WO2023175493A1 - Process and apparatus for the production of bio-oil from lignocellulosic biomass - Google Patents

Process and apparatus for the production of bio-oil from lignocellulosic biomass Download PDF

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Publication number
WO2023175493A1
WO2023175493A1 PCT/IB2023/052452 IB2023052452W WO2023175493A1 WO 2023175493 A1 WO2023175493 A1 WO 2023175493A1 IB 2023052452 W IB2023052452 W IB 2023052452W WO 2023175493 A1 WO2023175493 A1 WO 2023175493A1
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WIPO (PCT)
Prior art keywords
amount
biomass
lignocellulosic biomass
glycerol
process according
Prior art date
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PCT/IB2023/052452
Other languages
French (fr)
Inventor
Mario QUATTROPANI
Enrico Carlo FUMAGALLI
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Thermolysys S.R.L.
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Publication of WO2023175493A1 publication Critical patent/WO2023175493A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42Catalytic treatment
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42Catalytic treatment
    • C10G3/44Catalytic treatment characterised by the catalyst used
    • C10G3/48Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G3/00Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds

Definitions

  • the present invention relates to a process and apparatus for the production of biooil and biofuels from lignocellulosic biomass, particularly lignocellulosic biomass consisting of or including agricultural waste.
  • cellulosic biomass which is derived from low-cost and abundant feedstocks, can achieve high yields and enables the production of fuels with high octane and other properties.
  • lignocellulosic feedstocks such as woody plants, prairie grass blends, agricultural wastes, allows for environmental and economic benefits.
  • these biomass feedstocks require fewer agricultural inputs than annual crops and can be grown even on marginal agricultural land.
  • US 2014/0121423 outlines a method for digesting cellulosic biomass in a glycerol solvent system in a hydro-thermal digestion unit to produce fuel blends.
  • Sources of cellulosic biomass include: forest residues, agricultural residues, herbaceous material, woody materials.
  • the Applicant perceived the need to improve the known type processes for the production of bio-oil and biofuels from lignocellulosic biomass.
  • the Applicant perceived the need to improve the yield of known processes and the quality of the product(s) produced.
  • the Applicant particularly perceived the need to make the lignocellulosic biomass deconstruction process more efficient.
  • the Applicant found that deconstructing lignocellulosic biomass with chemical catalysts and at low temperature allows the raw materials to be broken down into intermediates that can be more easily liquefied in a subsequent hydrothermal liquefaction step.
  • the invention relates to a process for producing bio-oil from lignocellulosic biomass.
  • the process comprises the following steps: a) comminuting an amount of lignocellulosic biomass; b) deconstructing the amount of lignocellulosic biomass; c) adding glycerol in mixing with the amount of deconstructed biomass; d) bringing the amount of deconstructed biomass mixed with glycerol to pressures and temperatures that cause hydrothermal liquefaction; e) removing oxygen and moisture from the liquefied amount of biomass until a bio-oil, optionally hydrogenated, is obtained; wherein deconstructing the amount of lignocellulosic biomass comprises: adding at least one chemical catalyst and maintaining the amount of lignocellulosic biomass at a deconstruction temperature between 30°C and 90°C until said lignocellulosic biomass is deconstructed.
  • the invention in a second aspect, relates to an apparatus for producing bio-oil from lignocellulosic biomass configured to implement the process of the first aspect and/or according to at least one of the aspects that will follow.
  • the apparatus for producing bio-oil from lignocellulosic biomass comprises a reactor configured to receive the amount of lignocellulosic biomass and to perform at least steps b), c) and d) according to the first aspect.
  • the Applicant has verified that the invention makes it possible to increase the process efficiency and the yield of bio-oil obtained from biomass compared to processes of the prior art.
  • the Applicant has also verified that the invention makes it possible to improve the quality of the bio-oil obtained compared to the processes of the prior art.
  • the Applicant has verified that low-temperature deconstruction (i.e. at the indicated temperatures) allows the hard and rigid structure of the plant cell wall, which includes the biological molecules cellulose, hemicellulose and lignin bound tightly together, to be broken down into intermediates.
  • the lignocellulosic biomass consists of or comprises lignocellulosic raw materials, such as woody plants, prairie grass mixtures, agricultural wastes/scraps.
  • the agricultural wastes/scraps are that which are not directly related to food, such as: corn waste, wheat straw and rice straw, paper and wood processing waste, sugarcane waste.
  • the deconstruction temperature is between 40°C and 60°C.
  • the amount of lignocellulosic biomass is maintained at the deconstruction temperature for a sufficient time to achieve said deconstruction, wherein said deconstruction time is optionally between 10 minutes and 20 minutes.
  • said at least one chemical catalyst comprises a mixture of chemical substances.
  • said at least one chemical catalyst comprises sulfuric acid (H2SO4) and/or hydrogen peroxide (H2O2).
  • the sulfuric acid (H2SO4) added in the amount of lignocellulosic biomass is in the range of 1 .8% to 4%.
  • the hydrogen peroxide (H2O2) added in the amount of lignocellulosic biomass is in the range of 0.5% to 1.5%.
  • the amount of lignocellulosic biomass is shredded until it becomes like flour.
  • the amount of lignocellulosic biomass is shredded through the use of chippers and/or shredders.
  • the apparatus comprises at least one chipper and/or shredder configured to shred the amount of lignocellulosic biomass.
  • the process comprises: a') drying the comminuted amount of lignocellulosic biomass to remove at least some of the relative moisture.
  • drying a') is carried out in at least one drier, optionally hot air.
  • the drier has a heat source that heats a mass of air to increase its evaporative power.
  • the apparatus comprises at least one drier to a') dry the amount of comminuted lignocellulosic biomass.
  • glycerol is added in the range of 25% to 30%.
  • the glycerol added in mixing is industrial waste glycerol.
  • glycerol is waste from desalinated glycerol.
  • deconstructed biomass mixed with glycerol is raised to pressures between 50 bar and 100 bar, optionally between 60 bar and 80 bar.
  • deconstructed biomass mixed with glycerol is raised to temperatures between 180 °C and 300 °C, optionally between 200 °C and 275 °C.
  • the amount of deconstructed biomass mixed with glycerol is brought to the pressures and temperatures to cause hydrothermal liquefaction for a liquefaction time between 10 min and 60 min.
  • the hydrothermal liquefaction is implemented in a reaction environment with pH between 1 and 14.
  • the hydrothermal liquefaction is implemented in a reaction environment in the presence of solid-state salts with high corrosive action.
  • the amount of lignocellulosic biomass is mixed.
  • the removal of oxygen and moisture from the liquefied biomass is implemented by high-pressure hydrodeoxygenation (HDO).
  • HDO high-pressure hydrodeoxygenation
  • the high-pressure hydrodeoxygenation (HDO) is a high-pressure operation through which hydrogen is used to extract oxygen from bio-oil.
  • the high-pressure hydrodeoxygenation (HDO) is performed in the reactor.
  • the high-pressure hydrodeoxygenation (HDO) uses hydrodesulfurization (HDS) catalysts, such as cobalt M0S21 AI2O3.
  • HDS hydrodesulfurization
  • the removal of oxygen and moisture from the liquefied biomass is implemented by fast catalytic pyrolysis with zeolites.
  • the process can take place at atmospheric pressure because hydrogen is not required.
  • it is planned to extract liquefied biomass from the reactor and then perform fast catalytic pyrolysis with zeolites.
  • bio-oil In one aspect, it is planned also to process the bio-oil through fractional distillation until second-generation bio-fuels are obtained.
  • the apparatus comprises at least one distillation column to perform fractional distillation.
  • the reactor comprises: a tank (vessel) equipped with an upper opening for the introduction of the amount of lignocellulosic biomass, and optionally glycerol, and a lower opening for the exit of the liquefied biomass or bio-oil, optionally hydrogenated; a mixer/scraper placed inside the tank and coupled to a motor, to mix the amount of biomass in the tank; at least one conduit connected to a receptacle for said at least one chemical catalyst and having at least one end opening in the tank, to feed said at least one chemical catalyst into the tank; optionally, at least one conduit connected to a glycerol receptacle and having at least one end opening in the tank, to feed the glycerol into the tank; at least one heating element operationally active in the tank and configured to transfer heat to the amount of biomass; a cooling element operationally active in the tank and configured to absorb heat from the amount of biomass; a control unit operatively connected to the mixer/scraper motor, to pumps and/or valves located
  • control unit is configured for temperature programming and controlling through ramps, isotherms and thermal cycles.
  • control unit is managed by a PID (Proportional-lntegral-Derivate) algorithm.
  • the reactor comprises a pressure regulator operationally connected to the control unit to regulate the pressure in the tank.
  • the reactor comprises a vacuum pump connected to the tank and operationally connected to the control unit to extract vapors/gas from the tank.
  • the reactor comprises at least one thermocouple placed in the tank and operationally connected to the control unit to detect at least one temperature in the tank.
  • the reactor comprises at least one conduit connected to a hydrogen source and having at least one end opening in the tank; wherein the control unit is operationally connected to valves arranged on the conduit connected to the hydrogen source, to feed hydrogen into the tank.
  • control unit is programmed and/or configured to also implement step e) of the process through high-pressure hydrodeoxygenation (HDO), through control of the pumps and/or valves arranged on the duct connected to the hydrogen source and/or through control of the vacuum pump.
  • HDO high-pressure hydrodeoxygenation
  • said at least one heating element comprises at least one first coil arranged in the tank and containing a first heat transfer fluid stable at high temperatures, wherein the first coil is operationally connected to a high-temperature source to feed heat into the tank via the heat transfer fluid.
  • the first heat transfer fluid comprises a diathermic oil.
  • the first heat transfer fluid is a synthetic diathermic fluid, e.g. DelcoTerm® SODB.
  • said at least one cooling element comprises at least a second coil arranged in the tank and containing a second heat transfer fluid, wherein the second coil is connected to a low-temperature source to remove heat from the tank via the second heat transfer fluid.
  • the second heat transfer fluid comprises water or a coolant.
  • the mixer/scraper comprises a shaft connected to the motor, wherein said motor is arranged outside the tank.
  • the mixer/scraper is of the gate type and optionally comprises notched scraper blades.
  • said at least one conduit for said at least one chemical catalyst is fashioned into the shaft of the mixer and the respective open end is placed on said shaft.
  • said at least one duct for glycerol is fashioned into the shaft of the mixer and the respective open end is placed on said shaft.
  • the conduit connected to the hydrogen source is made in a tube arranged in the tank and presenting said at least one open end.
  • the tank and optionally also other elements in contact with the reaction is/are made of an alloy resistant to highly acidic and corrosive environments under high temperature and pressure conditions, optionally a Nickel alloy, optionally a Nickel-Molybdenum- Chromium alloy with added Tungsten, e.g. Hastelloy C-276.
  • FIG. 1 illustrates a flowchart of a process according to the invention
  • FIG. 2 shows a schematic view of an apparatus according to the invention
  • FIG. 3 is an elevation view of a reactor that is part of the apparatus in Figure 2.
  • FIG. 1 a process for producing bio-oil and biofuels from lignocellulosic biomass is schematically illustrated in the flowchart.
  • An apparatus for producing bio-oil and biofuels from lignocellulosic biomass is labeled as a whole with reference number 1 in Figure 2 and is configured to implement the process in Figure 1.
  • the apparatus 1 comprises a plurality of elements/machines/facilities that can also be placed/at different locations and used/at different times, as will be explained below.
  • an amount of lignocellulosic biomass (such as woody plants, prairie grass mixtures, agricultural wastes/scraps, such as com waste, wheat straw and rice straw, paper and wood processing waste sugarcane waste) is delivered to a pretreatment site where, by means of chippers and/or shredders 2, also of a type known per se and illustrated only schematically in Figure 2, the amount of lignocellulosic biomass is shredded to a comminuted lignocellulosic biomass having the consistency almost of flour.
  • chippers and/or shredders 2 also of a type known per se and illustrated only schematically in Figure 2
  • the amount of comminuted lignocellulosic biomass can then be stored in a warehouse 3 for a certain period of time so that it will dry in contact with the atmosphere and lose at least some relative humidity.
  • the comminuted lignocellulosic biomass can be treated with a drier 4 so as to give the biomass a desired relative humidity.
  • the drier 4 (which may also be of a type known per se) is of the hot-air type, that is, it is equipped with a heat source that heats the air mass to increase its evaporative power.
  • the amount (batch) of comminuted and dried lignocellulosic biomass is fed into a reactor 5 like the one shown in Figure 3.
  • Such a reactor 5 comprises a tank 6 (vessel) provided with an upper opening 7 for the introduction of the amount (batch) of lignocellulosic biomass.
  • the upper opening 7 is sealable by means of a door and special gaskets, e.g., graphite Flat Gasket - 538C type.
  • a shaft 8 of a mixer/scraper 9 passes through a passage made at the top of the tank 6 and is connected to a motor 10 arranged externally to the tank 6.
  • the mixer/scraper 9 is of the gate type.
  • a distal end of the shaft 6, opposite to that engaged with motor 10, carries notched scraper blades 11.
  • the aforementioned shaft 8 is hollow so as to confine a conduit internally.
  • the conduit is connected to a receptacle outside the tank 6 and containing or configured to contain a chemical catalyst comprising a mixture of sulfuric acid (H2SO4) and hydrogen peroxide (H2O2).
  • a chemical catalyst comprising a mixture of sulfuric acid (H2SO4) and hydrogen peroxide (H2O2).
  • the aforementioned conduit can also be connected with an additional receptacle outside the tank 6 and containing or configured to contain industrial waste glycerol.
  • the aforementioned conduit terminates in a plurality of nozzles 12 (i.e. , open ends of the conduit in the tank) carried by the shaft 8 and configured to alternately, i.e., at different times, feed chemical catalyst or glycerol into the tank 6 via pumps and/or valves arranged or operatively active on piping, not illustrated, connecting the aforementioned two receptacles with the shaft 8.
  • the conduit is connected only to the receptacle containing or configured to contain the chemical catalyst while the glycerol is fed through other conduits that terminate in the tank or through the top opening 7.
  • the tank 6 has a lower opening 13 that can be opened or closed via a respective valve and is connected to a cistern 14 ( Figure 1 ) via an appropriate pipeline or directly to a distillation column 15, which may be known in itself and is not described in detail here.
  • a first coil 16 is arranged in tank 6.
  • the first coil 16 contains or is configured to contain a first heat transfer fluid that is stable at high temperatures and is operationally connected to a high-temperature source, not shown and external to the tank 6.
  • the function of the first coil 16 (heating element) is to feed heat into the tank 6 via the first heat transfer fluid, which takes it from the high-temperature source and gives it to the tank 6.
  • the first heat transfer fluid is DelcoTerm® SODB, which is a eutectic mixture of diphenyl oxide and biphenyl, usable as a boiling-condensing heat transfer medium up to 750 °F (400 °C).
  • DelcoTerm® SODB offers excellent heat transfer properties for long periods of operation at temperatures up to 400°C. Maximum heat transfer to the tank 6 and/or to the equipment allows the use of smaller pumps, valves and heating coils. In addition, such spent fluid can be disposed of through a variety of environmentally acceptable methods, such as waste oil recycling or heavy fuel combustion.
  • a second coil 17 is arranged in tank 6.
  • the second coil 17 contains or is configured to contain a second heat transfer fluid and is operationally connected to a low- temperature source, not shown and external to the tank 6.
  • the function of the second coil 17 (cooling element) is to remove heat from the tank 6 via the second heat transfer fluid, which draws heat from the tank 6 and transfers it to the low- temperature source.
  • the second heat transfer fluid is, for example, water or a coolant.
  • a tube 18 housed in tank 6 is arranged parallel to the shaft 8 and is connected to a hydrogen source, such as a pressure cylinder, not shown and external to the tank 6.
  • the tube 18 has one or more openings that flow into the tank 6.
  • the tube 18 is configured to feed hydrogen into the tank 6 via valves arranged or operatively active on piping, not illustrated, connecting the hydrogen source with the tube 18.
  • the reactor 5 also comprises a pressure regulator 19 placed on top of the tank 6, a vacuum pump 20 connected to the tank 6 and at least one thermocouple 21 arranged in the tank 6.
  • the reactor 5 comprises a control unit 19, e.g., an electronic control unit operated by a PID (Proportional-lntegral-Derivate) algorithm and operationally connected to the motor 10 of the mixer/scraper 9, to the pumps and/or valves placed on the piping connected to the receptacle for the chemical catalyst, to the pumps and/or valves placed on the piping connected to the receptacle for glycerol, to valves placed between the first coil 16 and the high-temperature source, to valves placed between the second coil 17 and the low-temperature source, to the pressure regulator 19, to the vacuum pump 20, to the thermocouple 21 , to the valves placed between the hydrogen source and the tube 18, to the valve of the lower opening 13.
  • a control unit 19 e.g., an electronic control unit operated by a PID (Proportion
  • the tank 6 and also the other reactor elements 5, such as the first coil 16, the second coil 17, the mixer/scraper 9, and the tube 18, are made of an alloy resistant to highly acidic and corrosive environments under high temperature and pressure conditions, e.g., Hastelloy C-276.
  • the control unit CU is programmed and/or configured to control processes in the reactor 5, as shown below. Specifically, the control unit CU is configured to temperature programming and controlling using ramps, isotherms and thermal cycling.
  • the amount (batch) of comminuted and dried lignocellulosic biomass introduced into the tank 6 of the reactor 5 is first subjected to a deconstruction step, which consists of adding the chemical catalyst, i.e., sulfuric acid (H2SO4) e.g., in an amount between 1.8% and 4% and hydrogen peroxide (H2O2) e.g., in an amount between 0.5% and 1.5% and bring and maintain the resulting mixture at a deconstruction temperature between 40°C and 60°C for between 10 minutes and 20 minutes, i.e., sufficient to break down the raw materials into intermediates that can be more easily liquefied in the subsequent hydrothermal liquefaction step.
  • the chemical catalyst i.e., sulfuric acid (H2SO4) e.g., in an amount between 1.8% and 4%
  • H2O2O2 hydrogen peroxide
  • the control unit CU receives signals from the thermocouple 12 and controls the valves of the first coil 16 and/or the second coil 17, the pressure regulator 19 and the valves/pumps located on the piping connected to the receptacle for the chemical catalyst to achieve the above.
  • Deconstruction opens up the physical structure of biomass cell walls, making sugar polymers, such as cellulose and hemicellulose, more accessible. These polymers are then chemically broken down into simple sugar building blocks during the subsequent hydrolysis process.
  • industrial waste glycerol for example, is added in an amount between 25 percent and 30 percent to the amount of deconstructed biomass contained in the tank 6 and the amount of deconstructed biomass mixed with glycerol is brought to pressures and temperatures that cause hydrothermal liquefaction.
  • deconstructed biomass mixed with glycerol is brought to pressures between 60 bar and 80 bar and temperatures between 200 °C and 275 °C for a liquefaction time between 10 min and 60 min.
  • the control unit CU receives signals from the thermocouple 12 and controls the valves of the first coil 16 and/or the second coil 17, the pressure regulator 19 and the valves/pumps located on the piping connected to the glycerol vessel so as to achieve the above.
  • Hydrothermal liquefaction is usually implemented in a reaction environment with a pH between 1 and 14 and in the presence of solid-state salts with high corrosive action.
  • the process uses glycerin as a solvent and takes advantage of the increase in temperature to optimize the solubility of nonpolar compounds.
  • Hydrothermal liquefaction of biomass allows the solid bio-polymer structure to be broken down into totally liquid components.
  • the steps of biomass decomposition during the hydrothermal process can be summarized as follows: at about 100 °C, the water- soluble part of the biomass disperses into glycerol and hydrolysis occurs above 150 °C. Meanwhile, the biomass polymers, such as cellulose and hemicellulose, disintegrate into their monomeric chains. At about 200 °C and 1 MPa, the solid biomass becomes slurry. Finally, at about 300 °C and 10 MPa, liquefaction occurs and the oily product (bio-oil) is obtained.
  • the amount of lignocellulosic biomass is mixed by the mixer/scraper 9 actuated by the motor 10 through the electronic control unit CU.
  • bio-oil has low oxygen content and low stability over time, so its removal is necessary to make it similar to crude oil.
  • control unit CU controls the vacuum pump 20, which extracts gas, vapors and oxygen from the tank 6, and controls the valves located between the hydrogen source and the tube 18 to feed pressurized hydrogen into the tank 6, i.e. , to perform high-pressure hydrodeoxygenation (HDO), while the mixer/scraper 9 continues mixing.
  • HDO high-pressure hydrodeoxygenation
  • HDS hydrodesulfurization
  • High-pressure hydrodeoxygenation is a high-pressure operation through which hydrogen is used to extract oxygen from bio-oil, giving a high-quality petroleum product.
  • high-pressure hydrogenation can prevent carbon deposition on the catalyst surface, which facilitates reactor operation 5.
  • the hydrogenated bio-oil is either extracted from the tank 6 through the lower opening 13 and stored in cistern 14 and later taken to the distillation column 15 or directly fed into the distillation column 15.
  • the removal of oxygen and moisture from the liquefied biomass is implemented by fast catalytic pyrolysis with zeolites at atmospheric pressure. Therefore, according to this variant, the liquefied biomass is extracted from the reactor 5 at the end of hydrothermal liquefaction and sent to a subsequent tank configured to implement the aforementioned fast catalytic pyrolysis with zeolites. At the end of catalytic pyrolysis, the obtained bio-oil is stored in cistern 14 and/or sent to distillation column 15.
  • HDO high-pressure hydrodeoxygenation
  • distillation column 15 in a manner also known in itself, bio-oil is fractionated to obtain second-generation bio-fuels. Bio-oil is in fact a mixture that can be separated into fractions.
  • the bio-oil to be distilled enters distillation column 15 and the distillation products are separated and exit distillation column 15.
  • Distillation column 15 has outlets 21 at intervals along its vertical development so that multiple products having different boiling ranges can be taken by distilling a multicomponent feed stream. "Lighter" products with the lowest boiling points exit from the head 22 of the column and "heavier" products with the highest boiling points exit from the bottom 23.

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Abstract

A process for producing bio-oil from lignocellulosic biomass comprises the following steps: a) comminuting an amount of lignocellulosic biomass; b) deconstructing the amount of lignocellulosic biomass; c) adding glycerol in mixing with the amount of deconstructed biomass; d) bringing the amount of deconstructed biomass mixed with glycerol to pressures and temperatures that cause hydrothermal liquefaction; and e) removing oxygen and moisture from the amount of liquefied biomass until a hydrogenated bio-oil is obtained. Deconstructing the amount of lignocellulosic biomass comprises: adding at least one chemical catalyst and maintaining the amount of lignocellulosic biomass at a deconstruction temperature between 30°C and 90°C until the lignocellulosic biomass is deconstructed.

Description

PROCESS AND APPARATUS FOR THE PRODUCTION OF BIO-OIL FROM LIGNOCELLULOSIC BIOMASS
DESCRIPTION
Field of the invention
The present invention relates to a process and apparatus for the production of biooil and biofuels from lignocellulosic biomass, particularly lignocellulosic biomass consisting of or including agricultural waste.
State of the Art.
As global demand for fuels and chemicals increases and oil stocks are depleting, ethanol fuel producers are increasingly looking beyond com, potatoes and other starchy crops as biomass for ethanol fuel production.
Particularly promising is cellulosic biomass which is derived from low-cost and abundant feedstocks, can achieve high yields and enables the production of fuels with high octane and other properties. The use of lignocellulosic feedstocks, such as woody plants, prairie grass blends, agricultural wastes, allows for environmental and economic benefits. Compared with current sources of biofuels, these biomass feedstocks require fewer agricultural inputs than annual crops and can be grown even on marginal agricultural land.
Processes and plants for producing biofuels from lignocellulosic biomass are known. For example, US 2014/0121423 outlines a method for digesting cellulosic biomass in a glycerol solvent system in a hydro-thermal digestion unit to produce fuel blends. Sources of cellulosic biomass include: forest residues, agricultural residues, herbaceous material, woody materials.
US 2008/312346 outlines a method for preparing lignocellulosic biomass for slurry treatment and fuel production.
Also known is document US 2012/079760, which outlines a method for producing biodiesel from biomass in a reactor in which biomass is heated and mixed with a mixer using "super-heated" water as a solvent.
In this regard, the Applicant perceived the need to improve the known type processes for the production of bio-oil and biofuels from lignocellulosic biomass. In particular, the Applicant perceived the need to improve the yield of known processes and the quality of the product(s) produced.
The Applicant particularly perceived the need to make the lignocellulosic biomass deconstruction process more efficient.
Summary of the invention
The Applicant found that deconstructing lignocellulosic biomass with chemical catalysts and at low temperature allows the raw materials to be broken down into intermediates that can be more easily liquefied in a subsequent hydrothermal liquefaction step.
In a first aspect, the invention relates to a process for producing bio-oil from lignocellulosic biomass.
The process comprises the following steps: a) comminuting an amount of lignocellulosic biomass; b) deconstructing the amount of lignocellulosic biomass; c) adding glycerol in mixing with the amount of deconstructed biomass; d) bringing the amount of deconstructed biomass mixed with glycerol to pressures and temperatures that cause hydrothermal liquefaction; e) removing oxygen and moisture from the liquefied amount of biomass until a bio-oil, optionally hydrogenated, is obtained; wherein deconstructing the amount of lignocellulosic biomass comprises: adding at least one chemical catalyst and maintaining the amount of lignocellulosic biomass at a deconstruction temperature between 30°C and 90°C until said lignocellulosic biomass is deconstructed.
In a second aspect, the invention relates to an apparatus for producing bio-oil from lignocellulosic biomass configured to implement the process of the first aspect and/or according to at least one of the aspects that will follow.
In a third aspect, the apparatus for producing bio-oil from lignocellulosic biomass comprises a reactor configured to receive the amount of lignocellulosic biomass and to perform at least steps b), c) and d) according to the first aspect.
The Applicant has verified that the invention makes it possible to increase the process efficiency and the yield of bio-oil obtained from biomass compared to processes of the prior art. The Applicant has also verified that the invention makes it possible to improve the quality of the bio-oil obtained compared to the processes of the prior art.
In particular, the Applicant has verified that low-temperature deconstruction (i.e. at the indicated temperatures) allows the hard and rigid structure of the plant cell wall, which includes the biological molecules cellulose, hemicellulose and lignin bound tightly together, to be broken down into intermediates.
Additional aspects of the invention are presented below.
In one aspect, the lignocellulosic biomass consists of or comprises lignocellulosic raw materials, such as woody plants, prairie grass mixtures, agricultural wastes/scraps.
In one aspect, the agricultural wastes/scraps are that which are not directly related to food, such as: corn waste, wheat straw and rice straw, paper and wood processing waste, sugarcane waste.
In one aspect, the deconstruction temperature is between 40°C and 60°C.
In one aspect, the amount of lignocellulosic biomass is maintained at the deconstruction temperature for a sufficient time to achieve said deconstruction, wherein said deconstruction time is optionally between 10 minutes and 20 minutes. In one aspect, said at least one chemical catalyst comprises a mixture of chemical substances.
In one aspect, said at least one chemical catalyst comprises sulfuric acid (H2SO4) and/or hydrogen peroxide (H2O2).
In one aspect, the sulfuric acid (H2SO4) added in the amount of lignocellulosic biomass is in the range of 1 .8% to 4%.
In one aspect, the hydrogen peroxide (H2O2) added in the amount of lignocellulosic biomass is in the range of 0.5% to 1.5%.
In one aspect, the amount of lignocellulosic biomass is shredded until it becomes like flour.
In one aspect, the amount of lignocellulosic biomass is shredded through the use of chippers and/or shredders.
In one aspect, the apparatus comprises at least one chipper and/or shredder configured to shred the amount of lignocellulosic biomass.
In one aspect, after comminuting the amount of lignocellulosic biomass (step a) and before deconstructing it (step b), the process comprises: a') drying the comminuted amount of lignocellulosic biomass to remove at least some of the relative moisture. In one aspect, drying a') is carried out in at least one drier, optionally hot air.
In one aspect, the drier has a heat source that heats a mass of air to increase its evaporative power.
In one aspect, the apparatus comprises at least one drier to a') dry the amount of comminuted lignocellulosic biomass.
In one aspect, glycerol is added in the range of 25% to 30%.
In one aspect, the glycerol added in mixing is industrial waste glycerol.
In one aspect, glycerol is waste from desalinated glycerol.
In one aspect, in order to cause hydrothermal liquefaction, deconstructed biomass mixed with glycerol is raised to pressures between 50 bar and 100 bar, optionally between 60 bar and 80 bar.
In one aspect, in order to cause hydrothermal liquefaction, deconstructed biomass mixed with glycerol is raised to temperatures between 180 °C and 300 °C, optionally between 200 °C and 275 °C.
In one aspect, the amount of deconstructed biomass mixed with glycerol is brought to the pressures and temperatures to cause hydrothermal liquefaction for a liquefaction time between 10 min and 60 min.
In one aspect, the hydrothermal liquefaction is implemented in a reaction environment with pH between 1 and 14.
In one aspect, the hydrothermal liquefaction is implemented in a reaction environment in the presence of solid-state salts with high corrosive action.
In one aspect, during the deconstruction and/or liquefaction, the amount of lignocellulosic biomass is mixed.
In one aspect, the removal of oxygen and moisture from the liquefied biomass is implemented by high-pressure hydrodeoxygenation (HDO). The high-pressure hydrodeoxygenation (HDO) is a high-pressure operation through which hydrogen is used to extract oxygen from bio-oil.
In one aspect, the high-pressure hydrodeoxygenation (HDO) is performed in the reactor.
In one aspect, the high-pressure hydrodeoxygenation (HDO) uses hydrodesulfurization (HDS) catalysts, such as cobalt M0S21 AI2O3.
Alternatively, the removal of oxygen and moisture from the liquefied biomass is implemented by fast catalytic pyrolysis with zeolites. In this case, the process can take place at atmospheric pressure because hydrogen is not required. In one aspect, it is planned to extract liquefied biomass from the reactor and then perform fast catalytic pyrolysis with zeolites.
In one aspect, it is planned also to process the bio-oil through fractional distillation until second-generation bio-fuels are obtained.
In one aspect, the apparatus comprises at least one distillation column to perform fractional distillation.
In one aspect, the reactor comprises: a tank (vessel) equipped with an upper opening for the introduction of the amount of lignocellulosic biomass, and optionally glycerol, and a lower opening for the exit of the liquefied biomass or bio-oil, optionally hydrogenated; a mixer/scraper placed inside the tank and coupled to a motor, to mix the amount of biomass in the tank; at least one conduit connected to a receptacle for said at least one chemical catalyst and having at least one end opening in the tank, to feed said at least one chemical catalyst into the tank; optionally, at least one conduit connected to a glycerol receptacle and having at least one end opening in the tank, to feed the glycerol into the tank; at least one heating element operationally active in the tank and configured to transfer heat to the amount of biomass; a cooling element operationally active in the tank and configured to absorb heat from the amount of biomass; a control unit operatively connected to the mixer/scraper motor, to pumps and/or valves located on said at least one conduit connected to the receptacle for said at least one chemical catalyst, to pumps and/or valves located on said at least one optional conduit connected to the receptacle for glycerol, to said at least one heating element and to said at least one cooling element; wherein the control unit is programmed and/or configured to implement at least process steps b), c) and d).
In one aspect, the control unit is configured for temperature programming and controlling through ramps, isotherms and thermal cycles.
In one aspect, the control unit is managed by a PID (Proportional-lntegral-Derivate) algorithm. In one aspect, the reactor comprises a pressure regulator operationally connected to the control unit to regulate the pressure in the tank.
In one aspect, the reactor comprises a vacuum pump connected to the tank and operationally connected to the control unit to extract vapors/gas from the tank.
In one aspect, the reactor comprises at least one thermocouple placed in the tank and operationally connected to the control unit to detect at least one temperature in the tank.
In one aspect, the reactor comprises at least one conduit connected to a hydrogen source and having at least one end opening in the tank; wherein the control unit is operationally connected to valves arranged on the conduit connected to the hydrogen source, to feed hydrogen into the tank.
In one aspect, the control unit is programmed and/or configured to also implement step e) of the process through high-pressure hydrodeoxygenation (HDO), through control of the pumps and/or valves arranged on the duct connected to the hydrogen source and/or through control of the vacuum pump.
In one aspect, said at least one heating element comprises at least one first coil arranged in the tank and containing a first heat transfer fluid stable at high temperatures, wherein the first coil is operationally connected to a high-temperature source to feed heat into the tank via the heat transfer fluid.
In one aspect, the first heat transfer fluid comprises a diathermic oil.
In one aspect, the first heat transfer fluid is a synthetic diathermic fluid, e.g. DelcoTerm® SODB.
In one aspect, said at least one cooling element comprises at least a second coil arranged in the tank and containing a second heat transfer fluid, wherein the second coil is connected to a low-temperature source to remove heat from the tank via the second heat transfer fluid.
In one aspect, the second heat transfer fluid comprises water or a coolant.
In one aspect, the mixer/scraper comprises a shaft connected to the motor, wherein said motor is arranged outside the tank.
In one aspect, the mixer/scraper is of the gate type and optionally comprises notched scraper blades.
In one aspect, said at least one conduit for said at least one chemical catalyst is fashioned into the shaft of the mixer and the respective open end is placed on said shaft. In one aspect, said at least one duct for glycerol is fashioned into the shaft of the mixer and the respective open end is placed on said shaft.
In one aspect, the conduit connected to the hydrogen source is made in a tube arranged in the tank and presenting said at least one open end.
In one aspect, the tank and optionally also other elements in contact with the reaction (such as the first and second coils, the mixer, the tube), is/are made of an alloy resistant to highly acidic and corrosive environments under high temperature and pressure conditions, optionally a Nickel alloy, optionally a Nickel-Molybdenum- Chromium alloy with added Tungsten, e.g. Hastelloy C-276.
Further features and advantages will be elucidated by the detailed description of a preferred, but not exclusive, embodiment of a process and apparatus for the production of bio-oil and biofuels from lignocellulosic biomass, according to the present invention.
Description of drawings
This description will be given below with reference to the set of drawings, provided for illustrative and non-limiting purposes only, in which:
■ Figure 1 illustrates a flowchart of a process according to the invention;
■ Figure 2 shows a schematic view of an apparatus according to the invention;
■ Figure 3 is an elevation view of a reactor that is part of the apparatus in Figure 2.
Detailed description
Referring to Figure 1 attached herein, a process for producing bio-oil and biofuels from lignocellulosic biomass is schematically illustrated in the flowchart. An apparatus for producing bio-oil and biofuels from lignocellulosic biomass is labeled as a whole with reference number 1 in Figure 2 and is configured to implement the process in Figure 1. The apparatus 1 comprises a plurality of elements/machines/facilities that can also be placed/at different locations and used/at different times, as will be explained below.
In accordance with the process of the invention, an amount of lignocellulosic biomass (such as woody plants, prairie grass mixtures, agricultural wastes/scraps, such as com waste, wheat straw and rice straw, paper and wood processing waste sugarcane waste) is delivered to a pretreatment site where, by means of chippers and/or shredders 2, also of a type known per se and illustrated only schematically in Figure 2, the amount of lignocellulosic biomass is shredded to a comminuted lignocellulosic biomass having the consistency almost of flour.
The amount of comminuted lignocellulosic biomass can then be stored in a warehouse 3 for a certain period of time so that it will dry in contact with the atmosphere and lose at least some relative humidity. Instead of being stored in the warehouse 3 or after spending a certain period of time in the warehouse 3, the comminuted lignocellulosic biomass can be treated with a drier 4 so as to give the biomass a desired relative humidity. For example, the drier 4 (which may also be of a type known per se) is of the hot-air type, that is, it is equipped with a heat source that heats the air mass to increase its evaporative power.
The amount (batch) of comminuted and dried lignocellulosic biomass is fed into a reactor 5 like the one shown in Figure 3.
Such a reactor 5 comprises a tank 6 (vessel) provided with an upper opening 7 for the introduction of the amount (batch) of lignocellulosic biomass. The upper opening 7 is sealable by means of a door and special gaskets, e.g., graphite Flat Gasket - 538C type. A shaft 8 of a mixer/scraper 9 passes through a passage made at the top of the tank 6 and is connected to a motor 10 arranged externally to the tank 6. For example, the mixer/scraper 9 is of the gate type. A distal end of the shaft 6, opposite to that engaged with motor 10, carries notched scraper blades 11. In addition, the aforementioned shaft 8 is hollow so as to confine a conduit internally.
The conduit is connected to a receptacle outside the tank 6 and containing or configured to contain a chemical catalyst comprising a mixture of sulfuric acid (H2SO4) and hydrogen peroxide (H2O2).
The aforementioned conduit can also be connected with an additional receptacle outside the tank 6 and containing or configured to contain industrial waste glycerol. The aforementioned conduit terminates in a plurality of nozzles 12 (i.e. , open ends of the conduit in the tank) carried by the shaft 8 and configured to alternately, i.e., at different times, feed chemical catalyst or glycerol into the tank 6 via pumps and/or valves arranged or operatively active on piping, not illustrated, connecting the aforementioned two receptacles with the shaft 8.
Alternatively, the conduit is connected only to the receptacle containing or configured to contain the chemical catalyst while the glycerol is fed through other conduits that terminate in the tank or through the top opening 7. The tank 6 has a lower opening 13 that can be opened or closed via a respective valve and is connected to a cistern 14 (Figure 1 ) via an appropriate pipeline or directly to a distillation column 15, which may be known in itself and is not described in detail here.
A first coil 16 is arranged in tank 6. The first coil 16 contains or is configured to contain a first heat transfer fluid that is stable at high temperatures and is operationally connected to a high-temperature source, not shown and external to the tank 6. The function of the first coil 16 (heating element) is to feed heat into the tank 6 via the first heat transfer fluid, which takes it from the high-temperature source and gives it to the tank 6. For example, the first heat transfer fluid is DelcoTerm® SODB, which is a eutectic mixture of diphenyl oxide and biphenyl, usable as a boiling-condensing heat transfer medium up to 750 °F (400 °C). With low vapor pressure, high thermal conductivity and oxidation stability, DelcoTerm® SODB offers excellent heat transfer properties for long periods of operation at temperatures up to 400°C. Maximum heat transfer to the tank 6 and/or to the equipment allows the use of smaller pumps, valves and heating coils. In addition, such spent fluid can be disposed of through a variety of environmentally acceptable methods, such as waste oil recycling or heavy fuel combustion.
A second coil 17 is arranged in tank 6. The second coil 17 contains or is configured to contain a second heat transfer fluid and is operationally connected to a low- temperature source, not shown and external to the tank 6. The function of the second coil 17 (cooling element) is to remove heat from the tank 6 via the second heat transfer fluid, which draws heat from the tank 6 and transfers it to the low- temperature source. The second heat transfer fluid is, for example, water or a coolant.
A tube 18 housed in tank 6 is arranged parallel to the shaft 8 and is connected to a hydrogen source, such as a pressure cylinder, not shown and external to the tank 6. The tube 18 has one or more openings that flow into the tank 6. The tube 18 is configured to feed hydrogen into the tank 6 via valves arranged or operatively active on piping, not illustrated, connecting the hydrogen source with the tube 18.
The reactor 5 also comprises a pressure regulator 19 placed on top of the tank 6, a vacuum pump 20 connected to the tank 6 and at least one thermocouple 21 arranged in the tank 6. The reactor 5 comprises a control unit 19, e.g., an electronic control unit operated by a PID (Proportional-lntegral-Derivate) algorithm and operationally connected to the motor 10 of the mixer/scraper 9, to the pumps and/or valves placed on the piping connected to the receptacle for the chemical catalyst, to the pumps and/or valves placed on the piping connected to the receptacle for glycerol, to valves placed between the first coil 16 and the high-temperature source, to valves placed between the second coil 17 and the low-temperature source, to the pressure regulator 19, to the vacuum pump 20, to the thermocouple 21 , to the valves placed between the hydrogen source and the tube 18, to the valve of the lower opening 13.
The tank 6 and also the other reactor elements 5, such as the first coil 16, the second coil 17, the mixer/scraper 9, and the tube 18, are made of an alloy resistant to highly acidic and corrosive environments under high temperature and pressure conditions, e.g., Hastelloy C-276.
The control unit CU is programmed and/or configured to control processes in the reactor 5, as shown below. Specifically, the control unit CU is configured to temperature programming and controlling using ramps, isotherms and thermal cycling.
The amount (batch) of comminuted and dried lignocellulosic biomass introduced into the tank 6 of the reactor 5 is first subjected to a deconstruction step, which consists of adding the chemical catalyst, i.e., sulfuric acid (H2SO4) e.g., in an amount between 1.8% and 4% and hydrogen peroxide (H2O2) e.g., in an amount between 0.5% and 1.5% and bring and maintain the resulting mixture at a deconstruction temperature between 40°C and 60°C for between 10 minutes and 20 minutes, i.e., sufficient to break down the raw materials into intermediates that can be more easily liquefied in the subsequent hydrothermal liquefaction step. The control unit CU receives signals from the thermocouple 12 and controls the valves of the first coil 16 and/or the second coil 17, the pressure regulator 19 and the valves/pumps located on the piping connected to the receptacle for the chemical catalyst to achieve the above.
Deconstruction opens up the physical structure of biomass cell walls, making sugar polymers, such as cellulose and hemicellulose, more accessible. These polymers are then chemically broken down into simple sugar building blocks during the subsequent hydrolysis process. Once the aforementioned deconstruction has been achieved, industrial waste glycerol, for example, is added in an amount between 25 percent and 30 percent to the amount of deconstructed biomass contained in the tank 6 and the amount of deconstructed biomass mixed with glycerol is brought to pressures and temperatures that cause hydrothermal liquefaction.
For example, deconstructed biomass mixed with glycerol is brought to pressures between 60 bar and 80 bar and temperatures between 200 °C and 275 °C for a liquefaction time between 10 min and 60 min. The control unit CU receives signals from the thermocouple 12 and controls the valves of the first coil 16 and/or the second coil 17, the pressure regulator 19 and the valves/pumps located on the piping connected to the glycerol vessel so as to achieve the above. Hydrothermal liquefaction is usually implemented in a reaction environment with a pH between 1 and 14 and in the presence of solid-state salts with high corrosive action. The process uses glycerin as a solvent and takes advantage of the increase in temperature to optimize the solubility of nonpolar compounds. Hydrothermal liquefaction of biomass allows the solid bio-polymer structure to be broken down into totally liquid components. The steps of biomass decomposition during the hydrothermal process can be summarized as follows: at about 100 °C, the water- soluble part of the biomass disperses into glycerol and hydrolysis occurs above 150 °C. Meanwhile, the biomass polymers, such as cellulose and hemicellulose, disintegrate into their monomeric chains. At about 200 °C and 1 MPa, the solid biomass becomes slurry. Finally, at about 300 °C and 10 MPa, liquefaction occurs and the oily product (bio-oil) is obtained.
During deconstruction and/or liquefaction, the amount of lignocellulosic biomass is mixed by the mixer/scraper 9 actuated by the motor 10 through the electronic control unit CU.
At the end of hydrothermal liquefaction, oxygen and moisture are removed from the amount of liquefied biomass contained in tank 6 of reactor 5 until hydrogenated biooil is obtained. In fact, bio-oil has low oxygen content and low stability over time, so its removal is necessary to make it similar to crude oil.
For this purpose, the control unit CU controls the vacuum pump 20, which extracts gas, vapors and oxygen from the tank 6, and controls the valves located between the hydrogen source and the tube 18 to feed pressurized hydrogen into the tank 6, i.e. , to perform high-pressure hydrodeoxygenation (HDO), while the mixer/scraper 9 continues mixing. In high-pressure hydrodeoxygenation (HDO), hydrodesulfurization (HDS) catalysts, such as cobalt M0S2 1 AI2O3, are also preferably used.
High-pressure hydrodeoxygenation (HDO) is a high-pressure operation through which hydrogen is used to extract oxygen from bio-oil, giving a high-quality petroleum product. In addition, high-pressure hydrogenation can prevent carbon deposition on the catalyst surface, which facilitates reactor operation 5.
The hydrogenated bio-oil is either extracted from the tank 6 through the lower opening 13 and stored in cistern 14 and later taken to the distillation column 15 or directly fed into the distillation column 15.
According to a variant of the process, instead of by high-pressure hydrodeoxygenation (HDO) performed in the reactor 5, the removal of oxygen and moisture from the liquefied biomass is implemented by fast catalytic pyrolysis with zeolites at atmospheric pressure. Therefore, according to this variant, the liquefied biomass is extracted from the reactor 5 at the end of hydrothermal liquefaction and sent to a subsequent tank configured to implement the aforementioned fast catalytic pyrolysis with zeolites. At the end of catalytic pyrolysis, the obtained bio-oil is stored in cistern 14 and/or sent to distillation column 15.
In distillation column 15, in a manner also known in itself, bio-oil is fractionated to obtain second-generation bio-fuels. Bio-oil is in fact a mixture that can be separated into fractions. The bio-oil to be distilled enters distillation column 15 and the distillation products are separated and exit distillation column 15. Distillation column 15 has outlets 21 at intervals along its vertical development so that multiple products having different boiling ranges can be taken by distilling a multicomponent feed stream. "Lighter" products with the lowest boiling points exit from the head 22 of the column and "heavier" products with the highest boiling points exit from the bottom 23.
Items list apparatus 1 chippers and/or shredders 2 warehouse 3 drier 4 reactor 5 tank 6 upper opening 7 shaft 8 mixer/scraper 9 motor 10 notched scraper blades 11 nozzles 12 lower opening 13 cistern 14 distillation column 15 first coil 16 second coil 17 tube 18 pressure regulator 19 vacuum pump 20 outlets 21 head 22 bottom 23 control unit CU

Claims

1 . Process for the production of bio-oil from lignocellulosic biomass, comprising the following steps: a) comminuting an amount of lignocellulosic biomass; b) deconstructing the amount of lignocellulosic biomass; c) adding glycerol in mixing with the amount of deconstructed biomass; d) bringing the amount of deconstructed biomass mixed with glycerol to pressures and temperatures that cause hydrothermal liquefaction; e) removing oxygen and moisture from the liquefied amount of biomass until a hydrogenated bio-oil is obtained; characterized in that deconstructing the amount of lignocellulosic biomass comprises: adding at least one chemical catalyst and maintaining the amount of lignocellulosic biomass at a deconstruction temperature between 30°C and 90°C, optionally between 40°C and 60°C until said lignocellulosic biomass is deconstructed.
2. Process according to claim 1 , further comprising: treating hydrogenated biooil by fractional distillation until second-generation bio-fuels are obtained.
3. Process according to claim 1 or 2, wherein the amount of lignocellulosic biomass is comminuted until it becomes like flour, optionally through the use of chippers and/or shredders.
4. Process according to one of claims 1 to 3, wherein after shredding the amount of lignocellulosic biomass and before deconstructing it, the process comprises: a') drying the amount of comminuted lignocellulosic biomass to remove at least some of the relative humidity.
5. Process according to one of claims 1 to 4, wherein said at least one chemical catalyst comprises a mixture of chemicals, optionally sulfuric acid (H2SO4) and hydrogen peroxide (H2O2).
6. Process according to one of claims 1 to 5, wherein the glycerol added in mixing is industrial waste glycerol.
7. Process according to one of claims 1 to 6, wherein, in order to cause hydrothermal liquefaction, the deconstructed biomass mixed with glycerol is raised to pressures between 50 bar and 100 bar and temperatures between 180 °C and 300 °C.
8. Process according to one of claims 1 to 7, wherein the removal of oxygen and moisture from the liquefied biomass is carried out by high-pressure hydrodeoxygenation (HDO) or by fast catalytic pyrolysis with zeolites.
9. Apparatus for producing biofuels from lignocellulosic biomass, wherein said apparatus is configured to perform the process according to at least one of claims 1 to 8.
10. Apparatus according to claim 9, comprising a reactor (5) configured to receive the amount of lignocellulosic biomass and to perform at least steps b), c) and d).
PCT/IB2023/052452 2022-03-14 2023-03-14 Process and apparatus for the production of bio-oil from lignocellulosic biomass WO2023175493A1 (en)

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