• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A method of obtaining depolymerized lignin from biomass using a transition metal catalyst and a solvent mixture of organic solvent and water. The invention also relates to a compound obtainable by the method and prod
    公开号:BR112016011986B1
    申请号:R112016011986-0
    申请日:2014-11-27
    公开日:2020-11-24
    发明作者:Joseph Samec；Maxim Galkin
    申请人:Kat2Biz Ab；
    IPC主号:
    专利说明:

    [0001] [001] The present invention relates to a method of depolymerizing lignin from biomass using a transition metal catalyst. The present invention facilitates an integration of lignin depolymerization into a pulp manufacturing process. BACKGROUND
    [0002] [002] There is a growing interest in the use of biomass as a source for fuel production or fine chemical production. Biomass includes, but is not limited to, parts of plants, fruits, vegetables, waste for processing, wood chips, straw, grain, grasses, corn, corn straw, weeds, aquatic plants, hay, paper, derived products of paper, paper and products derived from recycled paper, lignocellulosic material, lignin and any biological material containing cellulose or material of biological origin.
    [0003] [003] An important component of biomass is the lignin present in the solid portions of the biomass. Lignin comprises chains of aromatic and oxygenated constituents forming larger molecules that are not easily treated. A major reason for the difficulties in treating lignin is the inability to disperse lignin to contact catalysts that can break down lignin.
    [0004] [004] Lignin is one of the most abundant natural polymers on earth. A common way to obtain lignin is by separating wood during pulp manufacturing processes. Only a small amount (1-2%) is used in specialty products, while the rest mainly serves as fuel. Even though burning lignin is a valuable way to reduce the use of fossil fuels, lignin has significant potential as a raw material for the sustainable production of chemicals and fuels.
    [0005] [005] Several lignins differ structurally depending on the source of raw material and subsequent processing, but a common feature is a common main structure consisting of several units of substituted phenyl propane that are linked to each other through aryl ether or carbon-carbon bonds. carbon. They are typically replaced by methoxy groups and the phenolic and aliphatic hydroxyl groups provide places for, for example, additional functionalization. Lignin is known to have a poor ability to absorb water compared to, for example, hydrophilic cellulose.
    [0006] [006] Nowadays lignin can be used as a component for, for example, granular fuel, or as a binder, but it can also be used by itself as an energy source due to its high energy content. Lignin has a higher energy content than cellulose or hemicelluloses and one gram of lignin averages 2.27 kJ, which is 30% more than the energy content of cellulosic carbohydrate. The energy content of lignin is similar to that of coal. Nowadays, due to its total value, the lignin that was removed using the kraft process, sulfate process, in a pulp or paper factory, is normally burned in order to provide energy to feed the production process and to recover the chemicals of the cooking liquor.
    [0007] [007] Lignin depolymerization (LDP) is a key step in its efficient use. The efficient LDP process is expected to lead to new green starting materials for manufacturing and fine chemicals. Likewise, the LDP process followed by a hydrodeoxygenation step (HDO) will be a direct route for fossil fuel substitutes. Among all the proposed methods for depolymerizing lignin, a neutral redox pathway that does not require any external hydrogen source is the most economical. The chemical structure of lignin is very complex, where the β — O — 4 'ether bond glycerolaryl represents the monomeric unit that is most commonly repeated in organosolv and enzymatic hydrolysis lignin.
    [0008] [008] Biofuel, such as biogasoline and biodiesel, is a fuel in which energy is primarily derived from biomass material or gases such as wood, corn, sugar cane, animal fat, vegetable oils and so on . However, the biofuel industries are facing problems such as the food vs. fuel debate, efficiency and the overall supply of raw materials. At the same time, the pulp or paper manufacturing industries produce large quantities of lignin which is often, as described above, only burned at the mill. Two common strategies for exploring biomass as a fuel or fuel component are to use pyrolysis oils or hydrogenated lignin.
    [0009] [009] A disadvantage of using lignin as a source for fuel production is the issue of providing lignin or lignin derivatives in a form suitable for hydrotreating or cracking (cracking) units. The problem is that lignin is not soluble in oils or in fatty acids which is, if not necessary, highly demanded.
    [0010] [010] The prior art provides several strategies for degrading lignin into small units or molecules in order to prepare processable lignin derivatives. These strategies include hydrogenation, deoxygenation and acid catalyst hydrolysis. WO2011003029 relates to a method of catalytic cleavage of carbon-carbon bonds and carbon-oxygen bonds in lignin. US20130025191 relates to a method of depolymerization and deoxygenation where lignin is treated with hydrogen together with a catalyst in an aromatic-containing solvent. All of these strategies relate to methods where the degradation is carried out before a possible mixture of fatty acids or oils. WO2008157164 discloses an alternative strategy where a first dispersing agent is used to form a biomass suspension to obtain better contact with the catalyst. These strategies usually also require isolation of the degradation products in order to separate them from undesirable agents such as solvents or catalysts.
    [0011] [011] Savings in the production of fuels or fine chemicals from biomass depend, for example, on an efficient process for preparing lignin and the preparation of lignin or lignin derivatives, so that fuel production is the most efficient possible. For example, the amount of oxygen should be as small as possible and the number of preparation steps should be as small as possible.
    [0012] [012] SUMMARY OF THE INVENTION
    [0013] [013] The purpose of the present invention is to provide a method of preparing depolymerized lignin from a biomass raw material.
    [0014] [014] A first aspect of the present invention relates to a composition comprising a solvent and one or more compounds having the formula:
    [0015] [015] where each R1 and R2 is H or OCH3 and R3 is (CH2) 2CH3, (CH2) 3OH or (CH) 2CH3
    [0016] [016] and in which at least one of the compounds is
    [0017] a. Providenciar biomassa em forma particulada, a biomassa contendo lignina, uma mistura de solventes compreendendo um solvente orgânico e água, e um catalisador de metal de transição; b. Misturar a biomassa, a mistura de solventes e o catalisador de metal de transição para obter uma mistura; c. Aquecer a mistura até pelo menos 80 °C; e d. Isolar opcionalmente a lignina espolimerizada. [017] A second aspect of the present invention relates to a method of preparing the composition depolymerizing lignin comprising The. Provide biomass in particulate form, biomass containing lignin, a mixture of solvents comprising an organic solvent and water, and a transition metal catalyst; B. Mix the biomass, the solvent mixture and the transition metal catalyst to obtain a mixture; ç. Heat the mixture to at least 80 ° C; and d. Optionally isolate spolimerized lignin.
    [0018] [018] A third aspect of the present invention relates to depolymerized lignin which can be obtained by the method according to the present invention.
    [0019] [019] Another aspect of the present invention relates to a method of producing one or more compounds having the formula of:
    [0020] a. Providenciar biomassa em forma particulada, a biomassa contendo lignina, uma mistura de solventes compreendendo um solvente orgânico e água, e um catalisador de metal de transição; b. Misturar a biomassa, a mistura de solventes e o catalisador de metal de transição para obter uma mistura; c. Aquecer a mistura até pelo menos 80 °C; e d. Opcionalmente isolar o um ou mais compostos. [020] where each R1 and R2 is H or OCH3 and R3 is (CH2) 2CH3, (CH2) 3OH or (CH) 2CH3 comprising: The. Provide biomass in particulate form, biomass containing lignin, a mixture of solvents comprising an organic solvent and water, and a transition metal catalyst; B. Mix the biomass, the solvent mixture and the transition metal catalyst to obtain a mixture; ç. Heat the mixture to at least 80 ° C; and d. Optionally isolate the one or more compounds.
    [0021] [021] Yet another aspect of the present invention relates to the use of the composition of the present invention for fuel production.
    [0022] [022] Yet another aspect of the present invention relates to a method of producing fuel comprising cracking or hydrotreating compounds according to the present invention in a refinery.
    [0023] [023] Yet another aspect of the present invention relates to a method of producing one or more compounds having the formula:
    [0024] a. Providenciar biomassa em forma particulada, em que a biomassa contém lignina, uma mistura de solventes compreendendo um solvente orgânico e água, e um catalisador de metal de transição; b. Misturar a biomassa, a mistura de solventes e o catalisador de metal de transição para obter uma mistura; c. Aquecer a mistura até pelo menos 80 °C e despolimerizar a lignina a uma pressão não superior a 5.000.000 Pa (50 bar), de preferência 3.500.000 Pa (35 bar) ou menos; e d. Isolar opcionalmente a lignina espolimerizada. [024] where each R1 and R2 is H or OCH3 and R3 is (CH2) 2CH3, (CH2) 3OH or (CH) 2CH3 comprising: The. Provide biomass in particulate form, where the biomass contains lignin, a mixture of solvents comprising an organic solvent and water, and a transition metal catalyst; B. Mix the biomass, the solvent mixture and the transition metal catalyst to obtain a mixture; ç. Heat the mixture to at least 80 ° C and depolymerize the lignin to a pressure not exceeding 5,000,000 Pa (50 bar), preferably 3,500,000 Pa (35 bar) or less; and d. Optionally isolate spolimerized lignin.
    [0025] [025] Figure 1. GPC chromatogram for lignin, moderately depolymerized lignin and depolymerized lignin.
    [0026] [026] Figure 2. GPC chromatogram for depolymerized lignin according to the present invention and solvolized lignin without palladium catalysis.
    [0027] [027] Figure 3. Recycling of Pd / C hydrogen transfer from ethanolaryl β — O — 4 'ethers. Reaction conditions: 80 ° C for 1 hour. Y is a percentage conversion and X is an execution number.
    [0028] [028] Figure 4. GPC of the lignin residues from the non-catalyzed reaction and treatments according to the present invention using various catalysts.
    [0029] [029] Figure 5. GC-MS of lignin residues after treatment using U-Fe-B catalyst.
    [0030] [030] Figure 6. GC-MS of lignin residues after treatment using Raney nickel catalyst.
    [0031] [031] Figure 7. GC-MS of lignin residues after treatment using Cu catalyst.
    [0032] [032] Figure 8. GC-MS of lignin residues after treatment using Fe catalyst.
    [0033] [033] DETAILED DESCRIPTION OF THE INVENTION
    [0034] [034] The present invention provides a simple method of depolymerizing lignin directly from biomass, without first isolating the lignin. The method according to the present invention makes the lignin more soluble and thus more lignin can be extracted from the biomass. In addition, the method can be implemented in existing techniques, such as the organosolv process.
    [0035] [035] The method of the present invention does not involve the use of an added hydrogen donor such as formic acid. In the method according to the present invention, an alcohol is not a hydrogen donor or is not, at least, the main hydrogen donor. Instead, without being limited by theory, it is believed that the hydrogen needed to depolymerize lignin comes from the biomass itself.
    [0036] [036] A desirable characteristic of the refinery raw material is a low oxygen content or the lowest possible oxygen to carbon ratio. The composition obtained by the present invention is believed to be a suitable raw material for refining since it can be dissolved in various solvents, including oils and fatty acids, and has a low oxygen to carbon content.
    [0037] [037] Biomass includes, but is not limited to, wood, fruit, vegetables, waste for processing, straw, grain, grasses, corn, corn straw, weeds, aquatic plants, hay, paper, paper products, paper and products derived from recycled paper, bark, seaweed, straw, tree bark or dried fruit bark, lignocellulosic material and any biological material containing cellulose or material of biological origin. In one embodiment, the biomass is wood, preferably particulate wood such as sawdust or wood chips. The wood can be any type of wood, hard or soft, coniferous tree or leafy tree. A non-limiting list of woods would be pine, birch, fir, maple, ash, mountain ash, sequoia, alder, elm, oak and beech. The present inventors have found that depolymerization of lignin according to the present invention is much more effective if the lignin is not pretreated or chemically modified, for example, reduced or oxidized. For example, kraft lignin or lignosulfate treated according to the present invention will be less depolymerized compared to sawdust or wood chips or organosolv lignin treated with the method according to the present invention. In one embodiment, the biomass contains lignin where the chemical structure or chemical composition of the lignin has essentially not changed. In one embodiment, the biomass is organosolv lignin, that is, lignin obtained from an organosolv process.
    [0038] [038] In this application, the term "derived from lignin" means molecules or polymers derived from lignin. In the present application, "lignin derivatives" and "lignin derivative molecules or polymers" are used interchangeably. These molecules or polymers can be a result of chemical modification or degradation of lignin or a source of lignin, for example when treating black or red liquor, to precipitate or separate lignin.
    [0039] [039] What the present inventors found was that even if the addition of a hydrogen donor (such as formic acid) resulted in selective β— O — 4 bond cleavage in a model study and depolymerization of the model polymer (Example 1 ), the conditions used did not result in any depolymerization of lignin, even at 160 ° C. When reacting lignin with Pd / C (5 mol%), sodium borohydride (10 mol%) in water / ethyl acetate at 160 ° C for 1 hour with autogenous pressure, the treatment only led to moderate depolymerization, see Figure 1.
    [0040] [040] Instead, the inventors took advantage of the conditions used during organosolv treatment of biomass. Organosolv is a pulp formation technique originating in the early 1930s, with the main development taking place during the late 1980s, where biomass is separated into cellulose and lignin and hemicellulose. The technique involves contacting lignocellulosic raw material such as wood cut with an aqueous organic solvent at a temperature between 140 ° C and higher, but not exceeding 220 ° C. This causes the hydrolytic depolymerization of the alpha aryl ether bonds into fragments that are soluble in organic solvent. Solvents include acetone, methanol, ethanol, butanol, ethylene glycol, formic acid and acetic acid. The concentration in the solvent in water can be between 40 to 80% by weight. Solvents with a high boiling point can be used and have the advantage that a lower process pressure can be used, but on the other hand such solvents are difficult to recover. The organosolv process can be a two or more stage process, where the same or different solvents are used in two stages. A base such as sodium hydroxide can be added, preferably in the second step, and the lignin can be isolated by lowering the pH using any suitable acid. In order to isolate the high molecular weight lignin from hemicellulose in the organosolv process, the lignin can be precipitated or the mixture can be filtered, evaporated, distilled or centrifuged.
    [0041] [041] When treating biomass, for example wood chips or sawdust, in an organic solvent in the presence of a transition metal catalyst at an elevated temperature, the present inventors found that the depolymerized lignin obtained had a molecular weight of less than 900 g / mol, while the control method without the catalyst resulted in lignin having a molecular weight of 6000 g / mol. The present invention can easily be integrated into a pulp manufacturing process involving an organosolv process giving rise to depolymerized lignin, but also high quality cellulose and hemi cellulose.
    [0042] [042] Depolymerized lignin comprises compounds with the formula:
    [0043] [043] where each R1 and R2 is H or OCH3 and R3 is (CH2) 2CH3, (CH2) 3OH or (CH) 2CH3.
    [0044] [044] Specific examples of said compounds are
    [0045] [045] where 1 is guaiacylpropane, 2 is guaiacylpropanol, 3 is syringylpropane, 4 is syringylpropanol and 5 is 2 — methoxy — 4— (prop— 1 — enyl) phenol. The method of the present invention generates a mixture of compounds. Fundamentally, the method results in compound 5 and only low levels of compounds 3 and 4 and, therefore, the compounds obtained by the present invention and the composition according to the present invention, have a low oxygen to carbon ratio. In one embodiment, the generated mixture comprises less than 10 mol% of each compound 1 to 4 and more than 50 mol% of compound 5. In one embodiment, the generated mixture comprises less than 5 mol% of each compound 1 to 4 and more than 70 mol% of compound 5, or the mixture generated comprises less than 5 mol% of compounds 1 to 4 and more than 80 mol% of compound 5. In one embodiment, the mixture comprises 1 to 10 wt% of compound 1 to 4. In another embodiment, the mixture comprises 70 to 90 wt% of compound 5. A higher degree of compound 5 can be beneficial, since it has a low ratio of oxygen to carbon and greater selectivity results in a mixture that is more predictable with regard to further treatments and thus easier to refine.
    [0046] [046] In one embodiment, biomass is a biomass that contains lignin, preferably wood, and where the biomass is particulate biomass such as sawdust or wood chips. The biomass can be ground to small particles or powder using any suitable technique. The particle size can be 10 cm or less, or 5 cm or less, or 2 cm or less, or 5 mm or less, or 1 mm or less or 500 μm or less.
    [0047] [047] The biomass is mixed with an organic solvent or a mixture comprising at least one organic solvent. In one embodiment, a mixture of solvents comprising an organic solvent and water is used. The organic solvent can be oxygenated such as an alcohol, ester, ketone, ether or furan or furfural based solvent. Preferred solvents are C1 — C10 alcohols, C2 — C10 ethers, C2 — C10 carboxylic acids, C3 — C10 ketones and C2 — C10 esters, for example methanol, ethanol, propanol, isopropanol, butanol, glycerol, acetone and butyl ether such as ether tert-butyl methyl; diethyl ether, diglyme, diisopropyl ether, dimethoxyethane, diethylene glycol diethyl ether, polyethylene glycol 1,4 — dioxane, acetic acid and tetrahydrofuran. In one embodiment, the solvent is selected from water, methanol, ethanol, butanol, propanol or acetone or a combination thereof. Preferred C1-C10 esters are organic esters, aromatic or non-aromatic esters, examples of esters are benzyl benzoate, various acetates such as methyl acetate, ethyl acetate and butyl acetate, various lactates such as ethyl lactates. In one embodiment, the solvent comprises a combination of C1-C10 alcohols, C2-C10 ethers, C2-C10 carboxylic acids and C2-C10 esters. In one embodiment, the solvent comprises two C1-C10 alcohols, for example ethanol and glycerol, and in another embodiment the solvent comprises propanol and glycerol. In one embodiment, the solvent comprises polyethylene glycol and a C1-C10 alcohol. In one embodiment, the solvent comprises furfural or furfuryl alcohol. When the solvent is a mixture of an organic solvent and water, the mixture may contain methanol and water, ethanol and water, isopropanol and water, acetic acid and water or ethyl acetate and water, preferably ethanol and water, isopropanol and water and methanol and water. The ratio of the organic solvent to water can be from 1:10 to 10: 1 (weight ratio between organic solvent: water), such as 1: 8 to 8: 1 preferably 1: 4 to 4: 1, or 1 : 2 to 2: 1 preferably about 1: 1. In one embodiment, the solvent mixture comprises 40-60% by weight of organic solvent and 40-60% by weight of water. The concentration of substrate, or biomass, in the solvent can be 0.1% by weight or more, or 0.5% by weight or more, or 1% by weight or more, or 2% by weight or more, or % by weight or more, or 10% by weight or more, or 20% by weight or more, or 30% by weight or more and can be 70% by weight or less or 50% by weight or less.
    [0048] [048] The method can be carried out without water, for example using only an organic solvent, but by adding water the method becomes more suitable for large scale production due to the reduced risk of explosions. There is no need to add base or any additional base to the reaction.
    [0049] [049] A transition metal catalyst is used to treat biomass and the transition metal can be selected from or based on, but not limited to, palladium (Pd), platinum (Pt), ruthenium (Ru), rhodium ( Rh) nickel (Ni), iron (Fe), copper (Cu), chromium (Cr), molybdenum (Mo), tungsten (W), preferably Pd, Pt, Fe, Ni or Cu. In one embodiment, the catalyst is Pd. In one embodiment, the catalyst is Pt. In one embodiment, the catalyst is W or W / C. In one embodiment, the catalyst is Fe. In one embodiment, the catalyst is Ni with a base such as Raney nickel. In one embodiment, the catalyst is Cu. The catalyst can also be a combination of said metals or bimetallic catalyst comprising at least one of said metals. In another embodiment, the catalyst is a palladium and / or platinum doped metal catalyst. The doped metal catalyst can be a copper, nickel or iron based catalyst that has been doped with palladium or platinum. The catalyst can be in the form of a powder, grains, coated surface or a solid material. In one embodiment, the catalyst is selected from Pd, Pd2 (dba) 3 (Tris (dibenzylidenoacetone) dipaladium (0)), Pd (OAc) 2 (palladium (II) acetate), Pd (PPh3) 4 (Tetrakis (triphenylphosphine) palladium (0)), Pd (PtBu3) 2 (Bis (tri-tert-butyl phosphine) palladium (0)) or Pd / C (palladium on carbon). In another embodiment, the catalyst is Pt, platinum black or PtO2. In another embodiment, the catalyst is Rh / C. In another embodiment, the catalyst is Ru / C. The catalyst can be pre-activated before use, for example by removing oxygen or oxides using a reducing agent. The catalyst can be added in at least catalytic amounts. In one embodiment, the amount of catalyst is 0.5 mol% or more, or 1 mol% or more, or 3 mol% or more, or 5 mol% or more, or 7 mol% or more, or 10% mol or more, or 100 mol% or less, or 50 mol% or less, or 25 mol% or less, or 15 mol% or less, or 12 mol% or less, in relation to the lignin content. It is believed that when using Pd or Pt based catalysts or Pd or Pt doped catalysts, the method becomes insensitive or at least less sensitive to water. It is preferred that the catalyst is in contact with the substrate or the biomass during the reaction.
    [0050] [050] The biomass and catalyst forms form a slurry or mixture in the solvent and the mixture is heated to at least 80 ° C, or at least 120 ° C, preferably 130 ° C or more, or 140 ° C or more, or 150 ° C or more, or 160 ° C or more, or 170 ° C or more, or 180 ° C or more, or 190 ° C or more, or 250 ° C or less, or 230 ° C or less, or 210 ° C or less, or 200 ° C or less. The treatment time depends on the solvent used and the volume to be treated. As an example, the mixture of biomass and catalyst in the solvent, can be heated for 30 minutes or more, or 1 hour or more, or 1.5 hours or more, or 2 hours or more when treating a volume of 3 ml. The treatment, or reaction, is quick and can be completed after 1 hour or less, or after 3 hours or less, or after 10 hours or less.
    [0051] [051] The reaction can be carried out in a closed or sealed container creating an autogenous pressure. The reaction is preferably conducted during continuous mixing. The pressure during depolymerization can be about 10,000,000 Pa (100 bar) or less, or 5,000,000 Pa (50 bar) or less, or 4,500,000 Pa (45 bar) or less, or 3,500,000 Pa (35 bar) or less, or 2,500,000 Pa (25 bar) or less, or 1,000. 000 Pa (10 bar) or less, for example 800,000 Pa (8 bar) or less, or 500,000 Pa (5 bar) or less, or 200,000 Pa (2 bar) or less, or 100,000 Pa (1 bar) or more. In one embodiment, the pressure during depolymerization is between 500,000 Pa and 4,500,000 Pa (5-45 bar), such as between 2,000. 000 Pa and 3,500,000 Pa (20-35 bar). However, a major advantage of the present invention is that hydrogen gas is not required. The reaction can also be carried out during reflux.
    [0052] [052] The treatment, or reaction, can be carried out in air, or in an atmosphere with reduced oxygen pressure, or in an inert atmosphere such as nitrogen or argon. When a palladium catalyst is used, using an inert atmosphere provides better results, but it is not necessary.
    [0053] [053] After treatment, depolymerized lignin can be isolated by filtration, evaporation, distillation or centrifugation or any suitable technique. It is believed that cellulose or hemicellulose will not be affected or at least only slightly depolymerized. This makes the present invention also an interesting method for producing high quality pulp and hemicellulose. By first treating the lignocellulosic raw material according to organosolv processes followed by the method according to the present invention, high quality pulp and hemicellulose as well as depolymerized lignin can be obtained.
    [0054] [054] The depolymerized lignin obtained has an average molecular weight (Mw) less than 1500 g / mol, or preferably less than 1200 g / mol, or less than 900 g / mol. In one embodiment, 80% or more of the obtained lignin has a molecular weight of less than 600 g / mol, or less than 400 g / mol. In one embodiment, 2 — methoxy — 4— (prop — 1 — enyl) phenol is obtained in 15% yield or more, or 20% yield or more.
    [0055] [055] By separating and recycling the catalyst, the process becomes more efficient and even more favorable from an economic point of view. The catalyst can be used several times before losing reactivity. Reactivation can be done by treating the catalyst with hydrogen. For example, the catalyst can be placed in alcohol such as ethanol and left for several hours (2 - 15 hours, for example) under pressure of hydrogen [300,000 Pa to 600,000 Pa (3-6 bar), for example]. Reactivation can be carried out at room temperature (20 ° C) and the reactivated catalyst can be rinsed with an alcohol, for example ethanol.
    [0056] [056] Depolymerized lignin, or compounds, obtained by the method of the present invention, and especially compounds with the formula
    [0057] [057] The compounds or composition according to the present invention can be hydrotreated or cracked in a refinery to produce fuel using well-known techniques. In addition, the compounds can be used to prepare fine chemicals such as phenols. EXAMPLES Example 1
    [0058] [058] Preliminary studies have shown that β — Ο — 4 'ethanolaryl ethers (50mg) undergo a slow oxidation of the benzyl hydroxyl group without cleavage to generate dimeric ketone in the presence of catalytic amounts of Pd / C (5 mol%) and air (Table 1, entry 1), 3 mL of ethyl acetate: water (ratio 3: 1). When the reaction was carried out under an inert atmosphere at 80 ° C, a very slow transformation was observed until the desired oxidized and cleaved products were obtained (Table 1, entry 2). We found that the addition of a catalytic amount of hydride or hydrogen donors had an effect on the reaction. By carrying out the oxidative oxidative cleavage reaction catalyzed Pd / C in the presence of sodium borohydride, a quantitative yield of the desired acetophenone and phenol was achieved within 40 minutes. Several hydrogen donors have been screened.
    [0059] [059] Ο degree of methoxylation of lignin aryls depends on their origin. The substitution of the substrate (Table 2) imitates the substitution pattern present in grasses, soft wood (pine, spruce, etc.) and hard wood (birch, etc.). The reactions gave rise to the corresponding products cleaved in quasi-quantitative yields at 80 ° C. For highly substituted substrates the reaction was slower and a longer reaction time was needed to achieve full conversion.
    [0060] [060] The next step for the depolymerization of lignin was to apply the method to a model polymer to reflect physical properties, for example solubility. The model polymer was subjected to β — 0—4 'catalyzed Pd / C bond cleavage reaction under treatment with the same conditions as dimer models.
    [0061] [061] The stability of our system in both acidic and basic environments must also be taken into account, since the lignins produced comprise considerable amounts of acids or base, depending on the processes used, in other words it is insensitive to pH. In the presence of 1M HCl or NaOH, the results were identical to neutral conditions. Interestingly, if the reaction of NaOH without palladium did not lead to any transformation of starting material, in the case of HCl several products were not identified with a small amount of guaicol (see S.I.). This means that catalytic amounts of palladium could protect post-extraction reconditioning lignin. The results obtained were encouraging and suggested that catalyzed depolymerization of Pd / C could be applicable by degradation of plant-derived lignin.
    [0062] [062] However, lignin under identical conditions did not undergo depolymerization. Reacting lignin with Pd / C (5 mol%), sodium borohydride (10 mol%) in water / ethyl acetate at 160 ° C for 1 hour with autogenous pressure, only led to moderate depolymerization, see Figure 1 . Example 2
    [0063] [063] Pine sawdust (Pinus Sylvestris) (10g) was mixed with a mixture of ethanol and water (100 mL, 1: 1 ratio) in the presence of Pd / C (5 mol% in lignin content) and heated to 195 ° C for 1 hour. A control experiment was also carried out, in which Pd / C was absent.
    [0064] [064] GPC analysis showed that all the lignin obtained was less than 900 g / mol (900 Da) Mw with more than 80% of the analyte belonging to monomers and dimers (less than 400 g / mol (400 Da) Mw)) (Control 6000 g / mol (6000 Da) to 1000 g / mol (1000 Da) 40% of the total), Figure 2. Both NMR and GC / MC analyzes showed the presence of a main product, 2 — methoxy— 4— (prop — 1 — enyl) phenol.
    [0065] [065] The purification of the oil obtained led to a 28% yield. Example 3
    [0066] [066] Catalyst recovery and reuse are important issues and as such, easy catalyst separation and recycling in successive batch operations can greatly increase the efficiency of the overall process. Performing the reaction using the same batch of catalyst led to a moderate decrease in reactivity during three runs. The reaction of Pd / C after the fifth pass with hydrogen proved to be successful in increasing the catalyst reactivity. See Figure 3. Reactivation was done by placing the catalyst in ethanol and applying a hydrogen pressure of 500,000 Pa (5 bar) and leaving the catalyst there for 12 hours at room temperature. The reactivated catalyst was then washed with ethanol. Example 4
    [0067] [067] Procedure: 5 g of dry birch chip were used together with 20 mol% of catalyst in relation to the lignin content (the MW of lignin monomer was assumed to be 243 g / mol, Klasson's method). The solvent system used was water / ethanol 1: 1, 180 ml. The reaction was carried out at 180-190 degrees for 1 hour in a sealed high pressure reactor. In all cases, the reactor was purged with nitrogen before use. The heating program was the same as for palladium.
    [0068] [068] Depolymerization of lignin catalyzed by added metal catalyst. The catalysts used are W / C, Urushibara catalyst U — Fe — B, Cu, Raney nickel (2800, Sigma Aldrich) and Fe. GPC analysis revealed a distinct depolymerization for all transition metal catalysts, Figure 4. GC —MS reveals lignin residues, Figure 5—8.
    [0069] 1. 2,6—dimetoxifenol 2. 4—hidroxi—3—metoxibenzaldeído 3. 2—metoxi—4—(prop—1—en—1—il)fenol 4. E/R—2,6—dimetoxi—4—(prop—1—en—1—il)fenol 5. 4—hidroxi—3,5—dimetoxibenzaldeido 6. E/R—2,6—dimetoxi—4—(prop—1—en—1—il)fenol 7. 2—metoxi—4—propilfenol 9. 1—(4—hidroxi—3,5—dimetoxifenil)prop—2—en—1—ona 10. 2—metoxifenol [069] Iron catalyst was prepared by reducing the source of iron (II) or (III) with sodium borohydride in water. The iron catalyst was used directly without pre-washing and filtration. U — Fe — Β was prepared according to a literature procedure. Copper was used as a fine metal powder. Subtitles for GC-MS 1. 2,6 — dimethoxyphenol 2. 4 — hydroxy — 3 — methoxybenzaldehyde 3. 2 — methoxy — 4— (prop — 1 — en — 1 — il) phenol 4. E / R — 2,6 — dimethoxy — 4— (prop — 1 — en — 1 — il) phenol 5. 4 — hydroxy — 3,5 — dimethoxybenzaldehyde 6. E / R — 2,6 — dimethoxy — 4— (prop — 1 — en — 1 — il) phenol 7. 2 — methoxy — 4 — propylphenol 9. 1— (4 — hydroxy — 3,5 — dimethoxyphenyl) prop — 2 — en — 1 — one 10. 2 — methoxyphenol
    权利要求:
    Claims (7)
    [0001]
    LIGNIN DEPOLIMERIZATION METHOD, characterized by understanding The. providing biomass in particulate form, in which the biomass contains lignin, a mixture of solvents, in which the solvent mixture is a mixture of an organic solvent and water in a weight ratio of 1: 4 to 4: 1, and a catalyst transition metal; where the biomass is wood in the form of sawdust or wood chips. B. mixing the biomass, the solvent mixture and the transition metal catalyst to obtain a mixture; ç. heat the mixture to at least 160 ° C and depolymerize the lignin to a pressure not exceeding 5,000,000 Pa (50 bar), preferably 3,500,000 Pa (35 bar) or less; and d. optionally isolate depolymerized lignin, in which no hydrogen gas is added and in which the solvent mixture contains methanol and water, ethanol and water, isopropanol and water, acetic acid and water or ethyl acetate and water.
    [0002]
    METHOD, according to claim 1, characterized in that the transition metal catalyst is based on palladium, preferably palladium on charcoal (Pd / C) and preferably the concentration of transition metal catalyst is at least 1 mol% based on in lignin content, preferably at least 3 mol%, or at least 5 mol%, or at least 10 mol%.
    [0003]
    METHOD according to either of claims 1 or 2, characterized in that the mixture is heated to at least 180 ° C, preferably at least 195 ° C, and wherein the mixture is preferably heated for at least 15 minutes, preferably at least 30 minutes, at least 1 hour, or at least 3 hours, or at least 5 hours.
    [0004]
    METHOD according to any one of claims 1 to 3, characterized in that the organic solvent is methanol or ethanol.
    [0005]
    METHOD according to any one of claims 1 to 4, characterized in that no additional base is used.
    [0006]
    METHOD according to any one of claims 1 to 5, characterized in that no formic acid or hydride is added.
    [0007]
    METHOD according to any one of claims 1 to 6, characterized in that depolymerization is conducted in air.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112016011986B1|2020-11-24|Lignin depolymerization method
    Cao et al.2018|Lignin valorization for the production of renewable chemicals: State-of-the-art review and future prospects
    Zhang et al.2018|Catalytic pyrolysis of biomass and polymer wastes
    JP6369873B2|2018-08-08|Composition of biomass material for refining
    JP6525343B2|2019-06-05|Composition comprising an ester of lignin and an oil or fatty acid
    Pineda et al.2016|Heterogeneously catalyzed lignin depolymerization
    JP2018500281A|2018-01-11|Ether-functionalized lignin for fuel production
    JP2017505300A|2017-02-16|Method for producing non-pyrolytic bio-oil from lignocellulosic material
    WO2017095316A1|2017-06-08|Depolymerized lignin in hydrocarbon oil
    Feng et al.2021|Catalytic hydrothermal liquefaction of lignin for production of aromatic hydrocarbon over metal supported mesoporous catalyst
    WO2015199608A1|2015-12-30|Depolymerisation of lignin
    Prakash et al.2015|Thermochemical valorization of lignin
    Zhang et al.2020|Influence of Ultrasonic/Torrefaction Assisted Deep Eutectic Solvents on the Upgrading of Bio-Oil from Corn Stalk
    Albrecht et al.2019|Upgrading Fast Pyrolysis Liquids
    Suresh et al.2021|Lignin waste processing into solid, liquid, and gaseous fuels: a comprehensive review
    US20180265794A1|2018-09-20|Continuous production of fuel grade hydrocarbons by hydrotreatment of forestry byproduct lignin
    Rishikesh et al.2021|A comprehensive review on lignin obtained from agro-residues: potential source of useful chemicals
    Xu et al.2021|Hydrothermal liquefaction of lignocellulose for value-added products: Mechanism, parameter and production application
    Chen et al.2020|Pyrolysis chemistry and mechanisms: interactions of primary components
    Roy2012|Hydrodeoxygenation of lignin model compounds via thermal catalytic reactions
    McDonald et al.2015|Upgrading biomass pyrolysis bio-oil to renewable fuels
    Yadav et al.2021|Valorization of Bio-Oils to Fuels and Chemicals
    Das2021|Hydrothermal liquefaction of lignocellulosic biomass using water and hydrogen-donor solvent mixtures to produce energy-dense heavy oil
    Braga et al.2021|Effect of pretreatment on pyrolysis products of Pennisetum purpureum Schum. by Py-GC/MS
    Ul-Islam et al.2022|Handbook of Biomass Valorization for Industrial Applications
    同族专利:
    公开号 | 公开日
    EP3074484B1|2020-04-15|
    JP2017502107A|2017-01-19|
    US10150790B2|2018-12-11|
    JP6573884B2|2019-09-11|
    WO2015080660A1|2015-06-04|
    CA2931672A1|2015-06-04|
    EP3074484A1|2016-10-05|
    EP3074484A4|2017-08-02|
    CN106133117A|2016-11-16|
    CN106133117B|2019-11-26|
    US20170152278A1|2017-06-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPH0336872B2|1984-11-09|1991-06-03|Kogyo Gijutsuin|
    US4647704A|1986-04-28|1987-03-03|Uop Inc.|Hydrocracking process for liquefaction of lignin|
    US5959167A|1997-08-25|1999-09-28|The University Of Utah Research Foundation|Process for conversion of lignin to reformulated hydrocarbon gasoline|
    US8013195B2|2007-06-15|2011-09-06|Uop Llc|Enhancing conversion of lignocellulosic biomass|
    WO2009037281A2|2007-09-18|2009-03-26|Basf Se|Method for hydrogenating separation of lignin using transition metal carbides|
    CN101768052B|2008-12-26|2012-09-26|中国科学院大连化学物理研究所|Method for preparing aromatic compound by catalytic hydrocracking of lignin|
    US8871989B2|2009-02-27|2014-10-28|Uop Llc|Combination of hydrogenation and base catalyzed depolymerization for lignin conversion|
    WO2011003029A2|2009-07-01|2011-01-06|The Regents Of The University Of California|Catalytic disproportionation and catalytic reduction of carbon-carbon and carbon-oxygen bonds of lignin and other organic substrates|
    US8404908B2|2009-10-13|2013-03-26|Uop Llc|Process for lignin conversion to chemicals or fuels with H2 generated from lignin depolymerization products|
    IT1399078B1|2010-03-24|2013-04-05|Eni Spa|PROCEDURE FOR THE CONVERSION OF LIGNIN WITH LIQUID HYDROCARBONS|
    KR101933726B1|2010-04-07|2018-12-28|리셀라 피티와이 엘티디|Methods for biofuel production|
    BR112012028438A2|2010-05-12|2016-07-19|Shell Int Research|processes for liquefying a cellulosic material to synthesize a liquefied product, and for producing a biofuel component from a cellulosic material, product, and, biofuel|
    CN103124780A|2010-07-07|2013-05-29|凯奇莱特能源有限公司|Solvent-enhanced biomass liquefaction|
    SE535691C2|2011-03-08|2012-11-13|Kat2Biz Ab|Reduction of C-O bonds via catalytic transfer hydrogenolysis|
    WO2012177138A1|2011-06-23|2012-12-27|Universiteit Utrecht Holding B.V.|Process for the liquid-phase reforming of lignin to aromatic chemicals and hydrogen|
    US8772557B2|2011-07-26|2014-07-08|Uop Llc|Aromatic hydrocarbons from depolymerization and deoxygenation of lignin|
    CN103173237B|2011-12-23|2015-01-21|中国林业科学研究院木材工业研究所|Biomass alcoholysis method and biomass alcoholysis oil preparation method|
    US20130232852A1|2012-03-09|2013-09-12|Thesis Chemistry, Llc|Method for tiered production of biobased chemicals and biofuels from lignin|CA3029301A1|2016-04-13|2017-10-19|Ecole Polytechnique Federale De Lausanne |Production of monomers from lignin during depolymerisation of lignocellulose-containing composition|
    WO2017184072A1|2016-04-22|2017-10-26|Kat2Biz Ab|Difunctional grafting agent based on phenolic backbone from lignin|
    CN106480766B|2016-09-05|2019-01-22|中国林业科学研究院林产化学工业研究所|A kind of wood fibre adds the method for hydrogen separating lignin|
    SG11201907634SA|2017-03-22|2019-09-27|Ren Fuel K2B Ab|Continuous production of fuel grade hydrocarbons by hydrotreatment of functionalized lignin|
    EP3612511A4|2017-04-20|2021-01-20|Spero Renewables, Llc.|Extraction of natural ferulate and coumarate from biomass|
    WO2019053287A1|2017-09-18|2019-03-21|Technische Universiteit Eindhoven|A method for obtaining a stable lignin: polar organic solvent composition via mild solvolytic modifications|
    US20200317593A1|2017-12-01|2020-10-08|Spero Renewables, Llc|Lignin conversion to phenolic molecules using transition metal catalysts|
    DK201870095A1|2018-02-16|2019-09-24|Københavns Universitet|A biofuel composition comprising lignin|
    WO2019183394A1|2018-03-23|2019-09-26|Domtar Paper Company, Llc|Methods of reducing odor in extruded lignin and extruded lignin with reduced odor|
    EP3810383A1|2018-06-25|2021-04-28|Katholieke Universiteit Leuven|Fractionation and depolymerisation of lignocellulosic material|
    WO2020263623A1|2019-06-26|2020-12-30|University Of Florida Research Foundation|Catalytic depolymerization of lignin to high value hydrocarbons|
    WO2021030690A2|2019-08-15|2021-02-18|Ebikade Elvis O|Low-pressure depolymerization of lignocellulosic biomass|
    WO2021058483A1|2019-09-23|2021-04-01|Université Catholique de Louvain|Process for producing lignin components from lignocellulosic biomass|
    CN110590498A|2019-09-29|2019-12-20|华南理工大学|Method for preparing monophenol chemicals through selective depolymerization of lignin based on microemulsion|
    法律状态:
    2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-06-30| B09A| Decision: intention to grant|
    2020-11-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/11/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    SE1351410-4|2013-11-27|
    SE1351410|2013-11-27|
    PCT/SE2014/051416|WO2015080660A1|2013-11-27|2014-11-27|Depolymerisation of lignin in biomass|
    [返回顶部]