Improved process for producing biooil

Abstract

The present invention relates to a process for producing a low carbon strength oil, comprising the steps of: providing a feed mixture comprising: a carbonaceous material; one or more alcohols and / or polyols in a concentration of at least 5% by weight; converting the feed mixture at a pressure of from 10 bar to 400 bar and a temperature of from 280 DEG C to 430 DEG C; recovering a low carbon strength oil from the converted feed mixture; recovering at least a portion of the gas produced from the converted feed mixture, the converted feed mixture comprising the carbon oxides resulting from the conversion, and providing at least a portion of the recovered gas to an alcohol production plant for alcohol production using hydrogen in an alcohol synthesis process; wherein the recovery gas from the converted feed mixture is used in the alcohol production plant to produce at least a portion of the alcohol forming portion of the feed mixture.

Description

TECHNICAL FIELD

[0001] The present invention relates to the technical field of producing oil from carbonaceous material, such as biomass, and more specifically to the technical field of thermochemically converting carbonaceous material in the presence of an alcohol component. BACKGROUND

[0002] Advanced liquid biofuels and chemicals produced from carbonaceous material, such as biomass, and residual steam have become a central focus point in mitigating global climate change caused by greenhouse gas emissions to develop a sustainable circular economy.

[0003] Several methods of converting biomass to advanced biofuels are being applied and developed, including biodegradation to produce liquids (e.g. ethanol) and gases (e.g. methane), and thermochemical conversion methods to produce advanced liquid biofuels. Thermochemical processes use temperature and pressure to break down biomass at the cellular level. Thermochemical conversion methods include gasification, pyrolysis, and hydrothermal technologies.

[0004] The present invention relates generally to thermochemical conversion methods. Despite extensive research into several promising avenues, there are several requirements for technical improvements, including improvements in yield, carbon intensity, improved product properties (such as more stable oil products), higher process efficiency (e.g. by using less stringent process conditions), easier to control processes, increased run factors (e.g. by reducing fouling and / or plugging), and reduced carbonization in the process. SUMMARY

[0005] OBJECTIVE

[0006] It is therefore an object of the present invention to provide an improved method of producing oil from carbonaceous material that is more efficient and has a lower carbon intensity than prior art methods.

[0007] Depending on certain additional parameters, the improvement can be one or more of the following: higher oil yield, less coking production, easier to control process, easier downstream product separation, less stringent operating conditions (meaning cheaper / more cost effective operation), and other additional benefits.

[0008] The improved method can further result in an improved product, meaning one or more of the following: more stable oil product, e.g. less corrosive (lower acid number) due to less ketone and aldehyde groups in esterified oils and carboxylic acids, valuable by-products (meaning a more cost effective method), better resource utilization (meaning increased circularity), reduced heating energy consumption due to lower heat capacity, which also means an advantage in the method due to processing in an organic solvent.

[0009] According to one aspect of the present application, the object of the present application is achieved by a process for producing a low carbon intensity oil, the process comprising the steps of:

[0010] a. providing a feed mixture, the feed mixture comprising:

[0011] i. a carbonaceous material;

[0012] ii. one or more alcohols and / or polyols in a concentration of at least 5 wt%;

[0013] b. converting the feed mixture at a pressure in the range of 10 to 400 bar and a temperature in the range of 280 to 430 °C;

[0014] c. recovering a low carbon intensity oil from the converted feed mixture;

[0015] d. recovering at least a part of the gas produced from the converted feed mixture, the converted feed mixture comprising carbon oxides obtained from the conversion, and providing at least a part of the recovered gas to an alcohol production facility for alcohol production using hydrogen in an alcohol synthesis process;

[0016] e. wherein at least a part of the alcohols of the feed mixture is produced in the alcohol production facility using the gas recovered from the converted feed mixture.

[0017] The carbonaceous material according to the present application typically contains oxygen, which is at least partly stripped during the conversion of the feed mixture to produce a bio-oil. In many embodiments, the oxygen removed from the carbonaceous material during the conversion of the feed mixture ends up as water and carbon oxides such as carbon monoxide CO and carbon dioxide CO2. Thus, the gas recovered from the converted feed mixture is typically rich in carbon oxides in the form of CO and CO2. Other compounds in the gas can include C1-C4 hydrocarbons, hydrogen as a condensable, such as water and alcohols. In many embodiments according to the present application, the condensables can be removed, e.g. by condensation, prior to the step of providing the recovered gas to the alcohol production facility for alcohol production according to the present application.

[0018] Carbon oxides can typically be about 50 to about 95% by dry weight of the gas produced from the conversion of the feed mixture. The specific concentrations of CO and CO2 depend on the specific process conditions and process configuration. According to many embodiments of the present application, the concentration of CO can be in the range of 0.05 to 85% by dry weight of the gas produced from the conversion of the feed mixture, for example in the range of 0.05 to 10% by dry weight, 0.1 to 5% by dry weight, 10 to 75% by dry weight, 20 to 70% by dry weight, 30 to 60% by dry weight. Typically, lower ranges of CO concentrations are obtained when the feed mixture is converted under basic conditions, and higher concentrations are obtained when converted under acidic conditions. According to the present application, CO2 can be in the range of about 10 to 95% by dry weight of the gas, for example 20 to 95% by dry weight of the gas. In some embodiments, the CO2 concentration is in the range of 30 to 95% by dry weight of the gas, for example 50 to 90% by dry weight of the gas.

[0019] Deoxidation of the carbonaceous material by conversion to carbon oxides in the gas represents a carbon loss to bio-oil. Therefore, by at least partially recovering the gas from the conversion of the feed mixture and converting the carbon oxides to alcohols by reaction with hydrogen in the alcohol production, carbon loss is minimized, thereby increasing the overall process efficiency and reducing the carbon intensity of the produced bio-oil.

[0020] In advantageous embodiments, the step of at least partially recovering the gas from the converted feed mixture is carried out at least partially at a pressure of 20 to 50 bar, for example at a pressure of 30 to 40 bar, and at a temperature of 80 to 260 °C, for example at a temperature of 150 to 250 °C.

[0021] Advantageously, the hydrogen added in the alcohol production facility comprises hydrogen produced by electrolysis using electricity generated from wind power, solar power, geothermal power, hydroelectric power, or a combination thereof, thereby reducing the carbon footprint of the process and the carbon intensity of the oil.

[0022] The alcohol synthesis step of the alcohol production facility according to the present application is typically carried out at a temperature in the range of 200 to 300 °C and at a pressure in the range of 50 to 100 bar in the presence of one or more metal catalysts.

[0023] In preferred embodiments, the metal catalyst comprises a copper zinc oxide catalyst, a copper zinc chromium catalyst, or an iron oxide catalyst.

[0024] In some preferred embodiments, the alcohol production facility further comprises means for adjusting the H2 / CO ratio to the level required for methanol synthesis prior to the methanol synthesis step.

[0025] In one embodiment, the means for adjusting the H2 / CO ratio comprises means for carrying out a reverse gas shift reaction.

[0026] In a preferred embodiment, the alcohol production facility further comprises means for removing impurities, such as sulfur compounds and / or nitrogen compounds and / or other trace elements, prior to the H2 / CO ratio adjustment step.

[0027] In an advantageous embodiment, the alcohol produced from the at least part of the recovered gas is methanol.

[0028] An advantageous embodiment of the present application comprises:

[0029] a. providing a feed mixture comprising:

[0030] - a carbonaceous material;

[0031] - a phenolic substance at a concentration of at least 3 wt%;

[0032] - one or more alcohols and / or polyols at a concentration of at least 5 wt%;

[0033] b. converting the feed mixture at a pressure in the range of 10 to 220 bar and at a temperature in the range of 280 to 410 °C;

[0034] c. recovering a low carbon intensity oil from the converted feed mixture;

[0035] d. recovering at least a part of the gas produced from the converted feed mixture, the converted feed mixture comprising carbon oxides obtained from the conversion, and providing at least a part of the recovered gas to an alcohol production facility for alcohol production using hydrogen in an alcohol synthesis process;

[0036] e. wherein at least a part of the alcohol of the feed mixture is produced in the alcohol production facility using the gas recovered from the converted feed mixture.

[0037] The carbonaceous material according to the present application is typically a carbon-containing material, such as an organic matter, such as biomass and / or waste. The carbonaceous material according to the present application is further described in the detailed description. The water content of the feed mixture provided according to the present application is typically lower compared to hydrothermal liquefaction processes. In embodiments according to the present application, water can constitute at most 40 wt% of the feed mixture, such as at most 30 wt%. In many advantageous embodiments, the water content of the feed mixture is at most 20 wt% of the feed mixture, such as at most 15 or at most 10 wt%.

[0038] In one embodiment of the present application, the produced oil has a carbon intensity of less than 20 g CO2 / MJ of produced oil, such as less than 15 g CO2 / MJ of produced oil. Preferably, the produced oil has a carbon intensity of less than 12.5 g CO2 / MJ of produced oil, such as less than 10 g CO2 / MJ of produced oil.

[0039] Phenolics in the present context are used to describe chemical compounds consisting of one or more hydroxyl groups (-OH) directly bonded to an aromatic hydrocarbon group.

[0040] In one embodiment of the application, the step of providing a feed mixture can comprise adding a phenolic at a concentration of at least 5 wt% to at least 7.5 wt%. Preferred embodiments of the application include embodiments wherein the concentration of phenolics in the feed mixture is at least 10 wt%, at least 12.5 wt%, at least 15 wt%, at least 15 wt% and at least 20 wt%.

[0041] In many embodiments, the ratio of the weight of phenolics to ash-free dry weight of the carbonaceous material is at least 0.2, for example at least 0.3; preferred embodiments include embodiments wherein the ratio of the weight of phenolics to ash-free dry weight of the carbonaceous material is at least 0.4, at least 0.5, at least 0.6, at least 0.7, for example at least 0.8. In further preferred embodiments, the ratio of the weight of phenolics to ash-free dry weight of the carbonaceous material is at least 0.9, at least 1.0 or at least 1.5.

[0042] In an advantageous embodiment, the phenolics added to the feed mixture comprise phenol at a concentration of at least 2 wt%, for example at a concentration of at least 4 wt%. In further advantageous embodiments, the feed mixture comprises phenol at a concentration of at least 6 wt%, at least 8 wt%, at least 10 wt%, at least 12 wt%, at least 15 wt%, at least 18 wt%, for example at least 20 wt%.

[0043] According to a particularly preferred embodiment of the application, the phenolics added to the feed mixture are produced from a renewable source, thereby reducing the carbon footprint of the oil.

[0044] In an advantageous embodiment, the phenolics in the feed mixture are at least partially produced by the process.

[0045] In one embodiment, the phenolics in the feed mixture are at least partially provided by recycling at least a portion of the crude oil produced by the process, for example a phenolic-rich fraction of the crude oil.

[0046] In a preferred embodiment, the ratio of the weight of the portion of recycled oil produced by the process to the ash-free dry weight of the carbonaceous material is at least 1.5, for example at least 2.0; preferably, the ratio of the weight of the recycled oil to the ash-free dry weight of the carbonaceous material is at least 2.5, for example at least 3.0. In other preferred embodiments, the ratio of the weight of the renewable oil to the ash-free dry weight of the carbonaceous material is at least 4, for example at least 5.

[0047] In an embodiment, the concentration of the one or more alcohols and / or polyols is at least 10 wt%, for example at least 15 wt%. In other preferred embodiments, the concentration of the one or more alcohols and / or polyols is at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%.

[0048] In an embodiment, the ratio of the weight of the one or more alcohols and / or polyols to the ash-free dry weight of the carbonaceous material is at least 0.5, for example at least 1. In other preferred embodiments, the ratio of the weight of the one or more alcohols and / or polyols to the ash-free dry weight of the carbonaceous material is at least 1.5, at least 2.0, at least 2.5, or at least 3.0.

[0049] In preferred embodiments, the one or more alcohols and / or polyols according to the present application comprise methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, glycerol, ethylene glycol, polyethylene glycol, propylene glycol, catechol, or a combination thereof.

[0050] The conversion of the carbonaceous material in the presence of phenolic species and alcohols according to the present application increases the yield and quality of the oil, provides increased solubility of the oily product, favors deoxygenation and hydrogenolysis reactions, and stabilizes reactive intermediates, for example by forming acetals with carbonyl groups (such as ketones and aldehydes) and esters with carboxylic acids, using the advantageous combination of solvents that act as an effective hydrogen donor for the conversion of biomass. Thus, the solvent composition retards re-polymerization reactions that can lead to high molecular weight products (commonly referred to as solid residue or char formation) and lower oil quality.

[0051] In advantageous embodiments, the one or more alcohols and / or polyols have a renewable origin. Thus, they contribute or further contribute to reducing the carbon intensity of the produced oil.

[0052] By producing alcohols at least partially from the process gas containing carbon oxides from the conversion process, the oil yield and overall process efficiency are increased. By using green hydrogen, such as produced from electrolysis using renewable electricity, the carbon footprint and carbon intensity of the produced oil are further reduced.

[0053] It is also noted that the production of alcohols from the process gas produced from the process conditions according to the present application avoids a capital and operating cost-intensive carbon capture step. Furthermore, the relatively high ratio of single carbon oxides to total carbon oxides leads to a lower hydrogen demand for alcohol synthesis. Typically, the hydrogen consumption for alcohol synthesis is at least 20% lower, for example at least 30% lower, than the hydrogen consumption for the production of methanol from carbon dioxide. In some embodiments, the hydrogen consumption for alcohol synthesis is at least 40% lower than the hydrogen consumption for the production of methanol from carbon dioxide.

[0054] One aspect of the present invention comprises producing phenolic substances from one or more carbonaceous materials in a separate conversion step under less severe conditions, and at least partly providing the phenolic substances to the feed mixture in the step of providing a feed mixture.

[0055] A preferred embodiment comprises producing phenolic substances by converting lignocellulosic material in a pre-conversion zone in the presence of phenolic substances, one or more alcohols and / or polyols, and one or more acid catalysts at a temperature of 150-240 °C and a pressure of 5-90 bar.

[0056] An advantageous embodiment of the present invention is where the acid catalyst comprises sulfuric acid in a concentration of 1 to 5 weight % of the feed mixture added to the pre-conversion zone.

[0057] By producing the phenolic substances added to the process from carbonaceous material in the form of lignocellulosic material, the overall carbon footprint and carbon intensity of the produced oil is reduced as it is produced from renewable energy (biological carbon).

[0058] Furthermore, by producing the phenolic substances in a separate conversion step, it is obtained that the process conditions in the pre-conversion step can be optimized for the production of phenolic substances, and the process conditions in the conversion step can be optimized for the yield and quality of the produced oil. Thus, the overall efficacy of the process is improved. BRIEF DESCRIPTION OF DRAWINGS

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

[0060] Figure 1 A schematic representation of a process for converting carbonaceous material to oil, gaseous product rich in carbon oxides, aqueous phase and solid phase according to the present invention is shown, wherein the gaseous product is converted to synthesis gas by an adding hydrogen gas preparation step and subjected to an alcohol synthesis step.

[0061] Figure 2 A schematic representation of another preferred embodiment of the process according to the present invention is shown, wherein the phenolic substances are at least partly provided by recycling at least a part of the crude oil produced by the process to the step of providing a feed mixture, e.g. recycling a phenolic substance rich fraction, and / or wherein the recovered alcohols / polyols are at least partly recovered and recycled to the step of providing a feed mixture;

[0062] Figure 3 A schematic representation of a system of an embodiment of the process according to the present invention is shown, wherein the phenolic substances are at least partly produced in a separate conversion step prior to the step of providing a feed mixture;

[0063] Figure 4schematic diagram of a system for producing methanol from a gas produced in a conversion process according to an advantageous embodiment of the present application, which further comprises the use of low-carbon intensity electricity, such as electricity generated from wind energy, solar energy, water energy, geothermal energy and / or nuclear energy.

[0064] Figure 5 schematic diagram of a system for producing methanol from a gas produced in a conversion process according to an advantageous embodiment of the present application, which further comprises the use of low-carbon intensity electricity, such as electricity generated from wind energy, solar energy, water energy, geothermal energy and / or nuclear energy.

[0065] Figure 6 schematic diagram of a system for producing methanol from a gas produced in a conversion process according to an advantageous embodiment of the present application, which further comprises the use of low-carbon intensity electricity, such as electricity generated from wind energy, solar energy, water energy, geothermal energy and / or nuclear energy. DETAILED DESCRIPTION

[0066] Figure 1 schematic diagram of a system for producing methanol from a gas produced in a conversion process according to an advantageous embodiment of the present application, which further comprises the use of low-carbon intensity electricity, such as electricity generated from wind energy, solar energy, water energy, geothermal energy and / or nuclear energy.

[0067] The conversion process according to the present application is carried out at a pressure of 10 bar to 220 bar and a temperature of 280 °C to 410 °C in the presence of a phenolic substance at a concentration of at least 3 wt.% and one or more alcohols and / or polyols at a concentration of at least 5 wt.% and the converted feed mixture is separated into individual products.

[0068] The carbonaceous material according to the present application is typically a carbon-containing material, such as an organic substance, such as biomass and / or waste material.

[0069] Non-limiting examples of carbonaceous materials according to the present application include lignin, cellulose, hemicellulose, lignocellulose, proteins, starch, sugars, lipids, woody biomass such as residues from forestry or paper industry operations, for example wood chips, hog fuel, sawdust, prunings, thinnings and waste, tree bark, leaves, park and garden waste and weeds, road excavations, wine lees, and the like; residues, by-products and waste streams from agricultural production, for example grass, straw, stalks, stover, chaff, corn cobs, husks, shells, kernels, leaves, pulp from, for example, wheat, barley, oat, rye, corn, rice, sunflower, rapeseed, flaxseed, nutshells, cotton, and the like; fruit string residues from palm oil production, oil manufacturer effluents (for example palm oil manufacturer effluent (POME) from palm oil manufacture), press residues from vegetable oil production, manure and bedding from animal production, green / organic household waste, greenhouse waste, and the like; energy crops, such as short-rotation coppice, willow, jatropha, sorghum, switchgrass and miscanthus; for example aquatic biomass, such as water hyacinth, duckweed, azolla, water fern; macroalgae / seaweeds, for example red, green and brown algae, for example sargassum, genus, caulerpa, euglena, ulcus, gracelaria, laminaria, macrocystis, porphyra, porphyridium, coccolithophores, and the like; microalgae, for example ankistrodemus, botryococcus, chlorella, chlorophyta, cryptophyta, dictyophaerium, dinophyta, green algae, cryptophyta, crypthecodinum, cyclotella, dunaliella, glaucophyta, haemacoccus, hydrodictyon, leteyorrhina, micromonas, microsphaeridium, neochloris, nitsschia, nitzschia, oscillatoria, phaodactylum, red algae, scenedesmus, stigonema, spirulina, phaodactylum, schizacytrium, schizochlamydomonas, tetraselmis, triophyta; bacteria such as cyanobacteria, industrial waste, residues and by-products, for example residues, by-products and waste streams from vegetable oil production, residues and by-products from fruit juice production, residues from wine production, residues, by-products and waste streams from vegetable oil production; residues, by-products and waste from food production, for example brewery spent grain and yeast; residues and by-products from fruit and vegetable processing, for example fruit pulp;Residues, by-products and waste streams from coffee production, residues, by-products and waste streams from cocoa production, residues and by-products from sugar production, such as bagasse, molasses, vinasse, residues and by-products from fermentation processes, such as vinasse, beer spent grain, residues and waste streams from paper production, such as paper sludge, black liquor, green liquor, white liquor; digestate from aerobic and anaerobic digestion; primary and / or secondary sludge from wastewater treatment, leachate, clarifier sludge, paper waste, organic fraction of municipal solid waste, catering waste, slaughterhouse waste, municipal solid waste, pulp household and / or municipal solid waste, used and recycled cooking oil, fats, glycerol, plastics and polymers and combinations thereof.

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

[0071] In one embodiment of the present application, the carbonaceous material comprises lignin at a concentration of at most 60% of the ash-free dry weight of the carbonaceous material, such as at most 50%, at most 40%, at most 30% of the ash-free dry weight of the carbonaceous material.

[0072] In a preferred embodiment according to the present application, the carbonaceous material comprises a combination of lignocellulosic material and plastic material. In some embodiments, the plastic material constitutes at most 50% of the ash-free dry weight of the carbonaceous material, such as at most 40%, while in other applications of the present application, the plastic material can constitute at most 35 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt% or at most 15 wt% of the ash-free dry weight of the carbonaceous material.

[0073] The carbonaceous material according to the present application can be in solid form and / or liquid form or a combination thereof, and can be comprised in one or more feedstocks. Furthermore, the carbonaceous material can be received in various sizes and shapes.

[0074] In many embodiments according to the present application, the step of providing a feed mixture comprises a pre-treatment step prior to further processing.

[0075] In a preferred embodiment according to the present application, the pre-treatment step comprises a size reduction step for homogenization and / or mixing of the carbonaceous material. The specific size reduction depends on the properties of the specific feedstock, and can comprise one or more cutting, crushing, grinding, attriting and / or milling operations. Non-limiting examples of sizes of suitable size reduction techniques according to the present application include chipper, macerator, chopper, hammer mill, knife mill, shear mill, roller mill, disc mill, pin mill, ball mill, colloid mill, stone mill and combinations thereof.

[0076] In many embodiments according to the application, the carbonaceous material is reduced in size 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.

[0077] In preferred embodiments according to the application, the carbonaceous material is reduced in size 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.

[0078] Advantageously, the carbonaceous material has a bimodal particle size distribution, i.e. consisting of two particle size distributions each having an average particle size.

[0079] In preferred embodiments, the first particle size distribution of the carbonaceous material has an average particle size of less than 200 microns (0.1 mm) and a standard deviation of at most 50 microns, for example an average particle size of less than 100 microns and a standard deviation of at most 30 microns, and the second particle size distribution of the carbonaceous material has an average particle size of at most 1500 microns (1.5 mm) and a standard deviation of at most 500 microns (0.5 mm), for example an average particle size of at most 1200 microns and a standard deviation of at most 300 microns (0.3 mm).

[0080] The control of the maximum particle size, average particle size and particle size distribution of the carbonaceous material is important for the rheological properties of the feed mixture and for the mass and heat transfer within the particles during the conversion step.

[0081] According to many applications of the application, the pre-treatment of the step of providing the carbonaceous material can further comprise measures to remove contaminants from the carbonaceous material prior to processing. Such contaminant removal can include means to remove surface dirt, metallic and non-metallic contaminants by washing, magnetic separators, cyclone separators and combinations thereof. By removing such contaminants in the pre-treatment step, the wear of equipment and piping, such as by erosion, is reduced. Another effect can be that the downstream processing is easier, for example the product separation and purification is easier, the overall yield of the desired product is higher.

[0082] The pressure during conversion of the feed mixture is typically at least 20 bar, for example at least 40 bar; preferably, the pressure during conversion of the feed mixture is at least 60 bar, for example at least 70 bar; more preferably, the pressure during conversion of the feed mixture is at least 80 bar, for example at least 90 bar; even more preferably, the pressure during conversion of the feed mixture is at least 100 bar, for example at least 110 bar.

[0083] In many applications, the pressure during conversion of the feed mixture is kept below 250 bar, for example below 220 bar. Typically, the pressure during conversion of the feed mixture is kept below 180 bar, for example below 160 bar. In some embodiments, the pressure during conversion of the feed mixture is below 150 bar, for example below 140 bar. In further embodiments, the pressure during conversion of the feed mixture is kept below 130 bar, for example below 120 bar.

[0084] In many embodiments, the pressure during conversion is kept in the range from 20 bar below the critical pressure of the fluid mixture to 20 bar above the critical pressure of the fluid mixture.

[0085] Advantageously, the pressure during conversion of the feed mixture is kept above the boiling point pressure of the fluid mixture in order to keep the fluid mixture in a liquid or supercritical state.

[0086] Conversion of the feed mixture is typically carried out at a temperature of at least 300 °C, for example at a temperature of at least 310 °C. In some embodiments, conversion of the feed mixture is carried out at a temperature of at least 320 °C, for example at a temperature of at least 330 °C. In other embodiments, conversion of the feed mixture is carried out at a temperature of at least 340 °C, for example at a temperature of at least 350 °C. In further embodiments, conversion of the feed mixture is carried out at a temperature of at least 360 °C, for example at a temperature of at least 370 °C.

[0087] Preferred embodiments include conversion of the feed mixture at a temperature of below 410 °C, for example at a temperature of below 400 °C. Typically, conversion of the feed mixture is carried out at a temperature of below 390 °C, for example at a temperature of below 380 °C. In some embodiments, conversion of the feed mixture is carried out at a temperature of below 360 °C, for example at a temperature of below 350 °C.

[0088] The rate of heating to the conversion temperature is preferably at least 50 °C / min, for example at least 75 °C / min according to the present application; more preferably, the rate of heating to the conversion temperature is at least 100 °C / min, for example at least 150 °C / min.

[0089] The residence time at the conversion temperature and pressure is typically at least 2 minutes, for example at least 5 minutes. In some embodiments, the residence time at the conversion temperature and pressure is at least 7.5 minutes, for example at least 10 minutes. In other embodiments, the residence time at the conversion temperature and pressure is at least 12.5 minutes, for example at least 15 minutes. In further embodiments, the residence time at the conversion temperature and pressure is at least 20 minutes, for example at least 30 minutes.

[0090] The residence time at the conversion temperature and pressure is typically less than 180 minutes, for example less than 120 minutes. Typically the residence time at the conversion temperature and pressure is less than 90 minutes, for example less than 60 minutes. In some embodiments, more preferably the residence time at the conversion temperature and pressure is less than 45 minutes, for example less than 30 minutes. In other embodiments, the residence time at the conversion temperature and pressure is less than 15 minutes, for example less than 10 minutes.

[0091] In preferred embodiments, the process of the application is continuous.

[0092] In one aspect of the application, the feed mixture comprises one or more acids selected from formic acid, acetic acid, citric acid, sulfuric acid and combinations thereof.

[0093] In preferred embodiments, the one or more acids are at least partially produced by the process. According to embodiments of the application, the acid concentration can be from about 3 wt% to about 10 wt%.

[0094] The oil product produced according to the process of the application typically has a low acid number. In preferred embodiments, the low carbon intensity oil has an acid number of less than 10 mg KOH / g, for example less than 7 mg / g, preferably less than 5 mg KOH / g, for example less than 3 mg KOH / g.

[0095] The low carbon intensity oil produced according to the application can have a 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.

[0096] Figure 2 A schematic representation of another preferred embodiment of the process according to the application is shown, wherein the phenolic species are at least partially provided by recycling at least a portion of the crude oil produced by the process to the step of providing the feed mixture, and / or wherein the alcohol is at least partially recovered and recycled to the step of providing the feed mixture.

[0097] The converted feed mixture is cooled and depressurized to the desired separation conditions and separated into an oil phase, a gas phase, an alcohol / polyol / water phase and a solid phase.

[0098] A preferred embodiment of the separation system comprises a gravity separation at a pressure of 30 to 120 bar and a temperature of 130 to 400 °C, for example at a pressure of 30 to 60 bar and a temperature of 150 to 260 °C.

[0099] In an advantageous embodiment, at least part of the separated crude oil is recycled to the step of providing a feed mixture.

[0100] In another advantageous embodiment, the alcohol is at least partially recovered from the converted feed mixture after separation and recycled to the step of providing a feed mixture.

[0101] In a preferred embodiment, the recovery of alcohol comprises one or more flash steps.

[0102] In an advantageous embodiment, the recovery of alcohol comprises separation of alcohol from water by distillation techniques.

[0103] In another advantageous embodiment, the recovery of alcohol comprises separation of alcohol from water using one or more membrane techniques.

[0104] Figure 3 A schematic representation of a system according to an embodiment of the process of the application is shown, wherein the renewable phenolic substance is at least partially produced from one or more carbonaceous materials in a separate pre-conversion zone (1) prior to the step of providing a feed mixture to the conversion zone (2) of the process.

[0105] The one or more carbonaceous materials are at least partially converted to phenolic substance in the presence of phenolic substance and one or more alcohols and / or polyols in the pre-conversion zone (1) to form a phenolic substance-rich oil, gas phase, aqueous phase and / or solid phase products. After separation from other products produced in the pre-conversion zone (1), the phenolic substance-rich oil phase is at least partially introduced to the step of providing a feed mixture to the conversion zone (2) of the process according to advantageous embodiments as described above in Figure 1 and Figure 2 are further described in detail.

[0106] According to a preferred embodiment of the application, the conversion temperature of the one or more carbonaceous materials in the pre-conversion zone (1) can be in the range of 150°C to 240°C, for example 160°C to 225°C. Preferably, the conversion temperature of the one or more carbonaceous materials in the pre-conversion zone (1) is in the range of 175°C to 210°C, for example 180°C to 200°C.

[0107] The pressure used for conversion of the one or more carbonaceous materials in the pre-conversion zone (1) is typically in the range of 5 bar to 90 bar, for example 8 bar to 80 bar. Preferably, the pressure used for conversion of the one or more carbonaceous materials in the pre-conversion zone (1) is in the range of 10 bar to 70 bar, for example 15 bar to 60 bar. More preferably, the pressure used for conversion of the one or more carbonaceous materials in the pre-conversion zone (1) is in the range of 15 bar to 50 bar, for example 20 bar to 40 bar.

[0108] In a preferred embodiment, the concentration of phenolic species added to the feed mixture to the pre-reforming zone (1) is at least 2 wt% of the feed mixture. In other embodiments, the concentration of phenolic species can be at least 3 wt% of the feed mixture, at least 5 wt% of the feed mixture, at least 8 wt% of the feed mixture, at least 10 wt% of the feed mixture, at least 12 wt% of the feed mixture, at least 15 wt% of the feed mixture, such as at least 20 wt% of the feed mixture.

[0109] Advantageously, the concentration of phenol in the feed mixture fed to the pre-reforming zone (1) is at least 1 wt% of the feed mixture. In other embodiments, the concentration of phenol can be at least 2 wt% of the feed mixture, at least 3 wt% of the feed mixture, at least 5 wt% of the feed mixture, at least 8 wt% of the feed mixture, at least 10 wt% of the feed mixture, at least 12 wt% of the feed mixture, at least 15 wt% of the feed mixture, such as at least 20 wt% of the feed mixture.

[0110] Advantageously, as shown in Figure 1, at least a portion of the phenolic species added to the feed mixture to the pre-reforming zone (1) is included by recycling at least a portion of the oil product produced in the pre-reforming zone (1). Figure 3

[0111] In preferred embodiments, the concentration of alcohol and / or polyalcohol in the feed mixture to the pre-reforming zone (1) can be at least 5 wt% of the feed mixture, such as at least 10 wt% of the feed mixture; preferably, the concentration of alcohol and / or polyalcohol in the feed mixture to the pre-reforming zone (1) is at least 15 wt% of the feed mixture, 20 wt% of the feed mixture, 30 wt% of the feed mixture, 40 wt% of the feed mixture, 50 wt% of the feed mixture, 60 wt% of the feed mixture.

[0112] Advantageously, the one or more alcohol and / or polyalcohol added to the feed mixture to the pre-reforming zone (1) has a renewable source, such as produced from a biological source and / or renewable electricity, thereby reducing the carbon footprint of the products from the process.

[0113] An advantageous embodiment is where the one or more alcohol and / or polyalcohol added to the feed mixture to the pre-reforming zone (1) comprises methanol produced from a process gas produced by the conversion process in Zone 1 and Zone 2.

[0114] In some preferred embodiments, the conversion of the one or more carbonaceous materials in the pre-reforming zone (1) is conducted in the presence of one or more acid catalysts.

[0115] ​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 1-5 wt% of the feed mixture, e.g. 2-4 wt% of the feed mixture added to the pre-conversion zone (1).

[0116] In many applications of the present application, the residence time in the pre-conversion zone (1) can be 1-180 minutes, e.g. 2-120 minutes. Preferably, the residence time in the pre-conversion zone (1) is 5-60 minutes, e.g. 10-30 minutes.

[0117] The one or more carbonaceous materials provided to the pre-conversion zone (1) are typically chosen such that the carbonaceous material contains lignin, e.g. a lignocellulosic material.

[0118] In a preferred embodiment of the present application, the lignin content of the carbonaceous material added to the pre-conversion zone (1) of the present application is at least 10% of the ash-free dry weight of the carbonaceous material, e.g. at least 15% of the ash-free dry weight. In some applications, the lignin content of the carbonaceous material added to the pre-conversion zone (1) of the present application is at least 20% of the ash-free dry weight of the carbonaceous material, e.g. at least 25% of the ash-free dry weight.

[0119] The phenolic substance-enriched oil phase from the pre-conversion zone (1) is at least partially added to the step of providing a feed mixture in the conversion zone (2), wherein the carbonaceous material is further converted as described above in Figure 1 and Figure 2 .

[0120] Thus, the phenolic substances used in the process are produced from renewable energy (biocarbon) in the process, thereby reducing the overall carbon footprint. Furthermore, by producing the phenolic substances in a separate conversion step, it is obtained that the process conditions in the pre-conversion step can be optimized for the production of phenolic substances, and the conversion step can be optimized for the yield and quality of the produced oil. Thus, the overall efficacy of the process and the carbon intensity of the oil product is improved.

[0121] Figure 4 A schematic drawing illustrating a preferred embodiment according to the present application is shown, which comprises a system for producing an alcohol from a gas produced in a conversion process of a carbonaceous material, and at least partially recycling the produced alcohol to the step of providing a feed mixture to the conversion process.

[0122] A conversion process is performed on one or more carbonaceous materials in the presence of one or more alcohols, thereby producing a converted carbonaceous material comprising an oil, a process gas, a biochar and water, as shown in Figure 4 .

[0123] The conversion process is typically carried out under pressure, for example at a pressure of at least 10 bar, 20 bar, 30 bar, 40 bar, 50 bar, 60 bar, 80 bar or 100 bar.

[0124] In many embodiments, the pressure during conversion of the carbonaceous material is less than 400 bar, 350 bar, 300 bar, 250 bar, 200 bar, 180 bar or 160 bar.

[0125] The temperature during conversion of the carbonaceous material is typically at least 280°C, for example at least 300°C. Preferably, the temperature during conversion of the carbonaceous material is at least 325°C, for example at least 350°C. More preferably, the temperature during conversion of the carbonaceous material is at least 370°C, for example at least 385°C.

[0126] The process gas produced by the conversion process of the carbonaceous material comprises carbon oxides, for example carbon dioxide and carbon monoxide, as main compounds. The amount of process gas and the composition of the gas depend on the specific operating conditions and the carbonaceous material being converted, but typically also comprises Ci to C4 hydrocarbons, hydrogen and condensable liquids, such as water and alcohols.

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

[0128] Typically, the alcohol synthesis step according to the present application comprises at least one catalytic reaction step for reacting carbon oxides in the process gas with hydrogen in the presence of one or more metal catalysts.

[0129] The catalytic reaction step is typically carried out at a pressure of 30 bar to 150 bar and a temperature of 200°C to 450°C, for example at a pressure of 50 bar to 100 bar and a temperature of 200°C to 300°C.

[0130] Suitable metal catalysts according to the present application include copper zinc oxide catalysts, copper zinc chromium catalysts, copper mixed oxide catalysts and iron oxide catalysts on an alumina, zirconia support or zeolite support material. For activity and selectivity enhancement, other metal promoters and modifications can be added to the catalyst structure.

[0131] In one embodiment, the catalytic reaction step is provided as a fixed bed reaction system comprising one or more fixed beds comprising the metal catalyst.

[0132] Another configuration of the catalytic reaction step according to the present application is as a fluidized bed reactor system containing the metal catalyst fluidized by the gas feedstock.

[0133] The conversion per pass in the catalytic reaction step is usually relatively low, for example in the range of 10-40%, such as 20 to 30%. Therefore, an advantageous embodiment is to at least partly recycle the unreacted carbon oxides and hydrogen back into the catalytic reactor after intermediate separation of the alcohol and water produced, as shown in Figure 4 Thus, the overall conversion is increased.

[0134] Also as shown in Figure 4 The alcohol produced from the process gas is at least partly recycled to the conversion process. Thus, the overall oil yield and efficiency of the conversion process of the carbonaceous material and the resulting carbon footprint of the oil produced are reduced.

[0135] Figure 5 A schematic diagram showing an embodiment of a system similar to Figure 4 where the alcohol produced from the process gas is methanol and where the hydrogen added to the methanol synthesis is produced by electrolysis. As shown, oxygen is produced as a by-product in the electrolysis.

[0136] As shown, the methanol and water produced in the methanol synthesis can be separated from the unreacted gases by flashing and can be at least partly recycled and mixed with the process gas entering the methanol to achieve a higher overall conversion. The liquid fraction from the flash separation (3) can be further separated (4) into a methanol stream and a water stream by conventional means, for example by distillation. As shown, the separated water can be at least partly recycled to the electrolysis unit (2) and the methanol produced can be at least partly recycled to the conversion process, thereby increasing the overall process efficiency and reducing the chemical consumption and carbon footprint of the oil produced from the carbonaceous material.

[0137] Figure 6 A schematic diagram showing an advantageous embodiment of a system for producing methanol from the gas produced in the conversion process according to the present application is shown, which further comprises the use of electricity produced in an electrolysis unit (2) using renewable energy sources, for example wind, solar and / or geothermal energy, thereby further reducing the carbon footprint of the oil produced from the carbonaceous material.

[0138] Figure 6 Also shown in the figure is a synthesis gas preparation unit (1) prior to the methanol synthesis step (3). The synthesis gas preparation unit (1) according to the present application can comprise means for adjusting the H2 / CO molar ratio to a value of 1.8 to 2.2, for example to a H2 / CO molar ratio of 2, and means for removing impurities, for example sulfur and nitrogen compounds and other trace elements, to prevent poisoning of the catalyst used in the methanol synthesis reaction. The purification can include adsorption methods, for example adsorption to metal oxide adsorbents (for example ZnO, zeolites or activated carbon), chemical and physical absorption techniques and membrane separation.

[0139] A preferred embodiment of sulfur removal includes adsorption to a mixed oxide adsorbent comprising ZnO. The adsorbent can be regenerated by steam treatment or reaction with hydrogen.

[0140] Another preferred embodiment of sulfur removal includes pressure swing adsorption to an activated carbon adsorbent or a zeolite adsorbent.

[0141] A preferred embodiment of nitrogen removal includes pressure swing adsorption, for example to activated carbon and / or zeolite adsorbents.

[0142] Adjustment of the H2 / CO molar ratio can be performed by various methods, for example by thermochemical, electrochemical or biotransformation methods and combinations thereof.

[0143] In one embodiment, the means for adjusting the H2 / CO molar ratio includes adding hydrogen, preferably electrolytic hydrogen produced at least in part from renewable electricity, to the syngas production unit.

[0144] In another embodiment, the means for adjusting the H2 / CO molar ratio includes performing a reverse water gas shift reaction (RWGS) in which CO2 and H2 react to produce CO and water vapor (H2O). The method of adjusting the H2 / CO ratio by the RWGS reaction can be performed by conventional means, for example by reaction in a catalytic reactor. Catalysts suitable for the RWGS reaction include supported bimetallic catalysts incorporating two or more different transition metals such as Fe, Co, Ni, Cr, Zn, Co, Cu, Ce on a high surface area porous support material such as alumina, silica, zeolite or carbon support.

[0145] The reaction temperature depends on the specific catalyst and process configuration.

[0146] One embodiment of the present invention includes a syngas production unit in which a reverse water gas shift reaction is used of a process gas operating at a temperature of 300°C to 500°C, such as 300°C to 400°C, and a pressure of 10 bar to 50 bar, such as 30 bar to 40 bar.

[0147] Another preferred embodiment is where the syngas production unit includes an electrochemical reverse water gas shift (eRWGS) process in which a process gas containing carbon oxides (CO, CO2) from a carbonaceous material conversion process is converted to syngas in an electrochemical unit.

[0148] The electrochemical unit can contain one or more catalysts to facilitate the reverse gas reaction. Typically, the operating temperature of the electrochemical unit is at least 400°C, 500°C, 600°C, 700°C, 800°C, 900°C and even at least 1000°C.

[0149] In a preferred embodiment, heat from the synthesis gas production and / or methanol is transferred to the conversion process of the carbonaceous material.

[0150] Definitions

[0151] Low carbon intensity oil

[0152] The term low-carbon intensity oil in the context of the present application is used to describe hydrocarbons and oxygenated hydrocarbons. The low-carbon intensity oil according to the present application typically has a significant / substantial decarbonization effect due to the avoidance of greenhouse gas emissions. The decarbonization effect can be due to the use of renewable carbonaceous materials such as biomass and / or other renewable raw materials to produce the oil, for example resulting in an oil product having a low-carbon intensity and / or having a high content of bio-carbon content, resulting in a significant / substantial decarbonization when used to replace fossil oil and / or chemicals.

[0153] Phenolic substance

[0154] Phenolics in the context of the present application are used to describe chemical compounds consisting of one or more hydroxyl groups (-OH) directly bonded to an aromatic hydrocarbon group.

[0155] Alcohol

[0156] An alcohol is a molecule containing a hydroxyl functional group (-OH) bonded to a carbon atom of an alkyl or substituted alkyl group.

[0157] Polyol

[0158] A polyol herein is an organic compound containing multiple hydroxyl groups.

Claims

1. A method for producing low-carbon strength oil, comprising the following steps: a. Providing a feed mixture, the feed mixture comprising: i. Carbonaceous materials; ii. One or more alcohols and / or polyols with a concentration of at least 5% by weight; b. Convert the feed mixture at a pressure of 10 bar to 400 bar and a temperature of 280°C to 430°C; c. Recover low-carbon strength oil from the converted feed mixture; d. Recover at least a portion of the gas produced by the converted feed mixture, the converted feed mixture containing carbon oxides obtained from the conversion, and provide at least a portion of the recovered gas to an alcohol production facility for alcohol production using hydrogen in the alcohol synthesis process; e. Wherein, at least a portion of the alcohol-forming portion of the feed mixture is produced using gas recovered from the converted feed mixture in the alcohol production facility.

2. The method according to claim 1, wherein, The gas recovered from the converted feed mixture contains a combination of CO and CO2, wherein the concentration of CO is from 0.1% to 80% by volume, and wherein the concentration of CO2 is from 10% to 95% by volume.

3. The method according to claim 1 or 2, wherein, The pressure of the gas recovered from the converted feed mixture is 20 bar to 50 bar.

4. The method according to any one of claims 1, 2, or 3, wherein, The hydrogen added in the alcohol production facility includes hydrogen produced by electrolysis using low-carbon-intensity electricity generated from wind, solar, geothermal, hydro, nuclear, or a combination thereof.

5. The method according to any one of the preceding claims, wherein, The alcohol synthesis process is carried out at a temperature of 200°C to 300°C and a pressure of 50 bar to 100 bar.

6. The method according to claim 5, wherein, The alcohol synthesis includes one or more catalytic reaction steps, wherein the recovered gas reacts with hydrogen in the presence of one or more metal catalysts to produce one or more alcohols.

7. The method according to claim 6, wherein, The metal catalyst includes copper-zinc oxide catalysts, copper-zinc-chromium catalysts, or iron oxide catalysts.

8. The method according to any one of the preceding claims, wherein, The alcohol production facility also includes equipment for adjusting the H2 / CO molar ratio to the level required for methanol synthesis prior to the methanol synthesis step.

9. The method according to claim 8, wherein, The apparatus for adjusting the molar ratio of H2 / CO includes a device for performing a reverse gas shift reaction.

10. The method according to any one of the preceding claims, wherein, The alcohol production facility also includes equipment for removing impurities such as sulfur compounds and / or nitrogen compounds and / or other trace elements prior to the H2 / CO molar ratio adjustment step.

11. The method according to any one of the preceding claims, wherein, The alcohol produced is methanol.

12. The method according to any one of claims 1-4, wherein, The concentration of alcohols and / or polyols in the raw materials is at least 10% by weight.

13. The method according to claim 1, wherein, The feed mixture contains phenolic substances at a concentration of at least 3% by weight.

14. The method according to claim 13, wherein, The concentration of the phenolic substances in the feed mixture is at least 10% by weight.

15. The method according to any one of the preceding claims, wherein, The phenolic substances in the feed mixture have a renewable source.

16. The method according to any one of the preceding claims, wherein, The phenolic substances in the feed mixture are produced through the process described above.

17. The method according to any one of the preceding claims, wherein, The concentration of water in the feed mixture is less than 40% by weight.

18. The method according to any one of the preceding claims, wherein, The process is continuous.

19. The method according to any one of the preceding claims, wherein, The pressure during the conversion of the feed mixture is at least 50 bar.

20. The method according to any one of the preceding claims, wherein, The pressure during the conversion of the feed mixture is kept below 350 bar.

21. The method according to any one of the preceding claims, wherein, The pressure is maintained in the range of 20 bar below the critical pressure of the fluid mixture to 20 bar above the critical pressure of the fluid mixture.

22. The method according to any one of the preceding claims, wherein, The pressure during the conversion of the feed mixture is maintained above the boiling point pressure of the fluid mixture to keep the fluid mixture in a liquid or supercritical state.

23. The method according to any one of the preceding claims, wherein, The conversion of the feed mixture is carried out at a temperature of at least 300°C.

24. The method according to any one of the preceding claims, wherein, The conversion of the feed mixture is carried out at a temperature below 400°C.

25. The method according to any one of the preceding claims, wherein, The alcohol is recovered from the converted feed mixture and recycled to the step of providing the feed mixture.

26. The method according to any one of claims 15-16, wherein, The phenolic substances are produced in a separate conversion step.

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