WO2017171652A1 - Procédé de dépolymérisation de lignine dans des conditions oxydatives neutres - Google Patents

Procédé de dépolymérisation de lignine dans des conditions oxydatives neutres Download PDF

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Publication number
WO2017171652A1
WO2017171652A1 PCT/SG2017/050177 SG2017050177W WO2017171652A1 WO 2017171652 A1 WO2017171652 A1 WO 2017171652A1 SG 2017050177 W SG2017050177 W SG 2017050177W WO 2017171652 A1 WO2017171652 A1 WO 2017171652A1
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lignin
solvent
polar aprotic
reaction
rhenium
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PCT/SG2017/050177
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English (en)
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Jayasree Seayad
Gowrisankar SARAVANAN
Balamurugan Ramalingam
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Agency For Science, Technology And Research
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids

Definitions

  • the present invention generally relates to a process for depolymerizing lignin to monomers and/or oligomers wherein the lignin is reacted under oxidation conditions at a neutral pH in the presence of a polar aprotic solvent at elevated temperatures.
  • the process is especially useful to make aromatic aldehydes and acids from lignin.
  • Biomass comprises algae and vascular plants whose support tissue consists to a large degree of lignin. Chemically, lignins are cross-linked phenolic polymers forming larger molecules of complexity. Unfortunately there are many challenges to use lignin in order to derive fine chemicals therefrom. Harsh reaction conditions and low yields often pose severe limitations. It is difficult to depolymerize and break down the complex structures of the molecules.
  • Lignin depolymerization is therefore a key process for an efficient use of biomass. Especially the synthesis of fine chemicals from lignin poses high requirements with regard to selectivity and yield.
  • Lignin due to its chemical structure may especially offer the synthesis of aromatic aldehydes and their oxidation products, if a depolymerization is done under oxidizing conditions.
  • lignin may be a source to make vanillin and vanillic acid.
  • the global consumption of vanillin is around 12000 tons per year (tpa). While its price is around $15 kg, if the vanillin is made from petrochemicals such as phenol derived guaiacol, prices for lignin based vanillin can reach $100- 200 kg, because it is in high demand in certain market sectors (fragrance industries, chocolate manufacturers etc.).
  • lignosulfonates are the sulfonated lignin byproducts from the production of wood pulp via the sulfite pulping process.
  • modern paper and pulp industries prefer Kraft pulping over sulfite pulping and hence there is only minimal availability of lignosulfonate for vanillin synthesis.
  • most of the vanillin plants based on sulfite liquor were closed down; also due to disposal issues of the large amounts of caustic soda wastes (-160 kg/kg of vanillin) generated during this process. Therefore there is a need for making vanillin from other sources such as the Kraft pulping processes and from the many emerging biorefineries.
  • a process for depolymerizing lignin to monomers and/or oligomers characterized in that the lignin is reacted with an oxidation agent at a pH between about 5.0 and about 8.0 in the presence of a polar aprotic solvent at elevated temperatures.
  • this process is suited for use in the production of monomers or oligomers from lignin, such as aromatic phenols, particularly aromatic aldehydes or acids in good yields avoiding the use of highly alkaline or highly acidic agents which are corrosive and cause significant waste disposal challenges.
  • lignin such as aromatic phenols, particularly aromatic aldehydes or acids
  • a polar aprotic solvent allows for lignin to be dissolved well at elevated temperatures.
  • the use of a polar aprotic solvent is further advantageous in the depolymerization process, because it allows the depolymerization under pH-neutral oxidative conditions, such as at a pH value between 5.0 and 8.0.
  • the process disclosed above further allows the product composition to be altered depending on the concentration of oxidation agent in the matrix used as well as the total pressure.
  • a high percentage of an aromatic aldehyde may be obtained by use of a diluted mixture of oxidation agent within a gaseous matrix or lower pressures, while a high percentage of an aromatic acid may be obtained by use of an undiluted mixture of the oxidation agent or higher pressures.
  • the yield of the process as disclosed above, depending on the employed reaction conditions can be as high as 7.3 wt% in the case of Kraft lignin.
  • the process can proceed without the use of any metal catalyst.
  • the process may comprise a transition metal complex to achieve improved yields particularly in the case of non-treated or partially pretreated lignin precursors.
  • the process can be used for processing a wide variety of lignins obtained from natural sources.
  • this process allows for easy separation of the reaction products in an industrially upscalable way.
  • the inventors have surprisingly found a process for the depolymerization of lignin as disclosed above, which can proceed under neutral conditions and therefore can be considered more environmentally benign, efficient and selective over the present state of the art.
  • lignin refers to any lignin or lignin derivative which include Brauns' lignin, cellulolytic enzyme lignin, dioxane acidolysis lignin, milled wood lignin, Klason lignin, periodate lignin, kraft lignin, softwood kraft lignin, hardwood kraft lignin, lignosulfates, lignosulfonates, organosolv lignin, and steam explosion lignin and other lignin's mentioned in the decription. It also refers to any substances made in whole or in part from lignin or any subunits, monomers, or other components derived therefrom.
  • lignin is meant to include lignin, and/or any compound comprising lignin or the residue thereof and refers to any polymer comprising p- hydroxyphenyl units, syringyl units, and guaiacyl units.
  • biomass refers to a facility that integrates biomass conversion processes and equipment to produce fuels, power, heat, and value-added chemicals from biomass.
  • oligomer refers to a molecular complex that consists of a few monomer units, in contrast to a polymer, where the number of monomers is, in principle, not limited.
  • the oligomer comprises 2 to 8, more preferably 2 to 5 monomer units.
  • polar solvent refers to a solvent wherein the solvent molecules have an uneven distribution of electron density.
  • aprotic solvent refers to a solvent that has no hydrogen atom bound to an oxygen (as in a hydroxyl group) or a nitrogen (as in an amine group).
  • the term "about”, in the context of concentrations of components of the formulations, typically means ⁇ 10% of the stated value, more typically ⁇ 7.5% of the stated value, more typically ⁇ 5% of the stated value, more typically ⁇ 4% of the stated value, more typically ⁇ 3% of the stated value, more typically, ⁇ 2% of the stated value, even more typically ⁇ 1% of the stated value, and even more typically ⁇ 0.5% of the stated value.
  • certain embodiments may be disclosed in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges.
  • a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range.
  • description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • FIG. 1 shows a typical reaction scheme for depolymerization of lignin according to the invention.
  • Fig.2 shows a typical reaction scheme for depolymerization of lignin according to the invention.
  • FIG. 2 shows an example of an upscalable version of the inventive process including separation and purification steps.
  • FIG. 3 shows typical GC spectra of the reaction product.
  • FIG. 4 A, B and C show the Gel Permeation Chromatography (GPC) results of Kraft Lignin (Lignin Alkali, 370959 Aldrich) and the oil before and after the oxidative depolymerization in a representative example.
  • GPC Gel Permeation Chromatography
  • FIG. 5 shows the typical linkages and functional groups in lignins that have been made the basis of the NMR analysis to measure the G/S ratios.
  • a process for depolymerizing lignin to monomers and/or oligomers characterized in that the lignin is reacted with an oxidation agent at a pH between 5.0 and 8.0 in the presence of a polar aprotic solvent at elevated temperatures.
  • the lignin is not limited to any specific type of lignin.
  • a lignin precursor can be used.
  • Kraft lignin, wheat straw lignin and lignin from empty palm fruit bunch (EFB lignin) also can be depolymerized. Kraft lignin may be particularly mentioned.
  • the lignin or its precursor may be selected from any kind of cellulosic biomass, wherein the cellulosic biomass is optionally selected from any kind of wood, for example from softwood and hardwood, or grass type biomass and agricultural/industrial wastes such as empty palm fruit bunch EFB, Cornstover, wheat straw, woodchips or Kraft lignin or mixtures thereof and wherein the cellulosic biomass is chemically or enzymatically pretreated or not pretreated.
  • the lignin can be from any kind of cellulosic biomass e.g.
  • any kind of wood, softwood/hardwood, or grass type biomass or agricultural/industrial wastes (empty palm fruit bunch EFB, Cornstover, Wheat straw, Woodchips, Kraft lignin etc.) chemically or enzymatically pretreated or not pretreated.
  • the process according to the invention may be also useful for the production of syringaldehyde, syringic acid, p-hydroxybenzaldehyde and p- hydroxy benzoic acid which depends on the type of biomass used.
  • the process according to the invention allows to use lignins such as Kraft lignin or lignins from biorefineries which otherwise are non usable in the aqueous or organic solvents of other known processes under neutral conditions. According to one embodiment higher yields of the desired reaction products may be achieved, if suitable soft wood lignins from biorefineries are used which are extracted under relatively mild processing conditions compared to the Kraft processing.
  • the term "monomers and/or oligomers” means molecules or oligomers derived from depolymerization of lignin, preferably under oxidative conditions. These molecules or oligomers may be a result of chemical modification or degradation of lignin during the process.
  • the obtained depolymerized lignin monomers and oligomers may have an average molecular weight (Mw) of less than 1600 g/mol, or less than 800 g/mol.
  • the depolymerization of lignin converts the complex polymer molecules of the lignin into its monomers, oligomers or a mixture of monomers and oligomers.
  • Typical monomers and oligomers include aromatic phenols, and under oxidative conditions particularly aromatic aldehydes or acids.
  • the monomers may be oxidized in the presence of the oxidation agent.
  • Preferred monomers and/or oligomers that can be obtained according to the process are therefore aromatic aldehydes, ketones and/or acids.
  • the process is especially well suited to make aromatic aldehydes and acids. Vanillin, vanillic acid and acetovanillone may be particularly mentioned as such lignin depolymerization products of the instant process.
  • the process may be preferably used to produce vanillin.
  • Figure 1 shows a typical reaction scheme.
  • the pH during the polymerization is a in a neutral range such as for instance about pH 5.0 to about pH 8.0.
  • Other ranges that can be mentioned include pH 5.0 to about pH 7.5, pH 5.0 to about pH 7.0, pH 5.5 to about pH 8.0, pH 6.0 to about pH 8.0, or pH 6.5 to about pH 7.5.
  • Further pH values that can be mentioned are about pH 5.3, 6.1, 6.3, 6.8, 7.2 and 7.7. The process avoids the use of highly alkaline or highly acidic agents which are therefore absent in the reaction medium.
  • the reaction is run in the presence of a polar aprotic solvent.
  • the solvent may be used in admixture with other aprotic solvents and/or water. Aqueous mixtures may be particularly mentioned.
  • the reaction may occur in a solvent that comprises at least 50 %, at least 70 % or 90% by volume, preferably about 95, 97 or 99 % by volume of an aprotic polar solvent or a mixture of polar aprotic solvents.
  • the reaction may alternatively occur in a solvent which substantially consists of a polar aprotic solvent or a mixture of such solvents.
  • the lignin may be fully or partially dissolved in the solvent. In one embodiment it is substantially dissolved.
  • the reaction is performed using about 1 to about 500 g lignin per liter of solvent. A range of about 5 to 100 g/1, or 8 to 80 g/1 may be particularly mentioned. Typical use rates are 10, 20 ,40 or 80 g/1.
  • polar aprotic solvents can be used.
  • the polar, aprotic solvent is selected from the group consisting of polar aprotic solvents that have a lactam, lactone, carbamate, urea, and carbonate functionality.
  • Preferred polar aprotic solvents include NMP, other N-alkyl pyrrolidinones, 2- pyrrolidone, ethylene carbonate, propylene carbonate, ⁇ -valerolactone (GVL), ⁇ -butyrolactone, dimethylacetamide (DMA), N- methyl-2-piperidone, 2-piperidone, other N-alkyl piperidones, caprolactam, dimethylbenzamide, diethylbenzamide, other dialkylacetamides, and combinations thereof.
  • the polar aprotic solvent is selected from dichloromethane, tetrahydrofuran, acetone, N,N-dimethylformamide, acetonitrile, dimethyl sulfoxide, ethylene carbonate, butylene carbonate and propylene carbonate, ⁇ -valerolactone (GVL), ⁇ -butyrolactone, and preferably is propylene carbonate or , ⁇ -valerolactone (GVL).
  • Such solvents are distinguished by their relatively high dielectric constants, high dipole moments, and solubility in water.
  • Preferred solvents have a high boiling point and flash point and hence lower vapor pressure and flammability, such as propylene carbonate and ⁇ -valerolactone (GVL). They are relatively safer to work under thermal oxidative conditions compared to highly flammable alcohols such as methanol and ethanol as solvents.
  • VTL propylene carbonate and ⁇ -valerolactone
  • the polar aprotic solvent has dielectric constant of at least 6, preferably at least 20, more preferably at least 50, and most preferably at least 60, at least 65 or at least 70.
  • the dielectric content may be preferably chosen in the range of 20 to 72 or 30 to 69.
  • the propylene carbonate used according to the examples has a dielectric constant of about 65, a high boiling point 242 °C of about and a flash point of about 132 °C and ⁇ -valerolactone (GVL), has a dielectric constant of about 36, a high boiling point of about 207 °C and flash point 96 °C.
  • the reaction is performed under oxidative conditions by utilizing an oxidation agent.
  • An oxidation agent is therefore present.
  • Various oxidation agents can be used. Typical oxidation agents comprise molecular oxygen, hydrogen peroxide or mixtures thereof. The use of oxygen is preferred.
  • the oxidation agents are used in the absence of a catalyst.
  • Depolymerization of lignin using such a catalyst free system according to the invention provides good yields of monomers. For instance treatment of Kraft lignin with propylene carbonate as the solvent at 120 to 220 °C and 6 to 30 bar of 8% 0 2 in nitrogen matrix resulted in yields of up to about 2.1 wt% (w.r.t lignin) of vanillin. The vanillin was obtained together with trace amounts of vanillic acid, acetovanillone and homovanillic acid.
  • the reaction occurs in the presence of a metal catalyst.
  • the metal of the metal catalyst may be selected from a transition metal.
  • the transition metal is selected from the group V to group IX elements, optionally from the transition metals rhenium, vanadium, cobalt, ruthenium and molybdenum.
  • the metal catalyst is a metal oxide or a metal complex.
  • the catalyst may be selected from the group consisting of rhenium trioxide, vanadium pentoxide, molybdenum di- or trioxide, rhenium (IV) oxide, rhenium (VII) oxide, ammonium perrhenate, potassium perrhenate, tetrabutylammonium perrhenate and methyl rhenium trioxide.
  • Methyl rhenium trioxide (MeRe0 3 or MTO) may be particularly mentioned.
  • the catalyst can be used in a wide concentration range. It may be used in a concentration of about 0.1 to about 50 wt. % (determined as metal wt% of the lignin). Other concentrations that can be used are 0.5 to about 20 wt. %, 1 to about 40 wt. %, 1 to about 20 wt. %. A concentration of 0.5 to about 5 wt. % may be particularly mentioned.
  • a pretreated lignin precursor refers to any biomass which is chemically or biologically pretreated removing hemicellulose and cellulose or both.
  • oxygen may be present in at least 2%, optionally at least 5%, optionally at about 8% or in about 2% to 40 % or in about 2% to 15 %, optionally in about 5 to 30 % by volume of an ambient gas/matrix gas.
  • Typical oxygen ratios that can by mentioned include 1,2, 4, 8, 12, 22, 36, 67, 75, 80, 95, 97, 99 % by volume of an ambient gas/matrix gas.
  • oxygen may be used in substantially undiluted form. Diluted oxygen may be particularly useful in embodiments for making vanillin.
  • the use of a catalyst and diluted oxygen may be another preferred embodiment for making vanillin.
  • Substantially undiluted oxygen may be preferred for making vanillic acid.
  • the oxygen may be also used in the form of air or mixtures of air with oxygen. In other embodiments it is used in the form of oxygen gas diluted in a matrix gas.
  • the matrix gas may be selected from an inert gas, such as nitrogen or argon. Nitrogen gas is particularly mentioned as matrix gas.
  • the oxidation agent may be added in various forms. It may be added as a solution with the polar aprotic solvent or may be bubbled into it as a gas, in pure form or in admixture with other gases. In another embodiment the oxidation agent may create an autogenous pressure in a closed or sealed container (autoclave) filled with lignin and optionally the catalyst in a solvent. The autoclave is then pressured with the oxidation agent.
  • autoclave closed or sealed container
  • the process according to the invention may be generally performed under pressure.
  • the pressure is at least 3 bar, preferably at least 5 bar. It can be in the range of about 3 to 40 bar or of about 5 to 35 bar, preferably of 8 to about 15 bar.
  • the pressure can be about 2, 4, 6, 8, 10, 15 or 20 bar.
  • the reaction can be also performed without applying a pressure (about 1 bar).
  • a tube reactor may be used wherein a mixture of the lignin, catalyst, oxidation agent and solvent is brought to reaction at elevated temperatures.
  • the process according to the invention is run at elevated temperature. Heating to at least room temperature, at least 25° C, at least 30° C, at least 40° C, at least 60° C, at least 80 °C may be suitable.
  • the temperature during the reaction may be in a range of between about 80 and about 300 °C, preferably between about 100 and about 250 °C, and most preferably between about 150 and 200 °C. Temperatures of about 35° C, 85° C, 110° C, 160 ° C, 260° C may be particularly mentioned.
  • the process described herein comprises preparing vanillin from lignin, whereby vanillin is obtained in a yield of about 1% to about 4% and 1 to 7.3% total yield of aromatic carbonyl compounds by weight of the lignin used as starting material.
  • vanillin is prepared from the lignin in a yield of about 2% to about 4% and 2 to 6 % total yield of aromatic carbonyl compounds by weight of the lignin. High yields may be obtained by using a transition metal catalyst in certain cases as described herein.
  • the process of the invention may be performed under agitation, such as mixing and stirring.
  • the process described herein comprises preparing vanillin and vanillic acid from lignin.
  • the process provided further allows the product composition to be altered depending on the concentration of oxidation agent in the matrix used as well as the total pressure. Accordingly, a high percentage of an aromatic aldehyde, such as vanillin, may be obtained by use of a diluted mixture of oxidation agent within a matrix or lower pressures, while a high percentage of an aromatic acid, such as vanillic acid, may be obtained by use of an undiluted mixture of the oxidation agent or higher pressures.
  • substantially undiluted oxygen or a matrix comprising at least 70 %, at least 80 %, at least 90 % or at least 99 % by volume of oxygen in a diluted form is preferred to obtain higher vanillic acid yields.
  • a typical pressure may then be 8 to 20 bar.
  • the depolymerization reaction according to the process of the invention is performed in a reaction time of about 1 h to 12 h, or optionally of about 5 h to 7 h.
  • Typical reaction times that can be mentioned are about 1, 2, 3, 4, 5, 6, 7 8, 9, 10 or 11 hours.
  • lignin may be isolated by filtration, evaporation, distillation or centrifugation or any suitable separation technique.
  • the process according to the invention may be combined with further process steps. According to one embodiment the steps of (a) reacting lignin or lignin containing biomass with an oxidation agent under pH neutral conditions in a polar aprotic solvent at elevated temperatures, and (b) separating the reaction mixture to obtain a first product mixture comprising the monomers and/or oligomers and the solvent and a second product mixture comprising the remaining lignin and by-products.
  • the separating step may be performed by filtration.
  • the monomers and oligomers remain in the solution of the first reaction mixture and can be processed further.
  • Another embodiment of such process comprises a purification step to remove the solvent of the first product mixture from the monomers and/or oligomers.
  • the purification step may be a distillation. It may be preferred to purify the first reaction mixture by distilling the monomer together with a high boiling solvent (azeotropic distillation) followed by fractional distillation. Alternatively the purification step may be a membrane separation. In another embodiment the solvent may be recycled back to step (a) after this purification step.
  • the process may comprise a catalyst removal step, wherein the catalyst is removed from the product mixture.
  • This purification may be performed by an aqueous extraction and subsequent removal of solvent.
  • FIG. 2 A typical industrially upscalable process is shown in Fig. 2.
  • Table 2 shows the results of the oxidative depolymerization of Kraft Lignin (Lignin Alkali, 370959Aldrich) using pure 0 2 or 22% 0 2 as the oxidant in a nitrogen matrix.
  • the reaction was conducted in a 50 ml hastelloy Parr batch autoclave reactor.
  • a weighed amount of the Kraft lignin (Indulin AT, MeadWestvaco) was added to the autoclave along with the catalyst and the solvent.
  • the reactor was pressurized to the desired pressure with 8% 0 2 and the reaction was performed at the desired temperature for the desired time (t) with stirring.
  • the reactor was cooled down to room temperature and depressurized.
  • the reaction mixture was diluted with acetone and passed through sintered glass filter. Internal standard (9-acetylphenanthrene) was added to the crude product and the yields of the products were determined by gas chromatography (GC) analysis.
  • GC gas chromatography
  • Table 3 shows the results of the oxidative depolymerization of Indulin AT (MeadWestvaco) using 8% 0 2 as the oxidant in nitrogen matrix.
  • the G/S ratio for this lignin was determined by 31 P NMR as 7.5 and the maximum possible amount of vanillin from this lignin was determined as 9.1 wt% by nitrobenzene oxidation.
  • the reaction was conducted in a 50 ml hastelloy Parr batch autoclave reactor.
  • a weighed amount of Wheat straw lignin (Protobind soda lignin) was added to the autoclave along with the catalyst and the solvent.
  • the reactor was pressurized to the desired pressure with 8% 0 2 and the reaction was performed at the desired temperature for the desired time (t) with stirring.
  • the reactor was cooled down to room temperature and depressurized.
  • the reaction mixture was diluted with acetone and passed through sintered glass filter. Internal standard (9-acetylphenanthrene) was added to the crude product and the yields of the products were determined by gas chromatography (GC) analysis.
  • Table 4 shows the results of the oxidative depolymerization of Wheat straw lignin using 8% 0 2 as the oxidant in nitrogen matrix. The G/S ratio for this lignin was determined by 31 P NMR as 0.8.
  • the reaction was conducted in a 50 ml hastelloy Parr batch autoclave reactor.
  • a weighed amount of EFB lignin (organosolv) was added to the autoclave along with the catalyst and the solvent.
  • the reactor was pressurized to the desired pressure with 8% 0 2 and the reaction was performed at the desired temperature for the desired time with stirring.
  • the reactor was cooled down to room temperature and depressurized.
  • the reaction mixture was diluted with acetone and passed through sintered glass filter. Internal standard (9-acetylphenanthrene) was added to the crude product and the yields of the products were determined by gas chromatography (GC) analysis.
  • GC gas chromatography
  • Table 5 shows the oxidative depolymerization of EFB lignin (organosolv) using 8% 0 2 as the oxidant in a nitrogen matrix.
  • EFB lignin organosolv
  • the G/S ratio for this lignin was determined by 3 IP NMR as 0.5.
  • the process as defined above may find a multiple number of applications in which lignin shall be depolymerized to fine chemical of value, such as for instance vanillin and vanillic acid.
  • the process may be upscalable for industrial processes make use of Kraft lignin or lignin from biorefineries.
  • the process is more environmentally benign and allows for efficient and selective methods for the oxidative depolymerization of lignins. It may replace existing technologies for lignin depolymerization.
  • the process may find use to make vanillin and vanillic acid for the fragrance and flavor industry from naturally available materials.
  • This process also may be useful for the production of syringaldehyde, syringic acid, p- hydroxybenzaldehyde and p-hydroxy benzoic acid which relay on the type of biomass used. Additionally these products can be used for further chemical and bio -conversions to form p- terephthalic acid and muconic acid and monomers for bio-based polymers.
  • the oligomers obtained may be used for the existing applications of lignosulfonates, as resins for polymers, as polyphenols, precursors for carbon fibres, lube additives and UV absorbers.

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Abstract

La présente invention concerne de manière générale un procédé de dépolymérisation de lignine en monomères et/ou oligomères, dans lequel on fait réagir la lignine dans des conditions d'oxydation à un pH neutre en présence d'un solvant aprotique polaire à températures et pression élevées. Le procédé est particulièrement utile pour produire des aldéhydes et des acides aromatiques tels que la vanilline et l'acide vanillique avec des rendements élevés à partir de lignine kraft en évitant les conditions fortement acides ou fortement alcalines. Ainsi, le procédé est mis en œuvre dans des conditions neutres sans aucun catalyseur métallique ou éventuellement en présence d'un catalyseur tel que le trioxyde de rhénium, le pentoxyde de vanadium, le dioxyde ou le trioxyde de molybdène, l'oxyde de rhénium (IV) oxyde, l'oxyde de rhénium (VII), le perrhénate d'ammonium, le perrhénate de potassium, le perrhénate de tétrabutylammonium et le trioxyde de méthylrhénium (MTO). Le solvant aprotique polaire préféré est le carbonate de propylène ou la γ-valérolactone qui sont biodégradables, présentent une faible pression de vapeur, un faible niveau d'odeur et une faible toxicité.
PCT/SG2017/050177 2016-03-30 2017-03-30 Procédé de dépolymérisation de lignine dans des conditions oxydatives neutres WO2017171652A1 (fr)

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CN109704931A (zh) * 2017-10-25 2019-05-03 中国科学院大连化学物理研究所 七氧化二铼催化氢解木质素芳醚键的方法
WO2020215561A1 (fr) * 2019-04-26 2020-10-29 福州大学 Procédé et application pour préparer un dispersant par utilisation d'un produit de dégradation de la lignine
CN111849534A (zh) * 2020-07-21 2020-10-30 贵州理工学院 一种秸秆生产生物质油的方法
CN111978164A (zh) * 2019-05-21 2020-11-24 中国科学院大连化学物理研究所 一种可见光催化氧化木质素制备芳香醛的方法
WO2021109533A1 (fr) * 2019-12-03 2021-06-10 中国科学院广州能源研究所 Procédé pour la préparation de composé monophénolique et la coproduction de cellulose par oxydation catalytique de biomasse par un oxyde de métal de transition

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CN109704931B (zh) * 2017-10-25 2021-12-28 中国科学院大连化学物理研究所 七氧化二铼催化氢解木质素芳醚键的方法
CN107857696A (zh) * 2017-10-31 2018-03-30 四川爱尔西科技有限公司 催化氧化木质素制备高纯度香草醛的方法
WO2020215561A1 (fr) * 2019-04-26 2020-10-29 福州大学 Procédé et application pour préparer un dispersant par utilisation d'un produit de dégradation de la lignine
US11479722B2 (en) 2019-04-26 2022-10-25 Fu Zhou University Method for preparing dispersant using lignin degradation products
CN111978164A (zh) * 2019-05-21 2020-11-24 中国科学院大连化学物理研究所 一种可见光催化氧化木质素制备芳香醛的方法
CN111978164B (zh) * 2019-05-21 2022-10-14 中国科学院大连化学物理研究所 一种可见光催化氧化木质素制备芳香醛的方法
WO2021109533A1 (fr) * 2019-12-03 2021-06-10 中国科学院广州能源研究所 Procédé pour la préparation de composé monophénolique et la coproduction de cellulose par oxydation catalytique de biomasse par un oxyde de métal de transition
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