Slurry hydroliquefaction of carbonaceous feedstock with recovery of oxygenates from the gaseous fraction by sponge oil adsorption

Abstract

Herein is described a method for the production of liquid hydrocarbon composition, comprising i) providing a bio-based carbonaceous feedstock (a); ii) removing at least part of the foreign coarse material (b) from the bio-based carbonaceous feedstock (a); iii drying and / or grinding to obtain a pretreated bio-based carbonaceous material (c); iv) subjecting the pretreated bio-based carbonaceous material (c) to catalytic hydroliquefaction to obtain a product composition; v) separating the liquid hydrocarbons and the off-gas from the product composition to obtain a liquid hydrocarbon fraction (f) and a first gaseous fraction (g-1); vi) subjecting the liquid hydrocarbon fraction (f) to catalytic upgrading; and vii) obtaining a sponge oil fraction (s-1) and contacting the sponge oil fraction (i) with the first gaseous fraction (g-1) to obtain an oxygen enriched sponge oil fraction (s-2) and a second gaseous fraction (g-2), and feeding the oxygen enriched sponge oil fraction (s-2) to catalytic upgrading.

Description

[0001] SLURRY HYDROLIQUEFACTION OF CARBONACEOUS FEEDSTOCK WITH RECOVERY OF OXYGENATES FROM THE GASEOUS FRACTION BY SPONGE OIL ADSORPTION

[0002] FIELD OF THE INVENTION

[0003] The present invention relates to hydroliquefaction of bio-based carbonaceous feedstock, in particular recycled bio-based carbonaceous feedstock. The present invention relates to a method for the production of hydrocarbon composition, in particular renewable hydrocarbon composition, for a bio-based carbonaceous feedstock. Specifically, the present invention relates to catalytic hydroliquefaction of bio-based carbonaceous feedstock, comprising foreign coarse material, such as sand and / or dirt, and having high oxygen content, e.g. due to comprising biomass feedstock, such as lignocellulosic biomass feedstock.

[0004] BACKGROUND OF THE INVENTION

[0005] Catalytic hydroliquefaction of carbonaceous feedstock comprising foreign coarse material and having high oxygen content in a slurry reactor environment results typically both in oxygen slip to the products as well as high catalyst consumption in the catalytic hydroliquefaction. The conditions, type of technology chosen and extension of treatment performed in each step are intrinsically connected and its optimization and integration impact directly on the process performance and the overall carbon footprint of the technology.

[0006] BRIEF DESCRIPTION OF THE INVENTION

[0007] An object of the present invention is thus to provide a method so as to overcome the above problems. The objects of the invention are achieved by a method which is characterized by what is stated in the independent claims. The preferred embodiments of the invention are disclosed in the dependent claims.

[0008] The invention is based on the surprising realization that issues caused by foreign coarse material present in waste-originating feedstock and carbon losses in the overall process can be solved simultaneously by performing the hydroliquefaction step in a slurry environment, removing the coarse foreign material while the feedstock is still in solid form and capturing slip-off oxygen to off-gas by using a part of the product of the catalytic upgrading as a sponge oil and returning it back to the catalytic upgrading. Carbon losses from the liquefaction step are thus minimized by process optimization and integration with adjacent processes for recovery and / or reuse in the process.

[0009] BRIEF DESCRIPTION OF THE DRAWINGS

[0010] In the following the invention will be described in greater detail by means of preferred embodiments with reference to attached drawings, in which

[0011] Figure 1 illustrates the 1 st exemplary process flow of the present method;

[0012] Figure 2 illustrates the 2nd exemplary process flow of the present method;

[0013] Figure 3 illustrates the 3rd exemplary process flow of the present method;

[0014] Figure 4 illustrates the 4th exemplary process flow of the present method.

[0015] DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention provides a method for the production of liquid hydrocarbon composition, comprising i) providing a bio-based carbonaceous feedstock (a) comprising wasteoriginating bio-based carbonaceous material (a1 ) and foreign coarse material (b), such as sand and / or dirt; ii) removing at least part, preferably most, more preferably essentially all, of the foreign coarse material (b) from the bio-based carbonaceous material (a); iii-a) drying the bio-based carbonaceous material (a); and iii-b) reducing the particle size of the bio-based carbonaceous material (a) to a predetermined particle size distribution D50; to obtain a pretreated bio-based carbonaceous material (c); iv) subjecting the pretreated bio-based carbonaceous material (c) dispersed in a liquid medium (d) to catalytic hydroliquefaction in the presence of hydrogen and a slurry hydroliquefaction catalyst (e) under mixing to obtain a product composition comprising liquid hydrocarbons and off-gas comprising at least light (C1-C5) hydrocarbons and light oxygenates; v) separating the liquid hydrocarbons and the off-gas to obtain a liquid hydrocarbon fraction (f) comprising liquid hydrocarbons and less than 15 wt% oxygen of the total weight of the liquid hydrocarbon fraction (f) measured as elemental oxygen and a first gaseous fraction (g-1 ) comprising at least light (C1-C5) hydrocarbons and light oxygenates; vi) subjecting the liquid hydrocarbon composition (f) to catalytic upgrading to obtain a liquid hydrocarbon product composition (h) comprising less than 1 wt% oxygen of the total weight of the liquid hydrocarbon product (h) measured as elemental oxygen; and vii) dividing a part of the liquid hydrocarbon product composition from the liquid hydrocarbon product (h) to obtain a sponge oil fraction (s-1 ) and contacting, preferably countercurrently, the sponge oil fraction (s-1 ) with the first gaseous fraction (g-1 ) to adsorb at least part of the oxygenates comprised in the first gaseous fraction (c-1 ) in the sponge oil fraction to obtain a oxygen enriched sponge oil fraction (s-2) and a second gaseous fraction (g-2) comprising less than 1 wt% oxygen covalently bound to oxygenates of the total weight of the second gaseous fraction (g-2) measured as elemental oxygen, and feeding the oxygen enriched sponge oil fraction (s-2) to catalytic upgrading.

[0017] In the present description, weight percentages (wt%) are calculated based on the total weight of the material in question (typically a blend or a mixture). Any amounts defined as ppm (parts per million), are based on weight (i.e. mg / kg). In the present description, volume percentages (v / v%) are calculated based on the total volume of the material in question (typically a gaseous mixture). “Essentially all” refers to substantially or most of the referred amount and may include, for example, 100%, at least 95%, at least 90%, at least 80%, at least 70%, and at least 60%.

[0018] Feedstock, Step i)

[0019] The term “carbonaceous feedstock” refers to carbonaceous material which is intended to be converted by hydroprocessing into liquid hydrocarbons, such as renewable hydrocarbons, or other valuable hydrocarbon products, such as valuable renewable hydrocarbon products, including fuels and fuel components, such as renewable fuels and renewable fuel components, but which need to be liquefied to allow further valorization of the material.

[0020] The term “renewable” in the context of renewable feedstock or renewable hydrocarbons or renewable fuel or fuel component refers to one or more organic compounds derived from any renewable source (contrary to source of fossil origin). Thus, renewable compounds or compositions are obtainable, obtained, derivable, derived, or originating from plants, animals and / or microbes, including compounds or compositions obtainable, obtained, derivable, derived, or originating from fungi and / or algae, in full or in part, whether these compounds or compositions are in their virgin, recycled or reclaimed form.

[0021] The 14C-isotope content can be used as evidence of the renewable or biological origin of a feedstock or product. Carbon atoms of renewable material comprise a higher number of unstable radiocarbon (14C) atoms compared to carbon atoms of fossil origin. Therefore, it is possible to distinguish between carbon compounds derived from biological sources, and carbon compounds derived from fossil sources by analyzing the ratio of 12C and 14C isotopes. Thus, a particular ratio of said isotopes can be used to identify and quantify renewable carbon compounds and differentiate those from non-renewable i.e. fossil carbon compounds. The isotope ratio does not change in the course of chemical reactions. Example of a suitable method for analyzing the content of carbon from biological sources is ASTM D6866 (2020). An example of how to apply ASTM D6866 to determine the renewable content in fuels is provided in the article of Dijs et al., Radiocarbon, 48(3), 2006, pp 315-323. For the purpose of the present invention, a renewable material, such as a feedstock or product, is considered to be of renewable origin if it contains 90 % or more modern carbon (pMC), such as about 100 % modern carbon, as measured using ASTM D6866.

[0022] Terms “fuel” and “fuel components” refer to fuels usable as such and as fuel components, respectively, which fulfill the requirements of standards for the respective use. For example, within the Ell, the standard for gasoline is EN 228:2017, for paraffinic diesel EN 15940:2023, and for aviation turbine fuel containing synthesized hydrocarbons D7566-22. The bio-based carbonaceous feedstock contemplated herein typically comprises high amounts of carbon and oxygen but relatively low amounts of hydrogen in form a solid material comprising said elements bound to various compounds. Carbon, oxygen and hydrogen may be present in the bio-based carbonaceous feedstock in various chemical forms in varying oxygen, carbon and / or hydrogen containing compounds, such as hydrocarbons, oxygen containing hydrocarbons, and / or polymers. For being able to produce renewable hydrocarbons from the biobased carbonaceous feedstock, it is therefore necessary to liquify the material and process it to lower the oxygen content and increase the hydrogemcarbon ratio. The bio-based carbonaceous feedstock may further comprise other heteroatoms, such as sulfur and nitrogen, and / or various inorganic compounds.

[0023] As used herein, “hydrocarbons” refer to compounds consisting of carbon and hydrogen. Examples of hydrocarbons include paraffins, including n-paraffins and i- paraffins, naphthenes, aromatics, and olefins (alkenes). “Oxygen containing hydrocarbons” and “oxygenates” refer herein to hydrocarbons comprising covalently bound oxygen and are used interchangeably.

[0024] The bio-based carbonaceous feedstock contemplated herein typically comprises at least 10 wt%, preferably at least 20 wt%, more preferably at least 30 wt%, oxygen on a dry basis (i.e. excluding water), measured as elemental oxygen. The bio-based carbonaceous feedstock may comprise up to 45 wt%, such as from 35 to 45 wt% oxygen, measured as elemental oxygen.

[0025] As used herein the oxygen content "on a dry basis" means that the oxygen content is determined under the assumption that all of the water is removed before determining the content. The oxygen content on a dry basis can be determined by drying the carbonaceous feedstock and determining the oxygen content (e.g. by elemental analysis). Alternatively, the oxygen content on a dry basis can be determined from a wet carbonaceous feedstock as follows: oxygen content (dry basis) = 100 percent * {(total oxygen content of the wet carbonaceous feedstock, e.g. by elemental analysis) - (oxygen contained in the wet carbonaceous feedstock in the form of water)} / {(mass of wet carbonaceous feedstock) - (mass of water in the wet carbonaceous feedstock)} The content (mass) of water contained in the wet bio-based carbonaceous feedstock can be determined by any suitable means (e.g. Karl-Fisher titration according to ASTM D6304, or distillation according to ASTM D95 or for solid feedstock ISO 18134-2:2017).

[0026] Further the bio-based carbonaceous feedstock typically comprises from 45 to 55 wt%, carbon, and less than 10 wt%, such as from 5 to 8 wt%, hydrogen, measured as elemental carbon and hydrogen on a dry basis, respectively.

[0027] Further, it is preferred that the total content of hydrogen (H) and carbon (C) in the carbonaceous feedstock, on a dry basis, is at least 50 wt%, preferably at least 55 wt%, more preferably at least 60 wt%. The contents of hydrogen and carbon in the bio-based carbonaceous feedstock can be determined by elemental analysis using e.g. ASTM D5291 or for solid biofuels ISO 16948:2015.

[0028] The process contemplated herein is suitable for bio-based carbonaceous feedstock comprising or consisting of, preferably consisting of, waste-originating biomass feedstock (a1 ), such as lignocellulosic biomass feedstock and foreign coarse materials (b), such as sand and / or dirt.

[0029] In particular, the process contemplated herein is suitable for bio-based carbonaceous feedstock comprising or consisting of, preferably consisting of, wasteoriginating bio-based biomass feedstock and foreign coarse material, such as sand and / or dirt. In an example the bio-based carbonaceous feedstock can be forestry residue, woodchip or sawdust which can contain various amounts of foreign inorganic materials such as sand and / or dirt. Typically, the bio-based carbonaceous material contemplated herein is solid at NTP (normal temperature and pressure, 25°C, 101 .325 kPa absolute).

[0030] The foreign coarse material particles referred to herein in particular have a median particle size (D50) of 0.05 mm or more, such as in the range of 0.10 to 10.0 mm, preferably 0.10 to 5.0 mm. Preferably, the coarse particles have a Mohs hardness of in the range of from 3 to 9, such as from 4 to 9, or from 5 to 7. The foreign coarse material preferably comprises sand. The sizes of the foreign coarse material particles may be determined e.g. by the use of sieves e.g. according to DIN 51938:2015 with laboratory test sieves conforming with ISO 3310. Considering that the coarse particles may have different origins and are thus non-uniform, the reference to Mohs hardness shall mean that more than 50% by mass of these particles have a hardness in the stated range.

[0031] The term “biomass” used herein includes, but is not limited to, algae, lignocellulosic biomass including lignocellulosic biomass components such as cellulose, hemicellulose, and / or lignin. The process contemplated herein is particularly suitable and optimized for lignocellulosic biomass and its components. Lignocellulosic biomass is essentially made up of three natural polymers: cellulose, hemicellulose, and lignin.

[0032] Prior to being fed to the hydroliquefaction step iv) the bio-based carbonaceous feedstock, such as the biomass feedstock, is first purified from foreign coarse materials, grinded and dried to obtain a pretreated bio-based carbonaceous material (c) and to render it processable in the hydroliquefaction step.

[0033] Step ii): Removing Foreign Coarse Material

[0034] The removal of the foreign coarse material may be accomplished by any conventional means found suitable for the purpose, considering that selective separation of the waste-originating bio-based carbonaceous material (a1 ) and foreign coarse material (b), such as sand and / or dirt is desired. In particular at least foreign coarse material particles having a median particle size (D50) of 1.0 mm or more, preferably 0.2 mm or more, more preferably of 0.1 mm or more are separated from the waste-originating bio-based carbonaceous material (a1 ). The separation of the foreign coarse particles may be performed by means of at least one device selected from the group consisting of roller screens, air classifiers, and cyclone-type separators.

[0035] In an embodiment of the invention, step ii) comprises separating foreign coarse material particles having a median particle size (D50) of 1.0 mm or more from the waste-originating bio-based carbonaceous material (a1 ) by using first an air-classifier to remove light foreign coarse material particles, such as plastics, from the wasteoriginating bio-based carbonaceous material (a1 ) and then as a second stage one or more roller screens to remove heavier coarse material particles, such as sand, from the waste-originating bio-based carbonaceous material (a1 ). The removal of the foreign coarse material lowers the slurry catalyst consumption of the catalytic hydroliquefaction step as the material does not get mixed with the slurry catalyst as mixed foreign coarse material and slurry catalyst are hard to separate.

[0036] Typically, the used catalyst is dispersed with carrier fluid and can have a similar size as the foreign coarse material present in the bio-based carbonaceous feedstock. Therefore, it is especially beneficial to remove the foreign coarse material, such as sand, from the biomaterial feedstock before catalytical hydroliquefaction, because performing this separation step at a latter stage would result in unwanted removal of the catalyst.

[0037] The pretreated bio-based carbonaceous material (c) preferably contains less than 2 wt%, preferably less than 1 .5 wt%, more preferably less than 1 wt% of foreign coarse material of the total weight of the pretreated bio-based carbonaceous material (c). The amount of foreign coarse material in the bio-based carbonaceous feedstock can be measured for example by measuring the ash content of the bio-based carbonaceous feedstock by e.g. SFS-EN ISO 18122:2022 and sieving the ash to be able to measure and deduct the amount of intrinsic inorganic impurities in the biobased carbonaceous feedstock.

[0038] Step iii): Drying and Reducing the Particle Size

[0039] In addition to removal of the foreign coarse material, the bio-based carbonaceous feedstock is subjected to iii-a) drying the bio-based carbonaceous material (a); and iii-b) reducing the particle size of grinding the bio-based carbonaceous material (a) to a predetermined particle size distribution D50 to obtain a pretreated bio-based carbonaceous material (c).

[0040] Drying and reducing the particle size, such as grinding, of the bio-based carbonaceous feedstock may be achieved by any conventional means found suitable for the purpose. Alternatively or in addition to grinding the feedstock may be subjected to milling and / or chipping to achieve the desired predetermined particle size distribution D50.

[0041] The predetermined particle size distribution D50 of the bio-based carbonaceous feedstock after the reduction of the particle size i.e. of the pretreated bio-based carbonaceous material (c) advantageously is less than 25 mm, such from 0.2 to 25 mm, preferably less than 5 mm, such as from 0.5 to 5 mm, more preferably less than 2 mm, as determined by sieving e.g. according to DIN 51938:2015 with laboratory test sieves conforming with ISO 3310 or for solid biofuels SFS-EN ISO 17827-1 :2016 with sieves of 3.15 mm and above SFS-EN ISO 17827-2:2016 for solid biofuels but with sieves of 3.15 mm and below. The desired particle size distribution optimizes the surface area i.e. the contact area of the pretreated bio-based carbonaceous material particles and further enhances homogeneous dispersion in step iv).

[0042] The moisture content of the dried bio-based carbonaceous feedstock i.e. the pretreated bio-based carbonaceous material (c) is preferably from 1 to 20 wt%, more preferably from 2 to 15 wt%, of the total weight of the pretreated bio-based carbonaceous material (c). The moisture content may be determined e.g. by SFS-EN ISO 18134-2:2024.

[0043] Steps ii) and iii), and in particular steps iii-a) and iii-b), can be performed in any order. In an embodiment, removing foreign coarse material from the bio-based carbonaceous feedstock in step ii) is done before drying and reducing the particle size of the bio-based carbonaceous feedstock in step iii). In an alternative embodiment the drying and reducing the particle size of the bio-based carbonaceous feedstock in step iii) is done before removing foreign coarse material from the bio-based carbonaceous feedstock in step ii). In a further embodiment the bio-based carbonaceous feedstock is first subjected to drying iii-a), then removing foreign coarse material from the biobased carbonaceous feedstock ii), and finally to reducing the particle size of the biobased carbonaceous feedstock iii-b).

[0044] Step iv): Catalytic Hydroliquefaction of the Feedstock

[0045] In step iv) the pretreated bio-based carbonaceous material (c) dispersed in a liquid medium (d) is subjected to catalytic hydroliquefaction in the presence of hydrogen and a slurry hydroliquefaction catalyst (e) under mixing to obtain a product composition comprising liquid hydrocarbons and off-gas comprising at least light (Ci- Cs) hydrocarbons and light oxygenates. Without bounding to theory, under the catalytic hydroliquefaction in step iv) the pretreated bio-based carbonaceous material (c) undergoes multiple reactions, including, but not limited to, any one or more of deoxygenation, such as decarbonylation, decarboxylation, hydrodeoxygenation (HDO), hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM), hydrodearomatization (HDA), hydrogenation, and hydrocracking, cleaving e.g. CO, CO2, H2, H2S, NH3, H2O, and lighter oxygenates and hydrocarbons from the various compounds and polymers composing the carbonaceous feedstock to render both gaseous and liquid hydrocarbons. The term “oxygenates" as used herein refers to oxygen containing hydrocarbons. The term “light oxygenates” refers to oxygenates retained in gaseous phase under the prevailing conditions.

[0046] In step iv) the pretreated bio-based carbonaceous material (c) is dispersed in a liquid medium (d) forming a slurry. The slurry may be formed either before step iv) or in step iv). Preferably the slurry is formed before step iv). Further the slurry catalyst utilized in step iv) may be added to the mixture and / or to the liquid medium (d) before it is fed to step iv).

[0047] The liquid medium (d) may be selected from renewable and / or fossil-based hydrocarbons, preferably from renewable hydrocarbons. The liquid medium (d) may be a process generated hydrocarbon stream from the same or adjacent, preferably the same, process or other diluent such as a recycled fraction of hydrotreatment effluent. The boiling point of the liquid medium is preferably from at least 100 °C, preferably at least 160 °C, more preferably at least 220 °C, so as to have suitable viscosity and / or preferably keep the liquid medium in liquid phase under the conditions of step iv). This enhances mixing in the slurry reactor and in particular the pumpability of the slurry. Thus, advantageously the amount of the liquid medium (d) in step iv) is such that the slurry viscosity is such that the mixture of the pretreated bio-based carbonaceous material (c) and the liquid medium (d) is pumpable. A skilled person will be competent to select the amount of the liquid medium such that the desired effect is attained.

[0048] Catalytic hydroliquefaction of the pretreated bio-based carbonaceous material (c) in a slurry reactor environment allows use of mild conditions, use of a variety of feedstocks including recycled feedstocks such as recycled wood and integration of the different process steps.

[0049] The term “catalytic hydroliquefaction” refers to conversion of carbonaceous material into liquid hydrocarbons suitable for use as drop-in fuels, fuel components and / or other valuable hydrocarbon products either directly and / or after further valorization.

[0050] Oxygen present in the carbonaceous feedstock is typically rejected as CO2, CO, H2O, and light oxygenates at the end of the catalytic hydroliquefaction and comprised in the produced off-gas when it is separated from the liquid hydrocarbons produced in the hydroliquefaction step iv). Advantageously, the produced liquid hydrocarbons comprise less than 15 wt% oxygen, preferably less than 10 wt% oxygen, such as 1 to 5 wt% oxygen of the total weight of the liquid hydrocarbons, when measured as elemental oxygen.

[0051] The catalytic hydroliquefaction in step iv) is typically carried out at a temperature from 250 to 450 °C, such as from 270 to 420 °C, preferably from 300 to 400 °C, more preferably from 320 to 390 °C. A skilled person will be competent to select a temperature within these ranges keeping in mind that increasing the temperature will increase the liquid hydrocarbon yield, but a higher temperature will also tend to increase gas yield and cracking, in particular at above 400 °C, Lower temperatures on the other hand will lead to incomplete conversion and higher amount of solids and increase of residence time.

[0052] The catalytic hydroliquefaction in step iv) is typically carried out at a pressure of at least 6 MPa, such as from 6 to 30 Mpa, preferably at least 7 MPa, such as from 7 to 16 MPa, more preferably at least 8 MPa, such as from 8 to 14 MPa, given as gauge pressure. A skilled person will be competent to select a pressure within these ranges keeping in mind that too low pressure leads to higher heavy oil yield due to incomplete deoxygenation during the hydroliquefaction step.

[0053] The residence time in the catalytic hydroliquefaction step may be from a few minutes up to a few hours depending on the temperature and pressure. A person skilled in the art will be competent to adjust the time to fit the intended purpose, appreciating that at higher temperatures and pressures a shorter residence time is sufficient. Typically, the residence time is from 10 minutes to 6 hours, preferably from 30 minutes to 4 hours, more preferably from 1 hour to 3 hours.

[0054] The catalytic hydroliquefaction step is advantageously performed under high hydrogen partial pressure. Typically, the hydrogen partial pressure at the inlet of the hydroliquefaction reactor is at least 5 MPa, such as from 5 to 26 MPa, preferably at least 7 MPa, such as from 6 to 14 MPa, more preferably at least 7 MPa, such as from 7 to 12 MPa, given as gauge pressure.

[0055] The catalytic hydroliquefaction step is performed in the presence of at least one slurry catalyst. Suitable slurry catalysts for the catalytic hydroliquefaction are known hydroconversion catalysts. Sulfided catalysts, such as sulfided heterogeneous metal catalysts comprising at least metal of IIIPAC group 6, 8, 9 or 10 of the Periodic Table of Elements, are preferred. Examples of suitable sulfided heterogeneous metal catalysts include, but are not limited to, sulfided NiMo, sulfided CoMo, and sulfided Mo based catalysts. The catalyst can be unsupported and / or supported. Examples of suitable supports include silica and / or alumina. Preferably the catalyst is unsupported. A person skilled in the art will be competent to adjust the catalyst type and the amount of the catalyst present in the hydroliquefaction step to fit the intended purpose. Suitably, the catalyst can be present in step iv) in an amount from 0.005 to 5 wt%, preferably from 0.01 to 3 wt%, more preferably from 0.1 to 1 wt%.

[0056] The catalytic hydroliquefaction in step iv) may be performed in any suitable slurry reactor such as a mixed tank reactor. Further, the catalytic hydroliquefaction in step iv) is advantageously performed in continuous mode. Typically, the catalytic hydroliquefaction in step iv) is performed in a continuous stirred tank reactor (CSTR). Preferably the step iv) is performed such that concentrations and the temperature are essentially the same in all parts of the reactor. Efficient mixing in the mixed tank reactor may be ensured by mechanical stirring and / or liquid recycling.

[0057] The catalytic hydroliquefaction step iv) can be accomplished in one stage or in two or more consecutive stages. For optimal performance the hydroliquefaction step is accomplished in two or more, preferably two consecutive stages.

[0058] Step v) Separation of the liquid hydrocarbons and the off-gas

[0059] In step v) the liquid hydrocarbons and the off-gas are separated to obtain a liquid hydrocarbon fraction (f) comprising liquid hydrocarbons and less than 15 wt% oxygen of the total weight of the liquid hydrocarbon composition (f) measured as elemental oxygen and a first gaseous fraction (c-1 ) comprising light (C1-C5) hydrocarbons and light oxygenates. Separation is typically achieved at high temperature and high pressure. It is preferred that the conditions of the preceding hydroliquefaction step iv) are essentially maintained in separation step v).

[0060] After the first high temperature and high pressure separation, the separation in step v) may comprise one or more, preferably one, further separation stage(s), each performed in lower temperature than the previous separation stage while the pressure typically remains essentially the same, to separate further condensables, such as condensable hydrocarbons and / or water, from the first gaseous fraction. The condensables separated in the further separation stages of step v) may be combined to the liquid hydrocarbon fraction (f).

[0061] Thus, typically the separation step v) is carried out at a pressure at least 6 MPa, such as from 6 to 30 Mpa, preferably at least 7 MPa, such as from 7 to 16 MPa, more preferably at least 8 MPa, such as from 8 to 14 MPa, given as gauge pressure. A skilled person will be competent to select a pressure for each consecutive stage within these ranges keeping in mind that preferably the last preceding catalytic hydroliquefaction stage determines the pressure of the following separation step.

[0062] Further, typically the first stage of the separation step v) is carried out at a temperature from 270 to 420 °C, preferably from 300 to 400 °C, more preferably from 320 to 390 °C. A skilled person will be competent to select a temperature for each consecutive stage within these ranges, keeping in mind that preferably the last preceding catalytic hydroliquefaction stage determines the temperature of the following first separation stage and the optional further separation stages are performed at a lower temperature.

[0063] The separation in step v) may be accomplished by any unit operation suitable for separation of a gaseous phase and a liquid phase and wherein the indicated conditions may be achieved, such as by a separator or by distillation, preferably by a separator.

[0064] After the separation the first gaseous fraction is subjected purification in step vii) and the liquid hydrocarbon fraction (f) is subjected to further valorization by catalytic upgrading in step vi) to allow utilization as fuels, fuel components, and / or other valuable hydrocarbon products, in particular renewable fuels, renewable fuel components, and / or other valuable renewable hydrocarbon products.

[0065] Step vi) Catalytic Upgrading

[0066] In step vi) the hydrocarbon fraction is subjected to further valorization by catalytic upgrading, such as catalytic hydroprocessing, to obtain renewable hydrocarbons such as e.g. drop-in renewable fuel(s), renewable fuel component(s) and / or other valuable renewable hydrocarbon products. Such catalytic upgrading processes include, but are not limited to, catalytic cracking, catalytic hydrocracking, thermo-catalytic cracking, catalytic hydrotreatment, fluid catalytic cracking, catalytic ketonization, and catalytic esterification. Such processes require the liquid feedstock to be sufficiently pure and free from impurities that may otherwise hamper the catalytic process or deactivate or poison the catalyst(s) present in the process.

[0067] Thus, the hydrocarbon fraction is preferably subjected to catalytic hydroprocessing.

[0068] The catalytic upgrading, preferably catalytic hydroprocessing, may be any upgrading process employing hydrogen and where the hydrocarbon fraction may be used as the process feed, optionally with a co-feed. For example, hydroprocessing may be an upgrading process to obtain liquid transportation fuel components, solvents, technical fluids, such as electrotechnical fluids, cracking feedstocks, such as feedstocks for thermal cracking and / or catalytic cracking, and / or base chemicals for different syntheses.

[0069] According to an embodiment, a co-feed of fossil and / or renewable origin is fed to catalytic upgrading.

[0070] The catalytic upgrading, preferably catalytic hydroprocessing, may comprise altering molecular weight, removal of heteroatoms, altering degree of saturation, rearranging molecular structure, or any combination thereof. The hydroprocessing comprises preferably altering molecular weight of the process feed or any intermediate stream or intermediate product derivable or derived therefrom, removal of heteroatoms from the process feed or any intermediate stream or intermediate product derivable or derived therefrom, altering degree of saturation of the process feed or any intermediate stream or intermediate product derivable or derived therefrom, rearranging molecular structure of the process feed or any intermediate stream or intermediate product derivable or derived therefrom, or any combination thereof.

[0071] In certain preferred embodiments, the catalytic hydroprocessing comprises hydrotreatment, isomerization, and / or cracking, preferably hydrodeoxygenation (HDO), hydroisomerization (HI), hydrodewaxing (HDW), and / or hydrocracking (HC), of the process feed or an intermediate stream or intermediate product derivable or derived therefrom, optionally followed by fractionation.

[0072] In certain preferred embodiments, the catalytic hydroprocessing comprises catalytic hydroprocessing converting the hydrocarbon fraction to one or more drop-in liquid transportation fuel(s), one or more liquid transportation fuel component(s) and / or other valuable hydrocarbon product(s)chemicals. The process comprises subjecting the process feed to hydroprocessing comprising hydrodeoxygenation, hydroisomerization, and optionally hydrocracking, followed by fractionation of the hydroprocessing effluent and recovery of one or more drop-in liquid transport fuel(s), one or more liquid transportation fuel component(s) and / or other valuable hydrocarbon products from the fractionation.

[0073] The catalytic upgrading, preferably the catalytic hydroprocessing, may occur in the presence of a catalyst selected from Pd, Pt, Ni, Co, Mo, Ru, Rh, W, or any combination of these, such as CoMo, NiMo, NiW, CoNiMo, NiMoW or together with SAPO-11 , SAPO-41 , ZSM-22, ZSM-23, ZSM-12, ZSM-48, ZSM-5, beta zeolites, ferrierite and mixtures thereof, such as Pt / SAPO-11 / AI2O3, Pt / ZSM-22 / AI2O3, Pt / ZSM-23 / AI2O3, Pt / SAPO-11 / SiO2, optionally on a support, wherein the support comprises preferably alumina and / or silica.

[0074] The obtained liquid hydrocarbon product (h) may be subjected to e.g. fractionating to provide at least a gasoline fraction and a middle distillate fraction. These fractions are the most valuable for transportation fuels and thus separating these fractions from less valuable fractions is favorable. In addition to a gasoline stream and a middle distillate stream, the fractions derived from the fractionation may comprise a gas stream and a distillation bottom. The fractionation may comprise any suitable distillation means, including distillation at normal pressure or distillation or evaporation under reduced pressure. Thus, in an embodiment the liquid hydrocarbon product (h) is fractionated into one or more of renewable aviation fuel, renewable marine fuel, renewable road transport fuel, steam cracker feed (LPG / naphtha), mixed aromatics stream.

[0075] The present method allows the production of fuels, fuel components, and / or other valuable hydrocarbon products with reduced oxygen and sulfur content as compared to corresponding products obtained with comparative conventional methods not utilizing intermediate partial oxidation of light hydrocarbons and shifting carbon monoxide to carbon dioxide as described herein. Further, the obtained products may have improved cloud point and aromatics content.

[0076] Step vii) recovery of oxygenates by sponge oil

[0077] In step vii) a part of the liquid hydrocarbon product composition (h) is separated from the main part to obtain a sponge oil fraction (i-1 ) which is then contacted, preferably countercurrently, with the first gaseous fraction (g-1 ) to adsorb at least part of the oxygenates comprised in the first gaseous fraction (c-1 ) to obtain an oxygen enriched sponge oil fraction (i-2) and a second gaseous fraction (g-2) comprising less than less than 1 wt%, preferably less than 0.5 wt%, more preferably less than 0.1 wt%, oxygen covalently bound to oxygenates of the total weight of the second gaseous fraction (g-2) measured as elemental oxygen. Advantageously essentially all, preferably at least 98% of the oxygenates present in the first gaseous fraction are removed in step viii). In addition to oxygenates, typically hydrocarbons heavier than propane are also adsorbed to the sponge oil.

[0078] After the recovery of the oxygenates the oxygen enriched sponge oil fraction (i- 2) is fed back to catalytic upgrading.

[0079] The sponge oil adsorption in step vii) is typically achieved at a pressure of 30 to 60 °C and a pressure of at least 6 MPa, such as from 6 to 30 Mpa, preferably at least 7 MPa, such as from 7 to 16 MPa, more preferably at least 8 MPa, such as from 8 to 14 MPa, given as gauge pressure. A skilled person will be competent to select a pressure and a pressure within these ranges keeping in mind that the last separation step v) determines the pressure of the sponge adsorption step vii). The sponge oil mass flow (ratio of the gas to the sponge oil) is advantageous 0.5 to 5 times, preferably 1 to 2.5 times the gas mass flow rate of the first gaseous fraction. Figure 1 illustrates a first exemplary process flow of the present method.

[0080] Referring to Figure 1 , a bio-based carbonaceous feedstock (a) 1 comprising wasteoriginating bio-based carbonaceous material (a1 ) and foreign coarse material (b), such as sand and / or dirt, is first subjected to removing 10 the foreign coarse material (b) 91 from the bio-based carbonaceous material (a) to obtain bio-based carbonaceous feedstock from which foreign coarse material has been removed 11 , which is then subjected to drying 20 to obtain a dried bio-based carbonaceous feedstock 12, which is then subjected to reducing the particle sizes, by e.g. grinding, 30 to a predetermined particle size to obtain a pretreated bio-based carbonaceous material (c) 31. The pretreated bio-based carbonaceous material (c) 31 dispersed in a liquid medium (d) 39 is then subjected to catalytic hydroliquefaction 40 in the presence of hydrogen and a slurry hydroliquefaction catalyst (e) (not shown) under mixing to obtain a product composition 41 comprising liquid hydrocarbons and off-gas comprising at least light (C1-C5) hydrocarbons and light oxygenates. The product composition 41 is then subjected to separation 50 of the liquid hydrocarbons and the off-gas to obtain a liquid hydrocarbon fraction (f) 51 comprising liquid hydrocarbons and less than 15 wt% oxygen and a first gaseous fraction (g-1 ) 81 comprising at least light (C1-C5) hydrocarbons and light oxygenates. Thereafter the liquid hydrocarbon fraction (f) 51 is subjected to catalytic upgrading 60, such as catalytic hydrotreatment, to obtain a liquid hydrocarbon product composition (h) 61 comprising less than 1 wt% oxygen. Then a part of the liquid hydrocarbon product composition is divided 70 from the liquid hydrocarbon product composition (h) 61 to obtain a sponge oil fraction (s-1 ) 71 and a main part of the liquid hydrocarbon product 62. Subsequently the sponge oil fraction (s-1 ) 71 is contacted 80, preferably countercurrently, with the first gaseous fraction (g-

[0081] 1 ) 81 to adsorb at least part of the oxygenates comprised in the first gaseous fraction (g-1 ) to the sponge oil fraction (s-1 ) to obtain a oxygen enriched sponge oil fraction (s-

[0082] 2) 72 and a second gaseous fraction (g-2) 82 comprising less than 1 wt% oxygen covalently bound to oxygenate. The oxygen enriched sponge oil 72 fraction (s-2) is then fed back to catalytic upgrading 60.

[0083] Figure 2 illustrates a second exemplary process flow of the present method.

[0084] Referring to Figure 2, a bio-based carbonaceous feedstock (a) 1 comprising waste-originating bio-based carbonaceous material (a1 ) and foreign coarse material (b), such as sand and / or dirt, is first subjected to removing 10 the foreign coarse material (b) 91 from the bio-based carbonaceous material (a) and then to reducing the particle sizes, by e.g. grinding, 30 to a predetermined particle size and then to drying 20 to obtain a pretreated bio-based carbonaceous material (c) 31 . The pretreated biobased carbonaceous material (c) 31 dispersed in a liquid medium (d) 39 is then subjected to catalytic hydroliquefaction 40 in the presence of hydrogen and a slurry hydroliquefaction catalyst (e) (not shown) under mixing to obtain a product composition 41 comprising liquid hydrocarbons and off-gas comprising at least light (C1-C5) hydrocarbons and light oxygenates. The product composition 41 is then subjected to separation 50 of the liquid hydrocarbons and the off-gas to obtain a liquid hydrocarbon fraction (f) 51 comprising liquid hydrocarbons and less than 15 wt% oxygen and a first gaseous fraction (g-1 ) 81 comprising at least light (C1-C5) hydrocarbons and light oxygenates. Thereafter the liquid hydrocarbon fraction (f) 51 is subjected to catalytic upgrading 60, such as catalytic hydrotreatment, to obtain a liquid hydrocarbon product composition (h) 61 comprising less than 1 wt% oxygen. Then a part of the liquid hydrocarbon product composition is divided 70 from the liquid hydrocarbon product composition (h) 61 to obtain a sponge oil fraction (s-1 ) 71 and a main part of the liquid hydrocarbon product 62. Subsequently the sponge oil fraction (s-1 ) 71 is contacted 80, preferably countercurrently, the sponge oil fraction (i) with the first gaseous fraction (g-1 ) 81 to adsorb at least part of the oxygenates comprised in the first gaseous fraction (g-1 ) to the sponge oil fraction (s-1 ) to obtain a oxygen enriched sponge oil fraction (s-2) 72 and a second gaseous fraction (g-2) 82 comprising less than 1 wt% oxygen covalently bound to oxygenates. The oxygen enriched sponge oil 72 fraction (s-2) is then fed back to catalytic upgrading 60.

[0085] Figure 3 illustrates a third exemplary process flow of the present method.

[0086] Referring to Figure 3, a bio-based carbonaceous feedstock (a) 1 comprising waste-originating bio-based carbonaceous material (a1 ) and foreign coarse material (b), such as sand and / or dirt, is first subjected to drying 20 and to removing 10 the foreign coarse material (b) 91 from the bio-based carbonaceous material (a) and then reducing the particle sizes, by e.g. grinding, 30 to a predetermined particle size to obtain a pretreated bio-based carbonaceous material (c) 31 . The pretreated bio-based carbonaceous material (c) 31 dispersed in a liquid medium (d) 39 is then subjected to catalytic hydroliquefaction 40 in the presence of hydrogen and a slurry hydroliquefaction catalyst (e) (not shown) under mixing to obtain a product composition 41 comprising liquid hydrocarbons and off-gas comprising at least light (C1-C5) hydrocarbons and light oxygenates. The product composition 41 is then subjected to separation 50 of the liquid hydrocarbons and the off-gas to obtain a liquid hydrocarbon fraction (f) 51 comprising liquid hydrocarbons and less than 15 wt% oxygen and a first gaseous fraction (g-1 ) 81 comprising at least light (C1-C5) hydrocarbons and light oxygenates. Thereafter the liquid hydrocarbon fraction (f) 51 is subjected to catalytic upgrading 60, such as catalytic hydrotreatment, to obtain a liquid hydrocarbon product composition (h) 61 comprising less than 1 wt% oxygen. Then a part of the liquid hydrocarbon product composition is divided 70 from the liquid hydrocarbon product composition (h) 61 to obtain a sponge oil fraction (s-1 ) 71 and a main part of the liquid hydrocarbon product 62. Subsequently the sponge oil fraction (s-1 ) 71 is contacted 80, preferably countercurrently, the sponge oil fraction (i) with the first gaseous fraction (g-1 ) 81 to adsorb at least part of the oxygenates comprised in the first gaseous fraction (g-1 ) to the sponge oil fraction (s-1 ) to obtain a oxygen enriched sponge oil fraction (s-2) 72 and a second gaseous fraction (g-2) 82 comprising less than 1 wt% oxygen covalently bound to oxygenates. The oxygen enriched sponge oil 72 fraction (s-2) is then fed back to catalytic upgrading 60.

[0087] Figure 4 illustrates a third exemplary process flow of the present method.

[0088] Referring to Figure 4, a bio-based carbonaceous feedstock (a) 1 comprising waste-originating bio-based carbonaceous material (a1 ) and foreign coarse material (b), such as sand and / or dirt, is first subjected to drying 20 and then reducing the particle sizes, by e.g. grinding, 30 to a predetermined particle size and then to removing 10 the foreign coarse material (b) 91 from the bio-based carbonaceous material (a) to obtain a pretreated bio-based carbonaceous material (c) 31. The pretreated bio-based carbonaceous material (c) 31 dispersed in a liquid medium (d) 39 is then subjected to catalytic hydroliquefaction 40 in the presence of hydrogen and a slurry hydroliquefaction catalyst (e) (not shown) under mixing to obtain a product composition 41 comprising liquid hydrocarbons and off-gas comprising at least light (C1-C5) hydrocarbons and light oxygenates. The product composition 41 is then subjected to separation 50 of the liquid hydrocarbons and the off-gas to obtain a liquid hydrocarbon fraction (f) 51 comprising liquid hydrocarbons and less than 15 wt% oxygen and a first gaseous fraction (g-1 ) 81 comprising at least light (C1-C5) hydrocarbons and light oxygenates. Thereafter the liquid hydrocarbon fraction (f) 51 is subjected to catalytic upgrading 60, such as catalytic hydrotreatment, to obtain a liquid hydrocarbon product composition (h) 61 comprising less than 1 wt% oxygen. Then a part of the liquid hydrocarbon product composition is divided 70 from the liquid hydrocarbon product composition (h) 61 to obtain a sponge oil fraction (s-1 ) 71 and a main part of the liquid hydrocarbon product 62. Subsequently the sponge oil fraction (s-1 ) 71 is contacted 80, preferably countercurrently, the sponge oil fraction (i) with the first gaseous fraction (g-1 ) 81 to adsorb at least part of the oxygenates comprised in the first gaseous fraction (g-1 ) to the sponge oil fraction (s-1 ) to obtain a oxygen enriched sponge oil fraction (s-2) 72 and a second gaseous fraction (g-2) 82 comprising less than 1 wt% oxygen covalently bound to oxygenates. The oxygen enriched sponge oil 72 fraction (s-2) is then fed back to catalytic upgrading 60.

Claims

CLAIMS1 . A method for the production of liquid hydrocarbon composition, comprising i) providing a bio-based carbonaceous feedstock (a) comprising wasteoriginating bio-based carbonaceous material (a1 ) and foreign coarse material (b), such as sand and / or dirt; ii) removing at least part, preferably most, more preferably essentially all, of the foreign coarse material (b) from the bio-based carbonaceous material (a); and iii-a) drying the bio-based carbonaceous material (a); and iii-b) reducing the particle size of grinding the bio-based carbonaceous material (a) to a predetermined particle size distribution D50; to obtain a pretreated bio-based carbonaceous material (c); iv) subjecting the pretreated bio-based carbonaceous material (c) dispersed in a liquid medium (d) to catalytic hydroliquefaction in the presence of hydrogen and a slurry hydroliquefaction catalyst (e) under mixing to obtain a product composition comprising liquid hydrocarbons and off-gas comprising at least light (C1-C5) hydrocarbons and light oxygenates; v) separating the liquid hydrocarbons and the off-gas to obtain a liquid hydrocarbon fraction (f) comprising liquid hydrocarbons and less than 15 wt% oxygen of the total weight of the liquid hydrocarbon fraction (f) measured as elemental oxygen and a first gaseous fraction (g-1 ) comprising at least light (C1-C5) hydrocarbons and light oxygenates; vi) subjecting the liquid hydrocarbon composition (f) to catalytic upgrading to obtain a liquid hydrocarbon product composition (h) comprising less than 1 wt% oxygen of the total weight of the liquid hydrocarbon product (h) measured as elemental oxygen; and vii) dividing a part of the liquid hydrocarbon product composition from the liquid hydrocarbon product (h) to obtain a sponge oil fraction (s-1 ) and contacting, preferably countercurrently, the sponge oil fraction (i) with the first gaseous fraction (g-1 ) to adsorb at least part of the oxygenates comprised in the first gaseous fraction (g-1 ) toobtain a oxygen enriched sponge oil fraction (s-2) and a second gaseous fraction (g- 2) comprising less than 1 wt%, preferably less than 0.5 wt%, more preferably less than 0.1 wt%, oxygen covalently bound to oxygenates of the total weight of the second gaseous fraction (g-2) measured as elemental oxygen, and feeding the oxygen enriched sponge oil fraction (s-2) to catalytic upgrading.

2. The method as claimed in claim 1 , wherein predetermined particle size distribution D50 of the bio-based carbonaceous feedstock of the pretreated bio-based carbonaceous material (c) advantageously is less than 25 mm, such from 0.2 to 25 mm, preferably less than 5 mm, such as from 0.5 to 5 mm, more preferably less than 2 mm.

3. The method as claimed in claim 1 or 2, wherein the moisture content of the pretreated bio-based carbonaceous material (c) is preferably from 1 to 20 wt%, more preferably from 2 to 15 wt%, of the total weight of the pretreated bio-based carbonaceous material (c).

4. The method as claimed in any one of claims 1 to 3, wherein in step ii) removing foreign coarse material is accomplished by means of at least one device selected from the group consisting of roller screens, air classifiers, and cyclone-type separators.

5. The method as claimed in any one of claims 1 to 4, wherein the pretreated bio-based material contains less than 2 wt%, preferably less than 1.5 wt%, more preferably less than 1 wt% of foreign coarse material of the total weight of the pretreated bio-based material.

6. The method as claimed in any one of claims 1 to 5, wherein the catalytic hydroliquefaction in step iv) is carried out at a temperature from 250 to 450 °C, such as from 270 to 420 °C, preferably from 300 to 400 °C, more preferably from 320 to 390 °C.

7. The method as claimed in any of claims 1 to 6, wherein the catalytic hydroliquefaction in step iv) is carried out at a pressure of at least 6 MPa, such as from 6 to 30 Mpa, preferably at least 7 MPa, such as from 7 to 16 MPa, more preferably at least 8 MPa, such as from 8 to 14 MPa, given as gauge pressure.

8. The method as claimed in any of claims 1 to 7, wherein the unsupported hydroliquefaction catalyst in the catalytic hydroliquefaction step iv) is selected from sulfided heterogeneous metal catalysts, preferably from sulfided NiMo, sulfided CoMo, and sulfided Mo based catalysts.

9. The method as claimed in any of claims 1 to 8, wherein the carbonaceous bio-based feedstock comprises, preferably consists of, biomass feedstock, such as lignocellulosic biomass feedstock.

10. The method as claimed in any of claims 1 to 9, wherein the carbonaceous feedstock comprises more than 10 wt%, preferably at least 20 wt%, more preferably at least 30 wt%, oxygen on a dry basis, measured as elemental oxygen.11 . The method as claimed in any of claims 1 to 10, wherein the carbonaceous feedstock comprises from 45 to 55 wt%, carbon, and less than 10 wt%, such as from 5 to 8 wt%, hydrogen on a dry basis, measured as elemental carbon and hydrogen, respectively.

12. The method as claimed in any of claims 1 to 11 , wherein the catalytic hydroliquefaction is accomplished in a continuous stirred tank reactor.

13. The method as claimed in any of claims 1 to 12, wherein the liquid hydrocarbon product (h) is fractionated into one or more of renewable aviation fuel, renewable marine fuel, renewable road transport fuel, steam cracker feed (LPG / naphtha), mixed aromatics stream.

14. The method as claimed in any of claims 1 to 13, wherein the bio-based carbonaceous material contemplated herein is solid at 25°C and 101.325 kPa absolute.

15. The method as claimed in any of claims 1 to 14, wherein the liquid medium is a process generated hydrocarbon stream from the same or adjacent, preferably the same, process or a recycled fraction of hydrotreatment effluent, the liquid medium is preferably having boiling point of at least 100 °C, more preferably at least 160 °C, even more preferably at least 220 °C.

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