected from formic acid, acetic acid, citric acid, lactid acid, levulinic acid, sulphuric acid, and combinations thereof.

[0095] In a preferred embodiment the one or more acids are at least partly produced by the process. The acid concentration may according to embodiments of the invention be in the range from about 0,1 % by weight to about 10 % by weight such from 1 % by weight to 5 % by weight.

[0096] In contrast to hydrothermal liquefaction processes, where water is the primary solvent, the present invention uses a unique organic solvent combination comprising an aromatic solvent (phenolics) and an alcohol and / or polyol as the primary solvent i.e. the present invention is a solvothermal liquefaction process rather than hydrothermal process. Water is further present in the feed mixture in a concentration in a concentration from 1 % by weight up to 40 % by weight.

[0097] The solvent combination may enhance the oil yield by formation by providing improved solubilization of the biomass compounds particularly at low temperature in the first part of the heating. The solvent combination further minimization of undesirable side reactions e.g. reactions leading to repolymerization and char formation reactions by stabilization of reactive intermediate compounds. Hereby an improved method for producing oil from carbonaceous materials that are more efficient and have lower carbon intensity than the prior art is provided. Hereby an objective of the invention is fulfilled.

[0098] The method according to the invention may further lead to an improved oil product such as an oil product having a lower Total Acid Number (TAN). In a preferred embodiment the total acid number (TAN) of the low carbon intensity oil is below 15 mg KOH / g such as below 10 mg / g, preferably less 7 mg KOH / g such as less than 5 mg KOH / g or less than 3 mgKOH / g.

[0099] The low carbon intensity oil produced according to the present invention may have higher heating value of at least 25 MJ / kg such as at least 30 MJ / kg, preferably the oil has a higher heating value of at least 32 MJ / kg such as at least 34 MJ / kg; more preferably the oil has a higher heating value of at least 34 MJ / kg such as at least 36 MJ / kg; even more preferably the oil product has a higher heating value of at least 38 MJ / kg such as a higher heating value of at least 40 MJ / kg.

[0100] FIG. 2 shows a schematic overview of another preferred embodiment of a process according to the invention, where phenolics are at least partly provided by recycling the at least part of the low carbon intensity crude oil produced by the process to the step of providing the feed mixture such as as a phenolics enriched fraction of the low carbon intensity crude oil, and / or where alcohol is at least partly recovered and recycled to the step of providing the feed mixture.

[0101] The converted feed mixture is cooled and depressurized to desired separations condition and separated into an oil phase, a gas phase, an alcohol / polyol / water phase and a solid phase.

[0102] A preferred embodiment of the separation system comprises a gravimetric separation at pressures of 30 to 100 bars and temperatures of 130 to 400 °C such as gravimetric separation at pressures of 50 to 10 bars and temperatures of 150 to 400 °C.

[0103] In an advantageous embodiment the separated oil phase is at least partly recycled to the step of providing the feed mixture, such as a phenolic enriched fraction. In another advantageous embodiment alcohol is at least partly recovered from the converted feed mixture after separation and recycled to the step of providing the feed mixture.

[0104] In a preferred embodiment the recovery of alcohol comprises one or more flashing steps.

[0105] In an advantageous embodiment the recovery of alcohol comprises separating or further separating alcohol from water by a distillation technique.

[0106] In another advantageous embodiment the recovery of alcohol comprises separating or further separating alcohol from water using one or more membrane techniques.

[0107] FIG. 3 shows a schematic drawing of a system of an embodiment of a process according to the invention, where renewable phenolics is at least partly produced from one or more carbonaceous material(-s) in a separate preconversion zone (1 ) prior to the step of providing the feed mixture to the conversion zone (2) of process.

[0108] One or more carbonaceous material(-s) is / are at least partly converted to phenolics in a pre-conversion zone (1) in the presence of phenolics and one or more alcohol and / or polyol to form an oil rich in phenolics, a gas phase, a water phase and / or a solid phase product. After separation from other product phases produced in the pre-conversion zone (1 ), the phenolic enriched oil phase is according to an advantageous embodiment at least partly introduced to the step of providing the feed mixture in the conversion zone (2) of the process as described in further details under FIG. 1 and FIG. 2 above. The temperature for conversion of the one or more carbonaceous materials in the pre-conversion zone (1 ) may according to a preferred embodiment of the present invention be in the range from 150 °C to 240 °C such as in the range 160 °C to 225 °C. Preferably, the temperature for conversion of the one or more carbonaceous materials in the pre-conversion zone (1 ) is in the range 175 °C to 210 °C such as in the range 180 °C to 200 °C.

[0109] The pressure for conversion of the one or more carbonaceous materials in the pre-conversion zone (1 ) is typically in the range 5 to 90 bar such as in the range 8 to 80 bar. Preferably the pressure for conversion of the one or more carbonaceous materials in the pre-conversion zone (1 ) is in the range 10 to 70 bar such as in the range 15 to 60 bar. More preferably the pressure for conversion of the one or more carbonaceous materials in the pre-conversion zone (1) is in the range 15 to 50 bar such as in the range 20 to 40 bar.

[0110] In a preferred embodiment the concentration of phenolics in the feed mixture added to the pre-conversion zone (1) is at least 2 % by weight of the feed mixture. In other embodiments the concentration of phenolics may be at least 3 % by weight of the feed mixture, at least 5 % by weight of the feed mixture, at least 8 % by weight of the feed mixture, at least 10 % by weight of the feed mixture by weight of the feed mixture, at least 12 % by weight of the feed mixture, at least 15 % by weight of the feed mixture such as at least 20 % by weight of the feed mixture to the pre-conversion zone (1 ).

[0111] Advantageously, the concentration of phenol in the feed mixture fed the preconversion zone (1 ) is at least 1 % by weight of the feed mixture. In other embodiments the concentration of phenol may be at least 2 % by weight of the feed mixture, at least 3 % by weight of the feed mixture, at least 5 % by weight of the feed mixture, at least 8 % by weight of the feed mixture, at least 10 % by weight of the feed mixture, at least 12 % by weight of the feed mixture, at least 15 % by weight of the feed mixture such as at least 20 % by weight of the feed mixture to the pre-conversion zone (1 ).

[0112] Advantageously, at least part of the phenolics added to the feed mixture to the pre-conversion zone (1 ) is provided by recycling at least part of the oil product produced in the pre-conversion zone (1) as shown in Fig. 3.

[0113] The concentration of alcohols and / or polyols in the feed mixture to the preconversion zone (1) may in a preferred embodiment be at least 5 % by weight of the feed mixture such as at least 10 % by weight of the feed mixture; preferably the concentration of alcohols and / or polyols in the feed mixture to the pre-conversion zone (1 ) is at least 15 % by weight of the feed mixture, 20 % by weight of the feed mixture, 30 % by weight of the feed mixture, 40 % by weight of the feed mixture, 50 % by weight of the feed mixture, 60 % by weight of the feed mixture.

[0114] Advantageously, the one or more alcohols and / or polyols added to the feed mixture to the pre-conversion zone (1 ) has a renewable origin e.g., is produced from biogenic resources and / or renewable electricity, whereby the carbon footprint of the products from the process is reduced.

[0115] An advantageous embodiment is where the one or more alcohols and / or polyols added to the feed mixture to the pre-conversion zone (1 ) comprises methanol produced from the process gas produced by the conversion process in zone 1 and 2.

[0116] In some preferred embodiments, the conversion of the one or more carbonaceous materials in the pre-conversion zone (1 ) is performed in the presence of one or more acid catalysts. In an advantageous embodiment, the acid catalyst added to the feed mixture added to the pre-conversion zone comprises sulphuric acid in a concentration of 1 to 5 % by weight of the feed mixture such as 2 to 4 % by weight of the feed mixture added to the pre-conversion zone (1 ).

[0117] The residence time in the pre-conversion zone (1 ) may in many applications of the present invention be in the range from 1 minutes to 180 minutes such as in the range from 2 minutes to 120 minutes. Preferably the residence time in the pre-conversion zone (1) is in range from 5 minutes to 60 minutes such as in the range from 10 minutes to 30 minutes.

[0118] The one or more carbonaceous material(-s) provided to the pre-conversion zone (1) is typically selected so that the carbonaceous material contains lignin such as lignocellulosic materials.

[0119] In a preferred embodiment of the invention, the lignin content of the carbonaceous material(-s) added to the pre-conversion zone (1 ) of the present invention is / are at least 10 % of the dry ash free weight of the carbonaceous material(-s) such as at least 15 % of the dry ash free weight. In some applications the lignin content of the carbonaceous material(-s) added to the pre-conversion zone (1) of the present invention is / are at least 20 % of the dry ash free weight of the carbonaceous material(-s) such as at least 25 % of the dry ash free weight.

[0120] The phenolic rich oil phase from the pre-conversion zone (1 ) is at least partly added to the step of providing the feed mixture in the conversion zone (2), where the carbonaceous material(-s) is / are further converted as described above under FIG. 1 and FIG. 2.

[0121] Hereby the phenolics used in the process are produced from a renewable source (biogenic carbon) in the process, whereby the overall carbon footprint is reduced. Further, by producing the phenolics in a separate conversion step it is obtained that process conditions in the pre-conversion step can be optimized for production of phenolics and the conversion step can be optimized for yield and quality of the oil produced. Hereby the overall efficacy of the process and carbon intensity of the oil product are improved.

[0122] FIG. 4 shows a schematic overview of a preferred embodiment according to the invention comprising a system for producing alcohol(-s) from the gas produced in the conversion process of the carbonaceous material, and at least partly recycling the alcohol produced to the step of providing the feed mixture of the conversion process.

[0123] One or more carbonaceous materials are subjected to a conversion process in the presence of one or more alcohols, thereby resulting in a converted carbonaceous material comprising oil, process gas, solids and water as illustrated in FIG. 4.

[0124] The conversion process is typically performed under pressure such as at a pressure of at least 10 bar, 20 bar, 30 bar, 40 bar, 50 bar, 60 bar, 80 bar, and 100 bar.

[0125] In many embodiments the pressure during the conversion of the carbonaceous material is below 400 bar, 350 bar, 300 bar, 250 bar, 200 bar, 180 bar, and 160 bar.

[0126] The temperature during the conversion process of the carbonaceous material is typically at least 280 °C such as at least 300 °C. Preferably, the temperature during the conversion process of the carbonaceous material is at least 325 °C such as at least 350 °C. More preferably the temperature during the conversion process of the carbonaceous material is at least 370 °C such as at least 385 °C. The process gas produced by conversion process of the carbonaceous material(-s) comprises carbon oxides such carbon dioxide and carbon mono oxide as the main compounds. The amount of process gas and the composition of the gas depend on the specific operating conditions, and carbonaceous material(-s) being converted, but often further comprises Ci to C4 hydrocarbons, hydrogen, and condensable liquids, like water and alcohol.

[0127] As shown in the FIG. 4, the process gas from the conversion process for carbonaceous material is subjected to an alcohol synthesis step, where the process gas is reacted with hydrogen to produce one or more alcohols with water as a by-product.

[0128] Typically, the alcohol synthesis step according to the present invention involves at least one catalytic reaction step for reacting the carbon oxides in the process gas with hydrogen in the presence of one or more metal catalyst(- s).

[0129] The catalytic reaction step is often performed at pressures in the range 30 to 150 bar, and temperatures in the range 200 to 450 °C such as pressures of 50 to 100 bar and temperatures in the range 200 to 300 °C.

[0130] Suitable metal catalysts according to the invention include copper zinc oxide catalysts, copper zinc chromium catalysts, copper mixed oxides catalysts, and iron oxide catalysts on an alumina, zirconia carrier or zeolite carrier material. Other metal promotors and modifications may be added to the catalyst structure for activity and selectivity enhancement.

[0131] In one embodiment, the catalytic reaction step is arranged as a fixed-bed reaction system comprising one or more fixed beds comprising the metal catalyst(-s). Another configuration of the catalytic reaction step according to the present invention is as a fluidized-bed reactor system containing the metal catalyst(-s) fluidized by the gas feedstock.

[0132] The conversion per pass in the catalytic reaction step is often relatively low e.g. in the range 10-40 % such as in the range 20 to 30 %. Hence, an advantageous embodiment is where the unreacted carbon oxides and hydrogen are at least partly recycled back into the catalytic reactor after intermediate separation of produced alcohol and water as shown in FIG. 4. Hereby the overall conversion is increased.

[0133] As also shown in the FIG. 4 the alcohol produced from the process gas is at least partly recycled to the conversion process. Hereby, the overall oil yield and efficiency of the conversion process for carbonaceous material and the resulting carbon footprint of the oil produced is reduced.

[0134] FIG. 5 shows a schematic overview of an embodiment of a system similar to FIG. 4, where the alcohol(-s) produced from the process gas is methanol, and where the hydrogen added to the methanol synthesis is produced by electrolysis. As seen from the figure oxygen is produced as a by-product in the electrolysis.

[0135] As illustrated the methanol and water produced in the methanol synthesis may be separated from unreacted gases by flashing and may be at least partly recycled and mixed with the incoming process gas to the methanol to achieve a higher overall conversion. The liquid fraction from the flash separation (3) may further separated (4) into a methanol stream and water stream by conventional means such as by distillation. As illustrated the separated water may at least partly be recycled to the electrolysis unit (2), and the methanol produced may be at least partly recycled to the conversion process thereby increasing the overall process efficacy, and reducing the chemical consumption as well as the carbon footprint of the oil produced from carbonaceous material.

[0136] FIG. 6 shows a schematic overview of an advantageous embodiment of a system for producing methanol from the gas produced in the conversion process according to the invention further comprising using low carbon intensity electricity produced renewable sources such as wind, solar and / or geothermal energy in the electrolysis unit (2), whereby the carbon footprint of the oil produced from the carbonaceous material is further reduced.

[0137] Also shown in FIG. 6 is a syngas preparation unit (1) prior to the methanol synthesis step (3). The syngas preparation unit (1) may according to the invention include means for adjusting Fb / CO-ratio in the range 1 ,8 to 2,2 as well as means for removing impurities such as sulphur and nitrogen compounds, and other trace elements, to prevent poisoning of the catalyst used in the methanol synthesis reaction.

[0138] The adjustment of the Fb / CO-ratio may be performed through a variety of processes such as thermochemical, electrochemical or biological conversion processes and combinations thereof.

[0139] In one embodiment, the means for adjusting the Fb / CO-ratio include adding hydrogen preferably low carbon intensity hydrogen such as produced by electrolysis using low carbon intensity electricity from wind, solar, hydro, geothermal or nuclear power to the syngas preparation unit.

[0140] In another embodiment, the means for adjusting the Fb / CO-ratio include performing a reverse water gas shift reaction (RWGS), where CO2 and F are reacted to produce CO and water vapor (H2O). The means for adjusting the Fb / CO-ratio by RWGS reaction may be performed by conventional means such as by reaction in a catalytic reactor. Suitable catalysts for the RWGS reaction include supported bimetallic catalysts combining two or more different transition metals such as Fe, Co, Ni, Cr, Zn, Co, Cu, Ce on a high surface area porous supporting material such as alumina, silica, zeolites or carbon supports.

[0141] The reaction temperature depends on the specific catalyst and process configuration.

[0142] One embodiment of the present invention comprises a syngas preparation unit where a reverse water gas shift reaction of the process gas operating at temperatures in the range 300 to 500°C such 300 to 400 °C and pressures in the range 10-50 bar such as 30 to 40 bar.

[0143] Another preferred embodiment is where the syngas preparation unit comprises an electrochemical reverse water gas shift (eRWGS) process where carbon oxide (CO, CO2) containing process gas from the conversion process of the carbonaceous material is converted to syngas in an electrochemical cell.

[0144] The electrochemical cell may comprise one or more catalyst(-s) to promote the reverse gas reaction. Often the operating temperature of the electrochemical cell is at least 400 °C, 500°C, 600 °C, 700 °C, 800 °C, 900 °C and even at least 1000 °C.

[0145] In a preferred embodiment heat from the syngas preparation and / or methanol is transferred to the conversion process of the carbonaceous material.

[0146] DEFINITIONS

[0147] Low carbon intensity oil The term low carbon intensity oil in the present context is used to describe hydrocarbons and oxygenated hydrocarbons. The low carbon intensity oil according to the present invention generally has a significant / substantial decarbonization effect due to avoided grenhouse gas emissions.The decarbonation effect may be due to avoidance of emissions related to alternative use of the carbonaceous feedstock, the use of renewable carbonaceous materials such as biomass and / or other renewable raw materials to produce the oil e.g. resulting in an oil product having a low carbon intensity and / or having a high content of biogenic carbon content and thus resulting in significant / substantial decarbonization when used to substitute fossil oils and / or chemicals.

[0148] Phenolics

[0149] Phenolics in the present context are used to describe chemical compounds consisting of one or more hydroxyl groups (-OH) bonded directly to an aromatic hydrocarbon group. Examples of phenolics according to the present invention are phenols, alkylated phenols, alkoxy phenols, methoxy phenols such as 2- methoxy-4-methyl-phenol, 2-methoxy-4-ethyl-phenol, 2,6 -dimethoxy-phenol, 2-methoxy-4-propyl-phenol, 2,3-dimethyl-phenol, 2,4- dimethyl-phenol, 3,4- dimethyl-phenol, 3,5-dimethyl phenol, 4-methyl-2,6-dimethoxy-phenol, 4-allyl- 2,6-dimethoxy-phenol, m-creosol,o-creosol, p-creosol, vanillin, flavanols, phenoxypropanol, thymol, benzene diols such as catecols, guaicol, alkoxy phenols, p-coumaryl alcohol, coniferyl alcohol, sinapyl alcohol and combinations thereof.

[0150] Alcohols

[0151] Alcohols are molecules containing the hydroxy functional group (-OH) that is bonded to the carbon atom of an alkyl or substituted alkyl.

[0152] Polyol A polyol in the current context is an organic compound containing multiple hydroxyl groups.

[0153] Carboxylic acid A carboxylic acid in the current context is a hydrocarbon compound having at least one carboxyl (-CO-OH) group.

[0154] Autogeneous pressure

[0155] The autogeneous pressure is defined as the highest pressure that is measured when the liquefaction reactions is carried out in a fully closed vessel.

Claims

CLAIMS1 . Method for producing a low carbon intensity oil comprising the steps of a. providing a feed mixture comprising i. a carbonaceous material ii. a primary organic solvent comprising phenolics in a concentration of at least 3 % by weight, and one or more alcohols and / or polyols in a concentration of at least 5 % by weight; iii. water in a concentration from 1 to 40 % by weight including moisture added with the carbonaceous material; b. converting the feed mixture by treating it at a pressure in the range 10 bar to 220 bar and at a temperature in the range of 280 °C to 410 °C in a predefined time; er recovering oil from the converted feed mixture.

2. Method according to claim 1 , where the weight ratio of alcohol to water in the feed mixture is in the range 4:1 to 1 :2.

3. Method according to any of the claims 1 -2, where the pH of the aqueous phase after recovering oil from the converted feed mixture is below 7.

4. Method according to any of the preceding claims, wherein the feed mixture comprises one or more carboxylic acids or a salt of a carboxylic acid in a concentration from 0,1 to 30 % by weight.

5. Method according to any of the claim 3, wherein the carboxylic acid added comprises formic acid, acetic acid, citric acid, levulinic acid, lactid acid and / or salts and / or esters thereof.

6. Method according to any of the preceding claims, wherein the feed mixture comprises or further comprises sulphuric acid in a concentration from 1 to 5 wt %.

7. Method according to any of the preceding claims, where the concentration of alcohol and / or polyol in the feed mixture is at least 20 % by weight.

8. Method according to any of the preceding claims, where the concentration of phenolics in the feed mixture is at least 5 % by weight.

9. Method according to any of the preceding claims, where the concentration of phenolics in the feed mixture is at least 10 % by weight.

10. Method according to any of the preceding claims, where the alcohol is methanol produced by adding hydrogen to the gas produced by conversion of the feed mixture and reacting the gas and hydrogen in a catalytic process.11 . Method according to any of the preceding claims, where the ratio of the weight of phenolics to the dry ash free weight of carbonaceous material is at least 0,1.

12. Method according to any of the preceding claims, where the phenolics in the feed mixture at least partly have a renewable origin, preferably a fully renewable origin.

13. Method according to any of the preceding claims, where the phenolics in the feed mixture are at least partly produced by the process.

14. Method according to claim 12-13, where at least part of the phenolics are provided by recycling part of the oil produced by the process such as a phenolic enriched fraction of the oil.

15. Method according to claim 14, where the ratio of the weight of oil to the dry ash free weight of the carbonaceous material is at least 1 ,5.

16. Method according to any of the claims 11 to 15, where the phenolics added to the feed mixture comprises phenols and / or alkylated phenols and / or alkoxy phenols and / or cresols in a concentration of at least 2 % by weight.

17. Method according to any of the preceding claims, where the total acid number (TAN) is below 15 mg KOH / g oil.

18. Method according to any of the preceding claims, where the higher heating value of the renewable oil is at least 25 MJ / kg.

19. Method according to any of the preceding claims, where the pressure during the conversion of the feed mixture is at least 60 bar.

20. Method according to any of the preceding claims, where the pressure during the conversion of the feed mixture is maintained below 150 bar.

21. Method according to any of the preceding claims, where the pressure is maintained in the range 20 bar below to 20 bar above the critical pressure of the fluid mixture.

22. Method according to any of the preceding claims, where the pressure is controlled to less than 90 % of the autogenous pressure at theprevailing temperature.

23. Method according to any of the preceding claims, where the pressure during the conversion of the feed mixture is maintained above the boiling point pressure of the fluid mixture when the conversion temperature is below the critical temperature of the fluid and above the critical pressure of the fluid mixture when the conversion temperature is above the critical pressure of the fluid mixture so as to maintain the fluid mixture in a liquid or supercritical state.

24. Method according to any of the preceding claims, where the conversion of the feed mixture is performed at temperatures of at least 300 °C.

25. Method according to any of the preceding claims, where the conversion of the feed mixture is performed at temperatures of less than 400 °C.

26. Method according to any of the preceding claims, where the conversion of the feed mixture is performed by treatment at a pressure in the range 80 to 150 bar, and a temperature in the range 330 to 385 °C.

27. Method according to any of the preceding claims, where the process is continuous.

28. Method according to any of the preceding claims, where the phenolics are produced in a separate conversion step.

29. Method according to claim 28, where the phenolics are produced by conversion of a lignocellulosic material in the presence of phenolicsand one or more alcohols and an acid at conversion temperatures in the range 160 to 260 °C and conversion pressures in the range 5 to 90 bar.

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