Solvolysis process for solid renewable feedstock

Abstract

The present disclosure relates to solvolysis of a substantially solid renewable feedstock (10) comprising forest industry residue(s). More in detail the disclosure relates to a process for converting substantially solid renewable feedstock (10) to renewable liquid product(s), wherein the process comprises feedstock conditioning (100); which comprises one or more of washing, mechanical dewatering (101), thermal drying (102) and pretreatment (103) in the presence of solvent (20) to obtain a feed mixture (30); subjecting the feed mixture (20) to solvolysis (200); fractionation (210); extraction (300) and optional upgrading of the obtained purified biocrude. The present disclosure further relates to the use of the obtained product(s).

Description

[0001] SOLVOLYSIS PROCESS FOR SOLID RENEWABLE FEEDSTOCK

[0002] FIELD OF THE DISCLOSURE

[0003] The present disclosure relates to the thermal liquefaction of a renewable feedstock, and more particularly to solvolysis of a substantially solid renewable feedstock chosen based on suitability for this technology. More in detail the disclosure relates to a process for converting substantially solid renewable feedstock to renewable liquid product(s), wherein the process comprises feedstock conditioning; which comprises one or more of washing, mechanical dewatering, thermal drying and pretreatment in the presence of solvent to obtain a feed mixture; subjecting the feed mixture to solvolysis; fractionation; extraction and optional upgrading of the obtained purified biocrude. The present disclosure further relates to the use of the obtained product(s).

[0004] BACKGROUND OF THE DISCLOSURE

[0005] Biomass is increasingly recognized as a valuable feedstock to be used as a sustainable alternative to petroleum for the production of biofuels and chemicals. Biocrude is the concentrated, synthetic bio-oil or biofuel substitute for petroleum crude oil, which is produced using thermochemical conversion of a wide range of biomass, such as algae, plant material, or organic waste. It is produced through various processes like pyrolysis, hydrothermal liquefaction, or other thermal conversion methods. The resulting crude-like substance is rich in hydrocarbons and can be refined into fuels similar to petroleum-based products, such as gasoline, diesel, or jet fuel. Biocrude is considered a renewable energy source and is part of efforts to reduce reliance on fossil fuels and lower carbon emissions.

[0006] Renewable energy sources represent the potential fuel alternatives to overcome the global energy crises in a sustainable and eco-friendly manner. In future, biofuels and biochemicals may replenish the conventional nonrenewable energy resources due to their renewability and several other advantages.

[0007] Biofuels and biochemicals are typically manufactured from feedstock originating from renewable sources, including oils and fats obtained from plants, animals, algal materials, and fish. One source is lignocellulosic biomass, which refers to plant biomass that is composed mainly of cellulose, hemicellulose, and lignin. Biofuels and biochemicals originating from lignocellulosic biomass can replace fossil fuels from an energy point of view. However, the conversion of especially solid renewable biomass into fuels and chemicals is challenging.

[0008] Converting biomass into renewable fuels and chemicals usually involves thermal treatment of the biomass and a promising technology is Hydrothermal Liquefaction (HTL). HTL is usually carried out with liquid water at temperatures between 320 °C and 400 °C. To keep the water in the liquid state or supercritical state very high operational pressures of 200 bar or above are needed.

[0009] Despite the ongoing research and development in the processing of feedstocks and manufacture of fuels and chemicals, there is still a need to provide an improved process for converting biomass, particularly substantially solid renewable feedstock, to valuable chemicals and hydrocarbons suitable as fuels or fuel blending components.

[0010] BRIEF DESCRIPTION OF THE DISCLOSURE

[0011] An object of the present disclosure is to provide a conversion process for a substantially solid renewable feedstock comprising plant-based forest industry residue(s) to valuable renewable products or components.

[0012] The disclosure is based on the idea of introducing a substantially solid renewable feedstock comprising forest industry residue(s) to a process according to the disclosure, wherein the substantially solid renewable feedstock is subjected to feedstock conditioning comprising thermal drying during pretreatment in the presence of solvent, and mechanical dewatering and / or an additional thermal drying, before subjecting the obtained feed mixture to solvolysis, fractionation, extraction and optional upgrading.

[0013] The object of the disclosure is achieved by the method and use of the obtained product(s) as characterized by what is stated in the independent claims. Some embodiments of the disclosure are disclosed in the dependent claims. An advantage of process of the disclosure is that the challenge of feeding solid woody particles into pressurized space is overcome by using solvolysis at low pressure.

[0014] Another advantage of the process of disclosure is that as the final drying will be done in the pretreatment section comprising thermal drying, the water content after mechanical dewatering and / or a first additional thermal drying can be left higher, and the capital cost can be minimized.

[0015] Typically, a belt dryer is used for the first additional thermal drying, if used before the pretreatment. An advantage of the belt dryer is that it enables use of waste heat for example in the form of hot water.

[0016] A further advantage of the process of the disclosure is that the biocrude obtained from the solvolysis process according to the disclosure is more easily pumped; stored; fed to further processes; and more compatible to chemical modification, processing, or extraction as compared to biomass. This especially true after the extraction of the process of the disclosure or after extraction and the optional stabilisation of the process of the disclosure.

[0017] Recirculating an oil fraction obtained by the process of the disclosure, typically at least a light fraction having a molecular weight between 100 g / mol and 250 g / mol obtained after solvolysis and fractionation of the obtained biocrude, as solvent in the solvolysis increases the oil yield, and helps avoiding formation of coke and undesired polymerization reactions. Further, the amount of oxygen in the oil products decreases. By adjusting process conditions, temperature and residence time, the oxygen content of the oil products can be altered where lower oxygen contents correspond to a product of better quality. Typically, a longer residence time corresponds to a product with lower oxygen content.

[0018] An advantage of extracting the concentrated biocrude obtained after solvolysis and fractionation is that impurities, which poison catalysts during hydrotreatment processes, are reduced. A further advantage of the extraction of the process of the disclosure is that at least part of the heavy fraction is removed without being polymerized, as heating is not needed. Since evaporation at high temperature is not needed, energy savings are also an advantage. A further advantage of the extracting of the disclosure is that although more impurities typically also dissolves if the yield increases by dissolving heavier biocrude components of the concentrated biocrude, most of the impurities can be removed by a purification with water, preferably by a three-phase separation in one process step including the extraction and the purification. As water immiscible solvent are used, a three-phase system (water+organic+ heavy residue) is formed and most of the metal impurities will be transported from the organic phase to the water phase. Since water forms its own phase, it can be removed together with the metals.

[0019] An advantage of the optional stabilisation of the process of the disclosure is that since the viscosity of the stabilised biocrude is below 250 cP (250 mPa-s), preferable below 150 cP (150 mPa-s) and more preferably below 100 cP (100 mPa-s) at 25 °C, it is pumpable and possible to store, load and transport.

[0020] The process of the disclosure is especially suitable for converting substantially solid renewable feedstock to valuable products or components, such as hydrocarbons and / or oxygen containing hydrocarbons suitable as fuels, fuel blending components or as feedstock for fuels and for compounds to chemical industry processes, especially components of kerosene, such as jet fuel and / or sustainable aviation fuel (SAF).

[0021] BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In the following the disclosure will be described in greater detail by means of preferred embodiments with reference to the accompanying drawings, in which:

[0023] Figure 1 shows a schematic flow diagram representing one embodiment of the conversion process.

[0024] The figure is for illustrative purposes only and are not shown in scale.

[0025] DETAILED DESCRIPTION OF THE DISCLOSURE

[0026] An industrially effective and sustainable process for recovering renewable products from substantially solid renewable feedstock comprising forest industry residue(s) is provided. The process has a high yield of liquid product(s) and the feedstock is effectively and economically converted to renewable products. The liquid product(s) and especially fractions thereof are particularly suitable as feedstock for upgrading for use in biofuels and biochemicals manufacture.

[0027] The disclosure relates to a process for converting renewable feedstock to renewable liquid product(s), wherein the process comprises the following steps,

[0028] (a) providing a substantially solid renewable feedstock comprising forest industry residue(s);

[0029] (b) preparing a feed mixture by directing the substantially solid renewable feedstock to feedstock conditioning comprising thermal drying during pretreatment in the presence of a solvent, and one or more of a mechanical dewatering and / or an additional thermal drying wherein at least part of the substantially solid renewable feedstock is subjected to dewatering and / or the additional thermal drying before pretreatment;

[0030] (c) followed by solvolysis of the feed mixture of step (b) by heating the feed mixture at a temperature between 300 and 420 °C, under a pressure from 10 bar to 80 bar and maintaining said temperature and pressure for 5 - 60 minutes to obtain a biocrude;

[0031] (d) followed by fractionation of the biocrude to obtain at least a fraction having a molecular weight between 100 g / mol and 250 g / mol and a concentrated biocrude, having a molecular weight above 250 g / mol; and

[0032] (e) followed by extraction of said concentrated biocrude, having a molecular weight above 250 g / mol, by an extractant chosen from a nonaromatic oxygenated solvent(s), wherein the extraction comprises separating a water phase (61) and a heavy residue (62) to obtain a purified biocrude, having a molecular weight below 1000 g / mol.

[0033] In the present specification and claims, the following terms have the meanings defined below.

[0034] The term "forest industry residue(s)", as used herein, refers to forest industry residue(s) from logging or cutting, sawing, debarking, and thinning of softwood and hardwood or combinations thereof, such as bark, sawdust, wood chips, branches, treetops or other wood residue(s) from wood processing industry, such as fines. Examples of softwood include pine and spruce and examples of hardwood includes birch, eucalyptus and aspen.

[0035] The term "substantially solid renewable feedstock" as used herein, refers to the feedstock being in substantially solid state. The substantially solid renewable feedstock may comprise moisture and / or traces or rests of for example oils. The substantially solid renewable feedstock of the process of the disclosure comprises forest industry residue(s) which are plant-based and can be combined with other substantially solid renewable feedstocks, such as other renewable residue(s), residue(s) from oil-bearing crops and / or lignin. Alternatively, the substantially solid renewable feedstock comprises no added lignin. The amount of other substantially solid renewable feedstocks is typically between 1 wt% and below 50 wt%, between 1 wt% and 40 wt, between 1 wt% and 20 wt% or between 1 wt% and 10 wt%, including the amount being between any of the following values; 1 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 40 wt% and 49 wt%. In other words, the amount of forest industry residue(s) is typically over 50 wt%, over 60 wt%, over 80 wt% or over 90 wt%, including the amount being between any of the following values; 51 wt%, 55 wt%, 60 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt% and 99 wt%. Alternatively, the substantially solid renewable feedstock consists of forest industry residue(s).

[0036] The term "residue(s) from oil-bearing crops", as used herein, refers to substantially solid residue(s) of oil-bearing crops such as shells, pod shells, husk, seedcakes from oil extraction, protein meals of oil-bearing crops such as soybeans, peanuts, cottonseed, pongamia seed Pongamia ((Millettia pinnata, formerly known as Pongamia pinnata)), macauba seed (Macauba (Acrocomia aculeata)), sunflower seed, flaxseed, safflower seed, rapeseed, sesame seed, castor beans, canola, rapeseed, brassica carinata and mustard seeds.

[0037] The term "lignin" as used herein, refers to lignin obtained from different sources. One example is kraft lignin obtained from kraft pulping but the lignin could also be obtained from other sources such as lignosulfonate lignin, soda lignin, hydrolysis lignin and organosolv lignin. The lignin obtained as a residue from the lignocellulosic process is also suitable feed for this invention and any other lignin obtained from other process. More in general lignin is a complex long-chain heterogeneous organic polymer composed largely of phenylpropane units which are most commonly linked by ether bonds. Oxidative coupling of primarily three p-hydroxycinnamyl alcohols (monolignols): p-coumaryl, coniferyl and sinapyl alcohols results in lignin. Lignin have generally been classified into three major groups based on the chemical structure of their monomer units: softwood lignin, hardwood lignin, and grass lignin. Hardwood lignin consists mainly of guaiacyl and syringyl units and low levels of p- hydroxyphenyl. Conifer lignin has higher levels of guaiacyl units and low levels of p-hydroxyphenyl. Grasses comprise guaiacyl, syringyl and p-hydroxyphenyl units. In some embodiments of the disclosure, the lignin feedstock of the embodiments of the disclosure is typically kraft lignin, which is separated from black liquor. The kraft lignin feedstock of the embodiments of the disclosure essentially consists of lignin, i.e. the feedstock is substantially free of impurities or residue(s) from black liquor, such as cellulose, hemicellulose, methanol, sulphur compounds and cooking chemicals from the kraft process.

[0038] The term "solvent", as used herein, refer to the solvent used for pretreatment of the renewable feedstock(s) of the process of the disclosure. Except for startup of the process, the solvent comprises an oil fraction(s), recycled from the process itself, typically a light fraction or a light and middle fraction or part thereof, separated from the biocrude by fractionation, for example by distillation or evaporation. Typically, a different solvent is used at start-up of the process before a recycled fraction to be recirculated in the process is obtained from the process itself. Typically, the recycled product fraction comprises the "light fraction" having a molecular weight of between 100 g / mol and 250 g / mol or part thereof. As the recycled fraction, is entirely recirculated from the process itself, the substantially solid renewable feedstock(s) of the process of the disclosure is the sole feedstock added to the process. According to some embodiments of the method of the disclosure the solvent further comprises part of the purified biocrude obtained after the extraction and / or part of the stabilised biocrude obtained after an optional stabilisation of the process of the disclosure. The term "feedstock conditioning" as used herein, refers to the process(es) of preparing raw materials for efficient and effective use in downstream processes. This preparation may involve physical, chemical, or thermal treatments, such as size reduction, moisture adjustment, impurity removal, or the addition of additives, such as solvent to enhance properties of the feedstock and making it suitable for further conversion or processing. Typically, the feedstock conditioning of the method of the disclosure comprises at least part of the feedstock being subjected to at least one of dewatering and an additional thermal drying, in addition to thermal drying during pretreatment in the presence of solvent.

[0039] The term "dewatering" as used herein, refers to mechanical dewatering performed during conditioning according to the feedstock of the method of the disclosure. If needed, the dewatering is performed before thermal drying, for example using a belt press. During dewatering moisture is typically released in liquid form.

[0040] The term "thermal drying" as used herein, refers to thermal drying done during the conditioning of the feedstock according to the method of the disclosure. Thermal drying is for example performed by pretreating the feedstock at elevated temperature in the presence of a solvent and in a first additional thermal drying for example using a belt dryer and / or by storing the feedstock at elevated temperature in the presence of a solvent. Typically, the feedstock of the disclosure is at least subjected to thermal drying during pretreatment in the presence of solvent. During thermal drying moisture is typically released in gas form.

[0041] The term "feed mixture", as used herein, refers to the heterogenous or homogeneous mixture obtained after feedstock conditioning of the substantially solid renewable feedstock(s) according to the disclosure. The feed mixture comprises the solvent added during the pretreatment. The pretreatment is always part of the feedstock conditioning.

[0042] The term "biocrude", as used herein, refers to the oil fraction produced by solvolysis according to the process of disclosure derived from a feed mixture which is obtained by subjecting a substantially solid renewable feedstock(s) to feedstock conditioning. The resulting crude-like substance is rich in oxygen containing aromatics and can be refined into for example renewable gasoline, diesel, sustainable aviation fuel or jet fuel.

[0043] The term "solvolysis", as used herein, refers to a non-catalytic thermal liquefaction using an organic solvent, without added hydrogen, without added carbon monoxide and without added alcohol. In general, solvolysis is a thermochemical conversion in which solvent is used to dissolve an organic molecule in order to form a new liquid product with less oxygen. Solvolysis is a type of nucleophilic substitution or elimination reaction, where the solvent acts as the nucleophile. The solvent used in the process of the disclosure is formed from the feedstock and recycled within the process. The solvolysis of the disclosure converts the feed mixture obtained from the feedstock conditioning of the substantially solid renewable feedstock(s) of the process of the disclosure, into biocrude.

[0044] The term "concentrated biocrude" as used herein, refers to the oil fraction produced by solvolysis and subjected to one or more fractionation(s) and from which an oil fraction, the light fraction, having a molecular weight of between 100 g / mol and 250 g / mol, is removed.

[0045] The term "fraction", "product fraction", "oil fraction", "volatile fraction", "light fraction", "middle fraction", "heavy fraction", "concentrated biocrude", "purified biocrude", "stabilised biocrude" as used herein, refers to fraction(s) obtained from the process itself by fractionation. A person skilled in the art can vary the fractionation, such as the distilling or evaporation conditions and change the temperature cut point as desired to obtain any desired fraction, boiling in predetermined ranges and having a predetermined average molecular weight. By changing temperature and pressure the skilled person can obtain corresponding fraction(s) to fraction(s) having a certain boiling point at atmospheric pressure, thus receiving fractions having corresponding features, leading to similar results when the fraction for example is used as the solvent in the feed mixture or recycled according to the process of the disclosure. The atmospheric pressure, i.e. standard atmosphere (atm) is a unit of pressure defined as 101.325 kPa. The corresponding fractions typically comprises corresponding compounds and / or has a corresponding average molecular weight. The average molecular weight is the mathematical mean of molar weight of the components based on gel permeation chromatography method calibrated on polystyrene. Typically, the corresponding fraction(s) is obtained at a pressure chosen from between 2 mbar and 1 bar. The fraction named "light fraction(s)" in the present disclosure, is a fraction having a molecular weight between 100 and 250 g / mol, which means that the fraction has an average molecular weight within this range based on polystyrene calibration. The light fraction typically comprises 5- and 6-carbon cyclic structures with double bonds or saturated ring, containing keto-groups and / or 1-3-methyl groups, phenolic structures with methyl-, methoxy-, propenyl-, carboxyl- side groups, and hydrated phenantrene 3-ring structures with 3-4 double bonds in the ring and side chains. Typically, the light fraction essentially consists of or comprises substantially mono- and diaromatics, preferably at least 90 wt-% mono- and diaromatics, more preferably at least 95 wt-% mono- and diaromatics. Part of the monoaromatics are oxygen containing monoaromatics. The fraction, named "middle fraction(s)" in the present disclosure, is a fraction having a molecular weight between above 250 g / mol and 3000 g / mol, which means that the fraction has an average molecular weight within this range based on polystyrene calibration. Typically, the middle fraction essentially consists of or comprises substantially di-, tri- and tetra-aromatics, preferably at least 90 wt- % di-, tri- and tetra-aromatics, more preferably at least 95 wt-% di-, tri- and tetra-aromatics. Part of the di-, tri- and tetra-aromatics are oxygen containing di-, tri- and tetra-aromatics. Typical middle fraction(s) comprises A: oc-aryl ether substructures (oc-O-4) and / or p-aryl ether substructures (p-O-4); B: resinol substructures (p-p); C: phenylcoumaran substructures (p-5), biphenyl substructures (5-5) and / or biphenyl ether (5-0-4). The fraction having a molecular weight above 3000 g / mol is typically named "heavy fraction". This means that the heavy fraction has an average molecular weight within this range based on polystyrene calibration. Volatiles are typically removed as an aqueous phase, i.e. a fraction comprising water and volatiles, having a boiling point at or below 120 °C at atmospheric pressure. Typically, the middle fraction does essentially not consist of compounds having a boiling point below 120 °C at atmospheric pressure. Typically, the light fraction does essentially not consist of compounds having a boiling point below 120 °C at atmospheric pressure.

[0046] The term "non-catalytic" refers to a process where no heterogeneous or homogeneous catalyst is added to the process and where the reaction(s) take place in the absence of an added catalyst. Typically, this means in practice that the reaction(s) take place, only between the materials fed into the reactor(s) and the reagents formed during the reaction(s), without a catalyst.

[0047] The term "purified biocrude" as used herein, refers to the oil fraction produced by solvolysis, fractionation(s) and extraction(s).

[0048] The term "stabilised biocrude" as used herein, refers to the oil fraction produced by solvolysis, fractionation(s).

[0049] Feedstock conditioning

[0050] Before entering the solvolysis the feedstock(s) of the method of the disclosure is subjected to feedstock conditioning. The feedstock conditioning typically comprises one or more physical, chemical, or thermal treatment(s), such as size reduction, moisture adjustment, impurity removal, or the addition of additives, such as solvent to enhance properties of the feedstock and making it suitable for further conversion or processing.

[0051] The feedstock conditioning of the method of the disclosure comprises subjecting the substantially solid renewable feedstock to one or more of; washing; dewatering, for example by a filter press; thermally drying, for example by a belt dryer; thermally drying by pretreating the feedstock(s) with solvent at elevated temperature, for example by mixing; and storing the obtained feed for example in a buffer tank.

[0052] The feedstock(s) of the method of the disclosure are optionally subjected to additional treatment(s) before entering the feedstock conditioning of the method of the disclosure.

[0053] Applicable feedstocks for the solvolysis of the disclosure are substantially solid renewable feedstocks comprising forest industry residue(s) such as sawdust and barks, optionally in combination with for example oil-bearing crops and / or lignin from different biomass fractioning processes. The forest industry residue(s) of the embodiments of the disclosure are typically substantially solid residue(s) from forest industry from logging or cutting, sawing, debarking, and thinning of softwood and hardwood or combinations thereof. Typically, solid forest industry residue(s) are bark, sawdust, wood chips, branches, treetops, or other wood residue(s) from wood processing industry, such as fines, or mixtures thereof, more preferably bark, sawdust, wood chips or mixtures thereof such as a mixture of bark and sawdust from one or more different hard- and / or softwood or a mixture of bark of at least one hardwood and at least one softwood. Examples of softwood include pine and spruce and examples of hardwood includes birch, eucalyptus and aspen.

[0054] Typical feedstock handling of forest industry residue(s), for example sawdust or barks comprises a receiving station, impurities removal (sand, soil and metals), storage bins, mechanical dewatering, thermal drying and crushing as part of the feedstock conditioning. After feedstock conditioning, including pretreatment, the moisture content is typically below 20 wt-% and the particle size is typically below 50 mm.

[0055] Typically, the substantially solid renewable feedstock is dried as part of the process of the disclosure to a moisture content below 20 wt%, preferably between 0 wt% and 20 wt% and most preferably between 1 wt% and 15 wt%, including the moisture content being between any of the values: 0 wt%, 1 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt% and 20 wt%, before it enters the solvolysis of the disclosure. At least part of the feedstock is subjected to dewatering or an additional thermal drying in addition to the thermal drying during pretreatment in the presence of solvent.

[0056] Typically, the particle size is below 50 mm, preferably below 30 mm, more preferably between 5 mm and 20 mm, most preferably between 10 mm and 15 mm including the size being between two of the following values; 5 mm, 10 mm, 15 mm, 20 mm, 25 mm, 30 mm, 35 mm, 40 mm, 45 mm and 50 mm before entering the pretreatment of the feedstock conditioning.

[0057] Typical compositions of different forest industry residue(s) of the embodiments of the disclosure are shown in Table 1. Table 1. Composition of different forest industry residue(s) by weight.

[0058] Typically, the ash content of the solid forest industry residue is 0.1 - 8 wt%, preferably 0.1 - 5 wt%, more preferably 0.1 - 2.5, most preferably 0.2 - 0.6 wt%, including the ash content being between two of the following values; 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, and 8 wt%. Typically, the ash content of sawdust used the solid forest industry residue is 0.1 - 5 wt%, preferably 0.1 - 4 wt%, more preferably 0.1 - 2.5, most preferably 0.2 - 0.6 wt%, including the ash content being between two of the following values; 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt% and 5 wt%.

[0059] Optionally, solid forest industry residue(s) such as sawdust and barks are combined with residue(s) of oil-bearing crops, and / or lignin as a combined substantially solid renewable feedstock. A typical example of husks, pod shells or de-oiled cake of oil-bearing crops of the embodiments of the disclosure is a composition comprising 93-99 wt% organics, 1 - 7 wt% ash and in addition 0 - 30 wt% moisture. Typically, the oxygen content of the composition is below 42 wt%. Typically, the ash content of the oil bearing crops between 1 wt% and 7 wt%, preferably between 1 wt% and 5 wt%, more preferably between 1 wt% and 4 wt%, including the ash content being between two of the following values; 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 5 wt%, 6 wt%, and 7 wt%.

[0060] A typical dry lignin feedstock of the embodiments of the disclosure is a composition comprising 85-98 wt% organics, 0.1 - 15 wt% ash and in addition 0 - 45 wt% moisture. Typically, the oxygen content of the composition is below 40 wt%, preferably from 20 to 36 wt%, most preferably from 25 - 36 wt% daf (dry-ash-free, i.e. without taking into account possible ash and moisture content). In preferred embodiments of the disclosure; the amount of organics is 90 - 98 wt%, more preferably 95 - 98 wt%,; the amount of ash is 0.1 - 7 wt%, more preferably 0.1 - 3 wt%, most preferably 0.1 - 1 wt%, including the ash content being between two of the following values; 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% and 15 wt%; and / or the amount of moisture is preferably 0 - 35 wt%, more preferably 0 - 20 wt%, most preferably 0 - 5 wt% including the amount of moisture being between two of the following values; 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 1 wt%, 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt% and 45 wt%.

[0061] According to some embodiments of the disclosure the feedstock conditioning comprises milling and / or washing of the substantially solid renewable feedstock. Milling reduces the size of biomass particles, increasing their surface area and making them more accessible for subsequent processing. This can be done for example with hammer, ball, knife, roller, or fluid energy mills or with an extruder. Washing of the substantially solid renewable feedstock can be done at a temperature between 40 and 180 °C, at substantially atmospheric pressure (101.325 kPa), for 10-30 min, including the temperature being a temperature between two of the following temperatures; 40 °C , 50 °C , 60 °C , 80 °C , 100°C , 120 °C , 140 °C, 150 °C, 160 °C, 170 °C and 180 °C for a reaction time, or a residence time in case this step is part of the continuous process of typically 5 minutes - 1.5 hours, preferably 5 - 30 minutes, more preferably 5 - 15 minutes, most preferably 5 - 10 minutes not including the heating time. In the embodiments of the disclosure the washing can be carried out batch-wise or in continuously operated reactors. Mixing of the feedstock with the water can be facilitated by mechanical treatment using different kind of mechanical equipment such as stirrer, pump etc, for example a piston pump. Biomass washing can be further facilitated by using an acid solution, commonly using acids like hydrochloric acid (HCI), sulfuric acid (H2SO4), or nitric acid (HNO3) and / or organic acids from feedstock conditioning. This process helps to remove inorganic components, particularly alkali and alkaline earth metals (AAEMs), which can interfere with subsequent thermal conversion processes. After acid washing, the biomass can be neutralized with a base (e.g., sodium hydroxide) to remove any residual acid and prevent corrosion of equipment. This step can ensure that the biomass is safe for further processing. After acid and / or neutralization step biomass is thoroughly rinsed with water to remove any remaining acid and impurities.

[0062] If the feedstock conditioning of the process of the disclosure comprises washing, the washing is followed by mechanical dewatering, typically using a filter press before the feedstock entering to the pretreatment comprising integrated thermal drying. During the mechanical dewatering of the process of the disclosure the moisture content of the feedstock is lowered, typically to a moisture content below 60 wt%, preferably between 40 wt% and 60 wt% and most preferably between 20 wt% and 40 wt% before it is entered into the pretreatment which is part of the feedstock conditioning.

[0063] Washing feedstock or part thereof is especially suitable for high ash containing feedstocks (> 1 wt-%). After the washing, the feedstock is mechanically dewatered before thermal drying for example using a belt dryer or heating, treating or storing the substantially solid renewable feedstock(s) in the presence of a solvent.

[0064] The feedstock conditioning of the method of the disclosure always comprises a pretreatment involving subjecting the feedstock(s) to a solvent.

[0065] According to embodiments of the disclosure the solvent is one or more oil fraction(s) produced by the process itself. Typically, the solvent is or comprises part of or the whole light fraction having a molecular weight of between 100 g / mol and 250 g / mol separated from the biocrude after solvolysis. The light fraction is separated by one or two fractionation(s), such as by distillation or evaporation. If needed, the solvent in addition comprises for example part of the purified biocrude obtained after extraction and / or the stabilised biocrude obtained after stabilisation.

[0066] In the embodiments of the disclosure, the amount of renewable feedstock of the feed mixture of the pretreatment is typically 5 wt% to 35 wt% and the amount of solvent correspondingly 65 wt% to 95 wt%. Preferably the amount of renewable feedstock is 8 wt% to 25 wt%, more preferably 10 wt% to 20 wt%, including the amount of renewable feedstock being between two of the following amounts; 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt% and 35 wt% of the feed mixture, the rest being solvent.

[0067] In embodiments of the disclosure, the ash content of the substantially solid renewable feedstock(s) entering the pretreatment, optionally after an optional washing followed by an optional mechanical dewatering, is typically below 8 wt%, preferably below 6%, preferably below 4 wt%, preferably below 2 wt%, more preferably below 1 wt%, most preferably below 0,2 wt%.

[0068] According to an embodiment of the disclosure the pretreatment of the process of the disclosure comprises preparing a feed mixture by adding solvent according to the process of the disclosure, to the substantially solid renewable feedstock(s) according to the process of the disclosure, at a temperature selected from between 100 and 320 °C, at a pressure of about 0.5 bar overpressure (about 50 kPa), for 1 - 60 min, including the temperature being a temperature between two of the following temperatures; 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, 230 °C, 240 °C, 250 °C, 260 °C, 270 °C, 280 °C, 290 °C, 300 °C, 310 °C and 320 °C. The reaction time, or the residence time in case this step is part of the continuous process, is typically 1 - 60 minutes, preferably 5 - 45 minutes, more preferably 5 - 60 minutes, most preferably 20 - 30 minutes not including the heating time. In the embodiments of the disclosure the pretreatment step can be carried out batch-wise or in continuously operated reactors. The mixing of the feedstock and the solvent can be facilitated by mechanical treatment using different kind of mechanical equipment such as stirrer, pump etc, for example a piston pump. The obtained feed mixture is pumpable. During the mixing the substantially solid renewable feedstock dissolves, at least partly, in the solvent.

[0069] The feedstock conditioning typically comprises directing the feed mixture to a buffer tank after pretreatment, where the feed mixture is kept for up to 60 min., at a similar temperature to pretreatment, at substantially atmospheric pressure. Preferably the temperature is below the solvolysis temperature, preferable below 300, even more preferably below 250, and most preferably below 200 °C.

[0070] Typically, an aqueous phase comprising water and light oxygenates, such as organic acids, aldehydes, ketones, alcohols, and furans, boiling substantially at a temperature below 120 °C at atmospheric pressure is removed by evaporation from the feedstock conditioning, typically from the buffer tank.

[0071] In one embodiment according to the disclosure the pretreatment is not part of the feedstock conditioning but instead performed in a single batch process together with the solvolysis.

[0072] Solvolysis and fractionation

[0073] The feed conditioning is followed by solvolysis. During solvolysis the feed mixture obtained from the feedstock conditioning is converted into biocrude by a non-catalytic thermal liquefaction using an organic solvent. Solvolysis will convert the renewable feedstock into biocrude without catalyst, without added hydrogen, without added carbon monoxide and without added alcohol.

[0074] According to the embodiments of the disclosure, the temperature of the solvolysis, is adjusted to a temperature selected from between 300 °C and 420 °C, preferably from between 300°C and 380°C, more preferably from between 330 °C and 380 °C, including the temperature being a temperature between two of the following temperatures; 300 °C, 310 °C, 320 °C, 330 °C, 340 °C, 350 °C, 360 °C, 370 °C, 375 °C, 380 °C, 385 °C, 390 °C, 395 °C, 400 °C, 405 °C, 410 °C, 415 °C and 420 °C for the heating of the feed mixture of the pretreatment step at a pressure from 10 bar to 80 bar, preferably from 20 bar to 60 bar, more preferably from 20 to 40 bar or alternatively from 20 bar to below 40 bar or from 20 bar to 35 bar, including the pressure being between two of the following pressures; 10 bar, 20 bar, 25 bar, 30 bar, 35 bar, 40 bar, 45 bar, 50 bar, 55 bar, 60 bar, 70 bar and 80 bar. The reaction time of the thermal liquefaction step or the residence time, in case this step is part of a continuous process, is typically 5 - 60 minutes, preferably 10 - 40 minutes, most preferably 10 - 20 minutes not including the heating time.

[0075] In the embodiments of the disclosure the biocrude obtained by the solvolysis is subjected to fractionation, typically by distillation or evaporation, for example in a distillation column or by flash evaporation for separating of a light fraction having a molecular weight between 100 g / mol and 250 g / mol and a concentrated biocrude having a molecular weight above 250 g / mol. Typically, an aqueous phase comprising water and organic compounds, such as organic acid(s), and boiling substantially at a temperature below 120 °C at atmospheric pressure, is also removed. Optionally, the first fractionation is followed by a second fractionation for example a vacuum distillation for improving separation of lights from the fraction having a molecular weight above 250 g / mol.

[0076] The light fraction or part thereof is recirculated back to the pretreatment step as solvent. The recycled oil fraction comprises at least part of or alternatively the whole light fraction having a molecular weight between 100 g / mol and 250 g / mol. The recycled light fraction is optionally combined with the aqueous fraction or part thereof removed during feedstock conditioning.

[0077] The disclosure further relates to use of the remaining fraction, the concentrated biocrude, as feed for further process steps of the disclosure such as extraction, stabilisation and / or hydroprocessing.

[0078] Typically, the concentrated biocrude obtained after solvolysis and removal of the light fraction by fractionation comprises below 45 wt% of the initial oxygen content of the substantially solid renewable feedstock, preferably below 40 wt% and more preferably below 35 wt% of the initial oxygen of the substantially solid renewable feedstock.

[0079] Extraction and removing of extractant

[0080] In the embodiments of the disclosure the concentrated biocrude obtained by solvolysis and fractionation, is subjected to extraction. Typically, the concentrated biocrude comprises the middle fraction(s) having a molecular weight between above 250 g / mol and 3000 g / mol and the "heavy fraction" having a molecular weight above 3000 g / mol.

[0081] The extraction is performed using a suitable equipment, typically Mixer settlers, Karr column, Pulsed disk and doughnut column (PDDC), Scheibel column, rotating disk column (R.DC) and / or centrifugal separators at a temperature selected from a temperature between 20 °C and 250 °C, preferably between 40 °C and 230 °C, more preferably between 50 °C and 230 °C including the temperature being a temperature between two of the following temperatures; 20 °C, 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, 230 °C, 240 °C, and 250 °C, at atmospheric pressure. The preferred temperature is typically dependent on the extractant boiling point.

[0082] The extractant to concentrated biocrude S / F ratio is typically below 25, preferably below 10, more preferably below 4 including the ratio being between two of the following values; 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 and 25.

[0083] The extraction can be co-, cross- or counter current and consist of one or several stages. Number of stages is typically 1 - 10, preferably 1 - 5, more preferably 1 - 3.

[0084] Selection of extractants is typically based on the chemical composition of the compounds to be dissolved: non-polar solvents dissolve non-polar compounds, while polar solvents dissolve polar compounds. Biocrude is a complex mixture containing various compounds with differing amounts of non-polar carboncarbon bonding sites (e.g., aromatic rings and long carbon chains) and oxygencontaining functional groups that increase polarity. Consequently, aromatic oxygenated solvents (e.g., cresol and benzyl alcohol) can almost completely dissolve biocrude. To enhance selectivity, extraction solvent may be a nonoxygenated aromatic solvent (e.g., toluene) or a non-aromatic oxygenated solvent (e.g., ether, alcohol, ketone, ester, such as methyl tertiary butyl ether (MTBE), diethyl ether 3-methyl-2-butanone, ethanol, and / or 2-propanol). This choice reduces the solubility of larger molecules, facilitating the separation of the heaviest molecules from the desired product compounds.

[0085] During the extraction process, some metal ions may be present in the product fraction. If the extraction solvent is substantially insoluble in water, the product fraction can be combined with water, followed by a liquid-liquid extraction to remove the metal ions. In this scenario, the metal ions are transferred from the organic phase to the more polar aqueous phase. Due to phase separation, the product and water fractions can be effectively separated.

[0086] In the embodiments of the process of the disclosure the extractant(s) are typically substantially water immiscible typically chosen from a non-aromatic oxygenated solvent(s), for example methyl tertiary butyl ether (MTBE), 1- pentanol, and / or 3-methyl-2-butanone. The solubility in water of the substantially water immiscible extractants of the process of the disclosure is typically at most 5 wt% and preferably at most 2 wt%.

[0087] As a substantially water-immiscible solvent(s) is used in the extraction step as extractant(s) and metals ions are water soluble, a water purification by a three- phase separation is possible. The phases are 1. extractant and product 2. water, and 3. heavy fraction, which are separated based on the difference in their density. Typically, the extraction comprises separating a water phase (61) and a heavy residue (62), preferably by three-phase separation with extractant and water in one step, to obtain a purified biocrude.

[0088] After extraction, the phase comprising the product and extractant is typically subjected to evaporation to remove the extractant before water purification or to obtain the purified biocrude. The evaporation is typically performed at a temperature selected from a temperature between 170 °C and 220 °C, including the temperature being a temperature between two of the following temperatures; 170 °C, 180 °C, 190 °C, 200 °C, 210 °C and 220 °C, at atmospheric pressure and at a temperature above the boiling point of the extractant.

[0089] Typically, 90 - 100 wt-% of the extractant is removed and optionally recycled to the extraction, preferably 95 - 100 wt-% is removed, more preferably over 95 wt-%, most preferably over 98 wt-% is removed and optionally recycled. The amount of heavy fraction having a molecular weight above 3000 g / mol removed is typically between 5 wt-% and 30 wt-% based on the feed to the extraction step (concentrated biocrude), i.e. based on the concentrated biocrude obtained after solvolysis and fractionation.

[0090] The objective of the extraction is to condition the concentrated biocrude for stabilisation and hydrotreatment by selective extraction of molecules having a molecular weight below 3000 g / mol, preferably below 2000 g / mol, more preferably below 1000 g / mol. Typically, the extraction solvent used is selective in the range up to the aforementioned cut-point to avoid loss of hydrotreatable biocrude fractions into the raffinate. Depending on the feedstock used, the yield of the extracted purified biocrude fraction will be over 45 wt%, preferably over 60 wt%, more preferably over 80 wt% and up to 95 wt% of the concentrated biocrude. Typically, the purified biocrude fraction is between 45 wt% and 95 wt% of the concentrated biocrude, preferably between 60 and 95 wt% of the concentrated biocrude, including the yield of purified biocrude being between any of 50 wt%, 55 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt and 95 wt% of the concentrated biocrude.

[0091] According to the present invention, the purified biocrude after extraction comprises significantly lower amounts of various impurities, including phosphorus, silicon, alkali metals, alkaline earth metals and other metals compared to the concentrated biocrude before extraction. Typically, the purified biocrude obtained after extraction comprises below 10 wt% of the initial impurities of the substantially solid renewable feedstock, preferably below 5 wt% and more preferably below 2 wt% of the initial impurities of the substantially solid renewable feedstock.

[0092] Along with the extracted fraction also major part of the metals, which acts as catalyst poisons in hydrotreatment, are removed. Typically, over 90 wt%, preferably over 95 wt%, more preferably over 99 wt% of the initial metal content in the substantially solid renewable feedstock is removed. If the initial metal content in the substantially solid renewable feedstock is high, metals content may still be too high for hydrotreatment. In this case additional metals removal can be applied, for example by adding water washing or purification by ion exchange resins. After extraction the viscosity of the purified biocrude is typically below 1000 cP (1 Pa-s) at 80 °C, preferable below 1000 cP (1 Pa-s) at 60 °C, more preferably below 1000 cP (1 Pa-s) at 40 °C. The viscosity of biocrude is determined as a function of temperature using a Brookfield DV-II + viscometer. Viscosity is a measure of a fluid's resistance to flow. The principle of operation of the DV-II + is to drive a spindle (which is immersed in the test fluid) through a calibrated spring. First, the biocrude is heated to make it flowable so that it could be transferred to the measurement container. The biocrude is then cooled back to room temperature, after which the temperature is increased in 10-degree Celsius intervals until the biocrude became flowable (measurement range 30- 130 °C). Heating is continued until the desired viscosity value is achieved.

[0093] The molecular weight of the purified biocrude is typically below 1000 g / mol or between 400 g / mol and 1000 g / mol, which means that the fraction has an average molecular weight within this range based on polystyrene calibration.

[0094] Stabilisation

[0095] After solvolysis and extraction the biocrude is typically not pumpable at ambient temperature. The required pumping temperature is typically 80-100 °C. In addition, the biocrude is typically not stable at elevated temperatures. At elevated temperature biocrude starts to repolymerize and thus increases the amount of heavies which are not suitable for downstream hydrotreatment.

[0096] To stabilize the purified biocrude and to enable the biocrude logistics from the initial solvolysis site to final upgrading site, the purified biocrude is typically stabilised at a temperature between 200 °C and 390 °C using a sulfidized bimetallic (transition metal) catalysts including NiMo or CoMo supported on AI2O3 or SiOz or AhCh / SiCh, preferably at a temperature between 290 °C and 350 °C. The H2partial pressure is typically between 90 and 120 bar; and the hydroprocessing feed rate WHSV (weight hourly spatial velocity) of the feedstock oil is proportional to an amount of the catalyst. The WHSV of the feed material is typically between 0.1 and 10, preferably between 0.5 and 4.

[0097] The stabilisation is typically carried out as a continues process, for example in a continues trickle bed reactor. Optionally a guard bed reactor can be added before the stabilisation. Typically, the stabilisation is done to an extent so that the stabilised biocrude is pumpable at 25 °C by having a viscosity below 250 cP (250 mPa-s), preferable below 150 cP (150 mPa-s) and more preferably below 100 cP (100 (mPa-s). Typically, the molecular weight of the stabilized biocrude is between 100 g / mol and 700 g / mol, preferably between 100 g / mol and 600 g / mol and more preferably between 100 g / mol and 500 g / mol, including the molecular weight being between any of 100 g / mol, 150 g / mol, 200 g / mol, 250 g / mol, 300 g / mol, 350 g / mol, 400 g / mol, 450 g / mol, 500 g / mol, 550 g / mol, 600 g / mol, 650 g / mol and 700 g / mol. This means that the fraction has an average molecular weight within this range based on polystyrene calibration.

[0098] The viscosity of biocrude is determined as a function of temperature using a Brookfield DV-II + viscometer. Viscosity is a measure of a fluid's resistance to flow. The principle of operation of the DV-II+ is to drive a spindle (which is immersed in the test fluid) through a calibrated spring. First, the biocrude is heated to make it flowable so that it could be transferred to the measurement container. The biocrude is then cooled back to room temperature, after which the temperature is increased in 10-degree Celsius intervals until the biocrude became flowable (measurement range 30-130 °C). Heating is continued until the desired viscosity value is achieved.

[0099] In the embodiments of the disclosure, part of the product mix, part of the liquid product mix, a light fraction or middle fraction obtained for example by fractionation of the product mix or liquid product mix, and / or any other fraction of the product mix, may be subjected to a catalytic hydroprocessing step carried out in the presence of hydrogen. Gasoline fractions that can be used as a bio-naphtha component or as raw material for bioplastics may also be produced.

[0100] The hydroprocessing step may be carried out for effecting at least one of hydrodeoxygenation, hydrodewaxing, hydroisomerization, hydrocracking, hydrodearomatization and ring opening reactions.

[0101] Hydroprocessing, such as hydrotreatment or hydrocracking may be performed using one or more hydroprocessing catalysts comprising one or more metals selected from Group VIA and Group VIII metals (Periodic Table of Elements). Particularly useful examples are Mo, W, Co, Ni, Pt and Pd. The catalyst(s) can also contain one or more support materials, for example zeolite, alumina (AI2O3), gamma-alumina, zeolite-alumina, alumina-silica (SiO2), ZrO2, alumina-silica-zeolite and activated carbon. Suitably a mixture of CoO and MoO3 (CoMo) and / or a mixture of NiO and MoO3 (NiMo), and / or a mixture of Ni, Mo and Co and / or NiW and one or more support materials selected from zeolite, alumina, silica, zeolite-alumina, alumina-silica, alumina-silica-zeolite and activated carbon. Also, noble metals, such as Pt and / or Pd dispersed on gamma-alumina may be used.

[0102] In an embodiment, the hydroprocessing is carried out under a pressure of 5 - 300 bar (total pressure, abs). In an embodiment, the pressure in the hydroprocessing is from 30 to 250 bar, suitably from 30 to 120 bar.

[0103] In an embodiment, hydrogen partial pressure is maintained in the range from 50 to 250 bar, suitably from 80 to 200 bar, particularly suitably from 80 to 120 bar.

[0104] The hydroprocessing is carried out at a temperature in the range of 100 to 450°C, suitably 280°C to 450°C, more suitably from320 °C to 400°C.

[0105] The hydroprocessing feed rate WHSV (weight hourly spatial velocity) of the feedstock oil is proportional to an amount of the catalyst. The WHSV of the feed material varies between 0.1 and 10, it is suitably in the range of 0.1- 5 and preferably in the range of 0.3 - 0.7.

[0106] The ratio of H2 / feed varies between 600 and 4000 Nl / I, suitably of 1300-2200 Nl / I.

[0107] The feed is pumped to the hydroprocessing reactor at a desired speed. Suitably the feed rate LHSV (liquid hourly space velocity) of the feed material is in the range of 0.01-10 h-1, suitably 0.1- 5 h-1.

[0108] The hydroprocessing step may be carried out as at least one-step process or as at least two-step process.

[0109] The liquid hydrocarbon stream obtained from the hydroprocessing includes fuel grade hydrocarbons having a boiling point of at most 380°C according to ISO EN 3405. The person skilled in the art is able to vary the distilling conditions and to change the temperature cut point as desired to obtain any suitable hydrocarbon product, boiling suitably in the transportation fuel ranges.

[0110] Moreover, the disclosure relates to use of hydroprocessed oil obtained when purified biocrude obtained after extraction of the process of the disclosure and / or stabilised biocrude obtained after stabilisation of the process of the disclosure, is directed to a hydroprocessing step to obtain a hydroprocessed oil. The hydroprocessed oil is preferably used in the production of chemicals or as drop-in fuels, preferably as diesel, naphtha, marine fuel or kerosene or components thereof.

[0111] In Figure 1 the substantially solid renewable feedstock 10 is a feedstock conditioning step 100 comprising optional mechanical dewatering 101 and / or thermal drying 102 before a pretreatment step 103 in the presence of a solvent 20 storing the obtained feed mixture in an optional buffer tank (not shown in the figure). The obtained feed mixture 30 is then fed to a solvolysis step 110 where it is heated. The biocrude 40 obtained from the solvolysis step 200 is directed to a fractionation step 210, comprising separating at least a light fraction 51, having a molecular weight between 100 g / mol and 250 g / mol and a concentrated biocrude 50, having a molecular weight above 250 g / mol. At least part of the light fraction 51 is recirculated to be used as at least part of the solvent 20 in the pretreatment step 103. The concentrated biocrude 50, having a molecular weight above 250 g / mol is fed to an extraction step 300 by an extractant 60 to obtain a purified biocrude 70 from which a heavy fraction and impurities 71 is removed. Typically, the extractant is removed by evaporation 301 and recycled to the extraction step 300. Optionally, the purified biocrude 70 is directed to a stabilisation step 400 or to hydroprocessing (not shown in the figure). Optionally, the stabilised biocrude 80 obtained from the stabilisation 400 is directed to hydroprocessing (not shown in the figure). The recycled light fraction is optionally combined with the aqueous fraction removed during feedstock conditioning (not shown in the figure).

[0112] The process of the embodiments of the disclosure, or parts thereof, can be a continuous, batch or semi-batch process. According to one embodiment of the disclosure a process for converting renewable feedstock to renewable liquid product(s) is provided, wherein the process comprises the following steps,

[0113] (a) providing a substantially solid renewable feedstock comprising forest industry residue(s), wherein the substantially solid renewable feedstock comprises over 80 wt% of forest industry residue(s);

[0114] (b) preparing a feed mixture by directing the substantially solid renewable feedstock to feedstock conditioning comprising thermal drying during pretreatment in the presence of a solvent, and one or more of a mechanical dewatering and / or an additional thermal drying wherein at least part of the substantially solid renewable feedstock is subjected to dewatering and / or the additional thermal drying before pretreatment;

[0115] (c) followed by solvolysis of the feed mixture of step (b) by heating the feed mixture at a temperature between 300 and 420 °C, under a pressure from 10 bar to 80 bar and maintaining said temperature and pressure for 5 - 60 minutes to obtain a biocrude;

[0116] (d) followed by fractionation of the biocrude to obtain at least a fraction having a molecular weight between 100 g / mol and 250 g / mol and a concentrated biocrude, having a molecular weight above 250 g / mol, wherein at least part of the fraction having a molecular weight between 100 g / mol and 250 g / mol is recycled to the pretreatment as at least part of the solvent.;

[0117] (e) followed by extraction of said concentrated biocrude, having a molecular weight above 250 g / mol, by an extractant chosen a non-aromatic oxygenated solvent(s), wherein the extraction comprises separating a water phase (61) and a heavy residue (62) in a three-phase separation to obtain a purified biocrude, having a molecular weight below 1000 g / mol; and

[0118] (f) followed by stabilising (400) said purified biocrude at a temperature between 200 °C and 390 °C using a supported sulfidized bi-metallic catalyst(s), to obtain a stabilised biocrude (80); and recovering the stabilised biocrude having a viscosity below 250 cP at 25 °C. EXAMPLES

[0119] Analysis methods used in the examples

[0120] The elemental composition of the liquid and solids was determined with an Interscience Flash 2000 elemental analyser. The water content of the aqueous phase was determined by Karl Fischer titrations using Hydranal composite 5, Metrohm 787 KFTitrino as titrant.

[0121] The contents of ash, volatile matter, moisture and fixed carbon in the feed (proximate analysis) was determined by measuring weight loss upon heating. These constituents will add up to 100%. Ash content determination was performed by heating a sample in air at a slow heating rate (5°C / min). Once the temperature reached 550 °C it was kept constant for 6 hours before the sample was weighted. The remaining weights measured at 520 °C represent the ash contents at these temperatures.

[0122] The combined content of fixed carbon and volatiles was determined by slowly heating a sample (5 °C / min) in nitrogen to 950 °C where it was maintained for 10 minutes before it was weighted. The measured weight loss represents the combined content of water and volatiles. The remaining weight represents the content of fixed carbon.

[0123] The moisture content of the sample was determined by a PMB-53 moisture analyzer of Adam Equipment.

[0124] Calculations of mass balance and yields

[0125] The mass balance distinguishes four different product phases - oil (o), aqueous phase (aq), gas (g) and solids (s). The produced amounts of each phase are determined as follows:

[0126] 1. Oil - is the organic phase dissolved in the solvent.

[0127] 2. Aqueous phase organics (water soluble organics - WSO) remain in the oil phase. Only when 20 wt% of water was used in the slurry mixture of feed and lights, a separate water layer was observed which contained almost no organics molecules.

[0128] 3. Gas - From the known volume of produced gas and GC composition, the weight of total gas is calculated and the amount of measured N2 is subtracted. The known volume of produced gas and the average molar weight of 33 g / mol are used to calculate the amount of gas produced. Nitrogen is subtracted based on the initial pressure and the approximate initial volume taken up by gas phase in the reactor at the start of an experiment.

[0129] 4. Solids - The amount of solids is determined directly by weighing dried solids when withdrawn from the oven.

[0130] Since all yields are given on dry feed basis, the amount of dry feed fed in the reactor is corrected for initial feed moisture as follows: mfeed,dry ~mfeed ' (1 ~ ^moisture, feed) (EQ-1)

[0131] The gas and solid yields are calculated by:

[0132] Ys is used for the solids and YG for the gas. The oil yield is calculated as 100 minus gas and char. When the yields are expressed on the feed intake, all solids and gas are first ascribed to the feed and after that, the amount of gas produced from the lights only are subtracted from the gas production from the feed. The oil yield from feed follows from 100 minus gas and solids from feed.

[0133] Examole 1 Feedstock conditioning and solvolysis

[0134] A mixture containing either 7.5 wt% of pine wood or 7.5 wt% of pine bark was used as feedstock and was fed to a 45 ml stirred reactor together with 92.5 wt% cresol, respectively. The compositions of the pine wood and pine bark are shown in Table 2. Table 2 Compositions of pine sawdust and pine bark (wt%)

[0135] The reactor temperature of the thermal liquefaction step was 360 °C and the reaction time was 20 minutes (at set-point). The yields expressed on dry feedstock basis are shown in Table 3. The liquid yield, however, includes water. The solid yield is the highest for pine bark.

[0136] Table 3 Solvolysis results for pine sawdust and pine bark

[0137] The following metals (mg / kg) were analysed with ICP-OES (method ASTM D 5185 / SFS-EN ISO 11885): Aluminium (Al), Arsenic (As), Boron (B), Barium (Ba), Calcium (Ca), Cadmium (Cd), Cobalt (Co), Chromium (Cr), Copper (Cu), Iron (Fe), Phosphorous (P), Potassium (K), Magnesium (Mg), Manganese (Mn), Molybdenum (Mo), Sodium (Na), Silicon (Si), Nickel (Ni), Lead (Pb), Selenium (Se) and Zinc (Zn). The result is shown in Table 3. The amount of metals (without phosphorous and silicon) were 933 mg / kg and 7076 mg / kg respectively.

[0138] Example 2 Extraction

[0139] Pine wood (sawdust) derived oil used for the extraction was produced by continuous solvolysis. The reactor temperature was 370 °C and the reaction time was 16 minutes (at set-point). The feeding rate was 5-10 kg / hr and the pressure was constant between 40 and 45 bar. The cooling temperature of the product vessel was 30 °C. After removal of cresol and water from the solvolysis liquid by vacuum distillation to obtain concentrated biocrude, 3-methyl-2- butanone was used as extraction solvent, i.e. extractant. The extractant to concentrated biocrude feed ratio was 9: 1. The aim was to remove the heavy part (molecules) from the concentrated biocrude. Two phases were obtained after centrifuge, an extract and a raffinate. The 3-methyl-2-butanone was evaporated from both phases and the products were weighed.

[0140] After removal of 3-methyl-2-butanone, water was used as solvent, i.e. extractant. The extractant to concentrated biocrude feed ratio was 9: 1. The aim was to remove the metals and other impurities from the concentrated biocrude. Two phases were obtained after settling, an extract and a water phase. Water was decanted from both phases and the products were weighed. The extract phase was used as feedstock in stabilisation.

[0141] The results for 3-methyl-2-butanone as extractant with and without water purification are found in Table 4.

[0142] Table 4 Extraction results (3-methyl-2-butanone) After the extraction according to the process of the disclosure using water purification, the amount of Mw>3000 g / mol was 1.6 wt% and the amount of Mw>1000 g / mol was 18.1 wt% in the extracted oil product.

[0143] The following metals and other impurities (mg / kg) were analysed with ICP-OES (method ASTM D 5185 / SFS-EN ISO 11885): Aluminium (Al), Arsenic (As), Boron (B), Barium (Ba), Calcium (Ca), Cadmium (Cd), Cobalt (Co), Chromium (Cr), Copper (Cu), Iron (Fe), Phosphorous (P), Potassium (K), Magnesium (Mg), Manganese (Mn), Molybdenum (Mo), Sodium (Na), Silicon (Si), Nickel (Ni), Lead (Pb), Selenium (Se) and Zinc (Zn). The result is shown in Table 4. The amount of metals (without phosphorous and silicon) was <34 mg / kg with water purification.

[0144] Example 3 Stabilisation

[0145] Stabilisation of the purified biocrude is performed using sulfided NiMO / AIzCh as catalyst (20 wt% on total intake) and stabilisation temperatures of 320 °C, 370 °C and 390 °C. The reaction time is 2 hours.

[0146] Gas is measured volumetrically, and subsequently its mass was calculated by the known density (composition known by GC). The stabilised oil yield was obtained by difference. The water content of the oils was measured. Coke was defined as the mass of Coke + Catalyst recovered, after acetone wash and drying, minus the mass of Catalyst fed.

[0147] The coke yield is typically below 0.5 wt% and the gas yield between 2.5 wt% and 5 wt%. The stabilisation liquid yield is calculated by difference taking the maximum coke yield and subtracting the gas yield. The stabilisation liquid yield is typically above 94 wt%. Water produced by oxygen removal from the feedstock oil is included in the stabilisation liquid yield.

[0148] The dynamic viscosity for the extracted and stabilised biocrude is measured at room temperature (25 °C). The viscosity of the oils was measured using a Brookfield DV-E viscosity dynamic viscosity meter. A spindle was immersed in a cup filled with oil. The cup was heat traced with thermal oil. The temperature could be controlled within 2 °C. After the viscosity value of the oil became stable it was recorded. The dynamic viscosity is typically below 250 cP (at 25°C).

[0149] Example 4 Different extraction solvents

[0150] A concentrated pine bark solvolysis oil of Example 2 was extracted using different extractants having a solubility in water of at most 2.6. The extractant to concentrated biocrude feed ratio was between 9: 1 and 10: 1. The results are found in Table 5.

[0151] Table 5 Extraction results with different extractants

[0152] As can be seen from the results the extractant selection effects the yield and Mw distribution of the extraction product. The amount of compounds with a molecular weight Mw <1000 g / mol varies between 50.8 wt% and 72.9 wt% and the amount of compounds with a molecular weight Mw >3000 g / mol varies between 2.6 and 18.8 for the product fraction.

Claims

CLAIMS1. A process for converting renewable feedstock to renewable liquid product(s), characterized in that the process comprises the following steps,(a) providing a substantially solid renewable feedstock (10) comprising forest industry residue(s);(b) preparing a feed mixture (30) by directing the substantially solid renewable feedstock (10) to feedstock conditioning (100) comprising thermal drying during pretreatment (103) in the presence of a solvent (20) and one or more of a mechanical dewatering (101) and / or an additional thermal drying (102), wherein at least part of the substantially solid renewable feedstock (10) is subjected to the mechanical dewatering (101) and / or the additional thermal drying (102) before the pretreatment (103) in the presence of solvent (20);(c) followed by solvolysis (200) of the feed mixture of step (b) by heating the feed mixture (30) at a temperature between 300 and 420 °C, under a pressure from 10 bar to 80 bar and maintaining said temperature and pressure for 5 - 60 minutes to obtain a biocrude (40);(d)followed by fractionation (210) of the biocrude (40) to obtain at least a fraction having a molecular weight between 100 g / mol and 250 g / mol (51) and a concentrated biocrude (50), having a molecular weight above 250 g / mol; and(e) followed by extraction (300) of said concentrated biocrude (50), having a molecular weight above 250 g / mol, by an extractant (60) chosen from a non-aromatic oxygenated solvent(s), wherein the extraction (300) comprises separating a water phase (61) and a heavy residue (62) to obtain a purified biocrude (70), having a molecular weight below 1000 g / mol.

2. The process according to claim 1, characterized in that the process further comprises that step (e) is followed by a step(f) stabilising (400) said purified biocrude in the presence of hydrogen and catalyst, to obtain a stabilised biocrude (80).

3. The process according to claim 2, characterized in that the stabilising (400) is performed at a temperature between 200 °C and 390 °C in the presence of hydrogen and catalyst; and recovering the stabilised biocrude having a viscosity below 250 cP at 25 °C.

4. The process according to any of claim 2 or 3, characterized in that the stabilising (400) is performed using a supported sulfidized bi-metallic catalyst(s).

5. The process according to any one of the preceding claims, characterized in that at least part of the fraction (51) of step (d) having a molecular weight between 100 g / mol and 250 g / mol is recycled to the pretreatment (103) as at least part of the solvent.

6. The process according to any one of the preceding claims, characterized in that the substantially solid renewable feedstock (10) comprises over 50 wt%, over 60 wt%, over 80 wt% or over 90 wt% of forest industry residue(s).

7. The process according to any one of the preceding claims, characterized in that the substantially solid renewable feedstock (10) consists of forest industry residue(s).

8. The process according to any one of the preceding claims, characterized in that the forest industry residue(s) is chosen from one or more of bark, sawdust, wood chips, branches, treetops or other wood residue(s) from wood processing industry, such as fines.

9. The process according to any one of the preceding claims, characterized in that the substantially solid renewable feedstock (10) comprises a mixture of different forest industry residue(s).10.The process according to any one of the preceding claims, characterized in that the substantially solid renewable feedstock (10) comprises no added lignin.

11. The process according to any one of the preceding claims, characterized in that a belt dryer is used for the additional thermal drying.12.The process according to any one of the preceding claims, characterized in that a belt press is used for the mechanical dewatering.13.The process according to any one of the preceding claims, characterized in that the feedstock conditioning further comprises milling and / or washing of the substantially solid renewable feedstock.14.The process according to any one of the preceding claims, characterized in that the substantially solid renewable feedstock (10) has a particle size below 50 mm, preferably below 30 mm, more preferably between 5 mm and 20 mm, most preferably between 10 mm and 15 mm before entering the pretreatment in the presence of solvent.15.The process according to any one of the preceding claims, characterized in that the feed mixture (30) has a moisture content below 20 wt%, preferably between 0 wt% and 20 wt% and most preferably between 1 wt% and 15 wt% before entering the solvolysis (200).16.The process according to any one of the preceding claims, characterized in that the solvolysis (200) is performed without added catalyst, hydrogen, carbon monoxide, and alcohol.17.The process according to any one of the preceding claims, characterized in that the solvolysis (200) is performed by heating the feed mixture (30) at a temperature between 300°C and 380°C.18.The process according to any one of the preceding claims, characterized in that the solvolysis (200) is performed at a pressure from 20 bar to 35 bar.19.The process according to any one of the preceding claims, characterized in that the concentrated biocrude obtained after solvolysis (200) and removal of the fraction (51) having a molecular weight between 100 g / mol and 250 g / mol by fractionation (210), comprises below 45 wt% of the initialoxygen content of the substantially solid renewable feedstock, preferably below 40 wt% and more preferably below 35 wt% of the initial oxygen of the substantially solid renewable feedstock (10). The process according to any one of the preceding claims, characterized in that the extractant (60) of step (e) is chosen from methyl tertiary butyl ether (MTBE), 1-pentanol, and / or 3-methyl-2-butanone. The process according to any one of the preceding claims, characterized in that the extractant (60) of step (e) has a solubility in water of at most 5 wt% . The process according to any one of the preceding claims, characterized in that the extraction (300) of step (e) is performed as a three-phase separation with extractant and water. The process according to any one of the preceding claims, characterized in that the extraction (300) of step (e) further comprises removal(s) of the extractant. The process according to any one of the preceding claims, characterized in that the purified biocrude (70) obtained after the extraction (300) comprises below 10 wt% of the initial impurities of the substantially solid renewable feedstock (10), preferably below 5 wt% and more preferably below 2 wt% of the initial impurities of the substantially solid renewable feedstock (10). The process according to any one of the preceding claims, characterized in that over 90 wt%, preferably over 95 wt%, more preferably over 99 wt% of the initial metal content of the substantially solid renewable feedstock (10) is removed from the purified biocrude (70) obtained after the extraction (300). The process according to any one of the preceding claims, characterized in that the purified biocrude (70) obtained after the extraction (300) has a viscosity below 1000 cP (1 Pa-s) at 80 °C, preferable below 1000 cP (1 Pa- s) at 60 °C, more preferably below 1000 cP (1 Pa-s) at 40 °C.27.The process according to any one of the preceding claims, characterized in that the molecular weight of the purified biocrude (70) obtained after the extraction (300) is between 400 g / mol and 1000 g / mol.28.The process according to any one of claims 2 - 27, characterized in that the stabilised biocrude (80) obtained after stabilisation (400) has a viscosity below 150 cP (150 mPa-s) at 25 °C or below 100 cP (100 (mPa-s) at 25 °C.29.The process according to any one of claims 2 - 28, characterized in that the molecular weight of the stabilized biocrude (80) is between 100 g / mol and 700 g / mol, preferably between 100 g / mol and 600 g / mol and more preferably between 100 g / mol and 500 g / mol.30.The process according to any one of the preceding claims, characterized in that in that at least part of the purified biocrude (70) obtained after extraction (300) is directed to a hydroprocessing step to obtain a hydroprocessed oil.31.The process according to any of claims 2 - 29, characterized in that or the stabilised biocrude (80) obtained after stabilisation (400) is directed to a hydroprocessing step to obtain a hydroprocessed oil.

32. Use of the hydroprocessed oil obtained by the process of claim 30 or claim 31 in production of chemicals or in drop-in fuels, preferably as diesel, naphtha, marine fuel or sustainable aviation fuel or components thereof.

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