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EP-4493644-B1 - PROCESS FOR THE PRODUCTION OF BIO-OIL FROM LIGNOCELLULOSIC BIOMASS

EP4493644B1EP 4493644 B1EP4493644 B1EP 4493644B1EP-4493644-B1

Inventors

  • QUATTROPANI, Mario
  • FUMAGALLI, Enrico Carlo

Dates

Publication Date
20260506
Application Date
20230314

Claims (15)

  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 comminuted 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, 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; 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.
  2. Process according to claim 1, further comprising: treating hydrogenated bio-oil 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.
  6. Process according to claim 5, wherein the mixture of chemicals comprises sulfuric acid (H 2 SO 4 ) and hydrogen peroxide (H 2 O 2 ).
  7. Process according to claim 6, wherein the sulfuric acid (H 2 SO 4 ) added in the amount of lignocellulosic biomass is in the range of 1.8% to 4%.
  8. Process according to claim 6 or 7, wherein the hydrogen peroxide (H 2 O 2 ) added in the amount of lignocellulosic biomass is in the range of 0.5% to 1.5%.
  9. Process according to one of claims 1 to 8, wherein the glycerol added in mixing is industrial waste glycerol.
  10. Process according to one of claims 1 to 9, wherein the glycerol is waste from desalinated glycerol.
  11. Process according to one of claims 1 to 10, 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.
  12. Process according to one of claims 1 to 11, wherein glycerol is added in the range of 25% to 30%.
  13. Process according to one of claims 1 to 12, wherein the deconstruction temperature is between 40°C and 60°C.
  14. Process according to one of claims 1 to 13, wherein the amount of lignocellulosic biomass is maintained at the deconstruction temperature for a deconstruction time between 10 minutes and 20 minutes.
  15. Process according to one of claims 1 to 14, wherein 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.

Description

Field of the invention The present invention relates to a process and apparatus for the production of bio-oil 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 corn, 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. Document US2020231879A1 discloses a process of producing a distillate fuel from lignin including: preparing a biomass-derived lignin solvent, dissolving the lignin in the biomass-derived solvent and separating undissolved lignin and mineral matter to produce a syncrude. Document US2017029739A1 discloses a preparation of low viscosity bio-oils from hydrothermal liquefaction (HTL) of lignocellulosic biomass in the presence of a crude glycerol and water mixture. 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. The invention relates to a process for producing bio-oil from lignocellulosic biomass according to the appended claims. An apparatus for producing bio-oil from lignocellulosic biomass is also disclosed. 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. Further features and advantages will be elucidated by the detailed description of a preferred, but not exclusive, embodiment of a process according to the present invention and of an apparatus for the production of bio-oil and biofuels from lignocellulosic biomass. 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 for carrying out the process 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 am