WO2020101563A1 - Procédé de formation de monomères et de furfural à partir de lignocellulose - Google Patents

Procédé de formation de monomères et de furfural à partir de lignocellulose Download PDF

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WO2020101563A1
WO2020101563A1 PCT/SE2019/051157 SE2019051157W WO2020101563A1 WO 2020101563 A1 WO2020101563 A1 WO 2020101563A1 SE 2019051157 W SE2019051157 W SE 2019051157W WO 2020101563 A1 WO2020101563 A1 WO 2020101563A1
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Prior art keywords
zeolite
mixture
solvent
solid catalyst
based solid
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PCT/SE2019/051157
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English (en)
Inventor
Elena SUBBOTINA
Alexandra Velty
Avelino Corma
Joseph Samec
Original Assignee
Kat2Biz Ab
Universitat Politècnica De València
Agencia Estatal Consejo Superior De Investigaciones Científicas, M.P.
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Priority to EP19809205.8A priority Critical patent/EP3880667A1/fr
Publication of WO2020101563A1 publication Critical patent/WO2020101563A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • C07D307/48—Furfural
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • C07C45/513—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/14—All rings being cycloaliphatic
    • C07C2602/24—All rings being cycloaliphatic the ring system containing nine carbon atoms, e.g. perhydroindane

Definitions

  • the present disclosure relates to a method of preparing monomers such as
  • the invention further relates to compositions obtained from the method and fuel obtained by treating the composition.
  • Lignocellulose is the most available source of biomass. Unlike crude oil, the most utilized source for the production of chemicals and fuels, biomass is renewable and “carbon neutral”. Thus, development of methods for biomass valorisation to platform chemicals or fuel precursors are of high importance.
  • Lignocellulose comprises three main components: lignin, cellulose, and hemicellulose.
  • Lignin is an aromatic hetero polymer linked together via C-C and C-0 bonds and mainly derived from three monolignols, coniferyl, p-coumaryl and sinapyl alcohols. Hemicellulose and cellulose both are polysaccharides, but with different structural properties.
  • Cellulose is a crystalline regular polymer consisting of glucose, and hemicellulose is an irregular amorphous polymer comprising C-5 and C-6 sugars.
  • hemicellulose is an irregular amorphous polymer comprising C-5 and C-6 sugars.
  • Acid-catalyzed pulping is a promising approach for catalytic fractionation of biomass, since potentially all three components can be transformed into valuable monomeric products.
  • the main obstacle of this approach is the formation of reactive intermediates during the depolymerization of lignin that react to form dimeric, oligomeric and polymeric by-products via C-C bond formation ( Figure 1).
  • “native” lignin may be isolated using various methods. For example this may be achieved by the addition of formaldehyde, which results in the formation of the acetal of lignin’s 1 ,3 - diols, and prevents formation of reactive benzylic carbocations.
  • Furfural is industrially produced from lignocellulosic biomass in the presence of sulphuric acid, through hydrolysis and dehydration of pentoses.
  • the production of furfural presents several drawbacks associated to the use of homogeneous acids such as corrosion and the production of large amount of acidic residues. Then investigations for optimizing cellulose conversion and furfural production continue to be of a great interest.
  • WO201 1003029 relates to a method for catalytic cleavage of carbon-carbon bonds and carbon-oxygen bonds in lignin.
  • US20130025191 relates to a depolymerisation and deoxygenation method where lignin is treated with hydrogen together with a catalyst in an aromatic containing solvent.
  • the object of the present disclosure is to take advantage of the catalytic properties and the pore size of protonic or acidic zeolites for organosolv pulping of biomass and to overcome the drawbacks of prior art.
  • the present disclosure presents a method to stabilize monomers and furfural released from all components: cellulose, hemicellulose and lignin.
  • the present zeolite-based solid catalysts have a porous system conferring high surface area and shape and size selectivity together with the possibility of accommodating different metals in its framework giving them acid/base or redox properties.
  • the substitution of aluminum for silicon in a silica covalent framework induces a charge unbalance that can be compensated by cation.
  • zeolite-based catalysts of the present disclosure may convert released monomers such as allylic alcohols and products derived from sugars via transfer hydrogenolysis reactions and dehydration, hampering their bimolecular condensations due to the pore size constraint and diffusion control, avoiding the usage of the trapping agents and transition metals.
  • This methodology also allows to preserve the core structure of the biomass components for example lignin is not modified as in organosolv processes.
  • the present disclosure relates to a method of producing monomers from lignocellulosic biomass by acid-catalyzed fractionation of lignocellulosic biomass, comprising the steps of: a. mixing the lignocellulosic biomass, a zeolite-based solid catalyst, and a solvent; and b. heating the mixture obtained in step a at a temperature of 120°C or higher.
  • the present disclosure relates to a method of producing monomers and / or furfural from biomass comprising the steps of:
  • the biomass contains lignin, cellulose and/or hemicellulose and wherein the zeolite-based solid catalyst preferably have pores with a diameter of 0.7nm (7A) or smaller but 0.4nm (0.4 ⁇ ) or larger.
  • the present disclosure relates to a method of producing monomers and / or furfural from biomass comprising the steps of:
  • the biomass contains lignin, cellulose and/or hemicellulose and wherein the zeolite-based solid catalyst preferably have pores with a diameter of 0.7nm or smaller but 0.4nm or larger.
  • the zeolite-based solid catalyst possesses a pores system without cavities. In another preferable embodiment of the method, the zeolite-based solid catalyst possesses a nanocrystalline structure.
  • the monomers produced comprise
  • the weight percent of the zeolite-based solid catalyst with respect of the weight of the lignocellulosic biomass or the lignin and/or cellulose containing biomass is 1-50 wt% and preferably 5-25 wt%.
  • the solid catalyst is separated from the mixture after completion of the heating or the heating step b of the method of the invention.
  • the method of the invention is performed in a stirred batch or a continuous stirred-tank reactor.
  • the content of furfural is 5% or more, 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, by weight of the composition.
  • the present disclosure relates to a method according to the present disclosure wherein the mixture such as in step b is heated at a temperature of 120- 250°C, preferably at 150-250°C, and most preferably at 200-240°C.
  • the mixture such as in step b is heated for 0.1 to 10 h, more preferably for 0.5 to 5h and most preferably for 2 h under a pressure from 1 to 80 bars.
  • the present disclosure relates to a method according to the present disclosure wherein the zeolite-based solid catalyst contents a trivalent metalloid or metal or mixture thereof, preferably Boron or Aluminum, and most preferably Aluminum.
  • the present disclosure relates to a method according to the present disclosure wherein the zeolite-based solid catalyst presents a framework Si/Al ratio in the range of 7-50, preferably in the range of 10-35.
  • the present disclosure relates to a method according to the present disclosure wherein the zeolite-based solid catalyst possesses a tridirectional or a bidirectional system of pores, preferably a tridirectional system of pores.
  • the present disclosure relates to a method according to the present disclosure wherein the zeolite-based solid catalyst possesses a topology of pores with at least 10 membered-ring and preferably 12 membered-ring.
  • the present disclosure relates to a method according to the present disclosure wherein the zeolite-based solid catalyst is beta zeolite.
  • the present disclosure relates to a method according to the present disclosure wherein the lignocellulosic biomass is hardwood or softwood or a mixture thereof.
  • the present disclosure relates to a method according to the present disclosure wherein the solvent is a polar solvent, such as methanol, ethanol, 1 -propanol, 2-propanol, 1 -butanol, 2-butanol 1, 4-dioxane or acetonitrile and preferably a mixture of a polar solvent and water wherein the water content is in the range of from 0.5 to 20 % of the total volume of solvent mixture, and most preferably wherein the mixture is a mixture of ethanol and water.
  • a polar solvent such as methanol, ethanol, 1 -propanol, 2-propanol, 1 -butanol, 2-butanol 1, 4-dioxane or acetonitrile
  • the water content is in the range of from 0.5 to 20 % of the total volume of solvent mixture, and most preferably wherein the mixture is a mixture of ethanol and water.
  • the present disclosure relates to a composition derived from wood comprising a mixture of monophenolic compounds and furfural.
  • composition further comprises esters of levulinic acid, and ethers of sugars, and/or 5-hydroxymethylfurfural.
  • Another aspect of the present disclosure relates to a composition obtainable or obtained by the method according to the present disclosure.
  • An additional aspect of the present disclosure relates to a fuel obtainable or obtained by hydroprocessing the composition of the present disclosure or a fraction of said compositions.
  • Figure 1 A schematic illustration of prior art disclosing recondensation reactions during acid-catalyzed pulping b. A schematic illustration of prior art disclosing prevention of recondensation reactions during pulping of biomass (previous reports) c. A schematic illustration of the reaction scheme of the present disclosure.
  • Figure 2 A schematic illustration of the release of allylic alcohols during organosolv pulping of lignocellulose
  • FIG. 3 A schematic illustration of the reaction of coniferyl alcohol 1 under
  • organosolv pulping conditions in the presence of beta- 1 zeolite in the presence of beta- 1 zeolite.
  • FIG. 6 Schematic scheme of the reaction of phenylacetaldehyde in the presence of zeolite.
  • Figure 7 Illustrative scheme pathway for lignin depolymerization and allylacohols conversion and stabilization in the presence of beta- 1 zeolite.
  • FIG 8 Scheme pathway for hemicellulose and cellulose depolymerization in the presence of beta- 1 zeolite.
  • Figure 9 Schematic representation of the location of transformation of components of biomass during zeolite-catalyzed pulping according to the present disclosure.
  • Figure 10 a) temperature and b) water content dependence of furfural and lignin monomers yield. Yield calculated as: mass of products/mass of lignin. Mass of furfural/ mass of (cellulose + hemicellulose). Reaction conditions: 200 mg of birch sawdust, 50 mg catalyst, E ⁇ 0H/3 ⁇ 40 5mL, 200 °C, 2h.
  • Figure 13 framework of a zeolite catalyst, a) framework type FAU (faujasite) viewed along [1 11], b) framework type BEA (beta) viewed along [100].
  • biomass includes, but is not limited to wood, fruits, vegetables, processing waste, chaff, grain, grasses, com, com husks, weeds, aquatic plants, hay, paper, paper products, recycled paper, shell, algae, straw, bark or nut shells, lignocellulosic material and any cellulose and/or lignin containing biological material or material of biological origin.
  • biomass is not limited to wood, fruits, vegetables, processing waste, chaff, grain, grasses, com, com husks, weeds, aquatic plants, hay, paper, paper products, recycled paper, shell, algae, straw, bark or nut shells, lignocellulosic material and any cellulose and/or lignin containing biological material or material of biological origin.
  • the biomass is
  • the biomass is wood, preferably particulate wood such as saw dust or wood chips.
  • the wood may be any kind of wood, hard or soft wood, coniferous tree or broad-leaf tree.
  • the biomass is hard wood or soft wood or a mixture thereof.
  • a non-limiting list of woods would be pine, birch, spruce, maple, ash, mountain ash, redwood, alder, elm, oak and beech.
  • the biomass contains lignin where the chemical structure or chemical composition of the lignin has essentially not been modified.
  • the biomass is organosolv lignin, i.e. lignin obtained from an organosolv process.
  • lignocellulose biomass such as wood
  • the reason for this is believed to be that isolated lignin or cellulose for example have already been treated in some way and the wanted lignin or cellulose may have formed bonds that are hard to break and the monomers or products that is supposed to be stabilized by the catalyst may already have recondensated or repolymerized.
  • Organosolv is a pulping technique originating from the early 1930’s while the main development was performed during the late 1980’s where biomass is separated in cellulose and, lignin and hemicellulose.
  • the technique involves contacting a lignocellulosic feedstock such as chipped wood with an aqueous organic solvent at temperatures ranging from 140°C and higher usually not higher than 220°C. This causes hydrolytic depolymerization of alpha aryl-ether links into fragments that are soluble in the organic solvent.
  • Solvents used include acetone, methanol, ethanol, butanol, ethylene glycol, formic acid, and acetic acid.
  • the concentration of the solvent in water may be in the range of from 40 to 80 wt%.
  • the organosolv process may be a two or more-stage process where the same or different solvents are used in the two stages.
  • a base such as sodium hydroxide may be added, preferably in the second stage and the lignin may be isolated by lowering the pH using any suitable acid.
  • the lignin may be precipitated or the mixture may be filtrated, evaporated, distilled or centrifuged.
  • pore means an elongated hole or void with an opening.
  • pore size, pore diameter and diameter of a pore denotes the same thing and refers to the size determined using nitrogen gas adsorption measured at 77K for pores with sizes up to lOOnm.
  • Pore size or pore diameter presented herein denotes the maximum size of pores constituting at least 90% or preferably at least 95% of the total pore volume.
  • a pore diameter of 0.7nm or 0.7nm or smaller denotes that at least 90% of the total pore volume is constituted by pores having diameters of 0.7nm or smaller.
  • a pore diameter of 0.7nm or smaller but 0.4nm or larger denotes that at least 90% of the total pore volume is constituted by pores having a diameter of 0.7nm or smaller and 0.4nm or larger.
  • cavity volume means a hole or void having a diameter larger than l . lnm (l lA).
  • cavity volume cavity diameter or cavity size denotes the same thing and refers to the size determined using nitrogen gas adsorption measured at 77K for cavities with sizes up to lOOnm.
  • the present disclosure provides a straightforward method of depolymerizing lignin direct from the biomass, without having to isolate lignin or cellulose or hemicellulose first. Furthermore, the method may be implemented into the already existing techniques such as the organosolv process. By providing a method that may be conducted in a one pot synthesis or one pot reaction the present disclosure presents a very efficient strategy for preparing furfural and monomers such as phenolic
  • An advantage of the present method is that the parameters of the method such as temperature or solvent used may be adjusted in order the increase the yield of furfural or monomers such as phenolic containing monomers or monophenolic monomers.
  • lignin first undergoes solvolytic depolymerization and releases reactive allylic alcohols, which afterwards get transformed inside the pores of the present zeolite-based catalyst over Bronsted acid active sites into the stabilized monophenolic products. Moreover, hemicellulose/ cellulose is partially transformed into furfural when in contact with the zeolite-based catalyst.
  • the present disclosure is a first example of a new additive and transition metal-free approach in the stabilization of monomers derived from pulping of biomass.
  • the method according to the present disclosure relates to treating biomass such as lignocellulosic biomass, lignin, cellulose or hemicellulose by acid-catalyzed
  • the biomass is mixed with a zeolite based solid catalyst and a solvent forming a first mixture which is heated at a temperature of 120°C or higher. This generates an intermediate product, a solvolysis product.
  • the mixture or first mixture is heated at 120-300°C, preferably at 120-25OC, more preferably at 150-25OC, more preferably at 180-240°C, more preferably at 200-240C, more preferably at 200-230°C.
  • the mixture or first mixture is preferably heated at 200- 240°C preferably around 220°C.
  • the mixture or first mixture is preferably heated at 180-220°C, preferably at 190-210°C, more preferably around 200°C.
  • the heating may be done for a suitable period of time preferably from 0.1 to lOh, preferably from 0.5 to 5h and more preferably for 2h. Still the time is dependent on the volume of the mixture.
  • a pressure may also be applied during the heating. In one embodiment the pressure is from 1 to 80 bar, preferably from 2 to 50 bar, more preferably from 5 to 20 bar. Applied pressure may shorten the treatment time and may increase the yield.
  • the method is conducted in a sealed container. In another embodiment the method is conducted at atmospheric pressure.
  • the amount zeolite catalyst with respect to the weight percent of the biomass in the mixture is preferably l-50wt% more preferably 5- 25wt%.
  • the pH of the mixture or the first mixture is preferably acidic. In one embodiment the pH is 2-6, preferably 3-5.
  • the zeolite-based solid catalyst In order to stabilize the monomers and furfural and to avoid that the monomers and furfural formed during the method undergo recondensation or repolymerization the zeolite-based solid catalyst needs to have large enough pores to allow the solvolysis products to enter the catalyst but small enough pores to reduce the amount of solvolysis products entering each pore.
  • the zeolite based solid catalyst may be in the form of a powder or particles.
  • the zeolite-based solid catalyst should be essentially free from any cavities such as cavities with a diameter of 1.1 nm (l lA) or larger, preferably lnm (lOA) or larger, preferably essentially free from cavities having a diameter of 0.9nm (9A) or larger.
  • the zeolite catalyst should be essentially free from any cavities having a volume larger than 6nm 3 (6000A 3 ).
  • a zeolite catalyst having pores with a diameter of 0.7nm (7 A) or smaller but 0.4nm (4A) or larger the catalyst allows the solvolysis products to enter but recondensation and repolymerization is reduced or avoided.
  • the maximum diameter of 0.7nm is believed to minimize the risk of fitting more than one monomer or compound in each pore of the zeolite and thereby limiting the amount of recondenzation or repolymerization.
  • Zeolites having larger pores or cavities fit two or more monomers which may then react and form dimers or trimers.
  • the zeolite-based solid catalyst has preferably at least one of the following features: - pores with a diameter of 0.7nm (7A) or smaller, preferably 0.65nm or smaller, more preferably 0.6nm or smaller but preferably 0.3nm (3 A) or larger, more preferably 0.4nm or larger, more preferably 0.45nm or larger, more preferably 0.5nm or larger,
  • - possesses a bidirectional or a bidirectional system of pores, preferably a bidirectional system of pores,
  • - possesses a topology of pores with at least 10 membered-ring and preferably 12 membered-ring,
  • the unit cell volume is 4-4.3 nm 3 (4000-4300A 3 ),
  • micropore volume of less than 0.25pm 3 /g, preferably less than 0.20pm 3 /g
  • the maximum diameter of a sphere that can be included is 0.8nm (8 A) or smaller, preferably 0.75nm or smaller, more preferably 0.7nm or smaller, but preferably 0.4nm or larger. In one embodiment the maximum diameter of a sphere that can be included is 0.6-0.7nm (6-7A),
  • the zeolite catalyst has a nanocrystalline structure with unit cells that preferably are tetragonal,
  • the zeolite catalyst is essentially free from cavities having a diameter of l. lnm (l lA) or larger, preferably lnm (lOA) or larger, preferably essentially free from cavities having a diameter of 0.9nm or larger,
  • the maximum diameter of a sphere that can diffuse along is 0.7nm (7A) or smaller, preferably 0.65nm or smaller, more preferably 0.6nm or smaller, preferably 0.4nm or larger, more preferably 0.45nm or larger, -a SBET (surface area) of less than 600m 2 / g.
  • zeolite catalysts have small enough pores to reduce the recondensation or repolymerization and also high enough acidity. A high yield and good control is obtained using these types of catalysts.
  • the unit cell of the zeolite-based solid catalyst has a volume of 6 nm 3 (6000A 3 ) or less, preferably 5 nm 3 or less, preferably 4.5 nm 3 or less, preferably 1 nm 3 or larger, more preferably 3 nm 3 or larger.
  • the maximum diameter of a sphere that can be included is less than 0.8nm (8 ⁇ ), preferably less than 0.7nm, but preferably 0.4nm or larger, or more preferably 0.5nm or larger.
  • the maximum diameter of a sphere that can diffuse along is 0.7nm or smaller, preferably 0.65nm or smaller, more preferably 0.6nm or smaller, preferably 0.4nm or larger, more preferably 0.45nm or larger.
  • the zeolite-based solid catalyst is essentially free from cavities or supercages.
  • the zeolite catalyst is essentially free from cavities having a diameter of l. lnm (l lA) or larger, preferably lnm (lOA) or larger, preferably essentially free from cavities having a diameter of 0.9nm or larger.
  • the zeolite based solid catalyst of the present disclosure has preferably a tridirectional system of pores, an acidity (Bronsted) of 200-270 pmol/g, preferably 220-260 pmol/g, more preferably 240-250 pmol/g when measured at 250°C and a Si/Al ratio of 7 to 50, preferably 10-35, more preferably 12-15 and/or a tetragonal crystal structure and/or tridirectional structure consists of straight 12-membered ring channels of a free aperture of 6.6*6.7 A along axis [100] and zigzag 12-membered rings channels of 5.6*5.6 A along axis [001], preferably without cavities and/or a micropore volume of less than 0.25pm 3 /g, preferably less than 0.20pm 3 /g.
  • the zeolite-based solid catalyst is beta zeolite or a zeolite having a BEA framework.
  • the beta zeolite is a beta 1 zeolite.
  • Suitable solvents are polar solvents or mixtures comprising a polar solvent and water or the solvent is a mixture of at least two polar protic solvents or is a mixture of at least one polar protic solvent and at least one aprotic solvent.
  • the polar solvent or the polar protic solvent is preferably selected from but not limited to alcohols preferably methanol, ethanol, 1 -propanol, 2 -propanol, 1 -butanol and 2 -butanol.
  • the solvent is or comprises a cyclic ether preferably 1,4-dioxane.
  • the solvent is or comprises acetonitrile.
  • the solvent is a mixture of at least two polar protic solvents or is a mixture of at least one polar protic solvent and at least one aprotic solvent wherein at least one of the solvents is selected from methanol, ethanol, 1 -propanol, 2 -propanol, 1 -butanol, 2- butanol 1,4-dioxane and acetonitrile.
  • the solvent is a mixture of at least two polar protic solvents wherein one polar protic solvent is water and wherein at least one solvent is preferably an alcohol preferably selected from methanol or ethanol more preferably ethanol.
  • the solvent is a mixture of at least one polar protic solvent and at least one aprotic solvent wherein the polar protic solvent is water and wherein the at least one aprotic solvent is a cyclic ether preferably dioxane.
  • the solvent is a mixture of a solvent and water the water content is in the range of from 0.5 to 20 % of the total volume of solvent mixture, preferably from 5 to 15%.
  • the volume ratio between water and the polar solvent preferably alcohol or the aprotic solvent is between 15: 1 to 1:4, preferably between 12: 1 to 5: 1, more preferably between 10: 1 to 8: 1 or around 9: 1.
  • the solvent is a mixture of at least one polar protic solvent and at least one aprotic solvent
  • the polar protic solvent is preferably water and the at least one aprotic solvent is a cyclic ether preferably dioxane or 1 ,4-dioxane.
  • the solvent is a mixture comprising ethanol and water in a volume ratio of 15: 1 to 1 :4, preferably 12: 1 to 5: 1, more preferably 10: 1 to 8: 1 or around 9: 1 (ethanol: water).
  • An advantage of said suitable solvents is that they result in high yield of wanted compounds.
  • a benefit of using water or a solvent mixture comprising water is that water promotes the cleavage of C-0 bond and results in an increase in the formation of furfural.
  • a high water content limits the formation of aromatic monomers or compounds.
  • the water content in the solvent mixture is at least 5 volume%, preferably at least 7 volume%, more preferably at least 10 volume%, more preferably at least 12 volume%.
  • the water content is 18-22 volume%, preferably around 20 volume%.
  • the biomass undergoes solvolysis forming solvolysis products.
  • the solvolysis products are then brought into contact with the catalyst optionally forming a second mixture. This may be done simultaneously as the solvolysis or may be done in one or more separate steps.
  • the whole method of the present disclosure is preferably conducted as a one pot synthesis where the mixing and heating is done in one pot.
  • Heating of the second mixture is preferably done in the same manner and/or at the same temperature as heating of the first mixture and is preferably done at a temperature of 120-300°C, preferably at 120-25OC, more preferably at 150-25OC, more preferably at 180-240°C, more preferably at 200-240C, more preferably at 200- 230° C.
  • the second mixture is preferably heated at 200-240°C preferably around 220°C.
  • the second mixture is preferably heated at 180-220°C preferably at 190-210°C, more preferably around 200°C.
  • the heating may be done for a suitable period of time preferably from 0.1 to lOh, preferably from 0.5 to 5h and more preferably for 2h. Still the time is dependent on the volume of the mixture.
  • a pressure may also be applied during the heating. In one embodiment the pressure during the heating of the second mixture is from 1 to 80 bar, preferably from 5 to 20 bar. Applied pressure may shorten the treatment time and may increase the yield. In one
  • the heating of the second mixture is conducted in a sealed container. In another embodiment the method is conducted at atmospheric pressure.
  • the pH of the second mixture is preferably acidic. In one embodiment the pH is 2-6, preferably 3-5.
  • the obtained monomers are preferably monophenolic monomers and preferably selected from compound 14 to 29 of Figure 7.
  • the yield of said compounds may be 10- 20%.
  • the major constituents of the monophenolic compounds are:
  • the obtained compounds from cellulose and / or hemicellulose may be furfural, esters of levulinic acid, ethylfurfuryl alcohol, ether and ethers of sugars such as ethyl glucosides and / or 5-hydroxymethylfurfural.
  • the yield of furfural may be at least 8%, preferably at least 10%.
  • a composition comprising monomers and / or furfural, solvent and catalyst is obtained after the heating.
  • the wanted products, monomers and/or furfural may be separated or isolated using any suitable technique such as filtration, distillation, solvent extraction etc. or combinations thereof.
  • the monomers are preferably monophenolic monomers.
  • the present method results in a composition comprising monophenolic compounds where the major constituents are:
  • the catalyst may be separated or isolated using any suitable technique preferably through filtration or sedimentation and decantation.
  • the zeolite catalyst may be regenerated and reused which is very beneficial.
  • the obtained composition comprises a mixture of monophenolic compounds and furfural where the mixture of monophenolic compounds preferably comprises compounds selected from compound 14 to 29 of Figure 7, and furfural.
  • the obtain composition may further contain esters of levulinic acid, ethylfurfuryl alcohol, ether and ethers of sugars such as ethyl glucosides and/or 5-hydroxymethylfurfural.
  • the obtained composition comprises a mixture of monophenolic compounds and furfural where the mixture of monophenolic compounds preferably comprises the following monophenolic compounds as its major constituents:
  • composition may preferably further comprise esters of levulinic acid, and ethers of sugars, and/or 5-hydroxymethylfurfural.
  • a carrier liquid may also be added to the composition in order to make the composition or the monophenolic compounds more suitable for further treatments in a refinery process such as a conventional refinery process.
  • the carrier liquid may be any suitable oil for example a hydrocarbon oil, crude oil, bunker oil, mineral oil, tall oil, creosote oil, tar oil, fatty acid or esterified fatty acid.
  • the carrier liquid is a fatty acid or a mixture of fatty acids.
  • the fatty acid may be a tall oil fatty acid (TOFA) or refined or distilled TOFA.
  • the carrier liquid is esterified fatty acids such as FAME (fatty acid methyl ester) or triglyceride.
  • the carrier liquid is a crude oil.
  • the carrier liquid is bunker fuel or bunker crude.
  • the carrier liquid is a hydrocarbon oil preferably a gas oil or a mineral oil.
  • the carrier liquid is a mixture of esterified fatty acid and a mineral oil, hydrocarbon oil, bunker fuels or crude oil.
  • the carrier liquid is a mixture of a hydrocarbon oil or a mineral oil and a fatty acid.
  • the carrier liquid is creosote oil or tar oil. Since the composition may be used for preparing fuels the carrier liquid does not have to be an already hydrotreated or cracked liquid such as diesel, instead the carrier liquid should be a liquid that may be hydrotreated or cracked in a refinery process in order to form fuel. By using a non-hydrotreated or non-cracked carrier liquid conventional refinery processes may be used and carrier liquids that any way would be refined can be used.
  • the composition may comprise 10-99 weight% of carrier liquid of the total weight of the composition, such as 20 weight% or more, or 40 weight% or more, or 60 weight% or more, or 80 weight% or more, or 99 weight% or less, or 85 weight% or less, or 65 weight% or less.
  • the amount of carrier liquid is 60-90 weight% such as 65-85 weight%.
  • the composition may comprise 1-90 weigh t% of monomers and/or furfural.
  • the composition comprises 10 weight% or more, preferably 20 weight% or more, or more preferably 40 weight% or more, but preferably 70 weight% or less, or preferably 60 weight% or less, or more preferably 50 weight% or less.
  • a fuel can be obtained from the present composition through hydroprocessing such as hydrotreatment or hydrocracking the composition.
  • hydrotreating the feed may be exposed to hydrogen gas (for example 20- 200bar) and a hydrotreating catalyst (NiMo (Nickel Molybdenum), CoMo (Cobalt Molybdenum) or other HDS, HDN, HDO catalyst) at elevated temperatures (200- 500° C).
  • a hydrotreating catalyst NiMo (Nickel Molybdenum), CoMo (Cobalt Molybdenum) or other HDS, HDN, HDO catalyst
  • HDS hydrodesulfurization
  • hydrodenitrogenation HDN
  • hydrodeoxygenation HDO
  • sulphurs, nitrogens and oxygens primarily are removed as hydrogensulfide, ammonia, and water. Hydrotreatment also results in the saturation of olefins and possibly also aromatic compounds.
  • Catalytic cracking is a category of the broader refinery process of cracking. During cracking, large molecules are split into smaller molecules under the influence of heat, catalyst, and/or solvent. There are several sub-categories of cracking which includes thermal cracking, steam cracking, fluid catalyst cracking and hydrocracking. During thermal cracking the feed is exposed to high temperatures and mainly results in homolytic bond cleavage to produce smaller unsaturated molecules.
  • Steam cracking is a version of thermal cracking where the feed is diluted with steam before being exposed to the high temperature at which cracking occurs.
  • a fluidized catalytic cracker (FCC) or“cat cracker” the preheated feed is mixed with a hot catalyst and is allowed to react at elevated temperature.
  • the main purpose of the FCC unit is to produce gasoline range hydrocarbons from different types of heavy feeds. During hydrocracking the hydrocarbons are cracked in the presence of hydrogen.
  • Hydrocracking also facilitates the saturation of aromatics and olefins.
  • Product 1 was synthesized according to the following 2 steps procedure: 3-(3,4- dihydroxyphenyljacrylic ac id (28mmol) was dissolved in MeOH (100 ml), 10 drops of H SO4 cone were added and mixture was refluxed 24 hours. MeOH was removed under reduced pressure; acid was neutralized by NaHC03 solution and product was extracted with dichloromethane, organic layers were washed with brine, dried over anhydrous Na S04 , filtrated, and concentrated in vacuo. Product was used for the next step without purification.
  • GC measurements were performed on a Shimadzu GC-2010 Plus equipped with a HP-5 MS capillary column (30m * 0.25 mm * 0.25 pm) and an FID detector. Dodecane was used an internal standard. GC-MS measurements were performed on a Shimadzu GC- MS-QP2020.
  • Textural properties including BET surface area and micropore volume of the samples were measured by N2 adsorption/ desorption in a Micromeritics ASAP2000 at 77 K.
  • the acidity of the catalysts was measured by IR spectroscopy (Nicolet 710 FTIR spectrophotometer) combined with adsorption-desorption of pyridine at 10 4 Torr at 250 °C and 350 °C using self-supported wafers of 10 mg cm 2 that were degassed overnight under vacuum (10 4 to 10 5 Pa) at 400 °C. After each desorption step, the spectrum was recorded at room temperature and the background subtracted. All the spectra were scaled according to the sample weight. The acidity of the catalysts was measured as pmol pyridine per gram of catalyst at different temperatures, calculated by using the extinction coefficients, from the area of the IR band of Bronsted and Lewis acid sites at ca. 1545 and 1450 cm 1 , respectively.
  • a stainless steel reactor purchased from Swagelok, equipped with a stir bar was loaded with the wood sawdust or model compound 1 and corresponding catalyst. Solvent was added and the reactor was sealed. The reaction mixture was stirring for specified time at specified temperature. After the completing of the reaction, reaction mixture was filtrated; internal standard (dodecane) was added to the solution and aliquot was taken and analyzed by GC-FID and GC-MS. Solvent and furfural were evaporated from the reaction mixture (in case of wood) and the oil residue was extracted with EtOAc/LEO. Organic layer was analyzed by GC-FID and GC-MS.
  • a microwave vial reactor equipped with a stir bar was loaded with 60 mg of the l-(3,4- dimethoxyphenyl)-2-(2-methoxyphenoxy) propane- 1 ,3-diol substrate (5) .
  • 2 mL of ethanol and water were added and 40 mg of water and the reactor was sealed.
  • the reaction mixture was stirring for 2 hours at 200 °C under microwave. After the completing of the reaction, reaction mixture was filtrated; internal standard (dodecane) was added to the solution and aliquot was taken and analyzed by GC-FID and GC-MS.
  • beta and HY zeolites both offering large pores structures that allow the diffusion of large molecules but with an important structural difference, namely presence of large cavities in case of faujasite (HY) zeolite and absence of those for beta zeolite.
  • HY faujasite
  • beta zeolite is a tridirectional structure with large pores, consisted by intergrowth of two pore systems without cavities.
  • Ultrastable HY zeolite has a tridirectionnal and large pore structure consisted of sodalite cages (supercage) which are connected through hexagonal prisms. The pore is formed by a 12-membered ring with a free aperture of 7.4
  • Lignin is a polymeric molecule consisting of assembling of three monolignols through etheric C-0 linkages (mostly a-O-4, b-O-4’, 4-0-5) and C-C linkages (e.g., 5-5', b- 1 , b- 5, b-b').
  • the etheric b-O-4’ linkage is the dominant one and corresponds up to 60% of total linkages in hardwood. Since C-0 ether bonds are significantly weaker than C-C bonds, the b-O-4’ linkage is a model linkage largely studied during the investigation of lignin depolymerization.
  • 2-methoxyphenol (8), dimethoxyphenylacetaldehyde (9), dimethoxyphenylacetaldehyde diethyl acetal (11) (3,4-dimethoxyphenyl)acrylaldehyde (10) are the products resulting from the b-O-4’ cleavage of model compound 5, showing that beta zeolite is enable to carry out the acidolysis of ether linkage (Table 3).
  • products of b-O-4’ cleavage were obtained in quite low yields, and substantial amount of dimers (5, 6 and 7) were detected in the reaction mixture.
  • steric factors and control by diffusion inside the pores contribute to the lower rate of conversion of dimer 5 in comparison to allylic alcohol 1.
  • the main pathway for the formation of monomers must be via homolysis of b-O-4’ and stabilization of released monomers in the pores of zeolite.
  • Ph-OH Aid Ph-OH Aid.
  • beta zeolite is a good candidate to stabilize allylic alcohols released from organosolv pulping in the presence of a reducing agent such as ethanol.
  • a reducing agent such as ethanol.
  • beta zeolite is able to promote b-O-4’ cleavage of possible dimers released from pulping through acidolysis without the need of use of capping agent or metal.
  • birch wood was treated under depolymerisation conditions, in the presence of beta 1 zeolite, in mixture ethanol/ water (v/v 9: 1) at temperature comprised between 180 and 220°C. After reaction, the crude mixture was filtered and concentrated under vacuum. Then, the bio-oil was extracted with EtOAc/EBO in order to separate the monophenolic compounds from the products derived from the carbohydrates.
  • both hemicellulose and cellulose can be converted to the furfural in presence of beta zeolites.
  • furfural was the main product detected deriving from the cellulose and hemicellulose fraction in the birch wood.
  • Identified products also included ethyl-levulinate and ethylfurfuryl alcohol ether, as well as small amounts of ethyl glucosides (Figure 8).
  • Maximum yield of furfural was obtained when reaction was performed with addition of 20 v% of water and constituted 23 mol% (14.3 wt%) accounting for the cellulose and hemicellulose content of wood.
  • Reaction conditions 50 mg catalyst, 200 mg wood, 4.5mL EtOH, 0.5 mL 3 ⁇ 40. Yield calculated as: mass of products/mass of lignin, and mass of furfural/ mass of (cellulose + hemicellulose).
  • b 4.75mL EtOH, 0.25 mL 3 ⁇ 40 c 4mL EtOH, 1 mL 3 ⁇ 40.
  • Ethanol was shown to be a reducing agent and a good hydride donor under the developed reaction conditions, since process in methanol resulted in lower yield of desired products (Table 2). From the results given in the Table 6 it can be noticed that addition of water is required, presumably to promote the cleavage of LCC, however, excess of water might lead to the deactivation of the catalyst or side-reactions of monomers. An optimal ratio ethanol/ water 9/ 1 was implemented.
  • This method is a new approach for prevention of recondensation reactions during pulping of biomass. This is achieved by tuning pore size of the zeolite in order to hamper the bimolecular condensations and favor monomolecular reactions. It has been demonstrate an additive and transition metal-free methodology that can be successfully applied to woody biomass. Studies with model compounds revealed the reaction pathway which is a transfer-hydrogenolysis of allylic alcohols inside the pores of zeolites. Yields of 20 wt% of monomers are superior to the previously reported for acid-catalyzed pulping of wood in absence of metals (2-10 wt%).

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Abstract

La présente invention concerne un procédé de production de monomères monophénoliques et de furfural à partir de biomasse lignocellulosique par agitation de la biomasse dans un solvant conjointement avec un catalyseur à base de zéolite.
PCT/SE2019/051157 2018-11-15 2019-11-14 Procédé de formation de monomères et de furfural à partir de lignocellulose WO2020101563A1 (fr)

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Citations (5)

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US20130025191A1 (en) 2011-07-26 2013-01-31 Uop Llc Aromatic hydrocarbons from depolymerization and deoxygenation of lignin
WO2013134754A1 (fr) * 2012-03-09 2013-09-12 Vertichem Corporation Procédé de production de bioproduits chimiques à partir de lignine végétale
WO2016025679A1 (fr) * 2014-08-14 2016-02-18 Shell Oil Company Production en boucle fermée de furfural à partir de biomasse

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WO2010026244A1 (fr) * 2008-09-08 2010-03-11 Basf Se Procédé de production intégrée de cellulose et de matière réutilisable de faible poids moléculaire
WO2011003029A2 (fr) 2009-07-01 2011-01-06 The Regents Of The University Of California Dismutation catalytique et réduction catalytique des liaisons carbone-carbone et carbone-oxygène de la lignine et autres substrats organiques
US20130025191A1 (en) 2011-07-26 2013-01-31 Uop Llc Aromatic hydrocarbons from depolymerization and deoxygenation of lignin
WO2013134754A1 (fr) * 2012-03-09 2013-09-12 Vertichem Corporation Procédé de production de bioproduits chimiques à partir de lignine végétale
WO2016025679A1 (fr) * 2014-08-14 2016-02-18 Shell Oil Company Production en boucle fermée de furfural à partir de biomasse

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