EP4574930A1 - Procédé de traitement d'une charge carbonée liquide issue d'un traitement de liquéfaction hydrothermale - Google Patents

Procédé de traitement d'une charge carbonée liquide issue d'un traitement de liquéfaction hydrothermale Download PDF

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Publication number
EP4574930A1
EP4574930A1 EP23315464.0A EP23315464A EP4574930A1 EP 4574930 A1 EP4574930 A1 EP 4574930A1 EP 23315464 A EP23315464 A EP 23315464A EP 4574930 A1 EP4574930 A1 EP 4574930A1
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EP
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Prior art keywords
liquid
phase
biocrude
diluent
separation
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP23315464.0A
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German (de)
English (en)
Inventor
Frédéric AUGIER
Romina Digne
Jan Henning Kleverud
Klaus Schoeffel
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IFP Energies Nouvelles IFPEN
Silva Green Fuel Da
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IFP Energies Nouvelles IFPEN
Silva Green Fuel Da
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Application filed by IFP Energies Nouvelles IFPEN, Silva Green Fuel Da filed Critical IFP Energies Nouvelles IFPEN
Priority to EP23315464.0A priority Critical patent/EP4574930A1/fr
Priority to PCT/EP2024/084369 priority patent/WO2025131655A1/fr
Publication of EP4574930A1 publication Critical patent/EP4574930A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
    • C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/02—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately
    • C10G21/04—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately by introducing simultaneously at least two immiscible solvents counter-current to each other
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/08—Inorganic compounds only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/28—Recovery of used solvent
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1018—Biomass of animal origin

Definitions

  • the present invention relates to the production of recoverable chemicals or biofuels from biomass, including lignocellulosic biomass. More specifically, the invention relates to biomass hydrothermal liquefaction processes, also known by the acronym HTL for "HydroThermal Liquefaction", which make it possible to transform biomass into a carbon feedstock called “biocrude”. This so-called “biocrude” must then be treated, including notably hydroconversion, hydrotreatment, hydrocracking, catalytic cracking, to obtain the desired chemicals to the desired specifications.
  • Hydrothermal liquefaction (see “ Continuous Hydrothermal Liquefaction of biomass: a critical review", D. Castello, T. H. Pederson, L. A. Rosendahl, Energys 2018, 11, 3165 ) is a process of converting a charge in the presence of water at a pressure between 100 and 350 bar (between 10 7 Pa and 3.5 7 Pa) and at a temperature between 250 and 450°C.
  • Catalysts can be used for hydrothermal liquefaction, like pH modifiers, NaOH, KOH, K 2 CO 3 , Na 2 CO 3 , etc.
  • Biocrude consisting mainly of organic molecules, an aqueous phase comprising water-soluble organic compounds (alcohols, acids, ketones, phenols, etc.) and salts, gases and possibly biochar.
  • Biochar is a carbon-rich solid product, "char” deriving from the English word “charcoal”.
  • the gas produced consists mainly of CO 2 but can also contain hydrogen, methane, and CO.
  • water may be present in liquid form or in a relatively dense supercritical state.
  • Water close to the critical point (374°C, 221 bar) has very different properties than those of water at room temperature. These near-critical properties allow water to play several roles in the conversion process such as being a reactant, a catalyst, or a source of hydrogen.
  • Near the critical point or in the supercritical state water has properties that facilitate liquefaction such as a low dielectric constant that allows solubilization of nonpolar molecules and an ionic product high enough to favor ionic reactions leading to liquid products over free radical reactions leading to solid or gaseous products.
  • the hydrothermal liquefaction feedstock can be biomass, preferably selected from plants, grasses, trees, wood chips, seeds, fibers, seed husks, aquatic plants, algae, hay, and other sources of lignocell,ulosic materials, such as those from organic waste, municipal waste, agri-food waste, animal waste, forestry waste, sawmill waste, logging residues, agricultural and industrial waste (such as sugarcane bagasse, oil palm waste, sawdust, or straw).
  • the feedstock of hydrothermal liquefaction can also come from paper pulp and paper by-products, recycled or not, or from by-products from paper mills, waste such as used plastics, worn tires.
  • the filler can also be a mixture of two or more of these materials.
  • Biocrude obtained by hydrothermal liquefaction is a complex mixture of compounds, consisting mainly of hydrocarbons and oxygenated compounds.
  • oxygenated compounds are organic acids, ketones, oxygenated aromatic compounds, alcohols, aldehydes, esters, ethers, and water. Water usually accounts for less than 15% by weight of the biocrude.
  • the biocrude contains compounds from cellulose, hemicellulose, and lignin (the structure found in lignocellulosic biomass).
  • the biocrude obtained by hydrothermal liquefaction has an oxygen, sulfur and nitrogen content that varies greatly depending on the feedstock of the hydrothermal liquefaction (algae, wood, etc.).
  • the biocrude from hydrothermal liquefaction of wood is generally made up of 5 to 20% weight of oxygen, less than 0.5% weight of sulfur and less than 5% weight of nitrogen in the dry biocrude (without water).
  • Biocrude can contain up to 4% weight of inorganics (mineral compounds), mainly metals such as sodium, potassium but also calcium, iron, etc. These mineral compounds can come from the catalysts used for hydrothermal liquefaction, from the hydrothermal liquefaction feedstock itself, and from the metals possibly used to grind the hydrothermal liquefaction feedstock.
  • Sodium and potassium can be present in relatively large quantities in the biocrude, as the hydrothermal liquefaction process typically uses alkali-based catalysts (NaOH, KOH, K 2 CO 3 , Na 2 CO 3 ...) in significant quantities.
  • biocrude To be transformed into biofuels (petrol, kerosene, diesel, marine fuel oil) or chemicals, biocrude must be processed, in particular with a view to reducing heteroatoms and more particularly the oxygen it contains.
  • This treatment may include at least one operation chosen from hydroconversion, hydrotreatment, hydrocracking, or catalytic cracking.
  • these operations use catalysts known to the skilled person as sensitive to metal content (in particular to alkali or alkaline earth metals such as Na, K, Ca, etc.). These metals poison the catalysts: they deactivate them at least partially.
  • the invention if it can be summarized synthetically, consists in integrating in a single process
  • this extract is an aqueous solution rich in mineral compounds, and recycling it in the separation step d) will allow these mineral compounds to be recycled, ultimately, towards step b) of liquefaction:
  • These mineral compounds include metal compounds from catalysts used in liquefaction. This recycling therefore makes it possible to reduce or even eliminate the consumption of catalysts in the hydrothermal liquefaction stage of the biomass.
  • Extracting in such a column requires a sufficient difference in density between the phases present (often greater than 50 kg/m 3 ), and the greater the difference in density, the easier it will be.
  • the viscosity of one or both phases plays an important role in this operation, as the more it increases, the more the transfer of material between phases will be slowed down on the one hand, and the more the capacity of the column is likely to decrease, in terms of the possible feedstock rate per column section unit on the other hand.
  • Counter-stream columns are interesting because they allow the desired solutes to be extracted much better than in a co-stream column or in a stirred tank. Indeed, the number of theoretical stages can reach high values (between 2 and 15 in the vast majority of cases), and with minimized solvent consumption.
  • the first so-called light organic phase obtained in step (j) can be at least partly recycled as the first organic phase in mixing stage (a).
  • At least part of the second liquid organic phase known as the biocrude obtained in step (c) of liquid /liquid/gas separation may be recycled as the first organic phase in mixing stage (a).
  • the method according to the invention may comprise a step (l) of at least partial recycling of the phase comprising the diluent obtained in step (g) of separation in step (c) of liquid/liquid/gas separation.
  • This recycling of the diluent phase which is in fact a light fraction of biocrude, at the c) liquid/ liquid/gas separation has been shown to improve the liquid /liquid/gas separation.
  • the method according to the invention may comprise a step (m) of at least partial recycling of the third liquid aqueous phase in mixing step (a).
  • This phase is aqueous and may contain mineral compounds, its recycling in mixing step a) reduces both the water and catalyst consumption of the hydrothermal liquefaction.
  • the method according to the invention may comprise at least a recycling step of the first organic phase and/or the second organic phase in the mixing step (a) (via flow 4 as detailed below).
  • This additional recycling option reduces the consumption in the organic phase required for the pre-liquefaction mixing operation.
  • step b) of hydrothermal liquefaction involves heating, at a temperature between 250°C and 450°C under a pressure between 100 bar (10 7 Pa ) and 350 bar (3.5.10 7 Pa), in the presence of at least one catalyst containing at least a pH modifier and/or an alkaline, such as Na or K, and/or an alkaline earth such as Ca.
  • the diluent used in the dilution step (e) is selected from a light cut in the biocrude filler or a chemical compound or mixture of chemical compounds, including alcohols, ethers, ketones, and hydrocarbons.
  • the process can be started with a diluent with a boiling temperature close to that of the phase comprising the diluent to be recycled according to step (g), which is a light cut of the biocrude, then this phase will gradually accumulate in the recycling loop over time and will thus gradually replace the initial diluent.
  • the diluent has a final boiling point of at most 150°C, preferably at most 100°C.
  • the dilute biocrude has a dynamic viscosity at 20°C of at most 7 cP, preferably at most 4 cP, and a density at 15°C of at most 950 kg/m 3 , preferably at most 900 kg/m 3 .
  • the ratio R of the flow rate Qd of the diluent to the flow rate Qb of the biocrude is at most 10, and in particular at least 0.1, with the ratio R preferably between 0.5 and 3.
  • contact step (f) is carried out at a pressure between 0.5.10 5 Pa and 15.1 Pa, and at a temperature between 15 and 1 50°C, while remaining below the boiling temperature of the diluent at the contact pressure.
  • step (d) of separation and/or step (g) of separation and/or step (j) of separation is a treatment consisting of at least evaporation, distillation, heating followed by separation.
  • the diluent used in step (e) of dilution is selected from a light cut in the biocrude filler or a chemical compound or mixture of chemical compounds, including alcohols, ethers, ketones, and hydrocarbons.
  • the solvent used in contacting step (f) is selected from at least one of the following solutions: pure aqueous solution, demineralized aqueous solution, aqueous solution containing soluble organic compounds, acidic aqueous solution.
  • an acidic aqueous solution it may contain from 10 ppm to 20% weight of an organic or mineral acid, strong or weak, such as acetic acid, nitric acid, sulfuric acid, hydrochloric acid, citric acid, oxalic acid, lactic acid, formic acid, or any other acid.
  • One or at least one of the solvents when there are several ones, may also be an aqueous solution acidified by injection of carbon dioxide into the aqueous solution (which may already contain one of the above-mentioned acids). Indeed, the hydrothermal liquefaction step prior to treatment according to the invention tends to generate carbon dioxide, which can therefore be advantageously used to acidify the solvent(s), if necessary.
  • this solvent used for contacting step (f) comes from the recycling of at least part of the first vapor phase from separation step (d), once condensed.
  • Only one type of solvent can be used, e.g., injected at the top, at the head of the column operating the liquid/liquid extraction (when it is vertically oriented), with a possible second injection point at an intermediate height.
  • two separate solvents can be used, which are brought into contact with the diluted biocrude in separate contact zones, e.g., with the first injected at the top/head of the column and the second at an intermediate column height.
  • the total height H is the useful height of the column, which is known in the field of liquid-liquid extraction or distillation columns. If the first solvent (or the second solvent) has a second inlet in the column at an intermediate height H 3 , then this intermediate height H 3 is preferably lower than the height H 2 of the inlet of the second solvent (or first solvent ).
  • this height H 3 of the second inlet of the first solvent (or of the second solvent) can be such that, H being the total height of the column, the ratio H 3 /H is between 0.05 and 0.4.
  • the solvent is preferably aqueous.
  • the first is at a neutral pH (between 6.5 and 7.5, possibly containing soluble organic molecules) while the second is acidic (pH less than 6.5, with the addition of acid (e.g. an acidic aqueous solution containing from 10 ppm to 20% weight of at least one strong or weak acid, organic or mineral, in particular selected from at least one of the following acids: acetic acid, nitric acid, sulfuric acid, hydrochloric acid, citric acid, oxalic acid, lactic acid, formic acid, and possibly soluble organic molecules).
  • acid e.g. an acidic aqueous solution containing from 10 ppm to 20% weight of at least one strong or weak acid, organic or mineral, in particular selected from at least one of the following acids: acetic acid, nitric acid, sulfuric acid, hydrochloric acid, citric acid, oxalic acid, lactic acid, formic acid, and possibly soluble organic molecules).
  • contacting step (f) includes a dedicated or additional settling (decantation) to improve the settling between the two aqueous and organic phases.
  • the settling device used e.g., a decanter
  • the extraction column or one of those used in step c) may have a short-residence time settling function, which tends to separate the phases in a non-optimal manner, and it is possible that a fraction of residual free water (droplets) may be entrained in the raffinate.
  • a decanter can be placed downstream (line 25 detailed below) to better separate the water (and not upstream of the column). If the contact between the two liquid phases is made via two separate columns, then a decanter can be placed between the two columns, or only one at the outlet of the second column (or no decanter at all).
  • step (f) of contacting the dilute biocrude (20) obtained in step (e) is carried out with at least two separate solvents, which are brought into contact with said dilute biocrude in separate contact zones and comprising a first solvent which is an aqueous liquid phase with a neutral pH, in particular between 6.5 and 7.5, and a second solvent which is an acidic aqueous liquid phase, having a pH of less than 6.5.
  • the invention also relates to a hydrothermal liquefaction facility of a feedstock derived at least in part from biomass, with a view to obtaining a so-called biocrude product, with a reduced content in mineral compounds, in particular metallics, which implements the process described above.
  • the invention also relates to a facility of hydrothermal liquefaction of an initial carbonaceous feedstock at least partly derived from biomass, in order to obtain a so-called biocrude product with a reduced content of mineral compounds, the said facility comprising the following devices :
  • the devices implementing the steps of the process described above are included. As already stated, some of the devices may be common to multiple steps/operations.
  • the (e) dilution device may be a tank-type device fed by both the biocrude feedstock and the diluent. It can also be achieved simply by a plurality of inlet pipes that converge to a common pipe(s) where mixing/dilution is carried out dynamically towards the contacting device, using appropriate valves.
  • the contacting device (f) is preferably a liquid/liquid extraction column with gravitational counter-stream. It can be a single column or a plurality of columns, mounted in series or in parallel.
  • the column(s) are generally equipped at the top and /or bottom of the column with settling devices (decantation devices), and additional settlers can be added at the top (light phase) outlet of each column, their role having been detailed above.
  • the facility according to the invention may also comprise a recycling device of at least part of the phase comprising the diluent obtained with device (g) as a diluent for the dilution device (e).
  • This recycling device can be made up of pipe(s) providing a fluidic connection between the two devices g) and f) and controlled in a known way by valves.
  • the facility according to the invention may provide that the contacting device (f) comprises a counter-stream liquid/liquid extraction column equipped at the bottom of the column and/or at the head of the column with a settling device f1), f2).
  • the contacting device (f) comprises a counter-stream liquid/liquid extraction column equipped at the bottom of the column and/or at the head of the column with a settling device f1), f2).
  • the facility according to the invention may also comprise a device (k) for recycling at least part of the phase comprising the diluent obtained with the separation device (g) as a diluent in dilution step (e).
  • the facility according to the invention may also comprise a device (l) for at least partial recycling of the phase comprising the diluent obtained with the separation device (g) into the liquid/liquid/gas separation device (c).
  • the facility according to the invention may also comprise a device for at least partial recycling of the first organic phase and/or the second organic phase (notably via the flow 4 detailed below) to the mixing device (a).
  • the or at least each of the recycling devices is preferably in the form of pipes or sets of pipes ensuring the appropriate fluidic connection to form recycling loops that can be controlled, in particular by means of valve systems (at least some of these recycles may also provide for intermediate storage of the streams to be recycled in tanks).
  • the separation device (d) by heating the liquid aqueous second phase and/or the separation device (g) and/or the separation device (j) comprises at least one device chosen from a distillation column, an evaporator, an exchanger followed by a separator flask, in particular a so-called “flash" separator flask.
  • the facility comprises a recycling device for at least part of the phase comprising the diluent obtained with the separation device (g) as a diluent for the dilution device (e).
  • the invention also relates to a biomass treatment process comprising hydrothermal liquefaction of biomass, then treatment to reduce the mineral content of the biocrude obtained, as described above, and then a conversion treatment of the treated biocrude such as hydroconversion, hydrotreating, hydrocracking, catalytic cracking in order to produce biofuels and/or other chemical compounds (called bio-based compounds).
  • a biomass treatment process comprising hydrothermal liquefaction of biomass, then treatment to reduce the mineral content of the biocrude obtained, as described above, and then a conversion treatment of the treated biocrude such as hydroconversion, hydrotreating, hydrocracking, catalytic cracking in order to produce biofuels and/or other chemical compounds (called bio-based compounds).
  • the initial feedstock may be a type of biomass or a mixture of two or more of these types of biomass. It cannot be ruled out that the initial feedstock may also contain a share of hydrocarbon feedstock that is not of biomass origin, but in this case this share is preferably (very) minority.
  • the characteristics of a biocrude-type feedstock after hydrothermal liquefaction of interest to the invention may be the following:
  • the biocrude obtained by hydrothermal liquefaction is a complex mixture of compounds consisting mainly of hydrocarbons and oxygenated compounds.
  • oxygenated compounds are organic acids, ketones, oxygenated aromatic compounds, alcohols, aldehydes, esters, ethers, and water. Water usually accounts for less than 15% by weight of the biocrude.
  • the biocrude obtained by hydrothermal liquefaction has an oxygen, sulfur and nitrogen content that varies greatly depending on the load of the hydrothermal liquefaction (algae, wood, etc.).
  • the biocrude from hydrothermal liquefaction of wood is generally made up of 5 to 20% weight of oxygen, less than 0.5% weight of sulfur and less than 5% weight of nitrogen in the dry biocrude (without water).
  • Biocrude can contain up to 4% weight of inorganics, mainly metals such as sodium, potassium but also calcium, iron, etc.
  • Inorganics can come from catalysts used for hydrothermal liquefaction, from the hydrothermal liquefaction charge, and from metals used to grind the hydrothermal liquefaction charge.
  • Sodium and potassium can be present in significant quantities in the biocrude because the hydrothermal liquefaction process uses alkali-based catalysts (NaOH, KOH, K 2 CO 3 , Na 2 CO 3 , etc.) in significant quantities.
  • the biocrude is generally characterized by a kinematic viscosity at 50°C between 10 and 40,000 cSt, a dynamic viscosity at 50°C between 10 and 40,000 cP, a density at 15°C between 0.9 and 1.2 and a final distillation temperature exceeding 750°C.
  • Biocrude has a very wide distillation range, from room temperature to over 750°C.
  • a biocrude from hydrothermal liquefaction of wood about 10% weight of the biocrude is vaporized in the range 20-180°C, 10% weight to 45% weight of the biocrude is vaporized in the interval 180-350°C and 45% weight to 80% weight of the biocrude is vaporized above 350°C.
  • Figure 1 shows a facility for implementing the invention, which will be described below.
  • the feedstock to be liquefied supplies the process with stream 1.
  • This feedstock 1 may be biomass preferably chosen from plants, grasses, trees, wood chips, seeds, fibers, seed husks, aquatic plants, algae, hay, and other sources of lignocellulosic materials, such as e.g., those from organic waste, municipal waste, agri-food waste, etc. animal waste, forestry waste, sawmill waste, felling residues, agricultural and industrial waste (such as sugar cane bagasse, waste from oil palm cultivation, sawdust, or straw).
  • the load of hydrothermal liquefaction can also come from paper pulp and paper by-products, recycled or not, or by-products from paper mills, waste such as used plastics, worn tires. Feedstock 1 can be a combination of the loads listed earlier.
  • This process feedstock 1 is mixed in mixer 29 with streams 2, 30 and 4:
  • Stream 3 from mixer 29 feeds into hydrothermal liquefaction section 5, where stream 3 is heated, pressurized, converted, and finally cooled to form stream 7.
  • Stream 7 feeds a gas-liquid-liquid separator 8.
  • the products coming out of separator 8 are a gas 31, an aqueous phase 10, an organic phase 18 called biocrude, part 4 of which is recycled to mixer 29, and the rest 19 is sent to the liquid-liquid extraction column 21.
  • An optional variant of the process is to mix stream 7 with stream 9 which is a fraction of stream 28, a light fraction of the biocrude accumulated in a recycling loop described below, in order to improve separation in separator 8.
  • the aqueous stream 10 undergoes a separation operation 11 by boiling temperature (flash, distillation, evaporation%) to concentrate the catalysts and chemicals in its liquid output 12, which is partly purged by stream 6 and partly recycled via stream 30 to the mixer 29.
  • the steam output 22 from separation 11 contains no minerals, and it is divided into 2 streams, stream 13 in vapor form and stream 17 in liquid form, obtained by condensation of a fraction of stream 22:
  • Biocrude 19 is mixed with stream 28 to form stream 20 called dilute biocrude.
  • Stream 28 is a light fraction of the biocrude, accumulated in a recycling loop described below. This mixture is made to reduce the density and viscosity of the biocrude (dilution) and thus make it easier to process in the gravity liquid-liquid extraction column 21.
  • the dilute biocrude 20 feeds the liquid-liquid extraction column known as gravity column 21 at its bottom and has a mass flow rate Qm.
  • Column 21 extends along a vertical or essentially vertical longitudinal axis.
  • Liquid-liquid extraction is carried out using a solvent 17 consisting of an aqueous solution, resulting from the condensation of steam 22 which may be treated or supplemented with additives.
  • a solvent 17 consisting of an aqueous solution, resulting from the condensation of steam 22 which may be treated or supplemented with additives.
  • It can be pure water, demineralized water, water with soluble organic molecules, an acidic aqueous solution containing from 10 ppm to 20% weight of an acid such as acetic acid, nitric acid, sulfuric acid, hydrochloric acid, citric acid, oxalic acid, lactic acid, formic acid or any other acid, or a mixture of these different aqueous solutions.
  • the liquid-liquid extraction column 21 is supplied at its bottom by stream 20.
  • the liquid-liquid extraction column 21 is fed at the head by stream 17 which is an aqueous solvent containing mainly water and water-soluble organic compounds.
  • An optional variant of the process is to inject another solvent of different composition, such as an acidic aqueous solvent 24, in an intermediate position on the height of column 21, in order to improve the extraction of inorganics.
  • another solvent of different composition such as an acidic aqueous solvent 24
  • Another optional variant if an injection of aqueous solvent acid 24 is used, is to inject a part of the non-acid aqueous solvent 17 into the lower position of the column (stream 23). In this case, stream 23 is injected lower than stream 24 into the column.
  • Biocrude 19 from the hydrothermal liquefaction unit has a flow rate of Qb.
  • Biocrude 19 is mixed with recycled diluent 28 with a flow rate of Qd such as 0.1 ⁇ Qd/Qb ⁇ 10 and preferably 0.5 ⁇ Qd/Qb ⁇ 3. Flow rates are measured in mass per unit of time.
  • biocrude + diluent called “dilute biocrude”
  • dilute biocrude has here a dynamic viscosity at 20°C less than or equal to 7 cP, preferably less than or equal to 4 cP and a density at 15°C less than or equal to 950 kg/m 3 , preferably less than or equal to 900 kg/m 3 , and generally not less than 600 kg/m 3 .
  • Diluent 28 can be a light cut present in the biocrude (the process can start with an initial diluent, which will gradually be replaced by the recycled phase containing the diluent, as indicated above) or a chemical compound (or a mixture of chemical compounds) present or not present in the biocrude.
  • the diluent can consist of compounds from the family of alcohols, ethers, ketones, and hydrocarbons, for example.
  • the final boiling point of diluent 28 is preferably less than or equal to 150°C, and preferably less than or equal to 100°C. It is preferably at least 60°C.
  • Solvent 17 feeds top of column 21 (column head) with a flow rate Qs.
  • the Qs flow rate of solvent 17 is chosen such as 0.05 ⁇ Qs/Qm ⁇ 5 and preferably 0.3 ⁇ Qs/Qm ⁇ 3.
  • Extraction column 21 has the following features:
  • the useful height of column 2 1 is between 1.5 m and 50 m high, preferably between 1.8 m and 25 m.
  • the column can be of different types: packed column, perforated plate column, mechanical stirring column, pulsed column or other.
  • the organic phase is called the light phase because its density is lower than the other phase, the aqueous phase.
  • the aqueous phase is called the heavy phase.
  • the dispersed phase can be the heavy phase (solvent 17) or the light phase (dilute biocrude 20), but preferably the light phase (dilute biocrude 20). If the dispersed phase is the heavy phase (solvent 17), the column is preferably equipped with a decanter at its bottom. The decanter will be at the head of the column if the dispersed phase is the light phase (dilute biocrude 20). It is also possible to provide a decanter at the bottom and at the head of the column. '
  • the biocrude obtained at the outlet of the hydrothermal liquefaction unit has a dynamic viscosity at 20°C of 142 cP, a density at 15°C of 985 kg/m 3 and contains 912 ppm weight of sodium Na, 640 ppm weight of potassium K and 30 ppm weight of calcium Ca.
  • This biocrude is sent to an inorganic reduction unit (demineralization) that is located at another site away from the hydrothermal liquefaction site.
  • inorganic reduction unit demineralization
  • the dilute biocrude has a mass flow rate of 400 kg/h, a dynamic viscosity at 20°C of 1.7 cP and a density at 15°C of 890 kg/m 3 .
  • the liquid-liquid extraction column has an estimated theoretical number of stages of about 3 under the conditions of use presented.
  • extract and rich in inorganics The product coming out at the bottom of the liquid-liquid extraction column, called extract and rich in inorganics, is sent to a water treatment section before being discharged.
  • a light fraction of biocrude 28 is obtained, which is remixed with fresh biocrude rich in inorganics 19 in order to reduce its density and viscosity before liquid-liquid extraction.
  • the liquid-liquid extraction column 21 is fed at its head by 200 kg/h of aqueous phase obtained by condensation of vapors from separator 11 of the hydrothermal liquefaction unit.
  • a light fraction of biocrude 28 is obtained, which is remixed with fresh biocrude rich in inorganics 19 in order to reduce its density and viscosity before liquid-liquid extraction in column 21.
  • the invention therefore makes it possible to drastically reduce the mineral compound content of the biocrude, while considerably reducing the utility consumption of the overall liquefaction + treatment process.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
EP23315464.0A 2023-12-20 2023-12-20 Procédé de traitement d'une charge carbonée liquide issue d'un traitement de liquéfaction hydrothermale Pending EP4574930A1 (fr)

Priority Applications (2)

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EP23315464.0A EP4574930A1 (fr) 2023-12-20 2023-12-20 Procédé de traitement d'une charge carbonée liquide issue d'un traitement de liquéfaction hydrothermale
PCT/EP2024/084369 WO2025131655A1 (fr) 2023-12-20 2024-12-02 Procédé de traitement d'une charge carbonée liquide issue d'un traitement de liquéfaction hydrothermale

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EP23315464.0A EP4574930A1 (fr) 2023-12-20 2023-12-20 Procédé de traitement d'une charge carbonée liquide issue d'un traitement de liquéfaction hydrothermale

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018177877A1 (fr) 2017-03-30 2018-10-04 Steeper Energy Aps Procédé de séparation destiné à un système de traitement à haute pression
WO2019092173A1 (fr) 2017-11-10 2019-05-16 Steeper Energy Aps Système de récupération pour système de traitement haute pression
WO2021121662A1 (fr) 2019-12-16 2021-06-24 Steeper Energy Aps Procédé et système de séparation et de purification de produits

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018177877A1 (fr) 2017-03-30 2018-10-04 Steeper Energy Aps Procédé de séparation destiné à un système de traitement à haute pression
WO2019092173A1 (fr) 2017-11-10 2019-05-16 Steeper Energy Aps Système de récupération pour système de traitement haute pression
US20190144757A1 (en) * 2017-11-10 2019-05-16 Steeper Energy Aps Recovery system for high pressure processing system
WO2021121662A1 (fr) 2019-12-16 2021-06-24 Steeper Energy Aps Procédé et système de séparation et de purification de produits

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
D. CASTELLOT. H. PEDERSONL. A. ROSENDAHL: "Continuous Hydrothermal Liquefaction of biomass: a critical review", ENERGIES, vol. 11, 2018, pages 3165

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