Method and system for producing low carbon strength oil

Abstract

The present invention relates to a process for producing a low carbon strength oil wherein the process comprises the step of providing a feed mixture comprising: a carbonaceous material; a primary solvent comprising a phenolic substance at a concentration of at least 3% by weight and one or more alcohols and / or polyols at a concentration of at least 5% by weight; water at a concentration of 1 to 40 wt%; converting the feed mixture by treating the feed mixture at a pressure of 10 bar to 220 bar and a temperature of 280 DEG C to 410 DEG C for a predetermined time and recovering oil from the converted feed mixture.

Description

TECHNICAL FIELD

[0001] The present invention relates to the field of producing liquid fuels and chemicals with low carbon intensity. More specifically, the present invention relates to an improved process and system for producing low carbon intensity oil from carbonaceous materials. BACKGROUND

[0002] The carbon intensity of advanced liquid biofuels and chemicals is a key characteristic determining the amount of greenhouse gases avoided by replacing fossil fuels and chemicals, and thus contributes greatly to the value of such advanced liquid biofuels and chemicals. As a result, advanced liquid biofuels and chemicals with low carbon intensity produced at least in part from renewable carbonaceous materials, such as biomass and residual streams, have become a central focus 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 biological decomposition to produce liquids (e.g. ethanol) and gases (e.g. methane), and thermochemical conversion processes 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 and solvothermal liquefaction (HTL) and (STL). While the water content should be below a certain level for gasification and pyrolysis processes, HTL and STL processes allow for direct treatment of wet carbonaceous materials and save significant amounts of energy that would otherwise be required for dewatering / drying prior to treating these materials.

[0004] Despite these disclosures and many other studies of the hydrothermal and solvothermal pathways, the hydrothermal and solvothermal processes for advanced liquid biofuels are still in the demonstration stage and have not been commercialized. There are still several requirements for improvements to the technology, including improvements in yield, reductions in carbon intensity, improved product properties (e.g. more stable oil products), higher process efficiency (e.g. by using less harsh process conditions), easier to control processes, increased run factors (e.g. by reducing fouling and / or plugging), and reductions in carbonization in the process. SUMMARY

[0005] OBJECTIVE

[0006] It is therefore an object of the present invention to provide an improved process for producing oil from carbonaceous materials that is more efficient than the prior art, and thus can achieve a lower carbon intensity.

[0007] Depending on the choice of process parameters, the improvements can be one or more of the following: higher oil yield, less coke production, easier to control process, easier downstream product separation, less stringent operating conditions, which means cheaper / more cost effective installation and operation.

[0008] The improved process can further result in an improved product, meaning one or more of: an oil product with a higher heating value, a lower oxygen content, a lower corrosivity (lower acid number), a more stable and less reactive oil product, a more valuable by-product (meaning a more cost-effective process), a better resource utilization by increasing the process efficiency (which means an increased circularity), a lower heating energy consumption due to a lower heat capacity, which also means an advantage in process efficiency due to processing in an organic solvent.

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

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

[0011] i. at least partially renewable carbonaceous material;

[0012] ii. a predominantly organic solvent comprising a phenolic substance in a concentration of at least 3 wt.%, and

[0013] one or more alcohols and / or polyols in a concentration of at least 5 wt.%;

[0014] iii. water in a concentration of 1 wt.% to 40 wt.%, including moisture added together with the carbonaceous material;

[0015] b. converting the feed mixture by treating the feed mixture at a pressure of 10 bar to 220 bar and a temperature of 280 °C to 410 °C for a predetermined time;

[0016] c. recovering an oil from the converted feed mixture.

[0017] The low-carbon-intensity oil according to the present invention results in a significant decarbonization effect due to avoided greenhouse gas emissions when replacing fossil oil and / or chemicals. The low-carbon intensity can be obtained due to the efficient use of renewable carbonaceous material and / or efficient processing with high carbon efficiency (e.g. high oil yield and / or high circularity) and / or efficient processing with minimal parasitic losses (e.g. efficient heat recovery and / or low consumption and / or use of renewable resources, such as renewable electricity and / or solvents with a renewable origin).

[0018] In one embodiment of the invention, the produced oil has a carbon strength of less than that of oil produced with 30 g CO2 / MJ, for example, less than that of oil produced with 20 g CO2 / MJ. Preferably, the produced oil has a carbon strength of less than that of oil produced with 15 g CO2 / MJ, for example, less than that of oil produced with 10 g CO2 / MJ. In some advantageous embodiments of the invention, the carbon strength of the oil can even be carbon-neutral or carbon-negative, for example, having a carbon strength equal to or less than that of oil produced with 0 g CO2 / MJ, for example, having a carbon strength equal to or less than that of oil produced with -10 g CO2 / MJ.

[0019] The carbonaceous materials according to the invention are generally carbon-containing materials, such as organic matter. The carbonaceous materials used in the invention typically contain renewable carbonaceous materials, thereby reducing carbon intensity. Examples of renewable carbonaceous materials are biomass and / or residue materials. The carbonaceous materials according to the invention are further described in the detailed description.

[0020] In contrast to hydrothermal liquefaction methods where water is the primary solvent, the primary solvent in the feed mixture according to the present invention is an organic solvent comprising at least 3% by weight of an aromatic solvent in the form of phenolic substances and at least 5% by weight of one or more alcohols and / or polyols; that is, the present invention is a solvothermal method rather than a hydrothermal method. Additionally, the feed mixture contains water, for example, at a concentration of 1 to 40% by weight, including the final moisture contained in the carbonaceous material.

[0021] Solvent combinations can improve oil yield by providing improved solubility of biomass compounds (especially at low temperatures) and minimizing undesirable side reactions (e.g., reactions leading to repolymerization and char formation through the stabilization of reactive intermediate compounds). Therefore, an improved method for producing oil from carbonaceous materials is provided, which is more efficient and has lower carbon strength than existing techniques. This achieves the main objective of the invention. On a carbon basis, char formation can be less than 20%, and in most cases less than 15% or 10%, a result of process efficiency, meaning that the carbon present in the feedstock is primarily found in the resulting oil and gas.

[0022] The weight ratio of alcohol to water in the feed mixture according to the invention is typically maintained at 4:1 to 1:2, for example, 4:1 to 1:1. Advantageously, the weight ratio of alcohol to water in the feed mixture according to the invention is 2:3 to 3:2, including water contained in the carbonaceous feedstock.

[0023] In a preferred embodiment of the invention, water may constitute up to 30% by weight of the feed mixture, for example, up to 25% by weight of the feed mixture. In many advantageous embodiments, the water content of the feed mixture is up to 20% by weight of the feed mixture, for example, up to 15% by weight or up to 10% by weight.

[0024] In this context, phenolics are used to describe chemical compounds consisting of one or more hydroxyl groups (-OH) directly bonded to an aromatic hydrocarbon group.

[0025] In one embodiment of the invention, the step of providing the feed mixture may include adding a phenolic substance at a concentration of at least 5% by weight, for example, at least 7.5% by weight. Preferred embodiments of the invention include those in which the concentration of the phenolic substance in the feed mixture is at least 10% by weight, at least 12.5% ​​by weight, at least 15% by weight, and at least 20% by weight.

[0026] In many embodiments, the weight ratio of the phenolic substance to the ash-free dry weight of the carbonaceous material is at least 0.2, for example, at least 0.3; preferred embodiments include those where the weight ratio of the phenolic substance to the 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 a further preferred embodiment, the weight ratio of the phenolic substance to the ash-free dry weight of the carbonaceous material is at least 0.9, at least 1.0, or at least 1.5.

[0027] In one advantageous embodiment, the phenolic substances added to the feed mixture comprise phenols and / or alkylphenols and / or alkoxyphenols at a concentration of at least 2% by weight, for example, at least 4% by weight. In a further advantageous embodiment, the feed mixture comprises phenols and / or alkylphenols and / or alkoxyphenols at a concentration of at least 6% by weight, 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.

[0028] According to a particularly preferred embodiment of the invention, the phenolic substances added to the feed mixture are produced from renewable energy sources, thereby reducing the carbon footprint of oil.

[0029] In one advantageous embodiment, the phenolic substances in the feed mixture are produced at least partially by this method.

[0030] In one embodiment, the phenolic substances in the feed mixture are provided at least in part by recycling at least a portion of the oil produced by the method, such as an oil fraction rich in phenolic substances.

[0031] In a preferred embodiment, the weight ratio of the recycled oil produced by this method to the ashless dry weight of the carbonaceous material is at least 1.5, for example, at least 2.0; preferably, the ratio is at least 2.5, for example, at least 3.0. In other preferred embodiments, the weight ratio of the renewable oil to the ashless dry weight of the carbonaceous material is at least 4, for example, at least 5.

[0032] In one embodiment, the concentration of one or more alcohols and / or polyols is at least 10% by weight, for example, at least 15% by weight. In other preferred embodiments, the concentration of 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, or at least 40% by weight.

[0033] In one embodiment, the weight ratio of 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 weight ratio of 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.

[0034] In a preferred embodiment, one or more alcohols and / or polyols according to the present invention include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, glycerol, ethylene glycol, polyethylene glycol, propylene glycol, catechol, or combinations thereof.

[0035] In one embodiment of the present invention, one or more alcohols and / or polyols include methanol and / or ethanol.

[0036] In the presence of a primary organic solvent containing at least one aromatic compound in phenolic and alcoholic forms according to the invention, the conversion of carbonaceous materials represents a favorable combination of organic solvents for improving oil yield and quality. The solvent combinations of the present invention effectively dissolve biomass components, particularly at low temperatures, and act as efficient hydrogen donors for biomass conversion, providing increased solubility of oily products, favoring deoxygenation and hydrogenolysis reactions, and stabilizing reactive intermediates, for example, by forming acetals (such as ketones and aldehydes) with carbonyl groups and esters with carboxylic acids. Therefore, the solvent composition delays repolymerization reactions that could lead to high molecular weight products (commonly referred to as solid residues or char formation) and lower oil quality.

[0037] In an advantageous embodiment, one or more alcohols and / or polyols have a renewable source. Therefore, they contribute to, or further contribute to, reducing the carbon strength of the produced oil.

[0038] The conversion method according to the invention is advantageously carried out under moderately acidic conditions in many applications, i.e., the pH value measured in the aqueous phase after oil recovery from the product is kept below 7, for example, 2 to 6 or 3 to 5.

[0039] The conversion method according to the invention, carried out under acidic conditions, is conducive to stabilizing the reaction, for example, forming acetals with carbonyl groups and esters with carboxylic acids.

[0040] In some applications, the formation of acidic byproducts eliminates the need to introduce additional acidic compounds to maintain the pH within the desired range.

[0041] In a preferred embodiment, the pH during the conversion process is controlled by adding one or more carboxylic acids and / or salts and / or esters of carboxylic acids to the feed mixture at a concentration of 0.1 to 30% by weight (e.g., 0.5 to 10% by weight, e.g., 1.0 to 8.0% by weight).

[0042] In an advantageous embodiment, the added carboxylic acid includes formic acid, acetic acid, citric acid, levulinic acid, lactic acid and / or its salts and / or esters.

[0043] In another advantageous embodiment of the invention, sulfuric acid is added to the feed mixture to maintain the desired pH during the conversion process. In many applications, the added sulfuric acid can be from 0.1 wt% to 5 wt%.

[0044] In yet another advantageous embodiment of the invention, the pH value during the conversion step is controlled by at least partially recycling the acid recovered from the product.

[0045] The pressure during the feed mixture conversion is typically at least 20 bar, for example at least 40 bar; preferably, the pressure during the feed mixture conversion is at least 60 bar, for example at least 70 bar; more preferably, the pressure during the feed mixture conversion is at least 80 bar, for example at least 90 bar; and even more preferably, the pressure during the feed mixture conversion is at least 100 bar, for example at least 110 bar.

[0046] In many applications, the pressure during feed mixture conversion is maintained below 220 bar, for example, below 200 bar. Typically, the pressure during feed mixture conversion is maintained below 180 bar, for example, below 160 bar. In some embodiments, the pressure during feed mixture conversion is below 150 bar, for example, below 140 bar. In further embodiments, the pressure during feed mixture conversion is maintained below 130 bar, for example, below 120 bar.

[0047] In a preferred embodiment of the invention, the pressure is maintained in the range of about 30 bar to about 120 bar, for example, in the range of 40 to 120 bar or 50 to 100 bar.

[0048] In many embodiments, the pressure during the conversion process 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.

[0049] Advantageously, the pressure during the conversion of the feed mixture is maintained above the boiling point pressure of the fluid mixture in order to keep the fluid mixture in a liquid or supercritical state, for example, at a pressure of 80 to 180 bar or 100 to 160 bar.

[0050] The conversion of the feed mixture is typically carried out at a temperature of at least 300°C, for example, at least 310°C. In some embodiments, the conversion of the feed mixture is carried out at a temperature of at least 320°C, for example, at least 330°C. In other embodiments, the conversion of the feed mixture is carried out at a temperature of at least 340°C, such as at least 350°C. In a further embodiment, the conversion of the feed mixture is carried out at a temperature of at least 360°C, for example, at least 370°C.

[0051] Preferred embodiments include converting the feed mixture at temperatures below 400°C, for example, below 390°C. Typically, the conversion of the feed mixture is carried out at temperatures below 385°C, for example, below 380°C. In some embodiments, the conversion of the feed mixture is carried out at temperatures below 374°C, for example, below 370°C.

[0052] Advantageously, the pressure and temperature during the conversion of the feed mixture are maintained above the boiling point pressure of the fluid mixture in order to keep the fluid mixture in a liquid or supercritical state, for example at a pressure in the range of 330°C to 400°C, or at a pressure in the range of 350°C to 385°C or 360°C to 380°C.

[0053] By maintaining the temperature above a range with high conversion rates, deoxygenation and a resulting low total acid number (TAN) and high calorific value are obtained, thus yielding an improved product, thereby achieving the objective of this invention. Furthermore, it is believed that when the temperature is sufficiently high, the solvent acts as an alkylating agent for the oil. Therefore, oil yield and miscibility between the oil and petroleum fractions can be improved.

[0054] The process gases produced by the conversion of carbonaceous materials contain carbon oxides, such as carbon monoxide as the main compound. In an advantageous embodiment, the alcohols and / or polyols added to the feed mixture in the step of providing the feed mixture comprise one or more alcohols produced by the gases generated during the conversion of carbonaceous materials.

[0055] One aspect of the invention relates to the production of alcohols from process gases by reacting a gas with hydrogen in a catalytic reaction step. Typically, the catalytic reaction step is carried out at a pressure of 30 to 150 bar and a temperature of 200 to 450°C, for example, at a pressure of 50 to 100 bar and a temperature of 200 to 300°C.

[0056] Suitable catalysts for the catalytic reaction step of synthesizing alcohols from process gases via hydrogen reaction include copper-zinc oxide catalysts, copper-zinc-chromium catalysts, copper mixed oxide catalysts, iron oxide catalysts on alumina, zirconium oxide supports, or zeolite supports. To enhance activity and selectivity, other metal promoters and modifiers can be added to the catalyst structure.

[0057] In a preferred embodiment, the hydrogen used in the catalytic reaction step for producing alcohols from process gases comprises green hydrogen, such as green hydrogen produced by using renewable electricity electrolysis, for example, green hydrogen produced by wind, solar and / or geothermal energy.

[0058] In some preferred embodiments, the catalytic reaction step of producing alcohol from process gas further includes a syngas preparation step prior to the alcohol synthesis step to adjust the H2 to CO ratio to the level required for alcohol synthesis.

[0059] In an advantageous embodiment, the syngas preparation step includes a reverse water-gas shift step.

[0060] By producing alcohols at least partially from process gases containing carbon oxides from the conversion process, oil yield and overall process efficiency are improved. The carbon footprint and carbon intensity of the produced oil are further reduced by using green hydrogen, such as that generated from electrolysis using renewable electricity.

[0061] It should also be noted that producing alcohols from process gases produced according to the process conditions of the present invention avoids capital- and operating-cost-intensive carbon capture steps, and furthermore, the relatively high ratio of carbon monoxide to total carbon oxides results in lower hydrogen demand for alcohol synthesis. Typically, hydrogen consumption for alcohol synthesis is at least 20% lower than that for methanol production from carbon dioxide, for example, at least 30% lower. In some embodiments, hydrogen consumption for alcohol synthesis is at least 40% lower than that for methanol production from carbon dioxide.

[0062] One aspect of the invention includes producing phenolic substances from one or more carbonaceous materials in a separate conversion step under less demanding conditions, and providing the phenolic substances to the feed mixture at least partially in a step of providing the feed mixture.

[0063] Preferred embodiments include producing phenolic substances by converting lignocellulosic materials in a pre-conversion zone at a temperature of 150-240°C and a pressure of 5-90 bar in the presence of phenolic substances, one or more alcohols and / or polyols and one or more acid catalysts.

[0064] An advantageous embodiment of the invention is wherein the acid catalyst comprises sulfuric acid at a concentration of 1 to 5% by weight of the feed mixture added to the pre-conversion zone.

[0065] By producing phenolic substances added to this method from carbonaceous materials in the form of lignocellulose, the total carbon footprint and carbon intensity of the produced oil are reduced because the produced oil is generated from renewable energy (biocarbon).

[0066] Furthermore, by producing phenolic compounds in a separate conversion step, the process conditions in the pre-conversion step can be optimized for phenolic compound production, and the process conditions in the conversion step can be optimized for the yield and quality of the produced oil. Therefore, the overall effectiveness of the method is improved. Attached Figure Description

[0067] The invention will be described in more detail below with reference to the embodiments shown in the accompanying drawings, wherein:

[0068] Figure 1 A schematic diagram of the method according to the present invention for converting carbonaceous materials into oil, gaseous products rich in carbon oxides, aqueous phase and solid phase in the presence of alcohols / polyols and phenolic substances is shown.

[0069] Figure 2 A schematic diagram of another preferred embodiment of the method according to the invention is shown, wherein phenols are provided at least partially by recycling at least a portion of crude oil (e.g., a phenol-rich fraction produced by the method) to a step of providing a feed mixture, and / or wherein at least a portion of alcohols / polyols are recovered and recycled to a step of providing a feed mixture;

[0070] Figure 3 A schematic diagram of a system according to an embodiment of the method according to the invention is shown, wherein phenolic substances are at least partially produced in a separate conversion step prior to the step of providing the feed mixture;

[0071] Figure 4 A schematic diagram of a preferred embodiment of the invention is shown, which includes a system for producing alcohols from carbon oxide-rich gases produced during a conversion process, and for recycling at least partially the produced alcohols to a step of providing a feed mixture in the conversion step;

[0072] Figure 5 A schematic diagram of an advantageous embodiment of the invention is shown, which includes a system for producing methanol from a carbon oxide-rich gas produced in a conversion process using hydrogen generated by electrolysis and recycling at least a portion of the methanol to a feed mixture for the conversion process;

[0073] Figure 6A schematic diagram of another advantageous embodiment of a system for producing methanol from a gas produced by the conversion method according to the invention is shown, which also includes the use of low-carbon-intensity electricity, such as electricity generated by wind, solar, hydro, geothermal and / or nuclear power. Detailed Implementation

[0074] Figure 1 Preferred embodiments of a production method for converting carbonaceous materials such as biomass and waste into the following substances in the presence of alcohols / polyols and phenolic substances: 1. a low-carbon-strength oil product, 2. a gaseous product containing carbon oxides such as carbon monoxide and carbon dioxide, 3. a solid product, and 4. a mixture of alcohols / polyols and water.

[0075] The conversion method according to the invention is carried out by: processing the carbonaceous material for a predetermined time at a pressure of 10 bar to 220 bar and a temperature of 280°C to 410°C, in the presence of a main organic solvent containing at least 3% by weight of phenolic substances and at least 5% by weight of one or more alcohols and / or polyols, and at a concentration of 1% to 40% by weight of water (including water added together with the carbonaceous material), and separating the converted feed mixture to recover oil from the converted feed mixture.

[0076] The carbonaceous materials according to the invention are typically carbon-containing materials, such as organic matter like biomass and / or waste. Generally, the carbonaceous materials added to the feed mixture according to the invention are carbon-neutral or renewable, i.e., they release the same amount of CO2 upon combustion as they absorb during their growth. Therefore, at least partial processing of renewable carbonaceous materials helps to reduce the carbon intensity or carbon footprint of the oils produced according to the invention.

[0077] Non-limiting examples of carbonaceous materials according to the invention include lignin, cellulose, hemicellulose, lignocellulose, protein, starch, sugars, lipids, lignobiomass such as residues from forestry or papermaking operations, such as sawdust, hog fuel, sawdust, prunings, thinnings and waste, bark, leaves, park and garden waste and weeds, road excavation, wine lees, etc.; residues, by-products and waste streams from agricultural production, such as grass, straw, stalks, stalks, husks, corn cobs, nut shells, shells, kernels, leaves, pulp from, for example, wheat, barley, oats, rye, corn, rice, sunflower, rapeseed, flaxseed, nut shells, cotton, etc.; fruit bunch residues from palm oil production, oil manufacturer effluents (e.g., palm oil manufacturer effluents from palm oil production (POME)). This includes: pressed residues from vegetable oil production; manure and bedding from animal production; green / organic household waste; greenhouse waste; energy crops such as short-rotation logging, willow, jatropha, sorghum, switchgrass, and miscanthus; aquatic biomass such as water hyacinth, duckweed, azolla, and water fern; large algae / seaweeds such as red algae, green algae, and brown algae, including Sargassum, *Gnaphalium*, *caulerpaf*, Euglena, *Ucus*, *Gracelaria*, kelp, giant kelp, reef algae, *Porphyra*, and coccolithia; and microalgae such as *Ankis*. Trodemus), *Botrytis*, *Chlorella*, *Chlorella*, *Cryptophyta*, *Dictyophaerium*, Dinophyta, Chlorophyta, Cryptophyta, *Cryptococcus*, *Cyclotella*, *Dunaliella*, *Glaucophyta*, *Haemacoccus*, *Hydrocotyle*, *Neochlorophyta*, *Nitschia*, *Nitschia*, *Oscillatoria*, Phaeophyceae, *Phaeda* (ctylum), red algae, Scenedesmus, Spirulina, Scenedesmus, Schizacytrium, Schizophyta, Flat algae, Marine streptococcus, Tribophyta; bacteria such as cyanobacteria; industrial waste, residues and by-products, such as residues, by-products and waste streams from vegetable oil production, residues and by-products from fruit juice production, residues from wine production, residues, residues, by-products and waste streams from vegetable oil production; residues, by-products and waste from food production, such as brewery waste grains and yeast; residues and by-products from fruit and vegetable processing, such as fruit meat;Residues, byproducts, and waste streams from coffee production; residues, byproducts, and waste streams from cocoa production; residues and byproducts from sugar production, such as bagasse, molasses, and distiller's grains; residues and byproducts from fermentation processes, such as distiller's grains and brewer's grains; residues and waste streams from paper production, such as paper sludge, black liquor, green liquor, and white liquor; digestate from aerobic and anaerobic digestion; primary and / or secondary sludge from wastewater treatment, leachate, clarifier sludge, paper waste, organic components of municipal solid waste, food waste, slaughterhouse waste, municipal solid waste, pulping household and / or municipal solid waste, used and recycled cooking oils, fats, glycerol, plastics, and polymers, and combinations thereof.

[0078] In many applications of the present invention, the carbonaceous material includes lignin, the concentration of which is at least 5% of the ash-free dry weight of the carbonaceous material, for example at least 10%, at least 15%, or at least 20% of the ash-free dry weight of the carbonaceous material.

[0079] In one embodiment of the present invention, the carbonaceous material includes lignin, the concentration of which is at most 60% of the ash-free dry weight of the carbonaceous material, for example, at most 50%, at most 40%, or at most 30% of the ash-free dry weight of the carbonaceous material.

[0080] In a preferred embodiment of the invention, the carbonaceous material comprises a combination of lignocellulosic material and plastic material. In some embodiments, the plastic material constitutes up to 50% of the ash-free dry weight of the carbonaceous material, for example, up to 40%, while in other applications of the invention, the plastic material may constitute up to 35% by weight, up to 30% by weight, up to 25% by weight, up to 20% by weight, or up to 15% by weight of the ash-free dry weight of the carbonaceous material.

[0081] The carbonaceous material according to the invention can be in solid and / or liquid form or a combination thereof, and can be contained in one or more raw materials. Furthermore, the carbonaceous material can be received in various sizes and shapes.

[0082] In many embodiments of the invention, the step of providing the feed mixture includes a pretreatment step prior to further processing.

[0083] In a preferred embodiment of the invention, the pretreatment step includes a size reduction step for homogenizing and / or mixing the carbonaceous material. The specific size reduction depends on the characteristics of the raw material and may include one or more cutting, crushing, grinding, atriting, and / or milling operations. Non-limiting examples of suitable size reduction techniques according to the invention include slicers, macerators, shredders, hammer mills, knife mills, shear mills, roller mills, disc mills, pin mills, ball mills, colloid mills, stone mills, and combinations thereof.

[0084] In many embodiments of the invention, the size of the carbonaceous material is 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.

[0085] In a preferred embodiment of the invention, the size of the carbonaceous material is 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.

[0086] Advantageously, carbonaceous materials have a bimodal particle size distribution, that is, they consist of two particle size distributions, each with an average particle size.

[0087] In a preferred embodiment, the first particle size distribution of the carbonaceous material has an average particle size of less than 200 micrometers (0.2 mm) and a standard deviation of up to 50 micrometers, for example, an average particle size of less than 100 micrometers and a standard deviation of up to 30 micrometers, and the second particle size distribution of the carbonaceous material has an average particle size of up to 1500 micrometers (1.5 mm) and a standard deviation of up to 500 micrometers (0.5 mm), for example, an average particle size of up to 1200 micrometers and an average particle size distribution of up to 300 micrometers (0.3 mm).

[0088] Controlling the maximum particle size, average particle size, and particle size distribution of carbonaceous materials is important for the rheological properties of the feed mixture and for intraparticle mass and heat transfer during the conversion process.

[0089] According to many applications of the invention, the pretreatment step of providing carbonaceous materials may further include measures to remove contaminants from the carbonaceous materials prior to processing. Such contaminant removal may include means of removing surface dirt, metallic and non-metallic contaminants by washing, magnetic separators, eddy current separators, and combinations thereof. By removing such contaminants in the pretreatment step, wear on equipment and piping, such as through corrosion, is reduced. Another effect may be easier downstream processing, such as easier product separation and purification, and a higher overall yield of the desired product.

[0090] The advantage of the main organic solvent combination according to the invention is that it is easier to prepare pumpable feed mixtures of carbonaceous materials with high dry matter content, which may be due to better affinity for carbonaceous materials compared to water and / or less swelling of carbonaceous materials.

[0091] In many applications of the invention, the dried carbonaceous material constitutes at least 15% by weight of the feed mixture, for example, at least 17.5% by weight of the feed mixture. Preferably, the dried carbonaceous material constitutes at least 20% by weight of the feed mixture, for example, at least 22.5% by weight of the feed mixture or at least 25% by weight of the feed mixture.

[0092] The pressure during the feed mixture conversion is typically at least 20 bar, for example at least 40 bar; preferably, the pressure during the feed mixture conversion is at least 60 bar, for example at least 70 bar; more preferably, the pressure during the feed mixture conversion is at least 80 bar, for example at least 90 bar; and even more preferably, the pressure during the feed mixture conversion is at least 100 bar, for example at least 110 bar.

[0093] In many applications, the pressure during feed mixture conversion is maintained below 220 bar, for example, below 200 bar. Typically, the pressure during feed mixture conversion is maintained below 180 bar, for example, below 160 bar. In some embodiments, the pressure during feed mixture conversion is below 150 bar, for example, below 140 bar. In further embodiments, the pressure during feed mixture conversion is maintained below 130 bar, for example, below 120 bar.

[0094] In a preferred embodiment of the invention, the pressure is maintained in the range of about 30 bar to about 120 bar, for example, in the range of 40 to 120 bar or 50 to 100 bar.

[0095] In many embodiments, the pressure during the conversion process is maintained in the range of 20 bar below the critical pressure of the fluid mixture at the conversion temperature to 20 bar above the critical pressure of the fluid mixture at the conversion temperature.

[0096] Advantageously, the pressure during the conversion of the feed mixture is maintained above the boiling point pressure or critical pressure of the fluid mixture in order to keep the fluid mixture in a liquid or supercritical state, for example at a pressure of 80 to 180 bar or 100 to 160 bar.

[0097] This allows for a more efficient method with lower carbon strength because the addition of latent heat of vaporization of the evaporated fraction is avoided. Another advantage of maintaining the pressure above the boiling point or critical pressure of the fluid mixture is the reduced risk of cavitation and / or liquid hammering due to two-phase flow.

[0098] The conversion of the feed mixture is typically carried out at a temperature of at least 300°C, for example, at least 310°C. In some embodiments, the conversion of the feed mixture is carried out at a temperature of at least 320°C, for example, at least 330°C. In other embodiments, the conversion of the feed mixture is carried out at a temperature of at least 340°C, such as at least 350°C. In a further embodiment, the conversion of the feed mixture is carried out at a temperature of at least 360°C, for example, at least 370°C.

[0099] Preferred embodiments include converting the feed mixture at temperatures below 400°C, for example, below 390°C. Typically, the conversion of the feed mixture is carried out at temperatures below 385°C, for example, below 380°C. In some embodiments, the conversion of the feed mixture is carried out at temperatures below 374°C, for example, below 370°C.

[0100] Advantageously, the pressure and temperature during the conversion of the feed mixture are maintained above the boiling point pressure of the fluid mixture in order to keep the fluid mixture in a liquid or supercritical state, for example at a temperature of 330 to 400°C, such as 330 to 385°C or 350 to 380°C.

[0101] Another advantage of the method according to the invention is the significant reduction in the energy required for heating, since the heat capacity of organic solvents such as phenols and alcohols is approximately half that of water. This improves overall efficiency and carbon strength.

[0102] The predetermined residence time at the conversion temperature and pressure is typically at least 2 minutes, for example, at least 4 minutes. In some embodiments, the residence time at the conversion temperature and pressure is at least 6 minutes, for example, at least 7.5 minutes. In other embodiments, the residence time at the conversion temperature and pressure is at least 10 minutes, for example, at least 12.5 minutes. In a further embodiment, the residence time at the conversion temperature and pressure is at least 15 minutes, for example, at least 20 minutes.

[0103] The residence time at the conversion temperature and pressure is typically less than 120 minutes, for example, less than 60 minutes. Typically, the residence time at the conversion temperature and pressure is less than 30 minutes, for example, less than 25 minutes. In some embodiments, more preferably, the residence time at the conversion temperature and pressure is less than 20 minutes, for example, less than 15 minutes. In other embodiments, the residence time at the conversion temperature and pressure is less than 12.5 minutes, for example, less than 10 minutes.

[0104] Typically, the residence time is chosen to be long enough to achieve the desired conversion rate of the feed mixture, and short enough to minimize the repolymerization of the resulting oil. In an advantageous embodiment, the predetermined time or residence time at the conversion pressure and temperature is kept relatively short, for example, 4 to 20 minutes, or even 6 to 15 minutes.

[0105] In a preferred embodiment, the method of the present invention is continuous.

[0106] In one aspect of the invention, the feed mixture comprises one or more acids selected from formic acid, acetic acid, citric acid, lactic acid, levulinic acid, sulfuric acid, and combinations thereof.

[0107] In a preferred embodiment, one or more acids are produced at least partially by the method. According to embodiments of the invention, the acid concentration can be from about 0.1% by weight to about 10% by weight, for example, from 1% by weight to 5% by weight.

[0108] In contrast to hydrothermal liquefaction methods where water is the primary solvent, this invention uses a unique combination of organic solvents comprising aromatic solvents (phenolic substances) and alcohols and / or polyols as the primary solvent; that is, this invention is a solvothermal liquefaction method rather than a hydrothermal method. Water is further present in the feed mixture at a concentration of 1% to 40% by weight.

[0109] The solvent combination can improve the yield of the formed oil by providing improved dissolution of biomass compounds, particularly at low temperatures, in the first heating stage. The solvent combination further minimizes undesirable side reactions, such as those leading to repolymerization and charring reactions by stabilizing reactive intermediate compounds. Therefore, an improved method for producing oil from carbonaceous materials is provided, which is more efficient and has lower carbon strength than existing techniques. Thus, the object of the invention is achieved.

[0110] The method according to the invention can further result in improved oil products, such as oil products with a lower total acid number (TAN). In a preferred embodiment, the total acid number (TAN) of the low-carbon strength oil is less than 15 mg KOH / g, for example less than 10 mg / g, preferably less than 7 mg KOH / g, for example less than 5 mg KOH / g or less than 3 mg KOH / g.

[0111] The low-carbon strength oil produced according to the present invention may have a higher calorific value of at least 25 MJ / kg, such as at least 30 MJ / kg; preferably, the oil has a higher calorific value of at least 32 MJ / kg, such as at least 34 MJ / kg; more preferably, the oil has a higher calorific value of at least 34 MJ / kg, such as at least 36 MJ / kg; and even more preferably, the oil product has a higher calorific value of at least 38 MJ / kg, such as at least 40 MJ / kg.

[0112] Figure 2 A schematic diagram of another preferred embodiment of the method according to the invention is shown, wherein phenols are provided at least partially by recycling at least a portion of the low-carbon strength crude oil produced by the method to a step of providing a feed mixture (e.g., a phenol-rich fraction of low-carbon strength crude oil), and / or wherein alcohols are recovered at least partially and recycled to a step of providing a feed mixture.

[0113] The converted feed mixture is cooled and depressurized to the required separation conditions and separated into an oil phase, a gas phase, an alcohol / polyol / water phase, and a solid phase.

[0114] Preferred embodiments of the separation system include gravimetric separation at pressures of 30 to 100 bar and temperatures of 130°C to 400°C, for example, gravimetric separation at pressures of 50 to 10 bar and temperatures of 150°C to 400°C.

[0115] In an advantageous embodiment, the separated oil phase is at least partially recycled to the step of providing a feed mixture, such as a fraction rich in phenolic substances.

[0116] 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 the feed mixture.

[0117] In a preferred embodiment, alcohol recovery includes one or more flash evaporation steps.

[0118] In an advantageous embodiment, alcohol recovery includes separating or further separating the alcohol from water using distillation techniques.

[0119] In another advantageous embodiment, alcohol recovery includes separating or further separating the alcohol from water using one or more membrane technologies.

[0120] Figure 3 A schematic diagram of a system according to one embodiment of the method according to the invention is shown, wherein renewable phenolic substances are at least partially produced by one or more carbonaceous materials in a separate pre-conversion zone (1) prior to the step of providing the feed mixture to the conversion zone (2) of the method.

[0121] One or more carbonaceous materials are at least partially converted into phenolic substances in a pre-conversion zone (1) in the presence of phenolic substances and one or more alcohols and / or polyols to form an oil rich in phenolic substances, gaseous phase, aqueous phase, and / or solid phase products. After separation from other product phases produced in the pre-conversion zone (1), the phenolic-rich oil phase is at least partially introduced into the pre-conversion zone (1) according to an advantageous embodiment. Figure 1 and Figure 2 The method described in further detail in the conversion zone (2) provides the step of feeding the mixture.

[0122] According to a preferred embodiment of the present invention, the conversion temperature of one or more carbonaceous materials in the pre-conversion zone (1) can be from 150°C to 240°C, for example from 160°C to 225°C. Preferably, the conversion temperature of one or more carbonaceous materials in the pre-conversion zone (1) is from 175°C to 210°C, for example from 180°C to 200°C.

[0123] The pressure used to convert one or more carbonaceous materials in the pre-conversion zone (1) is typically from 5 bar to 90 bar, for example from 8 bar to 80 bar. Preferably, the pressure used to convert one or more carbonaceous materials in the pre-conversion zone (1) is from 10 bar to 70 bar, for example from 15 bar to 60 bar. More preferably, the pressure used to convert one or more carbonaceous materials in the pre-conversion zone (1) is from 15 bar to 50 bar, for example from 20 bar to 40 bar.

[0124] In a preferred embodiment, the concentration of phenolic substances added to the feed mixture in the pre-conversion zone (1) is at least 2% by weight of the feed mixture. In other embodiments, the concentration of phenolic substances may be at least 3% by weight, at least 5% by weight, at least 8% by weight, at least 10% by weight, at least 12% by weight, at least 15% by weight, or, for example, at least 20% by weight of the feed mixture.

[0125] Advantageously, the concentration of phenols in the feed mixture fed into the pre-conversion 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, at least 3% by weight, at least 5% by weight, at least 8% by weight, at least 10% by weight, at least 12% by weight, at least 15% by weight, or, for example, at least 20% by weight of the feed mixture.

[0126] Advantageously, such as Figure 3 As shown, at least a portion of the phenolic substances are provided to the feed mixture added to the preconversion zone (1) by recycling at least a portion of the oil products generated in the preconversion zone (1).

[0127] In a preferred embodiment, the concentration of alcohols and / or polyols in the feed mixture entering the preconversion zone (1) can be at least 5% by weight of the feed mixture, for example, at least 10% by weight of the feed mixture; preferably, the concentration of alcohols and / or polyols in the feed mixture entering the preconversion zone (1) is at least 15% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, or 60% by weight of the feed mixture.

[0128] Advantageously, one or more alcohols and / or polyols added to the feed mixture in the pre-conversion zone (1) have a renewable source, such as those produced from biological sources and / or renewable electricity, thereby reducing the carbon footprint of the products from the method.

[0129] An advantageous embodiment is wherein one or more alcohols and / or polyols added to the feed mixture in the preconversion zone (1) comprise methanol produced by process gases produced by conversion methods in the preconversion zone 1 and conversion zone 2.

[0130] In some preferred embodiments, the conversion of one or more carbonaceous materials in the preconversion zone (1) is carried out in the presence of one or more acid catalysts.

[0131] In an advantageous embodiment, the acid catalyst added to the feed mixture added to the preconversion zone comprises sulfuric acid at a concentration of 1% to 5% by weight of the feed mixture, for example, 2% to 4% by weight of the sulfuric acid added to the feed mixture added to the preconversion zone (1).

[0132] In many applications of the present invention, the residence time in the pre-conversion zone (1) can be from 1 minute to 180 minutes, for example from 2 minutes to 120 minutes. Preferably, the residence time in the pre-conversion zone (1) is from 5 minutes to 60 minutes, for example from 10 minutes to 30 minutes.

[0133] Typically, one or more carbonaceous materials are selected to be provided to the preconversion zone (1), such that the carbonaceous materials contain lignin, for example, lignocellulose materials.

[0134] In a preferred embodiment of the invention, the lignin content of the carbonaceous material added to the pre-conversion zone (1) of the invention is at least 10% of the ash-free dry weight of the carbonaceous material, for example, 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 invention is at least 20% of the ash-free dry weight of the carbonaceous material, for example, at least 25% of the ash-free dry weight.

[0135] The step of adding at least a portion of the phenol-rich oil phase from the pre-conversion zone (1) to the feed mixture provided in the conversion zone (2), wherein, as described above, Figure 1 and Figure 2 The carbonaceous materials described in the text are further transformed.

[0136] Therefore, the phenolic compounds used in this method are produced from renewable energy sources (biocarbon) used in the process, thereby reducing the overall carbon footprint. Furthermore, by producing phenolic compounds in a separate conversion step, the process conditions in the pre-conversion step can be optimized for phenolic compound production, and the conversion step can be optimized for the yield and quality of the produced oil. Thus, the overall efficiency of the method and the carbon intensity of the oil product are improved.

[0137] Figure 4 A schematic diagram of a preferred embodiment of the invention is shown, comprising a system for producing alcohols from gases produced during the conversion of carbonaceous materials and at least partially recycling the produced alcohols to the feed mixture for providing the conversion process.

[0138] A conversion process involving one or more carbonaceous materials in the presence of one or more alcohols produces a carbonaceous material comprising the conversion of oil, process gases, solids, and water, such as... Figure 4 As shown.

[0139] The conversion process is usually carried out under pressure, such as at least 10 bar, 20 bar, 30 bar, 40 bar, 50 bar, 60 bar, 80 bar and 100 bar.

[0140] In many embodiments, the pressure during the conversion of carbonaceous materials is below 400 bar, 350 bar, 300 bar, 250 bar, 200 bar, 180 bar, and 160 bar.

[0141] The temperature during the conversion process of carbonaceous materials is typically at least 280°C, for example, at least 300°C. Preferably, the temperature during the conversion process of carbonaceous materials is at least 325°C, for example, at least 350°C. More preferably, the temperature during the conversion process of carbonaceous materials is at least 370°C, for example, at least 385°C.

[0142] Process gases produced by the conversion of carbonaceous materials contain carbon oxides, such as carbon dioxide and carbon monoxide, as the main compounds. The amount and composition of the process gases depend on the specific operating conditions and the carbonaceous materials being converted, but typically also contain C1 to C4 hydrocarbons, hydrogen, and condensable liquids such as water and alcohols.

[0143] like Figure 4 As shown, an alcohol synthesis step is performed on process gas from a carbonaceous material conversion process, wherein the process gas is reacted with hydrogen to produce one or more alcohols, with water as a byproduct.

[0144] Typically, the alcohol synthesis step according to the invention includes at least one catalytic reaction step for reacting carbon oxides in a process gas with hydrogen in the presence of one or more metal catalysts.

[0145] Catalytic reaction steps are typically carried out at pressures of 30 to 150 bar and temperatures of 200 to 450 °C, for example, at pressures of 50 to 100 bar and temperatures of 200 to 300 °C.

[0146] Suitable metal catalysts according to the present invention include copper-zinc oxide catalysts, copper-zinc-chromium catalysts, copper mixed oxide catalysts, and iron oxide catalysts on alumina, zirconia, or zeolite supports. Other metal promoters and modifications may be added to the catalyst structure to enhance activity and selectivity.

[0147] In one embodiment, the catalytic reaction step is configured as a fixed-bed reaction system comprising one or more fixed beds containing a metal catalyst.

[0148] Another configuration of the catalytic reaction step according to the invention is as a fluidized bed reactor system containing a metal catalyst, in which a gaseous feedstock is fluidized.

[0149] The conversion rate in each step of the catalytic reaction is typically relatively low, for example, 10-40%, such as 20-30%. Therefore, an advantageous implementation is, as... Figure 4 As shown, after the alcohol and water produced in the intermediate separation, the unreacted carbon oxides and hydrogen are at least partially recycled back to the catalytic reactor. Therefore, the overall conversion rate increases.

[0150] Similarly, Figure 4 As shown, alcohols produced from process gases are at least partially recycled back to the conversion process. This reduces the overall oil yield and efficiency of the carbonaceous material conversion process, as well as the resulting carbon footprint of the oil.

[0151] Figure 5 It shows something similar to Figure 4 A schematic diagram of an implementation of the system is shown, wherein the alcohol produced from the process gas is methanol, and wherein hydrogen added to the methanol synthesis is generated by electrolysis. As shown, oxygen is produced as a byproduct of the electrolysis.

[0152] As shown in the figure, methanol and water produced in methanol synthesis can be separated from unreacted gases by flash evaporation and can be at least partially recycled and mixed with the process gas entering methanol to achieve a higher overall conversion rate. The liquid fraction from the flash separation (3) can be further separated (4) into methanol and water streams by conventional means such as distillation. As shown in the figure, the separated water can be at least partially recycled to the electrolysis unit (2), and the produced methanol can be at least partially recycled to the conversion process, thereby improving overall process efficiency and reducing the chemical consumption of oil and carbon footprint from carbonaceous materials.

[0153] Figure 6A schematic diagram of an advantageous embodiment of a system for producing methanol from a gas generated during a conversion process according to the invention is shown, which also includes the use of low-carbon-intensity electricity generated by renewable energy sources, such as wind, solar and / or geothermal energy, in the electrolysis unit (2), thereby further reducing the carbon footprint of the oil produced from carbonaceous materials.

[0154] Figure 6 The diagram also shows a syngas preparation unit (1) prior to the methanol synthesis step (3). The syngas preparation unit (1) according to the invention may include apparatus for adjusting the H2 / CO ratio to a range of 1.8 to 2.2, and apparatus for removing impurities such as sulfur and nitrogen compounds, as well as other trace elements, to prevent catalyst poisoning in the methanol synthesis reaction.

[0155] The H2 / CO ratio can be adjusted through various methods, such as thermochemical, electrochemical, or biotransformation methods and combinations thereof.

[0156] In one embodiment, the means for adjusting the H2 / CO ratio includes adding hydrogen to the syngas production unit, preferably low-carbon-intensity hydrogen, such as hydrogen produced by electrolysis using low-carbon-intensity electricity from wind, solar, hydro, geothermal, or nuclear power.

[0157] In another embodiment, adjusting the H2 / CO ratio involves performing a reverse water-gas shift reaction (RWGS), in which CO2 and H2 react to produce CO and water vapor (H2O). Adjusting the H2 / CO ratio via RWGS can be carried out by conventional means, such as by reacting in a catalytic reactor. Catalysts suitable for RWGS reactions include supported bimetallic catalysts incorporating two or more different transition metals such as Fe, Co, Ni, Cr, Zn, Co, Cu, and Ce on a high-surface-area porous support material such as alumina, silica, zeolite, or carbon support.

[0158] The reaction temperature depends on the specific catalyst and process configuration.

[0159] One embodiment of the present invention includes a syngas preparation unit, wherein a reverse water-gas shift reaction of a process gas is operated 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.

[0160] Another preferred embodiment is in which the syngas preparation unit includes an electrochemical reverse water-gas shift (eRWGS) process, wherein process gases containing carbon oxides (CO, CO2) from carbonaceous material conversion processes are converted into syngas in the electrochemical unit.

[0161] The electrochemical unit may 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.

[0162] In a preferred embodiment, heat from syngas preparation and / or methanol is transferred to the conversion process of carbonaceous materials.

[0163] definition

[0164] Low carbon intensity oil

[0165] In the context of this invention, the term low-carbon-strength oil is used to describe hydrocarbons and oxidized hydrocarbons. Low-carbon-strength oils according to the invention typically exhibit a significant / substantial decarbonization effect due to the avoidance of greenhouse gas emissions. This decarbonization effect may be due to the avoidance of emissions associated with the alternative use of carbonaceous feedstocks, the use of renewable carbonaceous materials such as biomass and / or other renewable raw materials to produce the oil, resulting in oil products with low carbon strength and / or a high biomass content, thereby leading to significant / substantial decarbonization when used as an alternative to petroleum and / or chemicals.

[0166] Phenolic substance

[0167] In the context of this invention, phenolic substances are used to describe chemical compounds consisting of one or more hydroxyl groups (-OH) directly bonded to an aromatic hydrocarbon group. Examples of phenolic substances according to the invention are phenols, alkylated phenols, alkoxyphenols, methoxyphenols, such as 2-methoxy-4-methylphenol, 2-methoxy-4-ethylphenol, 2,6-dimethoxyphenol, 2-methoxy-4-propylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 4-methyl-2,6-dimethoxyphenol, 4-allyl-2,6-dimethoxyphenol, m-methoxyphenol, o-methoxycresol, p-methoxycresol, vanillin, flavanols, phenoxypropanol, thymol, phenyl glycols such as catechol, guaiacol, alkoxyphenol, p-coumarol, coniferyl alcohol, sinapyl alcohol, and combinations thereof.

[0168] Alcohol

[0169] Alcohols are molecules containing a hydroxyl functional group (-OH) bonded to a carbon atom of an alkyl or substituted alkyl group.

[0170] Polyol

[0171] The polyols mentioned in this article are organic compounds containing multiple hydroxyl groups.

[0172] Carboxylic acid

[0173] In the context of this invention, carboxylic acids are hydrocarbon compounds having at least one carboxyl (-CO-OH) group.

[0174] Autogenous pressure

[0175] Self-generated pressure is defined as the highest pressure measured when the liquefaction reaction takes place in a fully enclosed container.

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. The main organic solvent, which contains at least 3% by weight of phenolic substances, and One or more alcohols and / or polyols with a concentration of at least 5% by weight; iii. Water with a concentration of 1% to 40% by weight, including water added together with the carbonaceous material; b. The feed mixture is converted by processing the feed mixture at a pressure of 10 bar to 220 bar and a temperature of 280°C to 410°C for a predetermined time; c. Recover oil from the converted feed mixture.

2. The method according to claim 1, wherein, The weight ratio of alcohol to water in the feed mixture is 4:1 to 1:

2.

3. The method according to any one of claims 1-2, wherein, After oil is recovered from the converted feed mixture, the pH of the aqueous phase is below 7.

4. The method according to any one of the preceding claims, wherein, The feed mixture contains one or more carboxylic acids or carboxylate salts at a concentration of 0.1% to 30% by weight.

5. The method according to claim 3, wherein, The added carboxylic acids include formic acid, acetic acid, citric acid, levulinic acid, lactic acid and / or their salts and / or esters.

6. The method according to any one of the preceding claims, wherein, The feed mixture contains or further contains sulfuric acid at a concentration of 1 to 5% by weight.

7. The method according to any one of the preceding claims, wherein, The concentration of alcohols and / or polyols in the feed mixture is at least 20% by weight.

8. The method according to any one of the preceding claims, wherein, The concentration of phenolic substances in the feed mixture is at least 5% by weight.

9. The method according to any one of the preceding claims, wherein, The concentration of phenolic substances in the feed mixture is at least 10% by weight.

10. The method according to any one of the preceding claims, wherein, The alcohol is methanol produced by adding hydrogen to a gas produced from the conversion of the feed mixture and reacting the gas and hydrogen in a catalytic process.

11. The method according to any one of the preceding claims, wherein, The weight ratio of the phenolic substance to the ash-free dry weight of the carbonaceous material is at least 0.

1.

12. The method according to any one of the preceding claims, wherein, The phenolic substances in the feed mixture have at least a partially renewable source, preferably a fully renewable source.

13. The method according to any one of the preceding claims, wherein, The phenolic substances in the feed mixture are produced at least partially through the process.

14. The method according to claims 12-13, wherein, At least a portion of the phenolic compounds are provided by recycling a portion of the oil produced by the process, such as the phenolic resin-rich fraction of the oil.

15. The method according to claim 14, wherein, The ratio of the weight of the oil to the ashless dry weight of the carbonaceous material is at least 1.

5.

16. The method according to any one of claims 11 to 15, wherein, The phenolic substances added to the feed mixture comprise phenols and / or alkylated phenols and / or alkoxyphenols and / or cresols at a concentration of at least 2% by weight.

17. The method according to any one of the preceding claims, wherein, The total acid number (TAN) is less than 15 mg KOH / g oil.

18. The method according to any one of the preceding claims, wherein, The higher calorific value of renewable oils is at least 25 MJ / kg.

19. The method according to any one of the preceding claims, wherein, The pressure during the conversion of the feed mixture is at least 60 bar.

20. The method according to any one of the preceding claims, wherein, The pressure during the conversion of the feed mixture is maintained below 150 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 is controlled to be less than 90% of the autogenous pressure at the dominant temperature.

23. The method according to any one of the preceding claims, wherein, When the conversion temperature is below the critical temperature of the fluid, the pressure during the conversion of the feed mixture is maintained above the boiling point pressure of the fluid mixture, and when the conversion temperature is above the critical pressure of the fluid mixture, the pressure is maintained above the critical pressure of the fluid mixture, so as to keep the fluid mixture in a liquid or supercritical state.

24. 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.

25. 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.

26. The method according to any one of the preceding claims, wherein, The conversion of the feed mixture is carried out by treatment at a pressure of 80 to 150 bar and a temperature of 330°C to 385°C.

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

28. The method according to any one of the preceding claims, wherein, The phenolic substances are produced in a separate conversion step.

29. The method according to claim 28, wherein, The phenolic substances are produced by converting lignocellulose materials in the presence of phenolic substances and one or more alcohols and acids at a conversion temperature of 160°C to 260°C and a conversion pressure of 5 bar to 90 bar.

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