Biorefining process

Abstract

This invention relates to a method for processing nitrogen- and / or ash-rich carbonaceous material into a first liquid product and a second bio-oil product rich in nitrogen- and / or ash compounds. The method comprises the following steps: fractionating the carbonaceous material into a liquid product rich in nitrogen- and / or ash compounds and a nitrogen- and / or ash-depleted residual carbonaceous material; converting the residual carbonaceous material in a thermochemical conversion process at a pressure of 10 bar to 400 bar and a temperature of 280°C to 500°C; and recovering bio-oil from the converted residual carbonaceous material.

Description

Technical Field

[0001] This invention relates to the production of advanced liquid biofuels and chemicals from carbonaceous residues, as well as other valuable byproducts. More specifically, this invention relates to an improved method for converting nitrogen- and / or ash-rich carbonaceous materials into a first liquid product rich in nitrogen- and / or ash compounds and a second product comprising bio-oil. Background Technology

[0002] Advanced liquid biofuels and biochemicals produced from carbonaceous materials such as biomass and residual streams have become a central focus for mitigating global climate change caused by greenhouse gas emissions in order to develop a sustainable circular economy.

[0003] Several candidate carbonaceous materials are rich in nitrogen and / or ash, which limits their use in processes for producing advanced liquid biofuels due to processing problems, efficiency losses, and / or more complex upgrades to finished fuels.

[0004] For example, carbonaceous materials with high nitrogen content often lead to a high emulsification tendency in bio-oils, resulting in more difficult product separation in many processes, such as the separation of water and ash from the bio-oil. Furthermore, although the nitrogen content of the produced bio-oil is generally lower compared to the nitrogen content in unconverted carbonaceous materials, the nitrogen content in bio-oils produced by this method is often higher when processing nitrogen-rich carbonaceous materials. The high nitrogen content in the produced bio-oil often limits its direct use (e.g., combustion applications or in marine engines) due to increased NOx emissions. Therefore, further downstream processing, such as hydroprocessing, is often required to reduce the nitrogen content of the bio-oil. It is further well known that nitrogen in crude oil is generally more difficult to remove than oxygen in such hydroprocessing processes and often requires more demanding conditions. Therefore, reducing the supplied nitrogen content is desirable to avoid such problems.

[0005] Some candidate carbonaceous materials may have or further have high ash content, which may lead to process challenges such as increased wear on equipment and piping due to corrosion, and / or may lead to increased scaling of process piping and equipment (such as heat exchangers) and / or more difficult product separation and purification, which may result in lower total product yield and / or reduced quality of bio-oil products and / or by-products, making such high-ash feedstock less attractive.

[0006] Therefore, it is desirable to reduce the nitrogen and / or ash content of carbonaceous materials containing large amounts of nitrogen and / or ash in order to provide improved and more efficient solutions for the production of bio-oils and other valuable products from such nitrogen- and ash-containing carbonaceous materials. Summary of the Invention

[0007] Purpose of the invention

[0008] Therefore, the object of the present invention is to provide an improved method for producing bio-oil from nitrogen- and / or ash-containing carbonaceous materials, which is more efficient and leads to improvements, such as resulting in lower carbon strength of the bio-oil and / or a higher operating factor and / or better resource utilization, i.e., higher recyclability.

[0009] Invention Description

[0010] According to one aspect of the invention, the object of the invention is achieved by a method for processing a nitrogen- and / or ash-rich carbonaceous material into a first liquid product and a second bio-oil product rich in nitrogen and / or ash compounds, the method comprising the steps of: fractionating the carbonaceous material into a liquid product rich in nitrogen and / or ash compounds and a nitrogen- and / or ash-depleted residual carbonaceous material; converting the residual carbonaceous material in a thermochemical conversion process at a pressure of 10 bar to 400 bar and a temperature of 280°C to 500°C; and recovering bio-oil from the converted carbonaceous material.

[0011] The carbonaceous materials according to the present invention are generally carbon-containing materials, such as organic matter, like biomass and / or waste.

[0012] In the context of this invention, nitrogen-rich and / or ash-rich carbonaceous materials are understood to be dry, ash-free carbonaceous materials with a nitrogen content greater than 0.8% by weight, and / or carbonaceous materials with an ash content greater than 3% by dry weight.

[0013] In some embodiments, the nitrogen content of the carbonaceous material can be greater than 1.0% by weight of dry ashless carbonaceous material, greater than 1.25% by weight of dry ashless carbonaceous material, greater than 1.5% by weight of dry ashless carbonaceous material, greater than 2.0% by weight of dry ashless carbonaceous material, or even greater than 3.0% by weight of dry ashless carbonaceous material, such as greater than 4% by weight of dry ashless carbonaceous material.

[0014] In some embodiments, the ash content of the carbonaceous material can be greater than 4% by weight of dry carbonaceous material, greater than 5% by weight of dry carbonaceous material, greater than 6% by weight of dry carbonaceous material, greater than 7% by weight of dry carbonaceous material, or even greater than 10% by weight of dry carbonaceous material, such as greater than 15% by weight of dry carbonaceous material, such as greater than 20% by weight of dry carbonaceous material.

[0015] Advantageously, the step of fractionating the carbonaceous material (step a) includes contacting the carbonaceous material with a solvent at a temperature of 40 to 180°C, for example, at a temperature of 40 to 90°C or 40 to 70°C.

[0016] In one embodiment, the solvent in the step of fractionating carbonaceous materials includes an alkaline solvent, and the pH is maintained in the range of 7 to 12 during fractionation (step a).

[0017] In many preferred embodiments, the solvent includes sodium hydroxide and / or potassium hydroxide.

[0018] In another embodiment, the solvent comprises an acidic solvent, and the pH during fractionation is maintained in the range of 2 to 6, for example, in the range of 4 to 6.

[0019] In many embodiments of the invention, the acidic solvent includes sulfuric acid, acetic acid, hydrochloric acid, citric acid, oxalic acid, or combinations thereof.

[0020] In some embodiments, the solvent includes or further includes organic solvents and / or pH buffer solutions, such as phosphate-buffered saline (PBS) or Tris-HCl buffer solution.

[0021] In some applications of the present invention, the fractionation step (a) includes or further includes an enzyme treatment step, wherein the carbonaceous material or the residual carbonaceous material from the first fractionation is enzyme-treated to further reduce the nitrogen and / or ash content.

[0022] In one embodiment, the enzyme used for enzyme treatment includes a protease.

[0023] Enzyme treatment is typically performed at temperatures between 40 and 70°C.

[0024] In some preferred applications, the fractionation step (a) includes a first fractionation using an alkaline solvent, followed by a second fractionation step, wherein the residual carbonaceous material from the alkaline fractionation step is treated with an acidic solvent.

[0025] In other applications, the fractionation step (a) includes a first fractionation using an acidic solvent, followed by a second fractionation step, wherein the residual carbonaceous material from the acidic fractionation step is treated with an alkaline solvent.

[0026] Typically, the first liquid product from the fractionation step, rich in nitrogen and / or ash compounds, undergoes one or more further steps, including filtration, centrifugation, precipitation, ion exchange, and / or chromatographic techniques or combinations thereof, for concentrating and / or purifying the liquid product.

[0027] In some embodiments, the liquid product from the fractionation step, rich in nitrogen and / or ash compounds, may be subjected to or further subjected to microfiltration and / or ultrafiltration steps to further concentrate and / or purify the product.

[0028] The conversion of the residual material from fractionation step (b) is typically carried out under pressure, for example at a pressure of at least 10 bar.

[0029] In many embodiments of the invention, the pressure in the conversion step (b) is maintained in the range of 20 bar below to 20 bar above the critical pressure of the fluid mixture.

[0030] Advantageously, the conversion step (b) is carried out at a pressure above the pressure boiling point of the fluid mixture to maintain the fluid mixture in a liquid or supercritical state. For clarity, this is accomplished by maintaining the pressure above the critical pressure of the fluid mixture while the temperature is above the critical temperature.

[0031] In many embodiments, the temperature in conversion step (b) is at least 300°C, for example at least 310°C. Preferably, the temperature in conversion step (b) is at least 320°C, for example at least 350°C.

[0032] In many preferred embodiments, the conversion temperature of the residual carbonaceous material in conversion step (b) is less than 450°C, for example, less than 400°C, less than 385°C, less than 370°C, or less than 360°C.

[0033] In a preferred embodiment, the conversion of the residual carbonaceous material in conversion step (b) is carried out in the presence of phenolic substances at a concentration of at least 2% by weight, for example, at least 3% by weight.

[0034] In another preferred embodiment, the conversion of the residual carbonaceous material in conversion step (b) is carried out in the presence of one or more alcohols and / or polyols at a concentration of at least 5% by weight.

[0035] According to a particularly preferred embodiment, the phenolic substances in the conversion step of the residual carbonaceous material are produced from renewable energy sources, thereby further reducing the carbon footprint of oil.

[0036] In an advantageous embodiment, the phenolic substances used in the conversion step (b) are produced through this process.

[0037] In one implementation, phenolic substances are provided by recycling a portion of the oil produced by the process.

[0038] In another embodiment, phenolic substances are produced by converting lignocellulosic material in a separate conversion step at a conversion temperature of 160 to 260°C and a conversion pressure of 5 to 90 bar, in the presence of phenolic substances and one or more alcohols and acids. In some embodiments, the lignocellulosic material may contain residual carbonaceous material from the fractionation step.

[0039] In one embodiment of the present invention, the alcohol includes methanol and / or ethanol.

[0040] The process gas produced by the conversion of residual carbonaceous material contains carbon oxides, such as carbon monoxide as the main compound. In an advantageous embodiment, one or more alcohols added to the conversion step (b) are generated from gases extracted from the converted residual carbonaceous material by reacting the 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.

[0041] In many applications of the invention, the nitrogen concentration in the residual carbonaceous material is reduced by at least 40%, for example, by at least 50%, relative to the nitrogen content in the initial carbonaceous material. Preferably, the nitrogen content in the residual carbonaceous material is reduced by at least 60%, for example, by at least 70%, relative to the nitrogen content in the initial carbonaceous material.

[0042] In many applications according to the invention, the nitrogen concentration in the residual carbonaceous material is reduced to less than 0.8% by weight of dry ashless carbonaceous material, for example less than 0.6% by weight of dry ashless carbonaceous material.

[0043] In a preferred embodiment, the nitrogen content in the bio-oil recovered from conversion step (b) is less than 0.5% by weight, for example, less than 0.3% by weight. Preferably, the nitrogen content in the bio-oil recovered from conversion step (b) is less than 0.2% by weight, for example, less than 0.1% by weight.

[0044] In some applications of the present invention, carbonaceous materials have a high ash content, which can lead to processing challenges in the conversion step (b), such as increased wear on equipment and pipes due to corrosion and / or increased scaling in heat exchangers, which can lead to reduced process efficiency or reduced onstream factor due to blockage and / or make it more difficult to separate the product from the conversion process, which can lead to reduced process efficiency and product quality in the conversion step (b).

[0045] Therefore, according to a preferred embodiment of the invention, the ash content of the residual carbonaceous material is reduced by at least 60% relative to the ash content of the initial carbonaceous material prior to conversion step (b), for example, by at least 70% relative to the ash content of the residual carbonaceous material. In some advantageous embodiments, the ash content of the residual carbonaceous material is reduced by at least 80% relative to the ash content in the initial carbonaceous material, for example, by at least 90% relative to the ash content in the initial carbonaceous material.

[0046] In many implementations, the carbonaceous material has a high concentration of phosphorus, which can lead to processing challenges, such as fouling of the heat exchanger and / or can result in more difficult separation in the conversion step (b).

[0047] Therefore, an advantageous embodiment of the invention is wherein the phosphorus content of the residual carbonaceous material is reduced by at least 50% relative to the phosphorus content of the initial carbonaceous material, for example, by at least 60% relative to the phosphorus content of the initial carbonaceous material. In other advantageous embodiments, the phosphorus content is reduced by at least 70%, for example, at least 80% relative to the phosphorus content of the initial carbonaceous material.

[0048] 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 low-carbon-intensity hydrogen, such as that produced by electrolysis using low-carbon-intensity electricity (e.g., low-carbon-intensity electricity generated from wind, solar, hydropower, geothermal, and / or nuclear power, or combinations thereof).

[0049] By producing phenolic substances added to the process from carbonaceous materials in the form of lignocellulose, the total carbon footprint and carbon intensity of the produced oil are reduced because the oil is produced from renewable energy sources (i.e., biocarbon energy).

[0050] 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 low-carbon strength oil. Therefore, the overall efficiency of this method can be improved. Attached Figure Description

[0051] The invention will be described in more detail below with reference to the embodiments shown in the accompanying drawings, wherein:

[0052] Figure 1 A schematic diagram of a process according to the present invention for converting a nitrogen- and / or ash-rich carbonaceous material into a first liquid product and a second bio-oil product rich in nitrogen and / or ash is shown. The method includes the steps of fractionating the carbonaceous material into a first liquid product and residual carbonaceous material, which is further converted in a conversion step to recover bio-oil from the conversion step.

[0053] Figure 2 A schematic diagram of another preferred embodiment of the process according to the invention is shown, wherein the fractionation step further includes an enzyme treatment step.

[0054] Figure 3An overview of the process according to the invention for converting residual carbonaceous material into bio-oil, gaseous products, alcohol / polyol / aqueous phase, and optionally biochar products (solid products) is shown.

[0055] Figure 4 A schematic diagram of another preferred embodiment of the conversion process of residual carbonaceous material according to the present invention is shown, wherein phenolic substances are provided at least partially by recycling crude oil produced by the conversion process at least partially to the step of providing the feed mixture, and / or wherein the recovered alcohols / polyols are at least partially recovered and recycled to the step of providing the feed mixture;

[0056] Figure 5 A schematic diagram of a system according to an embodiment of the process according to the invention is shown, wherein phenolic substances are at least partially produced in a separate conversion step prior to the step of converting residual carbonaceous materials;

[0057] Figure 6 A schematic diagram of a preferred embodiment of the invention is shown, comprising a system for producing alcohols from gases generated during the conversion of residual carbonaceous material, and for recycling at least partially the produced alcohols back to the conversion step of the residual carbonaceous material;

[0058] Figure 7 A schematic diagram of an advantageous embodiment according to the invention is shown, comprising a system for producing methanol from gases generated during a conversion process using hydrogen produced by electrolysis and for recycling the methanol at least partially to a feed mixture for the conversion process; and

[0059] Figure 8 A schematic diagram of another advantageous embodiment of a system according to the invention for producing methanol from gases produced during the conversion of residual carbonaceous materials is shown, the system further comprising using electricity produced from renewable electricity (e.g., electricity generated from wind, solar and / or geothermal energy). Detailed Implementation

[0060] Figure 1 A schematic diagram of a preferred two-stage process according to the invention is shown, wherein a nitrogen- and / or ash-rich carbonaceous material is first fractionated into a liquid product rich in nitrogen- and / or ash compounds and a nitrogen- and / or ash-depleted intermediate residual carbonaceous material, which is then further processed in a conversion step, thereby recovering low-carbon-strength biocrude oil from the converted residual carbonaceous material.

[0061] The carbonaceous materials according to the present invention are generally carbon-containing materials, such as organic matter, like biomass and / or waste.

[0062] Some carbonaceous materials according to the invention have high nitrogen and / or ash content. Although the nitrogen content of the produced oil is generally lower compared to the nitrogen content in unconverted carbonaceous materials, the nitrogen content of the oil produced by the process is generally high when carbonaceous materials with high nitrogen content are processed according to the invention. The high nitrogen content in the produced oil generally limits its direct use (e.g., marine engines or combustion applications), thus requiring further downstream processing, such as hydrotreating, to reduce the nitrogen content of the oil. It is also known that nitrogen in crude oil is generally more difficult to remove than oxygen in such hydrotreating methods and requires more demanding conditions. Furthermore, the presence of nitrogen compounds in the liquefaction products generally has a high emulsification tendency, which can lead to greater difficulty in separating, for example, water and ash from crude oil products. Therefore, it is desirable to reduce the nitrogen content provided in the feed mixture to avoid such problems.

[0063] Some carbonaceous materials according to the invention have or further have a high ash content, which may lead to process disadvantages, such as increased wear on equipment and pipelines due to corrosion and / or increased scaling (e.g., heat exchangers) and / or more difficult product separation and purification, which may result in lower overall product yield and / or reduced quality of oil products and / or by-products.

[0064] In many applications according to the invention, nitrogen- and / or ash-rich carbonaceous materials may first undergo a washing stage, in which contaminants such as adhering dirt are removed. Microbial contamination is also typically reduced during this washing stage.

[0065] Typically, the washing step may include a homogenization step, such as size reduction of carbonaceous materials, for example, one or more grinding, cutting, crushing, slicing and / or milling operations. Non-limiting examples of suitable size reduction techniques include slicers, impregnators, shredders, hammer mills, knife mills, shear mills, roller mills, disc mills, pin mills, ball mills, colloid mills, stone mills, and combinations thereof.

[0066] Size reduction increases the surface area of ​​carbonaceous materials, promoting the release of nitrogen compounds such as proteins during subsequent fractionation. Furthermore, size reduction affects the rheological properties of the residual carbonaceous material in the feed to the conversion step.

[0067] 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.

[0068] 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.

[0069] In some applications, the washed and optionally sized materials are further subjected to mechanical dehydration and / or disintegration operations, such as pressing and / or extrusion, to produce protein-rich liquid products and intermediate residual carbonaceous material products.

[0070] In many embodiments, the fractionation step includes contacting the carbonaceous material with a solvent at a temperature of 40-180°C.

[0071] Solvents are added to help dissolve nitrogen compounds such as proteins and / or ash compounds, and to homogenize or further homogenize the mixture for further extraction. The choice of solvent depends on the specific carbonaceous material being processed and the desired liquid product to be produced.

[0072] In many preferred applications, the solvent in the fractionation step comprises an alkaline solvent, and the pH is maintained in the range of 7 to 12, for example, in the range of 8 to 12 or in the range of 8 to 10. Alkaline solvents may advantageously include sodium hydroxide and / or potassium hydroxide in many applications.

[0073] In other applications, the solvent includes acidic solvents, and the pH during fractionation can be maintained in the range of 2 to 6, for example, in the range of 4 to 6. In many applications, acidic solvents may advantageously include sulfuric acid, acetic acid, hydrochloric acid, citric acid, oxalic acid, or combinations thereof. In some preferred embodiments, the acidic solvent may also include sodium acetate.

[0074] In a further preferred embodiment, the solvent includes or further includes an organic solvent and / or a pH buffer solution, such as a phosphate buffer solution or a Tris-HCl buffer solution.

[0075] In some implementations, the temperature is in the range of 40 to 90°C, such as in the range of 40 to 70°C.

[0076] The advantage of acid pretreatment according to the present invention is that it reduces the content of nitrogen and inorganic matter (ash) such as phosphorus.

[0077] A further preferred embodiment includes a first fractionation using an alkaline solvent and subsequent treatment of the separated residual carbonaceous material from the alkaline fractionation with an acidic solvent in a further fractionation step.

[0078] Another implementation includes a first fractionation step using an acidic solvent and a further fractionation step using an alkaline solvent to separate the residual carbonaceous material from the acidic fractionation.

[0079] By performing this stepwise extraction, certain nitrogen compounds, such as certain proteins, peptides, and enzymes, that may be insoluble or unstable under alkaline or acidic conditions can be extracted and preserved, or certain nitrogen compounds or certain proteins or peptides can be selectively extracted and separated as individual products, while maintaining the overall nitrogen and / or ash reduction target of the residual carbonaceous material used in the conversion step.

[0080] Depending on the specific carbonaceous material being processed and the desired first product, the nitrogen- and / or ash-rich liquid produced during the fractionation of the carbonaceous material can undergo further concentration and purification steps, such as filtration, centrifugation, precipitation, and / or chromatographic techniques.

[0081] In some embodiments, the liquid product from the fractionation step, rich in nitrogen and / or ash compounds, may be subjected to or further subjected to microfiltration and / or ultrafiltration steps to further concentrate and / or purify the product.

[0082] In one embodiment, a first liquid product comprising dissolved nitrogen compounds and / or inorganic (ash) compounds is used, or it is further processed into a product for stimulating plant growth, such as a nutrient product for plant growth.

[0083] In another embodiment, the first liquid product includes one or more protein-rich products that can be used or further processed into products for use in feed, food, food ingredients, nutrition, or pharmaceutical applications.

[0084] Depending on the specific carbonaceous material being processed, the fractionation step according to the invention can be designed to reduce the nitrogen content or ash content, or both nitrogen and ash content, of the residual carbonaceous material fed into the conversion step.

[0085] In many applications, the nitrogen concentration in the residual carbonaceous material can be reduced by at least 40% by weight relative to the nitrogen content in the initial carbonaceous material; for example, the nitrogen concentration in the residual carbonaceous material can be reduced by at least 50% by weight relative to the nitrogen content in the initial carbonaceous material. Preferably, the nitrogen content in the residual carbonaceous material is reduced by at least 60% by weight relative to the nitrogen content in the initial carbonaceous material; for example, the nitrogen content in the residual carbonaceous material is reduced by at least 70% by weight relative to the nitrogen content in the initial carbonaceous material.

[0086] In one embodiment, the nitrogen content of the residual carbonaceous material fed into the conversion step is reduced to less than 0.8% by weight of dry, ashless residual carbonaceous material, for example, less than 0.6% by weight of dry, ashless residual carbonaceous material. In other preferred embodiments, the nitrogen content of the carbonaceous material supplied to the feed mixture is controlled to be less than 0.4% by weight, less than 0.3% by weight, or less than 0.2% by weight of dry, ashless residual carbonaceous material.

[0087] In a preferred embodiment of the invention, the ash content of the residual carbonaceous material provided to the conversion step is controlled to be less than 10% by weight, for example less than 8% by weight, 6% by weight, or 4% by weight.

[0088] In several applications of this invention, the carbonaceous materials have a high concentration of phosphorus, which may lead to processing challenges, such as fouling of heat exchangers and / or potentially more difficult product separation during conversion steps.

[0089] Therefore, an advantageous embodiment of the invention is that the phosphorus content of the residual carbonaceous material in the conversion step is reduced by at least 50% by weight, for example, by at least 60% by weight. In other advantageous embodiments, the phosphorus content is reduced by at least 70% by weight, for example, at least 80% by weight.

[0090] Several benefits are obtained by fractionating the carbonaceous material according to the invention, such as more efficient overall utilization of the carbonaceous material, resulting in a more sustainable, circular, and efficient method, allowing the production of valuable nitrogen- and / or ash-rich byproducts, and causing the residual carbonaceous material, after depletion of nitrogen- and / or ash-rich compounds, to be more effectively converted into bio-oil in the conversion step, for example, with higher bio-oil yields, lower crude oil carbon strength, lower nitrogen content in low-carbon-strength crude oil, higher operating factors, and more efficient separation. Another benefit is that the residual carbonaceous material has improved rheological properties and is easier to pump at high dry matter content.

[0091] Figure 2 A schematic diagram of another preferred embodiment of the process according to the invention is shown, wherein, prior to further reducing the nitrogen and / or ash content of the residual carbonaceous material fed to the conversion step, Figure 1 The residual carbonaceous material produced in the above fractionation step is further subjected to an enzyme treatment step.

[0092] The enzyme treatment according to the invention can be carried out under relatively mild conditions, for example at a temperature in the range of 40-70°C, such as 50°C.

[0093] Suitable enzymes for the enzyme treatment include acidic proteases.

[0094] Figure 3 A preferred embodiment of the production process for converting residual carbonaceous material into bio-oil in conversion step (b) is shown.

[0095] The residual carbonaceous material, after nitrogen and / or ash compounds have been depleted, is typically pressurized to a conversion temperature in the range of 10 bar to 220 bar and heated to a conversion temperature of 280 to 500 °C. The converted feed mixture is then separated into phases that mainly contain bio-oil, gas, water, and solid / biochar products.

[0096] In an advantageous embodiment, the conversion step (b) is carried out in the presence of phenolic substances and / or one or more alcohols and / or polyols, as indicated by the dashed arrow in the step of providing the feed mixture.

[0097] In the presence of phenolic substances and / or alcohols according to the invention, the conversion of residual carbonaceous material improves the yield and quality of bio-oil by applying one or more solvents (acting as effective hydrogen donors for converting residual carbonaceous products into bio-oil), provides increased solubility of the oily products, facilitates deoxygenation and hydrogenolysis reactions, and stabilizes reactive intermediates, for example, by forming acetals with carbonyl groups (e.g., ketones and aldehydes) and esters with carboxylic acids. Therefore, according to the invention, the conversion of carbonaceous material in the presence of solvents delays repolymerization into high molecular weight products (commonly referred to as solid residues or biochar) and may result in a decrease in the yield and quality of bio-oil.

[0098] 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.

[0099] In many applications, the pressure during feed mixture conversion is maintained below 250 bar, for example, below 220 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.

[0100] 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.

[0101] Advantageously, the pressure of the feed mixture during conversion is kept above the boiling point pressure of the fluid mixture in order to keep the fluid mixture in a liquid or supercritical state.

[0102] 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, for example, 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.

[0103] Preferred embodiments include converting the feed mixture at temperatures below 450°C, for example, below 410°C. Typically, the conversion of the feed mixture is carried out at temperatures below 390°C, for example, below 380°C. In some embodiments, the conversion of the feed mixture is carried out at temperatures below 360°C, for example, below 350°C.

[0104] In a preferred embodiment, the conversion of residual carbonaceous material is carried out in the presence of phenolic substances at a concentration of at least 5% by weight, preferably at least 7.5% by weight. Preferred embodiments of the invention include those in which the concentration of phenolic substances in the feed mixture is at least 7.5% by weight, at least 10% by weight, at least 12.5% ​​by weight, at least 15% by weight, at least 15% by weight, and at least 20% by weight.

[0105] In many embodiments, the weight ratio of the phenolic substance to the ash-free dry weight of the residual 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 residual carbonaceous material is at least 0.4, at least 0.5, at least 0.6, at least 0.7, or for example, at least 0.8. In further preferred embodiments, the weight ratio of the phenolic substance to the ash-free dry weight of the residual carbonaceous material is at least 0.9, at least 1.0, and at least 1.5.

[0106] In an advantageous embodiment, the added phenolic substance comprises phenol 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 phenol 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, or at least 18% by weight, for example, at least 20% by weight.

[0107] In an advantageous embodiment, the phenolic substances in the residue conversion step are at least partially produced through this process.

[0108] In one embodiment, the phenolic substances in the feed mixture are at least partially provided by recycling at least a portion of the bio-oil produced by the process.

[0109] In an advantageous embodiment, phenolic substances are produced by converting lignocellulosic materials in the presence of phenolic substances and one or more alcohols and acids at a conversion temperature of 160°C-260°C and a conversion pressure of 5 bar-90 bar.

[0110] Advantageous embodiments of the invention include those in which the conversion of residual carbonaceous material is carried out in the presence of one or more alcohols and / or polyols at a concentration of at least 5% by weight. In one embodiment, the concentration of one or more alcohols 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.

[0111] 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.

[0112] In a preferred embodiment, the process according to the invention is continuous.

[0113] In one aspect of the invention, the feed mixture comprises one or more acids selected from formic acid, acetic acid, citric acid, sulfuric acid, and combinations thereof.

[0114] In a preferred embodiment, one or more acids are at least partially produced by this process. According to embodiments of the invention, the acid concentration can be from about 3% by weight to about 10% by weight.

[0115] Bio-oil products produced by the methods of this invention typically have a low carbon footprint, for example, bio-oils with a carbon intensity of less than 20 gCO2 / MJ, or even less than 15 gCO2 / MJ. In some embodiments, the carbon intensity is less than 12.5 gCO2 / MJ, for example, less than 10 gCO2 / MJ.

[0116] Bio-oil products produced according to the method of the present invention typically have low acid values. In a preferred embodiment, the acid value of the low-carbon strength oil is 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.

[0117] The low-carbon strength oil produced according to the present invention can 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 bio-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.

[0118] Figure 4 A schematic diagram of another preferred embodiment of the method according to the invention is shown, wherein phenolic substances are provided at least in part by recycling at least a portion of the crude oil produced by the method to the step of providing the feed mixture, for example, recycling a phenol-rich fraction, and / or wherein at least a portion of the alcohol is recovered and recycled to the step of providing the feed mixture in the conversion step (b).

[0119] 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.

[0120] In a preferred embodiment, the separation system includes gravimetric 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 130 to 260°C.

[0121] In an advantageous embodiment, the separated oil phase is at least partially recycled to the step of providing the feed mixture.

[0122] In another advantageous embodiment, the alcohol is recovered at least partially from the converted feed mixture after separation and recycled to the step of providing the feed mixture.

[0123] In a preferred embodiment, alcohol recovery includes one or more flash evaporation steps.

[0124] In an advantageous embodiment, alcohol recovery includes separating the alcohol from water using distillation techniques.

[0125] In another advantageous embodiment, alcohol recovery includes separating the alcohol from water using one or more membrane technologies.

[0126] Figure 5 A schematic diagram of a system according to an embodiment of the conversion process according to the invention is shown, wherein, prior to the step of providing the feed mixture to the conversion step (b) of the process, a renewable phenolic substance is at least partially produced from one or more carbonaceous materials in a separate pre-conversion step.

[0127] 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 phenolic-rich oil, gas, aqueous, and / or solid 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) as described above, according to an advantageous embodiment. Figure 3 and Figure 4 The process of providing the feed mixture is described in further detail in the conversion steps.

[0128] 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.

[0129] The conversion pressure of 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 conversion pressure of 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 conversion pressure of 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.

[0130] 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.

[0131] Advantageously, the concentration of phenol 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.

[0132] Advantageously, such as Figure 3As shown, at least a portion of the oil products produced in the preconversion zone (1) are recycled to include at least a portion of the phenolic substances added to the feed mixture of the preconversion zone (1).

[0133] 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.

[0134] Advantageously, one or more alcohols and / or polyols added to the feed mixture in the pre-conversion zone (1) have renewable sources, such as those produced from biological resources and / or renewable electricity, thereby reducing the carbon footprint of the products from the process.

[0135] An advantageous embodiment is wherein one or more alcohols and / or polyols added to the feed mixture in the pre-conversion zone (1) comprise methanol produced from carbon oxide-rich process gases produced by the conversion processes in zones 1 and 2.

[0136] 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 acidic catalysts.

[0137] 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 added to the preconversion zone (1), for example, 2% to 4% by weight of the feed mixture.

[0138] 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.

[0139] 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.

[0140] 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.

[0141] 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 3 and Figure 4 The carbonaceous materials described in the text are further transformed.

[0142] Therefore, the phenols used in this process are produced from renewable energy sources (biocarbon) generated during the process, thereby reducing the overall carbon footprint. Furthermore, by producing phenols in a separate conversion step, the process conditions in the pre-conversion step can be optimized for phenol production, and the conversion step can be optimized for the yield and quality of the produced oil. Thus, the overall efficiency of the process and the carbon intensity of the oil products are improved.

[0143] Figure 6 A schematic diagram of a preferred embodiment of the invention is shown, comprising a system for producing alcohols from gases generated during the conversion of residual carbonaceous materials and at least partially recycling the produced alcohols to the feed mixtures providing the conversion process.

[0144] A conversion process involving residual carbonaceous material from a fractionation process in the presence of one or more alcohols, resulting in a converted residual carbonaceous material comprising oil, process gas, and an aqueous phase, and optionally a solid / biochar phase, such as... Figure 6 As shown.

[0145] The conversion process of residual carbonaceous materials is advantageously carried out under pressure, for example, at pressures of at least 10 bar, 20 bar, 30 bar, 40 bar, 50 bar, 60 bar, 80 bar, or 100 bar.

[0146] In many embodiments, the pressure during the conversion of residual carbonaceous material is below 400 bar, 350 bar, 300 bar, 250 bar, 200 bar, 180 bar, or 160 bar.

[0147] The temperature during the conversion of residual carbonaceous materials is typically at least 280°C, for example, at least 300°C. Preferably, the temperature during the conversion of residual carbonaceous materials is at least 325°C, for example, at least 350°C. More preferably, the temperature during the conversion of residual carbonaceous materials is at least 370°C, for example, at least 385°C.

[0148] Process gases produced by the conversion of residual 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 residual carbonaceous materials being converted, but typically also contain C1 to C4 hydrocarbons, hydrogen, and condensables such as water and alcohols.

[0149] like Figure 6 As shown, a methanol synthesis step is performed on process gas from the conversion of residual carbonaceous materials, wherein the process gas is reacted with hydrogen to produce one or more types of methanol, with water as a byproduct.

[0150] Typically, the alcohol synthesis step according to the invention includes 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.

[0151] 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.

[0152] 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 modifiers may be added to the catalyst structure to enhance activity and selectivity.

[0153] 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.

[0154] Another configuration of the catalytic reaction step according to the invention is a fluidized bed reactor system comprising a metal catalyst fluidized from a gaseous feedstock.

[0155] 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 6 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 efficiency increases.

[0156] Similarly, Figure 6 As shown, alcohols generated from process gases are at least partially recycled to the conversion process of residual carbonaceous materials. This reduces the overall bio-oil yield and efficiency of the carbonaceous material conversion process, as well as the resulting carbon footprint of the bio-oil.

[0157] Figure 7 It shows something similar to Figure 6A 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.

[0158] 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 produced from residual carbonaceous materials and the carbon footprint.

[0159] Figure 8 A schematic diagram of an advantageous embodiment of a system for producing methanol from a gas produced during the conversion of residual carbonaceous material according to the invention is shown, which also includes electricity generated in an electrolysis unit (2) using renewable energy sources (e.g., wind, solar and / or geothermal energy), thereby further reducing the carbon footprint of the oil produced from the residual carbonaceous material.

[0160] Figure 8 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 means for adjusting the H2 / CO molar ratio to 1.8 to 2.2, and means for removing impurities such as sulfur and nitrogen compounds and other trace elements to prevent poisoning of the catalyst used in the methanol synthesis reaction.

[0161] The H2 / CO molar ratio can be adjusted by various methods, such as thermochemical, electrochemical, or biotransformation methods and combinations thereof.

[0162] In one embodiment, means for adjusting the H2 / CO ratio includes adding hydrogen, preferably electrolyzed hydrogen produced at least partially by low-carbon-intensity electricity (e.g., low-carbon-intensity electricity generated by wind power, solar power, hydropower, geothermal energy, nuclear power, or a combination thereof), to the syngas preparation unit.

[0163] In another embodiment, the means of 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 means of adjusting the H2 / CO ratio via the RWGS reaction can be carried out by conventional methods, such as by reacting in a catalytic reactor. Suitable catalysts for the RWGS reaction 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.

[0164] The reaction temperature depends on the specific catalyst and process configuration.

[0165] One embodiment of the present invention includes a syngas preparation unit in which a reverse water-gas shift reaction is used with 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.

[0166] 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 the residual carbonaceous material conversion process are converted into syngas in the electrochemical unit.

[0167] 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, or 900°C, or even at least 1000°C.

[0168] In a preferred embodiment, the heat from syngas preparation and / or methanol is transferred to the conversion process of the residual carbonaceous material.

[0169] definition

[0170] bio-oil

[0171] In the context of this invention, the term "oil" is used to describe hydrocarbons and oxidized hydrocarbons produced from biocarbonaceous materials (such as biomass and residue materials). Bio-oils according to the invention typically exhibit a significant 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 oils, resulting in oil products with low carbon strength and / or high biocarbon content, and thus leading to significant / substantial decarbonization when used to replace petroleum and / or chemicals.

[0172] Low-carbon strength oil

[0173] 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.

[0174] Phenolic substances

[0175] In the context of this invention, phenolics are used to describe chemical compounds consisting of one or more hydroxyl groups (-OH) directly bonded to an aromatic hydrocarbon group.

[0176] alcohol

[0177] Alcohols are molecules containing a hydroxyl functional group (-OH) bonded to a carbon atom of an alkyl or substituted alkyl group.

[0178] polyols

[0179] In the context of this invention, polyols are organic compounds containing multiple hydroxyl groups.

[0180] Nitrogen-rich carbonaceous materials

[0181] In the context of this invention, nitrogen-rich carbonaceous material is a carbonaceous material having a nitrogen content of at least 0.8% by weight of dry ashless carbonaceous material.

[0182] Ash-rich carbonaceous materials

[0183] In the context of this invention, ash-rich carbonaceous material is carbonaceous material having an ash content of at least 3% dry weight.

Claims

1. A method for processing nitrogen- and / or ash-rich carbonaceous materials into a first liquid product and a second bio-oil product rich in nitrogen- and / or ash compounds, comprising the following steps: a. Fractionating the carbonaceous material into a liquid product rich in nitrogen and / or ash compounds and a residual carbonaceous material depleted of nitrogen and / or ash; b. The residual carbonaceous material is converted in a thermochemical conversion process at a pressure of 10 bar to 400 bar and a temperature of 280°C to 500°C, and the bio-oil is recovered from the converted residual carbonaceous material.

2. The method according to claim 1, wherein, The nitrogen content of the nitrogen-rich and / or ash-rich carbonaceous material is at least 0.8% by weight.

3. The method according to any one of claims 1 or 2, wherein, The ash content of the nitrogen-rich and / or ash-rich carbonaceous material is at least 4% by weight.

4. The method according to any one of claims 1 to 3, wherein, The step of fractionating the carbonaceous material (step a) includes contacting the carbonaceous material with a solvent at a temperature of 40°C to 180°C.

5. The method according to any one of claims 1 to 4, wherein, The solvent used in the fractionation of carbonaceous materials includes an alkaline solvent, and the pH is maintained in the range of 7 to 12 during fractionation (step a).

6. The method according to claim 5, wherein, The solvent includes sodium hydroxide and / or potassium hydroxide.

7. The method according to any one of claims 1 to 4, wherein, The solvent contains an acidic solvent, and the pH is maintained in the range of 2 to 6 during the fractionation.

8. The method according to claim 7, wherein, The acidic solvent includes sulfuric acid, acetic acid, hydrochloric acid, citric acid, oxalic acid, or combinations thereof.

9. The method according to any one of claims 7 or 8, wherein, The acidic solvent also includes sodium acetate.

10. The method according to any one of claims 7 to 9, wherein, The pH during the fractionation is maintained in the range of 4 to 6.

11. The method according to any one of the preceding claims, wherein, The temperature is between 40°C and 90°C.

12. The method according to any one of the preceding claims, wherein, The solvent includes or further includes organic solvents and / or pH buffer solutions.

13. The method according to any one of the preceding claims, wherein, The fractionation step (a) includes or further includes enzymatic treatment of the carbonaceous material or the residual carbonaceous material from the first fractionation to further reduce the nitrogen and / or ash content.

14. The method according to claim 13, wherein, Enzymes used for enzyme treatment include proteases.

15. The method according to claim 13 or 14, wherein, The enzyme treatment temperature is between 40°C and 70°C.

16. The method according to any one of the preceding claims, wherein, The fractionation step (a) includes a first fractionation using an alkaline solvent, followed by a second fractionation step, wherein the residual carbonaceous material from the alkaline fractionation step is treated with an acidic solvent.

17. The method according to any one of the preceding claims, wherein, The fractionation step (a) includes a first fractionation using an acidic solvent, followed by a second fractionation step, wherein the residual carbonaceous material from the acidic fractionation step is treated with an alkaline solvent.

18. The method according to any one of the preceding claims, wherein, The first liquid product, rich in nitrogen and / or ash compounds, is further subjected to one or more steps, including filtration, centrifugation, precipitation, and / or chromatographic techniques or combinations thereof.

19. The method according to claim 18, wherein, The first product comprises one or more products rich in proteins or peptides.

20. The method according to any one of the preceding claims, wherein, The first product contains a nutrient product or its precursor for plant growth.

21. The method according to any one of the preceding claims, wherein, The conversion of the residual carbonaceous material in conversion step (b) is carried out in the presence of phenolic substances at a concentration of at least 3% by weight.

22. The method according to any one of the preceding claims, wherein, The conversion of the residual carbonaceous material in conversion step (b) is carried out in the presence of one or more alcohols and / or polyols at a concentration of at least 5% by weight.

23. The method according to any one of claims 21 or 22, wherein, The phenolic substances are provided by recycling at least a portion of the oil produced by the process.

24. The method according to claim 23, 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.

25. The method according to any one of the preceding claims, wherein, The one or more alcohols and / or polyols are generated at least in part from carbon-rich oxide gases recovered from the converted residual carbonaceous material.

26. The method according to any one of the preceding claims, wherein, The nitrogen concentration in the residual carbonaceous material is reduced by at least 40% relative to the nitrogen content in the initial carbonaceous material.

27. The method according to any one of the preceding claims, wherein, The nitrogen concentration in the residual carbonaceous material is reduced to less than 0.5% by weight in the dry, ashless carbonaceous material.

28. The method according to any one of the preceding claims, wherein, The phosphorus content of the residual carbonaceous material is reduced by at least 50% relative to the phosphorus content of the initial carbonaceous material.

29. The method according to any one of the preceding claims, wherein, The ash content of the residual carbonaceous material is reduced by at least 60% relative to the ash content of the initial carbonaceous material.

30. The method according to any one of the preceding claims, wherein, The nitrogen content in the bio-oil recovered from the process is less than 0.5% by weight.

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