WO2025021269A1

WO2025021269A1 - Sequential method for production of bio-oil

Info

Publication number: WO2025021269A1
Application number: PCT/DK2024/000183
Authority: WO
Inventors: Steen Brummerstedt Iversen
Original assignee: Green Liquids Aps
Current assignee: Green Liquids Aps
Priority date: 2023-07-25
Filing date: 2024-07-15
Publication date: 2025-01-30
Anticipated expiration: 2026-01-25
Also published as: DK181783B1; DK202300693A1

Abstract

The invention relates to a method for producing a low carbon intensity oil comprising the steps of providing a first feed mixture comprising: a carbonaceous material; one or more alcohols and/or polyols in a concentration of at least 5 % by weight; phenolics in a concentration of at least 3 % by weight: converting the first feed mixture at pressures in the range 5 bar to 90 bar and at temperatures in the range 160 °C to 240 °C; at least partly recovering a phenolic rich oil from the converted first feed mixture; Providing a second feed mixture comprising a carbonaceous material; One or more alcohols and/or polyols in a concentration of at least 5 % by weight; Phenolics in a concentration of at least 3 % by weight; Converting the second feed mixture at pressures of 10 to 220 bar; and at temperatures in the range 280 to 410 °C; recovering a low carbon intensity oil from the converted feed mixture from the second conversion step (e); where at least part of the phenolics forming part of the second feed mixture is recovered phenolics rich oil from the conversion of the first feed mixture (b).

Description

Sequential method for production of bio-oil

Field of the invention

The present invention relates to the area of producing oil from carbonaceous materials biomass and more specifically to the area of thermo-chemical conversion of biomass in the presence of alcohols and phenolics.

Background of the invention

Advanced liquid biofuels and chemicals produced from carbonaceous materials such as biomass and residue streams have become a central focus to mitigate global climate change arising from greenhouse gas emissions to develop sustainable circular economies.

Several processes to convert biomass into advanced biofuels are being applied and developed including biological decomposition to produce liquids (e.g. ethanol) and gases (e.g. methane), and thermochemical conversion processes to produce advanced liquid biofuels. The thermochemical processes use temperature and pressure to break biomass at the cellular level. Thermochemical conversion processes include gasification, pyrolysis & hydrothermal techniques.

The present invention is generally related to thermochemical conversion processes. Despite extensive studies of several promising pathways, there are still several requirements for improvements of the technologies, including improvement of yields, improvement of carbon intensity, improved product characteristics such as more stable oil products, higher process efficiency e.g., by using less severe process conditions, easier controllable processes, increased on-stream factor e.g. by reduced fouling and/or clogging, and reduced charring in processes. Objective of the invention

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

The improvements may, dependent on certain additional parameters, be one or more of the following: higher oil yield, less char production, easier controllable process, easier downstream product separation, less severe operating conditions meaning cheaper/more cost-effective operations and other additional beneficial effects.

The improved process may further lead to an Improved product meaning one or more of the following: a more stable oil product, e.g., less corrosive (lower acid number) due to fewer ketones and aldehyde groups in oil and carboxylic acids esterified, valuable by-products meaning a more cost-effective process, better resource utilization meaning increased circularity, lower energy consumption for heating due to lower heat capacity, which again means an advantage in the process due to processing in organic solvents.

Description of the invention

According to one aspect of the present invention the objective of the invention is achieved through a method for producing a low carbon intensity oil comprising the steps of providing a first feed mixture comprising: a carbonaceous material; one or more alcohols and/or polyols in a concentration of at least 5 % by weight; phenolics in a concentration of at least 3 % by weight: converting the first feed mixture at pressures in the range 5 bar to 90 bar and at temperatures in the range 160 °C to 240 °C; at least partly recovering a phenolic rich oil from the converted first feed mixture; Providing a second feed mixture comprising: A carbonaceous material; One or more alcohols and/or polyols in a concentration of at least 5 % by weight; Phenolics in a concentration of at least 3 % by weight; Converting the second feed mixture at pressures of 10 to 220 bar; and at temperatures in the range 280 to 410 °C; recovering a low carbon intensity oil from the converted feed mixture from the second conversion step (e); where at least part of the phenolics forming part of the second feed mixture is recovered phenolics rich oil from the conversion of the first feed mixture (b).

One preferred embodiment is where the phenolics provided to the first feed mixture at least partly comprises recycled recovered phenolic rich oil (c) from conversion of the first feed mixture.

Another preferred embodiment is where the phenolics (d.iii) provided to the second feed mixture (d) is at least partly obtained by recycling at least part of the low carbon intensity oil produced in the second conversion step to the step providing the second feed mixture.

In contrast to hydrothermal liquefaction processes water is not the main solvent, and the water of the first feed mixture and the second feed mixture provided is generally low. In an embodiment according to the present invention the water in the first feed mixture and the second feed is below to 40 % by weight such as below 30 % by weight. Advantageous embodiments include embodiments where the water content of the first and second feed mixture are less than 20 % by weight, less than 15 % by weight, and less than 10 % by weight of the first and second feed mixture.

In a preferred embodiment the first feed mixture further comprises an acid catalyst such as sulphuric acid in a concentration from about 1 % by weight to about 5 % by weight. An advantageous embodiment is where the concentration of alcohols and/or polyols in the first feed mixture (a) and/or second feed mixture (d) is at least 10 % by weight such as at least 30 % by weight.

One preferred embodiment is where the alcohols and/or polyols provided to the first and/or second feed mixture comprises methanol.

Advantageously the methanol provided to the first feed mixture and/or second feed mixture is at least partly produced by recovering at least part of the gas produced by conversion of the first and/or second feed mixture and at least partly providing it to an alcohol production facility for alcohol production by reacting the recovered gas with hydrogen in the presence of one or more metal catalyst(-s) to produce one or more alcohols.

Another advantageous embodiment is where the concentration of phenolics in the first feed mixture and/or second feed mixture is at least 10 % by weight.

In one embodiment the temperature for conversion of the first feed mixture (b) is in the range 180 to 200 °C.

In a preferred embodiment the conversion of the second feed mixture is at performed at temperatures of least 320 °C such at temperatures of at least 350 °C. Further, the conversion of the second feed mixture is at performed at temperatures below 400 °C such as at temperatures below 385 °C.

In many applications of the present invention the pressure is maintained in the range 20 bar below to 20 bar above the critical pressure of the fluid mixture.

Advantageously the pressure during the conversion of the feed mixture is maintained above the boiling point pressure of the fluid mixture to maintain the fluid mixture in a liquid or supercritical state. Hereby it is obtained that phase transition to a gas phase is avoided and hence no latent heat of evaporation is required to be added i.e. the process is more energy efficient and the carbon footprint and carbon intensity of the oil is reduced.

In a preferred alcohol is at recovered from the converted first feed mixture and/or second feed mixture and recycled to the step of providing the first feed mixture and/or second feed mixture.

A carbonaceous material according to the present invention is generally a carbon containing material e.g. organic matter such as biomass and/or waste materials. Carbonaceous materials according to the invention are further described in the detailed description.

In one embodiment of the present invention the carbon intensity of the oil produced is below 20 g CO2/MJ oil produced such as below 15 g CO2/MJ oil produced. Preferably the carbon intensity of the oil produced is below 12,5 g CO2/MJ oil produced such as below 10 g CO2/MJ oil produced.

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

The step of providing the feed mixture may in an embodiment of the present invention comprises adding phenolics in a concentration of at least 5 % to by weight, at least 7,5 % by weight. Preferred embodiments of the invention include embodiments, where the concentration of phenolics in the feed mixture is at least 10 %, at least 12,5 % by weight, at least 15 % by weight, at least 15 % by weight and at least 20 % by weight.

The ratio of the weight of phenolics to the dry ash free weight of the carbonaceous material is in many embodiments at least 0,2 such as at least 0,3; Preferred embodiments include embodiments where the ratio of the weight of phenolics to the dry ash free weight of the carbonaceous material at least 0,4, at least 0,5, at least 0,6, at least 0,7 such as at least 0,8. In further preferred embodiments the ratio of weight of phenolics to the dry ash free weight of carbonaceous material is at least 0,9, at least 1 ,0 and at least 1 ,5.

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

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

In an advantageous embodiment, the phenolics in the feed mixture is at least partly produced by the process.

In one embodiment, the phenolics in the feed mixture is at least partly provided by recycling at least part of the oil produced by the process.

In a preferred embodiment the weight of recycled oil produced by the process to the dry ash free weight of the carbonaceous material is at least 1 ,5 such as least 2,0; preferably the ratio of the weight of recycled oil to the dry ash free weight of the carbonaceous material is at least 2,5 such as at least 3,0. In other preferred embodiments the ratio of the weight of renewable oil to the dry ash free weight of the carbonaceous material is at least 4 such as least 5. In one embodiment, the concentration of the one or more alcohols and/or polyols is at least 10 % by weight such as at least 15 % by weight. In other preferred embodiments the concentration of the one or more alcohols and/or polyols is at least 20 % by weight, at least 25 % by weight, at least 30 % by weight, at least 35 % by weight, at least 40 % by weight.

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

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

The conversion of the carbonaceous material in the presence of the phenolics and alcohol(-s) according to the present invention improves the yield and quality of the oil applying an advantageous combination of solvents that are acting as efficient hydrogen donors for the conversion of the biomass, provide increased solubility of oily products, favor deoxygenation and hydrogenolysis reactions, and stabilize the reactive intermediate products e.g. by forming acetals with carbonyl groups such as ketones and aldehydes and esters with carboxylic acids. Thereby the solvent composition retards repolymerization reactions that may lead to high molecular weight products often called solid residues or char formation and lower oil quality.

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

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

It shall further be noted that applying that producing alcohol from the process gas produced according to process conditions according to the present invention the capital and operating cost intensive carbon capture step is avoided and further the relative high ratio of carbon mono oxide to total carbon oxides results in a lower hydrogen demand for the alcohol synthesis. Often the hydrogen consumption for the alcohol synthesis is at least 20 % lower than the hydrogen consumption for production of methanol from carbon dioxide such as at least 30 % lower. In some embodiments the hydrogen consumption for the alcohol synthesis is at least 40 % lower than the hydrogen consumption for production of methanol from carbon dioxide.

An aspect of the present invention comprises at producing phenolics from one or more carbonaceous material(-s) in a separate conversion step at less severe conditions, and at least partly providing said phenolics to the feed mixture in the step of providing the feed mixture.

A preferred embodiment comprises producing the phenolics by conversion of lignocellulosic material in a pre-conversion zone in the presence of phenolics, one or more alcohols and/or polyols and one or more acid catalyst at temperatures in the range 150 to 240 °C and at pressures from 5 to 90 bar. An advantageous embodiment of the present invention is where the acid catalyst comprises sulphuric acid in a concentration of 1 to 5 wt % by weight of feed mixture added to the pre-conversion zone.

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

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

Brief description of the drawings

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

FIG. 1 shows a schematic overview of a process for converting carbonaceous material in the presence of phenolics and alcohols/polyols into an oil, a gaseous product, a water phase and a solid phase;

FIG. 2 shows a schematic overview of a preferred embodiment of a process, where phenolics are at least partly provided by at least partly recycling the crude oil produced by the process to the step of providing the feed mixture, and/or where alcohol/polyol recovered is at least partly recovered and recycled to the step of providing the feed mixture;

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

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

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

FIG. 6 shows a schematic overview of another advantageous embodiment of a system for producing methanol from the gas produced in the conversion process according to the invention further comprising using electricity produced by renewable electricity such as electricity produced from wind, solar and/or geothermal energy.

Description of a preferred embodiment

FIG. 1 shows an embodiment of a production process for conversion of carbonaceous material such as biomass and waste to 1. an oil product, 2. a gaseous product comprising carbon oxides such as carbon mono oxides and carbon dioxide, 3. a solid product, and 4. a mixture of alcohol/polyol and water.

The conversion process according to the present invention is performed at a pressure in the range 10 bar to 220 bar and a temperature of 280 to 410 °C the presence of phenolics in a concentration of at least 3 % by weight and one or more alcohols and/or polyols in a concentration of at least 5 % by weight and separating the converted feed mixture into the individual products.

A carbonaceous material according to the present invention is generally a carbon containing material e.g. organic matter such as biomass and/or waste materials.

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

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

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

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

The carbonaceous material may according to the present invention be in a solid form and/or liquid form or a combination thereof, and may be contained in one or more feedstock. Further the carbonaceous material(-s) may be received in various sizes and shapes.

In many embodiments according to the present invention the step of providing the feed mixture include a pretreatment step prior to further processing.

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

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

In a preferred embodiment according to the present invention the carbonaceous material is sized reduced to an average particle size of less than 2 mm, 1 ,5 mm, 1 ,25 mm, 1 ,0 mm, 0,75 mm, 0,5 mm, 0,25 mm, 0,1 mm or 0,05 mm. Advantageously the carbonaceous material has a bimodal size distribution i.e. is comprised of two particle size distributions each having an average particle size.

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

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

The pretreatment of the step of providing the carbonaceous material may according to many applications of the present invention further comprise measures for removal of contaminants from the carbonaceous material prior to processing. Such contaminant removal may comprise means removal of surface dirt, metallic and non-metallic contaminants by washing, magnetic separators, Eddy current separators and combinations thereof. By the removal of such contaminants in the pretreatment step of wear of equipment and pipes such as by erosion is reduced. A further effect may be easier down-stream processing such as easier product separation, and purification, a higher overall yield of desired product. The pressure during the conversion of the feed mixture is often at least 20 bar such as at least 40 bar; preferably the pressure during the conversion of the feed mixture is at least 60 bar such as at least 70 bar; more preferably the pressure during the conversion of the feed mixture is at least 80 bar such as at least 90 bar; even more preferably the pressure during the conversion of the feed mixture is at least 100 bar such as at least 110 bar.

In many applications the pressure during the conversion of the feed mixture is maintained below 250 bar such as below 220 bar. Often the pressure during the conversion of the feed mixture is maintained below 180 bars such as below 160 bar. In some embodiments the pressure during the conversion of the feed mixture is below 150 bars such as below 140 bar. In further embodiments the pressure during the conversion of the feed mixture is maintained below 130 bar such as below 120 bar.

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

Advantageously the pressure during the conversion of the feed mixture is maintained above the boiling point pressure of the fluid mixture so as to maintain the fluid mixture in a liquid or supercritical state.

The conversion of the feed mixture is often performed at a temperature of at least 300 °C such as a temperature of at least 310 °C. In some embodiments the conversion of the feed mixture is performed at a temperature of at least 320 °C such as at a temperature of at least 330 °C. In other embodiments the conversion of the feed mixture is performed at a temperature of at least 340 °C such as a temperature of at least 350 °C. In further embodiments the conversion of the feed mixture is performed at a temperature of at least 360 °C such as a temperature of at least 370 °C. Preferred embodiments include converting the feed mixture at a temperature of less than 410 °C such as a temperature of less than 400 °C. Often the conversion of the feed mixture is performed at a temperature of less than 390 °C such as at a temperature of less than 380 °C. In some embodiments the conversion of the feed mixture is performed at a temperature of less than 360 °C such as at a temperature of less than 350 °C.

The heating rate to the conversion temperature is according to the invention preferably at least 50 °C/min such as at least 75 °C/min; more preferably the heating rate to the conversion temperature is at least 100 °C/min such as at least 150 °C/min.

The residence time at the conversion temperature and pressure is generally at least 2 minutes such as at least 5 minutes. In some embodiments the residence time at the conversion temperature and pressure is at least 7,5 minutes such as at least 10 minutes. In other embodiments the residence time at the conversion temperature and pressure is at least 12,5 minutes such as at least 15 minutes. In further embodiments the residence time at the conversion temperature and pressure is at least 20 minutes such as at least 30 minutes.

The residence time at the conversion temperature and pressure is generally less than 180 minutes such as less than 120 minutes. Often the residence time at the conversion temperature and pressure is below 90 minutes such as below 60 minutes. In some embodiments more preferably the residence time at the conversion temperature and pressure is below 45 minutes such as below 30 minutes. In other embodiments the residence time at the conversion temperature and pressure is below 15 minutes such as below 10 minutes. In a preferred embodiment the process according to the invention is continuous.

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

In a preferred embodiment the one or more acids are at least partly produced by the process. The acid concentration may according to embodiments of the invention be in the range from about 3 % by weight to about 10 % by weight.

The oil product produced according to a method of the invention generally has a low acid number. In a preferred embodiment the acid number of the low carbon intensity oil is below 10 mg KOH/g such as below 7 mg/g, preferably less 5 mg KOH/g such as less than 3 mg KOH/g.

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

FIG. 2 shows a schematic overview of another preferred embodiment of a process according to the invention, where phenolics are at least partly provided by at least partly recycling the crude oil produced by the process to the step of providing the feed mixture, and/or where alcohol is at least partly recovered and recycled to the step of providing the feed mixture. The converted feed mixture is cooled and depressurized to desired Separations conditions and separated into an oil phase, a gas phase, an alcohol/polyol/water phase and a solid phase.

A preferred embodiment of the separation system comprises a gravimetric separation at pressures of 30 to 120 bars and at temperatures of 130 to 400 °C such as at pressures of 30 to 60 bars and temperatures of 130 to 260 °C.

In an advantageous embodiment the separated oil phase is at least partly recycled to the step of providing the feed mixture.

In another advantageous embodiment alcohol is at least partly recovered from the converted feed mixture after separation and recycled to the step of providing the feed mixture.

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

In an advantageous embodiment the recovery of alcohol comprises separating alcohol from water by a distillation technique.

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

FIG. 3 shows a schematic drawing of a system of an embodiment of a process according to the invention, where renewable phenolics is at least partly produced from one or more carbonaceous material(-s) in a separate preconversion zone (1 ) prior to the step of providing the feed mixture to the conversion zone (2) of process. One or more carbonaceous material(-s) is/are at least partly converted to phenolics in a pre-conversion zone (1) in the presence of phenolics and one or more alcohol and/or polyol to form an oil rich in phenolics, a gas phase, a water phase and/or a solid phase product. After separation from other product phases produced in the pre-conversion zone (1 ), the phenolic rich oil phase is according to an advantageous embodiment at least partly introduced to the step of providing the feed mixture in the conversion zone (2) of the process as described in further details under FIG. 1 and FIG. 2 above.

The temperature for conversion of the one or more carbonaceous materials in the pre-conversion zone (1 ) may according to a preferred embodiment of the present invention be in the range from 150 °C to 240 °C such as in the range 160 °C to 225 °C. Preferably, the temperature for conversion of the one or more carbonaceous materials in the pre-conversion zone (1 ) is in the range 175 °C to 210 °C such as in the range 180 °C to 200 °C.

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

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

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

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

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

Advantageously, the one or more alcohols and/or polyols added to the feed mixture to the pre-conversion zone (1 ) has a renewable origin e.g., is produced from biogenic resources and/or renewable electricity, whereby the carbon footprint of the products from the process is reduced. An advantageous embodiment is where the one or more alcohols and/or polyols added to the feed mixture to the pre-conversion zone (1 ) comprises methanol produced from the process gas produced by the conversion process in zone 1 and 2.

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

In an advantageous embodiment, the acid catalyst added to the feed mixture added to the pre-conversion zone comprises sulphuric acid in a concentration of 1 to 5 % by weight of the feed mixture such as 2 to 4 % by weight of the feed mixture added to the pre-conversion zone (1 ).

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

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

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

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

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

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

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

The conversion process is typically performed under pressure such as at a pressure of at least 10 bar, 20 bar, 30 bar, 40 bar, 50 bar, 60 bar, 80 bar, or 100 bar. In many embodiments the pressure during the conversion of the carbonaceous material is below 400 bar, 350 bar, 300 bar, 250 bar, 200 bar, 180 bar, or 160 bar.

The temperature during the conversion process of the carbonaceous material is typically at least 280 °C such as at least 300 °C. Preferably, the temperature during the conversion process of the carbonaceous material is at least 325 °C such as at least 350 °C. More preferably the temperature during the conversion process of the carbonaceous material is at least 370 °C such as at least 385 °C.

The process gas produced by conversion process of the carbonaceous material(-s) comprises carbon oxides such carbon dioxide and carbon mono oxide as the main compounds. The amount of process gas and the composition of the gas depend on the specific operating conditions, and carbonaceous material(-s) being converted, but often further comprises Ci to C4 hydrocarbons, hydrogen, and condensable liquids, like water and alcohol.

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

Typically, the alcohol synthesis step according to the present invention involves at least one catalytic reaction step for reacting the carbon oxides in the process gas with hydrogen in the presence of one or more metal catalyst(- s). The catalytic reaction step is often performed at pressures in the range 30 to 150 bar, and temperatures in the range 200 to 450 °C such as pressures of 50 to 100 bar and temperatures in the range 200 to 300 °C.

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

In one embodiment, the catalytic reaction step is arranged as a fixed-bed reaction system comprising one or more fixed beds comprising the metal catalyst(-s).

Another configuration of the catalytic reaction step according to the present invention is as a fluidized-bed reactor system containing the metal catalyst(-s) fluidized by the gas feedstock.

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

As also shown in the FIG. 4 the alcohol produced from the process gas is at least partly recycled to the conversion process. Hereby, the overall oil yield and efficiency of the conversion process for carbonaceous material and the resulting carbon footprint of the oil produced is reduced. FIG. 5 shows a schematic overview of an embodiment of a system similar to FIG. 4, where the alcohol(-s) produced from the process gas is methanol, and where the hydrogen added to the methanol synthesis is produced by electrolysis. As seen from the figure oxygen is produced as a by-product in the electrolysis.

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

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

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

The adjustment of the molar H2/CO ratio may be performed through a variety of processes such as thermochemical, electrochemical or biological conversion processes and combinations thereof.

In one embodiment, the means for adjusting the molar Fb/CO-ratio include adding hydrogen preferably electrolytic hydrogen at least partly produced by renewable electricity to the syngas preparation unit.

In another embodiment, the means for adjusting the molar Fb/CO-ratio include performing a reverse water gas shift reaction (RWGS), where CO2 and H2 are reacted to produce CO and water vapor (H2O). The means for adjusting the Fb/CO-ratio by RWGS reaction may be performed by conventional means such as by reaction in a catalytic reactor. Suitable catalysts for the RWGS reaction include supported bimetallic catalysts combining two or more different transition metals such as Fe, Co, Ni, Cr, Zn, Co, Cu, Ce on a high surface area porous supporting material such as alumina, silica, zeolites or carbon supports.

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

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

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

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

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

DEFINITIONS

Low carbon intensity oil

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

Phenolics

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

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

A polyol in the current context is an organic compound containing multiple hydroxyl groups.

Claims

1. Method for producing a low carbon intensity oil comprising the steps of a. providing a first feed mixture comprising: i. a carbonaceous material; ii. one or more alcohols and/or polyols in a concentration of at least 5 % by weight; iii. phenolics in a concentration of at least 3 % by weight: b. converting the first feed mixture at pressures in the range 5 bar to 90 bar and at temperatures in the range 160 °C to 240 °C; c. at least partly recovering a phenolic rich oil from the converted first feed mixture; d. Providing a second feed mixture comprising i. A carbonaceous material; ii. One or more alcohols and/or polyols in a concentration of at least 5 % by weight; iii. Phenolics in a concentration of at least 3 % by weight; e. Converting the second feed mixture at pressures of 10 to 220 bar; and at temperatures in the range 280 to 410 °C; f. recovering a low carbon intensity oil from the converted feed mixture from the second conversion step (e); g. where at least part of the phenolics forming part of the second feed mixture is recovered phenolics rich oil from the conversion of the first feed mixture (b).

2. Method according to claim 1 , where the phenolics provided to in the first feed mixture at least partly comprises recycled recovered phenolic rich oil (c) from conversion of the first feed mixture.

3. Method according to claim 1 or 2, where the phenolics (d.iii) provided to the second feed mixture (d) is at least partly obtained by at least partly recycling part of the low carbon intensity oil produced in the second conversion step to the step providing the second feed mixture.

4. Method according to any of the claims 1 , 2 or 3, where the concentration of water in the first feed mixture (a) and the second feed mixture (d) is less than 40 % by weight.

5. Method according to any of the preceding claims, where the first feed mixture further comprises an acid catalyst.

6. Method according to claim 5, where the acid catalyst comprises sulphuric acid in a concentration from about 1 % by weight to about 5 % by weight.

7. Method according to any of the preceding claims, where the concentration of alcohols and/or polyols in the first feed mixture (a) and/or second feed mixture (d) is at least 10 % by weight.

8. Method according to any of the preceding claims, where the concentration of alcohols and/or polyols in the first feed mixture and/or second feed mixture is at least 30 % by weight.

9. Method according to any of the preceding claims, where the methanol provided to the first feed mixture and/or second feed mixture is at least partly produced by recovering at least part of the gas produced by conversion of the first and/or second feed mixture and at least partly providing it to an alcohol production facility for alcohol production by reacting the recovered gas with hydrogen in the presence of one or more metal catalyst(-s) to produce one or more alcohols.

10. Method according to any of the preceding claims, where the alcohols and/or polyols in the first and/or second feed mixture comprises methanol.

11. Method according to any of the preceding claims, where the concentration of phenolics in the first feed mixture and/or second feed mixture is at least 10 % by weight.

12. Method according to any of the preceding claims, where the temperature for conversion of the first feed mixture (b) is in the range 180 to 200 °C.

13. Method according to any of the preceding claims, where the conversion of the second feed mixture is at performed at temperatures of least 320 °C.

14. Method according to any of the preceding claims, where the conversion of the second feed mixture is at performed at temperatures of least 350 °C.

15. Method according to any of the preceding claims, where the conversion of the second feed mixture is at performed at temperatures below 400 °C.

16. Method according to any of the preceding claims, where the conversion of the second feed mixture is at performed at temperatures below 385 °C.

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

18. Method according to any of the preceding claims, where alcohol is recovered from the converted first feed mixture and/or second feed mixture and recycled to the step of providing the first feed mixture and/or second feed mixture.

19. Method according to any of the preceding clams where the carbon intensity of the oil produced is below 20 g CO2/MJ.